JPH0859932A - Water dispersion composition - Google Patents

Abstract

(57) [Abstract] [Purpose] The present invention can form a coating film having excellent water resistance strength, flexibility, and adhesion, and further, storage stability, re-dissolvability (re-dispersibility), and prevention of skinning. An aqueous dispersion composition capable of forming a binder for an aqueous printing ink having excellent properties. [Composition] This aqueous dispersion composition comprises [A-1] (a) an aromatic vinyl compound; 10 to 80% by weight, and (b) an alkyl (meth) acrylate having 8 or more carbon atoms; 10 to 80% by weight. When,
(c) Another ethylenically unsaturated compound; an acrylic copolymer emulsion containing an acrylic copolymer with 0 to 80% by weight, or [A-2] polysilane complex emulsion,
[B] a water-soluble polymer, [C] a polyhydric alcohol,
[D] A polyvalent metal compound, and each of these components is contained in a specific amount.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention is capable of forming a coating film having excellent water resistance strength, flexibility and adhesiveness, and also has storage stability, re-solubility (re-dispersibility) and skin-preventing property. The present invention also relates to an aqueous dispersion composition which is excellent and can be suitably used as a binder for aqueous ink.

[0002]

2. Description of the Related Art Conventionally, organic solvent-containing gravure printing or flexographic ink printing inks have been used as printing inks for printing on paper or plastic films such as polyethylene and polyester. However, such an organic solvent-based printing ink has a risk of fire and explosion due to an organic solvent, and is a water-based solvent that does not contain an organic solvent or does not contain an organic solvent as much as possible in terms of safety and health, pollution, and resource saving. A shift to printing ink is desired.

By the way, generally, the performance of printing ink depends almost on the binder contained in the ink, and the selection of the binder is an important key for obtaining an excellent ink.

Various aqueous medium compositions such as emulsion type and water-soluble type have been proposed as binders for such aqueous inks. However, conventional emulsion type binders have
It is possible to form a dry coating film having excellent adhesion, etc., but it was unstable with respect to the mechanical share during dispersion of the pigment or during printing, and sometimes agglomeration occurred partially. Further, once dried, it is difficult to be redissolved (redispersed), which causes a problem such as plate clogging.

In order to solve such a problem, a method of adding a wetting agent or the like to the emulsion has been conventionally known, but the addition of the wetting agent lowers the performance such as the water resistance of the dry coating film. New problems arise.

On the other hand, the water-soluble type binder is excellent in re-dissolvability and stability against mechanical shear during printing, but has a problem that the dry coating film is inferior in water resistance and adhesion. .

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional techniques, and can form a coating film excellent in water resistance strength, flexibility, and adhesion, and can be stored. An object of the present invention is to provide an aqueous dispersion composition capable of forming a binder for an aqueous printing ink which is excellent in stability, re-dissolvability (hereinafter also referred to as re-dispersibility) and skin-proofing property.

[0008]

[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies to solve the above problems, and found that an acrylic copolymer obtained by copolymerizing a specific acrylic compound in a specific amount. An aqueous dispersion composition comprising a combined emulsion, a specific amount of a water-soluble polymer, a polyhydric alcohol, and a polyvalent metal compound with respect to the acrylic copolymer emulsion has water resistance, flexibility, and adhesion. The present invention has been completed by finding that it is possible to form a binder film for an aqueous printing ink which is capable of forming an excellent coating film, and is also excellent in storage stability, re-dissolution property, and anti-skinning property. .

That is, the first water dispersion composition according to the present invention comprises [A-1] (a) an aromatic vinyl compound;
(b) an alkyl (meth) acrylate having an alkyl group having 8 or more carbon atoms; 10 to 80% by weight, and (c) the above.
Other ethylenically unsaturated compound copolymerizable with (a) and (b); 0 to 80% by weight [total of (a) + (b) + (c) is 100% by weight] The acrylic copolymer emulsion containing the acrylic copolymer obtained in this manner and 100 parts by weight of the solid content in the acrylic copolymer emulsion [A-1], [B] a water-soluble polymer; 1 To 200 parts by weight, [C] polyhydric alcohol; 1 to 200 parts by weight, and [D] polyvalent metal compound; 0.1 to 10 parts by weight (as metal ion weight).

The second aqueous dispersion composition according to the present invention is [A-2] in the presence of the above-mentioned acrylic copolymer emulsion [A-1], an organosilane is added as an acrylic copolymer. 0.1 to 100 parts by weight of combined emulsion [A-1]
Polysilane complex emulsion obtained by condensation reaction in an amount of 500 parts by weight, and polysilane complex emulsion
[B] Water-soluble polymer; 1 to 200 parts by weight, and [C] polyhydric alcohol;
1 to 200 parts by weight, and [D] polyvalent metal compound; 0.1 to
And 10 parts by weight (as metal ion weight).

[0011]

DETAILED DESCRIPTION OF THE INVENTION The aqueous dispersion composition according to the present invention will be specifically described below. The first aqueous dispersion composition according to the present invention comprises [A-1] an acrylic copolymer emulsion, [B] a water-soluble polymer, and [C] a polyhydric alcohol.
The second aqueous dispersion composition of the present invention comprises [D] a polyvalent metal compound and [A-2] a polysilane complex emulsion, [B] a water-soluble polymer, and [C]. ] A polyhydric alcohol and [D] a polyvalent metal compound are contained,
First, each of these components will be described below.

[A-1] Acrylic Copolymer Emulsion The acrylic copolymer emulsion forming the aqueous dispersion composition according to the present invention comprises (a) an aromatic vinyl compound and (b)
Acrylic system obtained by copolymerizing alkyl (meth) acrylate having an alkyl group having 8 or more carbon atoms with (c) another ethylenically unsaturated compound copolymerizable with (a) and (b) above. It is an emulsion containing a copolymer.

Each of these compounds will be specifically described. (a) Aromatic vinyl compound Specific examples of the aromatic vinyl compound used in the present invention include styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene and 2-methoxystyrene. Hydroxymethylstyrene, 4-ethylstyrene, 4-ethoxystyrene, 3,4-dimethylstyrene, 2-
Examples thereof include chlorostyrene, 3-chlorostyrene, 4-chloro-3-methylstyrene, 4-t-butylstyrene, 2,4-dichlorostyrene, 2,6-dichlorostyrene, 1-vinylnaphthalene and divinylbenzene.

Of these, styrene, α-methylstyrene, divinylbenzene and the like are preferably used. These may be used in combination of two or more.

(B) an alkyl group having 8 or more carbon atoms
The alkyl (meth) acrylates are preferably alkyl group having 8 or more carbon used in the present invention the alkyl (meth) acrylate having an alkyl group having 8 to 18 carbon atoms, specifically, octyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate and the like can be mentioned.

Of these, 2-ethylhexyl (meth)
Acrylate, octyl (meth) acrylate, lauryl (meth) acrylate and the like are preferably used. These may be used in combination of two or more.

(C) Other copolymerizable ethylenic desaturation
Compound (a) used in the present invention, the other ethylenically unsaturated compound copolymerizable with (b), specifically, methyl (meth) acrylate, ethyl (meth) acrylate,
Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, n-amyl (meth) acrylate, i-amyl (meth) acrylate, hexyl (meth)
Alkyl (meth) acrylate other than (b) such as acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxy n-butyl (meth)
Acrylate, hydroxy i-butyl (meth) acrylate, hydroxy n-amyl (meth) acrylate, hydroxy i-amyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxy 2-ethyl (meth)
Acrylate, hydroxyalkyl (meth) acrylate such as hydroxy n-octyl (meth) acrylate,
Epoxy compounds such as allyl glycidyl ether, glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate,
Tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) ) Acrylate, polyfunctional compounds such as pentaerythritol tetra (meth) acrylate, (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N'-
Acid amide compounds such as methylenebisacrylamide, diacetone acrylamide, maleic acid amide, and maleimide, (meth) acrylic acid, fumaric acid, itaconic acid, monoalkyl itaconic acid, maleic acid, crotonic acid, 2-
Ethylenically unsaturated carboxylic acids such as (meth) acryloyloxyethylhexahydrophthalic acid, vinyl compounds such as vinyl chloride, vinylidene chloride, fatty acid vinyl ester, trifluoroethyl (meth) acrylate, pentadecafluorooctyl (meth) acrylate, etc. And a fluorine-containing compound, γ- (meth) acryloylpropanetrimethoxysilane, and silaplane FM0711 (trade name; manufactured by Chisso Corporation) and other reactive silicones and other silicone compounds.

Of these, methyl (meth) acrylate, n-butyl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyethyl (meth) acrylate and the like are preferably used.

These can be used in combination of two or more kinds. Preparation of Acrylic Copolymer Emulsion [A-1] The acrylic copolymer emulsion used in the present invention is prepared by emulsion-polymerizing or suspension-polymerizing the above compounds (a), (b) and (c). May be directly prepared as an emulsion, or may be prepared as an emulsion by emulsifying and dispersing the acrylic copolymer once obtained from (a), (b) and (c) in an aqueous medium. Good. Of these, it is preferable to directly prepare the acrylic copolymer emulsion by emulsion polymerization.

In forming the acrylic copolymer emulsion, when the total amount of (a), (b) and (c) is 100% by weight, the aromatic vinyl compound (a) is 10 to 8%.
0% by weight, preferably 15 to 70% by weight, more preferably 20 to 60% by weight, and (b) the alkyl (meth) acrylate having an alkyl group having 8 or more carbon atoms is 10 to 8%.
0% by weight, preferably 15 to 70% by weight, more preferably 20 to 60% by weight, and (c) the other ethylenically unsaturated compound is 0 to 80% by weight, preferably 0 to 70% by weight, more preferably 0% by weight. Used in an amount of ~ 60% by weight.

From the acrylic copolymer emulsion [A-1] formed from the above specified amounts of the respective components, an aqueous dispersion capable of forming a coating film excellent in water resistance strength, flexibility and adhesion. A composition can be obtained.

In the acrylic copolymer as described above, when the amount of (a) the aromatic vinyl compound is less than 10% by weight, an aqueous dispersion composition capable of forming a coating film having excellent water resistance strength. Is difficult to obtain, and on the other hand, if it exceeds 80% by weight, the flexibility may decrease. Further, (b) the amount of alkyl (meth) acrylate having an alkyl group having 8 or more carbon atoms is
If it is less than 10% by weight, it is difficult to obtain an aqueous dispersion composition capable of forming a coating film having excellent flexibility.

The acrylic copolymer emulsion [A-1] used in the present invention contains the above acrylic copolymer (solid content) in an amount of 30 to 80% by weight, preferably 40 to 70% by weight.
It is desirable to contain it in an amount of% by weight.

The acrylic copolymer emulsion used in the present invention has an average particle size of 10 to 500 nm, preferably 20 to 400 nm. A coating film having poor water resistance may be formed from the acrylic copolymer emulsion having an average particle size of more than 500 nm.

Further, the glass transition temperature of the acrylic copolymer contained in the acrylic copolymer emulsion (T
g) changes depending on the polymerization amount of the polymerizable compounds (a), (b) and (c), but is preferably -20 ° C or higher.

This glass transition temperature Tg is, for example, when the acrylic copolymer is a copolymer of (a) and (b), the glass transition of each of the homopolymers of (a) and (b). It can be calculated from the temperature by the following formula.

[0027]

[Equation 1]

In the formula, Tg: glass transition temperature of acrylic copolymer W (a): weight fraction of (a) in acrylic copolymer W (b): (b of acrylic copolymer ) Weight fraction Tg (a): glass transition temperature of homopolymer of (a) Tg (b): glass transition temperature of homopolymer of (b) The glass transition temperature thus obtained is Thus, from the acrylic copolymer having a temperature of -20 ° C or higher, preferably -10 ° C or higher, more preferably 0 ° C or higher, a coating film having excellent strength and adhesion can be formed on a paper or plastic film substrate. . When the glass transition temperature is lower than -20 ° C, a coating film having poor strength may be formed, and when the glass transition temperature is too high, a uniform coating film may not be formed by room temperature drying. The upper limit of the glass transition temperature is preferably 80 ° C or lower, more preferably 60 ° C or lower.

A method for preparing an acrylic copolymer emulsion by emulsion-polymerizing the above (a), (b) and (c) will be specifically described below. Polymerizable compound (a),
In order to obtain an acrylic copolymer emulsion by emulsion polymerization of (b) and (c), conventionally known emulsion polymerization methods are widely used. For example, in an aqueous medium, an emulsifier and a polymerization initiator may be used, if necessary. Polymerization reaction of (a), (b) and (c) at a temperature of 30 to 100 ° C. for about 1 to 30 hours in the coexistence of a chain transfer agent, a chelating agent, a pH adjusting agent and the like. .

The emulsifiers used in emulsion polymerization are as follows:
Components such as a polymerization initiator, a chain transfer agent, a chelating agent, and a pH adjuster will be specifically described. Emulsifiers As the emulsifiers, anionic emulsifiers, nonionic emulsifiers, amphoteric surfactants (emulsifiers), cationic surfactants (emulsifiers) and [B] water-soluble polymers described below can be used.

Examples of the anionic emulsifier used in the present invention include higher alcohol sulfuric acid ester sodium salt, alkylbenzene sulfonic acid sodium salt, succinic acid dialkyl ester sulfonic acid sodium salt, and alkyl diphenyl ether disulfonic acid sodium salt.

Of these, sodium dodecylbenzene sulfonate, sodium lauryl sulfate, polyoxyethylene alkyl (or alkylphenyl)
Ether sulfate and the like are preferably used.

Examples of the nonionic emulsifier include polyoxyethylene alkyl allyl ether and the like, and specific examples include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether and the like.

Examples of the amphoteric surfactant include lauryl betaine. Examples of the cationic surfactant include alkylpyridinyl chloride and alkylammonium chloride.

As the emulsifier, it is also possible to use a so-called reactive emulsifier which can be copolymerized with the above-mentioned polymerizable compounds (a), (b) and (c). For example, sodium styrene sulfonate, allylalkyl sulfonic acid. Sodium, alkylallyl sulfosuccinate, polyoxyethylene alkylallyl glycerin ether sulfate,
It is also possible to use polyoxyethylene alkylphenol allyl glycerin ether sulfate and the like.

The emulsifiers as described above may be used in combination of two or more kinds. In the present invention, as the emulsifier, the water-soluble polymer [B] shown in forming an aqueous dispersion composition as described below is preferably used as the emulsifier because it has excellent compatibility and redissolvability.

In the present invention, in the emulsion polymerization, the emulsifier is generally used in an amount of 0 to 30 parts by weight based on 100 parts by weight of the total of (a), (b) and (c). Polymerization Initiator Examples of the polymerization initiator include water-soluble persulfates such as sodium persulfate generally used in emulsion polymerization, hydrogen peroxide and the like.

It is also possible to use an oil-soluble polymerization initiator, for example, 2,2'-azobisisobutyronitrile, 2,2'-
Azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis-2,4-dimethylvaleronitrile, 1,
1'-azobis-cyclohexane-1-carbonitrile, benzoyl peroxide, dibutyl peroxide, cumene hydroperoxide (peroxide), isopropylbenzene hydroperoxide, paramenthane hydroperoxide, azobisisobutyronitrile, benzoylper oxide,
Examples thereof include t-butyl hydroperoxide, 3,5,5-trimethylhexanol peroxide, t-butyl peroxy (2-ethylhexanoate) and the like.

Among the oil-soluble polymerization initiators, cumene hydroperoxide, isopropylbenzene hydroperoxide, paramenthane hydroperoxide, azobisisobutyronitrile, benzoyl peroxide, t-
Butylhydroperoxide, 3,5,5-trimethylhexanol peroxide, t-butylperoxy (2-ethylhexanoate) and the like are preferably used.

These oil-soluble polymerization initiators can be used by dissolving them in a polymerizable compound or a solvent. In the present invention, a water-soluble persulfate such as sodium persulfate is preferably used as the polymerization initiator.

The above-mentioned polymerization initiators include (a), (b),
It is usually used in an amount of 0.1 to 3 parts by weight based on 100 parts by weight of (c) in total. Further, in emulsion polymerization, a reducing agent may be used in combination with the polymerization initiator.

Examples of such reducing agents include sodium pyrobisulfite, sodium hydrogen sulfite, sodium thiosulfate, L-ascorbic acid and salts thereof, sodium formaldehyde sulfoxylate and the like.

Chain Transfer Agent As the chain transfer agent, the following compounds are used. Halogenated hydrocarbons such as chloroform and bromoform, mercaptans such as n-dodecyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan, xanthogens such as dimethylxanthogen disulfide, diisopropylxanthogen disulfide, terpenes such as dipentene and terpinolene. Unsaturated cyclic hydrocarbon compounds such as 9,10-dihydroanthracene, 1,4-dihydronaphthalene, indene and 1,4-cyclohexadiene, xanthene, unsaturated heterocyclic compounds such as 2,5-dihydrofuran, (a ₁ ), (a ₂ ) and (a ₃ ) at least one kind, preferably (a ₁ ): {(a ₂ ) and / or (a ₃ )} (weight ratio) is 40 to 100: A compound of 0 to 60; (a ₁ ) α-methylstyrene dimer [2,4-diphenyl-4-methyl-1-pentene, (a ₂ ) 2, 4-diphenyl
4-methyl-pentene, (a ₃ ) 1,1,3-trimethyl-3-phenylindane and the like can be mentioned.

The chain transfer agent is composed of (a), (b) and (c) in total of 1
It is usually used in an amount of 0 to 5 parts by weight with respect to 00 parts by weight. Other compound chelating agents include, for example, glycine, alanine,
Examples thereof include ethylenediaminetetraacetic acid.

The chelating agent is usually used in an amount of 0 to 0.1 part by weight based on 100 parts by weight of the total of (a), (b) and (c). Examples of the pH adjusting agent include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, ammonia and the like.

The pH adjusting agent is a total of 1 of (a), (b) and (c).
It is usually used in an amount of 0 to 3 parts by weight with respect to 00 parts by weight. Emulsion polymerization carried out in the aqueous medium as described above may be carried out in the presence of a small amount of an organic solvent, if necessary,
For example, an organic solvent such as methyl ethyl ketone, acetone, trichlorotrifluoroethane, methyl isobutyl ketone, dimethyl sulfoxide, toluene, dibutyl phthalate, methyl pyrrolidone, ethyl acetate, alcohols, cellosolves, carbinols can be used.

This organic solvent is used within a range that does not impair workability, disaster prevention safety, environmental safety and manufacturing safety. Specifically, the total of (a), (b) and (c) is 100 It can be used in an amount of usually 5 parts by weight or less based on parts by weight.

The emulsion polymerization of the polymerizable compounds (a), (b) and (c) carried out in the coexistence of the above components is carried out by a batch method,
It can be carried out by a known method such as a semi-continuous method or a continuous method. Specifically, the polymerizable compound (a), (b) or (c) is added to the reaction system.
Method of charging all at once, the polymerizable compound (a), (b),
Depending on the method of charging a part of (c) and then reacting it and then charging the rest continuously or in a divided manner, the method of continuously charging the polymerizable compounds (a), (b) and (c) into the reaction system. It can be carried out.

[A-2] Polysilane Complex Emulsion The polysilane complex emulsion used in the present invention is
It can be obtained by subjecting organosilane to a condensation reaction in the presence of the above acrylic copolymer emulsion [A-1].

Examples of such organosilanes include alkoxysilane and organosiloxane.
The alkoxysilane used in the present invention has the formula R ^a _n Si (OR ^b ) _4-n (wherein R ^a is an organic group having 1 to 8 carbon atoms, and R ^b is an alkyl group having 1 to 5 carbon atoms). Alternatively, it is an acyl group having 1 to 4 carbon atoms, and n is an integer of 0 to 3.). Specific examples of the organic group R ^a 1 to 8 carbon atoms, such as methyl group, ethyl group, n- propyl group, an alkyl group such as i- propyl group, a vinyl group, .gamma.-chloropropyl group, 3, 3,3
-Trifluoropropyl group, γ-glycidoxypropyl group,
Examples thereof include γ-methacryloxypropyl group, γ-mercaptopropyl group, phenyl group, 3,4-epoxycyclohexylethyl group and γ-aminopropyl group.

As the alkyl group having 1 to 5 carbon atoms or the acyl group R ^b having 1 to 4 carbon atoms, for example, methyl group,
Ethyl group, n-propyl group, n-butyl group, sec-butyl group,
Examples thereof include t-butyl group and acetyl group.

Specific examples of the alkoxysilane represented by the above formula include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane and ethyl. Triethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-
Glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,4-epoxycyclohexyl Examples thereof include ethyltrimethoxysilane, 3,4-epoxycyclohexylethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane and γ-aminopropyltrimethoxysilane.

Of these, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldidiethoxysilane and the like are preferably used.

In the present invention, examples of the organosiloxane include cyclic siloxane and linear or branched siloxane. As such a cyclic siloxane,
For example, hexaphenylcyclotrisiloxane, octaphenylcyclotetrasiloxane, tetravinyltetramethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane,
Pentamethylcyclotetrasiloxane, hexamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane and the like can be mentioned.

In the present invention, the organosiloxane may be a linear or branched organosiloxane in addition to the cyclic siloxane described above. When the number of carbon atoms in the above groups R ^a , R ^b , R ^c or R ^d is the above number, the organosilane is excellent in water solubility and is absorbed in the acrylic copolymer emulsion. It is preferable because it is easy.

The above-mentioned organosiloxanes can be used in combination of two or more kinds. The organosiloxane can also be used in combination with a metal alkoxide such as titanium or aluminum. If necessary, a known silane coupling agent can be used in combination. Furthermore, these organosilanes can be used by dissolving them in an organic solvent, if necessary.

In the present invention, the polysilane complex emulsion [A-2] is prepared by subjecting the above organosilane to a condensation reaction in the presence of the acrylic copolymer emulsion [A-1]. The organosilane is 0.1 parts by weight based on 100 parts by weight of the acrylic copolymer emulsion [A-1].
It is desired to be used in an amount of ˜500 parts by weight, preferably 0.5 to 250 parts by weight, more preferably 1.0 to 100 parts by weight.

Water repellency, stain resistance and lubricity can be obtained from an aqueous ink containing as a binder an aqueous dispersion composition containing a polysilane composite emulsion [A-2] formed by using an organosilane in such an amount. An excellent coating film can be formed.

If the amount of this organosilane exceeds 500 parts by weight, the storage stability of the aqueous dispersion composition tends to deteriorate. When the condensation reaction of the organosilane in the presence of the acrylic copolymer emulsion [A-1] is performed, the organosilane should be sufficiently absorbed in the acrylic copolymer emulsion [A-1]. Is preferable, and it is preferable to prevent the condensation reaction from proceeding in a state where the organosilane is not sufficiently absorbed in the acrylic copolymer emulsion [A-1].

In the present invention, first, organosilane is added to the acrylic copolymer emulsion [A-1], and the mixture is sufficiently stirred so that the organosilane is absorbed in the acrylic copolymer emulsion [A-1]. It is preferable.

Further, when the organosilane is absorbed in the acrylic copolymer emulsion [A-1] as described above,
If necessary, a solvent having a water solubility of 10 ⁻³ wt% or less can be added in advance to the emulsion [A-1].

The pH value of the acrylic copolymer emulsion [A-1] at this time is preferably 4 to 10, preferably 5 to 9, more preferably 6 to 8, and the temperature is 90 ° C.
The temperature is preferably 70 ° C or lower, more preferably 50 ° C or lower, and particularly preferably 30 ° C or lower.

When the organosilane is subjected to a condensation reaction in the presence of the acrylic copolymer emulsion [A-1] as described above, the organosilane undergoes a condensation reaction using the acrylic copolymer in the emulsion as a seed.

The condensation reaction of the organosilane carried out in the presence of the acrylic copolymer emulsion [A-1] can be easily controlled by changing the reaction temperature and the hydrogen ion concentration, and the resulting polysiloxane ( The degree of polymerization of the polysilane complex) can be adjusted.

The condensation reaction of the organosilane is carried out at a temperature of 30 ° C.
Or more, preferably 50 ° C or more, more preferably 70 ° C
This can be done. The polysilane composite emulsion [A-2] thus obtained desirably contains the polysilane composite (solid content) in an amount of 30 to 80% by weight, preferably 40 to 70% by weight.

When forming the aqueous dispersion composition according to the present invention, the above polysilane complex emulsion [A-2] is used.
By using, the coating film formed from the aqueous ink containing the aqueous dispersion composition as a binder is excellent in water repellency and stain resistance.

[B] Water-Soluble Polymer Specific examples of the water-soluble polymer used in the present invention include:
Poly (meth) acrylic acid salt, copolymer salt of (meth) acrylic acid and (meth) acrylic acid ester, carboxylated aromatic vinyl copolymer salt such as styrene-maleic acid copolymer salt, styrene- (meth ) Acrylic acid copolymer salt, poly (meth) acrylamide-based copolymer salt, for example, copolymer salt of (meth) acrylic acid and (meth) acrylamide, water-soluble polyester resin, water-soluble epoxy resin, water-soluble urethane Examples thereof include water-soluble resins such as resins, and polymeric alcohols such as polyvinyl alcohol (PVA).

Of these, carboxylated aromatic vinyl copolymer salts such as (meth) acrylic acid ester copolymer salts, styrene-maleic acid copolymer salts and styrene- (meth) acrylic acid copolymer salts are , Acrylic copolymer emulsion [A-1] or polysilane complex emulsion
It is particularly preferable because it has excellent compatibility with [A-2] and stability of addition.

These may be used in combination of two or more kinds. The water-soluble polymer used in the present invention has an acid value of 3
0-500, preferably 50-400, more preferably 1
It is desirable that it is from 00 to 300.

When the acid value of the water-soluble polymer is less than 30, the water-dispersion composition containing it may be inferior in redissolvability, while when it exceeds 500, the water resistance of the coating film is lowered. It may end up.

The weight average molecular weight of the water-soluble polymer is 1
000-100,000, preferably 2000-50,0
00 is more preferably 2500 to 20,000.

When the molecular weight of the water-soluble polymer is less than 1000, the coating film formed from the aqueous dispersion composition containing the water-soluble polymer may be inferior in water resistance, while when it exceeds 100,000, the re-solubility is high. (Redispersibility) may be inferior.

[C] Polyhydric Alcohol The polyhydric alcohol used in the present invention is a compound having at least two hydroxyl groups in one molecule. In the present invention,
As the polyhydric alcohol, monomers, oligomers, polymers, etc. are used without limitation, and specifically, ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 2,2-dimethylpropanediol, 2,2'- Dihydric alcohols such as nitrilogiethanol, glycerin, trimethylolethane, trimethylolpropane, trihydric alcohols such as 1,2,6-hexanetriol, 2,2 ', 2 "-nitrilotriethanol, pentaerythritol, sorbitol, diglycerol Alcohols having a valence of 4 or more, such as dipentaerythritol, are used.

Of these, ethylene glycol, glycerin, pentaerythritol, etc. are excellent in compatibility and addition stability with the acrylic copolymer emulsion [A-1] or polysilane complex emulsion [A-2]. , Particularly preferably used.

These may be used in combination of two or more kinds. [D] Polyvalent Metal Compound Examples of the polyvalent metal compound used in the present invention include alcoholates such as aluminum and zirconium, and metal chelates obtained by reacting these with a known chelating agent.

Specific examples of the polyvalent metal compound include aluminum isopropylate, aluminum ethylate, alcoholates such as tetramethylzirconate, aluminum bis (ethylacetoacetate) monoisopropylate, aluminum tris (acetylacetonate). ), Aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum chelate HE
(Made by Kawaken Fine Chemicals Co., Ltd.), metal chelates such as tris (acetylacetone) monoethylacetoacetate zirconate, and the like.

Of these, aluminum acetoacetic acid ester chelates are excellent in compatibility and addition stability with the acrylic copolymer emulsion [A-1] or polysilane complex emulsion [A-2], Particularly preferably used.

Further, these may be used in combination of two or more kinds. Aqueous Dispersion Composition The first aqueous dispersion composition according to the present invention has the above [A-
1] An acrylic copolymer emulsion, [B] a water-soluble polymer, [C] a polyhydric alcohol, and [D] a polyvalent metal compound, and a second water dispersion according to the present invention. The composition contains [A-2] polysilane complex emulsion and these [B], [C] and [D].

In such an aqueous dispersion composition, when the solid content in the acrylic copolymer emulsion [A-1] or the polysilane complex emulsion [A-2] is 100 parts by weight,
[B] Water-soluble polymer, 1 to 200 parts by weight, preferably 3
To 150 parts by weight, more preferably 5 to 100 parts by weight, [C] polyhydric alcohol, 1 to 200 parts by weight, preferably 2 to 100 parts by weight, more preferably 5 to 50 parts by weight, [D] ] The polyvalent metal compound is contained in an amount of 0.1 to 10 parts by weight (as metal ion weight), preferably 0.2 to 5 parts by weight, more preferably 0.5 to 3 parts by weight.

However, the amount of the above water-soluble polymer [B] is
This value also includes the amount of the water-soluble polymer [B] used as an emulsifier when preparing the acrylic copolymer emulsion [A-1].

The water-dispersed composition may contain the above acrylic copolymer emulsion [A-1] and polysilane complex emulsion [A-2] in combination. Components [B], [C] and [D] are [A-1] and [A]
-2] It is used in the above amount based on 100 parts by weight of the total solid content contained in.

The aqueous dispersion composition according to the present invention is excellent in storage stability, re-dissolving property and anti-skinning property by containing the specific components in the specific amounts as described above, and further, the water resistance, flexibility, A coating film having excellent adhesion can be formed.

Such an aqueous dispersion composition according to the present invention is suitable as a binder for aqueous ink. In addition, the water dispersion composition exhibits the various excellent properties as described above by including the above components. For example, by using the water-soluble polymer [B] and the polyhydric alcohol [C] in combination, an aqueous dispersion composition having excellent re-solubility and excellent anti-skin property is obtained. When the water dispersion composition does not contain any one component of the [B] water-soluble polymer or the [C] polyhydric alcohol, the re-solubility and the skin-proofing property may be poor.

When the amounts of the above-mentioned [B] water-soluble polymer and [C] polyhydric alcohol are each less than 1 part by weight, the aqueous dispersion composition is apt to cause clogging of the plate due to reduction in re-solubility. On the other hand, if the amount exceeds 200 parts by weight, not only the water resistance of the coating film is lowered, but also a large amount of [D] polyvalent metal compound is required, which is economically disadvantageous. When the amount of the polyvalent metal compound [D] is less than 0.1 part by weight (as metal ion weight), the coating film of the water dispersion composition may be inferior in water resistance strength, while when it exceeds 10 parts by weight. Not only is it uneconomical, but storage stability may be reduced.

The aqueous dispersion composition according to the present invention is obtained by blending each of the above components [A-1] or [A-2], [B], [C] and [D]. However, the order of adding each component is not particularly limited.

For example, all the components may be blended at once, or the other components may be sequentially added to the component [A-1] or [A-2], or some components may be blended in advance and then the other components may be blended. The ingredients can be added in various orders such as by adding the ingredients alone or in advance.

Of these, the previously mixed [B] water-soluble polymer and [C] polyhydric alcohol were mixed with [A-1] acrylic copolymer emulsion (or [A-2] polysilane complex emulsion). It is preferable to add the polyvalent metal compound [D] to this after the addition.

When the components are blended as described above, it is preferable to add the components with stirring, and it is preferable to improve the compatibility between the components by aging treatment such as heating. The aging treatment may be carried out at any of the above-mentioned blending stages, and when the blending is carried out at a plurality of stages, it may be appropriately carried out at each blending stage.

Such aging (heating) treatment is usually performed at 30
℃ or more, preferably 50 ℃ or more, more preferably 70 ℃
Therefore, it is desirable that the time is usually 10 minutes or longer, preferably 30 minutes or longer.

The thus obtained aqueous dispersion composition of the present invention comprises the above-mentioned components [A-1] or [A-2],
If necessary, additives may be contained in addition to [B], [C], and [D].

Examples of such additives include known water-dispersible resins and additives, for example, resins such as water-dispersible epoxy resins and water-dispersible urethane resins, catalyst lubricants,
Examples include defoaming agents, wetting agents, leveling agents, pigments and the like.

Further, as additives, alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, methyl cellosolve, ethyl cellosolve, and propyl are added in order to improve film-forming property and wettability. Organic solvents such as cellosolve, butyl cellosolve, hexyl cellosolve, methyl carbitol, ethyl carbitol, methyl cellosolve acetate, ethyl cellosolve acetate and tributoxymethyl phosphate can be used.

This organic solvent is used within a range that does not impair the object of the present invention, but the solid content of the aqueous dispersion composition is 100%.
It is used in an amount of usually 20 parts by weight or less, preferably 10 parts by weight or less, based on parts by weight, if necessary.

Since the aqueous dispersion composition according to the present invention has the above-mentioned various excellent properties, it is formed from an aqueous printing ink containing the aqueous dispersion composition as a binder and an aqueous dispersion composition. Aqueous coating agents such as paints are particularly excellent in storage stability, re-dissolution (re-dispersion) property, and skin resistance, and can form a coating film excellent in water resistance strength, flexibility, and adhesion. it can.

An aqueous coating agent such as an aqueous printing ink or paint containing the aqueous dispersion composition according to the present invention as a binder exerts its performance sufficiently when dried at room temperature. However, addition of a film-forming aid or the like and high temperature drying. Alternatively, by using these in combination, a coating film having more excellent adhesion to the material to be coated and water resistance can be formed.

The thickness of the coating film is usually 1 to 150 μm.
However, it is also possible to make a thicker film by coating multiple layers. Such an aqueous dispersion composition according to the present invention is suitable for use as a binder for water-based printing inks, furniture, vinyl flooring materials, interior materials for aircraft, motorcycles, interior / exterior materials for automobiles, office equipment, and other coating agents. It is used for paper, plastic film, plastic, metal, rubber, wood, ceramics, etc., and is especially used as a binder for water-based printing inks with paper, plastic film, plastic, etc. It is preferably used.

When the aqueous printing ink is prepared, the pigment is usually added in an amount of 1 to 100 parts by weight based on 100 parts by weight (as a solid content) of the aqueous dispersion composition of the present invention.

[0098]

The water dispersion composition according to the present invention is excellent in water resistance strength, flexibility and adhesion and storage stability, and particularly excellent in re-dissolution (re-dispersion) property. In particular, it is preferably used as a binder for water-based printing ink, which has paper, plastic film, plastic or the like as a printing medium.

[0099]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples.

The properties of the aqueous dispersion compositions obtained in the following examples were as follows: paints (water-based printing inks) and coating test pieces were prepared from the aqueous dispersion compositions as described below. Was measured by the following method.

(I) Storage stability A coating material prepared from an aqueous dispersion composition was observed after being left at 50 ° C for 1 month. ◯: No change, Δ: Some change was observed, ×: Separation was observed.

(Ii) Re-dissolvability (re-dispersibility) A coating material prepared from an aqueous dispersion composition was applied on a glass plate at a film thickness of 5 μm, and was applied at 25 ° C. in an atmosphere of 63% RH for 10 minutes.
After being left for a minute, the re-solubility in the ethanol / water = 50/50 mixed solution was visually evaluated.

◯: Almost soluble, Δ: Partially soluble, ×: Insoluble at all

(Iii) Adhesiveness A cellotape (trade name; manufactured by Nichiban Co., Ltd.) peeling test was performed on the adhesive coating test piece, and the degree of peeling of the coating film was visually evaluated.

◯: The coating film is not peeled off, Δ: The coating film is partially peeled off, ×: The coating film is completely peeled off.

(Iv) Water Resistant Strength Coating test pieces were strongly rubbed with a cloth containing water and evaluated by the number of times the coating film started to peel off.

◯: 100 times or more, Δ: 50 to 100 times, ×: 50 times or less.

(V) Flexibility Coating Test pieces were visually evaluated for cracks generated when the test pieces were bent at 180 °. ○: No cracking occurred, ×: Cracking occurred.

(Vi) Water repellency (contact angle of water ) Using a contact angle measuring device manufactured by Elma Optical Co., Ltd., distilled water was dropped on the test piece for measurement.

[0110]

Example 1 Preparation of Acrylic Copolymer Emulsion (1) 120 parts by weight of water was placed in a stainless steel autoclave equipped with a stirrer, a thermometer, a pump for introducing a polymerizable compound, a heater and a nitrogen gas introducing device. 10 parts by weight of a water-soluble polymer SMA1625A (styrene-maleic acid resin; manufactured by Fujiyoshii Tsusho) as an emulsifier and 20 parts by weight of J-62 (styrene-acrylic water-soluble polymer; manufactured by Johnson Polymer Co., Ltd.) 0.5 parts by weight of sodium persulfate was charged, the gas phase was replaced with nitrogen gas for 15 minutes, and the temperature was raised to 75 ° C.

Then, an emulsion consisting of the following components was continuously added from another container over 3 hours to carry out emulsion polymerization. (a) Styrene as an aromatic vinyl compound; 60 parts by weight,
α-methylstyrene; 10 parts by weight, (b) 2-ethylhexyl acrylate as an alkyl (meth) acrylate having an alkyl group having 8 or more carbon atoms; 30 parts by weight After the addition of the emulsion is completed, it is further heated at 85 to 95 ° C. for 2 hours. After aging, it was cooled to 25 ° C. and adjusted with water so that the solid content concentration became 50% by weight.

Then, the mixture was filtered through a 200-mesh wire net to obtain an acrylic copolymer emulsion (1). Preparation of Water Dispersion Composition Acrylic Copolymer Emulsion (1) Obtained Above
J-6 as [B] water-soluble polymer premixed with 100 parts by weight (as solids part) while stirring
After gradually adding a mixture of 30 parts by weight of 79 (styrene acrylic water-soluble polymer; manufactured by Johnson Polymer Co., Ltd.) and 10 parts by weight of glycerin as [C] polyhydric alcohol, then [D] polyvalent metal. 1 part by weight (as metal ion weight) of aluminum chelate D (aluminum monoacetylacetonate bis (ethyl acetate)); Kawaken Fine Chemical Co., Ltd.) as a compound was added.

Preparation of coating material While stirring 20 parts by weight (as solid part weight) of the aqueous dispersion composition obtained as described above, 15 parts by weight of ethanol was added thereto, and phthalocyanine blue was further added as a pigment. After adding 13 parts by weight, water was added so that the total amount was 100 parts by weight, and the mixture was stirred for 15 minutes or more.

Furthermore, a coating material (water-based printing ink) was obtained by mixing the above-mentioned composition in a sand mill for 1 hour. Preparation of coating test piece The aqueous printing ink obtained as described above was coated on a corona discharge treated polyethylene film surface with a bar coater to a film thickness of about 5 μm, and then at 25 ° C., 6
A coating film was formed by leaving it in an atmosphere of 3% RH for 24 hours to obtain a coating test piece.

The characteristics as described above were evaluated for the obtained test pieces. The results are shown in Table 1.

[0116]

Comparative Example 1 An acrylic copolymer emulsion was obtained in the same manner as in Example 1 except that the polymerizable compound was used in the types and amounts shown in Table 1.

Further, an aqueous dispersion composition was obtained in the same manner as in Example 1 except that each component was used in the types and amounts shown in Table 1. A coating material and a test piece were obtained from this aqueous dispersion composition in the same manner as in Example 1. The results are shown in Table 1.

In Comparative Example 1, the aqueous dispersion composition was
(a) An acrylic copolymer emulsion containing an aromatic vinyl compound in an amount of more than 80% by weight was contained, and the coating film formed from this aqueous dispersion composition was inferior in flexibility.

[0119]

Example 2 An acrylic copolymer emulsion (2) was obtained in the same manner as in Example 1 except that the polymerizable compound was used in the types and amounts shown in Table 1.

In Example 1, the acrylic copolymer emulsion (1) was replaced with (2), and the water-soluble polymer [B] was J-62 (styrene-acrylic water-soluble polymer; Johnson Polymer Co., Ltd.). Manufactured by Kawaken Fine Chemical Co., Ltd., and glycerin was used in an amount as shown in Table 1 instead of aluminum chelate A (aluminum tris (acetylacetonate)); manufactured by Kawaken Fine Chemical Co., Ltd. An aqueous dispersion composition was obtained in the same manner as in Example 1 except for the above.

A coating material and a test piece were obtained from this aqueous dispersion composition in the same manner as in Example 1. The results are shown in Table 1.

[0122]

Comparative Example 2 An acrylic copolymer emulsion was obtained in the same manner as in Example 2 except that the polymerizable compound was used in the types and amounts shown in Table 1.

Further, an aqueous dispersion composition was obtained in the same manner as in Example 2 except that each component was used in the types and amounts shown in Table 1. A coating material and a test piece were obtained from this aqueous dispersion composition in the same manner as in Example 2. The results are shown in Table 1.

When the aqueous dispersion composition of Comparative Example 2 was formed, (b) an acrylic copolymer in which the amount of alkyl (meth) acrylate having an alkyl group having 8 or more carbon atoms was less than 10% by weight. Although it contained an emulsion, the coating film formed from the obtained aqueous dispersion composition was inferior in flexibility.

[0125]

Comparative Example 3 An acrylic copolymer emulsion was obtained in the same manner as in Example 2, except that the polymerizable compound was used in the types and amounts shown in Table 1.

Further, an aqueous dispersion composition was obtained in the same manner as in Example 2 except that each component was used in the types and amounts shown in Table 1. A coating material and a test piece were obtained from this aqueous dispersion composition in the same manner as in Example 2. The results are shown in Table 1.

In forming the aqueous dispersion composition of Comparative Example 3, (b) an acrylic copolymer in which the amount of alkyl (meth) acrylate having an alkyl group having 8 or more carbon atoms exceeds 80% by weight. Although it contained an emulsion, the coating film formed from the obtained water dispersion composition had poor water resistance.

[0128]

[Table 1]

[0129]

Example 3 Preparation of Acrylic Copolymer Emulsion (3) 90 parts by weight of water was added to a stainless steel autoclave equipped with a stirrer, a thermometer, a pump for introducing a polymerizable compound, a heater and a nitrogen gas introducing device. 0.5 parts by weight of polyoxyethylene alkylphenol allyl glycerin ether sulfate and 0.3 parts by weight of sodium persulfate were charged, the gas phase was replaced with nitrogen gas for 15 minutes, and then the temperature was raised to 75 ° C.

Then, an emulsion consisting of the following components was continuously added from another container over 3 hours to carry out emulsion polymerization. (a) Styrene as an aromatic vinyl compound; 15 parts by weight, (b) 2-Ethylhexyl acrylate as an alkyl (meth) acrylate having an alkyl group having 8 or more carbon atoms, 15 parts by weight, (c) Other ethylenically unsaturated Methyl methacrylate as a compound; 30 parts by weight, n-butyl acrylate; 36 parts by weight, hydroxyethyl methacrylate; 3 parts by weight, N-methylol acrylamide; 1 part by weight, alkylallyl sulfosuccinate salt; 2 parts by weight, water; 40 parts by weight After completion of addition of the emulsion, the mixture was aged at 85 to 95 ° C. for 2 hours, cooled to 25 ° C., and then pH was adjusted with aqueous ammonia.
After adjusting to 8, it was adjusted to 50% by weight of solid content with water.

Then, the mixture was filtered through a 200-mesh wire net to obtain an acrylic copolymer emulsion (3). Preparation of Water Dispersion Composition In Example 1, the acrylic copolymer emulsion (1) was replaced with (3), the component [C] was replaced with pentaerythritol, and each component was added in the amounts shown in Table 2. An aqueous dispersion composition was obtained in the same manner as in Example 1 except that it was used.

A coating material and a test piece were obtained from this aqueous dispersion composition in the same manner as in Example 1. Table 2 shows the results.

[0133]

Example 4 Preparation of Polysilane Complex Emulsion 100 parts by weight of the acrylic copolymer emulsion (3) obtained in Example 3 was placed in a stainless steel autoclave equipped with a stirrer, a thermometer, a heater and a nitrogen gas introducing device. Parts (as solid part weight) and 10 parts by weight of methyltriethoxysilane as organosilane were charged, the gas phase part was replaced with nitrogen gas for 15 minutes, and then stirred at 25 ° C. for 30 minutes to prepare methyltriethoxysilane. Absorbed in (3).

Next, the temperature was raised to 80 ° C., the condensation reaction was carried out for 5 hours, the temperature was cooled to 25 ° C., and the mixture was filtered through a 200-mesh wire net to obtain a polysilane complex emulsion. Preparation of Aqueous Dispersion Composition An aqueous dispersion composition was prepared in the same manner as in Example 3 except that the acrylic copolymer emulsion (3) was replaced with the polysilane complex emulsion obtained above. Obtained.

A coating material and a test piece were obtained from this aqueous dispersion composition in the same manner as in Example 3. Table 2 shows the results.

[0136]

Comparative Example 4 In Example 4, organosilane was used in Table 2
A polysilane complex emulsion was obtained in the same manner as in Example 4 except that the amount was used as shown in.

Further, an aqueous dispersion composition was obtained in the same manner as in Example 4 except that each component was used in the types and amounts shown in Table 2. A coating material and a test piece were obtained from this aqueous dispersion composition in the same manner as in Example 4. Table 2 shows the results.

When the aqueous dispersion composition of Comparative Example 4 was formed, the amount of organosilane was 500 with respect to 100 parts by weight (solid part weight) of the acrylic copolymer emulsion.
Although the polysilane complex emulsion is used in an amount of more than 1 part by weight, the obtained aqueous dispersion composition is inferior in storage stability.

[0139]

[Table 2]

[0140]

Comparative Examples 5 to 6 An aqueous dispersion composition was obtained in the same manner as in Example 3 except that the amount of the water-soluble polymer [B] shown in Table 3 was used.

A coating material and a test piece were obtained from this aqueous dispersion composition in the same manner as in Example 3. The results are shown in Table 3. The water dispersion composition obtained in Comparative Example 5 contained 100 parts of [B] water-soluble polymer (component [A-1] (solid part)).
Was less than 1 part by weight, and the resolubility was poor. On the other hand, in the water dispersion composition obtained in Comparative Example 6, the amount of the [B] water-soluble polymer exceeded 200 parts by weight, and the coating film obtained from this water dispersion composition had a water resistance strength. Was inferior to

[0142]

Comparative Examples 7 to 8 An aqueous dispersion composition was obtained in the same manner as in Example 1 except that [C] polyhydric alcohol was used in the amounts shown in Table 3.

A coating material and a test piece were obtained from this aqueous dispersion composition in the same manner as in Example 1. The results are shown in Table 3. The water dispersion composition obtained in Comparative Example 7 contained the amount of [C] polyhydric alcohol (component [A-1] (solid part) 10) in the composition.
(Relative to 0 part by weight) was less than 1 part by weight, and the redissolvability was poor. On the other hand, in the water dispersion composition obtained in Comparative Example 8, the amount of this [C] polyhydric alcohol exceeded 200 parts by weight, and the coating film obtained from this water dispersion composition had a water resistance strength. It was inferior.

[0144]

Comparative Examples 9 to 10 Example 1 was repeated except that [D] polyvalent metal compound was used in the amounts shown in Table 3.
An aqueous dispersion composition was obtained in the same manner as.

A coating material and a test piece were obtained from this aqueous dispersion composition in the same manner as in Example 1. The results are shown in Table 3. The water dispersion composition obtained in Comparative Example 9 contained 10 parts of the [D] polyvalent metal compound (component [A-1] (solid part)).
(Based on 0 parts by weight) was less than 0.1 parts by weight (as metal ions), and the coating film obtained from this water dispersion composition had poor water resistance. On the other hand, in the aqueous dispersion composition obtained in Comparative Example 10, the amount of this [D] polyvalent metal compound was 10
It was more than part by weight and was poor in redissolvability.

[0146]

[Table 3]

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location C08L 101/14 LTB C09D 11/10 PTK (72) Inventor Akio Hiraharu 2-chome Tsukiji, Chuo-ku, Tokyo 11-24 No. 24 within Nippon Synthetic Rubber Co., Ltd.

Claims (2)

[Claims] 1. [A-1] (a) aromatic vinyl compound; 10 to 8
0% by weight, (b) an alkyl (meth) acrylate having an alkyl group having 8 or more carbon atoms; 10 to 80% by weight,
(c) Other ethylenically unsaturated compounds copolymerizable with (a) and (b) above; 0 to 80% by weight [(a) + (b) + (c) total 1
00% by weight] and an acrylic copolymer emulsion containing an acrylic copolymer obtained by copolymerization with the solid content of 10 in the acrylic copolymer emulsion [A-1].
[B] water-soluble polymer; 1 to 200 parts by weight, [C] polyhydric alcohol; 1 to 200 parts by weight, and [D] polyvalent metal compound; 0.1 to 10 parts by weight relative to 0 parts by weight. Parts (as weight of metal ions). 2. [A-2] (a) aromatic vinyl compound; 10 to 8
0% by weight, (b) an alkyl (meth) acrylate having an alkyl group having 8 or more carbon atoms; 10 to 80% by weight, (c) another ethylene copolymerizable with the above (a) or (b). 0-80 wt% [(a) + (b) + (c) total is 1]
In the presence of an acrylic copolymer emulsion containing an acrylic copolymer obtained by copolymerizing the organosilane with 100 parts by weight of the organosilane emulsion to 100 parts by weight of the acrylic copolymer emulsion. Polysilane complex emulsion obtained by condensation reaction in an amount of ˜500 parts by weight, and solid content of 100 in polysilane complex emulsion [A-2]
1 to 200 parts by weight of [B] water-soluble polymer, 1 to 200 parts by weight of [C] polyhydric alcohol, and 0.1 to 10 parts by weight of [D] polyvalent metal compound based on parts by weight. (As metal ion weight).