JP5072171B2 - Interior paint composition - Google Patents

Description

  The present invention relates to an interior coating composition having a high adsorbability for volatile organic compounds in indoor air.

In recent years, problems related to allergic health damage have been widely taken up as social problems in detached houses and condominiums. This is commonly called “sick house syndrome” and is considered to be mainly caused by volatile organic compounds (hereinafter referred to as “VOC”) including formaldehyde present in the room.
This VOC is mainly contained in plywood and furniture used indoors, or adhesives, heat insulating materials, tatami mats, etc. used therefor, and when this is released indoors, it causes headaches, eyeaches, respiratory organs to the human body. It is thought to bring about health problems such as disabilities.

  Therefore, in recent years, there has been an active movement to make agreements on regulations and reference values for these problems, and the momentum for eliminating VOCs has increased.

  Examples of such a method for removing VOC include a method of frequently ventilating a room or a method of adsorbing and removing with a specific adsorbent. Examples of such an adsorbent include activated carbon and the like, and as a method, the activated carbon is disposed so as to be in contact with the VOC and removed by adsorption.

  Recently, attention has been paid to the fact that the VOC can be effectively removed by placing the adsorbent on the ceiling or wall where the area in contact with the air is large, and interior materials containing activated carbon as an adsorbent have been studied. (For example, Patent Document 1).

JP 2003-342530 A

However, when an organic carrier such as activated carbon is used, there are problems in heat resistance and durability. For this reason, when applied to a living space such as interior materials, there is a problem that the function as an adsorbent is deteriorated with time, discolors, and the aesthetics of the living space changes.
Furthermore, since activated carbon itself is colored, there is also a problem that when it is applied to a living space such as an interior material, the appearance style of the living space is limited.

In order to solve such problems, the present inventors have found that an interior coating composition containing a specific amount of a synthetic resin and a specific adsorbent has an excellent VOC adsorption ability and is effective for sick house syndrome and the like. I found out.
Furthermore, the adsorbent is excellent in transparency, and the interior coating composition containing such an adsorbent can give the desired aesthetics without limiting the appearance style by the adsorbent, Since the adsorbent is excellent in durability and can maintain aesthetics for a long period of time, it has been found that the adsorbent can be widely applied as an interior paint, and the present invention has been completed.

That is, the present invention has the following features.
1. (A) For 100 parts by weight of the synthetic resin,
(B) containing 0.1 to 30 parts by weight of an adsorbent, wherein the adsorbent is an amino acid in a porous inorganic powder mainly containing at least one phosphate compound selected from the following composition formulas 2 to 4 A coating composition for interiors, comprising a silicon compound having a group.
(Composition formula 2)
Zn _e X ² _f (PO ₄ ) _g Y _h · iH ₂ O
(X ² is one or more p-valent metal ions selected from Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Al ³⁺ , Bi ³⁺ , Co ³⁺ , Mn ³⁺ , Fe ^3+. (P is 2 or 3), Y is a q-valent anion (q is 1, 2 or 3), e, f, g and h are 2 × e + p × f− (3g + q × h) = 0, e: f = 10: 0 to 10: 8, e: g = 8: 2 to 2: 8, g: h = real number satisfying 10: 0 to 4: 6 (where e and g are positive real numbers, f and h are 0 or a positive real number), i is a real number greater than or equal to 0)
(Composition Formula 3)
Al _j X ³ _k (PO ₄ ) _l Y _m · nH ₂ O
(X ³ is one or more p-valent metal ions selected from Zn ²⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Bi ³⁺ , Co ³⁺ , Mn ³⁺ , Fe ^3+. (P is 2 or 3), Y is a q-valent anion (q is 1, 2 or 3), j, k, l, m is 3 × j + p × k− (3l + q × m) = 0, j: k = 10: 0 to 10: 8, j: l = 8: 2 to 2: 8, l: m = 10: 0 to 4: 6 real numbers (where j and l are positive real numbers, k and m are 0 or a positive real number), n is a real number greater than or equal to 0)
(Composition Formula 4)
Mg _r X ⁴ _s (PO ₄ ) _{t Yu u} vH ₂ O
(X ⁴ is one or more kinds of p-valent metal ions selected from Zn ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Al ³⁺ , Bi ³⁺ , Co ³⁺ , Mn ³⁺ , Fe ^3+. (P is 2 or 3), Y is a q-valent anion (q is 1, 2 or 3), r, s, t, u are 2 × r + p × s− (3t + q × u) = 0, r: s = 10: 0 to 10: 8, r: t = 8: 2 to 2: 8, t: u = real number satisfying 10: 0 to 4: 6 (where r and t are positive real numbers, s and u are 0 or a positive real number), v is a real number greater than or equal to 0)
2. (B) The adsorbent carries 0.1 to 30 wt% of a silicon compound having an amino group with respect to the porous inorganic powder. The coating composition for interiors described in 1.
3. (B) The average particle diameter of the adsorbent is 0.01 to 100 μm. Or 2. The coating composition for interiors described in 1.
4). (B) The specific surface area of the adsorbent is 10 m ² / g or more. To 3. The coating composition for interior according to any one of the above.

The interior coating composition of the present invention has a particularly high adsorbability for VOCs such as formaldehyde and is effective for sick house syndrome and the like.
In addition, the adsorbent used in the present invention is excellent in transparency, and the interior coating composition containing such an adsorbent gives a desired aesthetic appearance without limiting the appearance of the adornment. In addition, since the adsorbent is excellent in durability and can maintain aesthetics over a long period of time, it can be widely applied as an interior paint.

  Hereinafter, the best mode for carrying out the present invention will be described in detail.

  The interior coating composition of the present invention is also referred to as (B) an adsorbent (hereinafter referred to as “(B) component”) with respect to 100 parts by weight of (A) synthetic resin (hereinafter also referred to as “(A) component”). .) Contains 0.1 to 30 parts by weight.

The synthetic resin is not particularly limited as long as it can be used as an interior paint.
For example, acrylic resin, silicone resin, acrylic silicone resin, fluorine resin, vinyl acetate resin, acrylic / vinyl acetate resin, vinyl chloride resin, urethane resin, acrylic / urethane resin, epoxy resin, alkyd resin, polyvinyl alcohol resin, polyester resin, Water dispersion type such as ethylene resin, polyvinyl alcohol, cellulose and derivatives thereof, water soluble type, NAD type, solvent soluble type, solventless type and the like are mentioned. Can be used. In the present invention, it is particularly preferable to include a water-dispersed resin, a water-soluble resin, and further a water-dispersed resin.

  The glass transition temperature of the synthetic resin is preferably −40 to 60 ° C., more preferably −30 to 50 ° C. In such a range, even if the use of a film-forming aid, which is one of volatile organic compounds (VOC), is restricted, it is preferable because film formation is possible.

  The adsorbent which is the component (B) of the present invention has a chemical adsorption property to a volatile organic compound, and is a porous inorganic powder (mainly a phosphoric acid compound represented by the following composition formula 1). In the present invention, it is simply referred to as “porous inorganic powder”) and a compound having an amino group supported thereon.

(Composition Formula 1)
X ¹ _a (PO ₄ ) _b Y _c · dH ₂ O
(X ¹ is a p-valent metal ion (p is 2 or 3), Y is a q-valent anion (q is 1, 2 or 3), a, b and c are p × a− (3b + q × c) = Real numbers satisfying 0 (where a and b are positive real numbers, c is 0 or positive real numbers), d is a real number greater than or equal to 0)

X ¹ is a divalent or trivalent metal ion, for example, a divalent metal ion such as Zn ²⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Co ²⁺ , Ni ²⁺ or Cu ²⁺ , Al ^Examples thereof include trivalent metal ions such as ³⁺ , Bi ³⁺ , Co ³⁺ , Mn ³⁺ , and Fe ³⁺ .
Y is a monovalent, divalent, or trivalent anion, and examples thereof include OH ⁻ , CH ₃ COO ⁻ , SO ₄ ²⁻ , Cl ⁻ , NO ₃ ⁻ , and CO ₃ ²⁻ .

  a, b and c are not particularly limited as long as they are real numbers satisfying p × a− (3b + q × c) = 0 (where a and b are positive real numbers and c is 0 or positive real numbers). It is preferable that a: b = 8: 2 to 2: 8 and b: c = 10: 0 to 4: 6. Note that a, b, and c can be obtained by elemental analysis (EDS).

In the present invention, the above metal ions can be used alone or in combination of two or more. For example, the divalent metal ions (X 1'), when used in combination of two kinds of trivalent metal ions (X 1 '') is, X 1 a is, X 1'a'X 1'' a'' next, can be calculated as p × a = 2 × a'+ 3 × a''. The calculation can be performed in the same manner for a combination of a divalent metal ion and a divalent metal ion, a combination of a trivalent metal ion and a trivalent metal ion, or a combination of three or more metal ions.

As preferred forms of the porous inorganic powder used in the present invention, there are the following composition formula 2, composition formula 3, and composition formula 4.
The porous inorganic powder in such a form has a large specific surface area and excellent adsorption capacity. By using such a porous inorganic powder, it is inexpensive and non-polluting, heat resistance, transparency, and anticorrosion. An adsorbent with excellent performance can be obtained.

(Composition formula 2)
Zn _e X ² _f (PO ₄ ) _g Y _h · iH ₂ O
(X ² is a p-valent metal ion (excluding Zn) (p is 2 or 3), Y is a q-valent anion (q is 1, 2 or 3), e, f, g, h are Real number satisfying 2 * e + p * f- (3g + q * h) = 0 (where e and g are positive real numbers, f and h are 0 or positive real numbers), i is a real number of 0 or more)

X ² is a divalent or trivalent metal ion (excluding Zn), for example, divalent such as Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ^2+, etc. Metal ions, trivalent metal ions such as Al ³⁺ , Bi ³⁺ , Co ³⁺ , Mn ³⁺ , Fe ^{3+, and the} like. In the present invention, these metal ions can be used alone or in combination of two or more.
If e, f, g, and h are real numbers satisfying 2 × e + p × f− (3g + q × h) = 0 (where e and g are positive real numbers and f and h are 0 or positive real numbers), Although not limited, usually, e: f = 10: 0 to 10: 8 (preferably 10: 0 to 10: 6), e: g = 8: 2 to 2: 8, g: h = 10: 0 4: 6 is preferred. Note that e, f, g, and h can be obtained by elemental analysis (EDS).

(Composition Formula 3)
Al _j X ³ _k (PO ₄ ) _l Y _m · nH ₂ O
(X ³ is a p-valent metal ion (excluding Al) (p is 2 or 3), Y is a q-valent anion (q is 1, 2 or 3), j, k, l and m are Real number satisfying 3 × j + p × k− (3l + q × m) = 0 (where j and l are positive real numbers, k and m are 0 or positive real numbers, and n is a real number of 0 or more)

X ³ is a divalent or trivalent metal ion (excluding Al), such as Zn ²⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ^{2+ and the} like. And divalent metal ions such as Bi ³⁺ , Co ³⁺ , Mn ³⁺ and Fe ³⁺ . In the present invention, these metal ions can be used alone or in combination of two or more.
j, k, l, and m are real numbers satisfying 3 × j + p × k− (3l + q × m) = 0 (where j and l are positive real numbers and k and m are 0 or positive real numbers). Although not limited, j: k = 10: 0 to 10: 8 (preferably 10: 0 to 10: 6), j: l = 8: 2 to 2: 8, l: m = 10: 0 4: 6 is preferred. Note that j, k, l, and m can be obtained by elemental analysis (EDS).

(Composition Formula 4)
Mg _r X ⁴ _s (PO ₄ ) _{t Yu u} vH ₂ O
(X ⁴ is a p-valent metal ion (excluding Mg) (p is 2 or 3), Y is a q-valent anion (q is 1, 2 or 3), r, s, t, u are Real number satisfying 2 * r + p * s- (3t + q * u) = 0 (where r and t are positive real numbers, s and u are 0 or positive real numbers), and v is a real number of 0 or more)

X ⁴ is a divalent or trivalent metal ion (excluding Mg), for example, divalent such as Zn ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Co ²⁺ , Ni ²⁺ and Cu ^2+. Metal ions, trivalent metal ions such as Al ³⁺ , Bi ³⁺ , Co ³⁺ , Mn ³⁺ , Fe ^{3+, and the} like. In the present invention, these metal ions can be used alone or in combination of two or more.
r, s, t, and u are real numbers satisfying 2 × r + p × s− (3t + q × u) = 0 (provided that r and t are positive real numbers and s and u are 0 or positive real numbers). Although not limited, usually, r: s = 10: 0 to 10: 8 (preferably 10: 0 to 10: 6), r: t = 8: 2 to 2: 8, t: u = 10: 0 4: 6 is preferred. Note that r, s, t, and u can be obtained by elemental analysis (EDS).

The porous inorganic powder used in the present invention is not particularly limited as long as it is porous. Specifically, the specific surface area is preferably 10 m ² / g or more, more preferably 15 m ² / g or more.
The porous inorganic powder is excellent in adsorbability of volatile organic compounds and can increase the loading of compounds having amino groups, which will be described later, especially for removal of volatile organic compounds such as formaldehyde. An adsorbent with excellent performance can be obtained.

The average particle size of the porous inorganic powder is not particularly limited, but is preferably 0.01 μm to 100 μm, more preferably 0.1 μm to 50 μm. By being in such a range, while exhibiting excellent adsorption capacity, it has more excellent transparency.
The particle size distribution, particle shape, etc. of the porous inorganic powder may be set as appropriate.

It does not specifically limit as a method to obtain a phosphoric acid compound, It can manufacture by a well-known method. For example, in the case of obtaining zinc phosphate (composition formula 2), aluminum phosphate (composition formula 3), and magnesium phosphate (composition formula 4), the following methods are exemplified.
In addition, although the manufacturing method of zinc phosphate (composition formula 2) is described below, aluminum phosphate (composition formula 3) and magnesium phosphate (composition formula 4) can be manufactured by the same method. Therefore, in (), instead of the method for producing zinc phosphate (composition formula 2), aluminum phosphate (composition formula 3) is produced, and magnesium phosphate (composition formula 4) is produced. The substance name used for is shown.

1. A method of obtaining zinc phosphate (aluminum phosphate, magnesium phosphate) by a coprecipitation method from a mixed solution containing zinc ions (aluminum ions, magnesium ions) and phosphate ions as a solute (coprecipitation method).
2. A method (substitution method) in which an anion of a zinc compound (aluminum compound, magnesium compound) is partially or completely substituted with a phosphate ion.

(Coprecipitation method)
A method for producing zinc phosphate (aluminum phosphate, magnesium phosphate) by a coprecipitation method is to add a base solution to a mixed solution containing zinc ions (aluminum ions, magnesium ions) and phosphate ions as solutes, and then add zinc phosphate ( (Aluminum phosphate, magnesium phosphate) is deposited.
In such a coprecipitation method, zinc phosphate (aluminum phosphate, magnesium phosphate) precipitates rapidly, so the crystal growth of zinc phosphate (aluminum phosphate, magnesium phosphate) ends incompletely, It is estimated that porous zinc phosphate (aluminum phosphate, magnesium phosphate) is obtained.

A mixed solution containing zinc ions (aluminum ions, magnesium ions) and phosphate ions (hereinafter also simply referred to as “mixed solution”) is composed of zinc compounds (aluminum compounds, magnesium compounds), phosphoric acid and / or phosphorus. Obtained by dissolving the acid salt in a solvent. The mixed solution may be prepared by separately preparing a solution in which a zinc compound is dissolved and a solution in which phosphoric acid and / or a phosphate are dissolved, and then mixing the zinc compound (aluminum compound, magnesium compound) and phosphorus. The acid and / or phosphate may be dissolved in the same solvent.
Especially as a solvent, alcohol, such as water, methanol, ethanol, butanol, etc. can be used conveniently.

  In such a mixed solution, it is essential that zinc ions (aluminum ions, magnesium ions) and phosphate ions are used as solutes, but the composition of (Composition Formula 2) (Composition Formula 3) (Composition Formula 4) is In the range given, the above-mentioned divalent or trivalent metal ion, monovalent, divalent or trivalent anion may coexist.

Moreover, as a mixed solution, in order that zinc ion (aluminum ion, magnesium ion) and phosphate ion will melt | dissolve stably, it is desirable that pH is 7 or less, More preferably, it is 6 or less, More preferably, it is 5 or less.
Moreover, in order to adjust pH of a mixed solution, you may add an acid and an alkali.

  The acid at this time is not particularly limited and known acids can be used. For example, hydrochloric acid, nitric acid, acetic acid, sulfuric acid, formic acid, acetic acid, propionic acid, butanoic acid, butyric acid, succinic acid, malonic acid, citric acid , Tartaric acid, gluconic acid, salicylic acid, benzoic acid, acrylic acid, maleic acid, glyceric acid, eleostearic acid, polyacrylic acid, polymaleic acid, acrylic acid-maleic acid copolymer carboxylic acid, polycarboxylic acid, etc. it can.

  As the alkali, for example, ammonia, urea, potassium hydroxide, calcium hydroxide, sodium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate and the like can be used.

  Each zinc of a solution in which a zinc compound (aluminum compound, magnesium compound) is dissolved, a solution in which phosphoric acid and / or phosphate are dissolved, and a mixed solution in which zinc ions (aluminum ions, magnesium ions) and phosphate ions are dissolved The ion (aluminum ion, magnesium ion) concentration and phosphate ion concentration are not particularly limited, and a solution having a concentration up to the solubility limit can be used.

The zinc compound is not particularly limited, and examples thereof include zinc chloride, zinc sulfate, zinc nitrate, zinc acetate, zinc oxide, zinc formate, zinc lactate, and basic zinc carbonate. Among these, zinc chloride, zinc sulfate, zinc nitrate and the like are preferable because they are inexpensive and can provide a stable supply.
Moreover, although it is essential for a zinc compound to use a zinc ion as a component, at least one or more of the above-described divalent or trivalent metal ions may be included as a component.

Although it does not specifically limit as an aluminum compound, For example, aluminum chloride, aluminum sulfate, aluminum nitrate, aluminum acetate, aluminum oxide, aluminum formate, aluminum lactate, basic aluminum carbonate etc. are mentioned. Among these, aluminum chloride, aluminum sulfate, aluminum nitrate, and the like are preferable because they are inexpensive and provide stable supply.
Moreover, although it is essential for an aluminum compound to use aluminum ion as a component, at least 1 sort (s) or more may be included as a component among the above-mentioned divalent or trivalent metal ions.

The magnesium compound is not particularly limited, and examples thereof include magnesium chloride, magnesium sulfate, magnesium nitrate, magnesium acetate, magnesium oxide, magnesium formate, magnesium lactate, and basic magnesium carbonate. Of these, magnesium chloride, magnesium sulfate, magnesium nitrate, and the like are preferable because they are inexpensive and provide a stable supply.
Further, it is essential that the magnesium compound has magnesium ions as a component, but at least one or more of the above-described divalent or trivalent metal ions may be included as a component.

Examples of phosphoric acid and / or phosphate include phosphoric acid, disodium hydrogen phosphate, sodium dihydrogen phosphate, trisodium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, tripotassium phosphate, Examples thereof include diammonium hydrogen phosphate, ammonium dihydrogen phosphate, triammonium phosphate, calcium hydrogen phosphate, and the like. Among them, those that are easily soluble in water and give an acidic phosphoric acid or phosphate solution include phosphoric acid, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium dihydrogen phosphate, etc. It is preferable to use it.
Moreover, as phosphoric acid and / or a phosphate, it is essential that a phosphate ion is a component, but at least one or more of the above-described monovalent, divalent, or trivalent anions are used as a component. May be included.

  The base solution is not limited, but is a solution in which at least one base selected from ammonia, urea, potassium hydroxide, calcium hydroxide, sodium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate and the like is dissolved in a solvent. Can be used. The concentration of these base solutions is not limited, and solutions up to the concentration limit can be used.

  The temperature when the base solution is added to the mixed solution containing zinc ions (aluminum ions, magnesium ions) and phosphate ions as a solute is preferably 0 ° C to 100 ° C, more preferably 5 ° C to 60 ° C, more preferably 5 to 50 ° C. By being in such a temperature range, loss of porosity due to complete crystal growth of zinc phosphate (aluminum phosphate, magnesium phosphate) can be suppressed. If the temperature is higher than this range, the aggregation between particles proceeds greatly and the porosity disappears, so that a porous powder having good dispersibility and a large specific surface area cannot be obtained.

(Substitution method)
A zinc phosphate (aluminum phosphate, magnesium phosphate) production method by a substitution method is performed by adding phosphoric acid and / or a phosphate solution to a slurry in which a zinc compound is mixed, and all or part of the anion of the zinc compound. It is substituted with phosphate ions.
In the substitution method, when the anion of the zinc compound (aluminum compound, magnesium compound) is replaced by the phosphate ion, the vacancy on the crystal surface generated by the elution of the anion of the zinc compound (aluminum compound, magnesium compound) becomes phosphorus. It is presumed that porous zinc phosphate (aluminum phosphate, magnesium phosphate) is obtained without being completely filled with acid ions.

The zinc compound (aluminum compound, magnesium compound) used in the substitution method preferably has poor solubility in water, and zinc oxide (aluminum oxide) among the above zinc compounds (aluminum compound, magnesium compound). , Magnesium oxide) and basic zinc carbonate (basic aluminum carbonate, basic magnesium carbonate) are preferably used.
As the phosphoric acid and / or phosphate used in the substitution method, phosphoric acid, sodium dihydrogen phosphate, potassium dihydrogen phosphate, which are easily soluble and give an acidic phosphoric acid or phosphate solution, It is preferable to use ammonium dihydrogen phosphate or the like.

  When adding phosphoric acid and / or a phosphate solution to a slurry mixed with a zinc compound (aluminum compound, magnesium compound), the temperature is preferably 0 ° C. to 100 ° C., more preferably 4 ° C. to 60 ° C., more preferably 4 ° C to 50 ° C. By being in such a temperature range, loss of porosity due to complete crystal growth of zinc phosphate (aluminum phosphate, magnesium phosphate) can be suppressed.

  Zinc phosphate (aluminum phosphate, magnesium phosphate) produced by the coprecipitation method or the substitution method can be obtained by washing with water, alcohols, volatile organic solvents such as acetone, etc., and drying after precipitation. it can. The drying method at this time may be performed at 50 ° C. to 120 ° C. in the air, or may be performed by a freeze drying method or a vacuum drying method.

In the coprecipitation method and the substitution method, an organic dispersant may be added for the purpose of improving the dispersibility of the zinc phosphate to be produced (aluminum phosphate, magnesium phosphate).
In the coprecipitation method, the organic dispersant is preferably added before adding the base to the mixed solution containing zinc ions (aluminum ions, magnesium ions) and phosphate ions as solutes. In the substitution method, it is desirable to add phosphoric acid and / or a phosphate aqueous solution to a zinc compound (aluminum compound, magnesium compound) slurry before adding the aqueous solution.

  As the organic dispersant, those having water solubility are preferable, for example, alcohols, polyols, ketones, polyethers, esters, celluloses, saccharides, sulfonic acids, higher fatty acids, higher fatty acid salts, higher fatty acid salts. Examples thereof include phosphate esters of fatty acid alcohols, phosphoric acid and salts thereof, waxes, anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and coupling agents.

  More specifically, aliphatic alcohols such as methanol, ethanol, propanol, butanol, pentanol and hexanol, aliphatic polyhydric alcohols such as ethylene glycol, propanediol, butanediol, glycerin, polyethylene glycol and polypropylene glycol, phenol and catechol , Aromatic alcohols such as cresol, alcohols having a heterocyclic ring such as furyl alcohol, ketones such as acetone, methyl ethyl ketone, acetylacetone, ethyl ether, tetrahydrofuran, dioxane, polyoxyalkylene ether, ethylene oxide adduct, propylene oxide adduct Ethers or polyethers such as ethyl acetate, ethyl acetoacetate, glycine ethyl ester, carboxymethyl Rulose, monosaccharides such as glucose and galactose, polysaccharides such as sucrose, lactose, amylose, chitin and cellulose, alkylbenzene sulfonic acid, paratoluene sulfonic acid, alkyl sulfonic acid, α-olefin sulfonic acid, polyoxyethylene alkyl sulfonic acid , Sulfonic acids such as lignin sulfonic acid and naphthalene sulfonic acid and salts thereof, higher fatty acids such as lauric acid, palmitic acid, oleic acid, stearic acid, capric acid, myristic acid, linoleic acid, polycarboxylic acid, lithium of the above higher fatty acids Higher fatty acid salts such as salts with alkali metals such as salts, sodium salts and potassium salts, phosphate esters of higher fatty acid alcohols, for example, alkyl ethers such as lauryl ether phosphoric acid, stearyl ether phosphoric acid, and oleyl ether phosphoric acid. Higher fatty acids such as telluric acid, dialkyl ether phosphoric acid, alkylphenyl ether phosphoric acid, dialkylphenyl ether phosphoric acid, etc., or alkyl ether phosphates such as sodium oleyl ether phosphate and potassium stearyl ether phosphate, hexametaphosphoric acid and salts thereof -Based alcohol phosphates, coconut oil fatty acid monoethanolamide, alkylolamides such as lauric acid diethanolamide, polyoxyalkylphenyl ethers such as polyoxyethylene alkylphenyl ether, polyoxyethylene such as polyoxyethylene lauryl ether Ethylene alkyl ethers, polyethylene glycol fatty acid esters such as polyethylene glycol distearate, sorbitan monocaprate, monostearate Sorbitan fatty acid esters such as sorbitan acid and sorbitan distearate, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbit fatty acid esters, polyoxyethylene polyoxypropylene alkyl ethers, glycol ethers Nonionic surfactants such as, alkyltrimethylammonium salts such as lauryltrimethylammonium chloride, cetyltrimethylammonium bromide, stearyltrimethylammonium chloride, alkyl such as stearyldimethylbenzylammonium chloride, benzalkonium chloride, lauryldimethylbenzylammonium chloride Cationic surfactants such as dimethylbenzylammonium salts, palm oil alkyl beties Alkylbetaines such as lauryldimethylaminoacetic acid betaine, imidazolines such as Z-alkyl-N-carboxymethyl-N-hydroxyethylimidazoline betaine, glycines such as polyoctylpolyaminoethylglycine, etc. Examples include amphoteric activators, silane coupling agents, aluminum coupling agents, titanium coupling agents, and other coupling agents such as zirconium coupling agents, and one or more of these are used. be able to.

In the present invention, aliphatic alcohols such as methanol, ethanol, propanol, butanol, pentanol, and hexanol, and aliphatic polyhydric alcohols such as ethylene glycol, propanediol, butanediol, glycerol, polyethylene glycol, and polypropylene glycol are used. Is preferred.
By using such a dispersant, it is possible to control the growth of particles during the formation of zinc phosphate (aluminum phosphate, magnesium phosphate), and as a result, the crystal shape, average particle diameter, etc. can be controlled. It seems that it is possible to produce fine particles with uniform size.
The amount of these dispersants added is 0.05 to 15 wt%, preferably 0.1 to 10 wt%, based on the weight of the zinc phosphate (aluminum phosphate, magnesium phosphate) powder to be produced. It is. If it is less than this range, the addition effect of a dispersing agent is small.

The compound having an amino group used in the present invention enhances the adsorption ability by chemically bonding with a volatile organic compound such as formaldehyde.
Examples of the compound having an amino group include aliphatic amines, aromatic amines, alicyclic amines, amino acids and amino acids, or silicon compounds having an amino group.
Specifically, methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine , Aliphatic amines such as pentadecylamine, cetylamine, tetraethylenepentamine, diethylenetriamine,
Aniline, methylaniline, dimethylaniline, ethylaniline, diethylaniline, o-toluidine, m-toluidine, p-toluidine, benzylamine, dibenzylamine, tribenzylamine, diphenylamine, triphenylamine, α-naphthylamine, β-naphthylamine Aromatic amines, etc.
Cycloaliphatic amines such as cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine,
Amino acids and amino acids such as hexamethylenetetraming lysine, glutamic acid, aspartic acid, alanine, trimethylaminoethylalkylamide, alkylpyridinium sulfate, alkyltrimethylammonium halide, alkylbetaine, alkyldiethylenetriaminoacetic acid,
γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, Examples thereof include silicon compounds having an amino group such as dimethyltrimethyl-silylamine.
These organic compounds having an amino group can be used alone or in combination of two or more.
In the present invention, it is preferable to use an aliphatic amine or a silicon compound having an amino group, and it is more preferable to use a silicon compound having an amino group. When a silicon compound having an amino group is used, it is easily chemically bonded to the porous inorganic powder. For this reason, it is easy to carry | support to the porous inorganic powder firmly, it can suppress that the silicon compound which has an amino group from porous inorganic powder detachment | desorption, and can suppress the discoloration by an amine.

The adsorbent used in the present invention is formed by supporting a compound having an amino group on the porous inorganic powder. The compound having an amino group may be carried inside the pores of the porous inorganic powder, or may be carried exposed on the outermost surface of the porous inorganic powder.
The loading amount of the compound having an amino group in the present invention is preferably 0.1 wt% to 30 wt% (preferably 0.2 wt% to 20 wt%) with respect to the weight of the porous inorganic powder. When the supported amount is smaller than 0.1 wt%, the adsorbability for volatile organic compounds such as formaldehyde is not improved. When the loading amount is larger than 30 wt%, the compound having an amino group is detached and discolored, the transparency is impaired, and the compound having an amino group itself may cause a bad odor.

  The method for supporting the amino group-containing compound on the porous inorganic powder is not particularly limited. For example, a dry method in which a compound having an amino group is mixed with the porous inorganic powder, a porous inorganic powder and an amino group are mixed. Preferred examples include a wet method in which an aqueous solution of a compound having a group is mixed.

  As a dry method, the porous inorganic powder and the compound having an amino group are directly mixed in a known mixing apparatus such as a Henschel mixer, a vibration mill, a ball mill, a ribbon mixer, or a jet mill. At this time, in order to uniformly disperse the compound having an amino group in the porous inorganic powder, it is preferable to add a small amount of a dispersion medium (usually water or alcohols) and / or a known silane compound. A preferable temperature in mixing by this dry method is 0 ° C to 100 ° C, more preferably 5 ° C to 80 ° C.

  As a wet method, first, a compound having an amino group is dissolved in a solvent to prepare a solution. Next, after adding porous inorganic powder to this solution, it is stirred for 5 minutes to 12 hours, preferably for 10 minutes to 6 hours. The temperature at this time is 0 ° C to 100 ° C, preferably 4 ° C to 80 ° C. Furthermore, the target adsorbent can be obtained by washing the porous inorganic powder carrying the amino group-containing compound with water, etc., removing the compound having an excess amino group adhering to the surface, and drying. . The drying method at this time may be performed at 50 ° C. to 120 ° C. in the air, or may be performed by a freeze drying method or a vacuum drying method.

The average particle size of the adsorbent used in the present invention is preferably 0.01 μm to 100 μm, more preferably 0.1 μm to 50 μm. By being in such a range, while showing the outstanding gas adsorption ability, it is excellent in the dispersibility, and also is excellent in transparency.
Further, the specific surface area of the adsorbent of the present invention is preferably 10 m ² / g or more, more preferably 15 m ² / g or more. When the specific surface area is 10 m ² / g or more, the adsorption of harmful gas can proceed more efficiently.

Such an adsorbent is relatively inexpensive and non-polluting, and has environmental purification effects such as deodorization and air pollution purification. In addition, it is difficult for the compounds having an amino group to come into contact with each other, the dispersibility is excellent, the formation of secondary particles composed of the compound having an amino group can be suppressed, and the discoloration (yellowing) by the compound having an amino group can also be suppressed. Can do.
Moreover, such an adsorbent is excellent in transparency, and an interior coating composition containing such an adsorbent can give a desired aesthetic appearance without limiting the appearance style by the adsorbent. In addition, since the adsorbent is excellent in durability and can maintain aesthetics for a long time, it can be widely applied as an interior paint.

(B) component of this invention is mixed in the ratio of 0.1-30 weight part (preferably 0.5-20 weight part) with respect to 100 weight part of solid content of (A) component. The mixing method is not particularly limited, and may be mixed by a conventional method.
By mixing in such a range, it is possible to obtain an interior coating material that has excellent adsorbing ability and that is not easily brought into contact with each other and that has a compound having an amino group. When the amount of the component (B) is less than 0.1 parts by weight, the adsorption ability of volatile organic compounds such as formaldehyde may be inferior. When the amount is more than 30 parts by weight, there is a possibility that the adsorbents are aggregated, and there is a case where the adsorbability sufficient to match the mixing amount cannot be obtained.

  In addition to the components (A) and (B), the interior coating composition of the present invention is a color pigment, extender pigment, aggregate, fiber, water, solvent, plasticizer, preservative, antifungal agent, antifoam. Agents, thickeners, leveling agents, pigment dispersants, anti-settling agents, anti-sagging agents, matting agents, UV absorbers, light stabilizers, antioxidants, antibacterial agents, photocatalysts, etc. It can also be contained to such an extent that it does not. It can also be used in combination with other adsorbents.

  The interior coating composition of the present invention can be given aesthetics mainly by a color pigment, an extender pigment, an aggregate and the like. In the present invention, the total volume concentration of the color pigment, extender pigment and aggregate (hereinafter also referred to as “pigment volume concentration”) is preferably 20% or more, and preferably 30% to 90%. By being in such a range, while being able to give aesthetics, the adsorption performance of this invention adsorption agent can be used efficiently. When the pigment volume concentration is lower than 20%, the surface of the coating film is likely to be covered with the synthetic resin component, and the adsorption performance may be deteriorated.

The total volume concentration (pigment volume concentration) of the color pigment, extender pigment and aggregate is the volume concentration in the dry coating film of the paint for interior use of the present invention and can be expressed by the following formula.
Pigment volume concentration = (colored pigment weight / colored pigment specific gravity + external pigment weight / external pigment specific gravity + aggregate weight / aggregate specific gravity) / (colored pigment weight / colored pigment specific gravity + external pigment weight / external pigment specific gravity + aggregate weight) / Aggregate specific gravity + Synthetic resin weight / Synthetic resin specific gravity)

The coating composition for interior of the present invention can be used for new coating film renovation work and the like, and can be applied to building interior surfaces such as ceilings and wall surfaces.
The base material used for the interior surface of the building is not particularly limited as long as it is used as a general building material. For example, gypsum board, calcium silicate board, slate board, extruded board, concrete, siding A board, a plywood board, a veneer board, a metal board, a plastic board etc. are mentioned.
The interior coating composition of the present invention can be applied directly to such a substrate, or after being subjected to some surface treatment (such as a base treatment with a sealer, surfacer, filler, putty, etc.). Although it is possible, it is not specifically limited.

  As a coating method, it can be applied by various methods such as brush coating, trowel coating, spray coating, and roller coating. Further, it can be pre-coated using a roll coater, a flow coater or the like.

The application amount is not particularly limited, but is usually 0.2 to 5 kg / m ² , preferably 0.25 to 4 kg / m ² .
Moreover, the composition of this invention can also be diluted with water at the time of coating. The dilution ratio is usually 0 to 100% by weight, preferably 0 to 50% by weight.

  The coating composition of the present invention can also be formed into a sheet shape. In this case, it can be laminated on the surface of various base materials as described above. What is necessary is just to affix the obtained sheet | seat on an inner wall, a ceiling, etc. by a well-known method using an adhesive agent, an adhesive sheet, etc.

  Furthermore, in the present invention, after the interior coating composition is applied, a top coating can be applied to the extent that the effects of the present invention are not impaired.

  Examples and Comparative Examples are shown below to clarify the features of the present invention, but the present invention is not limited to these Examples.

(Evaluation of porous inorganic powder)
1. The crystal structure of the porous inorganic powder was analyzed by an X-ray diffractometer (RINT-1100, manufactured by Rigaku Corporation).
2. The composition of the porous inorganic powder was analyzed using an elemental analysis (EDS) apparatus attached to an electron microscope (JSM-5310, manufactured by JEOL Ltd.).
(Evaluation of adsorbent)
3. The particle shape and particle diameter of the adsorbent were observed with an electron microscope (JSM-5310, manufactured by JEOL Ltd.).
4). The specific surface area of the adsorbent was measured by BET method with a dead volume measuring gas: helium and an adsorbing gas: nitrogen using a surface area measuring device P-700 type manufactured by Shibata Scientific Instruments Co., Ltd.

(Manufacture of adsorbent)
(Adsorbent 1)
A mixed solution was prepared by mixing 1.0 L of a 0.3 mol / L zinc sulfate aqueous solution and 1.2 L of a 0.17 mol / L sodium dihydrogen phosphate aqueous solution. The pH of this mixed solution was 3.2.
While stirring this mixed solution at a speed of 500 rpm, a 20% aqueous sodium hydroxide solution is added dropwise to adjust the pH to 8.5, the powder is precipitated, washed with water and acetone, and then freeze-dried. A porous inorganic powder was obtained by drying.
It was confirmed that the obtained porous inorganic powder was a porous inorganic powder mainly composed of zinc phosphate represented by Zn ₃ (PO ₄ ) ₂ .4H ₂ O.
Next, 2.0 g of tetraethylenepentamine was added to a slurry prepared by suspending 38.5 g of the obtained porous inorganic powder in 1.0 L of ion exchange water, and the mixture was stirred for 1 hour. After stirring, it was filtered, washed with water, and dried at 60 ° C. to obtain an adsorbent 1 in which tetraethylenepentamine was supported on porous inorganic powder mainly composed of zinc phosphate.
The adsorbent 1 had an average particle size of 0.58 μm. Moreover, when the specific surface area was measured by BET method, it turned out that it has a specific surface area of 57 m < ² > / g.

(Adsorbent 2)
In the production of the adsorbent 1, an adsorbent 2 was obtained in the same manner as the production of the adsorbent 1 except that diethylenetriamine was used instead of tetraethylenepentamine.
The adsorbent 2 had an average particle size of 0.49 μm. Further, when the specific surface area was measured by the BET method, it was found to have a specific surface area of 31 m ² / g.

(Adsorbent 3)
In the production of the adsorbent 1, the adsorbent 3 was obtained in the same manner as in the production of the adsorbent 1 except that N-β (aminoethyl) -γ-aminopropyltrimethoxysilane was used instead of tetraethylenepentamine. It was.
The adsorbent 3 had an average particle size of 0.66 μm. Moreover, when the specific surface area was measured by BET method, it turned out that it has a specific surface area of 60 m < ² > / g.

(Adsorbent 4)
A mixed solution was prepared by mixing 3.0 L of a 0.6 mol / L zinc sulfate aqueous solution, 1.0 L of a 0.3 mol / L aluminum hydrochloric acid aqueous solution and 2.5 L of a 0.6 mol / L sodium dihydrogen phosphate aqueous solution. . The pH of this mixed solution was 1.7.
While stirring this mixed solution at a speed of 500 rpm, a 20% aqueous sodium hydroxide solution is added dropwise to adjust the pH to 8.5, the powder is precipitated, washed with water and acetone, and then freeze-dried. A porous inorganic powder was obtained by drying.
The obtained porous inorganic powder was confirmed to be a porous inorganic powder mainly composed of zinc phosphate / aluminum represented by Zn ₆ Al ₁ (PO ₄ ) ₅ · 12H ₂ O.
Next, 2.0 g of N-β (aminoethyl) -γ-aminopropyltrimethoxysilane was added to a slurry prepared by suspending 38.5 g of the obtained porous inorganic powder in 1.0 L of ion exchange water. Added and stirred for 1 hour. After stirring, it is filtered, washed with water, and dried at 60 ° C., so that N-β (aminoethyl) -γ-aminopropyltrimethoxysilane is added to the porous inorganic powder mainly composed of zinc phosphate / aluminum. A supported adsorbent 4 was obtained.
The adsorbent 4 had an average particle size of 0.42 μm. Moreover, when the specific surface area was measured by BET method, it turned out that it has a specific surface area of 72 m < ² > / g.

(Adsorbent 5)
A mixed solution was prepared by mixing 2.5 L of a 0.6 mol / L zinc sulfate aqueous solution, 1.0 L of a 0.3 mol / L calcium nitrate aqueous solution and 2.0 L of a 0.6 mol / L sodium dihydrogen phosphate aqueous solution. . The pH of this mixed solution was 3.4.
While stirring this mixed solution at a speed of 500 rpm, a 20% aqueous sodium hydroxide solution is added dropwise to adjust the pH to 8.5, the powder is precipitated, washed with water and acetone, and then freeze-dried. A porous inorganic powder was obtained by drying.
The obtained porous inorganic powder was confirmed to be a porous inorganic powder mainly composed of zinc phosphate / calcium represented by Zn ₅ Ca ₁ (PO ₄ ) ₄ .4H ₂ O.
Next, 2.0 g of N-β (aminoethyl) -γ-aminopropyltrimethoxysilane was added to a slurry prepared by suspending 38.5 g of the obtained porous inorganic powder in 1.0 L of ion exchange water. Added and stirred for 1 hour. After stirring, filtering, washing with water, and drying at 60 ° C., N-β (aminoethyl) -γ-aminopropyltrimethoxysilane is added to the porous inorganic powder mainly composed of zinc phosphate / calcium. A supported adsorbent 5 was obtained.
The adsorbent 5 had an average particle size of 0.49 μm. Moreover, when the specific surface area was measured by BET method, it turned out that it has a specific surface area of 69 m < ² > / g.

(Adsorbent 6)
A mixed solution was prepared by mixing 1.0 L of a 0.3 mol / L aluminum chloride aqueous solution and 1.2 L of a 0.27 mol / L sodium dihydrogen phosphate aqueous solution. The pH of this mixed solution was 1.2.
While stirring this mixed solution at a speed of 500 rpm, a 20% aqueous sodium hydroxide solution is added dropwise to adjust the pH to 8.5, the powder is precipitated, washed with water and acetone, and then freeze-dried. A porous inorganic powder was obtained by drying.
The obtained porous inorganic powder was confirmed to be a porous inorganic powder mainly composed of aluminum phosphate represented by AlPO ₄ .4H ₂ O.
Next, 2.0 g of tetraethylenepentamine was added to a slurry prepared by suspending 38.5 g of the obtained porous inorganic powder in 1.0 L of ion exchange water, and the mixture was stirred for 1 hour. After stirring, it was filtered, washed with water, and dried at 60 ° C. to obtain an adsorbent 6 in which tetraethylenepentamine was supported on a porous inorganic powder mainly composed of aluminum phosphate.
The adsorbent 6 had an average particle size of 0.52 μm. Moreover, when the specific surface area was measured by BET method, it turned out that it has a specific surface area of 83 m < ² > / g.

(Adsorbent 7)
In the production of the adsorbent 6, an adsorbent 7 was obtained in the same manner as in the production of the adsorbent 6 except that diethylenetriamine was used instead of tetraethylenepentamine.
The adsorbent 7 had an average particle size of 0.49 μm. Further, when the specific surface area was measured by the BET method, it was found to have a specific surface area of 79 m ² / g.

(Adsorbent 8)
In the production of the adsorbent 6, the adsorbent 8 was obtained in the same manner as in the production of the adsorbent 6 except that N-β (aminoethyl) -γ-aminopropyltrimethoxysilane was used instead of tetraethylenepentamine. It was.
The adsorbent 8 had an average particle size of 0.54 μm. Moreover, when the specific surface area was measured by BET method, it turned out that it has a specific surface area of 91 m < ² > / g.

(Adsorbent 9)
A mixed solution was prepared by mixing 2.3 L of 0.3 mol / L aluminum chloride aqueous solution, 1.0 L of 0.3 mol / L zinc sulfate aqueous solution and 3.8 L of 0.2 mol / L sodium dihydrogen phosphate aqueous solution. . The pH of this mixed solution was 1.7.
While stirring this mixed solution at a speed of 500 rpm, a 20% aqueous sodium hydroxide solution is added dropwise to adjust the pH to 8.5, the powder is precipitated, washed with water and acetone, and then freeze-dried. A porous inorganic powder was obtained by drying.
It was confirmed that the obtained porous inorganic powder was a porous inorganic powder mainly composed of zinc phosphate / aluminum represented by Al ₆ Zn ₃ (PO ₄ ) ₈ · 12H ₂ O.
Next, 2.0 g of N-β (aminoethyl) -γ-aminopropyltrimethoxysilane was added to a slurry prepared by suspending 38.5 g of the obtained porous inorganic powder in 1.0 L of ion exchange water. Added and stirred for 1 hour. After stirring, it is filtered, washed with water, and dried at 60 ° C., so that N-β (aminoethyl) -γ-aminopropyltrimethoxysilane is added to the porous inorganic powder mainly composed of zinc phosphate / aluminum. A supported adsorbent 9 was obtained.
The adsorbent 9 had an average particle size of 0.45 μm. Further, when the specific surface area was measured by the BET method, it was found to have a specific surface area of 77 m ² / g.

(Adsorbent 10)
A mixed solution was prepared by mixing 2.2 L of a 0.4 mol / L aluminum chloride aqueous solution, 1.0 L of a 0.3 mol / L calcium nitrate aqueous solution and 3.8 L of a 0.2 mol / L sodium dihydrogen phosphate aqueous solution. . The pH of this mixed solution was 1.7.
While stirring this mixed solution at a speed of 500 rpm, a 20% aqueous sodium hydroxide solution is added dropwise to adjust the pH to 8.5, the powder is precipitated, washed with water and acetone, and then freeze-dried. A porous inorganic powder was obtained by drying.
The obtained porous inorganic powder was confirmed to be a porous inorganic powder mainly composed of calcium phosphate / aluminum represented by Al ₆ Ca ₃ (PO ₄ ) ₈ · 12H ₂ O.
Next, 2.0 g of N-β (aminoethyl) -γ-aminopropyltrimethoxysilane was added to a slurry prepared by suspending 38.5 g of the obtained porous inorganic powder in 1.0 L of ion exchange water. Added and stirred for 1 hour. After stirring, filtering, washing with water, and drying at 60 ° C., N-β (aminoethyl) -γ-aminopropyltrimethoxysilane is added to the porous inorganic powder mainly composed of zinc phosphate / calcium. A supported adsorbent 10 was obtained.
The adsorbent 10 had an average particle size of 0.50 μm. Moreover, when the specific surface area was measured by BET method, it turned out that it has a specific surface area of 114 m < ² > / g.

(Adsorbent 11)
A mixed solution was prepared by mixing 1.0 L of a 0.3 mol / L magnesium sulfate aqueous solution, 2.0 L of a 0.3 mol / L aluminum chloride aqueous solution, and 2.0 L of a 0.4 mol / L sodium dihydrogen phosphate aqueous solution. . The pH of this mixed solution was 2.1.
While stirring this mixed solution at a speed of 500 rpm, a 20% aqueous sodium hydroxide solution is added dropwise to adjust the pH to 8.5, the powder is precipitated, washed with water and acetone, and then freeze-dried. A porous inorganic powder was obtained by drying.
It was confirmed that the obtained porous inorganic powder was a porous inorganic powder mainly composed of magnesium phosphate / aluminum represented by Al ₆ Mg ₃ (PO ₄ ) ₈ · 12H ₂ O.
Next, 2.0 g of N-β (aminoethyl) -γ-aminopropyltrimethoxysilane was added to a slurry prepared by suspending 28.5 g of the obtained porous inorganic powder in 1.0 L of ion exchange water. Added and stirred for 1 hour. After stirring, it is filtered, washed with water, and dried at 60 ° C. so that N-β (aminoethyl) -γ-aminopropyltrimethoxysilane is added to the porous inorganic powder mainly composed of magnesium phosphate / aluminum. A supported adsorbent 11 was obtained.
The average particle diameter of the adsorbent 11 was 0.44 μm. Moreover, when the specific surface area was measured by BET method, it turned out that it has a specific surface area of 118 m < ² > / g.

(Adsorbent 12)
A mixed solution was prepared by mixing 1.0 L of 0.3 mol / L magnesium sulfate aqueous solution and 1.0 L of 0.20 mol / L sodium dihydrogen phosphate aqueous solution. The pH of this mixed solution was 3.9.
While stirring this mixed solution at a speed of 500 rpm, a 20% aqueous sodium hydroxide solution is added dropwise to adjust the pH to 8.5, the powder is precipitated, washed with water and acetone, and then freeze-dried. A porous inorganic powder was obtained by drying.
It was confirmed that the obtained porous inorganic powder was a porous inorganic powder mainly composed of magnesium phosphate represented by Mg ₃ (PO ₄ ) ₂ · 8H ₂ O.
Next, 2.0 g of tetraethylenepentamine was added to a slurry prepared by suspending 26.5 g of the obtained porous inorganic powder in 1.0 L of ion exchange water, and the mixture was stirred for 1 hour. After stirring, it was filtered, washed with water, and dried at 60 ° C. to obtain an adsorbent 12 in which tetraethylenepentamine was supported on a porous inorganic powder mainly composed of magnesium phosphate.
The adsorbent 12 had an average particle size of 0.47 μm. Further, when the specific surface area was measured by the BET method, it was found to have a specific surface area of 89 m ² / g.

(Adsorbent 13)
In the production of the adsorbent 12, an adsorbent 13 was obtained in the same manner as in the production of the adsorbent 12 except that diethylenetriamine was used instead of tetraethylenepentamine.
The average particle diameter of the adsorbent 13 was 0.46 μm. Moreover, when the specific surface area was measured by BET method, it turned out that it has a specific surface area of 78 m < ² > / g.

(Adsorbent 14)
In the production of the adsorbent 12, the adsorbent 14 was obtained in the same manner as in the production of the adsorbent 12 except that N-β (aminoethyl) -γ-aminopropyltrimethoxysilane was used instead of tetraethylenepentamine. It was.
The average particle diameter of the adsorbent 12 was 0.51 μm. Moreover, when the specific surface area was measured by BET method, it turned out that it has a specific surface area of 96 m < ² > / g.

(Adsorbent 15)
A mixed solution was prepared by mixing 3.0 L of 0.6 mol / L magnesium sulfate aqueous solution, 1.0 L of 0.3 mol / L aluminum chloride aqueous solution and 2.5 L of 0.6 mol / L sodium dihydrogen phosphate aqueous solution. . The pH of this mixed solution was 2.1.
While stirring this mixed solution at a speed of 500 rpm, a 20% aqueous sodium hydroxide solution is added dropwise to adjust the pH to 8.5, the powder is precipitated, washed with water and acetone, and then freeze-dried. A porous inorganic powder was obtained by drying.
The obtained porous inorganic powder was confirmed to be a porous inorganic powder mainly composed of magnesium phosphate / aluminum represented by Mg ₆ Al ₁ (PO ₄ ) ₅ · 12H ₂ O.
Next, 2.0 g of N-β (aminoethyl) -γ-aminopropyltrimethoxysilane was added to a slurry prepared by suspending 28.5 g of the obtained porous inorganic powder in 1.0 L of ion exchange water. Added and stirred for 1 hour. After stirring, it is filtered, washed with water, and dried at 60 ° C. so that N-β (aminoethyl) -γ-aminopropyltrimethoxysilane is added to the porous inorganic powder mainly composed of magnesium phosphate / aluminum. A supported adsorbent 15 was obtained.
The average particle diameter of the adsorbent 15 was 0.45 μm. Moreover, when the specific surface area was measured by BET method, it turned out that it has a specific surface area of 91 m < ² > / g.

(Adsorbent 16)
A mixed solution was prepared by mixing 1.0 L of 0.2 mol / L magnesium sulfate aqueous solution, 1.0 L of 0.1 mol / L calcium nitrate aqueous solution and 1.0 L of 0.2 mol / L sodium dihydrogen phosphate aqueous solution. . The pH of this mixed solution was 3.1.
While stirring this mixed solution at a speed of 500 rpm, a 20% aqueous sodium hydroxide solution is added dropwise to adjust the pH to 8.5, the powder is precipitated, washed with water and acetone, and then freeze-dried. A porous inorganic powder was obtained by drying.
The obtained porous inorganic powder was confirmed to be a porous inorganic powder mainly composed of magnesium phosphate and calcium represented by Mg ₂ Ca ₁ (PO ₄ ) ₂ · 8H ₂ O.
Next, 2.0 g of N-β (aminoethyl) -γ-aminopropyltrimethoxysilane was added to a slurry prepared by suspending 28.5 g of the obtained porous inorganic powder in 1.0 L of ion exchange water. Added and stirred for 1 hour. After stirring, filtering, washing with water, and drying at 60 ° C., N-β (aminoethyl) -γ-aminopropyltrimethoxysilane is added to the porous inorganic powder mainly composed of zinc phosphate / calcium. A supported adsorbent 16 was obtained.
The average particle diameter of the adsorbent 16 was 0.50 μm. Further, when the specific surface area was measured by the BET method, it was found to have a specific surface area of 111 m ² / g.

(Adsorbent 17)
A mixed solution was prepared by mixing 1.0 L of a 0.4 mol / L zinc sulfate aqueous solution, 2.3 L of a 0.3 mol / L calcium nitrate aqueous solution and 3.8 L of a 0.2 mol / L sodium dihydrogen phosphate aqueous solution. . The pH of this mixed solution was 3.4.
While stirring this mixed solution at a speed of 500 rpm, a 20% aqueous sodium hydroxide solution is added dropwise to adjust the pH to 8.5, the powder is precipitated, washed with water and acetone, and then freeze-dried. A porous inorganic powder was obtained by drying.
The obtained porous inorganic powder was confirmed to be a porous inorganic powder mainly composed of zinc phosphate / calcium represented by Zn ₁ Ca ₂ (PO ₄ ) ₂ .4H ₂ O.
Next, 2.0 g of N-β (aminoethyl) -γ-aminopropyltrimethoxysilane was added to a slurry prepared by suspending 38.5 g of the obtained porous inorganic powder in 1.0 L of ion exchange water. Added and stirred for 1 hour. After stirring, filtering, washing with water, and drying at 60 ° C., N-β (aminoethyl) -γ-aminopropyltrimethoxysilane is added to the porous inorganic powder mainly composed of zinc phosphate / calcium. A supported adsorbent 17 was obtained.
The adsorbent 17 had an average particle size of 0.50 μm. Moreover, when the specific surface area was measured by BET method, it turned out that it has a specific surface area of 73 m < ² > / g.

(Adsorbent 18)
The porous inorganic powder (53 m ² / g) obtained in the production process of the adsorbent 1 was used as the adsorbent 18.

Example 1
Aqueous paint (pigment volume concentration: 100 parts by weight of acrylic emulsion (solid content 50%), 50 parts by weight of titanium oxide, 60 parts by weight of heavy calcium carbonate, 3 parts by weight of thickener, and 1 part by weight of adsorbent 1 41%) on an aluminum plate (70 mm × 150 mm × 0.8 mm) using a film applicator so that the coating thickness is 0.125 mm, at a temperature of 23 ° C. and a relative humidity of 50%. , Dried for 24 hours to obtain a test specimen, and the following test was conducted.

1. Evaluation test of formaldehyde removal ability After placing the test body in a Tedlar bag having a volume of 1.0 L, 1.0 L of 3.0 ppm of formaldehyde gas was sealed, and after 10 minutes, the change in formaldehyde concentration was measured with a gas-tech detector tube. did.
As a result, the formaldehyde removal rate after 10 minutes was 78%, confirming that it had excellent formaldehyde removal ability.

2. Yellowing resistance test After putting a test body into a thermostat and leaving still at 50 degreeC for 2 weeks, it evaluated by the color difference ((DELTA) b) before and behind leaving still for 2 weeks using a color difference meter (CM-3700d, the product made by Minolta Co., Ltd.). did.
As a result, the color difference (Δb) was 0.11.

(Example 2)
Except that the adsorbent 2 was used in place of the adsorbent 1, a test specimen was prepared in the same manner as in Example 1, and an evaluation test for formaldehyde removal ability and a yellowing resistance test were performed.
As a result, in the evaluation test of formaldehyde removal ability, the formaldehyde removal rate after 10 minutes was 70%, and it was confirmed that the formaldehyde removal ability was excellent.
In the yellowing resistance test, the color difference (Δb) was 0.13.

(Example 3)
Except that the adsorbent 3 was used instead of the adsorbent 1, a test specimen was prepared in the same manner as in Example 1, and an evaluation test for formaldehyde removal ability and a yellowing resistance test were performed.
As a result, in the evaluation test of formaldehyde removal ability, the formaldehyde removal rate after 10 minutes was 72%, and it was confirmed that the formaldehyde removal ability was excellent.
In the yellowing resistance test, the color difference (Δb) was 0.02.

Example 4
Except that the adsorbent 4 was used instead of the adsorbent 1, a test specimen was prepared in the same manner as in Example 1, and an evaluation test for formaldehyde removal ability and a yellowing resistance test were performed.
As a result, in the evaluation test of formaldehyde removal ability, the formaldehyde removal rate after 10 minutes was 70%, and it was confirmed that the formaldehyde removal ability was excellent.
In the yellowing resistance test, the color difference (Δb) was 0.04.

(Example 5)
Except that the adsorbent 5 was used instead of the adsorbent 1, a test specimen was prepared in the same manner as in Example 1, and an evaluation test for formaldehyde removal ability and a yellowing resistance test were performed.
As a result, in the evaluation test of formaldehyde removal ability, the formaldehyde removal rate after 10 minutes was 73%, and it was confirmed that the formaldehyde removal ability was good.
In the yellowing resistance test, the color difference (Δb) was 0.03.

(Example 6)
Except that the adsorbent 6 was used instead of the adsorbent 1, a test specimen was prepared in the same manner as in Example 1, and an evaluation test for formaldehyde removal ability and a yellowing resistance test were performed.
As a result, in the evaluation test of formaldehyde removal ability, the formaldehyde removal rate after 10 minutes was 75%, and it was confirmed that the formaldehyde removal ability was excellent.
In the yellowing resistance test, the color difference (Δb) was 0.11.

(Example 7)
Except that the adsorbent 7 was used in place of the adsorbent 1, a test specimen was prepared in the same manner as in Example 1, and an evaluation test for formaldehyde removal ability and a yellowing resistance test were performed.
As a result, in the evaluation test of formaldehyde removal ability, the formaldehyde removal rate after 10 minutes was 72%, and it was confirmed that the formaldehyde removal ability was excellent.
In the yellowing resistance test, the color difference (Δb) was 0.13.

(Example 8)
Except that the adsorbent 8 was used in place of the adsorbent 1, a test specimen was prepared in the same manner as in Example 1, and an evaluation test for formaldehyde removal ability and a yellowing resistance test were performed.
As a result, in the evaluation test of formaldehyde removal ability, the formaldehyde removal rate after 10 minutes was 75%, and it was confirmed that the formaldehyde removal ability was excellent.
In the yellowing resistance test, the color difference (Δb) was 0.02.

Example 9
Except that the adsorbent 9 was used in place of the adsorbent 1, a test specimen was prepared in the same manner as in Example 1, and an evaluation test for formaldehyde removal ability and a yellowing resistance test were performed.
As a result, in the evaluation test of formaldehyde removal ability, the formaldehyde removal rate after 10 minutes was 71%, and it was confirmed that the formaldehyde removal ability was good.
In the yellowing resistance test, the color difference (Δb) was 0.03.

(Example 10)
Except that the adsorbent 10 was used instead of the adsorbent 1, a test specimen was prepared in the same manner as in Example 1, and an evaluation test for formaldehyde removal ability and a yellowing resistance test were performed.
As a result, in the evaluation test of formaldehyde removal ability, the formaldehyde removal rate after 10 minutes was 78%, and it was confirmed that the formaldehyde removal ability was excellent.
In the yellowing resistance test, the color difference (Δb) was 0.02.

(Example 11)
Except that the adsorbent 11 was used in place of the adsorbent 1, a test specimen was prepared in the same manner as in Example 1, and an evaluation test for formaldehyde removal ability and a yellowing resistance test were performed.
As a result, in the evaluation test of formaldehyde removal ability, the formaldehyde removal rate after 10 minutes was 69%, and it was confirmed that the formaldehyde removal ability was good.
In the yellowing resistance test, the color difference (Δb) was 0.03.

(Example 12)
Except that the adsorbent 12 was used in place of the adsorbent 1, a test specimen was prepared in the same manner as in Example 1, and an evaluation test for formaldehyde removal ability and a yellowing resistance test were performed.
As a result, in the evaluation test of formaldehyde removal ability, the formaldehyde removal rate after 10 minutes was 80%, and it was confirmed that the formaldehyde removal ability was excellent.
In the yellowing resistance test, the color difference (Δb) was 0.10.

(Example 13)
Except that the adsorbent 13 was used in place of the adsorbent 1, a test specimen was prepared in the same manner as in Example 1, and an evaluation test for formaldehyde removal ability and a yellowing resistance test were performed.
As a result, in the evaluation test of formaldehyde removal ability, the formaldehyde removal rate after 10 minutes was 72%, and it was confirmed that the formaldehyde removal ability was excellent.
In the yellowing resistance test, the color difference (Δb) was 0.14.

(Example 14)
Except that the adsorbent 14 was used in place of the adsorbent 1, a test specimen was prepared in the same manner as in Example 1, and an evaluation test for formaldehyde removal ability and a yellowing resistance test were performed.
As a result, in the evaluation test of formaldehyde removal ability, the formaldehyde removal rate after 10 minutes was 77%, and it was confirmed that the formaldehyde removal ability was excellent.
In the yellowing resistance test, the color difference (Δb) was 0.02.

(Example 15)
Except that the adsorbent 15 was used in place of the adsorbent 1, a test specimen was prepared in the same manner as in Example 1, and an evaluation test for formaldehyde removal ability and a yellowing resistance test were performed.
As a result, in the evaluation test of formaldehyde removal ability, the formaldehyde removal rate after 10 minutes was 75%, and it was confirmed that the formaldehyde removal ability was excellent.
In the yellowing resistance test, the color difference (Δb) was 0.03.

(Example 16)
Except that the adsorbent 16 was used in place of the adsorbent 1, a test specimen was prepared in the same manner as in Example 1, and an evaluation test for formaldehyde removal ability and a yellowing resistance test were performed.
As a result, in the evaluation test of formaldehyde removal ability, the formaldehyde removal rate after 10 minutes was 76%, and it was confirmed that the formaldehyde removal ability was excellent.
In the yellowing resistance test, the color difference (Δb) was 0.02.

(Example 17)
Except that the adsorbent 17 was used in place of the adsorbent 1, a test specimen was prepared in the same manner as in Example 1, and an evaluation test for formaldehyde removal ability and a yellowing resistance test were performed.
As a result, in the evaluation test of formaldehyde removal ability, the formaldehyde removal rate after 10 minutes was 65%, and it was confirmed that the formaldehyde removal ability was excellent.
In the yellowing resistance test, the color difference (Δb) was 0.03.

(Comparative Example 1)
Except that the adsorbent 18 was used in place of the adsorbent 1, a test specimen was prepared in the same manner as in Example 1, and an evaluation test of formaldehyde removal ability was performed.
As a result, in the evaluation test of formaldehyde removal ability, the formaldehyde removal rate after 10 minutes was 50%, which was inferior to formaldehyde removal ability.

Claims (4)

(A) For 100 parts by weight of the synthetic resin,
(B) containing 0.1 to 30 parts by weight of an adsorbent, wherein the adsorbent is an amino acid in a porous inorganic powder mainly containing at least one phosphate compound selected from the following composition formulas 2 to 4 A coating composition for interiors, comprising a silicon compound having a group.
(Composition formula 2)
Zn _e X ² _f (PO ₄ ) _g Y _h · iH ₂ O
(X ² is one or more p-valent metal ions selected from Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Al ³⁺ , Bi ³⁺ , Co ³⁺ , Mn ³⁺ , Fe ^3+. (P is 2 or 3), Y is a q-valent anion (q is 1, 2 or 3), e, f, g and h are 2 × e + p × f− (3g + q × h) = 0, e: f = 10: 0 to 10: 8, e: g = 8: 2 to 2: 8, g: h = real number satisfying 10: 0 to 4: 6 (where e and g are positive real numbers, f and h are 0 or a positive real number), i is a real number greater than or equal to 0)
(Composition Formula 3)
Al _j X ³ _k (PO ₄ ) _l Y _m · nH ₂ O
(X ³ is one or more p-valent metal ions selected from Zn ²⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Bi ³⁺ , Co ³⁺ , Mn ³⁺ , Fe ^3+. (P is 2 or 3), Y is a q-valent anion (q is 1, 2 or 3), j, k, l, m is 3 × j + p × k− (3l + q × m) = 0, j: k = 10: 0 to 10: 8, j: l = 8: 2 to 2: 8, l: m = 10: 0 to 4: 6 real numbers (where j and l are positive real numbers, k and m are 0 or a positive real number), n is a real number greater than or equal to 0)
(Composition Formula 4)
Mg _r X ⁴ _s (PO ₄ ) _{t Yu u} vH ₂ O
(X ⁴ is one or more kinds of p-valent metal ions selected from Zn ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Al ³⁺ , Bi ³⁺ , Co ³⁺ , Mn ³⁺ , Fe ^3+. (P is 2 or 3), Y is a q-valent anion (q is 1, 2 or 3), r, s, t, u are 2 × r + p × s− (3t + q × u) = 0, r: s = 10: 0 to 10: 8, r: t = 8: 2 to 2: 8, t: u = real number satisfying 10: 0 to 4: 6 (where r and t are positive real numbers, s and u are 0 or a positive real number), v is a real number greater than or equal to 0) The interior coating composition according to claim 1, wherein (B) the adsorbent carries 0.1 to 30 wt% of a silicon compound having an amino group with respect to the porous inorganic powder.   (B) The interior coating composition according to claim 1, wherein the adsorbent has an average particle size of 0.01 to 100 μm. (B) The interior coating composition according to any one of claims 1 to 3, wherein the adsorbent has a specific surface area of 10 m ² / g or more.