JPH1157465A - Moisture controlling material for tatami mat and tatami mat using the material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a moisture controlling material for tatami mats which has high moisture absorbing and desorbing speed, excellent moisture controlling property, easily provides tatami mats with moisture controllability, and reliably and constantly produces comfortable moisture environments. SOLUTION: This moisture controlling material is made of polyurethane resin (U) obtained by reaction of a water-absorptive resin dispersion (D) and polyisocyanate compound (P) and made of a urethane resin composition U having water-absorptive resin (B) or its hydrous gel (B) dispersed therein. The water-absorptive resin dispersion (D) is produced by dispersing the water- absorptive resin (B) or its water-absorbing gel which is polymerixzed in an active hydrogen-containing organic compound (A) in the liquid or hot-melt organic compound (A).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a humidifying material for tatami and a tatami mat using the same, and more particularly, to a urethane resin composition using a water-absorbing resin dispersion having a fine dispersed particle size and good dispersion. And a tatami mat using the same.

[0002]

2. Description of the Related Art Conventionally, as a method for imparting humidity control to a tatami mat, Japanese Unexamined Utility Model Publication No. 63-129032 discloses a method of using polystyrene foam having a deodorant property and a moisture absorbing / releasing property with a tatami floor. Japanese Unexamined Patent Publication No. Hei 1-163634 discloses a method of using deodorizing paper having a moisture absorbing / releasing function obtained by mixing a powder of ceramic or the like with pulp, and Japanese Unexamined Patent Publication No. Hei 8-151774 discloses a method of using silica gel having moisture absorbing / releasing properties. Japanese Unexamined Patent Publication No. 8-105190 discloses a method of using a deodorizing sheet comprising a complex or a fiber or pulp containing a complex and pulverized B-type silica gel. A method of using a moisture-permeable base sheet in which granular silica gel is adhered to the surface of the base sheet, and a cover sheet coated on the side of the base sheet provided with silica gel. It is draft.

[0003]

However, in each case, there are problems such as a long moisture absorption / desorption time, and moisture absorption but not moisture release.

[0004]

Means for Solving the Problems In view of the above problems, the present inventors have been keen to obtain a tatami humidity control material having a fast moisture absorption / desorption time and excellent humidity control properties, and a tatami mat using the same. As a result of repeated studies, the present invention has been reached.

That is, the present invention comprises a urethane resin (U) obtained by reacting the following water-absorbent resin dispersion (D) with a polyisocyanate compound (P), wherein (U) contains a water-absorbent resin (B) or This is a tatami humidity controller made of a urethane resin composition in which the hydrogel is dispersed. Water-absorbing resin dispersion (D): water-absorbing resin (B) polymerized in (A) or a water-absorbing gel thereof dispersed in a liquid or hot-melt active hydrogen-containing organic compound (A) Resin dispersion.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the liquid or heat-meltable active hydrogen-containing organic compound (A) includes alcoholic hydroxyl group-containing compounds, phenolic hydroxyl group-containing compounds,
Examples thereof include a carboxyl group-containing compound, a thiol group-containing compound, and an amino group-containing compound.

Examples of the alcoholic hydroxyl group-containing compound include polyether monools and polyols, and among these, polyols are preferred. As the polyether monol, compounds having one active hydrogen atom (for example, C1 to C20 aliphatic, alicyclic or araliphatic alcohols, monohydric phenols, dialkylamines,
Morpholine, etc.) to which an alkylene oxide is added. Further, etherified products (eg, methyl ether, isopropyl ether, phenyl ether, etc.) and esterified products (eg, acetic acid ester and benzoic acid ester) in which hydroxyl groups are partially blocked with alcohol or carboxylic acid can be mentioned.

Examples of polyols include polyether polyols, polyester polyols, polyols having a carbon-carbon bond in the main chain, and other examples described in "Polyurethane Resin Handbook, edited by Keiji Iwata, published by Nikkan Kogyo Shimbun, published in 1987". And the like. Further, there may be mentioned etherified products and esterified products in which the hydroxyl groups of the polyol are partially blocked with alcohols or carboxylic acids. Of these, polyether polyols and polyester polyols are preferred.

[0009] Examples of the polyether polyol include a polyoxyalkylene polyol. As the polyoxyalkylene polyol, a compound having at least 2 (preferably 2 to 8) active hydrogen atoms (for example, a polyhydric alcohol, a polyhydric phenol, an amine, a polycarboxylic acid, phosphoric acid, or the like) has an alkylene oxide. Compounds with added structures and mixtures thereof are mentioned. Preferred among these are polyhydric alcohols. Examples of the polyhydric alcohol include divalent to octavalent alcohols. As the dihydric alcohol, ethylene glycol,
Diethylene glycol, propylene glycol, 1,3
-Or 1,4-butanediol, 1,6-hexanediol, alkylene glycols such as neopentyl glycol, and cyclohexanediol, xylylene glycol and diols having a cyclic group described in JP-B-45-1474; Trihydric alcohols include glycerin, trimethylolpropane, trimethylolethane, hexanetriol, triethanolamine; tetrahydric alcohols include pentaerythritol, methylene glycoside, diglycerin; pentahydric or higher alcohols Are pentitols such as adonitol, arabitol and xylitol; hexitols such as sorbitol, mannitol, ibitol, talitol, dulcitol; sugars such as glucose, mannose, Monosaccharides such as ketose and sorbose; oligosaccharides such as sucrose, crehalose, lactose and raffinose; glycols such as ethylene glycol and propylene glycol; glycosides of glycerin, trimethylolpropane and hexanetriol; polyglycerins such as triglycerin and tetraglycerin Polypentaerythritol such as dipentaerythritol and tripentaerythritol; and tetrakis (hydroxymethyl) cyclohexanol.

Examples of polyhydric phenols include monocyclic polyhydric phenols such as pyrogallol, hydroquinone and phloroglucin; bisphenols such as bisphenol A and bisphenolsulfone; condensates of phenol and formaldehyde (novolak), for example, described in US Pat. No. 3,265,641. And the like. Amines include ammonia, aliphatic amines, alicyclic amines, heterocyclic amines and aromatic amines.
Aliphatic amines include alkanolamines such as mono-, di- and tri-ethanolamine, isopropanolamine and amine ethylethanolamine;
C20 alkylamines; C2-C6 alkylenediamines such as ethylenediamine, propylenediamine, hexamethylenediamine; and polyalkyleneamines such as diethylenetriamine and triethylenetetramine. Examples of the alicyclic amine include isophoronediamine, cyclohexylenediamine, dicyclohexylmethanediamine, and the like. Heterocyclic amines include aminoethylpiperazine and other specialty
No. 5,210,44. Examples of the aromatic amine include aniline, phenylenediamine, diaminotoluene, xylylenediamine, methylenedianiline, and diphenyletherdiamine.

The alkylene oxide (hereinafter abbreviated as AO) to be added to the active hydrogen atom-containing compound includes ethylene oxide and propylene oxide (hereinafter abbreviated as EO and PO), 1, 2-, 1, 3-, 1, and 1, respectively. 4-
Or 2,3-butylene oxide, styrene oxide, and the like, and combinations thereof. Preferred are propylene oxide and combinations of ethylene oxide and propylene oxide. The form of addition of the alkylene oxide is not particularly limited, and examples thereof include block addition and random addition, and the following addition modes. PO-AO added in order (tip) PO-AO-PO-AO added (balanced) AO-PO-AO added PO-AO-PO added Block adducts such as those (active secondary) Random adducts in which PO and AO are mixed and added In the order described in JP-A-57-209920, added in the order described in JP-A-53-13700 Random-block adducts such as those

[0012] Ether compounds (eg, methyl ether, isopropyl ether, phenyl ether, etc.) and ester compounds (eg, acetic acid ester and benzoic acid ester) in which hydroxyl groups of the polyoxyalkylene polyol are further partially blocked with an alcohol or carboxylic acid are exemplified. Can be Examples of the polyester polyol include a condensation polyester polyol, a lactone polyester polyol (polymerization type), and a polycarbonate diol.

As the condensation-based polyester polyol,
Those obtained by a dehydration condensation reaction between a dibasic acid, a glycol and a triol may be mentioned. For example, ethylene adipate, diethylene adipate, butylene adipate, trimethylolpropane adipate and the like can be mentioned. Examples of the lactone-based polyester polyol include compounds obtained by ring-opening condensation of ε-caprolactam. Examples of the polycarbonate diol include compounds obtained by phosgenation of polyol, transesterification with diphenyl carbonate, and the like. Examples of the polyol having a main chain formed of a carbon-carbon bond include acrylic polyol, polybutadiene polyol, and polyvinyl alcohol. In the present invention, a combination of a polyether polyol, a polyester polyol, a polyol having a main chain composed of a carbon-carbon bond, and a low-molecular polyol (for example, the above-mentioned polyhydric alcohol, preferably a liquid at room temperature) may be used. .

Examples of the phenolic hydroxyl group-containing compound include monocyclic polyhydric phenols such as pyrogallol, hydroquinone and phloroglucin; bisphenols such as bisphenol A and bisphenolsulfone; condensates of phenol and formaldehyde (novolak);
And polyphenols described in Japanese Patent No. 265641. Examples of the carboxyl group-containing compound include aliphatic polycarboxylic acids such as adipic acid, succinic acid, sebacic acid, azelaic acid, fumaric acid, maleic acid and dimerized linoleic acid; aromatic polycarboxylic acids such as phthalic acid;
Isophthalic acid and terephthalic acid.

Examples of the thiol group-containing compound include monothiols such as dodecyl mercaptan and mercaptopropionic acid, dithiols such as hexanedithiol, dimercapto-1,8-dioxa-3,6-octane, and polyglycidyl compounds and hydrogen sulfide. Reaction products, and polythiols such as esterified products of mercaptopropionic acid or mercaptoglycolic acid and a polyhydric alcohol are exemplified.

Examples of the amino group-containing compound include aliphatic amines, alicyclic amines, heterocyclic amines and aromatic amines. Aliphatic amines include alkanolamines such as mono-, di- and tri-ethanolamine, isopropanolamine, aminoethylethanolamine; C1-C20 alkylamines;
6, alkylenediamines such as ethylenediamine, propylenediamine, and hexamethylenediamine; and polyalkyleneamines such as diethylenetriamine and triethylenetetramine. As the alicyclic amine, isophorone diamine, cyclohexylene diamine,
And dicyclohexylmethanediamine. Examples of the heterocyclic amine include aminoethylpiperazine and others described in JP-B-55-21044. Examples of the aromatic amine include aniline, phenylenediamine, diaminotoluene, xylylenediamine, methylenedianiline, and diphenyletherdiamine.

The molecular weight of (A) is usually from 100 to 10,000.
0, preferably 500 to 50,000, more preferably 1,000 to 20,000. When a polyoxyalkylene polyol is selected as (A), those having a hydroxyl value of usually 5 to 280, preferably 10 to 200, more preferably 20 to 150 can be used.

In the present invention, the water-soluble monomer includes a vinyl monomer having a carboxyl group, a vinyl monomer having a sulfonic acid group, a vinyl monomer having a phosphoric acid group, and salts and hydroxyl groups thereof. And a vinyl monomer having an ether group and a vinyl monomer having an ammonium group.

Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, crotonic acid, sorbic acid,
Maleic acid, itaconic acid, cinnamic acid and their acid anhydrides are included.

Examples of the vinyl monomer having a sulfonic acid group include aliphatic or aromatic vinyl sulfonic acids [vinyl sulfonic acid, allyl sulfonic acid, vinyl toluene sulfonic acid, styrene sulfonic acid, etc.]; (meth) acryl sulfonic acid [ (Meth) sulfoethyl acrylate, sulfopropyl (meth) acrylate and the like]; (meth) acrylamidosulfonic acid [2-acrylamido-2-methylpropanesulfonic acid and the like].

As the vinyl monomer having a phosphate group,
2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate and the like can be mentioned.

These vinyl monomers may be used as salts of the carboxylic acids, sulfonic acids and phosphoric acids. These salts include alkali metal salts (salts such as sodium, potassium and lithium), alkaline earth metal salts (salts such as calcium and magnesium), ammonium salts and amine salts (salts of alkylamine such as methylamine and trimethylamine). Alkanolamine salts such as triethanolamine and diethanolamine). Of these, alkali metal salts are preferred, and sodium salts and potassium salts are particularly preferred.

Examples of the vinyl monomer having a hydroxyl group include:
Examples thereof include hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate. Examples of the vinyl monomer having an ether group include ethylene glycol (meth) acrylate monomethyl ether and trioxyethylene glycol (meth) acrylate.
Examples of the vinyl monomer having an ammonium group include N, N,
N-trimethyl-N- (meth) acryloyloxyethylammonium chloride; N, N, N-triethyl-N- (meth) acryloyloxyethylammonium chloride;

The precursor of the water-soluble monomer is one that becomes water-soluble by hydrolysis, such as methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and acetic acid. Vinyl and (meth) acrylonitrile. These water-soluble monomers or precursors thereof may be used alone or in combination of two or more. Preferred are vinyl monomers having a carboxyl group.

Of these water-soluble monomers, a vinyl monomer having a carboxyl group, a vinyl monomer having a sulfonic acid group, and salts thereof are preferred.

In the present invention, other vinyl monomers can be used if necessary. Other vinyl monomers include aromatic vinyl monomers such as styrene, α-methylstyrene, hydroxystyrene, and chlorostyrene; unsaturated nitriles such as (meth) acrylonitrile; and alkyl groups having 1 to 30 carbon atoms. (Meth) acrylates such as alkyl (meth) acrylate and hydroxypolyoxyalkylene ether mono (meth) acrylate; olefins such as ethylene and propylene; perfluorooctylethyl methacrylate and perfluorooctylethyl acrylate Fluorine-containing vinyl monomers; vinyl monomers containing amino groups such as diaminoethyl methacrylate and morpholinoethyl methacrylate; and vinyl-modified silicon at both ends. Of these, aromatic vinyl monomers, unsaturated nitriles and (meth) acrylates are preferred from the viewpoint of copolymerizability and dispersion stability.

In the present invention, the crosslinking agent includes a copolymerizable crosslinking agent and other crosslinking agents. As the copolymerizable crosslinking agent, a compound having two polymerizable double bonds; and at least one functional group having at least one polymerizable double bond and being reactive with the water-soluble monomer. And compounds having the same.

The compounds having two polymerizable double bonds include the following. Bis (meth) acrylamide; N, N-alkylene (c1-c6) bis (meth) acrylamide (for example, N, N-methylenebisacrylamide). Polyesters of polyols or polyepoxides with unsaturated mono- or polycarboxylic acids, such as those derived from ethylene glycol, trimethylolpropane, glycerin, polyoxyethylene glycol, polyoxypropylene glycol or cyclohexene diepoxide and (meth) acrylic acid or maleic acid Ruji
Or tri- (meth) acrylate and di- or trimaleate. Carbamyl ester: polyisocyanate [tolylene diisocyanate, hexamethylene diisocyanate,
4,4'-diphenylmethane diisocyanate and N
A carbamyl ester obtained by reacting a CO group-containing prepolymer (obtained by reacting the above polyisocyanate with an active hydrogen atom-containing compound) and hydroxyethyl (meth) acrylate. Polyvinyl compounds: divinylbenzene, divinyltoluene, divinylxylene, divinylether, divinylketone, trivinylbenzene and the like. Di- or poly- (meth) allyl ether of polyol: poly (meth) allyl ether of polyols [alkylene glycol, glycerin, polyalkylene glycol, polyalkylene polyol, carbohydrate, etc.] (for example, polyethylene glycol diallyl ether,
Allylated starch and allylated cellulose). Polyallyl esters of polycarboxylic acids: diallyl phthalate, diallyl adipate and the like. Esters of unsaturated mono- or polycarboxylic acids with mono (meth) allyl etherified polyols: (meth) acrylates of polyethylene glycol monoallyl ether. Polyallyloxyalkanes: tetraallyloxyethane and the like.

Having at least one polymerizable double bond,
And at least one functional group reactive with the water-soluble monomer.
In the compound having two or more carboxyl groups, sulfonic acid groups, phosphoric acid groups, hydroxyl groups or hydroxyl groups in the water-soluble monomer, a hydroxyl group,
Epoxy groups and tertiary amine groups are exemplified. Examples of the compound include a hydroxyl group-containing ethylenically unsaturated compound [eg, N-methylol (meth) acrylamide and the like];
Epoxy group-containing ethylenically unsaturated compound [eg glycidyl (meth) acrylate etc.]; tertiary amino group-containing ethylenically unsaturated compound [eg dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate] And the like. Other crosslinking agents include polyvalent metal salts such as calcium oxide and zinc diacetate. Among these crosslinking agents, copolymerizable crosslinking agents are preferred, and N, N-methylenebisacrylamide, ethylene glycol diacrylate, trimethylolpropane triacrylate and tetraallyloxyethane are particularly preferred.

In the present invention, the polysaccharide is starch,
Cellulose and the like can be mentioned. Examples of starch include raw starch such as sweet potato starch, potato starch, wheat starch, corn starch, rice starch; oxidized starch, dialdehyde starch, alkyl etherified starch, aryl etherified starch, oxyalkylated starch, aminoethyl ether Modified starch such as modified starch. Examples of cellulose include cellulose obtained from wood, leaves, stems, ginseng, seed hair, and the like; and processed celluloses such as alkyl etherified cellulose, organic acid esterified cellulose, oxidized cellulose, and hydroxyalkyl etherified cellulose.

In the present invention, the dispersion can be obtained by the following method. Note that the water-soluble monomer or its precursor is abbreviated as (1), the other vinyl monomer is as (1 ′), and the crosslinking agent and / or polysaccharide is as (2). A liquid obtained by mixing (A) and, if necessary, an emulsifier is added dropwise to the aqueous solution or aqueous dispersion of (1), (2) and, if necessary, (1 ′), and if necessary, heated using a radical polymerization catalyst or irradiated Irradiation with an electron beam, ultraviolet rays, or the like. The aqueous solution or aqueous dispersion of (1), (2) and, if necessary, (1 ′) is added dropwise to (A), and the same operation is carried out using a radical polymerization catalyst and an emulsifier as necessary. The aqueous solution or aqueous dispersion of (1), (2) and, if necessary, (1 ′) is added dropwise to a mixture of (A) and water, and the same operation is carried out using a radical polymerization catalyst and an emulsifier as necessary. (A) A radical polymerization catalyst is optionally present in a dispersion comprising an emulsifier and water, and (1), (2) and (1 ′) are added dropwise as necessary, and the operation is carried out in the same manner as thereafter.

(1), (2) and if necessary (1 ′)
Is usually 2-120% based on the weight of (A),
Preferably 10 to 100%, more preferably 30 to 9
0%.

The amount of (1) used is usually at least 50%, preferably 60 to 99.9%, particularly preferably 75%, based on the total weight of (1), (2) and if necessary (1 ′).
~ 95%.

The amount of (2) used is usually 0.00 based on the total weight of (1), (2) and if necessary (1 ′).
It is from 1% to 20%, preferably from 0.01 to 10%, particularly preferably from 0.1 to 5%. The amount of (2) used is 0.0
If it is less than 01% or more than 20%, the water absorbing ability becomes insufficient.

The amount of other vinyl monomer (1 ') used is
It is usually 0 to 20%, preferably 0 to 10%, more preferably 0 to 5%, based on the total weight of (1), (2) and if necessary (1 ').

The amount of water used is 5 based on the weight of the dispersion.
５０50%, preferably 5-45%
%, More preferably 10 to 30%. If the amount of water used exceeds 50% or is less than 5%, it is difficult to produce a dispersion.

Examples of the radical polymerization catalyst include azo compounds [azobisisobutyronitrile, azobiscyanovaleric acid, 2,2'-azobis (2-aminodipropane) dihydrochloride, etc.], inorganic peroxides [hydrogen peroxide] ,
Ammonium persulfate, potassium persulfate, sodium persulfate, etc.], organic peroxides [benzoyl peroxide, di-t-
Butyl peroxide, cumene peroxide,
Redox catalysts [reducing agents such as alkali metal sulfites or bisulfites, ammonium sulfite, ammonium bisulfite, ascorbic acid, and alkali metal persulfate]; succinic peroxide, di (2-ethoxyethyl) peroxydicarbonate, etc. Consisting of a combination of an oxidizing agent such as a salt, ammonium persulfate, and peroxide]; and a combination of two or more of these. The amount of the catalyst used is usually 0.0005 to 5%, preferably 0.001 to 2%, based on the total weight of (1), (2) and if necessary (1 ′).

Examples of the emulsifier include nonionic surfactants such as lauryl alcohol ethylene oxide adduct, lauric acid ethylene oxide adduct, sorbitan lauric acid monoester, stearylamine ethylene oxide adduct, and nonylphenol ethylene oxide adduct. Cationic surfactants [lauryl alcohol sulfate, sodium alkylbenzene sulfonate, aerosol OT, dithiophosphate ester salts, etc.]; cationic surfactants [laurylamine acetate, triethanolamine monostearate formate, etc.]; Two or more of them may be used in combination. Preferred are nonionic surfactants. The amount of the emulsifier to be used is generally 0 to 20% by weight, preferably 0.1 to 10% by weight, based on the dispersion.

In the present invention, the ratio of (B) to the total weight of (A) and (B) is usually 1 to 70%, preferably 5 to 65%, particularly preferably 20 to 60%. When the content of the vinyl polymer chain exceeds 70%, the particles are easily aggregated and the dispersibility becomes unstable. The content of (A) is usually 30 to 99%, preferably 35 to 95%, based on the weight of the dispersion,
Particularly preferably, it is 40 to 80%. (A) content of 3
If it is less than 0, the particles aggregate and the dispersibility becomes unstable.

In the present invention, the urethane resin (U) is obtained by removing the dispersion (D) from water if necessary, and adding an organic polyisocyanate (P) and, if necessary, a catalyst for accelerating urethane formation,
It is obtained by reacting in the presence of a crosslinking agent, a foaming agent and a foam stabilizer. This production can be performed by a known method such as a one-shot method, a semi-prepolymer method, or a prepolymer method. In addition, a foamed or non-foamed water-absorbent polyurethane molded product can be produced by reacting in a closed mold or an open mold using a low-pressure or high-pressure molding device.

As the organic polyisocyanate, those conventionally used for producing polyurethane can be used. Such polyisocyanates include aromatic polyisocyanates having 6 to 20 carbon atoms (excluding carbon in the NCO group) (for example, 2,4- and / or 2,6-
Tolylene diisocyanate (TDI), crude TDI,
2,4′- and / or 4,4′-diphenylmethane diisocyanate (MDI), crude MDI [condensation product of crude diaminophenylmethane} formaldehyde and aromatic amine (aniline) or a mixture thereof: diaminodiphenylmethane and a small amount ( A phosgenated product of a mixture with a trifunctional or higher polyamine (for example, 5 to 20% by weight): polyallyl polyisocyanate (PAPI), etc.]; Alicyclic polyisocyanate having 4 to 15 carbon atoms (eg, isophorone diisocyanate, dicyclohexylmethane diisocyanate);
5 aromatic aliphatic polyisocyanates (eg, xylylene diisocyanate); and modified products of these polyisocyanates (urethane group, carbodiimide group, allophanate group, urea group, buret group, uretdione group, uretonimine group, isocyanurate group, Oxazolidone group-containing modified products); and JP-A-61-7
No. 6517, other polyisocyanates described above;
And mixtures of two or more of these. Preferred among these are the commercially available polyisocyanates such as 2,4- and 2,6-T
DI, and mixtures of these isomers, crude TDI,
4,4′- and 2,4′-MDI, and mixtures of isomers thereof, PAPI also referred to as crude MDI, and urethane groups, carbodiimide groups, allophanate groups, urea groups, and urea groups derived from these polyisocyanates. Modified polyisocyanates containing a let group and an isocyanurate group. In the present invention, the isocyanate index [NCO /
The equivalent ratio of active hydrogen atom-containing groups x 100] is usually 80 to
140, preferably 85 to 120, particularly preferably 9
5 to 115. The polyisocyanurate can also be introduced into the polyurethane with an isocyanate index significantly higher than the above range (e.g. 300 to 1000 or more).

Examples of the urethane-promoting catalyst include catalysts usually used in polyurethane reactions [for example, amine catalysts (eg, triethyleneamine, N-ethylmorpholine, etc.).
Secondary amines), tin-based catalysts (such as stannous octylate, dibutyltin dilaurate), and other metal catalysts (such as lead octylate). The amount of the catalyst used is about 0.001 to about 5% based on the total weight of the dispersion of the present invention and the organic polyisocyanate.

As a foaming agent, methylene chloride, monofluorotrichloromethane, water and the like can be used. Examples of the foam stabilizer include a silicone surfactant (polysiloxane-polyoxyalkylene copolymer). Other additives that can be used in the present invention include:
Known additives such as a flame retardant, a reaction retarder, a colorant, an internal mold release agent, an antioxidant, an antioxidant, a plasticizer, a bactericide, carbon black, and other fillers are exemplified.

In the present invention, the form of the urethane resin (U) is not particularly limited, and examples thereof include a plate shape, a needle shape, a fiber shape, and a chip shape. Moreover, the humidity control material for tatami of the present invention may be a material obtained by impregnating or coating the urethane resin of the present invention on another substrate (for example, synthetic and / or natural fiber, nonwoven fabric, paper, synthetic resin, etc.).

In the present invention, the content of the water-absorbing resin (B) in the urethane resin (U) is not particularly limited, and the content of the (B) is adjusted according to the purpose of use as the humidity-controlling tatami.
As a method of adjusting the content of (B), a method of adjusting the content to a target content when synthesizing a dispersion, adjusting the content when forming a urethane resin, for example, controlling the expansion ratio, etc. Is mentioned.

In the present invention, the average particle size of the water-absorbent resin (B) dispersed in the urethane resin (U) is usually 0.1.
It is from 0.01 to 100 μm, preferably from 0.05 to 10 μm, particularly preferably from 0.1 to 5 μm. If the dispersion average particle size exceeds 100 μm, the water absorption rate becomes low,
If it is less than 01 μm, problems such as aggregation of particles in the dispersion (D) occur.

The tatami-conditioning material manufactured as described above is, for example, a single layer or a plurality of layers if it is in the form of a plate.
If necessary, the tatami mat is installed on the back surface of the tatami mat by means of bonding or the like, or installed on at least one surface of the tatami mat floor, thereby completing the tatami mat. The material and type of the tatami mat, the tatami floor, the cushioning material and the like, and the method of manufacturing the tatami are not particularly limited, and known tatami mats can be used.

[0048]

The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. Hereinafter, unless otherwise specified, parts in Examples are parts by weight. The compositions of the raw materials used in Synthesis Examples 1 to 3, Examples 1 to 3, and Comparative Examples 1 to 3 are as follows. Amine catalyst: Triethylenediamine Tin catalyst: Stanas octoate Isocyanate: Tolylene diisocyanate (TDI-
80) Foam stabilizer: Silicone foam stabilizer (“X-20-1353” manufactured by Shin-Etsu Chemical Co., Ltd.) Water-absorbing resin: Crosslinked sodium polyacrylate-based water-absorbing resin (manufactured by Sanyo Chemical Industries, Ltd. Wet PA-20
0 ")

[Volume-Based Particle Diameter Measurement Method] The water-absorbent resin dispersion was diluted with the polyoxyalkylene compound used in the water-absorbent resin dispersion so that the transmittance of the laser beam became 70 to 90%. The particle diameter was measured by a distribution measuring device (laser diffraction / scattering type particle size distribution measuring device LA-700; manufactured by Horiba, Ltd.).

[Moisture Absorption and Release Test] The obtained tatami mat and the comparative tatami mat were allowed to stand in a thermostat at a humidity of 90% (25 ° C.) to change the amount of absorbed moisture with time. Was measured. Thereafter, the sample was allowed to stand still in a constant temperature / humidity chamber at a humidity of 40% (25 ° C.), and the amount of released moisture was measured. The amount of moisture absorption and release is based on the tatami conditioner 100
The amount of water absorbed and released per gram (g) is shown.

[Humidity Control Test-1] The obtained tatami mat and the comparative tatami mat were used in a sealed container (volume: 18 L) having a humidity of 90% (25 ° C.) and a humidity of 40% (25 ° C.). One for each
The amount of humidity in the container was measured one hour after the addition of 100 g.

[Humidity Control Test-2] The tatami mats obtained in the below-described use examples and comparative use examples were set in a tatami evaluation room having excellent airtightness, and the inside of the room was adjusted to a humidity of 60% (25 ° C.). After the adjustment, a container in which absorbent cotton sufficiently filled with water was placed (open at the top) was set in the center of the room, the room was sealed, and the room was left for 6 hours, and the humidity of the room was measured.

Synthesis Example 1 In a 2 l four-necked flask equipped with a temperature controller, a vacuum stirring blade, a nitrogen inlet and an outlet, at 25 ° C. or lower at 40 ° C. or lower.
After stirring and mixing 350 parts of an aqueous sodium hydroxide solution and 200 parts of a vinyl monomer ("acrylic acid" manufactured by Nippon Shokubai Kagaku),
0.02 parts of a copolymerizable crosslinking agent (“Methylevisacrylamide” manufactured by Nitto Chemical Industry Co., Ltd.) was further added and mixed with stirring to obtain a uniform solution (). In a 500 ml Erlenmeyer flask, a polyol (A): a polyether polyol having a hydroxyl value of 34, which is obtained by adding propylene oxide (PO) to glycerin and then adding ethylene oxide (EO) (EO content: 20%) (Sanyo Chemical Industries, Ltd.) 400 parts of “Sunnics KC-209” manufactured by K.K. and 4 parts of an emulsifier (“Emulmin 140” manufactured by Sanyo Chemical Industries, Ltd.) were mixed and stirred to form a uniform solution (). Then the solution ()
While stirring at 40 ° C. or lower while blowing in a nitrogen solution, the solution () was continuously charged over 1 hour to prepare a W / O emulsion. Furthermore, a radical polymerization catalyst (“ADVN” manufactured by Otsuka Chemical Co., Ltd.) was previously added to 0.1 part of toluene.
A solution in which 0.02 part was dissolved was added, and the mixture was heated to 50 ° C. with stirring to synthesize a water-absorbent resin dispersion (D1).

Synthesis Example 2 A water-absorbent resin dispersion (D2) was synthesized in the same manner as in Synthesis Example 1 except that the following compounds were used in place of the polyol (A) and the amounts were changed as follows. Polyol (B): a polyether polyol having a hydroxyl value of 50 (EO content: 70%) obtained by adding PO to glycerin and then adding EO (“SANNIX F” manufactured by Sanyo Chemical Industries, Ltd.)
A-103 ") = 600 parts

Synthesis Example 3 In Example 1, the vinyl monomer was replaced with 2-acrylamide-
A water-absorbing dispersion (D3) was synthesized in the same manner as in Example 1 except that 2-methylpropanesulfonic acid was used. Synthesis Example 1
Table 1 shows the particle diameters and viscosities of the dispersions (D1) to (D3) obtained in Nos. 1 to 3. The value of the particle size in Table 1 indicates a particle size corresponding to 50% of the cumulative distribution of the volume-based particle size distribution.

[0056]

[Table 1]

Example 1 100 parts of the dispersion (D1) obtained in Synthesis Example 1, 1 part of water,
0.3 part of the amine catalyst and 1 part of the foam stabilizer were mixed, and then adjusted to about 25 ° C. Then, 0.1 part of a tin catalyst was added, and 1
Mix for 0 seconds. To the obtained mixture, 6 parts of isocyanate at 25 ° C. was added and mixed for 7 seconds to prepare a tatami humidity control material T1. Tables 2 and 3 show the results of the moisture absorption / desorption evaluation and the humidity control test-1 of the obtained tatami conditioner T1.

Example 2 100 parts of the dispersion (D2) obtained in Synthesis Example 2, 0.1 part of a tin catalyst, 3.6 parts of isocyanate and 60 parts of toluene
The resulting mixture was impregnated with a polyester nonwoven fabric (AK-65 manufactured by Asahi Kasei Kogyo Co., Ltd.) so that the resin weight after drying was 200 g / m ^2, and then cured and dried at 110 ° C. for 15 minutes. To prepare a tatami humidity control material T2. Evaluation of moisture absorption / release properties and humidity control test of the obtained humidifier T2 for tatami-
The results of No. 1 are shown in Tables 2 and 3.

Example 3 100 parts of the dispersion (D3) obtained in Synthesis Example 3, 0.1 part of a tin catalyst, 3.8 parts of isocyanate and 10 parts of toluene
0 parts were mixed, and the resulting mixture was impregnated into a polyurethane foam (SH-10-2 manufactured by Shinden Co., Ltd.) so that the resin weight after drying was 200 g / m ^2.
And dried for 15 minutes to prepare a tatami humidity control material T3.
Tables 2 and 3 show the results of the evaluation of the moisture absorption / release properties and the humidity control test-1 of the obtained humidifier T3 for tatami.

Comparative Example 1 To 60 parts of the polyol (A) used in Synthesis Example 1, 40 parts of a water absorbent resin, 1 part of water, 0.3 part of an amine catalyst and 1 part of a foam stabilizer 1
The parts were mixed and then the resulting mixture was adjusted to 25 ° C. Next, 0.1 part of a tin catalyst was added and mixed for 10 seconds.
To the obtained mixture, 6 parts of isocyanate at 25 ° C. was added and mixed for 7 seconds to prepare a comparative tatami-conditioning material T4.
Tables 2 and 3 show the results of the moisture absorption / release properties evaluation and humidity control test-1 of the obtained comparative tatami-conditioning material T4.

Comparative Example 2 60 parts of the polyol (B) used in Synthesis Example 2, 40 parts of B-type silica gel, 0.1 part of tin catalyst, 3.6 parts of isocyanate and 60 parts of toluene were mixed, and the resulting mixture was mixed. Polyester nonwoven fabric (AK-6 manufactured by Asahi Kasei Corporation)
5) After impregnation so that the resin weight after drying was 200 g / m ² , it was cured and dried at 110 ° C. for 15 minutes to prepare a comparative humidity control material T5 for tatami mat. The obtained comparative humidity control material for tatami mat T5
Are shown in Tables 2 and 3.

Comparative Example 3 60 parts of the polyol (B) used in Synthesis Example 2, 40 parts of zeolite, 0.1 part of a tin catalyst, 3.8 parts of isocyanate and 100 parts of toluene were mixed, and the resulting mixture was mixed with polyurethane foam. (SH-10 manufactured by Shinden Co., Ltd.
In 2), after impregnating the resin weight after drying to 200 g / m ² , it was cured and dried at 110 ° C. for 15 minutes to prepare a comparative humidity control material T6 for tatami mat. The obtained comparative humidity control material for tatami mat T6
Are shown in Tables 2 and 3.

[0063]

[Table 2]

[0064]

[Table 3]

Use Examples 1 to 3 The tatami conditioners T1 to T3 of Examples 1 to 3 of the present invention were replaced by 184.
The sheet was cut into a size of cm × 92 cm and attached to the upper surface of a tatami floor where an insulation board was attached on expanded polystyrene. In addition, model tatami mats were created with many tatami floors.
Table 4 shows the results of evaluating the humidity control test-2 of these model tatami mats.
Shown in

Comparative Examples 1 to 3 T4 to T6 of Comparative Examples 1 to 3 were prepared in the same manner as in Examples 1 to 3.
Was used to create a model tatami mat. Table 4 shows the results of evaluating the humidity control test-2 of these comparative model tatami mats.

Comparative Use Example 4 As Comparative Use Example 4, the results of evaluating the humidity control test-2 using a normal insulation board tatami are shown in Table 4.

[0068]

[Table 4]

[0069]

According to the humidity control material for tatami of the present invention, the water absorbent resin is one.
It is uniformly dispersed as fine particles having a size of 00 μm or less, and has excellent moisture absorption / desorption speed and humidity control properties. Because of the above-described effects, the humidity control material for tatami obtained by the present invention is:
The tatami mat can be easily imparted with humidity control, and as a result, various materials, health, or hygiene caused by a humid environment can be prevented from being adversely affected.

Claims (10)

[Claims] 1. A urethane resin (U) obtained by reacting the following water-absorbent resin dispersion (D) with a polyisocyanate compound (P), wherein a water-absorbent resin (B) or a hydrogel thereof is contained in (U). Is a humidity control material for tatami made of a urethane resin composition in which is dispersed. Water-absorbent resin dispersion (D): In liquid or hot-melt active hydrogen-containing organic compound (A), (A)
A water-absorbent resin dispersion obtained by dispersing the water-absorbent resin (B) polymerized in water or its water-absorbing gel. 2. A water-absorbent resin wherein the water-absorbent resin (B) is formed by polymerizing a water-soluble monomer or a precursor thereof and a crosslinking agent and / or a polysaccharide in (A). The humidity control material for tatami according to claim 1, which is: 3. The tatami-conditioning material according to claim 1, wherein (A) in (D) is a polyol. 4. The polyol is a polyether polyol,
Polyester polyol, polybutadiene polyol,
The humidity control material for tatami according to claim 3, which is at least one member selected from the group consisting of polyvinyl alcohol and acrylic polyol. 5. The humidity control material for tatami according to claim 1, wherein the proportion of (B) to the total weight of (A) and (B) in (U) is 1 to 70%. 6. The humidifying material for tatami according to claim 1, wherein (B) dispersed in (U) or the water-absorbing gel thereof has an average particle size of 0.01 to 100 μm. 7. A method according to claim 1, wherein (D) is (A) in the presence of water, in the presence of water, at least one vinyl monomer having a carboxyl group or a sulfonic acid group, a copolymerizable crosslinking agent and, if necessary, another vinyl monomer. Is formed by polymerization of (B) or the water-absorbing gel thereof,
The humidity control material for tatami according to any one of claims 1 to 6, which is an absorbent resin dispersion (D) dispersed in (A). 8. (U) reacting the water absorbent resin dispersion (D) with an organic polyisocyanate compound in the presence of a foaming agent and, if necessary, a catalyst, a foam stabilizer and other additives. The humidity control material for tatami according to any one of claims 1 to 7, which is a polyurethane foam. 9. A tatami mat using the humidifying material for tatami according to any one of claims 1 to 8. 10. A tatami mat, wherein the tatami mat according to any one of claims 1 to 8 is used between a tatami mat surface and a tatami mat floor.