JPH02218605A - Sterilizer for skin or hair - Google Patents

Abstract

PURPOSE:To obtain a sterilizer for skin or hair which has high sterilizing power with markedly reduced skin irritation by using a specific quaternary ammonium salt as an essential component. CONSTITUTION:A compound of formula I [at least one selected from R1 to R3 is a 8-30C straight-chain or branched alkyl or alkenyl and the rest are methyl, ethyl, benzyl, formula II, formula III (n is 1 to 15), formula IV; R4 is methyl, ethyl, hydroxyethyl; counter anion X<-> is anionic residue of phosphate, phosphonate, sulfonate of 7 or more carbon atoms, or sulfate, anionic oligomer or copolymer of 3 or more polymerization degree] is used as an essential component, in a concentration of 0.005 to 90wt.%, preferably 0.01 to 50wt.% to give a sterilizer with reduced skin irritation which exerts excellent effect in sterilization of human body (hands, fingers, face, hair and scalp) or animal skin, barns or the like.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a sterilizing disinfectant, and more particularly, to a disinfectant for disinfecting hands and fingers.
A sterilizing disinfectant that exhibits excellent sterilizing efficacy in the field of disinfection and sterilization of human skin and hair such as facial skin, hair, and scalp, animal skin, and animal housing, and is less irritating to the skin. Regarding.

[Conventional technology and its problems]

Because quaternary ammonium salts have excellent bactericidal properties, they have been used in a wide range of fields, including sterilization and disinfection of buildings such as livestock barns and food factories, environments, and preservation of wood, as well as disinfection of hands and skin during surgery. It is also used in fields such as sterilization. However, quaternary ammonium salts are highly irritating to the skin, and regular use may cause severe roughness or rash, which limits the scope and concentration of their use, and they have not been able to exhibit sufficient effects.

Therefore, there is a need for a fungicide that causes less skin irritation, is safer, and has superior bactericidal activity.

[Means to solve problems]

As a result of intensive studies, the present inventors have discovered that a specific quaternary ammonium salt compound has extremely low skin irritation and excellent bactericidal activity, and has completed the present invention.

That is, the present invention provides a disinfectant for skin or hair, which is characterized by containing the compound represented by the general formula (1) as an essential component.

[In the formula, R+, R, and R5 have at least one carbon number of 8
~30 linear or branched alkyl groups or alkenyl groups, the rest are methyl group, ethyl group, benzyl group, -CH mushroom-ON +C)ltcHiO, H (n is an integer of 1 to 15) and, Cut-(C1l)
4CI'l! Of(individually or in combination, R4 is -CB, CIIzGHz, or -CL
CHtOH is indicated, and the counter anion χ indicates a phosphoric acid ester, a phosphonic acid ester, an anionic residue of a sulfonic acid or sulfuric acid ester having a hydrophobic group having 7 or more carbon atoms, or an anionic oligomer or copolymer with a degree of polymerization of 3 or more. ] The quaternary ammonium salt represented by the general formula (1) according to the present invention is characterized by a counter anion, and the counter anion is a phosphoric acid ester, a phosphonic acid ester, a sulfonic acid, a sulfuric acid ester, or a polymerization degree of 3 or more. It is important that the anionic oligomer or copolymer is an anionic oligomer or copolymer, which makes it possible to reduce irritation to the skin while maintaining bactericidal performance.

Preferred examples of the anion residue of the phosphate ester as a counter-anion include the phosphate ester represented by the following general formula (II).

(In the formula, at least one of R1 and R5 has H1 carbon number of 1 to
30 linear or branched alkyl groups, boroxyalkylene alkyl ethers, sugar alcohol residues, sugar residues, and glycerin derivatives, and the remainder consists of H or alkali metals such as Na, singly or in combination. ) Phosphoric esters of general formula (■) include molar alkyl phosphoric esters, monoalkenyl phosphoric esters, dialkyl phosphoric esters, dialkenyl phosphoric esters,
Examples include polyoxyalkylene alkyl ether phosphates, sugar phosphates, glycerin phosphates, etc., and the number of carbon atoms in the alkyl group or alkenyl group of the alkyl or alkenyl phosphate ester is 1 to 30, preferably 8 to 20. . As the polyoxyalkylene alkyl ether or polyoxyalkylene alkenyl ether, the number of added moles of ethylene oxide, propylene oxide, etc. is 3 to 60, preferably 3 to 30, and the number of carbon atoms in the alkyl group or alkenyl group is 1 to 30, preferably 8 to 20 are listed. Examples of sugar phosphate esters include glucose phosphate ester, glucose amine phosphate ester, maltose-1-phosphate, and cy-rlji phosphate ester. Examples of glycerin phosphate ester include phosphatidine, but are not limited to these sugars. Examples include acid-like phospholipids. In the case of a monosubstituted phosphate ester, the remaining one of R1 or R6 is H or,
It does not matter if it is replaced with Na or the like.

As the phosphonic acid ester residue, the following general formula (II) is used.
Examples include the counter anion of .

II 3 R? -P-0(III) R1-〇 (wherein R1 is a straight-chain or branched alkyl group or alkenyl group having 1 to 30 carbon atoms, R1 is H1 a straight-chain or branched alkyl group or alkenyl group, or In general formula (III), the alkyl group or alkenyl group of R7 has 1 to 30 carbon atoms, preferably 8 to 20 carbon atoms. R3 is H or a linear or branched alkyl group, alkenyl group, polyoxyalkylenealkyl group, or polyoxyalkylenealkenyl group, or an alkali metal such as Na, and the alkyl group and alkenyl group have 1 to 1 carbon atoms. 30, preferably 8 to 20, and the polyoxyalkylenealkyl group or polyoxyalkylenealkenyl group includes ethylene oxide,
Examples include those with an added mole number of 3 to 60, preferably 3 to 30, such as propylene oxide.

Examples of sulfuric esters having a hydrophobic group having a total carbon number of 7 or more include lauryl sulfate, myristyl sulfate,
Palmityl sulfate, stearyl sulfate, oleyl sulfate, linole sulfate, cetyl sulfate, higher alcohol/ether sulfate,
Examples include resin acid alcohol sulfate ester.

Examples of sulfonic acids having a hydrophobic group having a total carbon number of 7 or more include alkylbenzenesulfonic acids, higher alkylsulfonic acids, higher fatty acid ester sulfonic acids, higher alcohol ether sulfonic acids, alkylnaphthalenesulfonic acids, sulfosuccinates, and alkylphenolsulfones. Examples include alkyl sulfonic acids of higher fatty acid amides, alkylaryl ester sulfonic acids, alkyldiphenyl ether sulfonic acids, and alkylbenzimidazole sulfonic acids.

Examples of anionic oligomers and copolymers include the following (1
), (2), and a polymerization degree of 3 or more containing one or more selected from (2) is preferable.

(1) A polymer containing styrene sulfonic acid as an essential constituent monomer (2) A formalin condensate of a sulfonated polycyclic aromatic compound that may have a hydrocarbon group as a substituent Specific examples of the above compounds are shown below. Explain.

(1) Water-soluble or water-dispersible polymers containing styrene sulfonic acid as an essential constituent monomer Styrene sulfonic acid homopolymers are easily produced by polymerizing styrene sulfonic acid or by sulfonating polystyrene. be able to. The styrene sulfonic acid polymer has a skeleton represented by the following formula.

The molecular weight is 1,000 or more, preferably 1,000 to 500,000.

In addition, copolymers of styrene sulfonic acid and other monomers can be produced by copolymerizing styrene sulfonic acid and other monomers, or by sulfonating a copolymer of styrene and other monomers. It can be easily manufactured. The partner monomers for copolymerization include hydrophobic monomers such as alkyl acrylate, alkyl methacrylate, vinyl alkyl ether, vinyl acetate, ethylene, propylene, butylene, butadiene, diisobutylene, vinyl chloride, vinylidene chloride, acrylonitrile, and styrene. and acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, vinyl alcohol, acrylamide, methacrylamide,
Diacetone acrylamide, N-vinylpyrrolidone, 2
Hydrophilic monomers such as -acrylamide-2-methylpropanesulfonic acid, methacrylsulfonic acid, xylenesulfonic acid, and naphthalenesulfonic acid are used. A preferred copolymer is a (meth)acrylic acid-styrene sulfonic acid copolymer. The molar ratio of (meth)acrylic acid and styrene sulfonic acid in the copolymer is 1/10 to 1
0/1, preferably 1/3 to 4/1. In addition, the average molecular weight is 1000 to 1 million, preferably 1000 to 5
It is 00,000. In addition, sodium salt, potassium salt, ammonium salt, jetanolamine salt, triethanolamine salt, monoisopropanolamine salt, diisopropanolamine salt, triisopropanolamine salt, 2- Amino-2-methylpropane-1,
There may be a neutralizing portion of a salt such as a 3-diol salt.

(2) Formalin condensates of sulfonated polycyclic aromatic compounds that may have hydrocarbon groups as substituents Specifically, petroleum sulfonic acid derivatives, lignin sulfonic acid derivatives, naphthalene sulfonic acid derivatives, xylene sulfonic acid derivatives , formalin condensates such as alkylbenzenesulfonic acid derivatives.

The above compound (2) according to the present invention includes, for example, naphthalene,
It can be obtained by sulfonating alkyl-substituted benzene, alkyl-substituted naphthalene, anthracene, alkyl-substituted anthracene, lignin, petroleum residue having an aromatic ring, etc., and then condensing it with formalin. In this case, the degree of condensation is preferably 3 or more,
More preferably, it is 3-30. Here, when the degree of condensation is 2 or less, the effect of condensation is small, causing a practical problem.

Various aromatic compounds can be used, but lignin, xylene, toluene, naphthalene, or alkylnaphthalene having 1 to 6 carbon atoms may be used, and of course, mixtures thereof may also be used. good.

Furthermore, alkali metal salts such as sodium and potassium salts, alkaline earth metal salts such as calcium, and amine ammonium salts may also be used to the extent that performance is not impaired.

The quaternary ammonium salt represented by the general formula (1) according to the present invention can be produced by a known method.
After converting grade ammonium salt into OH type quaternary ammonium,
It is easily produced by neutralization with a compound having the above-mentioned anionic residue. In this case, some alkali metal salts, amine salts, organic amine salts, etc. may be included to the extent that the functions of the present invention are not inhibited. It is also possible to carry out the production by desalting and neutralizing with the above-mentioned anionic residues.

The compound represented by the general formula (1) used in the present invention can be formulated and used in pharmaceutical disinfectants, veterinary disinfectants, cosmetics, shampoos, soaps, conditioners, cleaning agents, etc. Examples of pharmaceutical sterilizing disinfectants include sterilizing disinfectants that are used by dipping hands and fingers in a dilute solution, scrub-type sterilizing cleaners that are used by rubbing hands together, and sterilizing disinfectants for surgical equipment and hospitals. Examples of medicinal disinfectants for animals include cleaning disinfectants for livestock barns, disinfectants for animal skin, etc., and examples of cosmetics include disinfectants such as germicidal creams, lotions, and germicidal hair products. It can also be used as a medicated shampoo, medicated soap, a disinfectant hand cleaner, and a medicated rinse. When formulating, o, oos
It can be used in concentrations ranging from ~90% by weight, preferably from 0.01 to 50% by weight.

In addition, when using the quaternary ammonium salt represented by the general formula (I) of the present invention, salts, surfactants, and water-soluble thickeners may be added to the formulation as necessary within a range that does not impede the effects of the present invention. It is also possible to use agents etc. together.

Examples of salts include carboxylic acid metal salts such as succinic acid, malonic acid, citric acid, gluconic acid, and glutaric acid, phosphoric acid compound metal salts such as tripolyphosphoric acid, hexametaphosphoric acid, and phosphoric acid, and inorganic salts such as Na*SOn and Mg5o4゜. Examples include salt. These can be used alone or in combination.

As the surfactant, nonionic surfactants, anionic surfactants and amphoteric surfactants are used, and examples of the nonionic surfactants and/or anionic surfactants include polyoxyethylene. (hereinafter referred to as POE) alkyl (6 to 22 carbon atoms) ether, POE alkyl (4 to 18 carbon atoms) phenol ether, polyoxypropylene polyoxyethylene (block or random) alkyl ether, poE phenylphenol ether, POE
OIII styrenated phenol ether, POE) non-ionic surfactants such as ribenzyl phenol ether, lignin sulfonate, alkylbenzene sulfonate, alkyl sulfonate, POE alkyl sulfonate, POE alkyl phenyl ether sulfonate,
POE alkylphenyl ether phosphate ester salt, P
OE phenylphenol ether sulfonate, poa
Examples of anionic surfactants include phenylphenol ether phosphate ester salt, naphthalene sulfonate, naphthalene sulfonic acid formalin condensate, POE) ribenzylphenol ether sulfonate, and POE tribenzyl phenylphenol ether phosphate ester salt. It will be done. These can be used alone or in combination. Its content is O to 20% by weight, preferably 1 to 10% by weight in the corrugating agent.

Examples of the amphoteric surfactant include alkylaminotrimethylglycine, alkyldimethylamine oxide, and alkyldiaminoethylglycine hydrochloride.

As water-soluble thickeners, any of natural, semi-synthetic and synthetic water-soluble thickeners can be used. Natural mucilages include xanthan gum and xanfro derived from microorganisms, pectin derived from plants,
Semi-synthetic mucilage materials include methylated products, carboxyalkylated products, hydroxyalkylated products of cellulose or starch derivatives (including methyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, etc.), sorbitol, etc., and synthetic mucilage materials include polyamide, etc. Specific examples include acrylates, polymaleates, polyvinylpyrrolidone, and pentaerythritol EO adducts. The water-soluble thickener is added in an amount of about 0 to 3.0% by weight of sodium bicarbonate, preferably about 0.05 to 0.5% by weight.

〔Example〕

EXAMPLES Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.

In addition, the compounds of the present invention (Nα1 to Nα6) used in the examples are shown below.
) and comparative compounds (Nα1-3) are shown.

<Compound of the present invention> Comparative compound> Table Example 1 The compound of the present invention and the comparative compound were applied to the back of a guinea pig with pricked hair every 24 hours at a concentration of 2.0% by weight.
After applying the solution dissolved in % ethanol, the irritation reaction of the skin was observed. The evaluation criteria for the strength of the stimulus response are as follows.

Reaction strength　O reaction not observed 1. Faint erythema 2 Clear erythema 3. Erythema with edema 4. Erythema and edema accompanied by dermatitis and necrosis The results are shown in Table-1.

Note) $1 The number indicates the average value of 6 animals.

Example 2 1.0% of the present compound and comparative compound on the inner side of human upper arm
The weight % aqueous solution was placed on a 2004 disc, an aluminum disc cap was placed, and the disc was fixed with a bandage. 48
After a period of time, the condition of the skin that had been in contact with the disk drug solution was observed, and the reaction strength was determined according to the following criteria.

reaction strength O reaction not observed 1. Faint erythema 2 Clear erythema 3. Erythema with edema The results are shown in Table-2.

Table-2 Note) *2 The numbers indicate the average value of 10 people.

Example 3 A hand disinfection cleaning test was conducted using formulations prepared according to Formulation Examples 1 to 4 below.

Preparation 5- of Formulation Examples 1 to 4 was placed in the palm of the hand and rubbed together for 1 minute, and then washed with running tap water for 30 seconds. After washing with water, the water was gently drained and the palm of the hand was lightly pressed onto the 5PCLD medium, and cultured at 28°C for 48 hours. The number of colonies generated after culturing was counted and determined as the number of viable bacteria.

In addition, 20 people were examined to see if their hands were getting rough after using it for 20 days, and the number of people who had rough hands was shown.

The results are shown in Table-3.

Formulation Example 1> Compound of the present invention or comparative compound 2 parts by weight hexadecyl phosphate triethanolamine salt
4 parts by weight polyoxyethylene sorbitan monooleate 2 parts by weight water 92 parts by weight Prescription Example 2> Compound of the present invention or comparative compound 2 parts by weight polyoxyethylene (30 mol addition) polyoxypropylene alkyl ether (block polymer M,・3000)
(Addition of 5 moles) Water formulation example 3> Compound of the present invention or comparative compound POE sodium alkyl sulfonate Example 4> Compound of the present invention or comparative compound lauryldimethylglycine 4 parts by weight 94 parts by weight 2 parts by weight 4 parts by weight Parts 94 parts by weight 2 parts by weight 4 parts by weight 94 parts by weight Table Example 4 Next, cosmetic compositions were prepared using the compounds of the present invention according to Formulation Examples 5 to 7 below, and applied to the hands, face, and hair. The number of bacteria was then measured.

Specifically, 10 people used the product on their hands and faces for 10 days, and bacteria were collected using the stamp method from 12.5 d of skin within 1 hour after treatment, and the treated and non-treated areas were compared. .

Regarding hair, 10 people used the product for 10 days, and the number of bacteria on the hair was measured within 1 hour after treatment by collecting 100 d of sterile water, and comparisons were made between treated and non-treated hair. .

In addition, formulation example 8 of shampoo composition using the compound of the present invention
- 9, and the number of bacteria was measured after use.

Formulation Example 5> Invention Compound 1 2 parts by weight Hydroxypropyl cellulose 1.5 parts by weight Isopropanol 100 parts by weight Formulation Example 6> Invention Compound 2 3 parts by weight Morse-colored petrolatum 50 parts by weight Vaseline oil
15 parts by weight purified petrolatum
32 parts by weight Prescription Example 7> Compound 3 of the present invention 3 parts by weight ethanol 67 parts by weight ethyl lactate
10 parts by weight C+x CI & fatty acid triglyceride 20 parts by weight Prescription Example 8> Compound 3 of the present invention 3 parts by weight Polyoxyethylene lauryl sulfate ester triethanolamine salt (EO-20 mol) 24 parts by weight Monoethanolamine oleate 2 parts by weight Propylene glycol
4 parts by weight Water 68 parts by weight Prescription Example 9 Compound 4 of the present invention 3 parts by weight Polyoxyethylene (EO-20 mol) Sorbitan monooleate 2
3 parts by weight lanolin 1 part by weight carboxymethyl cellulose 2 parts by weight water
71 parts by weight ■ These cosmetic compositions and shampoo compositions all suppressed the growth of bacteria and did not cause any irritation during use.

Claims (1)

[Claims] 1. A sterilizing agent for skin or hair containing a compound represented by general formula (I) as an essential ingredient. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In the formula, at least one of R_1, R_2, and R_3 represents a linear or branched alkyl group or alkenyl group having 8 to 30 carbon atoms, and the rest are methyl groups, ethyl group, benzyl group,
▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼ (n is an integer from 1 to 15) and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Indicates a single or combination selected from
H_3, -CH_2CH_3, or -CH_2CH_2
OH is indicated, and the counter anion X^■ indicates an anion residue of a phosphoric acid ester, a phosphonic acid ester, a sulfonic acid or a sulfuric acid ester having 7 or more carbon atoms, or an anionic oligomer or copolymer having a degree of polymerization of 3 or more. 2. The sterilizing composition for skin or hair according to claim 1, wherein the counter-anion X^■ is an anion represented by the general formula (II) or (III). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (In the formula, R_5 and R_6 are at least one H, a straight or branched alkyl group having 1 to 30 carbon atoms, polyoxyalkylene alkyl ether, sugar alcohol residue group, sugar residue, or glycerin derivative, and the remainder is selected from H or alkali metals, singly or in combination.) ▲Mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, R_7 has 1 to 30 carbon atoms. represents a straight-chain or branched alkyl group or alkenyl group, and R_8 represents H, a straight-chain or branched alkyl group or alkenyl group, or an alkali metal.) 3 The counter anion X^■ has a total carbon number of 7 or more. The disinfectant for skin or hair according to claim 1, which is an anionic residue of a sulfonic acid compound or a sulfuric acid ester compound having a hydrophobic group. 4 The anionic oligomer or copolymer is the following (1)
The disinfectant for skin or hair according to claim 1, which is a compound containing one or more selected from (2) and (2). (1) A polymer containing styrene sulfonic acid as an essential constituent monomer (2) A formalin condensate of a sulfonated polycyclic aromatic compound that may have a hydrocarbon group as a substituent 5 The compound according to claim 1 A scrub-type cleaning disinfectant containing as an active ingredient. 6. A shampoo or rinse composition containing the compound according to claim 1 as an active ingredient. 7. A cosmetic composition containing the compound according to claim 1 as an active ingredient.