TW200401654A - 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 with 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

200401654 (1) 发明. Description of the invention [Technical field to which the present invention belongs] The present invention relates to an aromatic agent which can be used indoors, in automobiles, in wooden rafters, around kitchens, and bathrooms, and is stable, gelatinous, and transparent. Resin composition made of fragrant agent and its raw materials. [Prior art] Conventionally, it has been known that the gelatinization energy of agar and carrageenan (A), a natural polymer, is used as a water-based gel-like aromatic agent (Japanese Patent Publication No. Sho 5 4 — 1 3 5 2 2 9 Gazette), (b) Crosslinking gelatin with an enzyme via a cross-linking agent (Japanese Patent Gazette No. 2-9 7 4 8 4; Japanese Patent Gazette No. 9-4042 8). In addition, the gelling agent has a high hydrophilicity and cannot be added with a large amount of fragrances. Furthermore, a large amount of a surfactant cannot be used in order to make it transparent, and therefore there is a problem that residues upon volatilization increase. On the other hand, it is known that an oily gel-like fragrance is added with terpene-based hydrocarbons and isoparaffin-based hydrocarbons, and a gelling agent is added with hardened ramie oil, sodium stearate, or 2] Flavoring agent of hydroxystearic acid (Japanese Patent Publication No. Sho 5 8 — 7 8 6 62, Japanese Patent Publication No. Sho 5-5-1 4 1 2 4 3, Japanese Patent Publication No. Sho 5 — 丨 〇 2 4 3 8). In addition, these gel fragrances only have a small amount of water or alcohol added, and therefore have a problem of poor taste and slow volatilization. [Summary of the invention] (2) (2) 200401654 The object of the present invention is to provide a fragrance that can be added in a larger amount than conventional water-based gel-like fragrance without using a surfactant, and can be added to a conventional oil-based gel. The fragrance contains a large amount of water or alcohol, and is a resin composition made of a transparent gel-like fragrance and its raw materials which volatilize quickly and have good taste. According to the present invention, there is provided an ethylene-based polymer containing 2 to 30% by weight of a diacetone acrylamide unit, and a polyfunctional hydrazine compound. 〇 ～~ 5% by weight, water 0.1 ~ 60% by weight, water-soluble solvents 5 ~ 95% by weight, and fragrances other than aldehydes 1 ~ 93% by weight resin composition. According to the present invention, a transparent gel-like fragrance containing the composition as a main component and having a transparent and gel-like form is provided. Best Mode for Carrying Out the Invention The present invention will be described in more detail below. The resin composition of the present invention contains a vinyl polymer (hereinafter referred to as a polymer (A), a polyfunctional hydrazine compound, water, a water-soluble solvent, and a fragrance) containing a diacetone propionate unit in a specific ratio. 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 monosystem include vinyl formate, ethyl acetate, Vinyl fatty acid vinyl esters such as vinyl propionate, trimethyl vinyl acetate; unsaturated monocarboxylic acids such as vinyl crotonic acid, acrylic acid, methacrylic acid and their vinegars, salts, anhydrides, amines or nitriles; Malay Unsaturated dicarboxylic acids, such as acids, itaconic acid, fumaric acid, and their salts; unsaturated dibasic acids, monoalkyl esters such as maleic acid monomethyl, itaconic acid monomethyl, and the like; carbon number 2 0 ~ 3 0 of α —-6- (3) (3) 200401654 Alkenes; Alkyl vinyl esters; Vinyl pyrrolidone, etc. When used, one or more of these may be used. Polymer (A) The manufacturing method can adopt conventional block polymerization, solution polymerization, suspension polymerization, milking Various methods such as polymerization, etc. The polymer obtained can also be modified through saponification, acetalization, urethane, etherification, grafting, phosphorylation, and butanone methylation. Among them, copolymerization From the viewpoints of physical properties, ease of handling, and properties of the gel-like fragrance produced, diacetone acrylamide-vinyl acetate copolymers and saponifications of the copolymers are most suitable. Polymers used in the present invention (A) The content ratio of amine diacetone acrylate units is preferably generally 0.5 mol% or more, more preferably 1.0 mol or more. The content ratio of amine diacetone amine units is less than 0.5 mol%, The obtained fragrance does not provide the desired gel strength. The polymer of the polymer (A) is not particularly limited, and the average degree of polymerization is preferably 50 to 5000. The degree of polymerization is too small for the gel The strength is weak, and the solution viscosity is too high if the polymerization degree is too large, so it may not be easy to handle. As the polymerization degree (A), the degree of saponification when using the diacetone amine acrylate-vinyl acetate copolymer is not particularly limited. , But according to water, water-soluble solvents, perfumes The content of the polymer (A) in the resin composition of the present invention is 2 to 30% by weight. If it is less than 2% by weight, it cannot be obtained with sufficient content. If the gel strength is more than 30% by weight, there is a problem that the residual amount of the gel-like fragrance produced is increased. The multifunctional hydrazine compound used in the present invention has ^ -7 in the molecule. -(4) (4) 200,401,654 or more hydrazine-based compounds which crosslink with diacetone acrylate amine in the polymer (A) in the solution to form a gel. The multifunctional hydrazine compound can be Examples include symmetric dihydrazine, dioxazine oxalate, dihydrazine malonate, dihydrazine succinate, dihydrazine glutarate, dihydrazide diadipate, dihydrazine pimelate, dihydrazine suberate, diazide azelarate , Dihydrazine sebacate, dodecanedihydrazine, hexadecanedihydrazine, dihydrazine terephthalate, dihydrazine isophthalate, dihydrazine isophthalate-5, sodium sulfonate, 2,6 —Dihydrazine naphthoate, 4,4 '—Diphenyldihydrazine, 1,4 monocyclohexanedihydrazine, diammonium tartrate, dimalate , Dihydrazine imino diacetate, N, N-hexamethylene diurea amino, dihydrazine itaconic acid, tetrahydrazine diamine tetraacetate, trihydrazine citrate, butanetricarboxyhydrazine, 1,2,3-benzenetriazine Hydrazine, 1,2; 4-phenyltrihydrazine, 1,4,5,8-naphthalenecarboxylic acid tetrahydrazine, cyanoacetic acid trihydrazine, cyclohexanetricarboxylic acid trihydrazine, 1,2,4 pyromellitic acid Trihydrazine, tetramethylene pyromellitic acid, N-amine polyacrylamide, etc., and one or a combination of two or more of them can be used when used. The content ratio of the polyfunctional hydrazine compound in the resin composition of the present invention is 0.01 to 5% by weight based on the total amount of the composition. If the weight is less than 0.001, there is a possibility that a gel having sufficient strength may not be obtained, and if the gel-like fragrance obtained is more than 5% by weight, there may be excessive residue after glowing. The water system used in the present invention serves as a carrier for perfumes and a solvent for the polyfunctional hydrazine compound. As a water system, during the cross-linking reaction of diacetone acrylamide in the polymer (A) and the polyfunctional hydrazine compound, metal ions and pH contained in water affect the reaction speed, so ions treated with an ion exchange resin are used. It is better to exchange water. The content ratio of the water in the resin composition of the present invention (5) (5) 200401654 Example 'The total amount of the composition is 0.1 to 60% by weight. If it is less than 0.00% by weight, the polyfunctional hydrazine cannot be dissolved, and if it exceeds 60% by weight, it cannot be used under the surfactant, and there is a possibility that fragrance cannot be added. The water-soluble solvent used in the present invention acts as a carrier for the fragrance, and then the fragrance is dissolved in water to act. In order to dissolve the fragrance with water, a water-soluble solvent having a solubility in water of 1.0% by weight or more is preferred. Examples of the water-soluble solvent include ethanol, n-propanol, isopropanol, n-butanol, isobutanol, first butanol, third butanol, n-pentanol, isoamyl alcohol, di-pentyl alcohol, and A divalent alcohol-based alcohol solvent; ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether diethylene glycol, and ethylene glycol mono alcohol. Methyl_monoethylene glycol monoethyl ether, propylene glycol, dipropylene glycol, hexanediol, 1,3-butanediol, 3-methyl-3, methoxy-1 monobutanol, and other polyvalent alcohols and the like Derivatives; benzyl alcohol, phenylethyl alcohol, etc. In use, it can be used in combination of 2 or more. The fragrance used in the resin composition of the present invention is limited to those other than aldehydes. When an aldehyde is added to a fragrance, the polyfunctional hydrazine reacts with the aldehyde, which not only causes a change in flavor but also prevents gelation. The content ratio of the composition of Ihai perfume is 0.1 to 93% by weight. In addition to the essential component, the resin composition of the present invention may contain other ingredients so as not to impair the desired effect of the present invention or to obtain the desired effect and other effects of the present invention. Other components include, for example, a polymer compound other than the copolymer (A) and / or a modified product thereof, a tackifier, a surfactant, a deodorant, a pigment, an oxidation inhibitor, an ultraviolet absorber, a preservative, Antibacterial agents and so on. Winter (6) (6) 200401654 Polymer compounds and tackifiers can be, for example, vinyl acetate copolymers, polynorbornane, polyethylene, polyvinyl ether, polybutadiene, polymethylheptene, polybutene , Polymethylmethacrylate, etc. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. As the deodorant, for example, an amphoteric surfactant type deodorant, a plant extract, a pyruvate, a fatty acid zinc salt, or the like is preferable. Examples of the oxidation preventing agent include B Η T and the like. Examples of the pigment system include phthalic oxide, zinc oxide, other colored pigments, and dyes. The content ratio when these other ingredients are contained may be determined according to the purpose. To prepare the transparent gel-like fragrance of the present invention, the above-mentioned resin composition of the present invention, such as the polymer (A), can be dissolved in a water-soluble solvent and / or perfume, and water, perfume, and a polyfunctional hydrazine compound can be added. If necessary, add other ingredients, stir and completely dissolve, then fill the container, and it can be prepared by placing it. The fragrance using the resin composition of the present invention can be used for fragrance and deodorization indoors, in toilets, wooden rafters, around kitchens, bathrooms, and the like, but is not particularly limited thereto. The transparent gel-like fragrance of the present invention can be added with a larger amount of perfume than the conventional water-based gel-like fragrance, and it is also possible to prepare a transparent gel-like fragrance containing water and containing no surfactant. In addition, the transparent gel of the present invention -10- (7) (7) 200401654 The gel fragrance is to add more water or alcohol than the conventional oily gel fragrance, so it has a good taste and a fast volatilization rate. [Embodiments] Examples Hereinafter, the present invention will be described in more detail through examples and comparative examples, but the present invention is not limited thereto. Synthesis Example 1 In a flask equipped with a stirrer, a thermometer, a low-pressure funnel, and a reflux cooler, 672 parts by weight of vinyl acetate, 10 parts by weight of diacetone acrylamide, and 178 parts by weight of methanol were added to the system. After the nitrogen was replaced, the temperature in the system was raised to 6 ° C. In the system, 1 part by weight of 2,2'-azobisisobutyronitrile was added to 50 parts by weight of the dissolved solution in methanol, and polymerization was started. The polymerization started Then, it took 5 hours to dissolve 5 parts by weight of diacetone acrylamide and 35 parts by weight of methanol at a certain rate, and after cooling for 6 hours, the polymerization was stopped. The polymerization yield was 78%. In the reaction, methanol vapor was added and the remaining ethyl acetate was distilled off to obtain a 50% by weight methanol solution of a vinyl acetate polymer containing diacetone acrylamide copolymerized. 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)).

It was determined by elemental analysis and measurement that the content of one acetone acrylamide unit in the copolymer (A-]) was 50% mole. The number of copolymers (A (8) 200401654 —]) has an average degree of polymerization of 1 7 50. Synthesis Example 2 50 parts by weight of a 50% by weight methanol solution of diacetone acrylamide-vinyl acetate copolymer prepared by the same method as Synthesis Example 1-50 parts by weight of methanol and sodium hydroxide were added 4 parts by weight of a 4% methanol solution was appropriately mixed to perform a saponification reaction. This mixture was further dried under vacuum ', and the obtained solid was pulverized to obtain a partial saponified product of a diacetone acrylamide-vinyl acetate copolymer (hereinafter, referred to as a copolymer (A-2)). The degree of saponification of the copolymer (A-2) was 10.0 mole%. Example 1 4.0 g of the copolymer (A-2) prepared in Synthesis Example 2 was dispersed in 3-methyl-3-methoxy-1; 55.7 g of [-butanol and heated to 90 °. (: It is completely dissolved. Then, the prepared solution is cooled to room temperature, and 35.0 g of ion-exchanged water, 0.2 g of adipic acid dihydrazide, 0.2 g of T,. G, and Using 5.0 g of aldehyde-mixed perfume, a transparent gel-like fragrance composition was prepared. Then, the prepared composition was left at room temperature for 1 day and a gel-like fragrance was obtained through a gelation reaction. The obtained gel fragrance is transparent and beautiful. In addition, when the gel fragrance is used for volatilization, a large amount of water is added, so the flavor is better than that of the conventional oily gel fragrance. (9) 200401654 Example 2 4.0 g of the copolymer (A — 1) prepared in Synthesis Example 1 was dispersed in 7 0 · 0 g of the fragrance without using aldehydes and heated to 6 0 ° C, continue to stir for 1 hour to completely dissolve. After cooling the prepared solution to room temperature, mix 19.9 g of diethylene glycol monomethyl ether, 5.8 g of ion-exchanged water, and hexane. Acid di • hydrazine 0.2g and BHTO.lg to prepare a transparent gel-like fragrance composition. Then, the prepared composition is placed in a chamber Let it stand at room temperature] for gelatinization to obtain a gel-like fragrance. The gel-like fragrance obtained is transparent and beautiful. In addition, when the gel-like fragrance is volatilized, a large amount of Water, it has better taste than conventional oil-based gel-like fragrances and water-based gel-like fragrances, and it can be maintained until the end is beautiful. Example 3 Copolymer (A-1) prepared in Synthesis Example 1 4.0 g, dispersed in 59.9 g of 3-methyl-3-methoxy-]-butanol and heated to 90 ° C to completely dissolve it. Then, the prepared solution was cooled to room temperature, and mixed. A transparent gel-like fragrance composition was prepared using 200 g of aldehyde-mixed fragrance, ion-exchanged water] 5 · 8 g, di 'hydrazine adipate 0.2 g, and β Η T 0 · 1 g. ^ The prepared composition is left at room temperature for 1 day, and is gelatinized to obtain a gel-like fragrance. The gel-like fragrance is transparent and beautiful. Furthermore, use the When the gel-like fragrance is volatilized, a large amount of water is added, so it is compared with conventional oily gel-like fragrances and water-based gel-like fragrances. It is better to produce a taste of -13- (10) (10) 200401654, and it can be maintained to the end. Comparative Example 1 4.0 g of the copolymer (A-1) prepared in Synthesis Example 1 was dispersed in 3-methyl -3 -methoxy-1 1-butanol 5 9.9 g and heated to 90 ° C to completely dissolve. Then, after the solution was cooled to room temperature, the fragrance 20.0 was used without mixing with aldehydes. g, 0.2 g of adipic acid dihydrazine, and ΒΗΤ0 1 g for preparing a composition for fragrance. In turn, when the prepared composition was left at room temperature for 1 day, diazid adipic acid precipitated and a gel could not be obtained. Like fragrance. Comparative Example 2 Mixed hardened ramie oil 1 2 0 g, 3-methyl-1, 3-methoxy-1, 1-butanol 5 1 .9 g, ion-exchanged water 1 6.0 g, Beta-0.1 g, and flavor 20.0 g and heated to After dissolving hardened ramie oil at 90 ° C, cool to room temperature. As a result, hardened ramie oil was separated from 3-methyl-1,3-methoxy-l-butanol and ion-exchanged water, and a gel-like fragrance could not be obtained. -14-

Claims (1)

(1) (1) 200401654, patent application scope 1 · A resin composition characterized by containing 2 to 30% by weight of an ethylene-based polymer containing diacetone acrylamide units, and a polyfunctional hydrazine compound 0 · 0] 1〜9 3 重量 ％。 ~ 5% by weight, water 〇] ~ 60 0% by weight, water-soluble solvents 5 ~ 9 5% by weight, and excluding fragrances other than awakening class 0.1 ~ 9 3% by weight. 2. The composition according to item 1 of the patent application scope, wherein the ethylene-based polymer is selected from the group consisting of a diacetone acrylamidine-vinyl acetate copolymer, a saponified product, and a mixture thereof. 3. The composition according to item 1 of the patent application range, wherein the average degree of polymerization of the ethylene-based polymer is 50 to 5000. 4. The composition according to item 1 of the scope of patent application, in which 尙 contains a polymer compound other than an ethylene-based polymer selected from diacetone acrylamide units, a tackifier, a surfactant, a deodorant, a pigment, and an oxidation agent. Preventives, UV absorbers, preservatives, antibacterials, and other ingredients in a mixture of these. 5. A transparent gel-like fragrance, characterized by being transparent and having a gel form, containing 2 to 30% by weight of an ethylene-based polymer containing diacetone acrylamide units, 0.01 to 5% by weight of a polyfunctional hydrazine compound, 1 to 93% by weight of a resin composition containing 0.1 to 60% by weight of water, 5 to 95% by weight of a water-soluble solvent, and a fragrance containing aldehydes removed. 200401654 柒, (1), the designated representative figure in this case is: None (二), the component representative symbol of this representative figure is simply explained: te 捌 If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: Turn E -4-