JP2018002928A - Coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating composition which has a high effect of suppressing odor emitted from the coating composition itself than conventional one.SOLUTION: A coating composition contains a resin emulsion composition (a) and an inorganic porous pigment (b) formed of zeolite, where a ratio of silica/alumina (mol/mol) in the zeolite is 15 or more, and a content of the zeolite to 100 pts.mass of a solid content in the resin emulsion composition (a) is 0.1-500 pts.mass.SELECTED DRAWING: None

Description

  The present invention relates to a coating composition. More specifically, the present invention relates to a coating composition that can reduce the odor emitted by the coating composition itself as compared with the conventional case.

  In recent years, from the viewpoint of stricter environmental regulations regarding the reduction of VOC content and toxicity, and from the viewpoint of resource saving, a rapid shift from solvent-based paints formulated with organic solvents to water-based paints formulated with water It is being made. A typical example of the paint is an aqueous emulsion resin paint composition. In particular, the interior coating of a living space or the like is desired to be odorless from the viewpoint of the owner and the painter as compared with the outdoors, and therefore, an aqueous emulsion resin coating composition is used. However, the unreacted monomer derived from the emulsion resin composition contained in the conventional aqueous emulsion resin coating composition, the high boiling point volatile organic compound contained in the film-forming aid, and the trace amount of volatile components are in a liquid state. Because it emits odor from the water-based emulsion resin coating composition or when the coating composition after coating volatilizes in the air in the process of forming a dry coating film, it is not in a comfortable state for the owner or the painter . Therefore, reduction of the odor emitted from the coating composition itself is demanded.

  Therefore, as a method for reducing the odor generated from the coating composition itself, a method for reducing the amount of volatile organic compounds in the film-forming aid is known (for example, see Patent Document 1). In addition, as a method for reducing the odor of ammonia or the like drifting in the living space, a method of adding an inorganic porous material to the aqueous paint resin composition and adsorbing the odor to the porous material is known (for example, , See Patent Document 2).

JP 2002-256202 A JP 2004-149686 A

  However, from the resin composition for water-based paints of Patent Document 1, unreacted monomers and the like that cause odors cannot be completely removed, and odor reduction is not sufficient. Moreover, the water-based coating composition of patent document 2 is only intended for adsorption of ammonia and formaldehyde drifting in the living space, and does not have a problem of reducing the odor emitted by the water-based coating composition itself.

  This invention is made | formed in view of the said subject, and is providing the coating composition which can reduce the odor which coating composition itself emits compared with the past.

  The present invention is a coating composition comprising a resin emulsion composition (a) and an inorganic porous pigment (b) made of zeolite, wherein the silica / alumina (mol / mol) ratio in the zeolite is 15 or more. And a coating composition having a zeolite content of 0.1 to 500 parts by mass with respect to 100 parts by mass of the solid content of the resin emulsion composition (a).

  In the present invention, the silica / alumina (mol / mol) ratio in the zeolite is preferably 30 or more.

  The zeolite of the present invention has at least one crystal structure selected from the group consisting of X-type, beta-type, MFI-type, ferrierite-type, mordenite-type, L-type and Y-type. Paint composition.

  The zeolite of the present invention is preferably an ion exchange type zeolite ion-exchanged with a metal ion other than proton or alkali metal.

  ADVANTAGE OF THE INVENTION According to this invention, the coating composition which can reduce the odor which coating composition itself emits than before can be provided.

  Hereinafter, embodiments of the present invention will be described. In addition, this invention is not limited to the following embodiment.

<Coating composition>
The coating composition according to the present embodiment includes a resin emulsion composition (a) and an inorganic porous pigment (b).

[Resin emulsion composition (a)]
The resin emulsion composition (a) according to this embodiment is a component that functions as a binder. Specifically, a synthetic resin emulsion comprising a resin component such as a vinyl acetate resin emulsion, a vinyl chloride resin emulsion, an epoxy resin emulsion, an acrylic resin emulsion, a urethane resin emulsion, an acrylic silicon resin emulsion, a fluororesin emulsion, or a composite system thereof. Can be used. The resin emulsion composition (a) according to this embodiment is not particularly limited, but an acrylic resin emulsion is preferably used.

  The acrylic resin emulsion according to the present embodiment can be obtained by a known polymerization method such as an emulsion polymerization method using a (meth) acrylic acid ester monomer as a medium. Moreover, the form of the resin emulsion composition (a) is not particularly limited, and may be either a one-component type or a two-component type.

Examples of the (meth) acrylic acid ester monomer according to this embodiment include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylate-n-propyl, ( (Meth) acrylic acid-i-butyl, (meth) acrylic acid-n-butyl, (meth) acrylic acid-t-butyl, (meth) acrylic acid-sec-butyl, (meth) acrylic acid isobutyl, (meth) acrylic 2-ethylhexyl acid, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, myristyl (meth) acrylate , Palmitic acid (meth) acrylate, glycidyl (meth) acrylate, trifluoroethyl (meth) acrylate N amyl (meth) acrylate, isoamyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, dodecenyl (meth) acrylate, (meth) acryl Octadecyl acid, cyclohexyl (meth) acrylate, (meth) acrylic acid-4-tert-butylcyclohexyl, phenyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid Examples include 2-phenylethyl, 2-methoxyethyl (meth) acrylate, and 4-methoxybutyl (meth) acrylate.
As these monomers, those provided with a reactive group such as a hydroxyl group, a carbonyl group, an epoxy group, an amide group, an amino group, a methylol group, or an isocyanate group can be used.

  The glass transition temperature (Tg) of the resin emulsion composition (a) is preferably −50 to 50 ° C. from the viewpoint of physical properties of the coating film. When the glass transition temperature (Tg) of the emulsion resin is in the range of −50 to 50 ° C., a favorable coating film can be formed in a room temperature environment when coating the interior surface of a building.

  5-25 are preferable and, as for the acid value of a resin emulsion composition (a), 10-20 are more preferable. If it is less than 5, sufficient curing of the coating film may not be obtained, and if it exceeds 25, storage stability may be deteriorated.

  The pH of the resin emulsion composition (a) is preferably used within the range of 5 to 10 by neutralizing with a base as necessary from the viewpoint of stability. Neutralization is performed by adding amines such as ammonia and dimethylethanolamine, sodium hydroxide, potassium hydroxide and the like.

  The solid content of the paint containing the resin emulsion composition (a) is preferably 1 to 90% by mass. When the solid content of the coating is within this range, it is possible to prevent the coating film from being lost due to the contraction of the coating film in the drying process after coating. A more preferable paint solid content is 10 to 50% by mass.

  The viscosity of the resin emulsion composition (a) is preferably 50 to 10,000 mPa · s, and more preferably 300 to 8,000 mPa · s under the same conditions. In addition, the said viscosity means the value measured using the E-type viscosity meter, for example.

[Inorganic porous material (b)]
The inorganic porous pigment (b) according to the present embodiment includes, for example, activated carbon, activated alumina, silica gel, hydroxyapatite, phosphoric acid as an inorganic compound having voids that can hold an odor component or the like in the porous portion. Zirconium, titanium phosphate, potassium titanate, hydrous bismuth, hydrous zirconium, hydrotalcite and the like can be mentioned. In this embodiment, zeolite is used.
The inorganic porous pigment (b) is an odor of the coating composition itself due to volatilization of the unreacted monomer contained in the coating composition and the volatile organic compound contained in the film-forming aid, and the adsorption site after coating. Ammonia and formaldehyde in the air can be adsorbed according to the unfilled amount. When the inorganic porous pigment (b) is added to the coating composition at a predetermined weight, it can adsorb the odor before and after coating and provide a coating composition having a high odor control effect.

  As the zeolite according to the present embodiment, both natural zeolite and artificially produced synthetic zeolite can be used. In particular, in view of ease of ion exchange and the like, it is preferable to use synthetic zeolite.

As the zeolite according to this embodiment, a zeolite having at least one crystal structure selected from the group consisting of X-type, beta-type, MFI-type, ferrierite-type, mordenite-type, L-type and Y-type is preferably used.
The zeolite has different adsorbable odor components depending on the crystal structure. Therefore, it is more preferable that two or more kinds of crystal structures are selected from the above crystal structures.

  A commercial product can also be used for the zeolite according to the present embodiment. For example, X type zeolite is manufactured by Tosoh Corporation: F9 series, beta type zeolite is manufactured by Tosoh Corporation: HSZ900 series, MFI type zeolite is manufactured by Tosoh Corporation: HSZ800 series, and ferrilite type is manufactured by Tosoh Corporation. : HSZ700 series, mordenite type manufactured by Tosoh Corporation: HSZ600 series, L type zeolite manufactured by Tosoh Corporation: HSZ500 series, Y type zeolite can be used HSZ300 series.

  In the case of producing zeolite by synthesis, any conventionally known method can be applied. For example, a method of obtaining a synthetic zeolite by crystallizing a composition containing a silica source, an alumina source, a quaternary ammonium salt, an alkali source and water is known. Specifically, pure water, sodium hydroxide, zeolite and seed crystal zeolite are added to a 35% quaternary ammonium salt aqueous solution, and the raw material composition is crystallized by stirring at 150 ° C. for 8 days. Is recovered after solid-liquid separation and pure water washing, and dried at 110 ° C. to obtain a synthetic zeolite.

  In addition, since the basic skeletons of the natural zeolite and synthetic zeolite described above are negatively charged, the ion exchange site may have alkali metal ions. Therefore, from the viewpoint of suppressing odor, this ion exchange site contains at least one ion exchange species selected from the group consisting of protons and metal ions other than alkali metals such as Cu ions, Ag ions, and Au ions. It is preferable. In particular, from the viewpoint of suppressing odor, zeolite substituted with metal ions such as Cu, Ag and Au capable of adsorbing odor components and decomposing odor components is more preferable. Ion exchange can be performed by a known method.

Any conventionally known method can be applied to the ion exchange in the zeolite of the present embodiment. For example, when adding protons (H ⁺ ) to the ion exchange site of Y-type zeolite, once the Y-type zeolite is mixed and stirred in an ammonium chloride aqueous solution and ion-exchanged with ammonia, the proton is calcined. Type Y zeolite is obtained. Moreover, when ion-exchanged to metal ions, such as Cu, after making Cu solution, such as copper chloride aqueous solution, and Y-type zeolite contact, it wash | cleans with ion-exchange water, and is made to dry after that. Thereby, Y type zeolite in which Cu ions are present at the ion exchange site is obtained.

  The odor components released from the coating composition include those derived from organic solvents. From the viewpoint of the adsorptivity of these odor components, the silica / alumina (mol / mol) ratio of zeolite is 15 or more. Adjusted to As the silica / alumina (mol / mol) ratio increases, the nature of the zeolite itself becomes hydrophobic. Thereby, it becomes possible to adsorb more odor components than water molecules at the adsorption point in the zeolite. Therefore, the silica / alumina (mol / mol) ratio of zeolite is more preferably adjusted to 30 or more. Further, when the silica / alumina ratio is adjusted to 5000 or more, the adsorption point of the odor component in the zeolite is extremely reduced, and the adsorption amount is reduced. For this reason, the silica / alumina ratio is preferably 5000 or less.

  The adjustment of the silica / alumina (mol / mol) ratio of the zeolite can be carried out, for example, by adjusting the mixing ratio of the raw material composition of the zeolite in the above-mentioned production stage. It can be performed by hydrothermal treatment or the like. For example, in the case of zeolite after commercialization, there are known methods such as hydrothermal treatment method, mineral acid treatment method, silicon substitution method and EDTA treatment to remove aluminum ions and increase the silica / alumina (mol / mol) ratio. Yes. In order to reduce the silica / alumina (mol / mol) ratio, a method is known in which zeolite is brought into contact with an aluminum source, washed with ion-exchanged water, and dried. In the present embodiment, the adjustment of the silica / alumina (mol / mol) ratio is not limited to these, and any known method can be applied.

  The dispersed particle size of the zeolite is preferably in the range of 0.1 to 100 μm. Since zeolite is a granular substance, when the dispersed particle size is larger than 100 μm, the appearance of irregularities based on zeolite appears in the coating film, and the design of the coating film deteriorates. On the other hand, when the dispersed particle size of the zeolite is smaller than 0.1 μm, the zeolite is buried in the coating film, and the pores of the zeolite may not be exposed on the coating film surface.

  The content of the inorganic porous pigment (b) according to the present embodiment is such that the content of the inorganic porous pigment (b) is 0.1 parts by mass with respect to 100 parts by mass of the solid content of the resin emulsion composition (a). It is -500 mass parts. When content of an inorganic porous pigment (b) is less than 0.1 mass part, the preferable odor suppression effect is not acquired about the coating film formed. Moreover, when content of an inorganic porous pigment (b) exceeds 500 mass parts, the viscosity of a coating composition becomes high too much and it becomes difficult to form a coating film. Moreover, the addition of an inorganic porous pigment (b) exceeding the necessary amount leads to unnecessary cost increase. Therefore, the content of the inorganic porous pigment (b) is preferably 1 part by mass to 500 parts by mass.

[Other ingredients]
The coating composition which concerns on this embodiment may contain the other component as needed. For example, the coating composition is a known color pigment, extender pigment, aggregate, fiber, plasticizer, preservative, ordinarily used as a component other than the above-described resin emulsion composition (a) or inorganic porous pigment (b). Antifungal agents, antifoaming agents, viscosity modifiers, leveling agents, pigment dispersants, anti-settling agents, anti-sagging agents, matting agents, UV absorbers, light stabilizers, antioxidants, antibacterial agents, adsorbents, photocatalysts Etc. can be blended alone or in combination.

  As the above-mentioned coloring pigments, titanium oxide, zinc oxide, carbon black, lamp black, bone black, graphite, black iron oxide, copper chrome black, cobalt black, copper manganese iron black, molybdate orange, permanent red, permanent carmine, Anthraquinone red, perylene red, quinacridone red, ferric oxide, yellow iron oxide, titanium yellow, first yellow, chrome green, ocher, ultramarine, bitumen, cobalt green, cobalt blue and other inorganic color pigments, azo, naphthol Organic color pigments such as pyrazolone, anthraquinone, perylene, quinacridone, benzimidazole, phthalocyanine, disazo, isoindolinone, quinophthalone, pearl pigment, aluminum pigment, gold Or glass flakes or a resin film coated with a metal oxide, hologram pigments, bright pigments such as cholesteric crystal polymer pigments, fluorescent pigments, phosphorescent pigments, and the like. The pigment volume concentration can be set as appropriate.

  Body pigments include heavy calcium carbonate, light calcium carbonate, clay, kaolin, talc, barium carbonate, white carbon, diatomaceous earth, cold water stone, china clay, barite powder, barium sulfate, precipitated barium sulfate, silica sand, Examples thereof include quartzite powder, quartz powder, resin beads, glass beads, and hollow balloons.

  The coating composition according to the present embodiment forms a dense coating film, is excellent in initial drying properties, durability, and film-forming properties. Therefore, depending on the application, a top coating material, an intermediate coating material, an undercoat It is also possible to apply to materials. Thereby, the coating composition which concerns on this embodiment can absorb each component, such as ammonia and formaldehyde emitted from coating compositions other than this invention.

<Method for producing coating composition>
As a method for producing the coating composition, methods usually used by those skilled in the art can be applied. The resin emulsion composition (a), the inorganic porous pigment (b), and other components are disperser, ball mill, S.P. G. It can be prepared by mixing with a mill, roll mill, planetary mixer or the like. A coating composition can be prepared by mixing a predetermined amount of the resin emulsion composition (a), the inorganic porous pigment (b) and other components.

<Formation method of coating film>
The method of forming a coating film with the coating composition according to the present embodiment is not particularly limited. For example, immersion, brush, roller, roll coater, air spray, airless spray, curtain flow coater, roller curtain coater, die coater, etc. The coating method generally used in (1) can be mentioned. These coating methods can be appropriately selected depending on the object to be coated and the application.

  The coating composition according to the present embodiment can be applied to an exterior surface or interior surface of a building. For example, mortar, concrete, gypsum board, siding board, extrusion board, slate board, asbestos cement board, fiber-mixed cement board, calcium silicate board, ALC board, metal, wood, glass, ceramics, fired The present invention can be applied to a substrate such as a tile, porcelain tile, plastic plate, wallpaper, and synthetic resin, or a coating film formed on the substrate.

  Next, the present invention will be described in more detail based on examples, but the present invention is not limited thereto. Unless otherwise specified, the unit is based on mass.

[Preparation of resin emulsion composition (a)]
An acrylic resin emulsion (a) having a pH of 8.5, an acid value AV of 15, a paint solid content (NV) of 50% by mass, and a viscosity of 2000 mPa · s was obtained by using a conventionally known polymerization reaction.

[Preparation of zeolite (b-1)]
189 g of amorphous aluminosilicate, 1.4 g of solid sodium hydroxide, 3.5 g of solid potassium hydroxide, and 480 g of 20% aqueous solution of tetraethylammonium hydroxide were stirred and mixed for 30 minutes to obtain a raw material for β-type zeolite. To this raw material was added sodium hydroxide aqueous solution, cesium chloride, water, and beta-type zeolite (HSZ930NHA) manufactured by Tosoh Corporation as a seed crystal, and sufficiently mixed with stirring to obtain a raw material slurry. The raw material slurry was crystallized at 150 ° C. for 96 hours. The slurry mixture after crystallization was subjected to solid-liquid separation, washed with a sufficient amount of pure water, and dried at 110 ° C. The dry powder was then fired at 600 ° C. under air flow. A beta zeolite having a silica / alumina (mol / mol) ratio of 36 was obtained.
The obtained beta-type zeolite was immersed in a solvent whose aluminum concentration was adjusted so that the silica / alumina (mol / mol) ratio was 30, and then washed with ion-exchanged water and dried to obtain silica / alumina (mol / Mol) ratio (zeolite (b-1)) adjusted to 30 was obtained.

[Preparation of zeolite (b-2)]
X-type zeolite was obtained using the same procedure as that for zeolite (b-1) except that Tosoh Corporation X-type zeolite (F-9: dispersed particle size 10 μm) was used as a seed crystal of the X-type zeolite. Thereafter, the silica / alumina (mol / mol) ratio was adjusted to 15 to obtain zeolite (b-2).

[Preparation of zeolite (b-3)]
MFI-type zeolite was obtained using the same procedure as zeolite (b-1) except that MFI-type zeolite (HSZ800: dispersion particle size: 10 μm) manufactured by Tosoh Corporation was used as a seed crystal of MFI-type zeolite. Thereafter, the silica / alumina (mol / mol) ratio was adjusted to 100 to obtain zeolite (b-3).

[Preparation of zeolite (b-4)]
X-type zeolite was obtained using the same procedure as that for zeolite (b-1) except that Tosoh Corporation X-type zeolite (F-9: dispersed particle size 5 μm) was used as the seed crystal of the X-type zeolite. Then, the silica / alumina (mol / mol) ratio was adjusted to 100, and further, ion exchange to Cu was performed and washed to obtain zeolite (b-4).

[Preparation of zeolite (b-5)]
X-type zeolite was obtained using the same method as zeolite (b-1) except that X-type zeolite (F-9: dispersed particle size 5 μm) manufactured by Tosoh Corporation was used as the seed crystal of the X-type zeolite. Thereafter, the silica / alumina (mol / mol) ratio was adjusted to 5 to obtain zeolite (b-5).

<Adjustment of coating composition>
[Adjustment of Examples 1 to 9 and Comparative Examples 1 to 3]
200 parts by mass of titanium oxide shown in Table 1, 300 parts by mass of calcium carbonate, 20 parts by mass of a pigment dispersant, 2 parts by mass of a defoaming material with respect to 200 parts by mass of the acrylic resin emulsion (a) obtained as described above. Parts, 10 parts by weight of a viscosity agent, 1 part by weight of an anti-algal and anti-fungal material, 400 parts by weight of water, and 50 parts by weight of zeolite (b-1) with respect to 100 parts by weight of the solid content of the synthetic resin emulsion (a). The coating composition of Example 1 was obtained by thoroughly stirring the mixture using a disper for 2 hours.
Similarly to Example 1, each zeolite shown in Table 2 was mixed at a predetermined ratio with respect to 100 parts by mass of the solid content of the acrylic resin emulsion (a), and the coating compositions of each Example and Comparative Example were mixed. Obtained.

  Subsequently, the following evaluation was performed on the coating compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 3.

<Evaluation of odor of coating composition>
The odor of the coating compositions prepared in each example and comparative example was evaluated according to the following evaluation criteria. The number of evaluators was 10, and the odor was evaluated based on the average value of the evaluations of 10 people. If the odor evaluation is 3, the odor property is good. In other words, it is evaluated as having almost no odor. The results are shown in Table 1.
[Evaluation]
3: No odor 2: Very weak odor 1: Slight odor 0: Odor

<Evaluation of film formation>
Assuming the inner wall of the living space, the possibility of film formation was evaluated. The coating composition according to the example and the comparative example was applied to a predetermined region with a brush so as to have a thickness of about 0.1 mm on a 450 mm × 900 mm × 3 mm slate plate. The presence or absence of film formation was observed. The results are shown in Table 1.
[Evaluation]
2: A coating film was formed.
1: A coating film was not formed.

  From the comparison between Examples 1 to 9 and Comparative Example 1, the coating compositions of Examples 1 to 9 containing zeolite with a high silica / alumina (mol / mol) ratio in the coating composition were silica / alumina (mol). It was found that the results of the odor evaluation test were superior to the coating composition of Comparative Example 1 containing zeolite with a low / mol) ratio. From this result, it was confirmed that the odor is suppressed when the resin emulsion composition (a) contains zeolite higher than a predetermined silica / alumina (mol / mol) ratio.

  From the comparison between Examples 1 to 5 and Comparative Example 2, at least the coating composition of Examples 1 to 5 containing 1 part by mass or more of zeolite (b-1) in the coating composition is zeolite (b-1). Compared with the coating composition of the comparative example 2 which is less than 1 mass part, it turned out that it is excellent in the result of an odor evaluation test. From this result, it was confirmed that the odor is suppressed when the resin emulsion composition (a) contains 1 part by mass or more, particularly 15 parts by mass or more of the inorganic porous pigment (b).

  Moreover, the coating film of the comparative example 3 containing 600 mass parts of zeolite (b-1) did not form a coating film. The inorganic porous pigment (b) is within the range of 0.1 to 500 parts by mass with respect to 100 parts by mass of the solid content of the resin emulsion composition (a), so that an excellent odor of the formed coating film can be obtained. It was confirmed that an inhibitory effect was obtained and a practical coating composition could be obtained.

  From Example 8, it was confirmed that the coating composition containing two types of zeolite (b-1) and zeolite (b-3) was excellent in the odor evaluation test.

  From Example 9, it was confirmed that the coating composition containing zeolite (b-4) ion-exchanged with Cu ions was excellent in the odor evaluation test.

Claims (4)

A resin emulsion composition (a);
An inorganic porous pigment (b) made of zeolite, and a coating composition comprising:
The silica / alumina (mol / mol) ratio in the zeolite is 15 or more,
The coating composition whose content of the said zeolite is 0.1-500 mass parts with respect to 100 mass parts of solid content of the said resin emulsion composition (a).   The coating composition according to claim 1, wherein the silica / alumina (mol / mol) ratio in the zeolite is 30 or more.   The coating composition according to claim 1 or 2, wherein the zeolite has at least one crystal structure selected from the group consisting of X-type, beta-type, MFI-type, ferrierite-type, mordenite-type, L-type and Y-type. .   The coating composition according to any one of claims 1 to 3, wherein the zeolite is an ion exchange type zeolite ion-exchanged with a metal ion other than a proton or an alkali metal.