JP2015183150A - Lubricant for plastic processing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel lubricant that is, even without the use of water-soluble inorganic salt having large environmental load, excellent in heat resistance, and that can exhibit, in the plastic processing of metallic material, excellent lubrication capability even in cold forging of large surface area expansion and the like.SOLUTION: The lubricant for plastic processing comprises at least one of organic phosphonic acids, organic phosphoric acid esters, and neutralization salts thereof, and a lubricating component.

Description

  The present invention relates to a plastic working lubricant, a metal material coated with the lubricant, and a method for producing a plastic worked metal material.

  Friction that occurs in plastic processing such as forging, wire drawing, tube drawing, roll forming, and pressing of metal materials causes increase in processing energy and heat generation. Conventionally, various lubricants have been used for plastic processing. It has been. For example, liquid lubricating oils such as mineral oil, synthetic oil and vegetable oil have been used for a long time. Although these lubricating oils can be applied to relatively simple plastic processing, the lubrication performance is insufficient in plastic processing that slides under high surface pressure and generates a large amount of heat.

  Therefore, in plastic working with large heat generation, there is a wide range of methods for forming a solid film on the surface of a metal material and suppressing direct contact between a processing tool such as a mold and the metal material to be processed. It has been adopted. As such a method, for example, a bond treatment in which a solid film such as a phosphate film is formed is widely adopted. In the bond treatment, a phosphate film is formed as a carrier on the surface of the metal material by a chemical reaction, and then sodium stearate or the like is adhered as a lubricant. Bonding treatment is widely used in plastic working with great heat generation by sliding under high surface pressure because it has excellent lubrication performance.

  However, in a method using a chemical reaction such as a bonder process, a pickling process and a lot of water washing processes are required between applying a lubricant to a metal material and performing plastic working. There is a problem of becoming longer. In addition, such a method requires a large amount of washing water, and there is a problem that a large amount of industrial waste such as sludge from the chemical conversion film is generated. Furthermore, temperature management for controlling the chemical reaction is also required, and there is a problem that the manufacturing cost increases.

  Thus, in recent years, attempts have been made to improve the lubrication performance of lubricants using solid coatings that do not use such chemical reactions. For example, Patent Document 1 discloses a method of forming a solid film by immersing a metal material in an aqueous solution or aqueous dispersion containing a synthetic resin and a water-soluble inorganic salt and drying it.

JP 2000-63880 A

  In a lubricant using a solid film that does not use a chemical reaction such as a bond treatment, such as the lubricant disclosed in Patent Document 1, generally, a synthetic resin and a water-soluble inorganic salt are the main components. The inorganic inorganic salt imparts the solid film with a strength that can withstand plastic working. As the water-soluble inorganic salt used in such a lubricant, borate or the like is used. However, water-soluble inorganic salts such as borates have a problem that the environmental load is large when discarded as industrial waste after use.

  Furthermore, in recent years, among plastic working, there is a demand for plastic working lubricants that can be suitably applied to cold forging with a large surface area expansion, but conventional plastic working containing a water-soluble inorganic salt such as borate. It has been difficult to apply a lubricant for cold forging with a large surface area.

  Under such circumstances, the present invention is excellent in heat resistance without using a water-soluble inorganic salt having a large environmental load, and in lubrication excellent in cold forging with a large surface area in plastic processing of metal materials. The main purpose is to provide a new lubricant that exhibits its performance.

The present inventor has intensively studied to solve the above problems. As a result, in a lubricant using a solid film that does not use a chemical reaction such as a bonde treatment, a water-soluble inorganic salt having a large environmental load, which has been conventionally used to give the solid film a strength that can withstand plastic working. Even if it is not used, it is excellent in heat resistance by using a plastic working lubricant containing at least one of organic phosphonic acid, organic phosphoric acid ester, and neutralized salts thereof, and a lubricating component. It has been found that in plastic working, excellent lubricating performance can be exhibited even in cold forging with a large surface area expansion.
In plastic processing of metal materials, generally, several hundred or more metal materials are continuously processed by a processing tool such as a mold. For this reason, the lubricant adhering to the mold or the like is gradually accumulated in the mold until cleaning or the like is performed. When lubricant accumulates in a mold or the like, the dimensional accuracy of the mold decreases, and it becomes impossible to perform plastic processing with a desired accuracy on a metal material gradually. Further, when the lubricant is accumulated in the mold or the like, there is a problem that resistance due to the accumulated lubricant is generated, and the processing energy necessary for plastic working is gradually increased. On the other hand, the plastic working lubricant as described above is excellent in seizure resistance to a processing tool or metal material after being subjected to plastic processing of a metal material, has high peelability, and is air blown after plastic processing. It has also been found that it has an unexpected effect that the accumulation of lubricant in a mold or the like can be effectively suppressed.
The present invention has been completed by further studies based on these findings.

［一般式（３）中、Ｒ²は、水素原子又はメチル基であり、Ｒ³は、炭素数２〜１２のアルキレン基であり、ｍは１〜３０の整数であり、Ｍ¹及びＭ²は、それぞれ独立に、水素原子、アルカリ金属、アルカリ土類金属、アルキルアンモニウム基、置換アルキルアンモニウム基、アルキル基、ヒドロキシアルキル基、又はアルケニル基である。］
項７． 前記有機ホスホン酸ポリマー及び前記有機リン酸エステルポリマーが、それぞれ、重合性二重結合を有するカルボン酸、重合性二重結合を有するスルホン酸、及び重合性二重結合を有するカルボン酸エステルからなる群から選択された少なくとも１種を単量体としてさらに含む、項３〜６のいずれかに記載の塑性加工用潤滑剤。
項８． 前記有機ホスホン酸がアルキルホスホン酸であり、前記有機リン酸エステルが、リン酸でんぷんである、項１または２に記載の塑性加工用潤滑剤。
項９． 前記有機ホスホン酸の中和塩及び前記有機リン酸エステルの中和塩の中和度が、それぞれ、１０％以上である、項１〜８のいずれかに記載の塑性加工用潤滑剤。
項１０． 前記潤滑成分が、ワックス、ポリテトラフルオロエチレン、炭化珪素、窒化ホウ素、脂肪酸またはその塩、脂肪酸アミド、二硫化モリブデン、グラファイト、フッ化黒鉛、雲母、及びメラミンシアヌレートからなる群から選択された少なくとも１種である、項１〜９のいずれかに記載の塑性加工用潤滑剤。
項１１． 前記有機ホスホン酸、前記有機リン酸エステル、及びこれらの中和塩の少なくとも１種の合計１００質量部に対して、前記潤滑成分を１〜９５質量部含む、１〜１０のいずれかに記載の塑性加工用潤滑剤。
項１２． 水溶性無機塩を実質的に含まない、項１〜１１のいずれかに記載の塑性加工用潤滑剤。
項１３． 前記有機ホスホン酸、前記有機リン酸エステル、及びこれらの中和塩の少なくとも１種が水に溶解しており、前記潤滑成分が前記水に分散または溶解している、水分散体または水溶液の形態である、項１〜１２のいずれかに記載の塑性加工用潤滑剤。
項１４． フィラーをさらに含む、項１〜１３のいずれかに記載の塑性加工用潤滑剤。
項１５． 項１〜１４のいずれかに記載の塑性加工用潤滑剤が表面に塗布された金属材料。
項１６． 項１〜１４のいずれかに記載の塑性加工用潤滑剤を金属材料の表面に塗布する工程と、
前記塑性加工用潤滑剤が表面に塗布された金属材料を塑性加工する工程と、
を備える、塑性加工された金属材料の製造方法。 That is, this invention provides the invention of the aspect hung up below.
Item 1. A plastic working lubricant comprising an organic phosphonic acid, an organic phosphoric ester, and at least one of these neutralized salts and a lubricating component.
Item 2. The neutralized salt of the organic phosphonic acid and the organic phosphoric acid ester is at least one salt selected from the group consisting of alkali metals, alkaline earth metals, amines, alkanolamines, alkylammonium hydroxides, and ammonia. Item 2. A plastic working lubricant according to Item 1.
Item 3. The organic phosphonic acid is an organic phosphonic acid polymer having a plurality of phosphonic acid groups: —P (═O) (OH) ₂ , and the organic phosphate ester has a plurality of phosphate groups: —O—P (═O Item 3. The lubricant for plastic processing according to Item 1 or 2, which is an organophosphate polymer having (OH) ₂ .
Item 4. The organic phosphonic acid polymer includes an organic phosphonic acid having a polymerizable unsaturated bond as a monomer, and the organic phosphoric acid ester polymer includes an organic phosphate ester having a polymerizable unsaturated bond as a monomer. Item 4. A plastic working lubricant according to Item 3.
Item 5. The organic phosphonic acid having a polymerizable unsaturated bond is represented by the following general formula (1):
R ¹ —P (═O) (OH) ₂ (1)
[In General formula (1), R < ¹ > shows a C2-C10 hydrocarbon group which has a polymerizable unsaturated bond. ],
The organic phosphate ester having a polymerizable unsaturated bond is represented by the following general formula (2):
R ¹ —O—P (═O) (OH) ₂ (2)
[In General formula (2), R < ¹ > shows a C2-C10 hydrocarbon group which has a polymerizable unsaturated bond. Item 5. A plastic working lubricant according to item 4, represented by
Item 6. The organic phosphonic acid having a polymerizable unsaturated bond is at least one selected from the group consisting of vinyl phosphonic acid, propene-1-phosphonic acid, and propene-2-phosphonic acid,
Item 6. The lubricant for plastic processing according to Item 4 or 5, wherein the phosphate ester having a polymerizable unsaturated bond is an ethylenically unsaturated monomer having a phosphate group represented by the following general formula (3): .

[In General Formula (3), R ² is a hydrogen atom or a methyl group, R ³ is an alkylene group having 2 to 12 carbon atoms, m is an integer of 1 to 30, M ¹ and M ² Are each independently a hydrogen atom, an alkali metal, an alkaline earth metal, an alkyl ammonium group, a substituted alkyl ammonium group, an alkyl group, a hydroxyalkyl group, or an alkenyl group. ]
Item 7. The organic phosphonic acid polymer and the organic phosphoric acid ester polymer are each composed of a carboxylic acid having a polymerizable double bond, a sulfonic acid having a polymerizable double bond, and a carboxylic acid ester having a polymerizable double bond. Item 7. The plastic working lubricant according to any one of Items 3 to 6, further comprising at least one selected from the above as a monomer.
Item 8. Item 3. The plastic working lubricant according to Item 1 or 2, wherein the organic phosphonic acid is an alkylphosphonic acid, and the organic phosphate ester is a starch phosphate.
Item 9. Item 9. The plastic working lubricant according to any one of Items 1 to 8, wherein the neutralization degree of the organic phosphonic acid neutralized salt and the organic phosphoric acid ester neutralized salt is 10% or more, respectively.
Item 10. The lubricating component is at least selected from the group consisting of wax, polytetrafluoroethylene, silicon carbide, boron nitride, fatty acid or salt thereof, fatty acid amide, molybdenum disulfide, graphite, fluorinated graphite, mica, and melamine cyanurate. Item 10. The plastic working lubricant according to any one of Items 1 to 9, which is one type.
Item 11. 1 to 95 parts of the lubricating component is contained in an amount of 1 to 95 parts by mass with respect to 100 parts by mass in total of at least one of the organic phosphonic acid, the organic phosphoric acid ester, and the neutralized salts thereof. Lubricant for plastic working.
Item 12. Item 12. The plastic working lubricant according to any one of Items 1 to 11, which is substantially free of a water-soluble inorganic salt.
Item 13. A form of an aqueous dispersion or aqueous solution in which at least one of the organic phosphonic acid, the organic phosphoric acid ester, and a neutralized salt thereof is dissolved in water, and the lubricating component is dispersed or dissolved in the water. The lubricant for plastic working according to any one of Items 1 to 12, wherein
Item 14. Item 14. The plastic working lubricant according to any one of Items 1 to 13, further comprising a filler.
Item 15. Item 15. A metal material, wherein the plastic working lubricant according to any one of Items 1 to 14 is applied to the surface.
Item 16. The step of applying the plastic working lubricant according to any one of Items 1 to 14 to the surface of the metal material;
Plastically processing a metal material having the plastic processing lubricant applied to the surface;
A method for producing a plastically processed metal material.

According to the present invention, in a lubricant using a solid film that does not use a chemical reaction such as a bonder treatment, even when a water-soluble inorganic salt having a large environmental load that is conventionally used in plastic processing of metal materials is used. It is possible to provide a lubricant for plastic working that exhibits excellent lubricating performance even in cold forging with a large surface area expansion, which has been difficult, and has excellent heat resistance.
Furthermore, the plastic working lubricant of the present invention is excellent in seizure resistance to processing tools and metal materials after being subjected to plastic processing of metal materials, has high peelability, and can be easily removed by air blow after plastic processing. Can be removed. For this reason, accumulation of a lubricant in a mold or the like can be effectively suppressed, and high dimensional accuracy of a processing tool such as a mold can be maintained over a long period of time. Further, according to the present invention, by using such a plastic working lubricant, a plastic-worked metal material can be produced simply and with high dimensional accuracy.

  The lubricant for plastic working of the present invention is characterized by containing at least one of organic phosphonic acid, organic phosphoric acid ester, and neutralized salts thereof, and a lubricating component. Hereinafter, the plastic working lubricant of the present invention and a method for producing a plastically processed metal material using the plastic working lubricant will be described in detail.

1. Lubricant for plastic working The lubricant for plastic working of the present invention contains at least one of an organic phosphonic acid, an organic phosphate ester, and a neutralized salt thereof, and a lubricating component. In the present invention, the organic phosphonic acid is an organic compound having one or more phosphonic acid groups (—P (═O) (OH) ₂ ) in the molecule. An organic phosphate is an organic compound having a phosphate group (—O—P (═O) (OH) ₂ ). In the present invention, the neutralized salt of organic phosphonic acid is a salt obtained by neutralizing at least one of the phosphonic acid groups (—P (═O) (OH) ₂ ) of the organic phosphonic acid with an alkali component. The neutralized salt of an organic phosphate is a product obtained by neutralizing at least one of the phosphate groups (—O—P (═O) (OH) ₂ ) of an organic phosphate with an alkali component. Hereinafter, “organic phosphonic acid or neutralized salt thereof” and “organic phosphoric acid ester or neutralized salt thereof” may be simply referred to as “organic phosphonic acid” and “organic phosphate ester”, respectively.

In the present invention, examples of the organic phosphonic acid include an organic phosphonic acid polymer having a plurality of phosphonic acid groups: —P (═O) (OH) ₂ or a salt thereof. Examples of the organic phosphate ester include an organic phosphate ester polymer having a plurality of phosphate groups: —O—P (═O) (OH) ₂ or a salt thereof. The organic phosphonic acid polymer neutralized salt is a salt obtained by neutralizing at least one of the phosphonic acid groups (—P (═O) (OH) ₂ ) of the organic phosphonic acid polymer with an alkali component, as described above. . Further, the neutralized salt of an organic phosphate polymer is, as described above, at least one of the phosphate groups (—O—P (═O) (OH) ₂ ) of the organic phosphonic acid polymer neutralized by an alkali component. It has been done. Hereinafter, an organic phosphonic acid polymer or a neutralized salt thereof may be simply referred to as “organic phosphonic acid polymer”, and an organic phosphoric acid ester polymer or a neutralized salt thereof may be simply referred to as “organic phosphoric acid ester polymer”.

The organic phosphonic acid polymer is not particularly limited as long as it is a polymer having a plurality of phosphonic acid groups (—P (═O) (OH) ₂ ) in the molecule, but a single organic phosphonic acid having a polymerizable unsaturated bond is used. It is preferable to include as a monomer. Further, the organic phosphate polymer is not particularly limited as long as it is a polymer having a plurality of phosphate groups (—O—P (═O) (OH) ₂ ) in the molecule, but has a polymerizable unsaturated bond. It is preferable to contain a phosphate group as a monomer.

The organic phosphonic acid having a polymerizable unsaturated bond is not particularly limited, but from the viewpoint of improving properties such as heat resistance, lubricating performance, seizure resistance, and peelability of the lubricant in plastic processing, the following general ones are preferred. Formula (1):
R ¹ —P (═O) (OH) ₂ (1)
[In General formula (1), R < ¹ > shows a C2-C10 hydrocarbon group which has a polymerizable unsaturated bond. ]
The compound (monomer) represented by these is mentioned.

The organic phosphate ester having a polymerizable unsaturated bond is not particularly limited, but from the viewpoint of improving properties such as heat resistance, lubrication performance, seizure resistance, and peelability of the lubricant in plastic processing, preferably General formula (2):
R ¹ —O—P (═O) (OH) ₂ (2)
[In General formula (2), R < ¹ > shows a C2-C10 hydrocarbon group which has a polymerizable unsaturated bond. ]
The compound (monomer) represented by these is mentioned.

In the general formulas (1) and (2), each of the hydrocarbon groups for R ¹ may be linear, branched or alicyclic. R ¹ is preferably a hydrocarbon group having 2 to 4 carbon atoms having a polymerizable unsaturated bond.

Particularly preferable specific examples of the organic phosphonic acid having a polymerizable unsaturated bond include vinylphosphonic acid (CH ₂ ═CH—P (═O) (OH) ₂ ), propene-1-phosphonic acid (CH ₃ —CH = CH-P (= O) (OH) 2), propen-2-phosphonic acid _{(CH 2 = C (CH 3} ) -P (= O) (OH) 2), allyl phosphonic acid, 3-butenylphosphonic acid The salt and / or ester thereof may be used.

  Moreover, as a particularly preferable specific example of the organic phosphate having a polymerizable unsaturated bond, an ethylenically unsaturated monomer having a phosphate group represented by the following general formula (3) can be given.

［一般式（３）中、Ｒ²は、水素原子又はメチル基であり、Ｒ³は、炭素数２〜１２のアルキレン基であり、ｍは１〜３０の整数であり、Ｍ¹及びＭ²は、それぞれ独立に、水素原子、中和塩種（例えば、アルキルアンモニウム基、置換アルキルアンモニウム基、アルカノールアミン類）、アルキル基、ヒドロキシアルキル基、又はアルケニル基である。］

[In General Formula (3), R ² is a hydrogen atom or a methyl group, R ³ is an alkylene group having 2 to 12 carbon atoms, m is an integer of 1 to 30, M ¹ and M ² Are each independently a hydrogen atom, a neutralized salt species (eg, alkylammonium group, substituted alkylammonium group, alkanolamines), alkyl group, hydroxyalkyl group, or alkenyl group. ]

  The organic phosphonic acid having a polymerizable unsaturated bond and the organic phosphoric acid ester having a polymerizable unsaturated bond may be used singly or in combination of two or more. Good.

  The organic phosphonic acid polymer and the organic phosphoric acid ester may further contain monomers other than the organic phosphonic acid having a polymerizable unsaturated bond and the organic phosphoric acid ester having a polymerizable unsaturated bond, respectively. As a monomer other than an organic phosphonic acid having a polymerizable unsaturated bond, an organic phosphate having a polymerizable unsaturated bond, an organic phosphonic acid having a polymerizable unsaturated bond, or a polymerizable unsaturated Although it is not particularly limited as long as it can be polymerized with an organic phosphate ester having a bond, it is preferably from the viewpoint of improving properties such as heat resistance, lubrication performance, seizure resistance, and peelability of the lubricant in plastic working. Carboxylic acid having a polymerizable double bond, sulfonic acid having a polymerizable double bond, carboxylic acid ester having a polymerizable double bond, and the like.

  Examples of the carboxylic acid having a polymerizable double bond include maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, citraconic acid, citraconic anhydride, and salts thereof. Examples of the sulfonic acid having a polymerizable double bond include vinyl sulfonic acid, styrene sulfonic acid, p-styrene sulfonic acid, (meth) allyl sulfonic acid, isoprene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, Examples include 3- (meth) allyloxy-2-hydroxypropanesulfonic acid, and salts thereof. Moreover, as carboxylic acid ester having a polymerizable double bond, alkyl ester of (meth) acrylic acid, methoxypolyethylene glycol monomethacrylate (n = 2 to about 100), polypropylene glycol monoacrylate (n = 2 to about 20) , Polyethylene glycol monomethacrylate (n = 2 to about 10), polypropylene glycol monomethacrylate (n = 2 to about 20), polyethylene glycol-polypropylene glycol monomethacrylate (n = 2 to about 20), stearoxy polyethylene glycol, 2 -Hydroxyethyl methacrylate and the like. In the alkyl ester of (meth) acrylic acid, the “alkyl ester” is preferably an alkyl ester having 1 to 10 carbon atoms, more preferably an ethyl ester or a butyl ester. Specific examples of alkyl esters of (meth) acrylic acid include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and stearyl (meth) acrylate. Dimethyl maleate, methyl crotonate, butyl itaconate and the like. Other monomers that can be contained in the organic phosphonic acid polymer include vinyl acetate, vinyl styrene styrene, styrene, p-chlorostyrene, p-cyanostyrene, p-methylstyrene, α-olefin, diisobutylene, Butadiene, (meth) acrylonitrile, (meth) acrylamide, ethylenically unsaturated monomer having a phosphate group (for example, ethylene glycol methacrylate phosphate, propylene glycol methacrylate phosphate, ethylene glycol acrylate phosphate, propylene glycol acrylate phosphate) Etc.). Monomers other than organic phosphonic acid having a polymerizable unsaturated bond may be used singly or in combination of two or more. In the present invention, “(meth) acryl” means “acrylic acid or methacrylic acid”, and the same applies to “acrylic acid or methacrylic acid”.

  When the organic phosphonic acid polymer further contains a monomer other than the organic phosphonic acid having a polymerizable unsaturated bond and the organic phosphoric acid ester having a polymerizable unsaturated bond, the organic phosphonic acid polymer and the organic phosphate polymer The ratio of the organic phosphonic acid having a polymerizable unsaturated bond in all monomers constituting the organic phosphonic acid polymer or the organic phosphate polymer, or the ratio of the organic phosphate having a polymerizable unsaturated bond is Although not particularly limited, from the viewpoint of enhancing properties such as heat resistance, lubrication performance, seizure resistance, and peelability of the lubricant in plastic working, each is preferably 3 mol% or more, more preferably 20 mol% or more, More preferably, it is 30 mol% or more, Most preferably, 50 mol% or more is mentioned. The organic phosphonic acid polymer and the organic phosphoric acid ester polymer may be either a random copolymer or a block copolymer, respectively.

  The weight average molecular weights of the organic phosphonic acid polymer and the organic phosphoric acid ester are not particularly limited, respectively, but from the viewpoint of improving properties such as heat resistance, lubricating performance, seizure resistance, and peelability of the lubricant in plastic processing, Preferably it is 2,000 or more, More preferably, it is about 5,000-3 million, More preferably, about 10,000-300,000 is mentioned. The weight average molecular weight is a value obtained by measuring polyethylene oxide as a standard substance by gel permeation chromatography (GPC).

  In the present invention, the organic phosphonic acid and the organic phosphate ester may be monomers, not a polymer such as an organic phosphonic acid polymer or an organic phosphate ester polymer. Examples of the monomer of organic phosphonic acid include alkylphosphonic acid. Specific examples of the alkyl phosphonic acid include octyl phosphonic acid, isooctyl phosphonic acid, octadecyl phosphonic acid, phenyl phosphonic acid, and benzyl phosphonic acid.

  Specific examples of the organic phosphate ester monomer include alkyl phosphate esters, aromatic phosphate esters, polyoxyalkylene alkyl ether phosphate esters, polyoxyalkylene aromatic phosphate esters, and the like. The alkyl group of the alkyl phosphate ester and the polyoxyalkylene alkyl ether phosphate ester is not particularly limited, but examples of the alkyl group include 1 to 30 carbon atoms. Specific examples of the alkyl group include octyl, isooctyl, decyl, dodecyl, cetyl, myristyl, stearyl, oleyl and the like. The aromatic groups of the aromatic phosphate ester and the polyoxyalkylene aromatic phosphate ester are not particularly limited, and examples thereof include phenyl, 2-phenoxyethyl, and naphthyl. The monomer of these organic phosphates may be a monoester, a diester, or a triester, but a monoester is preferable.

  The polyoxyalkylene group of polyoxyalkylene alkyl ether phosphate ester and polyoxyalkylene aromatic phosphate ester is a polymer of epoxy compounds such as ethylene oxide, propylene oxide, butylene oxide, and different epoxy compounds are copolymerized. It may be. Among these polyoxyalkylene groups, an ethylene oxide polymer is preferable. In this case, the degree of polymerization of ethylene oxide is not particularly limited, but is usually 1 to 50, preferably 2 to 10.

  Moreover, phosphoric acid starch is also mentioned as an organic phosphate ester. Specific examples of phosphoric acid starch include phosphoric acid starch, phosphoric acid distarch, acetylated phosphoric acid cross-linked starch, phosphoric acid monoesterified phosphoric acid cross-linked starch, phosphoric acid cross-linked starch and the like. Although there is no restriction | limiting in particular as a raw material starch, Takapio starch, potato starch, corn starch, wheat starch, etc. are mentioned.

  One of these organic phosphonic acid monomers and organic phosphoric acid ester monomers may be used alone, or two or more thereof may be used in combination. Further, it may be used in combination with an organic phosphonic acid polymer, an organic phosphate polymer, or other types of polymers.

  Examples of the neutralized salts of organic phosphonic acid and organic phosphoric acid ester include at least one salt selected from the group consisting of alkali metals, alkaline earth metals, amines, alkanolamines, and ammonia, respectively. It is done. Among these, from the viewpoint of improving characteristics such as heat resistance, lubricating performance, seizure resistance, and peelability of the lubricant in plastic working, at least one salt of an alkali metal and an alkaline earth metal is preferable. Examples of the alkali metal include lithium, sodium, and potassium, and among these, potassium is preferable. Examples of the alkaline earth metal include magnesium and calcium. Among these, magnesium is preferable. One type of neutralized salt of organic phosphonic acid may be used alone, or two or more types may be used in combination.

  Neutralized salts of organic phosphonic acid and organic phosphoric acid ester are alkali metal, alkaline earth metal, amines such as zinc, aluminum, barium and triethylamine, alkanolamines such as diethanolamine, alkylammonium hydroxide (tetramethyl), respectively. (Ammonium hydroxide, tetraethylammonium hydroxide, etc.) and ammonia can be easily produced by a conventional method using an ammonia component. For example, if it is a potassium salt of organic phosphonic acid and organic phosphoric acid ester, it can manufacture by making potassium hydroxide react as an alkaline component with organic phosphonic acid or organic phosphoric acid ester, respectively. That is, it can be produced by reacting a phosphonic acid group in an organic phosphonic acid or a phosphoric acid group in an organic phosphate ester with potassium hydroxide. Moreover, if it is an ammonium salt of organic phosphonic acid and organic phosphate ester, it can manufacture by making organic phosphonic acid or organic phosphate ester react with ammonia as an alkaline component.

  The degree of neutralization of the neutralized salt of the organic phosphonic acid and the organic phosphoric acid ester is not particularly limited, but the viewpoint of improving the properties such as heat resistance, lubricating performance, seizure resistance, and peelability of the lubricant in plastic working Is preferably 10% or more, more preferably 30% or more. Note that the alkaline earth metal salts of organic phosphonic acid or organic phosphoric acid ester tend to be hardly soluble in water. Therefore, as described later, when a solid film is formed by dissolving a neutralized salt of an organic phosphonic acid or an organic phosphate ester in water and drying it on the surface of the metal material, a medium with an alkaline earth metal salt is used. The sum is preferably 30% or less. In the present invention, the degree of neutralization of a neutralized salt of an organic phosphonic acid or an organic phosphate ester refers to the total moles of acidic functional groups such as phosphonic acid groups or phosphate groups contained in the organic phosphonic acid or organic phosphate ester. When the number is 100, it means the ratio of the number of moles of the acidic functional group neutralized by the alkali component.

  As the organic phosphonic acid, the organic phosphoric acid ester, or a salt thereof, a commercially available product may be used, or the organic phosphonic acid ester or the organic phosphoric acid ester may be produced by a known method. For example, in the case of an organic phosphonic acid polymer or an organic phosphoric acid ester polymer, adjustment of various polymerization conditions such as selection of monomer, polymerization initiator, chain transfer agent, solvent, etc., addition amount, polymerization temperature, dropping time, etc. By this, what has a desired composition, a weight average molecular weight, etc. is obtained.

  The lubricating component contained in the plastic working lubricant of the present invention is not particularly limited as long as it has lubricating performance, and a known lubricating component that can be blended in the plastic working lubricant can be used. The lubricating component is solid at normal temperature and has a function of reducing friction between the processing tool and the metal material to be processed during plastic processing. That is, in the solid film of the plastic working lubricant of the present invention, the lubricating component exists as a solid, and exhibits a function of suppressing an increase in frictional force due to plastic working. The lubricating component is preferably particles that are insoluble or hardly soluble in water and hardly absorb moisture, but water-soluble particles may also be used. Preferred lubricating components include, for example, wax, polytetrafluoroethylene (PTFE), silicon carbide, boron nitride, fatty acids or salts thereof, fatty acid amide, molybdenum disulfide, tungsten disulfide, graphite, melamine cyanurate, organically treated synthetic mica. And lamellar structure amino acid compounds. One lubricating component may be used alone, or two or more lubricating components may be used in combination.

  Specific examples of the solid lubricating component wax include polyethylene wax, paraffin wax, microcrystalline wax, polypropylene wax, and carnauba wax. Specific examples of fatty acids or salts thereof include myristic acid, palmitic acid, stearic acid, sodium myristic acid, potassium myristic acid, sodium palmitate, potassium palmitate, sodium stearate, potassium stearate, calcium stearate, zinc stearate, Examples thereof include barium stearate, magnesium stearate, lithium stearate and the like. Specific examples of the fatty acid amide include ethylene bislauric acid amide, ethylene bis stearic acid amide, ethylene bisbehenic acid amide, N, N′-distearyl adipic acid amide, ethylene bisoleic acid amide, ethylene bis erucic acid amide, hexa Examples include methylenebisoleic acid amide, N, N′-dioleyl adipic acid amide, and the like.

  In the lubricant for plastic working of the present invention, the use ratio of the organic phosphonic acid, the organic phosphate ester or a neutralized salt thereof and the lubricating component is not particularly limited, but the heat resistance of the lubricant in the plastic working, lubrication From the viewpoint of enhancing properties such as performance, seizure resistance, and peelability, the lubricating component is preferably 1 to 95 masses with respect to a total of 100 mass parts of the organic phosphonic acid, the organic phosphate ester, and the neutralized salts thereof. Part, more preferably about 2 to 50 parts by weight.

  The lubricant for plastic working of the present invention may further contain a filler in addition to the organic phosphonic acid, the organic phosphate ester, or a neutralized salt thereof, and the lubricating component. The filler is not particularly limited as long as it is insoluble or hardly soluble in water, and may be either an inorganic filler or an organic filler. A filler may be used individually by 1 type and may be used in combination of 2 or more types.

  Specific examples of the inorganic filler include silica, alumina, cordierite, mullite, talc, phosphate, carbonate, hydroxide, sulfate, colloidal silica, zirconia, colloidal zirconia, colloidal alumina, magnesia, titania, zeolite, Titanium oxide, iron oxide, ferrite, gypsum, zinc oxide, oxide powder, graphite, whisker, carbon fiber, glass fiber, Portland cement, metal powder, montmorillonite, smectite, hectorite, bentonite, organic bentonite, silicone, modified silicone, etc. The particle | grains comprised by these are mentioned.

  Specific examples of the organic filler include phenolic resin, amino resin (such as urea resin and melamine resin), polyamide (such as aramid), polyamideimide, polyacetal, fluororesin, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyimide, polyphenylene sulfide, Examples thereof include particles composed of alkyd resin, polyethersulfone, polyphenylene ether, polysulfone, melamine cyanurate, acetate fiber and the like.

The average particle diameter of the filler is not particularly limited as long as it does not inhibit the effect of the present invention, and may be, for example, about 0.001 to 30 μm, preferably about 0.1 to 10 μm. In addition, since the range of a preferable average particle diameter changes with kinds of filler, an average particle diameter can be suitably selected according to the kind of filler. The average particle diameter of the filler may be adjusted using a pulverizer such as a ball mill, a sand mill, or a bead mill. In the present specification, the average particle size of the filler refers to median diameter measured by a particle size distribution measuring apparatus (D _50).

  When the plastic working lubricant of the present invention contains a filler, the content thereof is not particularly limited as long as it does not impair the effects of the present invention. For example, organic phosphonic acids, organic phosphate esters, and these The total amount of the neutralized salt may be about 0.5 to 300 parts by mass, preferably about 5 to 100 parts by mass.

  The plastic working lubricant of the present invention may further contain a rust preventive component as necessary for the purpose of suppressing rust of the metal material to be processed. As the rust preventive component, a known component that can be blended with a plastic working lubricant can be used, for example, nitrite, phosphate, amines, azoles, permanganate, peroxide, carbonate, zirconium compound. , Calcium compounds, magnesium compounds, zinc compounds, bismuth compounds and the like can be used. One type of rust preventive component may be used alone, or two or more types may be used in combination. In the lubricant for plastic processing of the present invention, from the viewpoint of improving the properties of the lubricant in plastic processing, such as heat resistance, lubricating performance, seizure resistance, peelability, while suppressing rust of the metal material to be processed, It is preferable that content of a rust preventive component shall be about 0.01-5 mass parts with respect to a total of 100 mass parts of said organic phosphonic acid, organic phosphoric acid ester, and these neutralization salts.

  In addition, the plastic working lubricant of the present invention may contain a surfactant, a dispersing agent, and the like as required for the purpose of uniformly dispersing the lubricating component in the medium water. As the surfactant, known ones that can be blended in a plastic working lubricant can be used, such as nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. Can be used. Moreover, as a dispersing agent, the well-known thing which can be mix | blended with the lubricant for plastic working can be used, for example, carboxylic acid containing (co) polymer, amine (co) polymer, polyamino acid, sulfonic acid group containing (Co) polymer, carboxymethylcellulose, phosphate group-containing (co) polymer, phosphate ester group-containing (co) polymer, polyvinyl alcohol, polyphosphate, and the like can be used. A surfactant, a dispersant, and the like may be used singly or in combination of two or more. In the lubricant for plastic working of the present invention, from the viewpoint of enhancing the properties of the lubricant in plastic working, such as heat resistance, lubricating performance, seizure resistance, and peelability, while increasing the dispersibility of the lubricating component in water. In addition, the total content of the dispersant and the dispersant is preferably about 0.01 to 20 parts by mass with respect to 100 parts by mass in total of the organic phosphonic acid, the organic phosphate ester, and the neutralized salts thereof.

  As described above, in a lubricant using a solid film that does not use a chemical reaction such as a bonder treatment, a water-soluble inorganic salt having a large environmental load that is conventionally used to impart strength to a solid film to withstand plastic working. Even if it is not used, the plastic working lubricant of the present invention is excellent in heat resistance and exhibits excellent lubricating performance even in cold forging with a large surface area expansion in plastic working of metal materials. For this reason, it is preferable that the plastic working lubricant of the present invention does not substantially contain a water-soluble inorganic salt having a large environmental load. In addition, when the plastic working lubricant of the present invention contains such a water-soluble inorganic salt, it is preferably with respect to a total of 100 parts by mass of the above organic phosphonic acid, organic phosphoric acid ester, and neutralized salts thereof. 1000 parts by mass or less, more preferably 100 parts by mass or less, and further preferably 5 parts by mass or less. It is preferable that the water-soluble inorganic salt having a large environmental load is not substantially contained. Specific examples of water-soluble inorganic salts with high environmental impact include borates such as potassium tetraborate, sodium tetraborate, and ammonium tetraborate, and silicates such as sodium silicate, potassium silicate, and ammonium silicate. And molybdates such as sodium molybdate and potassium molybdate, vanadates such as sodium vanadate and potassium metavanadate, and tungstates such as sodium tungstate and potassium tungstate.

  The plastic working lubricant of the present invention can be formed on the surface of the metal material as a solid film by applying water or the like to the surface of the metal material to be processed and drying the water or the like. In the plastic working lubricant of the present invention, water is usually used as a medium, but a solvent such as an organic solvent may be added, or a medium such as a powder may be used without using a medium. For example, by mixing the above organic phosphonic acid, organic phosphate ester or neutralized salt thereof with the above lubricating component with water, the organic phosphonic acid, organic phosphate ester, or neutralized salt thereof is dissolved in water. An aqueous dispersion in which the lubricating component is dispersed in water or an aqueous solution in which the lubricating component is dissolved in water (hereinafter, “water dispersion or aqueous solution” is simply referred to as “water dispersion or the like”) is obtained. By applying this aqueous dispersion or the like to the surface of the metal material to be processed and drying the moisture, a solid film made of the plastic working lubricant of the present invention is formed on the surface of the metal material. The water used as the medium is not particularly limited, but deionized water, distilled water, and the like are preferable because it is desirable that there are few impurities. Note that alcohol or the like may be used as the medium. For example, by using a mixture of alcohol in water as a medium, moisture drying on the surface of the metal material can be accelerated.

  The plastic working lubricant of the present invention is a solid film on the surface of the metal material when it is subjected to plastic working, but when distributed and stored as a plastic working lubricant, It is common to have the form of such an aqueous dispersion. For example, the plastic working lubricant of the present invention having a form such as an aqueous dispersion can be produced by mixing at least one of the above organic phosphonic acid and organic phosphoric ester with water together with a lubricating component. In the case of using a neutralized salt of at least one of organic phosphonic acid and organic phosphoric acid ester, at least one of organic phosphonic acid and organic phosphoric acid ester is reacted with an alkali component in water to form organic phosphonic acid and organic phosphoric acid. It can be produced by preparing an aqueous solution containing a neutralized salt of at least one ester and mixing the above-described lubricating components. In addition, in order to adjust the solid content in the aqueous dispersion or the like, water may be further added. The plastic working lubricant of the present invention can be produced by mixing and homogenizing the components constituting the plastic working lubricant of the present invention and, if necessary, the medium. The homogenization method is not particularly limited, and for example, a method of stirring using a propeller, a mixer or the like can be employed. As the mixer, preferably, a high-speed disper, a homomixer, a ball mill, a coreless mixer, a stirring disper or the like having a high shearing force can be used. In addition, each component can be pulverized in the mixing process to further reduce the average particle size of each component.

The amount of use of the plastic working lubricant of the present invention in plastic working may be set as appropriate, from the viewpoint of enhancing the properties of the lubricant in plastic working, such as heat resistance, lubricating performance, seizure resistance, peelability, solid basis to the metal material surface, preferably 0.3~50g / m ² approximately, more preferably, to 1 to 30 g / m ² approximately. When the plastic working lubricant of the present invention is applied to a metal surface using a medium such as water, the amount (concentration) of the plastic working lubricant relative to the medium is appropriately adjusted so that the amount used is as described above. To do. For example, when the plastic working lubricant of the present invention has a form such as an aqueous dispersion, the solid content in the aqueous dispersion or the like can be about 1 to 60% by mass.

  The lubricant for plastic working of the present invention can be suitably used for plastic working of metal materials such as iron, steel, stainless steel, copper, copper alloy, aluminum, aluminum alloy, titanium, titanium alloy, particularly cold plastic working. it can. The shape of the metal material to be processed is not particularly limited, and examples thereof include a plate shape, a rod shape, a block shape, and a spherical shape.

  When a metal material is plastically processed using the plastic working lubricant of the present invention, generally, a metal material cleaning step, a lubricant application step, and a drying step are sequentially performed. Hereinafter, these steps will be described.

  First, before applying the plastic working lubricant of the present invention to a metal material, it is preferable to perform a known cleaning step such as shot blasting, sand blasting, peeling, alkali degreasing, or acid cleaning. The main purpose of the cleaning process is to remove oxide scales and various types of dirt (oil, etc.) grown by annealing of the metal material.

  Next, in the lubricant application step, the plastic working lubricant of the present invention is applied to the surface of the metal material. That is, as described above, the above-described organic phosphonic acid, organic phosphate ester, or a neutralized salt thereof, and an aqueous dispersion obtained by mixing the above lubricating component with water are applied to the surface of the metal material. The method for applying the aqueous dispersion or the like to the surface of the metal material is not particularly limited, and a known method such as a dipping method, a flow coating method, or a spray method can be used. In these methods, the surface of the metal material only needs to be sufficiently covered with an aqueous dispersion or the like, and the application time is not particularly limited. In addition, for the purpose of shortening the drying time of the water | moisture content in the subsequent drying process, you may apply | coat said aqueous dispersion etc., for example, heating a metal material to 60-80 degreeC. Moreover, you may apply | coat the water dispersion etc. which were heated at 40-80 degreeC to the metal material surface.

  Next, moisture such as the aqueous dispersion applied on the surface of the metal material is dried. Drying may be performed at room temperature, or, for example, the metal material may be subjected to drying at 60 to 150 ° C. for about 1 to 30 minutes.

  As described above, a metal material on which a solid film of the plastic working lubricant of the present invention is formed is obtained.

  As described above, when the lubricant accumulates in the mold or the like, the dimensional accuracy of the mold decreases, and it becomes impossible to perform the desired precision plastic processing on the metal material gradually. Further, accumulation of the lubricant in the mold or the like causes resistance due to the accumulated lubricant, and the processing energy necessary for plastic working gradually increases. On the other hand, the plastic working lubricant of the present invention is excellent in seizure resistance to the processing tool and the metal material after being subjected to the plastic working of the metal material, and has high peelability, so that after the plastic working It can be easily removed by air blow. The solid film of the plastic working lubricant of the present invention can be easily removed with water, and can also be removed by immersing in an aqueous alkaline cleaner or spray cleaning.

  In lubricants using solid coatings that do not use chemical reactions such as bondage treatment, water-soluble inorganic salts that have a large environmental impact and are conventionally used to impart strength that can withstand plastic working to solid coatings are not used. However, the plastic working lubricant of the present invention is excellent in heat resistance, and cold forging with a large surface area that was difficult even when using a water-soluble inorganic salt with a large environmental load in the plastic working of metal materials. Excellent lubrication performance. Furthermore, the plastic working lubricant of the present invention is excellent in seizure resistance to the work tool and the metal material after being subjected to the plastic working of the metal material, and has high peelability, such as washing and air blowing after the plastic working. Can be removed easily. For this reason, the lubricant for plastic working of the present invention can be suitably used for plastic working of metallic materials, particularly cold plastic working. That is, the plastic working lubricant of the present invention is suitable as a cold plastic working lubricant.

  The details of the mechanism by which the plastic working lubricant of the present invention exhibits such high lubricating performance are not necessarily clear, but can be considered as follows, for example. That is, phosphorus, phosphonic acid groups, and phosphoric acid groups are generally considered to have higher affinity and adsorbability to metal surfaces and higher binding energy than carboxyl groups. Accordingly, the phosphonic acid group of the organic phosphonic acid, the phosphoric acid group of the organic phosphoric acid ester, or a neutralized salt thereof contained in the plastic working lubricant of the present invention strongly binds to the metal surface to be processed. As a result, even when the surface area enlargement due to processing is wide, the lubricant follows without leaving the metal surface, preventing film breakage, preventing the metal surface from contacting the mold directly, and performance as a lubricant This is considered to be due to the fact that this is maintained.

2. Method for producing plastically processed metal material The method for producing a plastically processed metal material of the present invention comprises the following steps.
Applying the plastic working lubricant of the present invention to the surface of the metal material;
A step of plastic working a metal material having the plastic working lubricant applied to the surface.

  In the manufacturing method of the present invention, examples of the metal material to be processed include those described above. Moreover, the process of apply | coating the plastic working lubricant of this invention to the surface of the above metal materials can be performed like the above. Moreover, the plastic processing of a metal material can employ | adopt well-known plastic processing, for example, the process etc. which press a metal material using a metal mold | die etc. and are deform | transformed into a desired shape etc. are mentioned.

  According to the manufacturing method of the present invention, plastic processing is performed using the plastic processing lubricant of the present invention, so that the metal material can be plastic processed without using a water-soluble inorganic salt with a large environmental load. it can. Further, since the plastic working lubricant is excellent in seizure resistance and has high peelability, the lubricant adhering to the mold or the like can be easily removed by air blow or the like after plastic working. For this reason, accumulation of lubricant in the mold or the like is suppressed, and high dimensional accuracy of the mold or the like is maintained. Further, an increase in processing energy due to accumulation of the lubricant in the mold or the like is also suppressed. Therefore, according to the manufacturing method of the present invention, a metal material having high dimensional accuracy can be easily obtained.

  Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples. In the examples, “part” and “%” are based on mass unless otherwise specified.

Test Examples 1 to 27 and Comparative Test Examples 1 to 6
<Production of polymer used in each test example>
The polymers (organic phosphonic acid polymer, organic phosphoric acid ester polymer, and neutralized salts thereof) used in each test example shown in Table 1 were produced as follows. In each test example, the amount of the alkali component was adjusted so that the degree of neutralization would be the value shown in Table 1, respectively.

<Test Example 1: Potassium salt of polyvinylphosphonic acid 1>
The flask was charged with 60 g of isopropyl alcohol (IPA) and 270 g of water and heated to 85 ° C. under a nitrogen gas stream. Next, a monomer mixture obtained by mixing 130 g of vinylphosphonic acid, 30 g of IPA and 70 g of water, and a mixture of 3.5 g of azobis-2-amidinepropane (manufactured by Wako Pure Chemicals, V-50), 10 g of IPA and 90 g of water. It was added dropwise to the flask over 110 minutes. Thereafter, the temperature was kept for 1 hour to complete the polymerization, and then IPA was distilled off. Next, a 50% aqueous potassium hydroxide solution was added to neutralize, and the solid content was adjusted to obtain an aqueous solution of a potassium salt of polyvinylphosphonic acid 1 (solid content 40% by mass). The weight average molecular weight by GPC of the polymer was 52,000. In Test Example 1, an aqueous solution of polyvinyl phosphonic acid 1 potassium salt was used.

<Test Example 2: Potassium salt of polyvinylphosphonic acid 2>
IPA 60 g, water 270 g changed to IPA 430 g, water 30 g, a monomer mixture obtained by mixing vinylphosphonic acid 130 g, IPA 10 g, and water 90 g Azobis-2-amidinepropane (manufactured by Wako Pure Chemicals, V-50) 3 was changed to a mixture of 3.5 g of azobis-2-amidinepropane (manufactured by Wako Pure Chemicals, V-50), 10 g of IPA and 90 g of water. Polyvinyl phosphon in the same manner as the aqueous solution of the potassium salt of polyvinyl phosphonic acid 1 except that the mixture was changed to a mixed solution of 0.5 g, 85 g of IPA and 15 g of water, and dripping was carried out over 230 minutes over 110 minutes. An aqueous solution of a potassium salt of acid 2 was obtained (solid content 40% by mass). The weight average molecular weight of the polymer by GPC was 10500. In Test Example 2, an aqueous solution of polyvinyl phosphonic acid 2 potassium salt was used.

<Test Example 3: Potassium salt of polyvinylphosphonic acid 3>
An aqueous solution of a potassium salt of polyvinylphosphonic acid 3 in the same manner as the aqueous solution 1 of the above potassium phosphonic acid potassium salt, except that 270 g of water was changed to 120 g of water and the dropwise addition was performed over 110 minutes over 50 minutes. (Solid content 40% by mass) was obtained. The weight average molecular weight of the polymer by the GPC was 323,000. In Test Example 3, an aqueous solution of a potassium salt of polyvinylphosphonic acid 3 was used.

<Test Example 4: Vinylphosphonic acid / acrylic acid copolymer 1 potassium salt>
Aqueous solution of potassium salt of vinylphosphonic acid / acrylic acid copolymer 1 in the same manner as the aqueous solution of potassium salt of polyvinylphosphonic acid 1 except that 130 g of vinylphosphonic acid was changed to 110 g of vinylphosphonic acid and 25 g of acrylic acid. (Solid content 40% by mass) was obtained. The weight average molecular weight of the polymer by GPC was 49000. In Test Example 4, an aqueous solution of a potassium salt of vinylphosphonic acid / acrylic acid copolymer 1 was used.

<Test Examples 5, 8, 9, 10: Potassium salt of vinylphosphonic acid / acrylic acid copolymer 2>
Aqueous solution of potassium salt of vinylphosphonic acid / acrylic acid copolymer 2 in the same manner as the aqueous solution of potassium salt of polyvinylphosphonic acid 2 except that 130 g of vinylphosphonic acid was changed to 40 g of vinylphosphonic acid and 81 g of acrylic acid. (Solid content 40% by mass) was obtained. The weight average molecular weight by GPC of the polymer was 50500. In Test Examples 5, 8, and 9, an aqueous solution of a potassium salt of vinylphosphonic acid / acrylic acid copolymer 2 was used. In Test Example 10, an aqueous solution of vinylphosphonic acid / acrylic acid copolymer 2 was used.

<Test Example 6: Potassium salt of vinylphosphonic acid / acrylic acid copolymer 3>
Except that 130 g of vinylphosphonic acid was changed to 40 g of vinylphosphonic acid and 81 g of acrylic acid, an aqueous solution of potassium salt of vinylphosphonic acid / acrylic acid copolymer 3 was prepared in the same manner as the aqueous solution of potassium potassium polyvinylphosphonate 2 described above. Obtained (solid content 40% by mass). The weight average molecular weight of the polymer by GPC was 9800. In Test Example 6, an aqueous solution of a potassium salt of vinylphosphonic acid / acrylic acid copolymer 3 was used.

<Test Example 7: Potassium salt of vinylphosphonic acid / acrylic acid copolymer 4>
Except for changing 130 g of vinylphosphonic acid to 40 g of vinylphosphonic acid and 81 g of acrylic acid, an aqueous solution of a potassium salt of vinylphosphonic acid / acrylic acid copolymer 4 was prepared in the same manner as the aqueous solution of potassium potassium polyvinylphosphonate 3 above. Obtained (solid content 40% by mass). The weight average molecular weight of the polymer by GPC was 301,000. In Test Example 7, an aqueous potassium salt solution of vinylphosphonic acid / acrylic acid copolymer 4 was used.

<Test Example 11: Magnesium salt of vinylphosphonic acid / acrylic acid copolymer 2>
A vinylphosphonic acid / acrylic acid copolymer is the same as the aqueous solution of the potassium salt of vinylphosphonic acid / acrylic acid copolymer 2 described above except that the 50% aqueous potassium hydroxide solution is changed to magnesium hydroxide. 2 aqueous solution of magnesium salt was obtained (solid content 40% by mass). In Test Example 11, an aqueous solution of a magnesium salt of vinylphosphonic acid / acrylic acid copolymer 2 was used.

<Test Example 12: Sodium salt of vinylphosphonic acid / acrylic acid copolymer 2>
Vinylphosphonic acid / acrylic acid in the same manner as the aqueous solution of potassium salt of vinylphosphonic acid / acrylic acid copolymer 2 above, except that the 50% aqueous potassium hydroxide solution was changed to a 50% aqueous sodium hydroxide solution. An aqueous solution of sodium salt of copolymer 2 was obtained (solid content 40% by mass). In Test Example 12, an aqueous solution of a sodium salt of vinylphosphonic acid / acrylic acid copolymer 2 was used.

<Test Example 13: Sodium salt / magnesium salt of vinylphosphonic acid / acrylic acid copolymer 2>
Except that the 50% potassium hydroxide aqueous solution was changed to 50% sodium hydroxide aqueous solution and magnesium hydroxide, respectively, the vinyl phosphonic acid / acrylic acid copolymer 2 potassium salt aqueous solution was used in the same manner as above. A sodium salt / magnesium salt aqueous solution of phosphonic acid / acrylic acid copolymer 2 was obtained (solid content 40% by mass). In Test Example 13, a sodium salt / magnesium salt aqueous solution of vinylphosphonic acid / acrylic acid copolymer 2 was used.

<Test Example 14: Zinc salt of vinylphosphonic acid / acrylic acid copolymer 2>
A vinylphosphonic acid / acrylic acid copolymer is the same as the aqueous solution of potassium salt of vinylphosphonic acid / acrylic acid copolymer 2 described above except that the 50% aqueous potassium hydroxide solution is changed to zinc hydroxide. 2 was obtained (solid content 40% by mass). In Test Example 14, an aqueous solution of a zinc salt of vinylphosphonic acid / acrylic acid copolymer 2 was used.

<Test Example 15: Ammonium salt of vinylphosphonic acid / acrylic acid copolymer 2>
A vinylphosphonic acid / acrylic acid copolymer is prepared in the same manner as the aqueous solution of the potassium salt of vinylphosphonic acid / acrylic acid copolymer 2 except that the 50% aqueous potassium hydroxide solution is changed to 25% aqueous ammonia. An aqueous solution of an ammonium salt of coalescence 2 was obtained (solid content 40% by mass). In Test Example 15, an aqueous solution of an ammonium salt of vinylphosphonic acid / acrylic acid copolymer 2 was used.

<Test Example 16: Triethanolamine salt of vinylphosphonic acid / acrylic acid copolymer 2>
A vinylphosphonic acid / acrylic acid copolymer is the same as the aqueous solution of potassium salt of vinylphosphonic acid / acrylic acid copolymer 2 described above except that the 50% aqueous potassium hydroxide solution is changed to triethanolamine. 2 aqueous solution of triethanolamine salt was obtained (solid content 40% by mass). In Test Example 16, an aqueous solution of a triethanolamine salt of vinylphosphonic acid / acrylic acid copolymer 2 was used.

<Test Example 17: Potassium salt of vinylphosphonic acid / methacrylic acid copolymer 1>
Aqueous solution of potassium salt of vinylphosphonic acid / methacrylic acid copolymer 2 in the same manner as the aqueous solution of potassium salt of polyvinylphosphonic acid 2 except that 130 g of vinylphosphonic acid was changed to 40 g of vinylphosphonic acid and 92 g of methacrylic acid. (Solid content 40% by mass) was obtained. The weight average molecular weight of the polymer by GPC was 51,000. In Test Example 17, an aqueous solution of a potassium salt of vinylphosphonic acid / methacrylic acid copolymer 1 was used.

<Test Example 18: Potassium salt of vinylphosphonic acid / methacrylic acid / methoxypolyethylene glycol monomethacrylate copolymer>
Except for changing 130 g of vinylphosphonic acid to 34 g of vinylphosphonic acid and 132 g of methacrylic acid and 20 g of methoxypolyethylene glycol monomethacrylate, the same procedure as in the above aqueous solution of vinylphosphonic acid / acrylic acid copolymer 1 was used. An aqueous solution of a potassium salt of an acid / methoxypolyethylene glycol monomethacrylate copolymer was obtained (solid content 40% by mass). The weight average molecular weight of the polymer by GPC was 54500. In Test Example 18, an aqueous solution of potassium salt of vinylphosphonic acid / methacrylic acid / methoxypolyethylene glycol monomethacrylate copolymer was used.

<Test Example 19: Potassium salt of vinylphosphonic acid / vinylsulfonic acid copolymer>
Except for changing 130 g of vinylphosphonic acid to 32 g of vinylphosphonic acid and 121 g of vinylsulfonic acid, the same as the aqueous solution of potassium salt of polyvinylphosphonic acid 2 described above, the potassium salt of vinylphosphonic acid / vinylsulfonic acid copolymer An aqueous solution was obtained (solid content 40% by mass). The weight average molecular weight by GPC of the polymer was 50500. In Test Example 19, an aqueous solution of a potassium salt of vinylphosphonic acid / vinylsulfonic acid copolymer was used.

<Test Example 20: Potassium salt of propene-1-phosphonic acid / acrylic acid copolymer>
A propene-1-phosphonic acid / acrylic acid copolymer in the same manner as the aqueous solution of the potassium salt of polyvinylphosphonic acid 2 except that 130 g of vinylphosphonic acid was changed to 47 g of propene-1-phosphonic acid and 83 g of acrylic acid. An aqueous solution of potassium salt was obtained (solid content 40% by mass). The weight average molecular weight of the polymer by GPC was 52,000. In Test Example 20, an aqueous solution of a potassium salt of propene-1-phosphonic acid / acrylic acid copolymer was used.

<Test Example 21: Potassium salt of propene-2-phosphonic acid / acrylic acid copolymer>
A propene-1-phosphonic acid / acrylic acid copolymer in the same manner as the aqueous solution of the potassium salt of polyvinylphosphonic acid 2 except that 130 g of vinylphosphonic acid was changed to 47 g of propene-2-phosphonic acid and 83 g of acrylic acid. An aqueous solution of potassium salt was obtained (solid content 40% by mass). The weight average molecular weight of the polymer by GPC was 51500. In Test Example 21, an aqueous solution of a potassium salt of propene-2-phosphonic acid / acrylic acid copolymer was used.

<Test Example 22: Potassium salt of ethylene glycol methacrylate forte / methacrylic acid copolymer>
Acid phosphoxyethyl methacrylate / methacrylic acid copolymer is the same as the above aqueous solution of vinylphosphonic acid / acrylic acid copolymer 1 except that 130 g of vinylphosphonic acid is changed to 64 g of ethylene glycol methacrylate formate and 62 g of methacrylic acid. An aqueous solution of a combined potassium salt was obtained (solid content 40% by mass). The weight average molecular weight by GPC of the polymer was 53000. In Test Example 22, an aqueous solution of potassium salt of ethylene glycol methacrylate phosphate / methacrylic acid copolymer was used.

<Test Example 23: Potassium salt of ethylene glycol methacrylate phosphate / methacrylic acid / methoxypolyethylene glycol monomethacrylate copolymer>
Acid phosphoxy is similar to the above aqueous solution of vinyl phosphonic acid / acrylic acid copolymer 1 except that 130 g of vinyl phosphonic acid is changed to 55 g of acid phosphooxyethyl methacrylate, 50 g of methacrylic acid and 24 g of methoxypolyethylene glycol monomethacrylate. An aqueous solution of potassium salt of ethyl methacrylate / methacrylic acid / methoxypolyethylene glycol monomethacrylate copolymer was obtained (solid content 40% by mass). The weight average molecular weight by GPC of the polymer was 56000. In Test Example 23, an aqueous solution of a potassium salt of acid phosphooxyethyl methacrylate / methacrylic acid / methoxypolyethylene glycol monomethacrylate copolymer was used.

<Evaluation of film properties>
As shown in Table 1, the polymer and compound aqueous solutions obtained above were each applied to the surface of a SUS petri dish so that the solid content was 100 g / m ² and dried at 110 ° C. for 1 hour. A solid film was formed. The amount of solid content was set to be large in order to facilitate evaluation of film properties. Test Examples 24-27 are a mixture of an acrylic acid polymer and the compounds shown in Table 1, and the mass ratio of the acrylic acid polymer to the compound (acrylic acid polymer: the compound) is 30 respectively. : 70. Comparative Test Example 1 is polyvinyl alcohol, Comparative Test Example 2 is a urethane emulsion, Comparative Test Example 3 is starch, Comparative Test Example 4 is polyvinylpyrrolidone, Comparative Test Example 5 is hydroxypropylmethylcellulose, and Comparative Test Example 6 is potassium tetraborate. Each aqueous solution was used. Next, the properties of the solid films obtained in Test Examples 1 to 27 and Comparative Test Examples 1 to 6 were evaluated. The results are shown in Table 1. When all of the following items were satisfied, the film properties were evaluated as good (◯).
(1) Solid film was easily formed and it was not powdery
(2) The solid film was hard and easily broken. Specifically, the surface of the solid film was confirmed by rubbing with a spatula.
(3) The thickness of the solid film was uniform.
(4) The solid film could be easily washed away with water.
(5) The wettability of the solid film was low. Specifically, in a summer environment with a temperature of 35 ° C. and a humidity of about 80%, after forming a solid film, the film absorbs moisture after 60 minutes and the film properties change. The nature is high. On the other hand, in the same manner, when the properties of the solid film were not changed and there was no stickiness, the wettability was considered low.

Moreover, when the properties of the solid film are slightly inferior but there is no practical problem (Δ), and when the properties of the solid film are bad and practically problematic (×), individual evaluation results are shown below.
In Comparative Test Example 1, the film was soft and the film strength was low.
In Comparative Test Example 2, in Comparative Test Examples 3 to 5 where the film could not be easily washed away with water, the film was soft and the film strength was low. Moreover, in Comparative Test Example 3 using starch, there are also disadvantages that starch is easily rotted and storage stability is poor.
In Comparative Test Example 6, the properties of the film were good (◯), but there was a problem that the environmental load was large.

<Heat resistance evaluation>
The films obtained in Test Examples 1 to 27 and Comparative Test Examples 1 to 6 were left at 200 ° C. for 1 hour, the state of the film was visually observed, and the heat resistance was evaluated according to the following criteria. The results are shown in Table 1.
○: Little change in film color △: Film changed to light brown ×: Film changed to brown or carbonized

  As shown in Table 1, among Test Examples 1 to 23 using polymers or neutralization salts containing phosphonic acid groups or phosphate esters as monomers, among acrylic acid polymers and organic phosphonic acids or organic phosphate esters In Test Examples 24-26 using Japanese salt and Test Example 27 using phosphate starch, the heat resistance of the formed solid film and the properties of the film were excellent. In particular, the properties of these films were easily cracked and could be easily removed by air blow or the like. On the other hand, in Comparative Test Examples 1 to 5, the properties of the film were sticky and could not be easily removed by air blow or the like.

Examples 1 to 21 and Comparative Examples 1 and 2
An aqueous dispersion (solid content 20% by mass) was prepared by blending the polymer or compound, filler, lubricant component, and water used in the above test examples so as to have the composition shown in Table 2. In addition, as a polymer or a compound, as described in Table 2, those obtained in Test Examples 1, 2, 3, 5, 9 to 11, 20 to 27 and those used in Comparative Test Examples 3 and 6 are used. did. The average particle size of the filler was 0.3 μm for polyamideimide resin particles, 0.5 μm for melamine cyanurate particles, 1 μm for silica particles, and 1 μm for zinc oxide particles. As the polyethylene wax, an aqueous dispersion of polyethylene wax (molecular weight 11000 to 17000, average particle size 0.5 μm) was used.
Next, each of the aqueous dispersions was applied to the surface of the SUS petri dish in a range such that the solid content was 100 g / m ² and dried at 110 ° C. for 1 hour, and the lubricant solid was applied to the surface of the SUS petri dish. A film was formed. The amount of solid content was set to be large in order to facilitate evaluation of film properties. In order to confirm the performance of each lubricant, the following evaluation tests were conducted. Each result is shown in Table 3.

<Evaluation of film properties>
The properties of the lubricant films of Examples 1 to 21 and Comparative Examples 1 and 2 were evaluated in the same manner as in Test Examples 1 to 27 and Comparative Test Examples 1 to 6. As a result, in Comparative Example 1, the film was sticky and the film strength was low. Furthermore, since there was also a fault that storage stability was bad, in Comparative Example 1, the evaluation was x. Moreover, in comparative example 2, since film | membrane intensity | strength was weak, evaluation was set to x.

<Heat resistance evaluation>
The heat resistance of the lubricants of Examples 1 to 21 and Comparative Examples 1 and 2 was evaluated in the same manner as in Test Examples 1 to 27 and Comparative Test Examples 1 to 6.

<Reciprocating friction test>
An SPC steel plate was used as a test piece, and degreasing treatment was performed before applying the lubricant. A degreasing solution was prepared (adjusted to 55 ° C.) under the conditions usually used using Alkylene 2600 manufactured by Kiwa Chemicals as a degreasing agent. The SPC steel plate was immersed in a degreasing solution for 10 minutes, then washed with water and dried. Subsequently, the SPC steel plate after the degreasing treatment was immersed in the aqueous dispersion obtained in Examples 1 to 21 and Comparative Examples 1 and 30 for 30 seconds, and then dried at 110 ° C. for 1 hour to obtain a test piece. The formed solid film was 10 g / m ² .
Using a reciprocating friction tester (manufactured by Shinko Engineering Co., Ltd.), a test piece on which a solid film was formed under the conditions of a 3/16 inch hard ball as a friction ball, a load of 5 kg, a sliding distance of 20 mm, and a speed of 20 mm / s. Reciprocating sliding was performed, and the time until the friction coefficient reached 0.2 was measured and evaluated according to the following criteria.
◎: 30 minutes or more ○: 10 minutes or more and less than 30 minutes Δ: 3 minutes or more and less than 10 minutes ×: Less than 3 minutes

<Ring compression test>
The ring compression test is a test for evaluating the forging processability of the lubricant film based on the obtained friction coefficient, and was performed in accordance with the ring compression test described in JP2013-108138A. The material of the ring used for the ring compression test was steel (S45C), and the outer diameter was 21.0 mm, the inner diameter was 10.5 mm, and the thickness was 7.0 mm. The ring was immersed in the aqueous dispersions obtained in Examples 1 to 21 and Comparative Examples 1 and 2, and dried at 110 ° C. for 1 hour to form a film on the surface of the ring. Next, the ring was pressed with a load of 200 tons. The thickness and inner diameter of the ring after compression were measured, and the friction coefficient was measured. In addition, a ring compression test was performed three times for each of the cases where the compression ratio according to the following formula was 50% and 60%, and the average friction coefficient μ was obtained.
Compression rate (%) = (h ₀ −h) / h ₀ × 100
[Where h ₀ is 7 mm, h is thickness after compression (mm)]
In the ring compression test, the relationship between the shape after compression and the friction coefficient when the ring is compressed is known. When the coefficient of friction is small, the inner and outer diameters are compressed so as to project outward. Further, when the friction coefficient is large, the inner diameter projects to the inside and the outer diameter projects to the outside. Therefore, the dimensional change of the inner diameter portion can be measured and the friction coefficient can be calculated.

<Front shaft / rear can extrusion friction test>
The test was conducted in accordance with the front shaft / rear can extrusion friction test described in JP-A-2008-222890. The principle of the front shaft / rear can extrusion friction test is as follows. First, a cylindrical test piece having a film formed in a conical mold hole having an inlet diameter of 20 mm is inserted and pressed with a punch having a cross-sectional reduction rate Re = 50%. As the punch push-in amount Sp increases, the test piece first undergoes forward shaft extrusion, and when the forward push load including the frictional force of the conical die surface balances with the backward push load, the backward push occurs. For this reason, the forward extrusion amount Sf increases as the mold surface friction decreases. Therefore, a calibration diagram is created in advance using the two-dimensional rigid plastic FEM software DEFORM-2D from the relationship between the punch push amount Sp and the forward push amount Sf for different frictional shear coefficients mD on the mold surface, and the measured values are plotted. The frictional shear coefficient mD was determined by interpolation.

First, a cylindrical test piece (SCM420 annealed material) having a diameter of 20 mm × height of 20 mm was immersed in the aqueous dispersions obtained in Examples 1 to 21 and Comparative Examples 1 and 2, and dried at 110 ° C. for 1 hour for testing. A film was formed on the surface of the piece. Next, the test piece on which the film was formed was inserted into the conical mold hole of the above mold, and the test was carried out at a punch push-in amount Sp of 15 mm, 17 mm, or 19 mm according to the performance of the lubricant. The test was performed using a mechanical press with a maximum working load of 1.6 MN, a speed of 10 mm above the bottom dead center, and 80 mm / s. The die was a cemented carbide, the punch was SKH51, and the tool surface was finished to Rz = 0.3 μm or less. According to the above test, the frictional shear coefficient mD was determined, and the seizure state and the state of the residue remaining on the mold surface were evaluated according to the following criteria.
<Bake-in>
○: No seizure △: Partial seizure ×: Severe seizure <Dust pool>
○: No residue accumulation △: Small amount of residue accumulation ×: Large amount of residue accumulation

  As shown in Table 2 and Table 3, Examples 1 to 11, 14 to 16, 19 to 21 using a polymer containing a phosphonic acid group or a phosphate ester as a monomer, or a neutralized salt, a phosphate ester In the lubricants of Examples 12 and 17 using a neutralized salt of Example 13, Example 13 using a neutralized salt of an alkylphosphonic acid, and Example 18 using a starch phosphate, the heat resistance of the solid film formed, Excellent film properties. Also, the friction coefficient required by the reciprocating friction test and the ring compression test, and the results of the front shaft / rear can extrusion friction test were excellent, and there was no seizure and no residue accumulation. From these results, when using a polymer or neutralized salt containing a phosphonic acid group or phosphate ester, phosphate ester, alkylphosphonic acid, neutralized salt of phosphate starch, excellent plastic workability is obtained, Further, it can be seen that the solid film attached to the mold or the like after the plastic working can be easily removed. Further, in the forward shaft / rear can extrusion friction test of the comparative example, the frictional shear coefficient increases greatly as the forward extrusion amount increases to 15 (mm), 17 (mm), and 19 (mm). In the case of, the degree of increase was moderate. This indicates that the friction step coefficient can be kept low in strong processing, and therefore the lubricating performance can be maintained in the strong processing region. Therefore, according to the lubricant of this invention, it turns out that sufficient lubrication performance can be exhibited in the strong processing area | region which was difficult with the conventional lubricant.

  On the other hand, in Comparative Example 1 using starch, although it was excellent in heat resistance, the other tests were inferior to the lubricants of Examples 1 to 21. In addition, the lubricant of Comparative Example 2 using potassium tetraborate, which is a water-soluble inorganic salt, had excellent heat resistance and film properties as in Examples 1 to 21, but the lubrication of the present invention. Lubricating performance was inferior to the agent and seizure occurred. Furthermore, the potassium tetraborate used in Comparative Example 2 has a problem that the environmental load is large.

Claims (16)

  A plastic working lubricant comprising an organic phosphonic acid, an organic phosphoric ester, and at least one of these neutralized salts and a lubricating component.   The neutralized salt of the organic phosphonic acid and the organic phosphoric acid ester is at least one salt selected from the group consisting of alkali metals, alkaline earth metals, amines, alkanolamines, alkylammonium hydroxides, and ammonia. The plastic working lubricant according to claim 1. The organic phosphonic acid is an organic phosphonic acid polymer having a plurality of phosphonic acid groups: —P (═O) (OH) ₂ , and the organic phosphate ester has a plurality of phosphate groups: —O—P (═O 3) The plastic working lubricant according to claim 1 or 2, which is an organophosphate polymer having (OH) ₂ .   The organic phosphonic acid polymer includes an organic phosphonic acid having a polymerizable unsaturated bond as a monomer, and the organic phosphoric acid ester polymer includes an organic phosphate ester having a polymerizable unsaturated bond as a monomer. The plastic working lubricant according to claim 3, which is contained. The organic phosphonic acid having a polymerizable unsaturated bond is represented by the following general formula (1):
R ¹ —P (═O) (OH) ₂ (1)
[In General formula (1), R < ¹ > shows a C2-C10 hydrocarbon group which has a polymerizable unsaturated bond. ],
The organic phosphate ester having a polymerizable unsaturated bond is represented by the following general formula (2):
R ¹ —O—P (═O) (OH) ₂ (2)
[In General formula (2), R < ¹ > shows a C2-C10 hydrocarbon group which has a polymerizable unsaturated bond. ] The lubricant for plastic working of Claim 4 represented by these. The organic phosphonic acid having a polymerizable unsaturated bond is at least one selected from the group consisting of vinyl phosphonic acid, propene-1-phosphonic acid, and propene-2-phosphonic acid,
The plastic working lubricant according to claim 4 or 5, wherein the phosphate ester having a polymerizable unsaturated bond is an ethylenically unsaturated monomer having a phosphate group represented by the following general formula (3). Agent.

[In General Formula (3), R ² is a hydrogen atom or a methyl group, R ³ is an alkylene group having 2 to 12 carbon atoms, m is an integer of 1 to 30, M ¹ and M ² Are each independently a hydrogen atom, an alkali metal, an alkaline earth metal, an alkyl ammonium group, a substituted alkyl ammonium group, an alkyl group, a hydroxyalkyl group, or an alkenyl group. ]   The organic phosphonic acid polymer and the organic phosphoric acid ester polymer are each composed of a carboxylic acid having a polymerizable double bond, a sulfonic acid having a polymerizable double bond, and a carboxylic acid ester having a polymerizable double bond. The plastic working lubricant according to any one of claims 3 to 6, further comprising at least one selected from the above as a monomer.   The plastic working lubricant according to claim 1 or 2, wherein the organic phosphonic acid is an alkylphosphonic acid, and the organic phosphoric acid ester is a phosphoric acid starch.   The plastic working lubricant according to any one of claims 1 to 8, wherein the neutralization degree of the organic phosphonic acid neutralized salt and the organic phosphoric acid ester neutralized salt is 10% or more, respectively.   The lubricating component is at least selected from the group consisting of wax, polytetrafluoroethylene, silicon carbide, boron nitride, fatty acid or salt thereof, fatty acid amide, molybdenum disulfide, graphite, fluorinated graphite, mica, and melamine cyanurate. The lubricant for plastic working according to any one of claims 1 to 9, which is one type.   The lubricating component is included in an amount of 1 to 95 parts by mass with respect to a total of 100 parts by mass of at least one of the organic phosphonic acid, the organic phosphoric acid ester, and the neutralized salts thereof. The lubricant for plastic working as described.   The lubricant for plastic working according to any one of claims 1 to 11, which is substantially free from a water-soluble inorganic salt.   A form of an aqueous dispersion or aqueous solution in which at least one of the organic phosphonic acid, the organic phosphoric acid ester, and a neutralized salt thereof is dissolved in water, and the lubricating component is dispersed or dissolved in the water. The lubricant for plastic working according to any one of claims 1 to 12, wherein   The lubricant for plastic working according to any one of claims 1 to 13, further comprising a filler.   A metal material, wherein the plastic working lubricant according to claim 1 is applied to a surface. Applying the plastic working lubricant according to any one of claims 1 to 14 to the surface of the metal material;
Plastically processing a metal material having the plastic processing lubricant applied to the surface;
A method for producing a plastically processed metal material.