JP7305335B2 - Accumulator spray composition and spray formulation using the same - Google Patents

Description

The present invention relates to an accumulator spray composition for use in pump sprays, trigger sprays, and the like, and more particularly, to a pressure accumulator spray composition that does not cause problems with volatile organic compound regulations and provides a good spray condition. It relates to a product and a spray formulation using the same.

BACKGROUND ART Various spray-type air fresheners have been proposed in which perfumes and deodorant components are sprayed in order to impart fragrance to the air and deodorize bad odors. Further, in order to kill and repel indoor pests and the like, insect repellent components and spray-type insect repellents in which insecticidal components are sprayed have been proposed. In such a spray type preparation, various solvents, active agents, etc. are also blended in order to appropriately dissolve and suspend the active ingredient and obtain a favorable spray state.

By the way, in such a spray-type formulation, in addition to exhibiting the function as a formulation, the ingredients used include volatile organic compounds (hereinafter sometimes abbreviated as "VOC"). It is important to comply with product regulations. By VOC compounds is meant organic compounds with boiling points up to about 260° C. at standard pressure.

Regarding this VOC, there are regulations in various countries. Prohibits the sale, supply, offer for sale, or manufacture of consumer products that contain VOCs above specified limits when manufactured.

Therefore, several products have been proposed to comply with such VOC regulations. For example, Patent Document 1 discloses (a) a predetermined amount of alkylene glycol, (b) a predetermined amount of a surfactant containing at least a specific HLB, and (c) a predetermined amount of a compressed gas having a specific pressure. (d) an amount of a buffer system; (e) an amount of fragrance; First, an aqueous aerosol odor treatment composition wherein the fragrance is solubilized by (i) a surfactant, (ii) an alkylene glycol, or (iii) both, and the pH of the composition is from about 4 to about 8 disclosed.

Also, in Patent Document 2, a solvating active agent comprising a specified amount of a surfactant, a specified amount of an active agent, a specified amount of a compressed gas propellant and an aqueous carrier is added by a compressed gas contained therein. Disclosed are pressed water-based compositions having a weight ratio of surfactant to active agent of about 1:3 to 5:1 based on the total weight of the composition.

However, these are all compositions for spraying using liquefied gas such as LP gas and DME, and when this composition is applied to pump spraying without using gas, the particles of the sprayed composition become large. There is a problem of storage.

In addition, spraying using liquefied gas requires a complicated container structure, and even if a composition that complies with regulations on volatile organic compounds is created, the gas itself is released into the space. However, it also has the problem of being unfavorable for the usage environment.

Japanese Patent Publication No. 2013-529971 Japanese Patent Publication No. 2011-522953

The present invention has been made in view of the above circumstances. An object of the present invention is to provide a spray composition capable of stably spraying volatile active ingredients such as insect repellent ingredients and insecticidal ingredients into the air.

As a result of intensive research on a spray composition that does not cause the above problems, the present inventors have found that a It was found that the above-mentioned problems of spray compositions can be solved by spraying the composition with an accumulator spray container, and the present invention has been completed.

（式中、Ｒ^１及びＲ^５は低級アルキル基を、Ｒ^２は低級アルキル基又は水素原子
を、Ｒ^３はヒドロキシ基又は水素原子を、Ｒ^４は低級アルキル基または低級ヒ
ドロキシアルキル基を示す）
で表されるグリコールエーテル ５質量％～１６.５質量％
（Ｂ）一般式（II）

（式中、Ｌ^１及びＬ^２は同一または異なって、エチレン基又は分岐しても良い
プロピレン基、ブチレン基を示し、ｎは、１～４の数を意味する）
で表されるポリグリコール ４４質量％～５５質量％
（Ｃ）揮発性活性成分 ５質量％～１０質量％
（Ｄ）界面活性剤 ０.５質量％～１質量％
および
（Ｅ）水 １７.５質量％～３０質量％
を含有してなる蓄圧式スプレー用組成物を提供するものである。 That is, the present invention provides the following components, (A) to (D)
(A) general formula (I)

(Wherein, R ¹ and R ⁵ are lower alkyl groups, R ² is lower alkyl groups or hydrogen atoms, R ³ is hydroxy groups or hydrogen atoms, and R ⁴ is lower alkyl groups or lower hydroxyalkyl groups. show)
Glycol ether represented by 5% by mass to 16.5% by mass
(B) general formula (II)

(In the formula, L ¹ and L ² are the same or different and represent an ethylene group or an optionally branched propylene group or butylene group, and n is a number of 1 to 4.)
Polyglycol represented by 44% by mass to 55% by mass
(C) Volatile active ingredient 5% to 10% by mass
(D) Surfactant 0.5% by mass to 1% by mass
and (E) water 17.5% by mass to 30% by mass
To provide a composition for pressure accumulation type spray containing

The present invention also provides a spray formulation obtained by filling a pressure accumulation type spray container with the pressure accumulation type spray composition.

The pressure accumulating spray composition of the present invention can stably spray volatile active ingredients such as fragrances and insecticidal ingredients into the air even with an accumulator spray that does not use liquefied gas while complying with VOC regulations. .

According to a spray formulation in which the above composition is filled in an accumulator spray container, the volatile active ingredient can be appropriately sprayed into the air or environment economically without using liquefied gas.

In the present invention, accumulator spray means spraying without using a propellant (liquefied gas), such as pump spray, trigger spray, or compressed air spray. means a composition that is

The pressure accumulation type spray composition of the present invention (hereinafter sometimes simply referred to as "the composition of the present invention") contains the components (A) to (D).

（式中、Ｒ^１及びＲ^５は低級アルキル基を、Ｒ^２は低級アルキル基又は水素原子
を、Ｒ^３はヒドロキシ基又は水素原子を、Ｒ^４は低級アルキル基または低級ヒ
ドロキシアルキル基を示す） Among these, component (A) is a glycol ether represented by the following formula (I).

(Wherein, R ¹ and R ⁵ are lower alkyl groups, R ² is lower alkyl groups or hydrogen atoms, R ³ is hydroxy groups or hydrogen atoms, and R ⁴ is lower alkyl groups or lower hydroxyalkyl groups. show)

In each group of formula (I) above, the lower alkyl group refers to an alkyl group having 1 to 5 carbon atoms, and the lower hydroxyalkyl group refers to a hydroxy group having 1 to 5 carbon atoms and at least 1 or more. hydroxyalkyl group.

Specific examples of this glycol ether (I) include 3-methoxy-1-butanol, 1-methoxy-2-butanol, 1-methoxy-2-propanol, 3-methoxy-3-methyl-1-butanol, 3 -Methoxy-3-methyl-butyl acetate and the like. Among these, 3-methoxy-3-methyl-1-butanol is preferably used from the viewpoint of enhancing the dispersibility of oily volatile active ingredients.

（式中、Ｌ^１及びＬ^２は同一または異なって、エチレン基又は分岐しても良い
プロピレン基、ブチレン基を示し、ｎは、１～４の数を意味する） Component (B) blended in the composition of the present invention is a polyglycol represented by the following formula (II).

(In the formula, L ¹ and L ² are the same or different and represent an ethylene group or an optionally branched propylene group or butylene group, and n is a number of 1 to 4.)

Specific examples of this polyglycol (II) include diethylene glycol, dipropylene glycol, dibutylene glycol, triethylene glycol, tripropylene glycol, and tetraethylene glycol. Among these, dipropylene glycol is preferably used in terms of compatibility with the glycol ether (component (A)) and the volatile active component (component (C)) described later.

Further, the component (C) volatile active ingredient used in the composition of the present invention is an agent that is volatile at room temperature and exerts a predetermined effect in environmental space. Examples include insect repellent ingredients, insecticidal ingredients, antifungal ingredients, and pest repellent ingredients. These may be used alone or in combination of two or more depending on the field of application and required performance of the composition of the present invention.

Among these, the deodorizing ingredients include AiryDeo (registered trademark) Fragrance (manufactured by Takasago International Corporation) and stabilized chlorine dioxide. etc.

Examples of fragrances include, for example, animal fragrances such as musk, spirit cat scent, and dragon scent, abies oil, acujon oil, almond oil, angelica root oil, pager oil, bergamot oil, perch oil, boa burrose oil, and kayabuchi oil. , gananga oil, capsicum oil, caraway oil, cardamom oil, cassia oil, celery oil, cinnamon oil, citronella oil, cognac oil, coriander oil, cumin oil, camphor oil, dill oil, estogoran oil, eucalyptus oil, fennel oil, Vegetable fragrances such as garlic oil, ginger oil, grapefruit oil, hop oil, lemon oil, lemongrass oil, nutmeg oil, mandarin oil, peppermint oil, orange oil, sage oil, star anise oil, turpentine oil and the like can be mentioned. .

In addition to these natural fragrances, artificial fragrances such as synthetic fragrances or extracted fragrances can also be used. Examples include hydrocarbon fragrances such as pinene and limonene, linalool, geraniol, citronellol, menthol, borneol, benzyl alcohol, Alcohol fragrances such as anis alcohol and β-phenethyl alcohol; phenol fragrances such as anethole and eugenol; aldehyde fragrances such as n-butyraldehyde, isobutyraldehyde, hexylaldehyde, citral, citronellal, benzaldehyde and cinnamic aldehyde; , ketone fragrances such as camphor, acetophenone and ionone; lactone fragrances such as γ-butyl lactone, coumarin and cineol; mentioned. Furthermore, a compounded perfume in which two or more of the above perfumes are mixed can also be used.

Examples of insect repellent and insecticidal components include pyrethroid insect repellent and insecticidal components such as empenthrin, transfluthrin, allethrin, phenothrin, eminence, and profluthrin, paradichlorobenzene, naphthalene, camphor, and 2-phenoxyethanol. A species or a mixture of two or more species can be used.

As the antibacterial and antifungal component, an organic compound is preferable because it hardly affects other essential components. Specifically, N-(fluorodichloromethylthio)-phthalimide, N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfamide, 2-isopropyl-5-methylphenol, parachlorometaxylenol, Balachlorometacresol, hinokitiol, cedarwood oil, allyl isothiocyanate, eugenol, vanillin, isoborneol, salicylaldehyde and the like are preferred, and one or more of these can be used in combination.

Examples of pest-repellent components include N,N-diethyl-m-toluamide (DEET) and picarigin, and these can be used alone or in combination.

Furthermore, a surfactant is used as component (D) of the composition of the present invention. Component (D) is not particularly limited as long as it can dissolve components (A) to (C) in water, but a nonionic surfactant having an HLB value of 10 or more is preferred. Nonionic surfactants having an HLB value of 10 or more can be used regardless of their types.

Specific examples of component (D) include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether, polyethylene glycol monolaurate, Polyethylene glycol fatty acid esters such as polyethylene glycol monostearate, polyethylene glycol monooleate, polyethylene glycol distearate, polyoxyethylene effect castor oil, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan Polyoxyethylene sorbitan fatty acid esters such as monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, and polyoxyethylene sorbitan trioleate.

Among these, it is relatively safe, dissolves in water and solvents to some extent, is easy to mix when mixing the composition of the present invention, and is a liquid at room temperature to improve mixing workability. In view of this, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyethylene glycol monolaurate, polyethylene glycol monooleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monopalmitate, and polyoxyethylene sorbitan monolaurate are preferred. Examples include stearate and polyoxyethylene sorbitan monooleate, and more preferred examples include polyoxyethylene lauryl ether, polyethylene glycol monolaurate, and polyoxyethylene sorbitan monolaurate.

Furthermore, although water is used as the component (E) of the composition of the present invention, there are no particular restrictions on this water, and tap water, deionized water, distilled water and the like can be used.

The composition of the present invention is prepared according to a conventional method by mixing the above components (A) to (D) with a solvent and optionally other optional components and homogenizing them to prepare a formulation.

The blending amounts of each component in the production of the composition of the present invention are as follows. That is, the blending amount of component (A) is 5 to 16.5% by mass (hereinafter abbreviated as "%"), preferably 10 to 15%, in the total composition. If the amount of component (A) is 16.5% or more, the composition is subject to VOC regulations, and if it is 5% or less, the component (C) may not dissolve well.

The amount of component (B) is 44-55%, preferably 49-54%, of the total composition. If it is 55% or more, the viscosity of the composition as a whole increases, which may make it difficult to mist the fragrance composition when it is sprayed from a spray container. On the other hand, if it is 45% or less, it becomes a composition subject to VOC regulations.

Furthermore, the amount of component (C) to be blended can be determined according to the degree of action and effect required for the volatile active ingredient to be blended. For example, when the volatile active ingredient to be blended is a deodorant or perfume, it is generally preferably 5 to 10%, more preferably 7 to 10%, of the total composition. Even if the amount of component (C) blended is 10%, no significant difference in the deodorizing effect is observed, and if the amount is less than 5%, it may be difficult to develop a sufficient deodorizing effect.

In addition, when the volatile active ingredient to be blended is an insect repellent ingredient or repellent ingredient, it is generally preferably 5 to 10%, more preferably 7 to 10%, of the entire composition. Even if the amount of component (C) is 10%, no significant difference in insect repellent or repellent effect is observed, and if it is less than 5%, sufficient insect repellent or repellent effect may not be obtained.

Furthermore, the blending amount of component (D) is about 0.1 to 10%, preferably 0.5 to 1%, in the total composition. If it is 10% or more, when sprayed using an accumulator pump spray or trigger spray, the liquid becomes large particles and scatters on the walls, floors, and other parts of the room, which may cause stickiness, which is the skin. It may feel uncomfortable if it adheres to the surface. In addition, problems such as clogging of nozzles of pressure accumulation type pump sprayers and the like may occur.

Furthermore, the content of component (E) water is 17.5 to 30%, preferably 20 to 30%, in the total composition.

In the preparation of the composition of the present invention, in addition to the essential components described above, a solvent and other optional components can be used, if necessary, to the extent that the effects of the present invention are not impaired.

Examples of such solvents include alcohols such as methanol, ethanol, isopropanol, isobutanol, sec-butanol, tert-butanol, methyl cellosolve, ethyl cellosolve, glycerin; ethylene glycol dimethyl ether, 1,4-dioxane, ethers such as tetrahydrofuran; ketones such as acetone and methyl ethyl ketone; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; These can be used alone or in combination of two or more.

Examples of other optional components include thickeners, pigments, ultraviolet absorbers, antioxidants, deodorizing components such as acids and alkalis, antifoaming agents, and emulsifiers.

The composition of the present invention obtained as described above can be used as a spray formulation by filling a pressure accumulation type spray container, for example, a pressure accumulation type pump spray, trigger spray, compressed air spray, or the like. It is particularly preferable to fill a pump spray container.

This spray formulation can be used as a household deodorant for kitchens and toilets, a deodorant and fragrance for rooms, a portable deodorant and fragrance, an insect repellent for kitchens and rooms, and a pest repellent for the skin. Available.

In a preferred embodiment of the spray formulation of the present invention, the volatile active ingredient of the filled pressure-accumulator spray composition is a deodorizing ingredient or a perfume, the spray container is a pump spray container, and the outer shape is A shape and size suitable for carrying, for example, a cylindrical shape with a length of about 5 to 7 cm and a diameter of about 1.5 to 2.0 cm can be mentioned. If it is this thing, it is possible to always carry it and use it in a restroom or other places on the go.

In the thus obtained spray formulation, the composition of the present invention itself, which is filled, conforms to VOC regulations, and furthermore, volatile active ingredients such as fragrances and insecticidal ingredients are stably dispersed in the air as a uniform fine mist. Being nebulizable, it is possible to economically disperse volatile active ingredients into the air or into the environment without using compressed gas.

Next, the present invention will be described in more detail with reference to examples and comparative examples. It should be noted that the present invention is by no means limited to these examples.

Example 1
Each component was mixed according to the formulation shown in Table 1 below to prepare a liquid fragrance composition. Each obtained fragrance composition was placed in a pump spray container having a volume of 10 ml to prepare fragrance preparations of the present invention and comparative products. Each aromatic formulation obtained was tested for suitability for VOC regulations, evaluation of ease of pump spraying, degree of deodorization, and stickiness after spraying. The results are shown in Table 2 below.

<Evaluation of ease of pushing the pump>
Eight consumer monitors were asked to spray 10 times a fragrance preparation (pump sprayer) containing each fragrance composition, and to evaluate ease of pushing the pump according to the following criteria. Of these results, the one with the largest number of responses was evaluated as the state.

( Evaluation criteria )
situation
The pump can be pushed without problems 〇 The pump is a little difficult to push △
The pump is very hard to press ×

<Response to VOC regulations>
Those containing VOCs exceeding the specified limit (18 wt% as a VOC substance) in the General Consumer Products Regulations (Section 2) (regulations) of the State of California, USA were marked with x, and those containing no VOCs were marked with ○.

<Deodorant test>
(Preparation of malodorous sample)
Ammonia and hydrogen sulfide were used as representative examples of foul odors generated in toilets. First, an ammonia and hydrogen sulfide generating source was placed in a 10-liter airbag with a cock, which was then sealed with a clip and allowed to stand for a certain period of time.

( Test method )
A 10 L Tedlar bag filled with odorless air filtered with activated carbon and silica gel was prepared. The foul odor prepared in the preparation of the above foul odor sample was extracted from this Tedlar bag using a glass odor collection syringe, and the odor intensity was about 4.00 in the following odor intensity, and about -3 in the pleasant/unpleasant degree. was injected so as to be

The fragrance formulations of the present invention and comparative products were sprayed once into this, and after leaving for 15 minutes, the odor in each Tedlar bag was evaluated by eight panelists according to the following criteria in terms of odor intensity and comfort/discomfort. evaluated. From this evaluation result, the results of the odor only case, the present invention product and the comparative product were quantified, the average value of the eight panelists was calculated, and the malodor only numerical value (blank) and the present invention product and the comparative product were calculated. When the difference score was 0 to 1 point in the positive direction, it was x, and when it was 1 to 2 points, the effect was judged.

( Evaluation criteria )
Odor intensity;
Degree of odor Score No odor 0 points Barely perceivable odor 1 point Weak odor that you can identify what it is 2 points Easily perceivable odor 3 points Strong odor 4 points Strong odor 5 points

pleasure/discomfort;
Condition Score Extremely comfortable 4 points Very comfortable 3 points Comfortable 2 points Slightly comfortable 1 point Neither 0 point Slightly uncomfortable -1 point Uncomfortable -2 points Very uncomfortable -3 points Extremely uncomfortable -4 points

<Stickiness after spraying>
Eight consumer monitors were given the fragrance preparations of the present invention and the comparative product, and had them spray 10 times at a height of 1 m from the floor surface in their home toilets. The stickiness of the floor surface 1 minute after spraying was evaluated according to the following criteria, and among the results, the one with the most answers was evaluated as the condition.

( Evaluation criteria )
Condition evaluation Floor is not wet 〇 Floor is wet △
The floor is sticky ×

From the above results, the present invention obtained good results in all evaluation items. On the other hand, Comparative Product 1 was not satisfactory in terms of ease of spraying, Comparative Products 2 and 3 in terms of compliance with VOC regulations, and Comparative Product 4 in terms of stickiness after spraying. rice field.

The pressure accumulator spray composition of the present invention conforms to VOC regulations, and uses an atomizer that does not use compressed gas to stabilize volatile active ingredients such as fragrances and insecticidal ingredients as a fine mist. It can be sprayed into the air.

Therefore, spray formulations filled with this spray composition are safe and economical and can be widely used in the field of toiletries such as fragrances, deodorants, insect repellents, insecticides and repellents.

Claims (9)

The following components, (A)-(D)
(A) general formula (I)

(wherein R1 and R5 represent a lower alkyl group, R2 represents a lower alkyl group or a hydrogen atom, R3 represents a hydroxy group or a hydrogen atom, and R4 represents a lower alkyl group or a lower hydroxyalkyl group)
Glycol ether represented by 5% by mass or more and less than 16.5% by mass
(B) general formula (II)

(Wherein, L1 and L2 are the same or different and represent an ethylene group, an optionally branched propylene group, or a butylene group, and n is a number from 1 to 4.)
Polyglycol represented by 4 more than 5 % by mass and 55% by mass or less
(C) Volatile active ingredient 5% to 10% by mass
(D) Surfactant 0.5% by mass to 1% by mass
and (E) water 17.5% by mass to 30% by mass
A pressure accumulating spray composition (excluding those containing gluconate). The glycol ether of component (A) is 3-methoxy-1-butanol, 1-methoxy-2-butanol, 1-methoxy-2-propanol, 3-methoxy-3-methylbutanol and 3-methoxy-3-methyl - The composition for pressure accumulation type spray according to claim 1, which is one or more of -butyl acetate. The pressure accumulation type according to claim 1 or 2, wherein the polyglycol of component (B) is one or more of diethylene glycol, dipropylene glycol, dibutylene glycol, triethylene glycol, tripropylene glycol and tetraethylene glycol. Composition for spraying. 4. The pressure accumulating spray composition according to any one of claims 1 to 3, wherein the volatile active ingredient of component (C) is a deodorizing ingredient, a fragrance, an insect repellent ingredient, an insecticidal ingredient, an antifungal ingredient, or an insect repellent ingredient. . 5. The pressure accumulation spray composition according to any one of claims 1 to 4, wherein the surfactant of component (D) is a nonionic surfactant. 6. The accumulator spray composition according to any one of claims 1 to 5, wherein the surfactant of component (D) is polyoxyethylene monolaurate. 7. A spray formulation obtained by filling a pressure accumulation type spray container with the pressure accumulation type spray composition according to any one of claims 1 to 6. 8. The spray formulation according to claim 7, wherein said pressure accumulation type spray container is a pump spray container or a trigger spray container. 9. The volatile active ingredient of the filled pressure-accumulator spray composition is a deodorizing ingredient or perfume, and the spray container is a pump spray container having a shape and size suitable for portability. Spray formulation as described.