JPS6350463B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF THE INVENTION This invention relates to a method for removing soil from textiles using cyclic dimethylpolysiloxanes. especially,
This invention relates to the use of cyclic dimethylpolysiloxanes to remove oily/greasy stains from textiles. BACKGROUND OF THE INVENTION Fabrics and textiles such as carpets and upholstery often develop noticeable stains from inadvertent contact with food and other fat- and oil-containing substances. Various organic solvents, such as alcohols, petroleum hydrocarbons, and chlorinated hydrocarbons, have been used in cleaning compositions adapted for direct application to fabrics as stain removers. Several methods are known for formulating stain cleaning compositions. For example, non-residue cleaners are formulated with only volatile ingredients. After dissolving, mobilizing and removing the stain material, such formulations are intended to completely evaporate without leaving any residual components on the textile. Other cleaning compositions use a combination of solvent and solid sorbent particles. The solvent mobilizes the soil and the adsorbent solid attracts the soil and solvent to itself. It is intended that residual adsorbent solids be easily removed from the textile by brushing or vacuuming. Yet another method involves liquid cleaning compositions adapted as pre-wash stain removers. These compositions typically contain concentrated synthetic surfactants along with alcohols or other solvents. When used as a pre-wash stain remover, the non-volatile surfactant component remains as a residue on the textile, which is removed by normal household laundering operations. When washed with water, the pre-wash stain remover composition also acts like a heavy-duty laundry detergent. Although known stain cleaning compositions effectively remove some types of stains, other types of stains are unaltered or only incompletely removed by the compositions. In other cases, the cleaning composition itself damages the textile or leaves a residue on the textile in such a way that a visible ring forms around the treated area. The purpose of the present invention is to effectively mobilize oil and fat stains while not damaging a wide range of textiles, both synthetic and natural, and leaving no residue or visible rings on the treated textiles. The object of the present invention is to alleviate the problems associated with conventional cleaning compositions by providing a new method of cleaning stains using non-volatile silicone fluids. It is known from US Pat. No. 4,324,595 to remove tacky adhesives from substrates by using an octamethylcyclotetrasiloxane fluid to detackify the tacky adhesive.
Although this method is taught to be particularly effective for removing tacky adhesives from human skin, this method also has applications in removing tacky adhesives from a wide variety of substrates, including textiles. It has also been shown that it can be done. However, this patent only teaches the removal of tacky adhesives and does not suggest removing oil and fat stains with cyclic dimethylsiloxanes. JP-A-49-35681 discloses a stain removal composition containing a small amount (0.5-10% by weight) of silicone oil in combination with a cleaning solvent such as trichloroethane or petroleum hydrocarbons. There is.
Although the type of silicone oil used has not been further verified, it has been taught that the silicone remains on the fabric after cleaning to provide continued water repellency and stain resistance to the fabric. After all, it is clear that this publication does not foresee the use of completely volatile cyclic dimethylpolysiloxanes. The aerosol type water-based cleaning composition is manufactured by Tokukai Sho.
53-56203, which comprises a nonionic surfactant, an alkanolamine, a glycol ether, an alcohol, a propellant, and a linear dimethylpolysiloxane having 2 to 7 silicon atoms per molecule of 0.02 to 0.1% by weight. Contains %.
This publication only discloses the use of very small amounts of linear dimethylpolysiloxane and does not foresee the use of large, solvent-effective amounts of cyclic dimethylpolysiloxane. The use of tetraethoxysilane as a solvent for removing fat from knitted fabrics is covered by USSR patent 979548-
It is disclosed in Publication A. However, tetraethoxysilane is not stable in contact with water and hydrolyzes to alcohol and silica solids. A method for dry cleaning and waterproofing fabrics is disclosed in US Pat. No. 3,123,494, which uses silicone compositions diluted in common dry cleaning solvents. The recommended silicone composition is a mixture of linear dimethylpolysiloxane fluid and crosslinked methylsiloxane resin. Excess liquid cleaning mixture is removed from the fabric by centrifugation, while the retained silicone provides a continued waterproofing effect on the fabric. Again, this publication does not foresee the use of fully volatile cyclic dimethylpolysiloxanes as cleaning solvents. Liquid cleaning compositions for removing dust and coarse particles from solid surfaces are disclosed in U.S. Pat.
Disclosed in No. 2955047. The composition contains a surfactant, water, a water-miscible organic solvent, and an oil-in-water suspension of dimethylpolysiloxane oil. This particular siloxane is a linear polymer with a viscosity ranging from 200 to 350 centistokes. The siloxane polymer is said to impart high gloss to the treated surface by depositing a monolayer on the surface. Although somewhat similar,
U.S. Pat. No. 2,993,866 teaches an aerosol glass cleaner composition containing isopropanol, a fluorochlorohydrocarbon propellant, and a linear dimethylpolysiloxane having a viscosity of about 200 centistokes. An all-purpose cleaner composition containing a mixture of a surfactant, isopropyl alcohol, and a silicone defoamer is disclosed in US Pat. No. 4,311,608. The silicone defoamer is an oil-in-water suspension of dimethylsiloxane polymer. A cleaner (apparently a wiper type) impregnated with a composition containing mineral oil or alcohol together with organopolysiloxane was disclosed in Japanese Patent Application Laid-Open No. 1983-1983.
It is disclosed in Publication No. 161059. The organopolysiloxane is characterized by a viscosity of less than 30 centipoise at 20°C. SUMMARY OF THE INVENTION The present invention provides a liquid composition containing an effective amount of a cyclic siloxane selected from the group consisting of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane to aid in soil removal. and/or relates to a textile fabric cleaning method characterized in that the method is applied to a textile fabric soiled with fat to dissolve and/or loosen the dirt, and to remove a combination of dirt and cyclic siloxane from the textile fabric. . DETAILED DESCRIPTION In use, the novel textile cleaning composition is applied to soiled areas of clothing, carpets, and other textiles by spraying, showering, or by means of a cloth or sponge applicator. The composition may be rubbed or brushed into the fabric to aid in softening and dissolving soil components. The soil/solvent binder is then removed from the fabric by any of the well-known methods such as blotting with an absorbent material, vacuum cleaning after adsorption to particulate matter, or normal domestic laundry operations. . The cyclic siloxanes used in the liquid cleaning and stain removal compositions of the present invention are commercially available and may be prepared by well known methods such as hydrolysis and condensation of dimethyldichlorosilane. Ru. Compared to linear polydimethylsiloxane, the cyclic siloxane used in the present invention has a
It is a relatively volatile substance with a boiling point below 250°C. A single cyclic siloxane or a mixture of two or more cyclic siloxanes may be used in the liquid cleaning composition. Particularly preferred cyclic siloxanes for use in the present invention are octamethylcyclotetrasiloxane, decamethylpentasiloxane, and dodecamethylcyclohexasiloxane. Useful cyclic siloxane mixtures may contain, in addition to the preferred cyclic siloxane, small amounts of other cyclic siloxanes, such as hexamethylcyclotrisiloxane or higher cyclics such as tetradecamethylcycloheptasiloxane, etc. You should understand that it is good. Generally, the amount of these other cyclic siloxanes in a useful cyclic siloxane mixture will be less than about 10% based on the total weight of the mixture. The amount of cyclic siloxane used in the liquid cleaning compositions of the present invention is not critical so long as the amount is effective to aid soil removal from textiles. Generally, the cleaning composition will be comprised of e.g.
Contains 100% by weight cyclic siloxane. The cleaning composition preferably contains 5 to 100% by weight;
More preferably, it contains 10 to 100% by weight of cyclic siloxane. The liquid cleaning compositions of the present invention may also contain other adjuvants such as conventional cleaning solvents, adsorbent solid particulates, synthetic builders, water-soluble organic detergent compounds, and cationic antistatic materials. For example, non-residue stain cleaning compositions may contain conventional cleaning solvents along with the cyclic siloxanes of the present invention. Conventional cleaning solvents having boiling points below about 250°C can be mixed with the cyclic siloxanes to form liquid compositions useful in the present invention. Useful additional cleaning solvents include alcohols such as isopropanol and butanol, petroleum hydrocarbons such as mineral spirits, and chlorinated hydrocarbons such as methylene dichloride, tetrachloroethylene, and trichloroethylene. Surprisingly, mixtures of cyclic siloxanes and conventional cleaning solvents have been found to be more effective in mobilizing stains than either cyclic siloxanes alone or conventional solvents alone. Mixtures of cyclic siloxanes and conventional solvents selected from the group consisting of petroleum hydrocarbons and chlorinated hydrocarbons are particularly effective. Conventional cleaning solvent approximately 30-70% by weight and cyclic siloxane
Mixtures containing 30 to 70% by weight are particularly preferred due to their stain mobilization ability. Solvent/adsorbent type cleaning compositions are also useful in the method of the present invention. In addition to the cyclic siloxane, such cleaning compositions may incorporate any of the adsorbents known for such applications. Effective adsorbents are inorganic particulates such as silica, talc, diatomaceous earth, and kaolinite; organic particulates such as starch, modified starch, nut shell powder, and ground rice husk; synthetic porous polymers such as the urea-formaldehyde polymer particles described in U.S. Pat. No. 3,910,848, which describes Adsorbents are generally used in amounts of about 5 to 40% based on the weight of cleaning solvent in the composition. The solvent/sorbent cleaning composition may also include a cationic antistatic agent to facilitate particulate removal during brushing or vacuum cleaning of textiles. Effective cationic antistatic agents are quaternary nitrogen salts having at least one _C10 to _C24 aliphatic hydrocarbon substituent on the nitrogen, such as stearyltrimethylammonium chloride, and the like. Antistatic agents are generally used at about 0.1 to 3% by weight, based on the total weight of the cleaning composition. The fabric cleaning methods of the present invention also include the use of pre-wash stain remover compositions containing a non-volatile surfactant component in addition to the cyclic siloxane solvent. Such pre-launder stain remover compositions generally contain a water-soluble organic detergent and a synthetic builder in combination with a cyclic siloxane solvent. Detergent compounds useful in pre-launder stain removers are anionic, nonionic, zwitterionic, and amphoteric surfactant compounds. Such detergent compounds are well known to those skilled in the detergent art. Specific cleaning agents are described in "Surface Active Agents" by Stewarts and Peri and "Surface Active Agents and Detergents" by Stewarts, Peri and Belch.
Detergents (both Interscience Publishers, New York, NY). Particularly preferred detergents are nonionic surfactants which are condensation products of polyethylene oxide and organic hydrophobic compounds which are usually aliphatic or alkyl aromatic in nature. Specific nonionic surfactants are a condensate of polyethylene oxide and nonylphenol, and a condensate of polyethylene oxide and myristyl alcohol. Generally, from about 10 to 80% by weight surfactant may be used in the pre-wash stain removal compositions of the present invention.
More preferred pre-wash stain removal compositions contain 30-70% by weight nonionic surfactant. The pre-wash stain remover of the present invention may also contain sodium tripolyphosphate, sodium carbonate, sodium silicate, oxodisuccinic acid, oxodiacetic acid, carboxymethyloxymalonic acid, carboxymethyloxysuccinic acid, lactoxysuccinic acid, citric acid, etc. It may contain various builder compounds such as alkali metal salts, ammonium salts, and substituted ammonium salts of mellitic acid, tetrahydrofurantetracarboxylic acid, polyacrylic acid, nitrilotriacetic acid, oxidized starch, and mixtures thereof. Builders are generally added to pre-launder stain removal compositions in amounts ranging from 0 to about 50% by weight based on the total weight of the composition. The liquid compositions of the present invention are particularly suitable for direct application to stains and soils on fabrics and other textiles. This composition can be applied to soiled textiles by normal usage. The liquid composition may be showered or sprayed onto the stain. Alternatively, the composition may be brushed or rubbed onto the stained or soiled area using a brush containing the cleaning composition or an absorbent article such as a paper towel, cloth or sponge. It's okay to be hit. When the cleaning composition is applied to a soiled textile, the cyclic siloxane serves to dissolve and/or loosen the soil with which it comes into contact. The mobilized soil is then easily removed from the textile in combination with the cyclic siloxane. The cyclic siloxane/soil bond can be removed from the fabric by any convenient method, such as by blotting the fabric with a dry absorbent material. The textile may be treated with a blotting material, such as a sponge, paper towel, or cloth towel. Alternatively, the soil/cyclic siloxane bond may be removed by methods such as brushing, vacuum cleaning, or normal household laundry operations. Brushing and vacuum cleaning are particularly effective when solid adsorbent particles are used in the liquid cleaning composition. Normal household laundering is the preferred method of removal when non-volatile surfactants are used in combination with cyclic siloxanes in the cleaning composition. Cyclic siloxanes are sufficiently volatile that any residual cyclic siloxane on the fabric after soil removal readily evaporates leaving the treated area dry and clean. The method of the present invention can be used to remove a wide variety of soils and stains. Cyclic siloxanes are particularly effective in removing oil and fat stains. One of the special effects of cyclic siloxanes as cleaning solvents is that the formation of secondary stain rings is eliminated or the sharpness of their contours is greatly reduced. Another advantage is that cyclic siloxanes are essentially non-toxic and environmentally harmless. Additionally, cyclic siloxanes can be used on a wide variety of fabrics without damaging them or changing the appearance of the fabric in any way. The cleaning method of the present invention can be used on all types of textiles, including carpets and clothing and upholstery fabrics. The following examples are presented to illustrate the invention and are not intended to limit the scope of the invention in any way beyond what is fully specified in the claims. The artificial fats used in the examples below are palmitic acid (5g), stearic acid (2.5g), coconut oil (7.5g), paraffin (5g), spermaceti (7.5g), and olive oil (10g). ), squalene (2.5g), and cholesterol (2.5g)
, oleic acid (5g), linoleic acid (2.5g)
made from a base mixture with g). A molten (120°) 5 g portion of the base mixture was combined with oleic acid (4 g) and triethanolamine (8 g) and stirred at 120° until homogeneous. Air filter dust (12 g, +200 mesh) and deionized water (100 ml) were then added and the mixture was stirred for 10 minutes. Additional deionized water (900
ml) was added and the mixture was stirred with a homogenizer for 10 minutes. The mixture was stored in a 100° oven and shaken thoroughly before staining. Example 1 The following experiment demonstrates the stain removal ability of cyclic dimethylpolysiloxane on 100% cotton fabric. Used motor oil, cooking oil,
and a stain approximately 1 inch in diameter of artificial fat.
The stain was aged for 24 hours at room temperature. The stain was cleaned by placing the cloth strip on several absorbent paper towels and rubbing the stained area with the cleaning solution saturated paper towel for 20 seconds. The cyclic siloxane fluids tested were (A) octamethylcyclotetrasiloxane, (B) decamethylcyclopentasiloxane, and (C) about 91% by weight octamethylcyclotetrasiloxane and about 8% by weight decamethylcyclopentasiloxane. and (D) a cyclic siloxane mixture of about 1.3% by weight octamethylcyclotetrasiloxane, about 69.3% by weight decamethylcyclopentasiloxane, and about 29.1% by weight dodecamethylcyclohexasiloxane. For comparison, hexamethyldisiloxane, mineral spirits, tetrachloroethylene, isopropyl alcohol, and xylene were also used for stain cleaning. After drying, the stain removal of the cleaned cloth pieces was visually graded according to the following scale: 5 = complete removal 4 = slight stain remaining 3 = medium stain remaining 2 = slight stain Cut 1 = No change in stain Grading was performed by comparing the specimen to a series of standard stain swatches in a black box using a fluorescent light source. If there is a difference between the test piece and the standard stain, it is expressed as a grade with a fraction. The used motor oil tended to form double stains with a smaller deposit area near the center and a larger oil area extending beyond the point of application.
Some differences in the cleaning of these two areas of the stain were observed, so the cleaning of each area was graded separately. The results of the visual grading are shown in Table 1.

Table: Example 2 The stain removal test procedure of Example 1 was repeated using a 65/35 polyester/cotton fabric. The results of the black box visual grading of the cleaned fabrics are shown in Table 2.

[Table] Luxylene 3.0 4.0 5.0 3.0
Example 3 The stain removal test procedure of Example 1 was repeated using 100% polyester fabric. The results of the black box visual grading of the cleaned fabrics are shown in Table 3.

TABLE Example 4 The stain removal test procedure of Example 1 was modified by heat setting the stain before cleaning. The stain was set by placing the fabric in a high temperature automatic dryer that was set in two cycles of 60 minutes each. Polyester (100%) cloth was used for these tests. The results of the black box visual grading of the cleaned fabrics are shown in Table 4.

EXAMPLE 5 The following experiment demonstrates the relative efficiency of cyclic dimethylpolysiloxanes in spreading oil stains on fabrics. The degree of stain diffusion is related to the degree of mobilization of the stain by the test solvent. Generally, the more effectively a stain can be mobilized, the easier and more completely the stain can be removed from the fabric. A cotton fabric specimen (8 inches by 8 inches) was placed in an embroidery hoop and approximately 1 ml of cooking oil was applied to the center of the fabric. The stain was aged for 24 hours at room temperature. The cloth was then placed under the bottle containing the cleaning solution. 0.5 ml of the cleaning solution was applied onto the stain from the tip of the bottle directly above the stain. The fabric was dried at room temperature and the resulting stain size was measured. Generally, the stains were circular or slightly oval in shape. The approximate area of stains after diffusion treatment with various cleaning solutions is as follows.
shown in the table. In the case of oblong shaped stains, the approximate area was calculated as if the stain were circular with a diameter equal to the average of the length and width of the oblong. The cyclic siloxane fluids tested are described in Example 1. Table 5: Diffusion of Cooking Oil Stains on Cotton Cleaning Solution Stain Area (in square inches) No Stain 0.8 A > 50 B > 50 C > 50 D 26 [(CH ₃ ) ₃ Si] ₂ O 5.9 Mineral Spirits > 50 Tetrachlorethylene 4.9 Example 6 The stain diffusion procedure of Example 5 was repeated using 100% polyester fabric specimens. The approximate stain area after diffusion is shown in Table 6. Table 6: Diffusion of Cooking Oil Stains on Polyester Cleaning Solution Spot Area (in square inches) No Stain 0.8 A 16 B 16 C 19 D 22 [(CH ₃ ) ₃ Si] ₂ O 13 Mineral Spirits 25 Tetrachloroethylene 16 Examples 7 Example 5 using 65/35 polyester/cotton cloth
The stain diffusion procedure was repeated. The approximate stain area after diffusion is shown in Table 7. Table 7: Diffusion of Cooking Oil Stains on 65/35 Polyester/Cotton Cleaning Solution Stain Area (in square inches) No Stain 0.8 A 33 B 33 C 33 D 33 [(CH ₃ ) ₃ Si] ₂ O 27 Mineral Spirits 38 Tetrachlorethylene 5.9 Example 8 The following experiment well demonstrates the stain diffusion efficiency of blends of cyclic dimethylpolysiloxane with conventional cleaning fluids such as mineral spirits and tetrachlorethylene. A cooking oil stain was created on a 65/35 polyester/cotton fabric and the spreading procedure of Example 5 was repeated, except that 1 ml of the cleaning liquid blend was dropped onto the stain. Cleaning fluids were prepared by bridging octamethylcyclotetrasiloxane with either mineral spirits or tetrachloroethylene in various weight proportions. The approximate stain area after diffusion is shown in Table 8.

【table】

EXAMPLE 9 The stain diffusion procedure of Example 8 was repeated using decamethylcyclopentasiloxane blended in various weight proportions with either mineral spirits or tetrachloroethene. The approximate stain area after diffusion is shown in Table 9.

Table: Example 10 The following test demonstrates the use of cyclic dimethylpolysiloxane as a solvent component in pre-wash stain removal formulations used in domestic laundry. Used motor oil on polyester cloth specimen;
Approximately 1 inch straight stain of cooking oil and artificial fat was applied. The stain was heat set by placing the fabric in a high temperature automatic dryer that was set for two cycles of 60 minutes each. Each stain was treated with 2 ml of the test solution described in Example 1. Each solution was left on the stain for 1-2 minutes. The test strips were then laundered in a domestic automatic washing machine in a normal setting using the recommended level of phosphate-free detergent.
The fabric strips were dried in a permanent press set in an automatic dryer. The stain removal of the cleaned cloth pieces was visually graded according to the following scale: 5 = Complete removal 4 = Slight stain removal 3 = Moderate stain removal 2 = Slight stain removal 1 = No change in stain Grading was performed by comparing the specimens to a series of standard stain swatches in a blackbox using a fluorescent light source. The used motor oil tended to form double stains with a smaller deposit area near the center and a larger oil area extending beyond the point of application.
Some differences were observed in the cleaning of these two areas of the stain, so the cleaning of each area was graded separately. The results of visual grading are
10 shown in table.

[Table]

[Table] * Trimethylsilyl end-blocked linear dimer
chill siloxane polymer

Claims (1)

[Scope of Claims] 1. A liquid composition containing an effective amount of a cyclic siloxane selected from the group consisting of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane to aid in stain removal. Cleaning of textile fabrics, characterized in that it is applied to textile fabrics soiled with oil and/or fat to dissolve and/or loosen the dirt and to remove a combination of dirt and cyclic siloxane from the textile fabrics. Method. 2. The method of claim 1, wherein the liquid composition contains 1 to 100% by weight of cyclic siloxane. 3. The method of claim 2, wherein the liquid composition contains 5 to 100% by weight of cyclic siloxane. 4. The method of claim 3, wherein the liquid composition contains 10 to 100% by weight of cyclic siloxane. 5. Claims in which the liquid composition contains from 30 to 70% by weight of a cyclic siloxane and from 30 to 70% by weight of a cleaning solvent selected from the group consisting of petroleum hydrocarbons and chlorinated hydrocarbons. Method of Section 4. 6. The method of claim 5, wherein the liquid composition contains a cyclic siloxane and a mineral spirit. 7. The method of claim 5, wherein the liquid composition contains a cyclic siloxane and a chlorinated hydrocarbon cleaning solvent. 8. Claim 7, wherein the liquid composition contains cyclic siloxane and tetrachloroethylene.
Section method.