JP2003512480A - Nonflammable non-aqueous composition - Google Patents

Abstract

  (57) [Summary] Non-aqueous cleaning compositions and methods, especially for dry cleaning textiles, comprise from 0.5 to 80 wt% of at least one perfluoro compound, from 2 to 98 wt% of solvent naphtha, mineral spirits or medium aliphatic hydrocarbons, glycol ethers Alternatively, 1 to 98 wt% of glycol ether acetate is used.

Description

FIELD OF THE INVENTION The present invention relates to compositions intended to replace perchlorethylene for dry cleaning, as well as low flash point replacement solvents for perchlorethylene as a replacement. The present invention provides a method for substantially raising the flash point of low flash point petroleum-based solvents currently used in the dry cleaning industry. The present invention renders solvents non-flammable and non-flammable, but among the numerous contaminants from fabrics, fabrics and garments and uniforms commonly encountered in the dry cleaning industry, uniforms, fabrics and garments commonly encountered in the rental business, among others. Dirt, grease,
Enhances ability to remove fatty acids, oils and soil. The invention further relates to degreasing formulations for use in removing grease and oil from equipment, machinery and the like. In addition, the present invention further can be used to separate and concentrate oil from clothing by distillation, addressing the need to dispose of it as perchlorethylene contaminated hazardous waste.

BACKGROUND OF THE INVENTION Garments and other fabrics, including rugs, curtains, industrial uniforms, etc.
It becomes contaminated with pigments, fatty acids and other contaminants that attach to dust that is attracted to clothing during the normal course of wear.

Currently, these garments are primarily cleaned by dry cleaning and use perchlorethylene, which has no flash point. More recently, other fluids for dry cleaning have emerged. These fluids, typically non-halogenated petroleum-based solvents, seek new emergence of machines with oxygen sensors and / or nitrogen injection to prevent combustion or explosion in the equipment due to low flash point fluids. These solvents are generally called petroleum-based solvents. Most notably, stodda solvent
rd solvent), mineral spirits, Exxon Chemical
Dry-cleaning Fluids DF2000 and Exxsol D40, products with the trademark Drylene, and Shell Chemical
Shell Company 142HT from Al Company. All have a flash point of less than 150 ° F (about 65 ° C), are flammable and are therefore classified as IIIA solvents by the NFPA (Fire Fighting Association) due to their tendency to burn or explode in dry cleaning equipment. Usually, the ignition source for combustion is an electrostatic charge. The source of ignition is rarely a cigarette lighter inadvertently left in a pocket of clothing, but sometimes. In Japan and China, where stoddard solvents and mineral spirits are commonly used, fires and explosions often occur in dry cleaning equipment.

The present invention allows the use of these low flash point solvents by raising the flash point to eliminate flammability and flammability classifications and hazards.

OBJECT OF THE INVENTION To modify the flash point of flammable and combustible hydrocarbon solvents in a composition for commercial dry cleaning of fabrics and related products by utilizing components with zero ozone depletion potential. It is an object of the present invention to provide a composition having a flash point above 100 ° C.

Furthermore, it is a further object of the present invention to maintain the essential physical properties of petroleum-based solvents to maintain their suitability as dry cleaning fluids.

Yet another object of the present invention is to increase the vapor pressure of the solvent in order to maintain the high solvent flash point while at the same time promoting the drying of the garment.

SUMMARY OF THE INVENTION The present invention relates to compositions and methods for removing contaminants from fabrics and associated fabrics and garments, and grease and oil from machinery and associated equipment.
And it provides a high operational safety threshold due to its high flash point, does not pose a significant hazard to groundwater, is environmentally compatible and is substantially biodegradable. To use. Suitably, the composition according to the invention is substantially non-toxic, is a substantially biodegradable liquid above room temperature, is not a hazardous air pollutant (HAP) and has a slight VOC potential, It has zero ozone depletion potential and is effective in removing many contaminants from textiles, and especially clothing such as industrial uniforms and gloves.

The composition according to the invention avoids the use of perchlorethylene, mineral spirits or chlorinated fluorohydrocarbons (CFCs). The composition of the present invention can be used as an effective replacement for perchlorethylene in commercial cleaning processes, as well as as a degreasing agent.

The compositions of the present invention have many of the favorable physicochemical properties of perchlorethylene without the undesirable properties, most notably the environmental incompatibility of perchlorethylene.

The composition according to the invention does not present a threat of groundwater. Because, compared with the density of perchlorethylene of 13.47 lbs / gal, its density is 7.51 lbs / gal.
It is because it is ~ 8.2 lbs / gal. The compositions of the present invention may provide a surfactant that may help remove fatty acids, pigments, and other contaminants from textiles, especially clothing. In addition, the composition of the present invention is compatible with most, if not all, clothing fibers used in textiles. Advantageously, like perchlorethylene, the compositions of the invention do not substantially change shape or deform the fibers underlying the fabric. The composition is a dry-cleaner word, which is used to comfortably wear clothes (i
part a nice hand) (smooth feeling
el)), which is usually stable during cleaning operations and at drying, separation and distillation temperatures.

The cleaning composition is essentially non-aqueous and according to the invention: i. Glycol ether or glycol ether acetate about 1 wt% to about 9
8 wt%; ii. About 2 wt% to about 98 wt% solvent naphtha, mineral spirits, or medium aliphatic hydrocarbons; and iii. At least one perfluoro compound from about 0.5 wt% to about 80 wt%
With.

  The composition may further contain a hydrofluoroether.

Alternatively, the essentially non-aqueous composition is: i. Glycol ether or glycol ether acetate about 1 wt% to about 9
8 wt%; ii. At least one perfluoro compound from about 0.5 wt% to about 80 wt%; iii. Solvent naphtha, mineral spirits, or medium aliphatic hydrocarbons from about 2 wt% to about 98 wt%; and iv. Hydrofluoroether from about 0.5 wt% to about 80 wt% can be included.

In yet another embodiment, the essentially non-aqueous composition comprises i. Glycol ether or glycol ether acetate about 1 wt% to about 9
8 wt%; ii. About 2 wt% to about 98 wt% solvent naphtha, mineral spirits, or medium aliphatic hydrocarbons; and iii. Hydrofluoroether from about 0.5 wt% to about 80 wt% can be included.

As defined herein, "essentially non-aqueous" means that the composition contains less than about 1% water.

The preferred amount of glycol ether for the composition of the present invention is from about 1 wt% to about 98 w.
t%, more preferably about 3 wt% to about 60 wt%, and even more preferably about 4 wt%.
% To about 40 wt%, and even more preferably about 5 wt% to about 15 wt%. Suitable amounts of aliphatic hydrocarbons for use in the cleaning compositions of the present invention are about 2 wt% to about 98 wt%, more preferably about 30 wt% to about 97 wt%,
Even more preferably it ranges from about 63 wt% to about 95 wt%. The amount of perfluorocarbon compound in the cleaning composition according to the invention is preferably about 0.5.
wt% to about 80 wt%, more preferably about 2 wt% to about 60 wt%, even more preferably about 3 wt% to about 40 wt%, even more preferably about 3 wt% to about 3.
0 wt%, and even more preferably ranges from about 4 wt% to about 25 wt%. Suitable amounts of hydrofluoroether for use in the cleaning compositions of the present invention are from about 0.5 wt% to about 80 wt%, more preferably from about 2 wt% to about 60.
wt%, more preferably about 3 wt% to about 30 wt%, and even more preferably about 4 wt% to about 25 wt%.

The compositions according to the present invention may be formulated, for example, with antibacterial agents, textile finishing agents, anionic surfactants, to assist in formulating small amounts of water which help remove water-soluble soils from textiles and garments or their mixtures. At least 1 selected from the group consisting of
It may optionally contain one component.

The composition according to the invention generally has a density lower than water and is preferably biodegradable, suitably with a BOD of greater than about 20 ppm, more preferably greater than about 40 ppm. The compositions of the present invention are particularly environmentally advantageous as they are readily biodegradable and lighter than water. As such, the preferred composition of the present invention is
If there is, there is almost no danger of entering groundwater.

Further, the present invention is a method of removing one or more contaminants from a fabric, textile, garment, flexible or rigid surface, the method comprising removing the contaminant from the fabric, textile, garment, flexible or rigid surface. A method comprising depositing a non-aqueous composition of the present invention onto a fabric, fabric, garment, flexible or rigid surface in an amount effective to remove a substance. Optionally, the contaminants removed from the clothes that are initially present in the composition / contaminant mixture can be removed from the cleaning composition by distillation and can be recovered or isolated. They often contain oils and associated hydrocarbons that can be used as fuels, thereby addressing the need for distiller residue disposal as hazardous waste.

    Detailed Description of the Invention   The following definitions are used throughout the specification to define the present invention.

"Contaminant (s)" are not normally found in clean, uncontaminated fabrics or other flexible and rigid surfaces such as textiles or machinery and metal surfaces. And used to describe most substances that are usually removed from textiles or other surfaces during the cleaning process. Contaminants include fats, fatty acids, especially triglycerides and fatty acids, fat-like substances, salts, food waste, sweat, blood stains, soils, oils, greases, related lubricants and many other synthetic or natural or biological contaminants. Including but not limited to substances, or lubricants, they are not normally found on surfaces and fabrics cleaned according to the present invention. The most common contaminants removed by the compositions according to the invention are triglycerides, fatty acids, and related fatty food contaminants and greases, oils and related lubricants. One of ordinary skill in the art will appreciate that the present invention is effective in removing a wide range of surface contaminants: however, in many cases, depending on the contaminant chemistry, the compositions of the present invention , May require modification within the teachings of the present invention to maximize removal of certain contaminants.

Examples of hydrofluoroether compounds include, but are not limited to, ethoxynonafluorobutane, ethylperfluoroisobutylether, ethylperfluorobutylether, methoxynonafluorobutane, methylnonafluoroisobutylether, methylnonafluorobutylether and isomers thereof. .

The term "perfluoro compound" is a compound herein C _{n F} 2n _+
2 (n = 3-8).

The composition of the present invention further contains a hydrofluoroether / trans-1,2-dichloroethylene mixture. In one embodiment, it is an azeotrope. In another embodiment, the hydrofluoroether: trans-1,2-
The ratio of dichloroethylene is about 5:95 to about 95: 5.

The terms "glycol ether" and "glycol ether acetate" refer to
Used throughout the specification to indicate certain suitable ingredients for use in the compositions according to the invention. In principle, propylene glycol ethers and ether acetates and ethylene glycol ethers and ether acetates can be used. Typical glycoethers for use in the present invention are ethylene and propylene glycol substituted ethers such as propylene glycol ether t-butyl ether, ethylene glycol methyl ether, diethylene glycol methyl ether, diethylene glycol methyl ether, triethylene glycol methyl ether, ethylene glycol. Methyl ether, diethylene glycol ethyl ether, triethylene glycol ethyl ether, ethylene glycol n-propyl ether, diethylene glycol n-propyl ether, triethylene glycol n-propyl ether, ethylene glycol isopropyl ether, diethylene glycol isopropyl ether, triethylene glycol isopropyl ether, ethylene Glico Le n- propyl ether, diethylene glycol n- propyl ether, triethylene glycol n- propyl ether, ethylene glycol n- butyl ether, diethylene glycol n- butyl ether, triethylene glycol n
-Butyl ether, propylene glycol methyl ether (PM), dipropylene glycol methyl ether, dipropylene glycol dimethyl ether, tripropylene glycol methyl ether, propylene glycol ethyl ether,
Dipropylene glycol ethyl ether, tripropylene glycol ethyl ether, propylene glycol n-propyl ether (PnP), dipropylene glycol n-propyl ether, propylene glycol isopropyl ether,
Dipropylene glycol isopropyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, glycol ethers based on aromatics, ethylene glycol methyl ether acetate, diethylene glycol methyl ether acetate, propylene glycol methyl ether acetate, dipropylene glycol methyl Including ether acetates, and mixtures thereof,
Not limited. These compounds are, inter alia, Dow Chemical Cor
p. And Arco Chemical Company. The inclusion of equivalents of these glycol ethers and glycol ether acetates is also contemplated by the present invention.

Suitable glycol ethers and glycol ether acetates for use in the present invention have a relatively high vapor pressure and low boiling point to promote rapid drying of the fabric and to accelerate distillation.

The terms "aliphatic hydrocarbon", "solvent naphtha" and "mineral spirit" consist of two open and branched chain structures, linear and iso. The common, loosely defined term naphtha refers to a range of light petroleum distillates.

Included in the classification of naphtha is a boiling point of 32 ° to 100 ° C (90 ° to 175 ° F).
Light crude naphtha (LCM) liquid distillate fraction, and boiling range 163 ° -218
It is a heavy crude naphtha having a temperature of 325 ° to 425 ° F.

The following examples are provided to illustrate the present invention and should not be construed as limiting the scope of the invention in any way.

Example The challenge was to prepare a composition that enhances the performance characteristics of petroleum-based solvents, naphtha and mineral spirit solvents currently used in dry cleaning from both a safety and performance standpoint. In the present invention, they present severe ignition and explosion hazards in use. Strict constraints are placed in defining equipment that uses petroleum-based solvents because of the inherent fire hazards that storage and use of these low flash point solvents pose.

The following compositions were made and evaluated for their ability to clean typical contaminants from fabrics.

In addition, they were evaluated for solvent effect on typical fabrics and fabrics used in industrial gloves and uniforms, and conventional dry cleaning fabrics.

Each composition was tested using Tagart Cl to evaluate its flammability or flammability.
It was tested using the raised Test flash point method.

The following ingredients were used in the following examples to make typical compositions of the invention. Dipropylene glycol dimethyl ether (DMM) is commercially available from Dow Chemical Co. of Midland, Michigan. Obtained from COVI-OX-T-70 is a mixed tocopheral concentrate. COVL-OX-T-70 is available from Henkel Chemical Co. of Kankakee, Illinois. Obtained from HFE
-7100 and HFE-7200 are hydrofluoroethers. HFE
All the components represented by -7100, HFE-7200, and PF are perfluoro compounds. PF-5070, PF-5058, PF-5060, PF-505
2, PF-5056, and PF-5080 are St. Paul's t
Obtained from he 3M Company. Stoddard Solvent, Mineral Spirits and Shell Sol 142HT are in Houston, Texas.
Shell Chemical Co. DF-2000, available from Exxon Chemical Co. of Houston, Texas. Obtained from D
F-2000 and Shell Sol 142-HT are hydrotreated medium aliphatic hydrocarbon solvents.

In preparing the composition, the individual components can be added and agitated to provide a well mixed product. For the most part in these examples, the ingredients were added in the order in which they were presented. In most cases the product was transparent at room temperature.

Example 1 Ingredient wt% DMM ¹ 1.00 COVI-OX-T-70 ² 1.00 HFE-7100 ³ 1.00 PF-5058 ³ 1.00 Shell-Sol 142HT ⁴ 96.00 1-DMM, dipropylene glycol. Dimethyl ether. Propylene Glycol Methyl Ether, Propylene Glycol Ethyl Ether, Propylene Glycol n-Propyl Ether, and Dipropylene Glycol Methyl Ether are among the group of ethers that are useful in the present invention, although they have sufficiently high vapor pressure Is.

An antioxidant useful in preventing hydroperoxide formation in 2-glycol ether. 3-HFE-7100, HFE-7200, PF-5070, PF-
5080, PF-5058, PF-5052, PF-5056, and PF-5
060. Although useful, perfluoro compounds having carbon atoms varying from C3 to C18 are some of the group of perfluoro compounds used to effectively control the flash points of low flash point petroleum solvents and glycol ethers. .

4-naphtha, Shell Sol 142HT, DF-2000, stoddard solvent, and mineral spirits. A group of low flash point petroleum fractions, mainly C9-
A combination of C12 aliphatic hydrocarbons.

Example 2 DMM 5.00 COVI-OX-T-70 1.00 HFE-7100 5.00 PF-5058 3.00 Shell Sol 142HT 86.00 Example 3 DMM 15.00 COVI-OX-T-70 1.00 HFE-7100 10.00 PF-5058 5.00 Shell Sol 142 HT 69.00 Example 4 DMM 4.00 dimethyl polysiloxane. 10 HFE-7100 1.00 HFE-71DE 5.00 PF-5070 5.00 Shell Sol 142 HT 85.90 Example 5 DMM 4.00 Shell Sol 142 HT 75.00 HFE-71D90 5.00 HFE-7100 15. 00 PF-5058 1.00 Example 6 DMM 5.00 Shell Sol 142 HT 80.00 COVL-OX-T-70. 10 HFE-7100 10.00 PF-5060 4.90 Example 7 DMM 5.00 Shell Sol 142 HT 88.52 HFE-7100 4.00 COVL-OX-T-70. 10 PF-5060 2.38 Example 8 DMM 1.00 Stoddard Solvent 80.90 COVI-OX-T-70. 10 HFE-7100 10.00 PF-5058 8.00 Example 9 PNP 1.00 DF-2000 96.00 COVI-OX-T-70. 10 HFE-7100 1.90 PF-5058 1.00 Example 10 PNP 5.00 DF-2000 86.90 COVI-OX-T-70. 10 HFE-7100 5.00 PF-5058 3.00 Example 11 PNP 15.00 DF-2000 69.00 COVI-OX-T-70. 10 HEE-7100 10.00 PF-5058 5.90 Example 12 PNP 3.00 DPM 1.00 DF-2000 89.90 COVI-OX-T-70. 10 HFE-7100 1.00 PF-5070 5.00 Example 13 DMM 1.00 Odorless mineral spirits 80.90 COVI-OX-T-70. 10 HFE-7200 10.00 PF-5058 8.00 Example 14 DMM 5.00 DF-2000 80.02 COVI-OX-T-70. 10 HFE-7200 4.88 PF-5060 10.00 Example 15 DMM 1.00 DF-2000 90.02 COVI-OX-T-70. 10 HFE-7200 6.88 PF-5060 2.02 Example 16 DF-2000 93.00 HFE-7100 3.00 PF-5058 2.02 Example 17 DF-2000 90.00 HFE-7100 5.00 PF-5058 5.00 Example 18 Shell Sol 142-HT 95.00 HFE-7100 5.00 PF-5058 5.00 Example 19 Shell Sol 142-HT 92.00 HFE-7200 3.00 PF-5052 5.00 Example 20 Shell Sol 142-HT 95.00 HFE-7100 1.00 PF-5080 4.00 Example 21 Shell Sol 142-HT 95.00 HFE-7200 2.00 PF-5060 3.00 Example 22 Shell Sol 142 95.00 HFE -7100 1.00 F-5070 4.00 Example 23 DF-2000 92.00 HFE-7200 2.00 PF-5052 6.00 Example 24 DF-2000 96.00 HFE-7200 1.00 PF-5060 3.00 Example 25 DF- 2000 95.00 HFE-7100 1.00 PF-5080 4.00 Example 26 DF-2000 95.00 HFE-7100 1.00 PF-5070 4.00 Although specific aspects are disclosed herein, these aspects are disclosed. Are intended to be illustrative of some aspects of the invention. Any equivalent aspects are intended to be within the scope of this invention. Indeed, various modifications of the invention in addition to those shown herein will become apparent to those skilled in the art from the foregoing description. Such modifications are considered to be within the scope of the claims.

  Various publications are cited herein, the disclosures of which are incorporated by reference in their entireties.

─────────────────────────────────────────────────── ─── Continued front page    (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, I T, LU, MC, NL, PT, SE), OA (BF, BJ , CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, K E, LS, MW, MZ, SD, SL, SZ, TZ, UG , ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AU, BA, BB, BG, BR, CA, CN, CU, CZ, EE, GD, GE, H R, HU, ID, IL, IN, IS, JP, KP, KR , LC, LK, LR, LT, LV, MG, MK, MN, MX, NO, NZ, PL, RO, SG, SI, SK, S L, TR, TT, UA, UZ, VN, YU

Claims (20)

[Claims] 1. i. About 0.5 wt% of at least one perfluoro compound
About 80 wt%; ii. Solvent naphtha, mineral spirits, or medium aliphatic hydrocarbons from about 2 wt% to 98 wt%; and iii. A non-aqueous composition comprising about 1 wt% to about 98 wt% glycol ether or glycol ether acetate. 2. The composition comprises from about 3 wt% to about 40 wt%, more preferably from about 3 wt% to about 30 wt%, and most preferably from about 4 wt% to about 25 wt%.
The composition of claim 1 comprising at least one perfluoro compound. 3. The composition of claim 1 wherein said solvent naphtha, mineral spirits, or medium aliphatic hydrocarbons are selected from the group consisting of straight chain paraffins, isoparaffins and light petroleum distillates. 4. The composition of claim 3 wherein said composition comprises from about 30 wt% to about 97 wt%, or preferably from about 63 wt% to about 95 wt% petroleum distillate. 5. The composition of claim 2 wherein said perfluoro compound has from about 3 to about 18 carbon atoms. 6. The composition comprises from about 3 wt% to about 60 wt%, more preferably from about 4 wt% to about 40 wt%, or even more preferably from about 5 wt% to about 15.
The composition of claim 1 comprising wt% glycol ether. 7. The composition according to claim 1, further comprising a hydrofluoroether compound. 8. The composition according to claim 7, wherein the hydrofluoroether compound is hydrofluoroethylene. 9. A hydrofluoroether compound / trans-1,2
-Composition according to claim 1, comprising a mixture of dichloroethylene. 10. The composition according to claim 9, wherein the hydrofluoroether compound / trans-1,2-dichloroethylene mixture is a hydrofluoroethylene / trans-1,2-dichloroethylene mixture. 11. The composition according to claim 10, wherein the hydrofluoroethylene / trans-1,2-dichloroethylene mixture is an azeotrope. 12. The composition of claim 10 wherein the ratio of hydrofluoroethylene to trans-1.2-dichloroethylene is about 5:95 to about 95: 5. 13. The composition according to claim 1, wherein the composition further comprises at least one component selected from the group consisting of antibacterial agents, textile finishes, anionic surfactants and mixtures thereof. 14. i. At least one perfluoro compound about 0.5 wt
% To about 80 wt%; ii. About 2 wt% to about 98 wt% solvent naphtha, mineral spirits, or medium aliphatic hydrocarbons; and iii. An essentially non-aqueous composition comprising 0.5 wt% to about 80 wt% of a hydrofluoroether compound. 15. The composition comprises a hydrofluoroether / trans-1,2-
15. The composition of claim 14, which comprises a mixture of dichloroethylene. 16. i. About 1 wt% to about 98 wt% glycol ether or glycol ether acetate; ii. About 2 wt% to about 98 wt% solvent naphtha, mineral spirits, or medium aliphatic hydrocarbons; and iii. A non-aqueous composition comprising about 0.5 wt% to about 80 wt% hydrofluoroether compound. 17. A method of removing one or more contaminants from a fabric, fabric, garment, flexible or rigid surface, said stain comprising said fabric, fabric, garment, flexible or rigid surface. 17. A method comprising applying a non-aqueous composition according to claim 1, 14 or 16 to a material, fabric, garment, flexible or rigid surface in an amount effective to remove material. 18. The method of claim 17, wherein the flexible or rigid surface is a mechanical or metallic surface. 19. (a) recovering the composition / contaminant mixture; (b) distilling the composition / contaminant mixture of step (a) to separate the contaminant from the composition. 18. The method of claim 17, further comprising: (c) isolating the contaminant. 20. A fabric comprising the non-aqueous composition according to claim 1, 14 or 16.
17. A method for removing one or more contaminants from a fabric, fabric, garment, flexible or rigid surface, comprising applying to the fabric, garment, flexible or rigid surface. Use of the described composition.