JPH07216389A - Detergent composition and cleaning method - Google Patents

Abstract

PURPOSE:To obtain a detergent compsn. which prevents a washed article from being stained again by fine inorg. particles occurring during rinsing and which enables the removal of stains due to a polymerized oil attached to detergent the article by adding a minute amt. of an ultrahigh-mol.-wt. compd. to a deter gent compsn. CONSTITUTION:This detergent compsn. is prepd. by compounding a water-sol. detergent with an aq. amphoteric, cationic, anionic, or nonionic coagulating soln. contg. at least one substance selected from the group consisting of xanthan gum, a hyaluronic acid salt, and a polymer or a copolymer or their deriv. having an average mol.wt. of 1,000,000 or higher and obtd. by polymerizing a monomer component contg. at least one monomer selected from the group consisting of (meth)acrylic acid, maleic acid, fumaric acid, (meth)acrylamide, vinylpyrrolidone, and their derivs. When the polymer or the copolymer or their deriv. is used, it is compounded in an amt. of 1-500ppm based on the solids of the compsn.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The detergent composition and cleaning method of the present invention include: (a) household laundry, commercial cleaning, washing of linen supply textiles, and scouring step of textiles in dyeing and finishing operations; (B) A filter cloth for purifying air and wastewater, an inorganic filter material, and (c) other materials such as aqueous cleaning with less environmental pollution.

[0002]

2. Description of the Related Art Conventional aqueous detergent compositions and cleaning methods are
The polymer and / or copolymer, and / or the derivative thereof (hereinafter sometimes referred to as an ultra-high molecular compound) as described in [claim 1] are not used, but soap and others Surfactants (both may be referred to as oil-based detergents below), sodium metasilicate, sodium carbonate, and other inorganic detergents, sodium tripolyphosphate, sodium sulfate, and other builders, as well as various oxidizing and reducing agents. Bleach, enzymes, various water-soluble organic solvents, especially soot, dust,
For cleaning against dust, etc., sodium salt of carboxymethyl cellulose or other water-soluble cellulose
Derivatives, (hereinafter these may be referred to as CMC-Na), water-soluble polymer compounds such as sodium tripolyphosphate and sodium oxalate for removing iron rust.
A method of using a solution obtained by adding an organic solvent or the like to cold water or hot water and dissolving it has been widely adopted.

[0003]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention The cleaning composition and cleaning method of the present invention aim to solve the following problems which are technically difficult or low in productivity by the conventional methods.

(1) Prevention of recontamination of a substance to be washed with a stain substance (hereinafter, simply referred to as stain) generated at the time of rinsing after washing. (2) Prevents the transfer of dirt from the highly contaminated item to be washed to other contaminated items during washing. (3) Reduction of environmental pollution by not using oil-based detergents or reducing the amount used. (4) Reduce or reduce the generation of bubbles in the wastewater to reduce the environmental pollution of the river and the sea due to the wastewater, and shorten the work time by reducing the amount of rinse water and the number of rinses. (5) Conventional commercial cleaners that use high concentrations of oil-based detergents
Among the various regulated values related to drainage by the Prime Minister's Ordinance, which are difficult to achieve with conventional cleaning methods for cleaning and linen supply,
Especially difficult to achieve microbiological oxygen demand (hereinafter, BOD
Is written. ), Chemical oxygen demand (hereinafter referred to as COD), normal hexane extract content, phenols content, nitrogen content, phosphorus content, etc. within a limit value. (6) Providing technology that simplifies large-scale wastewater treatment facilities to meet even more stringent wastewater standards, which each prefecture has independently enacted by ordinance. (7) Reduce the load on sewage treatment equipment by reducing the total amount of substances in the waste liquid. (8) Solving obstacles to objects to be cleaned when using high hardness cleaning water. (9) Leaching of iron rust and polyvalent metal compounds. (10) Selective use of a formulation suitable for the type of stain. (11) Sterilization of fungi, pathogens, and spores of these that adhere to the object to be washed. (12) Due to the high cleaning efficiency, the cleaning time is shortened and the total mechanical impact is reduced, so that the fiber weight is reduced and the strength is reduced.
Delay with appearance deterioration. (13) Providing clothing with little skin irritation for sick people and infants. (14) Soot in the drainage, which is noticeable in light-colored and white objects to be washed,
To prevent recontamination in the rinsing process due to dust, muddy water, etc., simplification of rinsing and reduction of the amount of pollutants in wastewater by not using the CMC-Na high concentration liquid that has been used conventionally. (15) Alleviation of the strength reducing action of the bleaching agent on the fiber by using the aqueous solution of the ultra-high molecular compound in which the bleaching agent reacts more easily than the fiber. (16) For antifouling, wash stains adhered on the object to be washed that have been treated with a trace amount of ultra-high molecular weight compound with the washing liquid consisting of detergent and inorganic peroxide, by decomposing, leaching, rinsing, etc. After that, we propose a high-efficiency cleaning system with a low environmental load by performing antifouling treatment again with an ultra-high molecular compound and repeating the same cleaning. (17) To provide a redeposition preventive detergent with a detergent composition containing xanthan gum that is difficult to decompose with an oxidizing agent or an enzyme.

[0005]

The present invention comprises (1) a water-soluble detergent (A), acrylic acid, methacrylic acid, maleic acid, fumaric acid, acrylamide, methacrylamide, vinylpyrrolidone, and these. Polymers and / or copolymers having an average molecular weight of 1,000,000 or more and / or their derivatives, which are obtained by polymerizing one or more kinds selected from the group consisting of a), xanthan gum (b), hyaluronate (c)
And a coagulable aqueous solution (B) containing any one or more of the above and having any of amphoteric, cationic, anionic and nonionic chargeability as a necessary component at the time of use. The composition amount of the agent composition, (2) polymer and / or copolymerization and / or derivative thereof is in the range of 1 to 500 ppm of the weight of the cleaning liquid as a solid content of the cleaning liquid (1) The detergent composition described in (3), an aqueous solution of a polymer and / or a copolymer and / or a derivative thereof, and at least one inorganic carrier selected from the group consisting of anhydrous sodium sulfate, zeolite and apatargite. It is adsorbed on and mixed and dried (1)
Alternatively, the detergent composition according to (2), (4) (A) a water-soluble detergent, (d) one or more selected from the group consisting of sodium silicates, sodium bicarbonate and sodium carbonate; ) One or more selected from the group consisting of acetylene alcohol and / or derivatives thereof, perfluorocarbon-based surfactants, anionic surfactants, soaps, nonionic surfactants, amphoteric surfactants and enzymes. The cleaning composition according to any one of (1) to (3), wherein (5) xanthan gum is further selected from the group consisting of proteolytic enzymes, lipolytic enzymes and polysaccharide degrading enzymes. (6) The cleaning composition according to any one of (1) to (4), characterized in that
The detergent composition according to (1) further comprises a hypochlorite-based or inorganic peroxide-based bleaching agent, a zeolite, an optical brightening agent, oxalic acid or an alkali salt thereof, and / or an alkali salt of tetraacetylated ethylene. A washing method comprising adding one or more kinds selected from the group consisting of: anhydrous sodium sulfate and a water-soluble organic solvent, and washing the detergent composition according to (7) (1) as a solid, an aqueous solution, Add to slurry in water, dip,
The object to be washed is washed by a combination of two or more selected from the group of physical methods consisting of heating, mechanical vibration, rotation in a drum with a bow, stirring, tapping, rubbing, brushing, and ultrasonic vibration, and the liquid is drained. A washing method characterized by finishing by rinsing, etc. (8) The object to be washed is previously dipped and dried in an aqueous solution of the polymer and / or copolymer and / or derivative thereof described in (1). Characterized by (7)
A cleaning method as described is provided.

[Action]

(1) Types of dirt substances targeted by the cleaning agent of the present invention and an outline of the cleaning method of the present invention The main objects to be washed of the present invention are fibers such as clothes, and the dirt to be washed is (a) the human body. , Sweat, blood, sebum, pus, nasal discharge,
Urine, feces, sodium chloride, ammonia, urea, lactic acid, amino acids, fats, squalene, cholesterol esters, hydrocarbons, higher alcohols and other substances, (b) soot, dust, muddy, which adheres in the living environment There are dust, cigarette ash and tar, but soot is smoke, unburned organic matter in exhaust gas, dust is fiber waste, iron oxide, silicon oxide or calcium carbonate, gypsum, metal powder, cement powder Fine particles such as, (c) and stains include food and drink, cosmetics, paint, ink, machine oil, mud, clay, soot, mold, bacteria, etc., (d) Starch and synthetic resin treated on clothing There are various types of adhesives and softeners that have already adhered and absorbed dirt. Due to their solubility,
It can be classified into (A) water-soluble substance, (B) oil-soluble substance, and (C) insoluble substance, and can be classified into positively chargeable, negatively chargeable, amphoteric chargeable, and non-chargeable ones based on their chargeability. .

(2) Types of dirt adhesion mechanism and cleaning method of the present invention for each of them (a) Mechanical adhesion: dirt with large particles is easily removed by aqueous cleaning or mechanical impact.

(B) Adsorption by intermolecular suction force: In the case of dirt having a particle size of 1 μm or less, such as soot, the cleaning liquid is added with the ultrahigh molecular compound of the present invention to be absorbed and removed.

(C) Adhesion due to oil and fat film or oxidatively polymerized oil and fat film: Unpolymerized oil and fat-based stains are easily emulsified and removed by a normal detergent. Even if solid dirt adheres to the oil film, it can be removed in the same manner. However, once an oxidized polymerized oil film is formed,
It is necessary to use a high concentration of alkali, a strong oxidizing agent, a penetrating agent, a chelating agent, etc., but in principle it cannot be easily removed. Therefore, conventionally, a glue film of starch or synthetic resin having a concentration of about 1% to 2% is used to form a glue film so that the oxidized polymerized oil film is not directly formed on the fiber, and the subsequent washing is performed. However, it was not easy to completely decompose and remove this glue with an oxidizing agent or enzyme, and to prevent environmental pollution of this wastewater. In the case of the present invention, the principle is the same, but when an ultra-high molecular compound having a very strong formed film having an average molecular weight of 10,000,000 or more is used as the sizing agent, the concentration is 0.05% or less. , Even at a low concentration of 0.005% (50 ppm) or lower, it has the effect of preventing the formation of polymerized oil and fat film on fibers having the above-mentioned concentration of starch paste, and this film is easily decomposed by an aqueous solution of inorganic peroxide. -Can be removed and easily cleaned along with dirt.

(D) Adhesion by electrostatic attraction force: When the object to be washed and the dirt are oppositely charged, they are attracted to cause contamination. Further, even if the dirt does not have an electrostatic property, when the object to be washed is rubbed in a dry state, it is charged and the dirt is attracted and attracted to be adsorbed. The cleaning method of the present invention exhibits an excellent cleaning effect against such stains.

(E) Contamination due to difference in chargeability between fibers and dirt in the wash water: Fibers and ordinary dirt are generally negatively charged in the wash water, and soot, dust, metal oxides, inorganic fine particles, etc. , Many show positive charge, and pollution occurs in water due to electrostatic attraction. In addition, the polyvalent metal compound or its salt is ionized to form a polyvalent cation, which easily fixes anionic stains. Further, although clothes treated with a softener having strong ionicity may strongly adsorb the opposite ion stains, the stains can often be removed by the cleaning method of the present invention.

(3) Cleaning Agent Used in the Present Invention In the present invention, BOD and COD are 20,000,000 mg.
Oil / fat detergents of about 0 (Mn) / kg can also be effectively used, but sodium orthosilicate, sodium metasilicate, sodium silicates such as No. 1, No. 2, No. 3, etc. having these values of 0, sodium carbonate As an inorganic salt detergent such as
When used in combination with the ultra-high molecular weight compound of the present invention, a cleaning effect more than that of an oil-based detergent is often obtained.

(4) Example of the case where a surfactant is supplementarily added to an inorganic salt detergent in the present invention One of the methods is to use these inorganic salt detergents as a supplementary cleaning agent with a specific high penetration. And non-foaming or low-foaming acetylene alcohol and / or acetylene glycol derivative, and / or perfluorocarbon
When an extremely small amount of a bon-based derivative is used in combination, a cleaning formulation with extremely good cleaning efficiency, no foaming, and an extremely low load on wastewater treatment facilities can be obtained, as in the following example. If necessary, one or more kinds of anionic surfactant, soap, nonionic surfactant, amphoteric surfactant, and enzyme can be added in a smaller amount than usual.

Example of composition of low BOD / COD detergent BOD value COD value Blend amount mg 0 (Mn) / kg mg 0 (Mn) / kg (%) Sodium metasilicate pentahydrate: 0 0 85 2,4 , 7,9, -Tetramethyl-: 10,000 600,000 55-decyne 4,7-diol Ethylene oxide 4.5 mol adduct Anhydrous sodium sulphate (carrier): 0 0 10 of this mixture Calculated: 500 30,000-Calculated for 1% aqueous solution of this mixture: 5 300-Calculated for 0.2% aqueous solution of this mixture: 160-

An example of a non-foaming, non-foaming, high performance penetrant of similar structure and likewise is 3-methyl-1-butyne-3-.
Ol, 3-methyl-1-pentyne-3-ol, 3,
6, -dimethyl-4-octyne-3,6-ol, 2,
Examples thereof include 5-dimethyl-3-hexyne-2,5-diol and ethylene oxide adducts thereof. Since these have low solubility in water, the solubility is improved by adding alcohol having a carbon number of 3 or less to the cleaning liquid. These do not pose a problem when used in combination with an alkali metal percarbonate, but are not suitable for use in combination with perchlorate or persulfate.

If a perfluorocarbon-based surfactant is also used in a small amount in a cleaning liquid to which hypochlorite or an inorganic peroxide is added, an excellent permeation effect can be obtained even with a diluted aqueous solution of about 500 times. can get. The specific compounding example is given. Compound name Washing liquid blending amount Sodium metasilicate: 20 g / kg Sodium percarbonate: 2 g / kg Ultra high molecular compound (selecting a product type according to the purpose); 30 ppm Further, 10 mol of perfluoroalkyl ethylene oxide: 0. A 10% solution of isopropyl alcohol, 05 g / kg adduct, is added separately. This formulation has a fluorine content of 5 ppm, which meets the wastewater standards stipulated by many prefectural ordinances.

(4) Water-Soluble Ultra-High Polymer Compound Used in the Present Invention All the ultra-high-molecular compounds used in the present invention are generally known as polymer flocculants and have a molecular weight of 1,000,000.
Above, preferably 5,000,000 or more, more preferably about 15,000,000, and generally used as a coagulating sedimentation of various sludges or as a fining accelerator for water. These are classified into the following four types depending on the charge of the aqueous solution, and the specific examples are given below.

A polymer of (meth) acrylamide and / or a copolymer of (meth) acrylamide and vinylpyrrolidone and a small amount of another nonionic monomer such as an acrylate ester may also be used. Examples of nonionic polymers or copolymers.

1) of (meth) acrylamide and a polymerizable or copolymerizable acid such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, vinylsulfonic acid
Copolymerized with at least one species, or a nonionic polymer such as the above poly (meth) acrylamide hydrolyzed with an acid or an alkali, and an alkali metal salt or other water-soluble salt thereof. Are examples of anionic copolymers.

(Meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2- (meth) acroyloxyethyltrimethylammonium chloride, 2-hydroxy-3- (meth) Acrylic oxypropyltrimethylammonium chloride and the like, and copolymers with other cationic monomers are all examples of cationic copolymers.

Further, in an aqueous solution of poly (meth) acrylamide, an equivalent mole or less of formaldehyde and a secondary amine having the same number of moles and having 12 or less carbon atoms, such as dimethylamine, or 2-amino. Any of those obtained by reacting with an alkanolamine such as methyl 1-propanol (hereinafter referred to as Mannich reaction) is also an example of a cationic polymer or a copolymer.

The above-mentioned anionic copolymer further having a cationic group introduced into the same molecule by the Mannich reaction acts as a base against acidic stains,
It is an example of an amphoteric copolymer which has a characteristic of acting as an acid group for basic stains.

When terpolymerization of (meth) acrylamide, the above-mentioned anionic monomer and cationic monomer is carried out, ternary copolymerization is similarly carried out to obtain an amphoteric copolymer.

The hyaluronate, particularly sodium salt, produced by hydrolysis of chicken mackerel or culture using microorganisms is an anionic polymer having an average molecular weight of about 3,000,000, which is a wound on the human body. Since it has a restorative property, it is possible to provide a cleaning composition suitable for people with weak skin and people with allergies.

Similarly, xanthan gum produced by culturing using a microorganism is an anionic polymer having an average molecular weight of 2,000,000 or 40,000,000, and has excellent resistance to enzymatic degradation. Therefore, it is suitable for an enzyme-containing detergent composition.

(5) Cleaning action and anti-recontamination action of the ultra-high molecular compound used in the present invention When used in combination with a known detergent, the ultra-high molecular compound of the present invention exerting a unique washing effect remains as a powder. , Or in the form of an aqueous solution, or in the form of a solid solution such as powder, beads or flakes, which is obtained by dehydrating or spray-drying a concentrated solution in the form of fine particles of zeolite or a water-absorbing desiccant such as anhydrous sodium sulfate, or a penetrant. In the form of a gel swollen uniformly with water with or without addition, a solid, liquid slurry-like detergent and additives are mixed, poured into washing water, and heated and stirred. Etc. can be added and the washing can be started after completely dissolving.

However, this ultra-high molecular compound is a gel in which the shape of the molecule at the time of use is a string, and the solid content in the cleaning liquid is
In the case where it is 500 ppm or more and the molecular weight is 15,000 or more, the effect of preventing recontamination of the article to be cleaned cannot be obtained with a solution of 100 ppm or more. The solid content in the cleaning liquid is 1 to 500 ppm, preferably 1 to 10 ppm,
More preferably, at a low concentration of about 3 to 5 ppm, the polymer or copolymer is well dissolved in water, and is sufficiently linearly dissolved. In order to obtain the cleaning effect and the recontamination preventing effect, it is desirable that the ultra-high molecular compound satisfies the following points in use.

(A) The higher the molecular weight of the ultra-high molecular weight compound, the higher the adsorption capacity of the contaminants described below. Therefore, the number average molecular weight in use is at least 1,000,000, preferably 10,000,000. Above, most preferably 1
Maintain about 5,000,000. For this, use as high a molecular weight product as possible and, in order to avoid depolymerization, 300 r.p.m. for dissolution. p. m. It is forbidden to give a shear to an aqueous solution by the above high-speed rotation or to give an impact by ultrasonic vibration.

(B) In the case of the same monomer composition, the higher the molecular weight, the more rapidly the viscosity increases due to water absorption, so a dissolution apparatus that does not form a block is required.
Examples of a rapid dissolution apparatus for an ultrahigh molecular compound suitable for the purpose of the present invention include a drum having a crosspiece inside and rotating in the vertical direction, and a stirrer rotating at a low speed.

(C) Since dilute aqueous solutions of these ultra-high molecular compounds (other than xanthan gum) are depolymerized by microorganisms, it is desirable to add ethyl alcohol and other antibacterial agents when used in aqueous solutions. .

When the dilute aqueous solutions of the above-mentioned four kinds of ultra-high molecular weight compounds having different charging properties are mixed and used, there are the following restrictions in blending. The combinations that can be mixed at the time of use include (a) 4 kinds when used alone and (b) 4 kinds when mixed 2 kinds, except for the mixture of cationic and anionic 3 2 in the case of combining the cationic type, the anionic type and the other type from the 4 types in the case of combining 3 types of (c)
It is possible to use two types of combinations excluding types, and a total of nine types of mixtures can be used.
It may need to be tested before use because it may coagulate depending on the cationic and anionic strengths and the mixing ratio.

The suitability of dirt adsorption of these four types of dilute aqueous solutions of ultra-high molecular weight compounds having different electrification properties varies depending on, for example, the combination of the similarly charged object to be washed and dirt as shown in Table 1. In this case, a polyvalent metal sequestering agent such as zeolite is used together.

[0033]

[Table 1] Involved in cleaning Aqueous cleaning liquids Examples of substances that act on substances when each polymer compound is added Charge in non-ionic type Anion type Cationic amphoteric type Various fibers: Negative charge Physical adsorption By repulsive force Stain Selective adsorption is physical adsorption Strongly weakens and re-contaminates to disperse and causes inadequacy and chemical absorption prevention Effective with re-contamination prevention Clothing Normal: negatively charged material Same as above Same as above Chemical adsorption Same as above is mainly effective Metal Oxide: Positively charged Same as above Chemical adsorption Same as above Same as soot and dust Disperse effective ceramics: Same as above Same chemical adsorption Same as above Same as above Effective as filter agent Polyvalent metal compound: Cationized Same as above Disperse contaminants and their salts or coagulate

For home laundry and small-scale commercial cleaning in which various clothes are washed at the same time, it is convenient to use the anionic type and nonionic type which are the most difficult to coagulate in the washing liquid, but the amphoteric type is also alkaline side. It is relatively stable and has a large effect of preventing recontamination due to its chemical adsorption effect, so it can be used in the same manner. The anion type and the cation type may be more effective in cleaning the linen supply industry or the inorganic material in which dirt is specified. In commercial corning,
In particular, several examples of usage forms in which the recontamination preventing effect of the present invention is recognized are shown.

[0035]

[Table 2] Examples of ionic properties of ultra-high molecular compounds suitable for various textile products to be washed Examples of objects to be washed (dirt substances) Suitable ionic properties of ultra-polymer compounds a) Blackened Rays of polyester fiber: Anionic type, amphoteric type Skarten (soot, dust) (pollutants are mainly cationic) b) Dirty polyester / cotton blend wai: Amphoteric type, anion type shirt (human secretions, soot, etc.) ) (Pollutants are cationic and anionic) c) Thick cotton work gloves: anionic type, amphoteric type (doro, soot, iron rust) (Pollutants are mainly cationic) d) Ceramic oil miss in the kitchen : Cationic type, amphoteric type, nonionic type absorption filter (polymerized fats and oils) (the filter is cationic in water) e) Protein fiber: cationic type, nonionic type f) automobile or window glass: anionic type, both types Mold

When the ionicity, the monomer composition and the other washing conditions are the same, the higher the molecular weight and the lower the concentration of the aqueous solution, the stronger the ultra-high molecular compound will prevent recontamination of the object to be washed. Show the effect. For example, the molecular weight is about 1,000,000.
In the case of the ultra-high molecular compound, the effect is particularly excellent when the concentration in the washing aqueous solution is 30 ppm or less in solid content, and CMC-Na used for the same purpose as before has a molecular weight of about 40,000. Is normal, and the maximum is about 100,000. In the 0.2% solution (2,000 ppm), which is the standard use concentration of this, the ultra-high molecular compound of the present invention has too high an aqueous solution viscosity to penetrate into the object to be washed and prevent recontamination. Has no effect. However, the molecular weight is 1,000,0
The polymer of the present invention of about 00 showed a considerable recontamination preventing effect even at 200 ppm or less. This is because a dilute solution of an ultra-high molecular compound peels off emulsified and dispersed fine dirt from the object to be washed with a strong physical and / or chemical absorption power, and the washing liquid precipitates dirt substances until the wastewater treatment stage. Therefore, it was judged that it could be included stably.

(6) Environmental and Toxicity Problems of Ultra-High Polymer Compound Used in the Present Invention The solid content of the ultra-high-molecular compound used in the present invention has a BOD and COD value of 2,000,000 mg / kg. (M
n) before and after, the solid content concentration of these cleaning solutions is 1
These values are 2 to 2 in the case of a ~ 200 ppm aqueous solution.
It is about 00 mgO / kg, and the residual solid content in the wastewater can be easily precipitated by adding a small amount of aluminum chloride or an alum aqueous solution, and can be removed by a filtration method.
Wastewater treatment is easy.

The toxic unreacted monomer which may remain in this ultra-high molecular compound can be easily removed by washing with a lower alcohol. If you use a product number (Portable water grade) that is allowed to be added to water as a raw material, there is no possibility of causing toxicity problems.

(7) Action of Inorganic Carrier Although the amount of these ultra-high molecular compounds used is small, it takes a very long time to uniformly dissolve them in water. Even if it is directly added to the washing solution as a solid, it will not be completely dissolved within the usual washing time, so 1 kg of a 0.3% aqueous solution of a preliminarily prepared ultra-high molecular compound and 10 kg of anhydrous sodium sulfate as a carrier are well mixed. If left unattended, anhydrous sodium sulfate takes up water as water of crystallization even without heating, and it is dried, and a solid with a thin film of an ultra-high molecular compound that quickly dissolves in the washing liquid on the surface of the carrier is obtained. . In this case, the inclusion of the powder detergent of the following experimental example can prevent the solidification, and the addition of a small amount of the surfactant accelerates the dissolution rate in water. Further, in the case of a detergent containing an inorganic peroxide, the same action has the effect of delaying the decomposition due to moisture absorption. The aqueous solution containing these raw materials of the present invention can be pulverized with a known spray dryer.

(8) Action of inorganic peroxide on the ultra-high molecular compound of the present invention The following three types of inorganic peroxides are used in the present invention.
Any of them may be used for the purpose of bleaching stains in the wash-target and drainage, oxidative decolorization, facilitation of removal by breaking the bond between the fiber and the polymerized oil film, and sterilization. However, it is advisable to use the optimum product properly according to these individual characteristics.

(A) Hypochlorites: The amide group and effective chlorine of the ultra-high molecular weight compound of the present invention partially bind to form chloramide and maintain equilibrium. Suitable for applications that require holding for a long time.

(B) Peroxides forming free radicals such as persulfate and caroate: An aqueous solution such as sodium persulfate is used as a starch or polyvinyl chloride adhering to the object to be washed which has absorbed dirt during heating. -It is most suitable for the embodiment in which the ultra high molecular compound of the present invention used as a sizing agent such as alcohol or an antifouling agent is alkaline heated to be depolymerized / solubilized / leached for washing. However, it is unsuitable as a peroxide to be used in combination with a detergent and an ultra-high molecular compound when preventing recontamination such as soot and mud during cleaning.

(C) Alkali metal percarbonate, hydrogen peroxide, alkali metal perborate, etc .: Sodium percarbonate hardly depolymerizes ultra-high molecular weight compounds, so it is most suitable for cleaning only for preventing redeposition. Are suitable. Mixtures of hydrogen peroxide and alkali metal salts can be used for the same purpose. When used in combination with sodium silicates, it decomposes in a short time, so even if the rinsing is incomplete, the strength does not decrease so much. Sodium perborate also has almost the same effect as sodium percarbonate, but the latter is superior in terms of low toxicity.

(9) Action of other additives added in a small amount (a) Zeolite: Fine particles having a particle size of 5 μm or less and having a cation exchange capacity of 5.5 to 7.0 meq / g, even in a trace amount in the washing water. As a sequestrant for ions of polyvalent metals such as iron, aluminum and calcium that may be contained,
Used in a small amount to mix with detergent to prevent coagulation accidents of ultra-high molecular compound aqueous solution and performance deterioration. (B) Fluorescent whitening agent: In the case of a white object to be washed, there is a case where a material suitable for its material, chlorine resistance, alkali resistance, etc. is added to the cleaning liquid. (C) Oxalic acid, alkali salt of oxalic acid, and alkali salt of tetraacetic acid ethylene: Added as a remover for polyvalent metal compounds that cause iron rust and stains that are difficult to remove. (D) Water-soluble organic solvent: Mainly used in a small amount to improve the solubility of the poorly water-soluble penetrant in the cleaning liquid. For example, isopropyl alcohol is suitable.

[0045]

【Example】

Example 1 1 kg of a solid detergent composition was prepared by mixing the respective raw materials by the following method to prevent re-contamination, low foaming property, and can be used as an oil-based detergent instead of causing environmental pollution. In this case, the raw material 2. And 3. By utilizing the solidification property when the above was finally mixed, it was possible to obtain a stable tablet-made product in which all components were uniformly mixed with a tableting machine. No. Name of substance used as raw material, shape, preparation, treatment method Mixing amount (g) 1. Sodium metasilicate: 579 2. A 0.3% aqueous solution of a copolymer of acrylamide having a molecular weight of about 15,000,000 and acrylic acid: 50 at a weight ratio of 90/10. Anhydrous sodium sulfate (mixed with aqueous solution of 2. and dried at room temperature, coarse: 250 pulverized (content of solid content of copolymer: 0.15 g) 3. Sodium percarbonate 1.5 hydrate: 100 4. Zeolite fine powder: 10 5. Equivalent mixture of perfluoroalkyl-containing activator, ethylene oxide and pu: 1 ropylene oxide copolymer activator 6. Sodium oxalate 10 This detergent composition is , 4 to 6g / 〓 put in water and used for washing clothes, the same cleaning effect as the conventional oil and fat type cleaning agent can be obtained. be able to.

Example 2 and Comparative Example 1 5 pairs of dry new unbleached thick count yarn cotton gloves (work gloves) each were diluted with 15 times the amount of organically rich black clay soil in tap water. 1 to 50 with a bath ratio of 1/50 while stirring
Soak for 0 minutes, centrifuge and spin for 2 minutes in a home washing machine, 60
A contaminated sample was prepared by drying at ℃ for 1 hour.

These 5 pairs of samples were mixed at a bath ratio of 1/50 and 3
20% isopropyl alcohol solution of g / l No. 1 sodium silicate, 2 g / l sodium percarbonate, and 0.005 g / l perfluoroalkyl-containing oligomeric penetrant (Dainippon Ink and Chemicals, Inc. A cleaning solution (Comparative Example 1) consisting of a company product, Megafac F-179) and a cleaning solution comprising 10 g / l of a 0.1% aqueous solution of polyacrylamide having a degree of polymerization of about 15,000. In Example 2), the contaminated sample was separately immersed, the temperature was raised from room temperature to about 95 ° C. for about 15 minutes in a stainless steel container without stirring, the sample was taken out, rinsed well with a large amount of cold water, and centrifugally dehydrated for 2 minutes. Then, it was dried at 60 ° C. for 1 hour. By visual observation of the degree of contamination of the cleaning liquid, the liquid of Example 2 was slightly blacker than the liquid of Comparative Example 1, and it seemed that Comparative Example 1 was cleaned well at first glance.

However, in the observation after drying, the 5 pairs of gloves made with the cleaning solution of Example 2 almost completely lost the muddy, and the whiteness of the entire surface was considerably improved as compared with that before the contamination. On the other hand, in the 5 pairs of gloves of Comparative Example 1, it was observed that the muddy had fallen off considerably, but the entire surface was pale black, and recontamination due to muddy deposition was observed.

The COD value of the cleaning liquid of Example 2 by the back titration method with potassium permanganate / sodium oxalate was 1
The value of 8 mgO / kg and the cleaning liquid of Comparative Example 1 was 8 ppm.

Example 3 and Comparative Example 2 A well-washed white cotton / polyester fiber blend ratio of 3
Prepare two shirts of 5/65, one as a sample of (Comparative Example 2), and the other one having a molecular weight of 8,000,00.
0, 84% by weight acrylamide, 8% acrylic acid, 8% acrylic acid dimethylaminoethyl ester
The amphoteric ultra-high molecular compound obtained by copolymerizing and is 0.1% in solid form.
02 g / l, 0.05 g / l of 4.5 mol ethylene oxide adduct of 2,4,7,9-tetomethyl-5-decyne 4,7-diol, and 1 g / l of isopropyl. The sample was impregnated with an aqueous solution, centrifuged and dried, and then ironed to obtain a sample of (Example 3).

After dissolving 5 g of 60% sodium dialkylsulfosuccinate in 1 liter of water, 5 g of channel carbon, 30 g of tomato ketchup and 3 mayonnaise were added.
0 g was added and well stirred in a mixer, then the shirts of Comparative Example 2 and Example 3 were simultaneously added to this solution, stirred for 5 minutes, spin-dried, dried and ironed at 180 ° C. I hung it. Both the shirts of Comparative Example 2 and Example 3 were stained black and there was no difference in appearance.

60% sodium metasilicate, 30% sodium persulfate, Megafac F used in Example 2
A solid obtained by mixing 0.1% of the solid content of -179, 0.9% of fine powder of synthetic zeolite, and 9% of anhydrous sodium sulfate was dissolved in tap water at a rate of 10 g / l, Comparative Example 2 and the shirt of Example 3 were separately treated with a bath ratio of 1/50 in a stainless steel container at 65 ° C. for 20 minutes with gentle stirring and then centrifugally dehydrated, and it is apparent that the Examples The shirt of No. 3 had a whiteness higher than that of the shirt of Comparative Example 2, but still had a little dark stain.

After that, these shirts were separately washed, rinsed, centrifugally dehydrated and ironed by the methods of Example 2 and Comparative Example 1, and then the whiteness was observed to obtain the following results. Shirt Cleaning Method of Comparative Example 2 Example 2
Comparative Example 2: Very black (poor cleaning effect) Slightly black (very good cleaning effect) Example 2: Slightly black (good cleaning effect) Fairly white (good cleaning effect)

Example 4 700 g of an inorganic phosphorus type powder detergent having the following composition was prepared. (Original cleaning agent) (wt%) Sodium linear alkylbenzene sulfonate 15 Sodium sulfate ester of higher alcohol ethylene oxide adduct 7 Coconut oil fatty acid monoethanolamide 3 Zeolite 12 Sodium metasilicate 10 Sodium carbonate 12 Sodium sulfate 33 Soap 5 Average molecular weight 6,000 polyethylene glycols 2 fluorescent dyes, fragrances, colorants 1

Then, with respect to 240 g of anhydrous sodium sulfate, a 0.15% solution of sodium hyaluronate having an average molecular weight of 3,000,000 was mixed and stirred at a low speed of 60%,
When it becomes moist powder, add 50 parts of the above powder cleaning agent.
g was collected and mixed to obtain a powder having no caking property, and the whole was further mixed to obtain a total organic detergent of 20% lower than the original detergent of 1 kg. It was confirmed that this cleansing agent does not cause such skin damage to 3 people who usually get itchy skin and rough skin on the hands when contacted with an aqueous solution of the original cleansing agent. Due to the reduction of the redeposition property, the cleaning effect was rather excellent. Example 5 Xanthan gum (KELTR, a product of Merck & Co., Inc., USA) was used instead of sodium hyaluronate in the powder detergent of Example 4.
OL RD) 1% liquid was used, and the detergent was the same composition except that the detergent further contained 1% of encapsulated protease (trade name ALCALASE). Use sodium 3g / l, liquid temperature 55 ℃, pH 10.0, wash water with a washer that rotates in the vertical direction, using 25 times as much washing water as the weight of the work clothes of workers in the raw rubber incinerator. The removal rate of soot from the article to be cleaned in this case was extremely good, and the deodorizing effect was also good.

Since the present invention is constructed as described above, it has the following effects. (1) In the case of conventional detergents for textile products and filter materials made of organic / inorganic materials, when the detergent is a basic inorganic salt such as sodium metasilicate or sodium carbonate, it is saponified like an oil lipid. An excellent cleaning effect was obtained with respect to stains such as acids that are solubilized or neutralized by, and salts such as strong acid and weak base that undergo metathesis. However, the dirt is soot,
In the case of sand dust or inorganic dust, the dirt that has once fallen off due to swelling of the item to be washed causes recontamination of the item to be washed at the rinsing stage because the detergent has no surface activity, and these inorganic detergents Have been inferior to oil-based detergents having surface activity. However, by utilizing the cohesive force of an extremely small amount of an aqueous solution of an ultrahigh molecular compound, which is the essence of the present invention, the drawbacks of this inorganic detergent can be overcome. (2) Even when using soap or other oil-based detergents, in order to prevent this recontamination, in order to keep the fine particles such as soot well dispersed in the rinse step after washing, a high concentration Was required, but according to the present invention,
Even if the concentration is lowered, it is possible to improve the cleaning effect. As a result, it has become possible to significantly reduce the degree of environmental pollution of the cleaning wastewater. (3) Conventionally, in order to solve such a recontamination problem, a method in which CMC-Na having a maximum molecular weight of 100,000, usually about 40,000 is used in combination with a detergent has been carried out. Since the required concentration is high, the amount of rinsing water is large, and the environmental pollution of the wastewater is a major drawback.
The ultra-high molecular compound used in the present invention has an extremely low required concentration, is easily decomposed in the environment, and is easily separated by precipitation. (4) Among the fouling substances, those in which the polymerized fats and oils are directly bound to the article to be washed by heating or oxidation with time are very difficult to remove. Conventionally, starch and synthetic resin-based glues
Although it has been devised to easily remove stains by treating the object to be washed, this concentration is high, and the stains cannot be completely removed unless desizing with an enzyme system or peroxide is performed completely. The wastewater from this desizing also has a high BOD and COD, which inevitably causes an environmental pollution problem. In the present invention, the toughness of the film due to the unique high molecular weight of the ultra-high degree of polymerization compound, utilizing the high cohesive force, even if the concentration used is significantly reduced, the polymerized oil and fat is directly bonded to the object to be washed. I was able to prevent it. (5) Since the concentration of the ultra-high degree of polymerization compound of the present invention used is low, unlike starch or polyvinyl alcohol, when it is heated slightly and treated with a low-concentration aqueous solution of sodium persulfate during washing, the concentration becomes very high. The degree-of-polymerization compound decomposes rapidly and is leached together with dirt from the object to be washed. Then, by rinsing with water containing an ultra-high degree of polymerization compound, the next cleaning becomes easy and an excellent cleaning effect is obtained. In addition, the environmental pollution of wastewater due to this treatment was reduced. (6) Since the cleaning composition and the cleaning method of the present invention have a lower concentration and easier rinsing than the conventional methods, they have less physical and chemical obstacles to the object to be cleaned, The cycle can be extended significantly. (7) Since the cleaning composition of the present invention can be solidified by mixing all raw materials, there is no inconvenience in use as compared with conventional cleaning compositions. If necessary, the workability can be improved by using a solid composition and a liquid composition or a total amount of the liquid composition.

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Claims (8)

[Claims] 1. A water-soluble detergent (A), acrylic acid,
The average molecular weight obtained by polymerizing at least one selected from the group consisting of methacrylic acid, maleic acid, fumaric acid, acrylamide, methacrylamide, vinylpyrrolidone and derivatives thereof as an essential monomer component is 1 , 0
Amphoteric or cation containing any one or more of 00000 or more polymers and / or copolymers and / or their derivatives (a), xanthan gum (b) and hyaluronate (c). A cleaning composition comprising, as an essential component, an aggregating aqueous solution (B) having any of anionic, anionic and nonionic chargeability. 2. The blending amount of the polymer and / or copolymerization and / or derivative thereof is in the range of 1 to 500 ppm of the weight of the cleaning liquid as a solid content of the cleaning liquid. Cleaning composition. 3. An aqueous solution of a polymer and / or a copolymer and / or a derivative thereof is adsorbed on one or more inorganic carriers selected from the group consisting of anhydrous sodium sulfate, zeolite and apatargite, The cleaning composition according to claim 1 or 2, which is mixed and dried. 4. (A) As a water-soluble detergent, at least one selected from the group consisting of (d) sodium silicates, sodium bicarbonate and sodium carbonate; and (e) acetylene alcohol and / or these. And a perfluorocarbon-based surfactant, an anionic surfactant, soap, a nonionic surfactant, an amphoteric surfactant, and at least one selected from the group consisting of enzymes. The cleaning composition according to any one of claims 1 to 3. 5. The xanthan gum is used in combination with one or more selected from the group consisting of proteolytic enzymes, lipolytic enzymes and polysaccharide degrading enzymes. Cleaning composition. 6. The cleaning composition according to claim 1, which further comprises a hypochlorite-based or inorganic peroxide-based bleaching agent, zeolite, a fluorescent brightening agent, oxalic acid or its alkali salt, and / or 4 vinegar. A cleaning method comprising adding one or more kinds selected from the group consisting of an alkali salt of ethylene oxide, anhydrous sodium sulfate, and a water-soluble organic solvent for cleaning. 7. The detergent composition according to claim 1 is added to water in the form of a solid, an aqueous solution, or a slurry, and is immersed, heated, mechanically vibrated, rotated in a drum with a bar, stirred, and tapped. The object to be cleaned is washed with a combination of two or more selected from the group of physical methods consisting of, rubbing, brushing, and ultrasonic vibration.
A cleaning method characterized by finishing after draining and rinsing. 8. The cleaning method according to claim 7, wherein the object to be cleaned is preliminarily immersed and dried in an aqueous solution of the polymer and / or copolymer and / or derivative thereof according to claim 1. .