JP2621147B2 - Resin composition for water-based paint - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel and useful aqueous resin composition for water-based paint. More specifically, the present invention provides excellent whiteness when forming a film together with a specific aqueous resin binder (hereinafter, also referred to as an aqueous binder and a binder), and furthermore, is ionically bonded to the binder. Accordingly, the present invention relates to a novel resin composition for water-based paints, which contains non-film-forming polymer fine particles capable of forming a tough coating film.

[Related Art] Conventionally, as a resin composition for an aqueous paint as described above, monovinylidene aromatics as non-film-forming polymer fine particles as disclosed in JP-B-46-6524. Not less than 80% by weight (hereinafter referred to as wt%)
% Particle size obtained by emulsion polymerization of other monomers within%
Those using emulsion particles of 0.3 to 0.8 μm, and those disclosed in Japanese Patent Application Laid-Open No. 61-62510 filed by the present inventors in advance, which are polymerizable vinyl monomers and polyfunctional if necessary Particles having internal small pores obtained by emulsion polymerization of a monomer mixture having a solubility parameter difference of 0.1 or more from the polymer in the presence of an emulsion obtained by emulsion polymerization of a crosslinkable monomer Is known.

As a problem of such a conventional resin composition for water-based coatings, none of the non-film-forming resin emulsions has satisfactory whiteness. For example, Tokiko 46-65
JP-A-61-262510, compared to that obtained according to JP-A-24
Although the non-film-forming polymer fine particles obtained according to the above publication have better whiteness, at present, the whiteness has not been used to replace titanium oxide, which is a conventional white pigment.

Further, the non-film-forming polymer fine particles in the prior art are better than pigments such as titanium oxide in dispersibility in a binder, but the compound is separated chemically because they are not chemically bonded to the binder. In some cases, the physical properties of the coating film obtained when the film was formed were almost equivalent to those of titanium oxide.

[Means for Solving the Problems] In view of the above points, the present inventors have superior whiteness to the non-film-forming polymer fine particles obtained by the conventional technique, and chemically combine with the binder. Storage stability of the composition by binding and physical properties of a coating film from the composition,
In particular, as a result of intensive studies to obtain a resin composition for water-based paint containing the fine particles which improves the abrasion resistance, a water-based paint composition containing the fine particles obtained by the following specific composition as an essential component is satisfactory. It has been found that the present invention has the performance to perform the present invention.

Basically, (1) 100 parts by weight (based on solid content) of an aqueous resin binder having a carboxyl group in the molecule, and (A) α, β-ethylenic 5 to 70% by weight of the unsaturated carboxylic acid and 5 to 95% by weight of the alkyl (meth) acrylate having an alkyl group having 1 to 8 carbon atoms [The ratio is based on the total amount of the component (A). It shall be. Is emulsion-polymerized in the presence of 0.1 to 30 parts by weight of the component (A), and 0.1 to 10 parts by weight of a tertiary amino group-containing monomer as an essential component (B). % And 50% of the aromatic vinyl compound
999.9% by weight [The ratio is based on the total amount of the component (B). 70 to 99.9% by weight of the mixture consisting of
From 0.1 to 9900 parts by weight (based on solid content) of a non-film-forming polymer fine particle emulsion (also referred to as a non-film-forming polymer emulsion or a non-film-forming resin emulsion) obtained by emulsion polymerization of And (2) 100 parts by weight (based on solid content) of an aqueous resin binder having a carboxyl group in a molecule; and (A) an essential resin composition. As components, 5-70% by weight of an α, β-ethylenically unsaturated carboxylic acid and 5-95% by weight of an alkyl (meth) acrylate having an alkyl group having 1 to 8 carbon atoms, respectively , The ratio is based on the total amount of the component (A). Is emulsion-polymerized in the presence of 0.1 to 30 parts by weight of the component (A), and 0.1 to 10 parts by weight of a tertiary amino group-containing monomer as an essential component (B). % And 50% of the aromatic vinyl compound
999.9% by weight [The ratio is based on the total amount of the component (B). 70 to 99.9% by weight of the mixture consisting of
0.1-9900 parts by weight (solid basis) of a non-film-forming polymer fine particle emulsion (also referred to as a non-film-forming polymer emulsion or a non-film-forming resin emulsion) obtained by emulsion polymerization of And to provide a resin composition for water-based paints.

First, the aqueous resin binder constituting the aqueous paint resin composition according to the present invention, the above-mentioned aqueous resin binder, such as lysine, flat, gloss, elasticity and metal, such as a general aqueous paint composition As long as it can be used as a binder, any of them can be used without any particular problem. However, if only typical ones are exemplified, a carboxyl group-containing vinyl resin can be used. Emulsions, carboxyl group-containing vinyl water-soluble resins or carboxyl group-containing vinyl resin water-based dispersions.

Such resins may be in any form as long as a vinyl-based monomer as described below is prepared according to various known and common production methods.

If limited in particular, one such limitation is that the glass transition temperature (Tg) of each of the above resins is 60 ° C. or less, The solid content concentration (NV) of each of the above-mentioned resins is 20 to 60% by weight, preferably, Tg is 60 ° C. or less, and NV is within a range of 20 to 50% by weight. belongs to.

Next, the non-film-forming resin emulsion will be described.

Specific examples of the α, β-ethylenically unsaturated carboxylic acid used to produce the component (A) include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, or citraconic acid, and anhydride. Carboxyl group-containing monomers or dicarboxylic acids such as unsaturated alkyl group-containing monoalkyl carboxylic acids such as adducts of acid anhydride group-containing monomers such as maleic acid and itaconic anhydride with glycols; maleic anhydride, anhydride There are polycarboxylic acid anhydride group-containing unsaturated monomers such as itaconic acid, and these may be used alone or in combination of two or more. The amount of the α, β-ethylenically unsaturated carboxylic acid to be used is generally 5% by weight or more, preferably 5 to 70% by weight, based on the total amount of the component (A).
A range within is appropriate.

The component (A) is one of them, and one of them has 1 to 8 carbon atoms (hereinafter, abbreviated as C _1-8 ), linear, branched or cyclic. If only typical representative examples of the alkyl (meth) acrylate having an alkyl group are given below, methyl (meth) acrylate, ethyl (meth) acrylate,
Examples thereof include butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and cyclohexyl (meth) acrylate, and these may be used alone or in combination of two or more. The amount used is 5 to 5 based on the total amount of the component (A).
It is in the range of 95 wt%.

Examples of the aromatic vinyl compound include styrene and derivatives thereof such as styrene, α-methylstyrene, p-tert-butyl-styrene, and p-methylstyrene, and they can be used alone or in combination of two or more. The amount used is 0 to 50% by weight based on the total amount of the component (A).

Other examples of monomers that can be copolymerized with these monomers include the following, and these can also be used alone or in combination. The range which can be introduced into the component (A) is 0 to 50% by weight.

First, as the hydroxyl group-containing monomer, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl ( (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-
Hydroxyalkyl esters of (meth) acrylic acid such as chloro-2-hydroxypropyl (meth) acrylate and polyethylene glycol mono (meth) acrylate; di-hydroxyalkyl esters of polycarboxylic acids such as maleic acid and fumaric acid And hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether.

Other (substituted) aromatic nucleus-containing (meth) acrylates such as benzyl (meth) acrylate; diesters of unsaturated dicarboxylic acids and monohydric alcohols such as maleic acid, fumaric acid, and itaconic acid; vinyl acetate, benzoic acid Vinyl esters such as vinyl and "Veova" (vinyl ester manufactured by Shell); "Viscoat 8F, 8FM, 3
F, 3FM ”(fluorine-containing (meth) acrylic monomer manufactured by Osaka Organic Chemical Co., Ltd.), perfluorocyclohexyl (meth)
Vinyl esters containing (per) fluoroalkyl groups such as acrylates, di-perfluorocyclohexyl fumarate, or Ni-propyl perfluorooctanesulfonamidoethyl (meth) acrylate; vinyl chloride, vinylidene chloride, vinylidene fluoride, Olefins such as vinyl fluoride, chlorotrifluoroethylene, ethylene and propylene; (meth) acrylamide, N,
Carboxylic acid amide group-containing monomers such as N-dimethyl (meth) acrylamide, N-alkoxymethylated (meth) acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide; p-styrenesulfonamide, N Sulfonic acid amide group-containing monomers such as -methyl-p-styrenesulfonamide, N, N-dimethyl-p-styrenesulfonamide; N, N such as N, N-dimethylaminoethyl (meth) acrylate
-Dialkylaminoalkyl (meth) acrylates,
Or having both a polycarboxylic anhydride-containing monomer such as maleic anhydride and an active hydrogen group capable of reacting with a polycarboxylic anhydride such as N, N-dimethylaminopropylamine and a tertiary amino group Tertiary amino group-containing monomers such as adducts with compounds; cyano group-containing monomers such as (meth) acrylonitrile; α, β-ethylenically unsaturated carboxylic acids such as (meth) acrylic acid hydroxyalkyl esters Monomers having a phosphate group obtained by a condensation reaction between a hydroxyalkyl ester of an acid and a phosphate ester; 2-acrylamide-2
-A monomer having a sulfonic acid group such as methylpropanesulfonic acid, or an organic amine salt thereof.

Further, in order to improve the durability and solvent resistance of the finally obtained non-film-forming polymer fine particles, a crosslinkable monomer as shown below is optionally added to the component (A) component standard. 0
It is preferable that the content be contained in an amount of about 30 wt%.

Specific examples of the crosslinkable monomer include molecules such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, divinylbenzene, trivinylbenzene, and diallyl phthalate. A monomer having two or more polymerizable unsaturated groups therein; vinyltriethoxysilane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, γ- (meth) Acryloyloxypropyltriethoxysilane, γ- (meth)
There are hydrolyzable silyl group-containing monomers such as acryloyloxypropylmethyldiethoxysilane.

In order to produce the component (A), the required amount of each monomer group may be synthesized by a known and commonly used emulsion polymerization method in the presence of an emulsifier, a polymerization initiator and water. Examples of the emulsifier used in this case include anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers, other reactive emulsifiers, and substances having surface activity such as acrylic oligomers. Anionic emulsifiers are preferred because they produce less aggregates during polymerization and provide a stable emulsion. Representative examples of the nonionic emulsifier include polyoxyethylene alkylphenol ether, polyoxyethylene alkyl ether, polyoxyethylene higher fatty acid ester, ethylene oxide-propylene oxide block copolymer, and the like. Metal salts, alkyl sulfate alkali metal salts,
And polyoxyethylene alkylphenol sulfate alkali metal salts. Further, instead of or in combination with the above-mentioned anionic emulsifier, a water-soluble oligomer comprising a polycarboxylic acid or a sulfonate can be used. Further, a water-soluble polymer substance such as polyvinyl alcohol and hydroxyethyl cellulose, which is generally used occasionally in emulsion polymerization, can be used as a protective colloid. When these are used, the particle size of the obtained emulsion becomes large and the whiteness becomes good, but on the other hand, the water resistance and weather resistance of the coating film formed with the binder are reduced, so that the total monomer The amount used should be less than 5% by weight, preferably less than 2% by weight. The use amount of the above emulsifiers and the like is about 0.1 to 10% by weight based on the total monomer amount.

Next, the polymerization initiator is not particularly limited as long as it is generally used for emulsion polymerization. Specific examples thereof include water-soluble inorganic peroxides such as hydrogen peroxide; ammonium persulfate, and potassium persulfate. Organic peroxides such as cumene hydroperoxide and benzoyl peroxide; azo-based initiators such as azobisisobutyronitrile and azobiscyanovaleric acid; these may be used alone or in combination. You may. The amount used is preferably 0.1 to 2% by weight based on the total amount of monomers. It is needless to say that a method known as a so-called redox polymerization method using a combination of these polymerization initiators with a metal ion and a reducing agent may be used.

The component (A) is placed in a reaction vessel in a lump or divided or continuously in the presence of water, preferably ion-exchanged water and an emulsifier, or the like, or the above-mentioned monomer mixture constituting the component (A) as it is or is emulsified. The polymerization may be performed at a temperature of 0 to 100 ° C, preferably 30 to 90 ° C, in the presence of the polymerization initiator. The ratio of total monomer to water should be set so that the final solids content is in the range of 10-60 wt%, preferably 15-55 wt%. When adjusting the component (A), a so-called seed polymerization method may be used in which emulsion particles are previously present in an aqueous phase and polymerized in order to grow or control the particle diameter of the component (A) to be obtained.

(A) A vinyl copolymer emulsion as a component is prepared, and subsequently, based on the solid content of the emulsion.
In the presence of 0.1 to 30 parts by weight, 70 to 99.9 parts by weight of the monomer mixture constituting the component (B) is additionally polymerized to deposit and polymerize the component (B) on the emulsion particle surface of the component (A). Thus, a non-film-forming polymer fine particle emulsion which is an essential component of the present invention can be produced.

The monomers to be used in the component (B) of the present invention include:
α, β-ethylenically unsaturated carboxylic acid 0-10 wt%, tertiary amino group-containing monomer 0.1-10 wt%, aromatic vinyl compound 5
0 to 99.9 wt%, other monomers 0 to 4 copolymerizable with these
9.9 wt% (the above ratio is based on the total amount of the component (B)). Among them, the α, β-ethylenically unsaturated carboxylic acid and the aromatic vinyl compound may be appropriately selected from those described in detail for the component (A).

Further, the monomer copolymerizable _therewith has a C _1-8 linear, branched or cyclic alkyl group (meth)
Acrylic acid alkyl esters, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) Acrylate, 4-hydroxybutyl (meth) acrylate, 3-
Hydroxyalkyl esters of (meth) acrylic acid such as chloro-2-hydroxypropyl (meth) acrylate and polyethylene glycol mono (meth) acrylate; or di-hydroxyalkyl esters of polycarboxylic acids such as maleic acid and fumaric acid Polyhydroxyalkyl esters having an unsaturated group such as phenols; hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether; (substituted) aromatic nucleus-containing (meth) acrylates such as benzyl (meth) acrylate; maleic acid, fumaric acid, Diesters of an unsaturated dicarboxylic acid such as itaconic acid and a monohydric alcohol; vinyl esters such as vinyl acetate, vinyl benzoate, and “Veoba” (vinyl ester manufactured by Shell); “Biscoat 8F, 8FM, 3F,
3FM "(a fluorinated (meth) acrylic monomer manufactured by Osaka Organic Chemical Co., Ltd.), perfluorocyclohexyl (meth) acrylate, di-perfluorocyclohexyl fumarate, or Ni-propyl perfluorooctanesulfonamidoethyl (PAR) like (meth) acrylate
Vinyl esters containing a fluoroalkyl group; olefins such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, chlorotrifluoroethylene, ethylene and propylene; (meth) acrylamide, N-
Carboxylic acid amide group-containing monomers such as alkoxymethylated (meth) acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, etc .; p-styrenesulfonamide, N-methyl-p-styrenesulfonamide; ) Cyano group-containing monomers such as acrylonitrile; condensation reaction between hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acids such as (meth) acrylic acid hydroxyalkyl esters and phosphoric acid or phosphoric acid esters And a monomer having a sulfonic acid group such as 2-acrylamido-2-methylpropanesulfonic acid or an organic amine salt thereof.

The feature of the present invention is that a tertiary amino group-containing monomer is used as an essential component as the component (B) raw material. As the effect of introducing the monomer,
The non-film-forming polymer fine particles and binders in the finally obtained composition, which usually contain a carboxyl group, have a non-film-forming property due to a crosslinking effect due to salt formation with the binders. The polymer fine particles and the binder are firmly bonded to each other to improve the physical properties. Specifically, an improvement in storage stability such that separation of the binder from the non-film-forming polymer fine particles and the binder hardly occurs in the blend and an improvement in abrasion resistance when formed into a coating film are observed.

Specific examples of the monomer include N, N-dimethyl (meth)
Carboxylic acid amide group-containing monomers such as acrylamide and N, N-diethyl (meth) acrylamide; N, N-dialkylsulfonic acid amide group-containing monomers such as N, N-dimethyl-p-styrenesulfonamide; N N, N-dialkylaminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate; or polycarboxylic acid anhydride-containing monomers such as maleic anhydride. Mers and N, N
A tertiary amino group-containing monomer such as an adduct with a compound having an active hydrogen group capable of reacting with a polycarboxylic anhydride and a tertiary amino group such as dimethylaminopropylamine; The amount of the monomer used is 0.1 to 1
0 wt% is preferable, and if it is used more than that, it leads to generation of aggregates at the time of emulsion polymerization, which is not appropriate.

More preferably, in order to improve the durability and solvent resistance of the target product, a monomer having two or more polymerizable unsaturated bonds as described in the above-mentioned component (A) and / or hydrolysis It is desirable to introduce a crosslinkable monomer such as a monomer having a functional silyl group, and the amount used is in the range of 0 to 30 wt%.

In the polymerization of the component (B), since it is contrary to the purpose of the present invention that a large amount of particles of the component (B) are produced on a polymerization basis, the additional use of emulsifiers should be avoided as much as possible. If less than 5 wt% of the component (B),
It should preferably be less than 2 wt%. When the amount used exceeds 5 wt%, a large amount of emulsion particles of the component (B) alone are produced as a by-product, and for example, when the particle distribution is measured, an emulsion having two peaks is formed.

The polymerization initiator and the like are the same as those described in the section of the component (A).

The final solid content concentration is 20 to 60% by weight, preferably 30 to 60% by weight.
It should be in the range of ~ 55 wt%, and the particle size of the obtained emulsion particles is in the range of 0.3 to 1.5 µm. Further, generally, non-film-forming polymer fine particles are used as a method of using, for example, an aqueous emulsion as the above-mentioned binder, a water-soluble resin, and an aqueous dispersion. It is preferable that the basic substance such as morpholine or triethylamine hardly solubilizes or swells. More preferably, after contact between the fine particles and the basic substance, the volume of the fine particles changes by not more than twice the volume of the fine particles before the contact. Should. Those which give a volume change of twice or more have a remarkable lack of stability in an application mode in which they coexist with a basic substance for a long period of time, and cannot be used.
The non-film-forming polymer emulsion, which is an essential component of the present invention, is such that the volume change after contact with a basic substance is twice or less, and the stability to such a basic substance is defined in the claims of the present invention. This can only be achieved with the stated ranges.

The non-film-forming polymer fine particle emulsion obtained by the present invention can be powdered by a known and commonly used drying method. For example, spray drying at a temperature of 100-250 ° C, 50-
Tray drying at a temperature of 70 ° C. or fluidized bed drying can be performed.

The particle size of the obtained non-film-forming resin powder is generally an aggregate (secondary particle) of primary particles (fine particles having a particle size at the time of emulsion), but if necessary, a dispersant such as an emulsifier, a protective agent, or the like. Add the colloid and redisperse in water.

The ratio of the components can be used in the range of 0.1 to 9900 parts by weight based on 100 parts by weight of the solid content.

Next, specific examples of the component pigments include heavy calcium carbonate, light calcium carbonate, magnesium carbonate, precipitated barium sulfate, mica, and titanium oxide.
Inorganic pigments or fillers such as cold water powder, rice powder, kaolin, clay, calcined clay, talc, silica sand, silica lime, ultrafine silica, white carbon, asbestos, pulp powder, dolomite powder, zinc white, and carbon black;
There are phthalocyanine-based, azo-based, quinacridone-based organic pigments and their dispersed pigments. The amount of these pigments to be used is generally 0 to 300 parts by weight based on 100 parts by weight of the components.

The composition of the present invention can be obtained by these three components. In addition, various additives as shown below can be blended.

Chisso Sizer CS-12 (product of Chisso Corporation), butyl carbitol acetate, butyl cellosolve, carbitol, hexylene glycol, cellosolve, dibutyl glycol phthalate, dibutyl phthalate, benzyl alcohol, diisopropyl succinate, Pycal94
(Atlas Chemical Industries), Dalyad A (Dow Chemi
cal Co.); and phthalic acid esters such as dioctyl phthalate; aliphatic dibasic acid esters such as isodecyl succinate and dioctyl adipate;
Phosphate esters such as tricresyl phosphate, glycol esters such as diethylene glycol benzoate, epoxy plasticizers such as epoxidized soybean oil,
And various plasticizers such as chlorinated paraffins; various anionic and nonionic surfactants; salts of phosphoric acid derivatives such as pyrophosphoric acid, tripolyphosphoric acid and hexametaphosphoric acid, salts of polycarboxylic acids, and naphthalene sulfone Dispersants such as acid salts; drying regulators such as mineral spirit and terpen oil; freezing or melting stabilizing agents such as ethylene glycol, propylene glycol, glycerin and methanol; antifoaming agents such as silicone or acrylic oligomers; Other preservatives and the like can be mentioned, but the amount of these preservatives is determined according to use conditions and purposes.

[Effects of the Invention] The resin composition for water-based paint of the present invention has excellent whiteness due to the effect of the non-film-forming polymer fine particles, and thus reduces the amount of conventionally used pigments, particularly titanium oxide. In addition, the fine particles are chemically bonded to binders in the composition, so that a coating film having excellent storage stability and improved physical properties can be formed. The composition of the present invention can be used as a general or industrial water-based paint such as for lysine, flat, gloss, elasticity and metal, but is not particularly limited thereto.

[Examples] Next, the present invention will be specifically described with reference to Production Examples, Examples, and Comparative Examples. Hereinafter, all parts and percentages are by weight unless otherwise specified.

Production Example 1 In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen inlet tube and a thermometer, 50 parts of ion-exchanged water and 3.5 parts of an emulsifier (2 parts of Emulgen 920 manufactured by Kao Corporation and 10 parts of Emar 10)
Was added and stirred well. Next, the reaction vessel is heated and the internal temperature is kept at 80 ° C. to maintain acrylonitrile (AN) 3
, A mixture of 6 parts of n-butyl acrylate (BA) and 1 part of ethylene glycol dimethacrylate (EDMA) and a mixture of 0.25 parts of ammonium persulfate and 5 parts of ion-exchanged water were allowed to react dropwise over 1 hour, and further reacted for 1 hour. The temperature was maintained. Then, while maintaining the internal temperature at 80 ℃, styrene (ST) 10 parts, methyl methacrylate (MMA) 13 parts,
Methacrylic acid (MAA) 6 parts, divinylbenzene (DVB) 1
Part of the mixture and a mixture of 0.25 part of ammonium persulfate and 5 parts of ion-exchanged water were allowed to react dropwise over 1 hour, and the mixture was kept at the same temperature for 45 minutes. Then, it cooled and obtained the intermediate emulsion (A-1). The resulting emulsion had a solid concentration of 40.1%, pH 5.5, and an average particle size of 0.25 μm (Coult
er Counter N-4).

Production Example 2 In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen inlet tube and a thermometer, 50 parts of ion-exchanged water and 3.5 parts of an emulsifier (2 parts of Emulgen 920 manufactured by Kao Corporation and 10 parts of Emar 10
Was added and stirred well. Next, the reaction vessel was heated, the internal temperature was kept at 80 ° C, a mixture of 5 parts of MMA, 4.5 parts of t-butyl methacrylate, 0.5 parts of γ-methacryloyloxypropyltrimethoxysilane, and a mixture of 0.25 parts of ammonium persulfate and 5 parts of ion-exchanged water. Was added dropwise over 1 hour to cause a reaction, and the temperature was further maintained at the same temperature for 1 hour. Then, while maintaining the internal temperature at 80 ° C, ST3 part, MMA20 part, MAA5
Parts, a mixture consisting of 2 parts of DVB and ammonium persulfate 0.
A mixture of 25 parts and 5 parts of ion-exchanged water was allowed to react by dropping over 1 hour, and the mixture was kept at the same temperature for 1 hour. Then, it cooled and obtained the intermediate emulsion (A-2). The resulting emulsion had a solids concentration of 40.0%, pH 2.4, and an average particle size of 0.2.
It was 7 μm.

Production Example 3 A reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen inlet tube and a thermometer was charged with 60 parts of ion-exchanged water, and 85
The temperature was raised to ° C. Then, 0.5 part of sodium dodecylbenzenesulfonate was dissolved in 10 parts of ion-exchanged water, 17.9 parts of MMA,
A mixture consisting of 2 parts of MAA and 0.1 part of EDMA is added and emulsified.
A mixture of the emulsified product, 0.2 part of ammonium persulfate and 10 parts of ion-exchanged water is dropped into the above-mentioned reaction vessel over 2 hours to carry out polymerization. Further, the temperature is maintained at the same temperature for 1 hour to complete the reaction. Then, it cooled and obtained the intermediate emulsion (A-3). The resulting emulsion has a solids concentration
20.0%, pH 2.1, average particle size 0.24 μm.

Production Example 4 60 parts of ion-exchanged water were charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen inlet tube, and a thermometer.
The temperature was raised to ° C. Then, 0.5 parts of sodium dodecylbenzenesulfonate was dissolved in 10 parts of ion-exchanged water, 16.9 parts of MMA,
A mixture consisting of 3 parts of MAA and 0.1 part of EDMA is added and emulsified.
A mixture of the emulsified product, 0.2 part of ammonium persulfate and 10 parts of ion-exchanged water is dropped into the above-mentioned reaction vessel over 2 hours to carry out polymerization. Further, the temperature is maintained at the same temperature for 1 hour to complete the reaction. Then, it cooled and obtained the intermediate emulsion (A-4). The resulting emulsion has a solids concentration
20.2%, pH 2.2, and average particle size 0.22 μm.

Production Example 5 (Production of Non-Film Forming Polymer Emulsion) In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen inlet tube and a thermometer, 370 parts of ion-exchanged water, an intermediate emulsion (A- 1) Charge 100 parts and raise the temperature to 85 ° C. Next, 7 parts of sodium dodecylbenzenesulfonate was dissolved in 90 parts of ion-exchanged water, and ST336.24 parts and MAA18.
36 parts, DVB3.6 parts, dimethylaminoethyl methacrylate
A mixture consisting of 1.8 parts is added and emulsified. A mixture of the emulsified product, 3.6 parts of ammonium persulfate and 80 parts of ion-exchanged water is dropped into the reaction vessel over 2 hours to cause a reaction. After maintaining at the same temperature for 1 hour, the mixture was cooled to obtain the target emulsion (A-5). (A-
5) is a solid content concentration of 40.1%, pH 2.5, average particle size of 0.52 μm
Met.

Production Example 6 (same as above) A reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen inlet tube and a thermometer was charged with 370 parts of ion-exchanged water and 100 parts of the intermediate emulsion (A-2). Heat to ° C. Next, 5 parts of sodium dodecylbenzenesulfonate was dissolved in 90 parts of ion-exchanged water, and 327.6 parts of ST and MAA18 were dissolved.
, A mixture of 7.2 parts of γ-methacryloyloxypropyltrimethoxysilane and 7.2 parts of diethylaminoethyl methacrylate is added and emulsified. A mixture of the emulsified product, 3.6 parts of ammonium persulfate and 80 parts of ion-exchanged water is dropped into the reaction vessel over 2 hours to cause a reaction. After maintaining at the same temperature for 1 hour, the mixture was cooled to obtain the intended emulsion (A-6). (A-6) had a solid concentration of 40.3%, a pH of 2.5, and an average particle size of 0.49 μm.

Production Example 7 (same as above) A reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen inlet tube, and a thermometer was charged with 190 parts of ion-exchanged water and 300 parts of an intermediate emulsion (A-3). Heat to ° C. Next, 5 parts of sodium dodecylbenzenesulfonate was dissolved in 90 parts of ion-exchanged water, and ST320.62 parts and MAA11.
9 parts, DVB6.8 parts, dimethylaminoethyl methacrylate
A mixture consisting of 0.68 parts is added and emulsified. A mixture of the emulsified product, 3.4 parts of ammonium persulfate and 80 parts of ion-exchanged water is dropped into the reaction vessel over 2 hours to cause a reaction. After maintaining at the same temperature for 1 hour, the mixture was cooled to obtain the intended emulsion (A-7). (A-
7) is solid content concentration 40.0%, pH 2.2, average particle diameter 0.46 μm
Met.

Production Example 8 (same as above) A reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen inlet tube, and a thermometer was charged with 270 parts of ion-exchanged water and 200 parts of the intermediate emulsion (A-4). Heat to ° C. Next, 6 parts of sodium dodecylbenzenesulfonate was dissolved in 90 parts of ion-exchanged water, and 318.6 parts of ST and 19.8 parts of MAA were dissolved.
Parts, DVB18 parts, dimethylaminoethyl methacrylate 3.6
Of the mixture and emulsified. A mixture of the emulsified product, 3.6 parts of ammonium persulfate and 80 parts of ion-exchanged water is dropped into the reaction vessel over 2 hours to cause a reaction. After holding at the same temperature for 1 hour,
The target emulsion (A-8) was obtained. (A-8) had a solid concentration of 40.1%, a pH of 2.5 and an average particle size of 0.49 μm.

Comparative Production Example 1 A reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen inlet tube and a thermometer was charged with 370 parts of ion-exchanged water and 100 parts of the intermediate emulsion (A-1), and heated to 85 ° C. Raise the temperature. Next, 7 parts of sodium dodecylbenzenesulfonate was dissolved in 90 parts of ion-exchanged water, and ST336.24 parts and MAA18.
A mixture consisting of 36 parts and 3.6 parts of DVB is added and emulsified. The emulsion, 3.6 parts of ammonium persulfate and 80 ion-exchanged water
And the mixture is dropped into the reaction vessel over 2 hours to cause a reaction. After maintaining at the same temperature for 1 hour, the mixture was cooled to obtain a comparative emulsion (B-1).
(B-1) has a solid content of 40.1%, pH 2.7, and an average particle diameter of 0.5.
It was 1 μm.

Comparative Production Example 2 A reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen inlet tube and a thermometer was charged with 370 parts of ion-exchanged water and 100 parts of the intermediate emulsion (A-2), and was heated to 85 ° C. Raise the temperature. Next, 5 parts of sodium dodecylbenzenesulfonate was dissolved in 90 parts of ion-exchanged water, and 327.6 parts of ST and MAA18 were dissolved.
And a mixture consisting of 7.2 parts of γ-methacryloyloxypropyltrimethoxysilane. A mixture of the emulsified product, 3.6 parts of ammonium persulfate and 80 parts of ion-exchanged water is dropped into the reaction vessel over 2 hours to cause a reaction. After holding at the same temperature for 1 hour,
After cooling, a comparative emulsion (B-2) was obtained. (B
-2) is 40.0% solid concentration, pH 2.6, average particle size 0.56μ
m.

Comparative Production Example 3 190 parts of ion-exchanged water and 300 parts of an intermediate emulsion (A-3) were charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen inlet tube and a thermometer, and heated to 85 ° C. Raise the temperature. Next, 5 parts of sodium dodecylbenzenesulfonate was dissolved in 90 parts of ion-exchanged water, and ST320.62 parts and MAA11.
A mixture consisting of 9 parts and DVB 6.8 parts is added and emulsified. 3.4 parts of ammonium persulfate and 80 parts of ion-exchanged water
And the mixture is dropped into the reaction vessel over 2 hours to cause a reaction. After maintaining at the same temperature for 1 hour, the mixture was cooled to obtain a comparative emulsion (B-3).
(B-3) has a solid content of 40.1%, pH 2.6, and an average particle size of 0.4.
It was 9 μm.

Comparative Production Example 4 A reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen inlet tube and a thermometer was charged with 270 parts of ion-exchanged water and 200 parts of the intermediate emulsion (A-4), and was heated to 85 ° C. Raise the temperature. Next, 6 parts of sodium dodecylbenzenesulfonate was dissolved in 90 parts of ion-exchanged water, and 318.6 parts of ST and 19.8 parts of MAA were dissolved.
And a mixture consisting of 18 parts of DVB and emulsified. A mixture of the emulsified product, 3.6 parts of ammonium persulfate and 80 parts of ion-exchanged water is dropped into the reaction vessel over 2 hours to cause a reaction. After maintaining at the same temperature for 1 hour, the mixture was cooled to obtain a comparative emulsion (B-4).
(B-4) is a solid content concentration of 40.0%, pH 2.6, and an average particle diameter of 0.5.
It was 1 μm.

Examples 1-5 and Comparative Examples 1-5 Obtained in Production Examples 5-8 and Comparative Production Examples 1-4,
Each of emulsions (A-5) to (A-8) and (B-1) to (B-4) and "VONCOAT EC-880" as a binder emulsion [manufactured by Dainippon Ink and Chemicals, Inc. , A trade name of an acrylic-styrene copolymerized vinyl resin emulsion containing a carboxyl group; nonvolatile content = 50%], hydroxyethylcellulose as a thickener, and further in the case of Example 5 and Comparative Example 5. Represents a titanium oxide paste as shown in Table 1,
The components were separately compounded at the compounding ratios shown in Table 1 above, and the mixture was stirred until the viscosity became uniform to form a coating.

Then, each paint was separately applied on a glass plate and a matte PVC sheet with a 6 mil applicator, and then at room temperature for 1 day (PVC.
In the case of a sheet, it was left to dry for 7 days).

Thereafter, each of the thus obtained dried coating films was evaluated for light transmittance and abrasion resistance (PVC sheet). The results are summarized in Table 1.
Shown in

Further, in order to examine the storage stability of each paint, each paint was left in a thermo-hygrostat at 50 ° C. for 3 months. The results are summarized in Table 1.

Further, in order to investigate the storage stability of each emulsion, a predetermined amount of 14% aqueous ammonia was added, and the particle size was measured after leaving the emulsion at 50 ° C. for one month. The results are summarized in Table 1.

* 1) 70% aqueous dispersion of rutile-type titanium oxide * 2) Emulsions (A-5) to (A-
8) and control emulsions (B-1) to (B-
4) means the pigment volume concentration when the solid content of the titanium oxide paste is regarded as a pigment.

* 3) The light transmittance was measured with a turbidity meter manufactured by Nippon Denshoku Co., Ltd.

* 4) Apply the created paint to a test paper (manufactured by Nippon Test Panel Kogyo Co., Ltd.) using a 6-mil applicator.
Leave at 23 ° C for 1 day and set the diffuse reflectance of 45 ゜ / 0 ゜
Measured for each white background, calculated by the following formula.

Opacity = (Diffuse reflectance of 45 ゜ / 0 黒 on a black background) / (Diffuse reflectance of 45 ゜ / 0 ゜ on a white background) (JIS-k-5400) * 5) 6 mil applicator on matte PVC sheet And then dried for 7 days, then measured with a Gardner washing resistance tester.

◎; no peeling of coating film after 3,000 times.

×: Peeling of the coating film was observed at 3,000 times.

* 6) Leave in a thermo-hygrostat at 50 ° C for 3 months to determine the presence of aggregates.

◎: When no phenomena such as aggregates or precipitates are observed at all ○: When precipitates are present but can be easily dispersed by stirring ×: When aggregates are remarkably observed * 7) Emulsions (A-5) to (A-
8) and control emulsions (B-1) to (B-
4) To each, add 7.5 parts of 14% ammonia water,
Stir well, stopper tightly, and keep 50
Leave in a thermo-hygrostat at ℃.

◎: When the change in particle diameter is less than twice the initial particle diameter in terms of volume ×: The change in particle diameter is twice the initial particle diameter in terms of volume Excessive change is observed or aggregation is observed. Examples 6 to 13 Except that the respective non-film-forming polymer emulsions obtained in Production Examples 5 to 8 are changed to use. In the same manner as in Examples 1 to 5 and Comparative Examples 1 to 5, compounding was performed, and the mixture was formed into a paint, and then applied and dried.
The light transmittance and abrasion resistance were measured. The results are summarized in the same table.

In addition, storage stability was similarly measured. The results are also shown in the same table.

As shown in Tables 2 and 3, the resin composition for water-based paint according to the present invention has excellent whiteness and, more particularly, gives a coating film with improved abrasion resistance and the like. It is easy to know that it is extremely practical.

Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication C08F 265/00 MQM C08F 265/00 MQM C08L 25/02 LEG C08L 25/02 LEG 51/06 LKS 51/06 LKS

Claims (2)

(57) [Claims] 1. An aqueous resin binder having a carboxyl group in a molecule in an amount of 100 parts by weight (based on solid content), and (A) 5 to 5 parts of an α, β-ethylenically unsaturated carboxylic acid as an essential component. 70% by weight and 5 to 95% by weight of the alkyl (meth) acrylate having an alkyl group having 1 to 8 carbon atoms [The ratio is based on the total amount of the component (A). Is emulsion-polymerized in the presence of 0.1 to 30 parts by weight of the component (A), and 0.1 to 10 parts by weight of a tertiary amino group-containing monomer as an essential component (B). % And 50% of the aromatic vinyl compound
999.9% by weight [The ratio is based on the total amount of the component (B). Non-film-forming polymer fine particle emulsion obtained by emulsion polymerization of the mixture consisting of 0.1 to 9
A resin composition for water-based paint, comprising 900 parts by weight (based on solid content). 2. 100 parts by weight (based on solid content) of an aqueous resin binder having a carboxyl group in the molecule, and (A) 5 to 5 parts of α, β-ethylenically unsaturated carboxylic acid as essential components, respectively. 70% by weight and 5 to 95% by weight of the alkyl (meth) acrylate having an alkyl group having 1 to 8 carbon atoms [The ratio is based on the total amount of the component (A). Is emulsion-polymerized in the presence of 0.1 to 30 parts by weight of the component (A), and 0.1 to 10 parts by weight of a tertiary amino group-containing monomer as an essential component (B). % And 50% of the aromatic vinyl compound
999.9% by weight [The ratio is based on the total amount of the component (B). Non-film-forming polymer fine particle emulsion obtained by emulsion polymerization of the mixture consisting of 0.1 to 9
A resin composition for a water-based paint, comprising 900 parts by weight (solid content basis) and a pigment.