JP3433121B2 - Waterborne paint for indoor pollution control - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an indoor floor, wall surface,
Apply to plywood or vinyl wallpaper used for ceilings, furniture, etc., form a coating film that adsorbs or decomposes harmful substances such as formaldehyde and plasticizers that volatilize from these, and further volatilizes volatile organic compounds during application. Water-based paint for indoor pollution control with low emission.

[0002]

2. Description of the Related Art At present, the dry method occupies an extremely high proportion of domestic construction finishes, especially on indoor floors / walls and ceilings, gypsum boards, plywood and particle boards, and vinyl wallpaper. It is no exaggeration to say that most of the finishing uses vinyl chloride flooring as the interior material. Since these are low in production cost and easy to install,
Economically efficient. However, for finishing with these as interior materials, formalin (formaldehyde) normally contained in the adhesive part of plywood and plasticizers (DOP, TCP, DOA etc.) contained in vinyl materials, flame retardants (TCEP etc.)
Hazardous substances such as volatilize indoors. In recent years, the concentration of these harmful substances in the living space has increased remarkably as the airtightness of houses has increased, and the problem of adverse effects on the human body has arisen. For example, the relationship between atopy, allergic and carcinogenicity Is also being pointed out. In addition, vinyl wallpaper and vinyl chloride flooring have a serious environmental problem when they are discarded and old products are discarded.

To address the above-mentioned problems, the present applicant has previously proposed to use a water-based paint for renovating vinyl wallpaper in order to alleviate the problem of discarding vinyl wallpaper (Japanese Patent Laid-Open No. 8-4138).
3 gazette). According to this, when the vinyl wallpaper fades over time or stains such as tobacco tar occur, by coating the paint on the vinyl wallpaper, it is possible to remodel the vinyl wallpaper, which has been difficult in the past. Moreover, the effect of suppressing the volatilization of the plasticizer from the vinyl wallpaper was also obtained. Furthermore, it was proposed to use a coating material containing a specific cross-linkable emulsion resin and a pigment (Japanese Patent Laid-Open No. 10-1823023), and it was found that the resulting coating film has a high effect of suppressing the emission of harmful substances such as formalin. It was

[0004] However, conventional conventional dry water-based paint,
An organic solvent such as dibutyl phthalate, butyl cellosolve, or texanol or a plasticizer is contained to secure the film-forming property of the emulsion resin. Since these organic solvents or plasticizers in the coating material are adsorbed first to the pigment having an adsorbing action, the original adsorbing action is not sufficiently expressed, and it is necessary to blend a large amount of the pigment having the adsorbing action. there were. Further, although the organic solvent in the paint almost evaporates immediately after coating, some of the remaining solvent is gradually released after coating, so that an odor may remain for several days.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a water-based resin having a low film-forming temperature and a pigment having an adsorbing action further contain nitrogen containing aldehydes. The present inventors have found that a coating material containing a compound has almost no odor during and after coating, and forms a coating film capable of adsorbing and decomposing formaldehyde and the like immediately after coating, and thus reached the present invention.

That is, according to the present invention, (A) the minimum film forming temperature is 0 ° C.
It contains the following water-soluble or water-dispersible resin and (B) at least one pigment selected from diatomaceous earth, activated alumina, activated clay and zeolite .
Resin (A) contains one or more ethylenic unsaturation
Gas obtained by emulsion polymerization of a mixture of hydrated monomers
The core component is a copolymer having a lath transition temperature of 0 ° C or higher.
In an aqueous dispersion containing it, one or more kinds of
Emulsion polymerization is carried out by adding a mixture of ethylene unsaturated monomers.
The glass transition temperature obtained by and becomes −60 to 0 ° C.
Aqueous dispersion of core-shell particles containing copolymer as shell component
Liquid, or one or more ethylenically unsaturated compounds
Glass obtained by emulsion polymerization of a monomer mixture
A copolymer having a transition temperature of −60 to 0 ° C. as a core component
In an aqueous dispersion containing it, one or more kinds of
Emulsion polymerization is carried out by adding a mixture of ethylene unsaturated monomers.
Copolymers with glass transition temperature of 0 ℃ or higher
An aqueous dispersion of core-shell particles containing coalesced shell components.
And in the total monomer mixture used for these
A carbonyl group-containing monomer is contained in an amount of 0.5 to 8% by weight.
In the monomer mixture that forms the copolymer that becomes the
A carbonyl group-containing monomer,
The content of the component is 5 to 3 with respect to 100 parts by weight of the resin solid content.
The present invention provides a water-borne paint for indoor pollution control, characterized in that the content of the organic solvent is 50 parts by weight, and the content of the organic solvent having a boiling point of 50 to 250 ° C in the paint is 1% or less.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the water-soluble or water-dispersible resin (A) is a resin having a minimum film forming temperature of 0 ° C. or lower, and does not contain a film forming auxiliary such as an organic solvent or a plasticizer. It is a resin that can be formed into a film at room temperature. As such a water-soluble or water-dispersible resin (A), conventionally known water-soluble or water-dispersible resins can be used, but the following four types are particularly preferably used, and these can be used alone or in combination. You can use it.

(I) An aqueous dispersion of a copolymer having a glass transition temperature of 0 ° C. or lower, which is obtained by emulsion polymerization of a mixture of one or more ethylenically unsaturated monomers.
(II) A copolymer aqueous dispersion having a glass transition temperature of 0 ° C. or higher obtained by emulsion polymerization of a mixture of one or more ethylenically unsaturated monomers, and a glass transition temperature of −60 to An aqueous dispersion prepared by mixing an aqueous dispersion of a copolymer at 0 ° C. in a solid content ratio of 20/80 to 80/20, (III) one or more ethylenically unsaturated monomers A copolymer having a glass transition temperature of 0 ° C. or higher obtained by emulsion-polymerizing the mixture is used as a core component, and one or more ethylenically unsaturated monomer mixture is added to an aqueous dispersion containing the core component. In addition, an aqueous dispersion of core-shell particles containing as a shell component a copolymer having a glass transition temperature of −60 to 0 ° C. obtained by emulsion polymerization, and (IV) one or more ethylenic monomers Emulsion weight of saturated monomer mixture By using the copolymer having a glass transition temperature of −60 to 0 ° C. obtained as a core component, one or two or more ethylenically unsaturated monomer mixtures are added to an aqueous dispersion containing the core component. A core-shell particle aqueous dispersion containing as a shell component a copolymer having a glass transition temperature of 0 ° C. or higher, which is obtained by emulsion polymerization.
Is.

In any of the above, examples of the ethylenically unsaturated monomer include, for example, methyl (meth) acrylate,
Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, C1-C24 alkyl or cycloalkyl esters of (meth) acrylic acid such as isobornyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and the like ( C2 to C8 hydroxyalkyl ester of (meth) acrylic acid; acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formyl styrene, vinyl alkyl having 4 to 7 carbon atoms Ketones (eg vinyl methyl ketone, vinyl ether Ketone, carbonyl group-containing monomers such as vinyl butyl ketone) -; (meth) acrylic acid,
Maleic acid, β-carboxyethyl acrylate, sulfoethyl methacrylate and their sodium salts and ammonium salts; (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate; styrene , Vinyl aromatic compounds such as vinyltoluene; N-vinylpyrrolidone, ethylene, butadiene, chloroprene, vinyl propionate,
Examples thereof include vinyl acetate and (meth) acrylonitrile, and one or more of these are selected and used according to the desired performance. Especially from the durability and water resistance of the coating film,
It is desirable that the carbonyl group-containing monomer is contained in the total monomer mixture to be used in an amount of 10% by weight or less, preferably 0.5 to 8% by weight. In the above (III) and (IV), it is desirable that the monomer mixture forming the copolymer serving as the shell component contains the carbonyl group-containing monomer.

In the above-mentioned (III) and (IV), a polymerizable unsaturated monocarboxylic acid ester of polyvalent alcohol is added to the monomer mixture forming the copolymer as the core component.
It is desirable to contain 0.05 to 5% by weight of a polyunsaturated alcohol ester of a polybasic acid and a polyvinyl compound such as an aromatic compound substituted with two or more vinyl groups.

In any of the above (I) to (IV),
Emulsion polymerization of the monomer mixture is carried out using a polymerization initiator such as a persulfate or a peroxide in the presence of an emulsifier, and as the emulsifier, an anionic surfactant, a nonionic surfactant, etc. Is mentioned. Further, an oxidizing agent, a reducing agent or the like may be used in order to reduce the amount of residual monomers after the polymerization.

Further, in the above (III) and (IV), the solid content weight ratio of the copolymer as the core component to the copolymer as the shell component is 8 because of the film-forming property and the initial water resistance.
0/20 to 20/80, preferably 70/30 to 30 /
A value of 70 is suitable.

In the present invention, at least one kind of pigment (B) selected from diatomaceous earth, activated alumina, activated clay and zeolite is 5 to 300 parts by weight, preferably 20 to 10 parts by weight with respect to 100 parts by weight of the resin solid content. 200 parts by weight are blended.

Both activated alumina and activated clay are compounds having a porous structure having a large adsorption ability, and are industrially used for decolorizing and refining fats and oils and petroleum mineral oils.

Activated alumina has a pore structure obtained by calcining alumina hydrate such as gypsite, beehmite, bayerite, and amorphous hydrated gel at an appropriate temperature, usually 200 to 1,000 ° C. It is an intermediate alumina (transition alumina). Activated alumina is also called gamma-alumina. Examples of commercially available products include activated alumina KC-501 and KC-503 manufactured by Sumitomo Chemical Co., Ltd.

The activated clay is obtained by treating acid clay, which is one of clays containing montmorillonite group clay minerals and soluble silicic acid as main components, with an acid to elute a part of basic components. Commercially available products include activated clay from Japan Activated Clay Co., Ltd. and Galleon Eart from Mizusawa Chemical Co., Ltd.
h NV etc. are mentioned.

Zeolites include natural zeolite mainly composed of hydrous aluminosilicate and Na ₂ O.Al ₂ O ₃
-Synthetic zeolite mainly composed of xSiO ₂ · yH ₂ O is available. Synthetic zeolites, also called permtites, are produced by a dry method in which sodium carbonate, silica, alumina or kaolin is eutectic, or a wet method in which sodium silicate and sodium aluminate are combined to precipitate a gel. Both natural zeolites and synthetic zeolites have an ion-exchange capacity, the crystal structure does not change even when dehydrated, and molecular size pores are obtained after dehydration, which has a large adsorption capacity. Also, pores of a certain size can be obtained after crystallization and dehydration of sodium aluminosilicate gel by hydrothermal synthesis.
Molecular sieves and the like are also effective in the present invention.

Since diatomaceous earth is a hydrated silicon dioxide and has a porous structure, it has a property of absorbing liquid well. In non-paint applications, it is used as agricultural chemicals, filtering agents, and abrasives. It is used as a bulking agent and matting agent in paint applications. Examples of commercially available products include Radiolite F and Radiolite FO manufactured by Showa Chemical Industry Co., Ltd.

Further, in the coating material of the present invention, from the viewpoint of imparting antibacterial property and improving barrier property, 1 to 100 parts by weight, preferably 5 to 50 parts by weight of an inorganic oxide having photocatalytic activity is added to 100 parts by weight of resin solid content. It can be mixed in parts by weight. When the content is less than 1 part by weight, the antibacterial property and the barrier property cannot be sufficiently improved, and when it exceeds 100 parts by weight, the physical properties of the coating film are deteriorated, which is not desirable.

The inorganic oxide having photocatalytic activity is a semiconductor particle having a band gap, and is photoexcited when irradiated with light having an energy higher than the band gap (for example, sunlight or ultraviolet rays of artificial illumination light). The electrons and holes generated by the above move to the surface of the semiconductor particles and exert a function of decomposing bacteria, formalin and the like in contact with them due to their strong oxidizing ability. Specific examples of the inorganic oxide include TiO ₂ , RuO ₂ , CoO, and Ce _{2.
O 3, Cr 2 O 3,} Rh 2 O 3, V 2 O 5, ZnO or the like can be mentioned, TiO _2, Z particular safety from the viewpoint of economy
nO is preferred. There are three types of titanium oxide called TiO ₂ which are a rutile type and anatase type which belong to a tetragonal system and a brookite type which belongs to an orthorhombic system. Anatase is a titanium oxide having photocatalytic activity. Type titanium oxide.

The inorganic oxide having photocatalytic activity has an average particle size of 500 nm or less, preferably 3 to 300 nm. If the particle size exceeds 500 nm, the photocatalytic activity and dispersibility decrease, and the storage stability also decreases, which is not preferable.

In order to further enhance the photocatalytic activity of the above-mentioned inorganic oxide, Fe, Mo, Ru, O is formed on the surface of the inorganic oxide.
Metal components such as s, Re, V, Rh, Ag, Cu, and Zn can be supported in the form of oxides or metal ions. Among them, Ag, Cu, and Zn are added from the viewpoint of imparting antibacterial properties.
It is preferable to carry at least one antibacterial metal component selected from the following. As a method of supporting these metal components, a conventionally known method can be adopted. For example, in the case of supporting Ag, silver oxide is dissolved in aqueous ammonia to form an amine complex salt aqueous solution of silver, and after the inorganic oxide is added and stirred, It is suitable to obtain the filtration residue by heating and drying at 150 ° C. for 48 hours.

The composition of the inorganic oxide having photocatalytic activity is
For example, after directly mixing the powder of the inorganic oxide in the paint,
Although it may be dispersed with a stirrer such as a disperser, a sand mill, a shaker, etc., it may be mixed with the resin component to obtain an appropriate viscosity (5
It is desirable to disperse the resin into a paste and then to make a paint.

Inorganic oxide powder having photocatalytic activity may be blended as a solution to form colloidal particles.
Incorporation as an inorganic oxide colloidal solution is preferable from the viewpoint of photocatalytic activity and antibacterial property, since the above dispersion step is not necessary and the powder can be incorporated in a finer state in the water-based paint. Examples of the inorganic oxide colloidal solution include, for example, JP-A-6-80527 and JP-A-7-3361.
For example, colloidal particles of TiO ₂ single oxide and colloidal particles of complex oxide such as SiO ₂ · Al ₂ O ₃ · TiO ₂ are disclosed. These can be made into colloidal particles by adhering the above-mentioned antibacterial metal component to the surface of the colloidal particles or by mixing with the inorganic oxide.

Further, as a pigment component, if necessary, for example, coloring pigments such as titanium oxide, carbon black, red iron oxide, and phthalocyanine blue, and extender pigments such as calcium carbonate, talc, mica, clay, silica sand, and perlite. Aggregates and the like may be appropriately selected and mixed.

As a whole of the above pigment component, the volume ratio (PVC) of all pigments (including activated alumina, activated clay, zeolite, diatomaceous earth, and inorganic oxide having photocatalytic activity) to the total solid content in the coating material is 15 to. 70%, preferably 20-
It is desirable that the content is 60% from the viewpoint of the denseness and barrier property of the coating film.

In the coating composition of the present invention, a nitrogen-containing compound (C) having an aldehyde adsorption ability is further added to the coating solution in an amount of 0.1 to 0.1%.
It can be contained in a proportion of 3% by weight. The nitrogen-containing compound (C) is a -NH group,-in a molecule capable of capturing an aldehyde such as formaldehyde by a chemical bond.
It contains an NH ₂ group, such as primary amines or 2
Examples include primary amines, hydrazine, and hydrazine derivatives.

Examples of primary and secondary amines include dodecylamine, tridecylamine, tetradecylamine, imidazolidinone, and the amino acids lysine, arginine, histidine and their derivatives. The hydrazine derivative has at least two hydrazide groups or semicarbazide groups in one molecule. Examples of the hydrazine derivative include oxalic acid dihydrazide, malonic acid dihydrazide, glutaric acid dihydrazide, succinic acid dihydrazide, and adipic acid dihydrazide. , Saturated aliphatic carboxylic acid dihydrazides having 2 to 18 carbon atoms such as sebacic acid dihydrazide; monoolefinic unsaturated dicarboxylic acid dihydrazides such as maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide; phthalic acid, terephthalic acid or Isophthalic acid dihydrazide, and dihydrazide, trihydrazide or tetrahydrazide of pyromellitic acid; nitrilotriacetic acid trihydrazide, citric acid trihydrazide, 1,2,4-benzene Hydrazide, ethylenediaminetetraacetic acid tetrahydrazide, 1,4,5,8
Naphthoic acid tetrahydrazide, polyhydrazide obtained by reacting a low polymer having a carboxylic acid lower alkyl ester group with hydrazine or hydrazine hydrate (hydrazine hydrate) (see Japanese Patent Publication No. 52-22878); carbonic acid dihydrazide, bissemicarbazide A polyfunctional semicarbazide obtained by excessively reacting a diisocyanate such as hexamethylene diisocyanate or isophorone diisocyanate and a polyisocyanate compound derived therefrom with a dihydrazine compound or the above-exemplified dihydrazide An excess of the above-mentioned dihydrazide to the isocyanate group in the reaction product of the polyisocyanate compound and the active hydrogen compound containing a hydrophilic group such as polyether polyols and polyethylene glycol monoalkyl ethers. Aqueous system obtained by reacting with Functional semicarbazide, or polyfunctional semicarbazide and aqueous polyfunctional semicarbazide and mixtures (JP-A-8-151358, JP-A 8-2458
No. 78) and the like. Among these, hydrazine derivatives having a hydrazide group or a semicarbazide group having a molecular weight of 100 to 500, such as adipic acid dihydrazide and citric acid trihydrazide, are particularly preferable.

The content ratio of the nitrogen-containing compound (C) in the coating liquid is 0.1 to 3% by weight, preferably 0.3 to
It is desirable that the content be 2% by weight. If the use ratio exceeds 3% by weight, the water resistance of the coating film is lowered, which is not preferable. Further, when the resin (A) contains a carbonyl group, if the hydrazine derivative is used as a cross-linking agent component, it will be consumed for cross-linking and the aldehyde adsorbing ability will not be sufficiently obtained. It is desirable to mix it with. Specifically, the amount of the hydrazide group or semicarbazide group in the hydrazine derivative is 1 mol or more, preferably 1.2 mol or more, and more preferably 3 mol per 1 mol of the carbonyl group contained in the resin (A). Is blended with.

The coating composition of the present invention may further contain, if necessary, additives for coating such as a surfactant, a dispersant, a defoaming agent, a thickener and a preservative.

In the paint of the present invention, the content of the organic solvent having a boiling point of 50 to 250 ° C. in the paint is 1% or less, preferably 0.7.
% Or less is essential. Organic solvents such as film-forming aids and antifreezing agents that have been conventionally blended in water-based paints are not blended in this range.

The method for producing the coating composition of the present invention is not special and can be carried out by a method known per se. It can be carried out by adding a crosslinking agent, a pigment component and, if necessary, a coating additive to the copolymer emulsion and uniformly dispersing them by a known means such as a stirrer.

According to the present invention, the surface of the interior material applied to the floor, the wall surface, and the ceiling, particularly the surface of the interior material that volatilizes indoor pollutants, is coated with the indoor pollution control paint obtained as described above to prevent indoor pollution. To prevent.

Examples of interior materials applied to floors / walls and ceilings in the room include gypsum boards, plywood and particle boards, vinyl wallpapers, vinyl chloride flooring materials and the like. They are,
For example, formalin (formaldehyde) contained in the adhesive part of plywood and plasticizers (DOP, T contained in vinyl materials).
It volatilizes indoor pollutants such as CP, DOA, TCEP, etc.

The above indoor pollution control paint usually has about 0.1 to 0.1% on the surface of the interior material that volatilizes these indoor pollutants.
It is preferable that the coating amount is within the range of 0.5 kg / m ² (dry coating amount is about 50 to 250 g / m ² ).

The above-mentioned painting can be performed at any time, but since the volatilization amount of formalin is the largest at the time of new construction, for example, after the new construction, the ventilation is ensured to release the volatile matter, and immediately before moving in, the surface of plywood or plywood. Specifications such as coating the above paint on a vinyl wallpaper pasted on are appropriate.

[0037]

EXAMPLES The present invention will be described in more detail with reference to examples. In addition, "part" and "%" are based on weight unless otherwise specified.

Production of Copolymer Emulsion Production Example 1 Deionized water 232 was placed in a 2-liter four-necked flask.
And 2.3 parts of Newcol 707SF (manufactured by Nippon Emulsifier Co., Ltd., an anionic surfactant having a polyoxyethylene chain, nonvolatile content 30%) were added, and the temperature was maintained at 80 ° C. after nitrogen replacement. Add 0.7 parts of ammonium persulfate to this,
15 minutes after the addition, a pre-emulsion obtained by emulsifying the monomer mixture shown in Table 1 and deionized water was added dropwise over 3 hours.

Thirty minutes after the end of the dropping, 7.7 parts of a solution prepared by dissolving 0.7 part of ammonium persulfate in 7 parts of deionized water was started to be added, and the addition was completed over 30 minutes. This was kept at 80 ° C. for another 2 hours and then cooled to 45 ° C. Then pH with 20% aqueous sodium hydroxide
8 to adjust the solid content of the copolymer emulsion to 50% (A
-1) was obtained.

Production Examples 2, 6 and 7 The same procedure as in Production Example 1 was carried out except that the composition of the pre-emulsion was changed as shown in Table 1 to produce each copolymer emulsion (A) having a solid content of 50%. -2), (A-
6) and (A-7) were obtained.

Production Example 3 Deionized water 232 was placed in a 4-necked flask having a capacity of 2 liters.
And 30 parts of Newcol 707SF were added, the atmosphere was replaced with nitrogen, and the temperature was maintained at 80 ° C. To this, 0.7 part of ammonium persulfate was added, and 15 minutes after the addition, a pre-emulsion obtained by emulsifying the monomer mixture shown in Table 1 and deionized water was added dropwise over 3 hours.

Thirty minutes after the end of the dropping, 7.7 parts of a solution prepared by dissolving 0.7 part of ammonium persulfate in 7 parts of deionized water was started to be added, and the addition was completed over 30 minutes. This was kept at 80 ° C. for another 2 hours and then cooled to 45 ° C. Then pH with 20% aqueous sodium hydroxide
8 to adjust the solid content of the copolymer emulsion to 50% (A
-3) was obtained.

Production Example 4 232 parts of deionized water was placed in a four-necked flask having a capacity of 2 liters, and after purging with nitrogen, the temperature was kept at 80 ° C. 0.7 part of ammonium persulfate was added thereto, and 15 minutes after the addition,
A pre-emulsion obtained by emulsifying the monomer mixture shown in 1 and deionized water was added dropwise over 3 hours.

Thirty minutes after the end of the dropping, 7.7 parts of a solution prepared by dissolving 0.7 part of ammonium persulfate in 7 parts of deionized water was started to be added, and the addition was completed over 30 minutes. This was kept at 80 ° C. for another 2 hours and then cooled to 45 ° C. Then pH with 20% aqueous sodium hydroxide
8 to adjust the solid content of the copolymer emulsion to 50% (A
-4) was obtained.

Production Example 5 Deionized water 232 was placed in a 2-necked 4-necked flask.
And 2.3 parts of Newcol 707SF were added, and the atmosphere was replaced with nitrogen, and the temperature was maintained at 80 ° C. To this, 0.7 part of ammonium persulfate was added, and 15 minutes after the addition, a pre-emulsion obtained by emulsifying the monomer mixture shown in Table 1 and deionized water was added dropwise over 3 hours.

After 30 minutes had elapsed from the end of the dropping, 7.7 parts of a solution prepared by dissolving 0.7 part of ammonium persulfate in 7 parts of deionized water was started, and the dropping was started over 30 minutes. Later 2.6 parts of oxidant ("Kayacarban H-7
0 ", manufactured by Nippon Kayaku Co., Ltd.) was added to 10 parts of deionized water, and the mixture was kept at 80 ° C for 30 minutes. After that, 2.6 parts of a reducing agent (“Red C”, manufactured by Sumitomo Seika Chemicals, Ltd.) was added to 10 parts of deionized water, and the solution was added thereto. The temperature dropped. Next, the pH was adjusted to 8 with a 20% aqueous sodium hydroxide solution to obtain a copolymer emulsion (A-5) having a solid content of 50%.

Production Example 8 Deionized water 232 was placed in a 4-necked flask having a capacity of 2 liters.
And 2.3 parts of Newcol 707SF were added, and the atmosphere was replaced with nitrogen, and the temperature was maintained at 80 ° C. Ammonium persulfate (0.7 parts) was added thereto, and 15 minutes after the addition, a pre-emulsion obtained by emulsifying the monomer mixture for core component and deionized water shown in Table 2 was added dropwise over 2 hours.

After the completion of dropping, the mixture was kept at 80 ° C. for 2 hours, and then a pre-emulsion prepared by emulsifying the monomer mixture for shell component shown in Table 2 and deionized water and 0.3 part of 8.3 parts of a solution of ammonium persulfate dissolved in 8 parts of deionized water was added dropwise over 1 hour.

After the completion of dropping, this was kept at 80 ° C. for 2 hours and then cooled to 40 to 60 ° C. Then, adjust the pH to 8 with a 20% aqueous sodium hydroxide solution to obtain a solid content of 50%.
A copolymer emulsion (A-8) was obtained.

Production Examples 9 to 11 The same procedure as in Production Example 8 was repeated except that the composition of the pre-emulsion was changed as shown in Table 2, and each copolymer emulsion having a solid content of 50% (A-9) was used. ) ~ (A-1
1) was obtained. In Manufacturing Examples 10 and 11, the second dropping time was set to 2 hours.

[0051]

[Table 1]

[0052]

[Table 2]

Preparation of Paints for Countermeasures against Indoor Pollution Examples 1 to 16 and Comparative Examples 1 to 6 Composition ingredients for pigment paste shown in Table 3 were mixed in a 1-liter stainless steel container and stirred for 20 to 40 minutes. Each pigment paste was prepared by stirring. To this pigment paste, the copolymer emulsion obtained in the above Production Example and other components were blended in the compositions and blending amounts shown in Table 3, respectively.
Each paint was obtained by stirring for 0 minutes. These were subjected to the following test. The results are shown in Table 3. In addition, (Note 1) to (Note 8) in the table
Is as follows.

(Note 1) "Nopco Super 44C": manufactured by San Nopco, pigment dispersant (Note 2) "SN Deformer-364": manufactured by San Nopco, defoamer (Note 3) "Fujichem HEC KF-" 100 ": made by Fuji Chemical Co., Ltd., thickener (* 4)" Activated Alumina KC-503 ": made by Sumitomo Chemical Co., Ltd., adsorbent pigment (Note 5) Activated clay: made by Japan Activated Shirado Co., Ltd., adsorbent pigment (Note 6) ) "Titanium white JR-600A": manufactured by Teika,
Rutile-type titanium oxide (Note 7) Photoactive titanium oxide dispersion paste: Anatase-type titanium oxide (trade name "ST-157", average particle size 20 nm, manufactured by Teika) in a stainless steel container of 1 liter 2
10 parts, 300 parts of tap water and 9 parts of "Nopco Santo K" (manufactured by San Nopco Co., a dispersant) were blended, stirred for 20 minutes with a disperser, and further 20 with a 1-liter bench sand mill.
It was dispersed for a minute to prepare a photoactive titanium oxide dispersion paste.

(Note 8) "Neugen EA120": manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., emulsifier test method (* 1) VOC amount: 10 μl of the coating material obtained in each of the examples and comparative examples was injected into a gas chromatograph. Then, the amount of total volatile organic compounds (TVOC) in the paint was calculated and evaluated from the obtained peak by measuring under the following conditions.

Conditions Column: “WAX-10” (manufactured by Supelco) Column temperature: 70 ° C. → 5 ° C./min temperature increase → 200 ° C. Carrier gas: He Detector: FID Split ratio: 50/1 Standard ◎: 0. 1% or less ◯: 0.1 to 1% x: more than 1% (* 2) Low temperature film-forming property: The above-mentioned production on a flexible plate (slate) having a thickness of 6 mm specified by JIS A 5430. The copolymer emulsion prepared in Example 1 was diluted with tap water to form 2
The double-diluted solution was coated with a roller so that the coating amount was 40 g / m ^2, and after standing for 2 hours, the coating materials obtained in Examples and Comparative Examples were coated with an applicator having a gap of 150 μm. ,
It was left in an atmosphere of 5 ° C. After 2 days, the temperature was returned to room temperature and 2 hours later, the appearance of the coating film was observed and evaluated according to the following criteria.

⊚: A uniform coating film is formed without cracks. ○: Small cracks are found. Δ: Large cracks are found. X: Coating film is not formed due to tatter (* 3) Formaldehyde absorption capacity: 20 Each of the coating materials obtained above was applied on the surface of a glass plate of 50 mm by an applicator having a gap of 150 μm, and dried at room temperature for 7 days to prepare each test piece.

4 pieces of each test piece and 100 mg of 1% formaldehyde aqueous solution were sealed in a 2 liter glass container,
After 24 hours, the formaldehyde concentration was quantified with a detector tube (91L, manufactured by Gastec). The formaldehyde absorption capacity was evaluated based on the obtained formaldehyde concentration in air according to the following criteria.

◎: Color of detector tube does not change (below detection limit) ○: 0.1 to 15 ppm ×: 15 ppm or more (* 4) Ammonia absorption capacity: Each paint is applied by the same operation as above (* 3) Then, each test piece was created. Each test piece 4
One piece and 100 mg of 1% ammonium hydroxide aqueous solution were sealed in a 2 liter glass container, and after 24 hours, the ammonia concentration was quantified with a detector tube (3 L, manufactured by Gastec Co., Ltd.).
The formaldehyde absorption capacity was evaluated based on the obtained formaldehyde concentration in air according to the following criteria.

[0060] ◎: Color of detector tube does not change (below detection limit) ○: 0.5 to 30 ppm X: 30 ppm or more

[0061]

INDUSTRIAL APPLICABILITY According to the present invention, by applying the coating material of the present invention on plywood or vinyl wallpaper used for indoor floors, wall surfaces, ceilings, etc., harmful substances such as formalin and ammonia volatilized from these interior materials can be obtained. By blocking or absorbing / decomposing objects, indoor pollution can be effectively prevented.

[0062]

[Table 3]

[0063]

[Table 4]

─────────────────────────────────────────────────── --Continued from the front page (56) References JP 10-183023 (JP, A) JP 57-3857 (JP, A) JP 5-148446 (JP, A) JP 53- 78234 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C09D 7 / 12,5 / 00,5 / 02 C09D 133 / 04,201 / 00

Claims (4)

(57) [Claims] 1. A water-soluble or water-dispersible resin having a minimum film-forming temperature of 0 ° C. or lower, and (B) at least one pigment selected from diatomaceous earth, activated alumina, activated clay and zeolite. The water-soluble or water-dispersible resin (A) is
Mixture of one or more ethylenically unsaturated monomers
The glass transition temperature obtained by emulsion-polymerizing
Water containing 0% or more of the copolymer as the core component
One or more ethylenically unsaturated monomer in the dispersion
Obtained by adding a mixture of monomers and emulsion polymerization
Shell a copolymer with a glass transition temperature of -60 to 0 ° C
Core-shell particle aqueous dispersion as a component, or one type
Emulsify a mixture of two or more ethylenically unsaturated monomers
The glass transition temperature obtained by polymerization is -60.
Copolymer having a temperature of ~ 0 ° C as the core component and water containing it
1 or 2 or more types of ethylenically unsaturated monomer in the liquid
The gas obtained by emulsion polymerization of the body mixture
A copolymer having a lath transition temperature of 0 ° C. or higher is used as a shell component.
Which is an aqueous dispersion of core-shell particles
Monomers containing carbonyl groups in the total monomer mixture used
Of 0.5 to 8% by weight to form a shell component
Monomers containing carbonyl groups in the body-forming monomer mixture
The content of the component (B) is 5 to 300 parts by weight with respect to 100 parts by weight of the resin solid content , and the content of the organic solvent having a boiling point of 50 to 250 ° C. in the coating material is A water-based paint for indoor pollution control, which is 1% or less. 2. The water-based paint according to claim 1, wherein the nitrogen-containing compound (C) having an ability to adsorb aldehydes is contained in the paint liquid in a proportion of 0.1 to 3% by weight. 3. The nitrogen-containing compound (C) has a molecular weight of 100.
The water-based paint according to claim 2, which is a hydrazine derivative having a hydrazide group or a semicarbazide group of about 500. 4. Mean an inorganic compound having a particle diameter having a photocatalytic activity in 500nm or less, claims 1 to 3 of an aqueous coating composition according to any one containing 1 to 100 parts by weight based on the resin solid content of 100 parts by weight .