JP5036137B2 - Water-based rust preventive lubricant and metal processing method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To develop a rust preventive composition which exhibits excellent rust preventive effect when mixed with a water base lubricant used for working of metals, and to provide a water base rust preventive lubricant combining excellent rust preventive lubricating performance and stability by using the rust preventive composition. <P>SOLUTION: The water base rust preventive lubricant having excellent rust preventive lubricating performance and stability comprises water soluble alkali silicate as a rust preventive component, and comprises an organic silicon compound represented by general formula (2) as a gelling suppression component for the silicate. The rust preventive lubricating method and metal working method use the above lubricant. In the formula, n is an optional integer; m is an integer of 1 to 4; and R is a hydroxyl group or a 1 to 4C hydrocarbon group. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention relates to a rust preventive composition, an aqueous lubricant using the same, and a metal processing method using the aqueous rust preventive lubricant, and more specifically, a rust preventive composition having excellent rust preventive ability. And an anti-rust agent composition in an aqueous lubricant, it exhibits excellent lubrication when performing metal cutting, cutting, drilling, polishing, etc., and corrosion of the metal material to be processed The present invention relates to a water-based rust preventive lubricant and a rust preventive lubrication method that can effectively prevent rust.

  For example, as a rust inhibitor for iron-based metal materials such as steel, non-ferrous metal materials such as aluminum and titanium, especially aluminum and its alloys, phosphorus-based rust preventives such as phosphates and phosphate esters, or organic acids Organic rust preventives such as amine salts and heterocyclic compounds are widely used.

  However, even if these rust preventives are used in a water-based lubricant for processing such as metal cutting, cutting, drilling, and polishing, a satisfactory rust preventive effect may not be obtained. The reason is considered as follows. That is, the water-based lubricant as described above is usually used diluted 10 to 30 times with water, so that it is difficult to exert a satisfactory rust preventive effect due to insufficient concentration of the rust preventive component. Is generally alkaline (pH 8 or higher), and since the oil component in the aqueous lubricant acts as a corrosive component, especially in the case of aluminum or an alloy thereof, it is considered that the environment is easily corroded. Yes. In addition, phosphorus-based rust preventives also have a major problem of promoting the deterioration of spoilage caused by bacteria and fungi in the aqueous lubricant as described above.

  On the other hand, water-soluble alkali silicates represented by sodium silicate have been known for a long time as rust preventives for aluminum alloys, etc., and are very inexpensive and easily available. Exhibits rust prevention effect. Moreover, since it does not contain a phosphorus component, it does not promote the deterioration of the aqueous lubricant. However, alkali silicate has a serious disadvantage in practical use that it immediately causes gelation in an aqueous lubricant, and improvement is required from the viewpoint of stability over time.

  On the other hand, Patent Document 1 describes that when a specific silane compound is blended in an aqueous lubricant as a metal corrosion inhibitor, corrosion of a metal material such as an aluminum alloy can be prevented. Patent Document 2 discloses that an organosilicon compound obtained by hydrolyzing a hydrolyzable silane containing a nitrogen atom-containing organic group or a partially decomposed product thereof and a hydrolyzable silane or a partially hydrolyzed product thereof It is described that if it is added to a water-based lubricant as a corrosion inhibitor, it is effective for preventing corrosion of an aluminum alloy or the like.

However, in order to obtain a satisfactory corrosion prevention effect with the techniques described in Patent Documents 1 and 2, a silane compound or an organosilicon compound must be blended in a high concentration in an aqueous lubricant. In Document 1, since the silane compound is a monomer component, it is difficult to form a rust preventive film on the surface to be processed at the time of processing such as cutting or cutting, and there is a problem in sustainability of the rust prevention effect. Therefore, when a large amount of a silane compound is added to the aqueous lubricant in order to enhance the rust prevention effect, the system is alkaline, so that gelation occurs immediately and a problem arises in the stability as an aqueous lubricant.
Japanese Patent No. 3267653 JP 2003-268396 A

  The present invention has been made under these circumstances, and its purpose is to exhibit an excellent rust prevention effect by blending with a water-based lubricant used during processing such as metal cutting, cutting, drilling and polishing. In addition, by providing an appropriate amount of the rust preventive composition in an aqueous lubricant, an aqueous rust preventive lubricant having excellent rust preventive lubrication performance and stability is provided. Furthermore, it is providing the rust prevention lubrication method and metal processing method using this water-based rust prevention lubricant.

The rust preventive composition according to the present invention that has solved the above problems includes a water-soluble alkali silicate represented by the following general formula (1) as a rust preventive component, and gelation of the alkali silicate It is characterized in that it contains an organosilicon compound represented by the following general formula (2) as a suppression component.
M ₂ O · nSiO ₂ (1)
(In the formula, M represents an alkali metal, and n represents a positive number exceeding 0 and not exceeding 10)

(In the formula, n is an arbitrary integer, m is an integer of 1 to 4, and R represents a hydroxyl group or a hydrocarbon group having 1 to 4 carbon atoms)

  Among the organosilicon compounds represented by the above formula (2), an organosilicon compound represented by the following general formula (3) is particularly preferable.

(In the formula, n represents an arbitrary integer)

Further, the aqueous rust preventive lubricant according to the present invention is preferably blended with the above rust preventive composition in an aqueous lubricant, and preferably contains the alkali silicate when the total amount of the aqueous rust preventive lubricant is 100 parts by mass. Aqueous rust preventive lubrication with excellent rust prevention and lubricity when blended so that the amount is 0.01 to 10 parts by mass as SiO ₂ and the content of the organosilicon compound is 0.01 to 10 parts by mass This is also included in the technical scope of the present invention.

  Then, the above-mentioned aqueous rust preventive lubricant is used as a rust preventive lubricant for a metal which also serves as a rust preventive lubricant, or a metal with a water diluted solution of the aqueous rust preventive lubricant present on the processed surface. A metal anti-rust lubrication method for cutting, cutting, drilling or polishing a material is also a preferred embodiment of the present invention. The type of metal material to be processed is not particularly limited, and includes iron-based metal materials such as steel, non-ferrous metals such as aluminum, copper, and titanium, and alloys. Among these, the features of the present invention are most effective. It is aluminum or an aluminum alloy that is exhibited.

  According to the present invention, it is possible to use an alkali silicate that is inexpensive and excellent in rust-preventing ability as a rust-preventing component, and to prevent deterioration over time due to gelation, which is a drawback, by using a specific organosilicon compound in combination. In addition, since it does not contain any components that cause spoilage, the storage stability is good, and an inexpensive and high-performance water-based rust preventive lubricant can be provided. In addition, by using this water-based rust preventive lubricant, it is possible to provide a rust preventive lubrication method and a metal processing method suitable for practical use, which are both excellent in rust prevention and lubrication.

  The rust preventive composition of the present invention contains a water-soluble alkali silicate as a rust preventive component, and contains a specific organosilicon compound as a gelling suppression component of the alkali silicate.

  Hereinafter, the action and configuration of the water-soluble alkali silicate and the organosilicon compound constituting the present invention will be described.

  The water-soluble alkali silicate is a component that exhibits an original anticorrosive action as a rust preventive composition, and is represented by the general formula (1), specifically, sodium orthosilicate, sesquisilicate sodium, meta Examples include sodium silicate, No. 1 sodium silicate, No. 2 sodium silicate, No. 3 sodium silicate, No. 4 sodium silicate, potassium silicate, lithium silicate, and the like. Of these, sodium orthosilicate and potassium silicate are particularly preferable.

  These water-soluble alkali silicates exhibit a metal corrosion inhibition effect by chemisorbing on the surface of the metal in an aqueous medium to form a rust preventive film. It exists as a stable solution in alkaline aqueous media. However, when the pH is lower than 11, it gradually gels and becomes insoluble and separates, and the rust prevention effect also decreases. Furthermore, in an aqueous lubricant having a pH of about 8 to 11, gelation of alkali silicate is further promoted under the influence of an oily agent component such as a fatty acid. Therefore, there is a case where a solid alkali silicate is dissolved in an aqueous solution immediately before use to prepare a solution and used in a state as fresh as possible.

  However, in consideration of handling workability and process control, it is desirable that the gel is not gelled even after preparation as an aqueous liquid and is stable not only in appearance but also in rust prevention performance over the long term. Therefore, the inventors have studied various additives in order to keep the alkali silicate stable for a long period of time. As a result, when an appropriate amount of the organosilicon compound represented by the general formula (2) is blended, the stability as an aqueous solution of an alkali silicate and further as an aqueous lubricant containing an alkali silicate is remarkably improved. The inventors have found out that the present invention can not only prevent appearance deterioration but also exhibit extremely stable performance in terms of rust prevention ability, and arrived at the present invention.

  The organosilicon compound having such a stabilizing effect is a compound represented by the general formula (2), and the substituent represented by R in the organosilicon compound is a hydroxyl group or a hydrocarbon group having 1 to 4 carbon atoms. These organosilicon compounds may be used alone or in combination of two or more in any combination.

  The organosilicon compound represented by the general formula (2) can be obtained by the following reaction. That is, when an alkoxysilane compound having an epoxy group as shown below is heated to a temperature of about 60 to 100 ° C. in an aqueous medium in the presence of an alkali, a hydrolysis reaction occurs as shown by the following chemical formula, and an epoxy A polysiloxane skeleton is formed by ring opening of the group and elimination of the alkoxy group, and an organosilicon compound represented by the formula (2) is obtained.

(In the formula, n is an arbitrary integer, m is an integer of 1 to 4, R ^a and R ^b are a methyl group or an ethyl group, R ^c is a methoxy group, an ethoxy group, or a hydrocarbon group having 1 to 4 carbon atoms, R Represents a hydroxyl group or a hydrocarbon group having 1 to 4 carbon atoms)

Examples of the alkali used in the above reaction include common alkalis such as sodium hydroxide and potassium hydroxide, and the alkali component (M ₂ O) of the water-soluble alkali silicate shown as the general formula (1). Can also be used as alkali.

  Specific examples of the alkoxysilane compound having an epoxy group used in the above reaction include γ-glycidoxymethyltrimethoxysilane, γ-glycidoxymethyltriethoxysilane, γ-glycidoxymethylmethyldimethoxysilane, γ-glycidoxymethylmethyldiethoxysilane, γ-glycidoxymethylethyldimethoxysilane, γ-glycidoxymethylethyldiethoxysilane, γ-glycidoxymethylpropyldimethoxysilane, γ-glycidoxymethylpropyldioxysilane Ethoxysilane, γ-glycidoxymethylbutyldimethoxysilane, γ-glycidoxymethylbutyldiethoxysilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glycidoxyethyl Methyldimethoxysilane, γ-glyce Sidoxyethylmethyldiethoxysilane, γ-glycidoxyethylethyldimethoxysilane, γ-glycidoxyethylethyldiethoxysilane, γ-glycidoxyethylpropyldimethoxysilane, γ-glycidoxyethylpropyldiethoxysilane, γ-glycidoxyethylbutyldimethoxysilane, γ-glycidoxyethylbutyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane Γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylpropyldimethoxysilane, γ-glycidoxypropylpro Pyrdiethoxysilane, γ-glycidoxypropylbutyldimethoxysilane, γ-glycidoxypropylbutyldiethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, γ-glycid Xybutylmethyldimethoxysilane, γ-glycidoxybutylmethyldiethoxysilane, γ-glycidoxybutylethyldimethoxysilane, γ-glycidoxybutylethyldiethoxysilane, γ-glycidoxybutylpropyldimethoxysilane, γ- Examples thereof include glycidoxybutylpropyldiethoxysilane, γ-glycidoxybutylbutyldimethoxysilane, and γ-glycidoxybutylbutyldiethoxysilane.

  Among these, γ-glycidoxypropyltrimethoxysilane is particularly preferable. When this compound is heated and reacted in the presence of an alkali, the organosilicon compound represented by the general formula (3) is obtained.

  The rust preventive composition of the present invention contains the alkali silicate as a rust preventive component and contains the organosilicon compound as a gelation suppressing component of the alkali silicate, and water is used as a solvent, but is necessary. Thus, a mixed solvent to which water-soluble solvents such as alcohols, ketones such as acetone and methyl ethyl ketone, ethers such as dimethyl ether, and esters such as acetic acid ester are added can be used.

The content of each of the above components in the rust preventive composition according to the present invention is not particularly limited as long as it can be formulated as a liquid in consideration of the rust preventive ability and stability, but preferably the rust preventive composition. When the amount of the whole product is 100 parts by mass, the content of the silicate is 1 to 20 parts by mass, more preferably 2 to 10 parts by mass as the SiO ₂ component, and the content of the organosilicon compound is 1 to 50 parts by mass, more preferably 5 to 20 parts by mass.

  The aqueous rust preventive lubricant of the present invention is an aqueous lubricant containing an oily agent, an alkanolamine, and water (further, if necessary, an extreme pressure additive, a surfactant, a rust preventive, a preservative, an antifoaming agent, etc.). The antirust ability is imparted by blending the antirust composition.

A preferable content of each of the above components in the aqueous rust preventive lubricant is such that when the amount of the entire aqueous rust preventive lubricant is 100 parts by mass, the content of the alkali silicate is 0.01 parts by mass as a SiO ₂ component. Or more, 10 parts by mass or less, more preferably 0.02 parts by mass or more and 1 part by mass or less; the content of the organosilicon compound is 0.01 parts by mass or more and 10 parts by mass or less, more preferably 0.02 parts by mass. Or more, 1 part by mass or less; the content of the oily agent is 10 parts by mass or more and 90 parts by mass or less, more preferably 20 parts by mass or more and 70 parts by mass or less; the content of alkanolamine is 3 parts by mass or more and 30 parts by mass. Part or less, more preferably 5 parts by mass or more and 20 parts by mass or less.

  By the way, if the alkali silicate content is insufficient, the rust prevention ability seems to be insufficient, and conversely if the alkali silicate content is too high, the stability of the aqueous rust preventive lubricant is increased despite the combined use of organosilicon compounds. It tends to decline. In addition, when the content of the organosilicon compound is insufficient, the gelation suppressing effect on the alkali silicate becomes insufficient. Conversely, when the content of the organosilicon compound is too large, the gelation suppressing effect on the alkali silicate is saturated. However, adding more than that will only increase the cost, which is economically wasteful.

  In putting the aqueous rust preventive lubricant of the present invention into practical use, it is used for metal processing (cutting, cutting, drilling, polishing, etc.) as a 10-30 times diluted water. At this time, the pH of the water dilution is about 8 to 11, but in the present invention, the above-described organosilicon compound is coexisted with the alkali silicate, so that excellent gelation suppression is maintained, and the gel is formed during processing. There is no fear that the product will be generated and the rust prevention effect will be reduced, or that the appearance of the processed product will be impaired by the adhesion of the gel-like product.

  As described above, the water dilution obtained by diluting the aqueous rust preventive lubricant of the present invention with water contains an alkali silicate as the rust preventive component in addition to the lubricant component, and is on the metal processed surface. It forms a rust preventive film and exerts a rust preventive effect, and the coexisting organosilicon compound also prevents gelation during use of the alkali silicate, so regardless of the type of metal or type of processing A wide range of lubrication and rust preventives for cutting, cutting, drilling, and polishing non-ferrous metals such as steel, non-ferrous metals such as aluminum and titanium, and their alloys. It can be used effectively. However, when the water-based rust preventive lubricant of the present invention is used on aluminum and its alloys that are susceptible to corrosion due to oily agent components for lubrication in an alkaline environment, the characteristics of the present invention are exhibited more effectively, and excellent lubrication prevention is achieved. It is preferable because it exhibits rust ability.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. It is also possible to carry out and they are all included in the technical scope of the present invention.

Experimental Example A sample solution of the rust preventive composition is prepared at a blending ratio shown in Table 1 below. And about each, the stability test and the antirust test were done by the following method, and the result shown in Table 2, 3 was obtained.

[Examples 1-7]
An alkali silicate and γ-glycidoxypropyltrimethoxysilane are dissolved in water at the blending ratio shown in Table 1 below, and heated and stirred at 90 ° C. for 2 hours to prepare a clear aqueous liquid. This is used as a sample solution of the rust inhibitor composition. At this time, γ-glycidoxypropyltrimethoxysilane reacts with the alkali content of the alkali silicate to produce the organosilicon compound represented by the general formula (3).

[Comparative Examples 1-3]
The alkali silicate is dissolved in water at room temperature at the blending ratio shown in Table 1 below to prepare a clear aqueous liquid. This is used as a sample solution of the rust inhibitor composition.

[Comparative Example 4]
Γ-Glycidoxypropyltrimethoxysilane is dissolved in water at room temperature at the blending ratio shown in Table 1 below to prepare a clear aqueous liquid. This is used as a sample solution of the rust inhibitor composition.

"Stability test"
A sample solution of a rust preventive composition prepared with a formulation shown in Table 1 in 99 g of an aqueous lubricant containing 10 parts by mass of an oily agent, 20 parts by mass of alkanolamine and 70 parts by mass of water and having a pH of 9.2. 100 g of a water-based anti-rust lubricant containing 1 g of each was put in a glass bottle with a capacity of 200 cc, sealed, placed in a constant temperature bath at 40 ° C., and occasionally shaken to maintain the same temperature. Check the adhesion status visually.

"Rust prevention test"
A sample solution of a rust preventive composition prepared with a formulation shown in Table 1 in 99 g of an aqueous lubricant containing 10 parts by mass of an oily agent, 20 parts by mass of alkanolamine and 70 parts by mass of water and having a pH of 9.2. 1 g of each is blended to prepare 100 g of an aqueous rust preventive lubricant. And about the thing immediately after preparation of this aqueous | water-based antirust lubricant, and what was preserve | saved for one month in a 40 degreeC thermostat, each is diluted with water 20 times amount to make a water dilution liquid. The pH of each of the obtained water dilutions was about 9.2. Using this water diluted solution, a semi-immersion test (25 ° C., 2 days) of an aluminum alloy plate (JIS H 4000 A1050P) is performed in accordance with JIS K 2241, 7.9 (cutting fluid: metal corrosion test method). The rust prevention ability was evaluated according to the following criteria.
A: No discoloration, B: Slight discoloration, B: Brown discoloration, X: Black discoloration

  From Tables 1 to 3, it can be analyzed as follows.

  Example No. Examples 1 to 7 are examples that satisfy the specified requirements of the present invention, and contain an appropriate amount of an alkali silicate and an organosilicon compound that serves as a gelation inhibiting component of the silicate. Even after storage for 6 months, it is stable without causing gelation and has an excellent rust prevention ability.

  However, in Comparative Examples 1 to 3 in which an alkali silicate is used alone, the rust preventive ability immediately after production is good, but when stored at 40 ° C., a gel-like product is generated in just one day, and accordingly, rust prevention is performed. The performance is also greatly degraded. Further, if γ-glycidoxypropyltrimethoxysilane is used alone without being used in combination with an alkali silicate, the rust prevention effect is inferior and cannot be practically used.

Claims (6)

Contains a water-soluble alkali silicate represented by the following general formula (1) as a rust preventive component, an organosilicon compound having a polysiloxane skeleton represented by the following general formula (2) as a gelation inhibiting component of the silicate, and water And
When the total amount of the aqueous rust preventive lubricant is 100 parts by mass, the content of the silicate is 0.01 to 10 parts by mass as SiO ₂ and the content of the organosilicon compound is 0.01 to 10 parts by mass . ,
An aqueous rust preventive lubricant having a pH of 8 to 11 .
M ₂ O · nSiO ₂ (1)
(In the formula, M represents an alkali metal, and n represents a positive number exceeding 0 and not exceeding 10)
(In the formula, n is an arbitrary integer, m is an integer of 1 to 4, and R represents a hydroxyl group or a hydrocarbon group having 1 to 4 carbon atoms) The aqueous rust preventive lubricant according to claim 1, wherein the organosilicon compound is an organosilicon compound represented by the following general formula (3).
(Where n represents an arbitrary integer)   A metal rust preventive lubrication method, wherein the water-based rust preventive lubricant according to claim 1 or 2 is used as a lubricant that also serves as rust preventive.   When processing a metal material, the metal material processing method characterized by processing in the state which made the water dilution liquid of the water-based antirust lubricant described in the said Claim 1 or 2 exist in the processing surface.   The processing method according to claim 4, wherein the processing of the metal material is cutting, cutting, drilling or polishing.   The processing method according to claim 4 or 5, wherein aluminum or an aluminum alloy is used as the metal material.