JPH0246622B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to aerosol coating compositions, and more particularly to a novel propellant active carrier system for aerosol coating compositions.

Aerosol coating compositions are well known in the art, and these compositions utilize volatile organic solvents as carriers for film-forming polymers. The use of such organic solvents has raised toxicity and flammability problems, and regulatory authorities have become increasingly restrictive regarding the use of organic solvents in such compositions.

Prior art U.S. Patent Application No. 97152, filed November 23, 1979 (now U.S. Pat. No. 4,265,797), the disclosure of which is hereby incorporated by reference, includes:
Aqueous aerosol coating formulations are described which are sufficient to form high gloss, durable coatings on substrate surfaces. However, the compositions defined herein are limited to a narrow range of film-forming polymers.

However, surprisingly, by using a novel single phase propellant active carrier composition,
It has been found that satisfactory (e.g. in terms of coating properties and low corrosive effects on containers) spray-applied films can be formed based on a wide range of water-dilutable film-forming polymers in the form of solutions or emulsions. did.

The spray coating composition of the present invention comprises: (A) (I) about 6 to about 25% by weight of a film-forming polymer; () a propellant, water, and at least one water-soluble polar solvent; about 75% by weight of a propellant active carrier composition;
the film-forming polymer (I) is a water-soluble polymer; (3) from about 1 to about 30% by weight of the formula R-OH, where R
is an unsubstituted straight-chain or branched alkyl group having 1 to 6 carbon atoms. ) and at least one monohydric alcohol represented by
(B) a stabilizer sufficient to maintain the formulation at a pH of 7.2 to 10; , a spray coating composition that forms a continuous air-dried film on the surface of a support, characterized in that it is a single-phase composition. The proportions of each component total 100% and are sufficient to provide a single phase. The composition has a vapor pressure ranging from about 30 to about 85 psig at about 20°C (70°) in a pressurized aerosol packaging with an auxiliary gas propellant, if present.

Although the present invention first provides an aerosol coating composition, the propellant active carrier composition may be used for spray dispensing of various other active ingredients, such as in hair sprays and deodorants. It can be used for dispensing (dispensing).

The essential components of the propellant composition of the present invention are dimethyl ether, water, the above-mentioned ROH, a water-soluble organic coagulation solvent, and a PH stabilizer. Dimethyl ether is -
Colorless, odorless, and stable molar liquid with a boiling point of 25 °C and a vapor pressure of 4.2 bar at 20 °C.
liquid).

It has been proposed in the past to use this liquid as a propellant. US Pat. No. 1,800,156 discloses the use of dimethyl ether alone as a propellant for a wide variety of materials, and also describes paints. US Patent No.
No. 3207386 discloses the use of a combination of dimethyl ether and water as a propellant for a wide variety of products, including paints, and that by selecting the proportions of dimethyl ether and water, the combination of dimethyl ether and water can be used as a propellant. A homogeneous solution can be obtained, resulting in a composition consisting of 5-35% by weight of dimethyl ether and 95-65% by weight of water. No other solvent or propellant components are used in this prior art composition.

In the present invention, dimethyl ether is used in combination with water and a mixture of alcohol and a water-soluble organic coalescing solvent to form a single phase propellant-active carrier composition for water-reducible film-forming polymers in the form of an aqueous solution or an aqueous emulsion. The present invention provides a spray coating composition comprising:
Different purposes require different applications of dimethyl ether in different proportions than in the prior art.

Dimethyl ether represents about 20% to about 75% by weight of the propellant active carrier composition, preferably about 25% to about 40% by weight of the propellant active carrier composition.
% by weight, in particular about 40% by weight.

In the presence of conventional liquid propellants such as aliphatic hydrocarbons, fluorinated hydrocarbons and other organic solvents,
Although a dimethyl ether-only propellant is preferred due to system instability, in some cases up to about 50% by weight of another liquid propellant relative to the dimethyl ether may be present in the composition. .

For example, gaseous propellants such as nitrogen, carbon dioxide, nitrous oxide, etc. can be used to enhance the propellant effectiveness of dimethyl ether or combinations of dimethyl ether and other liquid propellants.

Another essential component of the propellant composition of the present invention is water. This component is from about 10 to about 50% by weight, based on the total propellant active carrier composition, preferably about
It is present in a concentration of 20 to about 35% by weight, especially about 30% by weight.

In an embodiment of the present invention, in the composition,
Water-soluble lower aliphatic monohydric alcohols are also used.
The monohydric alcohol used in the present invention has the formula R
-OH, in which R is 1 to
An unsubstituted straight or branched chain alkyl group containing 6 carbon atoms. Examples of suitable monohydric alcohols include methanol, ethanol, n-propanol, isopropanol, and n-butanol, of which ethanol or isopropanol is preferred.

The concentration of monohydric alcohol used in the compositions of the invention is based on the total propellant active carrier composition.
It can vary widely from about 1 to about 30% by weight, but preferably from about 5 to about 20%, especially about 15%.

In an embodiment of the invention, a water-soluble organic flocculating solvent is present along with the alcohol. The organic coalescing solvent aids in film formation and also acts as an agent to form water-soluble polymers.

The aggregation solvent may be any water-soluble polar organic solvent. Such organic solvents include, for example, glycol ethers, esters, ketones, and certain denatured alcohols, ranging from about 365 to about 572
It has a boiling point in the range of approximately 300°C). Suitable solvents include lower monoalkyl ethers of ethylene or propylene glycol, such as propylene glycol methyl ether and propylene glycol methyl ethyl ether, diacetone alcohol, and ester alcohols.
The amount of coalescing solvent present is from about 1 to about 15% by weight, preferably about 5% by weight, based on the total propellant active carrier composition.
~10% by weight, especially about 6% by weight. The combination of the monohydric alcohol and the coagulating solvent is about 2 to about 30
% by weight and together with selected proportions of dimethyl ether and water form a monolayer composition suitable for dissolving or suspending the active ingredient to be dispensed. .

The propellant active carrier compositions of the present invention have a constant vapor pressure when packaged in a pressurized container sufficient to effect dispensing of its contents. Its vapor pressure is usually about 30 to about 20℃ (70〓)
85 psig, preferably in the range of about 40 to about 60 psig.

Dimethyl ether constitutes the main propellant component of the composition. Water provides the main solvent and/or suspending phase for the active ingredient, which in the case of aerosol paints contains the film-forming polymer. The water-soluble organic solvent primarily acts as a solvent for the propellant, and the water prevents it from separating into liquid phases upon standing, so that a mixture consisting essentially of a single phase of each component is obtained.
By using a single phase propellant active carrier composition, the active ingredient can be dispensed more easily and efficiently than in an aerosol container.

The propellant-active carrier compositions of this invention have particular utility in providing aerosol aqueous coating compositions. Such coating compositions consist of a single-phase propellant-active carrier composition and a film-forming polymer dissolved and/or suspended therein. Pigments can also be added to color the spray-formed film.

Such aqueous aerosol coatings typically contain about 6% to about 25% by weight of the film-forming polymer, preferably about 12% to about 20% by weight of the propellant-active carrier.
~75% by weight, preferably from about 88% to about 80%, and pigments, surfactants, as further described below.
Consists of optional ingredients such as stabilizers, defoamers, and plasticizers.

Propellant-active carrier compositions are extremely versatile and effective and can be spray applied to a substrate surface with a wide variety of film-forming polymers to form continuous films with high flexibility retention and excellent durability. can be formed.
Depending on the nature of the polymer and other ingredients in the formulation, high gloss, medium gloss, low gloss, or matte films can be obtained.

Aerosol compositions formulated using the propellant-active carrier system of the compositions are rather substantially non-flammable, as tested in standard flammability tests for aerosols. For example, the spray can blow out candle lights.

The film-forming polymer may be any water-dilutable polymer, including water-soluble polymers and water-dilutable emulsifying polymers, and can be spray applied to form a continuous film on the surface of the support. A wide variety of polymers can be used including acrylic resins, alkyd resins, epoxy ester resins, and polyvinyl copolymers.

Acrylic resins include acrylic acid, methacrylic acid,
Esters of these acids, or thermoplastic or thermoset polymers or copolymers of acrylonitrile. Such resins can be modified in the presence of aromatic monovinylidene compounds, usually styrene. The molecular weight of acrylic resins typically ranges from about 100,000 to about 1,000,000.

An example of an acrylic resin suitable for formulation of the aqueous aerosol coating composition according to the present invention is available from Rohm and Haas under the designation "WL91".
Haas, Inc.). Another example is a resin available from Reichold Chemicals under the designation "90-587 resin."

Alkyd resins are dibasic acids or their anhydrides,
It is usually obtained by combining phthalic anhydride with a polyhydric alcohol, such as glycerol. Alkyd resins are often modified with natural drying oils such as linseed oil, soybean oil, and safflower oil at 30-60% by weight.

Examples of alkyd resins suitable for the formulation of aqueous aerosol coating compositions according to the invention include: For example, the products called "586" and "585" are registered as "AROLON" by Ashland Oil, Inc.
Oil Inc.).

Epoxy ester resins are resins containing reactive epoxy groups and are derived from polyols and epoxy group-containing compounds. other comonomers,
For example, it may be copolymerized with styrene. These resins, like alkyd resins, can be modified with natural drying oils. One example of an epoxy resin that may be used is commercially available from Reichold Chemicals under the designation "38-690."

Polyvinyl copolymers are obtained by copolymerizing vinyl chloride or vinyl acetate with copolymerizable monomers. An example of such a material suitable for formulation in an aqueous aerosol coating composition according to the present invention is available from BFGoodrich Company under the designation "514H."

Mixtures of two or more resins or resin types can be used in the aerosol aqueous coating compositions of the present invention.

As described above, an optional component that may be present in the coating composition is a pigment for coloring a film formed by spraying the composition. If pigments are used, up to about 15% by weight of the total composition, preferably from about 5% to
Approximately 15% by weight of pigment is used.

When such pigments are present, the amount of polymer used will usually be near the lower end of the above range. If such pigments are not present and a transparent film is desired, the amount of polymer used will be near the upper end of the above range.

If a pigment is present, it is usually necessary to add a surfactant to sufficiently suspend the pigment in the liquid vehicle. When the film-forming polymer is in the form of an emulsion, a certain amount of surfactant may be present with the film-forming polymer, but the amount of surfactant included will be controlled to suitably suspend the added pigment. is usually insufficient.

The total amount of surfactant present in the composition is
It must be sufficient to keep the solids in suspension, and ranges of up to about 3% by weight of the composition are common.

It is essential to add a PH stabilizer to the composition to achieve a final PH value of about 7.2 or more and about 10 or less to prevent corrosion of conventional pressurized metal containers in which coating compositions are stored for spray application. Invention can do it. Appropriate
PH stabilizers include morpholine, ammonia and triethanolamine. This component may be present in an amount up to about 2% by weight of the total composition.

An antifoaming agent is added to change the surface tension of the composition so that when the composition is sprayed onto the surface of a support, dissolved gases can be easily released, and the surfactant present in the composition can be easily released. The cleaning effect can be prevented. Nonionic blends of mineral oil and silica derivatives have been found to be suitable for defoaming purposes. If antifoaming agent is present, its usage amount is
Up to about 2% by weight of the total composition, preferably about
It is 0.4% by weight.

Another component added to the aerosol coating composition is a plasticizer to promote flexibility. Any of a wide variety of plasticizers may be used, including dioctyl phthalate. The plasticizer may be present in an amount up to about 2% by weight, preferably about 1% by weight of the total composition.

Therefore, the aerosol water-based coating composition provided by the present invention has a pH value of about 7.2 to about 10,
from about 6 to about 25% by weight (calculated as non-volatile content) of the at least one water-reducible film-forming polymer, preferably having a characteristic of from about 7.4 to about 7.9;
About 10 to about 40% by weight of water in dimethyl ether, about 1
~30% by weight of at least one monohydric alcohol of the formula R-OH, where R is an unsubstituted straight-chain or branched alkyl group having 1 to 6 carbon atoms; At least 1 to 15% by weight
a mixed solution of aqueous organic flocculating solvent of at least one species;
0 to about 3% by weight of a surfactant, 0 to about 15% by weight of at least one pigment, 0 to about 1% by weight of at least one PH stabilizer, and at least one antifoam. agent 0
~2% by weight and 0 of at least one plasticizer
~2% by weight.

The dimethyl ether, water and polar solvent are present in the composition in proportions to provide a single phase propellant active carrier system in which the remaining ingredients are dissolved or suspended.

Preferably, the composition comprises as its polar organic solvent component about 1% to about 20% by weight of at least one aliphatic monohydric alcohol containing 1 to 6 carbon atoms and at least one water-soluble from about 1% to about 10% by weight of organic coalescing solvent.

The weight percentages are based on the total aqueous coating composition.

Aerosol aqueous coating compositions formulated as described above using the propellant-active carrier systems of the present invention can be sprayed onto a substrate surface without foaming and are pigmented or non-pigmented continuous coating compositions. The film is removed rapidly, usually around 15
Dry to the touch in ~30 minutes, acceptable period of time, usually approx.
Fully water resistant in ~5 hours.

The invention will be illustrated by the following examples.

Examples 1-14 A number of aerosol waterborne coating formulations were prepared using various film-forming polymers and pigments and placed in aerosol cans. A film was sprayed onto the surface of the support. In each case, a continuous film was formed that was dry to the touch in 30 minutes, water resistant within 3 hours after application, and had salt spray resistance (ASTM test B117) for more than 50 hours. .

Examples of such formulations are shown below.

Example 1 Red oxide primer - mixed acrylic-epoxy resin component Weight % WL91 resin ⁽¹⁾ 3.6 38-690 resin ⁽²⁾ 14.5 Water 13.25 Isopropyl alcohol 15.0 Butyl cellosolve 4.0 Texanol 0.7 Red oxide pigment 5.0 Dryer - Mn 6%, Co6% 0.25 L475 ⁽³⁾ 0.2 Triethanolamine 1.0 Dioctyl phthalate 0.5 OK412 ⁽⁴⁾ 2.0 Dimethyl ether 40.0 Total 100.0 Note: (1) Acrylic resin manufactured by Rohm and Haas (2) Epoxy resin manufactured by Reichhold Chemicals (3) ) Antifoaming agent manufactured by Dow Chemical Company (4) Silica erasing agent Example 2 Purple - Acrylic resin component Weight % WL91 resin 22.0 Water 10.0 Isopropyl alcohol 15.0 Butyl cellosolve 4.5 Texanol 0.7 White pigment 2.3 Purple pigment 4.6 L475 0.2 5%NH ₄ OH 0.2 Dioctyl phthalate 0.2 Dimethyl ether 40.0 Total 100.0 Examples 3 to 7 A formulation was prepared according to Example 2 using WL91 as the resin with the pigments changed as follows.

Example 3...White Example 4...Red Example 5...Green Example 6...Black Example 7...Orange Example 8 Black without lint - Acrylic resin component Weight % WL91 resin 21.8 Water 9.5 Isopropyl alcohol 15.0 Butyl cellosolve 4.5 Texanol 0.7 Black pigment 5.0 L475 0.4 5%NH ₄ OH 0.5 ^Dioctyl phthalate 0.5 OK412 2.0 Triton Orange fluorescent - Acrylic resin component Weight% 90-587 resin ⁽¹⁾ 15.0 Water 12.7 Isopropyl alcohol 15.0 Butyl cellosolve 4.0 Flame orange pigment 11.7 L475 0.2 NH ₄ OH (concentrated) 1.3 Triton X405 ⁽²⁾ 0.1 Dimethyl ether 40.0 Total 100.0 Note: (1) Acrylic resin manufactured by Reichhold Chemicals (2) Nonionic surfactant manufactured by Rohm & Haas Example 10 Red oxide primer-alkyd-acrylic resin mixture components Weight % WL91 resin 18.00 Aloron 585 ⁽¹⁾ 5.75 Water 15.03 Isopropyl Alcohol 15.00 Butyl Cellosolve 4.50 Texanol 0.70 Red Oxide Pigment 8.00 L475 0.40 5%NH ₄ OH 0.02 Dioctyl Phthalate 0.50 OK412 2.00 Triton X100 0.10 Dimethyl Ether 30.00 Total 100 .00 Notes: (1) Example of alkyd resin manufactured by Ashland Oil Co., Ltd. 11 Purple - alkyd resin component Weight% Alolone 580 ⁽¹⁾ 27.0 Alorone 585 ⁽²⁾ 10.2 Water 8.8 Isopropyl alcohol 7.7 Butyl cellosolve 2.3 Purple pigment 2.1 White pigment 1.1 Dryer 0.3 L475 0.2 5% NH ₄ OH 0.1 Triton X100 0.3 Dimethyl ether Tel 40.0 total 100.0 Notes: (1) and (2) Ashland Oil Alkyd Resin Example 12 Red Oxide Primer-Epoxy Resin In the formulation of Example 1, substitute increased amounts of 38-690 resin for WL91 resin. , the amount of 38-690 resin in the resulting formulation was 18.1% by weight.

Example 13 Transparent PVC resin component Weight % 415H resin ⁽¹⁾ 25.0 Water 24.7 Isopropyl alcohol 15.0 Butyl cellosolve 5.0 L475 0.2 5% ammonia 0.1 Dimethyl ether 30.0 Total 100.0 Note: (1) Carboxy-modified polyvinyl chloride manufactured by B.F. Terpolymer Example 14 components Weight% styrenated epoxy ester ⁽¹⁾ 13.0 Water 31.0 White colorant ⁽²⁾ 13.5 Dryer (6% copper naphthenate, 6% manganese naphthenate) 0.2 Active 8 0.1 Concentrated ammonia 1.0 Byk020 (antifoam) 0.2 Byk351 (flow agent) 1.0 Dimethyl ether 40.0 Total 100.0 Notes: (1) 453V8 by CPV - Consists of 70% solids and 30% butyl cellosolve.

(2) Colorant composition: styrenated epoxy ester
23.5% by weight Concentrated Ammonia 1.5 〃 Water 15.0 〃 TiO ₂ 60.0 〃 100.0 〃 To summarize the present disclosure, the present invention therefore provides:
A novel propellant-active carrier composition is provided that is useful for spraying water-based coatings onto substrate surfaces. Various modifications are possible within the scope of the claims of the present invention.

Claims (1)

Claims: 1. (A)(I) from about 6 to about 25 percent by weight of a film-forming polymer, and () from about 94 to about 75 percent by weight of a propellant, water, and at least one water-soluble polar solvent. % of a propellant-active carrier composition, said film-forming polymer (I) is a water-soluble polymer, and said propellant-active carrier composition (1) contains from about 20 to about 75% by weight (2) from about 10 to about 50% by weight of water; (3) (a) from about 1 to about 30% by weight of the formula R-OH, where R has 1 to 6 carbon atoms; (Unsubstituted straight-chain or branched-chain alkyl group.)
and (b) about 1 to about 15% by weight of at least one monohydric alcohol represented by
a single phase comprising: a formulation of the species with a water-soluble organic flocculating solvent; and (B) a stabilizer sufficient to maintain the formulation (A) at a pH of 7.2 to 10. 1. A spray coating composition which forms a continuous air-drying film on the surface of a support. 2. The composition according to claim 1, which has a pH within the range of 7.4 to 7.9. 3 The monohydric alcohol is ethanol or propanol, and the water-soluble coagulation solvent is a lower alkyl ester of ethylene or propylene glycol,
The composition according to claim 1 or 2, characterized in that it is diacetone alcohol, ketone or ester alcohol. 4. The amount of propellant active carrier composition is from about 88 to about
80% by weight and the amount of film-forming polymer is approx.
A composition according to any one of claims 1 to 3, wherein the composition is from 12 to about 20% by weight. 5 Up to 15% by weight of at least one pigment, up to about 3% by weight of at least one surfactant, up to about 2% by weight of at least one antifoam agent, and about 2% by weight of the total composition A composition according to any one of claims 1 to 4, characterized in that at least one additional paint-forming component is present selected from the group consisting of at least one plasticizer: thing. 6 The amount of dimethyl ether in the total composition is approximately
20 to about 40% by weight, the amount of water is about 35% by weight, the amount of monohydric alcohol is about 5 to about 20% by weight, and the amount of coalescing solvent is about 5 to about 10% by weight. A composition according to any one of claims 1 to 5, characterized in that: 7. The composition according to any one of claims 1 to 6, wherein the film-forming polymer is an acrylic resin, an alkyd resin, an epoxy ester resin, or a polyvinyl copolymer. 8. The composition according to claim 7, wherein the film-shaped polymer is a water-soluble oil-modified alkyd resin.