JP3091841B2 - Antimicrobial detergent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is intended to perform antibacterial treatment simultaneously with washing for stubborn oil stains in workplaces such as corridors of food factories, floors, walls and ceilings and in food processing equipment and appliances. The present invention relates to an antibacterial detergent composition which is capable of suppressing the occurrence of rust on iron parts.

[0002]

2. Description of the Related Art Problems caused by microorganisms in food factories are often taken up, but contamination by harmful microorganisms such as bacteria is an important problem directly associated with food poisoning. On the other hand, periodic cleaning, including ventilation and antibacterial treatment, is inadequate, and the growth of harmful microorganisms such as bacteria cannot be suppressed. Harmful microbial contamination is spreading. Conventional methods for removing harmful microorganisms such as bacteria include alcohol-based (ethanol, isopropanol, etc.), aldehyde-based (formalin, glutaraldehyde, etc.), chlorine-based (sodium hypochlorite, chlorine dioxide, etc.), cationic interface Surfactants (benzalkonium chloride, benzethonium chloride, etc.), amphoteric surfactants (alkyl diaminoethyl glycine hydrochloride, alkyl polyaminoethyl glycine hydrochloride, etc.), biguanides (polyhexamethylene biguanide, chlorhexidine gluconate, etc.), phenols (Phenol, cresol soap solution, parachlorometaxylenol, etc.), iodine type (povidone iodine, etc.), oxygen type (hydrogen peroxide solution, ethylene oxide, ozone, peracetic acid, etc.), and others (acidic water; electrolytic acidic water, etc.) Anti Depending on the field of use (object of use) and the microorganism to be controlled, singly or in combination (in some cases, use sterilized warm water or hot water of 80 ° C or higher), wiping, washing, penetrating, spraying, spraying and gas We conduct antibacterial treatment of specific environment space and antibacterial treatment of objects and articles existing in the environment by fumigation and other methods. Amphoteric surfactants (alkyldiaminoethylglycine) and cationic surfactants (alkyldimethylbenzylammonium chloride,
Antibacterial agents such as alkyltrimethylammonium chloride) are usually formulated to be 5 to 15% by weight, and usually diluted 400 to 500 times with tap water, and 100 to 1000 times if necessary. Antibacterial treatment had been performed.

[0003]

However, these antibacterial detergents intended for antibacterial treatment do not have sufficient detergency, and amphoteric surfactants and cationic surfactants are usually used as detergents such as anionics. It is known that the antibacterial efficacy is significantly reduced when used in combination with a surfactant. Therefore, there has been a problem that cleaning and antibacterial must be performed in two steps in a food factory or the like. In addition, amphoteric surfactants and cationic surfactants violently foam,
There is a problem that a large amount of water and a lot of time are required for washing. Furthermore, since a normal cationic surfactant uses chlorine ions as a counter ion, and the amphoteric surfactant is also a hydrochloride, there is a problem that rust is generated on iron parts.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, have used a cationic surfactant whose counter ion is an organic carboxylate anion as an antibacterial component. By using a specific nonionic surfactant in combination, it has sufficient detergency, and it does not require a large amount of water and time when washing off due to low foaming,
Find an antibacterial detergent composition that does not generate rust on the iron part,
The present invention has been reached.

That is, the present invention provides a cationic antibacterial agent (A) comprising a cationic antibacterial agent (A1) represented by the following general formula (1) or a cationic antibacterial agent (A2) represented by the following general formula (2): And a nonionic surfactant (B1) represented by the following general formula (3), a nonionic surfactant (B2) represented by the following general formula (4), and a nonionic surfactant represented by the following general formula (5). Ionic surfactant (B3), nonionic surfactant (B4) represented by the following general formula (6)
And polyhydric alcohol type nonionic surfactant (B5)
An antibacterial detergent composition comprising at least one nonionic surfactant (B) selected from the group consisting of: General formula (1) n (R ₁ R ₂ R ₃ R ₄ N ⁺ ) · X ⁿ⁻ (1) wherein R ₁ , R ₂ , R ₃ and R ₄ each have the same or different carbon number of 1 to 1. 22 is a linear or branched alkyl group; n is a number of 1 to 4; X ^n- is an n-valent anion of an aliphatic organic carboxylic acid having 4 to 16 carbon atoms or an aromatic di, tri or tetracarboxylic acid. is there. General formula _{(2) n (R 5 R} 6 R 7 PhCH 2 N +) · X n- (2) [ wherein, R _5, R ₆ and R ₇ are the same or different carbon atoms of 1 to 22 Linear or branched alkyl group; n
Is a number of 1 to 4; X ^n- is an n-valent anion of an aliphatic organic carboxylic acid having 4 to 16 carbon atoms or an aromatic di, tri or tetracarboxylic acid. General formula (3) R ₈ O ｛(CH ₂ CH ₂ O) _m / (AO) _p ｝ H (3) wherein R ₈ is a linear or branched alkyl group having 1 to 22 carbon atoms, An alkenyl group or an alkylaryl group; A
Is an alkylene group having 3 or 4 carbon atoms; m is a number of 1 to 30; p is a number of 1 to 30; {(CH ₂ CH ₂ O) _m / (A
O) _p } may be block addition or random addition. General formula (4) HO ｛(CH ₂ CH ₂ O) _q / (AO) _r ｝ H (4) wherein A is an alkylene group having 3 or 4 carbon atoms;
R is a number of 20 to 80; ｛(CH ₂ CH
_{2 O) q / (AO)} r} may be random addition in block addition. General formula (5) R ₉ COO ｛(CH ₂ CH ₂ O) _q / (AO) _r ｝ H (5) wherein R ₉ is a linear or branched alkyl group having 1 to 22 carbon atoms or Alkenyl group; A is an alkylene group having 3 or 4 carbon atoms; q is a number from 1 to 200; r is a number from 20 to 80; {(CH ₂ CH ₂ O) _q / (AO) _r } is random even when a block is added. It may be added. General formula (6) R ₉ COO ｛(CH ₂ CH ₂ O) _q / (AO) _r ｝ COR ₉ (6) [wherein, R ₉ is a linear or branched alkyl group having 1 to 22 carbon atoms. A is an alkylene group having 3 or 4 carbon atoms; q is a number of 1 to 200; r is a number of 20 to 80; {(CH ₂ CH ₂ O) _q / (AO) _r } is a block addition Random addition may be used. ]

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The cationic antibacterial agent (A1) used in the present invention is a cationic surfactant represented by the following general formula (1). General formula (1)

In the formula, R ₁ , R ₂ , R ₃ and R ₄ are the same or different and each is a linear or branched alkyl group having 1 to 22 carbon atoms. Specifically, there are the following [1] and [2]. [1] R ₁ and R ₂ are linear or branched alkyl groups having 8 to 12 carbon atoms, and R ₃ and R ₄ are alkyl groups having 1 to 3 carbon atoms. [2] R ₁ is an alkyl group having 12 to 20 carbon atoms. In the case of a linear or branched alkyl group, R ₂ , R ₃ and R ₄ are preferably alkyl groups having 1 to 3 carbon atoms [1] and more preferably [1] among [1] and [2]. R ₁ and R ₂ are both decyl groups;
₃ and R ₄ are both methyl groups.

The following are specific examples of the quaternary ammonium group represented by the general formula (1). [1] octyl decyl dimethyl ammonium, dioctyl dimethyl ammonium, didecyl dimethyl ammonium, decyl dodecyl dimethyl ammonium, didodecyl dimethyl ammonium, octyl decyl methyl ethyl ammonium, dioctyl methyl ethyl ammonium, didecyl methyl ethyl ammonium, didodecyl methyl ethyl ammonium, [2] dodecyltrimethylammonium, tetradecyltrimethylammonium, hexadecyltrimethylammonium, octadecyltrimethylammonium, dodecyldimethylethylammonium, tetradecyldimethylethylammonium, hexadecyldimethylethylammonium, etc. Octadesi Dimethylethylammonium, dodecylmethyldiethylammonium, tetradecylmethyldiethylammonium, hexadecylmethyldiethylammonium, octadecylmethyldiethylammonium, etc.Of these, preferably octyldecyldimethylammonium, didecyldimethylammonium, decyldodecyldimethylammonium, Particularly preferred is didecyldimethylammonium.

The cationic antimicrobial agent (A) used in the present invention
2) is a cationic surfactant represented by the following general formula (2). General formula (2)

In the formula, R ₅ , R ₆ and R ₇ are the same or different and each is a linear or branched alkyl group having 1 to 22 carbon atoms. Preferably, R ₅ is a linear or branched alkyl group having 8 to 18 carbon atoms, and R ₆ and R ₇ are alkyl groups having 1 to 3 carbon atoms. More preferably _{R 5} is a linear or branched alkyl group having a carbon number of 10 to 16, _{R 6}
And R ₇ are both methyl groups. In the formula, Ph is a phenyl group.

Specific examples of the quaternary ammonium group represented by the general formula (2) include decyldimethylbenzylammonium, dodecyldimethylbenzylammonium, tetradecyldimethylbenzylammonium, hexadecyldimethylbenzylammonium, and coconut oil alkyldimethylbenzylammonium. And so on. Of these, dodecyldimethylbenzylammonium and tetradecyldimethylbenzylammonium are preferred.

As the cationic antibacterial agent (A) of the present invention,
(A1) or (A2) is essential, but (A1) is more preferable in terms of antibacterial properties. (A1) and (A2) may be used in combination.

The cationic antibacterial agent (A) used in the present invention
The organic carboxylic acid constituting the n-valent anion of the organic carboxylic acid represented by X ^n- in the general formula (2) of the general formula (1) and the cationic antibacterial agent (A2) is as follows. And the like, and usually have 1 to 4 valences, preferably 1 or 2 valences, and more preferably 2 valences. [1] Aliphatic monocarboxylic acids ・ Saturated monocarboxylic acids (butyric acid, isobutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, lauric acid, myristic acid, stearic acid, behenic acid, 2-
・ Ethylhexanoic acid, etc. ・ Unsaturated monocarboxylic acid (eg, oleic acid) ・ Aliphatic oxycarboxylic acid (tartaric acid, gluconic acid, citric acid, etc.) [2] Polycarboxylic acid ・ Saturated dicarboxylic acid (succinic acid, glutaric acid, adipine) Acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc.)-unsaturated dicarboxylic acid (maleic acid, fumaric acid, itaconic acid, etc.)-aromatic dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid, etc.)-tricarboxylic acid (Trimellitic acid, etc.) Tetracarboxylic acid (Pyromellitic acid, etc.) Among these, preferred are aliphatic organic carboxylic acids having 4 to 16 carbon atoms, and preferably [2] among [1] and [2]. And more preferably a saturated dicarboxylic acid. Particularly preferred are sebacic acid and / or adipic acid.

The nonionic surfactant (B) of the present invention includes a nonionic surfactant (B1), a nonionic surfactant (B2), a nonionic surfactant (B3), and a nonionic surfactant. One or more selected from the group consisting of the surfactant (B4) and the polyhydric alcohol-type nonionic surfactant (B5) can be used in combination.

The nonionic surfactant (B1) used in the present invention is represented by the following general formula (3). General formula (3) R ₈ O ｛(CH ₂ CH ₂ O) _m / (AO) _p ｝ H (3)

R ₈ in the general formula (3) has 1 to 22 carbon atoms.
A straight-chain or branched alkyl group, alkenyl group or alkylaryl group, preferably a straight-chain or branched alkyl group having 8 to 16 carbon atoms, an alkenyl group, or a straight-chain or branched alkyl group having 6 to 12 carbon atoms. It is an alkylaryl group. More preferably, it is a linear or branched alkyl group or alkenyl group having 8 to 12 carbon atoms, or 8 to 1 carbon atoms.
0 is a linear or branched alkylaryl group. R ₈
Examples of the methyl group, ethyl group, isopropyl group, propyl group, butyl group, hexyl group, octyl group,
Examples thereof include a 2-ethylhexyl group, a decyl group, a lauryl group, a myristyl group, a palmityl group, a stearyl group, an oleyl group, a coconut oil alkyl group, an octylphenol group, a nonylphenol group, and a decylphenol group. Preferred are octyl, decyl, lauryl, coconut oil alkyl, myristyl, palmityl, nonylphenol and decylphenol. Particularly preferred are a decyl group and a nonylphenol group.

A in the general formula (3) is an alkylene group having 3 or 4 carbon atoms, specifically, a propylene group and a butylene group, preferably a propylene group. Further, m in the general formula (3) represents the number of moles of ethylene oxide added, and p represents the number of moles of alkylene oxide added. m is a number of 1 to 30, and p is a number of 1 to 30. Preferably, m is a number from 2 to 20, and p is a number from 1 to 8. When m and p are more than 30, the cleaning property is reduced.

The addition form of ethylene oxide (EO) and alkylene oxide may be either block addition or random addition of ethylene oxide to propylene oxide or butylene oxide. Examples of the method for synthesizing the nonionic surfactant (B1) represented by the general formula (3) include the following. [1] Using potassium hydroxide as a catalyst for a higher alcohol,
Add propylene oxide. Next, ethylene oxide is block-added. [2] Higher alcohol with potassium hydroxide as catalyst
Add ethylene oxide. Next, propylene oxide is block-added. [3] Higher alcohol with potassium hydroxide as catalyst
A mixture of ethylene oxide and propylene oxide is added at random. Preferably, [1] and [3], more preferably [1]
And what is obtained is, for example, represented by the following formula.

Specific examples of the nonionic surfactant (B1) of the present invention include EO8 mol-PO7 mol block adduct of decyl alcohol and EO of decyl alcohol.
15 mol-PO8 mol block adduct, EO8 mol-PO7 mol block adduct of dodecyl alcohol, EO17 mol-PO6 mol block adduct of coconut oil alkyl alcohol, EO4 mol-P of nonylphenyl alcohol
O1 mol block adduct, EO8 mol-PO4 mol block adduct of nonylphenyl alcohol, EO6 mol-PO2 mol block adduct of octylphenyl alcohol, EO10 mol-PO of dodecylphenyl alcohol
Examples include a 3-mol block adduct, a EO8 mol-PO7 mol random adduct of decyl alcohol, and a EO8 mol-PO4 mol random adduct of nonylphenyl alcohol. Preferably EO8 mol-P of decyl alcohol
O7 mol block adduct, EO 8 mol-PO4 mol block adduct of nonylphenyl alcohol.

The nonionic surfactant (B2) used in the present invention is represented by the following general formula (4). General formula (4) HO ｛(CH ₂ CH ₂ O) _q / (AO) _r ｝ H (4)

Wherein A is an alkylene group having 3 or 4 carbon atoms; q is a number from 1 to 200; r is a number from 20 to 80;
{(CH ₂ CH ₂ O) _q / (AO) _r } may be block addition or random addition. A in the general formula (4) is an alkylene group having 3 or 4 carbon atoms, specifically, a propylene group or a butylene group, preferably a propylene group.

In the general formula (4), q represents the number of moles of ethylene oxide added, and r represents the number of moles of alkylene oxide added. q is 1 to 200, r is 20 to 80
Is the number of Preferably, q is 1-50 and r is 25-4
Number of 0. When q exceeds 200, the cleaning property is reduced. On the other hand, when r is less than 20 or more than 80, the cleaning property is reduced.

The form of addition of ethylene oxide (EO) and alkylene oxide may be either block addition or random addition of ethylene oxide to propylene oxide or butylene oxide. Examples of the method for synthesizing the nonionic surfactant (B2) represented by the general formula (4) include the following. [1] Propylene oxide is added to propylene glycol using potassium hydroxide as a catalyst. Next, ethylene oxide is block-added. [2] Ethylene oxide is added to ethylene glycol using potassium hydroxide as a catalyst. Next, propylene oxide is block-added. [3] A mixture of ethylene oxide and propylene oxide is randomly added to ethylene glycol or water using potassium hydroxide as a catalyst. Preferably, [1] and [3], more preferably [1]
And what is obtained is, for example, represented by the following formula.

The nonionic surfactant represented by the general formula (4) representing (B2) of the present invention includes: And so on. Preferably, It is.

The nonionic surfactant (B3) used in the present invention is represented by the following general formula (5). General formula (5) R ₉ COO ｛(CH ₂ CH ₂ O) _q / (AO) _r ｝ H (5)

R ₉ in the general formula (5) has 1 to 22 carbon atoms.
A linear or branched alkyl or alkenyl group of
Preferably, it is a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms. More preferably, it is a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms. Specific examples of R ₉ include methyl, ethyl, isopropyl, propyl, butyl, hexyl, octyl, 2-ethylhexyl, decyl, lauryl, myristyl, palmityl, stearyl, oleyl. And coconut oil alkyl groups. Preferably, octyl group, decyl group, lauryl group,
A coconut oil alkyl group, a myristyl group, a palmityl group, a stearyl group, and an oleyl group. Particularly preferred are a stearyl group and an oleyl group.

A in the general formula (5) is an alkylene group having 3 or 4 carbon atoms, specifically, a propylene group and a butylene group, preferably a propylene group. Further, in the general formula (5), q represents the number of moles of ethylene oxide added, and r represents the number of moles of alkylene oxide added. q is a number from 1 to 200, and r is a number from 20 to 80. Preferably, q is a number from 1 to 50 and r is a number from 25 to 40.
When q exceeds 200, the cleaning property is reduced. Also, if r is 2
If it is less than 0 or more than 80, the cleaning property is reduced.

The form of addition of ethylene oxide (EO) and alkylene oxide may be either block addition or random addition of ethylene oxide to propylene oxide or butylene oxide. Examples of the method for synthesizing the nonionic surfactant (B3) represented by the general formula (5) include the following. [1] Propylene oxide is added to propylene glycol using potassium hydroxide as a catalyst. Next, after block addition of ethylene oxide, an esterification reaction is performed with a higher fatty acid. [2] Ethylene oxide is added to ethylene glycol using potassium hydroxide as a catalyst. Then, after block addition of propylene oxide, an esterification reaction is performed with a higher fatty acid. [3] A mixture of ethylene oxide and propylene oxide is mixed with ethylene glycol or water using potassium hydroxide as a catalyst, and then esterified with a higher fatty acid. Preferably, [1] and [3], more preferably [1]
And what is obtained is, for example, represented by the following formula.

Specific examples of the nonionic surfactants (B3) of the present invention include: And so on. Preferably, It is.

The nonionic surfactant (B4) used in the present invention is represented by the following general formula (6). General formula (6) R ₉ COO ｛(CH ₂ CH ₂ O) _q / (AO) _r ｝ COR ₉ (6)

R ₉ in the general formula (6) has 1 to 22 carbon atoms.
A linear or branched alkyl or alkenyl group of
Preferably, it is a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms. More preferably, it is a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms. Specific examples of R ₉ include methyl, ethyl, isopropyl, propyl, butyl, hexyl, octyl, 2-ethylhexyl, decyl, lauryl, myristyl, palmityl, stearyl, oleyl. And coconut oil alkyl groups. Preferably, octyl group, decyl group, lauryl group,
A coconut oil alkyl group, a myristyl group, a palmityl group, a stearyl group, and an oleyl group. Particularly preferred are a stearyl group and an oleyl group.

A in the general formula (6) is an alkylene group having 3 or 4 carbon atoms, specifically, a propylene group and a butylene group, preferably a propylene group. Further, in the general formula (6), q represents the number of moles of ethylene oxide added, and r represents the number of moles of alkylene oxide added. q is a number from 1 to 200, and r is a number from 20 to 80. Preferably, q is a number from 1 to 50 and r is a number from 25 to 40.
When q exceeds 200, the cleaning property is reduced. Also, if r is 2
If it is less than 0 or more than 80, the cleaning property is reduced.

The form of addition of ethylene oxide (EO) and alkylene oxide may be either block addition or random addition of ethylene oxide to propylene oxide or butylene oxide. Examples of the method for synthesizing the nonionic surfactant (B4) represented by the general formula (6) include the following. [1] Propylene oxide is added to propylene glycol using potassium hydroxide as a catalyst. Next, after block addition of ethylene oxide, an esterification reaction is performed with a higher fatty acid. [2] Ethylene oxide is added to ethylene glycol using potassium hydroxide as a catalyst. Then, after block addition of propylene oxide, an esterification reaction is performed with a higher fatty acid. [3] A mixture of ethylene oxide and propylene oxide is mixed with ethylene glycol or water using potassium hydroxide as a catalyst, and then esterified with a higher fatty acid. Preferably, [1] and [3], more preferably [1]
And what is obtained is, for example, represented by the following formula.

Specific examples of the nonionic surfactant showing (B4) of the present invention include: And so on. Preferably, It is.

As the polyhydric alcohol type nonionic surfactant (B5) used in the present invention, in addition to the nonionic surfactant represented by the following general formula (7), fatty acid esters of glycerin or pentaerythritol, sorbit Or sorbitan fatty acid ester, sugar fatty acid ester, fatty acid alkanolamide, polyoxyethylene fatty acid alkanolamide and the like. General formula (7) R _10- [CH ₂ O _２ (CH ₂ CH ₂ O) _s / (AO) _t ｝ H] _u (7) In the general formula (7), R ₁₀ has 1 to 10 carbon atoms. A linear or branched divalent or trivalent aliphatic saturated hydrocarbon group, preferably a linear or branched divalent or trivalent aliphatic saturated hydrocarbon group having 2 to 6 carbon atoms, particularly preferably It is a straight-chain or branched trivalent aliphatic saturated hydrocarbon group having 2 to 4 carbon atoms.

Specific examples of R _{10 in} the general formula (7) include:

Preferably, Particularly preferably,

A in the general formula (7) is an alkylene group having 3 or 4 carbon atoms, specifically, a propylene group and a butylene group, preferably a propylene group. In the general formula (7), s represents the number of moles of ethylene oxide added, t represents the number of moles of added alkylene oxide, and u coincides with the valence of the aliphatic saturated polyhydric alcohol. s is a number of 1 to 10, t is 1 to 30, and u is a number of 2 or 3. Preferably, s is a number from 2 to 5, t is a number from 18 to 25, and u is 3. When s is more than 10, the cleaning property is reduced. On the other hand, when t exceeds 30, the cleaning property is reduced.

The addition form of ethylene oxide (EO) and alkylene oxide may be either block addition or random addition of ethylene oxide and propylene oxide or butylene oxide. The method for synthesizing the nonionic surfactant represented by the general formula (7) is as follows:
For example, the following are mentioned. [1] Propylene oxide is added to a dihydric or trihydric aliphatic polyhydric alcohol using potassium hydroxide as a catalyst. Next, ethylene oxide is block-added. [2] Ethylene oxide is added to a dihydric or trihydric aliphatic polyhydric alcohol using potassium hydroxide as a catalyst. Next, propylene oxide is block-added. [3] A mixture of ethylene oxide and propylene oxide is randomly added to a dihydric or trihydric aliphatic polyhydric alcohol using potassium hydroxide as a catalyst. Preferably, [1] and [3], more preferably [1]
And what is obtained is, for example, represented by the following formula.

Specific examples of the nonionic surfactant represented by the general formula (7) of the present invention include adducts of trimethylolpropane with 25 mol of PO and 5 mol of EO, and addition of trimethylolpropane with 23 mol of PO and 3 mol of EO. Body, PO20 mol of trimethylolpropane-EO
PO of 2-mol block adduct, trimethylolpropane
Examples include an adduct of 18 mol-EO2 mol block, an adduct of trimethylolbutane of P23 mol-EO3 mol, an adduct of trimethylolpropane of PO20 mol-EO2 mol, and the like. Preferably, it is an adduct of trimethylolpropane with a PO23 mol-EO3 mol block.

Among the polyhydric alcohol type nonionic surfactants (B5) used in the present invention, fatty acid esters of glycerin or pentaerythrit, fatty acid esters of sorbit or sorbitan, fatty acid esters of sugar, fatty acid alkanolamides and polyalcohols Fatty acids of oxyethylene fatty acid alkanolamides include octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and coconut oil fatty acids. Preferred are lauric acid, coconut oil fatty acid, myristic acid, palmitic acid, stearic acid and oleic acid, and particularly preferred are coconut oil fatty acid, stearic acid and oleic acid.

Among the polyhydric alcohol type nonionic surfactants (B5), glycerin or pentaerythrit fatty acid ester, sorbitol or sorbitan fatty acid ester, sugar fatty acid ester, fatty acid alkanolamide or polyoxyethylene fatty acid alkanolamide Specific examples of the lauric acid monoglyceride, oleic acid monoglyceride, pentaerythrit palmitic acid monoester, coconut oil sorbitan acid sorbitan, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, coconut oil diacid amide, Examples include lauric acid diethanolamide, polyoxyethylene (addition of 2 moles) coconut oil and fatty acid monoethanolamide, and the like.

Of these, sorbitan coconut oil-resistant sorbitan, sorbitan monooleate, coconut oil-diacid proof diethanolamide, and polyoxyethylene (2 mol adduct of ethylene oxide) coconut oil-resistant acid-proof monoethanolamide are particularly preferable. Preferred are coconut oil-resistant sorbitan and polyoxyethylene (2-mol adduct of ethylene oxide) coconut oil-resistant acid monoethanolamide.

The weight ratio (A) / (B) of the cationic antibacterial agent (A) and the nonionic surfactant (B) contained in the antibacterial detergent composition of the present invention is usually from 1/99 to 80. / 20
And preferably 20/80 to 60/40. Particularly preferably, it is 30/70 to 50/50. (A) /
If the weight ratio of (B) is less than 1/99, the antibacterial properties will be insufficient, and if it exceeds 80/20, the washing properties will be poor and the foam removal will be poor, which is not preferable.

The content of the cationic antibacterial agent (A) in the composition is usually 1 to 80% by weight, preferably 5 to 25% by weight. When the content of (A) in the composition is less than 1% by weight, when the product is used, it is usually diluted 400 to 500 times with tap water, and if necessary, diluted 100 to 1000 times. The antimicrobial properties of the diluent became insufficient, and 8
If the content exceeds 0% by weight, the washing property is poor and the bubble elimination property is also deteriorated. The content of the nonionic surfactant (B) in the composition is usually 2 to 99% by weight, preferably 10 to 30% by weight. When the content of (B) in the composition is less than 2% by weight, detergency is poor. If it exceeds 99% by weight, the antibacterial properties are inferior and are not preferred.

The antibacterial detergent composition of the present invention may optionally contain an amount of an anionic surfactant for imparting detergency which does not impair the effects of the present invention. Desired antifoaming agent (silicone emulsion, etc.), pH adjuster (monoethanolamine, diethanolamine, caustic soda, caustic potash, etc.), metal chelating agent (EDTA, etc.), and water solubility for the purpose of adjusting the viscosity of the composition A polymer can be contained.

Examples of the anionic surfactant include alkali salts of alkyl phosphates, alkali salts of polyoxyalkylene alkyl phosphates, alkali salts of higher fatty acids, and alkali salts of polyoxyethylene alkyl ether acetate.

Examples of the water-soluble polymer include polyoxyethylene glycol, polyvinyl alcohol, and polyvinylpyrrolidone.

The antibacterial detergent composition of the present invention is used by diluting with tap water or the like as an antibacterial detergent for food factories and the like. 400 to 5 for antibacterial cleaning of floors, walls, ceilings, etc.
A method of using such a method is used in which a diluted solution diluted 100-fold and, if necessary, diluted 100-1000-fold are sprayed, followed by brushing. In addition, food processing equipment and utensils are immersed in a diluent and left overnight to carry out antibacterial cleaning. In any case, wash with water after the antibacterial treatment is completed. The antibacterial detergent composition of the present invention is used for floors, walls, stubborn oil stains such as ceilings,
It is an antibacterial detergent composition that can perform an antibacterial treatment simultaneously with washing, easily removes bubbles when washed with water, and suppresses rusting of iron parts.

[0050]

The present invention will be further described by the following examples, which should not be construed as limiting the invention. The numerical values in the examples indicate% by weight.

Examples 1 to 5 were prepared in the proportions shown in Table 1.
And the antibacterial cleaning compositions of Comparative Examples 1 to 4 were prepared. In addition,
The compounds of the components described by the symbols in Table 1 are as follows. A1-1: Didecyldimethylammonium sebacic acid A1-2: Didecyldimethylammonium adipic acid A1-3: Cetyltrimethylammonium sebacic acid A2-1: Coconut oil alkyldimethylbenzylammonium sebacic acid B1-1: Polyoxyethylene (8 Mole addition) polyoxypropylene (7 mole addition) decyl ether B2-1: polyoxyethylene (25 mole addition) polyoxypropylene (30 mole addition) glycol B3-1: polyoxyethylene (5 mole addition) polyoxypropylene ( 30 mol addition) glycol stearic acid ester B4-1: polyoxyethylene (10 mol addition) polyoxypropylene (30 mol addition) glycol stearic acid diester B5-1: polyoxyethylene (3 mol addition) polyoxypropylene Pyrene (23 mole addition) Trimethylolpropane B5-2: Sorbitan coconut oil-resistant acid sorbitan B5-3: Polyoxyethylene (2 mole addition) coconut oil-resistant acid monoethanolamide C: Polyoxyethylene (5 mole addition) isostearyl ether Potassium phosphate D: Didecyldimethylammonium chloride E1: Polyethylene glycol monooleate E2: Polyoxyethylene (8 mole addition) nonylphenyl ether F: Sodium hypochlorite

[0052]

[Table 1]

The antibacterial detergent compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 4 were evaluated for the following properties. In addition, the evaluation of low foaming property used the sample solution diluted to 4000 times, and the evaluation of the detergency used the evaluation of the emulsifying property and used the sample solution diluted to 100 times. For the evaluation of rust prevention, a sample solution diluted 400 times was used. Table 2 shows the results.

<Evaluation of Low Foam Property> Ross Miles Method (JIS
K3362). (Judgment criteria) ○: Immediately; 0 to 50 mm, after 5 minutes; 0 to 10 mm △: Immediately; 0 to 50 mm, after 5 minutes; 10 to 20 mm ×: Immediately; After 50 mm, after 5 minutes;

<Evaluation of Emulsifying Property> The evaluation of detergency was performed by the following emulsifying property evaluation. Sample solution 5 in graduated cylinder with stopper
Add 10 ml of rapeseed oil to 0 g and infiltrate vigorously for 30 seconds. Thereafter, the mixture was allowed to stand, and the ratio of the emulsified oil layer portion to the separated oil layer portion after 30 minutes was observed. (Determination criteria) ○: emulsified oil layer / separated oil layer = 100/0 △: emulsified oil layer / separated oil layer = 90-100 / 10-0 ×: emulsified oil layer / separated oil layer = 0-90 / 10 90

<Evaluation of antibacterial activity> The minimum growth inhibitory concentration (MI
C) It was evaluated by a test. That is, Heart is used as a medium.
The measurement was carried out using an infusion broth (HIB) according to a dilution method (reference: microbiology training proposals, edited by the University of Tokyo Institute of Medical Science, Alumni Association). The antibacterial detergent compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 4 were diluted with HIB to prepare 25 ppm to 0.39 ppm (antibacterial agent component concentration) solutions. 50 μl of an overnight culture solution (medium: HIB, number of bacteria: 10 ⁶ cfu / ml) of the test strain Escherichia coli was added, and the mixture was cultured at 37 ° C. overnight. Thereafter, the presence or absence of growth of the test bacteria is observed, and the minimum growth inhibitory concentration (MI
C) was determined. (Judgment criteria) ○: MIC is 2 ppm or less △: MIC is 2 to 10 ppm ×: MIC is 10 ppm or more

<Evaluation of Rust Prevention Property> A degreased and polished steel sheet was immersed in a sample solution at room temperature for 24 hours, and the degree of rust generation was observed. (Judgment criteria) ：: No rust is observed. X: Rust is observed.

[0058]

[Table 2]

In Table 2, all of the present invention show excellent performance in low foaming property, emulsifying property, antibacterial property and rustproofing property.
However, Comparative Examples 1 and 2 have poor foaming properties and poor emulsifying properties, Comparative Example 3 has poor rust preventing properties, and Comparative Example 4 has poor emulsifying properties and rust preventing properties.

[0060]

The antimicrobial detergent composition of the present invention has the following effects. (1) It is excellent in antibacterial effect and microorganisms are sufficiently controlled. (2) Since it has excellent emulsifying properties with oil, it has good detergency. (3) It has excellent low-foaming properties and good foam removal during washing. (4) Do not rust iron parts.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C11D 10/02 C11D 10/02 (56) References JP-A-59-25896 (JP, A) JP-A-6-1222893 (JP) JP-A-58-109598 (JP, A) JP-A-7-53995 (JP, A) JP-A-5-311196 (JP, A) JP-A-11-35974 (JP, A) (58) Field surveyed (Int.Cl. ⁷ , DB name) C11D 1/62 C11D 3/48 C11D 1/66-1/74

Claims (8)

(57) [Claims] 1. A cationic antibacterial agent (A) comprising a cationic antibacterial agent (A1) represented by the following general formula (1) or a cationic antibacterial agent (A2) represented by the following general formula (2):
And a nonionic surfactant (B1) represented by the following general formula (3), a nonionic surfactant (B2) represented by the following general formula (4), and a nonionic surfactant represented by the following general formula (5). At least one selected from the group consisting of an ionic surfactant (B3), a nonionic surfactant (B4) represented by the following general formula (6), and a polyhydric alcohol-type nonionic surfactant (B5) An antibacterial detergent composition comprising the nonionic surfactant (B). General formula (1) n (R ₁ R ₂ R ₃ R ₄ N ⁺ ) · X ⁿ⁻ (1) wherein R ₁ , R ₂ , R ₃ and R ₄ each have the same or different carbon number of 1 to 1. 22 is a linear or branched alkyl group; n is a number of 1 to 4; X ^n- is an n-valent anion of an aliphatic organic carboxylic acid having 4 to 16 carbon atoms or an aromatic di, tri or tetracarboxylic acid. is there. General formula _{(2) n (R 5 R} 6 R 7 PhCH 2 N +) · X n- (2) [ wherein, R _5, R ₆ and R ₇ are the same or different carbon atoms of 1 to 22 Linear or branched alkyl group; n
Is a number of 1 to 4; X ^n- is an n-valent anion of an aliphatic organic carboxylic acid having 4 to 16 carbon atoms or an aromatic di, tri or tetracarboxylic acid. General formula (3) R ₈ O ｛(CH ₂ CH ₂ O) _m / (AO) _p ｝ H (3) wherein R ₈ is a linear or branched alkyl group having 1 to 22 carbon atoms, An alkenyl group or an alkylaryl group; A
Is an alkylene group having 3 or 4 carbon atoms; m is a number of 1 to 30; p is a number of 1 to 30; {(CH ₂ CH ₂ O) _m / (A
O) _p } may be block addition or random addition. General formula (4) HO ｛(CH ₂ CH ₂ O) _q / (AO) _r ｝ H (4) wherein A is an alkylene group having 3 or 4 carbon atoms;
R is a number of 20 to 80; ｛(CH ₂ CH
_{2 O) q / (AO)} r} may be random addition in block addition. General formula (5) R ₉ COO ｛(CH ₂ CH ₂ O) _q / (AO) _r ｝ (5) wherein R ₉ is a linear or branched alkyl group or alkenyl having 1 to 22 carbon atoms. A is an alkylene group having 3 or 4 carbon atoms; q is a number of 1 to 200; r is a number of 20 to 80; {(CH ₂ CH ₂ O) _q / (AO) _r } is a block addition or a random addition May be. General formula (6) R ₉ COO ｛(CH ₂ CH ₂ O) _q / (AO) _r ｝ COR ₉ (6) [wherein, R ₉ is a linear or branched alkyl group having 1 to 22 carbon atoms. Or an alkenyl group; A is an alkylene group having 3 or 4 carbon atoms; q is a number from 1 to 200; r is a number from 20 to 80; {(CH ₂ CH ₂ O) _q / (AO) _r } is a block addition Random addition may be used. ] 2. The antibacterial detergent composition according to claim 1, wherein (B) is at least one nonionic surfactant selected from the group consisting of (B1) to (B4). 3. A nonionic surfactant represented by the following general formula (7), a fatty acid ester of glycerin or pentaerythrit, a fatty acid ester of sorbit or sorbitan, a fatty acid ester of sugar, and a polyoxyethylene fatty acid. The antibacterial detergent composition according to claim 1 or 2, which is a nonionic surfactant selected from the group consisting of alkanolamides. R _10- [CH ₂ O ｛(CH ₂ CH ₂ O) _s / (AO) _t ｝ H] _u (7) [wherein, R ₁₀ is a straight-chain or branched 2 having 1 to 10 carbon atoms.
A is a trivalent or trivalent aliphatic saturated hydrocarbon group; A is an alkylene group having 3 or 4 carbon atoms; s is 1 to 10, t is 1 to 30,
u is a number of 2 or 3; {(CH ₂ CH ₂ O) _s / (A
O) _t } may be block addition or random addition. ] 4. In the general formula (1) or (2), X
The antibacterial detergent composition according to any one of claims 1 to 3, wherein ^n- is a divalent anion of sebacic acid and / or adipic acid. 5. A compound represented by the general formula (1) wherein R _{1 is}
And R ₂ is a linear or branched alkyl group having 8 to 12 carbon atoms, R ₃ and cationic antimicrobial agent R ₄ is an alkyl group having 1 to 3 carbon atoms, in the general formula (1), R ₁ Is a linear or branched alkyl group having 12 to 20 carbon atoms,
A cationic antibacterial agent wherein R ₂ , R ₃ and R ₄ are an alkyl group having 1 to 3 carbon atoms, or R ₅ in the general formula (2)
Is a linear or branched alkyl group having 8 to 18 carbon atoms, and R ₆ and R ₇ are cationic antibacterial agents each having an alkyl group having 1 to 3 carbon atoms. Composition. 6. The weight ratio (A) / (B) of the cationic antibacterial agent (A) to the nonionic surfactant (B) is from 1/99 to 8
The antibacterial detergent composition according to any one of claims 1 to 5, which is 0/20. 7. The antibacterial detergent composition according to claim 1, which does not contain an anionic surfactant. 8. The composition according to claim 1, further comprising one or more anionic surfactants selected from the group consisting of alkali salts of alkyl phosphates, alkali salts of polyoxyalkylene alkyl phosphates and alkali salts of polyoxyethylene alkyl ether acetate. Item 7. The antibacterial detergent composition according to any one of Items 1 to 6.