WO2019189136A1

WO2019189136A1 - Heat-treatment oil composition

Info

Publication number: WO2019189136A1
Application number: PCT/JP2019/012790
Authority: WO
Inventors: 立樹本間
Original assignee: 出光興産株式会社
Priority date: 2018-03-28
Filing date: 2019-03-26
Publication date: 2019-10-03
Also published as: TW201945528A; CN111868269A; JPWO2019189136A1; US20210002574A1

Abstract

Provided is a heat-treatment oil composition that makes it possible to suppress quenching distortion and distortion variation and to achieve improved quenching hardness. A heat-treatment oil composition that includes a base oil (A) and a vapor film rupturing agent (B). The heat-treatment oil composition makes it such that, on a cooling curve obtained in accordance with the cooling performance test method in JIS K2242:2012, the time in seconds to 300°C, e.g., the cooling time from 800°C to 300°C, is at least 6.5 seconds but less than 10 seconds. Component (B) includes a petroleum resin.

Description

Heat treated oil composition

The present invention relates to a heat-treated oil composition.

Metal materials such as steel are subjected to heat treatments such as quenching, tempering, annealing, and normalization for the purpose of improving their properties. Among these heat treatments, quenching is a treatment in which a heated metal material is immersed in a coolant and transformed into a predetermined quenching structure, and the treated product becomes very hard by this quenching. For example, when a heated steel material in an austenite state is immersed in a coolant and cooled at an upper critical speed or higher, it can be transformed into a quenched structure such as martensite.

As the coolant, an oil-based or water-based heat treatment agent is generally used. The quenching of the metal material using the oil-based heat treatment agent (heat treatment oil) will be described. When the heated metal material is put into the heat treatment oil as a coolant, it is usually cooled through three stages. Specifically, (1) a first stage (vapor film stage) in which the metal material is covered with a vapor film of heat-treated oil, (2) a second stage (boiling stage) in which the vapor film is broken and boiling occurs, (3) This is a third stage (convection stage) in which the temperature of the metal material is equal to or lower than the boiling point of the heat-treated oil and heat is taken away by convection. In each stage, the cooling rate is different because the atmosphere around the metal material is different, and the cooling rate in the second stage (boiling stage) is the fastest.

Generally, in the heat-treated oil, the cooling rate is rapidly increased when the vaporized film stage is shifted to the boiling stage. When the metal material is not a simple planar shape, the vapor film stage and the boiling stage are likely to be mixed on the surface of the metal material. When the mixture occurs, a very large temperature difference is generated on the surface of the metal material due to a difference in cooling rate between the vapor film stage and the boiling stage. And this temperature difference generates thermal stress and transformation stress and causes distortion in the metal material. Therefore, in heat treatment of metal materials, especially quenching, it is important to select heat treatment oils suitable for the heat treatment conditions. If the selection is inappropriate, the metal materials will be distorted and sufficient hardened May not be obtained.

The heat-treated oil is classified into 1 to 3 types according to JIS K2242: 2012, and 1 type 1 oil and 2 type oil, 2 types 1 oil and 2 type oil are used for quenching.
In JISK2242: 2012, the number of cooling seconds from 800 ° C. to 400 ° C. is defined as a measure of cooling performance. Type 1 No. 1 is 5.0 seconds or less, Type 1 No. 2 is 4.0 seconds or less, Type 2 No. 1 Is set to 5.0 seconds or less and Type 2 No. 2 is set to 6.0 seconds or less. The shorter the cooling time, the higher the cooling performance and the harder the metal material. Generally, the hardness and strain of a metal after quenching are in a trade-off relationship, and the harder the strain, the greater the strain.
Industrially, the number of seconds at 300 ° C. is also used as an index indicating the cooling property of the oil. The number of seconds at 300 ° C. is a cooling time from 800 ° C. to 300 ° C. of the cooling curve obtained in accordance with the cooling performance test method of JIS K2242: 2012.

The number of seconds (characteristic seconds; vapor film length) until reaching the temperature (characteristic temperature) from the start to the end of the vapor film stage is also used as an index indicating the cooling property of the oil agent. In general, the longer the vapor film stage, the longer the mixture time of the vapor film stage and the boiling stage, and the greater the distortion, the shorter the characteristic seconds, and the lower the characteristic temperature, the higher the cooling performance. . In JISK 2242: 2012, the characteristic temperature is also defined, Type 1 No. 1 is 480 ° C or higher, Type 1 No. 2 is 580 ° C or higher, Type 2 No. 1 is 500 ° C or higher, and Type 2 No. 2 is 600 ° C or higher. It has been established. These 1 type 1 and 2 oils correspond to cold oils used at low oil temperatures, and 2 types 1 oils correspond to semi-hot oils that can be used at higher oil temperatures. Oil corresponds to hot oil that can be used at high oil temperatures.

The user selects the quenching oil based on the above indicators in order to obtain the desired hardness and distortion. For example, the above-mentioned Type 2 No. 1 oil is widely used for quenching of gear parts for automobiles in which distortion is a problem. This is because the above-mentioned type 1 oil increases the strain and, depending on the part, the hardness is too high. In addition, although the type 2 No. 2 oil has less strain, the hardness is insufficient.

By the way, parts such as transmissions and reducers for automobiles are mass-produced in most cases, and so-called group quenching is performed in which a large amount of processed products are stacked on one tray and quenched at a time. At that time, there is a problem that the cooling performance varies depending on the position where the stacked components are set, and the hardness and strain of each component vary. For example, the hardness of the part set in the lower part is high, and the hardness of the part set in the upper part is low. In view of the above situation, the techniques of Patent Documents 1 to 4 have been proposed.

In patent document 1, the heat processing oil composition which reduces the dispersion | variation in the cooling performance at the time of group quenching is proposed, having cooling performance comparable as the said 2 type 1 oil. Specifically, 5% by mass of a low boiling point base oil having a 5% distillation temperature of 300 ° C. or more and 400 ° C. or less and less than 50% by mass, and 50% by mass of a high boiling point base oil having a 5% distillation temperature of 500 ° C. or more. A heat-treated oil composition comprising a mixed base oil comprising more than 95%.
In Patent Document 2, a base oil having a 40 ° C. kinematic viscosity of 5 mm ² / s to 60 mm ² / s is 50% by mass to 95% by mass based on the total amount of the composition, and a 40 ° C. kinematic viscosity is 300 mm ² / s or more. A heat-treated oil composition is proposed that can reduce variation in cooling performance during group quenching by blending 5% by mass to 50% by mass of the base oil, based on the total amount of the composition, and an α-olefin copolymer. ing.
Patent Document 3 includes a petroleum resin as a vapor film breaker as a heat-treating oil composition that reduces the variation in cooling performance during group quenching while having the same cooling performance as Type 2 No. 1 oil. A heat-treated oil composition has been proposed in which the number is 1.00 seconds or less and the 300 ° C. seconds are 6.00 seconds or more and 14.50 seconds or less.
In Patent Document 4, an alkenyl or alkyl succinimide is blended with a base oil having a kinematic viscosity at 40 ° C. of 4 mm ² / s or more and 20 mm ² / s or less as a heat-treated oil composition that can exhibit high cooling performance. Heat treated oil compositions have been proposed.

JP 2007-009238 A JP 2013-194262 A Japanese Unexamined Patent Publication No. 2016-151054 JP 2010-229479 A

There is a need for a heat treated oil composition having a good balance in cooling performance, quenching hardness, and quenching strain.

The present invention is as follows.
[1] comprising (A) a base oil and (B) a vapor film breaker;
The cooling time obtained from 800 ° C. to 300 ° C. of the cooling curve obtained in accordance with the cooling performance test method of JIS K2242: 2012 is 6.5 seconds or more and less than 10 seconds,
The component (B) is a heat-treated oil composition containing a petroleum resin.
[2] The heat-treated oil composition according to [1], wherein the characteristic seconds obtained from the cooling curve is 1 second or more.
[3] The heat-treated oil composition according to [1] or [2], further comprising (C) a metal-based detergent dispersant.
[4] The heat-treated oil composition according to [3], wherein the content of the component (C) is 0.01 to 10% by mass based on the total amount of the composition.
[5] The heat-treated oil composition according to any one of [1] to [4], wherein the characteristic number of seconds obtained from the cooling curve is 2.5 seconds or less.
[6] The heat-treated oil composition according to any one of [1] to [5], wherein the petroleum resin has a softening point of 40 to 150 ° C.
[7] The heat-treated oil composition according to any one of [1] to [6], wherein the petroleum resin has a number average molecular weight (Mn) of 200 to 5,000.
[8] The petroleum resin is at least one unsaturated compound selected from aliphatic olefins having 4 to 10 carbon atoms, aliphatic diolefins, and aromatic compounds having 8 or more carbon atoms having an olefinically unsaturated bond. The heat-treated oil composition according to any one of [1] to [7], wherein the compound is a polymerized or copolymerized resin.
[9] The petroleum resin includes an aliphatic petroleum resin, an aromatic petroleum resin, an aliphatic-aromatic copolymer petroleum resin, a dicyclopentadiene petroleum resin, and a dicyclopentadiene-aromatic copolymer petroleum resin. The heat-treated oil composition according to any one of [1] to [8], which is at least one selected from hydrogenated petroleum resins and modified petroleum resins.
[10] The heat-treated oil composition according to any one of [1] to [9], wherein the kinematic viscosity at 40 ° C. is 10 to 280 mm ² / s.
[11] The component (A), a high viscosity base oil is a low viscosity base oil and 40 ° C. kinematic viscosity 40 ° C. kinematic viscosity of less than ^{1 mm} 2 / s or more 85 mm ² / s is 85 ~ 550mm ² / s The heat-treated oil composition according to any one of [1] to [10].
[12] The heat-treated oil composition according to any one of [1] to [11], wherein the content of the petroleum resin is 0.1 to 90% by mass based on the total amount of the composition.
[13] The heat-treated oil composition according to any one of [1] to [12], wherein the content of the component (A) is 10 to 99.9% by mass based on the total amount of the composition.
[14] A method for quenching a metal material, comprising treating the metal material with the heat-treated oil composition according to any one of [1] to [13].
[15] The method for producing a heat-treated oil composition according to any one of [1] to [13], comprising mixing the component (A) and the component (B).

According to the present invention, there is provided a heat treated oil composition having a good balance of cooling performance, quenching hardness, and quenching strain.

Hereinafter, embodiments of the present invention will be described in detail. In addition, this invention is not limited to the following embodiment, In the range which does not deviate from the summary, it can change arbitrarily and can implement.

The present invention relates to a heat-treated oil composition comprising (A) a base oil and (B) a vapor film breaker. The heat-treated oil composition of the present invention has a cooling time of 300 ° C., which is a cooling time from 800 ° C. to 300 ° C. of the cooling curve obtained according to the cooling performance test method of JIS K2242: 2012, which is 6.5 seconds. For less than 10 seconds, the component (B) contains a petroleum resin.
The heat-treated oil composition of the present invention is excellent in the balance of cooling performance, quenching hardness, and quenching strain.

The heat-treated oil compositions described in Patent Documents 1 to 3 (JP 2007-009238 A, JP 2013-194262 A, JP 2016-151054 A) have a long cooling time and a reduced quenching strain. However, the quenching hardness may be insufficient for application to transportation parts such as automobile parts (for example, gears and bearings), and a further increase in hardness is required. On the other hand, the heat-treated oil composition described in Patent Document 4 (Japanese Patent Application Laid-Open No. 2010-229479) has a short cooling time and high quenching hardness, but has a large quenching strain and is difficult to be applied to parts having complicated shapes. . Accordingly, there is still a need for a heat treated oil composition that can be used in group quenching of parts and can achieve both high quenching hardness and reduced quenching distortion and strain variation.

The heat-treated oil composition of a preferred embodiment can achieve improved quenching hardness while suppressing quenching strain and variation in strain. The heat-treated oil composition of the embodiment can be suitably used in group quenching of parts because quenching strain and variation in strain are suppressed. The heat-treated oil composition of this embodiment can be suitably used for transportation parts such as automobile parts (for example, gears and bearings), particularly small parts.
Hereinafter, each component will be described in detail. The upper limit value and the lower limit value of the numerical ranges described in this specification can be arbitrarily combined. For example, when “A to B” and “C to D” are described, the ranges of “A to D” and “C to B” are also included in the scope of the present invention. Further, the numerical range “lower limit value to upper limit value” described in the present specification means that the value is not less than the lower limit value and not more than the upper limit value.

[Component (A): Base oil]
There is no restriction | limiting in particular as a base oil, Arbitrary things can be suitably selected and used from the mineral oil and synthetic oil conventionally used as a base oil of heat processing oil.

Mineral oil includes wax (gas) produced by paraffin-based mineral oil, intermediate-based mineral oil, naphthenic-based mineral oil, etc. obtained by ordinary refining methods such as solvent refining and hydrogenation refining, or Fischer-Tropsch process. (Turi Liquid Wax) and mineral oil-based waxes. These mineral oils may be used alone or in combination of two or more.
Mineral oil is classified into group 1, 2, or 3 in the API (American Petroleum Institute) base oil category. The mineral oil is preferably a mineral oil classified into Group 2 and Group 3 of the base oil category, and more preferably a mineral oil classified into Group 3.

Examples of synthetic oils include hydrocarbon synthetic oils and ether synthetic oils. Examples of the hydrocarbon-based synthetic oil include alkylbenzene and alkylnaphthalene. Examples of ether synthetic oils include polyoxyalkylene glycol and polyphenyl ether. These synthetic oils may be used alone or in combination of two or more.
Further, as the base oil, one or more mineral oils and one or more synthetic oils may be used in combination.

There is no particular limitation on the viscosity of the base oil. The kinematic viscosity at 40 ° C. of the base oil is preferably 40 to 500 mm ² / s, more preferably 50 to 350 mm ² / s, still more preferably 60 to 200 mm ² / s, and more preferably 80 to It is especially preferable that it is 120 mm < ² > / s. By making the 40 degreeC kinematic viscosity of a base oil into the said range, the essential cooling performance based on a component (A) can be ensured, and characteristic seconds and 300 degreeC seconds can be easily made into the range mentioned later.
In addition, when the base oil of a component (A) is a base oil with which 2 or more types of base oils were mixed, it is preferable that dynamic viscosity of mixed base oil satisfy | fills the said range.
In this specification, the kinematic viscosity at a predetermined temperature means a value measured according to JIS K2283: 2000.

The content of the base oil is preferably 10 to 99.9% by mass, more preferably 50 to 99% by mass, still more preferably 70 to 97% by mass, based on the total amount of the composition. It is particularly preferably 85 to 95% by mass.

In one embodiment of the present invention, the base oil has a kinematic viscosity at 40 ° C. of 1 mm ² / s or more and less than 85 mm ² / s (more preferably 20 to 82 mm ² / s, more preferably 40 to 80 mm ² / s). A low-viscosity base oil and a high-viscosity base oil having a kinematic viscosity at 40 ° C. of 85 to 550 mm ² / s (more preferably 88 to 520 mm ² / s, more preferably 90 to 490 mm ² / s).
The blending of the low-viscosity base oil and the high-viscosity base oil in the mixed base oil is performed by adding the low-viscosity base oil in the heat-treated oil composition in an amount of 0% by mass or more and less than 50% by mass (more preferably 3-30). It is preferable to contain 50% to 99.9% by mass (more preferably 65 to 95% by mass, still more preferably 80 to 90% by mass) of the high-viscosity base oil.

In another embodiment of the present invention, the base oil has a low viscosity having a kinematic viscosity at 40 ° C. of 1 to 90 mm ² / s (more preferably 20 to 82 mm ² / s, more preferably 40 to 80 mm ² / s). And a base oil and a high-viscosity base oil having a kinematic viscosity at 40 ° C. of 90 to 500 mm ² / s (more preferably 88 to 520 mm ² / s, still more preferably 90 to 490 mm ² / s).
The blending of the low-viscosity base oil and the high-viscosity base oil in the mixed base oil is performed by adding the low-viscosity base oil in the heat-treated oil composition in an amount of 0% by mass or more and less than 50% by mass (more preferably 3-30). It is preferable to contain 50% to 99.9% by mass (more preferably 65 to 95% by mass, still more preferably 80 to 90% by mass) of the high-viscosity base oil.

[Component (B): Vapor film breaker]
The heat-treated oil composition contains a petroleum resin as a vapor film breaker. By using petroleum resin, the vapor film stage can be shortened, and it is difficult to mix the vapor film stage and the boiling stage on the surface of the metal material. As a result, variations in cooling performance (hardness and distortion variations) for each component can be made difficult to occur during quenching. In addition, even in the case of a component having a complicated shape, it is difficult to cause variation in cooling performance for each location of the component, so that distortion of each component can be suppressed. Further, by containing the petroleum resin, the characteristic seconds in the initial stage of the heat treatment can be shortened, whereby excellent cooling performance can be imparted from the initial stage of the heat treatment. In addition to this, by using a petroleum resin, it is possible to suppress a change in the cooling performance of the heat-treated oil composition over time when the heat treatment of the metal material is repeated. Therefore, the life of the heat-treated oil composition can be extended by using a petroleum resin. The reason why the petroleum resin can exert these effects is considered to be the thermoplasticity of the petroleum resin and the excellent solubility in the base oil.

Petroleum resin is an aliphatic olefin or aliphatic diolefin having 4 to 10 carbon atoms or carbon number having an olefinic unsaturated bond obtained as a by-product during the production of olefins such as ethylene by thermal decomposition of petroleum such as naphtha. It is a resin obtained by polymerizing or copolymerizing one or two or more unsaturated compounds selected from eight or more aromatic compounds. For example, a petroleum resin is a resin (dicyclopentadiene-aromatic copolymer petroleum resin) obtained by copolymerizing an unsaturated compound containing dicyclopentadiene and an aromatic compound, the main raw material of which is a C5 fraction.
These petroleum resins include, for example, “aliphatic petroleum resins” obtained by polymerizing aliphatic olefins and / or aliphatic diolefins, and “aromatic petroleum resins obtained by polymerizing aromatic compounds having olefinic unsaturated bonds. And “aliphatic-aromatic copolymer petroleum resin” obtained by copolymerizing aliphatic olefins and / or aliphatic diolefins with an aromatic compound having an olefinically unsaturated bond.
Examples of the aliphatic olefins having 4 to 10 carbon atoms include butene, pentene, hexene, heptene and the like. Examples of the aliphatic diolefin having 4 to 10 carbon atoms include butadiene, pentadiene, isoprene, cyclopentadiene, dicyclopentadiene, and methylpentadiene. Examples of the aromatic compound having 8 or more carbon atoms having an olefinically unsaturated bond include styrene, α-methylstyrene, β-methylstyrene, vinyltoluene, vinylxylene, indene, methylindene, and ethylindene.
In addition, all the raw material compounds of petroleum resin do not have to be byproducts at the time of olefin production by thermal decomposition of petroleum such as naphtha, and chemically synthesized unsaturated compounds may be used. For example, “dicyclopentadiene-based petroleum resin” obtained by polymerization of cyclopentadiene or dicyclopentadiene (DCPD), or by copolymerizing these cyclopentadiene or dicyclopentadiene with an aromatic compound having an olefinically unsaturated bond. “Dicyclopentadiene-aromatic copolymer petroleum resin” (for example, dicyclopentadiene-styrene petroleum resin) can be used.

In this specification, petroleum resin includes derivatives of petroleum resin such as hydrogenated petroleum resin and modified petroleum resin.
The hydrogenated petroleum resin is a hydrogenated petroleum resin obtained by adding hydrogen atoms to the above petroleum resin. By hydrogenation, all or some of the double bonds in the molecule are hydrogenated. Accordingly, the hydrogenated petroleum resin may be a fully hydrogenated petroleum resin or a partially hydrogenated petroleum resin. When a partially hydrogenated product is used, it is easy to manufacture because of excellent cooling properties and a low softening point.
Examples of the modified petroleum resin include an acid-modified petroleum resin obtained by modifying the petroleum resin with an acidic functional group typified by carboxylic acid, and the acid-modified petroleum resin using a compound such as alcohol, amine, alkali metal, or alkaline earth metal. Reaction-modified resins are exemplified. Examples of the acid-modified petroleum resin include a carboxylic acid-modified petroleum resin obtained by modifying a petroleum resin with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride, and an acid anhydride-modified petroleum resin. Examples of unsaturated carboxylic acids include unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid; unsaturated polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid, and citraconic acid; monomethyl maleate, monoethyl fumarate, etc. Examples of unsaturated carboxylic acid anhydrides include unsaturated polyvalent carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride.

As the petroleum resin, a synthesized resin or a commercially available product may be used.
A petroleum resin may be used independently and may be used in combination of 2 or more type.

In one embodiment, the petroleum resin is an aliphatic petroleum resin, an aromatic petroleum resin, an aliphatic-aromatic copolymer petroleum resin, a dicyclopentadiene petroleum resin, and a dicyclopentadiene-aromatic copolymer petroleum. Resin, and at least one selected from hydrogenated petroleum resins and modified petroleum resins.

Among them, the petroleum resin is preferably an aliphatic-aromatic copolymer petroleum resin or a hydrogenated aliphatic-aromatic copolymer petroleum resin from the viewpoint that the characteristic seconds can be shortened. An added aliphatic-aromatic copolymer petroleum resin is preferred. For example, the petroleum resin is a dicyclopentadiene-aromatic copolymer hydrogenated petroleum resin.

The number average molecular weight (Mn) of the petroleum resin is preferably 200 to 5000, more preferably 250 to 2500, and further preferably 300 to 1500 in terms of characteristic seconds. Here, the number average molecular weight (Mn) can be measured by the VPO method.

The petroleum resin preferably has a softening point of 40 ° C or higher, more preferably 40 ° C or higher and 150 ° C or lower, still more preferably 60 ° C or higher and 150 ° C or lower, and 80 ° C or higher and 140 ° C or lower. More preferably, it is more preferably 100 ° C. or higher and 135 ° C. or lower, and particularly preferably 120 ° C. or higher and 130 ° C. or lower. In the present specification, the “softening point” can be measured by the ring and ball method of JIS K2207: 2006. By setting the softening point to 40 ° C. or higher, it is possible to make it difficult to cause variations in cooling performance (hardness and distortion variations) for each part during quenching, and cooling performance for each part location even when the part has a complicated shape. Variation can be made difficult, and distortion of each component can be suppressed. Furthermore, by setting the softening point to 40 ° C. or higher, it is possible to further suppress changes in the cooling performance with time (an increase in characteristic seconds with time and a decrease in kinematic viscosity with time) when heat treatment is repeatedly performed. The characteristic seconds in the initial stage can be shortened. By setting the softening point of the petroleum resin to 150 ° C. or less, the stickiness of the surface of the workpiece after cooling the workpiece such as a metal material with the heat treatment oil composition can be reduced. The softening point of the petroleum resin can be adjusted by the degree of polymerization of the petroleum resin, the modifying component, and the degree of modification.
In addition, when using 2 or more types of materials as petroleum resin, it is preferable that all the materials are the range of the said softening point.

The petroleum resin preferably has a density at 20 ° C. of 0.5 to 1.5 g / cm ³ measured in accordance with JIS K 0061: 2001 from the viewpoint of cooling performance, and preferably 0.7 to 1. More preferably, it is ³ g / cm ³ , and even more preferably 0.8 to 1.1 g / cm ³ .

The bromine number of the petroleum resin is preferably 30 g / 100 g or less, more preferably 20 g / 100 g or less, and even more preferably 10 g / 100 g or less from the viewpoint of cooling performance. The lower the bromine value, the better. The lower limit is not particularly limited, but is usually 1.0 g / 100 g or more, 1.5 g / 100 g or more, or 1.9 g / 100 g or more. Here, the bromine number is measured in accordance with JIS K 2605: 1996.

As the hue of petroleum resin, the Hazen color number measured in accordance with JIS K 6901: 2008 is preferably 50 or less, more preferably 40 or less, and even more preferably 30 or less. The lower the Hazen color number, the better. The lower limit is not particularly limited, but is usually 3 or more, 5 or more, or 7 or more.

The content of petroleum resin is preferably 0.1 to 90% by mass based on the total amount of the composition. If it is 0.1 mass% or more, the cooling performance can be improved. Petroleum resins generally have a high viscosity, and the viscosity of the composition tends to increase as the blending amount increases. If it is 90 mass% or less, it is preferable from the point of appropriate viscosity. The content of the petroleum resin is more preferably 1 to 60% by mass, and still more preferably 5 to 10% by mass from the viewpoint of appropriate viscosity and cooling performance.

The heat-treated oil composition may contain a vapor film breaker other than petroleum resin. Other vapor film breakers include terpene resins, terpene resin derivatives, rosin, rosin derivatives, and the like. The content of the other vapor film breaking agent is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less, based on the total amount of the composition. Particularly preferably, the heat-treated oil composition does not contain a vapor film breaker other than petroleum resin.
The heat-treated oil composition of one embodiment does not contain an α-olefin copolymer as a vapor film breaker.
The heat-treated oil composition of one embodiment does not contain asphalt as a vapor film breaker.

[Component (C): Metal-based detergent / dispersant]
The heat-treated oil composition may contain a metal-based cleaning dispersant. Cooling performance can be improved by including a metallic detergent-dispersant. By including (D) a metal-based detergent / dispersant together with (B) a petroleum resin used as a vapor film breaker, excellent cooling performance can be exhibited, and a further improvement effect of hardness during quenching can be obtained.

Examples of the (C) metallic detergent-dispersant include organometallic compounds containing a metal atom (preferably an alkaline earth metal atom) selected from alkali metal atoms and alkaline earth metal atoms. Include metal salicylates, metal phenates, metal sulfonates, and the like. As a metal atom, a sodium atom, a calcium atom, a magnesium atom, or a barium atom is preferable, a calcium atom or a magnesium atom is more preferable, and a calcium atom is more preferable. That is, in one embodiment, (C) the metal-based detergent dispersant includes at least one of calcium salicylate, calcium phenate, and calcium sulfonate. A metal type detergent dispersing agent may be used independently and may be used in combination of 2 or more type.

(C) The content of the metal-based detergent dispersant is preferably 0 to 10% by mass, more preferably 0.1 to 7.5% by mass, and further preferably 0.5 to 5% by mass based on the total amount of the composition. . The above range is preferable from the viewpoint of dispersibility in base oil and excellent cooling performance.

[Component (D): Other additives]
The heat-treated oil composition may further contain other additives such as an antioxidant and a glitter improvement agent. The content of other additives is preferably 10% by mass or less, more preferably 0.01 to 5% by mass, based on the composition.

(Antioxidant)
As an antioxidant, arbitrary things can be suitably selected and used from well-known antioxidant used as an antioxidant of the heat processing oil composition conventionally. For example, an amine antioxidant, a phenolic antioxidant, etc. are mentioned.

Examples of amine antioxidants include diphenylamine and diphenylamine antioxidants such as alkylated diphenylamine having an alkyl group having 3 to 20 carbon atoms; α-naphthylamine, alkyl substituted phenyl-α-naphthylamine having 3 to 20 carbon atoms, and the like. Naphthylamine antioxidants, and the like.

Examples of the phenolic antioxidant include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, and octadecyl-3- (3,5-diphenol). Monophenol antioxidants such as -tert-butyl-4-hydroxyphenyl) propionate; 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6) -Tert-butylphenol) and the like; hindered phenol antioxidants; and the like.

These antioxidants may be used alone or in combination of two or more.
The content of the antioxidant is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass, and still more preferably 0.05 to 3% by mass, based on the total amount of the composition.

(Illumination improver)
The glitter improvement agent can improve the appearance of the object to be processed. Examples of the glitter improving agent include fats and oils, fatty oils and fatty acids, alkenyl succinimides, substituted hydroxyaromatic carboxylic acid ester derivatives, and the like. These glitter improvement agents may be used alone or in combination of two or more.
The content of the glitter improving agent is preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, based on the total amount of the composition.

In one embodiment of the present invention, the total content of (A) the base oil and (B) the vapor film breaker in the heat-treated oil composition is 80 to 100% by mass based on the total amount of the composition (100% by mass). It is preferably 90 to 99.5% by mass, more preferably 97 to 99% by mass.
In one embodiment of the present invention, the total content of (A) base oil, (B) vapor film breaker, and (C) glitter improvement agent in the heat-treated oil composition is the total amount of the composition (100% by mass). The reference is preferably 90 to 100% by mass, more preferably 95 to 100% by mass, and particularly preferably 97.5 to 100% by mass.

[Physical properties of heat-treated oil composition]
The heat-treated oil composition of the present embodiment has a “300 ° C. second” that is a cooling time from 800 ° C. to 300 ° C. of the cooling curve obtained in accordance with the cooling performance test method of JIS K2242: 2012. It must be 5 seconds or more and less than 10 seconds. The number of seconds at 300 ° C. is more preferably 6.6 seconds or more and 9.5 seconds or less, and further preferably 6.8 seconds or more and 9.2 seconds or less, from the viewpoint of achieving both quenching hardness, strain, and variations thereof.
In order to set the 300 ° C. seconds of the heat-treated oil composition within the above range, (A) the content and kinematic viscosity of the base oil, (B) the content of the vapor film breaker (particularly petroleum resin), the softening point and the number It is preferable that the average molecular weight, the content of (C) the metal-based detergent dispersant, and the structure are within the range of the above-described embodiment.

The heat-treated oil composition having 300 ° C. seconds in the above range can be used as a heat-treated oil (semi-hot oil) having a cooling performance comparable to that of Type 2 No. 1 oil in JIS K2242: 2012. The heat-treated oil composition of the embodiment can realize quenching distortion variation and high quenching hardness as compared with conventional semi-hot oil.

The heat-treated oil composition of one embodiment is a cooling time from 800 ° C. to 400 ° C. of the cooling curve obtained according to the cooling performance test method of JIS K2242: 2012 from the viewpoint of cooling performance “400 The “° C. seconds” is preferably 2.0 to 4.5 seconds, more preferably 2.25 to 4.0 seconds, and even more preferably 2.3 to 3.5 seconds.

The heat-treated oil composition of the present embodiment has a characteristic number of seconds (vapor film length) obtained from a cooling curve obtained in accordance with a cooling performance test method of JIS K2242: 2012 from the viewpoint of reducing strain and variation. Is preferably 1 second or longer, more preferably 1.2 seconds or longer, and particularly preferably 1.3 seconds or longer. Further, from the viewpoint of reducing variation in cooling performance for each part during quenching, it is preferably 10 seconds or less, more preferably 5 seconds or less, and even more preferably 2.5 seconds or less.
For example, the characteristic seconds (vapor film length) obtained from the cooling curve is 1 second to 10 seconds, 1 second to 5 seconds, 1 second to 2.5 seconds, 1.2 seconds to 10 seconds, 1.2 seconds to 5 seconds, 1.2 seconds to 2.5 seconds, 1.3 seconds to 10 seconds, 1.3 seconds to 5 seconds, or 1.3 seconds to 2.5 seconds is there.
In order to set the characteristic seconds of the heat-treated oil composition within the above range, (A) base oil content and kinematic viscosity, (B) vapor film breaker (particularly petroleum resin) content, softening point and number average It is preferable that the molecular weight, the content and structure of the (C) metal-based detergent / dispersant are within the range of the above-described embodiment.

More specifically, the characteristic number of seconds can be calculated by the following (1) and (2).
(1) In accordance with the cooling performance test method of JIS K2242: 2012, a silver sample heated to 810 ° C. is charged into the heat-treated oil composition, and cooling is performed with time as the x axis and the temperature of the silver sample surface as the y axis. Find a curve.
(2) From the cooling curve, the number of seconds until reaching the temperature (characteristic temperature) at which the vapor film stage of the heat-treated oil composition ends is calculated by the tangential intersection method, and the number of seconds is defined as the characteristic number of seconds.
In the above (1), the measurement time interval is preferably 1/100 second.

The kinematic viscosity at 40 ° C. heat treatment oil composition, from the viewpoint of 300 ° C. seconds, preferably 10 ~ 280mm ² / s, more preferably 10 ~ 200mm ² / s, or, 65 ~ 230mm ² / s Gayori 115 to 180 mm ² / s is more preferable.
The kinematic viscosity at 100 ° C. heat treatment oil composition, from the viewpoint of 300 ° C. seconds, preferably 1 ~ 40mm ² / s, more preferably 5 ~ 30mm ² / s, more preferably 10 ~ 20mm ² / s.

[Method for producing heat-treated oil composition]
The manufacturing method of the heat-treated oil composition of the embodiment is not particularly limited. For example, the production method of the embodiment includes mixing (A) a base oil and (B) a vapor film breaker, and (C) a metal-based detergent dispersant and (D) other components as necessary. The components (A) to (D) may be blended by any method, and the blending order and method are not limited.

[Use of heat treatment oil composition, quenching method]
The heat-treated oil composition of the embodiment can exhibit excellent cooling performance in heat treatment of metal materials, and therefore, for example, various alloy steels such as carbon steel, nickel-manganese steel, chromium-molybdenum steel, and manganese steel are quenched. It can be suitably used as the heat treatment oil at the time. In particular, since the heat-treated oil composition of the embodiment can achieve improved quenching hardness while suppressing quenching distortion, for example, gears such as gears for automobiles, quenching oil used for group quenching of metal materials, etc. Can be suitably used.
The temperature range of the heat-treated oil composition when quenching a metal material using the heat-treated oil composition of the embodiment may be set to a range of 60 to 150 ° C., which is a normal quenching temperature. The temperature may be set at a high temperature of 170 to 250 ° C.
One embodiment of the present invention provides a method for heat treating a metal material. Specifically, the heat treatment method includes heat-treating a metal material using the heat-treated oil composition of the above embodiment.
One embodiment of the present invention provides a method for quenching a metal material. Specifically, the metal material is treated using the heat-treated oil composition of the above embodiment. In a preferred aspect, the method for quenching a metal material is characterized in that the metal material is treated using the heat-treated oil composition of the above embodiment in the group quenching of the metal material. One embodiment of the present invention provides a method for group quenching of a metal material, comprising treating the metal material with the heat-treated oil composition of the above-described embodiment.
In one embodiment, the method for quenching a metal material includes treating the metal material under an oil temperature of 60-200 ° C.

Hereinafter, although the present invention is explained in full detail with reference to an example, the technical scope of the present invention is not limited to this.
The measurement of each physical property of each raw material used in the Examples and Comparative Examples and the heat-treated oil compositions of each Example and each Comparative Example was determined according to the following procedure.

(1) Kinematic viscosity According to JIS K2283: 2000, the kinematic viscosity at 40 ° C. and the kinematic viscosity at 100 ° C. were measured using a glass capillary viscometer.
(2) Cooling performance of heat-treated oil composition In accordance with the cooling performance test method defined in JIS K2242: 2012, a silver sample heated to 810 ° C. is charged into the heat-treated oil composition, and a cooling curve of the silver sample is obtained. The following “characteristic seconds” and “300 ° C. seconds” were calculated. The oil temperature of the heat-treated oil composition before adding the silver sample was 120 ° C. in all Examples and all Comparative Examples.
<Characteristic seconds and characteristic temperature>
In the above cooling curve, the temperature at which the vapor film stage ends (characteristic temperature) was calculated in accordance with JIS K2242: 2012, and the number of seconds until the vapor film stage was reached was defined as characteristic seconds.
<300 ° C seconds>
The cooling time from 800 ° C. to 300 ° C. in the cooling curve was set to 300 ° C. seconds.
<400 ° C seconds>
The cooling time from 800 ° C. to 400 ° C. in the cooling curve was set to 400 ° C. seconds.
(3) Physical properties of petroleum resin (i) Softening point Measured according to JIS K2207: 2006.
(Ii) Number average molecular weight (Mn)
It was measured by the VPO method.
(Iii) Density The density at 20 ° C. was measured according to JIS K 0061: 2001.
(Iv) Hue The Hazen color number was measured according to JIS K 6901: 2008.
(V) Bromine value It measured based on JISK2605: 1996.

[Examples 1 and 2, Comparative Examples 1 to 7]
As shown in Table 1 below, each component shown in Table 1 below was blended with the base oil to prepare base oil and heat-treated oil compositions of Examples and Comparative Examples containing these components, and the heat treatment prepared The oil composition was evaluated for the following hardness and strain. The properties and evaluation results of the heat-treated oil compositions of Examples and Comparative Examples are shown in Table 1 below. The smaller the average ellipticity, the smaller the quenching strain, the smaller the ellipticity 3σ, the smaller the variation in the quenching strain, and the higher the average internal hardness, the higher the quenching hardness. The larger the average effective hardened layer depth and the average internal hardness, the higher the hardness of the treated product after quenching and the better the heat-treated oil with excellent cooling performance.

<Evaluation of hardness and strain>
Heat treatment (group quenching) under the following conditions using cylindrical hardened steel (outer diameter: φ85mm, height: 44mm, wall thickness: 4mm, material: chrome-molybdenum steel SCM415) as a material for quenching evaluation In addition, the following items were evaluated.
<Conditions for heat treatment>
Heat treatment conditions: carburizing step 930 ° C. × 150 minutes, carbon potential (CP) = 1.1 mass%
Diffusion process: 930 ° C. × 60 minutes, CP = 0.8 mass%
Soaking process: 850 ° C. × 20 minutes, CP = 0.8% by mass
Oil cooling conditions: Oil temperature 120 ° C., oil cooling time 10 minutes, stirring 20 Hz
Tempering conditions: 180 ° C x 60 minutes Setting method: sword rack (8 quenching workpieces, 4 pieces x 2 steps)
<Evaluation items>
・ Average ellipticity (mm)
・ Ellipticity 3σ (mm)
・ Average internal hardness (hardened material 1.5mm inside, HV)
・ Average effective hardened layer depth (mm)

The components used in Table 1 are as follows.
1. Base oil (component (A))
Base oil 1: paraffinic mineral oil (kinematic viscosity at 40 ° C. 480 mm ² / s) (high viscosity base oil)
Base oil 2: paraffinic mineral oil (40 ° C. kinematic viscosity 75 mm ² / s) (low viscosity base oil)
Base oil 3: paraffinic mineral oil (40 ° C. kinematic viscosity 97 mm ² / s) (high viscosity base oil)
Base oil 4: paraffinic mineral oil (40 ° C. kinematic viscosity 94 mm ² / s) (high viscosity base oil)
Base oil 5: paraffinic mineral oil (40 ° C. kinematic viscosity 395 mm ² / s) (high viscosity base oil)
Base oil 6: Paraffinic mineral oil (40 ° C. kinematic viscosity 31 mm ² / s) (low viscosity base oil)
Base oil 7: paraffinic mineral oil (40 ° C. kinematic viscosity 14 mm ² / s) (low viscosity base oil)
Base oil 8: paraffinic mineral oil (40 ° C. kinematic viscosity 21 mm ² / s) (low viscosity base oil)
Base oil 9: paraffinic mineral oil (40 ° C. kinematic viscosity 120 mm ² / s) (high viscosity base oil)
Base oil 10: Paraffinic mineral oil (40 ° C. kinematic viscosity 60 mm ² / s) (low viscosity base oil)
Base oil 11: Paraffinic mineral oil (40 ° C. kinematic viscosity 200 mm ² / s) (high viscosity base oil)
2. Vapor film breaker (component (B))
Petroleum resin 1: Fully hydrogenated aliphatic-aromatic copolymer petroleum resin (dicyclopentadiene-aromatic copolymer hydrogenated petroleum resin mainly containing C5 fraction; softening point: 125 ° C, number average Molecular weight: 820, density at 20 ° C .: 1.03 g / cm ³ , hue (Hazen color number): 20, bromine number: 2.5 g / 100 g)
Petroleum resin 2: Partially hydrogenated aliphatic-aromatic copolymer petroleum resin (dicyclopentadiene-aromatic copolymer hydrogenated petroleum resin with C5 fraction as main raw material; softening point: 110 ° C., number average Molecular weight: 760, density at 20 ° C .: 1.05 g / cm ³ , hue (Hazen color number): 25, bromine number: 6 g / 100 g)
α-olefin copolymer: α-olefin copolymer having a kinematic viscosity of 2000 mm ² / s at 100 ° C; Additives Metal-based detergent dispersant (component (C)): Calcium salicylate antioxidant: Phenol-based antioxidant Luster improvement agent: Fatty acid fatty acid

As shown in Table 1, (B) the heat-treated oil composition of the example containing a petroleum resin as a vapor film breaker and having a 300 ° C. seconds of 6.5 seconds or more and less than 10 seconds has an average of 400 Hv or more. It was confirmed that it had an internal hardness and an average effective hardening depth of 1.0 mm or more, and that the average ellipticity (less than 0.21) and its variation (ellipticity 3σ less than 0.18) were small. .
On the other hand, when the number of seconds at 300 ° C. is not in the range of 6.5 seconds to less than 10 seconds and / or does not include petroleum resin, desired hardness and low strain (average ellipticity, ellipticity 3σ) At least one or both of these were not obtained. Specifically, in Comparative Examples 5 to 7 where the number of seconds at 300 ° C. exceeds 10 seconds, the average internal hardness is less than 350 Hv. In Comparative Example 4 in which the number of seconds at 300 ° C. is less than 6.5 seconds and no petroleum resin is included, and in Comparative Examples 1 and 2 that do not include a petroleum resin, quenching strain (particularly, variation in quenching strain (ellipticity 3σ)) is observed. It was big.

The scope of the present invention is not limited to the above description, and other than the above-described examples, the scope of the present invention can be appropriately changed and implemented without departing from the spirit of the present invention. It should be noted that all documents and publications described in this specification are incorporated herein by reference in their entirety regardless of their purposes. In addition, this specification includes claims and contents of the description of Japanese Patent Application No. 2018-062472 (filed on Mar. 28, 2018), which is a Japanese patent application that is the basis of the priority claim of the present application. To do.

The heat-treated oil composition of the present invention can be suitably used for heat treatment such as quenching of a metal material.

Claims

Comprising (A) a base oil and (B) a vapor film breaker;
The cooling time obtained from 800 ° C. to 300 ° C. of the cooling curve obtained in accordance with the cooling performance test method of JIS K2242: 2012 is 6.5 seconds or more and less than 10 seconds,
The component (B) is a heat-treated oil composition containing a petroleum resin.
The heat-treated oil composition according to claim 1, wherein the characteristic seconds obtained from the cooling curve is 1 second or more.
The heat-treated oil composition according to claim 1 or 2, further comprising (C) a metal-based detergent dispersant.
The heat-treated oil composition according to claim 3, wherein the content of the component (C) is 0.01 to 10% by mass based on the total amount of the composition.
The heat-treated oil composition according to any one of claims 1 to 4, wherein the characteristic seconds obtained from the cooling curve is 2.5 seconds or less.
The heat-treated oil composition according to any one of claims 1 to 5, wherein the petroleum resin has a softening point of 40 to 150 ° C.
The heat-treated oil composition according to any one of claims 1 to 6, wherein the petroleum resin has a number average molecular weight (Mn) of 200 to 5,000.
The petroleum resin is a polymer of at least one unsaturated compound selected from aliphatic olefins having 4 to 10 carbon atoms, aliphatic diolefins, or aromatic compounds having 8 or more carbon atoms having an olefinically unsaturated bond. The heat-treated oil composition according to any one of claims 1 to 7, which is a copolymerized resin.
The petroleum resins include aliphatic petroleum resins, aromatic petroleum resins, aliphatic-aromatic copolymer petroleum resins, dicyclopentadiene petroleum resins, dicyclopentadiene-aromatic copolymer petroleum resins, and these The heat-treated oil composition according to any one of claims 1 to 8, which is at least one selected from hydrogenated petroleum resins and modified petroleum resins.
The heat-treated oil composition according to any one of claims 1 to 9, wherein the kinematic viscosity at 40 ° C is 10 to 280 mm 2 / s.
Wherein component (A) comprises a high-viscosity base oil is a low viscosity base oil and 40 ° C. kinematic viscosity 40 ° C. kinematic viscosity of less than 1 mm 2 / s or more 85 mm 2 / s is 85 ~ 550mm 2 / s, wherein Item 11. The heat-treated oil composition according to any one of Items 1 to 10.
The heat-treated oil composition according to any one of claims 1 to 11, wherein the content of the petroleum resin is 0.1 to 90% by mass based on the total amount of the composition.
The heat-treated oil composition according to any one of claims 1 to 12, wherein the content of the component (A) is 10 to 99.9 mass% based on the total amount of the composition.
A method for quenching a metal material, comprising treating the metal material with the heat-treated oil composition according to any one of claims 1 to 13.
The method for producing a heat-treated oil composition according to any one of claims 1 to 13, comprising mixing the component (A) and the component (B).