JP2000281867A - Water-dispersed liquid composition, coating agent and coating method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-dispersed liquid composition capable of forming a coating film having hydrophilicity and water-resistance on various substrates such as metals and plastics. SOLUTION: The objective water-dispersed liquid composition contains (A) a gel of cationic fine particles composed of a copolymer having recurring units originated from (a) a nonionic unsaturated monomer, recurring units originated from (b) an unsaturated monomer having t-amino group and recurring units originated from a monomer obtained by quaternarizing the t-amino group of the unsaturated monomer (b) having t-amino group and (B) a polyfunctional epoxy compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an aqueous dispersion composition, a coating agent and a coating method. The aqueous dispersion composition of the present invention, when cured, becomes a coating film having hydrophilicity while being water-resistant, and thus is useful as a coating agent or the like on the surface of a substrate having poor hydrophilicity such as metal and plastic. it can. In addition, the aqueous dispersion composition of the present invention can be used for antistatic agents, ion exchange resins, paints, and antibacterial agents.

[0002]

2. Description of the Related Art Generally, the surface of a base material such as a plastic molded product or a metal such as aluminum is poor in hydrophilicity. for that reason,
When such a substrate is used for an application requiring hydrophilicity, the surface of the substrate is hydrophilized. For example, a surface of an OHP film or the like used in an ink jet type color printer is coated with a hydrophilic film as an aqueous ink receiving layer.

[0003] As a coating for forming the receiving layer of the aqueous ink, for example, a water-soluble polymer such as polyvinyl alcohol, polyvinyl pyrrolidone and CMC containing a surfactant is coated. However, the water-soluble polymer that forms the receptor layer has a problem of low water resistance, such as swelling and dissolving with aqueous ink and becoming tacky.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a material capable of forming a hydrophilic and water-resistant coating film on various substrates such as metal and plastic. .

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a specific repeating unit having a tertiary amino group and a quaternary ammonium base as shown below. When the aqueous dispersion composition containing the cationic fine particle gel (A) and the polyfunctional epoxy compound (B) is used, the quaternary ammonium group of the cationic fine particle gel (A) makes the base material hydrophilic. And a tertiary amino group of the cationic fine particle gel (A) is cured by an epoxy group of the polyfunctional epoxy compound (B), and the cationic fine particle gel (A) The present inventors have found that a crosslinked structure is formed on the substrate and a coating film having water resistance can be obtained, and the present invention has been completed.

That is, the present invention relates to a repeating unit based on a nonionic unsaturated monomer (a), a repeating unit based on an unsaturated monomer (b) having a tertiary amino group, and a tertiary amino group. A cationic fine particle gel (A) comprising a copolymer having a repeating unit based on a quaternary amino group of an unsaturated monomer (b) having a quaternary amino group and a polyfunctional epoxy compound (B) An aqueous dispersion composition comprising: a coating agent using the aqueous dispersion composition; a coating film formed on the substrate surface by applying the coating agent to the substrate surface and then curing by heating and drying A method of coating a substrate.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The cationic fine particle gel (A) used in the present invention refers to a repeating unit based on a nonionic unsaturated monomer (a), an unsaturated monomer having a tertiary amino group ( a repeating unit according to b), and a third
A copolymer containing a repeating unit based on a quaternary amino group (quaternary ammonium base) of an unsaturated monomer (b) having a quaternary amino group, wherein the copolymer is A gel which is internally crosslinked to form a fine particle gel can be used without any particular limitation. There is no limitation on the internal crosslinked structure of the copolymer.

[0008] The average particle size of the fine particle gel is usually 300 n in a swollen state in water by a light scattering method.
m, preferably 150 nm or less, more preferably 100 nm or less.

The nonionic unsaturated monomer (a) constituting the cationic fine particle gel (A) is not particularly restricted but includes, for example, alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, polyethylene glycol (meth) (Meth) acrylates such as acrylate, methoxypolyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, and glycidyl (meth) acrylate; styrenes such as styrene, α-methylstyrene, and vinyltoluene; and other vinyl acetate Various known compounds such as vinyl esters can be used. Any of these can be used alone or as a mixture of two or more. The nonionic unsaturated monomer (a) is selected from styrenes and (meth) acrylates in consideration of copolymerizability with the unsaturated monomer (b) having a tertiary amino group. At least one of them is particularly preferred.

The proportion of the repeating unit based on the nonionic unsaturated monomer (a) in the copolymer constituting the cationic fine particle gel (A) is preferably about 75 to 94.5 mol%. When the proportion of the repeating unit based on the nonionic unsaturated monomer (a) is reduced, the film-forming property as a coating agent may be adversely affected, and considering these, the nonionic unsaturated monomer (a ) Is more preferably at least 80 mol%. Further, when the proportion of the repeating unit based on the nonionic unsaturated monomer (a) is increased, the proportion of other repeating units related to the quaternary ammonium base and the like is relatively decreased, and the hydrophilicity of the obtained coating film is reduced. Since it tends to decrease, the proportion of the repeating unit based on the nonionic unsaturated monomer (a) is preferably at most 90 mol%.

The repeating unit based on the unsaturated monomer (b) having a tertiary amino group includes the following general formula (1):

[0012]

Embedded image

(Wherein R ¹ is a hydrogen atom or a methyl group,
R ² and R ³ are an alkyl group having 1 to 4 carbon atoms, and A is —O
-Or -NH- or E represents an alkyl group having 2 to 4 carbon atoms or a hydroxy-substituted alkyl group).

The unsaturated monomer having a tertiary amino group (b) constituting the repeating unit includes, for example,
N, N-dimethylaminoethyl (meth) acrylate,
N, N-diethylaminoethyl (meth) acrylate,
N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide and the like can be mentioned. The unsaturated monomer (b) having a tertiary amino group may be a neutralized salt with an inorganic acid such as hydrochloric acid or sulfuric acid, or an organic acid such as acetic acid or (meth) acrylic acid. These can be used alone or in combination of two or more.

The proportion of the repeating unit based on the tertiary amino group-containing unsaturated monomer (b) in the copolymer constituting the cationic fine particle gel (A) is 0.5 to 5 mol%.
It is preferred to be on the order of magnitude. When the proportion of the repeating unit based on the unsaturated monomer (b) having a tertiary amino group is reduced, the crosslinked structure between the cationic fine particle gels is not sufficiently formed, and the water resistance tends to be deteriorated. The proportion of the repeating unit based on the unsaturated monomer (b) having a tertiary amino group is more preferably at least 1.5 mol%.
When the proportion of the repeating unit based on the unsaturated monomer (b) having a tertiary amino group is increased, the crosslinking reaction proceeds excessively in the aqueous dispersion composition, and the stability of the aqueous dispersion composition is impaired. Therefore, the ratio of the repeating unit based on the unsaturated monomer (b) having a tertiary amino group is 2 mol%.
It is more preferable to set the following.

The repeating unit based on the quaternary amino group (quaternary ammonium base) of the unsaturated monomer (b) having a tertiary amino group includes, for example, Equation (2):

[0017]

Embedded image

(Wherein, R ¹ , R ² , R ³ , A and E are the same as above, Y is a hydroxy-substituted aliphatic hydrocarbon residue having one allyl group or (meth) acryloyl group, vinyl aromatic) A hydrocarbon residue or an alkyl group having 1 to 9 carbon atoms or a benzyl group which may have an alkyl group having 1 to 9 carbon atoms, wherein X is a halogen atom, R ⁴ SO ₃ , R ⁴
A repeating unit represented by OSO ₃ (where R ⁴ represents an alkyl group having 1 to 20 carbon atoms or a phenyl group which may have an alkyl group having 1 to 20 carbon atoms) or CH ₃ COO; Can be illustrated.

The repeating unit based on the quaternary ammonium base is obtained by quaternizing the tertiary amino group of the unsaturated monomer (b) having a tertiary amino group with a quaternizing agent.

Various quaternizing agents can be used without particular limitation. For example, methyl chloride, benzyl chloride, dimethyl sulfate, diethyl sulfate, epichlorohydrin, alkyl glycidyl ether, phenyl glycidyl ether, sultone, substituted sulfonate, lactone, glycidyl (meth) acrylate, allyl glycidyl ether, p-chloromethyl styrene and the like can be mentioned. These may be used alone or in combination of two or more.

The proportion of the repeating unit based on the quaternary ammonium base in the copolymer constituting the cationic fine particle gel (A) is preferably about 5 to 20 mol%. When the proportion of the repeating unit based on the quaternary ammonium base is small, it is not preferable in terms of the hydrophilicity of the coating film obtained according to the present invention. Therefore, the proportion of the repeating unit based on the quaternary ammonium base is 10 mol% or more. Is preferred. When the proportion of the repeating unit based on the quaternary ammonium base increases, the stability of the aqueous dispersion of the cationic fine particle gel (A) tends to be impaired. 1
It is more preferable that the content be 2 mol% or less.

As the cationic fine particle gel (A) of the present invention, those containing the above repeating unit can be used without any particular limitation.
For example, it can be produced by the method described in International Patent Application WO 97/031045.

Specifically, a tertiary amino group in a copolymer obtained by copolymerizing a nonionic unsaturated monomer (a) and an unsaturated monomer having a tertiary amino group (b) is A quaternizing agent containing a quaternizing agent having a double bond (I)
By subjecting the unsaturated monomer (c) to microemulsion polymerization in the presence of a graded cationic copolymer,
The cationic fine particle gel (A) of the present invention is obtained.

The cationic polymer has a double bond introduced into the molecule thereof by the quaternizing agent (I) having a double bond, and is used for microemulsion polymerization of the unsaturated monomer (c). In addition, it functions not only as a polymerization emulsifier for the unsaturated monomer (c) but also as a crosslinking agent.

In preparing the cationic fine particle gel (A) by the above method, the cationic fine particle gel (A) contains the repeating unit and the repeating unit falls within the predetermined range. The amount of the unsaturated monomer or quaternizing agent to be used is appropriately adjusted and used. The cationic polymer may have an anionic structural unit composed of an anionic unsaturated monomer such as (meth) acrylic acid, as long as the effects of the present invention are not impaired.

The method for producing the copolymer is not particularly limited. For example, a solution polymerization method using water, isopropyl alcohol, or the like can be employed. The unsaturated monomers (a) and (b) may be supplied to the polymerization reaction system by any method such as batch addition, divisional addition, and continuous dropping. At the time of polymerization, usually, a polymerization initiator, the unsaturated monomer and, if necessary, a chain transfer agent are supplied under a stream of an inert gas such as nitrogen gas while stirring, and 60 to 9
The copolymerization may be performed at about 0 ° C. for about 1 to 8 hours. In the aqueous solution polymerization method, the polymerization initiator is not particularly limited as long as it is a polymerization initiator used in a general aqueous solution polymerization method. For example, persulfates such as potassium persulfate and ammonium persulfate can be used. Is, for example, 2,2'-azobis (2-aminopropane) dihydrochloride,
2,2'-azobis [2-methylpropionamidine]
It is preferable to use a water-soluble azo polymerization initiator such as dihydrochloride and 2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydrochloride. . On the other hand, in a solution polymerization method using isopropyl alcohol or the like, it is preferable to use an oil-soluble polymerization initiator such as a peroxide such as azoisobutyronitrile and benzoyl peroxide. The amount of the polymerization initiator used is preferably about 0.03 to 5 parts by weight based on 100 parts by weight of the total amount of the unsaturated monomers (a) and (b) in any of the above polymerization methods. .

After completion of the polymerization reaction, a copolymer in a dispersed or solubilized state is obtained by an aqueous solution polymerization method. on the other hand,
In the solution polymerization method using isopropyl alcohol or the like,
After the polymerization is completed, neutralization with the organic acid or inorganic acid or partial quaternization reaction with a quaternizing agent having no double bond may be performed to disperse or solubilize the polymer in water. If necessary, the solvent may be distilled off by steam distillation.

Next, the tertiary amino group in the copolymer dispersed or solubilized in water is quaternized with a quaternizing agent containing a quaternizing agent (I) containing a double bond. To obtain a cationic polymer. The quaternization reaction for introducing a polymerizable double bond is preferably performed in an atmosphere of oxygen gas or air, and a polymerization inhibitor may be added as necessary. The quaternization rate of the tertiary amino group in the copolymer is not particularly limited, but usually, a part of the tertiary amino group in the copolymer is quaternized. The tertiary amino group quaternization ratio in the copolymer is preferably about 85 to 100%.

Examples of the quaternizing agent (I) having a double bond include glycidyl (meth) acrylate, allyl glycidyl ether, p-chloromethylstyrene and the like among the quaternizing agents exemplified above. In the quaternization, a quaternizing agent having no double bond may be used in addition to the quaternizing agent (I) having a double bond. Quaternization with a quaternizing agent having no double bond does not introduce a polymerizable double bond into the molecule,
A quaternary ammonium group is introduced. Usually, the proportion of the quaternizing agent (I) having a double bond in the quaternizing agent is preferably about 7 to 43%. The quaternization with a quaternizing agent having no double bond is performed by converting the unsaturated monomer having a tertiary amino group (b) into a quaternary ammonium base-containing unsaturated monomer in advance. May be directly polymerized.

Although the molecular weight of the cationic polymer is not particularly limited, it is desirable that the weight average molecular weight is about 1,000 to 100,000, preferably about 10,000 to 50,000.

The unsaturated monomer (c) to be subjected to microemulsion polymerization in the presence of the cationic polymer is not particularly limited. For example, the above-mentioned nonionic unsaturated monomer (a), tertiary amino acid At least one kind of the unsaturated monomer (b) having a group can be used, but from the viewpoint of being easily solubilized in the cationic polymer, the unsaturated monomer (c) is preferably a nonionic monomer. The unsaturated monomer (a) is preferred, and at least one selected from styrenes and (meth) acrylates is particularly preferred. Further, when the amount of the water-soluble unsaturated monomer such as the unsaturated monomer (b) having a tertiary amino group increases, the unsaturated monomer (c) becomes a water-soluble unsaturated monomer. The monomer (b) is not solubilized in the cationic polymer but is solubilized in water, so that the polymerization of the unsaturated monomer (c) in water is likely to occur. Since the aqueous dispersion of the fine particle gel (A) tends to increase in viscosity, gelation, and aggregation of particles, the unsaturated monomer (c) may be a nonionic unsaturated monomer (a) in an amount of 100 to 100%. It is preferable to contain 70 mol%.

In the microemulsion polymerization of the unsaturated monomer (c), a crosslinking agent may be used as the unsaturated monomer (c), if necessary. Examples of the crosslinking agent include di (meth) acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate, methylenebis (meth) acrylamide, and ethylenebis (meth) acrylamide. Bis (meth) acrylamide such as hexamethylenebis (meth) acrylamide, divinyl esters such as divinyl adipate and divinyl sebacate, allyl (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, N-methylol ( Bifunctional monomers such as (meth) acrylamide, diallylamine, diallyldimethylammonium, diallylphthalate, diallylchlorendate, divinylbenzene; 1,3,5-tri Meth) acryloyl hexahydro -s- triazine, triallyl isocyanurate, triallyl amine, triallyl trimellitate, N, N-
Trifunctional monomers such as diallyl (meth) acrylamide; tetramethylolethanetetra (meth) acrylate, tetraallyl pyromellitate, N, N, N ', N'
And tetrafunctional monomers such as tetraallyl-1,4-diaminobutane, tetraallylamine salt, and tetraallyloxyethane. These can be used alone or in combination of two or more. The amount of the cross-linking agent is not particularly limited, but is preferably adjusted so that the amount of the cross-linking agent is usually about 0 to 3 mol% of the total amount of the unsaturated monomer (c).

The ratio of the cationic polymer to the unsaturated monomer (c) is determined by the reason that the particle size of the resulting cationic fine particle gel (A) becomes large, or the stability during polymerization decreases, and In order to eliminate the possibility of the occurrence of the polymer, the cationic polymer (in terms of solid content) is converted to the unsaturated monomer (c) 1
It is preferably used in an amount of 80 parts by weight or more, and more preferably 90 parts by weight or more based on 00 parts by weight. Further, in order to eliminate the possibility of becoming sol-like or gelling during the polymerization, the cationic polymer (in terms of solid content) is added in an amount of 300 parts by weight based on 100 parts by weight of the unsaturated monomer (c). Parts or less, preferably 250 parts by weight or less.

In the case where the unsaturated monomer (c) is subjected to microemulsion polymerization in the presence of the cationic polymer, various polymerization temperatures, polymerization times, polymerization initiators, chain transfer agents, polymerization media and the like may be used. The conditions are not particularly limited, and may be determined appropriately based on the conditions in ordinary emulsion polymerization. For example, specifically, many of the conditions may be the same as the production conditions for the cationic polymer. In the case of microemulsion polymerization, low molecular surfactants, casein, lecithin, polyvinyl alcohol, acrylamide copolymers and the like can be used as long as the performance of the obtained cationic fine particle gel (A) is not deteriorated. A water-soluble polymer compound can be used.

The cationic fine particle gel (A) obtained as described above usually has a solid content of 10 to 30% by weight,
It is an aqueous dispersion having a pH of 4 to 6 and a viscosity at 25 ° C of 500 cP or less.

As the polyfunctional epoxy compound (B) used in the present invention, a compound having at least two epoxy groups can be used without any particular limitation, but a water-soluble compound is preferably used. For example, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl Bifunctional epoxy compounds such as ether, 1,6 hexanediol diglycidyl ether, terephthalic acid diglycidyl ester, phthalic acid diglycidyl ester, spiroglycol diglycidyl ether, trifunctional epoxy compounds such as glycerin triglycidyl ether, pentaerythritol tetraglycerin 4-functional epoxy compound such as triglycidyl ether , Glycerol polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyfunctional epoxy compounds such as trimethylolpropane polyglycidyl ether, and the like.

The ratio of the polyfunctional epoxy compound (B) used in the present invention is 100 parts by weight of the tertiary amino groups contained in the cationic fine particle gel (A) and the epoxy of the polyfunctional epoxy compound (B) is used. Group is about 50-100 equivalents,
Preferably, it is used in an amount of 80 to 100 equivalents. When the proportion of the epoxy group contained in the polyfunctional epoxy compound (B) is small, a crosslinked structure between the cationic fine particle gels (A) is not sufficiently formed, and water resistance tends to be not obtained. It is more preferable to use the compound (B) such that the epoxy group of the compound (B) becomes 80 equivalents. When the proportion of the epoxy group contained in the polyfunctional epoxy compound (B) increases, unreacted epoxy groups remain, which may cause various adverse effects when using the coating agent. It is preferable that the epoxy group of ()) is not more than 100 equivalents.

The aqueous dispersion composition of the present invention containing the cationic fine particle gel (A) and the polyfunctional epoxy compound (B) is characterized in that the polyfunctional epoxy compound (B) is added to the aqueous dispersion of the cationic fine particle gel (A). It can be easily prepared by dissolving and mixing. Incidentally, the aqueous dispersion composition of the present invention, within a range that does not impair the effects of the present invention, a viscosity modifier, a leveling agent, a defoaming agent, a coloring agent, a stabilizer, a solvent for adjusting the solubility, and the like.
Various organic and inorganic additives can be added as needed.

The aqueous dispersion composition of the present invention is used, for example, as a coating agent and the like,
A coating film composed of an organic-inorganic hybrid is formed on the surface of the substrate by applying it to a substrate such as a metal and curing by heating and drying. When coating,
A primer can be coated in advance in order to increase the adhesion to the substrate. Examples of the primer include an N-methylpyrrolidone solution of a phenoxy resin (trade name: Fenote TP-50S, manufactured by Toto Kasei Co., Ltd.), an aqueous dispersion type acrylic reactive microgel, and the like.

As a method for applying the aqueous dispersion composition to a substrate, known techniques such as brushing, spraying, dipping, roll coating, and flow coating can be applied. Curing can be carried out by drying at room temperature, but usually 100 to 12
It is preferable to carry out the reaction at about 0 ° C. for about 1 minute to 15 minutes.

[0041]

According to the coating agent containing the aqueous dispersion composition of the present invention, a coating film having hydrophilicity and water resistance can be obtained. That is, the obtained coating film has good hydrophilicity and wets well with water, and when immersed in water and taken out and leveled, a water film is formed on the entire surface, and polka dots are not generated. Also, because of good water resistance,
Normally, no swelling, peeling or dissolution is observed even when immersed in water for 30 minutes or more. Further, the obtained coating film has good adhesion to the base material and has good flexibility as compared with inorganic materials. Further, transparency is good.

As described above, according to the aqueous dispersion composition of the present invention, a coating film having hydrophilicity and water resistance can be provided. It can be used as a coating agent for the substrate surface.

For example, the coating agent of the present invention is
When used as an ink jet receiving layer of an aqueous ink such as a film for P, the coating film forming the receiving layer has good water resistance, and therefore does not swell and dissolve with the aqueous ink to become tacky. Further, since the coating agent does not contain a surfactant or the like, there is no problem of deterioration in printability due to bleeding of the surfactant or the like.

Further, the coating agent of the present invention is also suitable for a stain-resistant paint used for maintaining the appearance of a building such as a building at the initial appearance. The stain-resistant paint suppresses the adsorption of particularly lipophilic dirt substances (exhaust gas, tire powder, asphalt dust, etc.) to the outer wall by increasing the hydrophilicity of the outer wall surface, or contaminants adsorbed on the outer wall in urban areas. Is easily washed away by rain or the like. The coating film obtained by the coating agent of the present invention can maintain high hydrophilicity and has sufficient water resistance, does not swell in water, and effectively functions as a stain-resistant paint. Further, transparency is not impaired unlike a stain-resistant paint using a hydrophilic inorganic substance such as ceramic fine particles or silica fine particles.

The coating agent of the present invention is also suitable as a coating agent for aluminum fins of heat exchangers and lithographic printing plates. In order to impart hydrophilicity to a coating agent such as aluminum fin of a heat exchanger, a coating of alkali silicate (water glass) (Japanese Patent Publication No. 53-48177) or a surfactant is generally used for aqueous paint. And those containing synthetic silica (Japanese Patent Application Laid-Open No. 55-164264) are used. However, in these methods, since the coating film becomes too hard, cracks occur in the recent precoating processing method. It is easy to perform, and the forming tool is significantly worn during press working. Further, the durability of the hydrophilic property over time is poor. The coating film obtained by the coating agent of the present invention is flexible and has good hydrophilicity.

The coating agent of the present invention is also suitable as an antistatic paint for plastics. In general, plastics such as polycarbonate are easily charged with static electricity, and therefore, there are many cases in which handling is impeded due to electrification due to friction, dust and the like adhering to the surface, and blocking between films. Conventionally, in order to suppress the generation of static electricity, a method of applying a surfactant to impart hydrophilicity,
Although a method of applying a resin layer mixed with a conductive powder such as metal or carbon has been tried, it is difficult to maintain the effect for a long time because the method of applying a surfactant has a problem with water resistance, The coating of the resin layer of the conductive powder has disadvantages such as loss of transparency and coloring. The coating film obtained by the coating agent of the present invention is hydrophilic, but has no remarkable lack of water resistance such as dissolution, swelling, and peeling of the film. In addition, there is no decrease in mechanical properties (hardness, strength, etc.) and adhesion due to the coating film.

In addition, the coating agent of the present invention can be used as an antifogging paint, a coating agent for a backlight display, and the like.

[0048]

Hereinafter, the present invention will be described in detail with reference to a synthesis example of an aqueous dispersion of the cationic fine particle gel (A) and an example of the aqueous dispersion composition of the present invention. It is not limited to examples and embodiments. In each example, all parts and percentages are by weight unless otherwise specified.

Synthesis Example 1 49.2 parts of styrene, 15.1 parts of butyl acrylate, 65 parts of N, N-dimethylaminoethyl methacrylate 65 were placed in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet tube and a thermometer. Parts, 77.7 parts of isopropyl alcohol, and 1.9 parts of azoisobutyronitrile as a polymerization initiator, and the mixture was stirred to make uniform. The temperature was raised to 80 ° C. while stirring under a nitrogen atmosphere, and the temperature was kept for 6 hours to complete the polymerization. After cooling to 60 ° C., 41 parts of diethyl sulfuric acid was added and the mixture was kept warm for 1 hour. Then, 5.3 parts of acetic acid was added and stirred for 30 minutes, and 642.7 parts of ion-exchanged water and 12.6 parts of glycidyl methacrylate were added. In addition, the mixture was heated to 60 ° C. in an air atmosphere and kept warm for 3 hours to obtain an aqueous solution (1) of a cationic polymer. The solid content of this aqueous solution (1) was 26.3%.

In the same reaction vessel, the aqueous solution (1) 15
After charging 0 parts and 209.3 parts of ion-exchanged water, 39.4 parts of styrene was added to the mixture while stirring to emulsify. Then
1.1 parts of 2,2′-azobis (2-aminopropane) dihydrochloride was added, and the mixture was heated to 80 ° C. and stirred for 4 hours while stirring under a nitrogen atmosphere to complete the polymerization. An aqueous dispersion of the fine particle gel (A1) was obtained.

Synthesis Example 2 59.6 parts of styrene, 24.5 parts of butyl acrylate, 70 parts of N, N-diethylaminoethyl methacrylate, and 7 parts of isopropyl alcohol were placed in the same reaction vessel as in Synthesis Example 1.
4.9 parts and 2.1 parts of azoisobutyronitrile as a polymerization initiator were charged and stirred to make the mixture uniform. The temperature was raised to 80 ° C. while stirring under a nitrogen atmosphere, and the temperature was kept for 6 hours to complete the polymerization. Cool to 60 ° C.,
One part was added and the mixture was kept warm for 1 hour. Then, 5.7 parts of acetic acid was added and the mixture was stirred for 30 minutes, and 639.8 parts of ion-exchanged water and 13.6 parts of glycidyl methacrylate were added. C. and heated for 3 hours to obtain a cationic polymer aqueous solution (2). The solid content of this aqueous solution (2) is 2
It was 6.6%.

In the same reaction vessel, the aqueous solution (2) 15
After charging 0 parts and 213.4 parts of ion-exchanged water, 39.9 parts of styrene was added to the mixture under stirring to emulsify. Then
1.1 parts of 2,2'-azobis (2-aminopropane) dihydrochloride was added, and the mixture was stirred at 80 ° C under a nitrogen atmosphere.
And the temperature was maintained for 4 hours to complete the polymerization to obtain an aqueous dispersion of the cationic fine particle gel (A2).

Synthesis Example 3 The same aqueous solution (2) 150 was placed in the same reaction vessel as in Synthesis Example 1.
And 213.6 parts of ion-exchanged water, and then 39.9 parts of methyl methacrylate was added thereto under stirring to emulsify. Then, 1.1 parts of 2,2'-azobis (2-aminopropane) dihydrochloride was added, and the mixture was heated to 80 ° C. with stirring under a nitrogen atmosphere and kept at that temperature for 4 hours to complete the polymerization. An aqueous dispersion of the cationic fine particle gel (A3) was obtained.

Synthesis Example 4 The same aqueous solution (2) 350 was placed in the same reaction vessel as in Synthesis Example 1.
And 498.2 parts of ion-exchanged water, 46.6 parts of styrene and 46.6 parts of methyl methacrylate were added thereto under stirring to emulsify. Then, 2.6 parts of 2,2′-azobis (2-aminopropane) dihydrochloride was added, and the mixture was heated to 80 ° C. and stirred for 4 hours while stirring under a nitrogen atmosphere to complete the polymerization. Cationic fine particle gel (A
An aqueous dispersion of 4) was obtained.

Synthesis Example 5 In a reaction vessel similar to that of Synthesis Example 1, 27.1 parts of styrene, 20.0 parts of butyl acrylate, 90 parts of N, N-diethylaminoethyl methacrylate, and isopropyl alcohol 6
6.0 parts and 1.7 parts of azoisobutyronitrile as a polymerization initiator were charged and stirred to make the mixture uniform. The temperature was raised to 80 ° C. while stirring under a nitrogen atmosphere, and the temperature was kept for 6 hours to complete the polymerization. Cool to 60 ° C.,
After adding 2 parts and keeping the temperature for 1 hour, 4.7 parts of acetic acid was added and the mixture was stirred for 30 minutes. Then, 648.1 parts of ion-exchanged water and 11.1 parts of glycidyl methacrylate were added, and the mixture was added under an air atmosphere. C. and kept at that temperature for 3 hours to obtain a cationic polymer aqueous solution (3). The solid content of this aqueous solution (3) is 2
6.5%.

In the same reaction vessel, the aqueous solution (3) 15
After charging 0 parts and 212.0 parts of ion-exchanged water, 39.8 parts of styrene was added to the mixture while stirring to emulsify. Then
1.1 parts of 2,2'-azobis (2-aminopropane) dihydrochloride was added, and the mixture was stirred at 80 ° C under a nitrogen atmosphere.
And the temperature was maintained for 4 hours to complete the polymerization to obtain an aqueous dispersion of the cationic fine particle gel (A5).

Example 1 Into an Erlenmeyer flask with a stopcock (100 ml) containing a stirrer, 40 parts (solid content: 8 parts) of the aqueous dispersion of the cationic fine particle gel (A1) obtained in Synthesis Example 1 was added and stirred. 0.0865 ethylene glycol diglycidyl ether
After stirring and mixing, the mixture was allowed to stand at room temperature for 24 hours to prepare an aqueous dispersion composition of the present invention.

Example 2 An Erlenmeyer flask with a stopcock containing a stirrer (100 ml) was charged with 40 parts (solid content: 8 parts) of the aqueous dispersion of the cationic fine particle gel (A2) obtained in Synthesis Example 2 and stirred. While adding 0.094 parts of ethylene glycol diglycidyl ether while stirring and mixing, the mixture was allowed to stand at room temperature for 24 hours to prepare an aqueous dispersion composition of the present invention.

Example 3 Into an Erlenmeyer flask with a stopcock (100 ml) containing a stirrer, 40 parts (solid content: 8 parts) of an aqueous dispersion of the cationic fine particle gel (A3) obtained in Synthesis Example 3 was added and stirred. While adding 0.094 parts of ethylene glycol diglycidyl ether while stirring and mixing, the mixture was allowed to stand at room temperature for 24 hours to prepare an aqueous dispersion composition of the present invention.

Example 4 Into an Erlenmeyer flask equipped with a stopcock (100 ml) containing a stirrer, 40 parts (solid content: 8 parts) of an aqueous dispersion of the cationic fine particle gel (A4) obtained in Synthesis Example 4 was added and stirred. While adding 0.094 parts of ethylene glycol diglycidyl ether while stirring and mixing, the mixture was allowed to stand at room temperature for 24 hours to prepare an aqueous dispersion composition of the present invention.

Example 5 In a Erlenmeyer flask with a stopcock (100 ml) containing a stirrer, 40 parts (solid content: 8 parts) of the aqueous dispersion of the cationic fine particle gel (A5) obtained in Synthesis Example 5 was added and stirred. While adding 0.0767 parts of ethylene glycol diglycidyl ether while stirring and mixing, the mixture was allowed to stand at room temperature for 24 hours to prepare an aqueous dispersion composition of the present invention.

Comparative Example 1 The aqueous dispersion of the cationic fine particle gel (A1) obtained in Synthesis Example 1 was directly evaluated.

Comparative Example 2 The aqueous dispersion of the cationic fine particle gel (A2) obtained in Synthesis Example 2 was directly evaluated.

Comparative Example 3 The aqueous dispersion of the cationic fine particle gel (A3) obtained in Synthesis Example 3 was directly evaluated.

Comparative Example 4 The aqueous dispersion of the cationic fine particle gel (A4) obtained in Synthesis Example 4 was directly evaluated.

Comparative Example 5 The aqueous dispersion of the cationic fine particle gel (A5) obtained in Synthesis Example 5 was directly evaluated.

The aqueous dispersion composition prepared in the Examples or Comparative Examples was applied to a polyethylene terephthalate film (clear sheet for PPC, manufactured by Gakken Co., Ltd.) using a bar coater (No. 18), and then applied to a film. C. for 20 minutes to form a coating film having a thickness of about 10 to 15 .mu.m. The obtained coating film was evaluated by the following method. Table 1 shows the results.

(Hydrophilic) The coating film was immersed in a beaker containing tap water, pulled up, and placed horizontally to determine the wet state of the coating film surface by visual observation.印: No polka dots are observed, and the entire surface is coated with water. 印: A small number of polka dots and a portion that is not wet with water is observed or the ratio is 1/2 or less. X: Many polka dots are generated. And the part that does not get wet is more than 1/2

(Water Resistance) The state of the coating film was visually determined when the coating film was immersed in a beaker containing tap water for 3 minutes. ○: no change △: swelling ×: dissolve

[0070]

[Table 1]

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C09D 163/00 C09D 163/00

Claims (9)

[Claims] 1. A repeating unit based on a nonionic unsaturated monomer (a), a repeating unit based on an unsaturated monomer (b) having a tertiary amino group, and an unsaturated unit having a tertiary amino group It comprises a cationic fine particle gel (A) comprising a copolymer having a repeating unit based on a quaternary amino group of a monomer (b) and a polyfunctional epoxy compound (B). Aqueous dispersion composition. 2. The cationic fine particle gel (A) comprises repeating units 75 to 9 based on a nonionic unsaturated monomer (a).
4.5 mol%, 0.5 to 5 mol% of a repeating unit based on the unsaturated monomer (b) having a tertiary amino group, and of the unsaturated monomer (b) having a tertiary amino group. Repeating units 5 to 20 based on quaternized tertiary amino groups
The aqueous dispersion composition according to claim 1, comprising mol%. 3. The cationic fine particle gel (A) is a copolymer of a nonionic unsaturated monomer (a) and a tertiary amino group-containing unsaturated monomer (b). In the presence of a cationic copolymer obtained by quaternizing a tertiary amino group with a quaternizing agent containing a quaternizing agent (I) having a double bond,
3. The aqueous dispersion composition according to claim 1, which is obtained by subjecting the unsaturated monomer (c) to microemulsion polymerization. 4. The aqueous dispersion composition according to claim 3, wherein the unsaturated monomer (c) is a nonionic unsaturated monomer (a). 5. The aqueous dispersion according to claim 1, wherein the nonionic unsaturated monomer (a) is at least one selected from styrenes and (meth) acrylates. Liquid composition. 6. The aqueous dispersion composition according to claim 1, wherein the polyfunctional epoxy compound (B) is water-soluble. 7. A polyfunctional epoxy compound (B) based on 100 equivalents of tertiary amino groups of the cationic fine particle gel (A).
The epoxy group of the polyfunctional epoxy compound (B) is 50 to
The aqueous dispersion composition according to any one of claims 1 to 6, which is used so as to be 100 equivalents. 8. A coating agent using the aqueous dispersion composition according to claim 1. 9. A method for coating a substrate, wherein the coating agent according to claim 8 is applied to the surface of the substrate and cured by heating and drying to form a coating film on the surface of the substrate.