JP2015071750A - Method for manufacturing metal workpiece - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a metal workpiece excellent in antifoaming properties of water soluble metal working oil and excellent in productivity and workability, including a step for circulating or a step for spraying the water soluble metal working oil.SOLUTION: There is provided a method for manufacturing a metal workpiece using water soluble metal working oil including a step of circulating or a step for spraying the water soluble metal working oil containing three or more valent polyoxyalkylene polyol (A) of 0.1 wt.% or more.

Description

The present invention relates to a method for producing a metal workpiece using a water-soluble metal working oil, and more specifically, a metal including steps such as cutting, grinding, polishing, rolling, pressing, forging, drawing, quenching, or die casting of a metal member. The present invention relates to a method for manufacturing a processed product.

  Conventionally, as a water-soluble metal processing oil for cutting or grinding metal members, for the purpose of eliminating the risk of fire, improving the cleanability, and improving the workplace environment because there is no oil mist. Water-soluble metalworking oil diluted with water is used (Patent Document 1).

Usually, water-soluble metalworking oil diluted with water is liable to generate bubbles, and there is a problem that the metalworking oil leaks from the tank when the metalworking oil is circulated and reused, and the surroundings are contaminated. Moreover, when spraying metal processing oil, there exists a problem which cannot apply processing oil uniformly to a metal member.
Therefore, as a countermeasure for suppressing the generation of bubbles, it is considered to use a compound having a high hydrophobicity. For example, it is known that a metal processing oil contains a silicon-based antifoaming agent or the like as a highly hydrophobic compound. (Patent Document 2).

  However, the water-soluble metal processing oil containing a highly hydrophobic compound such as the above silicon-based antifoaming agent adheres firmly to the metal surface, which is the workpiece, during processing. There is a problem that the system antifoaming agent and the like cannot be completely removed, which obstructs the surface treatment process such as the next painting, and the surface treatment properties such as paintability are deteriorated. In addition, it is known that antifoaming agents exhibit antifoaming properties by forming an emulsion in water-soluble metallized oil, but when circulating for a long time, the emulsion collapses and the antifoaming properties cannot be maintained. There's a problem. Furthermore, in processing such as cutting and grinding, silicon-based antifoaming agent or the like adheres firmly to the metal chips that are the work piece generated during the processing, so the processing proceeds and the amount of chips increases. Along with this, there is a problem that the foam suppression property is lowered and the foam suppression property cannot be maintained during processing.

JP 2010-111854 A JP 2011-079956 A

  Then, this invention is excellent in the foam suppression property of water-soluble metalworking oil, and excellent in productivity and workability in the manufacturing method of a metalworked product including the process of circulating the water-soluble metalworking oil, or the process of spraying. It aims at providing the manufacturing method of a metal workpiece.

The inventors of the present invention have reached the present invention as a result of studies to achieve the above object.
That is, the present invention uses a water-soluble metalworking oil comprising a step of circulating or spraying a water-soluble metalworking oil containing 0.1% by weight or more of a polyoxyalkylene polyol (A) having a valence of 3 or more. It is a manufacturing method of a metal workpiece.

  The method for producing a metal processed product according to the present invention has an effect that the foamed metal additive oil is excellent in foaming in a method for producing a metal processed product including a step of circulating or spraying a water-soluble metal processed oil.

  The present invention relates to metal processing using a water-soluble metalworking oil comprising a step of circulating or spraying a water-soluble metalworking oil containing 0.1% by weight or more of a polyoxyalkylene polyol (A) having a valence of 3 or more. The manufacturing method of goods is provided.

  The step of circulating the water-soluble metal working oil in the present invention refers to recovering the water-soluble metal working oil supplied to the workpiece or the processing tool when processing the metal, and removing the chips as it is or / and / or After cooling, etc., this is the process of supplying to the workpiece or processing tool again using a pump, etc., and in metal processing such as cutting, grinding, polishing, rolling, drawing, quenching, etc. This has the effect of reducing the usage and disposal of basic metal processing oil.

  For removal of chips, operations such as centrifugation, filter press, and membrane filtration may be performed.

  Examples of the centrifugation operation include use of a decanter type centrifuge or a centrifuge using a filter cloth. Examples of the membrane filtration operation include microfiltration (MF) and ultrafiltration (UF). Examples of the material of the filtration membrane include ceramics and organic membranes. The production method of the present invention is excellent in foam suppression and has an effect of high filtration efficiency because it contains a small amount of air when the water-soluble metal mineral oil is fed to the filtration device. Furthermore, since the metal processing oil does not need to contain a silicon-based antifoaming agent that closes the membrane as a highly hydrophobic compound, there is an effect of high filtration efficiency.

  The step of spraying the water-soluble metal working oil in the present invention is a step of spraying the water-soluble metal working oil on a workpiece or a processing tool when processing a metal, and cutting, grinding, polishing, or polishing a metal member. In metal processing such as rolling, pressing, forging, drawing, die casting, etc., even if a small amount of water-soluble metal processing oil is used, it can be supplied uniformly over a wide range, thus reducing the amount of water-soluble metal processing oil used and discarded effective. In the case where chips are generated during metal processing, it is preferable to include a treatment for removing chips from the collected water-soluble metal processing oil in the same manner as described above.

  In the present invention, the cutting of the metal member is a process of processing metal using an apparatus such as a lathe, a machining center, a drilling machine, a band saw machine, etc., and grinding is a grinding machine, a wire saw in addition to the same apparatus as the cutting. It is the process of processing a metal using fixed abrasives or loose abrasives using an apparatus such as.

  The method for producing a metal processed product of the present invention is a metal processed by a step of circulating or spraying a water-soluble metalworking oil containing 0.1% by weight or more of a polyoxyalkylene polyol (A) having a valence of 3 or more. A step of cleaning the workpiece may be included.

  Examples of the trivalent or higher polyoxyalkylene polyol (A) in the present invention include compounds obtained by addition polymerization of alkylene oxide to a compound (a) having 3 or more active hydrogens. Examples of the compound (a) having 3 or more active hydrogens include ammonia and a compound having active hydrogens in which the active hydrogen is a hydroxyl group / or an amino group.

  Specific examples of the compound (a) having three or more active hydrogens in the present invention include compounds having three active hydrogens [glycerin, trimethylolpropane, trimethylolethane, etc.]; compounds having four active hydrogens [Pentaerythritol, glucose, fructose, diglycerin, ethylenediamine, phenylenediamine, etc.]; Compounds having 5 active hydrogens [xylitol, triglycerin, diethylenetriamine, etc.]; Compounds having 6 active hydrogens [sorbitol, dipentaerythritol , Triethylenetetramine, triaminobenzene, etc.]; compounds having 7 active hydrogens [tetraethylenepentamine, etc.]; compounds having 8 active hydrogens [sucrose, pentaethylenehexamine, benzenetetramine, etc.]; Alkenyl alcohols, polyglycerol, polyethylene amines.

  Of these compounds (a) having 3 or more active hydrogens, preferred are compounds having 3 to 20 active hydrogens, more preferably 3 to 8 from the viewpoint of foam suppression and permeability. Glycerin, trimethylolpropane, trimethylolethane, ammonia, pentaerythritol, glucose, fructose, diglycerin, ethylenediamine, phenylenediamine, xylitol, triglycerin, diethylenetriamine, sorbitol, dipentaerythritol, triethylenetetraamine, Triaminobenzene, tetraethylenepentamine, sucrose, pentaethylenehexamine, and benzenetetramine. In the case of a compound having less than 3 active hydrogens, the antifoaming property deteriorates. When the number of active hydrogens is 20 or less, the permeability of the water-soluble metal working oil is improved, which is preferable from the viewpoint of lubricity and cooling properties.

The number average molecular weight of the polyoxyalkylene polyol (A) in the present invention is not usually limited, but is preferably 149 to 150,000. A number average molecular weight within this range is preferred from the viewpoint of lubricity and cooling properties of the water-soluble metalworking oil.
The number average molecular weight is a molecular weight determined by gel permeation chromatography (GPC).
The number average molecular weight is measured by GPC at 40 ° C. using polyethylene oxide as a reference material. [For example, apparatus main body: HLC-8120 (manufactured by Tosoh Corporation), column: TSKgel α6000, G3000 PWXL, manufactured by Tosoh Corporation, detector: differential refractometer detector built in apparatus main body, eluent: 0.5 wt% acetic acid Soda / water / methanol (volume ratio 70/30), eluent flow rate: 1.0 ml / min, column temperature: 40 ° C., sample: 0.25 wt% eluent solution, injection volume: 200 μl, standard substance: Tosoh (Manufactured by TSK STANDARD POLYETHYLENE OXIDE, data processing software: GPC-8020 model II (manufactured by Tosoh Corporation)).

In addition, the number of the hydroxyl groups of the polyoxyalkylene polyol (A) in the present invention is 3 or more, and can be calculated by the following formula.
Number of hydroxyl groups = [active hydrogen value of polyoxyalkylene polyol] / ([number average molecular weight of polyoxyalkylene polyol] / 56,100)
The active hydrogen value means [56,100 / molecular weight per active hydrogen] and corresponds to the hydroxyl value when the group having active hydrogen is a hydroxyl group. The method for measuring the active hydrogen value is not particularly limited as long as it is a method that can measure the value defined above, but in the case of the hydroxyl value, for example, the method described in JIS K1557-1 can be mentioned.
The number average molecular weight is the molecular weight by GPC described above.

  The HLB of the polyoxyalkylene polyol (A) in the present invention is not usually limited, but is preferably 8.0 to 18.5. Within this range, the permeability of the working fluid is further improved, and the functions of lubricity and cooling are improved.

Here, “HLB” is an index indicating a balance between hydrophilicity and lipophilicity, and is described in, for example, “Introduction to Surfactants” (published by Sanyo Chemical Industries, Ltd., 2007, Takehiko Fujimoto), page 212. It is known as the calculated value by the Oda method, not the calculated value by the Griffin method.
The HLB value can be calculated from the ratio between the organic value and the inorganic value of the organic compound by the following formula.
HLB = 10 × inorganic / organic The organic value and the inorganic value for deriving HLB can be calculated using the values in the table described in the above “Introduction to Surfactant” page 213.

  When the polyoxyalkylene polyol (A) in the present invention is an alkylene oxide adduct of the compound (a) having three or more active hydrogens, and the three or more active hydrogens are all hydroxyl groups, the polyoxyalkylene polyol (A1 ) Is represented by the following general formula (1).

R ¹ [—O— (A ¹ O) _m —H] _f (1)
[R ¹ represents a hydrocarbon group, and (A ¹ O) represents an oxyalkylene group having 2 to 4 carbon atoms. m is a number from ^{1 to} 450, a plurality of A ¹ may be the same or different, and (A ¹ O) _{m in} the case where m is 2 or more may be random addition or block addition. f is an integer of 3-20. ]

A ¹ O represents an oxyalkylene group having 2 to 4 carbon atoms, and specific examples thereof include an oxyethylene group, an oxypropylene group, and an oxybutylene group. In the case of an oxyethylene group, ethylene oxide, in the case of an oxypropylene group, 1,2-propylene oxide, 1,3-propylene oxide, in the case of an oxybutylene group, tetrahydrofuran, 1,2-butylene oxide and the like can be used.

  In the polyoxyalkylene polyol (A1) in the present invention, one of ethylene oxide, propylene oxide, tetrahydrofuran, and 1,2-butylene oxide is added alone to the compound (a) having 3 or more active hydrogens. Alternatively, two or more of these may be used in combination. From the viewpoint of foam suppression and lubricity, two or more of ethylene oxide, propylene oxide and tetrahydrofuran are preferably used in combination.

  The polyoxyalkylene polyol (A1) in the present invention may be added randomly or in a block addition manner when adding two or more alkylene oxides or tetrahydrofuran to the compound (a) having three or more active hydrogens. The order of adding two or more kinds of alkylene oxides, for example, ethylene oxide and propylene oxide, is not limited.

  m represents the number of added moles of alkylene oxide having 2 to 4 carbon atoms, and when two or more kinds of alkylene oxide are used in combination, it is the sum of the number of added moles of two or more kinds. m is preferably 1 to 450. If m is less than 1, the lubricity deteriorates. On the other hand, when m exceeds 450, the viscosity becomes too high, so that the permeability is lowered and the lubricity or cooling function is deteriorated.

(A ¹ O) _{m in} the formula (1) of the polyoxyalkylene polyol (A1) in the present invention can also be represented by the following general formula (2).

^{_{- (A 2 O) n (}} A 3 O) j (A 4 O) k - (2)

[(A ² O) represents an oxyethylene group, (A ³ O) represents an oxypropylene group, and (A ⁴ O) oxybutylene group. n is a number from 0 to 350, j and k are each a number from 0 to 100, and at least one of j and k is 1 or more, and n / (n + j + k) is 0 to 0.9. When n, j, and k are 2 or more, the addition format may be random addition or block addition. ]

(A ² O) _n (A ³ O) _j (A ⁴ O) _k is a structure added in any order when there are two or more oxyethylene groups, oxypropylene groups, and oxybutylene groups. In addition, when n, j, and k are 2 or more, it means that these two or more groups may have either a random addition or a block addition.

  n is preferably 0 to 350, more preferably 0 to 250, from the viewpoints of viscosity stability and permeability.

  j is preferably 0 to 100, more preferably 0 to 50, from the viewpoint of water solubility and viscosity stability.

  k is preferably 0 to 100, more preferably 0 to 50, from the viewpoint of water solubility and viscosity stability.

  n / (n + j + k) is not normally limited, but is preferably 0 to 0.9 from the viewpoint of permeability. Note that n + j + k = m.

  In the present invention, the polyoxyalkylene polyol (A) is an alkylene oxide adduct of the compound (a) having 3 or more active hydrogens, and the compound (a) having 3 or more active hydrogens is ammonia or active hydrogens. When all are amino groups, the polyoxyalkylene polyol (A2) is represented by the following general formula (3).

R ² [— (A ⁵ O) _p —H] _g (3)
[R ² is a residue obtained by removing active hydrogen from a hydrocarbon having an ammonia or amino group, and (A ⁵ O) represents an oxyalkylene group having 2 to 4 carbon atoms. p is a number from 1 to 450, and a plurality of A ⁵ may be the same or different, and when p is 2 or more, the (A ⁵ O) _p portion may be random addition or block addition. g is a number from 3 to 20. ]

A ⁵ O represents an oxyalkylene group having 2 to 4 carbon atoms, and the same one as A ¹ O can be used.

  The polyoxyalkylene polyol (A2) in the present invention is obtained by adding one of ethylene oxide, propylene oxide, tetrahydrofuran, and 1,2-butylene oxide alone to the compound (a) having 3 or more active hydrogens. Alternatively, two or more of these may be used in combination. From the viewpoint of foam suppression and lubricity, two or more of ethylene oxide, propylene oxide and tetrahydrofuran are preferably used in combination.

  In the polyoxyalkylene polyol (A2) in the present invention, the addition form when adding two or more alkylene oxides or tetrahydrofuran to the compound (a) having three or more active hydrogens may be random addition or block addition. The order of adding two or more kinds of alkylene oxides, for example, ethylene oxide and propylene oxide, is not limited.

  m represents the number of added moles of alkylene oxide having 2 to 4 carbon atoms, and when two or more kinds of alkylene oxide are used in combination, it is the sum of the number of added moles of two or more kinds. m is preferably 1 to 450. If m is less than 1, the lubricity deteriorates. On the other hand, when m exceeds 450, the viscosity becomes too high, so that the permeability is lowered and the lubricity or cooling function is deteriorated.

In the present invention, (A ⁵ O) _{p in} the formula (3) of the polyoxyalkylene polyol (A2) can also be represented by the following general formula (4).

^{_{- (A 6 O) q (}} A 7 O) r (A 8 O) s - (4)
[(A ⁶ O) represents an oxyethylene group, (A ⁷ O) represents an oxypropylene group, and (A ⁸ O) represents an oxybutylene group. q is a number from 0 to 350, r and s are each a number from 0 to 100, and at least one of r and s is 1 or more, and q / (q + r + s) is 0 to 0.9. When q, r, and s are 2 or more, the addition format may be random addition or block addition. ]

(A ⁶ O) _q (A ⁷ O) _r (A ⁸ O) _s is a structure added in any order when there are two or more oxyethylene groups, oxypropylene groups, and oxybutylene groups. In addition, when q, r, and s are 2 or more, it means that the structure in which two or more of these groups are added randomly or in blocks may be added.

  q is preferably 0 to 350, more preferably 0 to 250, from the viewpoints of viscosity stability and permeability.

  From the viewpoint of water solubility and viscosity stability, r is preferably 0 to 100, more preferably 0 to 50.

  s is preferably 0 to 100, more preferably 0 to 50, from the viewpoints of water solubility and viscosity stability.

  Although q / (q + r + s) is not normally limited, From the viewpoint of permeability, it is preferably 0 to 0.9. Note that q + r + s = p.

Specific examples of the polyoxyalkylene polyol (A) of the present invention include a random adduct of 5 mol of glycerin ethylene oxide (hereinafter sometimes abbreviated as EO) and 4 mol of propylene oxide (sometimes abbreviated as PO). Glycerin butylene oxide (hereinafter sometimes abbreviated as BO) 5 mol adduct, glycerin EO 31 mol and PO 23 mol random adduct, glycerin EO 39 mol and PO 55 mol random adduct, glycerin EO 113 mol and PO85 EO / PO random adducts of glycerin, such as random adducts of mol, EO 324 mol of glycerine and 132 mol of PO, random adducts of 964 mol and 284 mol of glycerin;
EO / THF random adduct of glycerin, such as a random adduct of 44 mol of glycerol and 27 mol of THF;
EO-PO block adducts of glycerin, such as block adducts of glycerin EO 7 mol and PO 10 mol, glycerin EO 108 mol and PO 55 mol, glycerin EO 179 mol and PO 15 mol block adduct;
PO adduct of glycerin such as PO3 mol adduct of glycerin, PO6 mol adduct of glycerin;
An EO adduct of glycerin, such as an EO 134 molar adduct of glycerin;
EO / PO random adducts of trimethylolpropane, such as a random adduct of 93 mol of trimethylolpropane and 69 mol of PO;
EO / PO random adducts of pentaerythritol, such as random adducts of 963 mol of pentaerythritol and 283 mol of PO;
EO-PO block adduct of pentaerythritol, such as a block adduct of 12 mol EO of pentaerythritol and 44 mol of PO;
EO / PO random adducts of sorbitol, such as a random adduct of 42 mol EO and 14 mol PO of sorbitol, a random adduct of EO 80 mol and PO 61 mol of sorbitol, 1928 mol EO of sorbitol and 569 mol of PO;
PO adducts of sorbitol EO / PO random adducts such as 44 mol of sorbitol EO and PO 30 mol adduct of PO 20 mol random adduct;
BO adduct of sorbitol EO / PO random adduct, such as BO15 mol adduct of sorbitol EO 32 mol and PO6 mol random adduct;
PO adduct of sorbitol EO / THF random adduct, such as PO 30 mol adduct of sorbitol EO 43 mol and THF 27 mol random adduct;
EO / PO random adducts of ammonia, such as 19 mol EO of ammonia and random adducts of PO35;
EO-PO block adducts of ethylenediamine such as block adducts of 80 mol EO and 20 mol PO of ethylenediamine;
EO / THF random adduct of diethylenetriamine such as 88 mol of diethylenetriamine EO and 85 mol of THF random adduct;
EO / PO random adducts of triethylenetetramine such as random adducts of 50 mol EO and 60 mol PO of triethylenetetramine;
PO adduct of tetraethylenepentamine EO / PO random adduct, such as PO20 mol adduct of 26 mol of EO of tetraethylenepentamine and 24 mol of random adduct of PO.
PO adducts of EO / THF random adducts of pentaethylenehexamine, such as PO 40 mol adducts of 45 mol of EO of pentaethylenehexamine and 43 mol of random adduct of THF;
EO / PO random of polyamide polyamines such as random adduct of 322 mol of PO and 612 mol of PO polyamid (weight average molecular weight 1,900) consisting of dimer acid of linoleic acid (Haridimer 216, manufactured by Harima Chemical Co., Ltd.) and pentaethylenehexamine Examples include adducts.

Among these, (A1) is preferably a polyoxyalkylene polyol of glycerin, trimethylolpropane, pentaerythritol and sorbitol, and (A2) is ammonia, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepenta. It is a polyoxyalkylene polyol of min, phenylenediamine, triaminobenzene, and benzenetetramine.
From the viewpoint of foam suppression and permeability, more preferably, an EO / PO random adduct of sorbitol, a PO adduct of EO / PO random adduct of sorbitol, a BO adduct of EO / PO random adduct of sorbitol, and penta It is a PO adduct of EO / THF random adduct of ethylenehexamine.

The content of the polyoxyalkylene polyol (A) in the present invention varies depending on the metal processing method, but is 0.1% by weight or more based on the weight of the water-soluble metal processing oil. The lower limit is preferably 0.3% by weight or more, and more preferably 1.0% by weight or more. The upper limit is preferably 95% by weight or less, and more preferably 90% by weight or less.
The water-soluble processing oil in the present invention is preferably used after being hydrated so that there is no risk of fire, and the water content is preferably 5% by weight or more based on the weight of the water-soluble metal processing oil, more preferably 10% by weight or more.

  The water-soluble metalworking oil used in the present invention may contain a polyoxyalkylene monool (B), but the content of (B) is preferably 30 from the viewpoint of foam suppression with respect to the weight of (A). % By weight or less, more preferably 20% by weight or less.

  Specific examples of the polyoxyalkylene monool (B) include allyl alcohol PO adducts, allyl alcohol BO adducts, allyl alcohol EO / PO random adducts, allyl alcohol EO-PO block adducts, and the like. It is done. (B) is a by-product generated when synthesizing (A), and tends to be generated more when the value of n / (n + j + k) or q / (q + r + s) is small. When the molecular weight of (A) per active hydrogen of the compound (a) having 3 or more active hydrogens is large, a large amount tends to be generated. That is, when (A) has the same molecular weight, the content of (B) decreases as the amount of active hydrogen possessed by (a) increases.

  The water used for the water-soluble metalworking oil used in the present invention may be any of pure water, ion exchange water, tap water, industrial water and the like.

  The water-soluble metal working oil used in the present invention may further contain a lubricant for the purpose of adjusting lubricity. Examples of the lubricant include polyether compounds such as polyethylene glycol, aliphatic monocarboxylic acids and their ester compounds (excluding formic acid and acetic acid), aliphatic dicarboxylic acids and their ester compounds, and the like.

  The water-soluble metalworking oil used in the present invention may further contain a rust preventive agent for the purpose of suppressing corrosion of the apparatus and the like. Examples of rust inhibitors include azole compounds such as benzotriazole, imidazoles, amidines such as 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), alkanolamines such as triethanolamine, or alkylenes thereof. And oxide adducts.

  An appropriate amount of a pH adjusting agent may be added to the water-soluble metal working oil used in the present invention for the purpose of adjusting the pH of the cutting fluid. Examples of such pH adjusters include basic compounds such as metal hydroxides (eg, sodium hydroxide, potassium hydroxide, etc.); organic acids (eg, acetic acid, formic acid, citric acid, etc. (excluding aliphatic carboxylic acids)) An acidic compound such as an inorganic acid (for example, phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, etc.);

  A dispersant may be added to the water-soluble metalworking oil used in the present invention for the purpose of adjusting the dispersibility of the chips. Such dispersants include polycarboxylates, naphthalene sulfonic acid formalin condensates and / or salts thereof, polystyrene sulfonate, polyvinyl sulfonate, polyalkylene glycol sulfate, polyvinyl alcohol phosphate, melamine Examples include sulfonate and lignin sulfonate.

  Examples of the metal processed product manufactured by the method of manufacturing a metal processed product of the present invention include frames used in aircraft, automobiles, ships, etc., structural members such as outer plates and wheels, metal materials such as engines and transmissions, and mobile phones. Cases of electronic devices used for tablets, electronic parts such as vibration motors and capacitors, silicon wafers used for solar cells, steel members used in construction, metal parts such as pipes, spirals, nails, etc. It is done.

  Hereinafter, although an example and a comparative example explain the present invention further, the present invention is not limited to these. Hereinafter, unless otherwise specified, “%” represents “% by weight” and “parts” represents “parts by weight”.

Production Example 1 <Production of glycerin EO / PO random adduct (A-1)>
A stainless steel pressure reactor was charged with 32.9 parts of glycerin and 0.05 part of sodium hydroxide. After purging with nitrogen, a mixed solution of 484 parts of ethylene oxide and 484 parts of propylene oxide was injected at 110 to 130 ° C. over 4 hours. .
The mixture was further reacted at the same temperature for 10 hours to obtain an EO / PO random adduct (A-1) of glycerin of the present invention (f (number of hydroxyl groups contained in the compound) = 3; number average molecular weight 2,800). The number average molecular weight is a molecular weight by GPC.

Production Example 2 <Production of glycerin EO / PO random adduct (A-2)>
In Production Example 1, the same operation as in Production Example 1 was carried out except that 1.56 parts of glycerin, 719 parts of ethylene oxide, and 280 parts of propylene oxide were used, and the EO / PO random adduct of glycerin of the present invention ( A-2) (f = 3; number average molecular weight 59,000) was obtained. Moreover, the EO / PO random adduct (B-1) (number average molecular weight 19,000) of allyl alcohol was obtained as a by-product, and was 30% with respect to the weight of (A-2).

Production Example 3 <Production of sorbitol EO / PO random adduct (A-3)>
In Production Example 1, the same operation as in Production Example 1 was conducted except that glycerin was changed to 1.54 parts sorbitol, 719 parts ethylene oxide and 280 parts propylene oxide, and the EO / PO of sorbitol of the present invention was used. A random adduct (A-3) (f = 6; number average molecular weight 118,000) was obtained. Moreover, EO / PO random adduct (B-2) (number average molecular weight 24,000) of allyl alcohol was obtained as a by-product, and was 30% based on the weight of (A-3).

Production Example 4 <Production of PO block adduct (A-4) of EO / PO random adduct of sorbitol>
In Production Example 3, the same operation as in Production Example 3 was performed, except that 36.4 parts of sorbitol, 482 parts of ethylene oxide, 134 parts of propylene oxide, and 2.5 parts of sodium hydroxide were used. 348 parts of propylene oxide was injected in 4 hours. The mixture was further reacted at the same temperature for 6 hours to obtain a PO block adduct (A-4) (f = 6; number average molecular weight 5,000) of the EO / PO random adduct of sorbitol of the present invention. Moreover, PO adduct (B-3) (number average molecular weight 450) of allyl alcohol was obtained as a by-product, and was 10% with respect to the weight of (A-4).

Production Example 5 <Production of BO block adduct (A-5) of EO / PO random adduct of sorbitol>
In Production Example 3, the same operation as in Production Example 3 was performed, except that 60.7 parts of sorbitol, 374 parts of ethylene oxide, 132 parts of propylene oxide, and 2.5 parts of sodium hydroxide were used. 432 parts of butylene oxide was injected in 6 hours. The reaction was further continued at the same temperature for 8 hours to obtain a BO block adduct (A-5) (f = 6; number average molecular weight 3,000) of the sorbitol EO / PO random adduct of the present invention. Moreover, the BO adduct (B-4) (number average molecular weight 300) of methylallyl alcohol was obtained as a by-product, and was 5% with respect to the weight of (A-5).

Production Example 6 <Production of ammonia EO-PO block adduct (A-6)>
A stainless steel pressure reactor was charged with 5.67 parts of ammonia, and after substitution with nitrogen, 44.0 parts of ethylene oxide was injected at 80 to 100 ° C. over 8 hours.
The mixture was further reacted at the same temperature for 4 hours. Next, 0.05 part of sodium hydroxide was added, and after purging with nitrogen, 244 parts of ethylene oxide was injected at 120 to 140 ° C. in about 4 hours.
The mixture was further reacted at the same temperature for 4 hours, and then 706 parts of propylene oxide was injected in 4 hours. The mixture was further reacted at the same temperature for 6 hours to obtain an EO-PO block adduct (A-6) (f = 3; number average molecular weight 3,000) of ammonia. Moreover, PO adduct (B-5) (number average molecular weight 400) of allyl alcohol was obtained as a by-product, and was 5% with respect to the weight of (A-6).

Production Example 7 <Production of PO block adduct (A-7) of EO / THF random adduct of pentaethylenehexamine>
A stainless steel pressure reactor was charged with 2.90 parts of pentaethylenehexamine, and after nitrogen substitution, 44.0 parts of ethylene oxide was injected at 80 to 100 ° C. over 8 hours.
The mixture was further reacted at the same temperature for 4 hours. Next, 415 parts of tetrahydrofuran and 2.02 parts of boron trifluoride tetrahydrofuran were charged. After purging with nitrogen, 222 parts of ethylene oxide was injected at 60 to 80 ° C. over 4 hours.
The mixture was further reacted at the same temperature for 4 hours, and then 290 parts of propylene oxide was injected in 4 hours.
The mixture was further reacted at the same temperature for 6 hours to obtain a PO block adduct (A-7) (f = 8; number average molecular weight 8,000) of an EO / THF random adduct of pentaethylenehexamine of the present invention. Moreover, PO adduct (B-6) (number average molecular weight 600) of allyl alcohol was obtained as a by-product, and was 11% with respect to the weight of (A-7).

Production Example 8 <Production of Polyamide Polyamine EO / PO Random Additive (A-8)>
2.00 parts of Halidimer 216 (manufactured by Harima Chemicals Co., Ltd.), 456 parts of pentaethylenehexamine, titanium catalyst {titanium dihydroxybis (triethanolaminate); described in JP-A-2006-243715} in a container capable of decompression Part preparation and dehydration condensation reaction were carried out at 150 ° C. for 5 hours to obtain polyamide polyamine (weight average molecular weight 1,900).
A stainless steel pressure reactor was charged with 5.80 parts of the polyamidopolyamine and 0.05 parts of sodium hydroxide. After purging with nitrogen, 795 parts of ethylene oxide and 199 parts of propylene oxide were injected over 12 hours at 110 to 130 ° C. did.
The mixture was further reacted at the same temperature for 4 hours to obtain an EO / PO random adduct (A-8) (g = 20; number average molecular weight 179,000) of polyamide polyamine. Moreover, the EO / PO random adduct (B-7) (number average molecular weight 8,000) of allyl alcohol was obtained as a by-product, and it was 14% with respect to the weight of (A-8).

Comparative Production Example 1 <Production of hexanediol EO / PO random adduct (A'-1)>
EO / PO random adduct of glycerin for comparison (A′-) except that hexanediol was 6.94 parts, ethylene oxide was 745 parts, and propylene oxide was 248 parts. 1) (f = 2; number average molecular weight 17,000) was obtained. Moreover, EO / PO random adduct (B-8) (number average molecular weight 2,000) of allyl alcohol was obtained as a by-product, and was 11% based on the weight of (A′-1).

Comparative Production Example 2 <Production of Polypropylene Glycol EO-PO Block Adduct (A'-2)>
A stainless steel pressure reactor was charged with 19.9 parts of propylene glycol and 0.05 parts of sodium hydroxide, and after nitrogen substitution, 580 parts of propylene oxide was injected at 120 to 140 ° C. over 4 hours.
The reaction was further carried out at the same temperature for 10 hours, and then 400 parts of ethylene oxide was injected in 4 hours. The mixture was further reacted at the same temperature for 6 hours to obtain an EO-PO block adduct (A′-2) (f = 2; number average molecular weight 2,920) of polypropylene glycol for comparison. Moreover, the EO-PO block adduct (B-9) (number average molecular weight 650) of allyl alcohol was obtained as a by-product, and was 11% with respect to the weight of (A′-2).

  Each component is blended at a blending ratio (parts by weight) shown in Table 1, and water-soluble metalworking oils of Examples 1 to 11 and Comparative Examples 1 to 5 are prepared. Performance evaluation was performed. Performance evaluation of processability, filterability, and foam suppression persistence was performed.

  “Polyethylene glycol” in Table 1 is polyethylene glycol 4,000,000 manufactured by Wako Pure Chemical Industries, Ltd. “Sunhibitor No. 50” is a rust inhibitor made by Sanyo Chemical Co., Ltd., and “Triethanolamine” is a rust inhibitor made by Mitsui Chemicals. “Silicone-based antifoaming agent” is KM-7752 manufactured by Shin-Etsu Chemical Co., Ltd.

<Evaluation of foam suppression>
The evaluation of foam suppression was performed by the following method.
(1) 175 mL of water-soluble metalworking oil is put into a 200 mL tall beaker having an inner diameter of 5.5 cm, and Biomixer (registered trademark) (manufactured by Nippon Seiki Seisakusho; BM-2) is placed 1 cm above the bottom of the tall beaker. The tip of the mold was adjusted.
(2) The distance from the bottom of the tall beaker to the liquid level (liquid level height: P (cm)) was recorded.
(3) The water-soluble metalworking oil contained in the tall beaker was temperature-controlled at 25 ° C., and then stirred for 2 minutes at a rotational speed of 8,000 rpm.
(4) 30 seconds after stirring was stopped, the distance from the bottom of the tall beaker to the highest bubble surface (bubble surface height: Q (cm)) was measured, and the ratio of the bubble surface height to the liquid surface height [Q / P] was recorded.

<Evaluation of foam suppression persistence-1>
In the evaluation of foam suppression, the same operation as in the evaluation of foam suppression was performed except that the stirring time was changed to 30 minutes, and foam suppression persistence-1 was evaluated.

The evaluation of foam suppression and foam persistence-1 was performed according to the following criteria.
A: [Q / P] is less than 1.20 O: [Q / P] is 1.20 or more and less than 1.40 X: [Q / P] is 1.40 or more

<Evaluation of cutting workability>
The machinability was evaluated by the following method.
(1) Metal cutting by a square end mill was performed using a machining center (manufactured by FANUC CORPORATION; ROBODRILL (registered trademark) α-T14iFa). 10 L of water-soluble metal working oil was put in a container, and the water-soluble metal working oil was supplied from the container to the processing point at a flow rate of 6.0 L / min using an electric pump. The diameter of the supply nozzle was 5 mm, and the tool and workpiece were supplied from two nozzles so that they were completely wetted. The supplied water-soluble metalworking oil was recovered, returned to the container again, and recycled.
Tool used: End mill (manufactured by OSG Corporation; WX-EDS4)
Workpiece: Carbon steel (S45C), 40 mm x 40 mm x 30 mm thickness
Tool rotation speed: 5950 rpm
Feeding speed: 235mm / min
Feed direction: Down cut Axial depth of cut: 10.0 mm (finishing), 5.0 mm (roughing)
Radial depth of cut: 0.2 mm (finishing), 0.4 mm (roughing)
Cutting part finished shape: 10 mm x 10 mm x 10 mm, corner radius 3.0 mm
(2) The surface roughness (Ra) of the corner portion was measured with a surface roughness meter (made by Taylor Hobson; Form Talysurf PGI Plus).
λs value: 2.5 μm
λc value: 0.8mm
Evaluation length: 4.0mm

The machinability was evaluated according to the following criteria.
A: Ra is less than 0.30 μm O: Ra is 0.30 μm or more and less than 0.50 μm ×: Ra is 0.50 μm or more

  As is clear from the results in Table 1, each of the water-soluble metalworking oils of the present invention of Examples 1 to 11 is excellent in foam suppression property, foam suppression persistence, and cutting workability. Examples 1, 2, 3, 6, 7, 8, 9, 10, and 11 in which the content of the polyoxyalkylene monool (B) is 20% by weight or less based on the weight of the polyoxyalkylene polyol (A) In particular, it is excellent in foam suppression and foam persistence. Examples 2 and 3 with a high content of polyoxyalkylene polyol (A), Examples 4, 5, and 11 with a high number average molecular weight, and Examples 8, 9, and 10 with a low HLB are particularly excellent in machinability. . On the other hand, Comparative Examples 1 and 2 using a polyoxyalkylene polyol having less than 3 valences are excellent in cutting workability, but are inferior in foam suppression and foam suppression persistence. Comparative Example 3 using a polyoxyalkylene polyol of less than 3 valences and adding a silicone-based antifoaming agent is excellent in cutting workability and foam suppression property, but is inferior in foam suppression persistence. Comparative Example 4 containing no polyoxyalkylene polyol is excellent in foam suppression and foam suppression persistence, but is inferior in cutting workability. Comparative Example 5 using a polyoxyalkylene polyol of less than 3 valences is inferior in antifoaming properties and antifoaming sustainability, HLB is too large, and molecular weight is too large, so that machinability is also inferior. From these results, in the processing having the step of circulating the water-soluble processing oil, by using the method for producing a metal processed product of the present invention, it is excellent in foam suppression performance without adding a silicone-based antifoaming agent. Since it withstands repeated use, it can be seen that the cost of the processing liquid and the antifoaming agent for addition can be reduced.

  Each component is blended at the blending ratio (parts by weight) shown in Table 2, and water-soluble metalworking oils of Examples 12 to 20 and Comparative Examples 6 to 10 are prepared. Cutting processability, filterability, and suppression after filtration. The foam performance was evaluated.

<Evaluation of cutting processability>
Evaluation of cutting workability was performed by the method shown below.
(1) A 125 mm square single crystal silicon ingot was used as a material to be cut, and a cutting test was performed with a diamond fixed abrasive wire and a single wire saw cutting machine (manufactured by Takatori Co., Ltd., WSD-K2).
Cutting conditions: Wire strand diameter 90 μm, wire tension 10 N, wire pitch width 350 μm, wire traveling speed 600 m / min, wire reciprocation 1 time / min, wafer cutting number 2 sheets, cutting speed 0.6 mm / min (lifting position 0 mm) ~ 113.5mm), 0.2mm / min (lifting position 113.5mm ~ 130mm)
(2) After cutting, the maximum height (Pz) of the cross-sectional curve of the wafer was measured using a surface roughness measuring instrument (SURF TEST SV-600, manufactured by Mitutoyo Corporation) for a portion 5 mm from the lower end of the wafer. When the cutting depth of the abrasive grains varies during cutting, the cross-sectional curve of the wafer in the direction perpendicular to the wire traveling direction is not flat. That is, in the cross-sectional curve, the maximum height (Pz) of the wafer cross-sectional curve from the reference line increases.
Measurement conditions: contour curve filter λs 2.5 μm, reference length 0.2 mm, evaluation length 4.0 mm, measurement length 5.0 mm

<Evaluation of filterability>
The filterability was evaluated by the method shown below.
(1) A filter holder (glass, capacity 150 ml) sandwiching a membrane filter (Merck, cellulose mixed ester, pore size 0.025 μm, diameter 47 mm) was set in a 300 ml suction bottle via a rubber stopper (made of silicon). .
(2) 10 ml of the water-soluble metallizing solution after the evaluation of cutting processability was poured onto the membrane filter, the suction bottle was depressurized (-95 kPa), and the time until the water-soluble processing solution was completely filtered was measured.

<Evaluation of foam suppression after filtration>
Evaluation of foam suppression after filtration was performed by the method shown below.
(1) 10 ml of the water-soluble metallurgical solution after evaluation of filterability was put into a 20 ml bottle with a lid, shaken vigorously up and down at 25 ° C. for 30 seconds, and then allowed to stand.
(2) The time until the bubbles generated by shaking disappeared was measured.

  As is clear from the results in Table 2, all of the water-soluble metalworking oils of the present invention of Examples 12 to 20 are excellent in cutting processability and filterability, and further in foam suppression after filtration. On the other hand, Comparative Examples 6 and 7 using a polyoxyalkylene polyol having less than 3 valences are excellent in cutting processability and filterability, but inferior in foam suppression after filtration. In Comparative Example 8 using a polyoxyalkylene polyol having less than 3 valences and adding a silicone-based antifoaming agent, the cutting processability was inferior, the filter was clogged, and filtration was not possible. Although the comparative example 9 which does not contain a polyoxyalkylene polyol is excellent in filterability and the foam suppression property after filtration, it is inferior in cutting workability. Comparative Example 10 using less than trivalent polyoxyalkylene glycol was excellent in cutting processability, but could not be filtered because the molecular weight was too large. From these results, by using the method for producing a metal processed product of the present invention, it is excellent in foam suppression without adding a silicone-based antifoaming agent. Therefore, it can be seen that the cost of the processing liquid and the antifoaming agent for addition can be reduced because the chips can be removed and the film can be used repeatedly. In particular, when processing silicon wafers for solar cells, chips can be efficiently removed, so that an effect of preventing wire breakage due to chips can be obtained.

  The method for producing a metal processed product of the present invention is excellent in economic efficiency because the amount of the processing fluid can be reduced by circulating the water-soluble metal mineral oil. In addition, since the amount of waste liquid can be reduced, there is an advantage that the environmental load is small. Therefore, it is useful as a method for producing a metal workpiece including processes such as cutting, grinding, polishing, rolling, pressing, forging, drawing, quenching, or die casting of metal members.

Claims (11)

  A method for producing a metal processed product using a water-soluble metalworking oil comprising a step of circulating a water-soluble metalworking oil containing 0.1% by weight or more of a polyoxyalkylene polyol (A) having a valence of 3 or more.   A method for producing a metal processed product using a water-soluble metalworking oil comprising a step of spraying a water-soluble metalworking oil containing 0.1% by weight or more of a polyoxyalkylene polyol (A) having a valence of 3 or more.   The manufacturing method of the metal workpiece using the water-soluble metal processing oil of Claim 1 or 2 including the process of wash | cleaning a metal workpiece.   The polyoxyalkylene polyol (A) is a compound obtained by addition polymerization of alkylene oxide to a compound (a) having 3 or more active hydrogens, wherein (a) is ammonia or an active hydrogen group is a hydroxyl group and / or an amino group. A method for producing a metal workpiece using the water-soluble metalworking oil according to any one of claims 1 to 3, wherein the compound has an active hydrogen which is The metal using the water-soluble metalworking oil according to any one of claims 1 to 4, wherein the polyoxyalkylene polyol (A) is a trivalent or higher polyoxyalkylene polyol (A1) represented by the following general formula (1). Manufacturing method of processed products.
R ¹ [—O— (A ¹ O) _m —H] _f (1)
[R ¹ represents a hydrocarbon group, and (A ¹ O) represents an oxyalkylene group having 2 to 4 carbon atoms. m is a number from ^{1 to} 450, a plurality of A ¹ may be the same or different, and (A ¹ O) _{m in} the case where m is 2 or more may be random addition or block addition. f is an integer of 3-20. ] Polyoxyalkylene polyol (A1) in the _- (A 1 ^O) m - method for producing a metal workpiece using a water-soluble metalworking oils described in claim 5 represented by the following general formula (2).
_{^{- (A 2 O) n (}} A 3 O) j (A 4 O) k - (2)
[(A ² O) represents an oxyethylene group, (A ³ O) represents an oxypropylene group, and (A ⁴ O) represents an oxybutylene group. n is a number from 0 to 350, j and k are each a number from 0 to 100, and at least one of j and k is 1 or more, and n / (n + j + k) is 0 to 0.9. When n, j, and k are 2 or more, the addition format may be random addition or block addition. ] The metal using the water-soluble metalworking oil according to any one of claims 1 to 4, wherein the polyoxyalkylene polyol (A) is a tri- or higher-valent polyoxyalkylene polyol (A2) represented by the following general formula (3). Manufacturing method of processed products.
R ² [— (A ⁵ O) _p —H] _g (3)
[R ² is a residue obtained by removing active hydrogen from a hydrocarbon having an ammonia or amino group, and (A ⁵ O) represents an oxyalkylene group having 2 to 4 carbon atoms. p is a number from 1 to 450, and a plurality of A ⁵ may be the same or different, and when p is 2 or more, the (A ⁵ O) _p portion may be random addition or block addition. g is a number from 3 to 20. ] The polyoxyalkylene polyol (A2) in the _- (A 5 ^O) p - method for producing a metal workpiece using a water-soluble metalworking oils described in claim 7 represented by the following general formula (4).
_{^{- (A 6 O) q (}} A 7 O) r (A 8 O) s - (4)
[(A ⁶ O) represents an oxyethylene group, (A ⁷ O) represents an oxypropylene group, and (A ⁸ O) represents an oxybutylene group. q is a number from 0 to 350, r and s are each a number from 0 to 100, and at least one of r and s is 1 or more, and q / (q + r + s) is 0 to 0.9. When q, r, and s are 2 or more, the addition format may be random addition or block addition. ]   The method for producing a metal workpiece using the water-soluble metalworking oil according to any one of claims 1 to 8, wherein the polyoxyalkylene polyol (A) has an HLB of 8.0 to 18.5.   The metal content using the water-soluble metalworking oil according to any one of claims 1 to 9, wherein the content of the polyoxyalkylene monool (B) is 30% by weight or less based on the weight of the polyoxyalkylene polyol (A). Manufacturing method of processed products.   The metal workpiece manufactured by the manufacturing method of the metal workpiece using the water-soluble metal processing oil in any one of Claims 1-10.