JPH05156201A - Water-paint composition - Google Patents

Abstract

PURPOSE:To obtain an odorless water-paint composition giving a tack-free finished coating film having clear luster and excellent water-resistance by using a specific acrylic emulsion resin and a specific film-forming assistant. CONSTITUTION:The objective water-paint composition free from odor, giving a tack-free coating film and capable of developing clear luster is produced by using (A) an acrylic emulsion resin (e.g. styrene/acrylate copolymer emulsion resin) and/or its mixture with a plasticizer (e.g. dibutyl phthalate) having an unreacted monomer content of <=0.05% and the lowest film-forming temperature of >=10 deg.C and <35 deg.C, (B) #20% (based on the solid content of the component A) of one or more kinds of film-forming assistants selected from diethylene glycol dibutyl ether, dipropylene glycol monobutyl ether and dipropylene glycol monopropyl ether and, as, necessary, (C) pigment, dispersing agent, defoaming agent, thickener, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-based coating composition, the purpose of which is to allow the work to be performed odorlessly without spreading the paint odor at the time of coating or drying of the coating film, and to make the finished coating film sticky. An object of the present invention is to provide a water-based coating composition that is free of brilliance and can provide excellent gloss and water resistance.

[0002]

BACKGROUND OF THE INVENTION Consumable paint types have been transferred from solvent-based paints to water-based paints, and the generation of unpleasant paint odors during coating and drying has become extremely small with the shift to water-based paints.
However, even with water-based paints, the generation of paint odors is certainly suppressed compared with solvent-based paints, but the current situation was that unpleasant paint odors were generated during coating and drying of the coating film. .. On the other hand, global environmental issues have been attracting worldwide attention, and in product development, from the concept of prioritizing the functions so far, "protecting the global environment" and "securing a healthy and comfortable living space" It has been transferred to the way of thinking. In the paint industry as well, the demand for creating a comfortable environment is increasing, and the development of "odorless paints" that can be suitably used as "paints that are kind to humans and the earth" and indoors are being carried out. There is.

[0003]

2. Description of the Related Art It is known that the cause of odor in water-based paints, that is, acrylic emulsion resin paints, is residual unreacted components in the resin and auxiliary substances such as film-forming aids and preservatives contained in the paint. ing. Therefore, in recent years, research has been conducted on residual unreacted components and auxiliaries that cause these paint odors, and "odorless paints" that do not emit paint odors during coating work have been developed. This "odorless paint" is one in which the residual unreacted component, which is one of the causes of odor, is reduced to 1/10 or less of that of a normal acrylic resin emulsion, and a low odor level auxiliary agent is selected and used. It was "matte paint".

As a low odor level auxiliary agent used in the "odorless matte coating", known film forming auxiliary agents such as dibutyl phthalate and 2-ethylhexyl phthalate are selectively used. Generally, these film-forming aids are those used as plasticizers for resins, and when added, a tackiness is expressed in the coating film, and in the case of a water-based matting paint,
It is suitable for use in water-based matte coatings because it contains more pigment than water-based paints that have a gloss and because the surface of the coating film is relatively rough, it is not affected by stickiness. It was the most suitable film-forming aid for deodorizing.

[0005]

However, in the case of a water-based glossy coating, the amount of pigment is smaller than that of a non-lustrous coating and the coating film surface is smooth, so that the above-mentioned dibutyl phthalate or 2-ethylhexyl phthalate is used. When a film-forming aid is used, deodorization of the coating material can be achieved, but the coating film becomes tacky and loses its function as a coating film, so that there is a problem that a practical coating material cannot be obtained.

[0006] In the industry, it has been desired to create an aqueous lustrous paint which is odorless, has no tackiness on the coating film, and can express a vivid gloss.

[0007]

In the present invention, the unreacted monomer content is 0.05% or less, and the minimum film forming temperature is 10 ° C.
An acrylic emulsion resin containing at least 35 ° C. and less than an acrylic emulsion resin alone and / or a plasticizer, and at least one or more film-forming aids selected from diethylene glycol dibutyl ether, dipropylene glycol monobutyl ether, and dipropylene glycol monopropyl ether. And a content of the film-forming auxiliary is 20% or less relative to the acrylic emulsion resin solid content and by providing an aqueous coating composition characterized by the above-mentioned conventional problems Dissolve in a grudge.

[0008]

The constitution of the aqueous coating composition according to the present invention will be described in detail below. In this invention, the unreacted monomer content is 0.05% or less, and the minimum film forming temperature is 10 ° C or more.
Acrylic emulsion resin alone which is less than 35 ° C. and / or emulsion resin containing a plasticizer is used as an essential component.

In the present invention, the reason why the unreacted monomer content is 0.05% or less is that the unreacted monomer content is 0.
If it exceeds 05%, the unpleasant odor generated from the monomer odor cannot be suppressed, which is not preferable as an odorless paint.

Further, the reason why the minimum film forming temperature of the acrylic emulsion resin and / or the acrylic emulsion resin containing a plasticizer is limited to 10 ° C. or more and less than 35 ° C. is that the coating film has a minimum film forming temperature of less than 10 ° C. This is because a sticky feeling appears and it is not preferable as a coating material, while at 35 ° C. or higher, the coating film becomes too brittle, which is not preferable in any case.

As the acrylic emulsion resin alone,
Acrylic copolymer emulsion resin or styrene / acrylic copolymer emulsion resin can be preferably exemplified, and the unreacted monomer content is 0.05% or less and the minimum film forming temperature is in the range of 10 ° C or higher and lower than 35 ° C. If,
There is no particular limitation, and any of them can be preferably used.

In the present invention, even an acrylic emulsion resin having a minimum film forming temperature of 35 ° C. or higher can be preferably used, which is less than 35 ° C. by adding a plasticizer. As the plasticizer, dibutyl phthalate, 2-ethylhexyl phthalate, butyl benzyl phthalate and the like can be preferably used because the minimum film forming temperature of the acrylic emulsion resin can be reduced to less than 35 ° C. without unpleasant odor. Acrylic emulsion resins having a minimum film-forming temperature within the range of 10 ° C. or higher and lower than 35 ° C. can also be suitably used.

As the film forming aid, at least one selected from specific film forming aids, that is, diethylene glycol dibutyl ether, dipropylene glycol monobutyl ether, and dipropylene glycol monopropyl ether, is selected and used. These film-forming aids have not been used at all as film-forming aids in the past, but they do not emit an unpleasant odor and can be smoothly formed into a film, and the film formation of an odorless coating film does not develop a sticky feeling after drying the coating film. It has been found that it can be used as an auxiliary agent, and as a result, it is used for the first time based on the experimental knowledge obtained by the inventors' earnest research that created an odorless paint.

That is, ethylene glycol monobutyl ether, benzine alcohol, and 2,2,4-trimethyl-1,3, which are generally used in conventional water-based glossy coatings.
-Pentanediol monoisobutyrate (Texanol and abbreviated as trade name below), toluene, xylene and other film-forming aids do not give a sticky feeling even when added until film formation, but an unpleasant odor can be obtained only by using a small amount. It becomes so strong that it cannot be used as an odorless paint, and by using at least one of diethylene glycol dibutyl ether, dipropylene glycol monobutyl ether, and dipropylene glycol monopropyl ether as a film-forming aid, it will be odorless. It is a water-based glossy coating that has excellent properties and does not have a tacky feeling on the coating film, and can develop vivid gloss.

The content of such a film-forming aid is 20% or less based on the solid content of the acrylic emulsion resin. The reason for this is that if the content of the film-forming auxiliary exceeds 20%, the odor becomes strong, which is not preferable as an odorless paint.

In the odorless water-based coating composition according to the present invention containing the above-mentioned essential components, in addition to the above, pigments, dispersants, defoamers, thickeners, preservatives, antifreezing agents, etc. Additives can also be used suitably.

[0017]

As described above in detail, the present invention has an unreacted monomer content of 0.05% or less and a minimum film forming temperature of 10%.
℃ or more and less than 35 ℃ acrylic emulsion resin alone and / or an acrylic emulsion resin containing a plasticizer, and at least one or more film-forming aid selected from diethylene glycol dibutyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether And a coating agent, and the content of the film-forming auxiliary is 20% or less based on the solid content of the acrylic emulsion resin, which is an aqueous coating composition. Eliminates pleasant sensations and does not make sick people and guests uncomfortable when painting the interior of hospitals and hotels,
In addition, it has an effect of being an excellent water-based coating composition which can be used immediately after drying and which can give a finished coating film with no tackiness, vivid gloss and excellent water resistance.

[0018]

[Test Example] Hereinafter, the effect of the water-based coating composition according to the present invention will be further clarified by a test example.

[0019]

【Example】

(Examples 1 to 10 and Comparative Examples 1 to 11) Examples 1 to 10
Was prepared according to the formulation in Table 1.

[0020]

[Table 1]

The aqueous coating compositions of Comparative Examples 1 to 11 were prepared according to the formulation shown in Table 2.

[0022]

[Table 2]

Resins I to VI were obtained by the following manufacturing method. (Resin I) Acrylic copolymer emulsion resin "Primal AC507" (trade name; manufactured by Rohm and Haas Japan Co., Ltd.) with a minimum film forming temperature of 14 ° C. is decompressed while blowing steam with a steam distillation device. The unreacted monomer content is 0.05% or less. Solid content 46.5%. (Resin II) Styrene / acrylic copolymer emulsion resin "Boncoat EC846" with a minimum film forming temperature of 28 ° C (trade name;
(Manufactured by Dainippon Ink and Chemicals, Inc.) with the content of unreacted monomer being 0.05% or less in the same manner as in Resin I above.
Solid content 50.0%. (Resin III) Acrylic polymerized emulsion resin "Minimal C72" (trade name; manufactured by Rohm and Haas Japan Co., Ltd.) with a minimum film formation temperature of 39 ° C is depressurized while blowing steam with a steam distillation device. After the unreacted monomer content was 0.05% or less, a plasticizer (dibutyl phthalate) was added at 2% and the minimum film forming temperature was adjusted to 29 ° C. Solid content 47.0%. (Resin IV) Styrene / acrylic polymerized emulsion "Polysol AP2681" (trade name; manufactured by Showa Highpolymer Co., Ltd.) with a minimum film forming temperature of 40 ° C was used in the same manner as in Resin III, and the unreacted monomer content was 0.05%. After the following, a plasticizer (dibutyl phthalate) was added at 2% and the minimum film forming temperature was adjusted to 30 ° C. Solid content 52.0%. (Resin V) Acrylic copolymer emulsion resin "Primal AC507" (trade name; manufactured by Rohm and Haas Japan Co., Ltd.) having a minimum film forming temperature of 14 ° C. Unreacted monomer content 1.0%. Solid content 46.5%. (Resin VI) Styrene / acrylic copolymer emulsion resin "Polysol AP2681" with a minimum film forming temperature of 40 ° C (trade name;
Showa Highpolymer Co., Ltd.). Unreacted monomer content 1.0%.
Solid content 52.0%.

The following were used as the dispersant, thickener, antifoaming agent and preservative. A dispersant: sodium polycarboxylic acid trade name: Orotan 731SD (manufactured by Rohm and Haas Co., Ltd.) B thickener: hydroxyethyl cellulose-based thickener trade name: Cellosize QP4400 (manufactured by Union Carbide Co., Ltd.) C defoaming agent: a mixture of mineral oil and nonionic sea surface active agent Trade name: SN Deformer 370 (San Nopco Ltd.)
Made) D preservative: 1,2-benzisothiazolone (trade name) Bestside FX (manufactured by Dainippon Ink and Chemicals, Inc.)

Test Example: Examples 1 to 10 and Comparative Example 1
The water-based coating compositions obtained in Nos. 11 to 11 were tested for each of the items shown below. The results are shown in Table 3.
And shown in Table 4.

Odor (odor sensor value) The odor was measured by New Cosmos Electric Co., Ltd. odor sensor XP-329. Examples 1-10 in a 100 ml mayonnaise bottle,
50 ml of each of the paints of Comparative Examples 1 to 11 was put, and the measurement (20 ° C.) was made at a portion 10 mm from the liquid surface. Odor sensor value 0 to 500: 〇 Slight resin odor and solvent odor, but not unpleasant 500 <～ 1000: × Unpleasant odor 1000 <： ×× Unpleasant unpleasant odor (Reference: Water odor sensor value is 0) Film formation temperature of coating material ℃ Measured with a thermal gradient tester (manufactured by Yasuda Seiki Co., Ltd.). Drying time It was measured according to JIS K 5660 4,6 and measured by semi-curing drying (20 ° C). Appearance of coating film JIS K 5660 4,7 was performed, and the appearance of the coating film was normal, and ◯, and those having any of holes, sagging, uneven gloss, and uneven color were evaluated as x. 60 degree specular gloss It was performed according to JIS K 5660 4,9. Water resistance According to JIS K 5660 4,10, if there is no abnormality in the coating film, ◯, wrinkle, swelling, peeling or peeling is marked as ×. Alkali resistance JIS K 5660 4,11 was used. If there were no abnormalities in the coating film, it was marked with ◯, and when there were wrinkles, blisters, cracks, peeling, holes, softening, or elution, it was marked with x. A B-type film applicator with a clearance of 0.1 mm was applied to a non-adhesive glass plate, and the paints of Examples and Comparative Examples were applied to the plate. After drying at room temperature for 7 days, 5 pieces of gauze were stacked and a 500 g weight was placed in the center of the gauze. After allowing to stand for a period of time, the gauze was separated from the coated surface, and the degree of adhesion between the coated surface and the gauze and the marks on the coated surface were examined. The case where there was no stickiness or the mark of the cloth was marked with ◯, and the case where there was any was marked with x.

[0027]

[Table 3]

[Table 4]

As is clear from the results of the above-mentioned test examples, the resins having an unreacted monomer content of more than 0.05% (Comparative Examples 1 to 3 and 8 to 11) had a strong unpleasant odor, and Even if the unreacted monomer content in the resin is 0.05% or less, an unpleasant odor is felt when ethylene glycol monobutyl ether, benzyl alcohol, or texanol is used as the film forming aid (Comparative Examples 4 to 6). I understand. In addition, the unreacted monomer content in the resin is 0.05
% Or less, and when dibutyl phthalate used in the conventional "water-based matting paint" is used as the film-forming aid (Comparative Example 7), no unpleasant odor is felt, but water resistance, alkali resistance, and tack-freeness It turns out that the sex becomes extremely poor.

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[Procedure amendment]

[Submission date] February 28, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0024

[Correction method] Change

[Correction content]

The following were used as the dispersant, thickener, antifoaming agent and preservative. A dispersant: sodium polycarboxylic acid trade name: Orotan 731SD (manufactured by Rohm and Haas Co., Ltd.) B thickener: hydroxyethyl cellulose-based thickener trade name: Cellosize QP4400 (manufactured by Union Carbide Co., Ltd.) C antifoaming agent: formulations tradename mineral oil and nonionic field surfactant) SN defoamer 370 (San Nopco Co.,
Made) D preservative: 1,2-benzisothiazolone (trade name) Bestside FX (manufactured by Dainippon Ink and Chemicals, Inc.)

Claims (1)

[Claims] 1. An acrylic emulsion resin containing an unreacted monomer content of 0.05% or less and a minimum film-forming temperature of 10 ° C. or more and less than 35 ° C. and / or an acrylic emulsion resin containing a plasticizer, and diethylene glycol dibutyl ether. , Dipropylene glycol monobutyl ether,
At least one film-forming aid selected from dipropylene glycol monopropyl ether is contained, and the content of the film-forming aid is 20% or less based on the solid content of the acrylic emulsion resin. An aqueous coating composition characterized by: