JPH03281679A - Dispersion for coating and its composition - Google Patents

Abstract

PURPOSE:To obtain the title dispersion which has excellent storage stability and gives a coating film excellent in hot water resistance, flexibility, adhesion, water repellency, and lubricating properties by allowing a specified copolymer to absorb an alkoxysilane in the presence of a water-soluble polymer and subjecting the alkoxysilane to condensation. CONSTITUTION:In the presence of 1-100 pts.wt. water-soluble polymer (A) (e.g. PVA), a copolymer (B) obtained by the emulsion polymerization of a monomer mixture containing 1-40 pts.wt. hydroxyalkyl (meth)acrylate (a), 5-75 pts.wt. aromatic vinyl monomer (b), 20-55 pts.wt. alkyl (meth)acrylate (c), and 0-14 pts.wt. ethylenically unsaturated monomer copolymerizable with (a) (b), and (c) ((a+b+c+d)=100 pts.wt.) is allowed to absorb an alkoxysilane (C) in an amount of 0.1-500 pts.wt. based on 100 pts.wt. (A+B), and component C is subjected to condensation to give the title dispersion containing compound polysiloxane particles.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention can be used as a coating agent for metals, plastics, wood, ceramics, etc., and is particularly preferably used for coating metals such as cans, aluminum sashes, and pre-coated metals. The present invention relates to coating dispersions and compositions thereof that have excellent storage stability, hot water resistance, flexibility, adhesion, lubricity, and water repellency.

[Prior Art] In recent years, solvent-based or organic solvent-containing water-based compositions have been proposed in which the lubricity and water repellency of the coating film are improved by incorporating polysiloxane into the coating agent (for example, Japanese Patent Application Laid-Open No. Publication No. 62-232468, No. 63-1627
Publication No. 72, etc.).

However, in view of pollution caused by solvents, health and safety, resource conservation, etc., it is desired to move to water-based systems that do not contain solvents or use as little solvent as possible, and the above proposal does not sufficiently reduce the amount of solvent used. Therefore, in the storage of hazardous materials,
Alternatively, safety and health issues remain during painting work.

In addition, in aqueous systems, there are problems with polymerization stability and storage stability due to the poor compatibility balance between polysiloxane, polymer, and water.Furthermore, due to the poor dispersibility of polysiloxane, sufficient hot water resistance and flexural stability are required. A coating film with good properties cannot be obtained.

[Problem to be solved by the invention]

The present invention was made against the background of the above-mentioned conventional technical problems, and has no problems in terms of storage stability, safety and hygiene, and has excellent physical properties of a coating film such as adhesion, hot water resistance, flexibility, slipperiness, and water repellency. The object of the present invention is to provide a coating dispersion and a composition thereof.

[Means to solve the problem]

The present invention comprises (a) 1 to 40 parts by weight of hydroxyalkyl (meth)acrylate, (b) 5 to 75 parts by weight of aromatic vinyl monomer in the presence of 1 to 100 parts by weight of water-soluble polymer (I). , (c) alkyl (meth)acrylate 20-55
parts by weight and (d) 0 to 14 parts by weight of an ethylenically unsaturated monomer copolymerizable with the above (a) to (c) (however, (a)
) ± (b) + (c) + (d) = 100 parts by weight), alkoxysilane (III) was added to the copolymer obtained by emulsion polymerization of 100% component (II) containing component (1) and (
n) After absorbing 0.1 to 500 parts by weight per 100 parts by weight of components in total, the condensation reaction of the alkoxysilane is allowed to proceed, thereby making it possible to contain polysiloxane composite particles in which polysiloxane is composited. The present invention provides a coating dispersion liquid (hereinafter referred to as "Dispersion ■") having characteristics.

Further, the present invention provides (a) water-soluble polymer (1) 1 to 100
In the presence of parts by weight, (a) hydroxyalkyl (meth)
1 to 40 parts by weight of acrylate, (1)) 5 to 75 parts by weight of aromatic vinyl monomer, (c) 20 to 55 parts by weight of alkyl (meth)acrylate, and (d) the above (a) to (c).
0 to 14 parts by weight of an ethylenically unsaturated monomer copolymerizable with
A monomer component (II) containing 0 parts by weight) and an amino resin (IV) obtained by emulsion polymerization of a charging component consisting of 0 to 100 parts by weight per 100 parts by weight of the total amount of components (1) and (II). After absorbing 0.1 to 500 parts by weight of alkoxysilane (I[l) per 100 parts by weight of the total amount of components (1) and (II) into the copolymer, a condensation reaction of the alkoxysilane is carried out. By progressing, a dispersion containing polysiloxane composite particles made of polysiloxane (hereinafter referred to as "dispersion ■"),
(hereinafter referred to as "coating dispersion") and (b) amino resin (hereinafter referred to as "(b) )
Amino resin (IV) and (b) amino resin are collectively referred to as "amino resin")
0 to 100 parts by weight and optionally 0 polyvalent metal compound
．． A coating dispersion composition (hereinafter referred to as "
Dispersion Composition (2)", and Dispersion Composition (2) and Dispersion Composition (2) to be described later may be collectively referred to as "Dispersion Composition for Coating").

The water-soluble polymer (1) used in the present invention is not particularly limited, but includes polyvinyl alcohol, polyacrylate, water-soluble (meth)acrylic acid ester copolymer, and styrene-maleic acid copolymer. Examples include coalescent salts, styrene-(meth)acrylic acid copolymer salts, poly(meth)acrylamide, and poly(meth)acrylamide copolymers.

The water-soluble polymer (I) is preferably partially saponified polyvinyl alcohol, water-soluble (meth)acrylic acid ester copolymer, styrene-maleic acid copolymer salt, or styrene-(meth)acrylic acid copolymer. Examples include salts of carboxylated aromatic vinyl copolymers such as polymer salts.

The amount of water-soluble polymer (1) to be used is the monomer component (I
I) 1 to 100 parts by weight, preferably 3 to 80 parts by weight, and more preferably 5 to 60 parts by weight per 100 parts by weight; less than 1 part by weight results in poor hot water resistance and adhesion; If it exceeds it, the hot water resistance will be poor.

The coating dispersion of the present invention comprises a monomer component (II) containing the components (a) to (d) and, if necessary, an amine resin (IV) in a specific ratio in the presence of the polymer (1). It is obtained by absorbing alkoxysilane (III) into a copolymer obtained by emulsion polymerization and subjecting it to a condensation reaction.

Here, (a) hydroxyalkyl (meth)acrylate includes hydroxymethyl (meth)acrylate,
Examples include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyamyl (meth)acrylate, hydroxyhexyl (meth)acrylate, and preferably hydroxyethyl (meth)acrylate, hydroxy Propyl (meth)acrylate.

This component (a) contains 1 to 4
0% by weight, preferably 5 to 35% by weight, more preferably 10 to 30% by weight; less than 1% by weight reduces the number of crosslinking points, resulting in poor hot water resistance of the coating, while more than 40% by weight This results in poor flexibility and hot water resistance of the coating film.

In addition, (b) aromatic vinyl monomers include, for example, styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene,
Methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, 4-ethylstyrene, 4-ethoxystyrene, 3,4-dimethylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-
Examples include chloro-3-methylstyrene, 4-t-butylstyrene, 2°.4-dichlorostyrene, 2,6-dichlorostyrene, 1-vinylnaphthalene, divinylbenzene, and styrene is particularly preferably used.

The amount of the component (20) in the monomer component (II) is 5 to 75% by weight, preferably 10 to 60% by weight, and more preferably 20 to 50% by weight. If it is less than 5% by weight, the hot water resistance of the coating film will deteriorate. On the other hand, if it exceeds 75% by weight, the flexibility will be poor.

Furthermore, (c) alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (
meth)acrylate, i-butyl(meth)acrylate, t-butyl(meth)acrylate, amyl(meth)acrylate, i-amyl(meth)acrylate, hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, n-octyl Examples include (meth)acrylate, preferably those in which the alkyl group has 1 to 8 carbon atoms, and more preferably methyl methacrylate, ethyl (meth)acrylate, etc.
meth)acrylate and butyl(meth)acrylate.

This component (c) contains 20 to 5
The content is 5% by weight, preferably 25 to 55% by weight, and more preferably 35 to 50% by weight. If it is less than 20% by weight, the flexibility will be poor, while if it exceeds 55% by weight, the hot water resistance will be poor.

Furthermore, (d) ethylenically unsaturated monomers copolymerizable with the above (a) to (c) include (meth)acrylic acid, fumaric acid, itaconic acid, monoalkylitaconate, maleic acid, and crotonic acid. , αβ-unsaturated carboxylic acids such as 2-methacryloyloxyethyl hexahydrophthalic acid,
Epoxy compounds such as allyl glycidyl ether, glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, divinylbenzene, ethylene glycol di(meth)acrylate, diethylene glycol di(
meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate
acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, ) acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and other polyfunctional monomers, (
meth)acrylamide, N-methylol(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N,N
'-Acid amide compounds such as methylenebisacrylamide, tiacetone acrylamide, maleic acid amide, maleimide, vinyl compounds such as vinyl chloride, vinylidene chloride, fatty acid vinyl ester, trifluoroethyl (meth)acrylate, pentadecafluorooctyl (meth) Examples include fluorine atom-containing monomers such as acrylate, T-methacryloylpropane trimethoxysilane, and silicone compounds such as reactive silicones such as Silabrene FM0711 manufactured by Chisso ■, which may be used alone or in combination of two or more. can do.

This component (d) is present in the monomer component (II) from 0 to 14
, weight %, preferably 0 to 10 weight %, more preferably 0. The content is 5 to 5% by weight, and if it exceeds 14% by weight, it is undesirable as it may deteriorate hot water resistance or increase the amount of coagulated material ordered during emulsion polymerization.

Furthermore, examples of the amino resin (IV) include fully alkyl-type methylated melamine resins such as hexamethoxymethylated melamine resins, partially alkylated methylated melamine resins, benzoguanamine resins, and alkyl etherified urea resins.

Note that this amino resin (IV) may be added during the polymerization step, or may be added after the polymerization, or furthermore, a part may be added during the polymerization step and the remainder may be added after the polymerization.

The amount of amino resin (IV) added in the polymerization process is (
The amount is 0 to 100 parts by weight per 100 iE parts in total of component 1) and component (II). When amino resin (IV) is added during the polymerization process of latex, a product with much better hot water resistance can be obtained than when added after polymerization. In order to obtain the effect of adding the amino resin (IV) to the polymerization step, the amount is preferably 5 to 100 parts by weight, more preferably 10 to 100 parts by weight.

The amino resin (IV) can be added, for example, by dissolving it in the monomer component (n), or by adding the amino resin (IV) to the reactor in advance and adding the monomer component in the presence of the amino resin (IV). Examples include a method of polymerizing component (II).

Emulsion polymerization in the present invention can be carried out under normal emulsion polymerization conditions. For example, a water-soluble polymer (
I), monomer component (II), amino resin (IV) used as necessary, emulsifier, polymerization initiator, chain transfer agent, chelating agent, pH adjuster, etc. are added, and the temperature is 30~
The reaction is carried out at 100''C for about 1 to 30 hours.

Here, the emulsifier used as necessary is anionic, nonionic, or a combination of anionic and nonionic, and in some cases, amphoteric surfactants and cationic surfactants are also used. be able to.

Examples of the anionic emulsifier include higher alcohol sulfuric ester sodium salt, alkylhenzenesulfonic acid sodium salt, succinic acid dialkyl ester sulfonic acid sodium salt, and sodium alkyl diphenyl ether disulfonate. Among these, sodium dodecylhenzenesulfonate, 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. −
For boat fishing, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, and the like are used as nonionic emulsifiers.

Lauryl betaine is suitable as an amphoteric emulsifier.

As the cationic surfactant, alkylpyridinyl chloride, alkylammonium chloride, etc. can be used.

Furthermore, so-called reactive emulsifiers, such as sodium styrene sulfonate and sodium allyl alkyl sulfonate, which are copolymerized with the monomer constituting the monomer component (n), may also be used as the emulsifier.

The amount of emulsifier used is usually monomer component (If) 100
The amount is 0 to 5 parts by weight, but from the viewpoint of hot water resistance, soap-free systems and systems using reactive emulsifiers are preferred.

As the polymerization initiator, for example, water-soluble persulfates, hydrogen peroxide, etc. can be used, and depending on the case, they can be used in combination with a reducing agent.

Examples of the reducing agent include sodium pyrobisulfite, sodium hydrogensulfite, sodium thiosulfate, L-ascorbic acid and its salts, and sodium formaldehyde sulfoxylate.

In addition, oil-soluble polymerization initiators such as 2,2'-abbisisobutyronitrile, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis-2, 4-dimethylvaleronitrile, 11'-azobis-cyclohexane-1-carbonitrile, benzoyl peroxide, dibutyl peroxide, cumene hydroperoxide, etc. can be used as monomers or dissolved in a solvent. Preferred oil-soluble polymerization initiators include cumene hydroperoxide, isopropylbenzene hydroperoxide, paramenthane hydroperoxide, azobisisobutyronitrile, benzoyl peroxide, L-butyl hydroperoxide, 3,5.5- Examples include trimethylhexanol peroxide and t-butylperoxy (2-ethylhexanoate).

The amount of these polymerization initiators used is based on the monomer component (It)
The amount is approximately 0.1 to 3 parts by weight per 100 parts by weight.

Chain transfer agents include halogenated hydrocarbons (e.g., quaternary carbon, chloroform, bromoform), mercaptans (e.g., n-dodecylmercaptan, t-dodecylmercaptan, n-octylmercaptan), xanthogens (e.g., dimethylxanthogen). disulfide, diisobrobyl xanthogen disulfide), terpenes (e.g. dipentene, turbinolene), α-
Methylstyrene dimer [2,4-diphenyl 4-methyl-1-pentene (a+), 2-4-diphenyl-4
-methyl-pentene (a, ), and at least one of 1-1-3-trimethyl-3-phenylindan (a3)
consisting of seeds, preferably (al)/(a2) and/
or (a3) (weight ratio) -40 to 10010 to 60]
, unsaturated cyclic hydrocarbon compounds (e.g., 9.10-dihydroanthracene, 1,4-dihydronaphthalene, indene, 1,4-cyclohexadiene), unsaturated heterocyclic compounds (e.g., xanthine, 25-dihydrofuran) etc. can be mentioned.

The amount of chain transfer agent used is about 0 to 5 parts by weight per 100 parts by weight of monomer component (n).

Examples of the chelating agent include glycine, alanine, and ethylenediaminetetraacetic acid, and examples of the pH adjuster include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and ammonia. The amounts of the chelating agent and the pHmFl adjuster used are approximately 0 to 0.1 parts by weight and 0 to 3 parts by weight, respectively, per 100 parts by weight of the hexamer component (II).

In addition, as a solvent used as necessary during emulsion polymerization, a small amount of methyl ethyl ketone,
Acetone, trichlorotrifluoroethane, methyl isobutyl ketone, dimethyl sulfoxide, toluene, dibutyl phthalate, methylpyrrolidone, ethyl acetate, alcohols, cellosolves, carbinols, etc. are used. The amount of this solvent used is 1
It is about 0 to 10 parts by weight per 00 parts by weight.

The emulsion polymerization in the present invention can be carried out by a known method, for example, a method in which the entire amount of the monomer component (II) is charged into the reaction system in the presence of the water-soluble polymer (1), or a method in which a portion of the monomer component (n) is added to the reaction system. After charging and reacting, the remaining monomer component (I
I) Continuously or dividedly charging method, monomer component (
This can be carried out by a method of continuously charging II), a method of adding the water-soluble polymer (1) in portions or continuously during the reaction of the monomer component (n), and the like.

In addition, when using the amino resin (IV) in the reaction step, it may be added in combination with the water-soluble polymer (I), or it may be added in the various methods described above with the monomer component (II). Examples include a method of adding in a similar manner, a method of adding by dissolving in the hexamer component (It) added by various methods, and a method of adding by combining at least two of these methods.

In addition, the glass transition temperature (Tg) of the copolymer in the copolymer dispersion obtained in this way is -40 to 90°C1
Preferably -20 to 90''C2, more preferably 40
-90°C, particularly preferably 50-75°C, -4
If the temperature is less than 0°C, the hardness will be poor, while if it exceeds 90°C, the flexibility will be poor.

Further, the toluene insoluble content of the entire copolymer dispersion obtained (corresponds to the total solid content of the copolymer dispersion; the same applies hereinafter) is 98% or less, preferably 40 to 98%, more preferably 60 to 98%. It is 95%, particularly preferably 70 to 95%, and if it exceeds 98%, the hot water resistance will be poor.

Furthermore, the acid value of the entire dispersion obtained is preferably 2 to 2.
60, more preferably 5-50, particularly preferably 5-50
If it is less than 2, the adhesion may be poor, while if it exceeds 60, the hot water resistance may not be sufficient.

Furthermore, the water-soluble polymer (1) and the monomer component (II
) The weight average molecular weight of the entire copolymer obtained by copolymerizing is preferably 200,000 or more, more preferably 300,000 or more, particularly preferably 40% or more, and if it is less than 200,000, the hot water resistance is insufficient. There is.

The alkoxysilane (I[l) to be absorbed as a seed with the copolymer obtained in this way has the formula -i RゎSi
(OR')=-, (wherein, R is an organic group having 1 to 8 carbon atoms, R' is an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 4 carbon atoms.
acyl group, n represents an integer of O to 3).

In the formula, R is an organic group having 1 to 8 carbon atoms, such as an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and a T-chloropropyl group or a T-chloropropyl group.
Chloropropyl group, vinyl group, 3.3.3-trifluoropropyl group, T-glycidoxypropyl group, γ-methacryloxypropyl group, γ-mercaptopropyl group, phenyl group, 3.4-epoxycyclohexylethyl group ,
Examples include T-aminopropyl group.

In the formula, R' is an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms, such as a methyl group, ethyl group, n-propyl group, n-acyl group, 5ec-butyl group. , t-butyl group, acetyl group, etc.

If the number of carbon atoms in R or R' in the formula becomes large, the water solubility decreases and the absorption rate of the alkoxysilane to the copolymer as a seed decreases, which is not preferable.

Specific examples of these alkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and n-propyltrimethoxysilane. Methoxysilane, n-propyltriethoxysilane,
i-propyltrimethoxysilane, i-propyltriethoxysilane, T-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3,3.
3-trifluoropropyltrimethoxysilane, 3,3.
3-) Lifluoropropyltriethoxysilane, T-glycidoxypropyltrimethoxysilane, T-glycidoxypropyltriethoxysilane, T-methacryloxypropyltrimethoxysilane, T-methacryloxypropyltriethoxysilane, γ -Mercaptopropyltrimethoxysilane, T-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, T-aminopropyltrimethoxysilane, 3.4-epoxycyclohexylethyltrimethoxysilane, 3.4-epoxycyclohexyl Examples include ethyltriethoxysilane, dimethyldimethoxysilane, dimethyljethoxysilane, diethyldimethoxysilane, etc., and preferred are tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, and dimethyljethoxysilane. Toxisilane. These alkoxysilanes can be used alone or in combination of two or more.

In the present invention, the amount of alkoxysilane (III) absorbed into the copolymer serving as a seed is 0.1 to 100 parts by weight in total of components (1) and (n) in the copolymer. 500 parts by weight, preferably 0.5-25
0 parts by weight, more preferably 1.0 to 100 parts by weight, less than 0.1 parts by weight will result in poor adhesion, water repellency, and slipperiness, while more than 500 parts by weight will result in poor flexibility and storage stability. Become something.

In the present invention, the method for absorbing the alkoxysilane into the copolymer can be easily achieved by adding the alkoxysilane to the copolymer dispersion in which the copolymer is dispersed and stirring well. be done.

In order to efficiently absorb the alkoxysilane into the copolymer serving as a seed, it is also possible to absorb a solvent having a solubility in water of 10-3% by weight or less into the copolymer in advance, if necessary. It is.

In addition, in order to prevent the reaction from proceeding without sufficient absorption of the alkoxysilane, the copolymer dispersion should be adjusted to a pH of 4 to 1.
0, preferably pH 5 to 9, more preferably pH 6 to
8 and the temperature is below 90°C, preferably 70°C
Hereinafter, it is desirable to add and absorb the alkoxysilane under conditions, more preferably at 50°C or lower, particularly preferably at 30°C or lower.

The condensation reaction of the alkoxysilane absorbed into the copolymer can be easily controlled by changing the reaction temperature and hydrogen ion concentration, and the degree of polymerization of the polysiloxane can be adjusted.

The condensation reaction of alkoxysilane can be carried out at a temperature of 30°C or higher, preferably 50°C or higher, more preferably 70°C or higher.

The average particle size of the polysiloxane composite particles thus obtained is usually 0.03 to 0.5 μm, preferably 0.03 μm to 0.5 μm.
05 to 0.3 μm, more preferably 0.05 to 0.2
If it is less than 0.03 μm, the viscosity of the dispersion will increase, and only a low solids dispersion can be obtained, and if the mechanical shear is severe due to the usage conditions, coagulation will occur, which is undesirable. On the other hand, if it exceeds 0.5 μm, the storage stability of the dispersion becomes poor, which is not preferable.

Adjustment of this average particle size is based on the amount of water-soluble polymer (1) used,
This is done by appropriately selecting the amount of emulsifier, the amount of alkoxysilane absorbed, etc.

Since the coating dispersion of the present invention has excellent hot water resistance and adhesion to a substrate, it can be used for coating without adding an amino resin.

However, when the amino resin is included, a coating dispersion composition with even better hot water resistance, flexibility, hardness, and adhesion to a substrate can be obtained.

The method of adding the amino resin is not particularly limited, but there is a method of adding the amino resin (IV) during the polymerization process of the dispersion liquid (2), a method of adding the amino resin (IV) to the dispersion liquid (2) after polymerization, Examples include a method of adding or a method of adding both.

The amount of the amino resin used is based on 100 parts by weight of the total amount of the water-soluble polymer (1) of the present invention and the 7-mer component (II).
The amino resin (IV) is 0 to 100 parts by weight, the amino resin (b) is 0 to 100 parts by weight, and the component (IV) and (
b) The total amount of components is 2 to 100 parts by weight, preferably 10 parts by weight.
~80 parts by weight, more preferably 15 to 50 parts by weight; less than 2 parts by weight results in poor hardness and hot water resistance;
If it exceeds 0 parts by weight, flexibility may be poor.

Furthermore, when a polyvalent metal compound salt is added to the dispersion composition (1) containing the amino resin, a tough coating film can be obtained due to the crosslinking effect, and the hot water resistance, flexibility, hardness, and adhesion to the substrate can be further improved. An excellent dispersion composition (2) is obtained.

Examples of the polyvalent metal compounds include oxides and salts of zinc, zirconium, magnesium, copper, iron, cobalt, nickel, aluminum, cadmium, and titanium, carbonic acid, acetic acid, formic acid, glutaric acid, benzoic acid, and oxalic acid. or by diluting an aqueous solution of these acids and polyvalent metal compounds with ammonia, amine, etc.
It can be obtained by adjusting H to 7 to 11, and can also include metal ion forms. Preferred polyvalent metal compounds are zinc ammonium carbonate, ammonium zirconate carbonate, zinc, zirconium oxides or salts.

The amines capable of forming a complex include morpholine, monoethanolamine, ethylenediamine, and diethylaminoethanol.

In addition, complexing agents such as combrexane such as ethylenediaminetetraacetate, glycine, alanine, etc. can also be used.

This dispersion composition (2) containing a polyvalent metal compound consists of a dispersion composition (2) containing an amino resin and a polyvalent metal compound, and the amount of the polyvalent metal compound used is determined by Total amount of polymer (1) and monomer component (II) 1
0.00 parts by weight, 0.05 to 20 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.3 to 5 parts by weight, and if it is less than 0.05 parts by weight, the hot water resistance is poor;
If it exceeds 20 parts by weight, flexibility and storage stability will deteriorate.

The following additives can be added to the dispersion liquid (1) and dispersion liquid compositions (2) to (2) of the present invention depending on the purpose.

The amount of this additive added is 50 parts by weight or less, preferably 40 parts by weight, based on the total of 100 parts by weight of the water-soluble polymer (1) and the hexamer component (II) of the aqueous copolymer dispersion for coating. It is as follows.

These additives include methyl alcohol, ethyl alcohol, propyl alcohol, methyl alcohol, amyl alcohol,
Alcohols such as hexyl alcohol, methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve, hexyl cellosolve, methyl calpitol, ethyl calpitol, methyl cellosolve acetate,
Organic solvents such as ethyl cellosolve acetate and tributoxymethyl phosphate can be used. The amount of this organic solvent used is 0% in the total dispersion or composition.
-20% by weight, preferably 0-10% by weight, more preferably 0-5% by weight.

In addition, additives other than the above-mentioned additives include the water-based polymer (1) as the water-based resin, other commonly used water-soluble polyester resins, water-soluble or water-dispersible epoxy resins, water-soluble or water-dispersible epoxy resins, In addition to carboxylated aromatic vinyl resins such as acrylic resins, styrene-maleic acid resins, urethane resins, lubricants, antifoaming agents, wetting agents, leveling agents, pigments, etc. can be used.

The coating dispersion and coating dispersion composition of the present invention form coatings with excellent hot water resistance, flexibility, hardness, and adhesion to substrates, so they can be used for coating metals, plastics, wood, ceramics, etc. coating agents, particularly preferably for undercoating and topcoating of cans, aluminum sash, pre-coated metal, etc.;
It can be used for electrodeposition paints, etc.

〔Example〕

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples unless the gist thereof is exceeded.

In addition, in the examples, parts and percentages indicating proportions are based on weight. In addition, measurements of various physical properties in Examples were based on the following methods.

(2) Expressed as the number of milligrams of potassium hydroxide required to neutralize 1 g of the entire coating dispersion.

Transformation Kei The conversion rate of alkoxysilane was measured by gravimetric method.

Silenced water 1 Place the test piece in an autoclave so that it is partially immersed in water, and heat it at 125°C for 30 minutes (hereinafter referred to as "
After treatment with hot water (referred to as "hot water treatment"), it was taken out and its appearance and adhesion were measured.

A test piece that did not whiten and had a good appearance was rated as ◎, one that did not whiten and had a normal appearance was rated O1, one that was slightly whitened was rated as △, and one that whitened was rated as ×.

Using a core rod with a diameter of 3 mm, the test piece was bent 180 degrees,
The occurrence of cracks was visually evaluated.

It was measured using a pencil scratch tester according to JIS K5401. If the hardness was below B, it was judged that the object of the present invention had not been achieved.

In accordance with JIS K5401, a test was conducted on 100 11111 squares, and the peeling state was confirmed using sellotape, and the number of adhered pieces out of 100 was expressed.

Dynamic friction coefficient (μ) of a test piece before and after hot water treatment under a load of 1 kg
, and the tensile speed was 250 ci/min.

Dynamic friction coefficient (μ) is 0. If the score was 3 or more, it was determined that the object of the present invention had not been achieved.

Using a contact angle measurement device manufactured by Elma Optical Co., Ltd., the contact angle with water before and after the hot water treatment was measured. It was judged that those without grooves having a contact angle of 60° did not achieve the object of the present invention.

[Storage stability The condition of the composition after storage for 3 months was confirmed.

Example 1 A stainless steel autoclave equipped with a stirrer, a thermometer, and a monomer addition pump was equipped with a heater and a nitrogen gas introduction device, and the autoclave was filled with 120 parts of water, polyvinyl alcohol (manufactured by Nippon Gosei Kagaku, Gohsenol G)
L-05) 1 part (solid content equivalent), ammonium salt of styrene-maleic acid resin UM Iyoshi Tsusho ■, ammonium salt of 2625A) 5 parts, ammonium salt of styrene-acrylic acid resin (manufactured by Johnson Polymer ■, J- 678 ammonium salt), 1 part of acrylamide, and 0.3 part of sodium persulfate were charged, the gas phase was replaced with nitrogen gas for 15 minutes, and the temperature was raised to 75°C. After that, from a separate container, 9 parts of n-butyl methacrylate and 2 parts of methyl methacrylate were added.
A mixture of 5 parts of 2-hydroxyethyl methacrylate, 15 parts of 2-hydroxyethyl methacrylate, 40 parts of styrene, and 10 parts of ethyl acrylate was continuously added over a period of 3 hours. After the addition was completed, the mixture was further aged at 85-95°C for 2 hours.
Cool to 25°C and adjust to pH 8 with dimethylethanolamine.
Adjusted to.

Next, 10 parts of methyltriethoxysilane was added and stirred vigorously for about 1 hour so that it was absorbed into the copolymer serving as a seed, and the temperature was further raised to 70° C. and a condensation reaction was carried out for 3 hours.

Thereafter, the mixture was cooled, the solid content concentration was adjusted to 45% with water, and then filtered through a 200-mesh wire mesh.

The average particle size of the entire aqueous copolymer dispersion obtained was 0.14.
It was μm. Note that the average particle size was measured using Nanosizer manufactured by Coulter.

In addition, the acid value of the entire copolymer dispersion obtained was 15,
The conversion rate of alkoxysilane was 99%.

The results for the aqueous copolymer dispersions are shown in Table 1.

While stirring 100 parts of this copolymer dispersion (in terms of solid content), 20 parts of a 50% aqueous solution of butyl cellosolve was added, and a plasticizer (manufactured by Chisso ■, Texanol C3-
After adding 4 parts of 1, 2), the mixture was stirred for over 1 hour. The obtained dispersion was coated on a #50 tin plate using a bar coater to a film thickness of about 5 μm, and heated at 210°C for 10 minutes.
A test piece was prepared by baking at 170° C. for 10 minutes, and hot water resistance was measured, and no whitening was observed.

On the other hand, 100 parts of the obtained copolymer dispersion (in terms of solid content)
While stirring, 20 parts of melamine resin dispersion (manufactured by Mitsui Cyanamid Co., Ltd., Cymel 303, Fujii Yoshitsusho ■262)
After gradually adding 0.2 parts of ammonia salt of 5A and 8 parts of water, 20 parts of a 50% aqueous solution of butyl cellosolve was added and stirred for over 1 hour to obtain an aqueous dispersion composition.

The resulting composition had a solid concentration of 44.5% and a solvent content of 3.7%.

This dispersion composition was spread on a #50 tin plate with a film thickness of 5 μm.
The test pieces were coated using a bar coater so as to have a coating thickness of m, and baked at 210°C for 10 minutes to evaluate the physical properties of the coating, namely hot water resistance, flexibility, pencil hardness, adhesion, lubricity, and water repellency. .

The results are shown in Table 1.

Furthermore, 100 parts of the aqueous dispersion composition (in terms of solid content)
130 parts of a rutile-type titanium white aqueous dispersion (manufactured by Dainippon Ink & Chemicals, Desverse Hoi SD-7021, non-volatile content 70%) was added to the mixture, and the mixture was stirred for over 1 hour to obtain a pigment-containing aqueous dispersion composition. Ta. Add this composition to #50
It was coated on a tin plate using a bar coater to a film thickness of 5 μm, and baked at 210° C. for 10 minutes to prepare a test piece, and the adhesion of the film was evaluated.

The results are shown in Table 1.

Example 2 An aqueous copolymer dispersion was prepared in the same manner as in Example 1, except that the types and amounts of the water-soluble polymer, monomer, and alkoxysilane were changed as shown in Table 1. I got it. The results are shown in Table 1.

Next, using this dispersion, a dispersion composition and a test piece were obtained in the same manner as in Example 1, except that butyl cellosolve was not used. The results are shown in Table 1.

Example 3 An aqueous copolymer dispersion was prepared in the same manner as in Example 1, except that the types and amounts of the water-soluble polymer, monomer, and alkoxysilane were changed as shown in Table 1. and its composition and test piece were obtained. The results are shown in Table 1.

Example 4 The melamine resin (manufactured by Mitsui Cyanamid Co., Ltd., Cymel 303) used in the aqueous copolymer dispersion composition of Example 1 was
It was used in the polymerization process of an aqueous copolymer dispersion. The melamine resin was added in the polymerization step by dissolving it in the monomer component that was continuously added over 3 hours, and adding it together with the heptamer component.

The results are shown in Table 1.

Examples 5 to 7 The same procedure was carried out except that 10 parts of a 5% aqueous ammonium zirconate carbonate solution (manufactured by Daiichi Kigenso ■) was added to each of the amino resin-containing aqueous copolymer dispersion compositions of Examples 1 to 3. A dispersion composition was obtained in the same manner as in Examples 1 to 3. The results are shown in Table 1.

Comparative Examples 1 to 2 An aqueous copolymer dispersion, its composition, and a test piece were prepared in the same manner as in Example 1, except that the amount of water-soluble polymer added was changed as shown in Table 1. I got it. The results are shown in Table 1.

From the results in Table 1, it is clear that when the total amount of water-soluble polymer is less than 1 part per 100 parts of monomer components, the adhesion is poor;
It can be seen that if the amount exceeds 0.00 parts, the hot water resistance is poor.

Comparative Examples 3 to 4 An aqueous copolymer dispersion, its composition, and tests were prepared in the same manner as in Example 3, except that the types and amounts of monomers were changed as shown in Table 1. Got a piece. The results are shown in Table 1.

From the results in Table 1, (a) hydroxyalkyl (meth)
It can be seen that if the amount of acrylate is less than 1 part, the hot water resistance is poor, while if it exceeds 40 parts, the hot water resistance and flexibility are poor.

Comparative Examples 5 to 6 An aqueous copolymer dispersion, its composition, and tests were prepared in the same manner as in Example 3, except that the types and amounts of monomers were changed as shown in Table 1. Got a piece. The results are shown in Table 1.

From the results in Table 1, it can be seen that (b) the amount of aromatic vinyl monomer is 5
It can be seen that if the amount is less than 75 parts, the hot water resistance is poor, while if it is more than 75 parts, the flexibility is poor.

Comparative Examples 7 to 8 In Example 1, the amount of alkoxysilane charged was changed to the first
An aqueous copolymer dispersion, its composition, and a test piece were obtained in the same manner as in Example 1, except for the changes shown in Table 1. The results are shown in Table 1.

From the results in Table 1, it can be seen that when the amount of alkoxysilane is less than 0.1 part, the lubricity and water repellency are poor, while when it exceeds 500 parts, the flexibility and storage stability are poor.

Comparative Example 9 In Example 1, 6 parts of sodium dodecylbenzenesulfonate was used instead of the water-soluble polymer, and the types and amounts of monomers were changed as shown in Table 1.
A coating dispersion and a test piece were obtained in the same manner as in Example 1.

The obtained test piece showed whitening in the hot water resistance test, and the object of the present invention was not achieved.

Next, an amino resin and the like were added in the same manner as in Example 1 to obtain a dispersion composition and a test piece.

The results are shown in Table 1.

Comparative Example 10 An aqueous copolymer dispersion was carried out in the same manner as in Example 1, except that 1 part of a reactive emulsifier (manufactured by Sanyo Kasei ■, Eleminol JS-2) was used instead of the water-soluble polymer. A liquid and a test piece were obtained.

The obtained test piece showed whitening in the hot water resistance test, and the object of the present invention was not achieved.

Next, an amino resin and the like were added in the same manner as in Example 1 to obtain an aqueous dispersion composition and a test piece.

The results are shown in Table 1.

From Comparative Examples 9 and 10, it can be seen that the conventional dispersion alone has poor hot water resistance.

Comparative Example 11 100 parts of methyltrimethoxysilane and 0.3 parts of sodium dodecylbenzenesulfonate (solid content equivalent) with a concentration of 10% were diluted with distilled water to 200 parts, and this was reacted using a reflux condenser and a stirrer. Pour into a container and mix well.

Thereafter, the temperature of the reaction vessel was raised to 70°C, and the reaction was carried out for 3 hours. A transparent aqueous polysiloxane dispersion was obtained with a conversion rate of 99%.

Furthermore, in Example 1, the same procedure as in Example 1 was carried out, except that 10 parts of the aqueous polysiloxane dispersion (in terms of solid content) was mixed instead of allowing the copolymer to absorb the alkoxysilane and cause the condensation reaction. A coating dispersion and a test piece were obtained.

The results are shown in Table 1. From Table 1, it can be seen that mere mixing with polysiloxane results in poor flexibility and storage stability.

[Effects of the Invention] The coating dispersion and the composition thereof of the present invention can be applied without impairing the properties of conventional solvent-based and solvent-containing water-based coating agents, such as excellent hot water resistance, adhesion, and storage stability. It has excellent properties such as hardness, flexibility, lubricity, and water repellency, and the organic solvent content can be significantly reduced, so it can be used for metal coatings such as can coating agents, electrodeposition paints, etc.

Claims (3)

[Claims] (1) In the presence of 1 to 100 parts by weight of water-soluble polymer (I), (a) hydroxyalkyl (meth)acrylate 1
~40 parts by weight, (b) 5 to 75 parts by weight of aromatic vinyl monomer, (c) 20 to 55 parts by weight of alkyl (meth)acrylate, and (d) copolymerizable with the above (a) to (c). 0 to 14 parts by weight of ethylenically unsaturated monomer (however, (a)
+ (b) + (c) + (d) = 100 parts by weight), alkoxysilane (III) was added to the copolymer obtained by emulsion polymerization of monomer component (II) containing (I) component and (II). It is characterized by containing polysiloxane composite particles in which polysiloxane is composited by adsorbing 0.1 to 500 parts by weight per 100 parts by weight of the total components and then proceeding with the condensation reaction of the alkoxysilane. Dispersion liquid for coating. (2) In the presence of (a) 1 to 100 parts by weight of water-soluble polymer (I), (a) 1 to 40 parts by weight of hydroxyalkyl (meth)acrylate, (b) 5 to 7 parts by weight of aromatic vinyl monomer
5 parts by weight, (c) alkyl (meth)acrylate 20~
55 parts by weight and (d) 0 to 14 parts by weight of an ethylenically unsaturated monomer copolymerizable with the above (a) to (c) (however,
(a) + (b) + (c) + (d) = 100 parts by weight), and amino resin (IV) (
Alkoxysilane (III) (I) is added to a copolymer obtained by emulsion polymerization of 0 to 100 parts by weight of charge components per 100 parts by weight of the total amount of components I) and (II).
0.0% per 100 parts by weight of the total amount of component and component (II).
After absorbing 1 to 500 parts by weight, a dispersion containing polysiloxane composite particles composited with polysiloxane by proceeding with a condensation reaction of the alkoxysilane, and (b) component (I) above. (II) Total amount of ingredients 1
0 to 100 parts by weight of amino resin to 00 parts by weight, and the total amount of component (IV) and component (b) is 2
100 parts by weight of a coating dispersion composition. (3) A coating dispersion composition comprising the coating dispersion composition according to claim 2 and a polyvalent metal compound as main components.