JP2002188076A - Composition for hydrophilizing treatment and member by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for hydrophilizing treatment, capable of forming a hydrophilic coating film having both of hydrophilicity and water resistance on the surfaces of various kinds of members. SOLUTION: This composition for the hydrophilizing treatment contains (a) a vinylpyrrolidone copolymer having a carboxy group, and (b) a cross-linking agent having three or more functional groups reactable with the carboxy group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for hydrophilic treatment and a member using the same.

[0002]

2. Description of the Related Art A composition for hydrophilizing treatment is applied to the surface of a member formed of metal, film, plastic or the like to form a hydrophilic film, so that the surface of various members is hydrophilized. Used for processing methods. For example,
In heat exchangers such as air conditioners, metal fins such as aluminum alloys are used.If moisture in the air adheres to the surface of the fins as condensed water, the heat exchange efficiency is reduced or the fins are corroded. Therefore, the surface of the fin is hydrophilized by the hydrophilizing composition to prevent the condensed water from adhering.

[0003] In the method of surface treatment for hydrophilicity using the composition for hydrophilicity treatment, however, it has not been possible to sufficiently impart a property having both hydrophilicity and water resistance to the surface of the member.
This is because, in a hydrophilic coating formed from the composition for hydrophilization treatment, it is difficult to suppress a decrease in water resistance, which is a contradictory property, when the hydrophilicity is increased. When the water resistance decreases, the hydrophilicity of the hydrophilic film decreases as the durability of the hydrophilic film decreases, so that a hydrophilic film having both hydrophilicity and water resistance can be formed. The composition has been longing.

JP-A-8-291269 discloses that a copolymer of vinylpyrrolidone and acrylic acid (a) and polyethylene glycol diglycidyl ether (b) are prepared by mixing (a) / (b) = 20 / 80-70 / 3
There is disclosed a composition for hydrophilization treatment, which contains the amines at a specific weight so as to be 0. In the composition for hydrophilization treatment, a hydrophilic coating film is formed by performing a curing reaction between (a) and (b). However, in order to impart water resistance, the acrylic acid ratio in (a) is reduced. Because of this, the copolymerization ratio of vinylpyrrolidone for imparting hydrophilicity is reduced. Therefore, in order to supplement the hydrophilicity, the weight ratio of (b) in (a) and (b) is 3
0% by weight or more is essential.

[0005] However, in such a composition for hydrophilization treatment, an amine is used as a catalyst in order not to decrease the water resistance as well as the hydrophilicity. Will occur. The occurrence of yellowing as described above is desired to be improved because the hydrophilic film is formed on the surface of the member. Therefore, the hydrophilic coating formed from the composition for hydrophilization does not cause problems such as yellowing, and has both hydrophilicity and water resistance, so that it is more suitably applied to the surface of various members. There was room for contrivance.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and has been made in view of the above circumstances. Therefore, a hydrophilic film having both hydrophilicity and water resistance can be formed on the surface of various members. It is an object to provide a treatment composition.

[0007]

SUMMARY OF THE INVENTION The present invention relates to a hydrophilizing method comprising a vinylpyrrolidone copolymer having a carboxyl group (a) and a crosslinking agent having at least three functional groups which react with the carboxyl group (b). It is a treatment composition. The present invention is also a composition for hydrophilization treatment, comprising a vinylpyrrolidone copolymer (a) having a carboxyl group and a metal crosslinking agent (c). The present invention is also a member having on its surface a hydrophilic coating formed from the composition for hydrophilization treatment.

The present inventors have studied various compositions for hydrophilization treatment capable of forming a hydrophilic film having both hydrophilicity and water resistance, and found that a copolymer formed essentially of vinylpyrrolidone was used. When a functional group is introduced, a curing reaction is performed between the functional group and a functional group of the crosslinking agent, and the copolymer is chemically bonded by the crosslinking agent, the functional group is caused by a monomer unit formed from vinylpyrrolidone. First of all, it is possible to impart hydrophilicity and also to impart water resistance, by introducing a carboxyl group into the copolymer, a crosslinking agent having three or more functional groups that undergo a curing reaction with the carboxyl group, By performing the curing reaction using a metal crosslinking agent, it is not necessary to cure with an amine catalyst, and it is possible to prevent the amine from causing yellowing of the hydrophilic film. Idashi Te, and conceived that can be admirably solved the above problems. Further, by using a copolymer having a high ratio of monomer units formed from vinylpyrrolidone, hydrophilicity will be more reliably exhibited, and further, regarding the crosslinking system of the composition for hydrophilization treatment,
When using a cross-linking agent having an oxazoline group as an essential component, if the carboxyl group of the copolymer is neutralized, it will have one-pack stability or be cured at room temperature by using zirconium. Have also been found, and have reached the present invention. Hereinafter, the present invention will be described in detail.

The composition for hydrophilization treatment of the present invention contains a vinylpyrrolidone copolymer having a carboxyl group (a) and a crosslinking agent having three or more functional groups which react with the carboxyl group (b). The vinylpyrrolidone copolymer (a) is not particularly limited as long as it is formed from a monomer component containing vinylpyrrolidone as an essential component and has an average of two or more carboxyl groups per molecule. . Such a vinylpyrrolidone copolymer (a)
May be used alone or in combination of two or more. The form of copolymerization may be, for example, any of random, block, and alternating.

The method for producing the vinylpyrrolidone copolymer (a) is not particularly limited. For example, (1) a monomer component containing vinylpyrrolidone and an unsaturated monomer having a carboxyl group as essential components A method of copolymerizing
(2) A method of graft-polymerizing a monomer component containing a carboxyl group-containing unsaturated monomer as an essential component onto a polymer obtained by polymerizing a monomer component containing vinylpyrrolidone as an essential component is preferable. It is.

The unsaturated monomer having a carboxyl group is not particularly limited. Examples thereof include (meth) acrylic acid, crotonic acid, itaconic acid, itaconic anhydride, maleic acid, maleic anhydride, fumaric acid, and butenetricarboxylic acid. Acid, polyfunctional (meth) acrylic acid, and the like. When a dibasic acid is used, it may be used as a half ester. These may be used alone or in combination of two or more. Among these, it is preferable to use (meth) acrylic acid. More preferably, it is acrylic acid.

The monomer components used in the above methods (1) and (2) may contain a polymerizable monomer copolymerizable with vinylpyrrolidone or an unsaturated monomer having a carboxyl group. Good. Examples of such a polymerizable monomer include (1) methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, and hydroxy (meth) acrylate. (Meth) acrylic esters such as ethyl; (2) (meth) acrylamide, N-monomethyl (meth) acrylamide, N-monoethyl (meth) acrylamide, N,
(Meth) acrylamide derivatives such as N-dimethyl (meth) acrylamide; (3) basic unsaturated monomers such as dimethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, vinylpyridine, and vinylimidazole And (4) imino ethers such as vinyl oxazoline; (5) vinyl esters such as vinyl acetate and vinyl propionate;
(6) vinyl ethylene carbonate and its derivatives;
(7) Styrene and its derivatives; (8) Ethyl (meth) acrylate-2-sulfonate and its derivatives; (9) Vinyl sulfonic acid and its derivatives; (10) Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and butyl vinyl ether Olefins such as ethylene, propylene, octene and butadiene; (12)
N-vinylacetamide, N-methyl-N-vinylacetamide, N-vinylformamide, N-methyl-N-
Examples include N-vinylamide monomers such as vinylformamide and N-vinylpropionamide. These may be used alone or in combination of two or more.

In the monomer components forming the vinylpyrrolidone copolymer (a), the weight ratio of vinylpyrrolidone to the unsaturated monomer having a carboxyl group is as follows:
For example, it is preferable to be 50/50 to 99/1.
If the vinylpyrrolidone content is less than 50/50, the hydrophilicity of the hydrophilic coating may not be sufficient. If the unsaturated monomer having a carboxyl group is less than 99/1, the vinylpyrrolidone copolymer (a) Is too small, the crosslinking agent (b) may not be able to sufficiently crosslink. More preferably, 7
0/30 to 99/1, more preferably 75/2
5 to 99/1. When the monomer component forming the vinylpyrrolidone copolymer (a) is 100% by weight,
It is preferable that the total weight ratio of vinylpyrrolidone and unsaturated monomer having a carboxyl group is 50 to 100% by weight. More preferably, it is 70 to 100% by weight, still more preferably 90 to 100% by weight.

In the above methods (1) and (2), the polymerization method is not particularly limited, and examples thereof include an aqueous solution polymerization method, a solution polymerization method in an organic solvent, a reversed phase suspension polymerization method, an emulsion polymerization method, A precipitation polymerization method and the like can be mentioned, and the reaction conditions and the like during the polymerization are not particularly limited. The polymerization initiator used is not particularly limited, and one or more conventionally known polymerization initiators can be used, and the amount used is not particularly limited. Further, instead of using a polymerization initiator, a polymerization method using heat, light, or radiation may be used.

The molecular weight of the vinylpyrrolidone copolymer (a) is, for example, from 1,000 to 5,000.
It is preferably 000000. If it is less than 1,000, the water resistance and mechanical strength of the hydrophilic coating may not be sufficient, and if it exceeds 5,000,000, the workability in forming the hydrophilic coating may not be sufficient.
More preferably, it is 5,000 to 1,000,000, and still more preferably, it is 10,000 to 500,000.

In the present invention, the crosslinking agent (b) having three or more functional groups that react with a carboxyl group includes a compound having three or more functional groups capable of crosslinking the vinylpyrrolidone copolymer (a) and a compound having a three or more functional group. It is not particularly limited as long as it is united. One of such crosslinking agents (b) may be used alone, or two or more thereof may be used in combination.

In the cross-linking agent (b), the functional group which reacts with the carboxyl group means that when the composition for hydrophilization cures, it reacts with the carboxyl group of the vinylpyrrolidone copolymer (a) to form a vinyl group. One or more functional groups capable of cross-linking the pyrrolidone copolymer (a) and the cross-linking agent (b), such as an oxazoline group, an epoxy group, a carbodiimide group, an aziridinyl group,
Isocyanate group, methylol group, vinyl ether group,
It is preferably at least one group selected from the group consisting of a cyclocarbonate group and an alkoxysilane group. Among these, it is preferable that an oxazoline group and / or an epoxy group are essential. Examples of the cross-linking agent (b) having three or more epoxy groups include, for example, glycidyl ethers of tri- or higher-functional polyethylene glycol, trimethylolpropane polyglycidyl ether, sorbitol polyglycidyl ether, and sorbitan. Polyglycidyl ether, polyglycerol polyglycidyl ether and the like are preferred.
These are Epolite (trade name) manufactured by Kyoeisha Chemical Co.,
Denasel (trade name) manufactured by Nagase & Co., Ltd. is applicable.

The crosslinking agent (b) is, for example, a compound having three or more of the above functional groups per molecule in the case of a compound, or a compound having an average of three or more of the above functional groups per molecule in the case of a polymer. Can be used. In such a cross-linking agent (b), even when the weight ratio of the cross-linking agent (b) is increased in the weight ratio of the vinyl pyrrolidone copolymer (a) and the cross-linking agent (b), for example, The product is sufficiently cured, and water resistance can be imparted to the hydrophilic coating without an amine catalyst.

In the present invention, when a crosslinking agent having an oxazoline group as an essential component is used, the carboxyl group of the vinylpyrrolidone copolymer (a) in the composition for hydrophilization treatment is neutralized with a base. Preferably. Thereby, the composition for hydrophilization treatment has one-pack stability, and the prepared composition for hydrophilization treatment can be stored at room temperature for a long time. The base used for neutralization of the carboxyl group is not particularly limited, and includes, for example, ammonia and sodium hydroxide, and it is preferable to use ammonia.

The weight ratio of the vinylpyrrolidone copolymer (a) to the crosslinking agent (b) in the composition for hydrophilization treatment is not particularly limited, and may be appropriately set depending on the type of the crosslinking agent (b) and the like. Good, for example, 10/90 to 90/1
It is preferably set to 0. From 10/90 the crosslinking agent (b)
If the weight ratio is too high, the crosslinking agent becomes excessive or the excess crosslinking agent elutes, resulting in insufficient water resistance.
If the weight ratio of the crosslinking agent (b) is smaller than 90/10, the vinylpyrrolidone copolymer (a) cannot be sufficiently crosslinked by the crosslinking agent (b), and the water resistance of the hydrophilic film becomes insufficient. In either case, a hydrophilic film having both hydrophilicity and water resistance cannot be formed.

In the present invention, the functional group ratio between the vinylpyrrolidone copolymer (a) and the crosslinking agent (b) in the composition for hydrophilization treatment is adjusted to be equimolar, that is, the vinylpyrrolidone copolymer (a It is preferable that the number of moles of the carboxyl group contained in ()) and the number of moles of the functional group contained in the crosslinking agent (b) are equivalent. As a result, the amount of functional groups remaining unreacted in the hydrophilic coating can be sufficiently reduced, and the water resistance of the hydrophilic coating is more reliably exhibited.

The hydrophilic treatment composition containing the vinylpyrrolidone copolymer (a) having a carboxyl group and the metal crosslinking agent (c) comprises a hydrophilic coating having both hydrophilicity and water resistance. Can be formed on the surface. Such a composition for hydrophilization treatment is also one of the present invention.

In the composition for hydrophilization treatment, the vinylpyrrolidone copolymer (a) is the same as described above. The metal crosslinking agent (c) is not particularly limited as long as it is a water-soluble metal compound or polymer that dissolves in water or an aqueous solvent to generate divalent or higher valent metal ions or complex ions. In such a water-soluble metal compound or polymer, a divalent or higher valent metal ion or complex ion generated from the metal compound or polymer has a function of crosslinking the vinylpyrrolidone copolymer (a). The term “water-soluble” means that a metal compound or a polymer is dissolved in water or an aqueous solvent in an amount of 1% by weight or more at normal temperature and normal pressure.

The divalent or higher valent metal ion or complex ion is not particularly limited as long as it is a metal ion or complex ion capable of undergoing a curing reaction with a carboxyl group.
Those having 4 to 4 valences are preferred. The metal species of these ions is not particularly limited, for example, magnesium (Mg),
Alkaline earth metals such as calcium (Ca), strontium (Sr) and barium (Ba); elements of Group 4A of the periodic table such as titanium (Ti) and zirconium (Zr); iron (F
e), metals of Group VIII of the Periodic Table such as ruthenium (Ru); copper (C
Group 11 metals such as u); Periodic table 1 such as zinc (Zn)
Group 2 elements: Group 13 elements of the periodic table such as boron (B) and aluminum (Al). Of these, zinc and zirconium are preferred, and zirconium is particularly preferred.

Examples of the form of the water-soluble metal compound or polymer that generates a divalent or higher valent metal ion or complex ion include halides such as fluorides and chlorides; perhalic acids such as perchlorates and the like. Salts; hydroxides; sulfates; nitrates; phosphates; ammonium hydroxide salts; ammonium carbonate salts; carboxylate salts such as acetate salts and propionate salts;
Among them, chlorides, nitrates, acetates, and ammonium carbonates are preferable as the form of the organic acid or the inorganic acid. In these forms of water-soluble metal compounds and polymers, for example, tartaric acid, gluconic acid or the like may be used after stabilization, and when dissolved in water or an aqueous solvent, the pH is appropriately adjusted. You may use it.

In the present invention, the metal crosslinking agent (c) includes
A compound having zirconium as a metal species is preferable. Thereby, the composition for hydrophilic treatment is to be cured by the volatilization of water in the composition,
The composition for hydrophilic treatment can be cured at room temperature. As the compound having such zirconium, specifically, for example, zirconium acetate, zirconium propionate, zirconium chloride, zirconium oxychloride, zirconium hydroxychloride, zirconium nitrate, basic zirconium carbonate, zirconium hydroxide,
Zirconium carbonate ammonium, zirconium carbonate
Potassium, zirconium sulfate, ammonium zirconium fluoride, zirconium phosphate and the like can be mentioned. Among these, ammonium zirconium carbonate is preferred.

As the metal crosslinking agent (c), zirconium
Compounds and polymers having metal species other than
Typically, magnesium chloride, magnesium sulfate,
Gnesium, magnesium phosphate, magnesium acetate, etc.
Magnesium compounds; calcium chloride, calcium perchlorate
Cium, calcium sulfate, calcium nitrate, calcium phosphate
Calcium compounds such as calcium and calcium acetate;
Titanium compounds such as tan and titanium sulfate; ammonium carbonate
Zinc compounds such as zinc; boron compounds such as borate; chlorides
Aluminum, aluminum chloride hydrate, aluminum hydroxide
Minium, basic polyaluminum hydroxide compound, myo
Aluminum compounds such as Uban and the like can be mentioned. Also,
As the basic polyaluminum hydroxide compound, the main component
Is the general formula (1); [Al_Two (OH)_n Cl_(6-n) ]_m ,
General formula (2); [Al (OH)_Three ] _n AlCl_Three ,or
Is represented by the general formula (3): Al_n (OH)_m Cl_(3n-m)Represented by
For example, [Al₆ (OH)₁₅]³⁺, [Al₈ (O
H)₂₀]⁴⁺, [Al₁₃(OH)₃₄]⁵⁺, [Al_{twenty one}(O
H)₆₀]³⁺Stable polymer polynuclear condensed ions such as basic
Water-soluble polyaluminum hydroxide contained in
It is. In the above general formulas (1), (2) and (3), n and
m represents a positive number. However, in the general formula (1)
Satisfies n <6, and in general formula (3), m <
3n is satisfied. Such basic polyaluminum hydroxide
Commercially available aluminum compounds include, for example, polyaluminum chloride.
Um (PAC) (trade name, manufactured by Taki Kagaku Co., Ltd.), polyhydroxylated
Aluminum (Paho) (trade name, manufactured by Asada Chemical Co., Ltd.),
Using Puragem WT (trade name, manufactured by Riken Green)
Can be

The weight ratio of the vinylpyrrolidone copolymer (a) and the metal crosslinking agent (c) in the composition for hydrophilization treatment is not particularly limited, and is appropriately set depending on the type of the metal crosslinking agent (c) and the like. For example, 50/50 ~
It is preferably 99/1. Thereby, a hydrophilic film having both hydrophilicity and water resistance can be formed on the surface of various members. More preferably, 70
/ 30 to 98/2, more preferably 80/20
９５95/5.

In the composition for hydrophilization treatment of the present invention,
The composition contains a vinylpyrrolidone copolymer (a), a crosslinking agent (b) and a metal crosslinking agent (c).
Further, if necessary, one or more compounds other than these may be contained. In this case, when the composition for hydrophilization treatment is 100% by weight, the total weight ratio of the vinylpyrrolidone copolymer (a) and the crosslinking agent (b) or the metal crosslinking agent (c) is 50 to 100% by weight. Preferably. The compound that can be compounded in the composition for hydrophilization treatment of the present invention is not particularly limited. For example, in addition to a lubricant such as waxes, polystyrene sulfonic acid (salt), polyethylene glycol, etc., silica fine particles, silane Ring agents, antibacterial agents and the like can be mentioned. Since the composition is sufficiently cured by the vinylpyrrolidone copolymer (a) and the crosslinking agent (b) or the metal crosslinking agent (c), the composition for hydrophilization treatment of the present invention contains amines as a catalyst. You don't have to. Therefore, the composition for hydrophilization treatment of the present invention is preferably in a form not containing amines, but amines can be used when there is no yellowing problem. However, this makes it possible to sufficiently suppress the yellowing of the hydrophilic film.

The use form of the composition for hydrophilization treatment of the present invention is preferably, for example, a treatment agent obtained by dissolving or dispersing the compound in water or an aqueous solvent. An aqueous solvent is
It refers to one or more mixed solvents of a solvent that can be mixed with water, and a mixed solvent obtained by mixing such a solvent with water as a main component. Further, a surfactant may be mixed with water or an aqueous solvent. Further, since the vinylpyrrolidone copolymer (a) may not be dissolved in an acidic state, it is preferable that the vinylpyrrolidone copolymer (a) is neutralized with a base and uniformly dissolved. The amount of solids in the treating agent is generally 50% by weight or less when the treating agent is 100% by weight, and it is preferable to appropriately change the amount depending on the coating method and the thickness.

In a member having on its surface a hydrophilic film formed from the composition for hydrophilization treatment of the present invention, a hydrophilic film having both hydrophilicity and water resistance is formed on the surface. Can be used in various applications. For example, a member having functions of preventing adhesion of condensed water and having antistatic performance by having hydrophilicity can be provided. Such a member is also one of the present invention. The shape of such a member is not particularly limited, and examples thereof include a thin plate, a film, a fiber, and a hollow fiber. The material of the member is not particularly limited, and examples thereof include metals such as aluminum and aluminum alloy; glass; and plastics such as acrylic resin, ABS resin, AS resin, polystyrene resin, and polycarbonate resin. Further, the surface of the member may be subjected to a treatment in advance for improving the adhesion with the composition for hydrophilization treatment. Examples of the treatment that can be performed on the surface of such a member include treatment with phosphoric acid chromate, chromate chromate, zircon, and the like; organic matter treatment; corona discharge treatment; low-temperature plasma treatment; .

As a method of forming a hydrophilic film from the composition for hydrophilization treatment on the surface of the member, any method such as coating and impregnation may be used. Specifically, it is preferable to apply the composition for hydrophilization treatment in the form of a treatment agent uniformly on the surface of the member, or to impregnate the member with the treatment agent and dry and cure. As a method of applying the treatment agent, for example, it can be industrially performed using a coating machine such as a roll coater. The conditions for drying and curing are not particularly limited, and may be appropriately selected depending on the crosslinking agent. For example, when the crosslinking agent (b) is used, the curing temperature is set to 120 to 300 ° C., and the curing time is set. 1
Preferably, it is 5 to 90 seconds. The same applies to the case where the metal cross-linking agent (c) is used. However, if a compound or a polymer having zirconium is used as the metal cross-linking agent (c), the water in the hydrophilizing composition is volatilized. Therefore, it can be cured at room temperature. Further, the thickness of the hydrophilic film may be appropriately set according to the use of the member, etc., for example, the thickness after drying and curing is preferably 1 to 100 μm.

The application of the above-mentioned member is not particularly limited as long as the surface is required to be hydrophilic, and can be suitably used for a heat exchanger such as an air conditioner. In this case, for example, after various processes such as a punching process and a bending process are performed to form a shape such as a fin, the fin is attached to a copper tube or the like.

[0034]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Examples 1 to 14 and Comparative Examples 1 to 4 Hydrophilic treatment compositions were prepared by using the vinylpyrrolidone copolymer and the crosslinking agent in the compositions shown in Tables 1, 2 and 3. . Using the composition for hydrophilization treatment, the following water resistance test and hydrophilicity test were performed.

[0036]Water resistance test (rubbing test)  Apply the composition for hydrophilic treatment to a glass plate with an applicator.
076 mm in thickness and (1) 150 ° C.
Drying and curing for 2 hours, (2) drying and curing for 1 hour at 120 ° C,
Has (3) a hydrophilic film that is dried and cured at room temperature for 1 day
A glass plate was produced. Gala with hydrophilic coating obtained
Water resistance test (rubbing test) using
0 times / 30 times). The results are shown in Tables 1, 2 and 3.
Was. Evaluation criteria ○: No change △: Peeled slightly ×: Peeled

[0037]Hydrophilicity test (contact angle measurement)  Apply the composition for hydrophilic treatment to a glass plate with an applicator.
076 mm in thickness and (1) 150 ° C.
Drying and curing for 2 hours, (2) drying and curing for 1 hour at 120 ° C,
(3) After drying and curing at room temperature for one day,
3 ° C) to produce a glass plate with a hydrophilic coating
Was. Using the obtained glass plate having a hydrophilic coating,
The contact angle of the on-exchange water was measured. 1 minute after the drop of water
The measured values are shown in Tables 1, 2 and 3.

[0038]

[Table 1]

The synthesis examples of the vinylpyrrolidone copolymers in Tables 1, 2 and 3 are described below. <Synthesis Example 1 of PVA-g-AA (80/20 wt%) Copolymer> An aqueous solution of polyvinylpyrrolidone K-30 (trade name, Wako Pure Chemical Industries Reagent) (weight average by gel permeation chromatography) was placed in a 500 ml separa flask. 182.
57 g (resin content 55.50 g) were charged, and 45.66 g of an aqueous acrylic acid solution (13.88 g of acrylic acid content) and 50 mol% of carboxyl groups neutralized with ammonia, and 3.05 g of aqueous ammonium persulfate solution (0.55 g of ammonium persulfate content) ) Was added dropwise at 85 ° C for 1.5 hours, reacted with stirring, and further reacted with an aqueous solution of V-50 (2,2'-azobis (2-methylpropionamidine) dihydrochloride, Wako Pure Chemical Industries reagent). Then, 00 g (0.34 g of V-50 minutes) was added and the mixture was aged for 4 hours. After the reaction,
A part of the reaction solution was collected, and the conversion of acrylic acid was analyzed by liquid chromatography to find that it was 97.7%. This confirmed that polyvinylpyrrolidone reacted almost quantitatively with the added acrylic acid. When the molecular weight of this solution was measured by gel permeation chromatography, the weight average molecular weight was 12.
It was 30,000.

<PVA-g-AA (85/15 wt%)
Synthesis Example 2 of Copolymer> Amount of Acrylic Acid Aqueous Solution with 50 mol% of Carboxyl Groups Neutralized with Ammonia 32.2
The synthesis was performed in the same manner as in Synthesis Example 1 except that the amount was changed to 0 g (acrylic acid content: 9.79 g). After the completion of the reaction, a part of the reaction solution was collected, and the conversion of acrylic acid was analyzed by liquid chromatography to find that it was 97.7%. This confirmed that polyvinylpyrrolidone reacted almost quantitatively with the added acrylic acid. The molecular weight of this solution was measured by gel permeation chromatography, and the weight-average molecular weight was 114,000.

<PVA-g-AA (90/10 wt%)
Synthesis Example 3 of Copolymer> Amount of aqueous solution of acrylic acid having 50 mol% of carboxyl groups neutralized with ammonia was adjusted to 20.2
The synthesis was carried out in the same manner as in Synthesis Example 1 except that the amount was changed to 6 g (acrylic acid content: 6.16 g). After the completion of the reaction, a part of the reaction solution was collected, and the conversion of acrylic acid was analyzed by liquid chromatography to find that it was 95.3%. This confirmed that polyvinylpyrrolidone reacted almost quantitatively with the added acrylic acid. The molecular weight of this solution was measured by gel permeation chromatography to find that the weight average molecular weight was 105,000.

Table 1 is described below. In the vinylpyrrolidone copolymer, PVP-g-AA (80 /
20 wt%) is a graft copolymer in which acrylic acid is grafted to an N-vinylpyrrolidone polymer (weight ratio of N-vinylpyrrolidone / acrylic acid = 80/20), and PVP-g-AA (90 / 10 wt%) means N
A graft copolymer (weight ratio of N-vinylpyrrolidone / acrylic acid = 90/10) obtained by grafting acrylic acid to a vinylpyrrolidone polymer. In the crosslinking agent, Epocross WS-500 (trade name, manufactured by Nippon Shokubai Co., Ltd.)
Is an oxazoline-based polymer crosslinking agent, and Baycoat 20 (trade name, manufactured by Nippon Light Metal Co., Ltd.) is ammonium zirconium carbonate.

[0043]

[Table 2]

Table 2 is described below. In the vinylpyrrolidone copolymer, PVP-g-AA (80 /
The term “20 wt%” means a graft copolymer in which acrylic acid is grafted to an N-vinyl pyrrolidone polymer (weight ratio of N-vinyl pyrrolidone / acrylic acid = 80/20). In the crosslinking agent, Denacol EX-313 (trade name, manufactured by Nagase & Co., Ltd.) is a glycidyl ether of bifunctional and trifunctional polyethylene glycol, and Denacol EX-614B (trade name, manufactured by Nagase & Co., Ltd.) It is a glycidyl ether of tetrafunctional polyethylene glycol, and is Denacol EX-421 (trade name, manufactured by Nagase & Co., Ltd.)
Is a glycidyl ether of trifunctional polyethylene glycol, and Denacol EX-512 (trade name, manufactured by Nagase & Co., Ltd.) is a glycidyl ether of tetrafunctional and pentafunctional polyethylene glycol, and is Denacol EX-
521 (trade name, manufactured by Nagase & Co., Ltd.) is a glycidyl ether of tetrafunctional and pentafunctional polyethylene glycol.

[0045]

[Table 3]

Table 3 is described below. In the vinylpyrrolidone copolymer, PVP-g-AA (85 /
15 wt%) is a graft copolymer (N-vinylpyrrolidone / acrylic acid weight ratio = 85/15) obtained by grafting acrylic acid to an N-vinylpyrrolidone polymer, and is PVP-g-AA (90 / 10 wt%) means N
A graft copolymer of acrylic acid and a vinylpyrrolidone polymer (weight ratio of N-vinylpyrrolidone / acrylic acid = 90/10), and a VP / AA random copolymer (75/25 wt%) , A random copolymer of N-vinylpyrrolidone and acrylic acid (weight ratio of N-vinylpyrrolidone / acrylic acid = 75/25). In the cross-linking agent, Denacol EX-512 (trade name, manufactured by Nagase & Co., Ltd.) is a glycidyl ether of tetrafunctional and pentafunctional polyethylene glycol, and Denacol EX-521 (trade name, manufactured by Nagase & Co., Ltd.) It is a glycidyl ether of tetrafunctional and pentafunctional polyethylene glycol.

[0047]

Since the composition for hydrophilization treatment of the present invention is constituted as described above, a hydrophilic film which has both hydrophilicity and water resistance and is suppressed from yellowing, It can be formed on the surface of various members such as metal, film and plastic.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 139/06 C09D 139/06 201/00 201/00 (72) Inventor Hideyuki Nishibayashi Nishi-Motobi, Suita-shi, Osaka 5-8 Machi Nippon Shokubai Co., Ltd. F-term (reference) 4F006 AA15 AA22 AA36 AB12 AB55 BA10 4J002 BJ001 BN201 CD012 DD036 DD046 DE046 DE196 DE206 DF036 DG046 DH046 EC006 ED026 EG016 EL106 ER006 EU016 EU216 EX036 FD142 FD146 GH04 MA04 NA06 PB05 PC02 PC08

Claims (4)

[Claims] 1. A composition for hydrophilization, comprising: a vinylpyrrolidone copolymer having a carboxyl group (a); and a crosslinking agent (b) having three or more functional groups that react with the carboxyl group. object. 2. The functional group that reacts with the carboxyl group includes an oxazoline group, an epoxy group, a carbodiimide group,
The composition for hydrophilization treatment according to claim 1, wherein the composition is at least one group selected from the group consisting of an aziridinyl group, an isocyanate group, a methylol group, a vinyl ether group, a cyclocarbonate group, and an alkoxysilane group. 3. A composition for hydrophilization comprising a vinylpyrrolidone copolymer having a carboxyl group (a) and a metal crosslinking agent (c). 4. A member having a hydrophilic film formed from the composition for hydrophilization treatment according to claim 1, 2 or 3 on the surface.