JP2002301144A - Antibacterial deodorant composition, antibacterial wiping sheet and deodorizing method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a deodorant composition having excellent deodorizing effect with respect to the malodor of a space, especially a malodor in a water treatment area such as sewerage or the like, and a deodorizing method for a space using the same. SOLUTION: The antibacterial deodorant composition contains a biguanidine polymer represented by formula (1), chloromethylisothiazolinone represented by formula (2) and/or methylisothiazolinone represented by formula (3), glycol and water. Especially, the antibacterial deodorant composition contains the biguanidine polymer and glycol in a weight ratio of 1:250-15:1. The space deodorizing method uses the antibacterial deodorant composition in a fine particulate state by atomizing the same.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial deodorant composition and an antibacterial wiping sheet, and a deodorizing method using the same, especially for eliminating so-called secondary malodors derived from microorganisms (smell and mold odors such as rags). Improving the odor effect.

[0002]

2. Description of the Related Art In recent years, various fragrances, deodorants, and deodorants have been developed and used in response to increasing values and needs of consumers who seek more comfortable living spaces. As a typical deodorant, many products for general household use which make the dosage form into a gel and volatilize an aromatic component and a deodorant component into the air are commercially available. However, in the present type of deodorant, due to the volatilization rate of the deodorant component, the contact between the malodorous molecules in the gas phase and the deodorant raw material is not sufficiently brought about, and the effect is not improved at present. In addition, deodorant products in combination with other fragrances are basically the same in terms of the volatilization rate of deodorant compounds as gel-based products.

On the other hand, in general households, particularly in summer, there is a problem that a bad smell derived from microorganisms generated from around water such as a kitchen sink is not easily deodorized by a method called masking. Also, garbage bits in garbage incineration plants and the like tend to decay when the temperature rises in summer or the like, and the odor tends to increase.

There are various types of odors generated by microorganisms. For example, a typical odor of mold generation is 2
-Methylisoborneol, diosmin, but the stench is also a mixture of several compounds because the flora is not a single species.

Therefore, many chemical deodorants have been proposed for deodorizing these various malodors.

[0006]

However, there has been no deodorant capable of sufficiently imparting a deodorizing effect to the malodor produced by such microorganisms. Because of the bad odor produced by microorganisms and drifting in the space, there is no deodorant that gives a sufficient effect because the activity of microorganisms produces bad odor again even if the chemical substances that constitute the bad odor are deodorized. It was.

At present, a deodorant composition having an antibacterial property capable of reliably, safely and easily removing malodors generated from microorganisms has not yet been developed.

[0008] Accordingly, an object of the present invention is to provide an antibacterial deodorant composition having an antibacterial property capable of reliably, safely and easily removing any malodor generated from microorganisms.

Regarding this point, Japanese Patent Application Laid-Open No. 9-26227
In No. 5, invention of a space deodorant composition using a biguanidine polymer is disclosed. Regarding the method of spatial deodorization using biguanidine polymer, it is possible to deodorize a wide range of foul odors that could not be achieved in the prior art, Was difficult to maintain the effect.

The biguanidine polymer has been shown to have an effective antibacterial effect at low concentrations on certain Gram-positive and Gram-negative bacteria. However, it is also known that the effect on bacterial spores and fungi is inferior. For example, FIG. 1 shows the minimum concentration at which the antimicrobial activity of the biguanidine polymer against six microorganisms is observed. FIG.
Thus, it shows significant efficacy against the gram-positive bacterium Staphylococcus aureus, but the fungus Aspergillus niger
lus niger) and Candida albicans (Candida)
albicans) does not show much antibacterial activity against other microorganisms. Therefore, it is difficult to maintain the deodorizing effect against the malodor produced by the fungus only with the biguanidine polymer.

The invention in Japanese Patent Application Laid-Open No. 9-262275 provides a formulation design in which the volatility of the formulation is small, taking into account the volatility of the formulation. Thereby, in the case of a deodorant composition which emits a deodorant composition by an aerosol or the like, it is possible to design a formulation that minimizes volatile residues.

On the other hand, Japanese Patent Application Laid-Open No. Hei 9-262275 is characterized by a highly volatile preparation formed by a combination of a lower alcohol and a biguanidine polymer. Therefore, the liquid phase state is short, for example, when sprayed in a space with a mist or the like, and the durability of the deodorant effect needs to be improved.

The biguanidine polymer having an excellent deodorizing effect against a wide range of malodors described in Japanese Patent Application Laid-Open No. 9-262275 has a characteristic that the polymer itself is dried and solidifies when the water content is reduced. Therefore, there is a problem that pores required for spraying such as nozzles of natural spray and aerosol are easily clogged.

The present invention has been made in view of the above-mentioned prior art, and a first object of the present invention is to provide a deodorant composition and a deodorizing method which are effective against malodors around water such as sewage. A second object of the present invention is to provide a deodorant composition having antibacterial properties against microorganisms that produce malodorous components. A third object of the present invention is to provide an excellent antibacterial wiping sheet.

[0015]

Means for Solving the Problems As a result of intensive studies by the present inventors to achieve the above object, an antibacterial deodorant containing a biguanidine polymer and chloromethylisothiazoline on and / or methylisothiazoline on as active ingredients. As a result of studying the composition, it was found that an antibacterial deodorant excellent in deodorant and antibacterial effect was obtained. Further, the present antibacterial deodorant composition further containing glycol is excellent in persistence of deodorant and antibacterial effects, and is also excellent in safety. As described above, it has been found that an antibacterial deodorant composition having excellent deodorizing effect, antibacterial effect and its persistence, and having high safety can be obtained, and the present invention has been completed.

That is, the antibacterial deodorant composition of the present invention comprises:
A biguanidine polymer represented by the following general formula (1),
It is characterized by containing chloromethylisothiazolinone represented by the following general formula (2) and / or methylisothiazolinone represented by the following general formula (3), glycol, and water.

Embedded image (Wherein, R is an alkylene group having 10 or less carbon atoms;
Means a positive number less than or equal to 20)

Embedded image

In the antibacterial deodorant composition of the present invention, the amount of the biguanidine polymer in the total amount of the composition is 0.0
1 to 20% by weight, and the blending amount of chloromethylisothiazolinone and / or methylisothiazolinone is 0.00% in the composition.
It is preferable that the content be from 0.0075 to 0.0075% by weight.

In the antibacterial deodorant composition of the present invention, the glycol is preferably one or more selected from propylene glycol, butylene glycol, isopropylene glycol, dipropylene glycol and polyethylene glycol. is there. The amount of the glycol is preferably 1 to 30% by weight in the composition.

It is preferable that the glycol has a biguanidine polymer: glycol ratio of 1: 250 to 15: 1.

In the above formula (1), R is -CH
₂ (CH ₂ ) ₄ CH ₂ — is preferred.

Further, the antibacterial deodorant composition of the present invention is characterized in that by spraying, the industrial odor composed of malodorous substances produced by mold and bacteria is deodorized.

The deodorizing method using the antibacterial deodorant composition of the present invention is characterized in that the antibacterial deodorant composition according to the present invention is formed into fine particles and diffused into the air. In addition, it is preferable that the particle diameter of the microbialized antibacterial deodorant composition is 10 to 500 μm.

[0023] The wiping sheet of the present invention is characterized in that the nonwoven fabric is impregnated with the antibacterial deodorant composition. The nonwoven fabric is made of at least one selected from a polyolefin-based resin, a polyester-based resin, a polyamide-based resin, a polyacrylate-based resin, a polyurethane-based thermoplastic resin, and a pulp-based fiber. Is preferred.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION The antibacterial deodorant composition of the present invention can be used as a deodorant for spraying, which is formed into a mist and diffused into the air, or as a cleaning sheet impregnated in a nonwoven fabric or the like. is there. Hereinafter, embodiments of the present invention will be described in detail.

[0025]Antibacterial deodorant composition  In the present invention, the biguanidine polymer is represented by the general formula
It means a compound having the structure shown in (1).

Embedded image (Wherein, R is an alkylene group having 10 or less carbon atoms;
Means a positive number less than or equal to 20)

In the above general formula (1), R represents 1 carbon atom.
Represents an alkylene group of 0 or less and may be linear or branched. Specific examples of R include, for example, methylene, ethylene, propylene, butylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, isopropylene, 2-methyl Although a hexamethylene group and the like can be mentioned, the biguanidine polymer of the present invention is particularly preferably polyhexamethylene biguanidine hydrochloride wherein R is a hexamethylene group.

The biguanidine polymer of the present invention can be synthesized by a known synthesis method, but a commercially available product may be used. As a commercial product, biguanidine polymer 2
As the 0% aqueous solution, for example, Proxel IB (trade name of AVICIA) and BG-1R (trade name of Sanyo Chemical Industries) are suitable. Guanidine and biguanidine-based compounds are compounds that have been conventionally recognized for their functional effects of deodorizing, and are disclosed in JP-A-5-56728, JP-B-51-5452, and JP-A-5-4542.
No. 225889 discloses a toilet preparation in which the dosage form is gel beads. However, these are solid or semi-solid, and are clearly different from the liquid deodorant composition of the present invention, which deodorizes the entire space, in terms of shape and usage.

The biguanidine polymer according to the present invention is also disclosed in US Pat. No. 4,946,672 as a deodorant component. However, there is no proposal in the above-mentioned U.S. patents in combination with an antibacterial agent effective against fungi. On the other hand, various antibacterial agents are known, but none of them is satisfactory as a deodorant for spatial application in terms of both safety and effect. Further, when the deodorant composition described in U.S. Pat. No. 4,946,672 is used as the deodorant composition for spraying as a deodorant composition for the purpose of the present invention, there is a problem of volatile residues. Further, the above-mentioned U.S. Patent does not disclose using glycol and water as a solvent at all, and of course, does not make any study on maintaining the effect of glycol and water and reducing clogging of micropores as much as possible. .

JP-A-4-99571, JP-A-10-32
In some inventions such as 8284 and JP-A-2000-005291, a disinfecting / deodorizing composition combining a disinfectant and a deodorant has been proposed. However, no consideration has been given to maintaining high safety and deodorizing effects.

The chloromethylisothiazolinone and / or methylisothiazolinone according to the present invention can be synthesized by a conventional method.
4-isothiazolin-3-one and / or 2-methyl-
KATHON CG (ROHM ANDHAA) consisting of an approximately 1-2% solution of an approximately 3: 1 mixture of both 4-isothiazolin-3-ones.
(Company S) may be used. The compound is easily soluble in water and is a suitable raw material for a deodorant for spraying.

In the antibacterial deodorant composition of the present invention, water and glycol are used as solvents. The present inventors have studied glycols, and found that glycols are propylene glycol, dipropylene glycol, 1,3 butylene glycol, 1,4 butylene glycol, 1,2 butylene glycol, isopropylene glycol, and PEG40.
It has been found that polyethylene glycols such as 0, PEG100, PEG1500 and PEG20000 maintain the deodorizing effect.
As for the glycol used in the present invention, ethylene glycol, propylene glycol, 1,
3-butylene glycol, isopropylene glycol and dipropylene glycol are preferred.

The amount of glycol in the antibacterial deodorant composition of the present invention is preferably 1 to 30% by weight based on the whole composition. If the amount is less than 1% by weight, it may not be possible to obtain a sustained deodorizing effect, which is not preferable.

When glycol is added as a solvent of the antibacterial deodorant composition of the present invention at a weight ratio of biguanidine polymer to glycol of 1: 250 to 15: 1, the biguanidine polymer may be dried. I found that nothing was obtained. The present antibacterial deodorant composition containing glycol is hard to dry, has excellent effect persistence, and does not cause clogging in pores such as nozzles even when sprayed.

In the antibacterial deodorant composition of the present invention, the amount of the biguanidine polymer in the total amount of the composition is 0.0
1 to 20% by weight, and the blending amount of chloromethylisothiazolinone and / or methylisothiazolinone is 0.00% in the composition.
Preferably, the amount is from 0.1 to 10% by weight, and more preferably from 0.1 to 10% by weight of the biguanidine polymer, and from 0.000015 to 0.0015% by weight of the chloromethylisothiazolinone and / or methylisothiazolinone. is there. If the compounding amount of the biguanidine polymer is less than 0.01% by weight, or the compounding amount of chloromethylisothiazoline on and / or methyl isothiazolin on is
If the amount is less than 075% by weight, a sufficient overall antibacterial effect on microorganisms producing malodorous components cannot be obtained, and the deodorizing effect may be inferior.

In the present invention, in addition to the above-mentioned essential components, other components usually used, for example, solvents, oils, surfactants, preservatives, ultraviolet absorbers, fragrances, coloring agents and the like are used in the present invention. Can be appropriately compounded within a range that does not impair.

Further, the antibacterial deodorant composition of the present invention is suitable for spraying in a malodorous environment containing a large amount of water in which microorganisms can easily inhabit.
It is suitable for deodorizing sewage odor, air conditioning odor from drain outlet, and the like.

[0037]Cleaning sheet  The antibacterial deodorant composition of the present invention is applied to a nonwoven fabric or
The impregnated cleaning sheet is one or more nonwoven fabrics
The laminated absorbent body contains the antibacterial deodorant composition of the present invention.
It is characterized by being made of a dipped sheet.

Japanese Patent Application Laid-Open No. 9-262275 describes that the biguanidine polymer as an active ingredient of the present invention is effective for deodorizing odors, especially tobacco odor, floating in a space by mist formation. There is no disclosure at all about making a wiping sheet.

As the nonwoven fabric used in the present invention, any material can be used without particular limitation as long as it is made of a material constituting the nonwoven fabric used for the wiping sheet. The basis weight of the nonwoven fabric is 10 to 80 g /
but is preferably m ^2, and even more preferably 30 to 60 g / ^{m 2.} If the basis weight is less than 10 g / m ² , problems such as breakage during processing occur, which is not preferable.
If it exceeds g / m ² , the texture is often not improved, which is not preferable.

The dry strength of the wiping sheet of the present invention is as follows:
The MD direction is preferably 1 to 10 kg / 25 mm, and the CD direction is preferably 0.8 to 5 kg / 25 mm. The wet strength is 0.5-5 kg / 25 in the MD direction.
mm, and the CD direction is 0.2 to 3 kg /
Preferably it is 25 mm. Here, the dry strength and the wet strength are each measured as follows. Drying strength: The wiping sheet of the present invention was cut out at a width of 25 mm to obtain a sample. In addition, as this sample,
A sheet in the MD direction and a sheet in the CD direction in the width direction were prepared. Using the Tensilon tensile tester, the obtained sample was measured for the strength at the time of breaking under the following conditions, and each of the MD direction and the CD direction was measured. Distance between chucks; 100 mm Pulling speed; 300
mm / min wet strength: The sample was impregnated with water at a weight of 200% by weight of the weight of the sample, and measured in the same manner as the above dry strength.

The basis weight of the entire wiping sheet of the present invention is:
It is preferably 30 to 60 g / m ^2, and the thickness is 0.1 g / m ² .
It is preferred to be 1 to 1.0 mm.

The wiping sheet of the present invention may further contain various additives which are added to a normal wiping sheet or the like.

The wiping sheet of the present invention is used for, for example, prevention of odors such as paper towels for adults, disposable rags, kitchen paper and trash boxes, and prevention of odors in waste boxes for sanitary products.

In the laminate, the number of the nonwoven fabrics is not particularly limited as long as a plurality of the nonwoven fabrics are laminated, but preferably 1 to 6 sheets.

The thickness of the nonwoven fabric is 0.1 to 1 m.
m, more preferably 0.1 to 0.3 mm.

[0046]Deodorizing method  As a deodorizing method using the antibacterial deodorant composition of the present invention,
A method of forming a mist and diverging the air is preferable. Ingredient
Physically, for aerosol preparations, fill and spray cylinders
Method, mist from the pores of the pumped antibacterial deodorant composition
Using a container such as an atomizer.
Atomization with a method of making
Method. For those who atomize by ultrasonic vibrator
The method can easily control the particle size and spray amount of mist.
You. The floating time is longer when the mist particle size is reduced.
Therefore, the deodorizing effect tends to be high, and the particle size is
20 to 500 μm, preferably 50 to 200 μm
is there.

As another deodorizing method using the antibacterial deodorant composition of the present invention, a method using the form of the wiping sheet can be exemplified. As the deodorizing method of applying or impregnating the antibacterial deodorant composition of the present invention to a nonwoven fabric and using it as a cleaning cloth, a method of deodorizing by wiping or wrapping a substance that generates a malodor, and further a method of generating a malodor It is preferable to use a method of pasting in a container such as a garbage bin in which is accumulated.

Hereinafter, the present invention will be described in detail with reference to specific examples.
I do. The amounts are by weight unless otherwise specified.Evaluation of the antibacterial deodorant composition of the present invention  The present inventors have determined that the biguanidine polymers shown in Table 1 and
Recall and chloromethylisothiazoline on antibacterial agent
Of the present invention containing methyl and methylisothiazolinone
The composition of Test Example 1 was used to confirm its deodorant effect, etc.
Was. The chloromethylisothiazoline on of Test Example 1 was used.
And 1,3-butylene except methylisothiazolinone
Compare those containing ethanol instead of glycol
A control was used.

[0049]

[Table 1]  Component Control Test Example 1  Biguanidine polymer (20% aqueous solution) 5.0 5.0 Ethanol 5.0 01,3 butylene glycol 0 5.0 Chloromethylisothiazolinone / methylisothiazolinone (total 1.5% aqueous solution) 0 0.5 Purification Water 90.0 89.5

<Deodorant Test> The antibacterial deodorant composition having the composition shown in Table 1 was subjected to a sensory evaluation using a general panel (n = 5). The experimental method was based on a simultaneous comparison using a 1 L Erlenmeyer flask. Ammonia and trimethylamine were used as odor sources. 0.02 m of an aqueous solution containing 0.01% by weight of ammonia in each of two flasks
1 for 10 minutes. Thereafter, the control and the deodorant according to Test Example 1 were added, and after 5 minutes, 30 minutes, 1 hour, and 1 hour.
Judgment was made after day. The judgment was made according to the judgment table in Table 2 below. In the same manner, 0.01% by weight of trimethylamine
A deodorizing test for amines was carried out using 0.02 ml of an aqueous solution of the above. In addition, sensory evaluation was performed for the kitchen drain using a general panel (n = 2). As for the experimental method, two triangle corners for garbage were prepared, and after being used for one week, immediately after spraying each deodorant (5 minutes), one hour, ten hours, one day, One week later was compared.

[0051]

[Table 2]  Odor intensity evaluation criteria  5 Feel very strong 4 Feel strong 3 Feel clearly 2 Feel faint 1 Don't feel

FIG. 2 shows the deodorizing effect of the antibacterial deodorant composition of the present invention on ammonia. As shown in FIG. 2, the sensory evaluation in the control for ammonia and the test example 1 showed that both were sufficiently deodorized at the initial stage (0 min) when compared with the control, but the test example 1 was more remarkably depleted over time. You can see that it smells.
From these results, it was shown that the antibacterial deodorant composition of the present invention effectively deodorized the odor of ammonia in a short time and maintained its effect.

FIG. 3 shows the effect of the antibacterial deodorant composition of the present invention on trimethylamine. As shown in FIG. 3, the sensory evaluation in the control for trimethylamine and the test example 1 showed that both were sufficiently deodorized at the initial stage (0 min) when compared with the control, but the test example 1 disappeared more remarkably over time. You can see that it smells. From these results, the antibacterial deodorant composition of the present invention,
Effectively deodorizes the odor of trimethylamine in a short time,
The effect was shown to be persistent.

FIG. 4 shows the deodorizing effect of the antibacterial deodorant composition of the present invention on the triangle corner of the kitchen. As shown in FIG. 4, the control for the triangle corner of the kitchen and the sensory evaluation in Test Example 1 were initially performed (0 mi).
In n), both are sufficiently deodorized as compared with the control, but it can be seen that Test Example 1 is more remarkably deodorized over time. From these results, the antibacterial deodorant composition of the present invention, the odor of the triangle corner of the kitchen,
It was shown that the odor was effectively eliminated in a short time and the effect was maintained.

The present inventors carried out a test on the composition of Test Example 1 with respect to nozzle clogging. <Nozzle Clogging Test> The nozzle clogging was repeated 10 weeks after spraying continuously with an atomizer tip having a nozzle diameter of 0.25 mm (φ) one week later. The evaluation criteria are shown below. [Nozzle clogging] ○ No clogging occurred △ Certain clogging × Clogging occurred

The present inventors visually evaluated the stability of the composition of Test Example 1. The evaluation criteria are as follows. [Stability] ○ No change in appearance of composition △ Slight change in appearance of composition × Change in appearance of composition

Table 3 shows the stability of Test Example 1 and the results of the nozzle clogging test. The present inventors have also summarized the results of the deodorization test in Table 3. In Table 3, the deodorizing effect after 5 minutes and after 1 week was evaluated. The evaluation criteria are as follows. [Deodorizing effect] ◎ Odor intensity is less than 2 ○ Odor intensity is 2 or more and less than 3 △ Odor intensity is 3 or more and less than 4 × Odor intensity is 4 or more

[0058]

[Table 3]  Component Control Test Example 1  Stability ○ ○ pH 5.44 5.47 Nozzle clogging (intermittent operation) × ○ Deodorizing effect after 5 minutes (ammonia) ○ ○ Deodorizing effect after 5 minutes (trimethylamine) ◎ ◎ Deodorizing after 5 minutes Effect (Kitchen triangle corner) ○ ○ Deodorization effect after one week (ammonia) ○ ◎ Deodorization effect after one week (trimethylamine) ○ ◎ Deodorization effect after one week (Kitchen triangle corner) △ ◎

As shown in Table 3, it was found that the sample (control) in which glycol was not blended exhibited a malfunction that was considered to be clogged, but the product in which glycol was blended (Test Example 1) was significantly improved. From these results, it was shown that the antibacterial deodorant composition of the present invention can effectively deodorize in a short period of time, and has a long-lasting effect and is excellent in clogging of nozzles during space spraying.

[0060]Chloromethylisothiazoline on and methyl
Luisothiazoline on content  The present inventors have responded to odors derived from microorganisms represented by fungi.
Of suitable formulation of antibacterial deodorant composition with high deodorizing effect
Was done. First, chloromethyi was prepared using the composition shown in Table 4 below.
Of luisothiazolinone and methylisothiazolineon
The mixing amount was examined.

[0061]

[Table 4]  Test Example Ingredients 2 3 4 5 6 Polyaniline polymer (20% aqueous solution) 4.0 4.0 4.0 4.0 4.0 1,3 Butylene glycol 5.0 5.0 5.0 5.0 5.0 KATHON CG (*) 0.0005 0.001 0.01 0.1 0.5 Purified water 90.9995 90.999 90.99 90.9 90.5  Compounding amount (chloromethylisothiazodolinon + methylisothiazodolinon) 0.0000075 0.000015 0.00015 0.0015 0.0075 Stability (appearance) ○ ○ ○ ○ ○ pH 5.43 5.43 5.43 5.44 5.45 Deodorizing effect after 5 minutes (ammonia) ○ ○ ○ ○ ○ 5 minutes Deodorizing effect after (trimethylamine) ◎ ◎ ◎ ◎ ◎ Deodorizing effect after 5 minutes (Kitchen triangle corner) ○ ○ ○ ○ ○ Deodorizing effect after 1 week (ammonia) ◎ ◎ ◎ ◎ ◎ Disappearing after 1 week Odor effect (trimethylamine) ◎ ◎ ◎ ◎ ◎ Deodorant effect after one week (Kitchen triangle corner) ○ ◎ ◎ ◎ ◎  * Chloromethylisothiazolin-on / methylisothiazolin-on (1.5% total aqueous solution)

As shown in Table 4, when the amount of KATHON CG was increased, there was no difference in the effect at the initial stage, but the sustained deodorizing effect was sometimes higher in the case of KATHON CG. Understand. Further, from the deodorizing effect after 1 week (kitchen triangle corner), the blending amount of chloromethylisothiazoline on and / or methyl isothiazolin on is more preferably 0.000015% by weight (0.001% by weight of aqueous solution) or more. You can see that.

[0063]Types of glycol  Next, about the kind of glycol by the composition of Table 5,
Study was carried out.

[0064]

[Table 5]  Ingredient Test Example 7 Test Example 8 Test Example 9  Biguanidine polymer (20% aqueous solution) 4.0 4.0 4.0 1,3 Butylene glycol 5.0 0 0 Propylene glycol 0 5.0 0 Polyethylene glycol 1500 0 0 5.0 KATHON CG (*) 0.1 0.1 0.1 Purified water 90.9 90.9 90.9  Stability ○ ○ ○ pH 5.43 5.44 5.41 Nozzle clogging ○ ○ ○ ~ △ Deodorizing effect after 5 minutes (Kitchen triangle corner) ○ ○ ○ Deodorizing effect after 1 week (Kitchen triangle corner) ◎ ◎ ◎  * Chloromethylisothiazolin-on / methylisothiazolin-on (1.5% total aqueous solution)

As is clear from Table 5, there is almost no difference in the effect of the type of glycol, but when the volatile residue and the state after volatilization are compared, the lower glycol is more scattered. In this case, it is presumed that it is preferable in terms of clogging of pores such as a nozzle.

[0066]Biguanidine polymer: weight of glycol
ratio  Further, the present inventors have determined the deodorant compositions shown in Tables 6 and 7 below.
Weight of biguanidine polymer: glycol
The ratio was examined. Test methods and evaluation criteria are as described above.
It is street, and deodorant effect is for kitchen triangle corner
It was conducted.

[0067]

[Table 6]  Test example Ingredient 10 11 12 13 14 15 16  Biguanidine polymer (20% aqueous solution) 0.08 0.4 1.0 2.4 5.0 5.0 5.0 1,3 Butylene glycol 50.0 40.0 25.0 20.0 15.0 10.0 1.0 KATHON CG (*) 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Purified water 49.91 59.59 73.99 77.59 79.99 84.99 93.99  Weight ratio (biguanidine polymer: glycol) 1: 3125 1: 500 1: 125 1:42 1:15 1:10 1: 1 Stability ○ ○ ○ ○ ○ ○ ○ pH 6.30 5.78 5.48 5.44 5.43 5.43 5.45 Deodorant effect (After 5 minutes) △ ○ ○ ○ ○ ○ ○ Deodorizing effect (after 1 week) △ △ ○ ◎ ◎ ◎ ◎  * Chloromethylisothiazolin-on / methylisothiazolin-on (1.5% total aqueous solution)

[0068]

[Table 7]  Example component 17 18 19 20 21  Biguanidine polymer (20% aqueous solution) 25.0 50.0 40.0 50.0 50.0 1,3 butylene glycol 1.0 1.0 0.4 0.4 0.08 KATHON CG (*) 0.01 0.01 0.01 0.01 0.01 Purified water 73.99 48.99 59.59 49.59 49.91  Weight ratio (peak anionic polymer: polycold) 5: 1 10: 1 20: 1 25: 1 125: 1 Stability ○ ○ ○ ○ ○ pH 5.51 5.51 5.53 5.52 5.53 Deodorant effect (after 5 minutes) ◎ ◎ ◎ ◎ ◎ ◎ Deodorizing effect (after one week) ◎ ◎ ○ ○ ○  * Chloromethylisothiazolin-on / methylisothiazolin-on (1.5% total aqueous solution)

From Tables 6 and 7, the contents were stable when the ratio of biguanidine polymer (20% aqueous solution) to 1,3 butylene glycol was 1: 3125 to 125: 1. Also, it can be seen that when the ratio of biguanidine polymer: glycol is about 1: 250 to about 15: 1, the deodorant effect tends to be persistent. However,
Regarding the sustained effect, the amount of biguanidine polymer and KATHON
It is necessary to examine the amount of glycol while keeping the CG constant to confirm the effect. When the amount of biguanidine polymer was 0.016% by weight (aqueous solution 0.08%) (Test Example 10), the deodorizing effect was weak. Also, it can be seen that the blending amount of glycol is about 1 to about 30% by weight, and the deodorizing effect tends to be maintained.

The present inventors further investigated the weight ratio of biguanidine polymer: glycol while keeping the amount of KATHON CG constant. Table 7 shows the composition containing 0.4% by weight of the biguanidine polymer, and Table 8 shows the composition containing 8.0% by weight. The test method and evaluation criteria are as described above, and the deodorizing effect is an effect on the kitchen triangle corner.

[0071]

[Table 8]  Test example Component 22 23 24 25 26 27 28 Polyaniline polymer (20% aqueous solution) 0.4 0.4 0.4 0.4 0.4 0.4 0.4 1,3-butylene glycol 40.0 20.0 4.0 2.0 1.0 0.4 0.08 KATHON CG (*) O.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Purified water 59.59 79.59 95.59 97.59 98.59 98.19 99.51  Weight ratio (biguanidine polymer: glycol) 1: 500 1: 250 1:50 1:25 1: 12.5 1: 5 1: 1 Stability ○ ○ ○ ○ ○ ○ ○ Deodorant effect (after 5 minutes) ○ ○ ○ ○ ○ ○ ○ Deodorizing effect (after one week) △ ○ ○ ○ ○ △ △  * Chloromethylisothiazolin-on / methylisothiazolin-on (1.5% total aqueous solution)

[0072]

[Table 9]  Test example Component 29 30 31 32 33 Polyaniline polymer (20% aqueous solution) 8.0 8.0 8.0 8.0 8.0 1,3 Butylene glycol 8.0 1.6 0.16 0.12 0.08 KATHON CG (*) 0.01 0.01 0.01 0.01 0.01 Purified water 83.99 90.39 91.83 91.87 91.91  Weight ratio (biguanidine polymer: glycol) 1: 5 1: 1 10: 1 13: 1 20: 1 Stability ○ ○ ○ ○ ○ Deodorizing effect (after 5 minutes) ◎ ◎ ◎ ◎ ◎ Deodorizing effect (1 week) After) ◎ ◎ ○ ○ ○  * Chloromethylisothiazolin-on / methylisothiazolin-on (1.5% total aqueous solution)

According to Tables 8 and 9, the biguanidine polymer (20% aqueous solution) was fixed at 0.4% and 8%, respectively, and an equal amount of KATHON CG was added to reduce the ratio of 1,3 butylene glycol to 1: 500-1: 1 and 1: 5-20:
It can be seen that the content state when the value is 1 is stable. When the weight ratio of biguanidine polymer: glycol is 1: 250-1: 1, the deodorizing effect is maintained. However, the amount of glycol in Test Examples 31 to 33 was 1% by weight.
Considering that less and that the persistence of the deodorizing effect was observed in Test Example 17 with a ratio of 10: 1, about 1:25
A range of 0 to about 15: 1 may be preferred. In addition, as for the amount of glycol, Test Example 11 (Glycol 40
(% By weight) and the fact that the deodorizing effects of Test Examples 31 to 33 (1% by weight or less of glycol) are reduced, the amount of glycol is about 1%.
It is found that about 30% by weight is suitable.

[0074]Sterilizing effect and growth inhibiting effect  Next, the present inventors studied the bactericidal effect and growth inhibition of the antibacterial deodorant composition.
The stopping effect and stability were evaluated. The test method is as follows
You. The evaluation criteria for stability are as described above.

The bactericidal effect and the growth inhibiting effect were measured by the following methods. That is, Pseudomonas aeruginosa IAMlOO7 as aerobic bacteria,
Escherichia coli ATCC8739,
Staphylococcus aurus
eus FDA209P), Propioni bacterium acnes ATCCl182 as an anaerobic bacterium
7), Trichophyton mentagrophytes as Trichophyton, Penicillium chrysogenum as fungus
And Candida albicans
According to a conventional method, the minimum bactericidal concentration (MCC: Minimum Cidal Concentration) was determined in a liquid medium system, and the presence and size of a growth inhibition zone were determined in an agar medium system. That is, a broth medium (Eiken) is used for aerobic bacteria, a GAM medium (Nissui) is used for anaerobic bacteria, and a Sabouraud medium (Nissui) is used for Trichophyton bacteria. 100 / ml of spores of each microorganism and pre-cultured
The antibacterial deodorant composition of the present invention was added therein in an amount of 0.05 to 10%, and after a certain period of time (10 minutes) had elapsed, 0.1 ml of the resultant was cultured in each medium. The minimum concentration (MCC) at which no growth was observed was determined. As for the minimum growth inhibitory concentration (MIC), bouillon agar medium (Eiken) was used for aerobic bacteria, GAM agar medium (Nissui) was used for anaerobic bacteria, and Sabouraud was used for Trichophyton. Using an agar medium (day water), spores of each bacterium and Trichophyton bacillus pre-cultured in a conventional manner are inoculated on the surface of each agar medium to a concentration of 100 / ml and dried. A filter paper strip coated with a sample to which 5% of the antibacterial deodorant composition of the present invention was added was placed thereon, cultured, and a growth inhibition zone (distance from the filter paper strip: mm) in which the growth of bacteria around the filter paper strip was suppressed. The size of was determined.

The antibacterial effects of the antibacterial deodorant compositions of Test Examples 34 to 38 were examined based on the above-mentioned test methods. As a comparison of the antibacterial deodorant compositions of Test Examples 35 to 38, Test Example 34 in which KATHON CG was not used was used.

[0077]

[Table 10]  Test example Ingredient 34 35 36 37 38 Polyaniline polymer (20% aqueous solution) 4.0 4.0 4.0 4.0 4.0 Propylene glycol 5.0 5.0 5.0 5.0 5.O KATHON CG (*) 0 0.5 0.05 0.005 0.0005 Purified water to 100 to 100 to 100 to 100 to 100  Amount (chloromethylisothiazodulin on + methylisothiazodolin on) 0 0.0075 0.00075 0.000075 0.0000075 Stability ○ ○ ○ ○ ○ pH 5.43 5.46 5.45 5.45 5.45  * Chloromethylisothiazolin-on / methylisothiazolin-on (1.5% total aqueous solution)

MCC (%) of the antibacterial deodorant composition in Table 10
Table 11 shows the results.

[0079]

[Table 11]  Test example 34 35 36 37 38 Shoot monas ・ Elkinosa ＞ 10 1 2 5 10 Escherichia ・ Cori 1 1 1 2 5 Staphylococcus ・ Aureus 0.5 0.5 0.5 0.5 0.5Fluoro-hyperacterium ・ Acnes 0.5 1 1 0.5 0.5 Trichophyton ・ Mentaclophytes ＞ 10 2 2 5 5 Penicillium ・ Chrysodeum ＞ 100 1 2 5 5

As is clear from the results in Table 11, KATHON
It can be seen that the deodorant composition containing no CG (Test Example 34) shows an effective bactericidal effect on only some of the microorganisms. On the other hand, an antibacterial deodorant composition containing 0.0005 to 0.5% by weight of KATHON CG (0.0000075 to 0.0075% by weight of chloromethylisothiazolinone + methylisothiazolinone) is used as a fungus for Penicillium chrysogenum. chrysogenu
m), Candida albican
It can be seen that it shows an effective bactericidal effect on all the microorganisms tested, including s).

Next, the results of the inhibition circle growth inhibition zone (mm) of the antibacterial deodorant composition are shown in Table 12.

[0082]

[Table 12]  Test example 34 35 36 37 38 Shoot Monas Elkinosa 2 28 20 10 4 Escherichia coli 1 26 18 12 3 Staphylococcus aureus 5 35 30 15 5 Prophylactic oncium Acnes 3 28 23 18 4 Trichophyton Mentaclophytes 0 15 13 10 1 Penicillium Chrysocanum 0 18 15 11 2 Candidates / Alphances 0 20 18 12 3

As is clear from Table 12, it can be seen that the deodorant composition not containing KATHON CG (Test Example 34) has a growth inhibitory effect on only a part of microorganisms. On the other hand, an antibacterial deodorant composition containing KATHON CG in an amount of 0.0005% by weight or more (chloromethylisothiazolinon + methylisothiazolinon in an amount of 0.0000075% by weight or more) is composed of fungi such as Penicillium chrysogenum and candy. It can be seen that it shows a growth inhibitory effect on all the microorganisms tested, including C. albicans. In order to obtain a more effective growth inhibitory effect, KA
It can be seen that the amount of THON CG is preferably about 0.001% by weight or more (chloromethylisothiazolinone + methylisothiazolinone about 0.000015% by weight or more).

As described above, the deodorant composition obtained by combining the biguanidine polymer, which is the active ingredient of the present invention, with chloromethylisothiazolinone and / or methylisothiazolinone can be used for the corners of kitchen kitchens, air conditioners and sewage pipes. Demonstrates an excellent deodorizing effect against the odors represented by mold. Then, by adding glycol to the deodorant composition obtained by combining the biguanidine polymer and chloromethylisothiazolinone and / or methylisothiazolinone, it is possible to maintain the durability by spraying into a space without any problems such as clogging. An antibacterial deodorant composition was completed.

[0085]

Hereinafter, embodiments of the present invention will be described.
The present invention is not limited to the following examples. Unless otherwise specified, the amounts are shown in% by weight.

[0086]Example 1 Deodorant  Biguanidine polymer 0.2 Propylene glycol 5 KATHON CG 0.5 Perfume Appropriate amount Metal chelating agent Appropriate amount Preservative Appropriate amount Brown inhibitor Appropriate amount Purified water Residue (Production method) Purified water, metal chelating agent, brown inhibitor, big
Dissolve anidine polymer, KATHON CG at room temperature
I do. Dissolve preservatives and fragrances in propylene glycol,
Mix and dissolve in the previous aqueous phase. Then it is filtered.

[0087]Example 2 Deodorant  Biguanidine polymer 0.2 Polyethylene glycol 1000 5 KATHON CG 0.01 Alcohol 2 Fragrance Appropriate amount Metal chelating agent Appropriate amount Preservatives Appropriate amount Anti-browning agent Appropriate amount Purified water Residue
Dissolve anidine polymer, KATHON CG at room temperature
I do. Dissolve preservatives and fragrances in alcohol and add to the aqueous phase
Mix and dissolve. Then filter

[0088]Example 3 Deodorant  Biguanidine polymer 15 Polyethylene glycol 400 2 Alcohol 2 KATHON CG 0.001 Fragrance Appropriate amount Metal chelating agent Appropriate amount Preservatives Appropriate amount Anti-browning agent Appropriate amount Purified water Residue
Dissolve anidine polymer, KATHON CG at room temperature
I do. Polyethylene glycol 400 in alcohol, preservative
Dissolve the agent and perfume and mix and dissolve in the aqueous phase. Then filter
Spend.

[0089]Example 4 Deodorant cloth  (Deodorant) Biguanidine polymer 0.5 Polyethylene glycol 1500 5 Alcohol 4 KATHON CG 0.2 Fragrance Appropriate amount Metal chelating agent Appropriate amount Preservative Appropriate amount Brown inhibitor Appropriate amount Purified water residue (Production method) Purified water, metal chelating agent, brown Inhibitor, big
Dissolve anidine polymer, KATHON CG at room temperature
I do. Polyethylene glycol, preservatives,
The perfume is dissolved and mixed and dissolved in the aqueous phase. Then filter
You. (Deodorant cloth) The above deodorant is weighed at 30 g / m.²Polyethylene
Deodorant solution of Example 4 on one side of a non-woven fabric made of cotton and cotton
Is 50 parts by weight with respect to 100 parts by weight of the nonwoven fabric.
To obtain a deodorant cloth.

[0090]Example 5 Deodorant cloth  (Deodorant) Biguanidine polymer 1.0 Propylene glycol 5 Alcohol 44 KATHON CG 0.2 Perfume Appropriate amount Metal chelating agent Appropriate amount Preservative Appropriate amount Anti-browning agent Appropriate amount Purified water Residue Agent, big
Dissolve anidine polymer and propylene glycol at room temperature
Disassembled and used as the aqueous phase. Dissolve preservatives and fragrances in alcohol,
It was mixed and dissolved in the previous aqueous phase. Then, it was filtered. (Deodorant cloth) The above deodorant is weighed 40 g / m.²Pulp and Les
Including the deodorant solution of Example 5 in a non-woven fabric
Impregnated, the impregnation amount is 50 weight parts with respect to 100 weight parts of nonwoven fabric
A deodorant cloth was prepared.

[0091]

According to the present invention, a conventional deodorant can be obtained by using an antibacterial deodorant composition containing a biguanidine polymer, glycol, and chloromethylisothiazolinone and / or methylisothiazolinone as active ingredients. A deodorant composition having a deodorizing effect on malodors derived from microorganisms including mold and a superior deodorizing effect on the duration thereof can be obtained as compared with the preparation. The antibacterial deodorant composition can be efficiently deodorized by spraying the composition in a space or applying or impregnating the nonwoven fabric. In addition, it is possible to obtain an excellent product which is more excellent in sustainability when the composition is sprayed in space, that is, has no problem in the spraying.

[Brief description of the drawings]

FIG. 1 is a view showing the antibacterial effect of a biguanidine polymer on each microorganism.

FIG. 2 is a view showing the persistence of the deodorizing effect on the ammonia of the antibacterial deodorant composition of the present invention.

FIG. 3 is a view showing the persistence of the deodorizing effect of the antibacterial deodorant composition of the present invention on trimethylamine.

FIG. 4 is a graph showing the persistence of the deodorizing effect of the antibacterial deodorant composition of the present invention on a kitchen triangle corner.

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Shigeyuki Ogawa 2-2-1 Hayabuchi, Tsuzuki-ku, Yokohama-shi, Kanagawa Prefecture Inside Shiseido Research Center (Shin-Yokohama) (72) Inventor Kenzo Ito Yokohama-shi, Kanagawa 2-2-1 Hayabuchi, Tsuzuki-ku Shiseido Research Center Co., Ltd. (Shin-Yokohama) F term (reference) 4C080 AA06 BB02 BB05 CC02 CC12 HH04 HH05 HH09 JJ06 KK03 KK06 KK08 LL03 LL04 LL10 MM17 MM18 MM28 NN15 NN27 QQ03

Claims (11)

[Claims] 1. A biguanidine polymer represented by the following general formula (1), chloromethylisothiazoline on represented by the following general formula (2) and / or methyl isothiazoline on represented by the following general formula (3): , A glycol and water. Embedded image (Wherein, R is an alkylene group having 10 or less carbon atoms, n
Is a positive number of 20 or less on average) 2. The composition according to claim 1, wherein the amount of the biguanidine polymer in the total amount of the composition is 0.01 to 20.
% By weight of chloromethylisothiazoline on and / or
Or the compounding amount of methyl isothiazoline on is 0.0000075 to
An antibacterial deodorant composition characterized by being 0.0075% by weight. 3. The composition according to claim 1, wherein
An antibacterial deodorant composition, wherein the glycol is one or more selected from propylene glycol, butylene glycol, isopropylene glycol, dipropylene glycol, and polyethylene glycol. 4. The composition according to claim 1, wherein the amount of the glycol is 1 to 30% by weight in the composition.
An antimicrobial deodorant composition characterized by the following. 5. The antibacterial deodorant composition according to claim 1, wherein the weight ratio of biguanidine polymer: glycol is 1: 250 to 15: 1. 6. The composition according to claim 1, wherein R in the general formula (1) is —CH ₂ (CH ₂ ) ₄ CH
_2- An antibacterial deodorant composition, 7. The antibacterial deodorant composition according to any one of claims 1 to 6, wherein an industrial odor composed of malodorous substances produced by microorganisms is sprayed by spraying. . 8. A deodorizing method comprising using the antibacterial deodorant composition according to claim 1 in the form of fine particles and atomized. 9. The deodorizing method according to claim 8, wherein the particle size of the microbialized antibacterial deodorant composition is 10 to 500 μm. 10. A wiping sheet characterized by impregnating a nonwoven fabric with the composition according to any one of claims 1 to 7. 11. The wiping sheet according to claim 10, wherein the nonwoven fabric is a polyolefin resin, a polyester resin,
A wiping sheet comprising at least one selected from a polyamide resin, a polyacrylate resin, a thermoplastic resin of a polyurethane resin, and a pulp fiber.