WO1997003018A1 - Silicates stratifies hydriques et compositions de detergents les contenant - Google Patents

Silicates stratifies hydriques et compositions de detergents les contenant Download PDF

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Publication number
WO1997003018A1
WO1997003018A1 PCT/JP1996/000342 JP9600342W WO9703018A1 WO 1997003018 A1 WO1997003018 A1 WO 1997003018A1 JP 9600342 W JP9600342 W JP 9600342W WO 9703018 A1 WO9703018 A1 WO 9703018A1
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WO
WIPO (PCT)
Prior art keywords
water
layered
lithium
acid
gayate
Prior art date
Application number
PCT/JP1996/000342
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English (en)
Japanese (ja)
Inventor
Fumitomo Noritake
Taketoshi Ito
Yutaka Owa
Original Assignee
Lion Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lion Corporation filed Critical Lion Corporation
Priority to DE19681492T priority Critical patent/DE19681492T1/de
Publication of WO1997003018A1 publication Critical patent/WO1997003018A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
    • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/02—Softening water by precipitation of the hardness

Definitions

  • the present invention relates to a novel hydrated layered gay acid salt, a method for producing the same, a water softener containing the same as an active ingredient, and a detergent composition containing the same. More specifically, the present invention has a high cation exchange capacity and an exchange rate-a novel crystalline hydrated layered gayate, a method for producing the same, and a water softener having excellent ion exchange properties using the same as an active ingredient. And a detergent composition containing the same.
  • Hardness components contained in tap water combine with surfactants contained in detergents and fatty acids contained in dirt to form water-insoluble salts when washing clothes, dishes, bathtubs, toilet bowls, etc. It has long been known that the cleaning effect is significantly reduced. To prevent this, a substance that normally traps or blocks the hardness component in tap water, that is, a water softener, is added to the detergent. For a detergent composition for clothing, tripolyphosphoric acid was used. Sodium has been used as a water softener. However, due to the problem of eutrophication of rivers, a search was made for a substitute for sodium tripolyphosphate, and A-type zeolite, a type of synthetic zeolite, was generally used as a water softener. .
  • the function of the water softener refers to the ability to capture calcium ions, the main hardness component in tap water, and this performance is primarily evaluated by the cation exchange capacity. If a softener is used, surfactants that coexist, fatty acids in the soil, etc. Since it is necessary to quickly capture or block the hardness component before the hardness component in the tap water and water combine, it is also important to increase the rate of capturing calcium ions (cation exchange rate).
  • a first problem to be solved by the present invention is to provide a novel hydrated layered gay acid salt having a high cation exchange capacity and an exchange rate and exhibiting properties suitable as a water softener.
  • a second object is to provide a method for easily producing such a hydrated layered gate acid from easily available raw materials.
  • a third object is to provide a high-quality water softener containing the water-containing layered gayate as an active ingredient.
  • a fourth object is to provide a detergent composition containing the water softener as a component.
  • the present inventors have conducted intensive studies to develop a novel water softener suitable for use as a component of a cleaning agent. As a result, the inventors have found that some of sodium in hydrated layered sodium gateate can be converted to another aqueous solution.
  • the hydrated layered silicate having a specific composition replaced by lithium metal or alkaline earth metal has a higher cation exchange capacity than the synthetic zeolite conventionally used as a water softener. It has been found that it is an excellent water softener and that it can be produced by simple processing using easily available minerals such as mahite as raw materials. Based on this, the present invention has been accomplished. That is, the present invention provides a composition formula
  • M 1 is at least one metal selected from lithium, lithium and alkaline earth metals
  • n is the valence of M 1
  • X, y and z are in the following ranges: 0 x ⁇ 0.5, 3 ⁇ y ⁇ 7.5, 1 ⁇ z ⁇ 20
  • 23 N a-spin-one-particle relaxation time measured by solid-state nuclear magnetic resonance
  • Kanemai Doo NaHSi 2 0 5 -3H 2 0
  • Makatai Doo Na 2 Si 4 0 9 ⁇ 5 ⁇ 2 0
  • Ayler eye Doo Na 2 Si 8 0 17 '10H 2 0
  • Magadiai door NasSi! 4 0 29 ⁇ 10 ⁇ 2 0
  • Kenya Ai door Na 2 Si 2O O 41', such as 10H 2 O
  • the hydrated layered maleate of the present invention has a composition similar to that of mashite, but has a different crystal structure.
  • the water-containing layered gayate of the present invention can also be obtained by modifying the natural maltite produced in, for example, Kenya [“Am. Mineral. J Vol. 55, p. 358 (1970)]”. can get.
  • the power strength can also be obtained by synthesizing, but an example of actually synthesizing macaite has been described as S i 0 2 -Na 2 0-H 2 0 [Z. Kristallogr., Vol. 197, Page 1 (1991)], and those synthesized with the addition of diethanolamine [[Z. Kristallogr. J, Vol. 159, Page 203 (1982)] In any case, the ion exchange capacity of the known mahite is extremely small and cannot be put to practical use.
  • composition formula (I) is, for example, a composition formula
  • M 2 is at least one metal selected from lithium, sodium, potassium and alkaline earth metals
  • m is the valence of M 2
  • y and z ′ are in the following ranges: is a number. 3 ⁇ y ⁇ 7. 5, after 0 ⁇ z' ⁇ 20
  • acid treatment layered Gay salt material represented by the reduced portion of the metal M 2 therein, Natoriumu compound
  • it can be produced by treating with an aqueous solution containing a sodium compound and at least one metal compound selected from lithium, potassium and alkaline earth metals.
  • M 1 in the water-containing layered gayate of the present invention represented by the above composition formula (I) is at least one metal selected from lithium, potassium and alkaline earth metals. Potassium is preferred because a remarkable improvement in the exchange rate is observed.
  • n is the valence of M 1, if M 1 is lithium, potassium 1, in the case of alkaline earth metals is 2.
  • X is a number in the range of 0 to 0.5, but is preferably in the range of 0 to 0.3 in consideration of the cation exchange rate.
  • y is a number in the range of 3 to 7.5. If y is less than 3, the desired crystal structure cannot be obtained, and if y exceeds 7.5, the cation exchange capacity and cation exchange rate may decrease.
  • positive ion exchange capacity, positive ion exchange rate, etc., y is preferably in the range of 3.5 to 5.
  • z is a number in the range of 1 to 20, and therefore, this water-containing layered gayate always contains water in the crystal molecule. Will be.
  • the distinction between the water contained in the crystal molecules and the water adsorbed on the crystal particle surface is that the water adsorbed on the particle surface desorbs at low temperature, but the water contained in the crystal molecules is more Since it desorbs at a high temperature, it can be quantitatively performed using this property.
  • the amount of water contained in the crystal molecule, that is, z is preferably in the range of 3 to 3 from the viewpoint of properties.
  • the crystalline alkali metal gaylate of the present invention is essential to contain water of crystallization as described above, and includes a crystalline alkali metal gaylate produced by firing at a temperature of 600 ° C. or more. Are essentially different.
  • hydrated layered Gay salts of the present invention 23 N a- solid-state nuclear magnetic resonance spectroscopy (23 N a- solid NMR) measured spin one-lattice relaxation time of preferably less 35 seconds 0. 0. 25 seconds or less It is necessary to be. Those with spin-lattice relaxation times longer than 0.35 seconds do not exhibit high cation exchange capacity.
  • any of the known force titers described above exhibit a spin-lattice relaxation time of 0.4 seconds or more.
  • the spin-lattice relaxation time indicates the environment of the sodium ions contained between the layers of the hydrated layered gaterate, and such a difference clearly indicates a structural difference.
  • the lower limit of the spin-lattice relaxation time of the water-containing layered gayate of the present invention is not particularly limited, and it has been confirmed that a high cation exchange capacity is exhibited even if it is as small as 10 to 3 seconds.
  • the spin-lattice relaxation time is a value obtained by the following method.
  • 23 Na-solid state NMR was measured by the following method under an angle spinning method using a single pulse of 23 Na under magic angle spinning under the following conditions. Then, the least-squares fitting using the exponential function was performed, and the 23 Na spin-single lattice relaxation time was analyzed.
  • the analysis result is considered as a sum of the plurality of components, it is necessary to 23 N a spin one-lattice relaxation time of at least one component is in the above range.
  • the water-containing layered gayate of the present invention has a X-ray diffraction diagram of a known mahite titer (a number JCPDS23 indicated by the Joint Committee on Powder Diffraction Standards). -703 diffraction data), no clear peak may be observed at all, and there are halos that are recognized as amorphous on X-ray diffraction. When diffraction lines are observed, they often include those that show 0.989 to 0.97 nm, 0.49 to 0.53 nm, and 0.366 to 0.376 nm. It is not particularly necessary in the invention.
  • the chemical shift measured by 29 Si-solid state nuclear magnetic resonance spectroscopy of this hydrated layered silicate shows that each silicate unit in the crystal is bonded to the other three silicate units. The chemical shift shown is observed. This indicates that it has a layered structure.
  • Hydrated layered Gay salts of the present invention having the above composition and crystal structure, 250 C a COsmgZg more often 300 C a CO 3 mgZg than It shows a high cation exchange capacity as above.
  • the addition amount of the seed crystal is suitably in the range of 0.1 to 50% by weight based on Sio 2 of the component (A).
  • the seed crystal it is preferable to use a product obtained in the previous manufacturing process, but a natural product or a product obtained by another method may be used.
  • any method may be used for solid-liquid separation, it is important that drying is performed at a temperature of 120 ° C or less. If the drying is performed at a higher temperature, the crystal structure is changed, and it becomes difficult to obtain a strong titer. At this time, organic salts and inorganic salts are not added to the reaction system. It is advantageous to add H 2 O 2 to the reaction system because the molar ratio of H 2 O ZNa 20 can be made higher than the above range and the crystallization time can be greatly reduced.
  • organic and inorganic salts can be used, and in particular, citric acid, tartaric acid, acetic acid, sulfuric acid, hydrochloric acid, hydrogen bromide, hydrogen peroxide, thiocyanic acid, nitric acid, chloric acid, etc.
  • Alkali metal salts are preferred.
  • These organic salts and inorganic salts may be used alone or in combination of two or more, but the addition amount is 0.1 to 300% by weight based on the solid content of the reaction system. Is preferred.
  • the layered gayate is prepared by Once the salt raw material is acid-treated to form a layered gayate or layered gay acid with a reduced amount of alkali metal or alkaline earth metal, sodium compound or sodium compound and lithium, potassium and aluminum
  • the treatment is performed using a compound of at least one metal selected from the alkaline earth metals, for example, a salt or hydroxide thereof.
  • the acid those having an pH of 7 or less, preferably 4 or less when converted to an aqueous solution are advantageous. This acid may be used alone or in combination of two or more.
  • mineral acids such as hydrochloric acid, sulfuric acid, and nitric acid are preferable from the viewpoint that they require a small amount of use and are inexpensive.
  • the acid treatment in this manner, 50% or more, and preferably almost all, of the metal ions between layers originally contained in the layered gayate raw material are replaced (ion-exchanged) by hydrogen ions, and the layered gayate material is substantially layered.
  • the power of being acid ⁇ This method is an important point.
  • This acid treatment is preferably carried out by dispersing the layered gateate raw material in an aqueous solution in which an acid is dissolved or added. This condition achieves the above-mentioned degree of ion exchange by hydrogen ions and the desired maintenance of the layered structure. Is selected within the range.
  • a salt or hydroxide of sodium-containing alkali metal which is usually selected from a sodium compound or a sodium compound and lithium, potassium or alkaline earth metal.
  • Suitable salts of these metals include water-soluble chlorides, sulfates, nitrates and carbonates.
  • these alkali metal or alkaline earth metal compounds for example, their salts and hydroxides may be used alone or in combination of two or more.
  • the treatment conditions are appropriately set within a range in which the layered gayate or the layered gay acid can be converted into the hydrated layered gayate of the present invention. If the pH of the aqueous solution is lower than the above range, it is difficult to convert the layered gayate or layered gay acid into the water-containing layered gayate of the present invention.
  • the concentration of the aqueous solution of the sodium compound or the other alkali metal or alkaline earth metal salt or hydroxide is not particularly limited, but the amount is not less than the equivalent of the layered gayate or the layered gay acid.
  • the layered gayate raw material is dispersed in an aqueous acid solution to form a layered gayate or layered gay acid having a reduced interlayer ion content, and then the above-mentioned sodium compound or lithium, lithium, aluminum, or aluminum lye is added to the dispersion. It can also be carried out by adding a compound of at least one metal selected from earth metals, for example, a salt or a hydroxide. After this treatment, ordinary solid-liquid separation and drying are carried out to obtain the hydrous layered gayate of the present invention. The drying at this time is desirably performed at 120 ° C.
  • the hydrating agent of the present invention contains the water-containing layered silicate of the present invention thus obtained, has a high cation exchange capacity and an exchange rate, and is suitably used as, for example, a component of a detergent.
  • the water-containing layered gay salt of the present invention has excellent properties as a water softener, it is used in combination as at least one detergent component selected from an anionic surfactant and a nonionic surfactant. This gives an excellent cleaning composition.
  • anionic surfactant olefin sulfonic acid salt and aniline surfactant are used.
  • Alkyl benzene sulfonates, alkyl sulfates, alkyl ethoxy sulfates, sulfo fatty acid ester salts, higher fatty acid salts, ie, soaps, are used.
  • nonionic surfactants include alcohol ethoxylate in which ethylene oxide is added to alcohol, nonylphenol ethoxylate, adduct in which propylene oxide and ethylene oxide are added to alcohol, fatty acid alcohol amide, Sucrose fatty acid esters, alkylamine oxides and the like are used.
  • the detergent composition of the present invention contains at least one selected from these anionic surfactants and nonionic surfactants, and the concentration is preferably 0.5 to 80% by weight.
  • the concentration of the hydrous layered gayate is preferably from 0.1 to 60% by weight.
  • the detergent composition of the present invention may further comprise, if necessary, other surfactants such as an amphoteric surfactant and a cationic surfactant, an alkali builder, a calcium ion trapping builder, and the like, in addition to the above essential components.
  • surfactants such as an amphoteric surfactant and a cationic surfactant, an alkali builder, a calcium ion trapping builder, and the like, in addition to the above essential components.
  • Builders, enzymes, bleaches, and other additives can also be included.
  • the matric titer was identified by comparison with the diffraction diagram of JCPDS 23-703, and the others were identified from the three with the highest diffraction intensity.
  • the presence of amorphous was determined by the presence or absence of halo derived from amorphous.
  • a 300 ml aqueous solution was prepared, added to the sample dispersion, and ion-exchanged at 25 ° C for 10 minutes. Then, the solution was filtered, and the calcium ion concentration of the filtrate was quantified using EDTA, and determined by the following equation.
  • the unit is C a C 0 3 mg / g. Min.
  • Clay which is mainly composed of crystalline minerals such as Riki Orinite and Vermiculite, was dried at 200 ° C for 30 hours and used as inorganic soil.
  • Table 1 shows the soil composition of the artificial soil cloth obtained by subjecting the cloth in the range of 42 ⁇ 2% to the soil cloth.
  • the washing machine used was a two-tub washing machine (Mitsubishi Electric Corporation "Chikuma" CW-660W type).
  • 10 pieces of the above-mentioned artificial soiling cloth are sewn to the worn skin shirt to make the total weight 1 kg.
  • the water content of the above composition indicates the sum of water of crystallization (z) and attached water. The same applies hereinafter.
  • the mixture was filtered, washed with ion-exchanged water, separated into solid and liquid, and then dried at 60 ° C.
  • the composition of the obtained powder is
  • Example 2 The water content of the commercially available aqueous sodium gayate solution (No. 3 water glass) used in Example 1 was adjusted at 120 ° C. so that the molar ratio of H 20 / Na 20 became 18. The mixture was placed in a stainless steel container, and in so that Do and 2 wt% with respect to S i 0 2 gay acid Natoriumu in aqueous solution Ma Katai bets prepared in Example 1, with stirring, after addition It was sealed and crystallized at 120 ° C for 20 hours. After that, it was discharged from the container, washed with water and dried at 105 ° C. The resulting powder composition N a 2. T S i 4 .. It 0 9 - 5. the results in conjunction with Ma force Thai preparative powder X-ray diffraction by IH 2 0 were observed.
  • Tables 2 to 4 show the properties of the maizeite before the acid treatment in Example 1. Comparative Example 2
  • Tables 2 to 4 show the properties of the maize tile before the acid treatment in Example 3. 6 Table 2 Composition
  • Example 1 0 4.0 0 5.0 0 25.2
  • Example 2 K 0.10 4.1 15.2 0.3 5.5
  • Example 3 K 0 .1 9 4.05 30.3.5.6
  • Example 4 K 0.40 4.0.4.9 0.3.5.2
  • Example 5 Ca 0.1.4 4.0.0 4.80.14.9
  • Example 6 0 4.1 5.1 0. 2 5.3 Comparative example 1 0 4. 1 4. 8 0. 1 4.9 Comparative example 2 0 3. 9 4. 6 0. 1 4.7
  • Example 4 0.220 Clear peaks were not observed.Example 5 0.12 20 Clear peaks were not observed.Example 6 0.188 0.93 30.5 0.52 1 0.375 Comparative Example 1 0.4.18 Matches JCPDS 2 3—7 0 3 None Comparative Example 2 0.432 JC PD S 2 3— Matches 7 0 3 None Table 4
  • a detergent slurry having a solid content of 45% was prepared using each component other than the nonionic surfactant, the enzyme and the flavor in the composition shown in Table 5.
  • the detergent slurry was dried using an AC spray drying tower at a hot air temperature of 380 ° C. to a water content of 5% to obtain a spray-dried product.
  • a nonionic surfactant and water were introduced into the above-mentioned dried product into a continuous kneader (KRC Kneader # 2, manufactured by Kurimoto Tetsusho Co., Ltd.) to obtain a dense and uniform kneaded product.
  • This kneaded product was made into a cylindrical pellet by passing through a perforated plate provided at the outlet of the cylinder.
  • the pellets are introduced into a crusher [Speed Mill ND-10 Type Okada Seie Co., Ltd.] together with the cooling air and pulverized.
  • a detergent composition having the composition shown in Table 5 was obtained.
  • Table 5 also shows the results of examining the detergency of these detergent compositions. 8 Table 5
  • a cleaning composition having the composition shown in Table 6 was prepared in the same manner as in Example 7.
  • Table 6 shows the detergency of these detergent compositions. 9 Table 6
  • the water-containing layered gay acid salt of the present invention has a high cation exchange capacity and an exchange rate, and has favorable properties as a water softener. Therefore, it can be suitably used as a water softener, a water treatment agent, a cleaning agent, and the like. Also this The detergent composition containing the compound shows superior detergency than the composition containing the conventional calcium ion trapping builder.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Detergent Compositions (AREA)

Abstract

On décrit des silicates stratifiés hydriques, représentés par la formule de composition (M1x/n, Na1-x/n)2SiyO2y+1.zH2O, où M1 représente au moins un métal choisi parmi lithium, potassium et des métaux alcalino-terreux, n représente la valence du métal M1; et x, y et z sont des nombres tels que 0 ≤ x ≤ 0,5, 3 ≤ y ≤ 7.5 et 1 ≤ z ≤ 20 respectivement. Ils présentent un temps de relaxation spin-réseau de 0,35 s ou moins, tel que déterminé par spectrométrie par résonance magnétique nucléaire du Na23 solide. Ces silicates présentent des capacités et vitesses élevées d'échanges cationiques et des propriétés les rendant appropriés pour des adoucisseurs d'eau, des produits de traitement des eaux, des détergents, etc.
PCT/JP1996/000342 1995-07-12 1996-02-16 Silicates stratifies hydriques et compositions de detergents les contenant WO1997003018A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE19681492T DE19681492T1 (de) 1995-07-12 1996-02-16 Hydratisiertes laminares Silicat und eine dieses enthaltende Waschmittelzusammensetzung

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP7/176398 1995-07-12
JP17639895 1995-07-12

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WO1997003018A1 true WO1997003018A1 (fr) 1997-01-30

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0799798A1 (fr) * 1996-04-01 1997-10-08 Hoechst Aktiengesellschaft Utilisation de silicates lamellaires
US9387471B2 (en) 2011-12-13 2016-07-12 Ecolab Usa Inc. Acid regeneration of ion exchange resins for industrial applications
RU2756808C2 (ru) * 2018-09-24 2021-10-05 Валерий Алексеевич Арабинский Применение отходов добычи и/или обогащения неметаллических полезных ископаемых, содержащих слоистые силикаты, в качестве компонентов моющего средства

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0141116B2 (fr) * 1984-04-11 1989-09-04 Hoechst Ag

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0141116B2 (fr) * 1984-04-11 1989-09-04 Hoechst Ag

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0799798A1 (fr) * 1996-04-01 1997-10-08 Hoechst Aktiengesellschaft Utilisation de silicates lamellaires
US5919371A (en) * 1996-04-01 1999-07-06 Clariant Gmbh Use of sheet silicates
US9387471B2 (en) 2011-12-13 2016-07-12 Ecolab Usa Inc. Acid regeneration of ion exchange resins for industrial applications
US9919935B2 (en) 2011-12-13 2018-03-20 Ecolab Usa Inc. Acid regeneration of ion exchange resins for industrial applications
RU2756808C2 (ru) * 2018-09-24 2021-10-05 Валерий Алексеевич Арабинский Применение отходов добычи и/или обогащения неметаллических полезных ископаемых, содержащих слоистые силикаты, в качестве компонентов моющего средства

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