KR100916360B1 - Colloidal solution of silver-sulfur-silica nano complex, water-soluble composition for processing metal including the nano complex and manufacturing methods therefor - Google Patents

Abstract

Method for preparing a colloidal solution of the silver-sulfur-silica nanocomposite of the present invention comprises the steps of preparing a colloidal solution of the silver-sulfur-silica nanocomposite particles, and the prepared silver-sulfur-silica nanocomposite colloidal solution of 1 to 3 Diluting in an alcohol solvent having 3 to 8 carbon atoms including a hydroxyl group, and aging the diluted silver-sulfur-silica nanocomposite colloidal solution at a temperature of about −10 to 25 ° C.

In addition, the water-soluble metal covalent composition of the present invention is about 30 to 70% by weight of at least one lubricant base oil, about 10 to 50% by weight of surfactant, about 3 to 50% by weight of additives and silver-sulfur- prepared by the above-described method. Silica nanocomposite colloidal solution comprises about 1 to 8% by weight.

The water-soluble metal-covalent composition of the present invention is a amine-based, boron-based, chlorine-based additives and sodium acetate, which exhibits continuous and excellent anti-corrosion by applying the silver-sulfur-silica nanocomposite as a preservative, and may adversely affect the human body or the environment. By eliminating this, it is safer for human body, has less environmental impact, and can be used semi-permanently when used industrially.

Silver-sulfur-silica nanocomposite, preservative, antibacterial, antifungal, water-soluble metal covalent, amine-free, environmentally friendly, human safety

Description

Silver-sulfur-silica nanocomposite colloidal solution and a water-soluble metal covalent composition comprising the same, and a method for preparing the same }

The present invention relates to a silver-sulfur-silica nanocomposite colloidal solution having excellent product stock stability and dispersibility as a preservative that can be blended into a water-soluble metal covalent covalent solution, a water-soluble metal covalent covalent composition comprising the same, and a method of preparing the same.

Specifically, the present invention provides a silver-sulfur-silica nanocomposite colloidal solution which is compoundable to water-soluble metal covalently used in metal processing such as metal cutting, and has excellent stability and dispersibility, and also provides amine, chlorine, boron, It excludes nitrite-based additives and formaldehyde or formaldehyde-releasing substances, and instead contains silver-sulfur-silica nanocomposite colloidal solution as antiseptic, which is safe for human body It relates to a technique for providing a composition.

 The general composition of the conventionally known water-soluble metal covalently consists of lubricating base oil, surfactant, and an additive. As the surfactant, anionic surfactants such as alkali salts of fatty acids and sulfone salts, and nonionic surfactants such as ethoxylates of fatty acids or fatty alcohols are used, and additives include synthetic esters, coupling agents, extreme pressure agents, antirust additives, and nonferrous metals. Preservatives, antifoaming agents, preservatives and other performance-related additives are used. In particular, alkanol amine compounds have been widely used as preservatives in consideration of emulsification performance and economic aspects.

In general, the conventional metal covalent sharing is largely divided into water-insoluble and water-soluble products. Recently, there has been an increase in the use of water-soluble metal covalently having excellent cooling action without fear of smoke and ignition.

On the other hand, water-soluble metal covalently is commonly used after dilution in water at an appropriate concentration in accordance with the required processing conditions, it is adopted to fill in a separate tank and circulate to supply to the processing site according to the processing equipment and conditions. However, there is a fundamental disadvantage in that the composition of the product has a condition that the organic matter is diluted with water and susceptible to decay due to an increase in liquidus temperature in use. In the industrial use of water soluble metal covalent, the replacement cycle of water soluble metal covalent is shortened due to deterioration of working environment due to deterioration of processing performance and deterioration caused by deterioration of required performance (lubrication, rust prevention, etc.) of product. Increasing generation of wastewater has become an important issue.

In order to solve the problem of the conventional water-soluble metal processing oil, phenol-based, formaldehyde-based, salicylic acid-based, guanidine-based, triazine-based, chitosan-based, etc. have been used as preservatives together with conventional alkanol amine-based. Is applied to the water-soluble metal-covalent solution in industrial use, the following problems arise in human and environmental aspects.

That is, the above-mentioned conventional preservatives exhibit the required performance for a specific microorganism, but the range of microorganisms exhibiting the required performance is narrow, loss and deterioration occurs over time, and the expression of resistant microorganisms occurs. As such, there is a problem in that the amount of the preservative is added or mixed with other preservatives. In addition, preservatives for inhibiting the growth of resistant microorganisms are mostly harmful to the human body, and when used with various types of preservatives, it is likely to cause oral toxicity to the human body, or to cause skin cracks, skin diseases, and skin cancer.

In addition, chlorine-based compounds to increase the extreme pressure performance of water-soluble metal covalently are suspected of causing ozone layer destruction, dioxin generation and VOC generation, and are being regulated globally. It is identified as one of the main causes.

In addition, amine compounds that exhibit emulsification, rust prevention, and antiseptic performance in water-soluble metal processing and boron-based compounds having antifungal performance are harmful to humans and wastewater generated when exchanging or disposing of the product with water pollutants. There are also problems with wastewater treatment.

On the other hand, the previously published patents related to the metal processing co-lubricating lubricant composition of the British castol company [Korean Patent No. 97-702353], the lubricant for hot rolling of high chromium stainless steel manufactured by Nisshin Seiko of Japan [Korean Patent No. 97-702354 No.], Lubricant for metal-powder composition of Sweden's Nagas Co., Ltd. [Korean Patent No. 97-703211], Cooling lubricant of Japan Japan Energy [Korean Patent No. 97-078831 and Korean Patent No. 97-078832] ], A water-soluble ironing lubricant composition of Nippon Seki Oil [Korean Patent Application Publication Nos. 98-024700 and Korean Patent Application Publication No. 98-024701], thiophosphoric acid ester and dithio of Ciba Specialty Chemicals Holding Inc., Switzerland Improved lubricant compositions comprising phosphoric acid esters [Korean Patent Application Laid-Open No. 99-029924], US Thickening Agent of S. Johnson & Sun Corporation Water [U.S. Patent No. 4,636,326], Chlorinated Fatty Acid Additive of U.S. Ferro Corporation [U.S. Patent No. 4,601,838], Lubricant Composition for Metal Processing of Japan Kwangkwang Heungsan Co., Ltd. Water-soluble high-speed cutting oil composition of Daedong Chemical Industry Co., Ltd. (JP-A-7-305085), cutting oil composition of Shin-Etsu Co., Ltd. [US Patent No. 5,693,596], cutting oil composition of US Xerox [US Patent No. 5,534,172], US Cincinnati Millacron Water-soluble cutting oil compositions of US Pat. No. 5,512,191, and water-soluble metal processing lubricants of Yushiro Chemical Co., Ltd. (JP-A-7-166181).

However, these conventional coolants come into contact with workers who perform cutting, bending, thread cutting and other metalworking operations and form mists in the parts of the workpiece that are still in operation. It moves and causes environmental pollution. In addition, problems such as dermatitis due to the continuous use of the amine-based compound, harmful to the human body is not easy to solve, causing significant damage to the worker.

In Europe, petroleum-based mineral oils, extreme pressure agents including sulfur, chlorine and phosphorus, formaldehyde-releasing preservatives and amines, which are known to adversely affect workers' health, are regulated. . Patents for this include water-soluble metal working oils including polyamido salts of Monsanto, USA (Korean Patent Publication No. 96-701798), polymer thickeners of copolymers of acrylamide, acrylate sodium salt and N-octyl acrylamide [ British Patent No. 2,252,103], Water Soluble Lubricant Composition Containing Metal Salt of Alkylamine Dicarboxylate from Diversity of Canada [UK Patent No. 2,285,630], Water Soluble Dietanol Sulfide Abrasive Agent of Penwalt, USA [US Patent No. 4,250,046] ], And a metal co-coating agent (Japanese Patent Laid-Open No. 7-166188) containing a triethanolamine salt of a fatty acid are known.

However, the technique disclosed in the above patent documents can solve the metal workability, but it is difficult to solve the harmfulness to the human body. Therefore, it is urgent to develop a water-soluble metal covalently having excellent metal processing performance but not affecting the human body.

In recent years, attempts have been made to reduce the effects on the human body. Patents for this include water-soluble cutting oil compositions using vegetable oils and synthetic esters (Korean Patent Publication No. 10-0486624), and There is a water-soluble cutting oil composition (Korean Patent No. 10-0665790) which does not contain petroleum mineral oil and alkanol amine, which are harmful to hygiene.

In addition, in order to develop a cutting oil having a low impact on the human body, an attempt has been recently made to apply silver nano as a preservative, and a patent for this is a water-soluble cutting oil component of nano silver colloid addition of Gain Co., Ltd. 10-0418258. The nano silver metal colloid applied in this patent uses pure silver nanoparticles. The known pure silver nanoparticles have a weak preservative effect on molds and yeasts, and are difficult to apply to water-soluble metal-coating furnaces in terms of functionality and cost because of their high price. Particularly, commercially available nano silver metal colloid products using pure silver nano particles are dispersed in water, and when they are added or added to water-soluble metal covalent products, coagulation phenomenon and precipitation phenomenon occur due to low stock stability, and low concentration of silver nano It is very difficult to apply in terms of gender and its scope of application is very limited.

On the other hand, a process for making high purity silver into nanoparticles and a method for making an antimicrobial product are disclosed in several documents. For example, a method in which one or two or more reducing agents such as hydrazine and NaBH _{4 is} added to a composite metal ion solution in which two or more salt compounds such as gold, silver, iron, platinum, and zinc are dissolved to reduce the composite metal particles. [Korean Patent Laid-Open Publication No. 2000-0018196], a method for producing an antimicrobial soap containing high concentration of silver using silver colloid [Korean Patent Laid-Open Publication No. 2001-0069644], and a mixed powder of silver and stannous oxide. A mixed acid solution of hydrochloric acid was gradually added, heated and stirred to dissolve silver, and then a caustic soda solution was added thereto to prepare a silver colloidal solution having a pH of 7.5. Stir with the prepared silver colloidal solution to make food-inorganic antimicrobial agents, and dilute these inorganic antimicrobials in a mixture of ocher and ceramic jijangsu to soak food packaging paper and dry them. W has the antibacterial method of producing a food wrapping paper [Republic of Korea Patent Publication No. 2001-0044617 Arc like.

However, the known colloidal solution of pure silver nanoparticles has a weak preservative effect on mold and yeast, and it is difficult to apply the water-soluble metal-coating furnace in terms of functionality and economics because of its high price. In particular, commercially available nano silver metal colloidal products are mostly products dispersed in water or ethanol, etc., when the mixture is added or added to a water-soluble metal covalent product, there is a problem in that coagulation phenomenon and precipitation phenomenon occur when the stock solution stability is low.

Therefore, it has antimicrobial effect and antifungal performance at the same time, can be mass-produced, it is inexpensive and can be blended in the production of water-soluble metal covalent at high concentration, dispersibility or mixing without coagulation and sedimentation with time after manufacture There is an urgent need for development of silver nano composites or silver nano composite colloidal solution products having excellent properties and securing dispersion technology.

Silver nanocomposites have recently been used as antimicrobial agents in many consumer products, but are quite expensive as additives for water-soluble metal-coating. In addition, since the composition or processing environment of the water-soluble metal-covalent solvent tends to decay, there is a limit to maintain a high concentration in order to exhibit effective anti-corruption performance, and due to its low compatibility with the product stock solution during manufacture and storage, precipitates or other additives There is a problem that is difficult to apply for reasons such as not performing performance due to unexpected reaction. In addition, since the known water-soluble metal-covalent product is produced in a undiluted state and diluted with water at the site, when the silver nanocomposite precipitates during storage and supply before application to the site, redispersion occurs due to aggregation between the silver nanocomposites. It is difficult and has the problem that the sterilization performance as nanoparticles is significantly reduced.

Therefore, in the technical field to which the present invention belongs, it is required to provide a technology for stabilizing the dispersion of the silver nanocomposite into the water-soluble metal covalent composition to have a uniform phase. At the same time, there is an increasing technical need to make the silver nanocomposite less or less reactive.

Therefore, the present invention was devised in response to the technical requirements as described above, and maintains or improves the processability, tool life extension, etc., which are the primary performances of the water-soluble metal covalently, and the secondary performances of the rust resistance, emulsion stability, detergency, and antifoam. The object of the present invention is to provide additives for exerting sex, anti-corrosion, etc. in an environment-friendly composition while minimizing human harm.

Specifically, it is an object of the present invention to replace the preservatives that may affect the human body and the environment in the composition of the water-soluble metal covalent, silver-sulfur-silica nanocomposite which is soluble in water-soluble metal covalent and excellent in stability and dispersibility. To provide a colloidal solution.

In addition, it is an object of the present invention to provide a semi-permanent water-soluble metal covalent composition comprising a silver-sulfur-silica nanocomposite colloidal solution as a preservative and safe to the human body and excellent in permeability.

The configuration of the present invention will be described in detail as follows.

The method for preparing a silver-sulfur-silica nanocomposite colloidal solution applied to the water-soluble metal covalent solution of the present invention includes preparing a colloidal solution of silver-sulfur-silica nanocomposite particles, and the prepared silver-sulfur-silica nanocomposite colloid Diluting the solution in an alcohol solvent having 3 to 8 carbon atoms including 1 to 3 hydroxyl groups, and aging the diluted silver-sulfur-silica nanocomposite colloidal solution at a temperature of about −10 to 25 ° C. do.

In one embodiment of the present invention, the silver-sulfur-silica nanocomposite colloidal solution commercially available (for example, product name NSSL30 manufactured by Nanobio Co., Ltd.) or prepared by a known process may be aged and stabilized. Then, it was applied as a preservative of the water-soluble metal covalent composition of the present invention. Accordingly, the present invention is characterized by diluting, aging and stabilizing a silver-sulfur-silica nanocomposite colloidal solution.

More specifically, the present invention is water or ethanol, which is a solvent of a known process (for example, a manufacturing process of the product name "NSSL30" manufactured by Nanobio Co., Ltd.) in the preparation of the silver-sulfur-silica nanocomposite colloidal solution. Is replaced with a hexylene glycol solvent to prepare a silver-sulfur-silica nanocomposite colloidal solution (hereinafter referred to as "NSSL30HG"), and then dilute to an appropriate concentration using an alcohol compound having 3 to 8 carbon atoms as a solvent. And aging to prepare a silver-sulfur-silica nanocomposite colloidal solution as a preservative for water-soluble metal covalent sharing.

On the other hand, the raw material of the silver-sulfur-silica nanocomposite used in the production of the silver-sulfur-silica nanocomposite colloidal solution is commercially available as described above (for example, the product name of Nanobio Co., Ltd. " NSSL30 ") can be used and can also be manufactured using a well-known method (Korean Patent Publication No. 10-2004-0039256).

Specifically, the raw material of the silver-sulfur-silica nanocomposite is 3- (mercaptopropyl) trimethoxysilane [(3-mercaptopropyl), which is a functional additive containing a sulfur component on the surface of nanosilica particles in a solvent of hexylene glycol. trimethoxysilane] is used to bind the silver ions, and is then prepared by reducing the silver ions using heat or sodium borohydride or ascorbic acid.

However, the present invention is not limited thereto, and the present invention is characterized by the dilution and aging step of the silver-sulfur-silica nanocomposite colloidal solution to stably disperse in the water-soluble metal covalent composition to increase the stock stability. The material may be used as long as it is known in the art.

In one embodiment of the present invention, the prepared silver-sulfur-silica nanocomposite colloidal solution is preferably diluted in the alcohol solvent at a concentration of about 5 to 25% by weight, more preferably about 10 to 20% by weight Dilution to a good concentration is good for preservative performance and product stability. As the dilution alcohol solvent used in the preparation of the silver-sulfur-silica nanocomposite colloidal solution, a C 3-8 alcohol solvent including 1 to 3 hydroxyl groups is preferable, and more preferably includes 2 hydroxyl groups. Alcohol solvents having 5 to 7 carbon atoms are good in terms of stability of the water-soluble metal covalent product. Even more preferably, hexylene glycol solvent is preferred as the dilution alcohol solvent.

In one embodiment of the present invention, the diluted silver-sulfur-silica nanocomposite colloidal solution is preferably aged for about 21 days to 45 days. Aging conditions in the preparation of the silver-sulfur-silica nanocomposite colloidal solution are preferably aged for about 21 to 45 days under about -10 to 25 ° C, more preferably about 3 to 7 under about -10 to 5 ° C. The two-step aging process of about 14-30 days at 15 ~ 25 ℃ is good in terms of product stability.

In the production method of the silver-sulfur-silica nanocomposite colloidal solution of the present invention, it is preferable that the content of the nanocomposite containing silver, which is an active ingredient having antiseptic properties, in the case of the raw material is about 10 to 30% by weight. Because, when the content of silver-containing nanocomposite is less than 10% by weight, it is difficult to expect the antiseptic performance compared to the added amount as the concentration is diluted during the aging stabilization process, and when the content of the nanocomposite is more than 30% by weight, the nanocomposite product is less stable and aggregates. This is because the gelation phenomenon has a disadvantage that proceeds.

In addition, the solvent used in the preparation or dilution of the silver-sulfur-silica nanocomposite colloidal solution functions as a coupling agent for water-soluble metal covalent, and the stability against aggregation and gelling phenomenon is at least about a week at room temperature, about -10 to 5 It is preferable that it is 30 days or more under ° C.

The water-soluble metal covalent composition of the present invention excludes amine-based compounds, which are main additives for preservative performance, and at the same time, excludes chlorine-based, boron-based, acetic acid-based additives and formaldehyde or formaldehyde-releasing substances that are harmful to the human body. It consists of

That is, the water-soluble metal covalent composition of the present invention comprises about 30 to 70% by weight of at least one lube base oil, about 10 to 50% by weight of surfactant, about 3 to 50% by weight of additive, and silver-sulfur- prepared by the above-described method. Silica nanocomposite colloidal solution comprises about 1 to 8% by weight.

As the lubricant base oil of the water-soluble metal covalent composition of the present invention, mineral oil, vegetable oil, vegetable oil ester, synthetic ester, etc. may be used alone or in combination of two or more thereof, and the amount of the additive is about 30 to 70% by weight, preferably about 40 to 65% by weight. %, More preferably about 45 to 60% by weight. If lubricating base oil is less than 30% by weight, it is difficult to obtain lubrication performance, and when it is more than 70% by weight, it is difficult to expect the physical properties required as water-soluble metal covalent because the amount of additives that give other required performance is small. Because.

On the other hand, mineral oil is composed of a molecular formula (CH ₂ ) _n (n = 12 ~ 55), the viscosity (40 ℃) 7 ~ 30 cst, hydrocarbon composition ratio of 49 ~ 78 wt%, 21 ~ 43 Preference is given to carbon paraffins, carbon naphthenes, and carbon aromatics in weight percents and 0.1 to 8.5 weight percents. In addition, vegetable oils and vegetable oil esters include soybean oil, castor oil, sunflower oil, rapeseed oil and the like, and alkyl (1 to 3 carbon atoms) esters thereof, and these may be used alone or in combination of two or more kinds. As the synthetic ester, trimethylolpropane (TMP) ester, pentaeryriol ester, glycerol ester and derivatives thereof may be used. However, the lubricating base oil of the present invention is not limited thereto and includes all lubricating base oils applicable to the present invention as used in the art.

As the surfactant of the water-soluble metal covalent composition of the present invention, anionic surfactants, nonionic surfactants, and the like may be used alone or in combination of two or more thereof, and the amount of the additive is about 10 to 50% by weight, preferably about 15 to 35 Use by weight, more preferably about 20-25%. This is because, if the surfactant is used less than 10% by weight, it is difficult to expect the emulsification performance, when using more than 50% by weight it is difficult to expect the lubricating performance.

Among the surfactants, anionic surfactants include fatty acids having 16 to 22 carbon atoms that may include double bonds, more specifically palmitic acid, palmitoic acid, stearic acid, Oleic acid, linoleic acid, linolenic acid, arachidic acid, arachidic acid, eicosenoic acid, behenic acid, erucic acid, etc. Potassium salts of naturally occurring fatty acids containing more than one species and petroluem sodium sulfonate are used. Preferably, 18 to 20 carbon atoms containing one or more double bonds, more specifically, natural extracted fatty acids including oleic acid (oleic acid), linoleic acid (linoleic acid), linolenic acid (rinolenic acid) as a main component Excellent lubricity and emulsification performance can be expected.

Among the surfactants, nonionic surfactants are preferably ethoxylates of fatty alcohols or fatty acids having 4 to 18 carbon atoms or more, and more preferably 12 to 18 fatty alcohols or fatty acids, more specifically, When ethoxylate of lauryl alcohol and ethoxylate of castor oil are used, water resistance and water resistance can be expected.

The additive of the water-soluble metal covalent composition of the present invention is at least one selected from the group consisting of a lubricant improver, a coupling agent, an antioxidant, a nonferrous metal corrosion inhibitor, an antirust additive, and an antifoaming agent.

As the lubrication improving agent, oleic acid, linoleic acid, ricinoleic acid, stearic acid, isostearic acid, condensate of palmitic acid and ricinoleic acid, or the like may be used alone or in combination of two or more types selected. It is preferred to use 10% by weight, preferably about 3-8% by weight, more preferably about 4-6% by weight. This is because when the amount is less than 1% by weight, there is no lubricity improvement effect or minimal performance, and when using more than 10% by weight, the water resistance is deteriorated.

The coupling agent is used to obtain a uniform liquid phase of the water-soluble metal-covalent product, and has 13 to 18 carbon atoms including water, ethylene glycol, diethylene glycol, propylene glycol, dimethyl propylene glycol, hexylene glycol, and one or more hydroxyl groups. Fatty alcohol and the like may be used alone or in combination of two or more kinds thereof. The amount of the coupling agent to be added may be suitably used in an amount that does not impair the effect of the water-soluble metal-covalent composition of the present invention, but is about 0 to 15% by weight, preferably about 2 to 13% by weight, based on the total weight of the composition. Preferably about 5 to 10% by weight is used. This is because it is difficult to obtain a uniform liquid product without using a coupling agent, and when 15 wt% or more is used, there is a disadvantage in that the lubricity and rust resistance are sharply lowered.

The antioxidant is used for the purpose of preventing oxidation of lubricant base oils and easily oxidizing additives. The antioxidants include oil-soluble phenols, oil-soluble secondary aryl amines and derivatives thereof having a steric hindrance in terms of chemical structure. Preference is given to using oil-soluble phenolic systems having chemical structural steric hindrance. The addition amount is preferably about 0.1 to 0.5% by weight, more preferably about 0.2 to 0.3% by weight. This is because it is difficult to expect anti-oxidation at an additive amount of 0.1 wt% or less, and there is a drawback of increasing viscosity due to oxidative polymerization of raw materials and emulsification during dilution when the water-soluble metal covalent composition product is stored for a long time. In addition, when 0.5 wt% or more is used, the performance does not improve in direct proportion to the amount of antioxidant added, and its performance does not improve any more than a certain concentration. This is because there is a possibility.

The non-ferrous metal corrosion inhibitor is used to prevent corrosion in the processing of metals other than iron, more specifically aluminum, copper, magnesium and alloys thereof, benzotriazole, tolytriazole, mercapto Benzothiazole, sodium metasilicate, potassium metasilicate, fatty phosphate, and derivatives thereof may be used, and the type and amount of the benzothiazole may be adjusted according to the processing material to which the water-soluble metal covalent composition is applied. The amount of addition is preferably about 0.05 to 1.5% by weight.

The rust preventive additive is used to prevent corrosion during processing of metals or alloys containing iron as a main component, and it is a dibasic fatty acid caprylic acid, capric acid, sebacic acid, pelagonic acid, adipic acid, acrylated fatty acid, fatty acid amide And these derivatives can be used individually or in mixture of 2 or more types. The addition amount is preferably about 1 to 10% by weight. It is more preferable to use about 1 to 5% by weight since the rust resistance of the water-soluble metal-covalent composition is also affected by other components other than the anti-rust additive. Because, if less than 1% by weight it is difficult to expect the required performance, and when used more than 10% by weight has a disadvantage that the emulsification performance is lowered and residues may remain on the surface of the workpiece.

As the antifoaming agent, silicone antifoaming agents such as polydimethylsiloxane, modified polydimethylsiloxane, organosilicon derivatives, silicone ethoxylates and silica may be used alone or in combination of two or more thereof. The addition amount is preferably about 0.1 to 5% by weight, preferably about 0.1 to 3% by weight, more preferably about 0.1 to 1% by weight. If the amount of the antifoaming agent is less than 0.1% by weight, antifoaming performance is difficult to be expected. If the amount of the antifoaming agent is more than 5% by weight, the dispersibility of the antifoaming agent is decreased, causing precipitation and flocculation. Because of this.

The amount of the silver-sulfur-silica nanocomposite colloidal solution used as a preservative of the water-soluble metal covalent composition of the present invention is about 1 to 8% by weight, preferably about 1.5 to 5% by weight, more preferably about 2 to 3.5% by weight. It is better to use%. Because, when using less than 1% by weight it is difficult to expect the antiseptic performance or show the minimum performance, when using more than 8% by weight has the disadvantage of deteriorating lubricity and rust resistance and is not economical.

When the silver-sulfur-silica nanocomposite colloidal solution of the present invention is applied as a preservative to a water-soluble metal covalent composition, unlike conventional silver nano-containing antimicrobial products, there is no continuous aggregation and precipitation of nanoparticles in the stock solution and diluent of water-soluble metal covalent fluid. Performance and antifungal effects can be achieved.

In addition, the silver-sulfur-silica nanocomposite colloidal solution of the present invention can be stored at room temperature for a long period of time through the aging process during preparation, and can be easily mixed with other antimicrobial products.

In addition, the water-soluble metal-covalent composition of the present invention by applying the silver-sulfur-silica nanocomposite as a preservative, and exhibits excellent sustained anti-perishability, amine-based, boron-based, chlorine-based additives and ah that can adversely affect the human body or the environment By excluding sodium acetate, it is safer for human body, has less environmental impact, and can be used semi-permanently when used industrially.

Furthermore, the water-soluble metal covalent composition of the present invention exhibits processing performance equivalent to or higher than known water-soluble metal covalent composition, even though the excluded compositions as described above are related to the main required performance of the water-soluble metal covalent composition. Its lifetime is semi-permanent, and the amount of waste liquid generated during the exchange or disposal of water-soluble metal-based covalent liquids can be reduced, and the impact on the environment can be minimized during waste water treatment.

Hereinafter, the present invention will be described in detail according to embodiments which do not limit the present invention. The following examples of the present invention are not intended to limit or limit the scope of the present invention only to embody the present invention. Therefore, what can be easily inferred by the expert in the technical field to which this invention belongs from the detailed description and the Example of this invention is interpreted as belonging to the scope of the present invention.

Examples 1 to 8 Preparation of Silver-Sulfur-Silica Nanocomposite Colloidal Solution Applied as Preservative to Water-Soluble Metal Covalent Compositions

Example 1

Except for the use of hexylene glycol of SHELL Korea as a solvent in place of water or ethanol, which is a solvent used in the manufacture of silver-sulfur-silica nanocomposite colloidal solution product (product name NSSL30) of Nanobio A silver-sulfur-silica nanocomposite colloidal solution product (hereinafter referred to as "NSSL30HG") was prepared in the same process as that of NSSL30 manufactured by Nanobio.

Example 2

While stirring 80 wt% of hexyleneglycol at room temperature and atmospheric pressure at 200 RPM, slowly added dropwise 20 wt% of silver-sulfur-silica nanocomposite colloidal solution product (NSSL30HG) and stirred at 500 rpm for 1 hour. . Then, after filling the sealed container to block the light and left for 7 days at -10 ~ 0 ℃. After aging for 14 days at room temperature, a silver-sulfur-silica nanocomposite colloidal solution as a preservative for water-soluble metal covalent formulation was prepared.

Example 3

At room temperature, atmospheric pressure, 80% by weight of hexyleneglycol (Hexyleneglycol) while stirring at a rotational speed of 200 RPM, 20 wt% of silver-sulfur-silica nanocomposite colloidal solution product (NSSL30HG) was slowly added dropwise, and stirred at a rotational speed of 500 RPM for 1 hour. Then, it was filled in an airtight container blocking the light and left for 3 days at -10 ~ 0 ℃. And again aged at room temperature for 30 days to prepare a colloidal solution of silver-sulfur-silica nanocomposite as a preservative for water-soluble metal covalent formulation.

Example 4

At room temperature, atmospheric pressure, 80% by weight of hexyleneglycol was slowly added dropwise while stirring the silver-sulfur-silica nanocomposite colloidal solution product (NSSL30HG) at a rotational speed of 200 RPM, and stirred at a rotational speed of 500 RPM for 1 hour. . Then, after filling in an airtight container to block light, aged for 15 days at 15 ~ 25 ℃ to prepare a silver-sulfur-silica nanocomposite colloidal solution as a preservative for water-soluble metal covalent formulation.

Example 5

10 wt% of silver-sulfur-silica nanocomposite colloidal solution product (NSSL30HG) was slowly added dropwise while stirring 90 wt% of hexyleneglycol at room temperature and atmospheric pressure at 200 RPM, and stirred at 500 rpm for 1 hour. . Then, it was filled in an airtight container blocking the light and left for 3 days at -10 ~ 0 ℃. And again aged 15 days at 15 ~ 25 ℃ to prepare a silver-sulfur-silica nanocomposite colloidal solution as a preservative for water-soluble metal covalent formulation.

Example 6

10 wt% of silver-sulfur-silica nanocomposite colloidal solution product (NSSL30HG) was slowly added dropwise while stirring 90 wt% of hexyleneglycol at room temperature and atmospheric pressure at 200 RPM, and stirred at 500 rpm for 1 hour. . Then, after filling the sealed container to block light, aged for 15 days at 15 ~ 25 ℃ to prepare a silver-sulfur-silica nanocomposite colloidal solution as a preservative for water-soluble metal covalent formulation.

Example 7

At room temperature and atmospheric pressure, 20 wt% of silver-sulfur-silica nanocomposite colloidal solution product (NSSL30HG) was slowly added dropwise while stirring 80 wt% of propyleneglycol at a rotational speed of 200 RPM, and stirred at a rotational speed of 500 RPM for 1 hour. Then, after filling the sealed container to block the light and left for 7 days at -10 ~ 0 ℃. And again aged for 15 days at 15 ~ 25 ℃ to prepare a silver-sulfur-silica nanocomposite colloidal solution as a preservative for water-soluble metal covalent formulation.

Example 8

Slowly add 20 wt% of silver-sulfur-silica nanocomposite colloidal solution (NSSL30HG) while stirring 80 wt% of dipropylene glycol at room temperature and atmospheric pressure at 200 RPM, and stir at 500 rpm for 1 hour. It was. Then, after filling the sealed container to block the light and left for 7 days at -10 ~ 0 ℃. And again aged for 15 days at 15 ~ 25 ℃ to prepare a silver-sulfur-silica nanocomposite colloidal solution as a preservative for water-soluble metal covalent formulation.

When the silver-sulfur-silica nanocomposite colloidal solution prepared by the method described in Examples 2 to 8 above is applied to the water-soluble metal covalent composition, there is no aggregation and precipitation phenomenon over time during manufacture and storage, and excellent in use. Preservative performance was shown (see Table 1, etc.).

Examples 9 to 12: Preparation of water-soluble metal cutting oil using the colloidal solution of the silver-sulfur-silica nanocomposite of the present invention as an antiseptic

Example 9

Add 0.2% by weight of antioxidant to 55% by weight of mineral oil, dissolve by stirring at 200RPM for 15 minutes at 50 ± 5 ℃, and keep 5% by weight of petroleum sulfonate and 10% of tall oil fatty acid under 30 ± 5 ℃ while maintaining the stirring speed. %, 3.5% by weight of acrylated fatty acid, 5% by weight of ricinoleic acid condensate, 3% by weight of ethoxylate of lauryl alcohol, 2% by weight of oleic acid amide, 2.5% by weight of potassium hydroxide, 2.5% by weight of distilled water, fatty alcohol ( 5% by weight of C _n H _{2n + 1-} OH (n: 14,15)) and 1.8% by weight of hexylene glycol were added in this order, stirred for 30 minutes, and 2.5% by weight of a colloidal solution of the silver-sulfur-silica nanocomposite. , 0.5% by weight of sodium metasilicate, 1.0% by weight of fatty phosphate, and 0.5% by weight of modified polydimethylsiloxane were added thereto, followed by stirring for 20 minutes to prepare a water-soluble metal-covalent metal of the present invention.

Example 10

Add 0.2% by weight of antioxidant to 35% by weight of mineral oil, dissolve by stirring at 200RPM for 15 minutes under 50 ± 5 ℃, and 17% by weight of trimethanol propane trioleate under 30 ± 5 ℃ while maintaining the stirring speed. 7.5% by weight of sodium sulfonate, 11% by weight of tall oil fatty acid, 3.5% by weight of acrylated fatty acid, 5% by weight of ricinoleic acid condensate, 3% by weight of oleic acid amide, 3% by weight of ethoxylate of lauryl alcohol, 2.5% of potassium hydroxide %, Distilled water 2.5% by weight, 5% by weight of fatty alcohol (C _n H _{2n + 1} -OH (n: 14,15)) in order and stirred for 30 minutes, the colloidal solution of the silver-sulfur-silica nanocomposite 2.8 A water-soluble metal covalent copolymer of the present invention was prepared by adding 20% by weight, 0.5% by weight of sodium metasilicate, 1.0% by weight of fatty phosphate, and 0.5% by weight of modified polydimethylsiloxane.

Example 11

Add 0.2% by weight of antioxidant to 28% by weight of mineral oil, dissolve by stirring at 200RPM for 15 minutes under 50 ± 5 ℃, and 28% by weight of trimethanol propane trioleate under 30 ± 5 ℃ while maintaining the stirring speed. 6% by weight of sodium sulfonate, 7.5% by weight of tall oil fatty acid, 3% by weight of acrylated fatty acid, 5% by weight of ricinoleic acid condensate, 5% by weight of oleic acid amide, 2.4% by weight of potassium hydroxide, 2.4% by weight of distilled water, fatty alcohol ( 7.5% by weight of C _n H _{2n + 1-} OH (n: 14,15)) was added sequentially and stirred for 30 minutes, 3% by weight of a colloidal solution of the silver-sulfur-silica nanocomposite, 0.3% by weight of tetraethylsilicic acid, 1.2% by weight of a fatty phosphate and 0.5% by weight of a modified polydimethylsiloxane were added thereto, followed by stirring for 20 minutes to prepare a water-soluble metal-covalent metal of the present invention.

Example 12

0.4% by weight of antioxidant was added to 55% by weight of soybean oil methyl ester, and dissolved by stirring at a speed of 200 RPM for 15 minutes at 50 ± 5 ° C., 8.5% by weight of tall oil fatty acid under 30 ± 5 ° C., and acrylated fatty acid while maintaining the stirring speed. % By weight, 2.5% by weight of ricinoleic acid condensate, 6% by weight of oleic fatty acid amide, 4.5% by weight of ethoxylate of lauryl alcohol, 2.5% by weight of potassium hydroxide, 2.5% by weight of distilled water, fatty alcohol (C _n H _{2n +} 10 wt% of _1- OH (n: 14,15)) was added sequentially, followed by stirring for 30 minutes, 2.5 wt% of a colloidal solution of the silver-sulfur-silica nanocomposite, 0.2 wt% of tetraethylsilicic acid, 1.0 wt% of fatty phosphate , 0.3 wt% of an organosilicon derivative and 0.1 wt% of a modified polydimethylsiloxane were added thereto, followed by stirring for 20 minutes to prepare a water-soluble metal covalent copolymer of the present invention.

Test Method 1

In the water-soluble metal covalent composition of the present invention, the stock solution stability test when applying the colloidal solution of the silver-sulfur-silica nanocomposite of the present invention and the conventionally commercialized silver nano-containing colloidal solution is as follows.

In the case of using the colloidal solution of the silver-sulfur-silica nanocomposite prepared in Example 2-8 (abbreviated as BIT-N) as the preservative for water-soluble cutting oil, and in the case of applying the conventionally commercialized silver nano-containing colloidal solutions, Appearance changes and precipitation over time at room temperature and 50 ℃ were evaluated based on the stability of the stock solution. The results are shown in Table 1. As a commercially available silver nano-containing colloidal solution, three kinds (name: S, X, B) added to paint, antibacterial spray, and antimicrobial coating solution in the market were selected.

Table 1: Comparison of the Stock Solution Stability of Water-Soluble Metal Covalent in the Application of the Silver-Sulfur-Silica Nanocomposite Colloidal Solution of the Present Invention and the Application of the Conventional Silver Nanocolloidal Solution

Test Method 2

Test method for the water-soluble metal covalent sharing of the present invention is as follows.

The anti-perishability experiment was performed with respect to the water-soluble cutting oil composition (The composition of Examples 9-12, hereafter BIT-1, BIT-2, BIT-3, BIT-4) of this invention. As a commercialized product using a conventional preservative, one excellent anticorrosive product and one of thirteen products were selected for the comparison of anticorrosion, and the reference product using the silver-sulfur-silica nanocomposite colloidal solution of Example 1 as a preservative. -1 (BIT-0) was prepared. The anti-corrosion experiment was carried out by decomposing the decay culture solution (10 ⁵ to 10 ⁶ bacteria) obtained by diluting the selected water-soluble cutting oil to 10% concentration in ion-exchanged water (150 mL). Periodically (2 times / 7 days) a predetermined amount (3 mL) was repeatedly injected and vibrated culture at 35 ℃ to evaluate the time and total number of bacteria. The results are shown in Table 2 as a result of the anti-corrosion test. Bacterial generation and total number of bacteria were used by SANICHECK AB of BIOSAN of USA and Microcount-combi of Schulke & Mayer of Germany. (Note: KSM-2173 standard method).

Table 2: Anticorrosion Comparison Test

On the other hand, the lubricity (site processing performance) was tested using a CNC equipment (equipment: DECKEL MAHO) and the test conditions are shown in Table 3. The lower the torque value that is the result of the evaluation of lubricity, the better the lubricity, and the torque value is about 1100 to 1500 for water-soluble cutting oils with excellent lubricity.

Table 3: Test conditions for water-soluble metal covalent lubricity of CNC equipment

Emulsification stability is generated after taking 100 mL of the diluted solution of water-soluble metal covalently to 10 wt% in tap water and calcium hardness 530ppm aqueous solution according to KSM-2525 standard test, filling 100 mL into the measuring cylinder, and leaving it at room temperature for 24 hours. The volume of the oil layer or cream layer is measured and evaluated. The oil and cream layers usually appear on top of the diluent when they occur, and the less the oil and cream layers separated, the more stable the emulsion. Specifications are 1 mL or less in volume for each oil and cream layer.

Corrosion resistance is to evaluate the ability to prevent rust on equipment and casting materials. In accordance with the DIN51360 / IP28744 standard test, filter paper is placed on a 50 mm diameter Petri dish, and 3 g of FC-25 casting chips are added to the sample liquid (aqueous cutting oil diluent). Fill approximately 15 mL, remove the sample solution using the dropper after about 1 minute, and cover the lid and leave at room temperature to determine whether or not the rust occurred by time (1, 2, 3, 6, 24 hours). In the general properties and test results of Examples 9 to 12 shown in Table 4, the presence and the degree of rust is judged by the number of rust points generated on the filter paper of the bottom side, ◎ indicates no rust, ○ indicates rust occurrence (10 points or less) and (triangle | delta) are a case of several tens (10-30 points) rust generation.

Permeability is an evaluation method to evaluate whether the oil can be supplied well between the material and the tool during processing, and the performance that no residue remains on the processed material, that is, the cleaning property. It is called iron pyramid method. In the center of 100mm glass shale, 50 ~ 140 mesh size iron is made into a conical shape (diameter 20mm, height 20mm) by using a mold, and 15mL of sample solution is supplied by pipette to the edge of shale. The results are obtained by measuring three times from the point of contact of the sample liquid to the edge of the iron cone bottom layer and the time of complete wet. Existing water-soluble metal covalently exhibits satisfactory performance within 2 minutes.

Al discoloration is an evaluation of corrosion and discoloration of aluminum-based materials after processing or processing when water-soluble metals are used.In a 100 mL beaker, 30 mL of a solution containing 10% by weight of water-soluble cutting oil diluted in tap water is filled into a specimen (standard: 50 × 20 × 10 (mm), material: Al606-T6) was added, and left for 24 hours at 50 ° C. to determine color change visually.

The antifoaming property is filled with 20L of a transparent plastic container (standard: 400 × 300 × 200 (mm)) of 8L of water-soluble metal covalently diluted 10% by weight in tap water, and then at a flow rate of 10L / min using a motor pump. Circulate and evaluate. At this time, the distance from the discharge portion of the motor pump to the sample liquid is about 25 cm, and the bubble height generated after 24 hours is measured. In the case of conventional water-soluble metal covalently, less than 10 is considered to exhibit excellent defoaming.

Results for the test items except for the anti-perishability test are shown as general properties and test results of Table 4.

Table 4: General properties and test results of Examples 9-12

Although the present invention has been described in accordance with the above-described embodiments, the present invention is not limited to the disclosed embodiments. Those skilled in the art will appreciate that modifications can be made in accordance with the spirit of the invention, and such modifications also fall within the scope of the invention.

Claims (11)

 Preparing a colloidal solution of silver-sulfur-silica nanocomposite particles, Diluting the prepared silver-sulfur-silica nanocomposite colloidal solution with an alcohol solvent having 3 to 8 carbon atoms including 1 to 3 hydroxyl groups; Method for producing a silver-sulfur-silica nanocomposite colloidal solution comprising the step of aging the diluted silver-sulfur-silica nanocomposite colloidal solution at a temperature of -10 ~ 25 ℃. The method of claim 1, In the step of preparing a colloidal solution of the silver-sulfur-silica nanocomposite particles, hexylene glycol is used as a solvent, the method for producing a silver-sulfur-silica nanocomposite colloidal solution. The method of claim 2, In preparing the colloidal solution of the silver-sulfur-silica nanocomposite particles, 3- (mergatopropyl) trimethoxysilane, which is a functional additive containing a sulfur component on the surface of the nanosilica particles under a solvent of hexylene glycol, After the silver ions are bonded using a method for producing a silver-sulfur-silica nanocomposite colloidal solution, characterized in that the silver ions are reduced using heat, sodium borohydride or ascorbic acid. The method according to any one of claims 1 to 3, The prepared silver-sulfur-silica nanocomposite colloidal solution is diluted in the alcohol solvent at a concentration of 5 to 25% by weight. The method of claim 4, wherein The alcohol solvent is hexylene glycol, characterized in that the silver-sulfur-silica nanocomposite method for producing a colloidal solution. The method according to any one of claims 1 to 3, In the step of aging, the diluted silver-sulfur-silica nanocomposite colloidal solution is characterized in that for 21 to 45 days of aging method of the silver-sulfur-silica nanocomposite colloidal solution. The method of claim 6, In the step of aging, the diluted silver-sulfur-silica nanocomposite colloidal solution is aged through a two-step aging process of 3 ~ 7 days at -10 ~ 5 ℃, 14 ~ 30 days at 15 ~ 25 ℃ Method for producing a silver-sulfur-silica nanocomposite colloidal solution characterized in that. Silver-sulfur-silica nanocomposites obtained according to the process defined in any one of claims 1 to 3, and 30 to 70% by weight of lubricant base oil, 10 to 50% by weight of surfactant, 3 to 50% by weight of additives, and A water-soluble metal covalent composition comprising 1 to 8% by weight of a colloidal solution. The method of claim 8, The lubricating base oil is water-soluble metal covalent composition, characterized in that any one or a mixture of two or more of mineral oil, vegetable oil, vegetable oil ester or synthetic ester. The method of claim 8, The surfactant is an anionic surfactant or a nonionic surfactant, or a water-soluble metal covalent composition, characterized in that a mixture of anionic surfactant and nonionic surfactant. The method of claim 8, The additive is a water-soluble metal covalent composition, characterized in that at least one selected from the group consisting of a lubrication enhancer, a coupling agent, an antioxidant, a non-ferrous metal corrosion inhibitor, an antirust additive and an antifoaming agent.