JP6108459B2 - Disinfectant impregnated carrier and process - Google Patents

Description

  The present invention relates to a disinfectant-impregnated carrier for impregnating a cationic disinfectant and a method for producing the same.

  Conventionally, for example, when sterilizing or disinfecting the outer skin, a carrier comprising a cellulosic fiber is impregnated with a solution containing a cationic disinfectant such as chlorhexidine gluconate (CHG) or benzalkonium chloride (BAC). use.

  However, when a carrier made of cellulosic fibers is impregnated with a cationic disinfectant, the cationic disinfectant is adsorbed on the cellulosic fibers.

  Such adsorption of the cationic disinfectant by the cellulosic fiber is considered to be due to a naturally-occurring carboxyl group in cellulose or a carboxyl group generated by oxidation of the 6-position hydroxyl group in the cellulose molecule in the bleaching step. That is, it is considered that the cationic disinfectant is adsorbed by electrical interaction because cellulose is negatively charged by the carboxyl group.

  Here, the adsorption of the cationic disinfectant has an upper limit in the amount of adsorption and is adsorbed only within a predetermined range. Therefore, when the cationic disinfectant has a high concentration, even if a certain amount of the cationic disinfectant is adsorbed, the relative concentration does not decrease and the disinfecting effect hardly decreases. On the other hand, when the cationic disinfectant is at a low concentration, if a certain amount of the cationic disinfectant is adsorbed, the concentration is greatly affected, and the concentration is relatively lowered and the disinfecting effect decreases. End up.

  Therefore, a configuration is known in which adsorption of a cationic disinfectant to a carrier is prevented by adding a divalent or higher metal salt to the cationic disinfectant (see, for example, Patent Document 1).

  Moreover, the structure which prevents adsorption | suction of a cationic disinfectant is known by using synthetic fibers, such as polyester and polyethylene with few surfactant, instead of a cellulose fiber as a support | carrier (for example, refer patent document 2). .)

  Furthermore, a method of preventing the adsorption of the cationic disinfectant by suppressing the oxidation of the cellulosic fibers by selecting the type of the bleach used in the bleaching process is known (for example, see Non-Patent Document 1). .

Japanese Patent Laid-Open No. 50-18618 JP 2005-13309 A

Haruhiko Tsujimoto, 2 others, “Selection of bleaching agent in absorbent cotton manufacturing process considering drug adsorption”, Hospital Pharmacy, 1999, vol. 25, no. 6, p. 614-620

  However, since the structure of Patent Document 1 described above may have various side effects such as irritation to the skin depending on the metal salt to be added, it is not suitable as a disinfectant-impregnated carrier used for skin disinfectants and the like. It is not considered.

  Moreover, even if it suppresses use of surfactant in the structure of the above-mentioned patent document 2, since a small amount of surfactant is contained, when the density | concentration of a cationic disinfectant is low, a cationic disinfectant The concentration of will decrease. In addition, when the surfactant is removed by washing or the like, the synthetic resin such as polyester cannot absorb the solution by the fiber itself and has water repellency, so it becomes difficult to hold the disinfectant on the carrier, There is a possibility that proper impregnation may not be possible.

  In the bleaching agent described in Non-Patent Document 1 described above, there are cases where cellulosic fibers cannot be sufficiently bleached. In addition, it is possible that adsorption of cationic disinfectants cannot be sufficiently prevented because the oxidation of cellulosic fibers is only suppressed by selecting the type of bleaching agent, but not the oxidation itself. .

  Therefore, for example, a carrier for disinfection impregnation that can be used for sterilization and disinfection of the outer skin and can not only properly impregnate the cationic disinfectant but also prevent adsorption of the cationic disinfectant when impregnated with the cationic disinfectant. Was demanded.

  The present invention has been made in view of these points, and an object thereof is to provide a disinfectant-impregnated carrier capable of preventing adsorption of a cationic disinfectant and a method for producing the same.

  The disinfectant-impregnated carrier according to claim 1 is a disinfectant-impregnated carrier for impregnating a cationic disinfectant, wherein a carboxyl group is bonded to a hydroxyl group in a cellulose molecule or a hydroxyl group between cellulose molecules. It is composed of esterified cellulosic fibers.

  The disinfectant-impregnated carrier according to claim 2 is the disinfectant-impregnated carrier according to claim 1, wherein the cellulosic fiber is a degreased and bleached natural cellulosic fiber or a regenerated cellulosic fiber. It is.

  The disinfectant-impregnated carrier according to claim 3 is the disinfectant-impregnated carrier according to claim 1 or 2, wherein the cationic disinfectant to be impregnated has an impregnation liquid amount of 3 ml / g or more and 15 ml / g or less, The concentration is 0.001 w / v% or more and 5 w / v% or less.

A method for producing a disinfectant-impregnated carrier according to claim 4 is a method for producing a disinfectant-impregnated carrier according to any one of claims 1 to 3, wherein a carrier comprising a cellulose fiber having a carboxyl group is used. The acid solution is immersed in at least one acid solution of hydrochloric acid, sulfuric acid, nitric acid, thionyl chloride, citric acid, phosphoric acid and acetic acid having an acid concentration of 0.0001 mol / L or more and 1 mol / L or less. the the carrier Ru der which water washing treatment.

A method for producing a disinfectant-impregnated carrier according to claim 5 is a method for producing a disinfectant-impregnated carrier according to any one of claims 1 to 3, wherein a carrier comprising a cellulose-based fiber having a carboxyl group is used. , Hydrochloric acid, sulfuric acid, nitric acid, thionyl chloride, citric acid, phosphoric acid and acetic acid are immersed in a mixed solution of an acid and an organic solvent, and the carrier containing this mixed solution is washed with water.

The method for producing a disinfectant-impregnated carrier according to claim 6 is the method for producing a disinfectant-impregnated carrier according to claim 5, wherein the organic solvent is a polar organic solvent or an aprotic organic solvent. A single organic solvent, or a mixed organic in which any one of a polar organic solvent and an aprotic organic solvent is mixed with at least one of a polar organic solvent, an aprotic organic solvent, and a nonpolar organic solvent It is a solvent.

Method for producing a disinfectant-impregnated carrier according to claim 7 is a method of manufacturing a disinfectant-impregnated carrier according to claim 5 or 6, wherein the acid is one that is strong.

The method for producing a disinfectant-impregnated carrier according to claim 8 is the method for producing a disinfectant-impregnated carrier according to any one of claims 5 to 7, wherein the mixed solution has an acid concentration of 0.0001 mol / L. The above is less than 0.1 mol / L.

  According to the invention described in claim 1, since the carboxyl group is esterified by bonding with a hydroxyl group in the cellulose molecule or a hydroxyl group between the cellulose molecules, the cellulose is hardly negatively charged, and the cationic disinfectant Adsorption can be prevented.

  According to the invention described in claim 2, even if the cellulosic fiber is natural cellulosic fiber or regenerated cellulosic fiber, the carboxyl group can be esterified to prevent adsorption of the cationic disinfectant.

  According to the invention described in claim 3, when impregnating liquid is impregnated with a cationic disinfectant having a concentration range of 0.001 w / v% or more and 5 w / v% or less with an amount of impregnation liquid of 3 ml / g or more and 15 ml / g or less. In addition, a decrease in the concentration of the cationic disinfectant can be effectively prevented.

  According to the invention described in claim 4, since the acid concentration is 0.0001 mol / L or more, the carboxyl group of the cellulosic fiber can be esterified, and adsorption of the cationic disinfectant can be prevented. In addition, since the acid concentration is 1 mol / L or less, deterioration of the carrier can be prevented.

In addition, since the acid is at least one of hydrochloric acid, sulfuric acid, nitric acid, thionyl chloride, citric acid, phosphoric acid and acetic acid, the carboxyl group of the cellulosic fiber can be esterified, and adsorption of the cationic disinfectant can be prevented. .

According to the invention described in claim 5 , since the carrier is immersed in the mixed solution, the carboxyl group of the cellulosic fiber can be esterified more effectively, and adsorption of the cationic disinfectant can be prevented.

According to the invention described in claim 6 , the organic solvent is either a single organic solvent composed of either a polar organic solvent or an aprotic organic solvent, or a polar organic solvent and an aprotic organic solvent. Because it is a mixed organic solvent that is mixed with at least one of polar organic solvent, aprotic organic solvent and nonpolar organic solvent, it can prevent adsorption of cationic disinfectant and prevent carrier deterioration It's easy to do.

According to the invention described in claim 7 , since the acid is a strong acid, the carboxyl group of the cellulosic fiber can be esterified more effectively, and adsorption of the cationic disinfectant can be prevented.

According to the invention described in claim 8 , since the acid concentration is 0.0001 mol / L or more, the carboxyl group of the cellulose fiber can be esterified, and adsorption of the cationic disinfectant can be prevented. In addition, since the acid concentration is less than 0.1 mol / L, deterioration of the carrier can be prevented.

It is a graph which shows the relationship between the solution temperature and the non-adsorption rate in Example 6 and Comparative Example 6. It is a graph which shows the relationship between the non-adsorption rate and logarithm value of immersion time in Example 7 and Comparative Example 7.

  Hereinafter, a first embodiment of the present invention will be described in detail.

  The disinfectant-impregnated carrier according to the present embodiment is impregnated with a cationic disinfectant such as chlorhexidine gluconate (CHG) or benzalkonium chloride (BAC), for example, when sterilizing or disinfecting the outer skin. It is what is done.

  This disinfectant-impregnated carrier is made of cellulosic fibers in which carboxyl groups are esterified.

  Cellulosic fibers include, for example, degreased and bleached natural cellulosic fibers such as cotton wool, degreased and bleached regenerated cellulosic fibers such as cupra, lyocell, rayon and acetate, and chemical fibers in the regenerated cellulose fibers. A composite cellulosic fiber is used.

  Cupra is manufactured by using short fibers (linter) remaining after removing cotton from real cotton as raw pulp, dissolving it in copper ammonia solution and spinning it as spinning solution, coagulating and regenerating cellulose. .

  The lyocell is produced by dissolving pulp with a special solvent and spinning it to coagulate and regenerate cellulose.

  Rayon reacts plant raw materials such as wood pulp and bamboo with alkali and carbon disulfide, dissolves them in an alkaline aqueous solution, extrudes them into a sulfuric acid aqueous solution from the base, and stretches them to solidify and regenerate the cellulose (cellulose). It is manufactured.

  Acetate is produced by coagulating and regenerating acetylcellulose subjected to acetic acid reaction using wood pulp as a raw material.

  The composite cellulosic fiber is formed by mixing a synthetic resin such as polyethylene terephthalate (PET), polyethylene (PE), and polypropylene (PP) with rayon, which is a regenerated cellulosic fiber, for example.

Then, by immersing a carrier made of cellulose fiber having such a carboxyl group in an acid solution, the carboxyl group of the cellulose fiber is esterified, and the carrier containing the acid solution is washed with water, and a disinfectant An impregnation carrier is produced.

  Here, cellulose is represented by the chemical formula shown in Chemical Formula 1.

  When cellulose is oxidized by bleaching of the carrier or the like, the 6-position hydroxyl group (CH 2 OH) is oxidized, and a carboxyl group (COOH) is generated as in the chemical formula shown in Chemical Formula 2.

  When the carrier is immersed in an acid solution in a state in which the carboxyl group is generated, either the 6-position carboxyl group and the 2,3,6-hydroxyl group are ester-bonded in the cellulose molecule as shown in Chemical Formula 3, or As shown in FIG. 4, ester bonds are formed between cellulose molecules. Therefore, the carboxyl group is esterified and substituted with another substituent.

The mechanism of a chemical reaction in which a carboxyl group is esterified in the presence of such an acid (H ⁺ ) is that a carboxyl group (COOH) is produced by the reversible reaction shown in Chemical Formula 5 continuously occurring using an acid as a catalyst. The reaction is based on the formation of ester (COOR).

  As the acid of the acid solution for esterifying the carboxyl group, it is preferable to use at least one of hydrochloric acid, sulfuric acid, nitric acid, thionyl chloride, citric acid, phosphoric acid and acetic acid.

  Further, when the acid concentration of the acid solution is less than 0.0001 mol / L, there is a possibility that the effect of preventing adsorption due to esterification of the carboxyl group may be difficult. On the other hand, if the acid concentration exceeds 1 mol / L, the support may deteriorate and the shape may not be maintained. Therefore, the acid concentration of the acid solution is preferably 0.0001 mol / L or more and 1 mol / L or less.

  Furthermore, when the acid temperature of the acid solution when dipping the carrier is less than 0 ° C., there is a possibility that the effect of preventing adsorption due to esterification of the carboxyl group may be difficult. On the other hand, if the temperature is higher than 50 ° C., the falling fibers of the carrier increase. If the temperature is higher than 80 ° C., the carrier may be deteriorated and the shape may not be maintained. Therefore, the temperature of the acid solution in which the carrier is immersed is preferably 0 ° C. or higher and 80 ° C. or lower, more preferably 0 ° C. or higher and 50 ° C. or lower.

  If the immersion time of the carrier in the acid solution is less than 5 minutes, it may be difficult to achieve an adsorption preventing effect by esterifying the carboxyl group. In addition, if it is longer than 72 hours, the carrier may deteriorate and the shape cannot be maintained. Therefore, the immersion time of the carrier in the acid solution is preferably 5 minutes or more and 72 hours or less.

  Here, since there is an upper limit on the amount of the cationic disinfectant adsorbed on the carrier, as the disinfectant concentration increases, the influence on the disinfectant concentration due to adsorption of the cationic disinfectant decreases. In the case of a cationic disinfectant having a concentration higher than 5 w / v%, even if the cationic disinfectant is adsorbed, the concentration is not significantly affected. Further, a cationic disinfectant having a concentration lower than 0.001 w / v% hardly exhibits an adsorption preventing effect. Therefore, it is preferable to use a cationic disinfectant having a concentration range of 0.001 w / v% or more and 5 w / v% or less because the effect of preventing the decrease in the concentration of the cationic disinfectant becomes clear.

  Next, the operation and effect of the first embodiment will be described.

According to the disinfectant-impregnated carrier, since the carboxyl group is esterified, the release of H ⁺ from the carboxyl group is prevented, and the cellulose is not easily negatively charged. Therefore, adsorption of the cationic disinfectant to the cellulosic fiber due to electrical interaction can be prevented, and a decrease in the concentration of the cationic disinfectant to be impregnated can be suppressed.

  In particular, when impregnating a cationic disinfectant having a concentration range of 0.001 w / v% or more and 5 w / v% or less, it is possible to effectively prevent a decrease in the concentration of the cationic disinfectant. For example, a low concentration cationic disinfectant can be used.

  And the carboxyl group of a cellulose fiber can be esterified by immersing the support | carrier which consists of a cellulose fiber in an acid solution.

  When the acid concentration of the acid solution is 0.0001 mol / L or more, the carboxyl group of the cellulosic fiber can be esterified, and adsorption of the cationic disinfectant can be prevented. In addition, when the acid concentration is 1 mol / L or less, deterioration of the carrier due to immersion of the carrier in the acid solution can be prevented, and the shape of the carrier can be maintained.

  When the temperature of the acid solution at the time of immersing the carrier is 0 ° C. or higher and 80 ° C. or lower, the carboxyl group can be esterified and adsorption of the cationic disinfectant can be prevented. In addition, by setting the temperature of the acid solution to 50 ° C. or lower, it is possible to prevent the deterioration of the carrier and maintain the shape of the carrier.

  By soaking in the acid solution of the carrier for 5 minutes or more, the carboxyl group can be esterified, and adsorption of the cationic disinfectant can be prevented. Moreover, by making immersion time 72 hours or less, deterioration of a support | carrier can be prevented and the shape of a support | carrier can be maintained.

  When the acid in the acid solution is at least one of hydrochloric acid, sulfuric acid, nitric acid, thionyl chloride, citric acid, phosphoric acid, and acetic acid, the carboxyl group can be esterified, and adsorption of the cationic disinfectant can be prevented.

  Even if the cellulosic fiber forming the carrier is a natural cellulosic fiber or a regenerated cellulosic fiber, the carboxyl group can be esterified to prevent adsorption of the cationic disinfectant.

  Next, a second embodiment will be described. The description of the same configuration and operation as those of the first embodiment is omitted.

The disinfectant-impregnated carrier according to the second embodiment is obtained by immersing a carrier made of cellulose fiber having a carboxyl group in a mixed solution of an acid and an organic solvent, and then washing the carrier containing the mixed solution with water. Manufactured.

  When the carrier is immersed in a mixed solution of an acid and an organic solvent as described above, either the 6-position carboxyl group or the 2,3,6-hydroxyl group in the cellulose molecule or between the cellulose molecules, as in the case of the immersion in the acid solution. Are ester-bonded within or between cellulose molecules. In the presence of an acid and an organic solvent, not only within the cellulose molecule and between the cellulose molecules, but also the 6-position carboxyl group of cellulose and an alcohol (alkyl group) are ester-bonded as shown in Chemical formula 6. In the chemical formula 6, R is a hydrocarbon group such as CH3- (methyl), CH3CH22- (ethyl), CH3CH2CH2CH2- (n-butyl).

Therefore, since the carboxyl group can be esterified more effectively than the case of using only the acid, it is possible to prevent the release of H ⁺ from the carboxyl group, and it is difficult to have a negative charge, thereby preventing the adsorption of the cationic disinfectant.

The mechanism of the chemical reaction in which a carboxyl group is esterified in the presence of such an acid (H ⁺ ) and an organic solvent is that the acid acts as a catalyst and the reversible reaction shown in Chemical Formula 7 is continuously generated. The reaction is based on the formation of an ester (COOR) from (COOH).

  Here, the organic solvent used in the mixed solution together with the acid is a single organic solvent composed of either one of a polar organic solvent and an aprotic organic solvent, or one of a polar organic solvent and an aprotic organic solvent, A mixed organic solvent obtained by mixing at least one of a polar organic solvent, an aprotic organic solvent, and a nonpolar organic solvent is preferable.

  Examples of the polar organic solvent include dehydrated methanol, industrial methanol, dehydrated ethanol, synthetic ethanol 99 degrees and butanol.

  Examples of the aprotic organic solvent include acetone.

  Nonpolar organic solvents include hexane and toluene.

  Acids used in mixed solutions with organic solvents include, for example, weak acids such as citric acid, phosphoric acid and acetic acid, methanolic hydrochloric acid, aqueous hydrochloric acid, sulfuric acid, nitric acid, and thionyl chloride. Since an effect can be improved, it is preferable.

  If the concentration of the acid in the mixed solution is less than 0.0001 mol / L, it may be difficult to achieve the adsorption preventing effect. Moreover, the adsorption preventing effect is in an equilibrium state at 0.1 mol / L or more. Furthermore, if it is 0.1 mol / L or more, the fibers of the carrier may fall off. Therefore, the acid concentration in the mixed solution is preferably 0.0001 mol / L or more and less than 0.1 mol / L. In consideration of damage to the carrier, it is preferable that the acid concentration is low. Therefore, the acid concentration in the mixed solution is more preferably 0.05 mol / L or less. Furthermore, when considering the balance between the effect of preventing adsorption and the prevention of damage to the carrier, 0.001 mol / L or more and 0.01 mol / L or less is more preferable.

  If the mixed solution has a liquid temperature of less than −80 ° C. when the carrier is immersed, there is a possibility that the adsorption preventing effect is hardly achieved. On the other hand, if the temperature is higher than 100 ° C., the carrier may deteriorate and the shape cannot be maintained. Therefore, the temperature of the mixed solution in which the carrier is immersed is preferably −80 ° C. or higher and 100 ° C. or lower. Further, if the temperature is 80 ° C. or higher, there is a possibility that the falling fibers of the carrier are generated. Furthermore, if it is 10 ° C. or higher, the adsorption preventing effect is remarkably improved. Therefore, considering the effect of immersion in the mixed solution and the deterioration of the carrier, the temperature of the mixed solution in which the carrier is immersed is more preferably 10 ° C. or higher and 50 ° C. or lower.

  Since the immersion time of the carrier is less than 5 minutes, it is difficult to achieve an adsorption preventing effect, and thus it is preferably 5 minutes or more. Further, if the immersion time exceeds 48 hours, the adsorption preventing effect is in an equilibrium state, so that the carrier immersion time is preferably 48 hours or less. Furthermore, if the immersion time is 1 hour or longer, the effect of preventing adsorption is likely to be obtained, and if it exceeds 24 hours, the carrier may be deteriorated, so that it is more preferably 1 hour or longer and 24 hours or shorter.

  In the following, examples and comparative examples of the present invention will be described because performance tests relating to the adsorption preventing effect of the cationic disinfectant and the maintenance of the shape of the carrier were carried out.

[Example 1]
A predetermined amount of hydrochloric acid is added to 12 mL of ion-exchanged water, and the molar concentration of hydrochloric acid is 0.0001 mol / L, 0.001 mol / L, 0.01 mol / L, 0.1 mol / L, 1 mol / L, 5 mol / L. A hydrochloric acid aqueous solution as an acid solution having a concentration of 10 mol / L is prepared, and about 0.4 g of absorbent cotton (5 balls of cotton balls No. 10 manufactured by White Cross Co., Ltd.) as a carrier made of cellulosic fibers is added to each hydrochloric acid aqueous solution. Soaked.

  With the absorbent cotton soaked in this manner, each aqueous hydrochloric acid solution was heated at 50 ° C. for 24 hours.

  After heating the hydrochloric acid aqueous solution, the absorbent cotton was pressed with a glass rod while suction filtration, the absorbent cotton was washed with ion-exchanged water, and lyophilized to prepare a specimen.

[Comparative Example 1]
A predetermined amount of hydrochloric acid is added to 12 mL of ion-exchanged water to prepare a hydrochloric acid aqueous solution having a molar concentration of hydrochloric acid of 0.00001 mol / L, and about 0.4 g of absorbent cotton (cotton ball no. 10 was immersed in 5 balls). Moreover, the absorbent cotton was immersed in 12 mL of ion exchange water to which hydrochloric acid was not added.

  These absorbent cottons were processed in the same manner as in Example 1 to prepare specimens.

  The shape of each specimen after washing in Example 1 and Comparative Example 1 was visually confirmed, and those that did not change in shape were marked with ◯, those that had many dropped fibers were marked with △, and the shape could not be maintained Was marked with x. The results are shown in Table 1.

  In addition, after quantifying the initial concentration of chlorhexidine gluconate (CHG) aqueous solution as a cationic disinfectant adjusted to 0.05 w / v%, this CHG aqueous solution was impregnated at a rate of 15 mL / g with respect to 80 mg of each specimen. And 0.22 μm polyvinylidene fluoride (PVDF) filter, and the filtrate was used as a test solution.

  Further, the CHG aqueous solution concentration of the test solution was quantified by high performance liquid chromatography (HPLC).

  In addition, CHG aqueous solution density | concentration of the measured test liquid turns into CHG density | concentration which is not adsorb | sucking to absorbent cotton. Therefore, the higher the concentration of the test solution can prevent adsorption.

Then, the non-adsorption rate (%) was calculated from the ratio of the test solution concentration to the initial concentration of the CHG aqueous solution. The results are shown in Table 1. The formula for calculating the non-adsorption rate is as follows.
Non-adsorption rate (%) = (Test solution concentration / initial concentration) × 100

  As shown in Table 1, Comparative Example 1 treated with an aqueous solution containing no acid (acid concentration 0 mol / L) has a non-adsorption rate of 38%, and the cationic disinfectant (CHG) is adsorbed to the absorbent cotton. It was.

  Further, Comparative Example 1 treated with an aqueous solution having an acid concentration of 0.00001 mol / L had a non-adsorption rate of 38% as in the case where no acid was used, and the cationic disinfectant was adsorbed.

  On the other hand, Example 1 treated with 0.0001 mol / L hydrochloric acid aqueous solution had a non-adsorption rate of about 50%, and the adsorption of the cationic disinfectant was suppressed. Further, as the acid concentration increased, the non-adsorption rate also improved. In each Example 1, adsorption of the cationic disinfectant was suppressed, and a decrease in the concentration of the cationic disinfectant was suppressed.

  In addition, the general cotton wool defatted and bleached through the degreasing step and the bleaching step is neutralized by adding an acid such as sulfuric acid in the neutralization step, and then washed with water. In the neutralization step, after the acid treatment, acid is added so that the pH is 6 to 7, that is, the acid concentration is about 0.000001 mol / L.

  Therefore, in Comparative Example 1 treated with an aqueous solution having a concentration of 0.000001 mol / L (pH 6) in the conventional absorbent cotton neutralization step and an acid concentration of 0.00001 mol / L (pH 5), although there was no adsorption prevention effect, In each Example 1 treated with an aqueous solution having an acid concentration of 0.0001 mol / L or more (pH 4 or less), an effect of preventing adsorption of a cationic disinfectant is exhibited.

  Here, as the acid concentration increases, the non-adsorption rate improves and approaches an equilibrium state. However, in the treatment of an aqueous solution having an acid concentration of 5 mol / L or more, the shape of the cotton ball cannot be maintained. . This is considered that the absorbent cotton was deteriorated by the action of acid.

  It is thought that the deterioration phenomenon of absorbent cotton is because oxygen (O) in a part forming a cellulose chain is damaged and a part of the chain is cut.

  Therefore, when the carrier made of cellulosic fibers is immersed in an acid solution, the acid concentration is preferably 0.0001 mol / L or more, and more preferably 1 mol / L or less in consideration of deterioration of cotton fibers.

[Example 2]
Hydrochloric acid is added to 12 mL of ion-exchanged water to prepare an aqueous hydrochloric acid solution having a molar concentration of hydrochloric acid of 1 mol / L, and about 0.4 g of absorbent cotton (5 balls of cotton balls No. 10 manufactured by White Cross Co., Ltd.) Was immersed.

  With the absorbent cotton soaked in this manner, the aqueous hydrochloric acid solution was heated at a predetermined temperature (0 ° C., 30 ° C., 50 ° C., 80 ° C., 100 ° C.) for 24 hours, and then treated in the same manner as in Example 1. A specimen was used.

[Comparative Example 2]
About 0.4 g of absorbent cotton (5 balls of cotton balls No. 10 manufactured by White Cross Co., Ltd.) was immersed in 12 mL of ion-exchanged water to which hydrochloric acid was not added.

  With the absorbent cotton soaked in this manner, ion-exchanged water was heated at 50 ° C. or 100 ° C. for 24 hours, and then treated in the same manner as in Example 2 to prepare a specimen.

  Then, for each specimen of Example 2 and Comparative Example 2, as in Example 1, the shape of the absorbent cotton was observed and the non-adsorption rate was measured. The results are shown in Table 2.

  As shown in Table 2, in Comparative Example 2 where no acid was used, the non-adsorption rate was less than 40% regardless of whether the ion-exchanged water temperature was 50 ° C. or 100 ° C., and the cationic disinfectant Was adsorbed.

  On the other hand, in Example 2 treated with the acid solution, the non-adsorption rate was 56% even when the temperature of the acid solution was 0 ° C., and adsorption of the cationic disinfectant was suppressed. Further, as the temperature of the acid solution increased, the non-adsorption rate was improved, the adsorption of the cationic disinfectant was more effectively suppressed, and the decrease in the concentration of the cationic disinfectant was suppressed.

  On the other hand, in Example 2, when the temperature of the acid solution was set to 80 ° C., the number of fibers dropped out, and when the temperature of the acid solution was set to 100 ° C., the absorbent cotton deteriorated and the shape of the cotton ball could not be maintained. .

  Therefore, the temperature of the acid solution at the time of immersing the carrier made of cellulosic fibers in the acid solution is preferably 0 ° C. or higher and 80 ° C. or lower, and more preferably 50 ° C. or lower in consideration of deterioration of the cotton fiber.

[Example 3]
Hydrochloric acid is added to 12 mL of ion-exchanged water to prepare an aqueous hydrochloric acid solution having a molar concentration of hydrochloric acid of 1 mol / L, and about 0.4 g of absorbent cotton (5 balls of cotton balls No. 10 manufactured by White Cross Co., Ltd.) is added to the aqueous hydrochloric acid solution. Was immersed.

  With the absorbent cotton soaked in this manner, the aqueous hydrochloric acid solution was heated at 50 ° C. for a predetermined time (5 minutes, 30 minutes, 1 hour, 24 hours, 48 hours, 72 hours, 168 hours). Samples were processed in the same manner.

[Comparative Example 3]
About 0.4 g of absorbent cotton (5 balls of cotton balls No. 10 manufactured by White Cross Co., Ltd.) was immersed in 12 mL of ion-exchanged water to which hydrochloric acid was not added.

  After the absorbent cotton was soaked in this way, ion-exchanged water was heated at 50 ° C. for 24 hours, and then treated in the same manner as in Example 3 to prepare a specimen.

  And about each sample of Example 3 and Comparative Example 3, similarly to Example 1, the shape of the absorbent cotton was observed and the non-adsorption rate was measured. The results are shown in Table 3.

  As shown in Table 3, in Comparative Example 3 where no acid was used, the non-adsorption rate was 38% even when immersed in ion exchange water at 50 ° C. for 24 hours, and the cationic disinfectant was adsorbed.

  On the other hand, in Example 3 treated with the acid solution, the non-adsorption rate was 50% even when the immersion time was 5 minutes, and the non-adsorption rate was 64% when the immersion time was 24 hours. Adsorption of disinfectant was suppressed. Further, as the immersion time was increased, the non-adsorption rate was improved, the adsorption of the cationic disinfectant was more effectively suppressed, and the decrease in the concentration of the cationic disinfectant was suppressed.

  On the other hand, as the immersion time is increased, the non-adsorption rate becomes an equilibrium state, and the non-adsorption rate is almost equal between 72 hours and 168 hours, but the absorbent cotton deteriorates at 168 hours, and the shape of the cotton ball Has become unmaintainable.

  Therefore, the immersion time when the carrier made of cellulosic fibers is immersed in the acid solution is preferably 5 minutes or more and 72 hours or less.

[Example 4]
Hydrochloric acid is added to 12 mL of ion-exchanged water to prepare an aqueous hydrochloric acid solution having a molar concentration of hydrochloric acid of 1 mol / L, and about 0.4 g of absorbent cotton (5 balls of cotton balls No. 10 manufactured by White Cross Co., Ltd.) is added to the aqueous hydrochloric acid solution. Was immersed.

  With the absorbent cotton soaked in this manner, the aqueous hydrochloric acid solution was heated at 50 ° C. for 24 hours, and then treated in the same manner as in Example 1 to prepare a specimen.

[Comparative Example 4]
About 0.4 g of absorbent cotton (5 balls of cotton balls No. 10 manufactured by White Cross Co., Ltd.) was immersed in 12 mL of ion-exchanged water to which hydrochloric acid was not added.

  After the absorbent cotton was soaked in this way, ion-exchanged water was heated at 50 ° C. for 24 hours, and then treated in the same manner as in Example 1 to prepare a specimen.

  For each specimen of Example 4 and Comparative Example 4, the shape of the absorbent cotton was observed in the same manner as in Example 1. The results are shown in Table 4.

  Moreover, after quantifying the initial concentration of the benzalkonium chloride (BAC) aqueous solution adjusted to 0.025 w / v% as a cationic disinfectant, this BAC aqueous solution was used for 80 mg of each specimen of Example 4 and Comparative Example 4. It was impregnated at a rate of 15 mL / g, and centrifuged through a 0.22 μm PVDF filter, and the filtrate was used as a test solution.

  And based on Japanese Pharmacopoeia, the BAC aqueous solution density | concentration of the test liquid was quantified by the titration method, and the non-adsorption rate was computed similarly to Example 1 based on this fixed_quantity | quantitative_assay result. The results are shown in Table 4.

  As shown in Table 4, in Comparative Example 4 where no acid was used, the non-adsorption rate was 12%, and a large amount of cationic disinfectant (BAC) was adsorbed.

  On the other hand, in Example 4 treated with the acid solution, the non-adsorption rate is 61%, the non-adsorption rate of the cationic disinfectant is improved, the adsorption of the cationic disinfectant (BAC) is suppressed, A decrease in the concentration of the cationic disinfectant was suppressed.

  Therefore, even if the BAC aqueous solution is used as the cationic disinfectant, the decrease in the disinfectant concentration can be suppressed similarly to the CHG aqueous solution. In this way, even if the chemical formulas are different, it is considered that a cationic disinfectant can suppress adsorption to a carrier even for cationic disinfectants other than BAC and CHG, and can suppress a decrease in disinfectant concentration. It is done.

[Example 5]
Each acid (hydrochloric acid, sulfuric acid, nitric acid, thionyl chloride, citric acid, phosphoric acid, acetic acid) is added to 12 mL of ion-exchanged water so that the molar concentration is 1 mol / L, and an acid solution is prepared. About 0.4 g (5 balls of cotton balls No. 10 manufactured by White Cross Co., Ltd.) was immersed.

  Each acid solution was heated at 50 ° C. for 24 hours with the absorbent cotton soaked in this manner, and then treated in the same manner as in Example 1 to prepare specimens.

[Comparative Example 5]
About 0.4 g of absorbent cotton (5 balls of cotton balls No. 10 manufactured by White Cross Co., Ltd.) was immersed in 12 mL of ion exchange water to which no acid was added.

  With the absorbent cotton soaked in this manner, ion-exchanged water was heated at 50 ° C. for 24 hours, and then treated in the same manner as in Example 5 to prepare a specimen.

  And about each sample of Example 5 and Comparative Example 5, similarly to Example 1, the shape of the absorbent cotton was observed and the non-adsorption rate was measured. The results are shown in Table 5.

  As shown in Table 5, in Comparative Example 5 in which no acid was used, the non-adsorption rate was 38%, whereas in Example 5, the non-adsorption rate was improved over Comparative Example 5, Adsorption of the cationic disinfectant was suppressed, and a decrease in the concentration of the cationic disinfectant was suppressed.

  Therefore, it is preferable to use at least one of hydrochloric acid, sulfuric acid, nitric acid, thionyl chloride, citric acid, phosphoric acid, and acetic acid as the acid.

  Although thionyl chloride is not itself an acid, it reacts with water to produce hydrogen chloride, so it was tested as a kind of acid. Further, since two hydrogen chloride molecules are generated from one molecule of thionyl chloride, the acid concentration is doubled compared to other acids. As a result, since the esterification efficiency is higher than that of other acids, adsorption of the cationic disinfectant is more effectively suppressed than other acids if the solution concentration is the same. On the other hand, since the acid concentration is higher than that of other acids, the absorbent cotton is likely to deteriorate, and the treated absorbent cotton has a larger number of fallen fibers.

[Example 6]
Hydrochloric acid was added to 12 mL of dehydrated methanol, which is an organic solvent, to prepare a mixed solution having a molar concentration of hydrochloric acid of 0.01 mol / L, and about 0.4 g of cotton wool (cotton ball No. 10 was immersed in 5 balls).

  With the absorbent cotton soaked in this manner, the mixed solution is kept at a predetermined temperature (−80 ° C., −10 ° C., 0 ° C., 10 ° C., 20 ° C., 30 ° C., 50 ° C., 80 ° C., 100 ° C.) for 24 hours. Heated. The freezing point of methanol is -97 ° C.

  After heating the mixed solution, the absorbent cotton was pressed with a glass rod while suction filtration, then washed in order with methanol and ion-exchanged water, and lyophilized to prepare a specimen.

[Comparative Example 6]
About 0.4 g of absorbent cotton (5 balls of cotton balls No. 10 manufactured by White Cross Co., Ltd.) was immersed in 12 mL of dehydrated methanol to which hydrochloric acid was not added.

  In the state where the absorbent cotton was immersed in this manner, dehydrated methanol was heated at a predetermined temperature (50 ° C., 100 ° C.) for 24 hours, and then treated in the same manner as in Example 6 to prepare a specimen.

  For each specimen of Example 6 and Comparative Example 6, the shape of the absorbent cotton was observed and the non-adsorption rate was measured in the same manner as in Example 1. The results are shown in Table 6.

  As shown in Table 6, Comparative Example 6 treated with a methanol solution without using an acid had a non-adsorption rate of 40% or less regardless of whether the solution temperature was 50 ° C. or 100 ° C. There was no change.

  In contrast, Example 6 treated with a mixed solution of an acid and an organic solvent had a non-adsorption rate of 51% when the solution temperature was −80 ° C., and adsorption of the cationic disinfectant was suppressed. Further, as the solution temperature increased, the non-adsorption rate was improved, the adsorption of the cationic disinfectant was more effectively suppressed, and the decrease in the concentration of the cationic disinfectant was suppressed.

  Here, when the relationship between the solution temperature and the non-adsorption rate is graphed as shown in FIG. 1, in Example 6 using a mixed solution of an acid and an organic solvent, the non-adsorption rate is increased when the solution temperature becomes 10 ° C. or higher. Significantly improved, the slope of the graph suddenly increases. Therefore, the solution temperature when using a mixed solution of an acid and an organic solvent is preferably 10 ° C. or higher.

  On the other hand, when the temperature of the solution was set to 80 ° C., the number of fallen fibers increased, and when the temperature of the solution was set to 100 ° C., the absorbent cotton deteriorated and the shape of the cotton ball could not be maintained.

  Accordingly, the solution temperature in the case of using a mixed solution of an acid and an organic solvent is preferably −80 ° C. or higher and 80 ° C. or lower. More preferred.

[Example 7]
Hydrochloric acid was added to 12 mL of dehydrated methanol, which is an organic solvent, to prepare a mixed solution having a molar concentration of hydrochloric acid of 0.01 mol / L, and about 0.4 g of cotton wool (cotton ball No. 10 was immersed in 5 balls).

  After the absorbent cotton was soaked in this manner, the mixed solution was heated at 50 ° C. for a predetermined time (5 minutes, 30 minutes, 1 hour, 24 hours, 48 hours), and then treated in the same manner as in Example 6 to obtain a specimen. It was.

[Comparative Example 7]
About 0.4 g of absorbent cotton (5 balls of cotton balls No. 10 manufactured by White Cross Co., Ltd.) was immersed in 12 mL of dehydrated methanol to which hydrochloric acid was not added.

  In the state where the absorbent cotton was immersed in this manner, dehydrated methanol was heated at 50 ° C. for 24 hours, and then treated in the same manner as in Example 7 to prepare a specimen.

  For each specimen of Example 7 and Comparative Example 7, the shape of the absorbent cotton was observed and the non-adsorption rate was measured in the same manner as in Example 1. The results are shown in Table 7.

  As shown in Table 7, the non-adsorption rate of Comparative Example 7 treated with a methanol solution without using an acid was 37%, whereas Example 7 treated with a mixed solution of an acid and an organic solvent was immersed. Even when the time was 5 minutes, the non-adsorption rate was 50%, and the adsorption of the cationic disinfectant was suppressed. In addition, as the immersion time was increased, the non-adsorption rate was improved, the adsorption of the cationic disinfectant was more effectively suppressed, and the decrease in the concentration of the cationic disinfectant was suppressed.

  Here, as shown in FIG. 2, when the relationship between the non-adsorption rate and the logarithmic value of the immersion time is graphed, the inclination of the graph from the immersion time of 5 minutes to 30 minutes and the inclination of the graph from 30 minutes to 1 hour In addition, the slope of the graph from the immersion time of 1 hour to 24 hours is almost equal to the slope of the graph from 5 minutes to 30 minutes.

  From this result, the adsorption preventing effect greatly changes when the immersion time is between 30 minutes and 1 hour. Therefore, in consideration of ensuring the adsorption preventing effect more reliably, the immersion time in the mixed solution is 1 hour. The above is preferable.

  Therefore, the immersion time of the carrier in the mixed solution is preferably 5 minutes or more and 48 hours or less. Moreover, considering secure ensuring of the adsorption preventing effect, 1 hour or more is more preferable, and a shorter immersion time is preferable because 24 hours or less is more preferable because damage to the carrier is less.

[Example 8]
Hydrochloric acid was added to 12 mL of dehydrated methanol, which is an organic solvent, to prepare a mixed solution having a molar concentration of hydrochloric acid of 0.01 mol / L, and about 0.4 g of cotton wool (cotton ball No. 10 was immersed in 5 balls).

  After the absorbent cotton was soaked in this manner, the mixed solution was heated at 50 ° C. for 24 hours, and then treated in the same manner as in Example 6 to prepare a specimen.

[Comparative Example 8]
About 0.4 g of absorbent cotton (5 balls of cotton balls No. 10 manufactured by White Cross Co., Ltd.) was immersed in 12 mL of dehydrated methanol to which hydrochloric acid was not added.

  In the state where the absorbent cotton was immersed in this manner, dehydrated methanol was heated at 50 ° C. for 24 hours, and then treated in the same manner as in Example 8 to prepare a specimen.

  And about each sample of Example 8 and Comparative Example 8, the shape of absorbent cotton was observed similarly to Example 1. The results are shown in Table 8.

  In addition, after quantifying the initial concentration of a benzalkonium chloride (BAC) aqueous solution as a cationic disinfectant adjusted to 0.025 w / v%, the BAC aqueous solution was impregnated at a rate of 10 mL / g with respect to 80 mg of each specimen. The solution was centrifuged with a 0.22 μm polyvinylidene fluoride (PVDF) filter, and the filtrate was used as a test solution.

  Moreover, based on Japanese Pharmacopoeia, the BAC aqueous solution density | concentration of the test liquid was quantified by the titration method.

  And the non-adsorption rate was computed similarly to Example 1 based on this fixed_quantity | quantitative_assay result. The results are shown in Table 8.

  As shown in Table 8, Comparative Example 8 treated with a methanol solution without using an acid had a non-adsorption rate of 12% even when a BAC aqueous solution was used as the cationic disinfectant, and a large amount of the cationic disinfectant was present. It was adsorbed.

  On the other hand, Example 8 treated with a mixed solution of an acid and an organic solvent has a non-adsorption rate of 88%, suppresses adsorption of the cationic disinfectant, and suppresses a decrease in the concentration of the cationic disinfectant. It was done.

  Thus, from the results of Example 8 and Comparative Example 8 above, it was confirmed that adsorption to the carrier could be prevented by using not only the CHG aqueous solution but also the BAC aqueous solution as the cationic disinfectant.

  Therefore, even if the chemical formula is different, it is considered that adsorption can be suppressed similarly to CHG and BAC even if the disinfectant is other than CHG and BAC as long as it is a cationic disinfectant.

[Example 9]
Hydrochloric acid is added to 12 mL of a single organic solvent of polar organic solvent (dehydrated methanol, industrial methanol, dehydrated ethanol, synthetic ethanol 99 degrees, butanol), aprotic organic solvent (acetone) or nonpolar organic solvent (hexane, toluene) Thus, a mixed solution having a molar concentration of hydrochloric acid of 0.01 mol / L was prepared.

  Also, a mixed organic solvent in which a polar organic solvent (industrial methanol) and an aprotic organic solvent (acetone) are mixed at a volume ratio of 1: 1, a polar organic solvent (industrial methanol) and a nonpolar organic solvent (toluene) Were mixed at a volume ratio of 1: 1, and a mixed organic solvent consisting of an aprotic organic solvent (acetone) and a nonpolar organic solvent (toluene) at a volume ratio of 5: 1 was prepared. Hydrochloric acid was added to 12 mL of these mixed organic solvents to prepare a mixed solution having a molar concentration of hydrochloric acid of 0.01 mol / L.

  In addition, dehydrated methanol has a water content of 0.005% or less, industrial methanol has a water content of 0.1% or less, dehydrated ethanol has a water content of 0.005% or less, and synthetic ethanol 99 degrees Moisture content is less than 1%.

  About 0.4 g of absorbent cotton (5 balls of cotton balls No. 10 manufactured by White Cross Co., Ltd.) was immersed in each mixed solution.

  After the absorbent cotton was soaked in this manner, the mixed solution was heated at 50 ° C. for 24 hours, and then treated in the same manner as in Example 6 to prepare a specimen.

[Comparative Example 9]
About 0.4 g of absorbent cotton (5 balls of cotton balls No. 10 manufactured by White Cross Co., Ltd.) was immersed in 12 mL of dehydrated methanol to which hydrochloric acid was not added.

  In the state where the absorbent cotton was immersed in this manner, dehydrated methanol was heated at 50 ° C. for 24 hours, and then treated in the same manner as in Example 9 to prepare a specimen.

  For each specimen of Example 9 and Comparative Example 9, the shape of the absorbent cotton was observed and the non-adsorption rate was measured in the same manner as in Example 1. The results are shown in Table 9.

  As shown in Table 9, the non-adsorption rate of Comparative Example 9 treated with a methanol solution without using an acid was 37%, whereas Example 9 treated with a mixed solution of an acid and a single organic solvent was used. No matter what organic solvent was used, the non-adsorption rate was higher than that of Comparative Example 9, and adsorption of the cationic disinfectant was suppressed.

  In addition, among alcohols that are polar organic solvents, the non-adsorption rate is higher when methanol solvents (dehydrated methanol and industrial methanol) are used than when ethanol solvents (dehydrated ethanol and synthetic ethanol) and butanol solvents are used. I was able to improve. This is presumably because the alkyl group having fewer carbon atoms can improve the esterification reaction efficiency with the hydroxyl group at the 2nd, 3rd or 6th position of cellulose.

  Furthermore, in the methanol solvent, the non-adsorption rate was improved when dehydrated methanol with a small amount of water was used, compared with when industrial methanol with a large amount of water was used. This is because the esterification reaction of a carboxyl group is an equilibrium reaction between a dehydration condensation reaction with a hydroxyl group and a hydrolysis reaction, and because of the presence of water, the equilibrium tends to the hydrolysis reaction and the esterification efficiency decreases. This is probably because the reaction efficiency of the esterification can be improved when the amount is less.

  In addition, not only polar organic solvent (alcohol) but also aprotic organic solvent (acetone) or nonpolar organic solvent (hexane and toluene), the non-adsorption rate is improved, The carboxyl group of cellulose is considered to be esterified not only with alcohol but also with hydroxyl groups at the 2nd, 3rd and 6th positions of cellulose.

However, when a nonpolar organic solvent (hexane and toluene) was used, the carrier deteriorated so that the shape of the cotton ball could not be maintained. This is presumed to be because, in a non-polar organic solvent, protons (H ⁺ ) cannot be liberated and thus are not dispersed, the concentration of hydrochloric acid is locally increased, and the hydrogen bond network and glycosidic bonds of the cellulose higher order structure are cleaved. Is done.

  Also, a mixed organic solvent consisting of a polar organic solvent and an aprotic organic solvent, a mixed organic solvent consisting of a polar organic solvent and a nonpolar organic solvent, and a mixed organic consisting of an aprotic organic solvent and a nonpolar organic solvent When a mixed solution of any of the solvents and the acid is used, the non-adsorption rate is higher than that of Comparative Example 9 and the adsorption of the cationic disinfectant is suppressed regardless of the combination of the mixed organic solvents. It was.

  On the other hand, for the carrier shape, a combination of a polar organic solvent and an aprotic organic solvent is good, but a combination of a polar organic solvent and an apolar organic solvent, and a combination of an aprotic organic solvent and an apolar organic solvent. In the case of using a nonpolar organic solvent as described above, dropped fibers were confirmed. However, by mixing a nonpolar organic solvent and an organic solvent having a different polarity, the shape of the carrier is maintained as compared with a case where only the nonpolar organic solvent is treated with a mixed solution mixed with an acid. This is because the non-polar organic solvent alone has a locally high hydrochloric acid concentration as described above, but the mixture of a polar organic solvent and an aprotic organic solvent locally increases the hydrochloric acid concentration. It is thought that it can be solved.

  In addition, although the result about the case where 3 types of organic solvents are mixed is not shown in this Example 9, even if it is a case where it processes with 3 types of mixed organic solvents, the same effect can be anticipated.

[Example 10]
Add any of strong acid (methanolic hydrochloric acid, aqueous hydrochloric acid, sulfuric acid, nitric acid, thionyl chloride) and weak acid (citric acid, phosphoric acid, acetic acid) to 12 mL of dehydrated methanol, which is an organic solvent. Was prepared, and about 0.4 g of absorbent cotton (5 balls of cotton balls No. 10 manufactured by White Cross Co., Ltd.) was immersed in the mixed solution.

  After the absorbent cotton was soaked in this manner, the mixed solution was heated at 50 ° C. for 24 hours, and then treated in the same manner as in Example 6 to prepare a specimen.

[Comparative Example 10]
About 0.4 g of absorbent cotton (5 balls of cotton balls No. 10 manufactured by White Cross Co., Ltd.) was immersed in 12 mL of dehydrated methanol to which no acid was added.

  In the state where the absorbent cotton was immersed in this manner, dehydrated methanol was heated at 50 ° C. for 24 hours, and then treated in the same manner as in Example 10 to prepare a specimen.

  For each specimen of Example 10 and Comparative Example 10, the shape of the absorbent cotton was observed and the non-adsorption rate was measured in the same manner as in Example 1. The results are shown in Table 10.

As shown in Table 10, the non-adsorption rate of Comparative Example 10 treated with a methanol solution without using an acid was 37%, whereas it was treated with Example 10 treated with a strong acid and a weak acid. In all of Examples 10, the non-adsorption rate was improved, and adsorption of the cationic disinfectant was suppressed even when other acids were used in addition to hydrochloric acid. In particular, the non-adsorption rate when a weak acid was used was around 50%, whereas the non-adsorption rate when a strong acid was used was about 80% or more. This is because a strong acid has a larger acid dissociation constant than a weak acid, and a large amount of acid (H ⁺ ) is released as a reaction catalyst for producing an ester (COOR) from a carboxyl group (COOH). It is considered that the reaction efficiency of esterification can be improved.

[Example 11]
Hydrochloric acid is added to dehydrated methanol, and the molar concentration of hydrochloric acid is 0.0001 mol / L, 0.0005 mol / L, 0.001 mol / L, 0.005 mol / L, 0.01 mol / L, 0.05 mol / L, 12 mL of mixed solutions of 0.1 mol / L were prepared, and about 0.4 g of absorbent cotton (5 balls of cotton balls No. 10 manufactured by White Cross Co., Ltd.) was immersed in each mixed solution.

  After the absorbent cotton was soaked in this manner, the mixed solutions were each heated at 50 ° C. for 24 hours, and then treated in the same manner as in Example 6 to prepare specimens.

[Comparative Example 11]
Hydrochloric acid is added to dehydrated methanol to prepare 12 mL of a mixed solution having a molar concentration of hydrochloric acid of 0.00001 mol / L, and about 0.4 g of absorbent cotton (5 balls of cotton ball No. 10 manufactured by White Cross Co., Ltd.) is added to the mixed solution. ). Further, about 0.4 g of absorbent cotton (5 balls of cotton balls No. 10 manufactured by White Cross Co., Ltd.) was immersed in 12 mL of dehydrated methanol to which hydrochloric acid was not added.

  After the absorbent cotton was soaked in this manner, the mixed solution and dehydrated methanol were heated at 50 ° C. for 24 hours, and then processed in the same manner as in Example 11 to prepare a specimen.

  For each specimen of Example 11 and Comparative Example 11, the shape of the absorbent cotton was observed and the non-adsorption rate was measured in the same manner as in Example 1. The results are shown in Table 11.

  As shown in Table 11, the non-adsorption rate of Comparative Example 11 treated with a methanol solution without using an acid was 37%.

  Further, when treated with a mixed solution having an acid concentration of 0.00001 mol / L, the non-adsorption rate was 37% as in the case where no acid was used, and the cationic disinfectant was adsorbed.

  On the other hand, when treated with a mixed solution having an acid concentration of 0.0001 mol, the non-adsorption rate was 46%, and adsorption of the cationic disinfectant was suppressed. Further, the non-adsorption rate is improved as the acid concentration in the mixed solution is increased. When the acid concentration was 0.1 mol / L, the non-adsorption rate was 100%, but when the acid concentration was 0.01 mol / L, the non-adsorption rate was 95%. It can be said that the non-adsorption rate does not change so much at a concentration of 0.01 mol / L or more. Further, when the acid concentration was 0.1 mol / L, there were many dropped fibers.

  Therefore, considering the adsorption preventing effect of the cationic disinfectant, the acid concentration in the mixed solution is preferably 0.0001 mol / L or more and 0.1 mol / L or less.

  Considering the deterioration of the cotton fibers, dropping fibers are generated at 0.1 mol / L. Therefore, the acid concentration in the mixed solution is preferably 0.05 mol / L or less.

  Further, since the non-adsorption rate is almost equal between the case where the acid concentration in the mixed solution is 0.01 mol / L and the case where it is 0.05 mol / L, in consideration of damage to the carrier, 0.01 mol having a low acid concentration is considered. / L or less is more preferable. That is, from the results of Example 11 and Comparative Example 11, in consideration of the non-adsorption rate and damage to the support, the acid concentration in the mixed solution is more preferably 0.001 mol / L or more and 0.01 mol / L or less.

[Example 12]
Hydrochloric acid was added to 12 mL of ion-exchanged water to prepare an aqueous hydrochloric acid solution having a hydrochloric acid molar concentration of 1 mol / L, and 0.4 g of each cotton material was immersed in the aqueous hydrochloric acid solution.

  As the cotton material, natural cellulose (absorbent cotton) and regenerated cellulose (cupra, lyocell, 70% rayon + 30% PET, 70% rayon + 30% PP · PE) were used.

  After each cotton material was immersed in this manner, the aqueous hydrochloric acid solution was heated at 50 ° C. for 24 hours, and then treated in the same manner as in Example 1 to prepare a specimen.

[Comparative Example 12]
The same cotton material as in Example 12 was used as it was as a specimen.

  And about each specimen of Example 12 and Comparative Example 12, the non-adsorption rate was measured similarly to Example 1. For each sample of Example 12, the shape of each cotton material was observed in the same manner as in Example 1. The results are shown in Table 12.

  As shown in Table 12, in Example 12, the non-adsorption rate is improved in any cotton material as compared with the result of Comparative Example 12. That is, not only degreased and bleached natural cellulose (absorbent cotton) and regenerated cellulose (cupra, lyocell) but also a carrier in which chemical fibers are combined with regenerated cellulose (rayon 70% + PET 30%, rayon 70% + PP · PE 30%) However, by treating with an acid solution, the non-adsorption rate can be improved and adsorption of the cationic disinfectant can be suppressed. Therefore, natural cellulose, regenerated cellulose, and composite cellulose in which cellulose and chemical fiber are combined can be used as the material for the disinfectant-impregnated carrier.

[Example 13]
Hydrochloric acid was added to 12 mL of dehydrated methanol as an organic solvent to prepare a mixed solution having a molar concentration of hydrochloric acid of 0.01 mol / L, and the same cotton material as in Example 12 was immersed therein.

  The mixed solution was heated at 50 ° C. for 24 hours in the state where each cotton material was immersed in this manner, and then treated in the same manner as in Example 6 to prepare a specimen.

[Comparative Example 13]
The same cotton material as in Example 13 was used as it was as a specimen.

  And about each sample of Example 13 and Comparative Example 13, the non-adsorption rate was measured similarly to Example 1. For each sample of Example 13, the shape of each cotton material was observed in the same manner as in Example 1. The results are shown in Table 13.

  As shown in Table 13, compared with the result of Comparative Example 13, in Example 13, the non-adsorption rate is improved in any cotton material. That is, not only degreased and bleached natural cellulose and regenerated cellulose, but also a carrier in which regenerated cellulose is combined with chemical fibers can be treated with a mixed solution to improve the non-adsorption rate and suppress the adsorption of cationic disinfectants. it can. Therefore, natural cellulose, regenerated cellulose alone, and a composite material of cellulose and chemical fiber can be used as a material for a disinfectant-impregnated carrier.

[Example 14]
Hydrochloric acid was added to 3000 mL of ion-exchanged water to prepare an aqueous hydrochloric acid solution having a molar concentration of hydrochloric acid of 1 mol / L, and about 100 g of absorbent cotton (made by White Cross Co., Ltd.) was immersed in the aqueous hydrochloric acid solution.

  With the absorbent cotton soaked in this manner, the aqueous hydrochloric acid solution was heated at 50 ° C. for 24 hours, and then treated in the same manner as in Example 1 to prepare a specimen.

[Comparative Example 14]
About 100 g of absorbent cotton (manufactured by White Cross Co., Ltd.) was used as it was.

  Predetermined initial concentrations (0.0005 w / v%, 0.001 w / v%, 0.005 w / v%, 0.01 w / v%, 0.1 w / v%, 0.1 g for each specimen of Example 14 and Comparative Example 14 were obtained. 02 w / v%, 0.05 w / v%, 0.2 w / v%, 0.5 w / v%, 1 w / v%, 2 w / v%, 5 w / v%, 10 w / v%) A predetermined amount (3 mL, 5 mL, 10 mL, 15 mL) of CHG aqueous solution was impregnated.

  As in Example 1, the liquid separated from each specimen was used as a test solution, and the CHG aqueous solution concentration of the test solution was quantified by HPLC. Further, as in Example 1, the non-adsorption rate was calculated from the quantitative result of the CHG aqueous solution concentration. These results are shown in Table 14.

  As shown in Table 14, in the CHG concentration ranges of 0.0005 w / v% and 10 w / v%, the non-adsorption rate in each impregnating liquid amount in Example 14 and Comparative Example 14 is almost the same, and absorbent cotton is used. There is little adsorption prevention effect by processing with an acid solution.

  On the other hand, in the CHG concentration range of 0.001 to 5 w / v%, the non-adsorption rate of Example 14 was higher than the non-adsorption rate of Comparative Example 14, and the decrease in the concentration of the cationic disinfectant was suppressed. .

  Since there is an upper limit to the amount of the cationic disinfectant adsorbed on the carrier, theoretically, the non-adsorption rate on the carrier increases as the concentration of the disinfectant and the amount of the impregnating solution increase. Therefore, when the concentration of the disinfectant solution is high, it becomes difficult to achieve the adsorption prevention effect by the treatment with the acid solution. However, in the concentration range of 0.001 to 5 w / v%, the adsorption prevention effect by the treatment with the acid solution is not achieved. confirmed.

  As the concentration of the disinfectant decreases, the difference between the non-adsorption rate of Example 14 and the non-adsorption rate of Comparative Example 14 increases, and when the carrier is impregnated with a low concentration disinfectant, an acid solution The anti-adsorption effect by the treatment in is clear.

[Example 15]
Hydrochloric acid was added to 3000 mL of industrial methanol to prepare a mixed solution of acid and organic solvent having a molar concentration of hydrochloric acid of 0.01 mol / L, and about 100 g of absorbent cotton (made by White Cross Co., Ltd.) was immersed in the mixed solution. .

  After the absorbent cotton was soaked in this manner, the mixed solution was heated at 50 ° C. for 24 hours, and then treated in the same manner as in Example 6 to prepare a specimen.

[Comparative Example 15]
About 100 g of absorbent cotton (manufactured by White Cross Co., Ltd.) was used as it was.

  Predetermined initial concentrations (0.0005 w / v%, 0.001 w / v%, 0.005 w / v%, 0.01 w / v%, 0.1 w / v%, 0.1 g for each specimen of Example 15 and Comparative Example 15 were obtained. 02 w / v%, 0.05 w / v%, 0.2 w / v%, 0.5 w / v%, 1 w / v%, 2 w / v%, 5 w / v%, 10 w / v%) A predetermined amount (3 mL, 5 mL, 10 mL, 15 mL) of CHG aqueous solution was impregnated.

  As in Example 1, the liquid separated from each specimen was used as a test solution, and the CHG aqueous solution concentration of the test solution was quantified by HPLC. Further, as in Example 1, the non-adsorption rate was calculated from the quantitative result of the CHG aqueous solution concentration. These results are shown in Table 15.

  As shown in Table 15, in the CHG concentration ranges of 0.0005 w / v% and 10 w / v%, the non-adsorption rate in each impregnation liquid amount of Example 15 and Comparative Example 15 is almost the same, and the absorbent cotton is used. There is little adsorption prevention effect by processing with a mixed solution.

  On the other hand, in the CHG concentration range of 0.001 to 5 w / v%, the non-adsorption rate of Example 15 is higher than the non-adsorption rate of Comparative Example 15, and the decrease in the concentration of the cationic disinfectant is suppressed. It was.

  As described above, theoretically, as the concentration of the disinfectant and the amount of the impregnating solution increase, the non-adsorption rate to the carrier increases. In the concentration range of 0.001 to 5 w / v%, the adsorption preventing effect by the treatment with the mixed solution was confirmed.

  As the concentration of the disinfectant decreases, the difference between the non-adsorption rate in Example 15 and the non-adsorption rate in Comparative Example 15 increases, and when the carrier is impregnated with a low concentration disinfectant, a mixed solution The anti-adsorption effect by the treatment in is clear.

Claims (8)

A disinfectant-impregnated carrier for impregnating a cationic disinfectant,
A disinfectant-impregnated carrier comprising a cellulose-based fiber esterified with a carboxyl group bonded to a hydroxyl group in a cellulose molecule or a hydroxyl group between cellulose molecules. The disinfectant-impregnated carrier according to claim 1, wherein the cellulosic fibers are degreased and bleached natural cellulosic fibers or regenerated cellulosic fibers. The cationic disinfectant to be impregnated has an impregnating liquid amount of 3 ml / g or more and 15 ml / g or less and a concentration of 0.001 w / v% or more and 5 w / v% or less. Disinfectant impregnated carrier. A method for producing a disinfectant-impregnated carrier according to any one of claims 1 to 3,
A carrier comprising a cellulose-based fiber having a carboxyl group is prepared by using at least one of hydrochloric acid, sulfuric acid, nitric acid, thionyl chloride, citric acid, phosphoric acid and acetic acid having an acid concentration of 0.0001 mol / L to 1 mol / L. Soak in acid solution,
A method for producing a disinfectant-impregnated carrier comprising washing the carrier containing the acid solution with water. A method for producing a disinfectant-impregnated carrier according to any one of claims 1 to 3,
A carrier comprising a cellulose-based fiber having a carboxyl group is immersed in a mixed solution of at least one acid of hydrochloric acid, sulfuric acid, nitric acid, thionyl chloride, citric acid, phosphoric acid and acetic acid and an organic solvent,
A method for producing a disinfectant-impregnated carrier comprising washing the carrier containing the mixed solution with water. The organic solvent is a single organic solvent composed of either a polar organic solvent or an aprotic organic solvent, or either a polar organic solvent or an aprotic organic solvent, and a polar organic solvent or aprotic organic solvent. 6. A method for producing a disinfectant-impregnated carrier according to claim 5 , wherein the organic solvent is a mixed organic solvent obtained by mixing at least one of a nonpolar organic solvent. The method for producing a disinfectant-impregnated carrier according to claim 5 or 6 , wherein the acid is a strong acid. The method for producing a disinfectant-impregnated carrier according to any one of claims 5 to 7 , wherein the mixed solution has an acid concentration of 0.0001 mol / L or more and less than 0.1 mol / L.

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