JPS6363231B2 - - Google Patents

Description

[Detailed description of the invention]

(Objective) The present invention relates to an aqueous gel fragrance composition that contains a fragrance used for odor generation or deodorization in an aqueous gel and is placed indoors, in a car, etc., and exhibits a long-term effect. (Prior Art) The mainstream of the above-mentioned aqueous gel fragrance compositions is one in which a fragrance is dispersed in an aqueous gel such as carrageenan or agar. However, in conventional aqueous gels, (1) a fragrance is added, dissolved by heating at 60 to 80°C, and gelled by cooling to room temperature. Therefore, fragrances that are sensitive to heat often change in quality when heated. (2) If the room temperature repeatedly rises above 50°C and drops below 0°C, liquefaction and syneresis phenomena occur. (3) At low temperatures, gel hardness decreases and water separation occurs. (4) The volatility of fragrance is uneven. There are drawbacks such as. (Structure of the Invention) In order to solve the above problems, the present inventors earnestly
Conducted research on aqueous gels. As we investigated compositions that would form a gel at room temperature, we found that polyvinyl alcohol with a specific crosslinking group had better water repellency when gelled with a fragrance, and the volatility of the fragrance. The purpose of the present invention can be achieved by containing a specific amount of a fragrance component, a nonionic surfactant, an anionic surfactant, and a specific water-soluble solvent in an aqueous gel consisting of a crosslinking agent (reacting agent). The present invention was completed by discovering that this can be achieved. That is, the present invention comprises 2 to 15% by weight of acetoacetylated polyvinyl alcohol and one or more reactants selected from aldehyde group-containing compounds, hydrazide group-containing compounds, amine group-containing compounds, and epoxy group-containing compounds. In an aqueous gel obtained by reacting a mixture consisting of 0.01 to 3% by weight and the balance water, 1 to 15% by weight of the fragrance component, 2 to 20% by weight of the nonionic surfactant, and the anionic surfactant. This is an aqueous gel fragrance composition containing 0.1 to 5% by weight and 2 to 40% by weight of a water-soluble polyhydric alcohol. The aqueous gel fragrance composition of the present invention overcomes all the drawbacks of the prior art described above. The acetylated polyvinyl alcohol used in the present invention can be obtained by reacting polyvinyl alcohol and diketene by a known method. For example, there is a method in which polyvinyl alcohol is dispersed in an acetic acid solvent and diketene is added thereto, or a method in which polyvinyl alcohol is previously dissolved in a solvent such as dimethyl formaldehyde or dioxane and diketene is added thereto.
It can also be obtained by directly contacting polyvinyl alcohol with diketene gas or liquid diketene. The polyvinyl alcohol used is polyvinyl alcohol with a degree of polymerization of 200 to 3000 obtained by saponifying polyvinyl acetate and a degree of saponification of 30 to 100 mol%, or a derivative thereof, or a monomer copolymerizable with vinyl acetate and acetic acid. It is preferably a saponified product of a copolymer with vinyl and is water-soluble. Among the acetylated polyvinyl alcohols obtained as described above, those used in the present invention have a degree of acetoacetylation of 2 to 20 mol%.
A 50% aqueous solution is preferred. The degree of acetoacetylation is
If it is less than 0.5 mol%, gelation will be difficult, and if it exceeds 20 mol%, water solubility will be lost, making it impractical. As the aqueous solution of the aldehyde group-containing compound as the reactant used in the present invention, mono- or dialdehyde group-containing compounds are suitable, such as monoaldehydes such as formaldehyde, acetoacetyl, propionaldehyde, crotonaldehyde, and benzaldehyde; Aqueous solutions of dialdehydes such as glyoxal, malondialdehyde, glutaraldehyde, dialdehyde starch are preferred. The concentration of the aqueous solution is usually 1 to 50%. As the hydrazide group-containing compound of the reactant used in the present invention, dihydrazide compounds or polyhydrazide compounds are suitable; for example, dihydrazide compounds, dihydrazide compounds such as hydrochloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid, thiocyanic acid, carbonic acid, etc. inorganic salts and organic salts such as formic acid and oxalic acid, methyl dihydrazide compounds,
Monosubstituted products such as ethyl, propyl, butyl, allyl, 1,1-dimethyl, 1,1-diethyl, 4-
asymmetric disubstituted products such as n-butyl-methyl, as well as 1,2-dimethyl, 1,2-diethyl, 1,2
Symmetrically disubstituted compounds such as -diisopropyl and the like. Particularly suitable hydrazide group-containing compounds are carbodihydrazide, oxalic acid dihydrazide,
malonic acid dihydrazide, succinic acid dihydrazide,
These include adipic acid dihydrazide, sebacic acid dihydrazide, dotecanedioic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, glycolic acid dihydrazide, and polyacrylic acid hydrazide. These hydrazide group-containing compounds usually have 1 to
Used in 40% aqueous solution. As the amine group-containing compound of the reaction agent used in the present invention, diamine compounds or polyamine compounds are suitable, such as chain aliphatic polyamines such as diethylenetriamine and triethylenetetramine, menthene diamine, isophorone diamine, etc. Fragrance amines such as cycloaliphatic polyamines and derivatives or modified products thereof, aliphatic polyamide amines, metaphenylene diamines, diaminodiphenylsulfones, and modified products thereof;
Or general formula (However, R ₁ , R ₂ , R ₃ are H or CH ₂ CH ₂ NH ₂ , x
and y is an integer), and the molecular weight is from 300 to
Polyethyleneimine with a molecular weight of about 100,000 is suitable. Low molecular weight liquids can be used as they are, but high molecular weight ones are preferably used as a 1-40% aqueous or alcohol solution. As the epoxy group-containing compound of the reaction agent used in the present invention, diepoxy compounds to polyepoxy compounds are suitable, such as ethylene glycol glycidyl ether, polyethylene glycol glycidyl ether, propylene glycol glycidyl ether, polypropylene glycol glycidyl ether, Pentyl glycol glycidyl ether, glycerol glycidyl ether, trimethylolpropane glycidyl ether, pentaerythritol glycidyl ether,
These include diglycerol glycidyl ether, sorbitol glycidyl ether, and bisphenol A/epichlorohydrin type epoxy resins. These epoxy group-containing compounds are usually 1 to 50%
Used as an aqueous or alcoholic solution. The aromatic components used in the present invention include monoterpene hydrocarbons such as limonene, myrcene, carene, ocimene, pinene, camphene, terbinolene, tricitalene, terbinene, huentien, phelandrene, sylvestrene, and savin, caryophyllene, santarene, and thujopsene. , sesquiterpene hydrocarbons such as cedrene, diterpene hydrocarbons such as abietin and camphorene,
aromatic hydrocarbons such as paracymene and styrene;
Isoamyl acetate, geranyl acetate,
citronellyl acetate, linalyl acetate,
Benzyl acetate, benzyl benzoate, benzyl salicylate, cinnamyl cinnamate,
These include carboxylic acid esters such as isoamyl undecylenate and cedryl acetate, terpene alcohols such as linalool, citronellol, and terpineol, and terpene aldehydes such as citral. Other deodorants include chlorine dioxide, lauryl methacrylate, geranyl crotonate, and chlorophyll. Nonionic surfactants used in the present invention include polyoxylethylene alkyl phenyl ether, polyoxyethylene alkyl ether, hydrogenated castor oil ethylene oxide adduct, polyethylene glycol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene Polyoxypropylene block polymers, etc. Particularly preferred are those with an HLB of 10 to 20. Examples of the anionic surfactant used in the present invention include sodium polyoxyethylene alkyl phenyl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, and sodium dialkyl sulfosuccinate. Therefore, in the present invention, the nonionic surfactant and the anionic surfactant are 2 to 20% by weight and 0.1 to 5% by weight, respectively, in the aqueous gel fragrance composition.
Must be used together within the range of weight percent. This is because nonionic surfactants have a great ability to solubilize fragrance components, but they have poor compatibility with acetoacetylated polyvinyl alcohol, so they tend to separate water, and anionic surfactants have a high ability to solubilize fragrance components. Although they have good compatibility and do not cause water syneresis, they have a low ability to solubilize fragrance components, resulting in separation of the fragrance components, making it undesirable to use each alone. Therefore, acetoacetylated polyvinyl alcohol, water, and fragrance ingredients are uniformly dissolved,
To prevent syneresis, it is important to maintain a quantitative balance between nonionic and anionic surfactants. If one of the surfactants is too large or too small, water separation becomes easy, and if the total amount of surfactant is small, the compatibility of the three will be insufficient.
If the amount is too large, separation of the surfactant will occur. Examples of the water-soluble polyhydric alcohol used in the present invention include hexylene glycol, ethylene glycol, propylene glycol, dipropylene glycol, glycerin, diethylene glycol, and triethylene glycol. The water-soluble polyhydric alcohol not only improves the volatility of fragrance components, but also has the effect of preventing syneresis. Next, the action of producing the aqueous gel fragrance composition of the present invention will be explained. Polyvinyl alcohol having an acetoacetyl group in its molecule and an aldehyde group-containing compound form a crosslinked structure according to a reaction mechanism as shown in the following formula, although it is a guess, and the aromatic component and others are encapsulated and gelled. Polyvinyl alcohol having an acetoacetyl group in the molecule and a compound containing a hydrazide group are:
Although it is a guess, a crosslinked structure is formed by the reaction mechanism as shown in the following formula, and the aromatic component and others are included and gelled. The polyvinyl alcohol having an acetoacetyl group in the molecule and the amine group-containing compound form a crosslinked structure according to a reaction mechanism as shown in the following formula, although it is only a guess, and gelatinizes the aromatic component and others. Although it is a guess, polyvinyl alcohol having an acetoacetyl group in the molecule and a compound containing an epoxy group form a crosslinked structure according to the reaction mechanism shown in the following formula, and form a gel containing the aromatic component and others. All of these reactions proceed at room temperature and produce aqueous gel fragrance compositions that are very clear and have moderate stiffness. The aqueous gel fragrance composition of the present invention contains a fragrance, a nonionic surfactant, an anionic surfactant, a water-soluble For example, a fragrance component is dissolved in an aqueous solution of a water-soluble polyhydric alcohol and a surfactant, and this aqueous solution is added to an acetoacetylated polyvinyl alcohol aqueous solution. It can be easily produced at room temperature by adding an aqueous solution of a reactant to form a gel. In addition, a fragrance component, a surfactant, and water are mixed and dissolved, and a water-soluble polyhydric alcohol is added to this.
Further, an acetoacetylated polyvinyl alcohol aqueous solution and a reactant aqueous solution may be added to form a gel. According to these methods, an aqueous gel fragrance composition with extremely good transparency can be obtained. Further, the fragrance component, surfactant, water-soluble polyhydric alcohol, acetoacetylated polyvinyl alcohol aqueous solution, and reactant aqueous solution may be mixed simultaneously. The aqueous gel fragrance composition may also contain a preservative, an antifoaming agent, an ultraviolet absorber, a coloring agent, and the like, if desired. (Effects) The aqueous gel fragrance composition of the present invention (1) can be gelled at room temperature, so temperature-sensitive fragrances do not deteriorate. (2) By selecting the gelling agent, the gelation time can be adjusted over a wide range. (3) There is no liquefaction or separation of water even if the ambient temperature rises above 50°C to around 80°C. (4) There is no change in gel hardness even at low temperatures.
It doesn't even separate from the water. (5) No syneresis even when repeatedly exposed to high temperatures of 50°C or higher and low temperatures of 0°C or lower. (6) The volatility of fragrance ingredients is uniform and gradual;
Lasts a long time. (7) Since it has appropriate rigidity, there is no need to put it in a container such as glass. (Example) Next, the present invention will be described with reference to Examples and Comparative Examples. Example 1 8 parts by weight of blended fragrance (kinmokusei type), 5 parts by weight of nonionic surfactant (polyoxyethylene nonyl phenyl ether HLB = 14.5), and anionic surfactant (sodium polyoxyethylene alkyl phenyl ether sulfate) (25% aqueous solution)7
Add parts by weight and mix uniformly. Then, while stirring, add 4 parts by weight of water, 12 parts by weight of ethylene glycol, 60 parts by weight of a 10% aqueous solution of acetoacetylated polyvinyl alcohol with a degree of acetoacetylation of 5 mol%, a degree of saponification of 88 mol%, a degree of polymerization of 1000, and adipic acid. A homogeneous mixture was prepared by sequentially adding 4 parts by weight of a 5% aqueous solution of hydrazide, and the mixture was left at room temperature for 10 minutes.
A transparent aqueous gel fragrance composition was obtained. Examples 2 to 7 In Example 1, the amount of 10% aqueous solution of acetoacetylated polyvinyl alcohol and water, nonionic surfactant, anionic surfactant, water-soluble polyhydric alcohol, and reaction agent were determined. An aqueous gel fragrance composition was obtained in the same manner as in Example 1 except for the changes shown in Table 1. Comparative Example 1 An aqueous gel fragrance composition was obtained in the same manner as in Example 1, except that no anionic surfactant was used in Example 1. Comparative Example 2 An aqueous gel fragrance composition was obtained in the same manner as in Example 4, except that ethylene glycol was not used in Example 4. Comparative Test The aqueous gel fragrance compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 2 were examined for transparency, water separation rate, surface film state, and volatility (fragrance intensity). The results were as shown in Table 1. (Test method) Transparency: Judgment by naked eye. ○: Transparent ×: Opaque Water separation rate (%): After being left at -10℃ for 24 hours, at 50℃ for 24 hours
Syneresis ratio (%) after repeating 5 cycles of leaving for a long time Surface film condition: Examine the surface condition after leaving for 1 month at 20°C and 65% RH. S: No film is formed on the surface and it is soft. H: Forms a film on the surface and is hard. Volatility (fragrance intensity): Examine the scent condition after being left for one month at 20°C and 65% RH. ○: Fragrance lasts long enough ×: Scent intensity is extremely reduced △: Between ○ and ×

【table】

[Table] As is clear from the results in Table 1, the aqueous gel fragrance composition of the present invention has good transparency, water separation rate,
It showed extremely excellent performance in terms of both surface film condition and scent volatility. Comparative Example 1 is an example in which the anionic surfactant was not used in Example 1, but the water separation rate was extremely poor and the transparency was also poor. Comparative Example 2 is an example in which the water-soluble polyhydric alcohol was not used in Example 4, but the surface film state was hard, so the fragrance volatility was extremely poor, and the water separation rate was also extremely poor.

Claims (1)

[Claims] 1 2 to 15% by weight of acetoacetylated polyvinyl alcohol, and 1 or 2 selected from aldehyde group-containing compounds, hydrazide group-containing compounds, amine group-containing compounds, and epoxy group-containing compounds
In an aqueous gel obtained by reacting a mixture consisting of 0.01 to 3% by weight of the above reaction agent and the balance water, 1 to 15% by weight of an aromatic component and 2 to 3% of a nonionic surfactant are added.
20% by weight of anionic surfactant, 0.1 to 5% by weight of anionic surfactant, and 2 to 40% by weight of water-soluble polyhydric alcohol.