JP2002338897A - Aqueous coating material for interior pollution remedy - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous coating material for an interior pollution remedy which forms a coating film by coating on plies and vinyl wall papers to be used in the floor, the wall surfaces, the ceiling, the furniture and the like in a room and can adsorb or decompose injurious substances such as formaldehyde and plasticizers volatilizable therefrom. SOLUTION: The aqueous coating material for an interior pollution remedy comprises (A) a water-soluble or water-dispersible resin other than a carbonyl group-containing copolymer emulsion, (B) a nitrogen-containing compound having adsorbability of aldehydes, and (C) at least one pigment to be selected from diatomaceous earth, activated alumina, activated clay, and a zeolite, and the amount of the component (B) to be used in the coating material is 0.1-3 wt.% and, simultaneously, the content of the component (C) is 5-300 pts.wt. based on 100 pts.wt. resin solid component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to indoor floors, walls,
The present invention relates to a water-based paint for indoor pollution control which is applied to plywood or vinyl wallpaper used for ceilings, furniture, etc., and forms a coating film which adsorbs or decomposes harmful substances such as formaldehyde and plasticizers volatilized therefrom.

[0002]

2. Description of the Related Art At present, dry construction methods occupy a very high proportion in domestic building finishes, especially for indoor floors, walls and ceilings, such as gypsum boards, plywood, particle boards and vinyl wallpaper. It is no exaggeration to say that most of the finishing uses a vinyl chloride floor material or the like as an interior material. Since these are low in production cost and easy to construct,
Good economic efficiency. However, in finishing using these as interior materials, usually, formalin (formaldehyde) contained in the adhesive part of plywood or plasticizer (DOP, TCP, DOA, etc.) contained in vinyl material, flame retardant (TCEP, etc.)
Harmful substances such as volatilize indoors. In recent years, the concentration of these harmful substances in the living space has been extremely increased due to the improvement of the hermeticity of houses, and the problem of adverse effects on the human body has arisen. For example, the relation with atopy, allergy and carcinogenicity has been raised. Are also being pointed out. In addition, vinyl wallpaper and vinyl chloride flooring have a problem of environmental pollution at the time of disposal of old products after replacement, which has exacerbated the situation.

[0003] In response to the above-mentioned problems, the present applicant has previously proposed using a water-based paint for renovating vinyl wallpaper in order to reduce the problem of discarding vinyl wallpaper (Japanese Patent Laid-Open No. 8-4138).
No. 3). According to this, when the vinyl wallpaper fades over time or stains due to cigarette tar etc. occur, by coating the paint on the vinyl wallpaper, the retrofitting of the vinyl wallpaper, which has been considered difficult, becomes possible. Also, the effect of suppressing the volatilization of the plasticizer from the vinyl wallpaper was obtained. Furthermore, it has been proposed to use a paint containing a specific cross-linked emulsion resin and a pigment (Japanese Patent Application Laid-Open No. 10-183023), and it has been found that the resulting coating film has a high effect of suppressing the volatilization of harmful substances such as formalin. Was.

[0004] In addition, it has been desired to develop a method for further increasing the ability to adsorb and decompose harmful substances such as formalin.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, a paint comprising a pigment having an adsorbing action and a nitrogen-containing compound having an adsorbing ability for aldehydes has been obtained. The present invention was found to form a coating film capable of adsorbing and decomposing formaldehyde and the like immediately after coating, and reached the present invention.

That is, the present invention relates to (A) a water-soluble or water-dispersible resin excluding a carbonyl group-containing copolymer emulsion;
(B) a nitrogen-containing compound capable of adsorbing aldehydes, and (C) at least one or more pigments selected from diatomaceous earth, activated alumina, activated clay and zeolite,
The proportion of the component (B) used in the paint is 0.1 to 3% by weight.
And a content of the component (C) is 5 to 300 parts by weight with respect to 100 parts by weight of the resin solid content.

[0007]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, the water-soluble or water-dispersible resin (A) excluding a carbonyl group-containing copolymer emulsion is a known water-soluble or water-dispersible resin conventionally used in the field of paints. Examples thereof include vinyl acetate emulsion, acrylic resin emulsion, vinyl acetate-acryl emulsion, ethylene-vinegar bi-emulsion, epoxy resin emulsion, urethane resin emulsion, and alkyd resin emulsion.

In the present invention, the nitrogen-containing compound (B) capable of adsorbing aldehydes contains -N in a molecule capable of capturing aldehydes such as formaldehyde by a chemical bond.
It contains an H group and a -NH ₂ group, and examples thereof include primary amines and secondary amines, hydrazine, and hydrazine derivatives.

The primary and secondary amines include, for example, dodecylamine, tridecylamine, tetradecylamine, imidazolidinone and the like, and the amino acids lysine, arginine, histidine and derivatives thereof.

The hydrazine derivative has at least two or more hydrazide groups or semicarbazide groups in one molecule. Examples of the hydrazine derivative include oxalic dihydrazide, malonic dihydrazide, glutaric dihydrazide, succinic dihydrazide, Saturated aliphatic carboxylic acid dihydrazides having 2 to 18 carbon atoms, such as adipic dihydrazide, sebacic dihydrazide and the like;
Monoolefinically 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-benzenetrihydrazide, ethylenediaminetetraacetic acid tetrahydrazide, 1,4,5,8
Polyhydrazide obtained by reacting naphthoic acid tetrahydrazide or a low polymer having a carboxylic acid lower alkyl ester group with hydrazine or hydrazine hydrate (hydrazine hydride) (see Japanese Patent Publication No. 52-22878);
Carbon dioxide dihydrazide, bissemicarbazide; diisocyanate such as hexamethylene diisocyanate and isophorone diisocyanate and a polyisocyanate compound derived therefrom are excessively reacted with a dihydrazine compound or the above-mentioned dihydrazide. The above-mentioned isocyanate group in the reaction product of the obtained polyfunctional semicarbazide, the polyisocyanate compound and an active hydrogen compound having a hydrophilic group such as polyetherpolyols or polyethylene glycol monoalkyl ethers is used. Aqueous polyfunctional semicarbazide obtained by excessively reacting the exemplified dihydrazide, or a mixture of the polyfunctional semicarbazide and the aqueous polyfunctional semicarbazide (JP-A-8-151358, JP-A-8-2458)
No. 78). Among these, hydrazine derivatives having a hydrazide group or a semicarbazide group having a molecular weight of 100 to 500, such as adipic dihydrazide and citrate trihydrazide, are particularly preferable.

The nitrogen-containing compound (B) is used in a coating liquid in an amount of 0.1 to 3% by weight, preferably 0.3 to 3% by weight.
It should be 2%. If the use ratio exceeds 3% by weight, the water resistance of the coating film is undesirably reduced.

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

Activated alumina and activated clay are both compounds having a porous structure having a large adsorptivity, and are industrially used for decolorization and purification of fats and oils and petroleum mineral oils.

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

Activated clay is obtained by treating acidic clay, which is a kind of clay mainly composed of a clay mineral of the montmorillonite family and soluble silicic acid, with an acid to elute a part of basic components. Commercially available products include activated clay manufactured by Japan Active Shirato Co., Ltd., and Galleon Eart manufactured by Mizusawa Chemical Co., Ltd.
h NV and the like.

The zeolites include natural zeolites containing hydrous aluminosilicate as a main component and Na ₂ O.Al ₂ O ₃
• There is a synthetic zeolite containing xSiO ₂ · yH ₂ O as a main component. Synthetic zeolites, also called palmuchits, 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 ability, the crystal structure does not change even when dehydrated, and pores of a molecular size are obtained after dehydration, and have a large adsorption ability. Also, pores of a certain size are obtained after hydrothermal synthesis and crystallization of sodium aluminosilicate gel and dehydration,
Molecular sieves and the like are also effective in the present invention.

Diatomaceous earth is a hydrated silicon dioxide having a porous structure, and thus has a property of absorbing liquid well. In non-paint applications, it is used for agricultural chemicals, filter agents, abrasives and the like. It is used as a bulking agent and matting agent in paint applications. Commercially available products include Radiolite F and Radiolite FO manufactured by Showa Chemical Industry Co., Ltd.

The coating composition of the present invention contains 1 to 100 parts by weight, preferably 5 to 50 parts by weight of an inorganic oxide having photocatalytic activity with respect to 100 parts by weight of the resin solid content from the viewpoint of imparting antibacterial properties and improving barrier properties. It can be blended by weight. When the amount is less than 1 part by weight, the antibacterial property and the barrier property cannot be sufficiently improved, and when the amount exceeds 100 parts by weight, the physical properties of the coating film are deteriorated.

The inorganic oxide having photocatalytic activity is a semiconductor particle having a band gap, and is photo-excited when irradiated with light having energy equal to or larger than the band gap (for example, sunlight or ultraviolet light of artificial illumination light). The electrons and holes generated by the reaction move to the surface of the semiconductor particles, and exert a function of decomposing bacteria, formalin and the like in contact with the semiconductor particles due to the strong oxidizing ability. As the inorganic oxide, specifically, for example, TiO ₂ , RuO ₂ , CoO, Ce ₂
O ₃ , Cr ₂ O ₃ , Rh ₂ O ₃ , V ₂ O ₅ , ZnO, and the like can be mentioned. In particular, TiO ₂ , Z
nO is preferred. Titanium oxide of TiO ₂ includes three types of crystal, a rutile type and an anatase type belonging to a tetragonal system, and a brookite type belonging to an orthorhombic system. Among titanium oxides having photocatalytic activity, anatase is used. Type titanium oxide.

The inorganic oxide having photocatalytic activity has an average particle diameter of 500 nm or less, preferably 3 to 300 nm. If the particle size exceeds 500 nm, the photocatalytic activity and dispersibility are reduced, and the storage stability is undesirably reduced.

In order to further enhance the photocatalytic activity, the above-mentioned inorganic oxide has Fe, Mo, Ru, O, O 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 preferred from the viewpoint of imparting antibacterial properties.
It is preferable to carry at least one antibacterial metal component selected from the group consisting of: As a method for supporting these metal components, a conventionally known method can be employed. For example, in the case of supporting Ag, silver oxide is dissolved in aqueous ammonia to form an aqueous solution of an amine complex salt of silver, and the inorganic oxide is stirred therein. It is appropriate to obtain the residue by heating and drying the residue at 150 ° C. for 48 hours.

The compounding of the inorganic oxide having photocatalytic activity is as follows:
For example, the powder of the inorganic oxide may be directly mixed into the coating material and then dispersed by a stirrer such as a disperser, a sand mill, a shaker or the like.
(100 KU), it is desirable to disperse in a paste and form a paint.

The inorganic oxide powder having photocatalytic activity may be blended as a solution in the form of colloidal particles.
When it is blended as an inorganic oxide colloid solution, the dispersion step as described above is unnecessary, and the powder can be blended in an aqueous paint in a finer state, which is preferable in terms of photocatalytic activity and antibacterial properties. Examples of the inorganic oxide colloid solution include, for example, JP-A-6-80527 and JP-A-7-3361.
Are disclosed in, for 6 JP include colloidal particles of composite oxide such as colloidal particles of TiO2 single oxide or _{SiO 2 · Al 2 O 3 ·} TiO 2 is. These can be made into colloidal particles by attaching the above-mentioned antibacterial metal component to the surface of the colloidal particles or mixing them with an inorganic oxide.

Further, as the pigment component, if necessary, coloring pigments such as titanium oxide, carbon black, red iron oxide and phthalocyanine blue; extender pigments such as calcium carbonate, talc, mica, clay, silica sand and pearlite; And aggregates may be appropriately selected and blended.

As for the entire pigment content, 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 50%. 70%, preferably 20 to
It is desirable to be blended so as to be 60% in terms of the denseness of the coating film and the barrier property.

The paint of the present invention may further contain, if necessary, a surfactant, a dispersant, an antifoaming agent, a thickener, a preservative, a film-forming auxiliary,
Additives for paints such as antifreezing agents and organic solvents can be blended.

The method for producing the paint of the present invention is not particularly limited 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 paint additive to the copolymer emulsion and uniformly dispersing the mixture by a known means such as a stirrer.

In the present invention, the interior pollution control paint obtained as described above is applied to the interior material surface applied to floors, walls, and ceilings, particularly to the interior material surface that volatilizes indoor pollutants, to reduce indoor pollution. It is to prevent.

As interior materials applied to floors, walls and ceilings in a room, there are gypsum board, plywood and particle board, vinyl wallpaper, vinyl chloride floor material and the like. They are,
For example, formalin (formaldehyde) contained in the adhesive part of plywood or plasticizer (DOP, T
It volatilizes indoor pollutants such as CP, DOA and TCEP.

The above-mentioned paint for indoor pollution countermeasures is usually applied to the surface of the interior material, which evaporates these indoor pollutants, by about 0.1 to 0.1%.
It is desirable that the coating be performed at a coating amount within a range of 0.5 kg / m ² (about 50 to 250 g / m ^{2 in a} dry coating amount).

The above coating can be carried out at any time. However, since the volatilization amount of formalin is the largest at the time of new construction, for example, after the new construction, ventilation is released after securing ventilation, and the plywood surface or plywood immediately before entering. It is appropriate to apply such a specification that the above paint is applied on the vinyl wallpaper stuck on the top.

[0032]

The present invention will be described in more detail with reference to the following examples. Note that “parts” and “%” are based on weight unless otherwise specified.

Preparation of Copolymer Emulsion Preparation Example 1 232 deionized water was placed in a two-liter four-necked flask.
2.3 parts of Newcol 707SF (manufactured by Nippon Emulsifier Co., Ltd., anionic surfactant having a polyoxyethylene chain, non-volatile content: 30%), and the mixture was kept at 80 ° C. after nitrogen replacement. 0.7 parts of ammonium persulfate was added thereto,
From 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 a lapse of 30 minutes from the end of the dropping, 7.7 parts of a solution in which 0.7 part of ammonium persulfate was dissolved in 7 parts of deionized water were started to be dropped, and the drop was completed over 30 minutes. This was kept at 80 ° C. for another 2 hours and then cooled to 45 ° C. Then pH is adjusted with 20% sodium hydroxide aqueous solution.
8 and a 50% solids copolymer emulsion (A
-1) was obtained.

Production Example 2 Each copolymer emulsion (A-2) having a solid content of 50% was prepared in the same manner as in Production Example 1 except that the composition of the pre-emulsion was as shown in Table 1. Obtained.

[0036]

[Table 1]

Preparation of Paint for Countermeasure for Indoor Pollution Examples 1-3 and Comparative Examples 1-3 A 1 liter stainless steel container was blended with the composition for pigment paste shown in Table 2, and the mixture was stirred for 20-40 minutes with a stirrer. Each pigment paste was prepared by stirring. To the 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 2, respectively.
Each coating was obtained by stirring for 0 minutes. These were subjected to the following tests. Table 2 shows the results. (Note 1) to (Note 7) in the table
Is as follows.

(Note 1) "Nopco Space 44C": a pigment dispersant manufactured by San Nopco Co., Ltd. (Note 2) "SN Deformer-364": an antifoaming agent, manufactured by San Nopco Co., Ltd. (Note 3) "Fujichem HEC KF-" 100 ": Fuji Chemical Co., Ltd., thickener (Note 4)" Titanium White JR-600A ": Teika Co., Ltd.
Rutile-type titanium oxide (Note 5) "Activated alumina KC-503": Adsorbent pigment manufactured by Sumitomo Chemical Co., Ltd. (Note 6) Activated clay: Adsorbent pigment manufactured by Nippon Activated Shirato Co., Ltd. (Note 7) Photoactive titanium oxide dispersion pen Anastase type titanium oxide (manufactured by Teica, trade name "ST-157", average particle size 20 nm) in a 1-liter stainless steel container 2
10 parts, 300 parts of tap water and 9 parts of "Nopco Santo K" (manufactured by San Nopco Co., Ltd.) were mixed, and the mixture was stirred for 20 minutes with a disper, and further mixed with a 1-liter desktop sand mill.
The mixture was dispersed for 1 minute to prepare a photoactive titanium oxide dispersion paste.

Test method (* 1) Formaldehyde absorption capacity: Each paint obtained above was applied to the surface of a glass plate of 20 × 50 mm with an applicator having a gap of 150 μm, dried at room temperature for 7 days, and dried. Test pieces were prepared.

Four test pieces and 100 mg of a 1% aqueous formaldehyde solution were sealed in a 2 liter glass container.
Twenty-four hours later, the formaldehyde concentration was determined using a detector tube (91 L, manufactured by Gastec). The formaldehyde absorption capacity was evaluated based on the obtained formaldehyde concentration in the air according to the following criteria.

◎: The color of the detector tube does not change (below the detection limit) ：: 0.1 to 15 ppm ×: 15 ppm or more

(* 2) Ammonia absorption capacity: above (* 1)
Each paint was applied in the same manner as described above to prepare each test piece. Four test pieces and 100% 1% aqueous ammonia
In a 2 liter glass container and after 24 hours,
The ammonia concentration was quantified using a detector tube (3 L, manufactured by Gastech). The ammonia absorption capacity was evaluated based on the obtained ammonia concentration in the air based on the following criteria.

◎: The color of the detection tube does not change (below the detection limit) ：: 0.5 to 30 ppm ×: 30 ppm or more

[0044]

According to the present invention, by applying the paint of the present invention on plywood or vinyl wallpaper used for indoor floors, walls, ceilings, etc., harmful substances such as formalin and ammonia volatilized from these interior materials are obtained. Objects can be blocked or absorbed / decomposed to effectively prevent indoor pollution.

[0045]

[Table 2]

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J038 CF021 CF051 CG001 DD121 DG001 GA08 HA146 HA436 HA526 JB17 KA08 MA08 MA10 NA27 PB02 PB05 PC04 PC08

Claims (3)

[Claims] 1. A water-soluble or water-dispersible resin (A) excluding a carbonyl group-containing copolymer emulsion, (B) a nitrogen-containing compound capable of adsorbing aldehydes, (C) diatomaceous earth, activated alumina, activated clay and It contains at least one or more pigments selected from zeolites, the proportion of the component (B) used in the paint is 0.1 to 3% by weight, and the content of the component (C) is 100% by weight of resin solids. Water-based paint for indoor pollution control characterized by being 5 to 300 parts by weight per part. 2. The method according to claim 1, wherein the nitrogen-containing compound (B) has a molecular weight of 100.
The aqueous paint according to claim 1, which is a hydrazine derivative having a hydrazide group or a semicarbazide group of from 500 to 500. 3. The water-based coating composition according to claim 1, comprising an inorganic compound having an average particle diameter of 500 nm or less and having photocatalytic activity in an amount of 1 to 100 parts by weight based on 100 parts by weight of the resin solid content.