JP2005287570A - Aqueous and fluorescent aromatic deodorant composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous and fluorescent aromatic deodorant solving disadvantages of a conventional technique, having a light emitting operation and an aromatic deodorizing operation, and having superior stability and aroma retaining property even in a state of aqueous solution. <P>SOLUTION: The aqueous and fluorescent aromatic deodorant composition is characterized in including a light accumulating pigment expressed by a general formula (1) MAl<SB>2</SB>O<SB>4</SB>(in the formula, M is at least one type or more metal element selected from a group of calcium, strontium and barium), amine oxide ampholytic surfactant and aroma. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an aqueous fluorescent aroma deodorant composition containing a specific phosphorescent pigment and an amine oxide type amphoteric surfactant. More specifically, the present invention is excellent in long-term fluorescence luminescence and stability, and a fragrance. The present invention relates to an aqueous fluorescent aroma deodorant composition having high retentivity.

  Conventionally, as an aqueous fragrance deodorant composition, a product obtained by solubilizing a fragrance using an emulsifier such as a surfactant, or a product obtained by gelling it with a water-soluble polymer has been commercialized. In addition, as the fluorescent fragrance deodorant, (1) a gel-like light-emitting deodorant (Patent Document 1) having both a light-emitting action and a deodorizing action by blending a phosphorescent pigment and a high water supply polymer (Patent Document 1) 2) An aroma composition (Patent Document 2) containing a phosphorescent pigment and an organoclay composite has been proposed.

  However, the gel-like light-emitting deodorant (1) has some problems due to the use of animal light pigments represented by zinc sulfide, calcium sulfide, cadmium zinc sulfide and the like. Was. In other words, in addition to the problem of chemical stability such as light resistance, zinc sulfide has low fluorescence luminance and afterglow as a fluorescent pigment, and has fluorescence enough to make the product worthy. There was a problem that not. In addition, calcium sulfide-based materials have the disadvantage of poor moisture resistance and extremely poor durability in the air, and cadmium zinc-based materials have low practicality because they contain cadmium called a pollution element. That was the current situation.

  Further, in the fragrance composition (2), when the water content increases, the phosphorescent pigment decomposes and does not cause fluorescence. Therefore, in order to keep the water content low, it is necessary to increase the alcohol content.

  On the other hand, aluminate-based phosphorescent pigments other than the above-mentioned phosphorescent pigments are not only excellent in fluorescence intensity and afterglow characteristics after light emission, but also in light resistance and chemical stability compared to conventional luminescent pigments. It is excellent in that it does not easily cause a decrease in fluorescence intensity or discoloration even when left outdoors for a long period of time, and it is extremely safe for the human body because it does not contain radioactive substances or harmful substances. However, since this aluminate-based phosphorescent pigment is easily hydrolyzed in the presence of moisture or alkali, it has a drawback that the components that can be blended are limited. In addition to the extremely large specific gravity of 3.6, the particle size dependence on luminance is extremely high, and it was necessary to stably disperse in the system without changing the particle size as much as possible. In the case of functional polymers and clay minerals, satisfactory results were not obtained.

  On the other hand, as a gel-like fragrance, an aqueous gel composition (Patent Document 3) containing an amine oxide amphoteric surfactant is known. However, the form is a gel-like fragrance, and there is no suggestion of a fragrance deodorant in the form of an aqueous solution, and there is no description that suggests an aqueous fluorescent fragrance deodorant composition by adding a phosphorescent pigment.

JP-A-6-39023 JP 10-330239 A JP 2003-155377 A

  Accordingly, it has been desired to develop an aqueous fluorescent aroma deodorant having a light emitting action and an aroma deodorizing action, and having excellent stability and perfume retention in an aqueous solution state.

  As a result of intensive studies to solve the above problems, the present inventors have blended a specific phosphorescent pigment and an amine oxide type amphoteric surfactant to produce a fluorescent emission effect and aroma for a long period in an aqueous system. It has been found that an aqueous fluorescent aroma deodorant composition having a deodorizing action and excellent in stability and aroma deodorizing action can be obtained, and the present invention has been completed.

That is, the present invention is as follows.
1. The following general formula (1)
MAl ₂ O ₄ (1)
(In the formula, M is at least one metal element selected from the group consisting of calcium, strontium, and barium.)
A water-based fluorescent aroma deodorant composition comprising: a phosphorescent pigment represented by formula (1); an amine oxide amphoteric surfactant; and a fragrance.
2. The amine oxide type amphoteric surfactant has the general formula (2):

（式中、Ｒ¹は炭素数８〜２２のアルキル基又は炭素数８〜２２のアルケニル基を示す。）で表わされるアミンオキシド型両性界面活性剤（２）、一般式（３）：

(Wherein R ¹ represents an alkyl group having 8 to 22 carbon atoms or an alkenyl group having 8 to 22 carbon atoms), an amine oxide type amphoteric surfactant (2) represented by the general formula (3):

（式中、Ｒ²は炭素数８〜２２のアルキル基又は炭素数８〜２２のアルケニル基を、ｌ及びｍはエチレンオキシドの平均付加モル数を表し、ｌ＋ｍは１〜１０の整数である。）で表わされるアミンオキシド型両性界面活性剤（３）、一般式（４）：

(In the formula, R ² represents an alkyl group having 8 to 22 carbon atoms or an alkenyl group having 8 to 22 carbon atoms, l and m represent an average number of added moles of ethylene oxide, and l + m is an integer of 1 to 10.) Amine oxide type amphoteric surfactant (3) represented by general formula (4):

（式中、Ｒ³は炭素数８〜２２のアルキル基又は炭素数８〜２２のアルケニル基を、ｎはエチレンオキシドの平均付加モル数を表し、ｎは１〜１０の整数である。）で表わされるアミンオキシド型両性界面活性剤（４）及び一般式（５）：

(Wherein R ³ represents an alkyl group having 8 to 22 carbon atoms or an alkenyl group having 8 to 22 carbon atoms, n represents an average added mole number of ethylene oxide, and n is an integer of 1 to 10). Amine oxide amphoteric surfactant (4) and general formula (5):

（式中、Ｒ⁴は炭素数８〜２２のアルキル基又は炭素数８〜２２のアルケニル基を示す）で表わされるアミンオキシド型両性界面活性剤（５）から選ばれる少なくとも１種のアミンオキシド型両性界面活性剤である上記１．に記載の水性蛍光芳香消臭剤組成物。
３． アニオン性界面活性剤、非イオン性界面活性剤及び一般式（２）乃至（４）で表されるアミンオキシド型両性界面活性剤以外の両性界面活性剤から選ばれる１種以上の界面活性剤を更に含有する上記１．又は２．に記載の水性蛍光芳香消臭剤組成物。
４． Ｌ−酒石酸、マレイン酸、コハク酸、リンゴ酸、クエン酸及び乳酸よりなる群から選ばれた１種以上の有機酸を更に含有する上記１．乃至３．のいずれかに記載の水性蛍光芳香消臭剤組成物。
５． 消臭剤及び忌避剤から選ばれる少なくとも１種以上の成分を更に含有する上記１．乃至４．のいずれかに記載の水性蛍光芳香消臭剤組成物。
６． 上記１．乃至５．のいずれかに記載の水性蛍光芳香消臭剤組成物に、カルボキシメチルセルロース多価金属塩、カラーギナン、寒天、ジェランガム、プルラン、カードラン、キサンタンガム、ペクチン、コンニャクグルコマンナン、キシログルカン、グアーガム、アラビアガム、ローカストビーンガム及びゼラチンから選ばれる１種以上のゲル化剤を添加してなる水性ゲル蛍光芳香消臭剤組成物。

(Wherein R ⁴ represents an alkyl group having 8 to 22 carbon atoms or an alkenyl group having 8 to 22 carbon atoms) at least one amine oxide type selected from amine oxide type amphoteric surfactants (5) 1. The above amphoteric surfactant. The aqueous fluorescent fragrance deodorant composition described in 1.
3. One or more surfactants selected from anionic surfactants, nonionic surfactants and amphoteric surfactants other than the amine oxide type amphoteric surfactants represented by the general formulas (2) to (4) Further contained above 1. Or 2. The aqueous fluorescent fragrance deodorant composition described in 1.
4). 1. The above-mentioned 1. further containing one or more organic acids selected from the group consisting of L-tartaric acid, maleic acid, succinic acid, malic acid, citric acid and lactic acid. To 3. The aqueous fluorescent aroma deodorant composition according to any one of the above.
5). The above-mentioned 1. further containing at least one component selected from deodorants and repellents. To 4. The aqueous fluorescent aroma deodorant composition according to any one of the above.
6). Above 1. To 5. Carboxymethylcellulose polyvalent metal salt, carrageenan, agar, gellan gum, pullulan, curdlan, xanthan gum, pectin, konjac glucomannan, xyloglucan, guar gum, gum arabic, An aqueous gel fluorescent aroma deodorant composition comprising one or more gelling agents selected from locust bean gum and gelatin.

  The aqueous fluorescent aroma deodorant composition of the present invention has a fluorescence emission effect and aroma deodorizing action for a long period in an aqueous system, and is excellent in stability and aroma deodorizing action.

  The present invention is described in detail below.

The phosphorescent pigment used in the present invention has the following general formula (1):
MAl ₂ O ₄ (1)
In the formula, M represents a metal atom, and examples of the metal atom M include calcium, strontium, and barium, and strontium is preferable. In addition, as a luminous pigment used by this invention, the luminous pigment which made the compound represented by the said General formula (1) the mother crystal may be sufficient.

  The phosphorescent pigment used in the present invention is represented by the above general formula (1), and the metal atom M is magnesium at least one metal atom selected from the group consisting of calcium, strontium and barium. It may be a phosphorescent pigment having a compound as a plurality of added metal atoms as a mother crystal.

  Furthermore, as the phosphorescent pigment used in the present invention, a compound obtained by adding europium as an activator in the range of 0.001% or more and 10% or less in terms of mol% with respect to the metal atom represented by M is used. May be.

  Furthermore, as a phosphorescent pigment used in the present invention, as a co-activator, from lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, manganese, tin, bismuth A compound obtained by adding at least one element selected from the group consisting of 0.001% to 10% in terms of mol% with respect to the metal element represented by M may be used.

  The production method of the phosphorescent pigment used in the present invention is not particularly limited. For example, the method described in JP-A-7-11250 and JP-A-9-13028 or a method analogous thereto can be employed. Moreover, you may use a commercial item as a luminous pigment of this invention.

  The blending amount of the phosphorescent pigment used in the aqueous fluorescent aroma deodorant composition of the present invention is not particularly limited, but preferably from 0.1 to 20 from the viewpoint of fluorescence sustainability, stability and economy. % By mass (hereinafter sometimes simply referred to as “%”).

Examples of the amine oxide type amphoteric surfactant used in the present invention include an amine oxide type amphoteric surfactant (2) represented by the general formula (2) and an amine oxide type amphoteric formula represented by the general formula (3). Selected from surfactant (3), amine oxide amphoteric surfactant (4) represented by general formula (4), and amine oxide amphoteric surfactant (5) represented by general formula (5) At least one can be mentioned.
General formula (2) representing an amine oxide type amphoteric surfactant (2):

において、Ｒ¹は直鎖状若しくは分岐鎖状の炭素数８〜２２、好ましくは１０〜１８のアルキル基、又は、直鎖状若しくは分岐鎖状の炭素数８〜２２、好ましくは１０〜１８のアルケニル基である。

R ¹ is a linear or branched alkyl group having 8 to 22 carbon atoms, preferably 10 to 18 carbon atoms, or a linear or branched carbon group having 8 to 22 carbon atoms, preferably 10 to 18 carbon atoms. An alkenyl group.

Specific examples of the amine oxide type amphoteric surfactant (2) include N-octyl-N, N-dimethylamine, N-decyl-N, N-dimethylamine, N-lauryl-N, N-dimethylamine, N-myristyl-N, N-dimethylamine, N-palmityl-N, N-dimethylamine, N-stearyl-N, N-dimethylamine, N-isostearyl-N, N-dimethylamine, N-coconut oil alkyl -N, N-dimethylamine, N-cured tallow alkyl-N, N-dimethylamine, alkyldimethylamines such as N-behenyl-N, N-dimethylamine; N-octenyl-N, N-dimethylamine, N- An amine such as alkenyldimethylamine such as oleyl-N, N-dimethylamine and N-docosenyl-N, N-dimethylamine can be reacted with a known method. Hydrogen and betaine compounds reacted can be mentioned, these compounds can be used alone or appropriately in combination.
General formula (3) representing the amine oxide type amphoteric surfactant (3):

において、Ｒ²は直鎖状若しくは分岐鎖状の炭素数８〜２２、好ましくは１０〜１８のアルキル基、又は、直鎖状若しくは分岐鎖状の炭素数８〜２２、好ましくは１０〜１８のアルケニル基である。又、ｌ及びｍはエチレンオキシドの平均付加モル数を表わし、ｌ＋ｍは１〜１０、好ましくは２〜８の整数である。

R ² is a linear or branched alkyl group having 8 to 22 carbon atoms, preferably 10 to 18 carbon atoms, or a linear or branched carbon group having 8 to 22 carbon atoms, preferably 10 to 18 carbon atoms. An alkenyl group. L and m represent the average number of moles of ethylene oxide added, and l + m is an integer of 1 to 10, preferably 2 to 8.

Representative examples of the amine oxide type amphoteric surfactant (3) include N-octyl-N, N-dipolyoxyethyleneamine, N-decyl-N, N-dipolyoxyethyleneamine, N-lauryl-N, N-dipolyoxyethyleneamine, N-myristyl-N, N-dipolyoxyethyleneamine, N-palmityl-N, N-dipolyoxyethyleneamine, N-stearyl-N, N-dipolyoxyethyleneamine, N-isostearyl-N, N-dipolyoxyethyleneamine, N-coconut oil alkyl-N, N-dipolyoxyethyleneamine, N-cured tallow alkyl-N, N-dipolyoxyethyleneamine, N-behenyl -Alkyldipolyoxyethyleneamines such as -N, N-dipolyoxyethyleneamine; N-octenyl-N, N-dipolyoxyethyleneamine , N-oleyl-N, N-dipolyoxyethyleneamine, N-docosenyl-N, N-dipolyoxyethyleneamine and other alkenyldipolyoxyethyleneamine and other amines reacted with hydrogen peroxide in a known manner The betaine compounds can be used, and these compounds can be used alone or in admixture of two or more. General formula (4) representing an amine oxide type amphoteric surfactant (4):

において、Ｒ³は直鎖状若しくは分岐鎖状の炭素数８〜２２、好ましくは１０〜１８のアルキル基、又は、直鎖状若しくは分岐鎖状の炭素数８〜２２、好ましくは１０〜１８のアルケニル基である。又、ｎはエチレンオキシドの平均付加モル数を表わし、ｎは１〜１０、好ましくは２〜８の整数である。

R ³ is a linear or branched alkyl group having 8 to 22 carbon atoms, preferably 10 to 18 carbon atoms, or a linear or branched carbon group having 8 to 22 carbon atoms, preferably 10 to 18 carbon atoms. An alkenyl group. N represents the average number of moles of ethylene oxide added, and n is an integer of 1 to 10, preferably 2 to 8.

Representative examples of the amine oxide type amphoteric surfactant (4) include N-octylpolyoxyethylene-N, N-dimethylamine, N-decylpolyoxyethylene-N, N-dimethylamine, and N-laurylpolyoxyethylene. -N, N-dimethylamine, N-myristyl polyoxyethylene-N, N-dimethylamine, N-palmityl polyoxyethylene-N, N-dimethylamine, N-stearyl polyoxyethylene-N, N-dimethylamine N-isostearyl polyoxyethylene-N, N-dimethylamine, N-coconut oil alkyl polyoxyethylene-N, N-dimethylamine, N-cured tallow alkyl polyoxyethylene-N, N-dimethylamine, N- Alkyl polyoxyethylene such as behenyl polyoxyethylene-N, N-dimethylamine Alkenyl such as N-octenyl polyoxyethylene-N, N-dimethylamine, N-oleyl polyoxyethylene-N, N-dimethylamine, N-docosenyl polyoxyethylene-N, N-dimethylamine Examples include betaine compounds obtained by reacting an amine such as polyoxyethylenedimethylamine with hydrogen peroxide by a known method, and these compounds can be used alone or in admixture of two or more.
General formula (5) representing an amine oxide type amphoteric surfactant (5):

において、Ｒ⁴は直鎖状若しくは分岐鎖状の炭素数８〜２２、好ましくは１０〜１８のアルキル基、又は、直鎖状若しくは分岐鎖状の炭素数８〜２２、好ましくは１０〜１８のアルケニル基である。

R ⁴ is a linear or branched alkyl group having 8 to 22 carbon atoms, preferably 10 to 18 carbon atoms, or a linear or branched carbon group having 8 to 22 carbon atoms, preferably 10 to 18 carbon atoms. An alkenyl group.

  Representative examples of the amine oxide type amphoteric surfactant (5) include N-octanoylamidopropyl-N, N-dimethylamine, N-decanoylamidopropyl-N, N-dimethylamine, N-lauroylamidopropyl- N, N-dimethylamine, N-myristoylamidopropyl-N, N-dimethylamine, N-palmitoylamidopropyl-N, N-dimethylamine, N-stearoylamidopropyl-N, N-dimethylamine, N-isostearoyl Alkanoylamidopropyldimethylamine such as amidopropyl-N, N-dimethylamine, N-behenoylamidopropyl-N, N-dimethylamine, N-cocoylamidopropyl-N, N-dimethylamine; N-octenoylamide Propyl-N, N-dimethylamine, N-oleoi Betaine compounds obtained by reacting amines such as alkenoylamidopropyldimethylamine such as amidopropyl-N, N-dimethylamine and N-docosenoylamidopropyl-N, N-dimethylamine with hydrogen peroxide by a known method These compounds can be used alone or in admixture of two or more.

  The compounding amount of the amine oxide amphoteric surfactant used in the aqueous fluorescent aroma deodorant composition of the present invention is not particularly limited, but from the viewpoint of fluorescence sustainability, stability and economy, it is 0.05 to It is preferably 20%, more preferably 0.5 to 10%.

  A perfume is added to the aqueous fluorescent fragrance deodorant composition of the present invention. As this fragrance | flavor, various synthetic fragrance | flavors, natural essential oil, synthetic essential oil, citrus oil, animal fragrance | flavor, etc. are mentioned, for example, Unexamined-Japanese-Patent No. 2003-190264 and Arctander S.A. "Perfume and Flavor Chemicals", published by the author, Montclair, N .; J. et al. (U.S.A.) A wide range of perfume ingredients such as those described in 1969 can be used. In the present invention, these fragrances can be used alone or as a blended fragrance appropriately blended.

    As typical fragrances, for example, α-pinene, limonene, cis-3-hexenol, phenylethyl alcohol, styryl acetate, eugenol, rose oxide, linalool, benzaldehyde, muscone, Tesalon (Takasago Fragrance Industry Co., Ltd.) Synthetic fragrances: natural essential oils such as bergamot oil, galvanum oil, lemon oil, geranium oil, lavender oil and mandarin oil.

  Although the compounding quantity of the said fragrance | flavor used in the aqueous | water-based fluorescent fragrance deodorant composition of this invention is not specifically limited, From a viewpoint of fragrance sustainability, stability, and economical efficiency, it is 0.1 to 20%. Preferably, it is 0.5 to 10%.

  In addition to the above components, the aqueous fluorescent aroma deodorant composition of the present invention includes an anionic surfactant, a nonionic surfactant, and an amine represented by the general formulas (2) to (4). One or more surfactants selected from amphoteric surfactants other than oxide-type amphoteric surfactants can also be added.

  Examples of the anionic surfactant include alkane sulfonate, alkylbenzene sulfonate, alkyl sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, and α-olefin sulfonate. be able to.

  Examples of nonionic surfactants include higher alcohol ethylene oxide adducts, alkylphenol ethylene oxide adducts, fatty acid ethylene oxide adducts, polyhydric alcohol fatty acid ester ethylene oxide adducts, higher alkylamine ethylene oxide adducts, and fatty acid alkanols. Amidoethylene oxide adduct, Fatty acid ethylene oxide adduct, Ethylene oxide-propylene oxide block copolymer, Glycerol fatty acid ester, Pentaerythritol fatty acid ester, Sorbitol and sorbitan fatty acid ester, Sucrose fatty acid ester, Polyhydric alcohol And alkyl ethers of the alkanolamines and fatty acid amides of alkanolamines.

  Examples of the amphoteric surfactants other than the amine oxide type amphoteric surfactants represented by the general formulas (2) to (4) include alkyl betaines and fatty acid amidopropyl betaines. An agent can be used individually or in mixture of 2 or more types as appropriate.

  The compounding amount of the amphoteric surfactant used in the aqueous fluorescent fragrance deodorant composition of the present invention is not particularly limited, but is 0.01 to 10% in order to fully develop the effects of each component. Is preferable, and it is more preferable that it is 0.1 to 3%.

    The aqueous fluorescent aroma deodorant composition of the present invention further comprises at least one selected from the group consisting of L-tartaric acid, maleic acid, succinic acid, malic acid, citric acid and lactic acid for the purpose of liquid stability. It is preferable to add an organic acid.

  The amount of the organic acid used in the aqueous fluorescent fragrance deodorant composition of the present invention is not particularly limited, but is preferably 0.0001 to 5% from the viewpoint of stability and economy. More preferably, the content is 0.001 to 1%.

  The aqueous fluorescent fragrance deodorant composition of the present invention preferably further includes at least one component selected from deodorants and repellents depending on the purpose of use, and there is no particular limitation on this component. Any of those conventionally used in aroma deodorant compositions can be used.

  Specific examples of the deodorant include, for example, active deodorants extracted from each part of plants such as leaves, petiole, berries, stems, roots and bark, lactic acid, gluconic acid, succinic acid, glutamic acid, adipine Acids, malic acid, tartaric acid, maleic acid, fumaric acid, itaconic acid, citric acid, benzoic acid, salicylic acid and other organic acids, various amino acids and their salts, glyoxal, oxidizing agents, flavonoids, catechins, polyphenols, alkyl groups Examples thereof include amphoteric surfactants such as alkyldimethylaminoacetic acid betaine having 8 to 20 carbon atoms, alkylimidazolinium betaine, and fatty acid amidopropyl betaine having 8 to 20 carbon atoms in the fatty acid residue.

  The types of plants for obtaining the above-mentioned deodorant active ingredients extracted from plants include, for example, Abies, Organum, Geranium, Sweet Orange, Bitter Almond, Peppermint, Lavender, Eucalyptus, Rosemary, Lemon, Oxalis, and Dokudami , Tsuga, ginkgo, black pine, larch, red pine, giraffe, holly mushroom, lilac, guinea pig, buffalo, azalea, tea or forsythia are preferred. However, it is not necessary to be limited to these, and a variety other than the above-mentioned aceae family plant, asteraceae plant, pine family plant, camellia plant, or a plant cell culture system induced and cultured from these plants can be used widely. it can. Moreover, a plant may use only 1 type or may use 2 or more types together.

  The method for extracting the deodorant component from the plant is not particularly limited. For example, water or an alcohol such as ethanol or methanol, or a ketone such as methyl ethyl ketone or acetone is used as an extraction solvent for the raw material plant. And a method of thermally extracting a deodorizing active ingredient using a Soxhlet extractor or the like, and the extraction solvent may be a mixed solvent of water and the hydrophilic organic solvent or the like. You may use together. The obtained extract is used, for example, as it is, or diluted with an appropriate solvent, concentrated, concentrated to dryness, or the like. Only 1 type may be used for a deodorizing active ingredient and the said extract, or 2 or more types may be mixed and used for it. The extraction operation is not limited to one-stage extraction, and if necessary, a hydrophobic organic solvent such as petroleum ether, hexane, ethyl acetate or the like is used to remove aroma components such as blue odor containing the raw material plant. Elution and removal may be performed in advance. This aroma component can be removed by a steam distillation method, and the deodorizing active ingredient extracted from a plant is generally non-volatile.

  Deodorants can be used alone or in admixture of two or more.

Specific examples of the repellent include, for example, N, N-diethyl-m-toluamide (diet), dimethyl phthalate, dibutyl phthalate, p-menthane-3,8-diol, 2-ethyl-1,3-hexanediol, Di-n-propylisocincomeronate, p-dichlorobenzene, di-n-butyl succinate, caran-3,4-diol, 1-methylpropyl-2- (2-hydroxyethyl) -1-piperidinecarboxylate And allyl isothiocyanate. Further, when natural allyl isothiocyanate is used, plants extracted from mustard ( Brassica juncea Czern. Et Coss ), black mustard ( Brassica nigra Koch. ), Wasabi ( Wasabia japonica Matsum. ), Etc. may be used. Moreover, a wood vinegar liquid etc. are illustrated as a repellent, and these can be used individually or in mixture of 2 or more types.

  The blending amount of at least one component selected from these deodorants and repellents is 0. 0% of the entire aqueous fluorescent aroma deodorant composition so that the effect of each component is fully expressed. It is preferably 1 to 15%, more preferably 1 to 10%.

  Water is used as the medium of the aqueous fluorescent fragrance deodorant composition of the present invention. For example, alcohols such as methanol, ethanol, propanol, isopropanol, and butanol are used as necessary to prevent freezing in severe cold; Polyhydric alcohols such as ethylene glycol, propylene glycol, 1,3-butanediol, hexylene glycol, and glycerin; glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and the like monomethyl ether and monoethyl ether Ethers and the like can be appropriately added to the aqueous fluorescent aroma deodorant composition of the present invention.

  On the other hand, it can be used as an aqueous gel fluorescent aroma deodorant composition by adding a gelling agent to the aqueous fluorescent aroma deodorant composition of the present invention.

  Examples of gelling agents that can be used in the present invention include carboxymethylcellulose polyvalent metal salt, carrageenan, agar, gellan gum, pullulan, curdlan, xanthan gum, pectin, konjac glucomannan, xyloglucan, guar gum, gum arabic, locust bean gum gelatin 1 or more types of gelling agents chosen from these can be mentioned.

  The carboxymethyl cellulose polyvalent metal salt is obtained by gelling carboxymethyl cellulose (hereinafter referred to as CMC), CMC sodium or CMC potassium (hereinafter collectively referred to as CMCs) with a polyvalent metal ion.

  As CMCs, 1% aqueous solution viscosity {anhydrous equivalent concentration, measured with a B-type viscometer at 25 ° C (rotation speed: 60 rpm) from the viewpoint of obtaining shape stability and gel strength required for aqueous gel products )} Is 5 mPa · s or more, preferably 50 mPa · s or more, and from the viewpoint of the handling properties of the aqueous solution of CMCs in the aqueous gel preparation stage, the 1% aqueous solution viscosity is 10000 mPa · s or less. It is desirable that it is 5000 mPa · s or less.

  In addition, as CMCs, it is desirable that the average degree of substitution of carboxymethyl group is 0.4 or more, preferably 0.5 or more in view of good solubility in water. When gelled with metal ions, intramolecular cross-linking proceeds preferentially due to the presence of a large amount of carboxymethyl groups in the molecule, and the resulting gel has a high cross-linking density and a stable aqueous gel is obtained. In order to eliminate the possibility of being lost, it is desirable that the average substitution degree of the carboxymethyl group is 2 or less, preferably 1.8 or less. The CMC may be used in combination of two or more.

  When the CMCs are gelled with polyvalent metal ions, an aqueous polyvalent metal salt solution can be used, and the polyvalent metal salt aqueous solution is selected from, for example, an aluminum salt, an iron salt, a calcium salt, and a barium salt. And an aqueous solution of at least one metal salt.

  Representative examples of aluminum salts include potassium alum, baked alum, aluminum acetate, aluminum sulfate, aluminum hydroxide, aluminum hydroxide gel, aluminum chloride, aluminum lactate, sodium aluminate, potassium aluminate, etc. As ferric chloride, ferrous sulfate, and the like, calcium hydroxide and the like as typical examples of calcium salts, and barium chloride and the like as typical examples of barium salts, respectively.

  Among the above polyvalent metal salts, aluminum salts are preferable from the viewpoint of coloring and economical efficiency peculiar to metal salts, that is, among CMC polyvalent metal salts, CMC aluminum salts are preferable.

  By adding an aqueous polyvalent metal salt solution to an aqueous solution of CMCs, a CMC polyvalent metal salt in which the CMCs are gelled with polyvalent metal ions can be obtained. In this case, this is added as an aqueous dispersion to an aqueous solution of CMCs, and the pH in the system is appropriately adjusted with an acidic substance or a basic substance to control the elution of polyvalent metal ions. A gelled CMC polyvalent metal salt can be obtained. The concentration of the polyvalent metal salt aqueous solution or the polyvalent metal salt water dispersion is not particularly limited, and may be adjusted as appropriate.

  When a CMC polyvalent metal salt is used as a gelling agent, the CMC content in the aqueous gel fluorescent aroma deodorant composition of the present invention varies depending on the viscosity of a 1% aqueous solution of CMC used, but sufficient gel strength is obtained. In addition, it is desirable that the amount in terms of anhydride is 1.5% or more, preferably 2% or more, the viscosity of the system before gelation becomes extremely high, and filling into a container at the time of commercialization is not difficult In order to do so, it is desirable that the amount in terms of anhydride is 5% or less, preferably 4% or less.

  The amount of the polyvalent metal salt in the aqueous gel fluorescent aroma deodorant composition varies depending on the type of polyvalent metal salt and the amount of CMC, but in order to obtain suitable gel strength, the aqueous gel composition It is desirable that 0.3% or more, preferably 0.5% or more, and 4% or less, preferably 3% or less of the product is composed of a polyvalent metal salt.

Carrageenan is a kind of galactan extracted from seaweeds ( Chondrus Crispus , GigartinaStellata , Chondrus Ocellatas, etc.) belonging to the family of red seaweeds, two kinds of galactose (1-3 linked β-D-galactose and 1- 4-linked 3,6-anhydro-α-D-galactose) is an acidic polysaccharide having a sulfate group. Carrageenan has the formula: depending on the position of the sulfate group and the presence or absence of 3,6-anhydro-α-D-galactose.

で表わされる繰り返し単位を有するκ−カラギーナン、式：

Κ-carrageenan having a repeating unit represented by the formula:

で表わされる繰り返し単位を有するι−カラギーナン及び式

Ι-carrageenan having the repeating unit represented by the formula

で表わされる繰り返し単位を有するλ−カラギーナンの３種に分類される。

Are classified into three types of λ-carrageenan having a repeating unit represented by:

  Since 3,6-anhydrogalactose is involved in the carrageenan gel formation, κ-carrageenan and ι-carrageenan having anhydrogalactose can be used as a gelling agent in the present invention. Among κ-carrageenan and ι-carrageenan, κ-carrageenan having a lower sulfuric acid content has higher gel-forming ability than ι-carrageenan, and λ-carrageenan may be used as an agent for improving gel properties.

  It can be easily hydrated by mixing carrageenan with water and heating, and when it is allowed to cool, it forms a gel, but by adding cations such as calcium ions and potassium ions, a stronger gel can be added. Can be formed.

  When carrageenan is used as a gelling agent, the amount of carrageenan in the aqueous gel fluorescent aroma deodorant composition of the present invention is 0.5% or more, preferably 1% or more in order to obtain sufficient gel strength. In order to prevent gelation from becoming difficult, it is desirable to be 5% or less, preferably 3% or less.

Agar, red algae Gelidium family (Gelidiaceae), contained in Gracilaria family (Gracilariaceae), Igisu family (Ceramiaceae), Norika (Gracilaria), Obakusa family (Pterocladia), rerun family (Ahnfeltia) cell membrane of various seaweed such as It is what is done. Agar has a shape such as amorphous, translucent powder, flake, fragment, rod, string, and the like, and is water-insoluble but water-swellable. Agar is easily dissolved in hot water and can be sufficiently gelled even at a low concentration of about 0.5%.

  When agar is used as a gelling agent, the amount of agar in the aqueous gel fluorescent aroma deodorant composition of the present invention is 0.2% or more, preferably 0.5% or more in order to obtain sufficient gel strength. In order not to make gelation difficult, it is desirably 5% or less, preferably 3% or less.

  Gellan gum has the formula:

で表わされる繰り返し単位を有する高分子多糖類である。

It is a polymeric polysaccharide which has a repeating unit represented by these.

  An aqueous dispersion of gellan gum can be heated to, for example, 90 ° C. or more to form an aqueous solution. However, since gel strength does not easily increase even when only this aqueous solution is cooled, for example, soluble salts and acids are preferably added to the gellan gum aqueous solution as a gel reinforcing agent in order to sufficiently gel the gellan gum.

  When gellan gum is used as a gelling agent, the amount of gellan gum in the aqueous gel fluorescent aroma deodorant composition of the present invention is 0.5% or more, preferably 1% or more in order to obtain sufficient gel strength. In order to prevent gelation from becoming difficult, it is desirable that the content be 10% or less, preferably 8% or less.

  Pullulan is a natural polysaccharide obtained by culturing Aureobasidium pullulans, which is a kind of black yeast, using starch as a raw material, and maltotriose is regularly α-1,6-linked.

  When pullulan is used as a gelling agent, the amount of pullulan in the aqueous gel fluorescent aroma deodorant composition of the present invention is 0.5% or more, preferably 1% or more in order to obtain sufficient gel strength. In order to prevent gelation from becoming difficult, it is desirable that the content be 10% or less, preferably 8% or less.

  Curdlan is a water-insoluble β-glucan composed of β-1,3-glucoside bonds, and has a property of forming a hard, elastic and heat irreversible gel when the suspension is heated.

  When curdlan is used as a gelling agent, the amount of curdlan in the aqueous gel fluorescent aroma deodorant composition of the present invention is 0.5% or more, preferably 1% or more in order to obtain sufficient gel strength. In order not to make gelation difficult, it is desirable to be 10% or less, preferably 8% or less.

Xanthan gum is a polysaccharide consisting of sodium, potassium and calcium salts of D-glucose, D-mannose and D-glucuronic acid obtained by separation from a culture solution of gram-negative bacteria ( Xanthomonas campestris ) using corn syrup as a substrate. The main chain is composed of D-glucose bonded to β-1,4, and D-mannose bonded to the main chain is acetylated. The side chain is in a form in which D-mannose 2 component and D-glucuronic acid are bonded to every other main chain, and the terminal D-mannose is in the form of pyruvate. The xanthan gum becomes a neutral solution when dissolved in water and hot water, and the locust bean gum forms a thermoreversible gel.

  When xanthan gum is used as a gelling agent, the amount of xanthan gum in the aqueous gel fluorescent aroma deodorant composition of the present invention is 0.5% or more, preferably 1% or more in order to obtain sufficient gel strength. In order to prevent gelation from becoming difficult, it is desirable that the content be 10% or less, preferably 8% or less.

  Pectin is a kind of polysaccharide contained between cells of plants and fruits, and is classified into two types according to the difference in chemical structure. High methoxyl (HM) pectin has a high amount of methoxyl groups. Those are called low methoxyl (LM) pectin, each with different properties. All natural pectin contained in fruits is HM pectin. LM pectin is artificially produced in the process of purifying powdered pectin from fruit.

  When pectin is used as a gelling agent, the amount of pectin in the aqueous gel fluorescent aroma deodorant composition of the present invention is 0.5% or more, preferably 1% or more in order to obtain sufficient gel strength. In order to prevent gelation from becoming difficult, it is desirable that the content be 10% or less, preferably 8% or less.

  Konjac glucomannan is a β-D1,4-linked glucomannan, the ratio of mannose to glucose is about 1.6 to 1, and one of about 19 sugar units is acetylated. It is.

When konjac glucomannan is used as a gelling agent, the amount of konjac glucomannan in the aqueous gel fluorescent aroma deodorant composition of the present invention is 0.5% or more, preferably 1 in order to obtain sufficient gel strength. % Or more, and in order not to make gelation difficult, it is 10% or less, preferably 8% or less.
Xyloglucan is the main component of the seeds of the leguminous plant Tamarindus indica (Tamarindus indica) mainly produced in the tropics, and the main chain consisting of β-1,4-glucan has xylos and galacto as side chains. It is a polysaccharide with a molecular weight of about 650,000, which has a structure in which a sugar is bound.

  When xyloglucan is used as a gelling agent, the amount of xyloglucan in the aqueous gel fluorescent aroma deodorant composition of the present invention is 0.5% or more, preferably 1% or more in order to obtain sufficient gel strength. In order not to make gelation difficult, it is desirable to be 10% or less, preferably 8% or less.

  Guar gum, also known as girl gum, is made from a mucus substance contained in the embryo part of the seed of the guar plant guar. Molecular weight: about 20,000, 80% composition is galactose and mannose, protein 5%, fiber 1%, ash 1%, galactose: mannose = 1: 2. Guar gum is dispersed in cold water to form a dispersion, but when heated, it completely dissolves and becomes a highly viscous solution.

  When guar gum is used as the gelling agent, the amount of guar gum in the aqueous gel fluorescent fragrance deodorant composition is desirably 0.5% or more, preferably 1% or more in order to obtain sufficient gel strength. In order not to make gelation difficult, it is desirable that the content be 10% or less, preferably 8% or less.

  Gum arabic is a gum obtained by drying a secretion obtained from the branch trunk of the African legume Acacia senegal or its genus. It is a polymer having a molecular weight of 24 to 580,000 mainly composed of arabinose, galactose, rhamnose, glucuronic acid and the like, and is commercially available as a colorless or pale yellow spherical mass, flake or powder.

  When gum arabic is used as a gelling agent, the amount of gum arabic in the aqueous gel fluorescent fragrance deodorant composition is 0.5% or more, preferably 1% or more in order to obtain sufficient gel strength. In order to prevent gelation from becoming difficult, it is desirable that the content be 10% or less, preferably 8% or less.

  Locust bean gum is a polysaccharide mainly composed of galactomannan, and the ratio of galactose and mannose is about 1: 4. Its structure is similar to guar gum, but the proportion of galactose and mannose is different from guar gum. This locust bean gum is dispersed in cold water to form a dispersion, but when heated, it is completely dissolved to form a high viscosity solution.

  When roast bean gum is used as the gelling agent, the amount of roast bean gum in the aqueous gel fluorescent aroma deodorant composition is 0.5% or more, preferably 1% or more in order to obtain sufficient gel strength. It is desirable that the amount be 10% or less, preferably 8% or less, so that gelation does not become difficult.

  Gelatin is obtained by partially hydrolyzing collagen, which is a protein constituting the connective tissue of animals, and industrially, cow bone, cow skin, and pig skin are used as raw materials. Gelatin swells without dissolving in cold water and dissolves in hot water or hot water to form a strong gel, but when the aqueous solution is boiled for a long time, gelatin undergoes low molecular weight due to hydrolysis, resulting in gel strength Will fall. Gelatin extraction is performed by immersing a raw material pretreated with acid or alkali in warm water.

  The chemical structure of gelatin is a long polypeptide in which 18 kinds of amino acids are peptide-bonded. The sol-gel change of gelatin gel is thermoreversible, and generally the melting point of a 10% gelatin solution is about 20-30 ° C.

  Such gelatin solutions are not suitable for gel compositions used in aqueous gel products. Therefore, a method can be employed in which insolubilization is performed by cross-linking reaction between gelatin molecules to maintain the high temperature stability of the gel. Examples of the crosslinking agent (curing agent) in this case include salts such as chrome, aluminum, and ferric iron, aldehydes, ketones, and quinones.

  When gelatin is used as a gelling agent, the amount of gelatin in the aqueous gel fluorescent aroma deodorant composition is desirably 0.5% or more, preferably 1% or more in order to obtain sufficient gel strength. In order not to make gelation difficult, it is desirable that the content be 10% or less, preferably 8% or less.

  The said gelling agent can be used individually or in mixture of 2 or more types as appropriate.

  Furthermore, the aqueous fluorescent aroma deodorant composition of the present invention is a solid, semi-solid, or liquid oil agent that is used for a normal aroma deodorant as long as it does not interfere with the effects of the present invention. Antibacterial agents, bactericides, antifungal agents, antiseptics, colorants, antioxidants, ultraviolet absorbers, chelating agents, and the like can be blended.

  The method for producing the aqueous fluorescent aroma deodorant composition of the present invention is not particularly limited. For example, an amine oxide amphoteric surfactant, a fragrance, and a phosphorescent pigment are added to water, mixed, and stirred. That's fine.

  Also, the production method of the aqueous gel fluorescent aroma deodorant composition is not particularly limited. For example, an amine oxide type amphoteric surfactant fragrance and a phosphorescent pigment are added to a gelling agent, mixed and stirred. do it. The timing of addition of the amine oxide type amphoteric surfactant is not particularly limited as long as it is before the gelling agent gels, and this aqueous gel fluorescent aroma deodorant composition is placed in a desired molding container. And the molding container can be cooled to obtain an aqueous gel fluorescent aroma deodorant product.

  In addition, although the temperature in the manufacturing process of the aqueous gel fluorescent aroma deodorant composition varies depending on the gelation mechanism of the gelling agent used, for example, when the gelling agent is the CMC polyvalent metal salt, In order to control the progress of the gelation, the temperature in the production process is preferably adjusted to a range of, for example, 5 to 60 ° C. in order to control the progress of gelation. When the temperature of this system is 60 ° C. or higher, for example, the loss of active ingredients due to the volatilization of low-volatile organic substances is caused, which is not preferable. In addition, when using the above-mentioned color ginnan, agar, gellan gum, pullulan, curdlan, xanthan gum, pectin, konjac glucomannan, xyloglucan, guar gum, gum arabic, locust bean gum and gelatin as gelling agents, It is preferable that after mixing the agent with water, the gelling agent is dissolved at 60 ° C. or higher and cooled to be gelled.

  The aqueous fluorescent fragrance deodorant composition of the present invention can be used as an indoor and in-car fragrance deodorant.

  Hereinafter, the present invention will be specifically described with reference to examples and comparative examples. However, the present invention is not limited to these examples, and may be changed without departing from the scope of the present invention. .

  In addition, unless otherwise indicated, the unit of the prescription described below means% by mass. Moreover, the fragrance | flavor used by the following Example and comparative example was prepared by the following prescription.

[Examples 1 to 5]
Aqueous fluorescent fragrance deodorant compositions shown in Table 2 were prepared, and their fluorescence intensity, stability over time and retention were evaluated.
[Comparative Examples 1 to 3]
The aqueous fluorescent fragrance deodorant composition shown in Table 2 was prepared without using an amine oxide type amphoteric surfactant, and its fluorescence intensity, stability over time and retention were evaluated.

  In Examples 1 to 5 and Comparative Examples 1 to 3, low illuminance type N night light (GLL-300, trade name) manufactured by Nemoto Special Chemical Co., Ltd. was used as a phosphorescent pigment.

[Example 6]
Aqueous fluorescent fragrance deodorant compositions shown in Table 3 were prepared, and their fluorescence intensity, stability over time and retention were evaluated. That is, carrageenan was dispersed in water and propylene glycol, heated to 90 ° C. with stirring, and completely dissolved, and a mixed solution of a fragrance, a surfactant, ethanol and an ultraviolet absorber was added thereto to obtain a uniform solution. After citric acid, preservative and phosphorescent pigment were added and stirred uniformly, the container was filled and allowed to cool to room temperature.

  Thus, the gel air freshener of Example 6 was stable and maintained fluorescence even after being left at 50 ° C. for 1 month and at room temperature for 6 months.

[Example 7]
Aqueous fluorescent fragrance deodorant compositions shown in Table 4 were prepared, and their fluorescence intensity, stability over time and retention were evaluated. That is, gelatin and a preservative were added to water and heated to 60 to 70 ° C. to completely dissolve, and a mixed solution of a fragrance, a surfactant and citric acid was added thereto to obtain a uniform solution. The phosphorescent pigment and isobutylene / maleic anhydride copolymer were added and stirred uniformly, and then filled into a container.

  Thus, the gel air freshener of Example 7 was stable and maintained fluorescence even after being allowed to stand at room temperature for 1 month.

[Example 8]
Aqueous fluorescent fragrance deodorant compositions shown in Table 5 were prepared and their fluorescence intensity, stability over time and retention were evaluated. That is, gellan gum was added to water, heated to 90 ° C. and completely dissolved, and a mixed solution of deodorant and amphoteric surfactant was added thereto to make the solution uniform. Preservatives, calcium chloride, citric acid, fragrance, p-menthane-3,8-diol (repellent) and phosphorescent pigment were added and stirred uniformly, and then filled into a container.

  Thus, the gel air freshener of Example 8 was stable and maintained fluorescence even after being left at room temperature for 1 month.

  The aqueous fluorescent aroma deodorant composition of the present invention has a fluorescence emission effect and aroma deodorizing action for a long period in an aqueous system, and is excellent in stability and aroma deodorizing action.

Claims (6)

The following general formula (1)
MAl ₂ O ₄ (1)
(In the formula, M is at least one metal element selected from the group consisting of calcium, strontium, and barium.)
A water-based fluorescent aroma deodorant composition comprising: a phosphorescent pigment represented by formula (1); an amine oxide amphoteric surfactant; and a fragrance. The amine oxide type amphoteric surfactant has the general formula (2):

(Wherein R ¹ represents an alkyl group having 8 to 22 carbon atoms or an alkenyl group having 8 to 22 carbon atoms), an amine oxide type amphoteric surfactant (2) represented by the general formula (3):

(In the formula, R ² represents an alkyl group having 8 to 22 carbon atoms or an alkenyl group having 8 to 22 carbon atoms, l and m represent an average number of added moles of ethylene oxide, and l + m is an integer of 1 to 10.) Amine oxide type amphoteric surfactant (3) represented by general formula (4):

(Wherein R ³ represents an alkyl group having 8 to 22 carbon atoms or an alkenyl group having 8 to 22 carbon atoms, n represents an average added mole number of ethylene oxide, and n is an integer of 1 to 10). Amine oxide amphoteric surfactant (4) and general formula (5):

(Wherein R ⁴ represents an alkyl group having 8 to 22 carbon atoms or an alkenyl group having 8 to 22 carbon atoms) at least one amine oxide type selected from amine oxide type amphoteric surfactants (5) The aqueous fluorescent aroma deodorant composition according to claim 1, which is an amphoteric surfactant. One or more surfactants selected from anionic surfactants, nonionic surfactants and amphoteric surfactants other than the amine oxide type amphoteric surfactants represented by the general formulas (2) to (4) The aqueous fluorescent aroma deodorant composition according to claim 1 or 2, further comprising: The aqueous fluorescent aroma deodorant according to any one of claims 1 to 3, further comprising one or more organic acids selected from the group consisting of L-tartaric acid, maleic acid, succinic acid, malic acid, citric acid and lactic acid. Agent composition. The aqueous fluorescent fragrance deodorant composition according to any one of claims 1 to 4, further comprising at least one component selected from a deodorant and a repellent. The aqueous fluorescent fragrance deodorant composition according to any one of claims 1 to 5, comprising carboxymethylcellulose polyvalent metal salt, carrageenan, agar, gellan gum, pullulan, curdlan, xanthan gum, pectin, konjac glucomannan, xyloglucan, An aqueous gel fluorescent aroma deodorant composition comprising one or more gelling agents selected from guar gum, gum arabic, locust bean gum and gelatin.