JPH04130167A - Wall coating material, and acrylic resin binder used for preparing the same - Google Patents

Abstract

PURPOSE:To prepare the title material having an excellent water-resistant adhesion, a high resistance to whitening by water, and a good applicability with a trowel without being affected by the temp. during application by compounding an aggregate, a water-sol. resin, and a specific alkyl (meth)acrylate copolymer emulsion. CONSTITUTION:The title material contains an aggregate, a water-sol. resin, and an emulsion of an alkyl (meth)acrylate copolymer having anionic groups and cationic groups. The emulsion of the copolymer is prepd., e.g. by the emulsion copolymn. of essential monomers consisting of an alkyl (meth)acrylate, a polymerizable monomer contg. an anionic group, and a polymerizable monomer contg. a cationic group, if necessary with a crosslinkable monomer and other comonomers. The emulsion of the copolymer contg. the crosslinkable monomer is pref. because of its excellence in water-resistant adhesion and resistance to whitening by water.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides water-resistant adhesion, water-whitening resistance, and troweling workability, regardless of the temperature during construction, whether at low temperatures in winter or high temperatures in summer. The present invention relates to an excellent wall coating material and an acrylic resin binder for wall coating materials used therein.

[Conventional technology]

Wall coating materials are generally composed of aggregates such as silica sand and water-soluble resins such as carboxymethyl cellulose salts, and are generally combined with water-based resin emulsions such as acrylic resin emulsions as binder components. As emulsions, there are known emulsions that use anionic acrylic resin emulsion (Japanese Unexamined Patent Publication No. 50-61436) and cationic acrylic resin emulsion (Japanese Unexamined Patent Publication No. 2-55773). There is.

[Problem to be solved by the invention]

However, wall coating materials using anionic acrylic resin emulsion as a binder have a relatively long pot life (and have excellent troweling workability, but have poor water-resistant adhesion and water-whitening resistance, especially when drying and curing at low temperatures). For example, there is a problem that water-resistant adhesion and water-whitening resistance during dry curing at 10''C or less are low.

In addition, those using a cationic acrylic resin emulsion as a binder dry and cure quickly, and have improved water-resistant adhesion and water-whitening resistance during low-temperature curing compared to those using the anionic binder. Moreover, there are problems in that the workability of troweling is poor and the pot life is short.

[Means for Solving the Problem] As a result of intensive research in view of the above situation, the present inventors have developed a (meth)acrylic acid alkyl ester copolymer emulsion having an anionic group and a cationic group. We have discovered that the wall coating material used as a binder component has excellent water-resistant adhesion and water-whitening resistance not only when dry-curing at high temperatures but also when dry-curing at low temperatures, and also has good workability when applied with a trowel. The present invention has now been completed.

That is, the present invention provides a water-based wall coating material containing an aggregate, a water-soluble resin, and an acrylic resin binder, which has an anionic group and a cationic group as the acrylic resin binder (
A wall coating material characterized by using a meth)acrylic acid alkyl ester copolymer emulsion (I), and a (meth)acrylic acid alkyl ester copolymer emulsion having an anionic group and a cationic group. (I
) An acrylic resin binder for wall coating materials is provided.

As the (meth)acrylic acid alkyl ester copolymer emulsion (I) having an anionic group and a cationic group used in the present invention, for example, (meth)acrylic acid alkyl ester (a) and an anionic group-containing polymerizable Monomer (
b) and a cationic group-containing polymerizable monomer (c) as essential components, and if necessary, further emulsify a crosslinkable monomer (d) and other copolymerizable monomers by a known method. Examples include those formed by polymerization, and among these, those containing the crosslinkable monomer (d) are preferable because they have excellent water-resistant adhesion and water-whitening resistance.

(meth)acrylic acid alkyl ester (a) used here
) refers to non-crosslinkable (meth)acrylic acid alkyl esters having no anionic group or cationic group, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, Examples include octyl (meth)acrylate, which usually have a calculated glass transition point (Tg) of 0 to 40°C, preferably 5 to 30°C.
℃ used alone or in combination of two or more.

Examples of the anionic group-containing polymerizable monomer (b) include (meth)acrylic acid, itaconic acid, crotonic acid, nyl sulfonic acid, and (anhydrous) maleic acid. (Anhydrous) maleic acid is preferred. These may be used alone or in combination of two or more.

Examples of the cationic group-containing polymerizable monomer (c) include dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate methyl chloride, diethylaminoethyl (meth)acrylate methyl chloride,
Examples include dimethyldiallylammonium chloride, among which dimethylaminoethyl (meth)acrylate, dimethylamineethyl (meth)acrylate methyl chloride, and dimethyldiallylammonium chloride are preferred. These may be used alone or in combination of two or more.

Examples of the crosslinkable monomer (d) include N-methylol (
N-methylolated products of acrylamide such as meth)acrylamide, N-propoxymethylacrylamide, N-butoxymethylacrylamide, and methylenebisacrylamide, or alkoxylated products in which the methylol group is etherified; side chains such as glycidyl methacrylate and allyl glycidyl ether Compound having an epoxy group; n-
Examples include polyfunctional group-containing compounds such as polyethylene glycol di(meth)acrylate, and these may be used alone or in a mixture of two or more. Among these, it is preferable to use a methylolated acrylamide and a compound having an epoxy group in the side chain in combination.

Examples of other copolymerizable monomers include vinyl acetate, vinyl propionate, acrylonitrile, styrene, and α-methylstyrene.

The usage ratio of the above four components (a), (b), (c) and (d) is, if the total of these four components is 100% by weight, component (a) is usually 75 to 95% by weight, ( Component b) is usually 0.1 to 10% by weight, preferably 0.5 to 5% by weight, and component (c) is usually 1 to 10% by weight, preferably 2% by weight.
to 5% by weight, and component (d) is usually in the range of 0 to 10% by weight, preferably 1 to 5% by weight.

The acrylic resin binder of the present invention is usually obtained by further adding film-forming aids, preservatives, etc. to the (meth)acrylic acid alkyl ester copolymer emulsion (I) obtained as described above.

As the film-forming aid, any known film-forming aid such as butylcarpitol, butylcarpitol acetate, texanol, dihenzoate derivatives, dibutyl phthalate, etc. can be used. The amount used is preferably such that the minimum film forming temperature of the acrylic resin binder is 5°C or less, preferably 0°C or less, and the resin content of the (meth)acrylic acid alkyl ester copolymer emulsion (I) is 10
Usually 1 to 30 parts by weight, preferably 5 to 30 parts by weight per 0 parts by weight
The range is 20 parts by weight. The film-forming aid may be added during the production of the (meth)acrylic acid alkyl ester copolymer emulsion.

As the aggregate used in the present invention, any known aggregate can be used without particular limitation, such as silica sand, calcium carbonate, precipitated barium sulfate, talc, sauce, agarite, glass powder,
Examples include hollow beads made of silicon compounds, etc., and these may be colored in advance with a coloring agent, or may be separately blended with an organic or inorganic pigment. These may be used alone or in combination of two or more.

As the water-soluble resin used in the present invention, any known ones can be used, such as carboxymethyl cellulose salt,
Examples include cellulose-based water-soluble resins such as hydroxyethyl cellulose and methyl cellulose, sodium alginate, and sodium polyacrylate. Among them, sodium salt of carboxymethyl cellulose is preferred. These may be used alone or in combination of two or more.

The wall coating material of the present invention comprises the above-mentioned aggregate and water-soluble resin (meth).
Acrylic acid alkyl ester copolymer emulsion,
Further, if necessary, it can be obtained by mixing with viscosity adjusting water. The proportion of its use is basically the same as that of conventional wall painting materials,
The total resin content of the aggregate, water-soluble resin, and (meth)acrylic acid alkyl ester copolymer emulsion (I) is 10
When it is 0% by weight, the aggregate is usually 70 to 98% by weight, the water-soluble resin is 0.3 to 3% by weight, and the resin content of the (meth)acrylic acid alkyl ester copolymer emulsion (I) is 1 to 98% by weight. It is in the range of 30% by weight.

Incidentally, an insolubilizing agent for water-soluble resin can be further added to the wall coating material of the present invention. Examples of the insolubilizing agent include polyvalent metal salts such as chromium acetate, magnesium sulfate, zinc acetate, nickel nitrate, aluminum phosphate, and basic aluminum acetate.
Usually 0 to 40 parts by weight, preferably 10 parts by weight
~20 parts by weight.

〔Example〕

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. Note that all parts and percentages in the examples are based on weight.

Example 1 40 parts of butyl acrylate, 52 parts of methyl methacrylate,
Emulsion polymerization of 2 parts of methacrylic acid, 2 parts of dimethylaminoethyl methacrylate methyl chloride, 2 parts of N-methylolacrylamide and 2 parts of glycidyl methacrylate to obtain a (meth)acrylic acid alkyl ester copolymer emulsion (I-1), Add butyl carpitol acetate to this at a ratio of 10 parts to 100 parts of resin, and maintain a minimum film forming temperature (MFT) of O'C or lower and a pH of 7.
An acrylic resin binder (I) having a resin content of 40% was obtained.

Next, mix each component with the following composition to create a wall coating material (
I) was obtained.

Yellow colored silica sand 100 parts Sodium salt of carboxymethyl cellulose 1 part Acrylic resin binder (I) 20 parts Water
44 copies total 165
The obtained wall coating material (I) was applied with a trowel to a thickness of 1 mm on two 10-thick mortar plates, and the temperature was 5°C and the humidity was 60% R.
H and temperature of 20°C and humidity of 60% RH for 48 hours to dry and cure, then immersed in water at 20°C, and after 1 hour, 3 hours, 12 hours, and 24 hours. Water-resistant adhesion and water-whitening resistance were evaluated by finger friction and visual observation according to the following criteria. The results are shown in Table-1. Note that the troweling workability was good.

Water resistant adhesion ◎No change due to two-finger touch friction.

○: The paint film fell off slightly due to.

△: The paint film gradually fell off due to

×: The paint film comes off easily.

Water whitening resistance ◎: No whitening.

O: Slight whitening.

△: Whitening occurs.

×: Significant whitening.

Example 2 40 parts of butyl acrylate, 40 parts of methyl methacrylate,
13 parts of styrene, 1 part of maleic anhydride, 2 parts of dimethylaminoethyl methacrylate, 2 parts of N-methylolmethacrylamide and 2 parts of glycidyl methacrylate were emulsion polymerized to form a (meth)acrylic acid alkyl ester copolymer emulsion (I-2). ) was obtained. Acrylic resin binder (2) in the same manner as in Example 1 except that this was used.
A wall coating material (2) was obtained, and water-resistant adhesion and water-whitening resistance were evaluated in the same manner. The results are shown in Table-1.

Note that the troweling workability was good.

Comparative Example 1 Anionic (meth)acrylic acid alkyl ester was prepared in the same manner as in Example 1 except that the addition of dimethylaminoethyl meth and acrylate methyl chloride was omitted and the amount of butyl acrylate used was changed to 42 parts. A polymer emulsion (I-1') was obtained.

An acrylic resin binder (I') and a wall coating material (I') were obtained in the same manner as in Example 1 except that this was used, and then water-resistant adhesiveness and water-whitening resistance were evaluated in the same manner. The results are shown in Table-1. Note that the troweling workability was good.

Comparative Example 2 A cationic (meth)acrylic acid alkyl ester copolymer emulsion (I-2 ') got. The acrylic resin binder (2'
) and wall coating material (2') were obtained, and then water-resistant adhesion and water-whitening resistance were evaluated in the same manner. The results are shown in Table-1. It should be noted that this wall coating material (2') had poor workability when applied with a trowel.

/ / / / Table = 1 [Effects of the Invention] The wall coating material using the acrylic resin binder for wall coating materials of the present invention has excellent water-resistant adhesion and water-whitening resistance without being affected by dry curing temperature, and Workability with troweling is also good.

Claims (1)

[Claims] 1. A water-based wall coating material containing aggregate, a water-soluble resin, and an acrylic resin binder, which has an anionic group and a cationic group as the acrylic resin binder (meth) A wall coating material characterized by using an acrylic acid alkyl ester copolymer emulsion (I). 2. (meth)acrylic acid alkyl ester copolymer emulsion having an anionic group and a cationic group (
I) is a (meth)acrylic acid alkyl ester (a), an anionic group-containing polymerizable monomer (b), a cationic group-containing polymerizable monomer (c), and a crosslinkable monomer (d). The wall coating material according to claim 1, which is obtained by polymerizing as an essential component. 3. The acrylic resin binder contains a (meth)acrylic acid alkyl ester copolymer having an anionic group and a cationic group and a film-forming aid,
Claim 2, wherein the minimum film forming temperature (MFT) is 5°C or less.
Wall painting materials listed. 4. (meth)acrylic acid alkyl ester copolymer emulsion having an anionic group and a cationic group (
I) An acrylic resin binder for wall coating materials. 5. (meth)acrylic acid alkyl ester copolymer emulsion having an anionic group and a cationic group (
I) is a (meth)acrylic acid alkyl ester (a), an anionic group-containing polymerizable monomer (b), a cationic group-containing polymerizable monomer (c), and a crosslinkable monomer (d). 5. The binder according to claim 4, which is obtained by polymerizing the following as an essential component. 6. It contains a (meth)acrylic acid alkyl ester copolymer emulsion having an anionic group and a cationic group and a film-forming aid, and has a minimum film-forming temperature (MFT) of 5°C. The binder according to claim 5, which is as follows.