JPWO2014087839A1 - Water absorbent resin composition - Google Patents

Abstract

The water absorbent resin composition includes a water absorbent resin and a hydrophobic bitter emetic agent such as brucine or octaacetylated sucrose. Since this water-absorbent resin composition can cause bitterness when an infant or the like accidentally puts it in the mouth, and can be discharged by the emetic effect, it can suppress accidental ingestion or accidental eating. In addition, since this water-absorbent resin composition uses a hydrophobic bitter emetic, separation due to outflow of the bitter emetic is suppressed even when the water absorbs water in contact with a liquid such as a body fluid. Can be maintained.

Description

  The present invention relates to a water-absorbing resin composition, and more particularly to a water-absorbing resin composition capable of suppressing accidental ingestion or accidental eating.

  Water-absorbing resin that can absorb water several hundred to several thousand times its own weight is a food freshness such as sanitary materials such as disposable diapers, sanitary napkins and incontinence pads, urine absorbing materials for pets, drip absorbing materials and cold insulation materials. It is used in various fields such as holding materials, gel fragrances, daily goods such as cooling bands, and learning materials.

  Since the water-absorbent resin is generally in the form of powder or granules, various absorbent articles using it are generally a liquid-permeable sheet (so-called top sheet) and a liquid-impermeable sheet (so-called back sheet). The water-absorbent resin is held between and packaged (see, for example, Patent Document 1). Since such an absorbent article is formed in a certain size according to the purpose of use, there is little possibility of accidental ingestion or accidental eating.

  However, an infant who uses a paper diaper, which is a form of absorbent article, may be interested in familiar items and dismantle the paper diaper. In general, infants tend to put anything in their mouths, and their ability to make judgments is not sufficient, so there is a risk of accidentally ingesting or accidentally eating water-absorbing resin that has leaked from a disassembled paper diaper.

  On the other hand, in elderly people, prejudice and carelessness may occur due to a decline in cognitive ability due to the elderly, and there is a risk of accidents in which the water-absorbent resin is accidentally swallowed or accidentally eaten with food or medicine such as jelly.

  In addition, there is a possibility that an accident such that a pet or other animal accidentally swallows or miseats a urine absorbing material itself such as a pet sheet or a water absorbent resin.

  In general, water-absorbing resins are made from materials that are not toxic to the body, and even if they are accidentally swallowed or accidentally eaten, they are discharged as they are, so that they are safe from a chemical or biological point of view. It is understood.

  However, since the water-absorbing resin expands due to water absorption, there is a risk of obstructing the digestive system, for example, the esophagus and the intestine, if a large amount is accidentally swallowed or accidentally eaten. Moreover, even if the amount is small, anxiety about the fact of accidental ingestion or accidental eating is difficult to be resolved.

WO2012 / 108253 publication

  The present invention is intended to enhance the safety of the water-absorbent resin when it is accidentally put into the mouth.

  The water absorbent resin composition of the present invention includes a water absorbent resin and a hydrophobic bitter emetic.

  The water-absorbent resin composition of the present invention makes it possible to feel bitterness when humans or animals accidentally put it in their mouths, and to vomit due to an emetic effect, thereby preventing accidental ingestion or accidental eating. In addition, since this water-absorbent resin composition uses a hydrophobic bitter emetic, even when it absorbs water in contact with a liquid such as body fluid, separation due to outflow of the bitter emetic is suppressed, and the required The effect can be maintained.

  The water absorbent resin composition of the present invention usually contains at least 0.005 parts by mass of a bitter emetic agent with respect to 100 parts by mass of the water absorbent resin.

  Moreover, the bitter emetic used in the water absorbent resin composition of the present invention is, for example, at least one of brucine and octaacetylated sucrose.

  An example of the method for producing the water-absorbent resin composition of the present invention includes a step of spraying a water-absorbent resin with an alcohol solution of a hydrophobic bitter emetic and then drying it.

  Another example of the method for producing the water-absorbent resin composition of the present invention is that the water-absorbent resin and an alcoholic solution of a hydrophobic bitter emetic are added to a non-polar solvent that hardly swells the water-absorbent resin and stirred and mixed. And removing the nonpolar solvent from the resulting mixture.

  The water absorbent resin composition of the present invention contains a water absorbent resin and a bitter emetic.

  The water-absorbent resin used in the composition of the present invention is not particularly limited, and various known ones. For example, a crosslinked product of partially neutralized acrylic acid polymer, a crosslinked product of starch-acrylate graft copolymer, a crosslinked product of vinyl alcohol-acrylate copolymer, a crosslinked product of maleic anhydride grafted polyvinyl alcohol, A saponified product of a crosslinked isobutylene-maleic anhydride copolymer or vinyl acetate-acrylic acid ester copolymer can be used. Among these water-absorbing resins, a large amount of liquid can be absorbed, and the absorbed liquid can be retained in the resin even when a certain load is applied. Is preferred.

  Two or more types of water-absorbing resins can be used in combination.

  The production method of the water-absorbent resin is not particularly limited, and those produced by various known methods including a reverse phase suspension polymerization method and an aqueous solution polymerization method can be used.

  As the water-absorbing resin, particles such as powder and granules are usually used. The water-absorbent resin may be obtained in the form of particles depending on the selection of the production method. However, when the water-absorbent resin is obtained in the form of a lump, the water-absorbent resin can also be made into particles by pulverization as appropriate.

  Bitter taste emetics are known to be hydrophilic, such as hydrophilic alkaloids such as denatonium benzoate and caffeine, and amino acids such as leucine and isoleucine, and hydrophobic.

  When a hydrophilic bitter emetic is used in the water absorbent resin composition, when a liquid such as a body fluid comes into contact with the water absorbent resin composition, the bitter emetic dissolves and flows out, and the bitter emetic is separated from the water absorbent resin. Therefore, it is difficult to maintain the required bitterness and emetic action in the water absorbent resin composition. Further, when the hydrophilic bitter emetic is separated from the water-absorbent resin and flows out, the hydrophilic bitter emetic can diffuse throughout the absorbent article and adhere to the user's skin, possibly causing skin damage.

  On the other hand, since the hydrophobic bitter emetic is difficult to dissolve in the liquid even when the water absorbent resin composition comes into contact with a liquid such as a body fluid, it is difficult to separate from the water absorbent resin.

  For the above reasons, a hydrophobic bitter emetic is used in the water absorbent resin composition of the present invention.

  The hydrophobic bitter emetic used in the composition of the present invention preferably exhibits an effective bitter emetic effect when used in a small amount. Such bitter emetics include, for example, terpenes such as brucine, theobromine, capsaicin, quinine, quinidine, cinchonine, berberine, nigaquinone, hydrophobic alkaloids such as methylnigaquinone, paraxatin and theophylline, cucurbitacin, cassiine and abstintin. And octaacetylated sucrose. Among these, brucine or octaacetylated sucrose is preferable because it is easily available industrially.

  Two or more bitter emetics can be used in combination.

  The content of the bitter emetic in the water-absorbent resin composition is usually the water-absorbent resin from the viewpoint of making it feel the required bitter taste and expressing the emetic action by just using a trace amount of the water-absorbent resin composition. The amount is preferably set to at least 0.005 parts by mass with respect to 100 parts by mass, and more preferably set to at least 0.01 parts by mass. The upper limit of the content of the bitter emetic is not particularly limited, but is usually preferably set to 1 part by mass or less in order to make it difficult to impair the liquid absorption performance of the entire water absorbent resin composition.

  The water-absorbent resin composition of the present invention makes it possible to feel bitterness when humans or animals accidentally put it in their mouths, and to vomit due to an emetic effect, thereby preventing accidental ingestion or accidental eating. In addition, since this water-absorbent resin composition uses a hydrophobic bitterness emetic, separation due to outflow of the bitter emetic is suppressed even when water is absorbed in contact with liquids such as body fluids and beverages. The required effect can be maintained.

  The water absorbent resin composition preferably has a bitter emetic on the particle surface of the water absorbent resin in order to effectively give a bitter taste and an emetic action with a slight amount. . For this reason, the water-absorbing resin composition is usually preferably produced by a production method in which the water-absorbing resin is surface-treated with a hydrophobic bitter emetic.

  As such a manufacturing method, the following manufacturing method 1 and manufacturing method 2 can be mentioned, for example. In any of the production methods, the water-absorbing resin is preferably adjusted to have a moisture content of 1 to 30% by mass, particularly 5 to 15% by mass in consideration of the efficiency of the surface treatment. The moisture content of the water-absorbent resin here is a value when measured according to the method described in Examples below.

<Manufacturing method 1>
In this production method, a water-absorbing resin is sprayed and mixed with an alcohol solution of a hydrophobic bitter emetic agent and then dried.

  Alcohols used for preparing a hydrophobic bitter emetic alcohol solution are those having good bitter emetic solubility and wettability to water-absorbent resins, such as methyl alcohol, ethyl alcohol, propyl alcohol Or lower alcohols, such as isopropyl alcohol, are preferable. The amount of alcohol used is preferably set to 1 to 50 parts by mass, more preferably 3 to 40 parts by mass, and 5 to 40 parts by mass with respect to 100 parts by mass of the water absorbent resin. Is particularly preferred.

<Manufacturing method 2>
In this production method, a water-absorbing resin and an alcohol solution of a hydrophobic bitter emetic are added to a non-polar solvent and mixed with stirring, and the resulting mixture is subjected to distillation at normal pressure or reduced pressure. The nonpolar solvent is removed by the method.

  The nonpolar solvent used in this method is difficult to swell the water absorbent resin. Examples of such nonpolar solvents include aliphatic hydrocarbons such as n-hexane, n-heptane and n-octane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, and aromatics such as benzene and xylene. There may be mentioned hydrocarbons. Of these, n-hexane, n-heptane or cyclohexane is particularly preferred because it is easily available industrially, has stable quality, and is inexpensive.

  Usually, it is preferable to set the usage-amount of a nonpolar solvent to 50-600 mass parts with respect to 100 mass parts of water absorbing resin, and it is more preferable to set to 80-550 mass parts.

  The alcohols used for preparing the alcoholic solution of the bitter emetic and the amount of use thereof are the same as in Production Method 1.

  Hereinafter, the present invention will be described in more detail based on synthesis examples, examples, and comparative examples, but the present invention is not limited to these examples.

Synthesis Example A 2 L round bottom cylindrical separable flask equipped with a stirrer, a two-stage paddle blade, a reflux condenser, a dropping funnel and a nitrogen gas introduction tube was prepared. 321 g of n-heptane was poured into this separable flask, and 0.92 g of sucrose stearate (trade name “Ryoto Sugar Ester S-370” from Mitsubishi Chemical Foods Co., Ltd.) was added thereto and stirred for 80 After dissolving by raising the temperature to 0 ° C., it was cooled to 50 ° C.

  On the other hand, 92.0 g of an 80% by mass acrylic acid aqueous solution was poured into a 500 mL Erlenmeyer flask, and 146.0 g of a 21% by mass sodium hydroxide aqueous solution was added dropwise while cooling this from the outside. The sum was done. Next, 0.11 g of potassium persulfate as a radical polymerization initiator and 9.2 mg of N, N′-methylenebisacrylamide as an internal crosslinking agent were added to an Erlenmeyer flask and dissolved to prepare an aqueous monomer solution.

  The total amount of the prepared monomer aqueous solution was added to a separable flask, and the system was sufficiently replaced with nitrogen. And it heated by immersing a separable flask in a 70 degreeC water bath, and superposition | polymerization was performed for 30 minutes.

  Next, the separable flask was heated by being immersed in an oil bath at 125 ° C., and 116.0 g of water was extracted out of the system while refluxing n-heptane by azeotropic distillation of n-heptane and water. Thereafter, 3.68 g of a 2% by weight aqueous solution of ethylene glycol diglycidyl ether was added to the reaction system and held at 80 ° C. for 2 hours. Subsequently, the separable flask was heated by being immersed in an oil bath at 120 ° C., and n-heptane and water were removed out of the system by distillation. When the residue in the separable flask was dried under a nitrogen stream, 98.2 g of a spherical and powdery water-absorbing resin was obtained. It was 8.9 mass% when the moisture content of this water absorbing resin was measured by the following method.

  About 2 g of the obtained water-absorbing resin was precisely weighed (Wa (g)) in a pre-weighed aluminum wheel case (No. 8). The precisely weighed water-absorbing resin is placed in a hot air dryer (ADVANTEC Co., Ltd.) with an aluminum wheel case set to an internal temperature of 105 ° C. for 2 hours, dried, allowed to cool in a desiccator, and dried. The mass Wb (g) of the conductive resin was measured. The water content of the water absorbent resin was calculated from the following formula.

Example 1
A 300 mL four-necked flask equipped with a reflux condenser, a dropping funnel, a nitrogen gas introduction tube, a stirrer and a stirring blade was prepared, and 50 g of the water-absorbent resin obtained in the same manner as in the synthesis example and n-heptane were prepared in this flask. 80 g was added. To this, 2.5 g of 0.1 mass% ethanol solution of brucine anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), which is a hydrophobic bitter emetic, was added and sufficiently stirred and mixed. This mixture was heated using an oil bath at 100 ° C. to remove n-heptane by distillation to obtain 50.0 g of a water-absorbent resin composition.

Example 2
To 50 g of the water-absorbing resin obtained in the same manner as in the synthesis example, 5.0 g of 0.1 mass% ethanol solution of brucine anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), which is a hydrophobic bitter emetic, is directly sprayed. And mixed thoroughly. And this mixture was dried by heating in a 100 ° C. oil bath for 30 minutes to obtain 50.0 g of a water absorbent resin composition.

Example 3
In place of the ethanol solution of brucine anhydride, 10.0 g of a 5% by mass ethanol solution of octaacetylated sucrose (trade name “Monopet SOA” from Daiichi Kogyo Seiyaku Co., Ltd.), which is a hydrophobic bitter emetic, was used. Except for the points, the same operation as in Example 2 was performed to obtain 50.5 g of a water absorbent resin composition.

Comparative Example 1
The water absorbent resin of Synthesis Example was used as it was as a water absorbent resin composition.

Comparative Example 2
The same operation as in Example 2 was performed except that 5.0 g of a 0.1% by weight aqueous solution of caffeine (manufactured by Tokyo Chemical Industry Co., Ltd.), which is a hydrophilic bitter emetic, was used instead of an ethanol solution of brucine anhydride. As a result, 50.0 g of a water absorbent resin composition was obtained.

About the water absorbing resin composition obtained by the evaluation example and the comparative example, the bitter taste emetic test before water absorption and after water absorption was implemented with the following method.

<Bitter taste emeticity before water absorption>
The strength of bitterness when the water-absorbent resin composition was directly included in the mouth was determined by five panelists according to the following criteria, and bitter emeticity was evaluated by the average value. The results are shown in Table 1.
5: Feels a strong bitterness 3: Feels a bitter taste 1: Feels little bitterness 0: Feels no bitterness

<Bitter taste emetic properties after water absorption>
In a 500 mL beaker, weigh 500 g of 0.9 mass% sodium chloride aqueous solution (saline) and add 2.0 g of the water-absorbent resin composition with stirring at 600 rpm to disperse it so as not to generate mako. It was. And the stirring state was maintained for 60 minutes and the water absorbing resin composition was fully swollen. Thereafter, the contents of the beaker are filtered using a standard sieve having a mesh opening of 75 μm, and left for 30 minutes in a state where the sieve is inclined at an inclination angle of about 30 degrees with respect to the horizontal. Excess water was filtered off. The panelists of the five panelists judged the strength of bitterness when the water-absorbing resin composition after water absorption obtained in this way was included in the mouth according to the same standard as bitter emeticity before water absorption, and the average value thereof Bitter taste emetic properties were evaluated. The results are shown in Table 1.

  The usage amount (parts by mass) of the bitter emetic agent shown in Table 1 is a conversion value with respect to 100 parts by mass of the water absorbent resin.

  As is apparent from Table 1, the water-absorbent resin compositions of Examples 1 to 3 felt bitter and exhibited emetic properties, and the same effect persisted after water absorption. On the other hand, the water absorbent resin composition of Comparative Example 1 does not give a bitter taste, and the water absorbent resin composition of Comparative Example 2 uses caffeine, which is a hydrophilic bitter emetic. Therefore, the bitterness after water absorption and the emetic effect are significantly reduced.

  The present invention can be implemented in various other forms without departing from the spirit or main features thereof. Therefore, the above-described embodiment or example is merely an example in all respects and should not be interpreted in a limited manner. The scope of the present invention is indicated by the scope of claims, and is not restricted to the text of the specification. Further, all modifications and changes belonging to the equivalent scope of the claims are within the scope of the present invention.

Claims (5)

A water absorbent resin,
A hydrophobic bitter emetic,
A water-absorbent resin composition comprising:   The water-absorbent resin composition according to claim 1, comprising at least 0.005 parts by mass of the bitter emetic agent with respect to 100 parts by mass of the water-absorbent resin.   The water-absorbent resin composition according to claim 1 or 2, wherein the bitter emetic is at least one of brucine and octaacetylated sucrose.   The manufacturing method of the water absorbing resin composition of Claim 1 including the process of spraying and mixing the alcoholic solution of hydrophobic bitter emetic to a water absorbing resin, and then drying. Adding a water-absorbing resin and an alcoholic solution of a hydrophobic bitter emetic to a non-polar solvent that hardly swells the water-absorbing resin, and stirring and mixing;
Removing the nonpolar solvent from the resulting mixture;
The manufacturing method of the water absorbing resin composition of Claim 1 containing this.