JP3336356B2 - Dry cleaning method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for dry-cleaning clothes.

[0002]

Clothes made of hair, silk, and the like, which are liable to cause damage such as shrinkage and shape loss due to water, are treated by dry cleaning. The cleaning agent used heretofore, considering the damage to clothing, perchlorethylene, which is effective in removing oily stains,
Dry cleaning using an organic solvent or the like, CFC-113 emphasizing texture, or a petroleum-based solvent are selectively used.

[0003] Laundry cleaning using water,
It is effective for removing water-soluble stains due to sweat from natural materials and absorbent fibers such as recycled fibers.However, the water used has a very high surface tension, Because it is difficult to penetrate, it is replenished by the combined use of surfactants and by taking time and using physical force. But the water is
After infiltration into the fiber, since the molecular diameter is small, it enters into a coarse portion such as an amorphous portion inside the fiber and swells the fiber.

[0004] For cellulose fibers and animal fibers, therefore, Hygral expansion (fiber expansion)
Causes shrinkage of the woven fabric. Further, in the case of wool fabric, the scale covering the fiber surface is opened, and the entanglement between the scales is remarkably increased by applying a physical force during washing, and a felting phenomenon occurs. In the case of a silk fabric, the glossiness of the surface is likely to be lost due to a lowness defect in which fine fibers (fibrils) are scattered on the fiber surface. Further, in the case of synthetic fibers such as polyester, fiber expansion occurs due to temperature, and solid particles easily enter the coarse fiber portion to cause re-contamination.

As described above, laundry causes swelling of fibers and causes injuries such as shrinkage of products, changes in form, changes in texture, and the like.

[0006] As a washing method for preventing the fibers from swelling, dry cleaning using an organic solvent has been developed. Since the organic solvent is a non-polar solvent, the amount of water dissolved is small, and the molecular weight of the organic solvent generally used at present is 133.5 to 187.5, which is very large as compared with the molecular weight of water. There is no permeation into the interior of the fiber and no swelling of the fiber. As the organic solvent used,
Perchlorethylene having a large ability to remove oily dirt, that is, a large KB value (kauributanol value) is most often used. However, textile products are those that have been subjected to various finishing processes, those that contain fats and oils themselves, such as hair products, pigment prints, and chemical agents that dissolve in solvents with high KB values as secondary materials. When washing with perchlorethylene having a large KB value, these substances are removed together with oily stains, resulting in a loss of product value.

As described above, water-soluble stains can be easily removed by laundry and oily stains can be easily removed by dry cleaning, but other stains include insoluble stains such as solid particles. This insoluble dirt causes electric repulsion and van de
Due to the difference from the r Waals attraction, they are attached to the fiber and must be removed by reducing these forces or by applying more energy than these forces.

[0008] Therefore, it is desirable that stains which are difficult to remove by laundry and dry cleaning be removed by dissolving them by adding a surfactant or the like, or by applying physical force such as stirring. Of course, the stain removal rate varies depending on the physical force and the amount and type of the additive, and the cleaning performance is evaluated as good or bad. Therefore, it is desirable that the solvent removes dirt as much as possible, but at the same time, it is important that the solvent does not damage the object to be washed.

Next, various values that need to be considered as solvents are shown in Table 1.
Shown in

[0010]

[Table 1] Although the fluorinated solvent CFC-113 in the table is used as a relatively mild dry cleaning solvent, it causes problems such as ozone depletion and global warming.
Production banned in 1995. As shown in Table 1, the requirements for the solvent vary widely, and a distinction is made between solvents used in laundry using water and dry cleaning using an organic solvent. However, the detergency and the damage to the object to be washed are in a reciprocal relationship, and if the removal rate of dirt is increased, the damage due to water or an organic solvent increases.

In recent years, the spread of luxury goods has increased the number of garments that value the delicate texture, and petroleum solvents and CFC-113 have been widely used as mild solvents having a low resin dissolving power (chemical power). It has become, but even in these KB
Although smaller in value than perchlorethylene, it has resin dissolving power and may cause injury. Furthermore, as shown in Table 1, petroleum-based solvents are flammable, so it is difficult to use them in urban areas and they are toxic. Also, it takes time to dry from the boiling point value. There is a problem in terms of risk of injury and productivity. In addition, all are organic solvents, and dissolve certain resins and plasticizers. HCFC-225 as other alternative Freon
HCFC-141b and the like can be mentioned, but these are also determined to be reduced stepwise, and furthermore, they may attack a part of the resin, so that they cannot be adopted like CFC-113.

[0012] As a washing method, the laundry to be washed with water is subjected to laundry, and the laundry not affected by the dissolving power of the organic solvent is subjected to dry cleaning with perchlorethylene. Items to be washed, which are difficult to treat by any of these methods, include petroleum solvents and CFC-113, which are relatively mild organic solvents having a halfway problem.
It is desirable to avoid dry cleaning which is highly dangerous by using a solvent, and to treat with a solvent having no resin dissolving power, that is, a small KB value.

[0013]

Accordingly, the present inventors have conducted various studies on substances which have no dissolving power, which is a drawback of dry cleaning, and have eliminated chemical damage to the object to be washed. And a hydrofluoroether-based solvent having a KB value of 5 to 10
It is merely a medium for dispersing dirt coming out of the object to be washed without dissolving most of the material, and has a property of eliminating the dissolving power (damage) given to the object to be washed. This solvent has a ratio of the number of fluorine atoms to the number of carbon atoms in one molecule of 1.8 such as 1,1,1,2,3,4,4,5,5,5-decafluoropentane is 1.8.
Larger solvent.

The present inventors use the properties of a hydrofluorocarbon-based solvent or a hydrofluoroether-based solvent as a cleaning agent and add them directly to this solvent or add various oils to the circulation path. It is an object of the present invention to provide a dry cleaning method in which an oil absorbing step is inserted by using an absorbent, an oil adsorbent, an organic solvent, or a combination thereof to remove non-flammable and environmentally safe oily stains.

The following Table 2 shows a comparison table of a hydrofluorocarbon solvent (HFC: C ₅ H ₂ F ₁₀ ) and a hydrofluoroether solvent (HFE: C ₄ F ₉ OCH ₃ ).

[0016]

[Table 2] Since the hydrofluorocarbon solvent of the present invention is composed of hydrogen (H), fluorine (F), and carbon (C), it is stable in the air and has an ozone destruction coefficient of 0. There is no problem of destruction.

Hydrofluorocarbon-based solvents such as 1,1,1,2,3,4,4,5,5,5-decafluoropentane are obtained from KB
Value of 5, and a hydrofluoroether-based solvent such as 1-methoxy-nonafluorobutane (C ₄ F ₉ OC
H _3), 1-ethoxy over nonafluorobutane (C ₄ F ₉ O
C ₂ H ₅ ) and the like have a KB value of 5 to 10. Therefore, the oil-based stain (solubility parameter (SP value))
Is less than 11 containing 50% of the oil), the oil-absorbing agent is added to these solvents,
Alternatively, the oil absorbing agent is used in combination, for example, by inserting an oil absorbing step to improve the cleaning property of oily stains and the ability to prevent re-contamination.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hydrofluorocarbon solvents used in the present invention include hydrofluoroether solvents such as 1,1,1,2,3,4,4,5,5,5-decafluoropentane. As the solvent, 1-methoxy-nonafluorobutane (C
₄ F ₉ OCH _3), 1- and ethoxy-nonafluorobutane _{(C 4 F 9 OC 2 H} 5) or the like, and used to oil absorbent (II)
The solvent is not particularly limited as long as it can effectively absorb or adsorb and remove oily dirt from the solvent, but is particularly excellent in the ability to remove oily dirt containing an oil having a solubility parameter of 11 or less of 50% or more. Monomer (A) having at least one polymerizable group in a molecule mainly composed of a monomer having a solubility parameter (SP value) of 9 or less
An oil-absorbing polymer (III) obtained by polymerizing a monomer component containing 0% by weight or more, and / or activated carbon;
At least one selected from the group consisting of oil adsorbents such as silica, zeolite, diatomaceous earth, activated alumina, montmorillonite, halloysite, allophane, atavulgite, and kaolin is preferred.

The oil absorbing polymer (III) used in the present invention
Is based on 96% by weight of a monomer (A) having one polymerizable group in a molecule containing a monomer having a solubility parameter (SP value) of 9 or less as a main component and at least two polymers in a molecule. There is no particular limitation as long as it is an oil-absorbing polymer obtained by polymerizing a monomer component comprising 4% by weight or less of a crosslinkable monomer (B) having an unsaturated group. Solubility parameters (SP
Value) exceeds 9 as the main component of the monomer (A), a polymer having high absorbency for oily dirt (I) cannot be obtained, and the ability to prevent re-contamination of the object to be washed is reduced. This is not preferable because the oil-absorbing polymer (III) may be reduced or the exchange life of the oil-absorbing polymer (III) may be shortened.

The solubility parameter (SP value) is generally used as a scale indicating the polarity of a compound. In the present invention, a value derived by substituting the aggregation energy constant of Hoy into the calculation formula of Small is applied. The unit is (C
al / cm ³ ) ^1/2 .

The polymerizable group of the monomer (A) having a solubility parameter (SP value) of 9 or less and having one polymerizable group in the molecule used in the present invention includes radical polymerization, radiation polymerization, and addition polymerization. There is no particular limitation as long as it is a polymerizable group capable of polymerizing an oil-absorbing polymer by a polymerization reaction such as polycondensation. Among them, a method of radically polymerizing a polymerizable unsaturated group,
A monomer having a polymerizable unsaturated group is particularly desirable because an oil-absorbing polymer can be industrially easily produced.

The monomer (A) which gives excellent oily soil absorbing ability includes at least one aliphatic hydrocarbon group having 3 to 30 carbon atoms and alkyl (meth) acrylate or alkylaryl (meth). At least one unsaturated compound (a) selected from the group consisting of acrylate, dodecyl acrylate, n-butyl acrylate, alkyl (meth) acrylamide, alkylaryl (meth) acrylamide, fatty acid vinyl ester, alkylstyrene and α-olefin; Those composed as a main component are preferred.

Such a solubility parameter (SP value)
Is used in the monomer (A) having a monomer of 9 or less as a main component in an amount of 50% by weight based on the total amount of the monomer (A).
The ratio is more preferably 70% by weight or more. When the amount of the monomer (A) having a solubility parameter (SP value) of 9 or less as a main component is less than 50% by weight, a polymer having high absorbency for oily soil (I) can be obtained. In addition, the ability to prevent recontamination of the substance to be cleaned is reduced, and the exchange life of the oil-absorbing polymer (III) is shortened.

Therefore, in the present invention, 50 monomers having a solubility parameter (SP value) of 9 or less are contained in the monomer (A).
% By weight, but the solubility parameter (SP value) is 50% by weight or less in the monomer (A).
May contain more than 9 monomers. Examples of such a monomer include (meth) acrylic acid, acrylonitrile, maleic anhydride, fumaric acid, hydroxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and methoxypolyethylene glycol (meth) acrylate. be able to.

The oil absorbing polymer (III) used in the present invention
It is only necessary that the oil-absorbing polymer can absorb the oily dirt (I) regardless of the presence or absence of crosslinking. However, the solubility parameter (SP value) is used to control the oil absorption ratio and to prevent contamination of the object to be washed by dissolving the oil-absorbing polymer (III) in an oily soil (I) or a hydrofluorocarbon-based or hydrofluoroether-based solvent. (A) having at least one polymerizable group in a molecule comprising a monomer having 9 or less as a main component is 96% by weight or more (96 to 99.999% by weight)
4% by weight or less (0.001 to 4% by weight) of a crosslinkable monomer (B) having at least two polymerizable unsaturated groups in the molecule thereof (provided that the monomers (A) and (B) Total is 10
0% by weight).

The crosslinkable monomer (B) used in the present invention includes, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate,
Polyethylene glycol di (meth) acrylate, polyethylene glycol-polypropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, neopentyl glycol di (meth)
Acrylate, 1,6-hexanediol di (meth) acrylate, N, N'-methylenebis (meth) acrylamide, N, N'-propylenebis (meth) acrylamide, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) ) Acrylate, tetramethylolmethane, tetra (meth) acrylate, polyfunctional (meth) obtained by esterification of alkylene oxide adduct of polyhydric alcohol (for example, glycerin, trimethylolpropane or tetramethylolmethane) with (meth) acrylic acid Examples thereof include acrylate and divinylbenzene, and one or more of these crosslinkable monomers can be used.

The ratio of the monomer (A) and the crosslinkable monomer (B) in the monomer components used in producing the oil-absorbing polymer (III) is such that the monomer (A) and the crosslinkable monomer The monomer (A) is 96 to 99.9 with respect to the total of the monomer (B).
In a range of 99% by weight, the crosslinkable monomer (B) is 0.001 to
A range of 4% by weight is more preferred.

When the amount of the monomer (A) is less than 96% by weight or the amount of the crosslinkable monomer (B) exceeds 4% by weight, the crosslinked density of the obtained crosslinked polymer becomes too high, and the oily soil absorbing ability is increased. However, it is not preferable because a polymer having a high water content cannot be obtained, leading to a decrease in absorption efficiency and an increase in cost. Further, if the crosslinkable monomer (B) is not added at all, the gel strength of the crosslinked polymer that has absorbed the obtained oily stain is reduced, so that absorption is difficult or filterability deteriorates, which is not preferable.

In order to produce the oil-absorbing polymer (III), the monomer component may be polymerized using a polymerization initiator or a catalyst. Further, polycondensation can also be performed by light such as ultraviolet rays, radiation, heat, or the like. The polymerization can be performed by a known method such as suspension polymerization, bulk polymerization, and emulsion polymerization.

In the suspension polymerization, for example, an emulsifier having a high HLB value or a protective colloid such as polyvinyl alcohol, hydroxyethylcellulose or gelatin is used, the monomer components are suspended in water, and an oil-soluble polymerization initiator is used. The polymerization may be carried out in the presence of As the polymerization initiator, for example, benzoyl peroxide, lauroyl peroxide, organic peroxides such as cumene hydroperoxide, 2,2'-azobisisobutyronitrile, 2,2'-azobisdimethylvaleronitrile and the like Azo compounds and the like can be used,
The polymerization temperature is preferably in the range of 0 to 150 ° C. 1 obtained
The aqueous suspension of the finely divided resin having a particle size of about 0 to 1000 μm is filtered and dried to obtain the desired oil-absorbing polymer (III).

The bulk polymerization is carried out, for example, by pouring a monomer component into a mold in the presence of the above-mentioned polymerization initiator and carrying out polymerization under the conditions of 0 to 150 ° C. Is obtained.

In the emulsion polymerization, for example, a monomer component is suspended in water using an anionic or nonionic or a composite emulsifier thereof, and a persulfate such as ammonium persulfate or potassium persulfate or a water-soluble azo compound is used. It can be used as a polymerization initiator, and can be polymerized while using a reducing agent, a pH regulator, an antioxidant, an antistatic agent, and the like, if necessary. As a result, the desired oil-absorbing polymer (III) is obtained.

In the ring-opening polymerization, the desired oil-absorbing polymer (III) can be obtained by, for example, a method of emulsion polymerization in alcohol or water using indium, ruthenium, osmium or the like as a catalyst, or a method of polymerization using a metathesis catalyst.

Examples of the form of the oil-absorbing polymer (III) used in the method for absorbing oily dirt of the present invention include water dispersions, granules, granules, pack-shaped oil absorbers, and porous oil absorbers. .

For example, the oil absorbing polymer (III) used in the present invention can granulate various fillers and hydrophobic substances. According to Japanese Patent Application No. 4-147313, an oil absorbing agent comprising an oil-absorbing polymer (III) and a metal salt of an organic acid having a solubility of 1 g or less in 100 g of water at 20 ° C.
According to No. 1390, an oil absorbing agent comprising an oil absorbing polymer (III) and a hydrophobic inorganic compound having a methanol value of 25% or more, such as hydrophobic silica, can be mentioned.

The oil-absorbing polymer (III) or its granulated product is filled and arranged in a container made of an oil-permeable material,
It is carried in a nonwoven fabric and inserted as an oil absorption step. JP-A-4-15286 discloses an oil-absorbing material in which a hydrophobic porous container is filled with an oil-absorbing polymer (III).
According to No. 30835, an oil-absorbing material obtained by filling a particle made of an oil-absorbing polymer (III) and an organic acid metal salt having a solubility in 100 g of water at 20 ° C. of 1 g or less into a container made of a porous material, Japanese Patent Application Laid-Open No. Hei 5-246491 discloses an oil-absorbing material in which an oil-absorbing material comprising an oil-absorbing polymer (III) described in JP-A-5-246492 and a hydrophobic inorganic compound such as hydrophobic silica having a methanol value of 25% or more is filled in an oil-permeable container. An oil-absorbing material in which the oil-absorbing polymer (III) of JP-A-41583 is supported on a hydrophobic porous substrate, and a granular material comprising the oil-absorbing polymer (III) of Japanese Patent Application No. 5-56920 and a water-insoluble compound. A porous oil-absorbing material supported on a porous substrate, the oil-absorbing polymer (III) of Japanese Patent Application No. 5-308463 and a methanol value of 25% of hydrophobic silica and the like
A porous oil-absorbing material in which the above-described oil-absorbing material made of a hydrophobic inorganic compound is supported on a porous substrate, and the like can be given.

Further, other preferred oil-absorbing polymers (II
Examples of the polymer (I) include a polymer containing at least one norbornene group, wherein the substituent is derived from ethylene and cyclopentadiene by Diels-Alder (Diels-Alder).
-Alder) reaction, for example, dicyclopentadiene, tetracyclododecene, methyltetracyclododecene, ethylidenetetracyclododecene, hexacycloheptadecene, methylhexacycloheptadecene, tricyclopentadiene, methyl Norbornene, ethylidene norbornene, vinyl norbornene, 5-methyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-
2-norbornene, 5-octyl-2-norbornene,
5-dodecyl-2-norbornene.

In the cleaning of the present invention, the oily soil (I) is dissolved in a trace amount in a hydrofluorocarbon or hydrofluoroether solvent, and the oily soil (I) dissolved in the hydrofluorocarbon solvent is removed by an oil absorbent. (II) is performed by absorption. Therefore, the hydrofluorocarbon-based solvent or the like serves as a medium for transferring the oily dirt (I) to the oil absorbent (II), and thus only dissolves a very small amount of the oily dirt (I). (I) does not reattach to the object to be washed.

In the cleaning method of the present invention, when the cleaning effect is hard to increase at room temperature, the speed of oil absorption into the oil absorbent (II) can be improved by heating.

Examples of the oil adsorbent used in the present invention include activated carbon, silica, zeolite, diatomaceous earth, activated alumina, montmorillonite, halloysite, allophane, atabalgitite, kaolin and the like. (Experiment) Removal of oily dirt Hydrofluorocarbon solvent, 1,1,1,2,3,4,4,5,
800 ml of 5,5-decafluoropentane was put into the circulation washing device shown in FIG. 1 and the oil absorbents (1) and (2) shown in Reference Examples 1 and 2 and activated carbon (average) Granule system 1.5 mm, total pore volume 0.8 cm ³ / g) Using 20 g of activated alumina, an oily soiled cloth (5 cm ×
5cm) 27 sheets and the blanket 1 are put, and the solvent flow rate is 750m.
The mixture was washed with stirring at 1 / min for 30 minutes.

The same experiment was conducted using a hydrofluoroether-based solvent, 1-methoxy-nonafluorobutane (C ₄ F ₉ OCH ₃ ), instead of the hydrofluorocarbon-based solvent. (Reference Example 1) In a 500 ml flask equipped with a thermometer, a stirrer, a gas inlet tube and a reflux condenser, 3 parts of polyoxyethylene alkyl ether (trade name: SOFTANOL 150, manufactured by Nippon Shokubai Co., Ltd.) are dissolved in 300 parts of water. Then prepare
The atmosphere in the flask was replaced with nitrogen under stirring, and the flask was heated to 40 ° C. in a nitrogen stream. Thereafter, 99.823 parts of dotesyl acrylate (SP value: 7.9) as a monomer (A) and 0.1 g of ethylene glycol diacrylate as a crosslinkable monomer (B).
A solution consisting of 177 parts and 0.5 part of benzoyl baroxide as a polymerization initiator was added all at once to the flask.
The mixture was stirred vigorously under the condition of 50 rpm.

Then, the temperature inside the flask was raised to 80 ° C., and the polymerization reaction was carried out at the same temperature for 2 hours. Thereafter, the temperature inside the flask was further raised to 90 ° C., and the temperature was maintained for 2 hours to complete the polymerization. As a result, an aqueous dispersion containing a crosslinked polymer (1) having an average particle size of 30 μm (resin pure content: 25% by weight) was obtained.

2 parts of a fine powder (average particle size: 4 μm) of hydrophobic silica (Nippeal SS-70, manufactured by Nippon Silica) in an aqueous solution obtained by dissolving 1.5 parts of the above polyoxyethylene alkyl ether in 150 parts of water. And 3 parts of aluminum stearate fine powder (average particle size: 5 μm)
The mixture was stirred under the condition of 00 rpm to obtain an aqueous dispersion of hydrophobic silica and aluminum stearate. Next, an aggregate comprising the crosslinked polymer (1), hydrophobic silica and aluminum stearate was obtained. Further, this aggregate was filtered off, dried at 80 ° C. and then pulverized to obtain an average particle size of 2 m.
Thus, an oil absorbent (1) granulated to a size of m was obtained. (Reference Example 2) In a 500 ml flask equipped with a thermometer, a stirrer, a gas inlet tube and a reflux condenser, 3 parts of gelatin was added to water 3
The mixture was dissolved in 00 parts and charged, and the inside of the flask was replaced with nitrogen under stirring and heated to 40 ° C. in a nitrogen stream. Then, n-butyl acrylate (SP value: 8.
8) A solution consisting of 99.907 parts, 0.093 parts of ethylene glycol dimethacrylate as a crosslinkable monomer (B) and 0.5 parts of benzoyl peroxide as a polymerization initiator was added all at once to the flask, and the mixture was stirred at 400 rpm. Stir vigorously under the conditions.

Then, the temperature in the flask was raised to 80 ° C., and the polymerization reaction was carried out at the same temperature for 2 hours. Thereafter, the temperature in the flask was further raised to 90 ° C., and the temperature was maintained for 2 hours to complete the polymerization. I let it. After the completion of the polymerization, the granular product is separated by filtration, washed with water, and dried at 60 ° C. to obtain an oil absorbent (2) comprising a crosslinked polymer (2) having an average particle size of 200 μm.
I got The cleaning rate and the recontamination rate are shown in Table 3, and for comparison, the cleaning rate and the recontamination rate without using the oil absorbent are also shown.

The oily soiled cloth used in this test was prepared by dissolving beef tallow, liquid paraffin, and oil red in carbon tetrachloride, dipping and attaching a white cloth, and air-dried.

The cleaning rate and the re-contamination rate are as follows:
The Y value of the white cloth was measured with a colorimeter (manufactured by Suga Test Instruments) and calculated by the following equation. Cleaning rate (%) = {(Y value after cleaning−Y value before cleaning) / (Y value of white cloth−Y value before cleaning)} × 100 Recontamination rate (%) = ｛(Y value of white cloth before cleaning−white cloth after cleaning) Y
Value) / Y value of white cloth before washing｝ × 100

[0047]

[Table 3] From this result, by adding a small amount of an oil-absorbing polymer or an oil adsorbent to a hydrofluorocarbon-based and / or hydrofluoroether-based solvent, oily dirt is almost removed, and it is effective in preventing re-contamination. You can see that. In the embodiment shown in FIG. 1, a circulation type in which an oil absorbing step is inserted in the middle of the circulation path is shown, but the oil absorbing agent is directly added to the solvent in the washing tank, or the oil absorbing agent is placed on the tea pack. The same effect can be obtained when packed and washed together with the object to be washed. As a method for introducing an oil absorbing step into a circulation furnace, for example, a method in which an oil absorbing agent (II) is filled in a column provided in a solvent circulation path and an oil-containing solvent is brought into contact with the oil absorbing agent (II) A sheet in which the oil absorbent (II) is supported on a porous substrate such as a nonwoven fabric, a woven fabric, or a net, or a pack filled in a bag made of the porous substrate is disposed in a circulation path as a filter cloth to remove the oil-containing solvent. Method of contacting with oil absorbent (II) Add oil absorbent (II) directly to the solvent, absorb oily dirt from oil-containing solvent into oil absorbent (II), and then insert wire mesh or filter cloth into circulation path And recovering the oil absorbent (II).

As a method of introducing an oil absorbing step into the batch type washing method, for example, an oil absorbing agent (II) is directly added to a solvent for washing.
After absorbing the oily dirt into the oil absorbent (II), recover the oil absorbent (II) by sedimentation, floating, filtration, etc. After washing the sheet carried on the porous substrate and the pack filled in the bag made of the porous substrate together with the object to be washed in a solvent,
A method of collecting sheets and packs is conceivable.

[0049]

According to the present invention, the use of specific chlorofluorocarbon, which is an ozone-depleting substance, and the use of petroleum-based solvents that are highly flammable and difficult to use in urban areas, are achieved.
In addition, petroleum solvents can damage clothes during drying,
Unlike the C-225, HCFC-141b, and the like, the resin does not attack a part of the resin, and since the KB value is 5 to 10, it is possible to wash clothes without fear of dissolution due to dissolution.

According to the washing method of the present invention, it is possible to remove oily stains that cannot be washed by dry cleaning without causing chemical damage to the article to be washed. In addition, it is not an ozone depleting substance such as CFC-113, but contains no chlorine atom in the molecule, and has a destruction coefficient of 0. No danger of ignition and low toxicity.

Further, CFC-1 which is widely used at present
Since the boiling point is close to 13, the conventional washing machine can be used as it is.

As can be seen from Tables 1 and 2, this solvent is even easier to dry because the heat of evaporation is lower than CFC-113, which is relatively low among the currently used dry cleaning solvents. It can be said that the effect of the mechanical injury is small. If the organic solvent to be used is recovered and reused for reasons such as toxicity and price, as in the case of dry cleaning solvents, the items to be washed should be dried using a tumble dryer using hot air. Perform drying. In such a case, as described above, a petroleum-based solvent (including n-decane or the like) having a high boiling point and a large heat of evaporation requires a long drying time, and therefore, the object to be washed is susceptible to mechanical (physical) damage.

That is, the dry cleaning method using a hydrofluorocarbon-based solvent or a hydrofluoroether-based solvent can prevent the chemical influence due to water or an organic solvent, and the drying step is easy. It is possible to significantly reduce mechanical damage caused by forced drying in dry cleaning. Also, since the surface tension is smaller than other liquids, the fibers can easily penetrate into the deep part of the fiber without swelling during the cleaning, so that the cleaning can be performed for a short time, thus reducing the mechanical damage during the cleaning. It can be said that it is possible.

Furthermore, since the heat of evaporation is small, drying is easy, so that the drying energy is small and the energy cost for washing can be reduced.

[Brief description of the drawings]

FIG. 1 shows a cleaning step.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-124997 (JP, A) JP-A-6-271488 (JP, A) JP-A-54-26809 (JP, A) 39191 (JP, A) JP-A-3-297494 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) D06L 1/00-1/10 C11D 7/50 D06F 43/08

Claims (4)

(57) [Claims] 1. A dry cleaning method in which a hydrofluorocarbon-based solvent and / or a hydrofluoroether-based solvent is used as a dry-cleaning solvent, and at the same time, an oily absorbent (II) is used in combination to remove oily dirt (I). The oil absorbent (II) has a solubility parameter (SP value) of 1
Oily dirt (I) containing 50% or more of 1 or less oil component
And a monomer (A) having one polymerizable group in a molecule mainly composed of a monomer having a solubility parameter (SP value) of 9 or less.
A dry cleaning method, characterized in that it is an oil-absorbing polymer (III) obtained by polymerizing a monomer component contained in a proportion of 0% by weight or more. 2. The dry cleaning method according to claim 1, wherein the removal of the oily dirt (I) is performed in a circulation path of the solvent. 3. An oil-absorbing polymer (III) comprising the monomer (A) 9
Claims are obtained by polymerizing a monomer component comprising 6% by weight or more and 4% by weight or less of a crosslinkable monomer (B) having at least two polymerizable unsaturated groups in a molecule. 2. The dry cleaning method according to 1. 4. The monomer (A) has at least one aliphatic hydrocarbon group having 3 to 30 carbon atoms, and has an alkyl (meth) acrylate, dodecyl acrylate, n-butyl acrylate, alkylaryl ( (Meth) acrylate, alkyl (meth) acrylamide, alkylaryl (meth) acrylamide, fatty acid vinyl ester,
4. The dry cleaning method according to claim 1, wherein at least one unsaturated compound (a) selected from the group consisting of alkylstyrene and α-olefin is used as a main component.