WO2004011549A1 - Resin compositions and transparent gel fragrances - Google Patents

Abstract

A transparent gel fragrance which can contain an enlarged amount (compared with the existing aqueous gel fragrances) of a perfume and an enlarged amount (compared with the existing oily gel fragrances) of water or alcohol, quickly undergoes sublimation and shows a favorable smell; and a resin composition which is usable as a raw material for the fragrance and contains from 2 to 30% by weight of a vinyl-based polymer having a diacetone acrylamide unit, from 0.01 to 5% by weight of a polyfunctional hydrazide compound, from 0.1 to 60% by weight of water, from 5 to 95% by weight of a water-soluble solvent and from 0.1 to 93% by weight of perfume(s) except aldehydes.

Description

 Resin composition and transparent gel-like fragrance

Technical field

 The present invention relates to a stable gel-form transparent gel-like fragrance which can be used for fragrances in rooms, in cars, in toilets, in clogs, around kitchens, bathrooms, and the like, and a resin composition used as a raw material thereof.

Background art

 Conventionally, as an aquatic gel-like fragrance, (A) agar utilizing natural polymers such as agar and power gelinan (Japanese Patent Application Laid-Open No. 54-135229), and (B) gelatin as a crosslinking agent or enzyme (Japanese Patent Application Laid-Open Nos. 1-297484 and 9-70428) are known. However, the above-mentioned gelling agent cannot mix a large amount of fragrance due to its strong hydrophilicity, and a large amount of surfactant must be used to make it transparent. Problem.

 On the other hand, as an oily gel-like fragrance, a fragrance containing hydrogenated castor oil, sodium stearate or 12-hydroxystearic acid as a gelling agent in addition to a terpene-based hydrocarbon, an isoparaffin-based hydrocarbon (Japanese Patent Application Laid-Open No. No. 78662, JP-A-55-141243, and JP-A-55-102438) are known. However, these gel-like fragrances have a problem that they have a bad smell and evaporate slowly because a small amount of water or alcohol cannot be used.

Disclosure of the invention

 An object of the present invention is to provide a larger amount of fragrance than conventional aqueous gel flavors even when no surfactant is used, and to provide a larger amount of water or water than conventional oily gel flavors. It is an object of the present invention to provide a transparent gel-like fragrance which can be blended with alcohol, which volatilizes quickly and has a good smell, and a resin composition serving as a raw material thereof.

According to the present invention, 2 to 30% by weight of a biel polymer containing diacetone acrylamide units, 0.01 to 5% by weight of a polyfunctional hydrazide compound, 0.1 to 60% by weight of water, and 5 to 50% of a water-soluble solvent are used. and 95 wt%, the resin sets formed containing a perfume 0 Yoo to 93 weight _^0/0 except aldehyde is provided.

Further, according to the present invention, the composition is transparent and has a gel-like form, A transparent gel-like fragrance is provided.

Preferred embodiments of the invention

 Hereinafter, the present invention will be described in more detail.

 The resin composition of the present invention specifies a butyl polymer containing a diacetone acrylamide unit (hereinafter abbreviated as polymer (A)), a polyfunctional hydrazide compound, water, a water-soluble solvent, and a fragrance. Include in percentage.

 The polymer (A) used in the present invention can be produced by copolymerizing diacetone acrylamide and an ethylenically unsaturated monomer. ·

 Examples of the ethylenically unsaturated monomers include: vinyl esters of fatty acids such as vinyl formate, vinyl acetate, vinyl propionate, and vinyl piperate; unsaturated monoesters such as crotonic acid, atarilic acid, and methacrylic acid; Oleic acid and its esters, salts, anhydrides, amides or nitriles; unsaturated dicarboxylic acids such as maleic acid, itaconic acid and fumaric acid and their salts; monomethyl maleate, monomethyl itaconate Monoalkyl esters of unsaturated dibasic acids, etc .; olefins having 2 to 30 carbon atoms; alkyl vinyl ethers; bierpyrrolidones; and the like, and one or more of these are used when used.

 As a method for producing the polymer (Α), various methods such as conventionally known bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be employed. The obtained polymer can be modified by a known method, for example, characterization, acetonolation, urethanization, etherification, grafting, phosphoric esterification, acetoacetylich and the like. Among them, from the viewpoint of copolymerizability, ease of handling, and physical properties of the obtained gel fragrance, a diacetone acrylamide-vinyl acetate copolymer and an oxide of the copolymer are preferable.

 In the polymer (Α) used in the present invention, the content ratio of diacetone acrylamide units is usually preferably 0.5 mol% or more, more preferably 1.0 mol% or more. If the content of the diaceton acrylamide unit is less than 0.5 mol%, it is not preferable because a desired gel strength cannot be imparted to the obtained fragrance.

The degree of polymerization of the polymer (Α) is not particularly limited, but the average degree of polymerization is preferably from 50 to 5,000. If the degree of polymerization is too low, the gel strength will be low, and if the degree of polymerization is too high, the solution viscosity will be high, which may make it difficult to handle. Diacetone acrylamide as polymer (Α) The degree of degradation in the case of using a vinyl acetate acetate copolymer is also not particularly limited, and can be appropriately selected according to the type of water, the water-soluble solvent and the fragrance, and the mixing ratio.

 In the resin composition of the present invention, the content of the polymer (A) is 2 to 30% by weight based on the total amount of the composition. If the amount is less than 2% by weight, a gel having sufficient strength cannot be obtained. If the amount exceeds 30% by weight, there is a problem that the residual amount of the obtained gel-like fragrance after volatilization increases.

 The polyfunctional hydrazide compound used in the present invention is a compound having two or more hydrazide groups in a molecule, and forms a gel by performing a cross-linking reaction with diacetone acrylamide in the polymer (A) in a solution. Compound.

 Examples of the polyfunctional hydrazide compound include, but are not limited to, hydro hydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic dihydrazide, suberic acid dihydrazide, and azerazide dihydrazide dihydrazide dihydrazide dihydrazine Acid dihydrazide, dodecandiohydrazide, hexadecandiohydrazide, terephthalic acid dihydrazide, isophthalic acid dihydrazide, isophthalic acid hydrazide-5-sodium sulfonate, 2,6-naphthoic acid dihydrazide, 4,4-bisbenzene Dihydrazide, 1,4-cyclohexanedihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, iminodiacetic acid dihydrazide, N, N-hexamethylene bissemicarbazide, itaconic acid dihydrazide, Ethylenediaminetetraacetic acid tetrahydrazide, citrate trihydrazide, butanetricarbohydrazide, 1,2,3-benzenetrihydrazide, 1,2,4-benzenetrihydrazide, 1,4,5,8-naphthoic acid tetrahydrazide , Trihydrazide, uretuloacetic acid, trihydrazide of hexahexanetricarboxylic acid, trihydrazide of 1,2,4-pyromellitic acid, tetrahydrazide of pyromellitic acid, N-aminopolyacrylamide, and the like. Alternatively, two or more kinds are used in combination.

In the resin composition of the present invention, the content ratio of the polyfunctional hydrazide compound is 0.01 to 5% by weight based on the total amount of the composition. / ₀ . If the content is less than 0.01% by weight, a gel having sufficient strength may not be obtained, and if the content is more than 5% by weight, the obtained gel-like fragrance may have a large amount of residue after volatilization.

The water used in the present invention is a fragrance carrier and a solvent for the polyfunctional hydrazide compound. Act as

 As water, a crosslinking reaction between diacetone acrylamide in the polymer (A) and the polyfunctional hydrazide compound affects the reaction rate depending on metal ions contained in the water and pH at that time. Therefore, ion-exchanged water or the like treated with an ion-exchange resin is preferable.

 In the resin composition of the present invention, the content ratio of the water is 0.1 to 60% by weight based on the total amount of the composition. If the amount is less than 0.1% by weight, the polyfunctional hydrazide compound cannot be dissolved. If the amount exceeds 60% by weight, a fragrance may not be compounded without substantially using a surfactant.

 The water-soluble solvent used in the present invention acts as a carrier for the perfume and acts to make the perfume and water compatible. In order to make the fragrance and water compatible, it is preferable to use a water-soluble solvent having a solubility in water of 1.0% by weight or more.

 Examples of the water-soluble solvent include ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secondary butanol, tertiary butanol, n-amyl alcohol, isoamyl alcohol, secondary amyl alcohol, Monohydric alcohol solvents such as triamyl alcohol; ethylene glycol, ethylene glycol monomethinoleate, ethylene glycolone monomethineoleate acetate, ethylene glycolone monoethylate ethereole, diethylene glycolonele, diethylene glycolonele Monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, dipropylene glycol, hexylene glycol, 1,3-butylene glycol, 3-methyl-3-methoxy-1-butanol Polyhydric alcohols and derivatives thereof; benzyl alcohol, phenylalanine ethyl alcohol. When used, they may be used alone or in combination of two or more.

 Flavors used in the resin composition of the present invention are limited to those other than aldehydes. When an aldehyde is blended in the fragrance, it reacts with the polyfunctional hydrazide compound, and not only causes odor change but also inhibits gelation.

 The content ratio of the fragrance in the composition is from 0 :! to 93% by weight. ·

The resin composition of the present invention contains, in addition to the above essential components, other components in a range that does not impair the desired purpose of the present invention, or other components to obtain the desired effects and other effects of the present invention It can also be done.

 Other components include a polymer compound other than the copolymers (A) and Z or a modified product thereof, a thickener, a surfactant, a deodorant, a dye, an antioxidant, an ultraviolet absorber, and a preservative. And antibacterial agents.

 Examples of the polymer compound and the thickener include biel acetate copolymer, polynorpolene, polyethylene, polyvinylinoleate, polybutadiene, polymethylpentene, polybutene, and polymethylmethacrylate.

 Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and the like.

 Preferred examples of the deodorant include amphoteric surfactant type deodorants, plant extracts, pyruvate esters, and zinc fatty acid salts.

 Examples of the antioxidant include BHT.

 Examples of the pigment include titanium oxide, zinc oxide # &, and other coloring pigments and dyes.

 The content ratio when these other components are contained can be appropriately determined according to the purpose.

 In order to prepare the transparent gel-like fragrance of the present invention, for example, the polymer (A) in the above-mentioned resin composition of the present invention is dissolved in a water-soluble solvent and / or fragrance, and water, fragrance, and polyfunctional The hydrazide compound and, if necessary, other components can be added, stirred and completely dissolved, and then filled in a container and left to stand.

 The fragrance using the resin composition of the present invention can be used for, but not limited to, fragrance deodorization in, for example, a room, a toilet, a clog box, around a platform, and a bathroom.

 The transparent gel-like fragrance of the present invention can contain a larger amount of fragrance than conventional aqueous gel-like fragrances. Further, a transparent gel-like fragrance containing water and containing no surfactant can be obtained. Further, since the transparent gel-like fragrance of the present invention can contain water or alcohol in a larger amount than the conventional oil-based gel-like fragrance, it has a good odor and a high volatilization rate.

Example

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Synthesis example 1

 A flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser was charged with 672 parts by weight of vinyl acetate, 10 parts by weight of diacetone acrylamide and 178 parts by weight of methanol, and the system was purged with nitrogen. Thereafter, the internal temperature was raised to 60 ° C. To this system, a solution of 1 part by weight of '2,2'-azobissiptyrronitrile dissolved in 50 parts by weight of methanol was added, and polymerization was started. A solution of 55 parts by weight of diacetone acrylamide and 35 parts by weight of methanol was added dropwise at a constant rate over 5 hours after the start of the polymerization, and after 6 hours, the solution was cooled to stop the polymerization. The polymerization yield was 78%.

 The remaining vinyl acetate was distilled off while adding methanol vapor to the obtained reaction mixture to obtain a 50% by weight methanol solution of a butyl acetate polymer containing a diacetone acrylamide copolymer component. The methanol solution was dried under vacuum, and the obtained solid was pulverized to obtain a diacetone acrylamide-vinyl acetate copolymer (hereinafter, referred to as a copolymer (A-1)).

Elemental analysis measurement, the content of diacetone acrylamide units in the copolymer (A-1) was found to be 5.0 mol _^0/0. The number average polymerization degree of the copolymer (A-1) was 1,750. Synthesis example 2

50% by weight of a diacetone acrylamide-biel acetate copolymer obtained by the same method as in Synthesis Example 1. / ₀ methanol solution 500 parts by weight was added to methanol 50 parts by weight and 4% methanol solution 4 parts by weight of sodium hydroxide was mixed well KoTsuta the鹼化reaction. Further, this mixture is vacuum-dried, and the obtained solid is pulverized to obtain a partial distillate of diacetoneacrylamide monoacetate copolymer (hereinafter, referred to as copolymer (A-2)). Was. The degree of conversion of the copolymer (A-2) was 10.0 mol%.

 Example 1

4.0 g of the copolymer (A-2) prepared in Synthesis Example 2 was dispersed in 55.7 g of 3-methyl-3-methoxybutanol and heated to 90 ° C. to completely dissolve. Then, after cooling the obtained solution to room temperature, 35.0 g of ion-exchanged water, 0.2 g of adipic dihydrazide, 5.0 g of a fragrance prepared without using BHTO.lg and aldehydes were mixed, and a transparent gel was obtained. A fragrance composition was prepared. Subsequently, the resulting composition was allowed to stand at room temperature for 1 day to cause a gelich reaction, whereby a gel-like fragrance was obtained. The obtained gel-like fragrance was transparent and beautiful. In addition, when the gel-type aromatic was volatilized, a large amount of water was added, so that the smell was better than conventional oil-based gel-type aromatics, and the residue after use was transparent. I was able to maintain beauty until the end.

 Example 2

4.0 g of the copolymer (Al) prepared in Synthesis Example 1 was dispersed in 70.0 g of a fragrance prepared without using aldehydes, heated to 60 ° C., and stirred for 1 hour to completely dissolve. Next, after cooling the obtained solution to room temperature, 19.9 _{g of} diethylene glycol monoethyl ether, 5.8 _g of ion-exchanged water 0.2 g of _N- adipate dihydrazide and BHT O.lg were mixed, and the composition for a transparent gel-like fragrance was mixed. Was prepared. Subsequently, the resulting composition was allowed to stand at room temperature for 1 day to allow a Gölic reaction to obtain a gel-like fragrance.

 The obtained gel-like fragrance was transparent and beautiful. In addition, when this gel-like fragrance was volatilized, it contained a large amount of water, so it had a better smell than conventional oil-based or water-based gel-like fragrances, and residue after use. Was also transparent and could maintain its beauty until the end.

 Example 3

 4.0 g of the copolymer (Al) prepared in Synthesis Example 1 was dispersed in 59.9 g of 3-methyl-3-methoxy-1-butanol and heated to 90 ° C to completely dissolve. Next, after cooling the obtained solution to room temperature, 20.0 g of a fragrance prepared without using aldehydes, 15.8 g of ion-exchanged water, 0.2 g of adipic dihydrazide and BHT O.lg were mixed, and a transparent gel-like aroma was mixed. A pharmaceutical composition was prepared. Subsequently, the obtained composition was left at room temperature for one day to cause a gelling reaction, whereby a gel-like fragrance was obtained.

 The obtained gel-like fragrance was transparent and beautiful. When the gel-based fragrance was volatilized, a large amount of water was added, so the fragrance was better compared to conventional oil-based gel-based fragrances and aqueous gel-based fragrances. It was transparent and maintained its beauty to the end.

 Comparative Example 1

4.0 g of the copolymer (Al) prepared in Synthesis Example 1 was dispersed in 75.7 g of small 3-methyl-3-methoxybutanol and heated to 90 ° C. to completely dissolve. Then, the obtained solution is brought to room temperature. After cooling, 20.0 _{g of} a fragrance prepared without using aldehydes, 0.2 _g of adipic dihydrazide and BHT O.lg were mixed to prepare a composition for a fragrance. Subsequently, when the obtained composition was allowed to stand at room temperature for 1 day, adipic dihydrazide was precipitated and a gel-like fragrance could not be obtained.

 Comparative Example 2

 12.0 g of hydrogenated castor oil, 51.9 g of 3-methyl-3-methoxy-1-butanol, 16.0 g of ion-exchanged water, BHT O.lg and 20.0 g of fragrance are mixed and heated to 90 ° C to dissolve the hardened castor oil. Then, it was cooled to room temperature. As a result, hydrogenated castor oil was separated from 3-methyl-3-methoxy-1-butanol and diion-exchanged water, and a gel-like fragrance could not be obtained.

Claims

The scope of the claims  1. 2% to 30% by weight of a bull-based polymer containing diacetone acrylamide units, 0.01% to 5% by weight of a polyfunctional hydrazide compound, and 0.:! A resin composition containing 60 to 60% by weight, a water-soluble solvent 5 to 95% by weight, and a fragrance excluding aldehydes 0.1 to 93% by weight.  2. The composition according to claim 1, wherein said biel-based polymer is selected from the group consisting of diacetone acrylamide-vinyl acetate copolymer, an oxide thereof, and a mixture thereof. 3. The composition according to claim 1, wherein the average degree of polymerization of the vinyl polymer is 50 to 5,000.  Polymers other than vinyl polymers containing diacetone acrylamide units, thickeners, surfactants, deodorants, pigments, antioxidants, ultraviolet absorbers, preservatives, antibacterial agents and請求 The composition according to claim 1, further comprising another component selected from the group consisting of these mixtures.  5. 2 to 30% by weight of a vinyl polymer having a transparent and gel form and containing diacetone acrylamide unit, 0.01 to 5% by weight of a polyfunctional hydrazide compound, and 7 0.1 to 60% by weight A transparent gel-like fragrance containing a resin composition containing 5 to 95% by weight of a soluble solvent and 0 to 90% by weight of a fragrance excluding aldehydes.