Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/507—Polyesters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/66—Polyesters containing oxygen in the form of ether groups
  • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/672—Dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3715—Polyesters or polycarbonates

Definitions

• ABSTRACT Continuation-impart of Ser. No, 193,569, Oct. 28, Process and composition for improving the subsequent 1971, abandoned. removability of oily soils and stains from polyester- 7 containing fabrics through application of a renewable [52] US. Cl. 252/8.6; 1 17/ 138.8 F; 260/292 E soil release finish to said fabrics from a dilute aqueous [51] Int. Cl D06m 13/20 solution having an acid pH. [58] Field of Search 252/8.6; 260/292 E;
• BACKGROUND OF THE INVENTION rics which employ combinations of polyester fibers and other fibers (e.g. 65 percent polyester, 35 percent cotton blends), is enhanced by applying to said fabrics, in an aqueous solution, a soil release agent which imparts hydrophilic character to the polyester fiber, said solution having an acid pH.
• a soil release agent which imparts hydrophilic character to the polyester fiber, said solution having an acid pH.
• solution refers to dispersion as well as true solution.
• fabrics which are woven from polyester fibers tend to be quite hydrophobic.
• the hydrophobic character of these fabrics prevents or reduces theability of water to wet the fabric, which is necessary to remove oily soil and oily stains during the washing process.
• hydrophilic/- hydrophobic character is due in part to the basic building blocks of the fibers themselves, i.e., since polyester fibers are copolymers of terephthalic acid and ethylene glycol, they have less affinity for water because there are fewer free hydrophilic groups, e.g., hydroxyl or carboxyl groups where hydrogen bonding can occur, than is the situation with cotton which is a cellulose derivative containing a large number of hydrophilic groups which are compatible with and have affinity for water.
• German Patent 1,194,363 describes the use of a polyethyleneglycolitaconic acid polymer as an anti-static agent for, synthetic fibers to reduce soil. pickup. Netherlands Application 65/02428 and Belgium Patent 641 ,882describe the treatment of polyester fibers with polyethylene glycol solutions to increase the hydrophilic character of the fiber.
• French Patent, 1,394,401 describes the treatment of a polyester fiber with an alcohol or glycol in the presence of a strong non-volatile acid to increase the hydrophilic character of the fabric.
• polyester and polyester/cotton fiber blends do not respond the same way during laundering as do typical cotton fabrics. It is well recognized that the problem with polyester and polyester/cotton blends is that because of the hydrophobic character of the fabrics they tend to stain easily with oily soil, and once stained, the oily soil or stain is difficult to remove. In fact it is well ent characteristics of the polyester fiber either by building into the polyester fiber greater hydrophilic charact er 'or by causing the fabric to have greater hydrophilic character through adsorption on the surface of the fiber of materials more hydrophilic in nature than the base polyester fiber.
• This invention concerns a process whereby soil release agents, hereinafter described more fully, can be applied to polyester-containing fabrics from dilute, aqueous, acid solution, preferably the rinse step of laundering, in order to effect easier removability of oily soils in subsequent washing.
• this invention concerns compositions of matter for use in said process.
• this invention concerns an improvement in the laundering of polyester-containing fabrics wherein a renewable soil release finish is applied to said fabrics from a dilute aqueous acidic solution of a soil release agent (hereinafter defined), thereby making oily soils which are subsequently deposited on the fabric more easily removable in the next laundering.
• a renewable soil release finish is applied in the final rinse step of the laundering process so as to facilitate the removal of subsequently deposited oily soils in the next laundering.
• the soil release agents of the invention are copolymers comprising:
• A is a bivalent organic radical selected from the group consisting of alkylene, arylene, aralkylene, alkarylene and cycloalkylene radicals having from 3 to about 14 carbon atoms,
• glycolic compound which is a polyglycol selected from the group consisting of compounds of the following general formula wherein B is a bivalent organic radical selected from the group consisting of alkylene and cycloalkylene radicals having from 2 to about 4 carbon atoms, and wherein n indicates the degree of polymerization and ranges from about 6 to about 500, and preferably, although not essential for the operability of the invention,
• a glycolic compound which is a glycol selected from the group consisting of compounds having the following general formula dodecylene and tetradecylene; where A is an arylene radical, examples of suitable radicals are phenylene and biphenylene; where A is an aralkylene radical, examples of suitable radicals are 2-phenylpropylene and 2-phenylbutylene; where A is an alkarylene radical, examples of suitable radicals are 2-propylphenylene and 2-ethylphenylene; and where A is a cycloalkylene radical, examples of suitable radicals are cyclobutylene, cylopentylene, cyclohexylene, cyclooctylene and cyclotetradecylene.
• the preferred radical is phenylene with the preferred dicarboxylic acid being terephthalic acid, because terephthalic acid is an integral part of the polyester sought to be rendered hydrophilic.
• terephthalic acid is an integral part of the polyester sought to be rendered hydrophilic.
• Butylene, biphenylene, and (methylene) ethylene are also preferred.
• B when B is an alkylene radical, examples of suitable radicals are ethylene, propylene, and butylene.
• B is a cycloalkylene radical, examples of suitable radicals are cyclopropylene and cyclobutylene.
• the preferred radical is ethylene and the preferred polyglycol is polyethylene glycol. Polyethylene glycol is preferred because it is the most hydrophilic of the polyglycols which can be used.
• Component (2) which is a polyglycol, has a degree of polymerization of from about 6 to about 500, e.g., from about 6 to about 500 alkenoxy or cycloalkenoxy groups make up the polyglycol chain.
• the polyglycol can be a homopolymer of the individual glycol.
• the polyglycol can be copolymers of mixtures of the individual glycols, with the individual glycols being randomly distributed in the polyglycol copolymer chain.
• the polyglycol can be copolymers of mixtures of homopolymers of the individual glycols with the homopolymers being randomly distributed in the polyglycol copolymer chain.
• a homopolymer of ethylene glycol is the preferred polyglycol.
• the degree of polymerization of from about 6 to about 500 results in a polyglycol molecular weight of from about 300 to about 20,000.
• the preferred polyglycol degree of polymerization is from about 30 to about 40 with a molecular weight of from about 1300 to about 1800.
• X is an alkylene radical
• suitable radicals are ethylene, propylene and butylene.
• X is a cycloalkylene radical
• suitable radicals are cyclopropylene and cyclobutylene.
• the preferred radical is ethylene and the preferred glycol is ethylene glycol.
• All copolymers of the invention comprise the dibasic acid and glycolic compounds in a 1:1 molar ratio and said copolymers have an average molecular weight of from about 1000 to about 100,000.
• the glycolic component of the polymer comprises a polyglycol and a glycol
• the molar ratio of polyglycol to glycol is from about 5:1 to about 1:5.
• the preferred soil release agent is a copolymer of tetrephthalic acid, a polyethylene glycol having a degree of polymerization of about 35, and ethylene glycol, the three components being present in a molar ratio of acid: polyglycolzglycol of 1:08:02 to 1:0.2:0.8 (i.e. a 1:1 molar ratio of acid to total glycolic compounds, and a 4:1 to 1:4 ratio of polyglycol to glycol) the average molecular weight of said polymer being about 3000 to about 5000.
• the most preferred ratio of terephthalic acid to polyethylene glycol to ethylene glycol for this polymer is l:0.45:0.55.
• the soil release agents hereinbefore described When the soil release agents hereinbefore described are present in a dilute aqueous solution into which polyester or polyester-blend fabrics are immersed, the soil release agents tend to adsorb onto the polyester fibers, forming a hydrophilic film which remains on the fibers after the fabric is removed from the solution and dried. This film makes the polyester fibers more wettable and thus oily soils and stains deposited on the fabric prior to the next laundering are more easily removed in said laundering than if the soil release agent were not present on said polyester fibers. Most of the soil release agent deposited on the polyester fibers from an aqueous bath, as described above, is removed in the first subsequent laundering, therefore it is preferable to apply a new film of soil release agent in the rinse step after each laundering.
• the soil release agent be applied in the last rinse, since subsequent rinses after application will remove some of the soil release agent from the fabric.
• the soil release agents are used at concentrations of from about 0.001 percent to about 1.0 percent by weight in the aqueous bath.
• concentration of soil release agent is from about 0.004 percent to about 0.25 percent by weight.
• the amount of fabric in the aqueous bath can vary widely, but is generally from about 1 to 50 percent by weight of the water and is preferably from about 3% to about 25% of the water.
• van emulsifying agent present in the aqueous bath containing the soil release agent to aid in keeping said agent evenly dispersed.
• Emulsifying agent levels of from about 0.00005 to about 0.05 percent of this aqueous solution are suitable for this purpose. A discussion of suitable emulsifying agents is given later in this specification.
• the temperature of the aqueous bath can be from about 50F to about 212F, but is preferably from about F to about F.
• the length of time the fabrics are present in the aqueous bath should be at least 0.5 minutes and is preferably from about 2 to about 9 minutes.
• the water hardness of the aqueous bath is not critical to the practice of the invention.
• the soil release agent be applied to the fabric in the final rinse step of the laundering operation.
• the use of acid pH (sour) in the final rinse step is common practice, therefore the use of the present invention in commercial laundering involves no basic change in customary practice.
• rinsing is normally performed at a pH of about 7 to 9, therefore the present invention does require a departure from common practice in the home.
• the soil release agents of the invention need not necessarily be applied to the polyestercontaining fabric in the rinse step of a laundering operation but may be applied to the fabric from a dilute acidic aqueous solution at any time prior to the soiling of the fabric.
• any acidic compound i.e. acid or acid salt
• the acidic compounds can be organic or inorganic, the only requirement being that they be soluble in water to a sufficient extent to provide the required acidity.
• Preferred acidic compounds are those which have found wide use in commercial laundering such as fluosilicic acid, sodium silicofiuoride, ammonium silicofluoride ammonium acid fluoride, acetic acid sodium acid fluoride, and hydrochloric acid.
• fluorinecontaining acids and acid salts are preferred because they are effective in removing rust stains in addition to providing acidity.
• the acidic compound is used in the aqueous solution of soil release agent at a level of about 0.001 percent to about 0.04 percent by weight, to achieve the desired pH, the actual usage level depending on the degree of acidity of the compound, the natural pH of the water supply, and the amount of alkalinity carried into the solution by the fabrics to be treated.
• the soil release agents of the invention and the acidic compounds can be added separately to water at the desired concentrations to provide the acid solutions of soil release agents for use herein, or the acidic compounds and soil release agents can be formulated into a single concentrated composition which can be dissolved in water to provide the desired acidic solution of soil release agent.
• the concentrated compositions herein generally comprise from about 2.5 percent to about 95 percent acidic compound and from about 97.5 percent to about 5 percent soil release agent by weight.
• the type and level of acidic compound in the composition is chosen so as to provide an acidic pH when the composition is added to water in an amount so as to provide a concentration of soil release agent between about 0.001% and about 1.0 percent by weight.
• the concentrated composition can also contain diluents such as salts (e.g. Na SO or NaCl) or solvents (e.g. water or alcohol) and can be formulated in solid, granular, powder, paste or liquid form.
• diluents e.g. Na SO or NaCl
• solvents e.g. water or alcohol
• emulsifiers or dispersing agents be present in the compositions. These can be surface active agents of the anionic, nonionic, ampholytic or zwitterionic type and normally comprise from about 0.1 to percent by weight of the composition.
• Suitable anionic surface active agents are sodium salts of fatty alcohol sulfates having from 8-18 carbon atoms in the fatty chain and sodium salts of alkyl benzene sulfonates, having from 9 to carbon atoms in the alkyl chain.
• suitable nonionic surface active agents are the polyethylene oxide condensates of alkyl phenols, wherein the alkyl chain contains from about 6 to 12 carbon atoms and the amount of ethylene oxide condensed onto each mole of alkyl phenol is from about 5 to moles. Specific examples are the condensation product of one mole of nonylphenol with 10 moles of ethylene oxide and the condensation product of one mole of C fatty alcohol and 10 moles of ethylene oxide.
• suitable ampholytic surface active agents are derivatives of aliphatic secondary or tertiary amines in which one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group, e.g. sulfate or sulfo.
• Specific suitable ampholytic surface active agents are sodium-3-dodecylaminopropionate and sodium-3-dodecyl amino propane sulfonate.
• suitable zwitterionic surface active agents are derivatives of aliphatic quaternary ammonium compounds in which one of the aliphatic constituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group.
• zwitterionic surface active agents are 3-(N,N-dimethyl- N-hexadecylammonio) propane-l-sulfonate and 3- (N,N-dimethyl-N-hexadecylammonio)-2-hydroxy propane-l-sulfonate.
• zwitterionic surface active agents are 3-(N,N-dimethyl- N-hexadecylammonio) propane-l-sulfonate and 3- (N,N-dimethyl-N-hexadecylammonio)-2-hydroxy propane-l-sulfonate.
• Many other suitable surface active agents are described in Detergents and Emulsifiers 1969 Annual by John W. McCutcheon Inc. which is incorporated by reference herein.
• textile treating agents such as blueing, optical brighteners and the like can be present in the aqueous acid solution of soil release agent herein, in order to provide simultaneous application of these textile treating agents along with the application of soil release agent.
• textile treating agents can be incorporated into the concentrated compositions herein.
• Cationic fabric softeners e.g. ditallow dimethyl ammonium chloride
• Cationic fabric softeners can also be present in the compositions and process of the invention but generally their presence is not preferred since they tend to retard the deposition of the soil release agent onto the polyester fibers at acid pH.
• 1,119,367 are said to impart permanent soil release finish to the polyester fiber, and this permanence is made possible by the use of the swelling agent.
• the present invention is intended to provide a non-permanent (i.e. renewable) soil release finish and therefore the compositions and method of the present invention are substantially free of swelling agents.
• 'U.S. Pat. No. 3,690,942, issued September 12, 1972 discloses acidic formulations for imparting a durable soil release finish to polyester fabrics said formulations containing a soil release agent of the present invention in combination with a synthetic acid emulsion polymer, (i.e. polymers which contain free acid groups) for example polymers made from acrylic acid, methacrylic acid, fumaric acid, maleic acid, and the like.
• a synthetic acid emulsion polymer i.e. polymers which contain free acid groups
• the compositions and process of the present invention are substantially free of synthetic acid emulsion polymers.
• EXAMPLE 1 White percent polyester fabric (Type 56 S/7l5 Texturized Double Knit from Test Fabrics Inc. of New York, NY.) was washed in 0.5 percent concentration of a commercial laundry detergent having the following composition by weight Anionic synthetic detergent 4.2% Nonionic synthetic detergent 4.1 Sodium tripolyphosphate 12.4 Sodium carbonate 18.5 Sodium hydroxide 15.5 Sodium metasilicate 34.5 Moisture and misc. to 100 The washing was done at 180F for l0 minutes, followed by four rinses at 160F., 140F, F, and 100F, respectively. Soft water (0 grains/ gallon CaCO equivalent) was used in all washes and rinses. The fabric was then cut into 5.5 inch square swatches for testing.
• test swatches Five 260 gram batches of test swatches (approximately 73 swatches per batch) were weighed out. Four batches of swatches were given a soil release treatment in soft water rinse solutions, the composition and pH of which are indicated in Table 1. The treatment consisted of immersing the fabrics in the rinse solution for 5 minutes at a temperature of 120F. The fabrics were then dried. 10 swatches from each of the five batches were then soiled with 1.6 ml of dirty crankcase oil by dropping the oil from a syringe onto the center of the swatch.
• the soil was allowed to set for approximately 10 minutes, and the light reflectance of the soiled spots as well as the light reflectance of the unsoiled swatches was determined by the L reading on a Gardner XL-lO Color Difference Meter (Gardner Laboratories, Chicago, 111.).
• the five separate batches of test swatches were then washed according to the procedure described above, except that a second wash at 0.1 percent detergent concentration was inserted after the first wash and before the 160F. rinse. and 1.6 ml of crankcase oil was added to the first 180F. wash solution, approximately 2.5 minutes after the first 180F. wash had ethylene glycol, in a molar ratio of 1:0.78:0.22, and having an average molecular weight of about 3,000 to 5,000.
• a copolymer of itaconic acid, and polypropylene started. After the final 100F. rinse the swatches'were 5 glycol having a degree of polymerization of about dried and reflectance readings were again taken. Per- 40, in a molar ratio .of 1:1, said copolymer having cent soil removal from the soiled swatches was calcua molecular weight of about 4,000 to 6,000.
• the soil release agent is a copolymer of terephthalic acid.
• polyethylene glycol having a degree of polymerization of about 35. and ethylene glycol.
• the ratio of terephthalic acid: polyethylene glycol:ethylene glycol being l:0.45:0.55 and the average molecular weight being from about 3000 to about 5000.
• the control received no rinse soil release treatment.
• the soil release agent of the above experiment is replaced on an equal weight basis by the following soil release agents, and trends in soil removal and whiteness retention results substantially similar to those reported above are obtained.
• a liquid concentrate soil release composition is prepared by mixing the following ingredients Soil release agent* 14.5 parts Ernulsifier** 0.5 Nal-lF 2.5 Water to 100 parts "A copolymer of terephthalic acid. polyethylene glycol having a degree of polymerization of about 35 and ethylene glycol, the ratio of terephthalic acid: polyethylene glycol: ethylene glycol being 1:0.45:0.55 and the average molecular weight being from about 3000 to about 5000 "The condensation product of a mixture of C to C secondary alcohols and ethylene oxide wherein the molar ratio of ethylene oxide to alcohol is about 9:1.
• composition is a cloudy, easily pourable, single phase liquid.
• the composition is dissolved in water at EXAMPLE III
• a solid concentrate soil release composition is prepared by mixing the following ingredients Soil release agent 83 parts Emulsifier** 3 parts NaHF l4 parts I parts
• the soil release agent of the composition of Example ll "The sodium salt of dodecylbenzcne sulfonic acid.
• the composition is a granular solid.
• the composition is dissolved in water at the rate of about 0.06 parts composition per 100 parts of water to form a dilute solution of soil release agent having a pH of about 5, said solution being suitable for applying the soil release agent to polyester-containing fabrics according to the process of the present invention.
• a composition of matter particularly suitable for use in preparing dilute aqueous acidic baths wherein a renewable soil release finish is applied to polyestercontaining fabrics, said compositions comprising from about 5 percent to about 97.5 percent by weight of a soil release agent, said soil release agent being a copolymer comprising 1.
• glycolic compound which is a polyglycol selected from the group consisting of compounds of the following general formula wherein B is a bivalent organic radical selected from the group consisting of alkylene and cycloalkylene radicals having from 2 to about 4 carbon atoms, and wherein n indicates the degree of polymerization and ranges from about 6 to about 500, and wherein the ratio of dicarboxylic acid to total glycolic compounds is 1:1 and the average molecular weight is from about 1,000 to about 100,000, and
• composition being substantially free of materials which cause swelling of polyester fibers and also being substantially free of synthetic acid emulsion polymers.
• composition of claim 1 wherein the bivalent organic radical, A, is selected from the group consisting of phenylene, butylene, biphenylene and (methylene) ethylene.
• composition of claim 2, wherein the bivalent organic radical A, is phenylene.
• composition of claim 3 wherein the polyglycol is polyethylene glycol.
• composition of claim 4 wherein the polyethylene glycol has a degree of polymerization of from about 30 to about 40.
• composition of claim 5 wherein the copolymer contains as a third component a glycol having the following general formula HO-X-OH wherein X is a bivalent organic radical selected from the consisting of alkylene and cycloalkylene radicals having from 2 to about 4 carbon atoms.
• composition of claim 7 wherein the molar ratio of dicarboxylic acid to polyethylene glycol to ethylene glycol in the copolymer is from about 1:08:02 to about 1:02:08.
• composition of claim 8 wherein the average molecular weight of the copolymer is from about 3000 to about 5000.
• composition of claim 9 wherein the acidic compound is selected from the group consisting of fluosilicic acid, sodium silicofluoride, ammonium silicofluoride, acetic acid, sodium acid fluoride and hydrochloric acid.
• composition of claim 10 containing as an additional ingredient from about 0.l percent to about 10 percent of an emulsifying agent.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Textile Engineering (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Detergent Compositions (AREA)
• Polyesters Or Polycarbonates (AREA)

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Cited By (154)

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Citations (2)

• 1972
  • 1972-10-26 CA CA154,901A patent/CA989557A/en not_active Expired
  • 1972-10-27 FR FR7238285A patent/FR2158036A1/fr not_active Withdrawn
  • 1972-10-28 DE DE2253063A patent/DE2253063A1/de active Pending
• 1973
  • 1973-02-01 US US328824A patent/US3893929A/en not_active Expired - Lifetime

Patent Citations (2)

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