JP3071680B2 - Water absorbent resin dispersion - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-absorbent resin dispersion and a method for producing a polyurethane resin, and more particularly, to a water-absorbent resin dispersion having a fine dispersion particle size and good dispersion stability, and a method for using the same. And a method for producing a polyurethane resin.

[0002]

2. Description of the Prior Art It is known to use polymer polyols as part of the polyol component for producing polyurethane resins. For example, JP-A-54-13359
No. 9 discloses the use of a hydrophilic vinyl monomer for producing such a polymer polyol. However, although a polymer polyol using a non-hydrophilic vinyl monomer such as styrene or acrylonitrile has been demonstrated to be a stable dispersion, it is unknown when a hydrophilic vinyl monomer is used. It is. On the other hand, a dispersion obtained by mixing a high molecular weight polyol and a water absorbent resin is also known.

[0003]

However, Japanese Patent Application Laid-Open No.
In the production method described in 133335, when a hydrophilic vinyl monomer is used, a stable dispersion cannot be obtained. Further, a mere mixture of a high-molecular-weight polyol and a water-absorbent resin has a disadvantage that the water-absorbent resin easily aggregates and precipitates.

[0004]

Means for Solving the Problems The present inventors have repeatedly studied the production of a water-absorbent resin dispersion which is easy to produce, has a fine particle diameter and good dispersion stability, and has reached the present invention. . That is, the present invention relates to a liquid or heat-meltable active hydrogen-containing organic compound (A) selected from the group consisting of alcoholic hydroxyl group-containing compounds, phenolic hydroxyl group-containing compounds, carboxyl group-containing compounds, thiol group-containing compounds and amino group-containing compounds. )), A water-absorbent resin (B) or a water-absorbent gel thereof is dispersed therein, and (B) in (A) in the presence of water, a water-soluble monomer or a precursor thereof and a crosslinking agent and / or
Or an active hydrogen-containing component for producing a polyurethane resin comprising a water-absorbent resin dispersion, which is formed by polymerizing a polysaccharide; and reacting the active hydrogen-containing component with an organic polyisocyanate compound. A polyurethane resin, comprising reacting the active hydrogen-containing component with an organic polyisocyanate compound in the presence of a foaming agent and, if necessary, a catalyst, a foam stabilizer and other auxiliaries. This is a method for producing a foam.

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, carboxyl group-containing compounds, thiol group-containing compounds and amino group-containing compounds. No.

[0006] Examples of the alcoholic hydroxyl group-containing compound include polyether monol and polyol, and among these, polyol is preferable. 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.

[0007] 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.

[0008] 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 cactose 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 the polyhydric phenol include monocyclic polyhydric phenols such as pyrogallol, hydroquinone, and phloroglucin; bisphenols such as bisphenol A and bisphenol sulfone; condensates of phenol and formaldehyde (novolak), for example, described in US Pat. 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

[0011] Ether compounds (eg, methyl ether, isopropyl ether, phenyl ether, etc.) and esterified compounds (eg, acetic acid ester and benzoic acid ester) in which hydroxyl groups of polyoxyalkylene polyol are further partially blocked with alcohol or carboxylic acid are mentioned. 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 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 and 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].

The vinyl monomers having a phosphate group include:
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 which 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, preferred are vinyl monomers having a carboxyl group, vinyl monomers having a sulfonic acid group, and salts thereof.

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.

The crosslinking agent of the present invention 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.

The polysaccharide of the present invention includes starch, cellulose and the like. Examples of starch include raw starch such as sweet potato starch, potato starch, wheat starch, corn starch, rice starch, and the like;
Modified starches such as oxidized starch, dialdehyde starch, alkyl etherified starch, aryl etherified starch, oxyalkylated starch, aminoethyl etherified starch and the like. As cellulose,
For example, 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 are exemplified.

The dispersion of the present invention 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 the 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 [lauryl alcohol ethylene oxide adduct, lauric acid ethylene oxide adduct, sorbitan lauric acid monoester, stearylamine ethylene oxide adduct, nonylphenol ethylene oxide adduct, etc.]; 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 10% by weight, preferably 0.1 to 5% by weight, based on the dispersion.

The particle size of the particles in the dispersion of the present invention is as follows:
Usually 0.01 to 100 μm, preferably 0.05 to 10
μm, particularly preferably 0.1 to 5 μm. When the dispersed particle diameter exceeds 100 μm, the stability of the dispersion becomes poor, and when the dispersed particle diameter is less than 0.01 μm, problems such as aggregation of the particles occur.

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.

The dispersion of the present invention can be applied to the production of a water-absorbing polyurethane resin. The water-absorbent polyurethane resin is prepared by reacting the dispersion of the present invention with an organic polyisocyanate, if necessary, by removing water, and optionally, in the presence of a urethane-promoting catalyst, a crosslinking agent, a foaming agent and a foam stabilizer. Obtained by: For this production, one-shot method,
It can be performed by a known method such as 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.]; aliphatic polyisocyanate having 2 to 18 carbon atoms (for example, hexamethylene diisocyanate, lysine diisocyanate, 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.

[0044]

The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. Parts in the examples are parts by weight. The compositions of the raw materials used in Examples 1 to 5, Use Examples 1 to 4, and Comparative Use Examples 1 to 4 are as follows. Polyoxyalkylene compound (A): Polyol A1: PO is added to glycerin and then EO
A polyether polyol having a hydroxyl value of 33 (E
O content 13%). Polyol A2: a polyether polyol having a hydroxyl value of 33 obtained by adding PO to glycerin. Polyol A3: a polyether polyol having a hydroxyl value of 55 obtained by adding PO to glycerin. Vinyl monomer (1): acrylic acid (manufactured by Nippon Shokubai Kagaku) Copolymerizable crosslinking agent (2): methylenebisacrylamide (manufactured by Nitto Chemical Industry Co., Ltd.) Radical polymerization catalyst: 2,2′-azobis (2- Aminodipropane) dihydrochloride Emulsifier: Sorbitan lauric acid monoester Amine catalyst: Triethylenediamine (DABCO) Tin catalyst: Stanas octoate (T-9) Isocyanate: Tolylene diisocyanate (TDI-
80) Foam stabilizer: Silicone foam stabilizer ("L-5" manufactured by Nippon Unicar)
20 ") Water-absorbing resin: Sunfresh ST-500TM (manufactured by Sanyo Chemical Industries, Ltd., starch grafted with acrylic acid)

[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.). Table 2 shows the obtained particle sizes. The value of the particle size in Table 2 is the cumulative distribution 50 of the volume-based particle size distribution.
% Is shown.

[Method of Evaluating Moisture Absorption and Desorption] The polyurethane foam was allowed to stand in a thermo-hygrostat at a humidity of 80% (25 ° C.), and the time change of the water absorption was measured. Then, a humidity of 40% (25
C) in a thermo-hygrostat, and the amount of water discharged was measured. The amount of water absorption and the amount of water discharge are indicated by the amount (g) of water absorbed or discharged per 50,000 cubic centimeters of apparent volume of the polyurethane foam.

The absorption amount and absorption rate of ion-exchanged water were measured by the following methods. [Absorbing amount] 1 g of an absorbing member was placed in a 250-mesh nylon net tea bag, immersed in a large excess of 0.9% saline for 1 hour to absorb, and then pulled up.
Drain for a minute and measure the weight gain. This value was taken as the absorption amount. [Absorptive speed] 1 g of an absorbent member is placed in a 250 mesh nylon net tea bag, immersed in a large excess of physiological saline for 2 minutes, pulled up and drained for 15 minutes, and the increased weight is measured. This value was taken as the absorption rate.

Examples 1 to 5 In a 1 L four-necked flask equipped with a temperature controller, vacuum stirring blade, nitrogen inlet and outlet, at a temperature of 40 ° C. or lower,
Table 1 shows water, sodium hydroxide, vinyl monomer (1), copolymerizable crosslinking agent (2), radical polymerization catalyst and emulsifier.
Was used in the amount described in Table 1. Thereafter, the polyols A1 and A2 used in the amounts shown in Table 1 were gradually added under stirring, and W /
Make an O-type emulsion, then 50-80 ° C under stirring
Polymerizes the vinyl monomer (1) with water-absorbent resin dispersion (D
1 to D5) were synthesized.

Example 6 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.
350 parts of an aqueous sodium hydroxide solution and 200 parts of a vinyl monomer (1) ("Acrylic acid" manufactured by Nippon Shokubai Kagaku) are stirred and mixed, and then a copolymerizable crosslinking agent (2) (Nitto Chemical Co., Ltd.
(Methylenebisacrylamide) (0.02 parts) was further added and mixed with stirring to obtain a homogeneous solution (). Also 500ml
Polyoxyalkylene compound (A): glycerin and propylene oxide (P
O) and then ethylene oxide (EO), and a polyether polyol having a hydroxyl value of 34 (EO content: 20%) ("SANNIX KC" manufactured by Sanyo Chemical Industry Co., Ltd.).
-209 ") and 4 parts of an emulsifier (" Emulmin 140 "manufactured by Sanyo Chemical Industry Co., Ltd.) were mixed and stirred to form a uniform solution (). Next, the solution () was continuously charged over 1 hour while stirring the solution () at a temperature of 40 ° C. or lower while blowing into a nitrogen solution to prepare a W / O emulsion. Further, a solution prepared by dissolving 0.02 part of a radical polymerization catalyst (“ADVN” manufactured by Otsuka Chemical Co., Ltd.) in 0.1 part of toluene is added in advance, and the mixture is heated to 50 ° C. with stirring to form a water-absorbent resin dispersion (D6). Synthesized.

Example 7 A water-absorbent resin dispersion (D7) was synthesized in the same manner as in Synthesis Example 1 except that the polyoxyalkylene compound was changed to the following compound and the amount was changed as follows in Example 6. Oxyalkylene chain-containing compound: glycerin and PO
And then EO added to the polyether polyol having a hydroxyl value of 50 (EO content: 70%) (“SANIX FA-103” manufactured by Sanyo Chemical Industries, Ltd.) = 600 parts

Example 8 In Example 6, the vinyl monomer was changed to 2-acrylamide-
A water-absorbing dispersion (D8) was synthesized in the same manner as in Example 1 except that 2-methylpropanesulfonic acid was used. Example 6
Are shown in Table 2.

[0052]

[Table 1]

[0053]

[Table 2]

Use Example 1 Dispersion D1, Polyol A3, Water, DABCO and L
-520 was mixed in the amounts shown in Table 3 and then adjusted to about 25 ° C. Then, the amount of T-9 shown in Table 3 was added, and 10
Mix for seconds. To the resulting mixture was added TDI-80 at 25 ° C. in the amount shown in Table 3 and mixed for 7 seconds to form a polyurethane foam F1. Table 4 shows the foam characteristics (foam density, moisture absorption / desorption performance) of the obtained polyurethane foam.

Use Examples 2 to 4 The dispersions obtained in Examples 6 to 8, water, DABCO and L-520 were mixed in the amounts shown in Table 3 and then mixed at about 25 ° C.
Was adjusted. Then, the amount of T-9 shown in Table 3 was added, and 1
Mix for 0 seconds. To the resulting mixture was added TDI-80 at 25 ° C. in the amount shown in Table 3 and mixed for 7 seconds to form polyurethane foams F2 to F4. Foam properties (foam density, 0.9%
Table 5 shows the amount of physiological saline absorbed and the rate of absorption.

Comparative Use Examples 1 and 2 Using the components shown in Table 3, the same operations as in Use Example 1 were carried out to produce polyurethane foams F5 and F6 of Comparative Use Examples 1 and 2. Table 4 shows the foam characteristics (foam density, moisture absorption / desorption performance) of the obtained polyurethane foam.

Comparative Use Examples 3 and 4 Use of the polyoxyalkylene compound (polyol A4) used in Example 7 according to the amounts shown in Table 3
In the same manner as in the above, polyurethane foams F7 and F8 were prepared. Table 5 shows properties (foam density, 0.9% physiological saline absorption amount, absorption rate) of the obtained polyurethane foam.

[0058]

[Table 3]

[0059]

[Table 4]

[0060]

[Table 5]

As shown in Tables 4 and 5, the water absorption of the polyurethane foam was significantly improved by using the superabsorbent dispersion according to the present invention.

[0062]

The superabsorbent dispersion of the present invention has a water-absorbent resin uniformly dispersed as fine particles of 100 μm or less, and has excellent dispersion stability. Furthermore, when the dispersion of the present invention is applied to the production of a polyurethane resin, a highly water-absorbing urethane resin can be obtained, and the obtained polyurethane resin exhibits excellent absorption capacity (water absorption and absorption rate). Due to the above effects, the water-absorbing tree dispersion obtained by the present invention and the absorbent member using the same are useful for various sanitary materials and absorbent articles such as disposable diapers and sanitary articles. In addition, sealing materials, freshness preservation materials for fruits and vegetables,
It is extremely useful for applications such as drip absorbents, moisture or humidity control materials, seedling raising sheets for rice, concrete curing sheets, and water blocking materials for communication cables and optical fiber cables.

────────────────────────────────────────────────── ─── Continuing on the front page (51) Int.Cl. ⁷ Identification symbol FI (C08G 18/62 101: 00) (72) Inventor Takao Ando 11-11, Hitotsubashi Nohonmachi, Higashiyama-ku, Kyoto Sanyo Chemical Industry Co., Ltd. (72) Inventor: Toru Nakanishi, 1-11 Sanyo Kasei Kogyo Co., Ltd., Hitotsubashi Nohonmachi, Higashiyama-ku, Kyoto City (72) Inventor Isao Ishikawa, 1-11 Sanyo Kasei Kogyo Co., Ltd. 72) Inventor Takayuki Tsuji 1-1-1, Hitotsubashi-Honcho, Higashiyama-ku, Kyoto City Examiner at Sanyo Chemical Industry Co., Ltd.Hiroki Amano (56) References JP-A-53-138500 (JP, A) JP-A-3-203921 ( JP, A) JP-A-6-206966 (JP, A) JP-A-59-117519 (JP, A) JP-A-2-86651 (JP, A) JP-A-55-38863 (JP, A) Hei 7-228616 (JP, A) Open flat 8-120009 (JP, A) (58 ) investigated the field (Int.Cl. ^7, DB name) C08G 18/00 - 18/87 C08F 2/00 - 2/60 C08L 101/14 CA (STN) REGISTRY (STN)

Claims (10)

(57) [Claims] An alcoholic hydroxyl group-containing compound, a phenolic hydroxyl group-containing compound, a carboxyl group-containing compound,
A water-absorbent resin (B) or a water-absorbent gel thereof is dispersed in a liquid or hot-melt active hydrogen-containing organic compound (A) selected from the group consisting of a thiol group-containing compound and an amino group-containing compound. B) Active hydrogen for producing a polyurethane resin comprising a water-absorbent resin dispersion formed by polymerization of a water-soluble monomer or a precursor thereof and a crosslinking agent and / or a polysaccharide in the presence of water in (A). Ingredients. 2. The active hydrogen-containing component according to claim 1, wherein (A) is a polyol. 3. The polyol is a polyether polyol,
The active hydrogen-containing component according to claim 2, wherein the active hydrogen-containing component is at least one selected from the group consisting of polyester polyol, polybutadiene polyol, and acrylic polyol. 4. The active hydrogen-containing component according to claim 1, wherein the proportion of (B) to the total weight of (A) and (B) is 1 to 70%. 5. The active hydrogen-containing component according to claim 1, wherein the (B) dispersed in (A) or the water-absorbing gel thereof has an average particle size of 0.01 to 100 μm. 6. The compound (B) formed by polymerizing one or more vinyl monomers having a carboxyl group or a sulfonic acid group, a copolymerizable crosslinking agent and, if necessary, other vinyl monomers. An active hydrogen-containing component according to any one of claims 1 to 5. 7. The amount of water to be present is from 5 to 50% by weight based on the total weight of (A), (B) and water.
An active hydrogen-containing component according to any one of claims 1 to 6. 8. The active hydrogen-containing component according to claim 1, wherein said component (B) is formed by polymerization in the presence of an emulsifier with water to form a gel. 9. A method for producing a polyurethane resin, comprising reacting the active hydrogen-containing component according to claim 2 with an organic polyisocyanate compound. 10. The reaction of the active hydrogen-containing component according to claim 2 with an organic polyisocyanate compound in the presence of a foaming agent and, if necessary, a catalyst, a foam stabilizer and other additives. A method for producing a polyurethane foam.