JP2517748B2 - Air can - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an aerosol can which can be filled with an aerosol composition which has been difficult to produce an aerosol product.

[Prior Art and Problems] Since an aerosol can used for an aerosol product is filled with various kinds of chemicals, a metal can is coated with a resin on its inner surface in order to provide chemical resistance. Epoxy resin is used as such a coating agent from the viewpoint of adhesion, corrosion resistance, and processability, but there is a problem with corrosion resistance in the epoxy resin coating, so pharmaceuticals, quasi-drugs, hair styling agents, etc. are aerosol composition. There are many prescription restrictions when trying to make things
Therefore, conventionally, only aerosol products with reduced effectiveness could be produced.

Further, there is no aerosol can capable of withstanding a polar medium mixture containing a highly corrosive acid or a compound capable of generating an acid and an oxidizing agent, and it has been difficult to aerosolize such a composition.

[Means for Solving the Problems] The present invention, which has solved the above problems, is characterized by employing a coating film containing polyvinylidene fluoride (hereinafter, referred to as PVdF) as a main component as an inner surface coating of an aerosol can. Is.

[Operation and Example] A coating film containing PVdF as a main component in the present invention (hereinafter referred to as PVdF
A coating film forming composition for forming a coating film) is PVdF
1 to 100 parts of binder resin to 100 parts (part by weight, the same applies below), if necessary, those containing up to 40 parts of ordinary paint additives such as pigments, fillers, dyes and lubricants are dissolved in a solvent Alternatively, it is preferably dispersed.

The PVdF may be a homopolymer of vinylidene fluoride (VdF) or a copolymer with other monomers, but when it is a copolymer, at least 75% (by weight) VdF is added to maintain chemical resistance. %, The same applies hereinafter). Examples of the copolymerizable monomer include ethylene,
Styrene, propylene, isobutene, vinyl chloride, vinylidene chloride, vinyl fluoride, chlorotrifluoroethylene, tetrafluoroethylene, trifluoropropylene, hexafluoropropylene, hexafluoroisobutylene, vinyl acetate, vinyl propionate, butyl butyrate, acrylic Acid, methacrylic acid, methyl acrylate, methyl methacrylate, fluoroalkyl acrylate, fluoroalkyl methacrylate, glycidyl methacrylate, allyl alcohol, butyl vinyl ether, ethyl vinyl ether, hydroxybutyl vinyl ether, maleic anhydride, vinyl methoxysilane and the like can be mentioned. . PVdF is a known method, for example, Japanese Patent Publication Nos. 46-9476, 46-26820, and 46-21214.
It can be produced by the methods described in Japanese Patent Publications Nos. 47-39592 and 58-34484.

The binder resin is preferably a thermosetting resin or a heat resistant resin. The binder resin is added to improve the adhesion of the PVdF coating film, and is 1 to 100 parts, preferably 5 to 70 parts, relative to 100 parts of PVdF. If too much, properties such as chemical resistance of PVdF are impaired. Specific examples of the binder resin include
For example, epoxy resin, phenol resin, amino resin,
Alkyd resin, amide imide resin, polyparabanic acid,
Glycidyl group-containing copolymer, hydroxyl group-containing copolymer, carboxyl group-containing copolymer, polyether sulfone, polyether ether ketone, polyimide, polysulfone, polyphenylene sulfide, aromatic polyamide, silicone resin, polyester and the like, PV
In the case of a resin having poor compatibility with dF, an appropriate amount of an acrylic resin containing a functional group such as a glycidyl group, a carbonyl group, an isocyanate group, a phosphono group, a phosphinico group and an amino group may be added.

Examples of the solvent include ketones, esters, ethers, amides, carbonates, nitriles, phosphates and the like. Specific examples include, for example, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, N-methylpyrrolidone, cyclohexanone, methyl cellosolve acetate, isophorone, methyl isoamyl ketone, γ-butyrolactone, cellosolve acetate,
Propylene carbonate, diisobutyl ketone, carbitol acetate, dimethyl phthalate, dimethyl acetamide, dimethyl formamide, trimethyl phosphate, diacetone alcohol, dibutyl phthalate, dimethyl carbitol, tetramethyl urea, acetylacetone, acetophenone, butyl cellosolve, acetone,
Cellosolve, dioxane, acetonitrile, triethyl phosphate, benzonitrile, triphenyl phosphate and the like can be mentioned.

The coating film-forming composition may be prepared by mixing the above components by a conventional method such as a ball mill, a sand mill, a paint mill, a homodisper or a homogenizer. The mixing temperature is preferably 50 ° C or lower. The amount of the solvent at that time varies depending on the coating method, but is usually 50 to 1000 parts, and it is preferable that the viscosity of the composition is 1 to 500 cP.

The method of forming a coating film is a method such as a spraying method, a roll coater method, a knife coater method, a curtain flow coater method, a dipping method, etc., with a coating film forming composition on the inner surface of a metal container formed into a predetermined aerosol can shape. Painted, about 80 ~
A method of baking at a temperature of 350 ° C., preferably about 150 to 330 ° C. may be mentioned. The thickness of the coating film is usually 1 to 50 μm, preferably 5 to 30 μm. If it is too thick, the coating will peel off during baking,
This may cause foaming, peeling of the coating film and crack formation during post-processing. If it is too thin, corrosion resistance is insufficient and pinholes may occur.

As the material of the metal container, a metal that is usually used for an aerosol can can be adopted, and examples thereof include iron, tin, aluminum,
Stainless steel, chin plate (surface treated laminated steel)
Are used.

Further, it is preferable to form the same PVdF coating film on other parts with which the aerosol composition comes into contact, for example, the valve made of the above metal, copper alloy, or tin alloy.

The aerosol cans of the present invention are particularly resistant to conventional aerosol compositions as well as polar media mixtures containing acids and / or acid-generating compounds and oxidants that are difficult to prepare in aerosol compositions. Examples of the acid or the compound capable of generating an acid include a carboxyl group-containing compound, an ester group-containing compound, a sulfonic acid group-containing compound, a sulfonyl group-containing compound, an organic acid salt, a mineral acid, a mineral acid salt and a quaternary ammonium salt. There are, for example, benzoic acid, citric acid, potassium citrate, lithium citrate, and the like.
Potassium acetate, sodium acetate, salicylic acid, sodium salicylate, methyl salicylate, glycol salicylate, tartaric acid, potassium tartrate, sodium tartrate, lactic acid, quinine sulfate, cinchonine sulfate, strychnine sulfate, morphine sulfate, morphine acetate, quinine tartrate, tannic acid, morphine hydrochloride , Boric acid, triethanolamine lauryl sulfate, stearyl trimethyl ammonium chloride, benzalkonium chloride, benzethonium chloride, thioglycolic acid, sodium thioglycolate and the like, but not limited to these.

As the oxidizing agent, hydrogen peroxide solution, sodium salt, potassium salt, calcium salt of perchloric acid, sodium salt, potassium salt, calcium salt of stabilized hypochlorous acid, stabilized chlorine dioxide, potassium salt of bromic acid, sodium salt , Sodium salt and potassium salt of perboric acid.

The polar medium in which these are dissolved or dispersed is a medium having a large hydrogen bonding force, and in addition to water, alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, ketones such as acetone and methyl ethyl ketone, ethylene glycol, Examples thereof include glycols such as propylene glycol and dipropylene glycol, ethers such as diglyme, tetraglyme, propylene glycol monomethyl ether and diethylene glycol monomethyl ether, alone or in a mixture. In addition, hydrocarbons such as nitromethane, toluene, cyclohexane, kerosene, and isoparaffin, which are nonpolar media, or halogenated hydrocarbons such as 1,1,1-trichloroethane, methylene chloride, carbon tetrachloride, dichloropentane, etc. , And can be used as a mixture with a polar medium.

The present invention uses a polar medium mixture in which these acids and / or compounds capable of generating an acid and at least one oxidizing agent are dissolved or dispersed in a polar medium as a stock solution, which is used together with a propellant to form the PVdF coating film on the inner surface. The present invention also relates to an aerosol product filled in an aerosol can.

The propellant preferably has at least one hydrogen atom in the molecule, and specific examples thereof include methyl chloride, dichloromonofluoromethane (CFC21), monochlorodifluoromethane (CFC22), and dichlorotrifluoroethane (CFC). 123), monochlorotetrafluoroethane (CFC124), dichlorodifluoroethane (CFC132), monochlorodifluoroethane (CFC1)
42b), difluoroethane (freon 152), dimethyl ether, propane, butane, isobutane and the like. In addition, compounds such as trichloromonofluoromethane (CFC 11), dichlorodifluoromethane (CFC 12) trichlorotrifluoroethane (CFC 113), and dichlorotetrafluoroethane (CFC 114), which have no hydrogen in the molecule, are also injected. It can be used as a mixture with an agent.

The formulation of each component of the stock solution, the mixing ratio of the stock solution and the propellant, etc. may be appropriately selected according to the application.

Next, the present invention will be described based on examples, but the present invention is not limited to only these examples.

Example 1 An aluminum aerosol can having an outer diameter of 50 mm and a height of 130 mm was subjected to the surface coating treatment shown in Table 1 and filled with an antiphlogistic analgesic having the following formulation, and the inner coating treatment shown in Table 1 was applied. An aerosol product was produced by mounting an aluminum valve provided with the above.

(Anti-inflammatory analgesic formulation) wt% Methyl salicylate 3.0 Glycol salicylate 2.0 Menthol 4.0 Ethanol 27.0 Purified water 43.7 Dimethyl ether 12.0 Butane 8.3 Each of these aerosol products is left to stand at 45 ° C for 3 months and at room temperature for 12 months, then the surface of the can. And the change of the state of the inner surface of the valve was investigated.

 The results are shown in Table 1.

 The evaluation was performed according to the following criteria.

◎: No abnormality ○: Some discoloration / softening in the coating layer △: Blister in the coating layer ×: Peeling of the coating layer and corrosion in the substrate Examples 2 to 8 Each aerosol formulation shown in Table 2 was filled in a container equipped with a valve in an aerosol can having a structure shown in Table 3, and the states of the inner surface of the can and the inner surface of the valve were examined in the same manner as in Example 1. .

 The results are shown in Table 3.

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide an aerosol can that has significantly excellent durability against compounds that have been difficult to use in conventional aerosol products, and to provide an aerosol product having a wide range of effectiveness that has never been achieved. Can be provided.

Front page continuation (72) Inventor Nobuyuki Tomihashi 20-3 Sakuragaokakitamachi, Takatsuki-shi, Osaka (72) Inventor Tsutomu Terada 1-7-15-203 Tsukahara, Takatsuki-shi, Osaka (72) Akira Chida, Settsu, Osaka 2-21-21 Ichitsuya, Ichi (56) References JP-A-62-184833 (JP, A)

Claims (3)

(57) [Claims] 1. An inner surface comprising a resin mixture of polyvinylidene fluoride and 1 to 100 parts by weight of a binder resin with respect to 100 parts by weight of the polyvinylidene fluoride, the binder resin being a phase of the polyvinylidene fluoride. An aerosol can made of a metal container coated with a coating film that is a thermosetting resin or a heat-resistant resin having good solubility. 2. The inner surface is made of a resin mixture of polyvinylidene fluoride and 1 to 100 parts by weight of a binder resin with respect to 100 parts by weight of the polyvinylidene fluoride, and the binder resin is mixed with the polyvinylidene fluoride. The aerosol can according to claim 1, further comprising a valve coated with a coating film which is a thermosetting resin or a heat resistant resin having good solubility. 3. An aerosol can according to claim 1, wherein the aerosol composition comprises an undiluted solution containing a solution in which an acid and / or a compound capable of generating an acid and an oxidizing agent are dissolved in a polar medium, and a propellant. An aerosol product that is filled.