JPS6365338B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Objects of the Invention) The present invention relates to an oil-based gel deodorant fragrance composition and a method for producing the same.

According to the ``Chemistry Dictionary'' published by Kyoritsu Shuppan Co., Ltd., ``gel'' is defined as colloidal particles or polymer solutions that lose their independent mobility due to interactions and aggregate into a solid structure. Refers to the condition. A gel that solidifies while still containing a dispersion medium is called a jelly, but in a narrower sense, the term ``gel'' refers to ``jelly.''

It is explained.

The term "gel" used in this application refers to the narrow meaning described above.

(Disadvantages of the prior art) In recent years, gel deodorizing and fragrance compositions that contain fragrances for deodorizing or scenting in a gel and are placed indoors, in cars, etc. to provide long-term effects have been widely used. I'm getting old.

The mainstream is one in which fragrance is dispersed in an aqueous gel such as carrageenan or agar, but such aqueous gel deodorizing and fragrance compositions can only contain up to 15% of the fragrance component. However, it has disadvantages such as freezing at low temperatures and not emitting fragrance, and the volatility of the fragrance being affected by atmospheric humidity.

In addition, as an oil-based gel fragrance composition, JP-A No. 58
- A method of absorbing fragrance into polyethylene swollen with castor oil, disclosed in No. 78662, and JP-A-Sho
No. 58-12654 discloses a method of impregnating an ethylene-vinyl acetate polymer with a fragrance and a sublimable substance, but in each case, the fragrance easily separates, the operation is difficult, and the fragrance evaporates too quickly. There are drawbacks.

Furthermore, the gel disclosed in JP-A-59-77859, which consists of dibenzylidene sorbitol, 3-methyl-3-methoxybutanol, and fragrance, is weak, the fragrance has poor volatility, and is opaque. However, there are drawbacks such as the need for heating.

In addition, the gel disclosed in JP-A No. 60-53148 that uses sodium stearate as a gel agent produces only a soft gel or a very hard gel, and the amount of fragrance mixed in may be increased. It has drawbacks such as being difficult to use, being opaque, and requiring heating.

(Means for Solving the Problem) As a result of intensive research to solve all of the above-mentioned drawbacks, the present inventors discovered an oil-based gel deodorizing fragrance composition having extremely excellent performance and a method for producing the same, and developed the present invention. completed.

That is, the present invention provides an oil-based gel deodorant fragrance composition in which an acetoacetylated oligomer having two or more acetoacetyl groups in one molecule is cross-linked and gelled including a deodorant component or a fragrance component. and acetoacetylated oligomers having two or more acetoacetyl groups in one molecule, compounds having two or more amine groups in one molecule, compounds having aldehyde groups, compounds having hydrazide groups, and epoxy groups. Using one or more crosslinking agents selected from compounds having methylol groups, compounds having a methylol group, alkoxides of metals such as titanium, zirconium, and aluminum, and metal chelates, a crosslinked gel containing a deodorant component or an aromatic component is produced. This is a method for producing an oil-based gel deodorizing fragrance composition.

According to the "Oligomer Handbook" (published by Kagaku Kogyo Nipposha on 52.3.31), oligomers are:
There is no strict definition, but the molecular weight is about 10,000 from dimer
It is often referred to as a medium-molecular polymer. More strictly speaking, it can be said to be a polymer with a molecular weight below a critical molecular weight where the melt viscosity increases rapidly, but its molecular weight is approximately 10,000. Therefore, oligomers are often in the form of viscous liquids. This is what is written.

Acetoacetylation (hereinafter referred to as
An oligomer (referred to as AA) is a specific oligomer that has been converted into AA with diketene.

That is, oligomers having two or more hydroxyl groups in one molecule, for example, two or more hydroxyl groups in one molecule with a number average molecular weight of 500 to 10,000.
2 or more OH group-containing liquid 1,2-polybutadiene in one molecule with a number average molecular weight of 500 to 8000.
2 or more OH group-containing liquid 1,4-polybutadiene in one molecule with a number average molecular weight of 500 to 8000.
OH group-containing liquid 1,4-butadiene-styrene copolymer with a number average molecular weight of 500 to 8000, containing two or more molecules in one molecule.
2 or more OH group-containing liquid 1,4-butaene-acrylonitrile copolymers in one molecule with a number average molecular weight of 500 to 8000.
Liquid polychloroprene containing OH groups (Oligomers with OH groups at both ends are obtained by living polymerization of diene monomers)
Others Liquid polyethylene glycol with a number average molecular weight of 200 to 600 Liquid polypropylene glycol with a number average molecular weight of 400 to 6000 Liquid polyoxypropylene polyoxyethylene block polymer with a number average molecular weight of 900 to 2500 Liquid polyglycerin with a number average molecular weight of 160 Liquid polytetramethylene ether glycol with a number average molecular weight of 200 to 2000 is reacted with diketene (ketene dimer) represented by the following formula in the presence of a catalyst such as triethylamine, sulfuric acid, sodium monochloroacetate, or sodium ethylate. That's fine.

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 caryophyllene, santarene, thujopsene, and cedrene, abietin,
Diterpene hydrocarbons such as camphorene, aromatic hydrocarbons such as paracymene and styrene, isocyamyl acetate, geranyl acetate, citronellyl acetate, linalyl acetate, benzyl acetate, benzyl benzoate, benzyl salicylate, cinnamyl cinnamate, isoamyl undecyle These include carboxylic acid esters such as ester, 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 compound having an amine group as a crosslinking agent used in the present invention has the general formula: (However, R ₁ , R ₂ , R ₃ are H or CH ₂ CH ₂ NH ₂ ,
X and Y are integers), and the molecular weight is 100 to
100,000 polyethyleneimine, chain aliphatic polyamines such as diethylenetriamine, triethylenetetramine, cyclic aliphatic polyamines such as menthene diamine, isophorone diamine, and derivatives or modified products thereof, metaphenylene diamine, diaminodiphenyl sulfone, etc. Aromatic polyamines and their modified products and aliphatic polyamidoamines are preferred.

Compounds having an aldehyde group used in the present invention include monoaldehydes such as formaldehyde, acetaldehyde, propionaldehyde, crotonaldehyde, benzaldehyde, and formamide; dialdehydes such as powdered glyoxal, malondialdehyde, glutaraldehyde, and terephthalaldehyde; Acrolein copolymerized acrylic resin is suitable. Among these, powdered glyoxal and glutaraldehyde are particularly preferred.

As the compound having a hydrazide group used in the present invention, dihydrazide compounds to polyhydrazide compounds are suitable; for example, dihydrazide compounds, organic salts of dihydrazide compounds such as formic acid and oxalic acid, and methyl, ethyl, propyl, and butyl dihydrazide compounds. , monosubstituted such as allyl, asymmetric disubstituted such as 1,1-dimethyl, 1,1-diethyl, 4-n-butyl-methyl, and 1,2-dimethyl, 1,2-diethyl,
Examples include symmetrically disubstituted compounds such as 1,2-diisopropyl. Particularly suitable hydrazide group-containing compounds are carbodihydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dotecanedioic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, glycolic acid dihydrazide, polyhydrazide Examples include acrylic acid hydrazide.

As the compound having an epoxy group 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, neopentyl glycol glycidyl ether, glycerol glycidyl ether,
These include trimethylolpropane glycidyl ether, pentaerythritol glycidyl ether, diglycerol glycidyl ether, sorbitol glycidyl ether, bisphenol A/epichlorohydrin type epoxy resin, and the like.

As the compound having a methylol group used in the present invention, a butylated urea resin initial condensate and a methylated or butylated melamine resin initial condensate are suitable.

Examples of metal alkoxides used in the present invention include tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate, and titanium titanate.
Ethylhexyl titanate, tetraethylzirconate, tetrapropylzirconate, tetrabutylzirconate, tetra2-ethylhexylzirconate, aluminum isopropylate, monosec-butoxyaluminum diisopropylate, aluminum sec-butyrate are preferred.

The metal chelates used in the present invention include titanium lactate, di-i-propoxy bis(acetylacetone) titanate, di-n-butoxy bis(triethanolamine) titanate, tetraoctylene glycol titanate, and zirconium tetraacetylacetonate. , ethyl acetate aluminum diisopropylate, and aluminum tris(ethyl acetoacetate) are preferred.

The oligomer having an acetoacetyl group in the molecule and the amine group-containing compound form a crosslinked structure according to the reaction mechanism shown in the following formula, although it is only a guess, and gel it by including the deodorant component or the fragrance component.
An oil-based gel deodorant fragrance composition is produced.

The oligomer having an acetoacetyl group in the molecule and the aldehyde group-containing compound form a crosslinked structure according to the reaction mechanism shown in the following formula, although it is a guess, and gel it by including the deodorant component or the fragrance component. An oil-based gel deodorant fragrance composition is produced.

The oligomer having an acetoacetyl group in the molecule and the hydrazide group-containing compound form a crosslinked structure according to the reaction mechanism shown in the following formula, although it is only a guess, and an oil-based gel deodorizing fragrance composition is produced in the same manner as above. do.

Although it is a guess, the oligomer having an acetoacetyl group in the molecule and the epoxy group-containing compound form a crosslinked structure according to the reaction mechanism shown in the following formula, and an oil-based gel deodorant fragrance composition is produced in the same manner as above. do.

Although it is a guess, the oligomer having an acetyl group in the molecule and the compound containing a methylol group form a crosslinked structure according to the reaction mechanism shown in the following formula, and an oil-based gel deodorant fragrance composition is produced in the same manner as above. do.

Although it is a guess, an oligomer having an acetoacetyl group in the molecule and a metal alkoxide or metal chelate form a crosslinked structure as shown in the following formula,
An oil-based gel deodorant fragrance composition is produced in the same manner as described above.

All of the above reactions do not require any heating and proceed rapidly at room temperature to produce a clear oily gel deodorant fragrance composition.

The oil-based gel deodorant fragrance composition of the present invention may contain colorants, ultraviolet absorbers, antioxidants, etc. depending on the purpose.

(Effects) The oil-based gel deodorant fragrance composition of the present invention: 1. Does not require heating and can be prepared at room temperature.

2. Extremely high transparency.

3. Non-volatile residue can be reduced.

4 Compared to aqueous gel systems, it has better volatility even at low temperatures and high humidity.

This effect is achieved.

Next, the present invention will be explained with reference to Examples.

Production Example 1 (Production of AA-modified oligomer) The production of AA-modified 1,4-polybutadiene oligomer will be explained as an example. (Other AA oligomers used in Examples were manufactured in accordance with this method) A flask equipped with a stirrer, thermometer, cooling tube, gas introduction tube, and dropping funnel had a number average molecular weight of 1100 and a hydroxyl value of 91.4 mgKOH/g. liquid 1,4-polybutadiene (product name Poly bd LM-10/Idemitsu Petrochemical
Co., Ltd.) and replaced it with nitrogen gas.
It was heated to 120°C and dehydrated for 30 minutes. Then 60℃
Cool to 60°C and add 163mg of triethylamine to 60°C.
While maintaining the temperature at ~63°C, 151 g (1.1 times equivalent) of diketene was dropped over 5 hours.
The mixture was further stirred and kept warm at ℃ for 5 hours.

After the reaction was completed, the pressure was reduced using an aspirator at 70° C. for 1 hour, and the remaining diketene and triethylamine were distilled off to obtain viscous acetoacetylated 1,4-polybutadiene.

When this was saponified with an alkali and the degree of AA conversion of the hydroxyl groups was measured, 95% was found to be AA.

The viscosity of this material was 2000 centipoise at 25°C.

Example 1 In a three-neck flask equipped with a stirrer, a reflux condenser, and a dropping funnel, 10 g of citrus flavor (FG3765/manufactured by Takasago Fragrance Co., Ltd.) and 78 g of d-limonene (volatile terpene hydrocarbon) prepared in Production Example 1 were placed. Acetoacetylated product of hydroxyl-terminated liquid 1,4-polybutadiene (degree of acetoacetylation 95%, viscosity 2000cP/25℃)
Add 10g and stir and mix at room temperature for 10 minutes. A mixed solution of 1 g of polyethyleneimine (trade name: Epomin SP003, molecular weight 300, manufactured by Nippon Shokubai Chemical Co., Ltd.) prepared separately and 1 g of ethanol is added to this mixture while stirring at room temperature, and mixed uniformly.

Gelation occurred after about 60 minutes and was completed after about 150 minutes, yielding a clear oily gel fragrance composition.

This product does not freeze even at -20℃, evaporates aroma, and can be used indoors at a temperature of 30℃ and humidity of 95%RH.
Emission of aroma was observed.

Moreover, the aromatic agent content was 88%.

Example 2 A sample was prepared in the same manner as in Example 1 using 85 g of chlorine dioxide and in accordance with Production Example 1. Liquid 1,2-polybutadiene with number average molecular weight 1460 and hydroxyl value 73.4mgKOH/g (Product name: NiSSO-PB, G-1000/Nippon Soda
10 g of an acetoacetylated product (degree of acetoacetylation: 98%, viscosity: approximately 9000 cP/25°C) manufactured by Co., Ltd.) was added, and the mixture was stirred and mixed at room temperature for 30 minutes. To this, 5 g of a separately prepared 50% isopropyl alcohol solution of aluminum isopropoxide was added with stirring at room temperature and mixed uniformly.

Gelation occurred after about 30 minutes, and gelation was completed after about 80 minutes, yielding a transparent oil-based gel deodorant composition.
This product did not freeze even at -20℃ and eliminated the odor inside the freezer. In addition, the deodorizing effect was observed even indoors at 30°C and 95% RH.

Moreover, the deodorant content was 85%.

Example 3 In the same manner as in Example 1, 10 g of FG3765 and d
-77g of limonene and hydroxyl-terminated liquid 1,4-polybutadiene (product name:
Poly bd R-45M/manufactured by Idemitsu Petrochemical Co., Ltd.) acetoacetylated product (degree of acetoacetylation 98%, viscosity
Add 10g of 10000cP/25℃) and stir and mix at room temperature for 15 minutes.

In addition to this, separately prepared titanium lactate
3 g of 50% toluene solution was added with stirring at room temperature and mixed uniformly.

Gelation occurred after about 2 hours and was completed in about 24 hours, yielding a clear oily gel fragrance composition. This product did not freeze even at -20°C and emitted its aroma, and the fragrance was observed even indoors at 30°C and 95% RH.

Moreover, the aromatic agent content was 87%.

Claims (1)

[Scope of Claims] 1. An oil-based gel deodorant fragrance composition in which an acetoacetylated oligomer having two or more acetoacetyl groups in one molecule is cross-linked and gelled including a deodorant component or a fragrance component. . 2 Acetoacetylated oligomers having two or more acetoacetyl groups in one molecule, compounds having two or more amine groups in one molecule, compounds having aldehyde groups, compounds having hydrazide groups, and epoxy groups Using one or more crosslinking agents selected from compounds, compounds with methylol groups, alkoxides of metals such as titanium, zirconium, and aluminum, and metal chelates, the deodorant component or fragrance component is included and crosslinked into a gel. A method for producing an oil-based gel deodorizing fragrance composition.