JP6776047B2 - Aerosol composition - Google Patents

Description

The present invention relates to aerosol compositions. More specifically, the present invention relates to an aerosol composition that can be discharged in a string shape, has high safety against fire, and is less likely to cause clogging of injection holes.

Conventionally, an aerosol composition for obtaining a string-shaped discharge is known. Patent Document 1 states that in an aerosol aqueous composition comprising an acrylic ester resin, an aqueous solution having an alcohol content of 15 to 30% by weight, and an aerosol propellant, the liquefied gas serving as a true solvent as an aerosol propellant is 15 to 50% by weight. An aerosol aqueous composition containing 15 to 35% by weight of the resin component and 15 to 33% by weight of an aqueous solution using a propellant composed of 50 to 85% by weight of a liquefied gas which is a poor solvent is disclosed. When the aerosol aqueous composition is discharged, the acrylic ester-based resin is precipitated to form a string-like discharged product.

Japanese Unexamined Patent Publication No. 5-179234

Since the aerosol aqueous composition described in Patent Document 1 contains water, some consideration is given to safety against fire. However, such aerosol aqueous compositions may be used in large quantities, for example as party renditions, or by children. Therefore, it is necessary to give more consideration to fire safety. Further, in such an aerosol composition discharged in a string shape, the aerosol composition remaining in the injection hole, the injection passage, or the like is likely to be clogged.

The present invention has been made in view of such conventional problems, and provides an aerosol composition that can be discharged in a string shape, has higher safety against fire, and is less likely to be clogged in an injection hole, an injection passage, or the like. The purpose is.

The discharge product of the present invention that solves the above problems mainly includes the following configurations.

(1) An aerosol composition containing an acrylic ester resin, an ester oil, and a liquefied gas, wherein the liquefied gas is a hydrofluoroolefin in which the dissolved amount of the acrylic ester resin composition is 1% by mass or less. ..

According to such a configuration, the hydrofluoroolefin has a dissolution amount of 1% by mass or less of the acrylic ester resin, and it is difficult to dissolve the acrylic ester resin. However, the aerosol composition of the present invention can dissolve an acrylic ester resin by blending an ester oil together with a hydrofluoroolefin. When such an aerosol composition is discharged into a space, the hydrofluoroolefin is vaporized, so that the blending ratio in the aerosol composition changes. As a result, in the discharged aerosol composition, the acrylic ester-based resin is likely to precipitate, and a continuous string-shaped discharged product can be formed. Further, the aerosol composition is unlikely to remain in the injection hole of the injection member after discharge, and even if the discharge material remains in the injection hole, it can be easily removed and clogging is unlikely to occur. Further, the hydrofluoroolefin is a liquefied gas having low combustibility. Therefore, the obtained aerosol composition is more highly safe against fire even if the hydrofluoroolefin remains in the discharged product.

(2) The aerosol composition according to (1), wherein the acrylic ester-based resin is contained in an aerosol composition in an amount of 5 to 30% by mass.

According to such a configuration, when the obtained aerosol composition is discharged into a space, it is easy to obtain a continuous string-shaped discharge product which is hard to be torn off.

(3) The aerosol composition according to (1) or (2), wherein the ester oil is contained in an aerosol composition in an amount of 1 to 20% by mass.

According to such a configuration, the obtained aerosol composition has a high effect of dissolving the acrylic ester resin more stably and preventing clogging in the injection holes and injection passages of the injection member.

(4) The aerosol composition according to any one of (1) to (3), wherein the ester oil is an ester of a fatty acid and a divalent alcohol.

According to such a configuration, the compatibility between the hydrofluoroolefin and the acrylic ester-based resin is enhanced. Therefore, the obtained aerosol composition is likely to suppress the adhesiveness of the string-shaped discharged product and has good peelability. As a result, the aerosol composition is less likely to be clogged in the injection holes, injection passages, and the like of the injection member after use. Furthermore, the string-shaped discharge is highly safe against fire.

(5) The aerosol composition according to any one of (1) to (4), further comprising a polyhydric alcohol.

According to such a configuration, the compatibility between the hydrofluoroolefin and the acrylic ester-based resin is enhanced. As a result, the aerosol composition is less likely to be clogged with the discharged material in the injection holes, injection passages, and the like of the injection member after use. In addition, the string-shaped discharge tends to be soft. Further, the aerosol composition has an excellent effect of suppressing the adhesiveness of the string-shaped discharged product and has good peelability.

(6) The aerosol composition according to any one of (1) to (5), further comprising a surfactant.

According to such a configuration, the aerosol composition can easily adjust the thickness and flexibility of the string-like discharge. In addition, the aerosol composition tends to contain water and is highly safe against fire.

(7) The aerosol composition according to any one of (1) to (6), further comprising water.

According to such a configuration, the aerosol composition is extremely safe against fire and does not ignite even if the fire is brought into direct contact with the string-like discharge.

According to the present invention, it is possible to provide an aerosol composition that can be discharged in a string shape, has higher safety against fire, and is less likely to be clogged in an injection hole, an injection passage, or the like.

<Aerosol composition>
The aerosol composition of one embodiment of the present invention mainly contains an acrylic ester resin, an ester oil, and a liquefied gas. Each configuration will be described below.

(Acrylic ester resin)
The acrylic ester-based resin is dissolved in the aerosol composition in the aerosol container, and when discharged to the outside, is precipitated by vaporization of the hydrofluoroolefin, and is a resin component for forming a string-shaped discharged product.

Examples of the acrylic ester resin include methacrylic ester resin, acrylic ester resin, and copolymer resins thereof.

The blending amount of the acrylic ester resin is not particularly limited. As an example, the blending amount of the acrylic ester resin is preferably 5% by mass or more, preferably 7% by mass or more, and more preferably 10% by mass or more in the aerosol composition. The blending amount of the acrylic ester resin is preferably 30% by mass or less, preferably 25% by mass or less, and more preferably 20% by mass or less in the aerosol composition. When the blending amount of the acrylic ester resin is less than 5% by mass, the obtained discharged material tends to be easily torn in the space and is difficult to be formed in a continuous string shape. On the other hand, when the blending amount of the acrylic ester resin exceeds 30% by mass, it tends to precipitate in the aerosol composition, and the aerosol valve, the injection hole of the injection member, the injection passage, and the like tend to be easily clogged.

(Ester oil)
The ester oil is used to improve the compatibility between the acrylic ester resin and the hydrofluoroolefin, suppress the adhesiveness of the string-like ejected material, improve the peelability, and prevent clogging in the injection holes and injection passages. It is compounded.

The ester oil is not particularly limited. As an example, an ester oil is an ester of a fatty acid and an alcohol. Examples of such an ester include methylpentanediol dineopenate, diethylpentanediol dineopenate, neopentyl glycol di-2-ethylhexanoate, neopentyl glycol dicaprate, propylene glycol dilaurate, ethylene glycol distearate, and diethylene glycol dilaurate. , Diethylene glycol distearate, diethylene glycol diisostearate, diethylene glycol dioleate, triethylene glycol dilaurate, triethylene glycol distearate, triethylene glycol diisostearate, diester of dihydric alcohol such as triethylene glycol diisostearate; monostearic acid Monoester of dihydric alcohol and fatty acids such as propylene glycol, propylene glycol monooleate, ethylene glycol monostearate; fatty acids such as glyceryl tri2-ethylhexanoate, tri (capryl capric acid) glycerin and trivalent alcohol Examples thereof include monoesters of fatty acids such as isopropyl myristate and isopropyl palmitate and monoesters of monovalent alcohols. Among these, ester oil has more excellent solubility between acrylic ester-based resin and hydrofluoroolefin, and is less likely to cause clogging in injection holes and injection passages, and suppresses flammability of string-like discharges. From the viewpoint of high safety against fire, esters of fatty acids and dihydric alcohols are preferable, and diesters of fatty acids and dihydric alcohols are particularly preferable.

The amount of the ester oil to be blended is not particularly limited as long as it can enhance the compatibility between the acrylic ester resin and the hydrofluoroolefin. As an example, the blending amount of the ester oil is preferably 1% by mass or more, and more preferably 2% by mass or more in the aerosol composition. The blending amount of the ester oil is preferably 20% by mass or less, more preferably 15% by mass or less in the aerosol composition. When the blending amount of the ester oil is less than 1% by mass, it becomes difficult to solubilize the acrylic ester resin, and the injection holes and injection passages of the injection member tend to be easily clogged. On the other hand, when the blending amount of the ester oil exceeds 20% by mass, the precipitation of the acrylic ester resin is delayed. Therefore, the obtained string-like discharge tends to be thin and easily torn, and to be difficult to dry.

In particular, the ratio of the content of the ester oil to the acrylic ester-based resin (ester oil / acrylic ester-based resin) is preferably 0.05 times or more, and more preferably 0.1 times or more. The ratio of the content of the ester oil to the acrylic ester resin (ester oil / acrylic ester resin) is preferably 0.7 times or less, and more preferably 0.65 times or less. By adjusting the content ratio within the above range, the obtained aerosol composition suppresses the adhesiveness of the string-like discharge and has very good peelability, and is easy to drop on the floor or carpet. Can be removed.

(Arbitrary component (oil component))
The aerosol composition of the present embodiment has optional components such as fats and oils, silicone oil, higher fatty acids, higher alcohols, etc., in addition to the above-mentioned ester oils, for the purpose of adjusting the dryness and hardness of the string-like discharge product. An oil component) may be blended.

Oils and fats include avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, sesame oil, castor oil, flaxseed oil, safflower oil, jojoba oil, malt oil, palm oil, palm. Oil and the like are exemplified.

Examples of the silicone oil include methylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, and methylpolycyclosiloxane.

Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, isostearic acid, linoleic acid, and linoleic acid.

Examples of higher alcohols include lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, lanolin alcohol, hexyldodecanol, cetostearyl alcohol, octyldodecanol, oleyl alcohol, and isostearyl alcohol.

When an oil component other than the ester oil is blended, the blending amount of the oil component is preferably 0.1% by mass or more, more preferably 0.5% by mass or more in the aerosol composition. The blending amount of the oil component is preferably 10% by mass or less, and more preferably 5% by mass or less in the aerosol composition. By blending the oil component within the above range, the discharged product is adjusted to an appropriate hardness and tends to be in the shape of a string.

(Other optional ingredients)
In addition to the above-mentioned raw materials, the aerosol composition of the present embodiment may contain a surfactant, a polyhydric alcohol, water, various additives and the like.

The surfactant is blended for the purpose of adjusting the dryness and hardness of the string-shaped discharge, increasing the safety against fire, making it easier to contain water, and the like.

Examples of the surfactant include polyoxyethylene sorbitan fatty acid esters such as monococoyl fatty acid POE sorbitan, monostearate POE sorbitan, monooleic acid POE sorbitan, and trioleate POE sorbitan; diglyceryl monooleate, diglyceryl monostearate, Diglyceryl monolaurate, diglyceryl monocaprate, hexaglyceryl monolaurate, hexaglyceryl monomyristate, pentaglyceryl monolaurate, pentaglyceryl monomyristate, pentaglyceryl monooleate, pentaglyceryl monostearate, pentaglyceryl hexastearate , Pentaglyceryl trimyristate, pentaglyceryl trioleate, decaglyceryl monolaurate, decaglyceryl monomyristate, decaglyceryl monostearate, decaglyceryl monoisostearate, decaglyceryl monooleate, decaglyceryl monolinolate, pentastearic acid Polyglycerin fatty acid esters such as decaglyceryl and decaglyceryl pentaoleate; polyoxyethylene polyoxypropylene alkyl ethers such as POE / POP cetyl ether and POE / POP decyltetradecyl ether; POE cetyl ether, POE stearyl ether, POE oleyl ether Polyoxyethylene alkyl ethers such as POE lauryl ether and POE behenyl ether; polyethylene glycol fatty acid esters such as polyethylene glycol monolaurate and polyethylene glycol monostearate; polyoxyethylene hydrogenated castor oil such as POE cured castor oil; POE monostearate Polyoxyethylene glycerin fatty acid esters such as glyceryl and POE glyceryl monooleate; polyoxyethylene alkyl ether fatty acid esters such as POE cetyl stearate ether and POE lauryl ether isostearate; POE sorbit monolaurate, POE sorbit tetrastearate, tetraolein Nonionic surfactants such as polyoxyethylene sorbit fatty acid esters such as acid POE sorbit; alkyl alkanol forms such as alkyl alkanolamides such as coconut oil fatty acid N-methylethanolamide; are exemplified. Among these, the surfactant is preferably a hydrophilic surfactant having an HLB of 10 to 20 because the hydrophilic group enhances the safety against fire.

When the surfactant is blended, the blending amount of the surfactant is preferably 0.1% by mass or more, more preferably 0.5% by mass or more in the aerosol composition. The blending amount of the surfactant is preferably 10% by mass or less, more preferably 8% by mass or less in the aerosol composition. When the blending amount of the surfactant is less than 0.1% by mass, it tends to be difficult to obtain the effect of facilitating the blending of water and the effect of increasing the safety against fire. On the other hand, when the blending amount of the surfactant exceeds 10% by mass, the obtained discharged product tends to be difficult to dry, have strong adhesiveness, and tend to have poor peelability.

The aerosol composition of the present embodiment is preferably blended with a polyhydric alcohol or water. The polyhydric alcohol adjusts the dryness of the obtained discharged product to soften it, suppresses adhesiveness to facilitate peeling, and prevents clogging due to residue remaining in the injection hole or injection passage of the injection member after discharge. Therefore, it is preferably blended.

Examples of the polyhydric alcohol include dihydric alcohols such as propylene glycol, 1,3-butylene glycol, hexylene glycol and dipropylene glycol, and trihydric alcohols such as glycerin.

When the polyhydric alcohol is blended, the blending amount is preferably 0.5% by mass or more, and more preferably 1% by mass or more in the aerosol composition. The blending amount of the polyhydric alcohol is preferably 20% by mass or less, and more preferably 15% by mass or less. When the blending amount of the polyhydric alcohol is less than 0.5% by mass, the effect of blending the polyhydric alcohol tends to be difficult to obtain. On the other hand, when the blending amount of the polyhydric alcohol exceeds 20% by mass, the obtained discharged product tends to be difficult to dry, has strong adhesiveness, and tends to have poor peelability. In addition, since it has poor drying properties, it tends to ignite easily when brought close to a fire.

Water is suitably blended in order to increase the safety against fire, such as not igniting even if an open flame is brought into contact with the obtained discharge, and not continuously burning even if ignited.

Examples of water include purified water and ion-exchanged water.

When water is blended, the blending amount is preferably 0.5% by mass or more, and more preferably 1% by mass or more in the aerosol composition. Further, the blending amount of water is preferably 30% by mass or less, and more preferably 20% by mass or less. When the blending amount of water is less than 0.5% by mass, the effect of blending water tends to be difficult to obtain. Further, when the blending amount of water exceeds 30% by mass, the solubility of the acrylic ester resin is lowered and lumps are likely to be formed, and even if the aerosol composition is mixed by shaking before use, it becomes difficult to discharge with a uniform composition. Tend.

In addition, the aerosol composition of the present embodiment may contain additives as appropriate. Additives include pigments and pigments that color the discharge, pest repellents that evaporate from the discharge to keep pests away, pesticides that evaporate from the discharge to exterminate pests, and fragrances that evaporate odors from the discharge. Examples include deodorants that deodorize odors.

The pigments are Amaranth (Red No. 2), Erythrosin (Red No. 3), New Coccin (Red No. 102), Floxin (Red No. 104), Resolsin Brown (Brown No. 201), Orange I (Yellow No. 402). ), Sunset Yellow (Yellow No. 5), Uranin (Yellow No. 202), Metanil Yellow (Yellow No. 406), Fast Green (Green No. 3), Alizarin Cyanin Green F (Green No. 201), Brilliant Blue FCF (Blue) Water-soluble pigments such as Indigo Carmine (Blue No. 2), Patent Blue NA (Blue No. 202), Arizuroll Purple (Purple No. 401), Naftor Blue Black (Black No. 401), and Rhodamine B steerate (No. 1) Red 215), Sudan III (Red 225), Medicinal Scarlet (Red 501), Dibrom Fluoresane (Orange 201), Orange SS (Orange 403), Fluolecein (Yellow 201), Kinolin Yellow SS (Yellow) 204), Kinizarin Green SS (Green No. 202), Stan Blue B (Blue No. 403), Arizulin Purple SS (Purple No. 201) and other oily pigments are exemplified.

Examples of pigments include resolerubin B (red 201), resolerubin BCA (red 202), lake red C (red 203), lake red CBA (red 204), resole red (red 205), resole red CA. (Red 206), Resole Red BA (Red 207), Resole Red SR (Red 208), Deep Maroon (Red 220), Truisin Red (Red 221), Permuton Red (Red 228), Brilliant Fast Scarlet (Red No. 404), Permanent Red F5R (Red No. 405), Permanent Orange (Orange No. 203), Benchjin Orange G (Orange No. 204), Hansa Orange (Orange No. 401), Benchjin Yellow G (Yellow 205) No.), Hansa Yellow (Yellow No. 401), Phtalocyanin Blue (Blue No. 404) and the like are exemplified.

Examples of the pest repellent include N, N-diethyl-m-toluamide (DEET), herbal extract and the like. Examples of the deodorant component include green tea extract, persimmon tannin, and silver.

Examples of the insecticide include phthalthrin, imiprothrin, allethrin, permethrin, cismesrin, propulserin, resmethrin, d-phenothrin, tefluthrin, benfluthrin, neopinamine forte, and Chrislon forte.

Examples of fragrances include limonene, various plant essential oils, fruit oils, synthetic fragrances, blended fragrances, and natural fragrances.

Examples of the deodorant include methacrylate methacrylate of lauric acid, methyl benzoate, methyl phenylacetate, geranyl chloride, acetophenone myristate, benzyl acetate, benzyl propionate, and green tea extract.

(Liquefied gas)
The liquefied gas is a liquid having a vapor pressure in the aerosol container, and is blended to vaporize the liquefied gas by being discharged to precipitate the acrylic ester resin in a string shape. The liquefied gas of the present embodiment mainly contains a hydrofluoroolefin in which the dissolved amount of the acrylic ester resin composition is 1% by mass or less.

Examples of the hydrofluoroolefin include trans-1,3,3,3-tetrafluoropropa-1-ene and trans-2,3,3,3-tetrafluoropropa-1-ene.

The blending amount of the hydrofluoroolefin is not particularly limited as long as it can discharge the acrylic ester resin in a string shape. As an example, the blending amount of the hydrofluoroolefin is preferably 40% by mass or more, and more preferably 45% by mass or more in the aerosol composition. On the other hand, the blending amount of the hydrofluoroolefin is preferably 80% by mass or less, and more preferably 75% by mass or less in the aerosol composition. When the blending amount of the hydrofluoroolefin is less than 40% by mass, the momentum at the time of discharge tends to be weak, the discharged material tends to adhere in the vicinity of the injection hole, and it tends to be difficult to form a continuous string. On the other hand, when the blending amount of the hydrofluoroolefin exceeds 80% by mass, the content of the acrylic ester-based resin, the ester oil, or the like is reduced, and a string-shaped discharge tends to be difficult to form.

The aerosol composition of the present embodiment may contain another liquefied gas or compressed gas as a propellant for the purpose of adjusting the pressure of the aerosol composition to adjust the injection distance. Examples of such propellants include propane, isobutane, normalbutane, and liquefied gas such as liquefied petroleum gas and dimethyl ether which are mixtures thereof; compression of nitrogen peroxide gas, carbon dioxide gas, nitrogen gas, compressed air, oxygen gas and the like. Gas is exemplified.

The method for producing the aerosol composition of the present embodiment is not particularly limited. As an example, the aerosol composition is prepared by mixing an acrylic ester resin, an ester oil, a polyhydric alcohol, water, a surfactant, an additive, etc. in advance to prepare a dispersion stock solution, and the dispersion stock solution is placed in a container. It can be produced by filling the inside of the container, attaching an aerosol valve to the container and sealing the container, filling the container with a hydrofluoroolefin, and dissolving an acrylic ester resin or the like in the container. Alternatively, a stock solution other than the acrylic ester resin may be prepared, and the stock solution and the acrylic ester resin may be separately filled in the container.

As described above, according to the aerosol composition of the present embodiment, the acrylic ester resin can be dissolved by blending the hydrofluoroolefin in which the dissolved amount of the acrylic ester resin is 1% by mass or less together with the ester oil. When such an aerosol composition is sprayed to the outside, the hydrofluoroolefin is vaporized and the blending ratio in the aerosol composition changes. As a result, the acrylic ester-based resin is likely to precipitate. As a result, the aerosol composition can obtain a continuous string-like discharge. Further, the aerosol composition is unlikely to remain in the injection hole of the injection member after discharge, and even if the discharge material remains in the injection hole, it can be easily removed, so that clogging is unlikely to occur. Further, the hydrofluoroolefin is a liquefied gas having low flammability. Therefore, the obtained aerosol composition is more highly safe against fire even if the hydrofluoroolefin remains in the discharged product.

Hereinafter, the present invention will be described in more detail with reference to Examples. The present invention is not limited to these examples.

(Example 1)
According to the following formulation, components other than hydrofluoroolefin (trans-1,3,3,3-tetrafluoropropa-1-ene) are filled in an aluminum pressure-resistant container, and then an aerosol valve is attached to the container to form a valve. Hydrofluoroolefin was pressure-filled from the above to prepare an aerosol composition. In addition, an aerosol product was manufactured by attaching an injection member to the stem of the valve. As the valve, a stem having two stem holes with square holes of 1.1 mm × 0.7 mm and a valve having a housing with a prepared hole having a hole diameter of φ1.5 mm and no horizontal holes are used as injection members. As the material, one having an injection hole having a hole diameter of φ0.7 mm was used.
(Prescription 1)
Acrylic ester resin (* 1) 19.5
Methylpentanediol dineopentane (* 2) 4.2
Dipropylene glycol 4.2
POE (20) Sorbitan trioleate (* 3) 2.1
Trans-1,3,3,3-tetrafluoropropa-1-ene 70.0
Total 100.0 (mass%)
* 1: Dianal BR-101 (trade name), manufactured by Mitsubishi Rayon Co., Ltd. * 2: Neosolue-MP (trade name), manufactured by Nikko Chemicals Co., Ltd. * 3: NIKKOL TO-30V (trade name) HLB11. 0, manufactured by Nikko Chemicals Co., Ltd.

(Example 2)
An aerosol composition was prepared in the same manner as in Example 1 except that the formulation was changed to the following formulation 2, and an aerosol product was prepared.
(Prescription 2)
Acrylic ester resin (* 1) 19.5
Methylpentanediol dineopentane (* 2) 4.2
1,3 Butylene glycol 4.2
POE (20) Sorbitan trioleate (* 3) 2.1
Trans-1,3,3,3-tetrafluoropropa-1-ene 70.0
Total 100.0 (mass%)

(Example 3)
An aerosol composition was prepared in the same manner as in Example 1 except that the formulation was changed to the following formulation 3, and an aerosol product was prepared.
(Prescription 3)
Acrylic ester resin (* 1) 16.5
Methylpentanediol dineopentane (* 2) 6.9
POE (20) Sorbitan trioleate (* 3) 1.7
Dipropylene glycol 13.8
Trans-1,3,3,3-tetrafluoropropa-1-ene 61.1
Total 100.0 (mass%)

(Example 4)
An aerosol composition was prepared in the same manner as in Example 1 except that the formulation was changed to the following formulation 4, and an aerosol product was prepared.
(Prescription 4)
Acrylic ester resin (* 1) 16.0
Methylpentanediol dineopentane (* 2) 6.7
POE (20) Sorbitan trioleate (* 3) 1.6
Dipropylene glycol 16.7
Trans-1,3,3,3-tetrafluoropropa-1-ene 59.0
Total 100.0 (mass%)

(Example 5)
An aerosol composition was prepared in the same manner as in Example 1 except that the formulation was changed to the following formulation 5, to prepare an aerosol product.
(Prescription 5)
Acrylic ester resin (* 1) 24.0
Methylpentanediol dineopentane (* 2) 7.5
POE (20) Sorbitan trioleate (* 3) 1.9
Trans-1,3,3,3-tetrafluoropropa-1-ene 66.6
Total 100.0 (mass%)

(Example 6)
According to the following formulation 6, components other than hydrofluoroolefin (trans-1,3,3,3-tetrafluoropropa-1-ene) are filled in an aluminum pressure resistant container, and then an aerosol valve is attached to the container. Hydrofluoroolefin was pressure-filled from the valve to prepare an aerosol composition. In addition, an aerosol product was manufactured by attaching an injection member to the stem of the valve. As a valve, a stem having a stem hole having a hole diameter of φ0.5 mm and a valve having a prepared hole having a hole diameter of φ1.5 mm and having a housing without a horizontal hole are used. As an injection member, the hole diameter is φ0. The one having an injection hole of 0.6 mm was used.
(Prescription 6)
Acrylic ester resin (* 1) 22.0
Methylpentanediol dineopentane (* 2) 9.3
POE (40) Hardened castor oil (* 4) 1.5
Purified water 13.3
Trans-1,3,3,3-tetrafluoropropa-1-ene 53.9
Total 100.0 (mass%)
* 4: NIKKOL HCO-40 (trade name) HLB12.5, manufactured by Nikko Chemicals Co., Ltd.

(Example 7)
An aerosol composition was prepared in the same manner as in Example 6 except that the formulation was changed to the following formulation 7, and an aerosol product was prepared.
(Prescription 7)
Acrylic ester resin (* 1) 16.3
Methylpentanediol dineopentane (* 2) 6.8
POE (40) Hardened castor oil (* 4) 3.3
Dipropylene glycol 3.4
Purified water 9.8
Trans-1,3,3,3-tetrafluoropropa-1-ene 60.4
Total 100.0 (mass%)

(Example 8)
An aerosol composition was prepared in the same manner as in Example 6 except that the formulation was changed to 8 below to prepare an aerosol product.
(Prescription 8)
Acrylic ester resin (* 1) 15.8
Methylpentanediol dineopentane (* 2) 9.9
POE (40) Hardened castor oil (* 4) 3.2
Purified water 14.1
Trans-1,3,3,3-tetrafluoropropa-1-ene 57.0
Total 100.0 (mass%)

(Comparative Example 1)
An aerosol composition was prepared in the same manner as in Example 1 except that the formulation was changed to the following formulation 9, and an aerosol product was prepared.
(Prescription 9)
Acrylic ester resin (* 1) 1.0
Trans-1,3,3,3-tetrafluoropropa-1-ene 99.0
Total 100.0 (mass%)

(Comparative Example 2)
An aerosol composition was prepared in the same manner as in Example 1 except that the formulation was changed to the following formulation 10, and an aerosol product was prepared.
(Prescription 10)
Acrylic ester resin (* 1) 19.5
Dimethylpolysiloxane (* 5) 4.2
Dipropylene glycol 4.2
POE (20) Sorbitan trioleate (* 3) 2.1
Trans-1,3,3,3-tetrafluoropropa-1-ene 70.0
Total 100.0 (mass%)
* 5: SH200 500cs (trade name, manufactured by Toray Dow Corning Co., Ltd.)

(Comparative Example 3)
An aerosol composition was prepared in the same manner as in Example 1 except that the formulation was changed to 11 below to prepare an aerosol product.
(Prescription 11)
Acrylic ester resin (* 1) 19.5
Kerosin (* 6) 4.2
Dipropylene glycol 4.2
POE (20) Sorbitan trioleate (* 3) 2.1
Trans-1,3,3,3-tetrafluoropropa-1-ene 70.0
Total 100.0 (mass%)
* 6: Neothiozol (trade name), manufactured by Chuo Kasei Co., Ltd.

(Comparative Example 4)
An aerosol composition was prepared in the same manner as in Example 1 except that the formulation was changed to the following formulation 12, and an aerosol product was prepared.
(Prescription 12)
Acrylic ester resin (* 1) 19.5
Dipropylene glycol 8.4
POE (20) Sorbitan trioleate (* 3) 2.1
Trans-1,3,3,3-tetrafluoropropa-1-ene 70.0
Total 100.0 (mass%)

(Comparative Example 5)
An aerosol composition was prepared in the same manner as in Example 1 except that the formulation was changed to the following formulation 13, and an aerosol product was prepared.
(Prescription 13)
Acrylic ester resin (* 1) 19.5
Methylpentanediol dineopentane (* 2) 4.2
Dipropylene glycol 4.2
POE (20) Sorbitan trioleate (* 3) 2.1
Liquefied petroleum gas 70.0
Total 100.0 (mass%)

With respect to the aerosol compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 5, the solubility of the resin, the safety to fire, the presence or absence of clogging, the shape of the discharged product, and the peelability according to the following evaluation methods. Was evaluated. The results are shown in Table 1.

(Solubility of resin)
The aerosol composition was filled in a transparent polyethylene terephthalate pressure-resistant container, and the appearance of the aerosol composition was observed.
(Evaluation criteria)
⊚: The resin was easily dissolved.
◯: The resin was dissolved when left to stand for 1 hour after filling.
X: The resin did not dissolve even after being left to stand for 1 day after filling, and remained in a solid state.

(Safety against fire)
The state when the discharged material was ignited with a lighter was evaluated.
(Evaluation criteria)
⊚: The discharged material did not ignite.
◯: The discharged material ignited for a moment, but immediately extinguished.
X: The discharged material ignited and the entire discharged material burned.

(Presence or absence of clogging)
4 g of the aerosol composition was discharged, and the aerosol composition was stored in a constant temperature room at 25 ° C. for 1 day with the injection member attached and dried. This was set as one cycle and 25 cycles were carried out.
(Evaluation criteria)
⊚: The aerosol composition could be discharged to the end without clogging.
◯: The aerosol composition adhered so as to close the injection hole, but the adhered matter could be easily removed and discharged.
X: The aerosol composition was clogged at the injection hole, and the clogged discharge was removed, but the aerosol composition remained in the injection passage and could not be discharged.

(Shape of discharge)
The length of the string-shaped ejected product formed by falling on the floor when discharged into the space from a height of 1 m was evaluated.
(Evaluation criteria)
⊚: The discharged material became a string of 100 cm or more with almost no tearing in the space.
◯: The discharged material was partially torn in the space, but became a string of 70 cm or more.
× 1: The discharged material adhered and entangled in the vicinity of the injection hole and did not form a string.
× 2: The discharged material was torn into small pieces in the space and did not form a string.

(Removability of discharged material)
The peelability was evaluated when the string-like discharge that was sprayed into the space from a height of 1 m and fell on the floor (carpet) and adhered was peeled off after 10 seconds.
(Evaluation criteria)
⊚: The discharged material was dry and could be peeled off in a string-like state.
◯: Most of the discharged material was dry, and although it was partially torn, it was peeled off in a string-like state.
X: The discharged product was not dry, had strong adhesiveness, was torn into small pieces, and was difficult to peel off.

As shown in Table 1, since the aerosol compositions of Examples 1 to 8 contained ester oils, they contained hydrofluoroolefins in which the dissolved amount of the acrylic ester resin composition was 1% by mass or less. Nevertheless, the solubility in the acrylic ester resin composition was excellent. In addition, all of the aerosol compositions of Examples 1 to 8 were highly safe against fire, and could not cause clogging or could be easily removed even if clogging occurred. Further, the aerosol compositions of Examples 1 to 8 could be discharged in the form of a substantially dry long string, and could be easily peeled off.

On the other hand, the aerosol composition of Comparative Example 1 did not contain an ester oil, and the resin did not dissolve. Therefore, the discharged material is not evaluated. Although the aerosol compositions of Comparative Examples 2 to 4 were able to dissolve the resin, they were inferior in safety to fire and were prone to clogging. Moreover, it was difficult for these discharges to be discharged in the form of a string. The aerosol composition of Comparative Example 5 did not contain a hydrofluoroolefin in which the dissolved amount of the acrylic ester resin composition was 1% by mass or less, and although the resin could be dissolved, it was safe to fire. It was inferior and prone to clogging.

Claims (12)

Contains acrylic ester resin, ester oil, and liquefied gas,
The liquefied gas is Ri hydrofluoroolefin der dissolution amount of the acrylic ester-based resin composition is not more than 1 wt%,
An aerosol composition that does not contain water . The aerosol composition according to claim 1, wherein the acrylic ester-based resin is contained in an aerosol composition in an amount of 5 to 30% by mass. The aerosol composition according to claim 1 or 2, wherein the ester oil is contained in an aerosol composition in an amount of 1 to 20% by mass. The aerosol composition according to any one of claims 1 to 3, wherein the ester oil is an ester of a fatty acid and a divalent alcohol. The aerosol composition according to any one of claims 1 to 4, further comprising a polyhydric alcohol. The aerosol composition according to any one of claims 1 to 5, further comprising a surfactant. Contains acrylic ester resin, ester oil, and liquefied gas,
The liquefied gas is a hydrofluoroolefin in which the dissolved amount of the acrylic ester resin composition is 1% by mass or less.
The ester oil is an aerosol composition which is an ester of a fatty acid and a dihydric alcohol. The aerosol composition according to claim 7, wherein the acrylic ester-based resin is contained in an aerosol composition in an amount of 5 to 30% by mass. The aerosol composition according to claim 7 or 8, wherein the ester oil is contained in an aerosol composition in an amount of 1 to 20% by mass. The aerosol composition according to any one of claims 7 to 9, further comprising a polyhydric alcohol. The aerosol composition according to any one of claims 7 to 10, further comprising a surfactant. The aerosol composition according to any one of claims 7 to 11, further comprising water.