JPS6221864B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to the field of metal processing, and in particular to a metal work that can be processed excellently and is easy to handle. For example, rolling processing, forging processing, hot pressing processing,
In metal processing operations such as blanking, bending, drawing, stretching, cutting, punching, and turning, lubricants are generally used to facilitate the operations. Lubricant greatly improves metalworking operations in that it reduces the force required for metalworking operations, prevents sticking, reduces die wear, chips, etc. Additionally, lubricants often impart rust protection to the metal being processed. After processing, the metal is typically subjected to various chemical treatments (eg, application of conversion coating solutions), so cleaning operations are necessary between processing steps. Therefore, in addition to the above properties, it is preferred that the lubricant be one that can be easily removed from metal surfaces by conventional detergents. Hitherto, lubricants applied for this purpose have usually been liquids. The equipment used to apply such liquids has often been expensive to maintain and inconvenient to use. In addition, drying ovens are typically required to remove water and solvent carriers from the liquid lubricant, which also increases cost, operating and maintenance costs.
In addition, the liquid lubricants normally applied to metals naturally wet the metals and make them slippery, causing various troubles in the continuous feeding and handling of metal blanks. Accordingly, an object of the present invention is to provide a metal workpiece (ie, a metal article to be worked) having a lubricating composition on its surface, which can be processed easily and is easy to handle. In addition, the purpose of this invention is to provide lubricity, corrosion resistance,
It imparts a unique combination of properties to the metal being machined, such as extreme pressure resistance and wear resistance on the machined parts, and also coats the metal surface with a lubricant that is relatively easily removed from the metal surface during a cleaning process after the machining operation is complete. Our goal is to provide metal processed products that have the following characteristics. Furthermore, it is an object of the present invention to provide a novel composition for use in the above method. Furthermore, it is an object of the invention to provide a method in which a solid metalworking composition is applied to the metal by melting, thus eliminating the need for a drying oven and without the disadvantages associated therewith. be. Furthermore, it is an object of the present invention that the above composition, after being applied to the metal, solidifies to form a non-tacky and relatively slip-free film, thus providing an economical and consistent automated supply of metal blanks. The purpose is to provide a method that enables handling. Furthermore, it is an object of the present invention to apply a molten composition to the surface of a metal (e.g., wire, tube, etc.) that is moving at a relatively high speed, thereby depositing a metalworking composition on the surface. The object of the present invention is to provide a method capable of forming a solid film. The gist of the present invention for achieving the above objects is that the metal to be processed contains an ester of carboxylic acid, melts at about 30 to 100°C,
Another object of the present invention is to apply a composition that imparts lubricity to the metal. Preferably, the composition melts to form an easily flowable liquid that can be easily and effectively applied to the metal surface. One of the advantages of such compositions (hereinafter sometimes referred to as "hot melt compositions") is that
Metals coated with this are easier to handle under normal storage conditions than metals coated with known lubricants. A fundamentally essential feature of this hot melt composition is its ability to impart lubricity to the metal. Such lubricity can be defined in a number of ways well known to those skilled in the art, and by test methods that mimic metal working operations. In this invention, a lubricating composition is considered to provide lubricity to a metal workpiece if the lubricating composition results in a deviation of 100 foot-pounds or less when tested according to the method described below. The method described above involves rolling a cold rolled steel strip measuring 2" x 131/2" between two dies of an Instron Universal Tester, model TT-C. Before rolling, the edges of the strip are straightened, the entire strip is degreased with steam and wiped with a clean cloth. Next, a lubricant for stretching is uniformly applied to this, and it is placed in the above-mentioned testing machine. The two dies were tightened with a torque wrench set to 40 foot-pound torque.
The strip is pulled 2 inches through a die at a rate of 5 inches per minute. The force or "load" (in foot-pounds) required to pull the strip through the die and the deviation from a uniform load are recorded on a chart. As previously mentioned, this hot melt composition melts in the range of 30 to 100°C. Therefore, it is usually solid at normal temperature and pressure. Its preferred melting point is 35 to 70°C, particularly preferably 38 to 55°C. Preferably, the composition melts into an easily flowable liquid. Since this composition melts at temperatures of about 30°C to 100°C, 30°C
At temperatures below 100°C, it is a solid, so it cannot be applied to metal workpieces, and at temperatures above 100°C, it is too fluid and is easily removed from the metal workpiece and hardly adheres to the metal workpiece. There's nothing to do. Also, the melting point is less than 30℃ or 100℃
If it exceeds this range, it is not possible to impart a combination of properties such as lubricity, corrosion prevention, extreme pressure properties, and wear resistance to machined parts to the metal workpiece. Also, the melting point is 100
Compositions at temperatures above 0.degree. C. may decompose. The main component of this hot melt composition is an ester of carboxylic acid. (In this specification, references to the singular form shall also refer to the plural form unless the context requires otherwise. For example, the term "ester" may refer to a mixture of two or more esters.) Typical esters have the formula R
(COOH) _n acid and an organic hydroxy compound of formula R'(OH) _o . In these formulas, each of m and n is an integer of 1 to 3, and each of R and R' is a hydrocarbon group. The term "hydrocarbon group" as used herein refers to a group primarily having hydrocarbon characteristics within the meaning of this invention. Such groups include: (1) Hydrocarbon group. aliphatic (e.g. alkyl or alkenyl), alicyclic (e.g. cycloalkyl or cycloalkenyl), aromatic, aliphatic or alicyclic-substituted aromatic, aromatic-substituted aliphatic or alicyclic It doesn't matter if it's a family, etc. (2) Substituted hydrocarbon group. That is, groups containing non-hydrocarbon substituents which do not change the predominant hydrocarbon character of this group within the meaning of this invention. Such substituents will be apparent to those skilled in the art. (3) Hetero group. That is, groups which exhibit predominantly hydrocarbon character within the meaning of this invention, but which contain atoms other than carbon atoms in their chains or rings. Suitable heteroatoms will be apparent to those skilled in the art. For example, nitrogen, oxygen and sulfur. Generally, the number of such substituents or heteroatoms present for every 10 carbon atoms in the hydrocarbon group will be up to about 3, preferably up to 1. The aforementioned acids and organic hydroxy compounds are generally those in which R and R' are free of acetylenic unsaturation and conjugated diene unsaturation;
Preferably, it contains only one olefinic double bond in addition. It is common for there to be no more than one such olefinic double bond per ester molecule. The acids typically contain about 4 to 20 carbon atoms. Preferred acids are aliphatic polycarboxylic acids, especially those in the above formula in which m is 2 or 3 and R is a branched or straight-chain alkyl or alkylene group. Examples include propionic acid, butyric acid, stearic acid, oleic acid, benzoic acid, maleic acid, fumaric acid, succinic acid, adipic acid, glutaric acid, pimelic acid, sebacic acid, azelaic acid, suberic acid,
These are phthalic acid, isophthalic acid, citric acid and trimellitic acid. Particularly preferred acids are aliphatic dicarboxylic acids having about 5 to 10 carbon atoms. The organic hydroxy compounds typically contain at least about 10, generally about 10 to 25 carbon atoms. Usually, in the above formula,
n is 1 and R' is an alkyl group (which may be branched or straight chain). Examples of this include 1-butanol, 2-butene-1-
and commercially available mixtures of such alcohols. Preferred alcohols are at least about
Saturated aliphatic alcohols containing 10 carbon atoms, especially C ₁₄ -C ₂₀ alkanols (i.e.
saturated monohydric alcohols) and more preferably predominantly linear alkanols. From what has been described above regarding suitable acids and organic hydroxy compounds, it will be appreciated that a wide variety of carboxylic acid esters may be used in this invention. The esters include neutral esters and acidic esters (for example, monoesters of dicarboxylic acids), but neutral esters are preferably used. Both mono- and bis-esters of polyhydroxy compounds are used. Particularly preferred esters are
Adipic acid, azelaic acid or sebacic acid
Neutral esters with C ₁₄ to _{C 20} predominantly linear alkanols or commercial mixtures of such alkanols. Preferred hot melt compositions contain, in addition to the esters mentioned above, one or more rust inhibitors and/or extreme pressure property improvers. Among the suitable rust inhibitors are carboxylic acids and their derivatives. Here, the "derivative" used for such a carboxylic acid refers to the following. Anhydrous. Esters (acidic or neutral). In particular, lower (this refers to those with up to 7 carbon atoms) saturated aliphatic monohydroxy or polyhydroxy compounds (e.g. methanol, ethanol, 1-butanol, n-hexanol, ethylene glycol, pentaerythritol), or Made from epoxides (e.g. ethylene oxide, propylene oxide). As should already be clear, esters derived from epoxides are hydroxy esters. It will be appreciated that if the derivative is an ester, the hot melt composition of the invention will contain at least two esters. neutral, acidic or basic, such that the cation is a group metal, a group metal, aluminium, tin, cobalt, lead, molybdenum, manganese, nickel or ammonium (this includes substituted ammoniums such as amines); salt. For example, salts of free acids and salts of hydroxy esters of free acids. Lithium salts are preferred for rust protection. Amides and amide-imide mixtures. In particular,
Those derived from aliphatic amines, more preferably those derived from lower aliphatic amines. Preferred amines are alkylene polyamines, especially ethylene polyamines. Derivatives of the type mentioned above can be obtained from the acids by known reactions. The free acid, its lithium salt as well as its anhydride are most useful. Preferred are aliphatic mono- and polycarboxylic acids (and their derivatives as mentioned above) containing at least 8 carbon atoms. Particularly desirable are dibasic acids, especially anhydrides of succinic acids having the above-mentioned hydrocarbon substituents,
For example, the reaction of maleic acid or maleic anhydride with a hydrocarbon-based compound containing at least 6, preferably about 6 to 75 and more preferably about 10 to 20 carbon atoms (details below). Manufactured by (mentioned). Preferred hydrocarbon compounds for preparing the substituted succinic acids are substantially saturated petroleum distillates and olefin polymers, especially monoolefins having from 2 to about 10 carbon atoms (especially monoolefins having 2 to about 10 carbon atoms). It is derived from oligomers of olefins. Therefore, the hydrocarbon compound may be derived from polymers such as ethylene, propene, 1-butene, 2-butene, isobutene, 3-pentene, 1-octene, and the like. Further useful are interpolymers of the olefins just mentioned and polymerizable olefin compounds such as styrene, chloroprene, isoprene, paramethylstyrene, and piperylene. Generally, these interpolymers contain at least about 80%, preferably at least about 95%, by weight units derived from the aliphatic monoolefin.
Contains. Other suitable hydrocarbon compounds are mixtures of saturated aliphatic hydrocarbons such as highly purified high molecular weight white oils and synthetic alkanes. In some instances, the hydrocarbon-based compound contains active polar groups to facilitate reaction with low molecular weight acid-generating compounds. Preferred active polar groups are halogen atoms, especially chlorine atoms, but other suitable groups include sulfide groups, disulfide groups, nitro groups, mercaptan groups, ketone groups and aldehyde groups. As already mentioned, a preferred method for preparing the carboxylic acid or its derivatives is by reaction of maleic acid or its anhydride with a hydrocarbon compound, especially a compound such as propene. The reaction simply involves heating the two reactants in the presence or absence of a substantially inert organic liquid diluent. In this case, an excess of liquid reactant can be used as the reaction medium. Other suitable reactions include hydrocarbon substitution 1,4-
Those that oxidize butanediol etc. with potassium permanganate, nitric acid or other oxidizing agents, those that ozonolyze hydrocarbon-substituted 1,5-dienes, etc., and bis-organometallic derivatives such as hydrocarbon-substituted 1,2-dihalides. There are methods that produce dinitrile and carbonate it with carbon dioxide, and methods that produce dinitrile and hydrolyze it. All these reactions are well known in the art. A preferred extreme pressure agent is of the formula It is a salt of a phosphorus-containing acid represented by In this formula,
M is a group metal, aluminum, tin, cobalt, lead, molybdenum, manganese, nickel or ammonium, each of R ¹ and R ² is a hydrocarbon group, X ¹ , X ² , X ³ and X ⁴ each of is oxygen or sulfur, and each of a and b is 0 or 1. In the above formula, each of R ¹ and R ² is a hydrocarbon group, as described above. Preferably,
They contain no acetylenic unsaturation, usually no additional ethylenic unsaturation, and about 30
and preferably up to 12 carbon atoms. These are usually hydrocarbon groups such as methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, decyl, dodecyl, vinyl, decenyl, cyclohexyl, phenyl, etc. , all isomers thereof are also included. Particularly preferred is the case where R ¹ and R ² are lower alkyl groups (the term "lower" has already been defined). It will be appreciated that the phosphorus-containing acids from which salts of the above formula are derived include dialkyl phosphoric acids, dialkyl phosphinic acids and their thio derivatives. Particularly preferred are salts of phosphorodithioic acids, i.e. in the above formula a and b are each 1,
This is a compound in which each of X ¹ and X ² is oxygen, and each of X ³ and X ⁴ is sulfur. In these salts, M can be any of the metals mentioned or ammonium (including substituted ammonium salts such as amine salts). M is preferably zinc or lead, especially zinc. The hot melt compositions often contain up to about 15% by weight of the carboxylic acid or derivative thereof and/or up to about 25% by weight of the phosphate salt. In particular, the invention includes a lubricant that imparts lubricity to metals and includes at least one of the aforementioned esters of carboxylic acids and carboxylic acids or derivatives thereof, and phosphates. This composition is about 30 to
Melts at 100℃. A small amount (typically about
It is also within the scope of this invention to add other additives (0.01 to 5.0% by weight). Particularly preferred further additives are antioxidants, especially hindered phenols. Such materials are well known in the art. Other suitable additives include: Surfactants, usually nonionic surfactants such as oxyalkylated phenols. Auxiliary extreme pressure agents, such as chlorinated waxes, sulfurized hydrocarbons, sulfurized esters, etc. Corrosion and wear inhibitors and supplementary rust inhibitors. Friction modifiers, such as alkyl or alkenyl phosphates or phosphites in which the alkyl or alkenyl group contains about 10 to 40 carbon atoms and their metal salts, especially zinc salts, C ₁₀ to C ₂₀ Fatty acid amides, C ₁₀ ~
C ₂₀ alkyl amines, especially tallow amines and their ethoxylated derivatives, salts of the amines mentioned here with acids such as boric or phosphoric acid, which have been partially esterified as mentioned above;
C ₁₀ -C ₂₀ alkyl-substituted imidazolines and similar nitrogen heterocycles, sulfurized derivatives of whale oil and other fatty oils, derived from such oils and amine-formaldehyde condensates, especially tallow amines as mentioned above. Examples include gels derived from basic barium salts or basic calcium salts of sulfonic acids, and basic alkaline earth metal salts of sulfonic acids. Melting point modifiers, typically relatively low melting point esters such as dioctyl phthalate. When the hot melt composition contains two or more components, the composition is preferably obtained by uniformly mixing each component in liquid form. It may be preferable to use a substantially inert liquid diluent to assist in this mixing. A "substantially inert" diluent is one that does not react in a significant manner with the components of the hot melt composition under the conditions under which the mixing is conducted.
Preferred such diluents are liquids that serve as solvents for the components to be mixed. Such solvents will be apparent to those skilled in the art. Preferably, it is made of a nonpolar liquid such as benzene, toluene, xylene, or chlorobenzene. Once mixing is complete, it is preferred to remove this dilution, typically by evaporation. The table below lists typical hot melt compositions of this invention.

Table: Any metal to be processed can be processed by the method of this invention. An example of this metal is
Alloys containing ferrous metals, aluminum, copper, magnesium, titanium, zinc and manganese, as well as alloys thereof and other components such as silicon. The method of this invention includes any method in which the metal workpiece is coated with the hot melt composition described above prior to or concurrently with the processing operation. For example, the composition may be applied to a cutting blade or a rolling die and transferred to the metal workpiece by contact. Most commonly, however, the workpiece is coated with the hot melt composition prior to the processing operation. The invention also contemplates metalwork having a solid or liquid coating of the hot melt composition on its surface. Although the hot melt composition normally forms a continuous film over the entire surface of the processed product, it is also within the scope of this invention to form a film on less than the entire surface. There are no limitations to the physical state of this hot melt composition when applied to a metal surface. It can therefore be applied as a solid (by rubbing) or as a liquid (by brushing, spraying, dipping, flow coating, roll coating, reverse roll coating, etc.). For ease and convenience of application, it is preferred to apply the composition in liquid form, in which case the metal is subsequently cooled to solidify the hot melt composition, or it can be applied while in liquid form. May be fed directly into metal fabrication operations. However, it is an advantage of the present invention that the hot melt composition solidifies to form a solid, non-stick, non-slip film on the metal workpiece, thus providing convenient, safe and inexpensive handling. That's why. To this end, the present invention heats and melts a solid metal processing composition at room temperature and pressure, such as the hot melt composition described above, to facilitate flow and uniform dispersion on the metal. Also includes a method of application comprising maintaining a temperature, applying the molten composition to the metal workpiece to form a film of the composition on the metal workpiece, and cooling and solidifying the film. It is something. The surface temperature of the metal at the time the hot melt composition is applied can vary, for example, from room temperature to just below the decomposition temperature of the composition. Factors that influence or determine the temperature of the metal at the time the composition is applied include the process to which the metal is subjected prior to or subsequent to application of the composition; and the temperature of the composition at the time of application. Using the hot melt compositions described above, it has been found to be particularly useful that the temperature of the metal surface at the time of application is between about 20 and 125°C. The temperature at which the hot melt composition is applied is above its melting point (preferably at least 10° C. above and usually about
(20 to 40°C higher). Prior to coil winding, the hot melt composition can be manufactured using existing equipment, such as coil winding machines used in steel mills, or which quickly solidifies at room temperature and is dry, non-tacky, and relatively non-slip. This allows it to be applied to metals using standard handling equipment such as take-up rollers and feed rollers in a minimum amount of space. Statzker etc. are also used. In the method of application of this invention, a drying oven is not required since the hot melt composition does not contain water or solvent to be removed. A method of applying the present invention will be specifically described below with reference to the accompanying drawings. A metal sheet or strip processing line L is schematically shown in FIG. 1 and includes a preferred apparatus 1 for applying a hot melt composition to a metal workpiece S. The metal workpiece S may be in the form of a strip or sheet cut to the desired length as shown, or it may be a continuous coil strip.
The continuous coil strip may be passed through the device 1 and then coiled again, or cut into sheets and stacked. In this case, conventional unwinding machines, recoiling machines and/or destackers, stackers, etc. are used. Regardless of the length of the metal workpiece S, it can be moved through the processing line L by means of conventional conveying and supply rolls 3. In the coating device 1 illustrated in FIGS. 1 and 2, the reservoir 5 of the hot melt composition M is located near (preferably below) the applicator for applying this composition to the metal. The composition is preferably heated by passing it through heating means such as a steam coil 6 (electrical or other heating methods are also suitable). The steam coil 6 is typically located within the storage tank 5 and this provides good temperature control over a suitable range such as 30 to 80°C to melt the composition and melt the composition. It is suitable for maintaining the composition in a liquid state even after it has been applied to the metal, and for preventing the composition from being heated above the decomposition temperature. The liquid composition is conveyed by a pump 15 through a circulation pipe 11 to an applicator. This pump 15 is, of course, of sufficient capacity to supply the liquid composition to the applicator at the desired pressure, e.g. storage tank 5
It has sufficient capacity to recirculate to As already mentioned, the applicator can be a spray head, brushing means, flow coating means, roll coater, or the like. A roll coater is preferred, the one shown in Figures 2 and 3 having two rubber applicator rolls 8 (which may be heated).
one of the rolls 8 is for coating each side of the workpiece 5. As shown in FIG. 3, the doctor roll 9 (which is in contact with the applicator roll 8) is horizontally adjustable to control the thickness of the composition M on the applicator roll 8; It is vertically adjustable to control the amount of composition M transferred to the workpiece S. A receiver 10 below the applicator returns excess hot melt composition M to the reservoir 5. The flow of hot melt composition M to the applicator can be controlled by valve 14. To assist in such control, the circulation pipe 11
It is desirable to divert a portion of the composition flow through the applicator to the applicator and recirculate it to the reservoir 5 through a suitable diverter tube 12 and valve 13. If steam, in particular low pressure steam, is used as the heat source for melting the composition and maintaining its temperature, this steam is introduced into the circulation pipe 11 via the conduit 16 and the valve 17 so that at the start of the operation the pipe 11 This has the advantage of being able to preheat and prevent solidification and deposition of the composition at the end of the operation. Alternatively, the circulation pipe 11 may be provided with a jacket in order to circulate the steam around it both at the beginning and at the end of the operation. It is also desirable to route the exhaust line 19, which carries the steam from the steam coil 6 to the aggregation trap 19, around or within the housing of the pump 15 to prevent solidification and build-up of the hot melt composition. An applicator (second applicator) suitable for adjusting the coating thickness of the hot melt composition on the surface of the metal workpiece
In addition to, or in place of, the use of coatings (such as those shown in the figures), other coating thickness control means may be used. Examples include temperature control of the hot melt composition and/or metal workpiece, selection of said compositions having different melting points (other factors being equal, the higher the melting point, the faster it will solidify;
There are also restrictions on the rate of cooling of the metal after the composition has been applied to the metal (thinner coating formed). The thickness of the coating can also be controlled using suitable removal means such as heated squeeze rubber rolls, air blowing at a defined temperature, and the like. Since the hot melt composition of the present invention does not contain water or solvent, no drying oven is required to dry the metal after it leaves the applicator 1. However, in order to cool the applied hot melt composition to its solidification temperature and form a solid, usually continuous, film on the metal, a suitable amount of time is required between the time the metal leaves the applicator 1 and before it is stacked or rewound. It is preferable to give distance. For example, if the metal is moving at a speed of 600 feet/minute,
The distance is 40 feet. This distance depends not only on the speed at which the metal moves, but also on the type and thickness of the metal, as well as its temperature. 1st
The figure shows a cleaning bath 25 for cleaning mill oil from metals, for example temperature controllable over a range of 35 to 75°C, and also a water rinsing bath temperature controllable over a similar temperature range. 26 is shown. Desirably, a pair of squeezing rubber rolls 27 are provided near the downstream end of the cleaning bath 25 to prevent contamination due to rinsing. Also,
A similar squeezing rubber roll 28 is provided near the downstream end of the rinse bath 26. In addition, air blowing may be provided. By means of the method of the invention, metal workpieces are obtained which are adequately lubricated during subsequent processing operations and during rolling, are protected against rust and are easily cleanable by conventional cleaning methods.

[Brief explanation of the drawing]

1 is a schematic diagram illustrating a metal processing line including equipment for applying a hot melt composition to metal workpieces according to the application method of the invention; FIG. FIG. 2 is a cross-sectional view taken along line 2--2 of FIG. FIG. 3 is a cross-sectional view taken along line 3-3 of FIG. S... Metal work piece, M... Hot melt composition, 1... Composition application device, 3... Transportation supply roll, 5... Storage tank, 6... Steam coil, 8... Application roll, 11... Circulation Pipe, 15...pump,
16... Conduit, 25... Cleaning bath.

Claims (1)

[Claims] 1 Comprising an ester of an alkanol having at least about 10 carbon atoms and an aliphatic polycarboxylic acid having about 4 to 20 carbon atoms, and at a temperature of about 30 to 100°C. A metal workpiece whose surface has a coating of a composition that melts within a temperature range. 2 Esters of alkanols having at least about 10 carbon atoms and aliphatic polycarboxylic acids having about 4 to 20 carbon atoms, carboxylic acids or derivatives thereof and formulas (where M is a group metal, aluminium, tin, cobalt, lead, molybdenum, manganese, nickel or ammonium, R ¹ and
Each of R ² is a hydrocarbon group, each of X ¹ , X ² , X ³ and X ⁴ is oxygen or sulfur, and a
and b is 0 or 1), which imparts lubricity to the metal surface, and which provides lubricity to the metal surface, and
A metal workpiece whose surface has a film of a composition that melts within a temperature range of 100°C to 100°C.