JP2009108000A - Germicidal composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a germicidal composition low in skin irritancy, and excellent in touch feeling in use, smell and bactericidal activity, and to provide a wet wiper using the same. <P>SOLUTION: The germicidal composition comprises (a) 0.1-20.0 mass% of a block-type alkylene oxide derivative of the formula (I) described below, (b) 1.0-70.0 mass% of an alcohol and (c) 0.01-2.0 mass% of a germicide. The formula (I) is as follows: Y-[O(EO)<SB>a</SB>-(AO)<SB>b</SB>-(EO)<SB>c</SB>-R<SP>1</SP>]<SB>k</SB>(wherein, Y is a residue freed from the hydroxy groups in a polyhydric alcohol having 3-6 hydroxy groups; k is the number of the hydroxy groups in the polyhydric alcohol; EO is an oxyethylene group, and AO is a 3-6C oxyalkylene group, being added in a block manner; a×k, b×k and c×k are the average addition numbers of moles of the oxyethylene groups, the 3-6C oxyalkylene groups and the oxyethylene groups, respectively, meeting the relationships: 0≤a×k≤50, 1≤b×k≤100, and 0≤c×k≤100, wherein 1<(a+c)×k; the proportion of the oxyethylene groups to the total of the 3-6C oxyalkylene groups and the oxyethylene groups is 10-80 mass%; and R<SP>1</SP>is a 1-4C hydrocarbon group). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a sterilizing composition, wet wipes, and more particularly to their skin irritation, odor reduction and improved feel to use.

  Wet wipers are generic terms such as “wet tissue”, “disposable wet towel”, “hand wipe”, “clean cotton”, “hand towel cloth”, “moisturizing tissue”, etc. (Japan Clean Cotton Industry Association: Wet Wiper) The company's own safety and health standards). These are widely used mainly as portable towels, and can remove a simple dirt such as sweat to obtain a refreshing clean feeling.

  Chemicals such as water, ethanol, and benzalkonium chloride are used for wet wipers such as wet tissues, disposable towels, hand towels, clean cotton, towel towels, and moisturizing tissues. Benzalkonium chloride, a representative chemical, is used in the medical, food, cosmetics, and industrial fields for the purpose of sterilization, deodorization, and anti-fungus. Has been. However, benzalkonium chloride has the drawbacks of skin irritation and smell.

  As means for solving this problem, a method of using tetrahydroabietic acid and ethanol in combination (for example, see Patent Document 1) and a method of blending alkyldimethylbenzylammonium (for example, see Patent Document 2) have been proposed.

However, although the method using tetrahydroabietic acid in combination with ethanol is excellent in bactericidal properties, skin irritation and usability, the effect is not satisfactory.
Although the method of blending alkyldimethylbenzylammonium is excellent in skin irritation and odor reduction, the feeling in use is not satisfactory.

There has also been a proposal of blending a linear polyalkylene oxide dialkyl ether derivative with low skin irritation and good use feeling (see, for example, Patent Document 3). However, although these proposals are excellent in reducing the feeling of use and irritation to the skin, they have not always obtained a satisfactory effect with respect to the odor over time.
Japanese Patent Laid-Open No. 5-15467 JP 2006-69919 A JP 2004-292395 A

  The present invention has been made in view of the above-described problems of the prior art, and an object thereof is to provide a sterilizing composition having low skin irritation, excellent use feeling, odor, and sterilizing action, and a wet wiper using the same. It is in.

  As a result of intensive studies by the present inventors in order to achieve the above object, the use of a specific block-type alkylene oxide derivative together with alcohol and a bactericidal agent results in low skin irritation even when a bactericidal agent is used. The present inventors have found that it is excellent in use feeling, has a low odor over time, and does not inhibit the bactericidal action.

  That is, the bactericidal composition according to the present invention comprises (a) 0.1 to 20.0% by mass of a block-type alkylene oxide derivative represented by the following formula (I) and (b) 1.0 to 70. 0 mass% and (c) 0.01-2.0 mass% of bactericides are contained, It is characterized by the above-mentioned.

(Chemical formula 1)
Y- [O (EO) _a- (AO) _b- (EO) _c -R ¹ ] _k (I)
(In the formula, Y is a residue obtained by removing a hydroxyl group of a polyhydric alcohol having 3 to 6 hydroxyl groups, k is the number of hydroxyl groups of the polyhydric alcohol, EO is an oxyethylene group, and AO is an oxy of 3 to 6 carbon atoms. Each of which is added in the form of a block with an alkylene group, wherein a × k, b × k and c × k are the average number of moles of oxyethylene group, oxyalkylene group having 3 to 6 carbon atoms, and oxyethylene group, 0 ≦ a × k ≦ 50, 1 ≦ b × k ≦ 100, 0 ≦ c × k ≦ 100, where 1 <(a + c) × k, which is an oxyethylene group and an oxyalkylene group having 3 to 6 carbon atoms. The ratio of the oxyethylene group to the total is 10 to 80% by mass, and R ¹ is a hydrocarbon group having 1 to 4 carbon atoms.

In the sterilizing composition, in the block-type alkylene oxide derivative represented by the formula (I), AO is preferably an oxybutylene group.
In the sterilizing composition, a is preferably 0 in the block-type alkylene oxide derivative represented by the formula (I).
Furthermore, the wet wiper according to the present invention is characterized in that the sterilizing composition is impregnated.

According to the present invention, by incorporating a block-type alkylene oxide derivative having a specific structure, it is possible to obtain a sterilizing composition that has low skin irritation even when an alcohol or a bactericidal agent is blended, and has an excellent odor and feel. Can do. Moreover, the composition retains a high bactericidal action.
Moreover, the wet wiper provided with the said function can be obtained by impregnating the said disinfection composition to a base fabric.

Hereinafter, preferred embodiments of the present invention will be described.
The composition for sterilization according to the present invention includes (a) a block-type alkylene oxide derivative having a specific structure, (b) an alcohol, and (c) a specific amount of a fungicide. Hereinafter, the essential components will be described in detail.

(A) Block-type alkylene oxide derivative In the present invention, a block-type alkylene oxide derivative represented by the following formula (I) can be applied.
(Chemical formula 2)
Y- [O (EO) _a- (AO) _b- (EO) _c -R ¹ ] _k (I)

In the block-type alkylene oxide derivative represented by the formula (I), Y is a residue obtained by removing a hydroxyl group of a polyhydric alcohol having 3 to 6 hydroxyl groups, and k is the number of hydroxyl groups of the polyhydric alcohol. ~ 6.
Examples of the polyhydric alcohol having 3 to 6 hydroxyl groups include glycerin with k = 3, trimethylolpropane, erythritol with k = 4, pentaerythritol, xylitol with k = 5, sorbitol with k = 6, Inositol.
That is, the block-type alkylene oxide derivative blended in the liquid detergent composition for kitchen according to the present invention excludes the hydroxyl group of one or a mixture of two or more polyhydric alcohols having 3 to 6 hydroxyl groups. The basic skeleton is the residue.

  In the present invention, in particular, Y is preferably a residue obtained by removing a hydroxyl group of a polyhydric alcohol having 3 to 4 hydroxyl groups, that is, it is preferable that 3 ≦ k ≦ 4 is satisfied. Specific examples of such polyhydric alcohols include glycerin and pentaerythritol. When k is 2 or less, when blended into a sterilizing composition, odor reduction over time is insufficient, which is not preferable. Further, if k is 7 or more, a sticky feeling may occur, which is not preferable.

  EO is an oxyethylene group. AO is an oxyalkylene group having 3 to 6 carbon atoms. Specifically, oxypropylene group, oxybutylene group, oxyisobutylene group, oxy t-butylene group, oxytetramethylene group, oxypentylene group, oxyhexylene Group, and the like. Preferred are an oxypropylene group and an oxybutylene group, and more preferred is an oxybutylene group. Moreover, 1 type (s) or 2 or more types can be used for AO.

  b × k is the total number of average added moles of AO, and 1 ≦ b × k ≦ 100, preferably 3 ≦ b × k ≦ 70, more preferably 5 ≦ b × k ≦ 50. a × k and c × k are average added moles of EO, and 0 ≦ a × k ≦ 50 and 0 ≦ c × k ≦ 100. a × k is preferably 0 ≦ a × k ≦ 30, and more preferably 0 ≦ a × k ≦ 20. Further, c × k is preferably 5 ≦ c × k ≦ 70, and more preferably 5 ≦ c × k ≦ 50. Further, the average added mole number (a + c) × k of all oxyethylene groups in the formula (I) is larger than 1, preferably 1 <(a + c) × k ≦ 200, and more preferably 10 ≦ (a + c). Xk≤140. AO becomes a hydrophobic site in the block-type alkylene oxide derivative according to the present invention. When b × k is 0, the sticky feeling and odor reduction with time are insufficient, and when it exceeds 100, the skin irritation is inferior. There is a tendency. Moreover, when (a + c) × k is 0, skin irritation may be inferior.

The ratio of the total EO in the said formula (I) with respect to the sum total of AO and EO in the said formula (I) is 10-80 mass%, More preferably, it is 20-70 mass%. If the ratio is less than 10% by mass, the skin irritation tends to be inferior, and if it is more than 80% by mass, a sticky feeling may appear.
The addition form of AO and EO is block-like, and the addition order is (AO)-(EO) order, (EO)-(AO) order, (EO)-( Any of the order of AO)-(EO) may be sufficient. In the present invention, the order of (AO)-(EO) with respect to Y in the formula, that is, a = 0 is particularly preferable.

In the formula (I), R ¹ is a hydrocarbon group having 1 to 4 carbon atoms, which is essential for reducing stickiness. Examples of such a hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and the like in the present invention. An ethyl group is preferred. A carbon number greater than 5 is not preferable because the effect of reducing odor over time is not sufficient. Further, it is not preferable that R ¹ is a hydrogen atom because a sticky feeling may occur.
In the block-type alkylene oxide derivative blended in the kitchen liquid detergent composition according to the present invention, R ¹ may be the same or different in one molecule, and may be the same R ¹ in one molecule. It may be a block type alkylene oxide derivative having a phenotype or a mixture of two or more having different R ¹ groups.

Specific examples of the block-type alkylene oxide derivative blended in the kitchen detergent composition according to the present invention include POB (30) POE (30) glyceryl trimethyl ether and POB (30) POE (35) glyceryl trimethyl ether. , POB (17) POE (28) glyceryl trimethyl ether, POB (27) POE (45) glyceryl trimethyl ether, POB (14) POE (34) glyceryl trimethyl ether, POB (22) POE (55) glyceryl trimethyl ether, POB (19) POE (55) glyceryl trimethyl ether, POB (40) POE (80) glyceryl trimethyl ether, POB (80) POE (40) glyceryl trimethyl ether, POB (30) POE (30) glyceryl tri Tyl ether, POB (30) POE (35) glyceryl triethyl ether, POB (14) POE (34) glyceryl triethyl ether, POB (30) POE (30) glyceryl tripropyl ether, POE (30) POP (30) glyceryl trimethyl ether , POE (35) POP (40) glyceryl trimethyl ether, POE (41) POP (48) glyceryl trimethyl ether, and the like.
The POE, POP, and POB are abbreviations for polyoxyethylene, polyoxypropylene, and polyoxybutylene, respectively, and may be abbreviated as follows.

  The block-type alkylene oxide derivative blended in the sterilizing composition according to the present invention can be produced by a known method. For example, it can be obtained by addition-polymerizing ethylene oxide and an alkylene oxide having 3 to 6 carbon atoms to a compound having a hydroxyl group, and then etherifying an alkyl halide in the presence of an alkali catalyst.

  As a compounding quantity of the block type alkylene oxide derivative obtained as mentioned above, it is preferable that it is 0.1-20.0 mass% with respect to the sterilization composition whole quantity concerning this invention, More preferably, it is 1. It is 0-10.0 mass%. If the blending amount is less than 0.1% by mass, the skin irritation may not be sufficiently reduced, and if the blending amount exceeds 20.0% by mass, stickiness tends to be felt after use, which is not preferable.

(B) Alcohol The alcohol that can be applied to the sterilizing composition according to the present invention is not particularly limited, and specific examples include ethanol, propanol, isopropanol, isobutyl alcohol, t-butyl alcohol, and the like. It is done. In the present invention, ethanol is particularly preferable.
The compounding quantity of the alcohol in the composition for sterilization of this invention is 1.0-70.0 mass% with respect to the composition whole quantity, Preferably it is 5.0-40.0 mass%. When the blending amount is less than 1.0% by mass, it feels sticky, and when it exceeds 70.0% by mass, skin irritation may be observed, which is not preferable.

(C) Disinfectant Examples of the disinfectant that can be applied to the disinfectant composition according to the present invention include cationic surfactants such as benzalkonium chloride, benzethonium chloride, and cetylpyridinium chloride. In the present invention, benzalkonium chloride is particularly preferable.
The compounding quantity of the disinfectant in the composition for disinfection of this invention is 0.01-2.0 mass% with respect to the composition whole quantity, Preferably it is 0.1-0.5 mass%. If the blending amount is less than 0.01% by mass, an effect as a bactericidal agent cannot be obtained, and if it exceeds 2.0% by mass, skin irritation may be observed, which is not preferable.

  The wet wiper of the present invention is obtained by impregnating the sterilizing composition with paper, nonwoven fabric, absorbent cotton rayon-stable cotton, or a base fabric in which a plastic film or the like is combined, specifically, , Wet tissue, disposable towel, hand towel, clean cotton, towel towel, moisturizing tissue, etc.

  In the wet wiper of the present invention, other components generally blended in the wet wiper, for example, oil, water, etc., can be blended within the range that does not impair the effects of the present invention. , Powders such as extender pigments, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, higher fatty acid alkanolamides, esters of fatty acids and polyhydric alcohols such as fatty acid monoglycerides, Moisturizers, lower alcohols, thickeners, chelating agents, preservatives, pigments, fragrances and the like can be blended.

  Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. The blending amount is expressed in mass% unless otherwise specified.

  The composition for sterilization (Examples 1-5, Comparative Examples 1-10) was prepared by a conventional method with the components and blending amounts shown in Table 2 below. Then, a 20 cm × 20 cm non-woven fabric was impregnated with the obtained solution of the composition to obtain a wet wiper. Each wet wiper was evaluated and evaluated for its characteristics.

About the (a) component in Table 2, the following were used.
<a component>
As the component (a), compounds a-1 to a-12 having structures shown in Table 1 below were used. Y in a-1 to a-10, a × k, b × k, c × k, AO, EO, and R ¹ represent a group and a numerical value in the following formula (I). In Table 1, Y represents the residue obtained by removing the hydroxyl group from each substance, and EOwt% represents the ratio of EO to the total of AO and EO. AO represents an oxyalkylene group, EO represents an oxyethylene group, PO represents an oxypropylene group, and BO represents an oxybutylene group.
(Chemical formula 3)
Y- [O (EO) _a- (AO) _b- (EO) _c -R ¹ ] _k (I)

(Table 1)

Each evaluation item in Table 2 is based on the following evaluation tests and standards. The evaluation results are also shown in Table 2.
"Evaluation (1): Skin irritation test"
The obstruction patch for 24 hours was applied to the inner side of the upper arm of 10 panelists, and then the average value was calculated according to the following criteria. ◎ or ○ was judged as having low skin irritation.
0: No abnormality is observed.
1 ... Slight redness is observed.
2… Redness is recognized.
3 ... Redness and papules are observed.
Evaluation criteria for the “skin irritation test” are as follows.
A: Average value of 10 panel members: less than 0.1 A: Average value of 10 panel members: 0.1 or more and less than 0.15 Δ: Average value of 10 panel members: 0.15 or more and less than 0.2 × Panel Average value of 10 people: 0.2 or more

"Evaluation (2): No stickiness on the skin"
An actual use test was conducted by 10 professional panelists on the non-stickiness of the skin during and after use. The evaluation criteria are as follows. ◎ or ○ was judged to be less sticky.
A: More than 8 professional panelists recognized that there was no stickiness on the skin during and after use.
○ ... 6 or more and less than 8 professional panelists recognized that there was no stickiness on the skin during and after use.
Δ: 3 or more and less than 6 professional panelists recognized that there was no stickiness on the skin during and after use.
X: Less than 3 professional panelists recognized that there was no stickiness on the skin during and after use.

"Evaluation (3): Smell over time"
About the composition for sterilization of each test example, it filled in the glass bottle immediately after manufacture, and the sensory evaluation was performed by 10 expert panelists about the smell after leaving at 50 degreeC for 6 weeks. ○ was judged to have good odor over time.
○… More than 6 professional panelists recognized that there was no unpleasant odor.
Δ: 3 or more and less than 6 professional panelists recognized that there was no unpleasant odor.
X: Less than 3 expert panelists recognized that there was no unpleasant odor.

"Evaluation (4): Bactericidal test (on skin)"
Both hands were wiped with wet wipes and clean cotton. After this operation was repeated twice, hand bacteria were collected by the glove juice method. The number of bacteria in the hand in Comparative Example 1 in which no bactericidal agent was blended was evaluated as a control. ○ was judged not to inhibit the bactericidal action.
○: The number of bacteria clearly lower than the number of viable bacteria in Comparative Example 1 was confirmed.
X: The number of bacteria substantially the same as the number of viable bacteria in Comparative Example 1 was confirmed.

(Table 2)

From the above results, the wet wipers of Examples 1 to 5 impregnated with the sterilizing composition of the present invention are excellent in skin irritation, non-stickiness, odor over time, and antibacterial properties. It was a thing.
On the other hand, the comparative example 1 which did not mix | blend an alkylene oxide derivative (a component) was inferior to the Example at the point of the stickiness of skin and the smell by time. In the comparative example 2 which mix | blended the compound a-6 which does not contain EO, skin irritation and the smell by time were inferior. The comparative example 3 which mix | blended the compound a-7 whose terminal is a hydroxyl group was inferior at the point of skin irritation, stickiness of skin, and the smell by time. The comparative example 4 which mix | blended the compound a-8 which has a hexyl group was inferior to the Example at the point of the smell with time. Comparative Example 5 containing Compound A-9 containing no AO was inferior in terms of skin stickiness and odor over time, and Comparative Example 6 containing Compound a-10 having a trehalose skeleton was inferior in stickiness. Met. Comparative Example 7 contains compound a-11 which is a dimethyl ether of a linear ethylene oxide / propylene oxide random copolymer, and Comparative Example 8 is a dimethyl ether of a linear ethylene oxide / propylene oxide block copolymer. A-12 was blended, but all the compositions were inferior to the examples in terms of odor over time.

Thus, in the compositions of Comparative Examples 1 to 8, none of the compositions satisfying all of skin irritation, feeling of use, odor over time, and antibacterial properties were found compared to Examples.
Therefore, by blending appropriate amounts of (a) a block-type alkylene oxide derivative having a specific structure, (b) alcohol, and (c) a bactericidal agent, the feeling of use and reduction of odor over time can be maintained while maintaining high antibacterial properties. An antibacterial composition that is improved and has low skin irritation can be obtained.

Claims (4)

(A) 0.1 to 20.0% by mass of a block-type alkylene oxide derivative represented by the following formula (I),
(B) 1.0-70.0 mass% of alcohol, and
(C) 0.01 to 2.0% by mass of a disinfectant,
A sterilizing composition comprising:
(Chemical formula 1)
Y- [O (EO) _a- (AO) _b- (EO) _c -R ¹ ] _k (I)
(In the formula, Y is a residue obtained by removing a hydroxyl group of a polyhydric alcohol having 3 to 6 hydroxyl groups, k is the number of hydroxyl groups of the polyhydric alcohol, EO is an oxyethylene group, and AO is an oxy of 3 to 6 carbon atoms. Each of which is added in the form of a block with an alkylene group, wherein a × k, b × k and c × k are the average number of moles of oxyethylene group, oxyalkylene group having 3 to 6 carbon atoms, and oxyethylene group, 0 ≦ a × k ≦ 50, 1 ≦ b × k ≦ 100, 0 ≦ c × k ≦ 100, where 1 <(a + c) × k, which is an oxyethylene group and an oxyalkylene group having 3 to 6 carbon atoms. (The ratio of the oxyethylene group to the total is 10 to 80% by mass. R ¹ is a hydrocarbon group having 1 to 4 carbon atoms.)   The sterilizing composition according to claim 1, wherein AO is an oxybutylene group in the block-type alkylene oxide derivative represented by the formula (I).   In the block-type alkylene oxide derivative represented by the formula (I), a is 0, and the composition for sterilization according to claim 1 or 2.   A wet wiper, wherein the sterilizing composition according to any one of claims 1 to 3 is impregnated.