JPH06322292A - Polymer composition for hydrophilic treatment - Google Patents

Abstract

PURPOSE:To obtain a polymer compsm. for a hydrophilic treatment which compsn. is excellent in hydrophilicity and resistance to dissolution in water. CONSTITUTION:A polymer compsn. for a hydrophilic treatment comprises as the main components [I] a combination of at least 2 kinds of polymers selected from the group consisting of (a) polymer of a kind such as a polyacrylic acid polymer, (b) a polymer capable of forming a polymer complex with the polymer (a) through a hydrogen bond, such as polyethylene oxide or polyvinylpyrrolidone, and (c) a polymer having carboxyl groups and proton-acceptive structural units interactive with a carboxyl group through a hydrogen bond, or the polymer (c) alone; and [II] a voltaic base capable of suppressing the formation of the polymer complex, such as ammonia. The compsn. is applied on the surface of a metal such as aluminum, and then heated to volatilize the voltaile base together with water to form the polymer complex which is insoluble in water.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polymer for hydrophilization which can be used for hydrophilizing the surface of aluminum or aluminum alloy such as aluminum heat exchanger fin material to suppress or prevent generation of water droplets. The present invention relates to a composition and a method for forming a hydrophilic polymer film.

[0002]

2. Description of the Related Art It is known that the fins of a heat exchanger such as an air conditioner tend to be clogged with water droplets due to the aggregation of water in the atmosphere during cooling. As a result of such clogging, ventilation resistance increases and the exchange efficiency of the heat exchanger decreases, or problems such as generation of noise and pollution due to scattering of water droplets occur. In order to prevent the occurrence of such a problem, a number of treatment methods have conventionally been proposed in which the surface of the fin material of the heat exchanger is hydrophilized to improve water wettability.

[0003] For example, Japanese Patent Publication No. 53-48177,
JP-B-55-1347 and JP-A-58-12698
No. 9, JP-A-59-13078 and the like disclose a method of hydrophilic treatment using a silicate such as water glass.

Further, as a hydrophilic treatment method using an organic resin, for example, JP-A-3-26381 and JP-A-1-299877 disclose polyvinyl alcohol, a specific water-soluble polymer and a water-soluble crosslinking agent. Methods for combined use are disclosed. In addition, JP-A 2-10
7678 and JP-A-2-202967 disclose a method of using a combination of a block copolymer composed of a hydrophilic polymer part composed of a specific hydrophilic monomer and a hydrophobic polymer part, and a metal chelate type crosslinking agent. It is disclosed. Further, JP-A-1-104667 and JP-A-1104667
-268747, and Japanese Patent Laid-Open No. 1-270977.
Japanese Patent Laid-Open Publications and the like disclose methods using a polyacrylamide resin.

[0005]

However, an inorganic treatment agent having good hydrophilicity such as silicate as proposed in the above publication has a peculiar odor, and fine powder is scattered due to decomposition of the coating film. There was a problem of doing. Further, when this inorganic treatment agent is applied to a so-called precoat treatment in which the aluminum plate is subjected to hydrophilic treatment and then processed into a heat exchanger, there is a problem that the mold is easily consumed during processing.

Further, in the case of the organic resin type treating agent as proposed in the above publication, the problem of odor and processability in the above inorganic type treating agent is small, but the problem of poor hydrophilicity is encountered. there were. In particular, in recent years, air conditioners have become smaller and lighter, and the fin spacing of heat exchangers has become smaller, and there is a demand for a treatment agent that can impart higher hydrophilicity. In the organic resin-based treatment agent proposed in the above publication, when an attempt is made to improve hydrophilicity by increasing the number of polar groups in the molecular structure of the resin, the water solubility of the treated film decreases, and Therefore, it becomes easy to dissolve in water and there is a problem that the hydrophilicity cannot be maintained. Further, when an antibacterial agent or the like is mixed for the purpose of preventing the generation of mold or the like, the effect of such an antibacterial agent or the like may not be maintained due to the dissolution of the coating film in water.

In recent years, an aqueous treatment agent which can use water as a solvent has been demanded from the viewpoint of environment and safety. In such an aqueous treatment agent, it becomes more difficult to satisfy both the hydrophilicity of the resin and the water resistance of the coating film after curing, and the organic resin type treatment agent proposed hitherto can satisfy such a requirement. could not.

The object of the present invention is to solve the above-mentioned problems of the prior art, to eliminate the problems of odor and processability in precoating treatment, to have excellent hydrophilicity, and to have an aqueous hydrophilization treatment excellent in water solubility. A polymer composition for use and a hydrophilic polymer film formed from the polymer composition.

[0009]

In order to solve the above problems, the inventors of the present invention have conducted earnest research on an aqueous polymer composition for hydrophilic treatment, which is excellent in hydrophilicity and water solubility. By using a polymer having a carboxylic acid group and a water-soluble polymer capable of forming a polymer aggregate, a so-called polymer complex, by associating with the polymer through hydrogen bonds, excellent hydrophilicity and excellent water solubility resistance can be obtained. The present invention has been completed by forming a polymer coating and finding that it can be used for hydrophilic treatment of aluminum fins of a heat exchanger.

That is, the polymer composition of the present invention comprises a combination of at least two polymers selected from the group consisting of polymers (a), (b) and (c), or polymer (c) alone [. I] and a volatile base [II].

The polymer (a) is a polymer obtained by polymerizing 50 mol% or more of an unsaturated monomer having a carboxylic acid group, which alone has no ability to form a polymer complex by hydrogen bond. The polymer (a) is a water-soluble polymer or a polymer which becomes soluble in water when neutralized with a base.

The polymer (b) alone does not have the ability to form a polymer complex by hydrogen bond, but the polymer (a) has a proton-accepting structural unit that interacts with the carboxylic acid group of the polymer (a) by hydrogen bond. Polymer inside (a)
It is a water-soluble polymer that can form a polymer complex by hydrogen bonding with.

The polymer (c) is formed by polymerizing 50 mol% or more of an unsaturated monomer having a carboxylic acid group, and has a proton-accepting structural unit which interacts with the carboxylic acid group in a hydrogen bond in the molecule. It is a polymer which has the ability to form a polymer complex by hydrogen bonding. The polymer (c) becomes soluble in water by neutralizing with a base.

An aqueous solution of such a polymer composition is applied onto the surface of an object to be treated such as aluminum or an aluminum alloy, and then the polymer composition is heated,
It is possible to evaporate the contained water and volatilize the volatile base in the polymer composition to form a polymer complex to form a water-insoluble polymer film, thereby forming a hydrophilic polymer film on the surface of the object to be treated. Can be formed.

That is, the method for forming a hydrophilic polymer coating of the present invention comprises the steps of applying an aqueous solution of the above-mentioned polymer composition onto the surface of the object to be treated, and heating the polymer composition applied onto the surface of the object to be treated. By so doing, a step of volatilizing a volatile base in the polymer composition to form the above-mentioned polymer complex to make it water-insoluble is characterized.

The hydrophilic polymer coating film of the present invention is a polymer coating film formed in this way and is selected from the group consisting of polymer (a), polymer (b) and polymer (c). It is characterized by containing a combination of at least two kinds of polymers or the polymer (c) alone as an essential component. The above-mentioned combination of at least two kinds of polymers means
Specifically, a combination of polymer (a) and polymer (b), a combination of polymer (a) and polymer (c), a combination of polymer (b) and polymer (c), and It means a combination of all three types of polymers: polymer (a), polymer (b) and polymer (c).

The first method of producing the polymer composition of the present invention
In the aspect (1), at least a part of the carboxylic acid group of the polymer (a) obtained by polymerizing 50 mol% or more of an unsaturated monomer having a carboxylic acid group, which has no ability to form a polymer complex by hydrogen bond by itself, is volatile. The step of neutralizing with a base [II] and a proton-accepting structural unit that does not have the ability to form a polymer complex by hydrogen bonding by itself, but interacts with the carboxylic acid group of the polymer (a) by hydrogen bonding force. And mixing the polymer (a), which is capable of forming a polymer complex by hydrogen bond with the polymer (a), with the neutralized polymer (a).

The second method of producing the polymer composition of the present invention
In the aspect 1, the step of neutralizing an unsaturated monomer having a carboxylic acid group with a volatile base [II] and polymerizing the neutralized unsaturated monomer in an amount of 50 mol% or more to form a polymer complex by a hydrogen bond alone. A step of preparing a polymer (a) having no function and a proton accepting property which does not have the ability to form a polymer complex by hydrogen bond by itself but interacts with the carboxylic acid group of the polymer (a) by hydrogen bonding force. And a polymer (b) having the structural unit (1) and capable of forming a polymer complex by hydrogen bonding with the polymer (a), are mixed with the polymer (a).

Third Method of Manufacturing Polymer Composition of the Present Invention
In the above aspect, the step of neutralizing the unsaturated monomer having a carboxylic acid group with a volatile base [II], and interacting with the carboxylic acid group by hydrogen bonding force with the neutralized unsaturated monomer of 50 mol% or more. Copolymerizing with a monomer having a proton-accepting structural unit to prepare a polymer (c) alone having the ability to form a polymer complex by hydrogen bonding.

The polymer complex by hydrogen bond in the present invention means that a polymer having a carboxylic acid group and a polymer having a proton-accepting structure interact with each other by hydrogen bond, and the interacting functional group is a polymer chain. The stable ensemble is formed by the entropy effect of being adjacent to each other along. Since the interaction between polymers is stronger than the interaction between each polymer molecule and the water molecule that is hydrated in the aqueous solution, the interaction between the polymer having a carboxylic acid group and the proton accepting property is When an aqueous solution of a polymer having a structure is mixed, both complexes are immediately formed to cause precipitation. Examples of such a hydrogen-bonded polymer complex include, for example, JOURNAL OF POLYMERSCIEN.
CE, Polymer Chemistry Edit
ion, VOL. 13, 1505-1514 (197)
5) and Chemical Review No. 40, 186-189 (198).
3), edited by The Chemical Society of Japan.

The unsaturated monomer having a carboxylic acid group in the polymer (a) in the present invention is not particularly limited as long as it is an unsaturated monomer having a carboxylic acid group, and examples thereof include acrylic acid and methacrylic acid. Mention may be made of monomers having carboxylic acid groups and vinyl groups such as acrylic acid, itaconic acid and maleic acid. Such unsaturated monomers may be used alone or in combination of 50 or more.
Polymerization is carried out by using more than mol% as a monomer component. When the amount of the unsaturated monomer having a carboxylic acid group is less than 50 mol%, good hydrophilicity may not be obtained, or the polymer complex may become unstable and the water solubility may decrease, which is desirable. Absent.

The polymer (a) in the present invention can be obtained by radical polymerization using 50 mol% or more of the unsaturated monomer as described above. In such polymerization, as the other copolymerization monomer other than the unsaturated monomer having a carboxylic acid group, for example, an acrylic acid ester, a methacrylic acid ester, and an unsaturated monomer used in ordinary radical polymerization such as styrene are used. be able to. The polymerization reaction can be produced by an ordinary method used for producing an aqueous polymer, such as aqueous solution polymerization using water as a medium, emulsion polymerization, and solution substitution with an organic solvent followed by solvent substitution. The molecular weight of the polymer (a) is not particularly limited, but an average molecular weight of 1,000 to 100,000 is preferable.

The polymer (b) in the present invention has a proton-accepting structural unit that interacts with the carboxylic acid group of the polymer (a) by hydrogen bonding force along the molecular chain. Then, it is not particularly limited as long as it can form a polymer complex with the polymer (a). Specifically, for example, a polyoxyethylene chain having at least 5 or more repeating units- (CH ₂ C
Examples thereof include polymers having H ₂ —O) _-n (n ≧ 5) and polymers having an average of 5 or more amide bonds in one molecule.

Specific examples of the polymer having a polyoxyethylene chain include the following. (B-1) The following general formula

[0025]

[Chemical 1]

A polyethylene glycol represented by: (B-2) Methanol, ethanol, propanol, phenol, propylene glycol, dipropylene glycol, neopentyl glycol, hexylene glycol, butanediol, hexanediol, cyclohexanedimethanol, bisphenol A, polypropylene glycol, glycerin, trimethylolethane, A compound having one or more active hydrogen functional groups in the molecule such as trimethylolpropane, pentaerythritol, ethylamine, and ethylenediamine is added with 5 mol or more of ethylene oxide per 1 mol of active hydrogen to give a hydroxyl group at the terminal. Having a polyether compound. For example, when the active hydrogen functional group-containing compound is glycerin, the following general formula

[0027]

[Chemical 2]

(L, m, n are the same or different, and all are ≧ 5). (B-3) Formic acid, acetic acid, propionic acid, butyric acid, glycolic acid, lactic acid, benzoic acid are added to some or all of the hydroxyl groups of the polyethylene glycol (b-1) and the terminal hydrogen-containing polyether compound (b-2). An ester compound obtained by reacting a monobasic acid such as. For example, in the case of polyethylene glycol, the following general formula

[0029]

[Chemical 3]

(R¹Is a monovalent organic catalyst R (CO)-
Rubonic acid group, R²Is hydrogen or R ¹be equivalent to. here
R is a monovalent organic residue, preferably alkyl or
Is aryl, more preferably alkyl having 1 to 12 carbons.
Or aryl. a compound as shown by n ≧ 5)
object. (B-4) The following general formula

[0031]

[Chemical 4]

(R ¹ is hydrogen or a methyl group,
² is hydrogen or a monovalent organic residue, preferably hydrogen, alkyl or aryl, more preferably hydrogen or alkyl or aryl having 1 to 6 carbon atoms. n
≧ 5), which can be copolymerized with or by polymerization of an unsaturated monomer having a polyoxyethylene chain represented by
Vinyl polymers obtained by copolymerization with unsaturated monomers such as styrene, acrylic acid and its ester, methacrylic acid and its ester.

(B-5) Polyethylene glycol having 5 or more repeating units is used alone or, if necessary, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, hexylene glycol, butanediol, hexanediol, Along with polyhydric alcohols such as cyclohexanedimethanol, hydrogenated bisphenol A, glycerin, trimethylolethane, trimethylolpropane and pentaerythritol, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid,
A polyester polymer obtained by reacting with a polybasic acid such as maleic acid, fumaric acid, adipic acid, succinic acid, sebacic acid, trimellitic acid and pyromellitic acid, and an anhydride thereof.

(B-6) Polyethylene glycol having 5 or more repeating units is used alone or, if necessary, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, hexylene glycol, butanediol, hexanediol, Along with polyhydric alcohols such as cyclohexanedimethalol, hydrogenated bisphenol A, glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol, tolylene diisocyanate, diphenylmethane diisocyanate, naphthylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone. Isocyanate compounds such as diisocyanate and dicyclohexylmethane diisocyanate, and their compounds Polyurethane polymer obtained by reacting a cyanurate-modified product.

In these polymers having a polyoxyethylene chain, the repeating unit of the polyoxyethylene chain has only to sufficiently obtain the entropy effect for complex formation, and is preferably 5 or more, more preferably It is 10 or more. Further, the content of the polyoxyethylene chain is preferably 50% by weight or more based on the hydrophilicity, and more preferably 70% by weight or more.

The polymer having an average of 5 or more amide bonds in one molecule is preferably one having an amide bond in the side chain of the polymer, and such compounds include the following. (B-7) The following general formula

[0037]

[Chemical 5]

(R ¹ is hydrogen or a methyl group,
² and R ³ are each independently hydrogen or a monovalent organic residue, or both ends of an organic chain forming a ring structure, preferably each independently hydrogen, alkyl,
Aryl, alkoxyalkyl or hydroxyalkyl, or both ends of an organic chain forming a ring structure consisting of carbon and hydrogen or carbon, hydrogen and oxygen, and more preferably independently hydrogen and C1-C1.
6 alkyl, aryl, alkoxyalkyl or hydroxyalkyl having 1 to 2 carbon atoms, or both ends of an organic chain forming a 5- to 8-membered ring structure composed of carbon and hydrogen or carbon, hydrogen and oxygen. ) An unsaturated amide monomer represented by and / or the following general formula

[0039]

[Chemical 6]

(R ¹ and R ² each independently represent hydrogen or a monovalent organic residue, or both ends of an organic chain forming a ring structure, and preferably each independently hydrogen or alkyl. , Aryl, or both ends of an organic chain forming a ring structure composed of carbon and hydrogen or carbon, hydrogen, and oxygen, and more preferably independently hydrogen, alkyl having 1 to 6 carbons, and aryl. Or both ends of an organic chain forming a 5- to 8-membered ring structure consisting of carbon and hydrogen or carbon, hydrogen, and oxygen). Polymerizable vinyl polymers obtained by copolymerization with unsaturated monomers such as styrene, acrylic acid and its ester, methacrylic acid and its ester.

Examples of the unsaturated amide monomer represented by the above general formula (Formula 5) are acrylamide, methacrylamide, N-methyl acrylamide, N-methyl methacrylamide, N, N dimethyl acrylamide, N, N dimethyl methacrylamide, N. Ethyl acrylamide, N ethyl methacrylamide, N, N diethyl acrylamide,
Examples thereof include N, N diethyl methacrylamide, N isopropyl acrylamide, diacetone acrylamide, N methylol acrylamide, N methylol methacrylamide, and acryloyl morpholine.

Examples of the N vinyl amide monomer represented by the above general formula (Formula 6) include N vinyl formamide, N vinyl N methyl formamide, N vinyl acetamide, N vinyl N methyl acetamide, N vinyl pyrrolidone and the like. To be Also, N vinyl carbamate compounds such as N vinyl oxazolidone and 5 methyl N vinyl oxazolidone, and N vinyl imide compounds such as N vinyl succinimide and N vinyl phthalimide may be used. (B-8) The following general formula

[0043]

[Chemical 7]

(R is hydrogen or a monovalent organic residue, preferably hydrogen, alkyl or aryl,
More preferably, it is hydrogen or alkyl or aryl having 1 to 6 carbon atoms. The polyoxazoline polymer obtained by carrying out the cationic ring-opening polymerization of 1 type (s) or 2 or more types of the oxazoline compound shown by these.

Examples of the oxazoline compound represented by the above general formula (Formula 7) include oxazoline, 2methyloxazoline, 2ethyloxazoline and the like. In the vinyl polymer (b-7), when the unsaturated amide monomer and / or the N vinylamide monomer is copolymerized with other unsaturated monomer, the unsaturated amide monomer and / or the unsaturated amide monomer and // Or N
The vinylamide monomer content is preferably 50 mol% or more, more preferably 70 mol% or more. Further, it is particularly preferable to use N-vinylpyrrolidrin from the viewpoint of stability.

When the hydrophilic structure of the polymer (b) in the present invention is not sufficient to make it water-soluble, in order to assist this, an anionic functional group such as a carboxylic acid or a sulfonic acid is added. It may be introduced into the molecule of the molecule (b) to neutralize it. These anionic functional groups have a function of the volatile base [II] for inhibiting complex formation with the polymer (a) or the polymer (c), or volatilization of the volatile base [II] during heating and drying. It is introduced in a range that does not impair the complex formation after the formation and the water solubility resistance of the formed complex. Specifically, the acid value is 10 to
A range of 100 is preferable.

The optimum molecular weight of the polymer (b) in the present invention varies depending on its structure and is not particularly limited, but the number average molecular weight is 500 to 5,000.
00 is preferable.

In the present invention, the polymer (c) alone having the ability to form a polymer complex has both the functions of the polymer (a) and the polymer (b) described above and has a carboxylic acid group. It is obtained by polymerizing 50% by mole or more of the unsaturated monomer which it has and also has a repeating unit capable of interacting with a carboxylic acid through a hydrogen bond in the molecule.
Specifically, for example, one or more kinds of monomers having a carboxylic acid group such as acrylic acid, methacrylic acid, itaconic acid and maleic acid and a vinyl group, and a polyoxy group represented by the general formula (Formula 4) Examples thereof include vinyl polymers obtained by copolymerizing an unsaturated monomer having a repeating unit capable of interacting with a carboxylic acid group through a hydrogen bond, such as an unsaturated monomer having an ethylene chain. In such polymerization, in addition to the unsaturated monomer having a repeating unit capable of interacting with a carboxylic acid group of an unsaturated monomer having a carboxylic acid group by hydrogen bond, for example, acrylic acid ester, methacrylic acid ester, and styrene. Unsaturated monomers used for ordinary radical polymerization may be copolymerized.

The polymerization reaction is an aqueous solution polymerization using water as a medium,
Alternatively, it can be produced by a usual method used for producing an aqueous polymer, such as solvent substitution after solution polymerization with an organic solvent. However, during the polymerization, thickening or gelation may occur due to the interaction between the carboxylic acid group and the repeating unit capable of interacting with it through a hydrogen bond. A monomer neutralized by reacting a base [II] is used for the polymerization, or a volatile base [II] is first charged in a polymerization reaction vessel, and then the monomer is added to the polymerization reaction and the neutralization reaction at the same time. It is preferable to proceed.

The molecular weight of the polymer (c) is not particularly limited, but the number average molecular weight is 1,000 to 10,000.
0 is preferable. In the present invention, the polymer (a),
The blending ratio of the polymer (b) and the polymer (c) is determined by the ratio of functional groups for complex formation. Proton acceptor interacting with carboxylic acid group in polymer (b) and polymer (c) by hydrogen bonding force to 1 mol of carboxylic acid group in polymer (a) and polymer (c). It is preferable that the structure is added in an amount of 0.1 to 10 mol, preferably 0.3 to 3 mol. Examples of the structure of the proton acceptor include the above oxyethylene structure and amide bond.

The volatile base [II] in the present invention is not particularly limited as long as it can inhibit the formation of the above-mentioned polymer complex by hydrogen bond and is volatile. Examples of such substances include ammonia, and organic amines having a boiling point of 150 ° C. or lower, more preferably 100 ° C. or lower, such as trimethylamine and triethylamine.
These volatile bases can be used alone or in combination of two or more. In addition, for example, a base such as tetramethylammonium hydroxide that decomposes into a low-boiling amine by heating may be used. Further, after applying the polymer composition for hydrophilic treatment of the present invention, a part of the base is lithium hydroxide, as long as it does not hinder the formation of the polymer complex when cured by heating and drying.
It may be replaced with a non-volatile base such as sodium hydroxide and potassium hydroxide.

In the present invention, the volatile base [II] undergoes a neutralization reaction with the carboxylic acid groups of the polymer (a) and the polymer (c), thereby suppressing the above-mentioned polymer complex forming reaction.

The method of adding such a volatile base [II] is not particularly limited except for the case of the polymer (c). For example, the following method may be used. It can be mixed with (b). (1) The polymer (a) and the volatile base (c) are mixed in advance so as to neutralize a part or all of the carboxylic acid groups in the polymer (a), and then the polymer (b) is added. (2) Polymerization is carried out by using a monomer obtained by reacting a carboxylic acid group of an unsaturated monomer having a carboxylic acid group with a volatile base (c) in advance to polymerize the polymer (a),
The polymer (b) is added to this. (3) After the polymer (a) and the polymer (b) are reacted to form a polymer complex precipitate, an appropriate amount of the volatile base (c) is added to make the polymer water-soluble.

In the case of the polymer (c), as described above,
In the polymerization reaction, it is preferable to perform a neutralization reaction with an unsaturated monomer having a carboxylic acid group in advance or at the same time as the polymerization reaction, from the viewpoint of stability of the polymerization reaction.

In any case, the volatile base [II] may be added in an amount necessary to inhibit the formation of the polymer complex. The addition amount of such a volatile base [II] depends on the structures of the polymer (a), the polymer (b) and the polymer (c), but is usually 5% of the total number of moles of carboxylic acid groups. It may be 10% or more. However, if the addition amount of the volatile base [II] is too small, the viscosity of the polymer composition may become too high even if the formation of the polymer complex is hindered. If the amount added is excessive, the polymer composition itself or the odor problem may occur during heat-drying and curing. Therefore, the addition amount of the volatile base [II] is more preferably 20% or more, and particularly preferably 30 to 100% of the total number of moles of carboxylic acid groups.

In the present invention, the above polymer (a),
In addition to the essential components of polymer (b), polymer (c) and volatile base [II], other components may be contained. For example, the water-based paint may contain a known cross-linking agent, and examples thereof include a water-soluble melamine resin, a urea resin, a phenol resin, an epoxy resin, and a metal cross-linking agent. By including these cross-linking agents, more excellent water solubility resistance can be imparted.
Further, by introducing a reactive functional group, any of the polymer (a), polymer (b) and polymer (c) may be a self-crosslinking polymer.

Further, in the present invention, if necessary, general-purpose optional components such as other water-soluble resins and water-dispersible resins, pigments, surfactants and defoaming agents can be contained.

The polymer composition for hydrophilic treatment of the present invention comprises
A hydrophilic and water-insoluble polymer coating can be obtained by heating after coating on the surface of the object to be treated such as a metal surface. The application of such an aqueous solution of the polymer composition can be carried out by a usual method such as dipping, brush coating, spraying or roll coating. The heating condition after coating may be any heating condition in which water and a volatile base [II] are volatilized to form a polymer complex, and usually 100 to 300 ° C x several seconds to several tens of minutes. Is.

[0059]

In the present invention, the formation of the polymer complex by hydrogen bonding is suppressed by the volatile base [II], and the water-soluble polymer composition is applied on the surface of the object to be treated, and then, together with the water content, The volatile base is volatilized to form the above-mentioned polymer complex to form a water-insoluble coating film.

The coating film of the polymer complex thus obtained is insoluble in water and is excellent in water solubility resistance, and since it is a polymer complex having a large number of hydrophilic groups, it is excellent in hydrophilicity. It is a thing.

Therefore, with the conventional organic resin type treating agent, it is possible to achieve both hydrophilicity and water dissolution resistance of the film, which were difficult to obtain, and to form a polymer film excellent in hydrophilicity and water solubility. be able to.

[0062]

The present invention will be specifically described with reference to the following examples.
Unless otherwise specified, parts and% mean parts by weight and% by weight.

[Aqueous solution of polymer (a) (volatile base [I
I] in advance] Preparation Example 1 100 parts of a 10% aqueous solution of a commercially available polyacrylic acid homopolymer (Jurimer AC-10L manufactured by Nippon Pure Chemical Industries, Ltd.) and 6.6 parts of 25% ammonia water and ions. 93.4 parts of exchanged water was added to prepare an aqueous solution of partially acrylic acid neutralized product of polyacrylic acid.

Preparation Example 2 A mixture of 32 parts of acrylic acid and 8 parts of acrylic acid 2-hydroxyethyl ester and 20 parts of a 10% ammonium persulfate aqueous solution were separately charged from 2 ports to 100 parts of ion-exchanged water at 80 ° C. under a nitrogen atmosphere. The mixture was added dropwise over a period of time, and the mixture was heated and stirred for another 3 hours for polymerization. Triethylamine 1
8.0 parts and 622.0 parts of ion-exchanged water were added to prepare an aqueous solution of a partially neutralized acrylic acid copolymer.

Preparation Example 3 Anion exchange aqueous solution 15.8 of 0.3% of anionic surfactant (Newcol 271NH manufactured by Nippon Emulsifier Co., Ltd.)
10.7 parts of methacrylic acid and methyl methacrylate 5.
0 part, n-butyl acrylate 4.3 parts and dodecyl mercaptan 0.2 part were added and stirred to prepare a monomer pre-emulsion.

This pre-emulsion and 8 parts of a 10% ammonium persulfate aqueous solution were separately dropped into 27.4 parts of ion-exchanged water at 80 ° C. in a nitrogen atmosphere for 3 hours, and heated and stirred for 1 hour to emulsify. Polymerized. To this, 8.5 parts of 25% aqueous ammonia and ion-exchanged water 320.1
Part was added to dissolve the emulsion to prepare an aqueous solution of a neutralized methacrylic acid copolymer.

[Preparation of Polymer (b) Aqueous Solution] Preparation Example 4 5 parts of commercially available high molecular weight polyethylene oxide (PEO-1 manufactured by Sumitomo Seika Chemicals Ltd.) was dissolved in 95 parts of ion-exchanged water to prepare a resin aqueous solution. Was prepared.

Preparation Example 5 Methacrylic acid polyethylene oxide ester having 10 repeating units (MA100 manufactured by Nippon Emulsifier Co., Ltd.)
40 parts and 20 parts of 10% ammonium persulfate aqueous solution are separately charged from different ports at 80 ° C. in a nitrogen atmosphere and deionized water 1
40 parts was added dropwise over 2 hours and heated and stirred for 3 hours to polymerize the aqueous solution. To this, 600 parts of ion-exchanged water was added and diluted to adjust the solid content concentration.

Preparation Example 6 Adipic acid 30.6 parts and isophthalic acid 28 parts, sodium 5-sulfoisophthalate 10.8 parts, neopentyl glycol 21.8 parts, ethylene glycol 13 parts, polyethylene glycol having an average molecular weight of 1000 0.12 parts of dibutyltin oxide was added to 124.8 parts of PEG-1000 manufactured by Sanyo Kasei Co., Ltd., and heated to 150 ° C. under a nitrogen atmosphere. 22 while removing generated water
The temperature was raised to 0 ° C. over 4 hours to allow the esterification reaction to proceed, and then the pressure was reduced to 1 mmHg over 1 hour.
The temperature was raised to 0 ° C over 3 hours, and polyoxyethylene chain 6
A polyester resin containing 0% was prepared. A resin aqueous solution was prepared by dissolving 5 parts of this resin in 95 parts of ion-exchanged water.

Preparation Example 7 A commercially available resin aqueous solution was prepared by dissolving 5 parts of commercially available polyvinylpyrrolidone (LUVISCOL K-17 manufactured by BASF Corporation) in 95 parts of ion-exchanged water.

Preparation Example 8 Azo initiator (V-produced by Wako Pure Chemical Industries, Ltd.) was added to 30 parts of dimethylacrylamide and 20 parts of hydroxyethyl acrylate.
601) 1 part was melt | dissolved, it dripped over 2 hours at 49 degreeC of isopropanol under nitrogen atmosphere at 80 degreeC, and also it heat-stirred for 3 hours, and superposed | polymerized. To this, 900 parts of ion-exchanged water was added and diluted to adjust the solid content concentration.

Preparation Example 9 21 parts of N-vinylpyrrolidone, 4 parts of N-methylolacrylamide, polyethylene oxide ester of mectalylic acid having 5 repeating units (MA5 manufactured by Nippon Emulsifier Co., Ltd.)
0) a mixture of 5 parts and dimethylethanolamine 0.5
A solution of 1 part of an azo-based initiator (ACVA manufactured by Otsuka Chemical Co., Ltd.) neutralized and water-solubilized in 20 parts of ion-exchanged water is ion-exchanged at a temperature of 80 ° C. under a nitrogen atmosphere from separate ports. 50 parts of water was added dropwise over 3 hours, and the mixture was heated with stirring for 2 hours to polymerize. To this, 500 parts of ion-exchanged water was added and diluted to adjust the solid content concentration.

[Aqueous solution of polymer (c) (volatile base [I
I] is previously contained) Preparation Example 10 22.7 parts of 25% ammonia water and ion-exchanged water 37.3
24 parts of acrylic acid was gradually added to the mixture of parts to neutralize it, to obtain an ammonium acrylate aqueous solution.
Acrylic acid polyethylene oxide ester of which the average number of repeating units is 8.4 and whose end is a methoxy group (light acrylate 130A manufactured by Kyoeisha Chemical Co., Ltd.) 1
An aqueous monomer solution was prepared by adding 6 parts.

This aqueous monomer solution and 20 parts of a 10% ammonium persulfate aqueous solution were added dropwise from separate ports to 80 parts of ion-exchanged water at 80 ° C. in a nitrogen atmosphere for 2 hours.
Polymerization was performed by further heating and stirring for 3 hours.

600 parts of ion-exchanged water was added to this to prepare an aqueous solution of neutralized acrylic acid copolymer. An aqueous solution of each polymer prepared based on the above preparation example and a water-soluble crosslinking agent of an optional component were blended at a ratio shown in Table 1 to obtain each polymer composition for hydrophilic treatment (Examples 1 to 13, Comparative Examples). 1-4)
Was prepared and tested according to the following procedure.

An aluminum plate (JIS A1100) of 50 mm × 100 mm × 0.1 mm was degreased with a surf cleaner 332N8 manufactured by Nippon Paint Co., Ltd. and chromated with phosphoric acid using Alsurf 407/47 manufactured by Nippon Paint Co., Ltd. Processed. After measuring the weight W of the treated plate that had been washed with water and dried, it was immersed in the above-mentioned polymer composition solution for hydrophilization treatment for 1 minute and heated at 180 ° C. for 10 minutes to dry and cure. After measuring the weight Wi of this test plate and measuring the water contact angle of the coating film 30 seconds after contact with water droplets using a CA-Z type fully automatic contact angle meter manufactured by Kyowa Interface Science Co., Ltd., 11 It was immersed for 10 days at room temperature in tap water overflowed at a flow rate of / min. After air-drying in the room for 1 day, the weight Wo of the test plate was measured, and the water contact angle was measured in the same manner.
The elution rate of the coating film was calculated by the following formula.

Film elution rate (%) = (Wi-Wo) / (W
Table 1 shows the blending ratio of each polymer composition for hydrophilic treatment and the evaluation results of the water contact angle and the film elution rate. The numerical value of the compounding here is the number of parts by weight of solid content.

[0078]

[Table 1]

1) Water-soluble melamine resin: Sumimar M
-50W (Sumitomo Chemical Co., Ltd.) 2) Urea resin: Cymel UFR-65 (Mitsui Toatsu Chemical Co., Ltd.) 3) Contact angle: ◎ = 20 ° or less ○ = 20-30 ° △ = 30 ~ 40
° × = 40 ° or more 4) Film elution rate: ◎ = 10% or less ○ = 10 to 25% △ = 25
-50% x = 50% or more As is clear from Table 1, Examples 1 to 13 according to the present invention
Shows a small water contact angle even after immersion in running water for a long time, and the elution rate of the coating film with respect to water is small. On the other hand, in the comparative example, it can be seen that the film having a high hydrophilicity elutes the film, and the film having a low film elution rate has a poor hydrophilicity.
Therefore, according to the present invention, both hydrophilicity and water solubility resistance can be imparted.

[0080]

INDUSTRIAL APPLICABILITY According to the present invention, a combination of at least two kinds of polymers (a), (b), and (c) or a reaction of polymer (c) alone is used. It forms a coating film of the polymer complex. Since this polymer complex is insolubilized in water, it is excellent in water solubility and also has excellent hydrophilicity because it contains a large number of hydrophilic groups in the polymer.

Therefore, according to the present invention, the hydrophilicity is excellent,
In addition, it is possible to form a polymer film for hydrophilic treatment which is excellent in water solubility resistance.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08F 220/56 MNC 226/02 MNL C09D 133/24 PFW 139/00 PGL 171/02 PLQ 201/08 PDG PDH F28F 1/32 H

Claims (13)

[Claims] 1. A polymer (a) obtained by polymerizing 50 mol% or more of an unsaturated monomer having a carboxylic acid group, which does not have the ability to form a polymer complex by hydrogen bond by itself [I], and by itself a hydrogen bond. It does not have the ability to form a polymer complex, but has a proton-accepting structural unit that interacts with the carboxylic acid group of the polymer (a) by hydrogen bonding force, and forms a polymer complex by hydrogen bond with the polymer (a). Polymer (b) capable of being polymerized with 50 mol% or more of an unsaturated monomer having a carboxylic acid group, and having a proton-accepting structural unit in the molecule that interacts with the carboxylic acid group by hydrogen bonding force. , A combination of at least two polymers selected from the group consisting of a polymer (c) which alone has the ability to form a polymer complex by hydrogen bonding. Or wherein the polymer (c) alone, in that it contains the [II] a volatile base,
A polymer composition for hydrophilic treatment. 2. In the polymer (b) and the polymer (c), the proton-accepting structural unit that interacts with a carboxylic acid group by hydrogen bonding force is an oxyethylene structure and / or an amide bond. The polymer composition for hydrophilic treatment according to item 4. 3. An oxyethylene structure and / or an amide bond in the polymer (b) and the polymer (c) to 1 mol of a carboxylic acid group in the polymer (a) and the polymer (c). Is blended in a proportion of 0.1 to 10 moles,
The polymer composition for hydrophilic treatment according to claim 2, wherein the volatile base [II] is blended in a proportion of 0.05 to 10 mol. 4. The polymer (b) and the polymer (c) are
A polymer in which the repeating unit has at least 5 or more polyoxyethylene chains, and / or an average of 5 in one molecule.
The polymer composition for hydrophilic treatment according to claim 2, which is a polymer having one or more amide bonds. 5. The polymer having an average of 5 or more amide bonds in one molecule is selected from the group consisting of N vinylamide compounds, N vinylimide compounds, (meth) acrylamide compounds, and 2-oxazoline compounds. The polymer composition for hydrophilic treatment according to claim 4, which is a polymer having a structure formed by polymerizing at least one of 6. The polymer composition for hydrophilic treatment according to claim 4, wherein the polymer having a polyoxyethylene chain whose repeating unit is at least 5 or more is a polymer having a polyoxyethylene chain of 50% by weight or more. object. 7. The volatile base [II] is ammonia or an organic amine having a boiling point of 150 ° C. or lower.
The polymer composition for hydrophilic treatment according to item 4. 8. The polymer composition for hydrophilic treatment according to claim 1, which contains an aqueous crosslinking agent [III]. 9. A method of forming a hydrophilic and water-insoluble polymer coating on the surface of a target object for hydrophilic treatment of the surface of the target object, the aqueous solution of the polymer composition according to claim 1. And a step of applying to the surface of the object to be treated, by heating the polymer composition applied to the surface of the object to be treated, the volatile base in the polymer composition is exhibited, and the polymer complex by hydrogen bonding is formed. Forming a water-insoluble substance, and forming the hydrophilic polymer film. 10. A polymer (a) obtained by polymerizing 50 mol% or more of an unsaturated monomer having a carboxylic acid group, which alone has no ability to form a polymer complex by hydrogen bond, and a polymer complex formation by hydrogen bond alone. It has no function, but has a proton-accepting structural unit in the molecule that interacts with the carboxylic acid group of the polymer (a) by hydrogen bonding force, and forms a polymer complex by hydrogen bond with the polymer (a). Polymer (b) capable of being polymerized with 50 mol% or more of an unsaturated monomer having a carboxylic acid group, and having a proton-accepting structural unit in the molecule that interacts with the carboxylic acid group by hydrogen bonding force. A combination of at least two kinds of polymers selected from the group consisting of a polymer (c) capable of forming a polymer complex by a hydrogen bond alone. Allowed, or characterized by containing the polymer (c) alone, the hydrophilic polymer coating. 11. Volatilization of at least a part of the carboxylic acid group of the polymer (a) obtained by polymerizing 50 mol% or more of an unsaturated monomer having a carboxylic acid group, which alone has no ability to form a polymer complex by hydrogen bond. And a proton-accepting structural unit that does not have the ability to form a polymer complex by hydrogen bonding by itself, but interacts with the carboxylic acid group of the polymer (a) by hydrogen bonding force. And a step of mixing a polymer (b) capable of forming a polymer complex by hydrogen bonding with the polymer (a) with the neutralized polymer (a). Manufacturing method. 12. A process of neutralizing an unsaturated monomer having a carboxylic acid group with a volatile base [II], and polymerizing the neutralized unsaturated monomer in an amount of 50 mol% or more, and by itself, a polymer complex having a hydrogen bond. A step of preparing a polymer (a) having no forming ability, and a proton acceptor which alone does not have a polymer complex forming ability by hydrogen bond but interacts with a carboxylic acid group of the polymer (a) by hydrogen bonding force Polymer composition for hydrophilic treatment, comprising a step of mixing a polymer (b) having a functional structural unit and capable of forming a polymer complex by hydrogen bond with the polymer (a) with the polymer (a). Method of manufacturing things. 13. A step of neutralizing an unsaturated monomer having a carboxylic acid group with a volatile base [II], wherein 50 mol% or more of the neutralized unsaturated monomer interacts with the carboxylic acid group by hydrogen bonding force. Copolymerizing a monomer having a proton-accepting structural unit to prepare a polymer (c) having the ability to form a polymer complex by hydrogen bonding alone, for the production of a polymer composition for hydrophilization treatment. Method.