Agent for imparting hydrophilic persistent effect and / or water-skiing property

Abstract

The present invention addresses the problem of providing an agent for imparting a hydrophilicity-sustaining effect and / or water-skiing properties, said agent being capable of forming a tangible substance such as a coating film having good hydrophilicity sustaining after repeated adhesion of low-ion water such as pure water and drying, and / or being capable of forming a tangible substance such as a coating film having good hydrophilicity and water-skiing properties. The hydrophilic-sustaining effect and / or water-sliding property imparting agent is characterized by comprising, as a constituent component, 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.

Description

TECHNICAL FIELD

[0001] The present application relates to a hydrophilicity-sustaining effect and / or a water-sliding property imparting agent. BACKGROUND

[0002] A heat exchanger has a heat-exchange plate such as an aluminum fin for performing heat exchange between a heat medium and air. When the heat exchanger is in operation, moisture in the air sometimes condenses on the surface of the aluminum fin, and if the condensed water thus produced becomes water droplets and bridges between the fins, an increase in power consumption due to an increase in ventilation resistance, scattering of the water droplets, and the like sometimes occur. In order to prevent such bridging by the condensed water, a hydrophilic treatment is often performed on the surface of the fin material.

[0003] As the above hydrophilic treatment, a method of forming a hydrophilic coating film by applying a resin composition in which hydrophilic particles are contained in a resin to the surface of a fin material is known. In the past, as the hydrophilic particles, inorganic particles such as silica and organic particles such as acrylic particles have been used. In addition, Patent Documents 1 and 2 describe the use of hydrophilic crosslinked polymer fine particles as the hydrophilic particles, the hydrophilic crosslinked polymer fine particles containing a copolymer of (a) 2 to 50% by weight of a hydrophilic monomer having a polymerizable double bond and a polyalkylene oxide chain or a polyvinylpyrrolidone chain, (b) 20 to 97% by weight of a (meth)acrylamide-based monomer, (c) 1 to 30% by weight of a crosslinkable unsaturated monomer, (d) 2 to 50% by weight of a carboxyl group-containing polymerizable unsaturated monomer, and (e) 0 to 50% by weight of another polymerizable monomer.

[0004] In addition, if the surface of the aluminum fin becomes wet with the condensed water, heat exchange efficiency decreases, the aluminum fin corrodes, bacteria and the like multiply, and various problems such as frosting occur. In order to solve this problem, it is important that the condensed water on the surface of the aluminum fin easily drains, that is, it is important to improve the water-sliding property of the surface of the aluminum fin.

[0005] In order to improve the drainability (water-sliding property) of the condensed water, a water-repellent treatment is also known for the surface of the aluminum fin. For example, Patent Document 3 discloses that a super water- and oil-repellent heat exchange member having excellent water-sliding property is obtained by providing a plurality of gold-leaf-shaped protrusions composed of silica or the like on the surface of a base material, and then forming a water- and oil-repellent antifouling film on the surface of the base material on which the gold-leaf-shaped protrusions are formed. In addition, Patent Document 4 discloses that a heat exchanger member having both excellent water-repellency and water-sliding property is obtained by applying a structure having a slip water-repellent layer on a base material, the slip water-repellent layer containing a polymer having a polyethyleneimine skeleton, a fluorine-containing compound, and silica.

[0006] On the other hand, Patent Literature 5 describes that by using, as a surface treatment agent for an aluminum-containing metal heat exchanger, a treatment agent in which a specific water-soluble resin (A), colloidal silica (B), an organic alkoxysilane and / or a hydrolyzate thereof (C), a crosslinking agent (D) capable of crosslinking with the water-soluble resin (A), and water (E) are mixed in a prescribed amount ratio, it is possible to hydrophilize the surface of the aluminum fins to prevent bridging by condensed water, and also to improve the drainability.

[0007] Prior Art Documents

[0008] Patent Literature

[0009] Patent Literature 1: Japanese Patent Application Laid-Open (JP-A) No. 9-87576

[0010] Patent Literature 2: Japanese Patent Application Laid-Open (JP-A) No. 2000-328038

[0011] Patent Literature 3: Japanese Patent Application Laid-Open (JP-A) No. 2013-92289

[0012] Patent Literature 4: International Publication No. 2020 / 213485

[0013] Patent Literature 5: International Publication No. 2014 / 147782 SUMMARY

[0014] Problems to be Solved by the Invention

[0015] The present application has as its object to solve the following 1st and / or 2nd problems.

[0016] (1st Problem)

[0017] However, for the above hydrophilic coating film, it is needless to say that the hydrophilicity of the coating film immediately after formation of the coating film (initial hydrophilicity) is required to be improved, and also that the hydrophilicity is required to be sustained. In addition, the hydrophilization of fin materials and coating films and the like applied to the surface thereof (hereinafter, substances having these shapes will be referred to as shaped substances) is not limited, and sometimes the hydrophilicity (initial hydrophilicity) of various shaped substances themselves or the surface thereof is required in various uses, and sometimes the hydrophilicity is also required to be sustained. In particular, fin materials of heat exchangers undergo a wet state in which condensed water is present on the surface of the fin material and a dry state in which the condensed water evaporates repeatedly over a long period of use. Therefore, for hydrophilic shaped substances such as hydrophilic coating films applied to fin materials of heat exchangers, it is required that the hydrophilicity of the shaped substances is sustained even after the attachment and drying of condensed water are repeated.

[0018] However, in the case where the above hydrophilic particles in the hydrophilization treatment are the conventional silica and acrylic particles, sometimes the hydrophilicity sustainability of the shaped substances after the attachment and drying of condensed water are repeated is not sufficient.

[0019] Furthermore, Patent Documents 1 and 2 describe that hydrophilicity persists even after repeated application and drying of tap water. However, the condensate adhering to the heat exchanger fins, like pure water, has a low ionic content (hereinafter referred to as "low-ion water"). Therefore, when using the hydrophilic particles described in Patent Documents 1 and 2, the hydrophilicity persistence after repeated application and drying of low-ion water is not sufficient.

[0020] Furthermore, the hydrophilic particles described in Patent Documents 1 and 2 require the use of organic solvents in their manufacture. In addition, the (meth)acrylamide monomers, which are the main components of these hydrophilic particles, are highly toxic and are not preferred from the perspectives of reducing environmental impact and safety.

[0021] Furthermore, patent documents 3 and 4 pertain to water-repellent treatment techniques, so the effect of continuous hydrophilicity cannot be expected.

[0022] Furthermore, Patent Document 5 makes no discussion whatsoever about the adhesion of condensed water and the persistence of hydrophilicity after repeated drying.

[0023] Therefore, the first objective of this invention is to provide a hydrophilicity-continuous effect imparting agent that can form a hydrophilic material (e.g., a coating film) with good hydrophilicity continuation after repeated adhesion and drying of low-ion water such as pure water (hereinafter sometimes referred to as "after wet / dry cycle").

[0024] Furthermore, for tangible objects placed in indoor environments (such as heat exchanger fins), oil stains, primarily composed of oily components (e.g., higher fatty acids, higher alcohols, etc.) originating from volatile or dispersed suspended matter from building materials, food, and household goods, may adhere to the surface of these objects. It is required that even after such oil stains adhere to the surface, the object still exhibits good hydrophilicity. Therefore, a preferred, albeit non-essential, objective of this invention is to provide a hydrophilicity-continuous effect imparting agent that maintains good hydrophilicity on the surface of tangible objects (e.g., fins) even after oil stains adhere.

[0025] (Topic 2)

[0026] As mentioned above, good water-repellent properties (hydrophobicity) of droplets are sometimes required for aluminum fins in heat exchangers.

[0027] However, patent documents 1 and 2 do not discuss the hydroplaning properties of droplets at all.

[0028] Furthermore, as described in Patent Documents 3 and 4, while improving the hydrophobicity of the substrate surface enhances the droplet's hydrophobicity, the increased contact angle makes it easier for tall droplets to form in the direction perpendicular to the substrate, leading to bridging between fins. In particular, in recent years, to improve the heat dissipation or cooling efficiency of heat exchangers, fin spacing has become extremely narrow, requiring a balance between hydrophilicity to suppress bridging between fins and hydrophobicity to improve droplet drainage.

[0029] Furthermore, while the surface treatment agent described in Patent Document 5 achieves a balance between hydrophilicity and drainage (hydrophobicity), it uses colloidal silica as the hydrophilic particles, which can lead to insufficient hydrophilic persistence. Additionally, it may produce the characteristic odor of silica and cause mold abrasion due to silica being a hard inorganic material. Therefore, there is a need to develop new surface treatment agents.

[0030] Therefore, a second objective of the present invention is to provide a novel hydrophobic agent capable of forming a tangible object (e.g., a coating film) with good hydrophilicity and hydrophobicity.

[0031] The object of the present invention is to solve at least one of the first problem and the second problem, and in a preferred embodiment, the object of the present invention is to solve both the first problem and the second problem.

[0032] Solution for solving the problem

[0033] In order to solve the aforementioned problem, the inventors have conducted repeated and in-depth research and found that by using particles containing cross-linked polymers with specific functional groups, the hydrophilicity persistence after wet / dry cycling can be improved.

[0034] Furthermore, the inventors have discovered that by using these particles, hydrophilicity can be improved while also improving water-slippery properties.

[0035] That is, the present invention includes the following inventions.

[0036] [1] A hydrophilic and / or hydrophobic imparting agent comprising particles of a crosslinked polymer having a -COOR group (R representing a hydrocarbon group, hydrogen atom, alkali metal atom or ammonium) and a hydroxyl group.

[0037] [2] According to the hydrophilicity retention effect and / or hydrophobicity imparting agent described in [1], wherein the crosslinked polymer comprises: 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.

[0038] [3] According to the hydrophilicity lasting effect and / or hydrophobicity imparting agent described in [2], wherein the structural unit derived from the monomer (AB1) is the structural unit represented by the following formula (1), and the structural unit derived from the monomer (C) is the structural unit derived from the polyfunctional olefin unsaturated monomer.

[0039] [Chemical Formula 1]

[0040]

[0041] In equation (1), R 1 [Indicates alkyl groups, hydrogen atoms, alkali metal atoms, or ammonium atoms with 1 to 4 carbon atoms]

[0042] [4] According to the hydrophilicity retention effect and / or hydrophobicity imparting agent described in [3], wherein the crosslinked polymer contains the crosslinked polymer represented by the formula (1) and R 1 It is a structural unit consisting of alkali metal atoms or ammonium.

[0043] [5] The hydrophilicity retention effect and / or hydrophobicity imparting agent described in any one of [2] to [4], wherein the content of the structural unit derived from the monomer (AB1) in the crosslinked polymer is 5% by mass or more.

[0044] [6] The hydrophilicity retention effect and / or hydrophobicity imparting agent described in 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% by mass.

[0045] [7] The hydrophilicity retention effect and / or hydrophobicity imparting agent described in any one of [2] to [6], wherein the crosslinked polymer further comprises a structural unit derived from an olefinic unsaturated monomer containing a polyoxyalkylene group.

[0046] [8] The hydrophilicity lasting effect and / or hydrophobicity imparting agent described in any one of [1] to [7], wherein the volume average particle size of the particles is 10 nm to 10 μm.

[0047] [9] The hydrophilicity lasting effect and / or hydrophobicity imparting agent described in any one of [1] to [8], wherein the particles are monolayer particles containing the crosslinked polymer, or are core-shell structure particles containing the crosslinked polymer in the shell layer.

[0048]

[10] The hydrophilicity-continuous effect and / or hydrophobicity imparting agent described in any one of [1] to [9], wherein the hydrophilicity-continuous effect and / or hydrophobicity imparting agent is used for the fin material of a heat exchanger.

[0049]

[11] The hydrophilicity lasting effect and / or hydrophobicity imparting agent as described in

[10] , wherein the fin material is used for aluminum fin material.

[0050]

[12] A resin composition having the hydrophilic sustained effect and / or hydrophobic imparting agent as described in any one of [1] to

[11] and a hydrophilic resin.

[0051]

[13] According to the resin composition described in

[12] , wherein the hydrophilic resin is a resin having at least one polar functional group in the group consisting of salts selected from carboxyl groups and carboxyl groups in its side chain.

[0052]

[14] The resin composition according to

[12] or

[13] further comprises a crosslinking agent.

[0053]

[15] A method for subjecting a tangible object to continuous hydrophilization and / or hydrophobicity, wherein the tangible object contains particles comprising a crosslinked polymer having a -COOR group (R representing a hydrocarbon group, a hydrogen atom, an alkali metal atom, or an ammonium) and a hydroxyl group.

[0054]

[16] A method for subjecting a substrate surface to continuous hydrophilicity and / or hydrophobicity by coating a composition containing particles comprising a crosslinked polymer onto the substrate, thereby forming a coating film containing the particles on the substrate surface, the crosslinked polymer having a -COOR group (R representing a hydrocarbon group, a hydrogen atom, an alkali metal atom, or an ammonium) and a hydroxyl group.

[0055]

[17] According to the method described in

[16] , wherein the substrate is a heat exchanger fin material.

[0056]

[18] According to the method described in

[16] or

[17] , wherein the composition further comprises a hydrophilic resin.

[0057]

[19] According to the method described in

[18] , wherein the hydrophilic resin is a resin having at least one polar functional group in the side chain composed of salts selected from carboxyl groups and carboxyl groups.

[0058]

[20] The method described in any one of

[16] to

[19] , wherein the composition further comprises a crosslinking agent.

[0059]

[21] The method described in any one of

[15] to

[20] , wherein the crosslinked polymer comprises: 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.

[0060]

[22] According to the method described in

[21] , the structural unit from which the monomer (AB1) is derived is the structural unit represented by the following formula (1), and the structural unit from which the monomer (C) is derived is the structural unit from a polyfunctional olefin unsaturated monomer.

[0061] [Chemical Formula 1]

[0062]

[0063] In equation (1), R 1 [Indicates alkyl groups, hydrogen atoms, alkali metal atoms, or ammonium atoms with 1 to 4 carbon atoms]

[0064]

[23] According to the method described in

[22] , wherein the crosslinked polymer contains R represented by the formula (1). 1 It is a structural unit consisting of alkali metal atoms or ammonium.

[0065]

[24] The method described in any one of

[21] to

[23] wherein the content of the structural unit from which the monomer (AB1) is derived is 5% by mass or more in the crosslinked polymer.

[0066]

[25] The method described in any one of

[21] to

[24] , wherein the content of the structural unit from which the monomer (C) is derived is 0.01% to 70% by mass in the crosslinked polymer.

[0067]

[26] The method described in any one of

[21] to

[25] , wherein the crosslinked polymer further comprises structural units derived from olefinic unsaturated monomers containing polyoxyalkylene groups.

[0068]

[27] The method described in any one of

[15] to

[26] , wherein the volume average particle size of the particles is 10 nm to 10 μm.

[0069]

[28] The method described in any one of

[15] to

[27] , wherein the particle is a monolayer particle containing the crosslinked polymer, or a core-shell structure particle containing the crosslinked polymer in the shell.

[0070] Invention Effects

[0071] The present invention can achieve the following first and / or second effects.

[0072] First effect: By using the particles of the present invention, the hydrophilicity persistence of the obtained material after wet / dry cycles can be improved. Furthermore, it is preferable that the hydrophilicity of the material after oil contamination can also be improved.

[0073] Second effect: By using the particles of the present invention, the obtained tangible material can be endowed with hydrophilicity and water-repellent properties.

[0074] Furthermore, the hydrophilic and / or hydrophobic agents with particles of the present invention as constituents are preferred in that they do not necessarily require the use of organic solvents (especially organic solvents that do not mix with water) or highly toxic monomers in their manufacture. Attached Figure Description

[0075] Figure 1 This is a schematic diagram illustrating the method for measuring the slip angle. Detailed Implementation

[0076] The present invention will now be described in detail. Hereinafter, a coating film will be used as an example of a tangible object, but as described below, the tangible object is not limited to a coating film.

[0077] 1. Hydrophilicity retention effect and / or hydrophobicity imparting agent

[0078] <Polymer Particles>

[0079] The hydrophilicity retention effect and / or hydrophobicity imparting agent of the present invention comprises particles (hereinafter, sometimes simply referred to as "polymer particles") of a crosslinked polymer having a -COOR group (R represents a hydrocarbon group, hydrogen atom, alkali metal atom, or ammonium) and a hydroxyl group. The crosslinked polymer constituting the polymer particles, by having a -COOR group and a hydroxyl group, exhibits excellent hydrophilic properties (initial hydrophilicity, hydrophilicity retention after wet / dry cycling, hydrophilicity after oil adhesion, etc.). Furthermore, by having a -COOR group and a hydroxyl group in the crosslinked polymer, excellent hydrophilicity and excellent hydrophobicity can be exhibited simultaneously. Further, by making the polymer having a -COOR group and a hydroxyl group a crosslinked polymer, the hydrophilicity retention effect and / or hydrophobicity imparting agent can be prevented from eluting in water, thereby improving the retention of the hydrophilic properties and hydrophobicity. Moreover, the hydrophilicity retention effect and / or hydrophobicity imparting agent of the present invention can achieve the above-mentioned effects even without using silica particles that may cause odor or mold abrasion, which is also preferable.

[0080] It should be noted that in this invention, "crosslinked polymer" refers to a polymer having a crosslinked structure. This crosslinked structure can be introduced into the crosslinked polymer by (co)polymerizing a monomer having two or more polymeric groups in one molecule. That is, the crosslinked polymer can be said to be a polymer containing structural units derived from monomers having two or more polymeric groups in one molecule.

[0081] The hydrocarbon group represented by R can be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group composed of these groups.

[0082] As an aliphatic hydrocarbon group, examples include:

[0083] Alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl (preferably alkyl groups with 1 to 4 carbon atoms);

[0084] Alkenyl groups such as vinyl, propenyl, isopropenyl, 1-butenyl, 2-butenyl, 1-pentenyl, 2-pentenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, and 3-methyl-1-butenyl (preferably alkenyl groups with 2 to 6 carbon atoms);

[0085] Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl and other cycloalkyl groups (preferably cycloalkyl groups with 3 to 8 carbon atoms), etc.

[0086] Examples of aromatic hydrocarbon groups include phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, 4-tert-butylphenyl, and naphthyl, with aromatic hydrocarbon groups having 6 to 10 carbon atoms being preferred.

[0087] Examples of groups formed by combining aliphatic and aromatic hydrocarbon groups include benzyl, phenylethyl, and other aralkyl groups, with aralkyl groups having 7 to 12 carbon atoms being preferred.

[0088] As the hydrocarbon group represented by R, alkyl is preferred, more preferably alkyl with 1 to 4 carbon atoms, even more preferably alkyl with 1 to 2 carbon atoms, and particularly preferably methyl.

[0089] Examples of alkali metal atoms represented by R include lithium, sodium, and potassium, with sodium and potassium being preferred, and sodium being even more preferred.

[0090] The ammonium represented by R is not limited to NH4. + The definition includes organic ammonium. Examples of organic ammonium include tetramethylammonium, tetrabutylammonium, and other tetraalkylammonium (preferably tetramethylammonium). 1-10 Quaternary ammonium compounds such as alkylammonium; ammonium compounds (primary to tertiary ammonium) formed by protonating an amine. Examples of such amines include trialkylamines (preferably trimethylamine), triethylamine, tributylamine, and other trialkylamines. 1-10 Alkylamines); monoethanolamine, diethanolamine, triethanolamine, and other hydroxyalkylamines (preferably mono-, di-, or tri-(hydroxyC) alkylamines). 1-10 Alkylamines, etc. That is, as ammonium represented by R, examples include NH4+. + Primary ammonium to quaternary ammonium, preferably tetramethylammonium, tetrabutylammonium, or other tetraalkylammonium (preferably tetramethylammonium). 1-10 Alkyl ammonium); trimethylammonium, triethylammonium, tributylammonium, and other trialkylammonium (preferably tri-C) 1-10 Alkyl ammonium); monoethanolammonium, diethanolammonium, triethanolammonium, and other hydroxyalkyl ammoniums (preferably mono-, di-, or tri-(hydroxyC) ammonium).1-10 (alkyl)ammonium); or NH4 + .

[0091] The crosslinked polymer may have only one type of -COOR group or multiple types of -COOR groups. When the crosslinked polymer has only one type of -COOR group, the R group is preferably hydrogen, an alkali metal, or ammonium, more preferably an alkali metal or ammonium. Alternatively, when the crosslinked polymer has multiple types of -COOR groups, the R group is preferably a combination of one or more selected from hydrogen, alkali metal, and ammonium with a hydrocarbon group (particularly an alkyl group having 1 to 4 carbon atoms), more preferably a combination of one or more selected from alkali metal and ammonium with a hydrocarbon group (particularly an alkyl group having 1 to 4 carbon atoms). Of all 100 mol% of R contained in the crosslinked polymer, the total proportion of R as hydrogen, alkali metal, or ammonium (hereinafter referred to as ionization rate) is, for example, 20 mol% to 100 mol%, preferably 40 mol% to 100 mol%, more preferably 50 mol% to 100 mol%. By adjusting the ionization rate to the above range, the hydrophilicity and hydrophobicity are improved. It should be noted that the upper limit of ionization rate can be below 95 mol% or below 90 mol%.

[0092] The hydroxyl value of the crosslinked polymer is preferably 20 mg KOH / g to 500 mg KOH / g, more preferably 40 mg KOH / g to 480 mg KOH / g, and even more preferably 70 mg KOH / g to 450 mg KOH / g.

[0093] The hydroxyl value refers to the amount (mg) of potassium hydroxide having the same amount of substance as the hydroxyl group contained in 1g of crosslinked polymer.

[0094] When the composition of a crosslinked polymer is well-defined, its hydroxyl value can be calculated by determining the amount of hydroxyl groups in the monomer components used as raw materials for the crosslinked polymer. For example, taking a crosslinked polymer prepared by polymerizing a monomer component containing 1% by mass of 2-hydroxyethyl methacrylate as a monomer with hydroxyl groups as an example, the hydroxyl value of this crosslinked polymer can be determined based on the following formula:

[0095] Formula: [Hydroxy value of cross-linked polymer] = [0.01 (content of 2-hydroxyethyl methacrylate as a mass basis in the monomer component used as cross-linked polymer raw material) / 130 (molecular weight of 2-hydroxyethyl methacrylate) × 1 (number of hydroxyl groups in 1 molecule of 2-hydroxyethyl methacrylate)] × 56.1 (mass of potassium hydroxide) × 1000 = 4.3 mg KOH / g.

[0096] Alternatively, when the composition of the crosslinked polymer is unclear, the hydroxyl value can be determined by calculating the amount (mg) of potassium hydroxide (KOH) required to neutralize the acetic acid bonded to the hydroxyl group when 1g of the crosslinked polymer is acetylated, in accordance with JIS K0070.

[0097] The hydroxyl value of a crosslinked polymer can be easily adjusted by regulating the amount of hydroxyl-containing monomers in the monomer components used as raw materials for the crosslinked polymer.

[0098] Relative to 100 moles of hydroxyl groups in the crosslinked polymer, the proportion of -COOR groups 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.

[0099] As described above, the crosslinked polymer comprises a structural unit derived from a monomer having two or more polymerizable groups in one molecule. Examples of monomers having two or more polymerizable groups in one molecule include monomers having two or more olefinic unsaturated bonds, preferably monomers with two or more terminal olefinic unsaturated bonds, i.e., monomers having two or more CH2=C< groups. Specifically, as the polymerizable group, groups containing olefinic unsaturated bonds, such as vinyl, allyl, and (meth)acryloyl groups, are preferred.

[0100] As a monomer having two or more polymerizable groups in one molecule, examples of monomers (A2), (B2), (AB2) and (C) can be given, with monomer (C) being preferred.

[0101] The content of monomer-derived structural units (preferably monomer (C)-derived structural units) having two or more polymeric groups in one molecule 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. By adjusting the content of monomer-derived structural units having two or more polymeric groups in one molecule to the above range, the hydrophilicity and hydrophobicity tend to be further improved.

[0102] The crosslinking polymer is preferably any one of the following methods 1 to 4, more preferably the crosslinking polymer of method 1, method 2 or method 4, and particularly preferably the crosslinking polymer of method 4. It should be noted that the R in the -COOR group in the following methods 1 to 4 is the same as that described above, and its preferred method is also the same.

[0103] Method 1: A crosslinked polymer comprising a structural unit derived from a monomer (hereinafter, monomer (A1)) having one or more -COOR groups and one polymerizable group in one molecule and not having a hydroxyl group, a structural unit derived from a monomer (hereinafter, monomer (B1)) having one or more hydroxyl groups and one polymerizable group in one molecule and not having a -COOR group, and a structural unit derived from a monomer (C) having two or more polymerizable groups in one molecule.

[0104] Method 2: A crosslinked polymer comprising structural units derived from monomers (A1) and / or monomers having one or more -COOR groups and two or more polymerizable groups but without hydroxyl groups (hereinafter, monomers (A2)), and structural units derived from monomers (B1) and / or monomers having one or more hydroxyl groups and two or more polymerizable groups but without -COOR groups (hereinafter, monomers (B2)), wherein the crosslinked polymer comprises at least structural units derived from monomers (A2) and / or monomers (B2).

[0105] Method 3: A crosslinked polymer comprising a structural unit derived from a monomer (hereinafter, monomer (AB2)) having one or more -COOR groups, one or more hydroxyl groups, and two or more polymerizable groups in one molecule.

[0106] Method 4: A crosslinked polymer comprising a structural unit derived from a monomer (hereinafter, 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 monomer (C).

[0107] It should be noted that, in this specification, "structural units derived from specified monomers" refers to structural units having the same structure as those formed by the polymerization of specified monomers. Typically, this means that the carbon-carbon double bonds in the specified monomers are replaced by carbon-carbon single bonds and two bond ends bonded to each carbon atom. It should also be noted that the structural units derived from specified monomers do not need to be structural units actually formed through the polymerization of specified monomers. As long as the structure is the same as that formed by the polymerization of specified monomers, even structural units formed by methods other than polymerization of specified monomers (e.g., structural units formed after polymerization followed by hydrolysis, neutralization, etc.) are included in the structural units derived from specified monomers.

[0108] The number of -COOR groups contained in the monomer (A1)1 molecule is preferably 1 to 3, more preferably 1.

[0109] The polymerizable groups contained in the monomer (A1) are preferably vinyl, allyl, (meth)acryloyl, or other groups containing olefinic unsaturated bonds, and more preferably (meth)acryloyl.

[0110] Examples of the monomer (A1) include monofunctional monomers containing carboxyl groups, salts of monofunctional monomers containing carboxyl groups, and (meth)acrylate monomers.

[0111] Specifically, examples of the carboxyl-containing monofunctional monomers include: unsaturated monocarboxylic acids such as (meth)acrylic acid and crotonic acid; and unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid. Among these, unsaturated monocarboxylic acids are preferred, (meth)acrylic acid is more preferred, and acrylic acid is particularly preferred.

[0112] Examples of salts of the carboxyl-containing monofunctional monomers include alkali metal salts and ammonium salts of carboxyl-containing monofunctional monomers. It should be noted that, in the salts of carboxyl-containing monofunctional monomers, the specific examples of the alkali metal atom and ammonium that form the salt with the carboxyl-containing monofunctional monomer are the same as those of the alkali metal atom and ammonium represented by R, and their preferred methods are also the same. Among these, salts of unsaturated monocarboxylic acids are preferred, and salts of acrylic acid are more preferred.

[0113] Specifically, examples of the (meth)acrylate monomers include: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and other alkyl methacrylates; phenyl methacrylate and other aryl methacrylates; benzyl methacrylate and other aryl methacrylates; wherein, alkyl methacrylates are preferred, and C-methacrylates are more preferred. 1-10 Alkyl esters, more preferably (meth)acrylic acid C 1-4 Alkyl esters.

[0114] The number of -COOR groups contained in the monomer (A2)1 molecule is preferably 1 to 3, more preferably 1.

[0115] The monomer (A2) preferably contains 2 to 6 polymerizable groups, more preferably 2.

[0116] The polymerizable groups contained in the monomer (A2) are preferably vinyl, allyl, (meth)acryloyl, or other groups containing olefinic unsaturated bonds, and more preferably (meth)acryloyl.

[0117] Examples of the monomer (A2) include 1-benzyl-3,4-divinyl-1H-pyrrole-2,5-dicarboxylic acid dimethyl ester and 1,1'-[2-[(ethoxycarbonyl)oxy]-1,3-propanediyl]bis(2-methyl-2-acrylate).

[0118] The monomer (B1)1 molecule preferably contains 1 to 3 hydroxyl groups, more preferably 1.

[0119] The polymerizable groups contained in the monomer (B1) are preferably vinyl, allyl, (meth)acryloyl, or other groups containing olefinic unsaturated bonds, and more preferably (meth)acryloyl.

[0120] Specifically, examples of the monomer (B1) include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, and other hydroxyalkyl methacrylates, wherein C-methacrylate is preferred. 1-8 Hydroxyalkyl esters, more preferably (meth)acrylic acid C 1-4 Hydroxyalkyl esters.

[0121] The monomer (B2)1 molecule preferably contains 1 to 3 hydroxyl groups, more preferably 1.

[0122] The monomer (B2)1 molecule preferably contains 2 to 6 polymerizable groups, more preferably 2.

[0123] The polymerizable groups contained in the monomer (B2) are preferably vinyl, allyl, (meth)acryloyl, or other groups containing olefinic unsaturated bonds, and more preferably (meth)acryloyl.

[0124] Specifically, examples of the monomer (B2) include polyols having n (n is an integer of 3 or more, preferably an integer of 3 to 6) hydroxyl groups, such as pentaerythritol tri(meth)acrylate and dipentaerythritol penta(meth)acrylate, and esters of (meth)acrylate having 2 or more and n-1 or less, as well as divinyl compounds having hydroxyl groups as represented by the following formula.

[0125] [Chemical Formula 2]

[0126]

[0127] The polymerizable groups contained in the monomer (C) are preferably vinyl, allyl, (meth)acryloyl, or other groups containing olefinic unsaturated bonds, more preferably vinyl or methacryloyl, and particularly preferably vinyl.

[0128] The molecular weight of the monomer (C) is preferably 50 or more and 1000 or less, more preferably 100 or more and 400 or less.

[0129] The monomer (C) is preferably a hydrocarbon crosslinking monomer, a divinyl ether monomer, a diallyl ether monomer, a poly(meth)acrylate, or a polyfunctional olefin unsaturated monomer having two or more groups containing olefin unsaturated bonds.

[0130] Examples of hydrocarbon crosslinking monomers include: aromatic hydrocarbon crosslinking monomers such as divinylbenzene, trivinylbenzene, divinylnaphthalene, divinyltoluene, and divinyldimethylbenzene; alicyclic hydrocarbon crosslinking monomers such as trivinylcyclohexane; and chain hydrocarbon crosslinking monomers such as 1,3-butadiene.

[0131] Examples of divinyl ether monomers include: diethylene glycol divinyl ether, dipropylene glycol divinyl ether, dibutyl glycol divinyl ether, and other dialkylene glycol divinyl ethers (preferably di-C). 1-4 Alkylene glycol divinyl ether); polyethylene glycol divinyl ether, polypropylene glycol divinyl ether, polybutylene glycol divinyl ether, and other polyalkylene glycol divinyl ethers (preferably polyC). 1-4 Alkyl glycol divinyl ether, etc. It should be noted that the number of repetitions of the alkyl glycol units in the polyalkyl glycol divinyl ether is not particularly limited, but preferably 3 to 10, more preferably 3 to 5.

[0132] Examples of diallyl ether monomers include: diethylene glycol diallyl ether, dipropylene glycol diallyl ether, dibutyl glycol diallyl ether, and other dialkylene glycol diallyl ethers (preferably diC). 1-4 Alkylene glycol diallyl ether); polyethylene glycol diallyl ether, polypropylene glycol diallyl ether, polybutane glycol diallyl ether, and other polyalkylene glycol diallyl ethers (preferably polyC). 1-4 Alkylene glycol diallyl ether, etc. It should be noted that the number of repetitions of the alkylene glycol units in the polyalkylene glycol diallyl ether is not particularly limited, but preferably 3 to 10, more preferably 3 to 5.

[0133] Examples of poly(meth)acrylates include: 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, neopentyl glycol di(meth)acrylate, and other mono-, di-, or polyalkylene glycol (preferably mono-, di-, or poly-C) acrylates. 2-4Di(meth)acrylate of alkylene glycols; tri(meth)acrylate of polyols such as trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate; tetra(meth)acrylate of polyols such as pentaerythritol tetra(meth)acrylate; penta(meth)acrylate of polyols such as dipentaerythritol penta(meth)acrylate; hexa(meth)acrylate of polyols such as dipentaerythritol hexa(meth)acrylate, etc. It should be noted that the number of repetitions of the alkylene glycol units in the polyalkylene glycol (meth)acrylate is not particularly limited, but is preferably 3 to 10, more preferably 3 to 5.

[0134] Among these, in terms of high resistance to hydrolysis, preventing the elution of the constituent components of the particles such as hydrophilic components, and improving the sustained hydrophilicity and / or water-repellent properties, polymethyl methacrylates such as mono-, di-, or polyalkylene glycols, trimethyl methacrylates, tetramethyl methacrylates, pentmethyl methacrylates, and hexamethyl methacrylates are preferred.

[0135] Among the polyfunctional olefinic unsaturated monomers, hydrocarbon crosslinking monomers and poly(meth)acrylates are preferred. In particular, hydrocarbon crosslinking monomers and poly(meth)acrylates are more preferred in terms of high resistance to hydrolysis and further improvement of hydrophilicity and / or hydrophobicity, aromatic hydrocarbon crosslinking monomers, mono-, di-, or polyalkylene glycol methacrylates are more preferred, and divinylbenzene is particularly preferred.

[0136] The number of -COOR groups contained in the monomer (AB1)1 molecule is preferably 1 to 3, more preferably 1.

[0137] The monomer (AB1)1 molecule preferably contains 1 to 3 hydroxyl groups, more preferably 1.

[0138] The polymerizable groups contained in the monomer (AB1) are preferably vinyl, allyl, (meth)acryloyl, or other groups containing olefinic unsaturated bonds, more preferably groups with olefinic unsaturated groups at the end (groups with CH2=C<), and even more preferably (meth)acryloyl.

[0139] The preferred monomer (AB1) is a hydroxymethyl methacrylate monomer represented by the following formula (2).

[0140] [Chemical Formula 3]

[0141]

[0142] In equation (2), R 1 [Indicates alkyl groups, hydrogen atoms, alkali metal atoms, or ammonium atoms with 1 to 4 carbon atoms]

[0143] R in the above equation (2) 1 Examples of alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. Preferably, the alkyl group has 1 to 2 carbon atoms, and more preferably, methyl.

[0144] R in the above equation (2) 1 The alkali metal atoms and ammonium represented are the same as the exemplified alkali metal atoms and ammonium represented by R above, and their preferred methods are also the same.

[0145] The number of -COOR groups contained in the monomer (AB2)1 molecule is preferably 1 to 3, more preferably 1.

[0146] The monomer (AB2)1 molecule preferably contains 1 to 3 hydroxyl groups, more preferably 1.

[0147] The monomer (AB2)1 molecule preferably contains 2 to 6 polymerizable groups, more preferably 2.

[0148] The polymerizable groups contained in the monomer (AB2) are preferably vinyl, allyl, (meth)acryloyl, or other groups containing olefinic unsaturated bonds, and more preferably (meth)acryloyl.

[0149] Specifically, examples of the monomer (AB2) include methyl 3,4-divinyl-5-(hydroxymethyl)-1-(phenylmethyl)1H-pyrrole-2-carboxylic acid, methyl 3-hydroxy-3-(2-propen-1-yl)-5-hexenoic acid, etc.

[0150] The crosslinked polymer of method 1 may contain structural units derived from one monomer (A1) or from two or more monomers (A1). Additionally, the crosslinked polymer of method 1 may contain structural units derived from one monomer (B1) or from two or more monomers (B1). Furthermore, the crosslinked polymer of method 1 may contain structural units derived from one monomer (C) or from two or more monomers (C).

[0151] In the crosslinked polymer of Method 1, the content of the structural unit derived from the monomer (A1) is preferably 1% to 98.99% by mass, more preferably 10% to 90% by mass, and even more preferably 10% to 50% by mass.

[0152] In the crosslinked polymer of Method 1, the content of the structural unit derived from the monomer (B1) is preferably 1% to 98.99% by mass, more preferably 10% to 90% by mass, and even more preferably 10% to 50% by mass.

[0153] In the crosslinked polymer of Method 1, the content of the structural unit derived from the monomer (C) (preferably a polyfunctional olefin unsaturated monomer) is preferably 0.01% to 70% by mass, more preferably 0.01% to 35% by mass, and even more preferably 5% to 20% by mass.

[0154] In the crosslinked polymer of Method 1, the total content of structural units from monomer (A1), structural units from monomer (B1), and structural units from monomer (C) is preferably 20% to 100% by mass, more preferably 30% to 100% by mass, and even more preferably 50% to 100% by mass.

[0155] The crosslinked polymer of method 1 may further comprise structural units derived from monomers other than monomer (A1), monomer (B1), and monomer (C). Other monomers, besides monomer (AB1), may include the following: olefinically unsaturated monomers containing polyoxyalkylene groups, styrene monomers, vinyl ester monomers, silane-containing monomers, nitrogen-containing monomers, oxygen-containing monomers, fluorine-containing monomers, epoxy-containing monomers, light-stable monomers, and ultraviolet-absorbing monomers.

[0156] The crosslinked polymer of method 2 may contain structural units derived from one monomer (A1) or from two or more monomers (A1). Additionally, the crosslinked polymer of method 2 may contain structural units derived from one monomer (A2) or from two or more monomers (A2). Furthermore, the crosslinked polymer of method 2 may contain structural units derived from one monomer (B1) or from two or more monomers (B1). Additionally, the crosslinked polymer of method 2 may contain structural units derived from one monomer (B2) or from two or more monomers (B2).

[0157] In the crosslinked polymer of method 2, the total content of structural units from monomer (A2) and structural units from monomer (B2) is preferably 0.01% to 70% by mass, more preferably 0.01% to 35% by mass, and even more preferably 5% to 20% by mass.

[0158] In the crosslinked polymer of method 2, the total content of structural units from monomer (A1), structural units from monomer (A2), structural units from monomer (B1), and structural units from monomer (B2) is preferably 20% to 100% by mass, more preferably 30% to 100% by mass, and even more preferably 50% to 100% by mass.

[0159] The crosslinked polymer of method 2 may further include structural units derived from monomers other than monomers (A1), (A2), (B1), and (B2). These other monomers, besides monomers (C), (AB1), and (AB2) not included in monomers (A2) and (B2), may include the following: olefinically unsaturated monomers containing polyoxyalkylene groups, styrene monomers, vinyl ester monomers, silane-containing monomers, nitrogen-containing monomers, oxygen-containing monomers, fluorine-containing monomers, epoxy-containing monomers, light-stable monomers, and ultraviolet-absorbing monomers.

[0160] The crosslinked polymer of method 3 may contain structural units derived from one monomer (AB2) or may contain structural units derived from two or more monomers (AB2).

[0161] In the crosslinked polymer of method 3, the content of the structural unit derived from monomer (AB2) is preferably 0.01% to 100% by mass, more preferably 5% to 70% by mass, and even more preferably 10% to 50% by mass.

[0162] The crosslinked polymer of method 3 may further include structural units derived from monomers other than monomer (AB2). Other monomers, besides monomers (A1), (A2), (B1), (B2), (C), and (AB1), may include olefinically unsaturated monomers containing polyoxyalkylene groups, styrene monomers, vinyl ester monomers, silane-containing monomers, nitrogen-containing monomers, oxygen-containing monomers, fluorine-containing monomers, epoxy-containing monomers, light-stable monomers, and ultraviolet-absorbing monomers.

[0163] As the crosslinking polymer of the present invention, the crosslinking polymer of embodiment 4 is preferred, which comprises structural units derived from monomer (AB1) and structural units derived from monomer (C). Particularly preferred are crosslinking polymers comprising structural units derived from hydroxymethyl methacrylate monomers represented by formula (2) and structural units derived from polyfunctional olefin unsaturated monomers. It should be noted that the crosslinking polymer of embodiment 4 may comprise a structural unit derived from one monomer (AB1) alone, or it may comprise structural units derived from two or more monomers (AB1). Furthermore, the crosslinking polymer of embodiment 4 may comprise a structural unit derived from one monomer (C) alone, or it may comprise structural units derived from two or more monomers (C).

[0164] The structural unit derived from the hydroxymethyl methacrylate monomer represented by formula (2) can be expressed as the structural unit represented by formula (1) below. In other words, the crosslinked polymer of method 4 is particularly preferably a crosslinked polymer containing the structural unit represented by formula (1) and the structural unit derived from the polyfunctional olefin unsaturated monomer.

[0165] [Chemical Formula 4]

[0166]

[0167] In equation (1), R 1 [Indicates alkyl groups, hydrogen atoms, alkali metal atoms, or ammonium atoms with 1 to 4 carbon atoms]

[0168] R in the above equation (1) 1 The alkyl, alkali metal and ammonium atoms with 1 to 4 carbon atoms represented are the same as R in the above formula (2). 1 The same applies to their preferred methods.

[0169] It should be noted that in R 1 In the case where the atom is an alkali metal, it is contained in the crosslinked polymer in the form of an alkali metal salt of a carboxylic acid, in R 1 In the case of ammonium, it is contained in the crosslinked polymer in the form of an ammonium salt of carboxylic acid.

[0170] The crosslinked polymer of method 4 preferably has multiple structural units represented by formula (1), wherein the multiple formulas (1) contain R 1 They can be the same individually or they can be different. When all are the same, it is considered as R. 1 Preferably, hydrogen atoms, alkali metal atoms, or ammonium, more preferably alkali metal atoms or ammonium. In the presence of different R... 1 In the case of R 1Preferably, it is a combination of one or more selected from hydrogen atoms, alkali metal atoms, and ammonium atoms with an alkyl group having 1 to 4 carbon atoms; more preferably, it is a combination of one or more selected from alkali metal atoms and ammonium atoms with an alkyl group having 1 to 4 carbon atoms. All R contained in the crosslinked polymer of method 4 1 In 100 mol%, R is a hydrogen atom, an alkali metal atom, or ammonium. 1 The total percentage (hereinafter referred to as ionization rate) is, for example, 20 mol% to 100 mol%, preferably 40 mol% to 100 mol%, more preferably 50 mol% to 100 mol%. By adjusting the ionization rate to the above range, the hydrophilicity and water-repellent properties are improved. It should be noted that the upper limit of the ionization rate can be 95 mol% or less, or 90 mol% or less.

[0171] In the crosslinked polymer of the above-mentioned monomer (AB1) source structural unit (especially the structural unit represented by formula (1)), the content is, for example, 5% to 99.9% by mass, preferably 10% to 99% by mass, more preferably 15% to 95% by mass, and even more preferably 15% to 90% by mass.

[0172] In particular, from the viewpoint of further improving hydrophilicity or achieving a better balance between hydrophilicity and hydrophobicity, the content of the structural unit (especially the structural unit represented by formula (1)) derived from the monomer (AB1) in the crosslinked polymer of the above-mentioned method 4 is preferably 45% to 99.9% by mass, more preferably 65% ​​to 99% by mass, and even more preferably 75% to 95% by mass.

[0173] The structural unit represented by equation (1) above can be formed by polymerization of the hydroxymethyl methacrylate monomer represented by equation (2) above, or by other methods. For example, R in equation (2) can be... 1 The monomers are alkyl groups with 1 to 4 carbon atoms polymerized, and then the ester groups are hydrolyzed by adding alkaline substances such as alkali metal hydroxides, ammonia, and amines, thereby forming R in the above formula (1). 1 The structural unit of alkali metals, or R 1 It is the structural unit of ammonium. It can also be formed by adding an appropriate amount of acid after hydrolysis for neutralization, thus forming R in the above formula (1). 1 It is the structural unit of the hydrogen atom.

[0174] It should be noted that the monomer represented by formula (2) above can be one type or two or more types. When the crosslinked polymer of method 4 contains two or more structural units represented by formula (1), it can be formed by polymerizing two or more monomers represented by formula (2) above, or by using R... 1It is formed by polymerizing the monomer represented by the above formula (2) which is an alkyl group having 1 to 4 carbon atoms, and then hydrolyzing the ester group or by hydrolyzing it with two or more alkaline substances.

[0175] As described above, the crosslinked polymer of method 4 has structural units derived from monomers (C), preferably structural units derived from polyfunctional olefinic unsaturated monomers. The crosslinked polymer of method 4 may contain only one type of structural unit derived from monomers (C), or it may contain two or more types of structural units derived from monomers (C). The monomers (C) are as described above, and their preferred methods are also the same.

[0176] In the crosslinked polymer of method 4, the content of structural units derived from monomer (C) (especially polyfunctional olefinic unsaturated monomers) 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. By adjusting the content of structural units derived from monomer (C) (especially polyfunctional olefinic unsaturated monomers) to the above range, the hydrophilicity and hydrophobicity tend to be further improved.

[0177] In addition, in the crosslinked polymer of method 4, the content of structural units derived from monomer (C) (especially polyfunctional olefinic unsaturated monomers) can be 0.01% to 10% by mass, 0.02% to 8% by mass, or 0.04% to 6% by mass.

[0178] In addition, in the crosslinked polymer of the fourth method, the content of the structural unit sourced from the monomer (C) (especially the polyfunctional olefin unsaturated monomer) 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, relative to 100 parts by mass of the structural unit sourced from the monomer (AB1) (especially the structural unit represented by formula (1)).

[0179] In the crosslinked polymer of method 4, the total content of structural units derived from monomer (AB1) and structural units derived from monomer (C) (especially the total content of structural units represented by formula (1) and structural units derived from polyfunctional olefin unsaturated monomers) is preferably 50% to 100% by mass, more preferably 70% to 100% by mass, and even more preferably 80% to 100% by mass. Furthermore, the upper limit of the total content can be 99.9% by mass or 99% by mass.

[0180] The crosslinked polymer of method 4 may further comprise one or more structural units derived from olefinically unsaturated monomers containing polyoxyalkylene groups. By including such structural units, the dispersion stability of the particles in the resin composition is improved, and as a result, further improvement in hydrophilic properties can be expected. Furthermore, by including such structural units, the hydrophobicity tends to be further improved.

[0181] Examples of olefinic unsaturated monomers containing polyoxyalkylene groups include compounds having groups containing polyoxyalkylene and olefinic unsaturated bonds with a repeating number of 2 or more oxyalkylene units, among which compounds represented by the following formula (3) are preferred.

[0182] [Chemical Formula 5]

[0183]

[0184] In equation (3), R 31 R represents a hydrogen atom or a methyl group. 32 [This refers to a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, or an aromatic hydrocarbon group with 6 to 20 carbon atoms, where m represents an integer from 1 to 4 and n represents an integer from 2 to 20.]

[0185] R 31 Preferred methyl group, R 32 Alkyl groups with 1 to 4 carbon atoms are preferred.

[0186] As R 32 The alkyl groups representing 1 to 4 carbon atoms, and R 1 The examples illustrated for alkyl groups with 1 to 4 carbon atoms are the same.

[0187] As R 32 Examples of aromatic hydrocarbon groups having 6 to 20 carbon atoms include phenyl groups having one or more alkyl groups having 1 to 10 carbon atoms (wherein the total number of carbon atoms is 20 or less), and naphthyl groups having one or more alkyl groups having 1 to 10 carbon atoms (wherein the total number of carbon atoms is 20 or less). Examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. Alkyl groups having 4 to 10 carbon atoms are preferred, and nonyl is more preferred.

[0188] As R 32 Preferably, it is a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, or a phenyl group having an alkyl group having 1 to 10 carbon atoms; more preferably, it is a hydrogen atom, a methyl group, or a phenyl group having a nonyl group.

[0189] C in equation (3) m H 2mThe structure referred to is an alkylene group, which can be linear or branched, but is preferably linear. It should be noted that the multiple Cs in formula (3) m H 2m The structures represented can be the same or different. In multiple C... m H 2m When the structures represented are different, -(C) in equation (3) m H 2m O) n - Preferably, it is a structure formed by bonding one or more -C2H4O- and one or more -C3H6O- in any order.

[0190] m is preferably an integer from 2 to 4, more preferably 2 or 3, and even more preferably 2.

[0191] n is preferably an integer from 2 to 15, and more preferably an integer from 2 to 10.

[0192] When the crosslinked polymer of the fourth method contains structural units derived from olefinic unsaturated monomers containing polyoxyalkylene groups, its content in the crosslinked polymer of the fourth method is preferably 0.1% to 30% by mass, more preferably 1% to 20% by mass, and even more preferably 3% to 15% by mass.

[0193] In addition, relative to 100 parts by mass of the structural unit (especially the structural unit represented by formula (1)) from the monomer (AB1), the content of the structural unit from the polyoxyalkylene unsaturated monomer is preferably 0.2 parts by mass to 30 parts by mass, more preferably 2 parts by mass to 20 parts by mass, and even more preferably 5 parts by mass to 16 parts by mass.

[0194] Furthermore, in the crosslinked polymer of method 4, the total content of structural units derived from monomer (AB1), structural units derived from monomer (C), and structural units derived from polyoxyalkylene-containing olefinic unsaturated monomers (especially the total content of structural units represented by formula (1), structural units derived from polyfunctional olefinic unsaturated monomers, and structural units derived from polyoxyalkylene-containing olefinic unsaturated monomers) is preferably 60% to 100% by mass, more preferably 80% to 100% by mass, and even more preferably 90% to 100% by mass. Additionally, the upper limit of the total content can be 99.9% by mass or 99% by mass.

[0195] The crosslinked polymer of method 4 may contain one or more of the following structural units: structural units derived from monomers (hereinafter referred to as "other monomers") other than structural units derived from monomers (AB1), monomers (C), and olefinic unsaturated monomers containing polyoxyalkylene groups.

[0196] Other monomers are not specifically limited and can include (meth)acrylic acid monomers, styrene monomers, carboxyl-containing monomers, salts of carboxyl-containing monomers, vinyl ester monomers, silane-containing monomers, hydroxyl-containing monomers, nitrogen-containing monomers, oxy-containing monomers, fluorine-containing monomers, epoxy-containing monomers, light-stable monomers, and ultraviolet-absorbing monomers.

[0197] Examples of (meth)acrylate monomers include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and other alkyl methacrylates, among which C-methacrylate is preferred. 1-10 Alkyl esters, more preferably (meth)acrylic acid C 1-5 Alkyl esters.

[0198] As styrene monomers, examples of styrene that can have one or more of the following substituents: halogen atoms (e.g., fluorine, chlorine, bromine, iodine), alkyl groups (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, etc.). 1-4 Alkyl groups, etc. Specifically, examples of styrene monomers include: styrene, α-methylstyrene, p-methylstyrene, tert-butylstyrene, chlorostyrene, vinyltoluene, etc., with styrene being preferred.

[0199] Examples of carboxyl-containing monomers 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.

[0200] Examples of salts containing carboxyl groups include alkali metal salts of carboxyl-containing monomers and ammonium salts of carboxyl-containing monomers. It should be noted that, in salts of carboxyl-containing monomers, specific examples of the alkali metal atom and ammonium that form the salt with the carboxyl-containing monomer are not specified in the R example. 1 The examples of alkali metal atoms and ammonium are the same, and their preferred methods are also the same. Among them, the salt of acrylic acid is preferred.

[0201] Examples of vinyl ester monomers include esters of saturated fatty acids and vinyl alcohols such as vinyl acetate and vinyl propionate, with C being the preferred choice. 1-5 Saturated fatty acids and ethylene alcohol esters.

[0202] Examples of silane coupling agents containing silane groups include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(methoxyethoxy)silane, γ-(meth)acryloyloxypropyltrimethoxysilane, and 2-styrylethyltrimethoxysilane; silane coupling agents containing alkoxysilane groups such as vinyltrichlorosilane; and silane coupling agents containing silanol groups such as γ-(meth)acryloyloxypropylhydroxysilane and γ-(meth)acryloyloxypropylmethylhydroxysilane.

[0203] Examples of hydroxyl-containing monomers include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, and 4-hydroxybutyl methacrylate, among other hydroxyalkyl methacrylates. Preferably, C-hydroxyethyl methacrylate is used. 1-8 Hydroxyalkyl esters, more preferably (meth)acrylic acid C 1-4 Hydroxyalkyl esters.

[0204] Examples of nitrogen-containing monomers include (meth)acrylamide, N,N-dimethyl (meth)acrylamide, dimethylaminoethyl (meth)acrylamide, N-vinylpyrrolidone, and (meth)acrylonitrile.

[0205] Examples of monomers containing oxygen groups include ethylene glycol methoxy (meth)acrylate.

[0206] Examples of monomers containing fluorine atoms include trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, and octafluoropentyl methacrylate, among which C(meth)acrylate is preferred. 1-10 Fluorinated alkyl esters, more preferably (meth)acrylic acid C 1-5 Fluorinated alkyl esters.

[0207] Examples of epoxy-containing monomers include glycidyl methacrylate, 2-glycidyl methacrylate, and other epoxy-containing (meth)acrylates.

[0208] Examples of photostable monomers include 2,2,6,6-tetramethylpiperidine-4-(meth)acrylate, 1,2,2,6,6-pentamethyl-4-piperidine (meth)acrylate, and other monomers having a 2,2,6,6-tetramethylpiperidine ring structure and polymerizable groups (e.g., (meth)acryloyl, vinyl, etc., groups containing olefinic unsaturated bonds).

[0209] Examples of ultraviolet-absorbing monomers include benzotriazole-based ultraviolet-absorbing monomers and benzophenone-based ultraviolet-absorbing monomers.

[0210] Other monomers preferred are (meth)acrylic acid monomers, styrene monomers, carboxyl-containing monomers, salts of carboxyl-containing monomers, and hydroxyl-containing monomers; more preferably, (meth)acrylic acid alkyl esters, (meth)acrylic acid, salts of (meth)acrylic acid, and styrene monomers; even more preferably, alkyl acrylates, acrylic acid, and salts of acrylic acid; and particularly preferably, acrylic acid and salts of acrylic acid.

[0211] In particular, the total content of structural units derived from acrylic acid and structural units derived from acrylic acid salts (especially the content of structural units derived from acrylic acid salts) in the crosslinked polymer of method 4 can be 0% to 40% by mass or 5% to 20% by mass.

[0212] In the crosslinked polymer of method 4, the content of structural units from other monomer sources 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.

[0213] The polymer particles may be entirely composed of the cross-linked polymer, or only a portion of the polymer particles may be composed of the cross-linked polymer. That is, the polymer particles may be a single-layer structure or a multi-layer structure. When the polymer particles are a single-layer structure, it is preferable that the entire particle is composed of the cross-linked polymer; when the polymer particles are a multi-layer structure, it is preferable that the outermost outer layer is composed of the cross-linked polymer. This configuration imparts the desired hydrophilic and hydrophobic properties.

[0214] Fabricating the polymer particles into a multilayer structure, preferably a core-shell structure, is also effective in further improving hydrophilicity and hydrophobicity. For example, by using the cross-linked polymer to form the outermost shell, it is possible to give it high hydrophilicity as a particle, or to impart hydrophobicity to the obtained material. On the other hand, by reducing the hydrophilicity of the inner layers, such as the core, it is possible to impart low solubility and low swelling in water to the particles. As a result, the degradation and elution of the obtained coating (material) can be suppressed. Therefore, by fabricating a core-shell structure, it is possible to achieve higher hydrophilicity (especially initial hydrophilicity) and hydrophobicity than in the case of a single layer.

[0215] Furthermore, the fins of heat exchangers used in outdoor units, automotive air conditioners, and other applications are sometimes exposed to pollutants such as urban dust and carbon black contained in vehicle exhaust. The adhesion of such pollutants can reduce the hydrophilicity of the coating (tangible object). If the polymer particles are made into a multi-layered structure such as a core-shell structure, it becomes easier to remove pollutants adhering to the surface of the coating (tangible object).

[0216] In the case where the polymer particles have a multilayer structure, it is preferable that the second polymer, which constitutes the outermost layer (e.g., the core in the case of core-shell particles), is different from the crosslinked polymer.

[0217] The second polymer preferably has one or more structural units composed of non-aqueous monomers, wherein the non-aqueous monomers do not have acidic groups such as carboxyl, hydroxyl, thiol, or silanol groups, or amino groups. This reduces the hydrophilicity of the inner layers, such as the core. Preferably, the non-aqueous monomer is a monomer composed of a hydrocarbon having one or more groups selected from ester, ether, amide, and halogen groups; more preferably, it is a monomer composed of a hydrocarbon having an ester group.

[0218] Specifically, examples of non-aqueous monomers include (meth)acrylic acid monomers, styrene monomers, vinyl ester monomers, oxy-containing monomers, fluorine-containing monomers, and epoxy-containing monomers. These (meth)acrylic acid monomers, styrene monomers, vinyl ester monomers, oxy-containing monomers, fluorine-containing monomers, and epoxy-containing monomers may be the same monomers described in the crosslinking polymer, and the preferred methods for each monomer are also the same.

[0219] As the non-aqueous monomer, (meth)acrylate monomers and styrene monomers are preferred, (meth)acrylate alkyl esters and styrene monomers are more preferred, and (meth)acrylate C is even more preferred. 1-5 Alkyl esters, styrene.

[0220] In the second polymer, the content of structural units derived from non-aqueous monomers is preferably 40% to 99% by mass, more preferably 50% to 90% by mass, and even more preferably 60% to 80% by mass.

[0221] The second polymer preferably also has structural units derived from one or more polyfunctional olefin unsaturated monomers. This can be expected to further improve the initial hydrophilicity, hydrophilic persistence, and hydrophobicity of the coating (tangible object) surface. Examples of the polyfunctional olefin unsaturated monomers include monomers identical to those described in the crosslinking polymer, preferably hydrocarbon crosslinking monomers, poly(meth)acrylates, more preferably aromatic hydrocarbon crosslinking monomers, mono-, di-, or polyalkylene glycol (meth)acrylates, and even more preferably divinylbenzene.

[0222] In the second polymer, the content of structural units derived from polyfunctional olefin unsaturated monomers is preferably 1% to 50% by mass, more preferably 10% to 45% by mass, and even more preferably 20% to 40% by mass.

[0223] Furthermore, in the second polymer, the content of structural units derived from polyfunctional olefin unsaturated monomers is preferably 10 to 70 parts by mass relative to 100 parts by mass of structural units derived from non-aqueous monomers, more preferably 20 to 60 parts by mass, and even more preferably 20 to 50 parts by mass.

[0224] Furthermore, in the second polymer, the total content of structural units derived from non-aqueous monomers and structural units derived from polyfunctional olefin unsaturated monomers is preferably 60% to 100% by mass, more preferably 80% to 100% by mass, and even more preferably 90% to 100% by mass. Additionally, the upper limit of the total content can be 99.9% by mass or 99% by mass.

[0225] The second polymer may contain one or more structural units derived from the monomer (AB1) (especially the structural units represented by formula (1)), but preferably does not contain such structural units. In the second polymer, the content (containment ratio) of the structural units derived from the monomer (AB1) (especially the structural units represented by formula (1)) is preferably less than the content (containment ratio) of the structural units derived from the monomer (AB1) (especially the structural units represented by formula (1)) in the crosslinked polymer, specifically, preferably 10% by mass or less, more preferably 5% by mass or less.

[0226] The second polymer may contain one or more of the following structural units: structural units derived from monomers having polymerizable groups such as a group containing a carbon-carbon double bond in one molecule, other than structural units derived from non-aqueous monomers, structural units derived from polyfunctional olefinic unsaturated monomers, and structural units derived from monomer (AB1).

[0227] As a second other monomer, examples include monomers having carboxyl, thiol, silanol, amino, etc., such as carboxyl-containing monomers, silyl-containing monomers, hydroxyl-containing monomers, nitrogen-containing monomers, light-stable monomers, and ultraviolet-absorbing monomers. These carboxyl-containing monomers, silyl-containing monomers, hydroxyl-containing monomers, nitrogen-containing monomers, light-stable monomers, and ultraviolet-absorbing monomers can be examples of the same monomers described in the crosslinking polymer, and the preferred methods for each monomer are also the same.

[0228] In the second polymer, the content of structural units derived from the second other monomer 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.

[0229] The volume average particle size of the polymer particles is, for example, 10 nm to 10 μm, preferably 10 nm to 5 μm, more preferably 20 nm to 1 μm, and even more preferably 30 nm to 500 nm. From the viewpoint of further improving the hydrophilicity after oil adhesion, it is preferably 10 nm to 500 nm, more preferably 15 nm to 300 nm, and even more preferably 20 nm to 100 nm. It should be noted that the volume average particle size can be determined, for example, by dynamic light scattering.

[0230] <Methods for Manufacturing Polymer Particles>

[0231] The method for manufacturing the polymer particles is not particularly limited, and any conventionally known method may be used. Preferably, the polymer particles are manufactured by polymerizing the monomers constituting the polymer particles (hereinafter, these are sometimes collectively referred to as "raw material monomer components") in an aqueous solvent and then partially or completely hydrolyzing them as needed. For example, in the case of manufacturing polymer particles containing the crosslinked polymer of method 4, it is preferable to use R in the hydroxymethyl acrylate monomer represented by formula (2) as a raw material monomer component. 1 The product is manufactured by polymerizing alkyl monomers having 1 to 4 carbon atoms (hereinafter referred to as hydroxymethyl acrylates), polyfunctional olefinic unsaturated monomers, olefinic unsaturated monomers containing polyoxyalkylene groups as needed, other monomers, non-aqueous monomers, and a second other monomer in an aqueous solvent, and then subjecting them to partial or complete hydrolysis as needed. By using hydroxymethyl acrylates, the product can be produced in particulate form even when polymerizing in an aqueous solvent where organic solvents are not required, thus it is preferred from the viewpoint of reducing environmental impact.

[0232] Examples of polymerization methods include suspension polymerization, emulsion polymerization, and dispersion polymerization. Among these, emulsion polymerization, in which the above-mentioned raw material monomer components are dispersed in an aqueous solvent in the presence of an emulsifier to carry out a (free radical) polymerization reaction, is preferred. Emulsion polymerization can be carried out in a single stage or in multiple stages. For example, by polymerizing a non-aqueous monomer, a polyfunctional olefin unsaturated monomer used as needed, a monomer (AB) (especially the monomer represented by formula (2)), and a second other monomer in an aqueous solvent in a first stage to synthesize seed particles forming a core (i.e., the second polymer mentioned above), and then polymerizing the monomers constituting the crosslinked polymer (preferably hydroxymethyl acrylate, polyfunctional olefin unsaturated monomer, olefin unsaturated monomer containing polyoxyalkylene used as needed, and other monomers) in a second stage to synthesize a shell (i.e., the crosslinked polymer mentioned above), it is possible to manufacture polymer particles with a core-shell structure.

[0233] As the emulsifier, one or more can be used, which can be a non-reactive surfactant that does not have polymerizable groups in its molecule, or a reactive surfactant that has polymerizable groups in its molecule (e.g., olefinic unsaturated groups).

[0234] Non-reactive surfactants include both anionic and nonionic surfactants. Examples of non-reactive anionic surfactants include fatty acid salts, alkyl (aryl) sulfonates, alkyl sulfate salts, and polyoxyethylene alkyl (phenyl) ether sulfates. Examples of non-reactive nonionic surfactants include polyoxyethylene alkyl (phenyl) ethers, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene polyoxypropylene block polymers.

[0235] Reactive surfactants include both anionic and nonionic surfactants. Examples of anionic reactive surfactants include ether sulfate reactive surfactants and phosphate ester reactive surfactants, but they are not limited to these.

[0236] The amount of emulsifier used relative to 100 parts by weight of the total raw material monomer components is preferably 0.05 parts by weight to 20 parts by weight, more preferably 0.1 parts by weight to 10 parts by weight, even more preferably 0.2 parts by weight to 5 parts by weight, and particularly preferably 0.3 parts by weight to 3 parts by weight.

[0237] The aqueous solvent can be categorized as water alone or a mixture of water and water-mixed organic solvents. Aqueous solvents typically refer to solvents with a water content exceeding 50% by volume. As water, ion-exchanged water (deionized water), distilled water, pure water, etc., can be used. As a water-mixed organic solvent, organic solvents that can be homogeneously mixed with water (e.g., C...) can be used. 1-4Alkyl alcohols and other lower alcohols). From the viewpoint of minimizing the residue of water-mixed organic solvents in polymer particles, it is preferable that the aqueous solvent is at least 80% by volume of water, more preferably at least 90% by volume of water, even more preferably at least 95% by volume of water, particularly preferably an aqueous solvent that is substantially composed of water (at least 99.5% by volume of water), and most preferably water alone.

[0238] When polymerizing raw material monomer components, methods such as polymerization initiators, ultraviolet light, radiation, and heat application can be used. Polymerization initiators are preferred. From the viewpoint of maximizing the reaction efficiency of the raw material monomer components and minimizing residual monomers, polymerization initiators that combine an oxidant and a reducing agent (redox polymerization initiators) are preferred. Examples of oxidants include persulfates such as ammonium persulfate and potassium persulfate, as well as peroxide-based polymerization initiators such as hydrogen peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, lauroyl peroxide, and ammonium peroxide. Examples of reducing agents include soluble sulfites and ascorbic acid.

[0239] In the reaction system of the above emulsion polymerization, additives such as chain transfer agents, pH buffers, and chelating agents can be added as needed. The amount of additives varies depending on their type and therefore cannot be generalized, but it is generally preferred to be 0.01 to 5 parts by mass relative to 100 parts by mass of the raw material monomer component, and more preferably 0.1 to 3 parts by mass.

[0240] Hydrolysis of polymer particles can be performed, for example, by adding aqueous solutions containing alkaline substances such as sodium hydroxide, amines such as cyclohexylamine, or ammonia. Furthermore, by appropriately adding an acid to the hydrolyzed solution, partial or complete neutralization can be achieved. Through hydrolysis and neutralization, the R-related groups (especially those corresponding to R in formula (1)) in the -COOR groups contained in the polymer particles can be neutralized. 1 The radicals (groups) can become hydrogen atoms, alkali metal atoms, or ammonium. This can be achieved by adjusting the amounts of acid and base used during polymerization, hydrolysis, and neutralization, or by adjusting R (especially R0). 1 The proportion of monomer units with hydrogen atoms can be adjusted to control the pH and hydrophilicity of the polymer, and tend to further improve the hydrophilic persistence and hydrophobicity of tangible materials such as hydrophilic coatings.

[0241] From the viewpoint of further improving hydrophilicity and hydrophobicity, the hydrolysis rate of the polymer particles disclosed herein is, for example, 20% to 100%, preferably 40% to 100%, and more preferably 50% to 100%. Furthermore, the hydrolysis rate can be 95% or less, or 90% or less. It should be noted that the hydrolysis rate can be calculated by the amount (mass) of alkaline substance added relative to 100 mol% of the structural units derived from the hydrolyzable monomers contained in the crosslinked polymer. Examples of hydrolyzable monomers include acrylic monomers such as alkyl acrylates and monomers represented by general formula (2). It should be noted that when calculating the hydrolysis rate by back-calculating the hydrolysis rate from the polymer, it can be assumed that all carboxylic acid groups in hydrolyzable monomers such as acrylic monomers and monomers represented by formula (2) exist in the form of esters, and the hydrolysis rate can be calculated accordingly.

[0242] The hydrophilicity retention effect and / or hydrophobicity imparting agent of the present invention must contain the polymer particles. The content of the polymer particles in the hydrophilicity retention effect and / or hydrophobicity imparting agent 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, further preferably 50% by mass or more, even more preferably 90% by mass or more, particularly preferably 98% by mass or more, and may also be 100% by mass or less, or 99.8% by mass or less.

[0243] The hydrophilicity retention effect and / or hydrophobicity imparting agent of the present invention may contain components other than the polymer particles. There are no particular limitations on the components other than the polymer particles, and examples include solvents such as aqueous solvents.

[0244] By using the polymer particles, hydrophilicity can be continuously imparted to tangible materials, such as the coating film, meaning the obtained tangible material can be continuously hydrophilized. Furthermore, by using the polymer particles, hydrophilicity and hydrophobicity can be simultaneously imparted to tangible materials, such as the coating film; that is, not only can the obtained tangible material be hydrophilized, but it can also be hydrophobic. For example, by forming a tangible material with continuous hydrophilicity on the surface of fins in a heat exchanger, bridging between fins caused by condensate can be suppressed for a long period. Moreover, by forming a tangible material with both hydrophilicity and hydrophobicity on the surface of fins in a heat exchanger, bridging between fins can be suppressed compared to techniques that improve hydrophobicity by imparting water-repellent properties to the fin surface.

[0245] The tangible article is preferably manufactured from a composition containing the polymer particles (i.e., a composition containing a hydrophilicity-continuous effect and / or a hydrophobicity imparting agent). The composition and the tangible article will be described below.

[0246] 2. Composition

[0247] The compositions of the present invention contain the polymer particles, that is, contain the hydrophilicity retention effect and / or hydrophobicity imparting agent. The content of the solid component (preferably the polymer particles) of the hydrophilicity retention effect and / or hydrophobicity imparting agent in the composition is not particularly limited, but is, for example, 1% to 80% by mass, preferably 5% to 50% by mass, and more preferably 8% to 30% by mass in 100% by mass of the solid component of the composition.

[0248] The composition preferably also contains a resin different from the polymer particles. Hereinafter, a composition containing a hydrophilic lasting effect and / or a hydrophobic agent and a resin is sometimes referred to as a resin composition. In this invention, the resin composition and the tangible product, as described below, include various substances, and the case of forming a hydrophilic coating film using a resin composition containing a hydrophilic lasting effect and / or a hydrophobic agent and a hydrophilic resin will be described here.

[0249] The hydrophilic resin is not particularly limited, but is preferably a resin having polar functional groups such as carboxyl groups, carboxyl salts, hydroxyl groups, sulfonic acid groups, amide groups, and amino groups in the side chain, or a resin having a polyether backbone and / or a polyamine backbone in the main chain, and more preferably a resin having polar functional groups in the side chain.

[0250] Resins with polar functional groups on their side chains may have one or more of the aforementioned polar functional groups. It should be noted that, in this specification, "carboxyl salt" refers to a functional group formed by replacing the hydrogen ion in the carboxyl group (-COOH) with a monovalent cation, preferably -COOR. a (R) a (Represents an alkali metal atom or ammonium). As R a The alkali metal atoms and ammonium represented are the same as R in the above formula (1). 1 The alkali metal atoms represented are the same as those in ammonium. Among them, R... a Preferably, alkali metal atoms or hydroxyalkylammonium atoms are used; more preferably, alkali metal atoms or mono-, di-, or tri-(hydroxyC) atoms are used. 1-10 Alkyl ammonium, further preferably sodium, mono(hydroxyl C) 1-5 Alkyl ammonium.

[0251] As the polar functional group, carboxyl groups and their salts are preferred, carboxyl groups and their alkali metal salts are more preferred, and sodium salts of carboxyl groups and their sodium salts are even more preferred.

[0252] Specifically, examples of the hydrophilic resin include: (co)polymers of (meth)acrylic acid, (co)polymers of maleic acid, and other polymers containing carboxyl groups; (co)polymers of (meth)acrylates, (co)polymers of maleate salts, and other polymers containing carboxyl groups; (co)polymers of (meth)acrylic acid hydroxy esters, (co)polymers of polyvinyl alcohol, and other polymers containing hydroxyl groups; (co)polymers of 2-acrylamido-2-methylpropanesulfonic acid, and other polymers containing sulfonic acid groups; (co)polymers of acrylamide, (co)polymers of N-vinyl-2-pyrrolidone, and other polymers containing amide groups; (co)polymers of diethylaminoethyl (meth)acrylate, and other polymers containing amino groups; polyether-based (co)polymers such as polyethylene glycol; and polyamine-based (co)polymers such as polyethyleneimine. It should be noted that the term "co)polymer" can refer to either a polymer as a homopolymer or a copolymer as a copolymer. It should be noted that the hydrophilic resin can be a thermoplastic resin or a thermosetting resin, preferably a thermosetting resin. Thermosetting resins have excellent mechanical strength and heat resistance; therefore, by using a thermosetting resin as the hydrophilic resin, it is easier to maintain the uneven shape of the obtained tangible surface, further improving the hydrophilicity and hydrophobicity. The hydrophilic resin can be used alone or in combination with two or more types.

[0253] In particular, from the viewpoint of further improving the aforementioned hydrophilicity retention effect and / or the effect of the hydrophobicity imparting agent (the improved hydrophilicity and hydrophobicity of the obtained tangible material), the hydrophilic resin is more preferably a resin having at least one polar functional group selected from the group consisting of salts containing carboxyl groups and carboxyl groups in its side chain, and more preferably a (co)polymer of (meth)acrylic acid (salt). It should be noted that (meth)acrylic acid (salt) refers to (meth)acrylic acid and / or salts of (meth)acrylic acid, and a copolymer of (meth)acrylic acid (salt) refers to a copolymer of (meth)acrylic acid (salt) with other comonomers. Examples of other comonomers include monomers other than (meth)acrylic acid and polyfunctional olefinic unsaturated monomers constituting the polymer particles. Among these, (meth)acrylic acid monomers, styrene monomers, and hydroxyl-containing monomers are preferred, and alkyl (meth)acrylic acid esters and styrene monomers are more preferred. Other comonomers may be used individually or in combination of two or more.

[0254] In the (co)polymer of (meth)acrylic acid (salt), the total proportion of (meth)acrylic acid and (meth)acrylic acid salt-derived structural units (especially the proportion of (meth)acrylic acid salt-derived structural units) is, for example, 30% by mass or more, preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, and can be 100% by mass.

[0255] The content of the solid component (preferably the polymer particles) of the hydrophilicity retention effect and / or hydrophobicity imparting agent in the resin composition is not particularly limited, but is preferably 0.1 parts by weight or more, more preferably 5 parts by weight or more, and even more preferably 15 parts by weight or more, relative to 100 parts by weight of the hydrophilic resin. By setting it within the above range, the hydrophilicity retention effect and / or hydrophobicity of the hydrophilic coating tend to be further improved. In particular, from the viewpoint of further improving the hydrophobicity of the hydrophilic coating, the content of the solid component (preferably the polymer particles) of the hydrophilicity retention effect and / or hydrophobicity imparting agent is preferably 40 parts by weight or more, more preferably 60 parts by weight or more, and even more preferably 80 parts by weight or more, relative to 100 parts by weight of the hydrophilic resin.

[0256] There is no particular limit to the upper limit of the content, but it is preferably 200 parts by weight or less, more preferably 150 parts by weight or less, relative to 100 parts by weight of hydrophilic resin.

[0257] That is, relative to 100 parts by weight of hydrophilic resin, the content is preferably 0.1 parts by weight to 200 parts by weight, more preferably 5 parts by weight to 200 parts by weight, further preferably 15 parts by weight to 200 parts by weight, even more preferably 40 parts by weight to 200 parts by weight, particularly preferably 60 parts by weight to 200 parts by weight, and most preferably 80 parts by weight to 150 parts by weight.

[0258] 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.

[0259] The composition (preferably a resin composition) preferably further comprises a crosslinking agent. By including a crosslinking agent, the strength of the hydrophilic coating film can be improved. Furthermore, by including a crosslinking agent, the durability of the hydrophilic coating film is improved, resulting in improved hydrophilicity retention and, as shown in the examples below, improved hydrophobicity after thermal cycling. A single crosslinking agent can be used alone, or two or more can be used in combination. Preferably, the crosslinking agent is a compound having two or more groups per molecule that can react with the polar functional groups present in the hydrophilic resin. Examples of groups that can react with polar functional groups include epoxy groups, oxazoline groups, carbodiimide groups, isocyanate groups, etc., which can be appropriately selected according to the hydrophilic resin used. For example, when using a resin (preferably a (co)polymer of (meth)acrylate (salt)) whose side chain has at least one polar functional group selected from the group consisting of carboxyl groups and salts of carboxyl groups as a hydrophilic resin, 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). By using this combination, the aforementioned durability improvement effect tends to be further enhanced.

[0260] From the viewpoint of excellent crosslinking performance, water-soluble oxazoline compounds are preferred as crosslinking agents having two or more oxazoline groups per molecule; furthermore, polymers containing oxazoline groups are preferred. The aforementioned polymers containing oxazoline groups can be manufactured using conventionally known manufacturing methods. Examples include: methods for polymerizing one or more addition-polymerizable oxazolines; or methods for polymerizing monomer components comprising addition-polymerizable oxazolines and monomers capable of copolymerizing with addition-polymerizable oxazolines.

[0261] Examples of addition-polymerizable oxazolines include: 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, 2-isopropenyl-5-ethyl-2-oxazoline, and other compounds with polymerizable unsaturated groups and oxazoline groups within their molecules.

[0262] As monomers capable of copolymerizing with addition-polymerizable oxazolines, monomers that do not have functional groups that react with oxazoline groups and can copolymerize with addition-polymerizable oxazolines are preferred. Examples include: (meth)acrylic monomers such as (meth)acrylates; styrene monomers such as styrene, α-methylstyrene, and chloromethylstyrene; vinyl monomers such as vinyl acetate, vinyl chloride, and vinyl benzoate; acrylonitrile; (meth)acrylamide monomers such as acrylamide; and olefin monomers such as ethylene and propylene.

[0263] Among the oxazoline-containing polymers, water-soluble oxazoline-containing polymers are preferred, and can be manufactured by the same method as the above-described method for manufacturing oxazoline-containing polymers. Examples of such water-soluble oxazoline-containing polymers include polymers with (meth)acrylic resins as the main chain and oxazoline groups in the side chains.

[0264] Commercially available products can also be used as polymers containing oxazoline groups. For example, water-soluble polymers such as EPOCROS WS-500 and EPOCROS WS-700 manufactured by Nippon Shokubai Co., Ltd., and emulsion polymers such as EPOCROS K-2010E, EPOCROS K-2020E, and EPOCROS K-2035E can be cited.

[0265] The content of the crosslinking agent is not particularly limited, but is preferably 0.1 to 50 parts by weight relative to 100 parts by weight of the hydrophilic resin, more preferably 1 to 40 parts by weight, and even more preferably 5 to 30 parts by weight.

[0266] In the solids component of the composition (preferably the resin composition), the total content of the solids component of the hydrophilicity retention effect and / or hydrophobicity imparting agent (preferably the polymer particles), the hydrophilic resin and the crosslinking agent is, for example, 80% by mass or more, preferably 90% by mass or more, more preferably 97% by mass or more, and may also be 100% by mass.

[0267] The composition (preferably a resin composition) may also contain a solvent. By including a solvent, the coatability of the composition (preferably a resin composition) becomes good. As a solvent, an aqueous solvent is preferred from the viewpoint of reducing environmental impact. As said aqueous solvent, the same aqueous solvent used in emulsion polymerization is preferred.

[0268] The solvent content in the composition (preferably the resin composition) can 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, particularly preferably 80% by mass or more, preferably 99.9% by mass or less, and more preferably 99% by mass or less. That is, the solvent content in the composition (preferably the resin composition) can be 0% by mass to 99.9% by mass, preferably 0.1% by mass to 99.9% by mass, more preferably 40% by mass to 99.9% by mass, even more preferably 60% by mass to 99.9% by mass, and particularly preferably 80% by mass to 99% by mass.

[0269] The composition (preferably a resin composition) may contain other additives without impairing the effects of the present invention. As other additives, additives commonly used in the art can be used, such as compounds with hydroxyl groups, for example: L-ascorbic acid, gallic acid, tannic acid, gluconic acid-δ-lactone, gluconic acid, and other water-soluble low-molecular-weight compounds with hydroxyl groups, or high-molecular-weight compounds with hydroxyl groups such as polyvinyl alcohol.

[0270] The molecular weight of the water-soluble low-molecular-weight compound having hydroxyl groups is not particularly limited, for example, it is 50 to 2,000, preferably 100 to 2,000.

[0271] The weight-average molecular weight of the polymeric compound containing hydroxyl groups is not particularly limited, but may be, for example, 3,000 to 100,000.

[0272] As the hydroxyl-containing compound, compound (A) that satisfies requirements 1 to 4 below is preferred. By including compound (A) in the composition (preferably a resin composition), the hydrophilic persistence of the obtained tangible material is easily improved. It should be noted that the above-mentioned hydrophilic persistence improvement effect brought about by compound (A) is more easily achieved when the composition includes the crosslinking agent, that is, compound (A) is preferably used in combination with the crosslinking agent. In particular, the above-mentioned hydrophilic property improvement effect is more easily enhanced when compound (A) and the oxazoline-based crosslinking agent are used in combination.

[0273] Requirement 1: It must be water-soluble.

[0274] Requirement 2: Acid dissociation constant pKa A (Temperature: room temperature (25℃), solvent: water) is below 12.

[0275] Requirement 3: It has at least one hydroxyl group, and the total number of hydroxyl and carboxyl groups contained in one molecule is more than two.

[0276] Requirement 4: It has at least one high-acidity group selected from hydroxyl and carboxyl groups with an acid dissociation constant pKa (temperature: room temperature (25°C), solvent: water) of less than 12.

[0277] As described in Requirement 1, the compound (A) is a water-soluble compound. In this specification, "water-soluble" means that the water solubility at 20°C (hereinafter, water solubility (20°C)) is 20 g / L or more; that is, it can be said that the water solubility (20°C) of the compound (A) is 20 g / L or more. In this specification, in a constant temperature and humidity chamber at 20°C, in a 100 cc spiral tube, 50 cc of ion-exchanged water (temperature: 20°C) is added to the compound (X g, temperature: 20°C). After stirring for 5 minutes using a magnetic stirrer (rotor: 10 mm × φ4 mm), and then allowed to stand for 10 minutes, the obtained solution is visually confirmed. If the obtained solution is uniform and transparent, the water solubility (20°C) of the compound is judged to be 20 g / L or more (Y = 20X). If the obtained solution is not uniform and transparent, the water solubility (20°C) of the compound is judged to be less than 20 g / L (Y = 20X). That is, compound (A) in this invention can be described as a compound whose solution is uniformly transparent when 1 g of the compound is used in the above-mentioned determination of water solubility (20°C). It should be noted that uniform transparency means that no phase separation is observed visually, and no turbidity is observed.

[0278] The acid dissociation constant pKa in requirement 2 AThis refers to the value measured at room temperature (25°C) using water as a solvent. For compounds that undergo multiple ionizations, the acid dissociation constant pKa1 of the first stage is taken as the acid dissociation constant pKa. A The pKa of compound (A) A Preferably 11 or less, more preferably 10 or less, and even more preferably 5 or less.

[0279] As described in requirement 3, the compound (A) is a compound having at least one hydroxyl group, and the total number of hydroxyl and carboxyl groups contained in one molecule of compound (A) is two or more. 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.

[0280] The total number of hydroxyl and carboxyl groups in the molecule of compound (A)1 is, for example, 2 to 30, preferably 2 to 6, and more preferably 3 to 6.

[0281] As described in requirement 4, the compound (A) has at least one high-acidity group selected from a hydroxyl group (hereinafter, sometimes referred to as hydroxyl (1)) and a carboxyl group with a pKa of 12 or less. By making at least one of the hydroxyl and carboxyl groups in the compound (A) a high-acidity group, it can react with the crosslinking agent (preferably an oxazoline-based crosslinking agent) to easily obtain the improved hydrophilicity effect brought about by the compound (A).

[0282] The pKa of the high acidity group is preferably 11 or less, more preferably 10 or less, and even more preferably 5 or less.

[0283] The compound (A)1 molecule preferably has 1 to 3 high acidity groups, more preferably 1.

[0284] The compound (A) preferably satisfies, in addition to the requirements 1 to 4, the following requirement 5.

[0285] Requirement 5: A hydroxyl group having at least one acid dissociation constant pKa (temperature: room temperature (25°C), solvent: water) greater than 12.

[0286] By including the compound (A) with a hydroxyl group (hereinafter, sometimes referred to as hydroxyl (2)) with a pKa greater than 12, the initial hydrophilicity and hydrophilic persistence of the obtained tangibles are further improved.

[0287] The pKa of the hydroxyl group (2) is more preferably 14 or higher, and even more preferably 15 or higher. Furthermore, the upper limit of the pKa of the hydroxyl group (2) is not particularly limited, but is preferably 20 or lower.

[0288] The number of hydroxyl groups (2) in the molecule of compound (A)1 is preferably 1 to 20, more preferably 3 to 5.

[0289] As compound (A), L-ascorbic acid, gallic acid, tannic acid, and gluconic acid are preferred, more preferably L-ascorbic acid, gallic acid, and gluconic acid, and particularly preferably L-ascorbic acid.

[0290] It should be noted that when making the composition contain compound (A), compound (A) can be added directly, or the composition can be made to contain compound (A) by adding compound (B) that will be modified into compound (A). Examples of compound (B) include compounds that are modified into compound (A) by hydrolysis upon reaction with water at room temperature (25°C), specifically glucono-δ-lactone.

[0291] The content of the hydroxyl-containing compound (preferably compound (A)) is not particularly limited, and is, for example, 0 to 100 parts by mass relative to 100 parts by mass of the hydrophilic resin, 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.

[0292] Furthermore, there is no particular limitation on the amount of compound (A) and compound (B) added, which is, for example, 0 to 100 parts by mass relative to 100 parts by mass of the hydrophilic resin, 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.

[0293] In the solids component of the composition (preferably the resin composition), the total content of the solids component of the hydrophilicity retention effect and / or hydrophobicity imparting agent (preferably the polymer particles), the hydrophilic resin, the crosslinking agent (preferably an oxazoline crosslinking agent), and the compound having hydroxyl groups (preferably compound (A)) in 100% by mass is, for example, 80% by mass or more, preferably 90% by mass or more, more preferably 97% by mass or more, and may also be 100% by mass. That is, it is particularly preferable to adjust the total content of the polymer particles, the hydrophilic resin, the oxazoline crosslinking agent, and the compound (A) in the solids component of the resin composition to the above range.

[0294] The method for manufacturing the composition of the present invention is not particularly limited, and may include, for example, a step (also called mixing step (A)) of mixing a hydrophilic persistence effect and / or hydrophobicity imparting agent, and a hydrophilic resin, crosslinking agent, solvent, and other additives as needed. Mixing step (A) may be carried out, for example, in the presence of a solvent (preferably an aqueous solvent) or in the absence of a solvent. It should be noted that the crosslinking agent may be added after film formation as described below.

[0295] 3. Hydrophilic coatings as tangible materials

[0296] The hydrophilic coating film formed from the composition (preferably a resin composition) as a tangible object, due to the inclusion of the hydrophilicity-continuous effect and / or hydrophobicity-imparting agent (especially the polymer particles), not only possesses good hydrophilicity but also a hydrophilicity-continuous effect and / or good hydrophobicity. Furthermore, the hydrophilicity of the coating film (tangible object) is preferably enhanced even after oil contamination. Therefore, the hydrophilicity-continuous effect and / or hydrophobicity-imparting agent of the present invention is suitable for tangible objects requiring both hydrophilicity and hydrophilicity-continuous effect and / or hydrophobicity, and is particularly suitable for hydrophilic coating films used in heat exchanger fin materials.

[0297] It should be noted that when a tangible object such as a coating exhibits a sustained hydrophilic effect, for example, the tangible object preferably satisfies the following (a) and (b).

[0298] (a) The initial contact angle (θ0) measured by the method described in the <Evaluation of Initial Hydrophilicity> in the following examples is less than 40°.

[0299] (b) The contact angle (θ2) after wet / dry cycling, as measured by the method described in <Evaluation of the persistence of hydrophilicity after wet / dry cycling 2> in the following examples, is less than 40°.

[0300] The initial contact angle (θ0) of the tangible object is preferably less than 35°, more preferably less than 30°, even more preferably less than 20°, and particularly preferably less than 15°. The lower limit of the initial contact angle (θ0) is not particularly limited, for example, it is 5° or more.

[0301] The contact angle (θ2) of the tangible object is preferably less than 35°, more preferably less than 30°, further preferably less than 26°, even more preferably less than 20°, and particularly preferably less than 15° or less. The lower limit of the contact angle (θ2) is not particularly limited, for example, it may be 2° or more or 8° or more.

[0302] In a more preferred embodiment, the relationship between the initial contact angle (θ0) and the contact angle (θ2) of the tangible object satisfies the following (c) or (d).

[0303] (c) Contact angle (θ2) ≤ initial contact angle (θ0)

[0304] (d) The contact angle (θ2) is greater than the initial contact angle (θ0), and the absolute value of the difference between the contact angle (θ2) and the initial contact angle (θ0) is less than 20°.

[0305] When the relationship between the initial contact angle (θ0) and the contact angle (θ2) of the tangible object satisfies (c), the absolute value of the difference between the contact angle (θ2) and the initial contact angle (θ0) is preferably any value, more preferably 1° or more, and even more preferably 3° or more. Furthermore, there is no particular upper limit to the absolute value of the difference, for example, it is 15° or less.

[0306] When the relationship between the initial contact angle (θ0) and the contact angle (θ2) of the tangible object satisfies (d), it is preferred that the absolute value of the difference between the contact angle (θ2) and the initial contact angle (θ0) is smaller, specifically 20° or less, preferably 15° or less, and more preferably 10° or less.

[0307] The contact angle (θ1) after wet / dry cycling, measured using the method described in <Evaluation of the Hydrophilicity Persistence Effect After Wet / Dry Cycling 1> in the following examples, is, for example, less than 40°, preferably less than 35°, more preferably less than 30°, further preferably less than 26°, even more preferably less than 20°, and particularly preferably less than 15° or less. The lower limit of the contact angle (θ1) is not particularly limited, for example, it is 2° or more or 8° or more. It should be noted that Evaluation 1 of the Hydrophilicity Persistence Effect After Wet / Dry Cycling is performed under more stringent conditions than Evaluation 2 of the Hydrophilicity Persistence Effect After Wet / Dry Cycling, therefore the contact angle (θ1) tends to become larger than the contact angle (θ2).

[0308] In a more preferred embodiment, the relationship between the initial contact angle (θ0) and the contact angle (θ1) of the tangible object satisfies the following (e) or (f).

[0309] (e) Contact angle (θ1) ≤ Initial contact angle (θ0)

[0310] (f) The contact angle (θ1) is greater than the initial contact angle (θ0), and the absolute value of the difference between the contact angle (θ1) and the initial contact angle (θ0) is less than 20°.

[0311] When the relationship between the initial contact angle (θ0) and the contact angle (θ1) of the tangible object satisfies (e), the absolute value of the difference between the contact angle (θ1) and the initial contact angle (θ0) is preferably any value, more preferably 1° or more, and even more preferably 3° or more. Furthermore, there is no particular upper limit to the absolute value of the difference, for example, it is 15° or less.

[0312] When the relationship between the initial contact angle (θ0) and the contact angle (θ1) in the tangible object satisfies (f), it is preferred that the absolute value of the difference between the contact angle (θ1) and the initial contact angle (θ0) is smaller, specifically 20° or less, preferably 15° or less, and more preferably 10° or less.

[0313] The contact angle (θ3) after oil adhesion, as measured by the method described in the "Evaluation of Hydrophilicity after Oil Adhesion" section of the following examples, is preferably less than 35°, more preferably less than 30°, even more preferably less than 26°, and particularly preferably less than 15°. The lower limit of the contact angle (θ3) is not particularly limited, for example, it is 3° or more.

[0314] In a more preferred embodiment, the relationship between the initial contact angle (θ0) and the contact angle (θ3) of the tangible object satisfies the following (g) or (h).

[0315] (g) Contact angle (θ3) ≤ Initial contact angle (θ0)

[0316] (h) The contact angle (θ3) is greater than the initial contact angle (θ0), and the absolute value of the difference between the contact angle (θ3) and the initial contact angle (θ0) is less than 20°.

[0317] When the relationship between the initial contact angle (θ0) and the contact angle (θ3) of the tangible object satisfies (g), the absolute value of the difference between the contact angle (θ3) and the initial contact angle (θ0) is preferably any value, more preferably 0.1° or more. Furthermore, there is no particular upper limit to the absolute value of the difference, for example, it is 15° or less.

[0318] When the relationship between the initial contact angle (θ0) and the contact angle (θ3) of the tangible object satisfies (h), it is preferred that the absolute value of the difference between the contact angle (θ3) and the initial contact angle (θ0) of the tangible object is smaller, specifically less than 20°, preferably less than 15°, and more preferably less than 10°.

[0319] In addition, when a tangible object such as a coating exhibits both hydrophilicity and hydrophobicity, it is preferable, for example, that the tangible object satisfies the above-mentioned initial contact angle (θ0) and (i) below.

[0320] (i) The slip angle (θs) measured by the method described in the <Evaluation of Water-Slippery Properties> in the following examples is less than 30°.

[0321] The slip angle (θs) of the tangible object is preferably 20° or less, more preferably 15° or less, even more preferably 12° or less, and particularly preferably 10° or less.

[0322] It should be noted that previous methods for measuring the slip angle did not consider the effect of droplet wetting and spreading caused by the hydrophilicity of the substrate surface. Therefore, while previous methods may yield good slip angles for hydrophilic materials, they do not necessarily indicate good hydrophobicity. Specifically, in previous methods, the material with the water droplet placed on it was tilted, allowing the droplet to move a certain distance in the slip direction. The tilt angle of the material at this point was defined as the slip angle. However, when a water droplet is placed on a hydrophilic material, wetting and spreading of the droplet can be observed. If the slip angle is measured under these conditions, both slip and wetting movements are observed simultaneously, sometimes making it difficult to accurately evaluate hydrophobicity. Furthermore, measuring the slip angle after the wetting and spreading movement reaches an equilibrium point is also considered, but there is a possibility that the water in the droplet may evaporate before reaching the equilibrium point, which is not preferable. Therefore, to ensure good hydrophobicity for hydrophilic materials, a small slip angle is required in a measurement system that considers the effect of droplet wetting and spreading.

[0323] On the other hand, in the evaluation of the hydroplaning properties of the present invention, the following evaluation method was adopted: The aim was to eliminate the influence of endpoint movement caused by wetting spread from the endpoint movement of the water droplet in the sliding direction, and to extract the endpoint movement caused by sliding. In this evaluation method, the tangible object of the present invention, which can reduce the sliding angle, can be said to have good hydroplaning properties, even though it is hydrophilic.

[0324] In this invention, by including the aforementioned polymer particles in a tangible object, the object can be endowed with good hydrophilicity, while simultaneously possessing a sustained hydrophilic effect and / or hydrophobicity. That is, in this invention, by including the aforementioned polymer particles in a tangible object, the object can be continuously hydrophilized and / or hydrophobically treated. The shape of the tangible object is not limited to the shape of the coating described above and can include, but is not particularly restricted to, the following forms: planar (film, sheet, plate), granular, powder, block, aggregated particles, spherical, ellipsoidal, lenticular, columnar, rod-shaped, conical, cylindrical, needle-shaped, fibrous, fibrous aggregate (e.g., woven fabric, nonwoven fabric, etc.), hollow fiber, porous, etc. It should be noted that the tangible object of this invention is preferably a coating.

[0325] For example, when the tangible object is planar (preferably a coating formed from the composition (especially a resin composition)), its film thickness is not particularly limited, for example, 0.1 μm to 80 μm, preferably 0.1 μm to 50 μm, more preferably 0.1 μm to 10 μm, and even more preferably 0.3 μm to 5 μm.

[0326] The method for manufacturing the tangible article is not particularly limited, as long as a conventionally known method is appropriately employed. For example, a tangible article can be obtained by molding or forming the composition (preferably a resin composition). Furthermore, when a resin composition is made, the resin contained in the resin composition is not limited to the aforementioned hydrophilic resin, and various resins selected from thermoplastic resins and thermosetting resins can be used.

[0327] Furthermore, according to the present invention, by having a tangible object containing the aforementioned polymer particles on the surface of a tangible object (hereinafter referred to as a substrate) that does not contain the aforementioned polymer particles, it is also possible to impart a continuous hydrophilic effect and / or hydrophobicity to the surface of the substrate. That is, according to the present invention, by having a tangible object containing the aforementioned polymer particles on the surface of the substrate, it is possible to continuously hydrophilize and / or hydrophobize the surface of the substrate. In either the case of molding a tangible object containing polymer particles or the case of forming a tangible object containing polymer particles on the surface of a substrate, the molding or forming method is not particularly limited, as long as it is appropriately selected according to the type of composition used and the shape of the target tangible object. Examples of molding or forming methods include: a method of forming a film by coating a composition (preferably a resin composition) containing the aforementioned polymer particles onto a substrate using methods such as coating, spraying, printing, or impregnation; a method of forming a molded article by injection molding, extrusion molding, vacuum molding, compression molding, blow molding, etc., of a composition (preferably a resin composition) containing polymer particles; and a method of laminating a tangible object (molded article, etc.) containing polymer particles onto the surface of a substrate. Preferably, a coating containing polymer particles is formed on the surface of the substrate by applying a composition (preferably a resin composition) containing the polymer particles to the substrate.

[0328] In addition to the hydrophilic resins used in the molding or forming process, other examples of resins that can be used include polyester, polyethylene, polypropylene, triacetyl cellulose, polystyrene, polycarbonate, polyethersulfone, celluloid, polyamide, polyvinyl alcohol, polyacetal, polyphenylene ether, polyphenylene sulfide, polyimide, polyamide-imide, polyetherimide, polyetheretherketone, polytetrafluoroethylene, fluoropolymers such as ABS resin, NORYL resin, acrylic resin, epoxy resin, and celluloid. Furthermore, in addition to the resins, other materials that can be used as the substrate include inorganic materials such as glass, slate, and mortar; metals such as stainless steel, iron, copper, aluminum, magnesium, and zinc, and their alloys; however, the present invention is not limited to the examples described above. The substrate may consist of a single layer or may have a multilayered structure. In particular, the substrate is preferably a heat exchanger fin material, and more preferably an aluminum fin material.

[0329] When a coating (hereinafter, a hydrophilic coating) is produced by applying the composition (preferably a resin composition) to a substrate using methods such as coating, spraying, printing, or impregnation, a crosslinking agent can be pre-mixed into the composition or added after film formation if a crosslinking agent is used in the hydrophilic coating. It should be noted that when the tangible material (preferably a coating) of the present invention is applied to the fin material (especially aluminum fin material) of a heat exchanger, film formation can be performed directly on the surface of the fin material (especially the aluminum plate constituting the aluminum fin material) (i.e., the fin material (especially the aluminum plate constituting the aluminum fin material) can be directly laminated with the tangible material), or film formation can be performed with a base layer such as a chemical conversion treatment layer and / or a resin coating layer disposed on the surface of the fin material (especially the aluminum plate constituting the aluminum fin material) for the purpose of preventing corrosion of the fin material (especially the aluminum constituting the aluminum fin material) (i.e., the fin material (especially the aluminum plate constituting the aluminum fin material) is laminated with the tangible material with the base layer).

[0330] As the chemical conversion treatment layer, conventionally known chemical conversion treatment layers can be used, such as layers composed of inorganic oxides or inorganic-organic composite compounds. The inorganic material constituting the inorganic oxide or inorganic-organic composite compound is preferably composed of chromium, zirconium, or titanium as the main component. Layers composed of inorganic oxides can be formed, for example, by treating the fin material (especially the aluminum plate constituting the aluminum fin) with chromate phosphate, zirconium phosphate, zirconium oxide, chromate chromate, zinc phosphate, or titanate phosphate. Alternatively, layers composed of inorganic-organic composite compounds can be formed, for example, by treating the fin material (especially the aluminum plate constituting the aluminum fin) with coating-type chromate or coating-type zirconium. Specific examples of such inorganic-organic composite compounds include acrylic-zirconium composites.

[0331] The resin coating layer can be formed, for example, by applying a resin-containing coating to the fin material (especially the aluminum plate constituting the aluminum fin material or the chemical conversion treatment layer) and curing it by drying or the like. As the resin, conventionally known resins can be used, including various polyester-based, polyolefin-based, epoxy-based, urethane-based, and (meth)acrylic-based resins. One or a mixture of two or more of these resins can be used. (Meth)acrylic resins are preferred, but polymers with (meth)acrylic resins as the main chain and containing oxazoline groups in the side chains can also be used.

[0332] In addition to the above-mentioned components, the resin coating layer may contain any other arbitrary components without impairing the effects of the present invention. Examples of arbitrary components include various coating additives used to improve coatability, workability, and coating properties, such as aqueous solvents, crosslinking agents, surfactants, film-forming aids, surface conditioners, wetting and dispersing agents, anti-settling agents, antioxidants, defoamers, rust inhibitors, antibacterial agents, and mildew inhibitors. One or more of these coating additives may be used.

[0333] The manufacturing method of the hydrophilic coating is not particularly limited, and can include a drying process and a curing process after the above-mentioned film-forming processes such as coating, spraying, printing, and impregnation.

[0334] This application claims priority based on Japanese Patent Application No. 2023-094540, filed June 8, 2023, and Japanese Patent Application No. 2023-162888, filed September 26, 2023. The entire contents of the descriptions of Japanese Patent Application No. 2023-094540, filed June 8, 2023, and Japanese Patent Application No. 2023-162888, filed September 26, 2023, are incorporated herein by reference.

[0335] Example

[0336] The present invention will be described in more detail below with examples, but the present invention is of course not limited to the following examples, and may be implemented by appropriate modifications within the scope of the preceding and following text, all of which are included within the technical scope of the present invention. It should be noted that, unless otherwise specified, "parts" refers to "parts by mass" and "%" refers to "% by mass".

[0337] [Experimental Example 1]

[0338] <Determination of volume average particle size>

[0339] The polymer particle aqueous dispersion was diluted with ion-exchanged water to a polymer particle concentration of 0.01%–0.05% by mass. The resulting material was measured using a light scattering particle size analyzer (Spectris "Zetasizer Ultra"), and the volume average particle size (nm) of the polymer particles was determined by dynamic light scattering method.

[0340] <Evaluation of initial hydrophilicity>

[0341] Using an automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., "CA-X"), a 2 μL droplet of pure water was prepared at 25°C and attached to the surface of the tangible object (coating surface of the film-forming sample) prepared in the examples, comparative examples, or reference examples. The contact angle was calculated using the θ / 2 method. It should be noted that the contact angle value 30 seconds after droplet attachment was taken as the measured value, and five measurements were performed. The average of the three points excluding the maximum and minimum values ​​was taken as the initial contact angle of the tangible object (coating). It should be noted that the initial hydrophilicity of the tangible object (coating) was quantitatively evaluated according to the following criteria.

[0342] ◎: Initial contact angle less than 15°

[0343] ○: Initial contact angle is greater than 15° and less than 40°

[0344] ×: Initial contact angle is 40° or higher

[0345] <Evaluation of the persistence of hydrophilicity after wet / dry cycling 1>

[0346] The tangible objects (specifically film-forming samples) prepared in Examples 1-1 to 1-5, Examples 1-8, Comparative Examples 1-1 to 1-2, and Reference Example 1-1 were immersed in pure water for 6 hours. Then, at 25°C and 50% humidity, the removed tangible objects (film-forming samples) were placed on a lint-free sheet with the contact angle measuring surface (or the coated surface of the sample if it is a film-forming sample) as the upper surface. Another lint-free sheet was then placed on top and maintained for 5 seconds. The tangible objects were then removed, and the contact angle measuring surface was evacuated until visually identifiable water droplets disappeared, thereby removing excess moisture. The samples were then dried in air at 80°C for 12 hours using a blower-controlled thermostat (Yamato Scientific "DNF400"). These operations were repeated 5 times to obtain tangible objects (film-forming samples) after wet / dry cycles.

[0347] Using an automated contact angle meter (manufactured by Kyowa Interface Science, Inc., "CA-X"), a 2 μL droplet of pure water was prepared at 25°C and applied to the surface of a tangible object (the coating surface of the film-forming sample) after wet / dry cycling. The contact angle was calculated using the θ / 2 method. It should be noted that the contact angle value 30 seconds after droplet application was used as the measured value. Five measurements were performed, and the average of the three points excluding the maximum and minimum values ​​was taken as the contact angle after wet / dry cycling. It should be noted that the hydrophilicity persistence of the tangible object (coating) after wet / dry cycling was quantitatively evaluated according to the following criteria.

[0348] ◎: The contact angle after wet / dry cycling is less than 15°

[0349] ○: The contact angle after wet / dry cycling is greater than 15° and less than 40°.

[0350] ×: The contact angle after wet / dry cycling is above 40°.

[0351] <Evaluation of the persistence of hydrophilicity after wet / dry cycling 2>

[0352] The tangible objects (film-forming samples) prepared in Examples 1-6 to 1-7 and Reference Example 1-2 were immersed in pure water for 12 hours. Excess moisture was then wiped away, and the samples were allowed to air dry. These operations were repeated 5 times to obtain tangible objects (film-forming samples) after wet / dry cycles. It should be noted that in the preparation of tangible objects after wet / dry cycles, when wiping away excess moisture, it is recommended to place the immersed tangible object on a lint-free paper with the contact angle measuring surface (or the coated surface of the sample if it is a film-forming sample) as the upper surface, cover it with another lint-free paper from above, maintain this state for 5 seconds, and then wipe away excess moisture. Furthermore, during air drying, it is recommended to blow air onto the contact angle measuring surface (or the coated surface of the sample if it is a film-forming sample) until visually identifiable water droplets disappear, and then air dry (or allow to stand) at 25°C and 50% humidity for 12 hours.

[0353] Using an automated contact angle meter (manufactured by Kyowa Interface Science, "CA-X"), a 2 μL droplet of pure water was prepared at 25°C and applied to the surface of a tangible object (the coating surface of the film-forming sample) after wet / dry cycling. The contact angle was calculated using the θ / 2 method. It should be noted that the contact angle value 30 seconds after droplet application was used as the measured value, and five measurements were performed. The average of the three values ​​excluding the maximum and minimum values ​​was taken as the contact angle after water immersion treatment. It should be noted that the hydrophilicity persistence of the tangible object (coating) after wet / dry cycling was quantitatively evaluated according to the following criteria.

[0354] ◎: The contact angle after wet / dry cycling is less than 15°

[0355] ○: The contact angle after wet / dry cycling is greater than 15° and less than 40°.

[0356] ×: The contact angle after wet / dry cycling is above 40°.

[0357] <Evaluation of hydrophilicity after oil stain adhesion>

[0358] The tangible objects (specifically film-forming samples) prepared in Examples 1-1 to 1-5, 1-8 or Reference Example 1-1 were immersed in pure water for 6 hours. Then, in an environment of 25°C and 50% humidity, the removed tangible objects (film-forming samples) were placed on lint-free paper with the contact angle measuring surface (or the coated surface of the sample if it is a film-forming sample) as the upper surface. Another lint-free paper was then placed on top and maintained in this state for 5 seconds. Then, the tangible objects were removed, and excess moisture was removed by blowing air onto the contact angle measuring surface until the water droplets could be visually confirmed to disappear. The tangible objects were then dried in air at 80°C for 12 hours using a blower-controlled thermostat (Yamato Scientific "DNF400") to obtain the water-immersed tangible objects (film-forming samples). A water-treated sample (film-forming sample) and 10g of stearic acid (as a simulated contaminant, oil) were placed in a stainless steel square container (lock-lock, 3400mL, AS ONE) without direct contact between them. The container was sealed and heated at 100°C for 24 hours using a blower-controlled thermostat (Yamato Scientific, DNF400) to obtain the oil-coated sample. Using an automatic contact angle meter (Kyowa Interface Science, CA-X), a 2μL droplet of pure water was prepared at 25°C and attached to the surface of the oil-coated sample (the coating surface of the film-forming sample). The contact angle was calculated using the θ / 2 method. It should be noted that the contact angle value 30 seconds after droplet attachment was used as the measured value. Five measurements were performed, and the average of the three values ​​excluding the maximum and minimum values ​​was taken as the contact angle after oil adhesion. It should be noted that the hydrophilicity of tangible materials (coatings) after oil contamination is quantitatively evaluated according to the following criteria.

[0359] ◎: The contact angle after oil stains adhere is less than 15°

[0360] ○: The contact angle after oil contamination is greater than 15° and less than 35°.

[0361] ×: The contact angle of the oil stain after it adheres is greater than 35°.

[0362] [Polymer Synthesis]

[0363] <Manufacturing Example 1-1>

[0364] In a stainless steel reactor equipped with a stirrer, thermometer, and cooler, 1101 parts by mass of deionized water and 1.92 parts by mass of a substance prepared by diluting anionic reactive emulsifier ADEKA REASOAP SR-20 (100% by mass of active ingredient, manufactured by ADEKA Corporation), which is mainly composed of ether sulfate-type ammonium salts, to 25% by mass of active ingredient with deionized water (hereinafter referred to as "SR-20 (25% by mass of active ingredient)") were added. The internal temperature was raised to 75°C and maintained at this temperature. On the other hand, in a container different from the above reactor, 180.0 parts by mass of methyl 2-hydroxymethyl methacrylate (hereinafter referred to as "RHMA") and 20.0 parts by mass of divinylbenzene (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., hereinafter referred to as "DVB810") were mixed to prepare a monomer composition of 200.0 parts by mass. After purging the reactor with nitrogen, 40.0 parts by weight of the monomer composition, 21.0 parts by weight of hydrogen peroxide aqueous solution (hydrogen peroxide concentration 1.28 wt%), and 21.0 parts by weight of L-ascorbic acid aqueous solution (L-ascorbic acid concentration 1.90 wt%) were added to the reactor. The internal temperature was maintained at 75°C, and the initial polymerization reaction was carried out for 2 hours. Next, the remaining 160.0 parts by weight of the monomer composition, 479.0 parts by weight of hydrogen peroxide aqueous solution (hydrogen peroxide concentration 0.22 wt%), 479.0 parts by weight of L-ascorbic acid aqueous solution (L-ascorbic acid concentration 0.33 wt%), and 486.04 parts by weight of a mixture of SR-20 (active ingredient 25 wt%) were uniformly added dropwise to the reactor from their respective inlets over 4 hours. After the addition is complete, the internal temperature is raised to 85°C and maintained at this temperature for 2 hours for aging. The reaction solution is then cooled to obtain a polymer aqueous dispersion 1-1 containing polymer particles.

[0365] Ten parts by mass of the obtained polymer aqueous dispersion 1-1 and 1.1 parts by mass of an ammonia aqueous solution (concentration 25.0% by mass) as an alkaline aqueous solution were added to a reaction vessel and stirred overnight at 25°C to obtain a polymer particle aqueous dispersion (a1-1) containing partially hydrolyzed polymer particles (1-1). The volume average particle size of the obtained polymer particles (1-1) was 393 nm.

[0366] <Manufacturing Examples 1-2>

[0367] The alkaline aqueous solution was replaced with 1.4 parts by mass of a sodium hydroxide aqueous solution (concentration 20.0%), and otherwise, a polymer particle aqueous dispersion (a1-2) containing hydrolyzed polymer particles (1-2) was obtained in the same manner as in Manufacturing Example 1-1. The volume average particle size of the obtained polymer particles (1-2) was 399 nm.

[0368] <Manufacturing Examples 1-3>

[0369] In a stainless steel reactor No. 1, equipped with a stirrer, thermometer, and cooler, 1128 parts by mass of deionized water and 1.05 parts by mass of a substance prepared by diluting anionic reactive emulsifier ADEKA REASOAP SR-20 (100% by mass of active ingredient, manufactured by ADEKA Corporation), which is mainly composed of ether sulfate-type ammonium salt, to 10% by mass of active ingredient with deionized water (hereinafter referred to as "SR-20 (10% by mass of active ingredient)") were added. The internal temperature was raised to 75°C and maintained at that temperature. Meanwhile, in a reactor No. 2, different from the reactor No. 1, 70 parts by mass of methyl methacrylate (hereinafter referred to as "MMA") and 30 parts by mass of DVB810 were mixed to prepare monomer composition A of 100 parts by mass. Further, in a reactor No. 3, different from the reactor No. 1 and the reactor No. 2, 90 parts by mass of RHMA and 10 parts by mass of DVB810 were mixed to prepare monomer composition B of 100 parts by mass. Next, after purging the first reactor with nitrogen, 100 parts by weight of monomer composition A, 20 parts by weight of hydrogen peroxide aqueous solution (concentration 3.35% by weight), and 20 parts by weight of L-ascorbic acid aqueous solution (concentration 5.0% by weight) were added to the first reactor. The internal temperature was maintained at 75°C, and the initial polymerization reaction was carried out for 2 hours. Then, 100 parts by weight of monomer composition B, 100 parts by weight of hydrogen peroxide aqueous solution (concentration 0.83% by weight), 100 parts by weight of L-ascorbic acid aqueous solution (concentration 1.25% by weight), 7.04 parts by weight of SR-20 (active ingredient 10% by weight), 0.36 parts by weight of ammonia aqueous solution (concentration 28% by weight), and 100 parts by weight of a mixture of ion-exchanged water (92.6% by weight) were uniformly added dropwise to the first reactor through their respective inlets over 3 hours. After the addition is complete, the internal temperature of the first reaction vessel is maintained at 75°C. After aging at this temperature for 2 hours, the reaction solution is cooled to obtain a polymer aqueous dispersion 1-3 containing polymer particles.

[0370] Ten parts by mass of the obtained polymer aqueous dispersion 1-3 and 1.1 parts by mass of an ammonia aqueous solution (concentration 25.0% by mass) as an alkaline aqueous solution were added to the first reaction vessel, and the mixture was stirred overnight at 25°C to obtain a polymer particle aqueous dispersion (a1-3) containing partially hydrolyzed polymer particles (1-3). The volume average particle size of the obtained polymer particles (1-3) was 331 nm.

[0371] <Manufacturing Examples 1-4>

[0372] The alkaline aqueous solution was replaced with 1.4 parts by mass of a sodium hydroxide aqueous solution (20% concentration), and the amount of reactive emulsifier was adjusted appropriately to achieve the target particle size. Otherwise, a polymer particle aqueous dispersion (a1-4) containing hydrolyzed polymer particles (1-4) was obtained in the same manner as in Manufacturing Examples 1-3. The volume average particle size of the obtained polymer particles (1-4) was 58.4 nm.

[0373] <Manufacturing Examples 1-5>

[0374] 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 BLEMMERPME400 (hereinafter referred to as PME400) manufactured by Nippon Oil Company. The alkaline aqueous solution was changed to 1.2 parts by mass of sodium hydroxide aqueous solution (concentration 20%). The amount of reactive emulsifier was adjusted appropriately to achieve the target particle size. Otherwise, a polymer particle aqueous dispersion (a1-5) containing hydrolyzed polymer particles (1-5) was obtained in the same manner as in Manufacturing Examples 1-3. The volume average particle size of the obtained polymer particles (1-5) was 64.6 nm.

[0375] <Manufacturing Examples 1-6>

[0376] In a stainless steel reactor equipped with a stirrer, thermometer, and cooler, 832.0 parts by weight of deionized water and 0.96 parts by weight of SR-20 (25.0% by weight of active ingredient) were added, and the internal temperature was raised to 75°C and maintained at that temperature. Meanwhile, in a different container than the reactor described above, 180.0 parts by weight of RHMA and 20.0 parts by weight of DVB810 were mixed to prepare a monomer composition of 200.0 parts by weight.

[0377] After purging the reactor with nitrogen, 40.0 parts by weight of the monomer composition, 21.0 parts by weight of hydrogen peroxide aqueous solution (hydrogen peroxide concentration 1.28 wt%), and 21.0 parts by weight of L-ascorbic acid aqueous solution (L-ascorbic acid concentration 1.90 wt%) were added to the reactor to initiate the initial polymerization reaction. Next, the remaining 160.0 parts by weight of the monomer composition, 479.0 parts by weight of hydrogen peroxide aqueous solution (hydrogen peroxide concentration 0.22 wt%), and 486.04 parts by weight of a mixture of 479.0 parts by weight of L-ascorbic acid aqueous solution (L-ascorbic acid concentration 0.33 wt%) and 7.04 parts by weight of SR-20 (active ingredient 25.0 wt%) were uniformly added dropwise to the reactor over 4 hours through their respective inlets. After the addition is complete, the internal temperature is maintained at 75°C for 2 hours for aging. Then, the reaction solution is cooled to obtain a polymer aqueous dispersion 1-6 containing polymer particles. The volume average particle size of the polymer particles is 221 nm.

[0378] 100 parts by weight of the polymer particle aqueous dispersion 1-6 and 15 parts by weight of an aqueous sodium hydroxide solution (concentration 20.0% by weight) as an alkaline aqueous solution were mixed and stirred overnight at 25°C to obtain a polymer particle aqueous dispersion (a1-6) containing partially hydrolyzed polymer particles (1-6). At this time, the volume average particle size of the obtained polymer particles (1-6) was 389 nm.

[0379] <Manufacturing Examples 1-7>

[0380] In manufacturing examples 1-6, the sodium hydroxide aqueous solution was replaced with 5 parts by mass of ammonia aqueous solution (concentration 25.0%). Otherwise, a polymer particle aqueous dispersion (a1-7) containing partially hydrolyzed polymer particles (1-7) was obtained in the same manner. At this time, the volume average particle size of the obtained polymer particles (1-7) was 379 nm.

[0381] [Table 1]

[0382]

[0383] In Table 1, the amount of alkaline aqueous solution added represents the number of moles of alkali added when the molar number of RHMA in the polymer particles is set to 100 mol%, which is equivalent to the ionization rate and hydrolysis rate.

[0384] [Example 1-1]

[0385] <Preparation of film-forming sample A1-1>

[0386] EPOCROS K-2035E (manufactured by Nippon Shokubai Co., Ltd.; solid content 40% by mass) as a water-based resin and CS-12 (manufactured by JNC Corporation; active ingredient 100% by mass) as a film-forming aid were compounded at a ratio of 100:25 based on the ratio of active ingredients (by mass), and diluted with pure water to a final solid content of 10% by mass to obtain a composition for substrate coating.

[0387] Next, the substrate coating composition was applied to an aluminum plate (length: 150mm, width: 60mm, thickness: 0.100mm) using a bar coater, so that the coating thickness was 1.1μm. The plate was then dried at 160°C for 11 seconds using an automatic discharge dryer (AT-101 (standard type) manufactured by Tokage Thermal Engineering Co., Ltd.) to obtain an aluminum plate with a substrate coating.

[0388] A water-based polyacrylic acid resin (weight average molecular weight of about 5000), a polymer particle aqueous dispersion (a1-1), and a water-based crosslinking agent (EPOCROS WS-700 manufactured by Nippon Shokubai Co., Ltd.; solid content 25% by mass) were compounded in a ratio of 100:25:18 (by mass) based on solid content, and diluted with pure water to a final solid content of 5% by mass to obtain composition A1-1 for coating.

[0389] Next, on the substrate-coated surface of the aluminum plate with the substrate layer prepared above, the coating composition A1-1 was applied using a bar coater to achieve a film thickness of 0.70 μm. The film was then dried at 200°C for 11 seconds using an automatic discharge dryer (AT-101 (standard type) manufactured by Tokage Thermal Engineering Co., Ltd.) to obtain a film-forming sample A1-1 with a laminated coating. The evaluation results of the obtained film-forming sample are shown in Table 2.

[0390] [Examples 1-2 to 1-5]

[0391] <Preparation of film-forming samples A1-2 to A1-5>

[0392] The polymer particle aqueous dispersion was changed to the substance described below, and the addition amount of each polymer particle was changed to the amount described in Table 2, which is 100 parts of the solid component of the aqueous polyacrylic acid resin. Otherwise, film-forming samples A1-2 to A1-5 were prepared in the same manner as in Examples 1-1. The evaluation results of the obtained film-forming samples are shown in Table 2.

[0393] Examples 1-2…Polymer particle aqueous dispersions (a1-2)

[0394] Examples 1-3…Polymer particle aqueous dispersions (a1-3)

[0395] Examples 1-4…Polymer particle aqueous dispersions (a1-4)

[0396] Examples 1-5…Polymer particle aqueous dispersions (a1-5)

[0397] [Comparative Examples 1-1, 1-2]

[0398] The polymer particle aqueous dispersion was changed to the following substances, and film-forming samples B1-1 and B1-2 were prepared in the same manner as in Example 1-1. The evaluation results of the obtained film-forming samples are shown in Table 2.

[0399] Comparative Example 1-1… Silica particles (Snowtex N manufactured by Nissan Chemical Co., Ltd., average particle size 12 nm)

[0400] Comparative Examples 1-2… Acrylic granules (EPOSTAR MX100W manufactured by Nippon Shokubai Co., Ltd., average particle size 150nm)

[0401] [Refer to Example 1-1]

[0402] Film-forming samples C1-1 were prepared in the same manner as in Examples 1-1, except that the polymer particle aqueous dispersion was not incorporated. The evaluation results of the obtained film-forming samples are shown in Table 2.

[0403] [Examples 1-6]

[0404] (1) Preparation of hydrophilic resin

[0405] Monoethanolamine was added to an aqueous solution of polyacrylic acid with a weight average molecular weight of 4000, the pH was adjusted to 7.0, and then adjusted with pure water to obtain an aqueous solution of polycarboxylate resin (Z-1a) containing polycarboxylate resin (Z-1) at a solid content concentration of 54%.

[0406] (2) Preparation of coating composition

[0407] An aqueous solution of polycarboxylate resin (Z-1a) and an aqueous dispersion of polymer particles (a1-6) were mixed at a ratio of 100:10 (solid content of resin (Z-1) to polymer particles (a1-6)). The mixture was diluted with pure water to a final solid content of 5% by mass and then stirred thoroughly with a stirring head to obtain a coating composition.

[0408] (3) Preparation of film-forming sample A1-6

[0409] Wipe the coated surface of the aluminum test panel (Nippon Test Panel, A1050P, 150mm x 70mm x 0.800mm) with acetone-containing lint-free paper until no black stains remain. Next, apply Ultra Sealer III (Nippon Paint) to the acetone-cleaned aluminum test panel using a bar coater, achieving a film thickness of 11.5μm. Dry the panel at 100°C for 10 minutes using a blower-controlled thermostat (Yamato Scientific "DNF400") to prepare the surface-modified aluminum test panel.

[0410] The coating composition was applied to the modified surface of the aluminum test panel prepared above using a bar coater, resulting in a film thickness of 45.8 μm. The film was then dried at 200°C for 1 minute using a blower-controlled thermostat (Yamato Scientific "DNF400") to obtain film-forming samples A1-6 with the coating layered on top. The evaluation results of the obtained film-forming samples are shown in Table 2.

[0411] [Examples 1-7]

[0412] The prepared polymer particle aqueous dispersion was changed to a polymer particle aqueous dispersion (a1-7). The polycarboxylate resin aqueous solution (Z-1a) and the polymer particle aqueous dispersion (a1-7) were prepared in a ratio of resin (Z-1) to polymer particles (a1-7) of 100:20 based on solid content. Otherwise, film-forming samples A1-7 were obtained in the same manner as in Examples 1-6. The evaluation results of the obtained film-forming samples are shown in Table 2.

[0413] [Examples 1-8]

[0414] Coating composition A1-8 was used instead of coating composition A1-1. Coating composition A1-8 was obtained by combining an aqueous polyacrylic resin (weight average molecular weight approximately 5000), a polymer particle aqueous dispersion (a1-5), an aqueous crosslinking agent (EPOCROS WS-700 manufactured by Nippon Shokubai Co., Ltd.; solid content 25% by mass), and L-ascorbic acid in a ratio of 100:100:18:20 (by mass) and diluted with pure water to a final solid content of 5% by mass. Otherwise, film-forming samples A1-8 were obtained in the same manner as in Examples 1-1. The evaluation results of the obtained film-forming samples are shown in Table 2.

[0415] [Refer to Examples 1-2]

[0416] Film-forming sample C-2 was prepared in the same manner as in Examples 1-6, except that it was not combined with an aqueous dispersion of polymer particles. The evaluation results of the obtained film-forming samples are shown in Table 2.

[0417] [Table 2]

[0418]

[0419] It should be noted that in Table 2, "particle addition amount" refers to the amount of particles added when the solid component of the hydrophilic resin is set to 100 parts (solid component conversion).

[0420] The results in Table 2 show that the hydrophilicity retention and / or hydrophobicity imparting agents of the present invention, which are composed of specific particles, can impart a hydrophilicity retention effect to tangible materials such as coatings, which continues to be hydrophilic even after wet / dry cycles. Furthermore, they can impart good hydrophilicity even after oil stains adhere.

[0421] [Experimental Example 2]

[0422] <Determination of volume average particle size>

[0423] The volume average particle size (nm) of the polymer particles was determined using the same method as in Experimental Example 1, which is used for the determination of volume average particle size.

[0424] <Evaluation of hydrophilicity>

[0425] Using the same method as in the evaluation of initial hydrophilicity in Experimental Example 1, the initial contact angle of the tangible material (coating) was determined, and the hydrophilicity of the tangible material (coating) was quantitatively evaluated according to the following criteria.

[0426] ◎: Initial contact angle less than 15°

[0427] ○: Initial contact angle is greater than 15° and less than 40°

[0428] ×: Initial contact angle is 40° or higher

[0429] <Evaluation of Water-Slippery Properties>

[0430] As an evaluation of slip properties, the slip angle of a water droplet relative to a tangible surface (the coating surface of the film-forming sample) is measured.

[0431] Specifically, after immersing the tangible object (film-forming sample) in pure water at 25°C for 1 hour, it is placed on clean paper with the slip angle measuring surface (or the coated surface of the sample if it is a film-forming sample) as the upper surface, and covered with another clean paper from above for 5 seconds. The tangible object is then removed, and the slip angle measuring surface is blasted until visually identifiable water droplets disappear, thus removing excess moisture. It is then dried at 80°C for 2 hours using a blower-controlled thermostat (Yamato Scientific "DNF400") to obtain a tangible object (film-forming sample) that reproduces the fin material (with condensate adhesion and heated drying) during heat exchanger use. Hereinafter, the tangible object subjected to the above treatment will be referred to as the "tangible object after thermal cycling" (specifically, the film-forming sample after thermal cycling).

[0432] Using an automatic contact angle meter (manufactured by Kyowa Interface Science, "CA-X"), a 10 μL droplet of pure water was prepared at 25°C and attached to the surface of a horizontally positioned, thermally cycled material (the coating surface of the thermally cycled film sample). Starting 0.1 seconds after the droplet attached, the surface was gradually tilted at a rate of 2° / second, increasing by 0.5° each time. The angle at which the droplet began to move was taken as the measurement value. Five measurements were performed, and the average of the three points excluding the maximum and minimum values ​​was taken as the slip angle θs. Then, the hydrophobicity of the material (coating) was quantitatively evaluated according to the following criteria.

[0433] ◎: The slip angle θs is less than 15°

[0434] ○: The slip angle θs is greater than 15° and less than 30°

[0435] ×: The slip angle θs is 30° or higher.

[0436] It should be noted that regarding the determination of water droplet movement, such as... Figure 1 As shown, 0.1 seconds after a water droplet adheres to the surface of the object 1, the endpoint of the water droplet (2a) on the opposite side of the sliding direction is defined as R0, and the endpoint on the sliding direction side is defined as L0. At the tilt angle θ, the endpoint of the water droplet (2b) on the opposite side of the sliding direction is defined as Rθ, and the endpoint on the sliding direction side is defined as Lθ. The distance the endpoint of the water droplet moves on the opposite side of the sliding direction is defined as dR = -|Rθ-R0|, and the distance the endpoint on the sliding direction side of the water droplet moves is defined as dL = |Lθ-L0|. When dR + dL > 1.00 mm is first satisfied, the water droplet is determined to have moved. The tilt angle θ at this time is defined as the sliding angle θs. This definition aims to eliminate the influence of endpoint movement caused by wetting spread from the endpoint movement of the water droplet in the sliding direction, and to extract an evaluation method for endpoint movement caused by sliding.

[0437] [Polymer Synthesis]

[0438] <Manufacturing Example 2-1>

[0439] In a stainless steel reactor No. 1, equipped with a stirrer, thermometer, and cooler, 1128 parts by mass of deionized water and 1.05 parts by mass of SR-20 (10% by mass of active ingredient) were added, and the internal temperature was raised to 75°C and maintained at that temperature. Meanwhile, in a reactor No. 2, different from the reactor No. 1, 70 parts by mass of MMA and 30 parts by mass of DVB810 were mixed to prepare monomer composition A (100 parts by mass). Further, in a reactor No. 3, different from the reactors No. 1 and No. 2, 90 parts by mass of RHMA and 10 parts by mass of DVB810 were mixed to prepare monomer composition B (100 parts by mass). Next, after purging the first reactor with nitrogen, 100 parts by weight of monomer composition A, 20 parts by weight of hydrogen peroxide aqueous solution (concentration 3.35% by weight), and 20 parts by weight of L-ascorbic acid aqueous solution (concentration 5.0% by weight) were added to the first reactor. The internal temperature was maintained at 75°C, and the initial polymerization reaction was carried out for 2 hours. Then, 100 parts by weight of monomer composition B, 100 parts by weight of hydrogen peroxide aqueous solution (concentration 0.83% by weight), 100 parts by weight of L-ascorbic acid aqueous solution (concentration 1.25% by weight), and 100 parts by weight of a mixture of SR-20 (active ingredient 10% by weight), 0.36 parts by weight of ammonia aqueous solution (concentration 28% by weight), and 92.6 parts by weight of ion-exchanged water were uniformly added dropwise to the first reactor through their respective inlets over 3 hours. After the addition is complete, the internal temperature of the first reaction vessel is maintained at 75°C. After aging at this temperature for 2 hours, the reaction solution is cooled to obtain a polymer aqueous dispersion 2-1 containing polymer particles.

[0440] Ten parts by mass of the obtained polymer aqueous dispersion 2-1 and 1.4 parts by mass of an alkaline aqueous solution of sodium hydroxide (concentration 20%) were added to the first reactor and stirred overnight at 25°C to obtain a polymer particle aqueous dispersion (a2-1) containing hydrolyzed polymer particles (2-1). The volume average particle size of the obtained polymer particles (2-1) was 330 nm.

[0441] <Manufacturing Example 2-2>

[0442] 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 alkaline aqueous solution was changed to 1.2 parts by mass of sodium hydroxide aqueous solution (20% concentration). Otherwise, a polymer particle aqueous dispersion (a2-2) containing hydrolyzed polymer particles (2-2) was obtained in the same manner as in Manufacturing Example 2-1. The volume average particle size of the obtained polymer particles (2-2) was 302 nm.

[0443] [Table 3]

[0444]

[0445] In Table 3, the amount of alkaline aqueous solution added represents the number of moles of alkali added when the molar percentage of RHMA in the polymer particles is set to 100 mol%, which is equivalent to the ionization rate and hydrolysis rate.

[0446] [Example 2-1]

[0447] <Preparation of film-forming sample A2-1>

[0448] A water-based polyacrylic acid resin (weight average molecular weight of about 5000), a polymer particle aqueous dispersion (a2-1), and a water-based crosslinking agent (EPOCROS WS-700 manufactured by Nippon Shokubai Co., Ltd.; solid content 25% by mass) were compounded in a ratio of 100:100:18 (by mass) based on solid content, and diluted with pure water to a final solid content of 5.45% by mass to obtain a coating composition A2-1.

[0449] Next, 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, resulting in a film thickness of 1.00 μm. The film was then dried at 200°C for 1 minute using an automatic discharge dryer (AT-101 (standard type) manufactured by Tokage Thermal Engineering Co., Ltd.) to obtain a film-forming sample A2-1 with the coating layered on top. The evaluation results of the obtained film-forming sample are shown in Table 4.

[0450] [Example 2-2]

[0451] <Film Formation Sample A2-2>

[0452] The polymer particle aqueous dispersion was changed to polymer particle aqueous dispersion (a2-2), and the film-forming sample A2-2 was prepared in the same manner as in Example 2-1. The evaluation results of the obtained film-forming samples are shown in Table 4.

[0453] [Refer to Example 2-1]

[0454] Except for the absence of a polymer particle aqueous dispersion, film-forming sample C2-1 was prepared in the same manner as in Example 2-1. The evaluation results of the obtained film-forming samples are shown in Table 4.

[0455] [Table 4]

[0456]

[0457] It should be noted that in Table 4, "particle addition amount" refers to the amount of particles added when the solid component of the hydrophilic resin is set to 100 parts (solid component conversion).

[0458] The results in Table 4 show that the hydrophilicity retention effect and / or hydrophobicity imparting agent of the present invention, which is composed of specific particles, can impart good hydrophilicity to tangible objects such as coatings, and at the same time impart good hydrophobicity.

[0459] Symbol Explanation

[0460] 1: Tangible objects

[0461] 2a: Water droplets 0.1 seconds after attachment

[0462] 2b: Water droplet at tilt angle θ

[0463] R0: The endpoint of the water droplet on the opposite side of its sliding direction 0.1 seconds after the droplet adheres.

[0464] L0: The endpoint of the water droplet on the side of the sliding direction 0.1 seconds after the droplet adheres.

[0465] Rθ: The endpoint of the water droplet on the opposite side of its sliding direction at the tilt angle θ.

[0466] Lθ: The endpoint on the side of the water droplet's sliding direction when tilted at angle θ.

Claims

1. A hydrophilicity-sustaining effect and / or slip imparting agent, which comprises, as a constituent ingredient, particles of a crosslinked polymer having a -COOR group and a hydroxyl group, wherein, In the -COOR group, R represents a hydrocarbon group, a hydrogen atom, an alkali metal atom, or an ammonium.

2. The hydrophilic lasting effect and / or slip imparting agent according to claim 1, wherein, 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.

3. The hydrophilic lasting effect and / or slip imparting agent according to claim 2, wherein, The structural unit derived from the monomer (AB1) is a structural unit represented by the following formula (1), and the structural unit derived from the monomer (C) is a structural unit derived from a polyfunctional olefinically unsaturated monomer, [Chemical Formula 1] In formula (1), R 1 represents an alkyl group having 1 to 4 carbon atoms, a hydrogen atom, an alkali metal atom, or an ammonium.

4. The hydrophilic lasting effect and / or slip imparting agent according to claim 3, wherein, The crosslinked polymer contains structural units represented by the formula (1) and R 1 is an alkali metal atom or ammonium.

5. The hydrophilic lasting effect and / or slip imparting agent according to claim 2, wherein, In the crosslinked polymer, the content of the structural unit derived from the monomer (AB1) is 5% by mass or more.

6. The hydrophilic lasting effect and / or slip imparting agent according to claim 2, wherein, In the crosslinked polymer, the content of the structural unit derived from the monomer (C) is 0.01 to 70% by mass.

7. The hydrophilic lasting effect and / or slip imparting agent according to claim 2, wherein, The crosslinked polymer further contains a structural unit derived from an olefinically unsaturated monomer containing a polyoxyalkylene group.

8. The hydrophilic lasting effect and / or slip imparting agent according to claim 1, wherein, The volume average particle diameter of the particles is 10 nm to 10 μm.

9. The hydrophilic lasting effect and / or slip imparting agent according to claim 1, wherein, The particles are single-layer particles containing the crosslinked polymer, or particles of core-shell structure containing the crosslinked polymer in a shell layer.

10. The hydrophilic lasting effect and / or slip imparting agent according to claim 1, wherein, The hydrophilicity-sustaining effect and / or water-sliding property-imparting agent is used for a fin material of a heat exchanger.

11. The hydrophilic lasting effect and / or slip imparting agent according to claim 10, wherein, The fin material is used for an aluminum fin material.

12. A resin composition having the hydrophilicity-sustaining effect and / or water-sliding property-imparting agent according to any one of claims 1 to 11 and a hydrophilic resin.

13. The resin composition according to claim 12, wherein, The hydrophilic resin is a resin having at least one polar functional group selected from the group consisting of a carboxyl group and a salt of a carboxyl group in a side chain.

14. The resin composition according to claim 12, wherein, The resin composition further contains a crosslinking agent.

15. A method of performing sustained hydrophilization and / or hydrophobization of a tangible object, comprising incorporating into the tangible object particles comprising a crosslinked polymer having -COOR groups and hydroxyl groups, wherein, In the -COOR group, R represents a hydrocarbon group, a hydrogen atom, an alkali metal atom, or an ammonium.

16. A method for continuously hydrophilizing and / or water-slipping a surface of a substrate by applying a composition containing particles comprising a crosslinked polymer having a -COOR group and a hydroxyl group to the substrate to form a coating film containing the particles on the surface of the substrate, wherein, In the -COOR group, R represents a hydrocarbon group, a hydrogen atom, an alkali metal atom, or an ammonium.

17. The method of claim 16, wherein, The substrate is a fin material of a heat exchanger.

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