JPH04149281A - Aqueous coating composition for gloss coating - Google Patents

Abstract

PURPOSE:To obtain the subject composition excellent in coating-workability and leveling properties of a coated film and high in the content of non-volatile components by carrying out emulsion polymerization of polymerizable unsaturated monomers in the presence of a reactive emulsifier and using the resultant emulsion polymer as an essential component. CONSTITUTION:Polymerizable unsaturated monomers (preferably alpha,beta-ethylenic unsaturated monomer and alpha,beta-ethylenic unsaturated carboxylic acid) are subjected to emulsion polymerization in the presence of a reactive emulsifier (e.g. vinylsulfonic acid) and the resultant emulsion polymer is used as an essential vehicle component, thus obtaining the objective composition. In addition, as the ratio of the reactive emulsifier to the polymerizable unsaturated monomers, the former emulsifier is preferably 0.3-10.0 pts.wt. based on 100 pts.wt. latter monomers. As the ratio of the alpha,beta-ethylenic unsaturated monomer to the alpha,beta-ethylenic unsaturated carboxylic acid, the latter is preferably 1.0-10.0 pts.wt. based on 99.0-90.0 pts.wt. of the former.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to new and useful aqueous coating compositions.

More specifically, the present invention provides a polishing aqueous paint comprising, as an essential vehicle component, an emulsion polymer obtained by emulsion polymerization of a specific polymerizable unsaturated monomer in the presence of a reactive emulsifier. Regarding the composition.

(Prior Art) Many types of polishing water-based paint compositions containing polymer emulsion as a vehicle have been used as polishing agents for flooring materials such as chemical tiles and marble. Ta.

However, conventional products typically have a low nonvolatile content, so it is necessary to coat them two or more times in order to obtain the required gloss and durability.

(Problems to be Solved by the Invention) As described above, as long as conventional techniques are followed, so-called overcoating is inevitable.

By the way, recently 1. In order to shorten the maintenance period, products with high non-volatile content are required to reduce the number of recoatings, but simply increasing the non-volatile content of conventional products will result in poor quality of the product. This is undesirable because the viscosity becomes high, resulting in disadvantages such as poor workability during coating and poor leveling of the coating film.

However, the object of the present invention is to provide a polishing water-based paint composition with high non-volatile content without impairing painting workability or leveling properties, and this is the problem to be solved by the invention. .

(Means for Solving the Problems) Therefore, the present inventors have focused on the problems to be solved by the invention as described in [7], and as a result of intensive studies, they have hereby completed the present invention. I came to the conclusion.

In the present invention, as an essential vehicle component, polymerizable unsaturated monomers, especially α and β, are used in the presence of a reactive emulsifier.
- An object of the present invention is to provide a polishing aqueous coating composition comprising a polymer emulsion obtained by emulsion polymerization of an ethylenically unsaturated monomer and an α,β ethylenically unsaturated carbo/acid. .

First, in the present invention, the term "reactive emulsifier" is
Like a normal surfactant, it not only exhibits an emulsifying effect, but also has a functional group that can react with, for example, a polymerizable unsaturated monomer2, and can react with such a functional group. For example, it is used to refer to something that is incorporated into the backbone of a polymer.

Typical examples of the reactive emulsifier used in the present invention include vinyl sulfonic acid, sulfoalkyl (meth)acrylate, styrene sulfonic acid, and 1-noralkyl itaf non-sulfuric acid. Compounds such as esters that have both a polymerizable unsaturated double bond (unsaturated group) and a sulfonic acid group or a sulfate group, or salts thereof.

The reactive emulsifier is used in an amount of 0.00 parts by weight per 100 parts by weight of the polymerizable unsaturated monomer. 3-10.0, preferred.

0. Suitably, it is used in a range of 5 to 5.0 parts by weight.

If the amount of the reactive emulsifier is less than 0.03 based on 100 parts by weight of the polymerizable unsaturated monomer, the leveling property will be poor when the nonvolatile content of the resulting polish water-based coating composition is made to have a high a degree. On the other hand, if the amount of the reactive emulsifier exceeds 10.0 parts by weight, the non-volatile content of the aqueous polishing coating composition will be reduced by 25%. If it is more than that, the viscosity of the product becomes high, which not only deteriorates the workability and leveling property but also results in poor water resistance of the formed coating film, which is not preferable.

Next, to exemplify only particularly representative α,β-ethylenically unsaturated monomers mentioned above, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, , acrylic acid 1so-
Acrylic esters such as nonyl or lauryl acrylate; methyl methacrylate, ethyl methacrylate,
Methacrylic acid esters such as n-butyl methacrylate, 1so-butyl methacrylate, t-butyl methacrylate or lauryl methacrylate; esters of maleic acid, fumaric acid or itafonic acid; vinyl acetate, vinyl propionate or Vinyl esters such as tertiary vinyl carbhonate; aromatic compounds such as styrene, α-methylstyrene or vinyltoluene; heterocyclic vinyl compounds such as vinylpyrrolidone; halogenated vinylidene compounds such as vinylidene chloride or vinylidene fluoride. α-olefins such as ethylene or propylene; or dienes such as butadiene, as well as acrylonitrile, vinyl ketone or vinylamide, and optionally diallylphthalate, divinylbenzene, allyl acrylate or trimethylolfuroban triacrylate. It is also possible to use monomers having two or more unsaturated double bonds in the molecule, such as -monomers having both an α,β-monoethylenically unsaturated double bond and an alkoxysilyl group. Monomers and the like can also be used.

Typical examples of such alkoxysilyl group-containing vinyl monomers include vinyltriethquinsilane, γ-(meth)acryloyloxypropyltrimethoxysilane, and γ-(meth)acryloyloxyfurovir. Methyldimethoxysilane, γ-(meth)acryloyloxypropyltriethoxysilane, γ-(
Examples include di- or trialkoxysilane compounds such as meth)acryloyloxyfurobylmethyljethoxysilane, divinylditriethoxysilane, or divinyldi-β-triethoxysilane.

On the other hand, the above-mentioned α,β-ethylenically unsaturated carboxylic acids are exemplified by ethylenically unsaturated basic carboxylic acids such as acrylic acid, methacrylic acid, or crotonic acid; ethylenically unsaturated dibasic carboxylic acids such as itaconic acid, maleic acid or fumaric acid; or monoalkyl esters of ethylenically unsaturated dibasic carboxylic acids.

And these α, β-ethylenically unsaturated monomers and α
, β-ethylenically unsaturated carboxylic acid is defined as 990 to 90.0 parts by weight of the former monomer and 990 to 90.0 parts by weight of the latter monomer, when the total of these two components (acrylic monomer component) is 100 parts by weight. The ratio of 1.0 to 10.0 parts by weight of the former: the latter: 92.0 to 98.0: 2.0 to 8.0
(parts by weight ratio) is appropriate.

α,β-ethylenically unsaturated carboxylic acid or 1. If the amount is less than 0 parts by weight, the alkali removing property of the alkali remover will be poor, while if the amount of α,β-ethylenically unsaturated carboxylic acid exceeds 10.0 parts by weight, the nonvolatile content of the product will be reduced. If it exceeds 25%, the viscosity increases and the workability and leveling properties deteriorate, so it is not preferable in either case.

By the way, the calculated Tg range of the acrylic monomer component used in the present invention is usually 20 to 1.
00°C can be used, or 30 to 80°C in terms of heel mark properties and dirt pick-up properties.
It is desirable that it be within the range.

In emulsion polymerization, a known and commonly used chain transfer agent may be used to adjust the molecule.

During the synthesis of the emulsion polymer according to the present invention, known emulsifiers can also be used in combination.

Typical examples of such emulsifiers include sodium lauryl sulfate, sodium alkylbenzene sulfonate, alkylaryl sulfosuccinate salt, polyoxyethylene alkylphenyl ether sulfate, and polyoxyethylene stylphenyl ether. Anionic emulsifiers such as sulfates; or nonionic emulsifiers such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene styryl acupoints, niyl ethers, and polyoxyethylene-borioxopropylene bronoch copolymers. A suitable emulsifier can be selected and used.

The amount of such secondary emulsifier used should be limited to about 0.5-10% by weight based on the total monomer amount.

As an emulsion polymerization method for obtaining an aqueous dispersion resin using the various raw materials listed above: 1, any known method can be applied.

That is, for example, based on the total monomer weight (total monomer amount), about 0.5 to 10% by weight of an emulsifying dispersant is used, and a peroxide such as potassium persulfate or ammonium persulfate is used as a catalyst. free radical polymerization using 0.1 to 2%, based on the total monomer amount, at a temperature ranging from room temperature to 90° C. to obtain a solids content of 30 to 55%.
% by weight aqueous dispersion is prepared.

In addition to the emulsion polymer (aqueous dispersion) as an essential component, the polishing coating composition of the present invention contains wax, wetting agents, emulsifiers, dispersants, alkali-soluble resins, polyvalent metal compounds, and fungicides. Alternatively, it can be mixed with an antifreeze agent and made into a paint by a conventional method.

Here, we will only exemplify particularly representative waxes. Examples of natural waxes include animal waxes such as beeswax, amniotic membrane, and spermaceti; carnauba wax, candelilla wax, and wood wax. or mineral waxes such as montan wax, ceresin wax, paraffin wax, and microcrystalline wax. In addition, as synthetic waxes, 1,
Fatty acid esters such as 2-hydroquine stearic acid glycol ester; glycerides such as hydrogenated castor oil; dialkyl ketones such as stearone; fatty acid amides such as stearyl amide; substituted amides such as methylene bis stearyl amide; Semi-synthetic waxes; polyethylene waxes having a molecular weight of 2.000 to 4.000; waxy telomerization products such as chlorinated paraffins or chlorinated naphthalenes, or telomers of ethylene and halogenated acetic acids.

These waxes are formulated neat or in aqueous suspension.

In addition, only typical examples of alkali-soluble resins include styrene-maleic anhydride copolymer, colophonium maleic anhydride copolymer,
Or Sheratsk, etc.

(Example) Next, the present invention will be explained by reference examples, examples, and comparative examples.
Although the layers will be specifically explained, the present invention is not limited to the following examples. In the following, parts and percentages are based on weight unless otherwise specified.

Reference Example 1 (Example of Preparation of Emulsion Polymer) 2-Ethylhexyl acrylate 35 parts Methyl methacrylate Acrylic acid γ-Methacrylic acid Amfurovir Trimethquine Silane Sodium lauryl sulfonate 60 parts 5 parts 0.1 part 3 parts Styrene sulfone Acid sodium salt 3 parts Ion-exchanged water 150 parts Ammonium persulfate 0.5 parts I-lium bisulfite
0.2 parts First, a surfactant and ion-exchanged water were placed in a four-pro flask, and 6 parts were added in a nitrogen gas stream.
It was heated to 0''C, and each monomer was added dropwise over a period of 3 hours.The reaction temperature at this time was maintained in the range of 60 to 70'C, but even after the dropwise addition was completed, the reaction temperature was kept in the same temperature range for 2 hours. Stir, cool, and adjust the pH to 6~6 with approximately 14% aqueous ammonia.
7 and the solid content was adjusted to 40% to obtain an aqueous resin dispersion which was a stable emulsion polymer. Viscosity is 50cp
It was s.

Reference Examples 2 to 11 Various aqueous resin dispersions were prepared in the same manner as in Example 1, except that ammonium persulfate and sodium bisulfite were removed and the raw materials shown in Table 1 were used. .

Examples 1-5 and Comparative Examples 1-6 Reference Examples 1-1
Each emulsified dispersion (aqueous dispersion resin) obtained in 1.
A polishing paint composition of the present invention and a target polishing paint composition were prepared by blending and forming paints according to the paint formulations shown in Table 2.

The results of a comparative study of the various performances of each paint are as follows:
All are shown in the same table.

(Effects of the Invention) As described above, the aqueous coating composition for polishing of the present invention is excellent not only in painting workability but also in the layering properties of the coating film.

In addition, the present invention provides an aqueous polish coating composition with a high non-volatile content.

Claims (1)

[Claims] 1. A water-based paint characterized by containing as an essential vehicle component an emulsion polymer obtained by emulsion polymerization of a polymerizable unsaturated monomer in the presence of a reactive emulsifier. Composition. 2. The aqueous coating composition according to claim 1, wherein the emulsion polymer is obtained from an α,β-ethylenically unsaturated monomer and an α,β-ethylenically unsaturated carboxylic acid. 3. The above-mentioned reactive emulsifier and polymerizable unsaturated monomer,
0.3 to 100 parts of the former emulsifier to 100 parts of the latter monomer
The aqueous polishing coating composition according to claim 1 or 2, which is obtained by using the aqueous coating composition in a proportion of 10.0 parts by weight. 4. The above α,β-ethylenically unsaturated monomer and α,β
- ethylenically unsaturated carboxylic acid and 99% of the former monomer.
．． 0 to 90.0 parts by weight, 1.0 to 90.0 parts by weight of the latter monomer
The polishing aqueous coating composition according to claim 1, 2 or 3, which is obtained by using in a proportion of 10.0 parts.