JP2016056200A - Method for producing antibacterial agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an antibacterial agent composition having excellent solubility in water.SOLUTION: The present invention provides a method for producing an antibacterial agent composition having the step of heating (A) a phenolic antibacterial agent and (B) a polyol at 110-180°C in the presence of an aqueous medium.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing an antimicrobial composition.

Antibacterial substances are widely incorporated into products such as cosmetics, pharmaceuticals, foods, daily necessities, etc. for the purpose of preventing contamination and alteration of products by microorganisms or prevention of infectious diseases. From the viewpoint of quality control and public health Very useful. Among these, phenolic antibacterial agents such as isopropylmethylphenol and parabens are known to have an excellent antibacterial action.
Phenol-based antibacterial agents are solid at room temperature and often have poor water solubility. The use form is generally used by dissolving in ethanol, but the feeling of use tends to be impaired by the stimulation of ethanol to the skin. Moreover, the composition which can be applied will be restrict | limited.

  Therefore, a technique for solubilizing a poorly water-soluble antibacterial substance in water has been studied, and an isopropylmethylphenol glycoside in which a sugar such as glucose is bound to isopropylmethylphenol has been proposed (Patent Document 1). In addition, a method of micellizing triclosan using a surfactant (Non-patent Document 1), a method of solubilizing isopropylmethylphenol using a surfactant and a wetting agent (Patent Document 2), etc. have been reported. Yes.

JP 2005-82506 A JP2011-98919A

C. Grove et al., “J. Cosmet. Sci.”, 2003, 54, p. 537

However, although isopropylmethylphenol glycoside has high solubility in water, the cost is high due to the complicated manufacturing process. For this reason, it is economically not preferable to use isopropylmethylphenol glycoside instead of isopropylmethylphenol. Moreover, in the method of solubilizing an antibacterial substance using a surfactant, sufficient solubility and antibacterial effect may not be obtained.
Therefore, the present invention seeks to provide a new method for producing an antibacterial agent composition having excellent solubility in water.

  The present inventors have made various studies on the solubilization technology of phenolic antibacterial agents, and in the presence of an aqueous medium, the phenolic antibacterial agent and the polyol are heat-treated at 110 ° C. or higher to obtain a normal phenolic antibacterial agent. The concentration of the phenolic antibacterial agent is drastically increased compared to the solubility of the above, and in the composition having undergone such treatment, precipitation of the phenolic antibacterial agent is suppressed even at room temperature, and high solubility is maintained. In addition, it was found that even when the composition was diluted to a desired concentration, precipitation of the phenolic antibacterial agent was suppressed and stability was high.

  That is, this invention is obtained by the manufacturing method of an antibacterial agent composition including the process of heat-processing (A) phenolic antibacterial agent and (B) polyol at 110-180 degreeC in presence of an aqueous medium, and this manufacturing method. An antibacterial agent composition and a cosmetic containing the antibacterial agent composition are provided.

  According to the present invention, an antibacterial agent composition having excellent solubility in water can be produced at a low cost. By using this antibacterial agent composition, the use of ethanol can be reduced or avoided, so that it is possible to provide an aqueous product with less skin irritation.

In the manufacturing method of the antibacterial agent composition of this invention, the process of heat-processing (A) phenolic antibacterial agent and (B) polyol at 110-180 degreeC in presence of an aqueous medium is included.
The phenolic antibacterial agent (A) used in the present invention has poor water solubility, for example, a solubility in water at 25 ° C. of 0.5 g / L or less, further 0.3 g / L or less, and further 0.2 g. Those having a / L or less are preferably applicable. Here, the solubility represents the number of grams of solute dissolved in 1 L of the solution, and the unit is [g / L].
Specific examples include chlorophenol antibacterial agents such as triclosan, chlorthymol, carbachlor, chlorophene, dichlorophene, hexachlorophene, chloroxylenol, chlorocresol; O-phenylphenol, isopropylmethylphenol, and the like. Of these, triclosan and isopropylmethylphenol are preferable, and isopropylmethylphenol is more preferable. The phenolic antibacterial agent may be one type or a mixture of two or more types.

The (B) polyol used in the present invention is a generic name for alcohols in which two or more hydrogen atoms of a hydrocarbon are substituted with a hydroxyl group. For example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butane Examples include alkylene glycols such as diols; polyalkylene glycols such as diethylene glycol, dipropylene glycol, polyethylene glycol, and polypropylene glycol; glycerins such as glycerin, diglycerin, and triglycerin. Of these, ethylene glycol, propylene glycol, 1,3-butanediol, dipropylene glycol, polyethylene glycol, glycerin, and diglycerin are preferable from the viewpoint of solubilization of the phenolic antibacterial agent, and further propylene glycol and 1,3-butane. Diol and glycerin are preferred. The weight average molecular weight of polyethylene glycol is preferably 200 to 20,000.
A polyol can be used individually or in combination of 2 or more types.

The aqueous medium used in the present invention refers to water and an aqueous solution of an organic solvent. Examples of water include tap water, distilled water, ion exchange water, and purified water. The organic solvent is not particularly limited as long as it is uniformly mixed with water. As the organic solvent, monohydric alcohols having 4 or less carbon atoms are preferable, propanol and ethanol are more preferable, and ethanol is more preferable from the viewpoint of being applicable to cosmetics.
When an organic solvent is used, the solubility of the (A) phenolic antibacterial agent in water increases, but it is desirable to reduce the amount used from the viewpoint of irritation to the skin. The concentration of the organic solvent in the aqueous solution is preferably 0 to 60% by mass (hereinafter simply referred to as “%”), more preferably 0 to 30%, still more preferably 0 to 10%, and still more preferably 0 to 1%. More preferably, it is substantially 0%, that is, does not contain an organic solvent.

  (A) The phenolic antibacterial agent may be (B) dispersed in a polyol solution in which a polyol is dissolved in an aqueous medium and subjected to a heat treatment in a slurry state. You may heat-process, after mixing the thing melt | dissolved in the polyol with an aqueous medium.

When using for heat processing, the heat processing raw material containing an aqueous medium, (A) phenolic antibacterial agent, and (B) polyol is prepared, and heat processing is performed.
The content of the (A) phenolic antibacterial agent in the heat treatment raw material varies depending on the type, but is usually 0.5 g / L or more, further 0.7 g / L or more, and further 1 g / L from the viewpoint of fluidity. In addition, 1.1 g / L or more, further 1.2 g / L or more, further 1.3 g / L or more, further 1.4 g / L or more is preferable, and 100 g / L or less, further 75 g / L or less, It is preferably 50 g / L or less, further 30 g / L or less, further 20 g / L or less, further 10 g / L or less, and further 9 g / L or less. Moreover, 0.5-100 g / L is preferable, 0.7-75 g / L is more preferable, 1-50 g / L is still more preferable, 1.1-30 g / L is further more preferable, 1.2-20 g / L Is more preferable, 1.3 to 10 g / L is more preferable, and 1.4 to 9 g / L is more preferable.

  Although the content of the (B) polyol in the heat treatment raw material varies depending on the type, it is usually 1 g / L or more, further 5 g / L or more, further 10 g / L or more, further 12 g / L or more from the viewpoint of fluidity. 15 g / L or more, more preferably 20 g / L or more, 800 g / L or less, further 700 g / L or less, further 600 g / L or less, further 300 g / L or less, further 100 g / L or less, further 50 g / L. The following is preferred. Moreover, 1-800 g / L is preferable, 5-700 g / L is more preferable, 10-600 g / L is still more preferable, 12-300 g / L is still more preferable, 15-100 g / L is still more preferable, 20-50 g / L L is more preferable.

  In the heat-treated raw material, the mass ratio [(A) / (B)] of component (A) to component (B) is 0.001 or more, and further 0 from the viewpoint of the solubility of the antibacterial agent composition obtained after cooling. 0.003 or more, further 0.005 or more, further 0.01 or more, further 0.02 or more, more preferably 0.025 or more, 0.2 or less, further 0.15 or less, further 0.13 or less, It is preferably 0.12 or less, more preferably 0.11 or less, and further preferably 0.1 or less. Moreover, 0.001-0.2 is preferable, 0.003-0.15 is still more preferable, 0.005-0.13 is still more preferable, 0.01-0.12 is still more preferable, 0.02-0 .11 is more preferable, and 0.025 to 0.1 is more preferable.

  In the production method of the present invention, it is desirable to reduce the amount of surfactant used from the viewpoint of (A) maintaining the antibacterial activity of the phenolic antibacterial agent. The content of the surfactant in the heat treatment raw material is preferably 0 to 1 g / L, more preferably 0 to 0.5 g / L, further preferably 0 to 0.1 g / L, substantially 0 g / L, That is, it is more preferable not to contain a surfactant.

The method for heat-treating (A) the phenolic antibacterial agent and (B) the polyol in the presence of the aqueous medium is not particularly limited, and a known method can be applied.
The temperature of the heat treatment is 110 to 180 ° C. from the viewpoint of (A) improved solubility and thermal stability of the phenolic antibacterial agent, more preferably 110 to 170 ° C., still more preferably 120 to 160 ° C., 120 More preferred is ~ 150 ° C. Examples of the heating means include water vapor and electricity.

  The pressure during the heat treatment is preferably 0 to 10 MPa, more preferably 0.1 to 8 MPa, further preferably 0.1 to 6 MPa, further preferably 0.2 to 6 MPa, and further preferably 0.2 to 4 MPa in terms of gauge pressure. Preferably, 0.25 to 2 MPa is more preferable, 0.3 to 1.5 MPa is further preferable, and 0.3 to 0.6 MPa is further preferable. The gauge pressure is a pressure at atmospheric pressure of 0 MPa. Moreover, it is preferable to set it more than the saturated vapor pressure of water. Gas may be used for pressurization, and examples of the gas used include inert gas, water vapor, nitrogen gas, helium gas, and the like. The pressurization may be adjusted by a back pressure valve without using gas.

The heat treatment can be performed by any method such as a batch method, a semi-batch method, and a distribution method. Among these, the flow method is preferable in terms of easy control of the heat treatment time.
The time for the heat treatment is preferably 0.1 to 30 minutes after the aqueous medium reaches the temperature for the heat treatment from the viewpoint of improving the solubility and heat stability of the (A) phenolic antibacterial agent, and more preferably 0.2 -15 minutes, more preferably 0.5-8 minutes.
When the flow method is used, the heat treatment time is an average residence time calculated by dividing the volume of the high-temperature and high-pressure part of the reactor by the supply rate of the aqueous medium.

  The flow rate of the aqueous medium in the flow method varies depending on the volume of the reactor. For example, when the reactor volume is 500 L, it is preferably 15 to 5,000 L / min, and more preferably 30 to 2,500 L / min. Further, 60 L / min to 1,000 L / min is preferable.

  In the manufacturing method of this invention, it is preferable to include the process of cooling the heat processing liquid obtained by heat-processing to 90 degrees C or less, Preferably it is 50 degrees C or less, More preferably, it is 30 degrees C or less. When obtaining a liquid antibacterial agent composition, 0 degreeC or more is preferable and 10 degreeC or more is preferable.

  The cooling rate of the heat treatment liquid calculated from the time required to decrease from the heat treatment temperature to 90 ° C. is 0.2 ° C./s or more, further 0.5 ° C./s or more, 1 ° C./s or more, and further 3 It is preferably at least 5 ° C./s, and more preferably The solubility of the phenolic antibacterial agent can be improved as the cooling rate increases. For this reason, although the upper limit of a cooling rate is not specifically defined, 100 degree C / s or less, for example, 50 degrees C / s or less are preferable from viewpoints, such as restrictions of manufacturing equipment.

  Furthermore, it is preferable from the viewpoint of dissolution stability of the obtained antibacterial agent composition to carry out a step of removing the solid matter remaining without being dissolved from the heat treatment liquid. The method for removing the solid matter is not particularly limited, and can be performed by, for example, centrifugation, decantation, or filtration.

The antibacterial agent composition thus obtained suppresses the precipitation of the phenolic antibacterial agent even at room temperature despite the high content of the (A) phenolic antibacterial agent. Moreover, it is excellent in solubility in water.
The content of the component (A) in the antibacterial agent composition of the present invention is preferably 0.5 g / L or more, more preferably 1 g / L or more, further 1.5 g / L or more, from the viewpoint of physical distribution and usability. Furthermore, 2 g / L or more is preferable.

  In the antibacterial agent composition of the present invention, the amount of the component (A) dissolved in water at 25 ° C. is preferably 0.5 g / L or more, further 0.7 g / L or more, further 1 g / L or more, 1.1 g / L or more, further 1.2 g / L or more, further 1.3 g / L or more, further 1.4 g / L or more, further 1.5 g / L or more, more preferably 2 g / L or more, and 100 g / L or less, further 75 g / L or less, further 50 g / L or less, further 30 g / L or less, further 20 g / L or less, further 10 g / L or less, and further preferably 9 g / L or less. Moreover, 0.5-100 g / L is preferable, 0.7-75 g / L is more preferable, 1-50 g / L is still more preferable, 1.1-30 g / L is further more preferable, 1.2-20 g / L Is more preferable, 1.3 to 10 g / L is more preferable, and 1.4 to 9 g / L is more preferable.

  The mass ratio [(A) / (B)] of the (A) phenolic antibacterial agent to the (B) polyol in the antibacterial agent composition of the present invention is 0.005 or more from the viewpoint of the stability of the antibacterial agent composition. Further, 0.01 or more, further 0.012 or more, further 0.015 or more, further 0.02 or more, further 0.025 or more, more preferably 0.03 or more, preferably 0.2 or less, further 0.18. Hereinafter, 0.15 or less, further 0.12 or less, further 0.1 or less, and further 0.09 or less are preferable. Moreover, 0.005-0.2 is preferable, 0.01-0.2 is more preferable, 0.012-0.18 is more preferable, 0.015-0.15 is still more preferable, 0.02-0 .12 is more preferable, 0.025 to 0.1 is more preferable, and 0.03 to 0.09 is still more preferable.

  In the antibacterial agent composition of the present invention, the content of the organic solvent is preferably 0 to 60%, more preferably 0 to 30%, and preferably 0 to 10% from the viewpoint of irritation to the skin. More preferably, it is more preferably 0 to 1%.

  In the antibacterial agent composition of the present invention, the content of monohydric alcohol having 4 or less carbon atoms is preferably 0 to 60%, more preferably 0 to 30%, from the viewpoint of irritation to the skin. 0 to 10% is more preferable, 0 to 1% is more preferable, 0 to 0.1% is more preferable, and no inclusion is more preferable.

  In the antibacterial agent composition of the present invention, the content of the surfactant is preferably 0 to 0.1% from the viewpoint of maintaining the antibacterial activity of the (A) phenolic antibacterial agent, and is preferably 0 to 0.5. % Is more preferable, 0 to 0.01% is more preferable, and no inclusion is more preferable.

  The antibacterial agent composition of the present invention can be used for various products such as cosmetics, pharmaceuticals, foods and daily necessities. In particular, it is useful to use for water-based products. Examples of cosmetics or pharmaceuticals include cleaning agents, lotions, makeup cosmetics, sunscreen cosmetics, acne cosmetics, deodorant cosmetics, shampoos, dentifrices, mouth washes, gargles, and the like. .

  The antibacterial agent composition of the present invention may be diluted with water or the like according to the use of the product. The concentration of the antibacterial agent composition after dilution is preferably 0.1 to 3 g / L, more preferably 0.2 to 2 g / L, and further preferably 0.5 to 1.5 g / L from the viewpoint of the bactericidal effect. The antibacterial agent composition of the present invention can be diluted to a desired concentration even though the dissolution concentration of the phenolic antibacterial agent has dramatically increased as compared with the solubility of ordinary phenolic antibacterial agents. Even in such a case, the precipitation of the phenolic antibacterial agent is suppressed, and the stability is high.

  Aspects and preferred embodiments of the present invention are shown below.

<1> A method for producing an antibacterial agent composition comprising a step of heat-treating (A) a phenolic antibacterial agent and (B) a polyol at 110 to 180 ° C. in the presence of an aqueous medium.

<2> (A) The phenolic antibacterial agent has a water solubility at 25 ° C. of preferably 0.5 g / L or less, preferably 0.3 g / L or less, more preferably 0.2 g / L. The manufacturing method of the antibacterial agent composition as described in <1> which is the following compounds.
<3> (A) The phenolic antibacterial agent is preferably one selected from triclosan, chlorthymol, carbachlor, chlorophene, dichlorophen, hexachlorophene, chloroxylenol, chlorocresol, O-phenylphenol and isopropylmethylphenol Or it is 2 or more types, More preferably, it is 1 type, or 2 or more types selected from triclosan and isopropylmethylphenol, More preferably, it is isopropylmethylphenol, The antimicrobial agent composition as described in <1> or <2> Manufacturing method.
<4> (B) The polyol is preferably one or more selected from alkylene glycols, polyalkylene glycols and glycerols, more preferably ethylene glycol, propylene glycol, 1,3-butanediol. Any one of <1> to <3>, which is one or more selected from dipropylene glycol, polyethylene glycol, glycerin and diglycerin, more preferably propylene glycol, 1,3-butanediol and glycerin A method for producing the antibacterial agent composition according to claim 1.
<5> In the step of heat treatment, the mass ratio [(A) / (B)] of (A) phenolic antibacterial agent to (B) polyol is preferably 0.001 or more, more preferably 0.003 or more, and further Preferably it is 0.005 or more, more preferably 0.01 or more, more preferably 0.02 or more, further preferably 0.025 or more, preferably 0.2 or less, more preferably 0.15 or less, More preferably, it is 0.13 or less, More preferably, it is 0.12 or less, More preferably, it is 0.11 or less, More preferably, it is 0.1 or less, Preferably it is 0.001-0.2, More preferably Is 0.003 to 0.15, more preferably 0.005 to 0.13, still more preferably 0.01 to 0.12, and still more preferably 0.02 to 0.11. Further Method of manufacturing preferably is 0.025 to 0.1 <1> - antimicrobial composition according to any one of <4>.
<6> In the heat treatment step, (A) the phenolic antibacterial agent is preferably 0.5 g / L or more in the heat treatment raw material containing the aqueous medium, (A) the phenolic antibacterial agent and (B) polyol. Preferably 0.7 g / L or more, more preferably 1 g / L or more, more preferably 1.1 g / L or more, still more preferably 1.2 g / L or more, more preferably 1.3 g / L or more, more preferably 1.4 g / L or more, preferably 100 g / L or less, more preferably 75 g / L or less, still more preferably 50 g / L or less, still more preferably 30 g / L or less, still more preferably 20 g / L or less, further Preferably it is 10 g / L or less, more preferably 9 g / L or less, preferably 0.5 to 100 g / L, preferably 0.7 to 75 g / L, more preferably 1 to 50 g / L. More preferably, 1.1 to 30 g / L, more preferably 1.2 to 20 g / L, still more preferably 1.3 to 10 g / L, and still more preferably 1.4 to 9 g / L. 5> The manufacturing method of the antibacterial agent composition in any one of.
<7> In the heat treatment step, the (B) polyol is preferably 1 g / L or more, more preferably 5 g / L in the heat treatment raw material containing the aqueous medium, the (A) phenolic antibacterial agent and the (B) polyol. More preferably, it is 10 g / L or more, more preferably 12 g / L or more, further preferably 15 g / L or more, more preferably 20 g / L or more, and preferably 800 g / L or less, more preferably 700 g / L. In the following, it is more preferably 600 g / L or less, more preferably 300 g / L or less, further preferably 100 g / L or less, more preferably 50 g / L or less, and preferably 1 to 800 g / L, preferably 5 to 700 g. / L, more preferably 10 to 600 g / L, more preferably 12 to 300 g / L, more preferably 15 to 100 g / L, Method of manufacturing preferably comprises 20 to 50 g / L <1> ~ antimicrobial composition according to any one of <6>.
<8> The aqueous medium is preferably an aqueous solution of water or an organic solvent, more preferably an aqueous solution of water or a monohydric alcohol having 4 or less carbon atoms, more preferably an aqueous solution of water or ethanol, still more preferably. The method for producing an antibacterial agent composition according to any one of <1> to <7>, which is water.
<9> The concentration of the organic solvent in the aqueous solution of the organic solvent is preferably 0 to 60% by mass, preferably 0 to 30% by mass, more preferably 0 to 10% by mass, and still more preferably 0. The method for producing an antibacterial agent composition according to <8>, which is ˜1% by mass, and more preferably not contained.
<10> In the heat treatment step, the surfactant is preferably 0 to 1 g / L, more preferably 0 to 0 in the heat treatment raw material containing an aqueous medium, (A) a phenolic antibacterial agent and (B) polyol. The manufacturing method of the antibacterial agent composition in any one of <1>-<9> which contains 0.5 g / L, More preferably 0-0.1 g / L, More preferably it does not contain.
<11> The temperature of the heat treatment is 110 to 180 ° C, preferably 110 to 170 ° C, more preferably 120 to 160 ° C, and still more preferably 120 to 150 ° C. <1> to <10> The manufacturing method of the antibacterial agent composition in any one of.
<12> Furthermore, the manufacturing method of the antibacterial agent composition in any one of <1>-<11> including the process of cooling the heat processing liquid obtained by heat-processing.
<13> In the step of cooling the heat treatment liquid, the cooling rate from the heat treatment temperature to 90 ° C. is preferably 0.2 ° C./s or more, more preferably 0.5 ° C./s or more, more preferably 1 ° C. / S or higher, more preferably 3 ° C./s or higher, more preferably 5 ° C./s or higher, preferably 100 ° C./s or lower, more preferably 50 ° C./s or lower <1> to <12 The manufacturing method of the antibacterial agent composition in any one of>.
<14> An antibacterial composition obtained by the production method according to any one of <1> to <13>.
<15> The content of the (A) phenolic antibacterial agent in the antibacterial agent composition is preferably 0.5 g / L or more, more preferably 1 g / L or more, still more preferably 1.5 g / L or more, even more preferably. Is an antibacterial agent composition as described in <14> which is 2 g / L or more.
<16> (A) The amount of the phenolic antibacterial agent dissolved in water at 25 ° C. is preferably 0.5 g / L or more, more preferably 0.7 g / L or more, still more preferably 1 g / L or more, still more preferably Is 1.1 g / L or more, more preferably 1.2 g / L or more, more preferably 1.3 g / L or more, more preferably 1.4 g / L or more, more preferably 1.5 g / L or more, and further preferably Is 2 g / L or more, preferably 100 g / L or less, more preferably 75 g / L or less, further preferably 50 g / L or less, more preferably 30 g / L or less, still more preferably 20 g / L or less, Preferably it is 10 g / L or less, more preferably 9 g / L or less, preferably 0.5 to 100 g / L, more preferably 0.7 to 75 g / L, still more preferably 1 to 50 g / L, Preferably it is 1.1-30 g / L, More preferably, it is 1.2-20 g / L, More preferably, it is 1.3-10 g / L, More preferably, it is 1.4-9 g / L <14> or <15>.
<17> The mass ratio [(A) / (B)] of (A) phenolic antibacterial agent to (B) polyol is preferably 0.005 or more, more preferably 0.01 or more, and still more preferably 0.012 or more. More preferably, it is 0.015 or more, More preferably, it is 0.02 or more, More preferably, it is 0.025 or more, More preferably, it is 0.03 or more, Preferably it is 0.2 or less, More preferably, it is 0.18. Or less, more preferably 0.15 or less, still more preferably 0.12 or less, still more preferably 0.1 or less, still more preferably 0.09 or less, and preferably 0.005 to 0.2, more preferably Is from 0.01 to 0.2, more preferably from 0.012 to 0.18, more preferably from 0.015 to 0.15, still more preferably from 0.02 to 0.12, and even more preferably from 0.025 to 0. . , More preferably from 0.03 to 0.09 <14> - antimicrobial composition according to any one of <16>.
<18> The content of the organic solvent in the antibacterial agent composition is preferably 0 to 60% by mass, more preferably 0 to 30% by mass, still more preferably 0 to 10% by mass, and still more preferably 0 to 1% by mass. The antibacterial agent composition according to any one of <14> to <17>.
<19> The content of monohydric alcohol having 4 or less carbon atoms in the antibacterial agent composition is preferably 0 to 60% by mass, more preferably 0 to 30% by mass, still more preferably 0 to 10% by mass, and still more preferably. Is 0 to 1% by mass, more preferably 0 to 0.1%, and even more preferably, the antibacterial agent composition according to any one of <14> to <18>.
<20> The content of the surfactant in the antibacterial agent composition is preferably 0 to 0.1% by mass, more preferably 0 to 0.5% by mass, and still more preferably 0 to 0.01% by mass. The antibacterial composition according to any one of <14> to <19>.
<21> Cosmetics containing the antibacterial agent composition in any one of <14>-<20>.
<22> A cosmetic for a deodorant containing the antibacterial agent composition according to any one of <14> to <20>.
<23> An acne cosmetic comprising the antibacterial agent composition according to any one of <14> to <20>.
<24> A cleaning material comprising the antibacterial agent composition according to any one of <14> to <20>.

[Quantification of isopropylmethylphenol]
Using a high-performance liquid chromatograph manufactured by Hitachi, Inc., a column Cadenza CD-C18 (4.6 mmφ × 150 mm, 3 μm) manufactured by Intact was installed, and the gradient method was performed at a column temperature of 40 ° C. The mobile phase A solution was 0.05 mol / L acetic acid aqueous solution, the B solution was acetonitrile, and the solution was fed at 1.0 mL / min. The gradient conditions are as follows.
Time (min) A liquid (%) B liquid (%)
0 85 15
20 80 20
35 10 90
50 10 90
50.1 85 15
60 85 15
The sample injection amount was 10 μL, and detection was quantified by absorbance at a wavelength of 283 nm.

[Stability evaluation of diluted products]
The isopropylmethylphenol composition or liquid part was diluted with water so that the isopropylmethylphenol concentration in the composition or liquid part was 0.05% by mass or 0.1% by mass, and stored at 25 ° C. for 1 month. . The state of precipitation of the diluted product was observed to give an appearance after storage.

[raw materials]
Isopropylmethylphenol (IPMP, Osaka Kasei Co., Ltd., purity 100%)
1,3-butanediol (1,3-BG, manufactured by KH Neochem, purity 100%)
Diglycerin (DG, Sakamoto Pharmaceutical Co., Ltd., purity 100%)
Propylene glycol (PG, manufactured by ADEKA Corporation, purity 100%)
Dipropylene glycol (DPG, manufactured by Asahi Glass Co., Ltd., purity 100%)
Polyethylene glycol (PEG, Sanyo Chemical Industries, 100% purity)
Ethylene glycol (EG, manufactured by Kao Corporation, purity 100%)
Glycerin (Gly, Kao Corporation, purity 100%)

Example 1
Isopropylmethylphenol and 1,3-butanediol were added to distilled water at 1.43 g / L and 47.5 g / L, respectively, and the resulting slurry was added to a 190 mL stainless batch reactor (Nitto High Pressure). (Made by Co., Ltd.). After reaching 150 ° C., the temperature was maintained for 1 minute and quickly cooled to room temperature (25 ° C.) (cooling rate 0.5 ° C./s). The pressure during the heat treatment was 0.4 MPa. After cooling, the heat treatment solution was immediately extracted and filtered through a PTFE filter having a pore size of 0.2 μm to obtain an isopropylmethylphenol composition.
Table 1 shows the treatment conditions, the isopropylmethylphenol concentration in the composition and the measurement of 1,3-butanediol, and the appearance of the diluted product after storage (the same applies in the following examples).

Example 2
Isopropylmethylphenol and diglycerin were added to distilled water so as to be 1.46 g / L and 47.5 g / L, respectively, and heat treatment was performed in the same manner as in Example 1 to obtain an isopropylmethylphenol composition.

Example 3
Isopropylmethylphenol and propylene glycol were added to distilled water so as to be 1.43 g / L and 47.5 g / L, respectively, and heat-treated in the same manner as in Example 1 to obtain an isopropylmethylphenol composition.

Example 4
Isopropylmethylphenol and dipropylene glycol were added to distilled water so as to be 1.43 g / L and 47.5 g / L, respectively, and heat-treated in the same manner as in Example 1 to obtain an isopropylmethylphenol composition.

Examples 5-7
Isopropylmethylphenol and polyethylene glycol (molecular weights 1540, 4000, 20000) were added to distilled water so as to be 1.43 g / L and 47.5 g / L, respectively, and heat-treated in the same manner as in Example 1 to produce an isopropylmethylphenol composition. I got a thing.

Example 8
Isopropylmethylphenol and ethylene glycol were added to distilled water at 1.66 g / L and 47.5 g / L, respectively, and heat-treated in the same manner as in Example 1 to obtain an isopropylmethylphenol composition.

Example 9
Isopropylmethylphenol and glycerin were added to distilled water so as to be 1.66 g / L and 47.5 g / L, respectively, and heat-treated in the same manner as in Example 1 to obtain an isopropylmethylphenol composition.

Example 10
Isopropyl methylphenol was dissolved in 1,3-butanediol so as to be 35 g / L. Supply the solution and distilled water to a stainless steel flow reactor (manufactured by Nitto Koatsu Co., Ltd.) having an internal volume of 100 mL so that the flow rate of the solution is 5 ml / min and the flow rate of distilled water is 95 ml / min. Heat treatment was performed (average residence time 1 minute). The pressure was adjusted to 0.5 MPa (gauge pressure) by the outlet side valve. The heat treatment liquid is extracted from the outlet of the reactor, cooled to room temperature (25 ° C.) with a heat exchanger, passed through a sintered metal filter with a pore size of 0.5 μm, and then the pressure is returned to atmospheric pressure with an outlet valve to isopropylmethylphenol. A composition was obtained. The cooling rate obtained from the cooling time from 150 ° C. to 90 ° C. was 2 ° C./s.

Comparative Example 1
Component (B) Polyol was not added, and 1.5 g / L of isopropylmethylphenol was dispersed in distilled water to obtain an isopropylmethylphenol composition in the same manner as in Example 1. Table 2 shows the treatment conditions and the results of measuring the isopropylmethylphenol concentration in the composition.

Comparative Example 2
Isopropylmethylphenol and 1,3-butanediol were added to distilled water so as to be 1.43 g / L and 47.5 g / L, respectively, and 50 g of the slurry was stirred for 3 days (stirrer, 500 r / min). Was filtered off. The results of measuring the isopropylmethylphenol concentration and the 1,3-butanediol concentration in the liquid part are shown in Table 2.

Comparative Example 3
Isopropylmethylphenol and diglycerin were added to distilled water at 1.46 g / L and 47.5 g / L, respectively, and 50 g of the slurry was stirred for 3 days (stirrer, 500 r / min), and the solid matter was filtered off. . Table 2 shows the results of measuring the isopropylmethylphenol concentration and the diglycerin concentration in the liquid part.

Comparative Example 4
Isopropylmethylphenol and propylene glycol were added to distilled water so as to be 1.43 g / L and 47.5 g / L, respectively, and 50 g of the slurry was stirred for 3 days (stirrer, 500 r / min), and the solid matter was separated by filtration. . The results of measuring the isopropylmethylphenol concentration and propylene glycol concentration in the liquid part are shown in Table 2.

Comparative Example 5
Isopropylmethylphenol and polyethylene glycol (molecular weight 4000) were added to distilled water to 1.43 g / L and 47.5 g / L, respectively, and 50 g of the slurry was stirred for 3 days (stirrer, 500 r / min), Was filtered off. Table 2 shows the results of measuring the isopropylmethylphenol concentration and the polyethylene glycol concentration in the liquid part.

Example 11
Add isopropylmethylphenol and propylene glycol to distilled water at 1.66 g / L and 47.5 g / L, respectively, and heat-treat with a 190 mL stainless batch reactor (made by Nitto Koatsu Co., Ltd.). went. After reaching 120 ° C., the temperature was maintained for 5 minutes and quickly cooled to room temperature (25 ° C.) (cooling rate 0.7 ° C./s). The pressure during the heat treatment was 0.14 MPa. After cooling, the heat treatment solution was immediately extracted and filtered through a PTFE filter having a pore size of 0.2 μm to obtain an isopropylmethylphenol composition. The results of measurement of the treatment conditions, the isopropylmethylphenol concentration and the propylene glycol concentration in the composition, and the appearance of the diluted product after storage are shown in Table 3 (hereinafter the same in the examples).

Example 12
An isopropylmethylphenol composition was obtained in the same manner as in Example 11 except that the heating temperature was 135 ° C. and the holding time was 5 minutes.

Example 13
An isopropylmethylphenol composition was obtained in the same manner as in Example 11 except that the heating temperature was 140 ° C. and the holding time was 1 minute.

Example 14
An isopropylmethylphenol composition was obtained in the same manner as in Example 11 except that the heating temperature was 145 ° C. and the holding time was 1 minute.

Example 15
An isopropylmethylphenol composition was obtained in the same manner as in Example 11 except that the heating temperature was 150 ° C. and the holding time was 1 minute.

Comparative Example 6
An isopropylmethylphenol composition was obtained in the same manner as in Example 11 except that the heating temperature was 80 ° C. and the holding time was 5 minutes. Table 3 shows the treatment conditions and the results of measuring the isopropylmethylphenol concentration and the propylene glycol concentration in the composition.

Comparative Example 7
An isopropylmethylphenol composition was obtained in the same manner as in Example 11 except that the heating temperature was 100 ° C. and the holding time was 5 minutes. Table 3 shows the treatment conditions and the results of measuring the isopropylmethylphenol concentration and the propylene glycol concentration in the composition.

Example 16
Isopropylmethylphenol and propylene glycol were added to distilled water so as to be 1.81 g / L and 100 g / L, respectively, and heat treatment was performed in the same manner as in Example 1 to obtain an isopropylmethylphenol composition. Table 4 shows the treatment conditions, the results of measuring the isopropylmethylphenol concentration and the propylene glycol concentration in the composition, and the appearance of the diluted product after storage.

Comparative Example 8
Isopropylmethylphenol and propylene glycol were added to distilled water so as to be 1.81 g / L and 100 g / L, respectively, and 50 g of the slurry was stirred for 3 days (stirrer, 500 r / min), and the solid matter was separated by filtration. Table 4 shows the results of measuring the isopropylmethylphenol concentration and the propylene glycol concentration in the liquid part.

Example 17
Isopropylmethylphenol and propylene glycol were added to distilled water so as to be 2 g / L and 300 g / L, respectively, and heat treatment was performed in the same manner as in Example 1 to obtain an isopropylmethylphenol composition. Table 4 shows the treatment conditions, the results of measuring the isopropylmethylphenol concentration and the propylene glycol concentration in the composition, and the appearance of the diluted product after storage.

Comparative Example 9
Isopropylmethylphenol and propylene glycol were added to distilled water so as to be 2 g / L and 300 g / L, respectively, and 50 g of the slurry was stirred for 3 days (stirrer, 500 r / min), and the solid matter was filtered off. Table 4 shows the results of measuring the isopropylmethylphenol concentration and propylene glycol concentration in the liquid part, and the appearance of the diluted product after storage.

Example 18
Isopropylmethylphenol and propylene glycol were added to distilled water so as to be 5 g / L and 400 g / L, respectively, and heat treatment was performed in the same manner as in Example 1 to obtain an isopropylmethylphenol composition. Table 4 shows the treatment conditions, the results of measuring the isopropylmethylphenol concentration and the propylene glycol concentration in the composition, and the appearance of the diluted product after storage.

Comparative Example 10
Isopropylmethylphenol and propylene glycol were added to distilled water so as to be 5 g / L and 400 g / L, respectively, and 50 g of the slurry was stirred for 3 days (stirrer, 500 r / min), and the solid matter was filtered off. Table 4 shows the results of measuring the isopropylmethylphenol concentration and propylene glycol concentration in the liquid part, and the appearance of the diluted product after storage.

Example 19
Isopropylmethylphenol and propylene glycol were added to distilled water so as to be 20 g / L and 500 g / L, respectively, and heat treatment was performed in the same manner as in Example 1 to obtain an isopropylmethylphenol composition. Table 4 shows the treatment conditions, the results of measuring the isopropylmethylphenol concentration and the propylene glycol concentration in the composition, and the appearance of the diluted product after storage.

Comparative Example 11
Isopropyl methylphenol and propylene glycol were added to distilled water so as to be 20 g / L and 500 g / L, respectively, and 50 g of the slurry was stirred for 3 days (stirrer, 500 r / min), and the solid matter was separated by filtration. Table 4 shows the results of measuring the isopropylmethylphenol concentration and propylene glycol concentration in the liquid part, and the appearance of the diluted product after storage.

Example 20
Isopropylmethylphenol and propylene glycol were added to distilled water so as to be 50 g / L and 600 g / L, respectively, and heat treatment was performed in the same manner as in Example 1 to obtain an isopropylmethylphenol composition. Table 4 shows the treatment conditions, the results of measuring the isopropylmethylphenol concentration and the propylene glycol concentration in the composition, and the appearance of the diluted product after storage.

Comparative Example 12
Isopropylmethylphenol and propylene glycol were added to distilled water so as to be 50 g / L and 600 g / L, respectively, and 50 g of the slurry was stirred for 3 days (stirrer, 500 r / min), and the solid matter was separated by filtration. Table 4 shows the results of measuring the isopropylmethylphenol concentration and propylene glycol concentration in the liquid part, and the appearance of the diluted product after storage.

Example 21
Isopropylmethylphenol and 1,3-butanediol were added to distilled water at 1.81 g / L and 100 g / L, respectively, and heat-treated in the same manner as in Example 1 to obtain an isopropylmethylphenol composition. Table 5 shows the treatment conditions, the results of measuring the isopropylmethylphenol concentration and the 1,3-butanediol concentration in the composition, and the appearance of the diluted product after storage.

Comparative Example 13
Isopropylmethylphenol and 1,3-butanediol are added to distilled water to give 1.81 g / L and 100 g / L, respectively, and 50 g of the slurry is stirred for 3 days (stirrer, 500 r / min). Separated. The results of measuring the isopropylmethylphenol concentration and the 1,3-butanediol concentration in the liquid part are shown in Table 5.

Examples 22-24
Add 1,3-butanediol to distilled water to 300 g / L and isopropylmethylphenol to 2 g / L, 5 g / L, and 10 g / L, respectively, and heat-treat in the same manner as in Example 1 to obtain an isopropylmethylphenol composition. I got a thing. Table 5 shows the treatment conditions, the results of measuring the isopropylmethylphenol concentration and the 1,3-butanediol concentration in the composition, and the appearance of the diluted product after storage.

Comparative Example 14
Isopropylmethylphenol and 1,3-butanediol were added to distilled water so as to be 5 g / L and 300 g / L, respectively, and 50 g of the slurry was stirred for 3 days (stirrer, 500 r / min), and the solid matter was separated by filtration. . Table 5 shows the results of measuring the isopropylmethylphenol concentration and 1,3-butanediol concentration in the liquid part, and the appearance of the diluted product after storage.

Examples 25-27
Add 1,3-butanediol to distilled water at 400 g / L and isopropylmethylphenol to 5 g / L, 10 g / L, and 20 g / L, respectively, and heat-treat in the same manner as in Example 1 to obtain an isopropylmethylphenol composition. I got a thing. Table 5 shows the treatment conditions, the results of measuring the isopropylmethylphenol concentration and the 1,3-butanediol concentration in the composition, and the appearance of the diluted product after storage.

Comparative Example 15
Isopropylmethylphenol and 1,3-butanediol were added to distilled water so as to be 10 g / L and 400 g / L, respectively, and 50 g of the slurry was stirred for 3 days (stirrer, 500 r / min), and the solid matter was separated by filtration. . Table 5 shows the results of measuring the isopropylmethylphenol concentration and 1,3-butanediol concentration in the liquid part, and the appearance of the diluted product after storage.

Examples 28-32
Example 1 was added to distilled water so that 1,3-butanediol was 500 g / L and isopropylmethylphenol was 10 g / L, 20 g / L, 25 g / L, 27.5 g / L, and 30 g / L, respectively. In the same manner as above, heat treatment was performed to obtain an isopropylmethylphenol composition. Table 6 shows the treatment conditions, the results of measuring the isopropylmethylphenol concentration and the 1,3-butanediol concentration in the composition, and the appearance of the diluted product after storage.

Comparative Example 16
Isopropylmethylphenol and 1,3-butanediol are added to distilled water to 27.5 g / L and 500 g / L, respectively, and 50 g of the slurry is stirred for 3 days (stirrer, 500 r / min). Separated. Table 6 shows the results of measuring the isopropylmethylphenol concentration and 1,3-butanediol concentration in the liquid part, and the appearance of the diluted product after storage.

Examples 33-36
1,3-butanediol was added to distilled water to 600 g / L and isopropylmethylphenol to 20 g / L, 30 g / L, 40 g / L, and 50 g / L, respectively, and heat-treated in the same manner as in Example 1. Thus, an isopropylmethylphenol composition was obtained. Table 6 shows the treatment conditions, the results of measuring the isopropylmethylphenol concentration and the 1,3-butanediol concentration in the composition, and the appearance of the diluted product after storage.

Comparative Example 17
Isopropylmethylphenol and 1,3-butanediol were added to distilled water so as to be 50 g / L and 600 g / L, respectively, and 50 g of the slurry was stirred for 3 days (stirrer, 500 r / min), and the solid matter was separated by filtration. . Table 6 shows the results of measuring the isopropylmethylphenol concentration and 1,3-butanediol concentration in the liquid part, and the appearance of the diluted product after storage.

As is clear from Tables 1 to 6, an isopropylmethylphenol composition having a high isopropylmethylphenol content could be obtained, and the solubility of isopropylmethylphenol could be remarkably increased.
Moreover, when the isopropylmethylphenol composition obtained in Examples 1 to 36 was stored at room temperature for 1 month, a stable dissolved state was maintained without precipitation. Furthermore, as shown in Tables 1-6, even when the isopropylmethylphenol composition obtained in Examples 1-36 was diluted to a desired concentration, a stable dissolved state was maintained without precipitation. It was. On the other hand, when the heat treatment of the present invention was not performed, as shown in the comparative example, when the isopropylmethylphenol composition was diluted to a desired concentration, precipitation was observed after storage, resulting in poor stability. It was confirmed.

Example 37
To 4.08 g of the isopropylmethylphenol composition produced in Example 31, 10 g of aluminum hydroxychloride, 0.2 g of polyoxyethylene hydrogenated castor oil, and 0.05 g of fragrance were added, and purified water was added to prepare 100 g of a deodorant lotion. The composition is as follows.
IPMP 0.1 (mass%)
1,3-BG 2.04
Aluminum hydroxychloride 10.0
Polyoxyethylene (40) hydrogenated castor oil 0.2
Fragrance 0.05
Purified water balance <br/> Total 100.0

Example 38
78.74 g of the isopropylmethylphenol composition produced in Example 1 was 6 g of 1,3 butylene glycol, 0.1 g of oleyl alcohol, 0.4 g of POE (20) oleyl alcohol ether, 0.2 g of methyl paraben, and 0.2 g of dipotassium glycyrrhizinate. 0.04 g of fragrance was added, and purified water was added to prepare 100 g of acne lotion. The composition is as follows.
IPMP 0.1 (mass%)
1,3-BG 9.74
Oleyl alcohol 0.1
POE (20) oleyl alcohol ether 0.4
Methylparaben 0.2
Dipotassium glycyrrhizinate 0.2
Perfume 0.04
Purified water balance <br/> Total 100.0

Example 39
As the oil phase, 12 g of stearic acid, 14 g of myristic acid, 5 g of lauric acid, 3 g of jojoba oil, 14.047 g of sorbit, 10 g of glycerin, and 10 g of 1,3-butylene glycol were heated and dissolved and kept at 70 ° C. 5 g of potassium hydroxide was dissolved in 21.053 g of the isopropylmethylphenol composition produced in Example 18, and the oil phase was slowly added with stirring. 4 g of N-methyltaurine was further added and the mixture was stirred for 10 minutes to sufficiently carry out a neutralization reaction, and then 1.9 g of POE (20) glycerol monostearate was added. A hand wash was prepared by slowly cooling to 25 ° C (cooling). The composition is as follows.
Stearic acid 12.0 (mass%)
Myristic acid 14.0
Lauric acid 5.0
Jojoba oil 3.0
Sorbit (70% aqueous solution of sorbitol)
Glycerin 10.0
1,3-BG 10.0
Potassium hydroxide 5.0
N-methyl taurine 4.0
POE (20) glycerol monostearate 1.9
IPMP 0.1
PG 8.421
Purified water balance <br/> Total 100.0

Claims (6)

  The antibacterial agent composition obtained by the manufacturing method including the process of heat-processing (A) phenolic antibacterial agent and (B) polyol at 110-180 degreeC in presence of an aqueous medium.   The antibacterial agent composition according to claim 1, wherein the mass ratio [(A) / (B)] of (A) phenolic antibacterial agent to (B) polyol is 0.005 to 0.2.   (A) The antibacterial agent composition according to claim 1 or 2, wherein the amount of the phenolic antibacterial agent dissolved in water at 25 ° C is 0.5 g / L or more.   The antibacterial agent composition according to any one of claims 1 to 3, wherein the content of the monohydric alcohol having 4 or less carbon atoms in the antibacterial agent composition is 0 to 1% by mass.   The antibacterial agent composition according to any one of claims 1 to 4, wherein the content of the surfactant in the antibacterial agent composition is 0 to 0.1% by mass.   Cosmetics containing the antibacterial agent composition of any one of Claims 1-5.