JP2003180810A - Composition for deodorization - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for deodorization capable of efficiently eliminating acidic odors and basic odors which are malodorous causative substances, such as filth odors and body odors. <P>SOLUTION: The composition for deodorization is prepared by respectively suitably and selectively compounding a copolymer essentially consisting of alkyl vinyl ethers of ≥2 in carbon number of an alkyl group bonded to an oxygen atom and/or a derivative of this copolymer, and further an inorganic metal compound, fatty acid metal salt and carbonyl compound. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a deodorant composition. More specifically, the present invention relates to a novel deodorant composition that is effective in deodorizing odors such as dirt and body odor.

[0002]

2. Description of the Related Art In recent years, as the standard of living has improved, interest in environmental hygiene has increased, and deodorization and deodorization have become major issues. As a method of removing the malodorous component from the past,
Chemical methods such as masking offensive odors with fragrances, physical methods such as adsorption with porous absorbents such as activated carbon, alumina and zeolite, catalytic combustion methods, oxidation methods with ozone, neutralization methods using chemicals, etc. Alternatively, biochemical methods such as decomposition by bacteria are known.

For deodorization in parts familiar to daily life, liquid deodorants by spraying, deodorants installed in the room in the form of gel or particles are used. However, the most widely used liquid deodorant wets the surroundings and stains clothes, and is not preferable for care products such as diapers that touch the skin or clothes. In addition, both the sheet impregnated with a deodorant and the activated carbon sheet have a sticky feeling, and the activated carbon sheet is not particularly effective against the smell of ammonia.

[0004]

As described above, none of the conventional deodorants has satisfactory performance. In addition, familiar malodors that are actually a problem in daily life consist of various components such as acidic odors and basic odors, and effective deodorization is effective against any malodorous component. It must be an agent.

It is an object of the present invention to provide a deodorant composition having an excellent deodorant ability, particularly a deodorant composition effective in daily life, for example, for deodorizing diapers.

[0006]

Means for Solving the Problems As a result of intensive studies for achieving the above object, the present inventor has found that an alkyl vinyl ether having an alkyl group bonded to an oxygen atom having 2 or more carbon atoms and maleic anhydride are used. It has been found that an excellent deodorizing effect is exhibited by using a composition containing a copolymer as an essential constituent and / or a derivative of the copolymer, and has completed the present invention.

That is, the present invention provides a copolymer and / or a derivative of the above copolymer containing, as essential components, an alkyl vinyl ether in which an alkyl group bonded to an oxygen atom has 2 or more carbon atoms and maleic anhydride. The present invention provides a deodorant composition containing:

In order to improve the deodorizing effect, the deodorant composition of the present invention contains an inorganic metal compound, a fatty acid metal salt and a carbonyl compound in the copolymer and / or the derivative of the copolymer. You may mix | blend 1 or more types selected.

Further, the deodorant composition of the present invention is incorporated into the above-mentioned copolymer and / or a derivative of the above-mentioned copolymer, or the above-mentioned copolymer and / or the above-mentioned, in order to impregnate a non-woven fabric or paper. It is also possible to add one or more selected from an inorganic metal compound, a fatty acid metal salt and a carbonyl compound to the derivative of the copolymer, and add water and / or an organic solvent to make it in a fluid state.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.

A copolymer according to the present invention containing an alkyl vinyl ether having an alkyl group bonded to an oxygen atom having 2 or more carbon atoms and maleic anhydride as essential components (hereinafter referred to as a copolymer A). The alkyl vinyl ethers in which the alkyl group bonded to the oxygen atom has 2 or more carbon atoms, which is an essential component of, preferably has 2 to 18 carbon atoms, more preferably has 2 to 12 carbon atoms, More preferably, it is an alkyl vinyl ether having 2 to 6 carbon atoms, specifically, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, n-hexyl vinyl ether, n-octyl. Vinyl ether, lauryl vinyl ether, octadecyl vinyl ether And the like, is used by being appropriately selected.

The copolymer A according to the present invention may be a binary copolymer of the above-mentioned alkyl vinyl ethers and maleic anhydride, but other than that, it contains a polymerizable unsaturated monomer as a constituent component. It may be contained. The polymerizable unsaturated monomer is not particularly limited as long as it can be copolymerized with the alkyl vinyl ethers and maleic anhydride, but the general formula (1):

[0013]

[Chemical 2]

(In the formula, R ¹ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms, R ² represents a hydrogen atom, a halogen atom or a methyl group, and R ³ has 1 to 20 carbon atoms. An alkyl group, an alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylcarbonyloxy group having 1 to 10 carbon atoms, an alkylcarbonylamino group having 1 to 10 carbon atoms,
Alternatively, it represents a cyclic amide group having 3 to 6 carbon atoms. It is preferable that at least one member selected from the group consisting of polymerizable unsaturated monomers represented by the formula (1) is contained as a constituent component. Specific examples of the polymerizable unsaturated monomer include olefins such as propylene, 1-butene, isobutene, 1-hexene, 1-octene, 1-dodecene, and 1-octadecene; methyl (meth) acrylate. , (Meth) acrylate,
Butyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate and other (meth) acrylic acid alkyl esters; fatty acids such as vinyl acetate, isopropenyl acetate and vinyl propionate Examples include alkene esters; N-vinyl fatty acid amides such as N-vinyl acetamide and N-vinyl propionamide; cyclic amide compounds such as N-vinyl pyrrolidone and N-vinyl oxazolidone, which are appropriately selected and used for copolymerization. be able to.

When the copolymer A according to the present invention is a binary copolymer of the alkyl vinyl ethers and maleic anhydride, the molar ratio of the alkyl vinyl ethers to maleic anhydride is 60:40 to 40:60. Is preferable, and it is most preferable to contain substantially equimolar amount. When the copolymer A contains the polymerizable unsaturated monomer, the total number of moles of the alkyl vinyl ethers and maleic anhydride is relative to the total number of moles in the copolymer A,
Preferably at least 50%, copolymer A
The molar ratio of the above-mentioned alkyl vinyl ethers to maleic anhydride is preferably 60:40 to 40:60, and most preferably approximately equimolar.

The copolymer A according to the present invention can be prepared by appropriately selecting various conventionally known polymerization methods. For example, bulk polymerization, solution polymerization, emulsion polymerization,
Examples thereof include precipitation polymerization and suspension polymerization.

Further, the derivative of the copolymer A according to the present invention (hereinafter referred to as the copolymer B) may be one obtained by modifying the copolymer A. For example, the free acid of the copolymer A The free acid form of the copolymer A, the form of the salt of the free acid of the copolymer A, the ester derivative of the copolymer A, the amide derivative of the copolymer A, and the like. The ester derivative of copolymer A is preferred. The free acid form of the copolymer A means a hydrated maleic anhydride moiety, and the salt form of the free acid of the copolymer A means a hydrated maleic anhydride moiety. The neutralized form is represented, the ester derivative of the copolymer A is a half ester derivative in which a maleic anhydride moiety and an alcohol are reacted, and the amide derivative of the copolymer A is a maleic anhydride moiety and an amine. Represents a half amide derivative reacted with a class. In order to obtain the salt form of the free acid of the copolymer A, it is sufficient to neutralize the free acid form of the copolymer A with a basic substance, and as the basic substance used for the neutralization, Examples include, but are not limited to, alkali metal oxides and hydroxides, alkaline earth metal oxides and hydroxides, amines such as ammonia and methylamine, ethylamine, dimethylamine, diethylamine, triethylamine, and tributylamine. Can be mentioned. The alcohol used to obtain the ester derivative of the copolymer A is not particularly limited, but methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, hexanol, cyclohexanol, octanol, lauryl alcohol, stearyl alcohol, etc. Is mentioned. The amines used for obtaining the amide derivative of the copolymer A are not particularly limited, and examples thereof include methylamine, ethylamine, dimethylamine, diethylamine, triethylamine, tributylamine, hexylamine, octylamine, laurylamine, stearylamine and the like. To be

In the deodorant composition of the present invention, the copolymer A and / or the copolymer B of the present invention is blended with one or more kinds selected from inorganic metal compounds, fatty acid metal salts and carbonyl compounds. You can

As the inorganic metal compound, oxides, hydroxides, inorganic metal salts and the like of metals such as calcium, magnesium, copper, iron, zinc and titanium can be used. Specific examples of oxides include calcium oxide, magnesium oxide, alumina, zinc oxide, cuprous oxide, cupric oxide, iron oxide, diiron trioxide, and titanium oxide; specific examples of hydroxides , Calcium hydroxide, magnesium hydroxide, iron hydroxide, zinc hydroxide, titanium hydroxide; examples of the inorganic metal salt include chlorides, sulfates and nitrates of the above metals, preferably zinc oxide and zinc hydroxide. , Ferrous sulfate, iron hydroxide, copper sulfate, copper nitrate and the like. The content of the inorganic metal compound is 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the total amount of the copolymer A and the copolymer B used as the deodorant composition. It is a department.

The fatty acid metal salt has 1 to 3 carbon atoms.
Zero saturated or unsaturated fatty acid metal salts can be used. Specific examples of the fatty acid metal salt include saturated fatty acids such as acetic acid, propionic acid, undecylenic acid, palmitic acid, lauric acid, myristic acid, stearic acid, and behenic acid; or oleic acid, linoleic acid, linolenic acid, sorbic acid. Acids, metal salts of unsaturated fatty acids such as ricinoleic acid and arachidonic acid are preferred. Specific examples of the metal include zinc, copper, iron, molybdenum, cobalt, aluminum, titanium, manganese, nickel and silver, and zinc salt and aluminum salt are preferable. The amount of the aliphatic metal salt compounded is 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the total amount of the copolymer A and the copolymer B used as the deodorant composition. Parts by weight.

As the carbonyl compound, ketocarboxylic acid, aldehydecarboxylic acid or the like can be used. Specific examples thereof include glyoxylic acid, aldehyde nonanoic acid, levulinic acid, pyruvic acid, and glycerin aldehyde, which are appropriately selected and blended. The amount of the carbonyl compound blended is 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the total amount of the copolymer A and the copolymer B used as the deodorant composition. Is.

In the deodorizing composition of the present invention, the copolymer A and the copolymer B have an excellent adsorption force and deodorizing effect on basic odors such as amines and decomposition products thereof such as ammonia. Show. Therefore, when most of the bad odors such as diapers are amine compounds, the copolymer A and / or
Alternatively, even if the copolymer B is used alone, a sufficient deodorizing effect can be obtained. On the other hand, the aliphatic metal salt, the inorganic metal compound and the carbonyl compound have excellent adsorption power and deodorizing effect on acidic odors such as hydrogen sulfide and mercaptan. Therefore, when the offensive odor-causing substance contains a sulfur-based odor, it is preferable that the copolymer A and / or the copolymer B is used in combination with one or more selected from inorganic metal compounds, fatty acid metal salts and carbonyl compounds. .

In actual use, the deodorant composition of the present invention is applied or impregnated on a substrate having various shapes to increase the surface area of the deodorant composition and improve the deodorant effect. In order to achieve the above, copolymer A and / or copolymer B, or copolymer A and / or copolymer B
It is also possible to use a mixture of one or more selected from an inorganic metal compound, a fatty acid metal salt and a carbonyl compound, which is added with water and / or an organic solvent to be in a fluid state. When a solvent is used, the deodorizing composition containing the copolymer may be in a fluid state, for example, water, methanol, ethanol, n-propanol, isopropanol, 1-butanol, 2-butanol, methyl. Cellosolve, ethyl cellosolve, butyl cellosolve, ethyl acetate, methyl acetate, acetone, methyl ethyl ketone, N, N-dimethylformamide, N,
Examples thereof include N-dimethylacetamide. The amount of these solvents used is 0.01 to 100 parts by weight, preferably 0.1 to 100 parts by weight based on 1 part by weight of the total amount of the copolymer A and the copolymer B.
˜50 parts by weight.

Examples of the substrate include non-woven fabrics, woven fabrics, yarns, fibrous substances such as monofilaments, granular substances, paper or porous substances such as zeolite, sepiolite, diatomaceous earth, and activated carbon. Alternatively, two or more kinds can be used in combination. As another form in actual use, it may be dispersed or mixed in various polymer compounds, or dissolved in a base polymer to form a polymer blend, and the mixture may be molded into a sheet or a film. it can.

The copolymer A and the copolymer B according to the present invention can be prepared by selecting the kind of the alkyl vinyl ether to be used, the polymerizable unsaturated monomer and the modification method. The softening point (melting point) of B, the decomposition temperature, the compatibility with other polymer compounds, and the solubility with respect to a solvent can be freely adjusted. Therefore,
When the copolymer A and / or the copolymer B according to the present invention is used as a deodorant composition, the handling property is improved, and the deodorizing effect is maintained for a long time, and the adhesion to the substrate is improved. The effect of improving the hydrolysis resistance can be obtained.

[0026]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. (Production Example) The method described in U.S. Pat. No. 3,368,896 (copolymerization of n-butyl vinyl ether and maleic anhydride in a benzene solvent, and after the polymerization, the precipitated copolymer is collected and dried. Then, n-butyl vinyl ether /
An n-butyl vinyl ether / maleic anhydride copolymer was prepared according to the method for obtaining a maleic anhydride copolymer).

50 equipped with a stirrer, thermometer, dropping funnel
A 0 ml reaction vessel was charged with 20 g of maleic anhydride, 240 ml of benzene and 100 mg of benzoyl peroxide, and heated and stirred until the internal temperature reached 70 ° C. The reaction was carried out under a nitrogen gas atmosphere throughout. When the internal temperature reached 70 ° C, 4 g of n-butyl vinyl ether was added all at once. While stirring for a while, the internal temperature rose to 83 ° C and benzene began to reflux. Then, 16 g of n-butyl vinyl ether was added dropwise over 30 minutes so that benzene was gently refluxed. After completion of the dropping, the mixture was further heated and stirred for 2 hours at a temperature at which benzene gently refluxed (internal temperature: 83 ° C.). After completion of the reaction, the mixture was left standing overnight and cooled to room temperature. The precipitated polymer was collected and dried under vacuum at 50 ° C. for 10 hours. The obtained polymer aggregate was pulverized with a pulverizer and further dried under reduced pressure at 50 ° C. for 10 hours to obtain 32 g of a white powdery polymer (yield 81%). (Example 1) A predetermined amount of the powder n-butyl vinyl ether / maleic anhydride copolymer (hereinafter referred to as BVE / MAN) obtained in the production example was used, and the following ammonia deodorizing test (Test method 1) was used. ). The results are shown in Table 1. (Test method 1) 1) Non-woven bag (60 cm x 60 cm) ^{1) A} predetermined amount of BVE / MA
Put N into a 3L odor bag (material: PET) ²⁾ . 2) After injecting 3 L of odorless air, the inlet is tightly closed with a silicone rubber stopper. 3) Ammonia standard gas with a set concentration of 500 ppm
³⁾ is injected into the odor bag with a syringe equipped with an injection needle,
Then, it is sealed. 4) Leave at 25 ° C for a predetermined time. 5) Using the gas sampler and gas detector tube ⁴⁾ , measure the atmospheric concentration while preventing the entry of outside air. 6) In addition, the same operation is performed without adding a sample to give a blank. * 1) Nankoku Pulp Industry Co., Ltd. Paper making name: Heatron Paper type: GS-22 * 2) Omi Odo Air Service Co., Ltd. Trademark: Flek-Sampler Name: Odor bag type / standard: 3L * 3) Ammonia standard gas; Ammonia concentration = 9.14% by volume (N ₂ balance),
Injection volume = 16.4 ml * 4) Gas detector tube; No. 3M
And 3L

[0028]

[Table 1]

From Table 1, the copolymer according to the present invention (BVE / M
It can be seen that AN) has the deodorizing effect of ammonia even in a small amount. (Example 2) A mixture of BVE / MAN obtained in Production Example and zinc oxide (manufactured by Wako Pure Chemical Industries, Ltd.) was used in a predetermined amount, and subjected to the following hydrogen sulfide deodorizing test (Test Method 2). The results are shown in Table 2.
Shown in. (Test method 2) 1) Nonwoven fabric bag (60cm x 60cm) ¹⁾ Predetermined amount of BVE / MA
3L odor bag containing N and zinc oxide (Material: PE
T) Put in ²⁾ . 2) After injecting 3 L of odorless air, the inlet is tightly closed with a silicone rubber stopper. 3) Hydrogen sulfide standard gas with a set concentration of 50 ppm ⁵⁾
Is injected into the odor bag with a syringe equipped with an injection needle, and then sealed. 4) Leave at 25 ° C for a predetermined time. 5) Collect the gas in the odor bag and perform gas chromatography
Measure the gas concentration in ⁶⁾ . 6) In addition, the same operation is performed without adding a sample to give a blank. * 1) Nankoku Pulp & Paper Co., Ltd. Paper making name: Heatlon paper type: GS-22 * 2) Omi Odo Air Service Co., Ltd. Trademark: Flek-Sampler Name: Odor bag type / standard: 3L * 5) Hydrogen sulfide standard gas Concentration = 6,110 ppm (N ₂ balance), injection amount =
25.0 ml * 6) Gas chromatography; Instrument: GC-14A (manufactured by Shimadzu Corporation), Detector: FP
D, column temperature = 70 ° C. Column used: liquid phase; 1,2,3-tris (2-cyanoethoxy) propane 25% carrier; Shimalaite AW-DM-CS-ST 80-100 mesh Column size: φ3 mm × 3 M

[0030]

[Table 2]

From Table 2, the deodorant composition (B
It can be seen that the mixture of VE / MAN and zinc oxide) has a deodorizing effect on hydrogen sulfide even in a small amount.

[0032]

The copolymer A and the copolymer B according to the present invention can be prepared by selecting the kind of the alkyl vinyl ether to be used, the polymerizable unsaturated monomer and the modification method. The softening point (melting point) of the polymer B, the decomposition temperature, the compatibility with other polymer compounds, and the solubility with respect to the solvent can be freely adjusted. Therefore,
When the copolymer A and / or the copolymer B according to the present invention is used as a deodorant composition, the handling property is improved and the deodorant effect can be maintained for a long period of time.
The effects of improving the adhesion to the base material and improving the hydrolysis resistance can be obtained. Further, the deodorizing composition of the present invention can effectively deodorize acidic odors and basic odors, which are substances causing bad odors such as filth odors and body odors.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4C080 AA05 AA06 BB02 CC05 CC07                       HH05 JJ01 KK01 LL03 MM22                       MM26 NN01 NN14                 4C083 AB21 AC24 AD09 AD11 CC17                       EE18

Claims (3)

[Claims] 1. A deodorant comprising a copolymer and / or a derivative of the copolymer, which are essentially composed of an alkyl vinyl ether having an alkyl group bonded to an oxygen atom having 2 or more carbon atoms and maleic anhydride. Composition. 2. The copolymer has the general formula (1): (In the formula, R ¹ is a hydrogen atom, a halogen atom or a carbon number 1
To R 6 represent an alkyl group, R ² represents a hydrogen atom, a halogen atom or a methyl group, and R ³ represents an alkyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, and 1 to 10 carbon atoms. Alkylcarbonyloxy group, carbon number 1
Represents an alkylcarbonylamino group having 10 to 10 or a cyclic amide group having 3 to 6 carbon atoms. The deodorant composition according to claim 1, which is a copolymer containing at least one monomer selected from the group consisting of polymerizable unsaturated monomers represented by the formula (1) as a constituent. 3. The copolymer and / or the derivative of the copolymer is blended with one or more kinds selected from an inorganic metal compound, a fatty acid metal salt and a carbonyl compound. Deodorant composition.