JP2003096155A - Polyalkylene oxide modified product and gelled substrate composed of the modified product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyalkylene oxide modified product having excellent injection molding properties, and a gelled substrate which does not desorb the gel for a long period of time even after absorbing a liquid, can maintain the shape and size of a gel for a long period of time, and can diffuse and emanate a fragrant component for a long period of time. SOLUTION: The polyalkylene oxide modified product having excellent injection molding properties can be obtained by reacting a mixture composed of 1 mol polyalkylene oxide and 0.5-3 mol polyol with an isocyanate compound of 0.8-1.2 mol times the total molar number of the above polyalkylene oxide and polyol, and has a melt viscosity at 170 deg.C under a load of 5 MPa of 80-2,000 Pa.s and a water absorption of 10-50 g/g.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyalkylene oxide-modified product excellent in injection moldability and a gelling substrate comprising the polyalkylene oxide-modified product.

[0002]

2. Description of the Related Art Conventionally, a water absorbent resin or a water absorbent resin and another thermoplastic resin have been used as a carrier for an aromatic agent, a deodorant and the like.
A gelling substrate made of a water absorbent resin composition in which an elastomer, rubber, etc. are mixed is used.

[0003] Fragrances, deodorants, etc. are often used indoors and in toilets, etc., and aesthetics are important. A gelling group that serves as a holder for the aromatics and deodorants as well as the container. There are many demands on the shape and color of materials.

As the water-absorbent resin used for such gelling base material, ionic water-absorbent resin, nonionic water-absorbent resin and the like are known. Since the water absorption mechanism of the ionic water-absorbent resin utilizes the osmotic pressure generated by the difference in ion concentration, when the liquid contains ions such as aroma components and deodorant components, the water absorption performance is Is extremely low, and the gel after absorbing water also has poor transparency, which is not aesthetically preferable. Therefore, it is necessary to reduce the concentrations of the fragrance component and the deodorant component to improve the water absorption performance.

Further, since the ionic water-absorbent resin does not have thermoplasticity, it is necessary to mix it with other thermoplastic resins and mold it into various shapes. However, when mixing the ionic water-absorbent resin and the thermoplastic resin, it is difficult to uniformly disperse the ionic water-absorbent resin, only the ionic water-absorbent resin swells after the resulting molded article absorbs water, There is a problem that the gel is separated from the molded body.

On the other hand, nonionic water-absorbent resins such as modified polyalkylene oxides have thermoplasticity and excellent moldability, and can be molded by various molding methods. Further, even when the liquid contains ions, the water absorption performance is not significantly deteriorated. However, in some molding methods, particularly in injection molding, the molding temperature is high and pressure is applied, so the polyalkylene oxide modified product decomposes,
When the obtained injection-molded body is used as a gelling base material, the shape of the gel may change when the gel obtained by absorbing the liquid is left for a long period of time, or the active ingredient may diffuse or have a short diffusion period. There is still room for improvement.

Further, when a resin composition containing these nonionic water-absorbent resin and another thermoplastic resin is molded and the molded body obtained is allowed to absorb water, gels such as those found in ionic water-absorbent resin are obtained. Does not occur. However, when a molded body obtained by injection molding of the resin composition is used as a gelling base material, the gel is cracked when the aqueous component evaporates, the surface area becomes large, and the diffusion / emission period of the active ingredient becomes short. At the same time, there is a problem that it is aesthetically unfavorable.

[0008]

DISCLOSURE OF THE INVENTION The object of the present invention is to provide a modified polyalkylene oxide having excellent injection moldability and a gel form which does not separate from the gel for a long period of time even after absorbing liquid, even after absorbing liquid. Another object of the present invention is to provide a gelling base material which can maintain its size for a long period of time and can diffuse and diffuse a fragrance component for a long time.

[0009]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the inventors have found that a specific polyalkylene oxide-modified product has excellent injection moldability, and
A gelling substrate comprising the polyalkylene oxide modified product and a gelling substrate comprising a water absorbent resin composition containing the polyalkylene oxide modified product and a specific ethylene-based copolymer in a specific amount even after absorbing liquid The present invention has been completed by finding that there is no separation of the gel for a long period of time, the shape and size of the gel can be maintained for a long period of time, and the aroma component can be diffused and diffused for a long period of time.

That is, according to the present invention, a mixture of 1 mol of polyalkylene oxide and 0.5 to 3 mol of polyol, and 0.8 to 1.2 based on the total number of mols of the polyalkylene oxide and the polyol. 170 ° C., 5MP obtained by reacting with a double mole of isocyanate compound
a melt viscosity at a load of 80 to 2000 Pa · s,
The present invention relates to a polyalkylene oxide modified product having a water absorption amount of 10 to 50 g / g and excellent in injection moldability, and a gelling base material comprising the modified product. The present invention also relates to a gelling substrate comprising a resin composition containing 100 parts by weight of the modified polyalkylene oxide and 30 to 130 parts by weight of an ethylene copolymer.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The polyalkylene oxide used in the present invention has a number average molecular weight of 5,000 to 3,000.
0 polyethylene oxide, polypropylene oxide,
Examples thereof include ethylene oxide / propylene oxide copolymers, polybutylene oxide and mixtures thereof. Among these, polyethylene oxide having a number average molecular weight of 5,000 to 30,000 and ethylene oxide / propylene oxide copolymer are preferably used from the viewpoint that the obtained polyalkylene oxide modified product is excellent in hydrophilicity. When the number average molecular weight is less than 5,000, the obtained polyalkylene oxide-modified product has high melt viscosity, and it is necessary to raise the molding temperature during injection molding.
Therefore, the polyalkylene oxide-modified product is decomposed and the resulting injection-molded product is colored, which is not preferable. When the number average molecular weight exceeds 30,000, the strength of the gel obtained by absorbing the obtained polyalkylene oxide modified product becomes weak, which is not preferable.

As the polyol used in the present invention,
Organic compounds having two hydroxyl groups (-OH) in the same molecule, for example, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, hexylene glycol, octy Examples thereof include len glycol, glyceryl monoacetate, glyceryl monobutyrate, 1,6-hexanediol and 1,9-nonanediol. Among these, 1,4-butanediol is preferably used from the viewpoint of compatibility with polyalkylene oxide and reactivity.

The amount of the polyol mixed is 0.5 to 3 times, preferably 1 to 2 times the mol of the polyalkylene oxide. When the amount of the polyol mixed is less than 0.5 times the molar amount, the strength of the gel obtained by absorbing the polyalkylene oxide-modified product obtained is weakened, which is not preferable. If the mixing amount of the polyol exceeds 3 times by mole, the melt viscosity of the obtained polyalkylene oxide modified product becomes high, and it is necessary to raise the molding temperature during injection molding. The obtained injection molded body is colored. In addition,
The number of moles of polyalkylene oxide can be determined by dividing its weight by the number average molecular weight.

The isocyanate compound used in the present invention includes an isocyanate group (-NCO) in the same molecule.
An organic compound having two or more of, for example, dicyclohexylmethane-4,4′-diisocyanate (HMDI),
Xylylene diisocyanate (XDI), 4,4'-diphenylmethane diisocyanate (MDI), 1,6-
Hexamethylene diisocyanate (HDI), 1,6-
Examples thereof include dimethyl benzene-2,4-diisocyanate and 2,4-tolylene diisocyanate (TDI). Among these, dicyclohexylmethane-4,4′-diisocyanate is preferably used from the viewpoint of excellent weather resistance and gel stability of the obtained gelling substrate.

The amount of the isocyanate compound used is 0.8 to 1.2 times, preferably 0.9 to 1.2 times the total number of moles of the polyalkylene oxide and the polyol.
It is 1.1 times the molar amount. When the amount of the isocyanate compound used is less than 0.8 times by mole, the strength of the gel obtained by absorbing the modified polyalkylene oxide-modified product is weakened. When the amount of the isocyanate compound used exceeds 1.2 times by mole, the melt viscosity of the obtained polyalkylene oxide modified product becomes high, and it is necessary to raise the molding temperature during injection molding. Therefore, the polyalkylene oxide modified product is required. And the resulting injection-molded body is colored.

As a method for reacting the mixture of the polyalkylene oxide and the polyol with the isocyanate compound, it is possible to react in a solution using a suitable solvent such as toluene, xylene or dimethylformamide. A method of reacting in a dispersed state or a method in which both are uniformly mixed in a powder form or a solid form and then heated to a predetermined temperature to react can be used. From the viewpoint of industrial implementation, a method in which the respective raw materials are continuously supplied in a molten state and mixed and reacted in a multi-screw extruder is preferable. The temperature of the above reaction is
Usually, it is desirable that the temperature is 70 to 210 ° C. In addition, triethylamine, triethanolamine, dibutyltin diacetate, dibutyltin dilaurate,
The reaction can also be promoted by adding a small amount of stannous octoate, triethylenediamine or the like.

The polyalkylene oxide-modified product obtained by the above-mentioned production method is usually obtained in the form of pellets, sheets, films and the like. The obtained polyalkylene oxide-modified product can be used in the form of pellets, sheets, films, etc., but may be crushed by a crusher or the like and used.

The melt viscosity of the polyalkylene oxide-modified product obtained by the present invention is 80 to 2000 Pa · s, preferably 100 to 1500 Pa · s. If the melt viscosity of the polyalkylene oxide-modified product is less than 80 Pa · s, the polyalkylene oxide-modified product may squeeze out of the mold during injection molding, resulting in excess polyalkylene oxide-modified product being attached to the injection-molded product, and moldability It becomes worse, and the strength of the gel obtained by absorbing the resulting polyalkylene oxide-modified product is weakened. If the melt viscosity of the polyalkylene oxide-modified product exceeds 2000 Pa · s, defective filling occurs during injection molding, and it is necessary to raise the molding temperature to solve the defective filling. The decomposition of the product and the coloring of the obtained injection molded product occur.

The melt viscosity in the present invention means a temperature of 170.
Viscosity when measured at a temperature of 5 ° C and a load of 5 MPa.
Specifically, 1.5 g of modified polyalkylene oxide
Flow tester (Shimadzu product name: CFT-
500C), measurement temperature 170 ° C, load 5MP
a, a value measured under conditions of a die diameter of 1 mm and a die length of 1 mm.

The water absorption of the polyalkylene oxide-modified product obtained by the present invention is 10 to 50 g / g, preferably 15 to 40 g / g. If the water absorption of the polyalkylene oxide-modified product is less than 10 g / g, the water absorption of the resulting polyalkylene oxide-modified product will be low, and the effect persistence of the fragrance component will be poor when used as a fragrance. When the water absorption of the polyalkylene oxide-modified product exceeds 50 g / g, the strength of the gel obtained by absorbing the polyalkylene oxide-modified product with liquid becomes weak.

The water absorption amount in the present invention means a value measured and calculated by the following method. First, 100m of deionized water
1 g of modified polyalkylene oxide was added to 1 and 2
Gently agitated for 4 hours to allow sufficient swelling. Next, the swollen gel was filtered through a JIS standard metal sieve having an opening of 75 μm whose weight (Wa) g was measured. The metal sieve containing the swollen gel was left for 30 minutes in an appropriately tilted state to remove excess water. Weight of metal sieve containing swollen gel (W
b) g was measured, and the water absorption amount was calculated from the following formula.

Water absorption (g / g) = [Wb-Wa] (g)
/ Weight of polyalkylene oxide modified product (g)

The gelled substrate of the present invention comprises the above-mentioned modified polyalkylene oxide, and can be obtained, for example, by injection-molding the modified polyalkylene oxide.

Examples of the method for injection-molding the polyalkylene oxide-modified product include a method using a plunger type injection molding machine, an in-line screw type injection molding machine and the like which are used for general thermoplastic resins. Among these, an inline screw type injection molding machine capable of uniformly melting is preferably used. Molding temperature is 1
00 ° C to 220 ° C is desirable. If the molding temperature is lower than 100 ° C., the flow into the mold may be poor, and filling failure may occur easily. If the molding temperature exceeds 220 ° C., the polyalkylene oxide-modified product may decompose and the viscosity may become too low, resulting in a state in which excess resin is attached to the outside of the mold. Injection conditions vary depending on the shape, wall thickness, size, and type of mold of the injection molded product,
Injection molding can be performed under the same conditions as general thermoplastic resins. The injection pressure is preferably in the range of 6 to 20 MPa.

The gelling substrate of the present invention also comprises a resin composition containing the above-mentioned modified polyalkylene oxide and a specific amount of an ethylene copolymer.

Examples of the ethylene-based copolymer used in the present invention include ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer, ethylene / acrylic acid copolymer, ethylene / ethyl acrylate copolymer and the like. Can be mentioned. Among these, ethylene / vinyl acetate copolymer, from the viewpoint of good compatibility with the modified polyalkylene oxide, and the obtained injection-molded article having excellent hydrophilicity,
An ethylene / vinyl alcohol copolymer is preferably used.

The ethylene-based copolymer is used in an amount of 30 with respect to 100 parts by weight of the modified polyalkylene oxide.
To 130 parts by weight, preferably 40 to 120 parts by weight, and more preferably 50 to 100 parts by weight. When the amount of the ethylene copolymer used is less than 30 parts by weight, the shape and size of the obtained gel are poor in long-term maintainability. When the amount of the ethylene-based copolymer used exceeds 130 parts by weight, the water absorption amount of the gelled base material obtained is low.

As the method for producing the resin composition, for example, a predetermined amount of a modified polyalkylene oxide or an ethylene copolymer is mixed using a mixer such as a Henschel mixer or a blender to prepare a mixture. Then, the obtained mixture is melt-kneaded by using various kneaders such as a kneader, a roll, and an extruder, and is molded into a desired shape, for example, a pellet shape. In addition, after melt-kneading, injection molding may be performed in a molten state.

Examples of the method of injection molding the obtained resin composition include a method of using a plunger type injection molding machine, an in-line screw type injection molding machine and the like which are used for general thermoplastic resins. Among these, an inline screw type injection molding machine capable of uniformly melting is preferably used. Molding temperature is 150 ℃ -220
℃ is desirable. If the molding temperature is lower than 150 ° C., the flow into the mold will be poor and there is a risk of defective filling. If the molding temperature exceeds 220 ° C., the polyalkylene oxide-modified product may decompose and the viscosity may become too low, resulting in a state in which excess resin is attached to the outside of the mold. The injection conditions differ depending on the shape, wall thickness, size, and type of mold of the injection-molded article, but injection molding can be performed under the same conditions as for a general thermoplastic resin. Injection pressure is 6
The range of ˜30 MPa is preferably used.

Further, in the gelling base material of the present invention, a compatibilizer for the purpose of improving the compatibility between the modified polyalkylene oxide and the ethylene copolymer, a stabilizer for the purpose of preventing the decomposition of the resin, and a weather resistance. An ultraviolet absorber may be added for the purpose of improving the properties, and a pigment or the like may be added for the purpose of coloring.

The gelled substrate obtained by the present invention is a gel capable of maintaining the shape and size of the gel for a long period of time even after absorbing liquid, maintaining the shape and size of the gel for a long period of time, and diffusing and releasing a fragrance component for a long period of time. give. Therefore, it is possible to use the fragrance alone as an interior of a figurine or the like without using a container or the like.

[0032]

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Further, the gelling base material made of the polyalkylene oxide modified product obtained in Examples and Comparative Examples, and the gelling base material made of the resin composition containing the polyalkylene oxide modified product were evaluated according to the following methods. . However, as to the method for preparing the liquid-absorbent gel obtained by absorbing the aromatic component in the gelled base material, the following preparation method was applied to both gelled base materials.

1. Preparation of absorbent gel 15 g of a gelling base material was placed in a 200 ml glass sample bottle with a lid, and an aromatic solution (propylene glycol: ethanol: sorbitan ester: lemon fragrance: pure water = 3: 5: 3: 5: 84). (Weight ratio)) 100 g was added, the lid was closed, and the aromatic component was absorbed to obtain a liquid absorbent gel.

2. Evaluation of Gelled Substrate Made of Polyalkylene Oxide Modified Product (1) Gel State The obtained absorbent gel was evaluated according to the following criteria, visually and by touch with a finger. ⊚: The shape of the gelled base material is maintained and swells, and there is no adhesion between gels. ◯: The shape of the gelled base material is maintained and swelled, but the gels are partially adhered to each other because they are soft. X: The gel is soft, the shape of the gelled substrate is broken, and the gels adhere to each other and are integrated.

(2) Shape retention The gel state of the obtained absorbent gel after standing at 25 ° C. for 2 months was visually observed and evaluated according to the following criteria. ◯: Swelling while maintaining the shape of the gelled substrate. X: The shape of the gelled substrate is broken.

(3) Sustainability of effect The obtained absorbent gel was allowed to stand at 25 ° C. for 2 months, and then the odor was evaluated according to the following criteria. Good: No change with the initial odor. X: There is no odor.

3. Evaluation of Gelling Substrate Made of Resin Composition Containing Polyalkylene Oxide Modified Product (1) Gel State The obtained liquid-absorbent gel was evaluated according to the following criteria visually and by touch with a finger. ⊚: The shape of the gelled base material is maintained and swells, and there is no adhesion between gels. ◯: The shape of the gelled base material is maintained and swelled, but the gels are partially adhered to each other because they are soft. X: The gel is soft, the shape of the gelled substrate is broken, and the gels adhere to each other and are integrated.

(2) Shape retention The gel state of the obtained absorbent gel after standing at 25 ° C. for 2 months was visually observed and evaluated according to the following criteria. ◯: Swelling while maintaining the shape and size of the gelled substrate. Δ: The shape of the gelled substrate is maintained, but the size is reduced. X: The shape of the gelled substrate is broken.

(3) Sustainability of effect The obtained absorbent gel was allowed to stand at 25 ° C. for 2 months, and then the odor was evaluated according to the following criteria. Good: No change with the initial odor. X: There is no odor.

Example 1 100 parts by weight of sufficiently dehydrated polyethylene oxide having a number average molecular weight of 20,000 and 1,2-butanediol 0.32 were placed in a storage tank A equipped with a stirrer and kept at 70 ° C.
Parts by weight and 0.1 part by weight of dibutyltin dilaurate were added and stirred in a nitrogen gas atmosphere to obtain a uniform mixture (1,4 mol per 1 mol of polyethylene oxide).
-Butanediol 0.7 mol). Apart from this, 30 ℃
Dicyclohexylmethane-4,4'-diisocyanate was put into the storage tank B kept at a temperature of 1 and stored under a nitrogen gas atmosphere.

Using a metering pump, the mixture in storage tank A at a rate of 420 g / min and dicyclohexylmethane-4,4'-diisocyanate in storage tank B at 7.45 g.
At a rate of 0.8 / min (0.8 times the moles of the total moles of polyethylene oxide and 1,4-butanediol).
The mixture was continuously fed to a twin-screw extruder set at ˜140 ° C., mixed and reacted in the extruder, a strand was discharged from the extruder outlet, and pelletized by a pelletizer to obtain a polyalkylene oxide-modified product. The obtained polyalkylene oxide modified product has a melt viscosity of 250 Pa · s and a water absorption of 4
It was 5 g / g.

The obtained polyalkylene oxide-modified product was subjected to in-line screw injection molding machine (screw diameter: 4
0 mm, mold clamping pressure; 40 t), molding temperature 170
Injection molding under conditions of ℃ and injection pressure 8MPa, diameter 10m
A spherical gelled substrate of m was obtained. With respect to the obtained gelled base material, the gel state, shape retention and effect persistence were evaluated by the above methods. The evaluation results are shown in Table 1.

Example 2 100 parts by weight of sufficiently dehydrated polyethylene oxide having a number average molecular weight of 20,000 and 0.54 of 1,4-butanediol were placed in a storage tank A equipped with a stirrer and kept at 70 ° C.
Parts by weight and 0.1 part by weight of dibutyltin dilaurate were added and stirred in a nitrogen gas atmosphere to obtain a uniform mixture (1,4 mol per 1 mol of polyethylene oxide).
-Butanediol 1.2 mol). Apart from this, 30 ℃
Dicyclohexylmethane-4,4'-diisocyanate was put into the storage tank B kept at a temperature of 1 and stored under a nitrogen gas atmosphere.

Using a metering pump, the mixture in storage tank A at a rate of 420 g / min and dicyclohexylmethane-4,4'-diisocyanate in storage tank B at 10.82.
at a rate of g / min (0.9 times mole based on total moles of polyethylene oxide and 1,4-butanediol)
Continuously feed to a twin-screw extruder set at 0 to 140 ° C,
Mixing and reaction were carried out in an extruder, a strand was taken out from the extruder outlet, and pelletized by a pelletizer to obtain a polyalkylene oxide modified product. The polyalkylene oxide-modified product thus obtained had a melt viscosity of 400 Pa · s and a water absorption of 40 g / g.

The polyalkylene oxide modified product thus obtained was subjected to in-line screw type injection molding machine (screw diameter: 4
0 mm, mold clamping pressure; 40 t), molding temperature 170
Injection molding under conditions of ℃ and injection pressure 9MPa, diameter 10m
A spherical gelled substrate of m was obtained. With respect to the obtained gelled base material, the gel state, shape retention and effect persistence were evaluated by the above methods. The evaluation results are shown in Table 1.

Example 3 100 parts by weight of sufficiently dehydrated polyethylene oxide having a number average molecular weight of 20,000 and 1,4-butanediol 0.81 were placed in a storage tank A equipped with a stirrer and kept at 70 ° C.
Parts by weight and 0.1 part by weight of dibutyltin dilaurate were added and stirred in a nitrogen gas atmosphere to obtain a uniform mixture (1,4 mol per 1 mol of polyethylene oxide).
-Butanediol 1.8 mol). Apart from this, 30 ℃
Dicyclohexylmethane-4,4'-diisocyanate was put into the storage tank B kept at a temperature of 1 and stored under a nitrogen gas atmosphere.

Using a metering pump, the mixture in storage tank A at a rate of 420 g / min and the dicyclohexylmethane-4,4'-diisocyanate in storage tank B at 16.79.
at a rate of g / min (1.1 times moles based on the total moles of polyethylene oxide and 1,4-butanediol)
Continuously feed to a twin-screw extruder set at 0 to 140 ° C,
Mixing and reaction were carried out in an extruder, a strand was taken out from the extruder outlet, and pelletized by a pelletizer to obtain a polyalkylene oxide modified product. The polyalkylene oxide-modified product thus obtained had a melt viscosity of 850 Pa · s and a water absorption of 30 g / g.

An in-line screw type injection molding machine (screw diameter; 4
0 mm, mold clamping pressure; 40 t), molding temperature 170
Injection molding under conditions of ℃ and injection pressure of 10 MPa, diameter 10
A spherical gelled substrate of mm was obtained. With respect to the obtained gelled base material, the gel state, shape retention and effect persistence were evaluated by the above methods. The evaluation results are shown in Table 1.

Example 4 100 parts by weight of sufficiently dehydrated polyethylene oxide having a number average molecular weight of 20,000 and 1,4-butanediol 1.26 were placed in a storage tank A equipped with a stirrer and kept at 70 ° C.
Parts by weight and 0.1 part by weight of dibutyltin dilaurate were added and stirred in a nitrogen gas atmosphere to obtain a uniform mixture (1,4 mol per 1 mol of polyethylene oxide).
-Butanediol 2.8 mol). Apart from this, 30 ℃
Dicyclohexylmethane-4,4'-diisocyanate was put into the storage tank B kept at a temperature of 1 and stored under a nitrogen gas atmosphere.

Using a metering pump, the mixture in storage tank A at a rate of 420 g / min and dicyclohexylmethane-4,4'-diisocyanate in storage tank B at 24.75.
at a rate of g / min (1.2 times moles based on the total moles of polyethylene oxide and 1,4-butanediol), 11
Continuously feed to a twin-screw extruder set at 0 to 140 ° C,
Mixing and reaction were carried out in an extruder, a strand was taken out from the extruder outlet, and pelletized by a pelletizer to obtain a polyalkylene oxide modified product. The polyalkylene oxide-modified product thus obtained had a melt viscosity of 1200 Pa · s and a water absorption of 15 g / g.

The obtained polyalkylene oxide-modified product was subjected to in-line screw injection molding machine (screw diameter: 4
0 mm, mold clamping pressure; 40 t), molding temperature 170
Injection molding under conditions of ℃ and injection pressure 12MPa, diameter 10
A spherical gelled substrate of mm was obtained. With respect to the obtained gelled base material, the gel state, shape retention and effect persistence were evaluated by the above methods. The evaluation results are shown in Table 1.

Example 5 In a storage tank A equipped with a stirrer kept at 70 ° C., 50 parts by weight of sufficiently dehydrated polyethylene oxide having a number average molecular weight of 20,000 and an ethylene oxide / propylene oxide copolymer having a molecular weight of 15,000 (= 80 / 20 (weight ratio) 50 parts by weight, 1.04 parts by weight of 1,4-butanediol and 0.1 parts by weight of dibutyltin dilaurate were added and stirred under a nitrogen gas atmosphere to obtain a uniform mixture (ethylene oxide). / 2 moles of 1,4-butanediol to 1 mole of propylene oxide copolymer). Separately from this, dicyclohexylmethane-4,4′-diisocyanate was put into a storage tank B kept at 30 ° C. and stored under a nitrogen gas atmosphere.

Using a metering pump, the mixture in storage tank A at a rate of 420 g / min and the dicyclohexylmethane-4,4'-diisocyanate in storage tank B at a rate of 19 g / min (1% ethylene oxide / propylene oxide copolymer). , 1-fold mol relative to the total mol number of 4-butanediol), continuously supplied to a twin-screw extruder set at 110 to 140 ° C., mixed and reacted in the extruder, and then stranded from the extruder outlet. Was taken out, pelletized by a pelletizer, and the obtained pellets were frozen and pulverized to obtain a polyalkylene oxide-modified product. The obtained polyalkylene oxide-modified product has a melt viscosity of 100 Pa · s and a water absorption of 30 g /
It was g.

The polyalkylene oxide modified product thus obtained was subjected to in-line screw type injection molding machine (screw diameter: 4
0 mm, mold clamping pressure; 40 t), molding temperature 170
Injection molding under conditions of ℃, injection pressure 7MPa, diameter 10m
A spherical gelled substrate of m was obtained. With respect to the obtained gelled base material, the gel state, shape retention and effect persistence were evaluated by the above methods. The evaluation results are shown in Table 1.

Comparative Example 1 100 parts by weight of sufficiently dehydrated polyethylene oxide having a number average molecular weight of 20,000 and 0.14 of 1,4-butanediol were placed in a storage tank A equipped with a stirrer and kept at 70 ° C.
Parts by weight and 0.1 part by weight of dibutyltin dilaurate were added and stirred in a nitrogen gas atmosphere to obtain a uniform mixture (1,4 mol per 1 mol of polyethylene oxide).
-Butanediol 0.3 mol). Apart from this, 30 ℃
Dicyclohexylmethane-4,4'-diisocyanate was put into the storage tank B kept at a temperature of 1 and stored under a nitrogen gas atmosphere.

Using a metering pump, the mixture in storage tank A at a rate of 420 g / min and dicyclohexylmethane-4,4'-diisocyanate in storage tank B at 4.28 g.
At a rate of 0.6 / mole (0.6 times the moles of the total moles of polyethylene oxide and 1,4-butanediol).
The mixture was continuously fed to a twin-screw extruder set at ˜140 ° C., mixed and reacted in the extruder, a strand was discharged from the extruder outlet, and pelletized by a pelletizer to obtain a polyalkylene oxide-modified product. The obtained modified polyalkylene oxide has a melt viscosity of 30 Pa · s and a water absorption of 52.
It was g / g.

The polyalkylene oxide modified product thus obtained was subjected to in-line screw type injection molding machine (screw diameter: 4
0 mm, mold clamping pressure; 40 t), molding temperature 170
Injection molding under conditions of ℃, injection pressure 5MPa, diameter 10m
A spherical gelled substrate of m was obtained. With respect to the obtained gelled base material, the gel state, shape retention and effect persistence were evaluated by the above methods. The evaluation results are shown in Table 1.

Comparative Example 2 100 parts by weight of sufficiently dehydrated polyethylene oxide having a number average molecular weight of 20,000 and 1,4-butanediol 1.44 were placed in a storage tank A equipped with a stirrer and kept at 70 ° C.
Parts by weight and 0.1 part by weight of dibutyltin dilaurate were added and stirred in a nitrogen gas atmosphere to obtain a uniform mixture (1,4 mol per 1 mol of polyethylene oxide).
-Butanediol 3.2 mol). Apart from this, 30 ℃
Dicyclohexylmethane-4,4'-diisocyanate was put into the storage tank B kept at a temperature of 1 and stored under a nitrogen gas atmosphere.

Using a metering pump, the mixture in storage tank A at a rate of 420 g / min and dicyclohexylmethane-4,4'-diisocyanate in storage tank B at 31.86.
at a rate of g / min (1.4 times moles based on the total moles of polyethylene oxide and 1,4-butanediol)
Continuously feed to a twin-screw extruder set at 0 to 140 ° C,
Mixing and reaction were carried out in an extruder, a strand was taken out from the extruder outlet, and pelletized by a pelletizer to obtain a polyalkylene oxide modified product. The polyalkylene oxide-modified product thus obtained had a melt viscosity of 4500 Pa · s and a water absorption of 9 g / g.

The polyalkylene oxide modified product thus obtained was subjected to in-line screw type injection molding machine (screw diameter: 4
0 mm, mold clamping pressure; 40 t), molding temperature 170
Injection molding under conditions of ℃ and injection pressure 21MPa, diameter 10
A spherical gelled substrate of mm was obtained. With respect to the obtained gelled base material, the gel state, shape retention and effect persistence were evaluated by the above methods. The evaluation results are shown in Table 1.

[0061]

[Table 1]

From Table 1, it was found that the gelled base materials obtained in Examples 1 to 5 had a good gel state and were excellent in shape retention and effect sustainability. On the other hand, Comparative Example 1
The gelled base materials obtained in Nos. 2 and 2 had a poor gel state and were inferior in shape retention and effect retention.

Example 6 100 parts by weight of the modified polyalkylene oxide obtained in Example 1 and an ethylene / vinyl acetate copolymer (trade name of Sumitomo Chemical Co., Ltd .: Evatate D2011)
40 parts by weight were kneaded with a single screw extruder to obtain a resin composition.
The obtained resin composition was injection-molded using an in-line screw injection molding machine (screw diameter: 40 mm, mold clamping pressure: 40 t) under conditions of a molding temperature of 170 ° C. and an injection pressure of 14 MPa, and a spherical gel having a diameter of 10 mm. The chemical base material was obtained.
About the obtained gelled substrate, gel state, shape retention,
The duration of effect was evaluated by the above method. The evaluation results are shown in Table 2.

Example 7 100 parts by weight of the modified polyalkylene oxide obtained in Example 2 and an ethylene / vinyl acetate copolymer (trade name of Sumitomo Chemical Co., Ltd .: Evatate D2011)
60 parts by weight and ethylene / vinyl alcohol copolymer (trade name of Kuraray Co., Ltd .: Eval EP-E105
B) 50 parts by weight were kneaded with a single screw extruder to obtain a resin composition. The obtained resin composition is processed with an in-line screw injection molding machine (screw diameter: 40 mm, mold clamping pressure: 40 t).
Was used for injection molding under the conditions of a molding temperature of 190 ° C. and an injection pressure of 20 MPa to obtain a spherical gelled substrate having a diameter of 10 mm. With respect to the obtained gelled base material, the gel state, shape retention and effect persistence were evaluated by the above methods. The evaluation results are shown in Table 2.

Example 8 100 parts by weight of the modified polyalkylene oxide obtained in Example 3 and an ethylene / vinyl acetate copolymer (Sumitomo Chemical Co., Ltd. trade name: Evatate D2011)
70 parts by weight were kneaded with a single screw extruder to obtain a resin composition.
The obtained resin composition was injection-molded using an in-line screw injection molding machine (screw diameter: 40 mm, mold clamping pressure: 40 t) under conditions of a molding temperature of 170 ° C. and an injection pressure of 14 MPa, and a spherical gel having a diameter of 10 mm. The chemical base material was obtained.
About the obtained gelled substrate, gel state, shape retention,
The duration of effect was evaluated by the above method. The evaluation results are shown in Table 2.

Example 9 100 parts by weight of the modified polyalkylene oxide obtained in Example 4 and an ethylene / vinyl acetate copolymer (trade name of Sumitomo Chemical Co., Ltd .: Evatate D2011)
40 parts by weight of ethylene / vinyl alcohol copolymer (trade name of Kuraray Co., Ltd .: Eval EP-E105
B) 40 parts by weight were kneaded with a single screw extruder to obtain a resin composition. The obtained resin composition is processed with an in-line screw injection molding machine (screw diameter: 40 mm, mold clamping pressure: 40 t).
Was used for injection molding under the conditions of a molding temperature of 190 ° C. and an injection pressure of 15 MPa to obtain a spherical gelled substrate having a diameter of 10 mm. With respect to the obtained gelled base material, the gel state, shape retention and effect persistence were evaluated by the above methods. The evaluation results are shown in Table 2.

Example 10 100 parts by weight of the modified polyalkylene oxide obtained in Example 5 and an ethylene / vinyl acetate copolymer (trade name of Sumitomo Chemical Co., Ltd .: Evatate D2011)
A resin composition was obtained by kneading 60 parts by weight with a single screw extruder.
The obtained resin composition was injection-molded using an in-line screw injection molding machine (screw diameter: 40 mm, mold clamping pressure: 40 t) under conditions of a molding temperature of 170 ° C. and an injection pressure of 12 MPa, and a spherical gel having a diameter of 10 mm. The chemical base material was obtained.
About the obtained gelled substrate, gel state, shape retention,
The duration of effect was evaluated by the above method. The evaluation results are shown in Table 2.

Comparative Example 3 100 parts by weight of the modified polyalkylene oxide obtained in Comparative Example 1 and an ethylene / vinyl acetate copolymer (trade name of Sumitomo Chemical Co., Ltd .: Evatate D2011)
40 parts by weight were kneaded with a single screw extruder to obtain a resin composition.
The obtained resin composition was injection-molded using an in-line screw injection molding machine (screw diameter: 40 mm, mold clamping pressure: 40 t) under conditions of a molding temperature of 170 ° C. and an injection pressure of 12 MPa, and a spherical gel having a diameter of 10 mm. The chemical base material was obtained.
About the obtained gelled substrate, gel state, shape retention,
The duration of effect was evaluated by the above method. The evaluation results are shown in Table 2.

Comparative Example 4 100 parts by weight of the modified polyalkylene oxide obtained in Comparative Example 1 and an ethylene / vinyl acetate copolymer (trade name of Sumitomo Chemical Co., Ltd .: Evatate D2011)
60 parts by weight and ethylene / vinyl alcohol copolymer (trade name of Kuraray Co., Ltd .: Eval EP-E105
B) 50 parts by weight were kneaded with a single screw extruder to obtain a resin composition. The obtained resin composition is processed with an in-line screw injection molding machine (screw diameter: 40 mm, mold clamping pressure: 40 t).
Was used for injection molding under the conditions of a molding temperature of 190 ° C. and an injection pressure of 22 MPa to obtain a spherical gelled substrate having a diameter of 10 mm. With respect to the obtained gelled base material, the gel state, shape retention and effect persistence were evaluated by the above methods. The evaluation results are shown in Table 2.

Comparative Example 5 In Example 6, ethylene / vinyl acetate copolymer (trade name of Sumitomo Chemical Co., Ltd .: Evatate D2011)
A spherical gelled substrate having a diameter of 10 mm was obtained in the same manner as in Example 6 except that the amount used was 5 parts by weight. With respect to the obtained gelled base material, the gel state, shape retention and effect persistence were evaluated by the above methods. The evaluation results are shown in Table 2.

Comparative Example 6 In Example 7, an ethylene / vinyl acetate copolymer (trade name of Sumitomo Chemical Co., Ltd .: Evatate D2011) was used.
80 parts by weight of ethylene / vinyl alcohol copolymer (trade name of Kuraray Co., Ltd .: Eval EP-E1
A spherical gelled substrate having a diameter of 10 mm was obtained in the same manner as in Example 7, except that the amount of 05B) used was changed to 70 parts by weight. With respect to the obtained gelled base material, the gel state, shape retention and effect persistence were evaluated by the above methods. The evaluation results are shown in Table 2.

[0072]

[Table 2]

From Table 2, it was found that the gelled base materials obtained in Examples 6 to 10 had a good gel state and were excellent in shape retention and effect sustainability. On the other hand, the gelled base materials obtained in Comparative Examples 3 to 6 were good in gel state, but poor in shape retention or effect retention.

[0074]

According to the present invention, a modified polyalkylene oxide having excellent injection moldability can be obtained. A gelled substrate made of the modified product, or a gelled substrate made of a resin composition containing the modified product and a specific ethylene copolymer, even after absorbing liquid, without separation of the gel for a long period of time, It gives a gel that can maintain the shape and size of the gel for a long period of time and can diffuse and diffuse aroma components for a long time.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4C080 AA04 CC01 CC13 HH04 LL07                       MM31 NN28                 4J034 BA08 CA04 CB03 CB07 CC03                       DB04 DC50 DG02 DG03 DG04                       DG09 DG10 HA01 HA06 HA07                       HC03 HC12 HC17 HC22 HC61                       HC64 HC67 HC71 HC73 JA02                       JA14 KA01 KB02 KC17 KD02                       KD12 KD27 KE02 QA05 QA07                       QB00 QB04 QB19 QC06 QD01                       RA17 RA19 SA02 SD03 SE01

Claims (7)

[Claims] 1. A mixture of 1 mol of polyalkylene oxide and 0.5 to 3 mol of polyol, and the total number of mols of the polyalkylene oxide and the polyol,
Obtained by reacting with 0.8 to 1.2 times mol of isocyanate compound, the melt viscosity at 170 ° C. and 5 MPa load is 80 to 2000 Pa · s, and the water absorption is 10 to 50.
A polyalkylene oxide-modified product having an excellent injection moldability of g / g. 2. The modified polyalkylene oxide according to claim 1, wherein the polyalkylene oxide is polyethylene oxide having a number average molecular weight of 5,000 to 30,000 or an ethylene oxide / propylene oxide copolymer. 3. The polyalkylene oxide-modified product according to claim 1, wherein the polyol is 1,4-butanediol. 4. The isocyanate compound is dicyclohexylmethane-4,4′-diisocyanate.
The modified polyalkylene oxide according to 1. 5. A mixture comprising 1 mol of polyalkylene oxide and 0.5 to 3 mol of polyol, and the total number of mols of the polyalkylene oxide and the polyol,
Obtained by reacting with 0.8 to 1.2 times mol of isocyanate compound, the melt viscosity at 170 ° C. and 5 MPa load is 80 to 2000 Pa · s, and the water absorption is 10 to 50.
A gelling base material made of a polyalkylene oxide-modified product having an excellent injection moldability of g / g. 6. A mixture comprising 1 mol of polyalkylene oxide and 0.5 to 3 mol of polyol, and the total number of mols of the polyalkylene oxide and the polyol,
Obtained by reacting with 0.8 to 1.2 times mol of isocyanate compound, the melt viscosity at 170 ° C. and 5 MPa load is 80 to 2000 Pa · s, and the water absorption is 10 to 50.
100 parts by weight of a polyalkylene oxide-modified product having an excellent injection moldability of g / g, and an ethylene-based copolymer 30-
A gelled substrate comprising a resin composition containing 130 parts by weight. 7. A liquid-absorbent gel obtained by absorbing an aromatic component into the gelled substrate according to claim 5 or 6.