JP3528039B2 - Deodorants - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a deodorant.
More specifically, the present invention relates to a deodorant having a characteristic that it exerts an excellent effect in removing various malodorous components and that the effect lasts for a long period of time.

[0002]

It is a well known fact that cigarette smoke, formaldehyde contained in paints for building materials, adhesives and the like have an adverse effect on the human body.
Particularly in new buildings, formaldehyde emitted from paints and adhesives contained in building materials and the like causes sick house syndrome, which is a major social problem. Furthermore,
It has been confirmed that the emission of formaldehyde does not stop only at the time of new construction, but continues even after several years to a dozen years after construction.

On the other hand, it is also known that a hydrazide compound represented by adipic acid dihydrazide has a formaldehyde removing effect (Japanese Patent Laid-Open No. 8-280781).
And Japanese Patent Laid-Open No. 10-36681). When processing building materials such as plywood using a hydrazide compound,
A method of dissolving or dispersing the hydrazide compound in water and applying it to a building material is generally adopted. However, with such a method, the effect of removing formaldehyde decreases with time, and an excellent removing effect cannot be exhibited for a long period of time.

[0004]

As a result of intensive studies to solve the above problems, the present inventor exerts an excellent effect of removing various malodorous components, and the effect lasts for a long time. We succeeded in developing a new deodorant with the characteristics. The present invention has been completed based on such knowledge.

That is, the present invention relates to a deodorant containing (a) a hydrazide compound and (b) a polyoxyethylene alkyl ether type nonionic surfactant.

According to the present invention, by applying or impregnating the deodorant of the present invention onto a building material such as plywood, it is possible to remarkably prevent malodorous components such as formaldehyde emitted from the building material over a very long period of time. A removal effect can be expressed.

Further, according to the deodorant of the present invention, it is possible to uniformly apply or impregnate a deodorant component to a base which is required to be deodorized. There is very little variation in odor performance.

Furthermore, the deodorant of the present invention has the advantage that it does not affect the performance of the substrate to be coated.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The deodorant of the present invention contains (a) a hydrazide compound and (b) a polyoxyethylene alkyl ether type nonionic surfactant.

The hydrazide compound which is the component (a) is not particularly limited, and conventionally known compounds can be used. For example, a monohydrazide compound having one hydrazide group in the molecule and two hydrazide compounds in the molecule. Examples thereof include a group-containing dihydrazide compound and a polyhydrazide compound having three or more hydrazide groups in the molecule.

Specific examples of the monohydrazide compound include:
For example, the general formula _{^{R 2 -CO-NHNH 2 (1}} ) wherein, R ² represents an aryl group which may have a hydrogen atom, an alkyl group or a substituent. ] The monohydrazide compound represented by these can be mentioned.

In the above general formula (1), the alkyl group represented by R ² is, for example, a methyl group, an ethyl group,
n-propyl group, n-butyl group, n-pentyl group, n-
Carbon number 1 such as hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group
The straight-chain alkyl group of ~ 12 can be mentioned. Examples of the aryl group include a phenyl group, a biphenyl group,
Examples thereof include a naphthyl group, and among these, a phenyl group is preferable. Further, as the substituent of the aryl group,
For example, a hydroxyl atom, a halogen atom such as fluorine, chlorine and bromine,
Examples thereof include a linear or branched alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a tert-butyl group and an iso-butyl group. be able to.

Specific examples of the monohydrazide compound represented by the general formula (1) above include lauric acid hydrazide, salicylic acid hydrazide, form hydrazide, acetohydrazide, propionic acid hydrazide, p-hydroxybenzoic acid hydrazide, naphthoic acid hydrazide, Examples thereof include 3-hydroxy-2-naphthoic acid hydrazide.

Specific examples of the dihydrazide compound include, for example, the general formula H ₂ NHN-X-NHNH ₂ (2) [wherein X represents a group -CO- or a group -CO-A-CO-. A represents an alkylene group or an arylene group. ] The dihydrazide compound represented by these can be mentioned.

In the general formula (2), the alkylene group represented by A is, for example, methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group. , A linear alkylene group having 1 to 12 carbon atoms such as a nonamethylene group, a decamethylene group, and an undecamethylene group. As the arylene group, for example,
Examples thereof include a phenylene group, a biphenylene group, a naphthylene group, an anthrylene group, and a phenanthrylene group.
Among these, a phenylene group and a naphthylene group are preferable. Examples of the substituent of the alkylene group and the arylene group include a hydroxyl group and the like.

Specific examples of the dihydrazide compound represented by the general formula (2) include carbohydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide and dodecane didecane. Dibasic acid such as acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, diglycolic acid dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, dimer acid dihydrazide, etc. 2,6-naphthoic acid dihydrazide, etc. Can be mentioned. Furthermore, various dibasic acid dihydrazide compounds described in JP-B-2-4607, 2,4
-Dihydrazino-6-methylamino-sym-triazine and the like can also be used as the dihydrazide compound of the present invention.

Specific examples of the polyhydrazide compound include polyacrylic acid hydrazide.

Among these, dihydrazide compounds are preferable, and carbohydrazide and dibasic acid dihydrazide are particularly preferable. Among dibasic acid dihydrazide, such as adipic acid dihydrazide, sebacic acid di hydrazide <br/> de, dodecanedioic acid dihydrazide or the like is more preferable.

The above hydrazide compounds may be used alone or in combination of two or more.

The content of the dihydrazide compound in the deodorant of the present invention can be appropriately selected from a wide range according to the type thereof, the type and content of the surfactant to be used in combination therewith and the like. It may be about 0.1 to 50% by weight, preferably about 0.5 to 20% by weight.

In the present invention, it is essential to mix a polyoxyethylene alkyl ether type nonionic surfactant (component (b)) with a hydrazide compound which is a specific deodorant component.

As the polyoxyethylene alkyl ether type nonionic surfactant, known ones can be used. For example, the general formula R ¹ O (CH ₂ CH ₂ O) _n H (3) [wherein R ¹ is An alkyl group having 8 to 18 carbon atoms is shown. n
Represents an integer of 2 to 4. ] The polyoxyethylene alkyl ether type nonionic surfactant etc. which are represented by these can be mentioned.

In the general formula (3), the alkyl group having 8 to 18 carbon atoms represented by R ¹ may be linear or branched, and may be saturated. It may be present or unsaturated. Examples of such an alkyl group having 8 to 18 carbon atoms include an octyl group,
Nonyl group, dodecyl group, hexadecyl group, octadecyl group, 9-octadecyl group, 1- (n-propyl) pentyl group, 1- (n-butyl) pentyl group, 1-ethylhexyl group, 1- (n-propyl) hexyl group Group, 1- (n-
Examples thereof include a butyl) hexyl group, a 1- (n-pentyl) hexyl group, a 1,2-dimethylheptyl group, a 1-methyl-4-heptenyl group, and a 1- (n-propyl) decyl group. Among these, those having 8 to 12 carbon atoms are preferable, and those having 9 carbon atoms are particularly preferable.

Specific examples of the polyoxyethylene alkyl ether type nonionic surfactant of the above general formula (3) include, for example, polyoxyethylene octyl ether, polyoxyethylene nonyl ether, polyoxyethylene lauryl ether and polyoxyethylene. Cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene 1-
Examples include (n-butyl) pentyl ether and polyoxyethylene 1-ethylhexyl ether. Among these, polyoxyethylene octyl ether, polyoxyethylene nonyl ether and polyoxyethylene lauryl ether are preferable, and polyoxyethylene nonyl ether is particularly preferable.

The content of the above-mentioned nonionic surfactant in the deodorant of the present invention can be appropriately selected from a wide range depending on the kind thereof, the kind and content of the hydrazide compound used in combination, and the deodorant of the present invention is usually used. The amount may be about 0.001 to 10% by weight, preferably about 0.005 to 1% by weight.

One embodiment of the deodorant of the present invention is the above (a).
The hydrazide compound as the component and the nonionic surfactant as the component (b) are dissolved, dispersed or emulsified in water and / or an organic solvent.

In the present invention, water, an organic solvent and a mixed solvent thereof can be used as a medium for dissolving, dispersing or emulsifying the hydrazide compound and the nonionic surfactant. The organic solvent is not particularly limited, and any known organic solvent can be used as long as it does not adversely affect the above-mentioned active ingredient. For example, a linear or branched aliphatic saturated group having about 1 to 8 carbon atoms can be used. Alcohols, cyclopentanol,
Alicyclic alcohols such as cyclohexanol, polyhydric alcohols such as ethylene glycol, chain, branched or cyclic aliphatic hydrocarbons having about 1 to 8 carbon atoms, aromatics such as benzene, toluene and xylene Hydrocarbons, dialkyl ethers in which the alkyl portion is linear or branched alkyl having about 1 to 8 carbon atoms, diaryl ethers,
Cyclic ethers such as tetrahydrofuran and dioxane,
Examples thereof include ketones, esters, nitriles such as acetonitrile, polar solvents such as dimethylformamide and dimethylsulfoxide, and phosphoric acid esters.
Among these, linear or branched aliphatic saturated alcohols having 1 to 4 carbon atoms and aromatic hydrocarbons are preferable. Such organic solvents can be used alone or in combination with 2
More than one species can be used together.

The deodorant of the present invention contains, if necessary, an antioxidant, an ultraviolet absorber, and
General additives such as antistatic agents, flame retardants, bactericides, fungicides, insect repellents, pigments, coloring agents, and flavoring agents may be added.

The deodorant of the present invention is prepared by a conventional mixing means.
It can be produced by mixing a predetermined amount of component (a) and component (b) with water and / or an organic solvent.

When applying the deodorant of the present invention to a substrate, a usual coating or impregnation method can be adopted. The base material is composed of one or more materials such as wood, paper, fibers, metals, ceramics, inorganic fibers, and synthetic resins. Specifically, veneer board, MDF plywood (medium quality Examples thereof include a fiber board), a decorative board, a nonwoven fabric, a ceiling material, a film, a filter, and a synthetic resin sheet (for example, an acrylic resin sheet).

In coating or impregnating the substrate with the deodorant of the present invention, known methods can be employed, for example, brush coating,
Examples of the method include spray coating and dipping. The amount of the deodorant of the present invention applied or impregnated is not particularly limited, and is wide depending on the types and contents of the active ingredients (a) and (b), the use of the substrate to be applied or impregnated, and the like. It can be appropriately selected from the range, but usually the deodorant has a unit area of
² ) per 1 mg to 1 g, preferably 10 mg to 1
It may be applied or impregnated so that the amount becomes about 00 mg.

After coating or impregnating the deodorant of the present invention on the substrate, the drying may be carried out according to a usual method such as air drying, drying using a dryer or the like, or drying in a dryer such as a thermostat. Good.

[0033]

EXAMPLES The present invention will be specifically described with reference to Examples and Comparative Examples below. Example 1 Carbohydrazide (a deodorant component) and the following polyoxyethylene alkyl ether type nonionic surfactant were dissolved in water to prepare a deodorant of the present invention.

The concentration of carbohydrazide is 1% by weight,
The concentration of the polyoxyethylene alkyl ether type nonionic surfactant was 1% by weight. No. 1: Polyoxyethylene alkyl ether (polyoxyethylene alkyl ether type nonionic surfactant, trade name; Laol XA-60-50, alkyl group having 9 carbon atoms, manufactured by Lion Corporation) No. 2: Polyoxyethylene alkyl ether (polyoxyethylene alkyl ether type nonionic surfactant, trade name; Newcalgen D-1208, alkyl group having 13 carbon atoms, manufactured by Takemoto Yushi Co., Ltd.). Comparative Example 1 A deodorant was produced in the same manner as in Example 1 except that the anionic surfactant was not used.

Test Example 1 Regarding the various deodorants obtained in Example 1 and Comparative Example 1,
"Japanese agricultural and forestry standards, ordinary plywood, formaldehyde emission"
The deodorizing performance was evaluated according to the following method according to the measuring method of.

(1) Preparation of sample From commercially available plywood (plywood or MDF plywood), length 15
A rectangular piece having a width of 0 mm and a width of 50 mm was cut into 10 pieces, and 1 piece was added to each of the deodorants obtained in Example 1 and Comparative Example 1.
Soak for 5 seconds, remove, air dry overnight, 10
A piece sample was made.

As for the veneer plywood, samples subjected to "spray treatment" separately were prepared, and their formaldehyde emission concentrations (mg / liter) were measured. More specifically, a deodorant was uniformly spray-coated with a sprayer on the above-mentioned veneer plywood piece having a predetermined size, and this was used as a sample piece.

(2) Collection of formaldehyde At the bottom of a desiccator having a size of 240 mm specified in JSI R 3503, a crystal dish having a diameter of 120 mm and a height of 60 mm containing 300 ml of distilled water is placed, and a supporting metal fitting is placed thereon. After fixing 10 test pieces so as not to contact with each other, at room temperature (20 to 25 ° C.) for 24 hours,
After standing for 1 month or 3 months, formaldehyde emitted from plywood which is a test piece was absorbed in distilled water to prepare a sample solution. In Table 1 below, the term "immediately after treatment" in the section of elapsed time means "left for 24 hours". The same applies to the tables below.

(3) Determination of formaldehyde concentration Formaldehyde concentration in sample solution (mg / liter)
Was colorimetrically determined by a spectrophotometer or photoelectric colorimeter by the acetylacetone method. The colorimetric determination was carried out according to the method detailed in “Japanese Agricultural Standards / Plywood / Formaldehyde Emission”.

The results (formaldehyde concentration (mg / liter) = formaldehyde concentration released from the plywood of the sample) are shown in Table 1.

As a blank, the concentration of formaldehyde released from untreated plywood is also shown.

[0042]

[Table 1]

From Table 1, it is clear that the deodorant of the present invention containing a hydrazide compound and a nonionic surfactant exhibits an excellent formaldehyde removing effect for a long period of time.

Example 2 The deodorant of the present invention was produced in the same manner as in Example 1 except that adipic acid dihydrazide was used as the deodorant component instead of carbohydrazide.

Comparative Example 2 A deodorant was produced in the same manner as in Example 2 except that the surfactant was not used.

Test Example 2 As in Test Example 1, formaldehyde emission concentration (mg
/ Liter) was measured to evaluate the deodorizing performance of the various deodorants obtained in Example 2 and Comparative Example 2. The results are shown in Table 2.

[0047]

[Table 2]

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-7-8546 (JP, A) JP-A-8-280781 (JP, A) JP-A-11-20088 (JP, A) JP-A-11- 59744 (JP, A) JP-A-11-290432 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) A61L 9/00-9/22

Claims (9)

(57) [Claims] 1. A deodorant containing (a) a hydrazide compound and (b) a polyoxyethylene alkyl ether type nonionic surfactant and containing no binder resin.
Wood, paper, fiber, metal, ceramics, inorganic fiber and
Or applied to a base material made of one or more of synthetic resins or
A deodorant characterized by being used by being impregnated . 2. The deodorant according to claim 1, wherein (a) a hydrazide compound and (b) a polyoxyethylene alkyl ether type nonionic surfactant are dissolved, dispersed or emulsified in water and / or an organic solvent. Agent. 3. The hydrazide compound as the component (a) has the general formula H ₂ NHN—X—NHNH ₂ [wherein X represents a group —CO— or a group —CO—A—CO—. A represents an alkylene group or an arylene group. ] The claim 1 or claim 2 which is the dihydrazide compound which is displayed with
Deodorant described in. 4. (a) hydrazide compound adipic acid component, deodorant according to claim 1 or claim 2 is at least one selected from the group consisting of sebacic acid dihydrazide and dodecane diacid dihydrazide . 5. A polyoxyethylene alkyl ether type nonionic surfactant of component (b) has a general formula R ¹ O (CH ₂ CH ₂ O) _n H [wherein R ¹ is an alkyl group having 8 to 18 carbon atoms]. Indicates a group. n
Represents an integer of 2 to 4. ] The deodorant of Claims 1-4 which is a compound represented by these. 6. R is a straight chain or branched chain having 8 to 12 carbon atoms.
The deodorant according to claim 5, which is an alkyl group of. 7. The deodorant according to claim 5, wherein R is a linear or branched alkyl group having 9 carbon atoms. 8. The component (a) is added in an amount of 0.1 to 5 in the total amount of the deodorant.
The deodorant according to claim 1, which contains 0% by weight and 0.001 to 10% by weight of the component (b). 9. A building material coated or impregnated with the deodorant according to claim 1.