WO1994020561A1

WO1994020561A1 - Water-absorbent resin and water-absorbent resin composition containing the same

Info

Publication number: WO1994020561A1
Application number: PCT/JP1994/000372
Authority: WO
Inventors: Manabu Nagata; Shinichi Takemori; Hitoshi Ozawa
Original assignee: Sumitomo Seika Chemicals Co., Ltd.
Priority date: 1993-03-10
Filing date: 1994-03-09
Publication date: 1994-09-15
Also published as: JPH06316623A

Abstract

A modified polyalkylene oxide having a melt viscosity of 5-400 thousand poises at 170 °C under the load of 50 kg/cm2; a solvent-soluble water-absorbent resin composition comprising 100 parts by weight of the modification and 5-3,000 parts by weight of a thermoplastic resin or elastomer; and a product of molding thereof. The composition comprises components each with a good dispersibility, has excellent processability, hydrophilicity and antistatic quality, and is soluble in various solvents.

Description

Description Water-absorbing resin and water-absorbing resin composition containing the resin

TECHNICAL FIELD The present invention relates to a water-absorbing resin used alone or in combination with other general-purpose resins to be processed into a form of a film, a sheet, a fiber, a sealing material, and the like, and a water-absorbing resin composition containing the resin. Furthermore, the present invention relates to a water-absorbent molded product obtained by molding the water-absorbent resin or the water-absorbent resin composition.

Conventional technology

The thermoplastic resin elastomer used in various forms is a hydrophobic material, and it is necessary to impart water absorption or water retention depending on the application. Conventionally, as a method of imparting water absorbency to these materials, for example, a method of chemically treating the surface thereof, a method of mixing a water absorbing substance, and the like are known. In the latter category, many water-absorbent resin compositions in which a water-absorbent resin is dispersed, melted, and kneaded in a thermoplastic resin or an elastomer have been proposed. Many of such water-absorbent resin compositions are prepared by mixing a water-absorbent resin with a thermoplastic resin such as polyethylene or polypropylene, or an elastomer such as rubber, and melt-kneading the mixture with a kneader, a Banbury mixer, an extruder, or the like. It can be molded into pellets or the like and crushed.

However, in the above-mentioned production method, there is a problem that, when kneading the thermoplastic resin or the elastomer with the water-absorbing resin, the compatibility between the components is low and a uniformly dispersed product cannot be obtained.

In order to solve such a problem, a uniform water-absorbing resin composition having improved compatibility between a polyolefin resin and a water-absorbing resin has been disclosed in No. 9 proposes a resin composition containing a polyethylene oxide-modified water-absorbent resin and adding a specific third component resin, particularly a polyamide or polyoxymethylene having a melting point of less than 200 ° C. to the resin composition. Have been.

Purpose of the invention

However, even in the method described in JP-A-11-163229, depending on the type of the polyalkylene oxide-modified product used as the water-absorbing resin, the obtained molded product may have an external appearance. Although the number of bubbles has been reduced and their size has also been reduced, when observed in detail with an electron microscope, water-absorbent resin is scattered, which causes a drop in workability, sufficient hydrophilicity, antistatic effect, etc. Satisfactory performance may not be exhibited.

An object of the present invention is to provide excellent dispersibility when used alone or in combination with other general-purpose resins to form films, sheets, fibers, or the like, or when dissolved in an organic solvent and applied to a substrate. It is an object of the present invention to provide a solvent-soluble water-absorbing resin as described above and a composition containing the same. A water-absorbent molded product or processed product obtained from the resin or a composition containing the resin has hydrophilicity and an antistatic effect, and is used for various purposes.

Description of the invention

In view of the situation described above, the present inventors have intensively studied to solve the above-mentioned problems. As a result, the modified polyalkylene oxide having a specific melt viscosity as a water-absorbing resin is soluble in an organic solvent, and when the modified polyalkylene oxide is used, the dispersibility with respect to a thermoplastic resin or an elastomer is greatly increased. It was found that a water-absorbent resin composition in which these components were uniformly dispersed was obtained, and the present invention was completed.

That is, the present invention

An isocyanate compound of a polyalkylene oxide and an active hydrogen-containing compound The present invention provides a solvent-soluble modified polyalkylene oxide having a melt viscosity of 500,000 to 400,000 vise at 170 ° C. and a load of 5 O kgZcm ² obtained by reacting is there. Another object of the present invention is to provide a water-absorbent molded product obtained by molding the above-mentioned modified polyalkylene oxide itself and a solvent-soluble water-absorbent resin composition obtained by mixing a thermoplastic resin or an elastomer with the modified product.

The water absorbent resin used in the present invention is a modified polyalkylene oxide obtained by reacting a polyalkylene oxide with an active hydrogen-containing compound with an isocyanate compound. As the polyalkylene oxide, those having a weight-average molecular weight of 100,000 to 100,000 are used, and examples thereof include polyethylene oxide, polypropylene oxide, ethylene oxide / propylene oxide copolymer, and polybutylene. And the like and mixtures thereof. In particular, polyethylene oxide, polypropylene oxide, a mixture thereof or a copolymer thereof having a weight average molecular weight of 2000 to 100,000 is preferable.

When the weight average molecular weight is less than 100, the resulting polyalkylene oxide-modified product has an extremely low water absorption or an extremely high melt viscosity, so that a water-absorbing resin composition is molded. Unless the processing temperature at the time is increased, dispersibility may deteriorate, which is not preferable. On the other hand, if the weight average molecular weight is more than 100,000, the crosslinked density of the resulting polyalkylene oxide-modified product will be low and sufficient water absorption will not be obtained, or the water-absorbing resin composition will be formed into a molded product. In such a case, the gel is eluted on the surface at the time of water absorption, which deteriorates the surface state, which is not preferable.

Examples of the active hydrogen-containing compound used in the present invention include water, polyols, amines, and carboxylic acids. Examples of polyols include organic compounds having two or more hydroxyl groups (_OH) in the same molecule, such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, and trimethylene glycol. 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, hexylene glycol, octylene glycol, glyceryl monoacetate, glyceryl monobutyrate, 1 , 6-hexanediol, 1,9-nonanediol, bisphenol A, glycerin and the like. Preferably, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol and the like are used. Amines are compounds having two or more amino groups (one NH ₂ ) in the same molecule, such as ethylenediamine, 1,4-diaminobutane, 1,3-diaminopropane, 1,5-diaminopentane, and propylenediamine. , 2,4-diaminotoluene, 2,6-diaminotoluene and the like. Preferably, 1,4-diaminobutane and 1,3-diaminobutane are used.

Carboxylic acids are compounds having two or more carboxyl groups (one COOH) in the same molecule, such as adipic acid, oxalic acid, malonic acid, glutaric acid, succinic acid, pimelic acid, and azelaic acid. Can be Preferably, adipic acid, glutaric acid, pimelic acid, and azelaic acid are used. These active hydrogen-containing compounds are used alone or in combination. The active hydrogen-containing compound is usually added at the time of reaction between the polyalkylene oxide and the isocyanate compound, but may be added at the end of the reaction. By adding an active hydrogen-containing compound, the resulting polyalkylene oxide-modified product The melt viscosity can be reduced, and the effect of improving processability can be obtained.

The isocyanate compound used for crosslinking the above-mentioned polyalkylene oxide and the active hydrogen-containing compound includes an isocyanate group in the same molecule.

Organic compounds having one or more (one NCO), for example, n-propyl isocyanate, n-butyl isocyanate, n-hexyl isocyanate, dodecyl isocyanate, cyclohexyl isocyanate Benzyl isocyanate, phenyl isocyanate, 4,4'-diphenylmethanediisocyanate (MDI) hexamethylene diisocyanate, 1,8-dimethylbenzoyl-1,4-diisocyanate, 2,4-triisocyanate Urethane succinate compounds obtained by reacting polyols such as range isocyanate (TD I), trimers of TDI, polymethylene polyphenyl isocyanate, and trimethylolpropane with the number of moles of diisocyanate corresponding to the number of active hydrogens And polyisocyanate adducts. Preferably, 4,4'-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate, 2,4-tolylene diisocyanate (TDI) and the like are used.

In the present invention, the ratio of the polyalkylene oxide, the active hydrogen-containing compound and the isocyanate compound used is determined by the sum of the number of terminal hydroxyl groups of the polyalkylene oxide and the active hydrogen of the active hydrogen-containing compound and the number of isocyanate groups of the isocyanate compound. The ratio (R value) (one NCO group / H) is in the range of 0.5 to 2.0, preferably in the range of 0.8 to 1.8. When the R value is less than 0.5, the crosslink density becomes low and a water-absorbent resin having sufficient water absorbency cannot be obtained. On the other hand, when the R value exceeds 2.0, the crosslink density is increased, and the melt viscosity is increased, so that the processability during molding is deteriorated. I don't.

The number of moles of the polyalkylene oxide can be determined by dividing the weight by the average molecular weight.

The amount of the isocyanate compound to be used varies depending on the type of the isocyanate compound and conditions such as the reaction, but generally 0.5 to 80 parts by weight, based on 100 parts by weight of the polyalkylene oxide, Preferably, it is in the range of 1 to 50 parts by weight. If the amount is less than 0.5 part by weight, sufficient cross-linking density of the obtained polyalkylene oxide modified product will not be obtained, and sufficient gel strength cannot be obtained. The melt viscosity of the oxide-modified product becomes too high, and the processing temperature for molding the above-mentioned polyalkylene oxide-modified product or a composition containing the same into a film, a sheet, a fiber or the like becomes high. Therefore, molding becomes difficult and dispersibility also deteriorates, which is not preferable.

As a method of reacting a polyalkylene oxide and an active hydrogen-containing compound with an isocyanate compound, a method of reacting in a solution using an appropriate solvent is generally used. Alternatively, a method in which both are uniformly mixed and then heated to a predetermined temperature to cause a reaction can be used.

The reaction temperature is usually 50 to 150 ° C. The reaction can be promoted by adding a small amount of triethylamine, triethanolamine, dibutyltin laurate, dibutyltin acetate, triethylenediamine, or the like to this reaction system.

Thus, by reacting the polyalkylene oxide and the active hydrogen-containing compound with the isocyanate compound, the melt viscosity at a temperature of 170 ° C. and a load of 5 O kg / cm ² is 500-400. 10,000 Boys Polyalkylene Oxide Modified You can get things.

The modified polyalkylene oxide having the above melt viscosity is itself soluble in a solvent, and exhibits excellent workability when molded into a sheet, film, or fiber.

Solvents in which the modified polyalkylene oxide is soluble include alcohols such as methanol, ethanol, propanol, and butanol; esters such as ethyl acetate and butyl acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Ketones such as cellosolve, tetrahydrofuran, etc .; Nitrogen-containing organic solvents such as dimethylformamide, triethanolamine, etc .; Halogenated hydrocarbons such as chloroform, carbon tetrachloride: benzene, toluene And aromatic hydrocarbons such as xylene, and mixtures thereof.

The above-mentioned modified polyalkylene oxide is formed into a sheet by using a commonly used material such as a hot press, an extruder (T die) or a calender roll, and heating to 80 to 180 ° C. A sheet having a water absorbency of usually 0.5 to 5 mni is obtained.

To form a film, an extruder (inflation die) is used to heat and melt to obtain a water-absorbing film. Also, a film can be obtained by dissolving in the above solvent and casting. Thus, a film having a thickness of 5 to 500 m is obtained.

In order to convert the fiber into a fiber, a water-absorbing fiber having a diameter of 10 to 300 is obtained by a usual method using a melt spinning machine.

In the water absorbent resin composition of the present invention, a modified polyalkylene oxide obtained by reacting the above polyalkylene oxide and an active hydrogen-containing compound with an isocyanate compound is used as the water absorbent resin. This polyalkyl As described above, the melt viscosity of the modified oxide at a temperature of 170 ° C. and a load of 50 kg / cm ² is 500,000 to 400,000 boise. This melt viscosity is a measure of the compatibility with the thermoplastic resin or the elastomer.

If the melt viscosity is less than 50,000 voids, when the water-absorbent resin composition is molded, the gel is eluted on the surface when absorbing water, and the surface condition is deteriorated. On the other hand, a resin having a melt viscosity of more than 400,000 Boys is not preferred because the compatibility with a thermoplastic resin or an elastomer is lowered and a uniformly dispersed water-absorbent resin composition cannot be obtained. This time, for such temperature 1 7 0 ° C, 5 O kg / cm 2 melt viscosity at weights 5 0 0 0-4 00 000 Boyes polyalkylene O sulfoxides modified product thermoplastic resin or elastomer one By using It was found that a water-absorbent resin composition having good compatibility and having these components uniformly dispersed was obtained. The thermoplastic resin used in the composition of the present invention is not particularly limited, and ordinary resins such as polyolefin resin, polyamide resin and polyester resin are used. These thermoplastic resins may be used alone or in combination of two or more.

Examples of polyolefin resins include vinyl group-containing homopolymers such as polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyvinyl acetal, polystyrene, polyacrylate, and polymethacrylate, and ethylene-acryl. Acid copolymer, ethylene-vinyl acetate copolymer, acrylonitrile, styrene-butadiene copolymer, acrylic rubber-acrylonitrile-styrene terpolymer, acrylonitrile-styrene-butadiene copolymer, chlorinated polyethylene-acrylonitrile Styrene graft polymer, chlorosulfonated polyethylene, acrylonitrile-ethylene-ethylene-propylene rubber terpolymer and the like. Preferably, polyethylene, polypropylene, polychlorinated Use of vinyl, ethylene acrylate, ethylene methacrylate, ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer, acrylonitrile-styrene-butane-gen copolymer, chlorosulfonated polyethylene, etc. 6-nylon, 6,6-nylon, 6,10-nylon, 11-nylon, 12-nylon and the like. Examples of the polyester resin include polyethylene terephthalate and polybutylene terephthalate.

The elastomer used in the composition of the present invention includes natural rubber (NR), isoprene rubber (IR), styrene-butadiene rubber (SBR), butadiene rubber (BR), nitrile rubber (NBR), and ethylene propylene rubber. (E PDM), Fluoro rubber (FKM), Chloroprene rubber (CR) and Styrene Butagennostyrene (SBS :), Styrene Isoprenenostyrene (SIS), Styrene Z Ethylenebutylenenostyrene (SEBS). Styrene Ethylene-propylene / And thermoplastic elastomers such as styrene (SEPS). Preferably, natural rubber (NR), styrene-butadiene rubber (SBR :), styrene Z butadiene styrene (SBS) or the like is used.

The mixing ratio between the thermoplastic resin or the elastomer and the modified polyalkylene oxide is 5 to 3,000 parts by weight, preferably 30 to 2 parts by weight, based on 100 parts by weight of the modified polyalkylene oxide. 000 parts by weight.

When the amount of the thermoplastic resin or the elastomer is less than 5 parts by weight, when the obtained water-absorbent resin composition is molded and absorbed, the water-absorbing gel is detached from the thermoplastic resin or the elastomer and elutes on the surface to change the surface state. It is not preferable because it deteriorates. On the other hand, if it exceeds 3000 parts by weight, hydrophilicity and charge It is not preferable because the effect of providing the prevention cannot be sufficiently recognized.

In order to obtain the water-absorbent resin composition of the present invention by mixing the above-mentioned thermoplastic resin or the elastomer and the modified polyalkylene oxide, a usual melt-mixing means such as a kneader-banbury mixer or an extruder is used. Further, the water-absorbent resin composition of the present invention can contain additives such as a plasticizer, a stabilizer, a filler, a pigment-vulcanizing agent, and a vulcanization accelerator, if desired.

The water-absorbent resin composition of the present invention may be used alone in various forms, but may be used as a compound (master batch) and blended with other general-purpose resins. In addition, after being dissolved in various solvents, it can be used by forming a coating film by applying it to a substrate.

Usually, the crosslinked polyalkylene oxide obtained by reacting only the polyalkylene oxide with the isocyanate compound is insoluble in the solvent or shows only a small solubility, so that the crosslinked polyalkylene oxide was uniformly dissolved. Although it is difficult to obtain a solution, the modified polyalkylene oxide of the present invention itself shows solubility in a solvent as described above. Further, depending on the thermoplastic resin or the elastomer, by mixing them with the composition to form a composition, the solubility in the solvent is further increased, and a solution in which the modified polyalkylene oxide is uniformly dissolved can be obtained. . Usually, the solution is a water-absorbent resin composition.

Use in the concentration range of 5 to 40%.

As the solvent, the same solvent as used for dissolving the above-mentioned modified polyalkylene oxide is used.

In addition, a method of molding into a molded product such as a sheet, a film, or a fiber using the water-absorbent resin composition can be applied as it is to the method used for molding the modified polyalkylene oxide.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to these examples. The melt viscosity of the modified polyalkylene oxide obtained in the example, the measurement of water absorption capacity, the stability over time of water absorption capacity, and the formation of a solvent-soluble water-absorbent resin composition containing the modified polyalkylene oxide. The molded product or processed product obtained as described above was evaluated according to the following method.

Evaluation of modified polyalkylene oxide

(1) Measurement of melt viscosity

As a measurement sample, 1.5 g of a modified polyalkylene oxide was used, and the measurement was performed using a flow tester (CFT-500C manufactured by Shimadzu Corporation) under the following conditions.

Weight 50 kg / cm ²

Measurement temperature 170 ° C

Die diameter 1 mm

Die: Length 1 mm

(2) water absorption capacity (g (H ₂ 0) Bruno g (resin): pure water) Determination of

Polyalkylene oxide-modified lg was added to 200 ml of pure water, stirred for 1 hour, and then filtered through a 200-mesh wire gauze. The weight of the gel after filtration was regarded as the water absorbing ability.

(3) Evaluation of stability over time

After storing the modified polyalkylene oxide in a constant temperature bath at 50 ° C for 2 months, the water absorption capacity was measured.

Molded product evaluation method

An article obtained by molding or processing the solvent-soluble water-absorbent resin composition was evaluated according to the following method.

(1) Dispersibility evaluation

The water-absorbent resin composition is hot-pressed into a sheet with a thickness of 1 to 2 mm. Agent dissolved in it is applied to a substrate to form a coating film, by observing the front surface state of the sheet or coating with the naked eye and an electron microscope (100-fold), _c criteria of evaluation of dispersibility Is as follows.

〇: Observation with the naked eye is good, and no particles are observed under electron microscope observation.

Δ: The observation with the naked eye is good, but particles are observed under an electron microscope.

X: Bubbles of particles are observed by visual observation.

(2) Water absorption state

The water-absorbent resin composition is formed into a sheet having a thickness of 1 to 2 mm by hot pressing, or dissolved in a solvent and applied to a substrate to form a coating film. After being cut out and immersed in pure water for one day, the surface condition was observed. The evaluation criteria are as follows.

〇: Good surface condition, no gel detachment, no slimy feeling.

Δ: Surface condition is good, but slimy.

: Gel detached from the surface and felt slimy.

Example 1

A 1-liter 4-neck separable flask equipped with a condenser, nitrogen inlet tube, thermometer and stirrer is charged with polyethylene oxide having a weight-average molecular weight of 20000 10 Os toluene 55 Oml, and then distilled to remove water. Distilled 200 ml of toluene. Thereto were added 3,4′-diphenylmethanedithiocyanate 3.lg, 1.42 butanediol 0.72 g and triethylenediamine 0.023 g, and the mixture was reacted at 110 ° C. for 3 hours. Thereafter, 175 ml of hexane was added, and the mixture was cooled to room temperature to precipitate a polymer. The slurry was filtered under pressure and dried under reduced pressure at a temperature of 170. C, 50kg Roh cm ² pressure As a result, 100 g of a modified polyethylene oxide having a melt viscosity of 50,000 Boys in weight was obtained.

The water absorption capacity (g / g: pure water) was 32 gZg. The modified polyethylene oxide includes methanol, ethanol, propanol, butanol, ethyl acetate, butyl acetate, acetone, methylethyl ketone, methyl isobutyl ketone, cyclohexanone, cellosolve, tetrahydrofuran, dimethylformamide. It was soluble in organic solvents such as triethanolamine, chloroform, carbon tetrachloride, benzene, toluene and xylene.

The resulting polyalkylene oxide-modified product was spun with a die (d = lniDi, 12 holes) using a 20 extruder (150 ° C.) to obtain a fiber having a diameter of 50 zm. The obtained fiber could be drawn 5 times at room temperature.

Example 2

Polyethylene oxide having a weight average molecular weight of 8,500 was used as the polyalkylene oxide, 2,4-tolylene diisocyanates TD1) (4.5 g) as the cross-linking agent, and 1.25 g of 1.9-nonanediol as the diol were used, and 0.17 g of triethylamine was added. Otherwise in the same manner as in Example 1, 100 g of a modified polyalkylene oxide having a melt viscosity of 100,000 voids at a temperature of 170 ° C. and a load of 50 kg / cm ² was obtained. The water absorption capacity (gZg: pure water) was 20 gZg.

90 g of methanol was added to 10 g of the resulting polyalkylene oxide-modified product, and the mixture was heated and dissolved. The obtained solution was cast on a glass plate and then dried to obtain a film having a thickness of 20 m.

Example 3

The same procedure as in Example 1 was carried out except that polyethylene oxide having a weight average molecular weight of 100,000 was used as the polyalkylene oxide, 1.6 g of hexamethylene diisocyanate as the crosslinking agent, and 1.0 g of 1,6-hexanediol as the diol. As a result, 100 g of a modified polyalkylene oxide having a melt viscosity of 20,000 voids at a temperature of 170 ° C. and a load of 5 OkgZcra ² was obtained. The water absorption capacity (g / g: pure water) was 38 gZg.

The resulting polyalkylene oxide-modified product was heated and pressed (150 ° C, 7 min, 5 Okg / cm ² ) to obtain a lmm thick sheet.

Example 4

A mixture of 80 g of polyethylene oxide having a weight average molecular weight of 11,000 as a polyalkylene oxide and 20 g of polypropylene oxide having a weight average molecular weight of 4,000, 7.5 g of 4,4'-diphenylmethane diisocyanate as a crosslinking agent, and 1,1 as a diol. 4 except for using an butanediol 0.73g in the same manner as in example 1 to obtain a temperature 170 ^e C, 5 OkgZcni ² melt in weight viscosity 150,000 Boyes polyalkylene O sulfoxides modified product 100 g. The water absorption capacity (g / g: pure water) was 18 gZg.

The obtained polyalkylene oxide-modified product was extruded using an inflation die in a 30 extruder (180 ° C) to obtain a film having a thickness of 50 m.

Example 5

Conducted except using 100 g of polypropylene having a weight average molecular weight of 2000 as polyalkylene oxide, 2 lg of hexamethylene diisocyanate as a cross-linking agent, 9.35 g of 1,4-diaminobutane as an active hydrogen-containing compound, and 7 g of triethylamine. In the same manner as in Example 1, 100 g of a modified polyalkylene oxide having a melt viscosity of 8,000 voids was obtained. The water absorption capacity (gZ g: pure water) was 48 gZ.

Example 6

100g of ethylene oxide / propylene oxide (85Z15) copolymer with weight average molecular weight of 11000 as polyalkylene oxide, crosslinker Of poly (alkylene oxide) having a melt viscosity of 18,000 boys in the same manner as in Example 1 except that 3.2 g of 2,4-tolylene diisocyanate was used as the active compound and 0.18 g of pure water was used as the active hydrogen-containing compound. 100 g of the denatured product was obtained. The water absorption capacity (gZg: pure water) was 25 g / g.

Example 7

Using 100 g of polyethylene glycol having a weight average molecular weight of 20000 as polyalkylene oxide, 2.5 g of hexamethylene diisocyanate as a cross-linking agent, 1.0 g of glutaric acid as an active hydrogen-containing compound, and adding 0.1 g of stannasquatate In the same manner as in Example 1, 100 g of a modified polyalkylene oxide having a melt viscosity of 75,000 Boys was obtained. The water absorption capacity (g / g: pure water) was 23 gZg.

Example 8

100 g of polybutylene oxide having a weight average molecular weight of 4000 as polyalkylene oxide, 13.3 g of 4.4'-diphenylmethane diisocyanate as a cross-linking agent, 0.07 g of 1,3-diaminobutane as an active hydrogen-containing compound and 0.06 g of pure water g, and 100 g of a modified polyalkylene oxide having a melt viscosity of 350,000 vise was obtained in the same manner as in Example 1 except that 1.5 g of dibutyltin acetate was added. The water absorption capacity (gZg: pure water) was 27 gZg.

Comparative Example 1

In the same manner as in Example 1 except that 1,4-butanediol was not added, 100 g of a modified polyalkylene oxide having a melt viscosity of 500,000 Voy at a temperature of 170 ° C. and a load of 5 OkgZcm ² was obtained. The water absorption capacity (gZg: pure water) was 35 g / g.

The resulting modified polyalkylene oxide is methanol, ethanol, propanol, butanol, ethyl acetate, butyl acetate, acetone, methyl Insoluble in ethyl ketone, methyl isobutyl ketone, cyclohexanone, cellosolve, tetrahydrofuran, dimethylformamide, triethanolamine, chloroform, carbon tetrachloride, benzene, toluene, xylene

Die the modified polyalkylene oxide with a 2 Omm extruder (150 ° C)

I tried spinning at 12 holes), but the yarn was broken and no fibrous material could be obtained.

Comparative Example 2

In the same manner as in Example 2 except that 1,9-nonanediol was not added, 100 g of a modified polyalkylene oxide having a melt viscosity of 700,000 voids at a temperature of 170 ° C. and a load of 5 OkgZcin ² was obtained. The water absorption capacity (g / g: pure water) was 15 gZg.

Example 9

To 100 parts by weight of the modified polyethylene oxide obtained in Example 1, 50 parts by weight of low-density polyethylene (trade name: Sumikacene G-801, MI = 20 manufactured by Sumitomo Chemical Co., Ltd.) was kneaded with a 4-inch roll (170 ° Cx). 1 Omin) to obtain a water-absorbent resin composition of the present invention.

The composition was soluble in toluene.

The above composition was spun with a die (d = lmm, 12 holes) using a 20 mm extruder (150 ° C) to obtain a fiber having a diameter of 50 m.

Example 10

To 100 parts by weight of the modified polyalkylene oxide obtained in Example 2, 900 parts by weight of polypropylene (trade name: Noblen Y101, MI = 12, manufactured by Sumitomo Chemical) are kneaded with a 3 Omra extruder (LZD = 24). (190 ° C) to obtain a water-absorbent resin composition of the present invention. The obtained water-absorbent resin composition was obtained using an inflation die with a 30 mm extruder (180 ° C) to obtain a film having a thickness of 50 / πι.

The wettability of the film was measured by the method described in JIS K6768 using a standard solution of wetting index and found to be 4 Odyn / cra. On the other hand, a film having a thickness of 50 m obtained in the same manner as described above using only polypropylene had a wetting index of 3 OdynZcm.

Example 11

100 parts by weight of the modified polyalkylene oxide obtained in Example 3 and 700 parts by weight of polyvinyl chloride (K-1507: manufactured by Kondo Chemical Industry) are kneaded with a 3 Omni extruder (L / D = 24) (160). ° C), the composition obtained from the water-absorbent resin composition of the present invention was hot-pressed (160 ° C x 7 min) to obtain a sheet having a thickness of 1 m. When the molded product of the obtained sheet was evaluated by the above method, the water absorption state of the sheet surface was good without gel detachment and no slimy feeling, and the dispersibility of the modified polyalkylenoxide and polyvinyl chloride was good. Was also good.

It was also the seat of the charging property of the hypersonic megohmmeter (DKK-TOA Ltd. SM- 8210) The surface resistance was measured and evaluated by (measurement voltage 100 V, application time 1 · min) 2.0 X 10 η ^Ω. On the other hand, a sheet having a thickness of 1 and obtained in the same manner as described above using only polyvinyl chloride had a surface resistance of 5 × 10 ¹² Ω.

Example 12

100 parts by weight of the modified polyalkylene oxide obtained in Example 3 and 50 parts by weight of an ethylene / vinyl acetate copolymer (trade name: Evatate 2021_F, MI = 12, manufactured by Sumitomo Chemical Co., Ltd.) were tested with a 4-inch test roll. The mixture was kneaded (100 ° C. × 1 Omin) to obtain a water-absorbent resin composition of the present invention.

The resulting composition is hot-pressed (100 ° C for 7 minutes) to form a sheet with a thickness of ιπιπι. Obtained. The molded product of the obtained sheet was evaluated by the above method. Table of results

See Figure 2.

Example 13

100 parts by weight of the modified polyalkylene oxide obtained in Example 4 and 300 parts by weight of ABS resin (trade name: CLASTIC GA-501, manufactured by Sumitomo Dow) are kneaded with a pressure kneader having a 1-liter internal volume. (170 ° C x 1 Omin) to obtain a water-absorbent resin composition of the present invention.

The obtained composition was hot-pressed (150 ° C x 7 min) to obtain a lmm-thick sheet. The molded product of the obtained sheet was evaluated by the above method. Table 2 shows the results.

Example 14

100 parts by weight of the polyalkylene oxide-modified product obtained in Example 6 and 500 parts by weight of polyethylene terephthalate (C, TOBR: manufactured by Unitika Ltd.) were kneaded with a 30 extruder (LZD = 24) (260). C) A water-absorbent resin composition of the present invention was obtained.

The obtained composition was hot-pressed (250 ° C x 15 min) to obtain a sheet having a thickness of 1 min. The moldability of the obtained sheet was evaluated by the above method. Table 2 shows the results.

Example 15

100 parts by weight of the modified polyalkylene oxide obtained in Example 7 and 1900 parts by weight of 12-nylon (Diamid L 2140: manufactured by Daicel Huls) are kneaded with a 4-inch test roll (190 ° C. × 1 Omin). Thus, a water-absorbent resin composition of the present invention was obtained.

The obtained composition was hot-pressed (180 ° C x 1 Omin) to obtain a lmm-thick sheet. The moldability of the obtained sheet was evaluated by the above method. result Is shown in Table 2.

Example 16

100 parts by weight of the modified polyalkylene oxide obtained in Example 8 and 30 parts by weight of an ethylene acrylic acid copolymer (Primacol 3440, manufactured by Dow Chemical Company) were kneaded with a 4-inch test roll (180 ° C x 1). Omin) to obtain a water-absorbent resin composition of the present invention. The obtained composition was hot-pressed (150 ° C × 7 Omin) to obtain a lmm-thick sheet. The moldability of the obtained sheet was evaluated by the above method. Table 2 shows the results.

Example 17

To 100 parts by weight of the modified polyalkylene oxide obtained in Example 3, 137.5 parts by weight of styrene-butadiene rubber (trade name: Dipole, 1778 J, manufactured by Zeon Corporation) was added, and the water-absorbent resin of the present invention was added. A composition was obtained.

Further, 20 parts by weight of carbon black (HAF, made by Asahi Carbon, # 70), 50 parts by weight of bentonite (trade name: Wenger, manufactured by Toyojun Yoko), 3 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 4 parts by weight Parts, vulcanization accelerator TT (trade name: Noxeller TT, manufactured by Ouchi Shinkosha) 1.75 parts by weight, vulcanization accelerator DM (tradename: Noxeller DM, manufactured by Ouchi Shinkosha) 0.7 parts by weight, 6 inch open roll After kneading with, the mixture was vulcanized by hot pressing (150 ° C x 3 Omin) to obtain a sheet having a thickness of 2 讓. The molded product of the obtained sheet was evaluated by the above method. Table 3 shows the results.

Example 18

100 parts by weight of natural rubber (smoked sheet, # 1) was added to 100 parts by weight of the modified polyalkylene oxide obtained in Example 1 to obtain a water-absorbent resin composition of the present invention.

In addition, 5 parts by weight of zinc white, an antioxidant (trade name: Nocrack NS-6, 1 part by weight, 15 parts by weight of calcium carbonate, 20 parts by weight of carbon black SRF (trade name, # 50, manufactured by Asahi Carbon Co.), process oil (trade name: Aroma 790, manufactured by Sun Oil Co., Ltd.) 5 1 part by weight of vulcanization accelerator (trade name: Noxera I CZ, manufactured by Ouchi Shinko Co., Ltd.), 1 part by weight, kneaded with 6 inch open roll, and vulcanized with hot press (150 ° C x 3 Omin) A sheet with a thickness of 2 was obtained. The molded product of the obtained sheet was evaluated by the above method (the results are shown in Table 3).

Example 19

100 parts by weight of the modified polyalkylene oxide obtained in Example 2 was used as a thermoplastic elastomer, and 50 parts by weight of styrene-butadiene styrene (trade name: Force Reflex TR1101, manufactured by Shell Chemicals) was 1 liter in internal volume. The mixture was kneaded with a pressure kneader (170 ° C. × 3 Omin) to obtain a water-absorbent resin composition of the present invention. This composition was hot-pressed (170 ° C. × 1 Omin) to obtain a sheet having a thickness of 2 mm. The molded product of the obtained sheet was evaluated by the above method. Table 3 shows the results.

Example 20

A water-absorbent resin composition of the present invention was obtained in the same manner as in Example 17 except that the modified polyalkylene oxide obtained in Example 5 was used.

The resulting composition was hot-pressed (150 ° C x 3 Omin) to obtain a sheet with a thickness of 1 band. The moldability of the obtained sheet was evaluated by the above method. Table 3 shows the results.

Example 21

A water-absorbent resin composition of the present invention was obtained in the same manner as in Example 19, except that the modified polyalkylene oxide obtained in Example 7 was used.

The resulting composition was hot-pressed (170 ° C x 1 Omin) and a 1 mm thick sheet I got it. The moldability of the obtained sheet was evaluated by the above method. Table 3 shows the results.

Example 22

To 100 parts by weight of the modified polyalkylene oxide obtained in Example 2, 200 parts by weight of ethylene methacrylate (manufactured by Ciebron Chemical Co., Ltd., PE2255, MI = 2) was added. Thus, a water-absorbent resin composition of the present invention was obtained. To this composition, 10 parts by weight of a filler (trade name: AEROSIL R-805, manufactured by Nippon AEROSIL Co., Ltd.) was added, and after kneading with a 30 mm extruder (about 190 ° C), the pellet was removed. The powder was pulverized with a pulverizer to obtain a powder of 200 mesh or less.

800 parts by weight of toluene was added to 100 parts by weight of the powder, dissolved and dispersed, and then applied on an OPP film (50 m), and the coating sheet of the water-absorbent resin composition was applied. Obtained. The dispersibility of the composition in the sheet and the processed product in the state of water absorption were evaluated by the above method. Table 4 shows the results.

Example 23

To 100 parts by weight of the modified polyalkylene oxide obtained in Example 1 was added 200 parts by weight of chlorosulfonated polyethylene (Nodipalon 20, manufactured by Showa Neoprene Co.), and the water-absorbent resin composition of the present invention was added. I got something. The composition further contains 80 parts by weight of tribasic lead maleate, 4 parts by weight of phthalic acid, 20 parts by weight of rutile-type titanium dioxide, and 3 parts by weight of Noxera-I TET (manufactured by Ouchi Shinkosha) for 6 inches. After kneading with an open roll, 6 parts by weight of hydrogenated hydrogen chloride, 992 parts by weight of toluene and 248 parts by weight of butanol were added to the kneaded material and dissolved. The obtained solution was applied on an 85 πι polyester film to obtain a coating sheet of a water-absorbent resin composition having a thickness of about 70 zm. The processed products of the sheets were evaluated by the above method. Table 4 shows the results.

Example 2 4 100 parts by weight of the modified polyalkylene oxide obtained in Example 2 was copolymerized with ethylene-acrylic acid (trade name: Primacol 590, MI = 1300, manufactured by Dow Chemical Company). 100 parts by weight were kneaded (about 150 ° C.) with a 30 extruder, and the obtained pellets were frozen and pulverized to obtain a water-absorbent resin composition of the present invention. This is dissolved in isopropanol 1 7 0 0 0 parts by weight triethanolamine 4 0 0 by weight unit, then 2 0 O GZm ² applied to the surface of the polyester non-woven, having a thickness of about 2 0 water absorbent resin composition A coating sheet was obtained. The processed product of the sheet was evaluated by the above method. Table 4 shows the results.

Example 2 5

A water-absorbent resin composition of the present invention was obtained in the same manner as in Example 22 except that the modified polyalkylene oxide obtained in Example 5 was used.

The obtained composition was hot-pressed (180 ° C. × 1 O min) to obtain a sheet having a thickness of 1 band. The moldability of the obtained sheet was evaluated by the above method. Table 4 shows the results.

Example 26

A water-absorbent resin composition of the present invention was obtained in the same manner as in Example 23 except that the modified polyalkylene oxide obtained in Example 7 was used.

The obtained composition was hot-pressed (150 ° C. × 1 O min) to obtain a lmm-thick sheet. The moldability of the obtained sheet was evaluated by the above method. Table 4 shows the results.

Comparative Examples 3-4

Using the modified polyalkylene oxide obtained in Comparative Example 1, a sheet having a thickness of l mm was obtained in the same manner as in Examples 12 to 13. The molded article of the obtained sheet was evaluated by the above method. Table 2 shows the results.

Comparative Examples 5 to 8 In Examples 17 to 20, a molded product of a water-absorbent resin composition was prepared in the same manner as in Examples 17 to 20 except that the modified polyalkylene oxide obtained in Comparative Examples 1 and 2 was used. Or obtained a processed product.

Evaluation of the dispersibility, water absorption state, and the like of the composition in the obtained molded product and processed product was performed by the above method. Table 3 shows the results.

Comparative Examples 9 to 12

Examples 22 to 25 In the same manner as in Examples 22 to 25 except that the modified polyalkylene oxide obtained in Comparative Examples 1 and 2 was used, a molded article or processed product of the water-absorbing resin composition was used. I got Evaluation of the dispersibility, water absorption state, and the like of the composition in the obtained molded product and processed product was performed by the above method. Table 4 shows the results.

Polyalkylene acid Active hydrogen R value Melt viscosity Water absorption capacity Stability over time Oxidate compound NCO / H xlO ⁴ Boys g / g Water absorption capacity Molecular weight

Example 1 PE0 20,000 HDI 1, -BDO 0.95 5.0 32 32

2 PE0 8500 TDI 1.9-NDO 1.32 10 20 21

3 PE0 100,000 11DI 1,6-HDO 1.0 2.0 38 39

4 PE0 11000 HDI 1, -BDO 1.51 15 18 18

PP0 4000

5 PE0 2000 HDI 1, 4-DAB 0.8 0.8 48 49

6 E0 / P0 11000 TDI Water 0.95 1.8 25 26

7 PE0 20,000 HDI Glutar β 1.2 7.5 23 24

8 PB0 4000 HDI 1, 3-DAB 1.8 35 27 28

water

Comparative Example 1 PE0 20,000 HDI 2.5 50 35 Dissolved, no gel

2 PE0 8500 TDI 2.2 70 15 Dissolve, no gel

PEO: Polyethylene oxide 1, 4-BD0: 1,4-butanediol PP0: Polypropylene oxide 1, 9-ND0: 1,9-Nonanediol E0: Ethylene oxide 1, 6-HD0: 1,6- Xandiol P0: Propylene oxide 1,4-DAB: 1,4-Diaminobutane PB0: Polybutylene oxide 1,3- MB: 1,3-Diaminobutane DI: 4, 4'-Diphenylmethanediisocia Nate

TDI: 2,4-tolylene diisocyanate

HDI: Hexamethylene diisocyanate

Polyalkylene Thermoplastic resin or water-absorbing state Dispersible to oxide-modified product Elastomer Kneading method Evaluation Electron microscope observation

Example Melt viscosity

Example 12 Example 3 20,000 Ethyl vinyl acetate Lorenole 〇〇

Union

13 4 150,000 ABS resin Pressurized 〇〇

---

14 6 1.8 thousand polyethylene Extruder 〇〇

Shiretsunono 1, ~ k P

15 7 750,000 12-nylon roll 〇〇

16 8 350,000 Ethanolacrylic acid Lorenole 〇〇

Copolymer

Comparative Example 3 Comparative Example 1 500,000 Vinyl Ethyl Vinyl Oxide Roll X X

Copolymer gel detachment

4 1 500,000 ABS resin pressurized X Δ

Niego gel desorption

CO Polyalkylene Thermoplastic resin or water absorbing state Dispersibility

Modified oxide Elastomer Kneading method Evaluation Electron microscope observation

Example Melt viscosity

Example 17 Example 3 20,000 Styrene-butadiene Rhonore 〇〇

18 1 Top ϋ ノ J Natural rubber Lonoré 〇〇

19 2 100,000 Styrene / butadiene / styrene Pressurized 〇〇

Negu

20 500,000 Styrene-butadiene 口〇

21 7 75 000 Styrene 〃Yu Gen / Styrene Pressurized 〇〇

Seconder

Comparative Example 5 Comparative Example 1 500,000 Styrene-butadiene

6 1 500,000 Natural rubber Mouthpiece X X

7 1 500,000 Styrene / butadiene / styrene Pressurized X X

Two-one

8 2 700,000 Styrene-butadiene XX

Polyalkylene Thermoplastic resin or water absorbing state Dispersibility Oxide modified Elastomer Kneading method Evaluation Electron microscope observation Example Melt viscosity

Example 22 Example 2 100,000 ethylene methacrylate extruder 〇〇

23 150,000 Kusulfonated polyethylene Lorenole 〇〇

24 2 100,000 Ethylene-acrylic acid copolymer Extruder 〇〇

25 500,000 Ethylene methacrylate extruder 〇〇

26 7 75 000 Kusulfonated Polyethylene Roll 〇〇 Comparative Example 9 Comparative Example 1 500,000 Ethylene Methacrylate Extruder X Δ

10 1 500,000 Kusulfonated polyethylene Mouthpiece X X

11 1 500,000 Ethylene acrylate copolymer extrusion machine X X

12 2 700,000 Ethylene methacrylate extruder XX

As described above, according to the present invention, a water-absorbent resin soluble in an organic solvent, and a solvent-soluble water-absorbent resin composition in which a thermoplastic resin or an elastomer and the water-absorbent resin are uniformly dispersed are obtained. Molded products such as films and sheets obtained by molding the water-absorbent resin and the composition alone or as a blended component, or processed products obtained by applying a solution to a substrate have excellent hydrophilicity and antistatic properties. Becomes

Claims

The scope of the claims

1. A solvent-soluble modified polyalkylene oxide having a melt viscosity of 5,000 to 400,000 vise at 170 ° C. and a load of 5 OkgZcm ² obtained by reacting a polyalkylene oxide and an active hydrogen-containing compound with an isocyanate compound.

2. The claim that the polyalkylene oxide is at least one selected from the group consisting of polyethylene oxide and polypropylene oxide having a weight average molecular weight of 10 to 1,000,000, a mixture thereof, and a copolymer thereof. Item 6. The modified polyalkylene oxide according to Item 1.

3. The modified polyalkylene oxide according to claim 1, wherein the active hydrogen-containing compound is at least one selected from the group consisting of water, polyol, amine and carboxylic acid.

4. The polyalkylenoxide according to claim 3, wherein the polyol is at least one selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, and 1,9-nonanediol. Denatured product.

5. The modified polyalkylene oxide according to claim 3, wherein the amine is at least one member selected from the group consisting of ethylenediamine, 1,4-diaminobutane, and 1,3-diaminobutane.

6. The modified polyalkylene oxide according to claim 3, wherein the carboxylic acid is at least one selected from the group consisting of adipic acid, glutaric acid, pimelic acid, and azelaic acid.

7. which comprises reacting a polyalkylene O sulfoxides and active hydrogen-containing compound and the Isoshianeto compound, 170 ° (:, All the 5 OkgZcm ² weight A method for producing a modified polyalkylene oxide having a melt viscosity of 500,000 to 400,000 vise.

8.1000 parts by weight of a solvent-soluble modified polyalkylene oxide having a melt viscosity of 500 to 40,000 boise at 170 ° C and a load of 5 O kgZcm ² and a thermoplastic resin or elastomer 5 to A solvent-soluble water-absorbent resin composition obtained by mixing 300 parts by weight.

9. Polyalkylene oxide and an active hydrogen-containing compound are reacted with an isocyanate compound. The melt viscosity at 170 ° C. and 5 O kg / cm ² weight is 500,000 to 400,000 boilers. A molded product obtained by molding a modified solvent-soluble polyalkylene oxide.

100. The polyalkylene oxide and the active hydrogen-containing compound are reacted with the isocyanate compound to obtain a melt viscosity at 500 ° C. and 170 kg / cm ^{2 at a} load viscosity of 500,000 to 400,000 boise. A molded product obtained by molding a water-absorbent resin composition obtained by mixing 100 parts by weight of a certain solvent-soluble polyalkylene oxide modified product with 5 to 300 parts by weight of a thermoplastic resin or an elastomer.