KR20150121664A - Composition for humidity control construction material and humidity control construction material - Google Patents

Abstract

The present invention provides a humidity control construction material having excellent shape stability during absorption and desorption of moisture, no coloration, and excellent intensity as a construction material while having enough absorption and desorption properties of moisture to control indoor humidity at the same time. Also, the present invention provides a composition for a humidity control construction material for producing the humidity control construction material. The composition for a humidity control construction material of the present invention comprises a polymer having at least one type of group selected from the group consisting of a group represented by -SO_3^-(M^n+)_1/n and a group represented by -COO^-(M^n+)_1/n (herein, n is an integer of 1 to 2, and M^n+ represents hydrogen ion, monovalent metal ion, divalent metal ion, or onium ion); and an inorganic material.

Description

TECHNICAL FIELD [0001] The present invention relates to a composition for a humidity control building material and a moisture control construction material,

The present invention relates to a composition for a humidity control building material and a humidity control building material obtained by molding the composition for the humidity control building material.

For example, in Japanese wooden houses, since the construction material having the humidity control property such as the toe wall is used, proper humidity control, antifouling property and antifungal property have been realized. However, in recent years, from the viewpoint of improvement of the earthquake resistance, such an earth wall has been lightened, and the milling of the building has been proceeding to avoid intrusion of pollutants in the room into the room.

On the other hand, with the recent increase in temperature and humidity due to the recent climate change, it has become difficult to keep the room at a comfortable humidity with conventional building materials. In order to solve this problem, there has been proposed a method of controlling humidity by using a porous inorganic material such as zeolite or diatomaceous earth, which is similar to a conventional humidity control apparatus such as a soil wall as described in Patent Document 1 or Patent Document 2 Construction materials are being reviewed.

On the other hand, the polymers including the organic materials described in Patent Document 3 and Patent Document 4 are characterized by a large amount of moisture absorption per unit weight and a high moisture absorption rate. However, the volume change during water absorption / desorption is large, It is difficult to achieve both of the appropriate strength and humidity control required for the humidity control building material.

Japanese Patent Laid-Open No. 2013-1589 Japanese Patent Application Laid-Open No. H02-214931 Japanese Patent Application Laid-Open No. 2009-74098 Japanese Patent Application Laid-Open No. 2013-107070

An object of the present invention is to provide a humidity-sensitive building material having sufficient moisture absorptive and desorptive properties for controlling the humidity of the room, excellent shape stability at the time of moisture absorptive and desorptive, free from coloration, and excellent in strength as a construction material, And to provide a composition for a humidity control building material for manufacturing the humidity control building material.

The present invention has been made to solve at least a part of the above-described problems, and can be realized as the following aspects or applications.

[Application Example 1]

One form of the composition for a humidity-sensitive building material according to the present invention is a composition for a humidity-

At least one group selected from the group consisting of a group represented by -SO ₃ ^- (M ^{n +} ) _{1 / n} and a group represented by -COO ^- (M ^{n +} ) _{1 / n} wherein n is an integer of 1 to 2 And M ^{n +} represents a hydrogen ion, a monovalent metal ion, a divalent metal ion or an onium ion)

Inorganic material

. ≪ / RTI >

[Application example 2]

In the composition for a humidity control building material of Application Example 1,

When the total content of the polymer and the inorganic material is 100 mass%, the content of the inorganic material may be 50 mass% or more and 99 mass% or less.

[Application Example 3]

In the composition for humidity-sensitive building material of Application Example 1 or Application Example 2,

The total number of moles of groups represented by -SO ₃ ^- (M ^{n +} ) _{1 / n} and -COO ^- (M ^{n +} ) _{1 / n} in the polymer may be 1.5 mmol / g or more.

[Application example 4]

According to one aspect of the humidity conditioning construction material of the present invention,

And is produced by molding a composition for a humidity control building material of any one of Application Examples 1 to 3.

According to the composition for a humidity-sensitive building material of the present invention, it is possible to provide a moisture-proof construction material having sufficient moisture absorptive and desorptive properties for controlling the humidity of the room, excellent in shape stability at the moisture absorptive and desorptive manner, Can be provided.

Hereinafter, preferred embodiments of the present invention will be described in detail. It is to be understood that the present invention is not limited to the embodiments described below, but includes various modifications embodied in the scope of the present invention. The term " (meth) acrylic acid " in the present specification is a concept encompassing both of " acrylic acid " and " methacrylic acid ". The term " (meth) acrylate " is a concept covering both of " acrylate " and " methacrylate ".

Hereinafter, the composition for a humidity control building material according to the present embodiment and the humidity control construction material formed by molding the composition for the humidity control building material will be described in detail.

1. Composition for humidity control building material

The composition for a humidity control building material according to the present embodiment is at least one kind selected from the group consisting of a group represented by -SO ₃ ^- (M ^{n +} ) _{1 / n} and a group represented by -COO ^- (M ^{n +} ) _{1 / n} (Hereinafter, also referred to as " specific polymer ") having a group represented by the formula: (wherein n is an integer of 1 to 2 and M ^{n +} represents a hydrogen ion, a monovalent metal ion, a divalent metal ion or an onium ion) Material.

1.1. Specific polymer

1.1.1. The structure of a specific polymer

At least one member selected from the group consisting of a group represented by -SO ₃ ^- (M ^{n +} ) _{1 / n} and a group represented by -COO ^- (M ^{n +} ) _{1 / n} contained in the composition for a humidity control building material according to the present embodiment The polymer (specific polymer) having a species group includes a polymer having at least one structural unit selected from the group consisting of a structural unit represented by the following formula (2) and a structural unit represented by the following formula (6) . Further, by using a polymer having a group represented by -COO ^- (M ^{n +} ) _{1 / n} , the coloring of the resulting humidity-sensitive building material can be suppressed more effectively, and therefore, it can be more preferably used.

Wherein R ⁵ to R ⁷ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁸ is a group represented by -SO ₃ ^- (M ^{n +} ) _{1 / n} , -COO ^- (M ^{n +} _{1 / n} , a group represented by the following formula (3), a group represented by the following formula (4) or a group represented by the following formula (5), and n is an integer of 1 to 2 , M ^{n +} represents a hydrogen ion, a monovalent metal ion, a divalent metal ion or an onium ion)

(6), R ⁹ to R ¹⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a group represented by -SO ₃ ^- (M ^{n +} ) _{1 / n} and -COO ^- (M ^{n +} ) _{1 / n} , and at least one of R ⁹ to R ¹⁶ is a group represented by -SO ₃ ^- (M ^{n +} ) _{1 / n} or -COO ^- (M ^{n +} ) _{1 / n} , n is an integer of 1 to 2, and M ^{n +} represents a hydrogen ion, a monovalent metal ion, a divalent metal ion, or an onium ion)

In the general formula (2) and the formula (6), R ⁵ to R ⁷ and R ⁹ to as R ¹⁶ an alkyl group having 1 to 3 carbon atoms, which can take a methyl group, an ethyl group, an propyl, R ⁸ and R ⁹ to groups and -COO represented by _{^{(M n +) 1 / n}} - - R 16 is -SO ₃ that can be taken in groups represented by _{^{(M n +) 1 / n}} , n is an integer from 1 to 2, M ^{n +} is A hydrogen ion, a monovalent metal ion, a divalent metal ion, or an onium ion. As the monovalent metal ion, an alkali metal ion is preferable, and sodium, potassium, lithium and the like can be exemplified, and as the divalent metal ion, magnesium, calcium, barium and the like can be mentioned. The use of a monovalent metal ion such as sodium or potassium as the metal ion is preferable because it provides excellent moisture absorptive and desorptive performance of the obtained humidity-sensitive building material. In addition, these cationic species can be exchanged with other kinds of cationic species by various ion exchange methods.

The content of the specific polymer in the composition for a humidity control building material according to the present embodiment is preferably 1% by mass or more and 50% by mass or less based on 100% by mass of the total content of the specific polymer and the below- More preferably not less than 40% by mass, and particularly preferably not less than 5% by mass and not more than 30% by mass. When the content of the specific polymer is within the above range, it is possible to produce a moisture-resistance building material excellent in balance of moisture absorptive and desorptive properties, shape stability at the time of moisture absorption and desorptation, and strength as a construction material.

1.1.2. Method for producing a specific polymer

A method for producing a polymer having at least one group selected from the group consisting of -SO ₃ ^- (M ^{n +} ) _{1 / n} and a group represented by -COO ^- (M ^{n +} ) _{1 / n} in the present invention The following method can be mentioned. N represents an integer of 1 to 2, and M ^{n +} represents a hydrogen ion, a monovalent metal ion, a divalent metal ion, or an onium ion.

A monomer having at least one group selected from the group consisting of (1) -SO ₃ ^- (M ^{n +} ) _{1 / n} and a group represented by -COO ^- (M ^{n +} ) _{1 / n} and a crosslinkable monomer (Hereinafter also referred to as " production method (1) ").

(2) a group represented by -SO ₃ ^- (M ^{n +} ) _{1 / n} and a group represented by -COO ^- (M ^{n +} ) _{1 / n} , After copolymerizing the monomers, at least one group selected from the group consisting of groups represented by -SO ₃ ^- (M ^{n +} ) _{1 / n} and -COO ^- (M ^{n +} ) _{1 / n} is introduced into the copolymer (Hereinafter also referred to as " production method (2) ").

(3) a method of polymerizing a monomer having at least one group selected from the group consisting of -SO ₃ ^- (M ^{n +} ) _{1 / n} and a group represented by -COO ^- (M ^{n +} ) _{1 / n} Hereinafter also referred to as " production method (3) ").

The polymer thus produced may be produced by exchanging a part or the whole of M ^{n +} with a different ion, if necessary, by ion exchange or the like.

(1) a method for producing a polymer having at least one group selected from the group consisting of -SO ₃ ^- (M ^{n +} ) _{1 / n} and a group represented by -COO ^- (M ^{n +} ) _{1 /} (3) will be described in detail.

≪ Production method (1) >

The production process (1) is a process for producing a polymer comprising a monomer having at least one group selected from the group consisting of a group represented by -SO ₃ ^- (M ^{n +} ) _{1 / n} and a group represented by -COO ^- (M ^{n +} ) _{1 /} Thereby crosslinking the crosslinkable monomer.

The monomer having a group represented by -SO ₃ ^- (M ^{n +} ) _{1 / n} (hereinafter also referred to as a "sulfonic acid group-containing monomer") has a group represented by -SO ₃ ^- (M ^{n +} ) _{1 / n} , A compound having an unsaturated group is used. Specific examples thereof include sulfonic acid group-containing aromatic vinyl compounds such as styrenesulfonic acid; Sulfonic acid group-containing aliphatic diene-based compounds such as isoprene sulfonic acid (i.e., 2-methyl-1,3-butadiene-1-sulfonic acid); (Meth) acrylates such as vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, 2-acrylamide-2-methyl-1-propanesulfonic acid, sulfopropyl 2-hydroxypropanesulfonic acid, and salts thereof. Among them, the reactivity of the monomers is high, and a group represented by -SO ₃ ^- (M ^{n +} ) _{1 / n} can be easily introduced into the polymer, so that isoprenesulfonic acid, 2-acrylamide- desirable. The sulfonic acid group-containing monomers may be used singly or in combination of two or more.

_{^{-COO - (M n +) 1}} / a monomer having a group represented by _n (hereinafter also referred to as "carboxylic acid group-containing monomer") include, -COO ^- has an (M ^{n +)} represented by the _{1 / n,} addition polymerizable A compound having an unsaturated group is used. Specific examples thereof include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, and fumaric acid, and salts thereof. Of these, acrylic acid and methacrylic acid are preferable since the reactivity of the monomers is high and a group represented by -COO ^- (M ^{n +} ) _{1 / n} can be easily introduced into the polymer. The carboxylic acid group-containing monomers may be used singly or in combination of two or more.

The monomer having at least one group selected from the group consisting of -SO ₃ ^- (M ^{n +} ) _{1 / n} and the group represented by -COO ^- (M ^{n +} ) _{1 / n} has a molar ratio , Preferably 5 to 97 mol%, and more preferably 20 to 95 mol% based on the total amount of the copolymer. The molar ratio of the monomer having at least one group selected from the group consisting of -SO ₃ ^- (M ^{n +} ) _{1 / n} and the group represented by -COO ^- (M ^{n +} ) _{1 / n} is in the above range, It is possible to produce a moisture-proof building material having moisture absorption and desorptive properties.

As the crosslinkable monomer, those having at least two polymerizable unsaturated groups or reactive groups in one molecule are preferable. Specific examples thereof include N, N'-methylenebis (meth) acrylamide, diacetone acrylamide, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, (Meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylol propane tri (meth) acrylate, ethylene oxide modified trimethylol propane tri (meth) acrylate, pentaerythritol tetra (Poly) ethyleneglycol diglycidyl ether, (poly) propyleneglycol diglycidyl ether, glycerol di (meth) acrylate, triethylene glycol diisocyanate, triallyl isocyanurate, triallyl phosphate, triallyl amine, Glycidyl ether, ethylene glycol, polyethylene glycol, propylene glycol, glycerin, pentaerythritol, ethylenediamine, polyethyleneimine, glycidyl (meth) acrylate, (Meth) acrylate, ethoxylated glycerin triacrylate, propoxylated glycerin triacrylate, glycerol ((meth) acrylate, (Poly) glycidyl ether, polyglycidyl ether, polyglycidyl ether, polyglycidyl ether, polyglycidyl ether, polyglycidyl ether, polyglycidyl ether, polyglycidyl ether, polyglycidyl ether, (Poly) glycidyl ether, polyfunctional (meth) acrylamide, and the like. These crosslinkable monomers may be used alone, or two or more kinds may be used in combination.

The amount of the crosslinkable monomer is preferably 3 to 60 mol%, more preferably 5 to 50 mol% with respect to the molar ratio of the total monomers to be polymerized. When the molar ratio of the crosslinkable monomer is within the above range, at least one kind of group selected from the group consisting of a group represented by -SO ₃ ^- (M ^{n +} ) _{1 / n} and a group represented by -COO ^- (M ^{n +} ) _{1 /} The moisture-impermeable building material having good moisture absorptive and desorptive properties, in which stickiness is suppressed, can be produced.

In the present invention, the term " water-soluble " means that the solubility in 1 g of water is 0.01 g or more at 1 atm and 23 ° C. The term "water-insoluble" in the present invention means that the solubility in 1 g of water at 1 atm and 23 ° C. is less than 0.01 g.

When a specific polymer is polymerized, a monomer having a group represented by -SO ₃ ^- (M ^{n +} ) _{1 / n} , a monomer having a group represented by -COO ^- (M ^{n +} ) _{1 / n} and a monomer other than a crosslinkable monomer The external monomers may also be copolymerized. Examples of other monomers include aromatic vinyl compounds, conjugated diene compounds, (meth) acrylic acid esters, acrylonitrile, vinyl cyanide compounds, and acrylamides.

The polymerization method includes aqueous solution polymerization, solution polymerization, emulsion polymerization, mini-emulsion polymerization, suspension polymerization, reversed-phase suspension polymerization, precipitation polymerization and the like.

≪ Production method (2) >

Preparation method (2) -SO ₃ ^- (M ^{n +),} a group represented by _{1 / n,} and -COO ^- monomers that do not contain a group of at least one member selected from the group consisting of groups represented by (M ^{n +)} _{1 / n} And at least one member selected from the group consisting of a group represented by -SO ₃ ^- (M ^{n +} ) _{1 / n} and a group represented by -COO ^- (M ^{n +} ) _{1 / n} in the copolymer after copolymerization with a crosslinkable monomer Is introduced.

-SO ₃ ^- (M ^{n +)} a group represented by _{1 / n,} and -COO ^- (M ^{n +)} as the monomer does not contain a group of at least one member selected from the group consisting of groups represented by _{1 / n,} an aromatic vinyl monomer And at least one of the aliphatic vinyl-based monomers, preferably the glass transition temperature is easily adjusted, and may suitably include other monomers.

Examples of the aromatic vinyl-based monomer include styrene, vinylnaphthalene,? -Methylstyrene, o-methylstyrene, p-methylstyrene and m-methylstyrene. Of these, styrene is preferably used. The aromatic vinyl monomers may be used singly or in combination of two or more.

Examples of the aliphatic diene monomer include 1,3-butadiene, 1,2-butadiene, 1,2-pentadiene, 1,3-pentadiene, 2,3-pentadiene, isoprene, , 3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 2,3-hexadiene, 2,4-hexadiene, 2,3- 1,3-heptadiene, 1,4-heptadiene, 1,5-heptadiene, 1,6-heptadiene, 2,3-heptadiene, 2, Heptadiene, cyclopentadiene, dicyclopentadiene, ethylidene norbornene, and the like, and branched aliphatic or alicyclic dienes having 4 to 7 carbon atoms, such as 4,4'-heptadiene, 3,5-heptadiene, 3,5- . Of these, 1,3-butadiene and isoprene are preferably used.

As the crosslinkable monomer, those similar to the monomers exemplified in the above-mentioned Production Method (1) can be used.

Examples of the polymerization method include solution polymerization, emulsion polymerization and the like. Subsequently, a monomer which does not contain at least one group selected from the group consisting of -SO ₃ ^- (M ^{n +} ) _{1 / n} and a group represented by -COO ^- (Mn ⁺ ) _{1 / n} and a crosslinkable monomer the copolymer in the sulfonation or by hydrolysis, the copolymer -SO ₃ ^- (M ^{n +)} a group represented by _{1 / n,} and -COO ^- (M ^{n +)} is selected from the group consisting of groups represented by _{1 / n} At least one kind of group is introduced. However, as a method of introducing these functional groups, there are known methods, for example, a method described in the edited Japanese Chemical Society, New Experiment Lecture (Vol. 14, p. 1773), Japanese Patent Application Laid- Method can be used. Further, JP-A-2001-11320 or JP-A No. 2000-17101 discloses -COO by hydrolysis or the acid anhydride, ester, amide hydrolysis of the nitrile or the like as set forth ^- (M ^{n +)} _{1 /} a group represented by _n may be introduced into the copolymer. The polymer thus prepared can be appropriately used in the present embodiment by timely adjusting the kind of M ^{n +} by performing ion exchange or the like.

As a method of sulfonation, specifically, it can be obtained by sulfonating a double bond moiety or an aromatic ring in a copolymer with a sulfonating agent, suitably a solvent, and, if necessary, reacting with water or a basic compound. At the time of sulfonation, the double bond is opened to form a single bond, or a hydrogen atom is substituted with a group represented by -SO ₃ ^- (M ^{n +} ) _{1 / n} , leaving a double bond. In the case of aromatic rings, the para position is primarily sulfonated.

Suitable examples of the sulfonating agent include sulfuric acid, chlorosulfonic acid, fuming sulfuric acid, hydrogen sulfite (Na salt, K salt, Li salt and the like) in addition to complexes of anhydrous sulfuric acid and anhydrous sulfuric acid with electron donor compounds.

Examples of the electron donor compound include ethers such as N, N-dimethylformamide, dioxane, dibutyl ether, tetrahydrofuran and diethyl ether; Amines such as pyridine, piperazine, trimethylamine, triethylamine, and tributylamine; Sulfides such as dimethyl sulfide and diethyl sulfide; And nitrile compounds such as acetonitrile, ethylnitrile and propylnitrile. Among these, N, N-dimethylformamide and dioxane are preferable in order to stably proceed sulfonation.

As the solvent, a solvent inert to the sulfonating agent is used. Specifically, halogenated hydrocarbons such as chloroform, dichloroethane, tetrachloroethane, tetrachlorethylene and dichloromethane; Nitro compounds such as nitromethane and nitrobenzene; Aliphatic hydrocarbons such as liquid sulfur dioxide, propane, butane, pentane, hexane, and cyclohexane; Ether solvents such as dioxane and tetrahydrofuran; Water and the like. These solvents may be used alone or in combination of two or more.

Examples of the basic compound include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide; Alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium methoxide, sodium-t-butoxide and potassium-t-butoxide; There may be mentioned methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, amyl lithium, propyl sodium, methyl magnesium chloride, ethyl magnesium bromide, propyl magnesium iodide, diethyl magnesium, diethyl zinc, Organometallic compounds such as butyl aluminum; Amines such as ammonia water, trimethylamine, triethylamine, tripropylamine, tributylamine, pyridine, and piperazine; And metal compounds such as sodium, lithium, potassium, calcium and zinc. These basic compounds may be used alone, or two or more of them may be used in combination. Among these basic compounds, alkali metal hydroxide and ammonia water are preferable, and sodium hydroxide, potassium hydroxide and lithium hydroxide are particularly preferable.

≪ Manufacturing method (3) >

The production method (3) is a production method in which a monomer having at least one group selected from the group consisting of a group represented by -SO ₃ ^- (M ^{n +} ) _{1 / n} and a group represented by -COO ^- (M ^{n +} ) _{1 /} And polymerizing.

^{_{-SO 3 - (M n +)}} 1 / Examples of the monomer having a group represented by _n, as in the production method ^{_{(1) -SO 3 - (M}} n +) having a group represented by _{1 / n,} also having a polymerizable unsaturated group Compounds are used. Specific examples thereof include sulfonic acid group-containing aromatic vinyl compounds such as styrenesulfonic acid; Sulfonic acid group-containing aliphatic diene-based compounds such as isoprene sulfonic acid (i.e., 2-methyl-1,3-butadiene-1-sulfonic acid); (Meth) acrylates such as vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, 2-acrylamide-2-methyl-1-propanesulfonic acid, sulfopropyl 2-hydroxypropanesulfonic acid, and salts thereof. Among them, the reactivity of the monomers is high, and a group represented by -SO ₃ ^- (M ^{n +} ) _{1 / n} can be easily introduced into the polymer, so that isoprenesulfonic acid, 2-acrylamide- desirable. The monomer containing a group represented by -SO ₃ ^- (M ^{n +} ) _{1 / n} may be used singly or in combination of two or more.

-COO ^- As the monomer having a group represented by _{^{(M n +) 1 / n}} , as in the production method (1) -COO ^- having a group represented by _{^{(M n +) 1 / n}} , also a compound having a polymerizable unsaturated group Is used. Specific examples thereof include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, and fumaric acid, and salts thereof. Of these, acrylic acid and methacrylic acid are preferable since the reactivity of the monomers is high and the group represented by -COO ^- (M ^{n +} ) _{1 / n} can be easily introduced into the polymer. The group-containing monomers represented by -COO ^- (M ^{n +} ) _{1 / n} may be used alone or in combination of two or more.

The monomer having at least one group selected from the group consisting of -SO ₃ ^- (M ^{n +} ) _{1 / n} and the group represented by -COO ^- (M ^{n +} ) _{1 / n} has a molar ratio , Preferably from 20 to 95 mol%, based on the total amount of the polymer. The molar ratio of the monomer having at least one group selected from the group consisting of -SO ₃ ^- (M ^{n +} ) _{1 / n} and the group represented by -COO ^- (M ^{n +} ) _{1 / n} is in the above range, It is possible to produce a moisture-proof building material having moisture absorption and desorptive properties.

The monomer having at least one group selected from the group consisting of -SO ₃ ^- (M ^{n +} ) _{1 / n} and a group represented by -COO ^- (Mn ⁺ ) _{1 / n} is copolymerized with other monomers . Examples of other monomers include aromatic vinyl compounds, conjugated diene compounds, (meth) acrylic acid esters, acrylonitrile, vinyl cyanide compounds, and acrylamides.

The polymerization method includes (water) solution polymerization, emulsion polymerization, mini-emulsion polymerization, suspension polymerization, reversed-phase suspension polymerization, precipitation polymerization and the like. The weight average molecular weight of the polymer thus obtained is preferably from 2000 to 1000000, more preferably from 5000 to 500000, when the polymer is dissolved in the eluent of GPC (ultrapure water / acetonitrile / sodium sulfate).

1.1.3. Characteristics of Specific Polymers

The total number of moles of the group represented by -SO ₃ ^- (M ^{n +} ) _{1 / n} and -COO ^- (M ^{n +} ) _{1 / n contained} in the specific polymer is 1.5 mmol / g or more in the specific polymer And more preferably 3 to 15 mmol / g. The content of at least one group selected from the group consisting of -SO ₃ ^- (M ^{n +} ) _{1 / n} and a group represented by -COO ^- (M ^{n +} ) _{1 / n} is within the above range, Sufficient moisture absorption performance can be imparted to the building material.

In the present invention, the total number of moles of the group represented by -SO ₃ ^- (M ^{n +} ) _{1 / n} and the group represented by -COO ^- (M ^{n +} ) _{1 / n} is sufficiently dried, And 15 g of ion exchange water and 15 g of an acid type ion exchange resin are added to the solution and stirred at room temperature for 5 hours and then the filtrate after suction filtration is titrated using a 5 mass% aqueous sodium hydroxide solution.

Also, -SO ₃ contained in the specific polymer ^- (M ^{n +)} a group represented by _{1 / n,} and -COO ^- group of at least one kind selected from a group represented by (M ^{n +)} _{1 / n,} the cation (M ^{n +} ) as the counter ion. However, not all of the counter ions need to be a homogeneous cation, and at least a part of them may be at least one selected from a hydrogen ion, a monovalent metal ion, a divalent metal ion, and an onium ion. Examples of the monovalent metal ion include alkali metal ions such as sodium, potassium and lithium.

When the counter ion M ^{n +} is an onium ion, an organic onium ion is preferred. Examples of the organic onium ion include quaternary ammonium ion, phosphonium ion, oxonium ion, and sulfonium ion. Of these, quaternary ammonium ions are preferred, and specific examples include ions represented by the following formula (1).

(In the formula (1), R ¹ to R ⁴ each independently represent one selected from a hydrogen atom, an alkyl group and an alkylol group, provided that they are not all hydrogen atoms)

Examples of the quaternary ammonium ion include an aliphatic ammonium ion, a pyridinium ion, a quinolinium ion, an imidazolium ion, a pyrrolidinium ion, a piperidinium ion, a betaine, and lecithin. Specific examples thereof include hydroxypolyoxyethylene trialkylammonium, hydroxypolyoxypropylene trialkylammonium, di (hydroxypolyoxyethylene) dialkylammonium, di (hydroxypolyoxypropylene) dialkylammonium, dimethyldioctylammonium , Dimethyldidodecylammonium, methylethyldioctylammonium, methylethyldioctylammonium, methyltrioctylammonium, methyltridodecylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, benzylmethyldioctylammonium, benzylmethyldido Decyl ammonium, benzyl ethyl dioctyl ammonium, benzyl ethyl dioctyl ammonium, benzyl trioctyl ammonium, benzyltridecyl ammonium and the like.

These cationic species are capable of exchanging with other species of cationic species by various ion exchange techniques.

1.2. Inorganic material

As inorganic materials contained in the composition for a humidity control building material according to the present embodiment, inorganic oxides, inorganic hydroxides, inorganic sulfates, inorganic carbonates and the like can be preferably exemplified. Examples of inorganic oxides include silicon dioxide, aluminum oxide and calcium oxide. Examples of inorganic hydroxides include aluminum hydroxide and calcium hydroxide. Examples of the inorganic sulfate include aluminum sulfate and calcium sulfate. Examples of the inorganic carbonate include inorganic carbonate Calcium carbonate, and the like.

The inorganic material contained in the composition for a humidity control building material according to the present embodiment is preferably an inorganic porous material. In the present invention, the inorganic porous material is an inorganic material having a plurality of fine pores inside the material. By using an inorganic porous material as an inorganic material, it is presumed that moisture absorbed by a specific polymer is transferred to fine pores of an inorganic porous material to accumulate moisture. This action greatly improves the moisture absorptive and desorptive characteristics of the humidity control construction material.

Examples of the inorganic porous material include diatomaceous earth, siliceous shale, alpaine, imoglitol, sepiolite, zeolite, activated clay, dagok stone, silica gel and the like. It is preferable to use silica gel or activated clay. These inorganic porous materials may be classified depending on the desired color. For example, when white is required, silica gel, activated clay and the like can be used, and when dark brown is required, silica shale, alpaine, etc. can be used.

In the present invention, the shape of the inorganic porous material can be timely selected according to the characteristics required for the humidity control building material manufactured using the composition for a humidity control building material according to the present embodiment. Specifically, it may be a particle shape, a flake shape, a needle shape, or a fiber shape.

A commercially available building material may be used as long as the inorganic material contained in the composition for a humidity control building material according to the present embodiment includes the above-mentioned inorganic oxide, inorganic hydroxide, inorganic sulfate, inorganic carbonate and the like. As such commercially available building materials, for example, cement, mortar, diatomaceous earth, gypsum, plaster or the like can be used.

The content of the inorganic material in the composition for a humidity control building material according to the present embodiment is preferably 50 mass% or more and 99 mass% or less when the total content of the specific polymer and the inorganic material is 100 mass%, more preferably 60 mass% More preferably not less than 97% by mass, and particularly preferably not less than 70% by mass and not more than 95% by mass. When the content of the inorganic material is within the above range, it is possible to produce a moisture-resistance building material excellent in balance of moisture absorptive and desorptive properties, shape stability at the time of moisture absorption and desorptation, and strength as a construction material.

1.3. additive

The composition for a humidity control building material according to the present embodiment may contain a crosslinking agent, a leveling agent, a wettability improver, a surfactant, a plasticizer, an ultraviolet absorber, a defoaming agent, an antiseptic agent, a thickener, an antioxidant, an antistatic agent, a silane coupling agent, May contain additives.

When the polymer contained in the composition for a humidity control building material according to the present embodiment is a polymer obtained without using a crosslinkable monomer as in the above-mentioned production method (3), it is preferable to add a crosslinking agent.

The crosslinking agent which can be added is not particularly limited as long as it can form a crosslinked structure with the above-mentioned specific polymer, and the following crosslinking agents can be used. Preferred examples of such crosslinking agents include crosslinking agents such as melamine crosslinking agents, epoxy crosslinking agents, carbodiimide crosslinking agents, dihydrazide crosslinking agents, (block) isocyanate crosslinking agents, oxazoline crosslinking agents and aziridine crosslinking agents; Alkoxide crosslinking agents having an inorganic metal such as silicon, zinc, titanium, and zirconia, and chelating crosslinking agents. The amount of the crosslinking agent to be added is 1 to 100 parts by mass, preferably 1 to 50 parts by mass with respect to 100 parts by mass of the specific polymer. These crosslinking agents to be added may be used singly or in combination of two or more.

2. Humidity building material

The humidity control building material according to the present embodiment can be produced by molding the composition for a humidity control building material, or by supporting it on a substrate or the like. The moisture-proof construction material manufactured and manufactured using the above method can be preferably used for ceiling materials for interior use, wall materials, flooring materials, and storage materials.

When the humidity control building material is molded by molding the above-described composition for a humidity control building material, for example, a composition for a humidity control building material may be introduced into a mold having a desired shape, the medium may be removed, the press may be molded or extruded, Or may be formed by directly applying it by using a trowel or the like on a base material and then drying or by curing the above specific polymer by crosslinking or the like.

When the humidity control building material is produced by supporting the above-described composition for a humidity control building material on a substrate, the substrate is not particularly limited and examples thereof include nonwoven fabric, mesh, paper, pulp, resin, metal and glass. There are no particular restrictions on the method of impregnation, but there are no particular limitations on the method of impregnation, such as brushing, brushing, trowelling, bar coater, knife coater, doctor blade, screen printing, spray application, spin coater, applicator, roll coater, flow coater, centrifugal coater, (Micro) gravure coater, dip coating, flexo printing, potting, papermaking, or the like, and may be transferred onto other substrates, for example, after being applied onto a transfer substrate.

If by molding the above-described humidity control architecture damper composition of manufacturing a humidity control building material, -SO ₃ to be contained in the above-described humidity control architecture damper composition ^- (M ^{n +)} _{1 / n} groups and -COO represented by ^- (M ^{n +)} _{1 /} a group of at least one member selected from the group consisting of groups represented by _n polymer having a (where n is an integer from 1 to 2, M ^{n +} represents a hydrogen ion, monovalent metal ion, a bivalent metal ion or an onium ion) Preferably has a cross-linked structure among the moisture-proof construction materials. Such a crosslinking structure may be crosslinked in a molding process for preparing a humidity control building material by adding a crosslinking agent to the above composition for a humidity control building material and molding the composition for a humidity control building material and the specific polymer contained in the above- It may be crosslinked. The humidity-conditioning building material contains a specific crosslinked polymer, so that it is possible to obtain a moisture-resistance building material having a small change in the volume of the obtained building material and having excellent shape stability.

A polymer having at least one group selected from the group consisting of -SO ₃ ^- (M ^{n +} ) _{1 / n} and -COO ^- (Mn ⁺ ) _{1 / n} is produced by the above- , The amount of the crosslinkable monomer is 3 to 60 mol%, preferably 5 to 50 mol%, based on the molar ratio of the total monomers to be polymerized. When the molar ratio of the crosslinkable monomer is within the above range, stickiness of the obtained humidity-sensitive building material can be suppressed. When the molar ratio of the crosslinkable monomer is within the above range, at least one kind selected from the group consisting of a group represented by -SO ₃ ^- (M ^{n +} ) _{1 / n} and a group represented by -COO ^- (M ^{n +} ) _{1 / n} The molar ratio of the monomer having a group is increased, so that the moisture absorptive and desorptive property of the obtained humidity-sensitive building material can be improved.

3. Example

Next, the present invention will be described in detail by way of examples, but the present invention is not limited thereto, and can be applied to a processing method according to a manufacturing method of a humidity control construction material. In the following, "% " means " mass% " unless otherwise specified. The term " part " means " part by mass " unless otherwise specified.

3.1. Synthetic example

3.1.1. Synthesis Example 1

301 parts of a 40% aqueous solution of sodium isoprene sulfonate, 141 parts of an acrylic acid 80% aqueous solution and 102 parts of a 20% aqueous solution of diacetone acrylamide were mixed to prepare a monomer aqueous solution. The molar ratio of the isoprenesulfonic acid sodium salt, acrylic acid, and diacetone acrylamide in the aqueous monomer solution is 30/65/5. 224 parts of water and 4 parts of 35% aqueous hydrogen peroxide were placed in a 1-liter four-necked separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a nitrogen gas introducing tube and the monomer aqueous solution was maintained at 100 deg. Was added dropwise over 2 hours. After the addition of the aqueous monomer solution was completed, the polymerization was continued for another hour, and then 29 parts of 48% sodium hydroxide aqueous solution was added to perform partial neutralization. The weight average molecular weight of the resulting partially neutralized isoprenesulfonic acid sodium salt-acrylic acid-diacetone acrylamide copolymer was 30,000.

Subsequently, 3 parts of a 40% aqueous solution of a dihydrazide crosslinking agent (adipic acid dihydrazide) as a crosslinking agent was added to 100 parts of a 33% aqueous solution of the partial neutralized product of the obtained copolymer to prepare an aqueous curable composition solution (A-1) having a solid content concentration of 33% ≪ / RTI >

3.1.2. Synthesis Example 2

326 parts of a 40% aqueous solution of isoprene sulfonic acid sodium salt and 221 parts of an 80% aqueous solution of acrylic acid were mixed to prepare a monomer aqueous solution. The molar ratio of the sodium salt of isoprenesulfonic acid salt and acrylic acid in the monomer aqueous solution is 25/75. 165 parts of water and 26 parts of 35% aqueous hydrogen peroxide were placed in a 1-liter four-necked separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a nitrogen gas introducing tube and the monomer aqueous solution was maintained at 100 deg. Over 2 hours. After the addition of the aqueous monomer solution was completed, the polymerization was continued for another hour, and then 45 parts of 48% sodium hydroxide aqueous solution was added to perform partial neutralization. The weight average molecular weight of the partially neutralized isoprenesulfonic acid sodium salt-acrylic acid copolymer thus obtained was 15,000.

Subsequently, 32 parts of a 25% aqueous solution of an oxazoline crosslinking agent (Epochros WS-700, Nippon Shokubai) as a crosslinking agent was added to 100 parts of a 40% aqueous solution of the partial neutralized product of the copolymer to prepare an aqueous solution of a curable composition having a solid concentration of 36% A-2).

3.1.3. Synthesis Example 3

681 parts of ion-exchanged water, 90 parts of 2-acrylamido-2-methylpropanesulfonic acid, 10 parts of N, N'-methylenebisacrylamide and 20 parts of a 5% aqueous solution of sodium persulfate were added and dissolved in the beaker to prepare a water-soluble monomer solution .

1300 parts of cyclohexane and 7.1 parts of a 70% solution of sodium di (2-ethylhexyl) sulfosuccinate (RICASURF M-30) were dissolved in a separate beaker to prepare an emulsifier solution.

The emulsifier solution was slowly added dropwise to the aqueous monomer solution prepared above with stirring, and the whole amount was added. Thereafter, while cooling in an ice bath, ultrasonic irradiation for 120 seconds was performed three times using an ultrasonic disperser (" UH-600S ", manufactured by SMT) to obtain a reversed phase emulsion. The resulting emulsion was transferred into a separable flask and heated at 70 캜 for 3 hours. Thereafter, the resultant was dried under reduced pressure to obtain 2-acrylamide-2-methylpropanesulfonic acid-methylenebisacrylamide copolymer particles. The obtained copolymer particles (curable composition: A-3) were dried and observed with a transmission electron microscope (H-7650, manufactured by Hitachi Hi-tech Co., Ltd.).

3.1.4. Synthesis Example 4

301 parts of a 40% aqueous solution of sodium isoprene sulfonate, 141 parts of an acrylic acid 80% aqueous solution and 102 parts of a 20% aqueous solution of diacetone acrylamide were mixed to prepare a monomer aqueous solution. The molar ratio of the isoprenesulfonic acid sodium salt, acrylic acid, and diacetone acrylamide in the aqueous monomer solution is 30/65/5. 224 parts of water and 4 parts of 35% aqueous hydrogen peroxide were placed in a 1-liter four-necked separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a nitrogen gas introducing tube and the monomer aqueous solution was maintained at 100 deg. Was added dropwise over 2 hours. After the addition of the aqueous monomer solution was completed, the polymerization was continued for another hour, and then 29 parts of 48% sodium hydroxide aqueous solution was added to perform partial neutralization. The solid concentration of the partially neutralized product of the isoprenesulfonic acid sodium salt-acrylic acid-diacetone acrylamide copolymer (curable composition: A-4) was 33% and the weight average molecular weight was 30,000.

3.1.5. Synthesis Example 5

336 parts of ion-exchanged water, 97 parts of acrylic acid 80% aqueous solution, 10 parts of N, N'-methylenebisacrylamide, 12 parts of polyoxyethylene distyrenated phenyl ether 10% aqueous solution (Emulgen A-60) % Aqueous solution was added and dissolved to prepare a water-soluble monomer solution.

927 parts of n-heptane and 7.5 parts of sorbitan monooleate were dissolved in a separate beaker to prepare an emulsifier solution.

The emulsifier solution was slowly added dropwise to the above-prepared water-soluble monomer solution with stirring, and the whole amount was added and stirred to obtain a reversed phase emulsion. The resulting emulsion was transferred into a separable flask and heated at 80 캜 for 3 hours. Thereafter, the acrylic acid-methylene bisacrylamide copolymer particles were obtained by drying under reduced pressure. The obtained copolymer particles (curable composition: A-5) were dried and observed with a transmission electron microscope (H-7650, manufactured by Hitachi Hi-tech Co., Ltd.), and the primary particle diameter was about 50 μm.

3.1.6. Synthesis Example 6

34 parts of ion-exchanged water, 97 parts of acrylic acid 80% aqueous solution, 1 part of N, N'-methylenebisacrylamide, 12 parts of polyoxyethylene distyrenated phenyl ether 10% aqueous solution (Emulgen A-60) % Aqueous solution was added and dissolved to prepare a water-soluble monomer solution.

927 parts of n-heptane and 7.5 parts of sorbitan monooleate were dissolved in a separate beaker to prepare an emulsifier solution.

The emulsifier solution was slowly added dropwise to the above-prepared water-soluble monomer solution with stirring, and the whole amount was added and stirred to obtain a reversed phase emulsion. The resulting emulsion was transferred into a separable flask and heated at 80 캜 for 3 hours. Thereafter, the acrylic acid-methylene bisacrylamide copolymer particles were obtained by drying under reduced pressure. The obtained copolymer particles (curable composition: A-6) were dried and observed with a transmission electron microscope (H-7650, manufactured by Hitachi Hi-tech Co., Ltd.).

3.2. Evaluation of polymer

(1) Solid concentration

Each of the polymer aqueous solutions obtained in Synthesis Examples 1, 2 and 4 was weighed in an amount of 1 g into an aluminum dish and the content of the polymer contained in each polymer aqueous solution was calculated from the weight change after heating on a hot plate at 200 캜 for 30 minutes, Respectively.

(2) GPC measurement

The weight average molecular weights of the polymers obtained in Synthesis Examples 1, 2 and 4 were measured by gel permeation chromatography under the following conditions and expressed as polystyrene conversion values.

Apparatus: HLC-8220GPC (manufactured by TOSOH CORPORATION),

Column: TSK-gel GWPWXL (manufactured by TOSOH CORPORATION),

Eluent: Ultrapure water / acetonitrile / sodium sulfate,

Flow rate: 1.0 mL / min, measurement temperature 40 DEG C

(3) Determination of solubility

The polymers obtained in Synthesis Examples 1 to 6 were dissolved in water at 1 atm and 23 占 폚 to determine the solubility. When the solubility in 1 g of water was 0.01 g or more, it was judged that the polymer was "water-soluble". When the solubility was less than 0.01 g, the polymer was judged as "water-insoluble".

3.3. Examples and Comparative Examples

3.3.1. Example 1

16 parts by mass of diatomaceous earth and 68 parts by mass of beta hemihydrate gypsum were added as an inorganic material to 50 parts by mass of the curable composition aqueous solution (A-1) obtained in Synthesis Example 1, and the mixture was stirred with a mixer to obtain a slurry having a width of 25 cm x 15 cm, The slurry was introduced into a liberated box frame, the upper part was integrated, lightly squeezed with a roll, and dried at 150 ° C for 30 minutes to produce a molded article for a humidity-resistant building material. The obtained molded article was evaluated for moisture absorptive and desorptive properties, shape stability, coloration and bending strength in a medium humidity region. The results are shown in Table 1. The total amount of hydrophilic functional groups in the table means the total of groups represented by -SO ₃ ^- (M ^{n +} ) _{1 / n} and -COO ^- (M ^{n +} ) _{1 / n} contained in the polymer (A- The number of moles (mmol / g). The evaluation method is as follows.

(1) Absorption and desorption characteristics of humidity region

The surface of the molded article was exposed and the remaining five surfaces (side and back surfaces) were sealed with aluminum and left in an atmosphere of 23 deg. C and 50% RH in advance, And allowed to stand for 12 hours, and then allowed to stand for 12 hours in an atmosphere of 23 ° C and 50% RH to evaluate the moisture absorptive and desorptive amount. When the mass ratio of the composition for moisture-conditioning building material contained in the formed article was 10% by mass or more, the obtained moisture absorptive and desorptive amount was judged as " Good ", and when it was less than 10% The better the numerical value, the better the humidity control performance as a humidity control building material.

(2) Shape stability

The deformation and stickiness of the molded article after the moisture absorptive and desorptive property test of the above-mentioned moisture humidity were evaluated. When the molded article after the test has no deformation or stickiness, and the shape stability is good, the symbol "? &Quot; indicates that the molded article has no deformation but a little sticky, , And those having insufficient shape stability were evaluated as " X ".

(3) coloration

The coloration of the obtained molded article was visually judged. &Quot;, " good ", " good ", and " good "

(4) Bending strength

JIS A 1408 < / RTI > The test specimen prepared from the molded body is placed on the supporting portion of the bending tester and the suspension is put on the center portion of the specimen, and the suspension is pressed at 250 N / min. The load when the specimen was broken was defined as the bending strength. A " indicates that the obtained bending strength value is equal to or higher than that of the formed article without the humidity-conditioning construction composition of the present invention, and " B " indicates that the bending strength was slightly deteriorated .

3.3.2. Example 2

18 parts by mass of diatomaceous earth and 64 parts by mass of β-hemihydrate as an inorganic material were added to 50 parts by mass of the aqueous solution (A-2) of the curable composition obtained in Synthesis Example 2 and stirred with a mixer to prepare a slurry, A molded body for building materials was produced. The obtained molded article was evaluated in terms of moisture absorptive and desorptive properties, shape stability, coloring and bending strength in the same manner as in Example 1 above. The results are shown in Table 1.

3.3.3. Example 3

To 16 parts by mass of the curing composition (A-3) obtained in Synthesis Example 3, 34 parts by mass of water, 16 parts by mass of diatomaceous earth as the inorganic material and 68 parts by mass of the beta hemihydrate were added and stirred with a mixer to obtain a slurry. Thereby forming a molded article for a humidity-control building material. The obtained molded article was evaluated in terms of moisture absorptive and desorptive properties, shape stability, coloring and bending strength in the same manner as in Example 1 above. The results are shown in Table 1.

3.3.4. Examples 4 to 12 and Comparative Examples 1 to 4

(Slurry) for the humidity control building material of Examples 4 to 12 and Comparative Examples 1 to 4 was prepared in the same manner as in Examples 1 to 3, and the same process as in Example 1 was carried out to produce a molded article for a humidity control building material. The obtained molded article was evaluated in terms of moisture absorptive and desorptive properties, shape stability, coloring and bending strength in the same manner as in Example 1 above. The results are shown in Tables 1, 2, and 3.

The following materials were used as components of the inorganic materials shown in Tables 1 to 3.

<Polymer>

The curable compositions (A-1) to (A-6)

<Inorganic materials>

Diatomaceous earth: Wako Pure Chemical Industries, Ltd.

Silica gel B: trade name &quot; Dryyan &quot;, manufactured by Yamani Chemical Industry Co., Ltd.

Zeolite: Product name "Y-type zeolite 320HOA", manufactured by TOSOH CORPORATION

CaCl ₂ : manufactured by Wako Pure Chemical Industries, Ltd.

· Β-half gypsum: trade name "TA-85N", manufactured by Noritake Co., Ltd.

As shown in Tables 1 to 3, the humidity-sensitive building material obtained in Examples 1 to 12 of the present invention has moisture-proof performance in a humidity range required as a humidity-conditioning construction material, shape stability to withstand repeated use, All were found to be good. On the other hand, according to Comparative Examples 1 to 4, it was found that if one of the requirements of the present invention was insufficient, it was not balanced. In other words, Comparative Examples 1 to 4 do not include the curable composition. Comparing these, it has been found that when the curable composition is not contained, the lack of moisture absorptive and desorptive ability or the shape stability may become insufficient.

Claims (4)

At least one group selected from the group consisting of a group represented by -SO ₃ ^- (M ^{n +} ) _{1 / n} and a group represented by -COO ^- (M ^{n +} ) _{1 / n} wherein n is an integer of 1 to 2 And M ^{n +} represents a hydrogen ion, a monovalent metal ion, a divalent metal ion or an onium ion)
Inorganic material
Wherein the composition is a composition for a humidity-sensitive building material. The composition for a humidity-sensitive building material according to claim 1, wherein the content of the inorganic material is 50% by mass or more and 99% by mass or less, when the total content of the polymer and the inorganic material is 100% by mass. The polymer according to claim 1 or 2, wherein the total mol number of the group represented by -SO ₃ ^- (M ^{n +} ) _{1 / n} and the group represented by -COO ^- (M ^{n +} ) _{1 / n} in the polymer is 1.5 mmol / g &lt; / RTI &gt; A humidity-sensitive building material produced by molding a composition for a humidity-conditioning building material according to any one of claims 1 to 3.