JPS6363230B2 - - 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 aroma compositions are those 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) These aqueous gels themselves have poor transparency. (3) When the room temperature reaches 50℃ or higher, liquefaction and syneresis phenomena appear. (4) At low temperatures, gel hardness decreases and water separation occurs. 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 with a specific cross-linking group would improve transparency, water repellency, and deterioration of the fragrance when gelled with a fragrance. The present invention was completed based on the discovery that an aqueous gel composed of alcohol and a crosslinking agent (reacting agent) is extremely suitable for the purpose of the present invention. That is, the present invention comprises 2 to 50% by weight of acetoacetylated polyvinyl alcohol and 0.01% of one or more reactants selected from aldehyde group-containing compounds, hydrazide group-containing compounds, amine group-containing compounds, and epoxy group-containing compounds. ~10% by weight
This is an aqueous gel fragrance composition in which an aromatic component is contained in an aqueous gel obtained by reacting a mixture consisting of the following: and the remainder water. The acetoacetylated 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 acetoacetylated polyvinyl alcohols obtained as described above, those used in the present invention are preferably 2-50% aqueous solutions having a degree of acetoacetylation of 0.5-20 mol%. If the degree of acetoacetylation is less than 0.5 mol%, it will be difficult to gel, 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, acetaldehyde, propionaldehyde, crotonaldehyde, and benzaldehyde, glyoxal Aqueous solutions of dialdehydes such as , malondialdehyde, glutaraldehyde, and dialdehyde starch are suitable. 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, such as dihydrazide compounds, dihydrazide compounds such as hydrochloric acid, sulfuric acid, nitric acid, nitrous acid, phosphorus, thiocyanic acid,
Inorganic salts such as carbonic acid and organic salts such as formic acid and oxalic acid; monosubstituted dihydrazide compounds such as methyl, ethyl, propyl, butyl, and allyl;
1,1-dimethyl, 1,1-diethyl, 4-n-
Asymmetric disubstituted products such as butyl-methyl, as well as 1,2-dimethyl, 1,2-diethyl, 1,2-
Examples include symmetrically disubstituted compounds such as diisopropyl. 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, dodecanedioic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, glycolic acid dihydrazide, and polyacrylic acid hydrazide. These hydrazide group-containing compounds usually have 1
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. Cycloaliphatic polyamines and derivatives or modified products thereof, aromatic amines such as 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 10
Ten-man polyethyleneimine is preferred. 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. Examples of the epoxy group-containing compound as a reactant used in the present invention include diepoxy compounds to polyethylene glycol glycidyl ether, polyethylene glycol glycidyl ether, propylene glycol glycidyl ether, polypropylene glycol glycidyl ether, neopentyl glycol glycidyl ether, glycerol glycidyl ether, Examples include methylolpropane glycidyl ether, pentaerythritol glycidyl ether, 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. Next, the action of producing an aqueous gel used in 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 and gel through a reaction mechanism as shown in the following formula, although this is speculation. 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 and gelled by the reaction mechanism as shown in the following formula. Polyvinyl alcohol having an acetoacetyl group in its molecule and an amine group-containing compound form a crosslinked structure and gel through a reaction mechanism as shown in the following formula, although this is speculation. Although it is a guess, polyvinyl alcohol having an acetoacetyl group in its molecule and a compound containing an epoxy group form a crosslinked structure and gel through a reaction mechanism as shown in the following formula. All of these reactions proceed at room temperature and produce aqueous gels that are very transparent and have moderate stiffness. The aromatic agents used in the present invention include limonene,
myrcene, carene, ocimene, pinene, camphene, terbinolene, tricitalene, terbinene,
Monoterpene hydrocarbons such as huentien, phelandrene, sylvestrene, and savin; sesquiterpene hydrocarbons such as caryolephyrene, santarene, thujopsene, and 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,
Examples 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. The aqueous gel fragrance composition of the present invention is a composition in which a fragrance is contained in an aqueous gel obtained by reacting acetoacetylated polyvinyl alcohol with a reaction agent as described above. It can be easily produced at room temperature by dissolving a fragrance in an aqueous solution of the agent, adding this aqueous solution to an aqueous solution of acetoacetylated polyvinyl alcohol, and then adding an aqueous solution of a reactant to form a gel. Further, these three types of aqueous solutions may be mixed at the same time. (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) Because it is extremely transparent, decorations such as characters can be embedded in it. It also provides a sense of transparency even when colored. (4) There will be no liquefaction or syneresis even if the ambient temperature rises from 50℃ to 80℃. (5) There is no change in gel hardness even at low temperatures.
It doesn't even separate from the water. (6) 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 4 parts by weight of a nonionic surfactant and 2 parts by weight of an anionic surfactant were added to 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%, and a degree of polymerization of 1000. Department,
6 parts by weight of benzyl acetate, 10 parts by weight of glyoxal
% aqueous solution and 18 parts by weight were added, mixed uniformly, and left at room temperature for 5 hours to obtain an aqueous gel fragrance composition. Example 2 In Example 1, 10% glyoxal aqueous solution
10 parts by weight of 4% aqueous solution of adipic acid dihydrazide
The procedure of Example 1 was repeated except that the amount was changed to 10 parts by weight, and the composition was left at room temperature for 5 minutes to obtain an aqueous gel fragrance composition. Example 3 In Example 1, 10% glyoxal aqueous solution 10
The procedure was the same as in Example 1 except that the parts by weight were changed to 10 parts by weight of a 10% aqueous solution of polyethyleneimine, and 1% was added at room temperature.
The aqueous gel fragrance composition was obtained by standing for a minute. Example 4 In Example 1, 10% glyoxal aqueous solution 10
An aqueous gel fragrance composition was obtained in the same manner as in Example 1, except that the weight part was changed to 10 parts by weight of a 10% aqueous solution of polyethylene glycol glycidyl ether, and left at room temperature for 3 days. Comparative Example 1 6 parts by weight of benzyl acetate and carrageenan
2.5 parts by weight of locust bean gum, 0.2 parts by weight of locust bean gum, 4 parts by weight of nonionic surfactant, and 2 parts by weight of anionic surfactant were added to 85.3 parts by weight of water, and mixed at 70 to 80°C. After heating for a time to uniformly disperse the mixture, the mixture was allowed to cool at room temperature for 1 hour to obtain an aqueous gel aroma composition. Comparative Test The aqueous gel fragrance compositions obtained in Examples 1 to 4 and Comparative Example 1 were examined for transparency, heat resistance, cold resistance, and aroma deterioration. The results were as shown in Table 1.

[Table] (Test method) Transparency: Determine transparency with the naked eye. 〇: Uniformly transparent △: Cloudy and translucent ×: Opaque Heat resistance: Determine the syneresis state after being left in an atmosphere of 70°C for 24 hours. 〇: Water syneresis rate 1% or less △: 〃 1 to 10% ×: 〃 10% or more Cold resistance: After being left in an atmosphere of -20°C for 24 hours, it was further left to stand at room temperature for 24 hours, and the water separation state was determined. The criteria are the same as those for heat resistance. Fragrance alteration: Sensory test 〇: Not at all △: Slightly present ×: Yes

Claims (1)

[Claims] 1 2 to 50% 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
An aqueous gel fragrance composition comprising a fragrance component contained in an aqueous gel obtained by reacting a mixture consisting of 0.01 to 10% by weight of the above reaction agent and the balance water.