JPS583066B2 - Sentaku no Saiorimono Ni Techiyosarel Ichijijitekiyogoreridatsuseifuyojiyushi - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a washing method and a novel washing composition used to temporarily impart soil release properties to textiles or textiles.

It has been known for some time that, especially in the case of synthetic fabrics made from polyester or polyester/polyester blend fibers, deeply ingrained oil stains are difficult to remove even when washed.

The inventors have discovered a method of treating textiles with acrylic resin at the final stage of washing.

The method involves impregnating textiles with the resin to impart stain releasability for a temporary period of time.

Impregnating the fabric with resin helps remove deep-seated dirt and at the same time imparts stain resistance to the fabric.

Therefore, even if dirt does accumulate later on, it will not go deep and will not stick permanently. Most of the impregnated resin will be removed the next time the fabric is washed, providing optimal dirt removal properties. A new application of resin must be applied with each subsequent wash to ensure retention.

Acrylic resin is added at the final stage of washing, which is usually an acid treatment.

Additionally, this resin can be used with other textile finishing treatments such as bluing,
This acrylic resin can be added in gluing, brightening or softening, as long as the treatment is the final operation.

The concentration of resin in the souring solution or other finishing solution is such that the amount of resin remaining on the fabric after drying provides an effective means for removing soil.

This is known as the effective amount of acrylic resin.

Generally, the concentration of resin in the treatment composition is at least 0.25 parts resin per 5000 parts by weight of acid solution or other treatment liquid such as a tinting liquid or a thickening agent.

Although the preferred concentration range is 0.5 to 1 part resin per 5000 parts acid solution or other processing solution,
Resin concentrations as high as 3 parts per 1,000 parts have been used to restore heavily soiled clothing.

Although acrylic resins are generally aqueous solutions, some resins can be in the form of aqueous emulsions.

The pH of the resin treatment liquid must be within the range of 4 to 6.5, preferably within the range of 4.5 to 6.0.

The temperature of the impregnation process is not critical, but is usually 70°C.
-180'F (21-82°C), preferably 95-180'F (35-82°C).

These temperature and pH conditions apply to acid solutions or other textile finishing solutions containing acrylic resins in suspension or solution.

After the resin treatment liquid is separated from the fabric by conventional washing methods, a wet and resin-impregnated fabric remains.

The fabric is then dried by conventional washing methods, leaving behind a resin on the fabric.

Drying temperatures of 70-350°F (21 to 177°C) are satisfactory.

The amount of resin remaining on the fabric after drying is approximately 0.005 to 0.05% by weight.

The preferred amount of resin is 0.01-0.02% by weight (dry weight)
It is.

The resin retained on the fabric thus acts as a layer or film that pulls subsequently deposited soils away from the fibers and allows easy removal of this soil in subsequent washing operations.

Removal of the resin itself in subsequent washing operations further facilitates soil removal.

Moreover, the impregnated resin attacks deep-seated, pre-existing oil stains, so that repeated treatments with the resin will eventually restore even heavily soiled fabrics to a usable condition.

Generally, about three washes, each cycle including treatment with a resin, are required to recover the fabric.

The acrylic resin used in the method of the present invention is acrylic acid,
It is a mixture of one or more homopolymers and copolymers obtained from methacrylic acid and alkyl esters thereof.

The resin treatment methods described above are well suited for modern washing, and for washing and rinsing, the normal washing conditions of temperature and detergent concentration prevail over resin treatment of textiles.

The inventors have also discovered new resin compositions for treating textiles during washing to temporarily impart soil release properties to the textiles.

The composition consists of an aqueous mixture of the acrylic resin described above, a washing acid solution and/or a textile finishing agent (eg bluing, brightener, thickening agent and fabric softener).

Sufficient acid treating agent must be present in the washing acid solution to provide a pH range of 4 to 6.5, preferably 4.5 to 6.0.

The same conditions of pH and acrylic resin concentration apply to other textile finishing compositions consisting of water, resin and textile finishing agents (eg blue tints, thickeners, plitoners or softeners).

In another aspect of the invention, a soil release acrylic resin (hereinafter simply referred to as soil release resin or acrylic resin) can be applied by spraying to pre-dried fabric.

The propellant for spraying can be air, carbon dioxide, hydrocarbons or fluorocarbons.

After spraying, the fabric is dried to remove the spray liquid.

The fabric may be dried on a rack or by tumbling or ironing in a fabric air dryer.

Drying temperatures can range from room temperature to 350'F (177°C).

Example 8 below illustrates this aspect of the invention.

In recent years, the use of fabrics made by blending different fibers has become increasingly popular.

One of the most commonly used blends is
It is often a polyester-noodle blend containing 50-90% polyester.

These fabrics are frequently treated to impart improved strength to the fabric, to improve the feel or quality of the fabric, to impart permanent press properties, and to impart soil release properties.

It has generally been observed that polyester and other synthetic fibers, with or without permanent pressing, or with or without other resin treatments, are unusually difficult to clean by conventional washing operations.

More specifically, polyester noodles are particularly sensitive to oil stains, which penetrate deep and are not easily removed.

Because polyester fibers are relatively hydrophobic, conventional washing systems cannot penetrate the fabric and therefore cannot reach and remove soils.

Dry cleaning is used today to remove these deep-seated oil stains from treated or untreated blends, but it has the disadvantage of being relatively much more expensive than washing, and The water-soluble part of the dirt, which is usually present in large quantities, is not removed quickly.

The present inventor has developed a method for treating textiles in the final washing process so that oil stains do not stick deeply or permanently, and can be easily removed in subsequent washing operations. discovered.

The essence of this discovery is to temporarily impregnate textiles with acrylic resin.

The acrylic resin provides a means for cleaning soils subsequently deposited on the fabric during the next wash.

This resin is not permanently attached to the fabric, and most of it is generally removed during the next wash.

The resin stays on long enough to remove all of it the next time you wash it, helping to remove any dirt that may have built up later.

Since most of the applied resin is removed the next time the fabric is washed, a fresh application of resin must be applied for each subsequent wash to provide and maintain optimum soil release.

In addition to its ability to facilitate and retard stain removal after application, the resin treatment discovered by the inventors aids in the removal of deeply embedded stains prior to application.

The inventor of the present invention has discovered that the dirt that has penetrated deep into the
Virtual removal was observed after ~3 treatments with the resin.

Many fabrics that were extremely soiled and could not be cleaned by conventional washing were restored to normal acceptability as a result of continuous treatment in accordance with the present invention.

An unexpected advantage of this treatment is that it generally requires about three or more repetitions of the method (or three or more cycles of the method) to restore extremely soiled clothing. The resulting fabric had significantly improved hand, sizing and hand, which made it easier to process and more aesthetically appealing.

Essential to the invention is the discovery that acrylic resins of the type described below can be applied to textiles as part of the final stage of the washing operation, and that very low levels of resin impregnation of the textiles are thereby achieved.

The amount of acrylic resin impregnated into the fabric is 0.005 to 0.05
It is in the order of weight % (dry weight).

The preferred amount is 0.01-0.2% by weight.

It was an unexpected discovery that this small amount of resin impregnation aids in the removal of deep-seated soils, and that it also provides the fabric with the ability to inhibit soils that adhere after impregnation.

Also, repeating the process of impregnating the fabric with small amounts of acrylic resin, which is temporary, is superior in performance to the much more expensive method of permanently attaching stain release resins by chemical means during the fabric manufacturing process. It was unexpected to find that it provides stain release properties equal to and a desirable finish.

Resins All resins suitable for practicing the invention are derived from homopolymers and copolymers of acrylic acid and meccrylic acid.

Homopolymeric polyacrylic acid and polymetharylic acid form suitable soil release resins.

Either the homopolymer or the mixture of homopolymers provides a satisfactory textile soil release resin in the process of this invention.

In addition to the above homopolymers, various copolymers formed by copolymerizing acrylic acid or metharylic acid with alkyl esters of acrylic acid or alkyl esters of metharylic acid are suitable stain release resins. It is.

In these copolymers, the molar ratio of acrylic acid or metharylic acid to alkyl ester of acrylic acid or alkyl ester of metharylic acid is such that the copolymer is water soluble or any mixing ratio suitable for practicing the invention. Provides a stain removal resin.

A preferred temporary soil release system consists of a mixture of a homopolymer of acrylic acid and a copolymer formed from ethyl acrylate and methacrylic acid.

The above-mentioned homopolymers, copolymers and mixtures thereof which provide satisfactory soil release resins in the novel cleaning methods and compositions of the present invention are hereinafter collectively referred to as acrylic resins.

The resin homopolymers and copolymers are conveniently added to the washing machine in the form of an aqueous solution, emulsion or dispersion.

For example, polyacrylic acid is 25% by weight? Commercially available as a solution.

Although acrylic resin is usually added directly to the acid solution in the wash machine, it could be added to an optional pre-supply of acid solution.

Acid liquid An acid liquid is also called a souring liquid, and is generally a solution of an acid produced from a type of silicate such as sodium silicate.

The concentration of resin in the acid solution is not critical.

However, the stain release resin must be at least 1:1 to provide water dispersibility to the garment when the garment is dried.

Any acid to ester ratio (including acid homopolymers) greater than 1:1 provides a suitable soil release resin.

Alkyl substituents are C-C4 groups. Mixtures of these copolymers are also satisfactory stain release resins.

Esters suitable for copolymerization with acrylic or metharylic acid to form this satisfactory soil release resin include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, acrinoisobutyl, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate,
They are isopropyl methacrylate, n-butyl methacrylate and isobutyl methacrylate.

In addition to the above-mentioned copolymers as temporarily deposited stain release resins, mixtures of these various copolymers and the previously described homopolymers may be used as temporary deposit stain release resins. Particularly useful.

Sufficient resin must be present in the acid solution so that the homopolymer or mixture of homopolymers and copolymers remain on the fabric in sufficient quantities to provide a means of removing soil.

The concentration of resin in the acid solution is known as the effective amount.

In general, the resin concentration in the acid solution is 1 part by weight of resin per 5000 parts of acid solution.3 Good results were obtained with 0.5 parts of resin per 5000 parts of acid solution;
．． Even with 25 parts, the stain releasability was improved to some extent.

Higher resin concentrations are generally unnecessary for garments amenable to conventional resin treatments.

However, higher concentrations can be used for restoring heavily soiled clothing.

In this particular treatment, the concentration of resin in the acid solution is 5
3.0 parts of resin per 000 parts by weight can be reached.

If the resin impregnation of the fabric is carried out separately from the acid treatment operation, and in combination with or separately from some other textile finishing operation, the concentration and pH of the resin in this separate treatment liquid will be It must be the same as for the acid solution.

In the commercial washing method, acid treatment is generally the final step of washing.

For economic reasons, the application of soil release resins is combined with acid treatment operations to avoid cleaning separation operations.

However, if for some reason it is not desirable to combine acid treatment and soil release resin impregnation, they can be carried out separately, as long as the resin treatment is the final operation of the wash.

Impregnation with resin must be the final operation so that the resin is not lost by any subsequent washing operations (such as soaking the fabric in water or rinsing it with water) that have carried off most of the resin.

Acid treatment removes alkalinity from the fabric that is not removed by water rinsing.

Generally, two to four water rinses are used before acid treatment.

The first rinse is usually 180-190°F (82-8
The washing temperature is 8°C).

Subsequent rinsing is carried out for the second and third time by gradually lowering the temperature to room temperature.

If almost all of the alkali cannot be removed, human skin will become irritated by the fabric.

Acid solutions are made from salts of acids and other acidic substances.

Silicates are the most common acid treating agents.

The silicate can be obtained in the form of ammonium silicate, sodium silicate, magnesium silicate or zinc silicate.

Other materials used in cleaning acid treatments are sodium acid fluoride and ammonium acid fluoride, ammonium chloride and acetic acid.

The liquid acid treating agent sources are hydrofluoric acid and fluorosilicic acid.

Acid treatment operations are generally conducted in the pH range of 4 to 6.5, and the amount of acid treatment agent added varies depending on the residual alkali from the wash cycle, the alkalinity of the water used, and the desired pH.

Generally, 1 to 12 ounces (28 to 340 g) of acid solution is
00 pounds (45 kg) of dry fabric.

Generally 350-500 pounds (159-227 kg)
of water is used on 100 pounds (45 kg) of dry fabric for each wash run.

The combined acid treatment and application to the stain release acrylic resin is carried out at temperatures within the range of 70 to 180 degrees Fahrenheit (21-82 degrees Celsius).

Preferably, the temperature is between 95°F and 180°F (35°F and 180°F).
82°C).

In combining the application of the acid solution and the soil release resin to the fabric, steps must be taken to ensure uniform mixing and suspension of the resin.

A normal rotation of the washer is sufficient for this purpose.

One or more of the following textile finishes may be combined with the acid treatment of the textile and the application of resin to the textile: Blue tints are generally applied at a rate of 1/32 oz. The brightener is applied at a rate of 1 ounce (28 g) per 100 pounds (45 kg) of dry fabric; the softener is applied at a rate of 1.88 g (1.88 g) per 100 pounds (45 kg) of dry fabric. The acid solution is applied at a rate of 5 to 2 ounces (42.5 to 57 g).

The thickener may be compatible with the acid solution and the soil release resin.

Thickening materials are generally wheat or grain starches and are used at concentrations of 8 ounces to 1 pound (227-45 kg) per 100 pounds (45 kg) of fabric.

Starch is added to the acid solution at the same concentration.

The above concentrations provide effective amounts of textile finish.

It will be appreciated that the concentration of textile finishing agents in acid solutions is well known in the art world.

These concentrations will depend on local water conditions and the desired effect of the particular washing operation.

The acid treatment operation combined with dry resin impregnation and/or other textile finishing treatments is accomplished within about 3 to 10 minutes, preferably within 5 to 8 minutes.

After being treated with an acid solution containing acrylic resin, the fabric is separated from the acid solution and then dried.

Separation of the resin monoacid treatment solution is usually accomplished by centrifugal extraction or by hydraulic pressing.

Generally, after separation of the acid solution or other textile finishing fluid onto the textile,
Approximately equal weight of processing liquid remains.

There are approximately 100 pounds (45 kg) of acid solution per 100 pounds (45 kg) of treated dry fabric.

The concentration of resin in the acid solution is 1 resin per 5000 parts by weight of acid solution.
100 pounds (45 kg) of woven fabric retains 1/50 pound (9 g) or 0.02% resin.

The concentration of resin in the acid solution is 0 resin per 5000 parts by weight of acid solution.
．． 25 parts, the retention value of the resin on the fabric is approximately 0.
．． 005% by weight.

At 0.5 parts of resin per 5000 parts of acid solution, the amount of resin impregnated on the fabric after drying is about 0.01% by weight.

At 2.5 parts of resin per 5000 parts of acid solution, the resin impregnation on the fabric is approximately 0.05% by weight.

The preferred pick-up level on the dry fabric is about 0.01-0.02% by weight.

The wet resin-impregnated fabric is heated from room temperature to approximately 350°F (177°C).
) is dried at a temperature in the range.

Drying is accomplished in a conventional textile air dryer or by ironing or pressing.

Ironing temperature is usually around 350°F (177°C)
It is.

Temperatures somewhat lower than this are commonly used in air dryers, and satisfactory drying can be achieved at air temperatures as low as 70°F (21°C) or room temperature.

Water is removed more quickly at higher temperatures, so 15
Temperatures of 0-350°F (66-177°C) are preferred.

The best mode of carrying out the invention may be understood by reference to the following examples.

Example 1 A Milnor Washer with a dry fabric capacity of 35 pounds (15.9 kg)
r), Model #600-CWM-5 with 24 lbs (10.9 kg) of noodle pieces and 1
A 1 pound (450 g) 0 in (25 cm) square white shirt fabric test piece (polyester ramen (65:35) blend processed with durable press resin) was placed.

Fill this washing machine up to 16 gallons (6 0.6 l), and add 0.00 ml of stencil all-in-one cleaning agent.
Added 25 lbs (113g).

Water temperature was 150°F (66°C).

After stirring for 10 minutes, the system was drained, refilled with water, and 0.125 pounds (57 g) of detergent was added.

This was stirred for 5 minutes at 150°F (66°C) and then drained.

Rinsed four times with 30 gallons (114 l) of water.

The first time was 150°F (66°C), the second time was 130°F (
54°C), the third time below 110°C (43°C), and the fourth time at 90°F (32°C).

After rinsing four times, add 115°F (46°C) water to a volume of 16 gallons (60.6 liters) and adjust the pH to 4.5 by adding a sodium silicofluoride washing acid solution; The system was then stirred for 1 minute.

At this point, it contains 3.9% by weight of a 25% by weight polyacrylic acid solution and 9.6% by weight of a 20% by weight acrylic acid-ethyl meccrylic acid (molar ratio 1:2.7) copolymer. One pint (0.47 l) of aqueous resin solution was added.

1 pint (0.47 l) of resin solution with 4.

This gives 4 grams of polyacrylic acid and 8.71 grams of copolymer.

The system was agitated for over 8 minutes, drained, and centrifuged for 1 minute.

The noodle pieces and shirt fabric specimens were then dried by ironing at 350°F (177°C) for 15 seconds.

The specimen was contaminated by placing 5 drops of refined mineral oil and 5 drops of used motor oil, respectively, at two separate locations on the specimen.

These soiled areas were then blotted and allowed to sit for a minimum of 30 minutes.

The method of staining and evaluation was the American Association of Textile Chemistry and Colorists standard method, Test 130-1969.

A control piece (hereinafter referred to simply as the control piece) prepared from the same fabric as the test piece was washed in exactly the same manner as described above, except that the polymer-copolymer mixture was not added to the acid treatment step.

The test and control specimens were then further subjected to three steps of washing, treatment with a polymer-copolymer solution, drying, and staining.
Circulated.

Incidentally, the oil stains after the second time were placed on the small piece in a different position from the previous time.

Test specimens were run with resin added after each acid treatment step, and control specimens were run without resin added at any time.

After ironing each piece, the color intensity of the soiled area was evaluated.

A rating of 5 represents complete disappearance of the stain.

The results after four working cycles are shown in Table 1: After the first wash after treatment and staining with resin, the stains on the treated fabrics are slightly lighter than those on the untreated fabrics. was observed.

That is, the washing step after resin treatment was more effective in removing soil than the untreated case.

After completing four cycles of operation, the stain applied at the end of the first cycle had almost completely disappeared in the case of the resin-treated specimens, but was still clearly visible in the case of the untreated control fabric. It looked like.

Example 2 In a Milner Washer, model s6o00-OWM-5, with a melt capacity of 35 lbs., 24 lbs. (10.9 kg) of noodle pieces and 10 lbs.
(25cm) square white shirt fabric test piece [Polyester noodles processed with durable press resin (
65:35) 1 pound (450.9') of blended yarn was added.

The washer was filled with water to the appropriate level and 0.25 pounds (113 g) of a commercially available all-in-one cleaner was added.

The water temperature was below 150°C (66°C). After stirring for 10 minutes, drain the system, refill with water, and add 0. 1. Added 25 lbs (57g).

This was stirred for 5 minutes at 150°F (66°C) and then drained.

Rinse 4 times with plenty of water. The first time was 150'F (66°C)
), the second at 130°F (54°C), the third at 110°F (43°C), and the fourth at 90'F (32°C).

120°F (49°C) water at low water level [16 gallons (6
It was raised to 0.6l)).

Three pints (1.4 liters) of the aqueous resin solution of Example 1 were added to the water.

The resulting pH was 6.1.

The system was agitated for 5 minutes, drained, and centrifuged for 1 minute.

Next, a small piece of noodles and a shirt fabric test piece were held at 73°.
It was air-dried at F (23°C) for 2.5 hours.

The test piece was contaminated by placing 5 drops of purified mineral oil and 5 drops of used motor oil at two separate locations on the test piece.

These soiled areas were then rubbed and allowed to sit for a minimum of 30 minutes.

Control pieces were prepared in exactly the same manner except that the resin mixture was not added in the final step.

Clean once, then apply stain release resin, stain,
After one more wash, the results were 3.5 with mineral oil for the control piece.
+, motor oil grade 2 stone and test piece mineral oil grade 3.5
+ Motor oil showed a grade of 3, O.

Example 3 The same experiment was conducted on the test and control specimens of Example 1 except that the temperature of the solution was varied when applying the soil release polymer to the fabric.

The results are shown in Table 1; it can be seen that even at applied solution temperatures as low as 70°F (21°C) there is a small effect of polymer treatment.

Further noticeable effects are obtained at temperatures below 95°C (35°C) and above.

Example 4 The same experiment was conducted on the test and control specimens of Example 1 except that the wet specimens were tumbled in a hot air oven at 150° F. (66° C.) after centrifugal extraction.

The results after 4 cycles of resin impregnation treatment are shown in the following table along with a reference for comparison: Example 5 Milner Washer, Model 600-OWM- with a capacity of 35 pounds (15.9 kg).
24 pounds of small pieces of noodles (1 0.9 kg)
) and a 1 pound (450 g) 10 inch (25 cm) square white shirt fabric test piece (polyester rumen (65:35) blend treated with durable press resin).

The washer was filled with water to the appropriate level and 0.25 pounds (113 g) of a commercially available all-in-one cleaner was added.

Water temperature was 150°F (66°C).

After stirring for 10 minutes, the system was drained, refilled with water, and 0.125 pounds (57 g) of detergent was added.

This was stirred for 5 minutes at 150°F (66°C) and then drained.

Rinse 4 times with plenty of water.

150°F (66°C) the first time, 130°F the second time
(54°C), the third at 110°F (43°C), and the fourth at 90°F (32°C).

The 120°F (49°C) water was then raised to the low water level (16 gallons (60.6 A)).

By adding silicate ammonium acid solution, the pH
was adjusted to 4.1 and then 5 oz (142 g) of wheat starch was added to the acid solution.

After stirring for 1 minute, 1 pint (0.477) of the resin solution described in Example 1 was added.

The system was agitated for over 8 minutes and then centrifuged for 1 minute.

Thereafter, the fabric was heated to 200°F (93°C) in a hot air dryer.
) Dry under tumble at air temperature.

The specimen was contaminated by placing 5 drops of refined mineral oil and 5 drops of used motor oil at two separate locations on the specimen.

These soiled areas were rubbed and allowed to sit for a minimum of 30 minutes.

A control piece was prepared in exactly the same manner as described above, except that the polymer-copolymer mixture was not added to the acid treatment step.

The control and test specimens were further subjected to three cycles of washing, treatment with polymer monocopolymer solution, drying, and staining.

For the second and subsequent stains, the stain was placed on a small piece of fabric in a different location from the previous stain.

Test specimens were run with polymer added at each acid treatment step, and control specimens were run without polymer added at any time.

The results after 4 cycles are shown in Table ■: Example 6 Experiments of Example 1 using various amounts of sodium sulfate acid treatment to vary the pH of the system when applying the soil release polymer to textiles. I did it.

The results are listed in Table ■; the improved stain removal compared to the control piece was approximately 6.5
It is observed that a pH range of ˜4 is obtained for the processing solution.

At a pH lower than 4, the solution results in fabric weakening (tendering) and other undesirable side effects.
It is not normally used for commercial washing work.

It has been observed that the preferred pH range is about 4.5-5.8.

Example 7 The method of Example 1 was carried out with various fabrics.

As these fabrics, wrinkle-proofed polyester-noodle (65:35) blend, rayon, pure noodle, silk, nylon, pure polyester (Dacron) wool, and acrylic fabric were used.

Stain removal was markedly improved in all cases except for the mork oil stain removal on rayon, which was only marginally improved compared to the control.

Example 8 25% by weight aqueous polyacrylic acid solution, about 3.9% by weight based on the total solution, and 20% by weight ethyl acrylate-methacrylic acid (27:73 molar ratio) copolymer solution into the total solution. An aqueous solution containing 9.6% by weight based on fluorocarbon propellant was charged into a pressurized vessel together with a fluorocarbon propellant.

This mixture was sprayed onto a clean and dry wrinkle-resistant polyester noodles (65:35) blend until the fabric was slightly damp to the touch.

This wet weight gain was approximately 3% of the dry weight, representing approximately 0.09% polymer addition to the dry fabric.

The fabric piece is then dried by ironing at 360°F (182°C), contaminated with 5 drops of motor oil, aged for at least 30 minutes, and washed in a conventional household washing machine. temperature to 110°F (43°F) using
℃).

After removal from the washing machine, the damp fabric piece was dried, sprayed again with the polymer solution and dried at ambient temperature.

After 4 cycles of treatment, the fabric sprayed with the polymer solution has a 3.
Motor oil stain rating of 5+ (3.0+ for control) and 5
．． It showed a mineral oil stain rating of 0 (3.0 + for the control).

Example 9 Example 1 by changing the mixing ratio of the acid solution and the polymer solution added to it
I used this method.

The results of this experiment are listed in Table ■.

Percentages are by weight. Example 10 The procedure of Example 1 was followed except that the amount of soil release polymer added to the acid solution was varied.

The results are reported in Table 1; slightly improved results are obtained when adding a small amount, such as 0.25 pints (0.12 l) of polymer solution to 25 pounds (11.3 kg) of fabric. That is understood.

Good improvement was obtained at 0.5 pints (0.24A) per 25 pounds (11.3 kg), and the best results were obtained at 1 pint (0.24 A) per 25 pounds (11.3 kg) of fabric. .47 l) or more.

Example 11 The experiment and procedure of Example 1 was repeated with varying ratios of ethyl acrylate to methacrylic acid making up the copolymer.

Generally, good results are obtained when the copolymer contains more than about 1 mole of methacrylic acid per mole of ethyl acrylate because the copolymer is water soluble or dispersible.

Conversely, when a copolymer contains less than about 1 mole of methacrylic acid per mole of ethyl acrylate, the copolymer is essentially insoluble and therefore it is not useful in the practice of this invention.

Compositions containing up to 100% methacrylic acid and containing pure polymethacrylic acid (100% methacrylic acid) show satisfactory performance.

Example 12 Using a blend of noodles and raw polyester-noodles (65:35) as a fabric and adding a commercially available starch containing 4 ounces (11 kg) per 25 pounds (11.3 kg) of fabric.
Example 1 except that 3 g) was added to the acid solution together with the polymer solution.
An experiment was conducted.

Example 13 Blue work clothes at an auto repair shop, jacket and pants 4 2
in (107cm) diameter x 84 in (2
13 cm) in a stainless steel washer.

This machine washes 200 pounds of polyester (65:35) blended clothing with a permanent press finish (91
kg) was added.

In a washing machine with hot water at 190°F (88°C),
15 cm) of water (170 gallons (644 l)).

The clothes were agitated for 6 minutes by rotating the washing machine to remove easily separated oil stains.

The next step is to add 190°F (88°C) water to the washer to the same level, and then add alkaline all-in water to the same level.
Added 6 lbs (2.7 kg) of One Cleaner.

Additionally, 3 pints (1.41 liters) of emulsifying kerosene were added to improve detergency.

After stirring for 20 minutes, the washer was drained.

Fill the washing machine again with water at the same temperature to the same level,
The clothes were then stirred without refilling and then drained.

Fill the washing machine with water at the same temperature again to the same level.

3 lbs (1.4 kg) of alkaline cleaner and 1.5
A pint (0.71 l) of emulsifying kerosene was added and the system was stirred for 15 minutes.

After draining the system, it was rinsed five times.

Each time, water was added to a level of 12 in (30.5 cm) [262 gallons (992 l)] and 2 in.
After stirring for a minute, it was drained.

The temperature was lowered each time. The initial temperature is 190°F (8
8°C), and the final rinse temperature was 120°F.
(49°C).

For the final step, the washing machine should be heated to 120°F (49°C).
of water to a level of 6 inches (15 cm).

Six ounces (170 g) of the silicate sodium acid solution and 36 ounces (1.02 kg) of starch-based thickener were added and dispersed by stirring for 2 minutes.

Next, 3.9% by weight of a 25% by weight polyacrylic acid aqueous solution and 20% by weight of ethyl acrylate-methacrylic acid (
Six quarts (6.84 liters) of a polymer solution containing 9.6% by weight of the copolymer (1:2.7 molar ratio) were added and the system was stirred for an additional 8 minutes.

The clothes were then extracted with a hydraulic extractor after draining the washer.

Finally, the garments were tumble dried in a hot air dryer at 180°F (82°C).

To test the composition, clothing worn at an auto repair shop was cleaned as described above and then returned to the repair shop for two weeks of use.

After 6 months, there were 12 cycles of cleaning and use.

There were only two or three light residual stains on the clothes, and the overall appearance was considered to be good.

At the same time, a control experiment was conducted on the same clothing worn in an auto repair shop.

That is, the garments were subjected to exactly the same wash cycle except that no polymer solution was added to the acid solution.

After six months, the garments were generally dark in appearance and had numerous dark oil stains.

Approximately 20% of the garments were not aesthetically or sensory acceptable and had to be discarded.

Example 14 The remaining unacceptably soiled clothing of the Example 13 control was washed in exactly the same manner as in the Example 13 main test.

However, as the acid solution, 25% by weight polyacrylic acid aqueous solution 3
．． 9% by weight and ethyl acrylate-methacrylic acid (1:
Twelve quarts (14.3 liters) of a polymer solution containing 9.6% by weight of the copolymer (2.7 molar ratio) were added.

After two subsequent washes and polymer treatment, a noticeable improvement in appearance was observed.

After four cycles of polymer treatment and washing (without being worn), most of these garments were clean and generally improved in appearance to the extent that they were suitable for regular use.

There was further improvement in appearance after multiple polymer treatment and washing operations over 6 cycles.

However, at higher number of treatments, little improvement was observed over 6 cycles.

Example 15 The following copolymer composition could be prepared by standard aqueous polymerization methods.

Ester Acid Ratio of esters Butyl acrylate Methacrylic acid 6.071 Methyl acrylate Acrylic acid 2.5/1 Isopropyl acrylate Methacrylic acid 1.5/1 Butyl acrylate Acrylic acid 9.0/1 Ethyl methacrylate Acrylic acid 1 5.0/
1 Butyl methacrylate Methacrylic acid 6.0/
1 Methyl methacrylate Acrylic acid 3.0/
1 These copolymers are useful as temporarily deposited or impregnated soil release resins in the practice of this invention.

Example 16 The experiment of Example 1 was carried out, except that two parts by weight of a quaternary ammonium type fabric softener was added to the acid solution before adding the acrylic resin to the acid solution.

This softener is 2-heptadecyl-1-methyl-1-
(“(2-stearoylamide)monoethyl]imadazolinium methyl sulfate.

A comparison of the test piece and control piece is shown in Table ■:

Claims (1)

[Claims] 1. A method of washing textiles comprising washing the textile with an aqueous detergent solution, rinsing with water to remove dirt and substantially all of the detergent, and finally drying the textile, comprising: Immediately before the final drying of the rinsed fabric, the fabric is washed with a material selected from the group consisting of polyacrylic acid, polymethacrylic acid, and a copolymer of acrylic acid or methacrylic acid with an alkyl ester of acrylic acid or meccrylic acid. The fabric is brought into contact with an aqueous solution of an acrylic resin having a pH of 4.0 to 6.5 to temporarily impart stain releasability to the fabric, provided that the resin content in the aqueous solution is 0.25 parts by weight of resin per 5000 parts by weight of the solution.
~3 parts by weight, and the alkyl substituent of the ester has 1 to 4 carbon atoms, and the acid/ester molar ratio of the copolymer is at least 1/1. How to wash textiles. 2. It consists of washing the fabric with an aqueous alkaline cleaning agent, rinsing with water to remove dirt and most of the alkaline cleaning agent, then treating with an acid solution to remove any remaining alkaline content, and finally drying. A method for washing textiles, characterized in that an effective amount of acrylic resin is added to an acid solution to temporarily impart stain release notes to the textile, and the acrylic resin is polyacrylic acid, polymethacrylic acid, acrylic acid, etc. or methacrylic acid and an alkyl ester of acrylic acid or meccrylic acid, provided that the alkyl substituent of said ester has 1 to 4 carbon atoms and The acid/ester molar ratio shall be at least 1/1 and the amount of resin added to the acid solution shall be 0.00 parts by weight of resin per 5000 parts by weight of solution.
A method for washing textiles, characterized in that the amount is in the range of 25 to 3 parts by weight. 3 Wash the fabric with an alkaline detergent, rinse with water to remove dirt and substantially all of the alkaline detergent, treat with an acid solution to remove any remaining alkaline content, and then rinse with an aqueous solution of a textile finish. A method of washing fabrics comprising treating and finally drying the fabrics by adding an effective amount of acrylic resin to an aqueous solution of a fabric finish with a pH in the range of 4 to 6.5 before drying the fabrics. The acrylic resin is characterized by temporarily imparting stain releasability, and the acrylic resin is made of polyacrylic acid, polymethacrylic acid, or a copolymer of acrylic acid or meccrylic acid and an alkyl ester of acrylic acid or meccrylic acid. provided that the alkyl substituent of said ester has 1 to 4 carbon atoms and the acid/ester molar ratio of said copolymer is at least 1/1, and said textile finish The amount of resin added to the aqueous solution is 0.2 resin per 5000 parts by weight of solution.
A method for washing textiles, characterized in that the amount is in the range of 5 to 3 parts by weight.