Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
  • C10M101/02—Petroleum fractions
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
  • C10M159/005—Macromolecular compounds, e.g. macromolecular compounds composed of alternatively specified monomers not covered by the same main group
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
  • C10M159/02—Natural products
  • C10M159/04—Petroleum fractions, e.g. tars, solvents
• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
  • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
  • C21D1/56—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering characterised by the quenching agents
  • C21D1/58—Oils
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
  • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
  • C10M2203/102—Aliphatic fractions
  • C10M2203/1025—Aliphatic fractions used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/003—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
  • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
  • C10N2020/02—Viscosity; Viscosity index
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
  • C10N2020/04—Molecular weight; Molecular weight distribution
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/02—Pour-point; Viscosity index
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/20—Metal working
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/20—Metal working
  • C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/20—Metal working
  • C10N2040/242—Hot working
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
  • C10N2060/02—Reduction, e.g. hydrogenation
• • C10N2220/021—
• • C10N2220/022—
• • C10N2240/404—

Definitions

• the present invention relates to heat treatment oil composition.
• a metal material such as a steel material
• heat treatments such as quenching, tempering, annealing, and normalizing, for improving the property thereof.
• quenching is a treatment for transforming a heated metal material to a prescribed hardened structure by immersing the metal material in a cooling medium, and the quenching makes the treated product very hard.
• a heated steel material in an austenite state is cooled at the upper critical cooling rate or higher by immersing in a cooling medium, the material can be transformed to a hardened structure, such as martensite.
• an oily or aqueous heat treatment agent is generally used as the cooling medium.
• the quenching of a metal material with an oily heat treatment agent i.e., a heat treatment oil
• a heat treatment oil i.e., a heat treatment oil
• the stages include (1) the first stage where the metal material is enclosed with a vapor blanket of the heat treatment oil (vapor blanket stage), (2) the second stage where the vapor blanket is ruptured, and boiling occurs (boiling stage), and (3) the third stage where the temperature of the metal material becomes the boiling point of the heat treatment oil or lower, and the heat is removed through convection (convection stage).
• the cooling rates in the stages are different from each other due to the difference of the atmosphere surrounding the metal material, and the cooling rate in the second stage (boiling stage) is the largest.
• the cooling rate is generally increased quickly in the transition from the vapor blanket stage to the boiling stage.
• the metal material does not have a simple flat shape
• the vapor blanket stage and the boiling stage tend to be mixedly present on the surface of the metal material.
• an extremely large temperature difference occurs on the surface of the metal material due to the difference in cooling rate between the vapor blanket stage and the boiling stage.
• the temperature difference forms temperature stress and transformation stress, which cause distortion of the metal material.
• Heat treatment oils are classified into Classes 1 to 3 according to JIS K2242:2012, and the No. 1 oil of Class 1, the No. 2 oil of Class 1, the No. 1 oil of Class 2, and the No. 2 oil of Class 2 are used for quenching.
• JIS K2242:2012 determines the cooling rate in second from 800° C. to 400° C. as an index of the cooling capability, which is 4.0 seconds or less for the No. 2 oil of Class 1, 5.0 seconds or less for the No. 1 oil of Class 2, and 6.0 seconds or less for the No. 2 oil of Class 2.
• a smaller cooling rate in second means a higher cooling capability and increase the hardness of the metal material.
• the hardness and the distortion after quenching the metal are in a trade-off relationship, and a larger hardness involves a larger distortion.
• the 300° C. number of second is a cooling time from 800° C. to 300° C. in a cooling curve that is obtained according to the cooling capability test method of JIS K2242:2012.
• a user selects a quenching oil based on the aforementioned indices for providing target hardness and distortion.
• the No. 1 oil of Class 2 is widely used. This is because the oils of Class 1 may cause large distortion, and may increase the hardness excessively for some components, and the No. 2 oil of Class 2 may cause small distortion, but the hardness may be insufficient.
• Components of a transmission and a speed reducer for an automobile are mass-produced in most cases, in which a large number of components to be treated are stacked on one tray and are quenched all at one time, i.e., mass quenching is performed.
• mass quenching is performed.
• the stacked components undergo fluctuation in hardness and distortion due to the fluctuation in cooling capability depending on the positions of the components placed. For example, a component that is placed at a lower position has a larger hardness, but a component that is placed at a higher position has a smaller hardness.
• PTL 1 proposes the addition of special devices, such as a vibrator and an injection device.
• the vapor blanket stage is prolonged, the period of time where the vapor blanket stage and the boiling stage are mixedly present is also prolonged, which may increase the distortion. Therefore, it is preferred to reduce the number of second (characteristic time) until reaching the temperature (characteristic temperature) where the vapor blanket stage ends.
• PTL 2 proposes the method, in which for avoiding the influence of the characteristic time, oil quenching is performed after cooling with gas to the characteristic temperature or lower.
• PTL 3 proposes the method, in which for removing the temperature difference in the treated material due to the cooling unevenness, the treated material is once taken out from the quenching oil and soaked at a temperature immediately above the martensitic transformation start temperature.
• the methods of PTLs 2 and 3 involve increase of the cost and the treating time, as compared to the simple oil quenching. Furthermore, the methods of PTLs 2 and 3 are for reducing the distortion, but cannot reduce the fluctuation in hardness and distortion among components subjected to mass quenching.
• PTL 4 proposes the heat treatment oil composition that causes less cooling unevenness in quenching of a metal material to ensure hardness of a quenching treated material, and is capable of reducing quenching distortion, which is the heat treatment oil composition containing a mixed base oil formed of from 50 to 95% by weight of a low viscosity base oil having a kinetic viscosity at 40° C. of from 5 to 60 mm 2 /s and from 50 to 95% by weight of a high viscosity base oil having a kinetic viscosity at 40° C. of 300 mm 2 /s or more.
• the heat treatment oil composition that reduces the fluctuation in cooling capability in mass quenching while having a cooling capability equivalent to the No. 1 oil of Class 2.
• the heat treatment oil composition contains a mixed base oil formed of 5% by mass or more and less than 50% 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 more than 50% by mass and 95% or less of a high boiling point base oil having a 5% distillation temperature of 500° C. or more.
• the heat treatment oil compositions of PTLs 4 and 5 have a long characteristic time due to the absence of a vapor blanket breaking agent used, and cannot reduce the fluctuation in hardness and distortion among components subjected to mass quenching.
• PTL 6 proposes the heat treatment oil composition that is capable of reducing the fluctuation in cooling capability in mass quenching, by blending a base oil having a 40° C. kinetic viscosity of 5 mm 2 /s or more and 60 mm 2 /s or less in an amount of 50% by mass or more and 95% by mass or less, a base oil having a 40° C. kinetic viscosity of 300 mm 2 /s or more in an amount of 5% by mass or more and 50% by mass or less, and an ⁇ -olefin copolymer.
• the heat treatment oil composition of PTL 6 has a problem that the cooling capability thereof is deteriorated with the lapse of time under repeated quenching.
• the present invention has been made under the circumstances, and an object thereof is to provide a heat treatment oil composition that is capable of reducing the fluctuation in cooling capability among components subjected to mass quenching while retaining a cooling capability equivalent to the No. 1 oil of Class 2 of JIS K2242:2012 in a heat treatment of a metal material, such as quenching, and is capable of suppressing deterioration in cooling capability thereof with the lapse of time under repetition of the heat treatment.
• one embodiment of the present invention provides a heat treatment oil composition containing (A) a base oil and (B) at least one selected from a petroleum resin and/or a derivative of a petroleum resin, wherein the heat treatment oil composition has a characteristic time obtained from a cooling curve obtained according to the cooling capability test method of JIS K2242:2012 of 1.00 second or less, and a 300° C. number of second, which is a cooling time from 800° C. to 300° C. in the cooling curve, of 6.00 seconds or more and 14.50 seconds or less.
• the heat treatment oil composition of the present invention is capable of reducing fluctuation in cooling capability among components subjected to mass quenching while retaining a cooling capability equivalent to the No. 1 oil of Class 2 of JIS K2242:2012 in a heat treatment of a metal material, such as quenching. Furthermore, the heat treatment oil composition of the present invention is capable of suppressing deterioration in cooling capability thereof with the lapse of time under repetition of a heat treatment of a metal material.
• the heat treatment oil composition of the embodiment contains (A) a base oil and (B) at least one selected from a petroleum resin and/or a derivative of a petroleum resin, and has a characteristic time obtained from a cooling curve obtained according to the cooling capability test method of JIS K2242:2012 of 1.00 second or less and a 300° C. number of second, which is a cooling time from 800° C. to 300° C. in the cooling curve, of 6.00 seconds or more and 14.50 seconds or less.
• Examples of the base oil as the component (A) include a mineral oil and/or a synthetic oil.
• Examples of the mineral oil include a paraffin-based mineral oil, an intermediate-based mineral oil, and a naphthene-based mineral oil, which are obtained by an ordinary refining method, such as solvent refining and hydrogenation refining; and a wax isomerized oil, which is produced through isomerization of wax, such as was produced by the Fischer-Tropsch process or the like (gas-to-liquid wax), and mineral oil wax.
• a paraffin-based mineral oil obtained by an ordinary refining method, such as solvent refining and hydrogenation refining
• a wax isomerized oil which is produced through isomerization of wax, such as was produced by the Fischer-Tropsch process or the like (gas-to-liquid wax), and mineral oil wax.
• Examples of the synthetic oil include a hydrocarbon synthetic oil and an ether synthetic oil.
• Examples of the hydrocarbon synthetic oil include an alkylbenzene and an alkylnaphthalene.
• Examples of the ether synthetic oil include a polyoxyalkylene glycol and a polyphenyl ether.
• the base oil as the component (A) may be a single component system using one of the mineral oils and the synthetic oils described above, or may be a mixed system obtained by mixing two or more of the mineral oils, mixing two or more of the synthetic oils, or mixing one or two or more each of the mineral oils and the synthetic oils.
• the base oil as the component (A) preferably has a 40° C. kinetic viscosity of 40 mm 2 /s or more and 500 mm 2 /s or less, more preferably 50 mm 2 /s or more and 350 mm 2 /s or less, and further preferably 60 mm 2 /s or more and 200 mm 2 /s or less.
• the essential cooling capability based on the component (A) can be easily ensured to control the characteristic time and the 300° C. number of second to the ranges described later.
• the mixed base oil preferably has a kinetic viscosity that satisfies the aforementioned range.
• the kinetic viscosity of the base oil and the heat treatment oil composition can be measured according to JIS K2283:2000.
• the content ratio of the base oil as the component (A) based on the total amount of the heat treatment oil composition is preferably from 10 to 99.9% by mass, more preferably from 50 to 98% by mass, and further preferably from 80 to 95% by mass.
• the content ratio of the component (A) is 80% by mass or more, the essential cooling capability based on the component (A) can be ensured, and when the content ratio of the component (A) is less than 100% by mass, the amount of the petroleum resin and/or the derivative of a petroleum resin as the component (B) used can be ensured to facilitate the effect based on the component (B) described later.
• the heat treatment oil composition of the embodiment contains (B) at least one of a petroleum resin and/or a derivative of a petroleum resin.
• the petroleum resin and/or the derivative of a petroleum resin as the component (B) has a function of a vapor blanket breaking agent.
• the use of the petroleum resin and/or the derivative of a petroleum resin as a vapor blanket breaking agent can shorten the vapor blanket stage, and the cooling capability of the heat treatment composition can be easily equivalent to the No. 1 oil of Class 2 of JIS K2242:2012.
• the use of the petroleum resin and/or the derivative of a petroleum resin can shorten the vapor blanket stage, and thus the vapor blanket stage and the boiling stage can be suppressed from being mixedly present on the surface of the metal material. Accordingly, the use of the petroleum resin and/or the derivative of a petroleum resin can suppress the fluctuation in cooling capability (i.e., the fluctuation in hardness and distortion) among components subjected to mass quenching from being formed. In the case where the component has a complex shape, the use of the petroleum resin and/or the derivative of a petroleum resin can suppress the fluctuation in cooling capability among portions of the component, and thus the distortion of the component can be suppressed.
• the use of the petroleum resin and/or the derivative of a petroleum resin can suppress the deterioration in cooling capability of the heat treatment oil composition with the lapse of time.
• the increase with the lapse of time of the number of second (characteristic time) until reaching the temperature where the vapor blanket stage ends and the decrease with the lapse of time of the kinetic viscosity can be suppressed. Accordingly, the use of the petroleum resin and/or the derivative of a petroleum resin can prolong the lifetime of the heat treatment oil composition.
• the petroleum resin and/or the derivative of a petroleum resin can shorten the characteristic time in the initial stage of the heat treatment.
• the petroleum resin and/or the derivative of a petroleum resin can exhibit the aforementioned effects due to the thermoplastic characteristics of the petroleum resin and/or the derivative of a petroleum resin and the excellent solubility thereof in the base oil.
• the petroleum resin is a resin that is obtained through polymerization or copolymerization of one kind or two or more kinds of an unsaturated compound selected from an aliphatic olefin compound and an aliphatic diolefin compound having a number of carbon atoms of from 4 to 10 obtained as a by-product in the production of an olefin, such as ethylene, through thermal cracking of a petroleum product, such as naphtha, and an aromatic compound having a number of carbon atoms of 8 or more and having an olefinic unsaturated bond.
• an unsaturated compound selected from an aliphatic olefin compound and an aliphatic diolefin compound having a number of carbon atoms of from 4 to 10 obtained as a by-product in the production of an olefin, such as ethylene, through thermal cracking of a petroleum product, such as naphtha, and an aromatic compound having a number of carbon atoms of 8 or more and having an olefinic
• the petroleum resin can be roughly classified, for example, into an “aliphatic petroleum resin” obtained through polymerization of an aliphatic olefin compound or an aliphatic diolefin compound, an “aromatic petroleum resin” obtained through polymerization of an aromatic compound having an olefinic unsaturated bond, and an “aliphatic-aromatic copolymerized petroleum resin” obtained through copolymerization of an aliphatic olefin compound or an aliphatic diolefin compound and an aromatic compound having an olefinic unsaturated bond.
• Examples of the aliphatic olefin compound having a number of carbon atoms of from 4 to 10 include butene, pentene, hexene, and heptene.
• Examples of the aliphatic diolefin compound having a number of carbon atoms of from 4 to 10 include butadiene, pentadiene, isoprene, cyclopentadiene, dicyclopentadiene, and methylpentadiene.
• Examples of the aromatic compound having a number of carbon atoms of 8 or more and having an olefinic unsaturated bond include styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, vinyltoluene, vinylxylene, indene, methylindene, and ethylindene.
• the raw material compound of the petroleum resin may not be entirely a by-product in the production of an olefin through thermal cracking of a petroleum product, such as naphtha, and a chemically synthesized unsaturated compound may also be used.
• a dicyclopentadiene petroleum resin obtained through polymerization of cyclopentadiene or dicyclopentadiene
• a dicyclopentadiene-styrene petroleum resin obtained through copolymerization of cyclopentadiene or dicyclopentadiene and styrene.
• Examples of the derivative of a petroleum resin include a hydrogenated petroleum resin obtained by adding hydrogen atoms to the aforementioned petroleum resin.
• Examples of the derivative of a petroleum resin also include an acid-modified petroleum resin obtained through modification of the petroleum resin with an acidic functional group represented by a carboxylic acid, and a compound obtained through reaction modification of the acid-modified petroleum resin with a compound, such as an alcohol, an amine, an alkali metal, and an alkaline earth metal.
• the acid-modified petroleum resin can be roughly classified into a carboxylic acid-modified petroleum resin and an acid anhydride-modified petroleum resin obtained through modification of the petroleum resin with an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride.
• the unsaturated carboxylic acid include an unsaturated monocarboxylic acid, such as acrylic acid and methacrylic acid; an unsaturated polybasic carboxylic acid, such as maleic acid, fumaric acid, itaconic acid, and citraconic acid; and a partial ester compound of an unsaturated polybasic carboxylic acid, such as monomethyl maleate and monoethyl fumarate, and examples of the unsaturated carboxylic acid anhydride include an unsaturated polybasic carboxylic acid anhydride, such as maleic anhydride and itaconic anhydride.
• the petroleum resin or the derivative of a petroleum resin is preferably an aliphatic-aromatic copolymerized petroleum resin or a hydrogenated aliphatic-aromatic copolymerized petroleum resin since the characteristic time tends to be decreased.
• the number average molecular weight of the petroleum resin or the derivative of a petroleum resin is preferably from 200 to 5,000, more preferably from 250 to 2,500, and further preferably from 300 to 1,500, from the standpoint of easily exhibiting the effect of the embodiment.
• the petroleum resin and/or the derivative of a petroleum resin preferably has a softening point measured by the ring and ball method of JIS K2207:2006 of 40° C. or more, more preferably 60° C. or more and 150° C. or less, further preferably 80° C. or more and 140° C. or less, and still further preferably 85° C. or more and 130° C. or less.
• the softening point of the petroleum resin and/or the derivative of a petroleum resin is 40° C. or more, the fluctuation in cooling capability (i.e., the fluctuation in hardness and distortion) among components subjected to mass quenching can be prevented from being formed, and simultaneously in the case where the component has a complex shape, the fluctuation in cooling capability among portions of the component can be prevented from being formed, and thus the distortion of the component can be suppressed.
• the fluctuation in cooling capability i.e., the fluctuation in hardness and distortion
• the softening point of the petroleum resin and/or the derivative of a petroleum resin is 40° C. or more, the deterioration in cooling capability with the lapse of time (i.e., the increase of the characteristic time with the lapse of time and the decrease of the kinetic viscosity with the lapse of time) in the case where the heat treatment of the metal material is performed repeatedly can be suppressed, and simultaneously the characteristic time in the initial stage of the heat treatment can be decreased. Accordingly, when the softening point of the petroleum resin and/or the derivative of a petroleum resin is 40° C.
• the cooling capability of the heat treatment oil composition can be retained not only in the initial stage but also after the repeated use, and the fluctuation in cooling capability among components subjected to mass quenching and the distortion of the component can be suppressed over a prolonged period of time.
• the softening point of the petroleum resin and/or the derivative of a petroleum resin is 150° C. or less, stickiness on the surface of the processed material, such as the metal material, having been cooled with the heat treatment oil composition can be suppressed.
• the softening point of the petroleum resin and/or the derivative of a petroleum resin can be controlled by the polymerization degree of the petroleum resin, the modification component therefore, and the modification degree thereof.
• all the materials preferably have a softening point within the aforementioned range.
• the content ratio of the petroleum resin and/or the derivative of a petroleum resin as the component (B) based on the total amount of the heat treatment oil composition is preferably from 0.1 to 90% by mass, more preferably from 2 to 50% by mass, and further preferably from 5 to 20% by mass.
• the content ratio of the component (B) is 0.1% by mass or more, the effect based on the component (B) described above can be easily obtained.
• the content ratio of the component (B) is 90% by mass or less, the amount of the base oil being the component (A) used, which secures the essential cooling capability, can be ensured to impart the cooling capability to the heat treatment oil composition.
• the total content of the component (A) and the component (B) is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 100% by mass, based on the total amount of the heat treatment oil composition.
• the heat treatment oil composition may contain an additional vapor blanket breaking agent other than the petroleum resin and/or the derivative of a petroleum resin, in such a range that does not impair the effect of the embodiment.
• additional vapor blanket breaking agent include a terpene resin, a derivative of a terpene resin, rosin, and a derivative of rosin.
• the heat treatment oil composition of the embodiment may contain an additive, such as an antioxidant and a cooling capability improver.
• the content ratios of the antioxidant, the cooling capability improver, and the like each are preferably 10% by mass or less, and more preferably from 0.01 to 5% by mass based on the total amount of the heat treatment oil composition.
• the heat treatment oil composition of the embodiment necessarily has a characteristic time obtained from a cooling curve obtained according to the cooling capability test method of JIS K2242:2012 of 1.00 second or less.
• the characteristic time of the heat treatment oil composition is preferably 0.95 second or less, and more preferably 0.90 second or less.
• the characteristic time can be more specifically calculated by the following procedures (1) and (2).
• the time interval of measurement is preferably 1/100 second.
• the heat treatment oil composition of the embodiment necessarily has a “300° C. number of second”, which is a cooling time from 800° C. to 300° C. in a cooling curve obtained according to the cooling capability test method of JIS K2242:2012, of 6.00 seconds or more and 14.50 seconds or less.
• the 300° C. number of second of the heat treatment oil composition is preferably from 6.50 to 13.50 seconds, and more preferably from 7.00 to 12.50 seconds.
• the content and the 40° C. kinetic viscosity of the component (A) and the content, the softening point, and the number average molecular weight of the component (B) are preferred.
• the heat treatment oil composition of the embodiment preferably has a 100° C. kinetic viscosity of from 10 to 30 mm 2 /s, and more preferably from 15 to 20 mm 2 /s.
• a case hardened steel having a cylindrical shape (outer diameter: 85 mm, height: 44 mm, thickness: 4 mm, material: SCM415) was subjected to a heat treatment or the like under the following conditions, and was further evaluated for the following items.
• Oil cooling condition oil temperature: 120° C., oil cooling time: 10 min, agitation: 20 Hz
• the temperature (characteristic temperature) where the vapor blanket stage of the heat treatment oil composition ended was calculated, and the number of second until reaching the temperature was designated as the characteristic time.
• the cooling time from 800° C. to 300° C. was designated as the 300° C. number of second.
• the result in the item A-2 above was designated as the result before the repeated quenching deterioration test.
• the repeated quenching deterioration test was then performed under the following condition. After performing the repeated quenching deterioration test, the same test and evaluation as in the item A-2 were performed to obtain a result, which was designated as the result after the repeated quenching deterioration test.
• the change rate before and after the test was calculated by the following expression (2).
• the heat treatment oil composition was measured for the 100° C. kinetic viscosity before and after the repeated quenching deterioration test of the item A-3.
• Heat treatment oil compositions having the compositions shown in Table 1 were prepared and evaluated and measured according to the items A-2 and A-4 above. The results are shown in Table 1.
• Example 1 Base oil 1 85 85 85 85 85 85 85 85 85 100 (% by mass) Vapor Material petroleum petroleum petroleum petroleum petroleum petroleum petroleum petroleum petroleum petroleum petroleum petroleum petroleum petroleum petroleum petroleum petroleum — blanket 1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-8 1-9 breaking Content ratio 15 15 15 15 15 15 15 15 — agent (% by mass) Total 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100
• Base oil 1 mineral oil, 40° C. kinetic viscosity: 90 mm 2 /s
• Petroleum 1-1 partially hydrogenated aliphatic-aromatic copolymerized petroleum resin, softening point: 110° C., number average molecular weight: 760
• Petroleum 1-2 aliphatic petroleum resin, softening point: 99° C., number average molecular weight: 1,300
• Petroleum 1-3 aliphatic-aromatic cop olymerized petroleum resin, softening point: 103° C., number average molecular weight: 900
• Petroleum 1-4 hydrogenated aliphatic petroleum resin, softening point: 105° C., number average molecular weight: 400
• Petroleum 1-5 hydrogenated aliphatic petroleum resin, softening point: 125° C., number average molecular weight: 430
• Petroleum 1-6 hydrogenated aliphatic petroleum resin, softening point: 87° C., number average molecular weight: 370
• Petroleum 1-7 hydrogenated aliphatic petroleum resin, softening point: 103° C., number average molecular weight: 410
• Petroleum 1-8 partially hydrogenated aromatic modified petroleum resin, softening point: 102° C., number average molecular weight: 500
• Petroleum 1-9 aliphatic petroleum resin, softening point: 124° C., number average molecular weight: 430
• the heat treatment oil compositions of Examples 1-1 to 1-9 each have a short characteristic time. Accordingly, it is understood that the suppression of the fluctuation in cooling capability among components subjected to mass quenching and the suppression of the distortion of the component can be expected by the use of the heat treatment oil compositions of Examples 1-1 to 1-9.
• Heat treatment oil compositions having the compositions shown in Table 2 were prepared and evaluated and measured according to the items A-1 to A-4 above.
• the 100° C. kinetic viscosity of the item A-4 was measured before and after the repeated quenching deterioration test of the item A-3.
• the results are shown in Table 2.
• Example 2-1 Example 2-2 Base oil Base oil 2-1 90 — — (% by mass) Base oil 2-2 — 91 — Base oil 2-3 — — 99.25 Vapor blanket Petroleum resin 2 10 — — breaking agent ⁇ -Olefin copolymer — 8 — (% by mass) Antioxidant — 1 0.75 Total 100 100 100 Hardness and Average ellipticity (mm) 0.120 0.170 0.197 distortion Ellipticity 3 ⁇ (mm) 0.142 0.174 0.240 Average taper distortion (mm) 0.078 0.069 0.093 Taper distortion 3 ⁇ (mm) 0.040 0.035 0.058 Average internal hardness (HV) 346 322 328 Average effective hardened layer 0.94 0.91 0.85 depth (mm) Cooling Before test 100° C.
• HV internal hardness
• Base oil 2-1 mineral oil, 40° C. kinetic viscosity: 120 mm 2/ s
• Base oil 2-2 mineral oil, 40° C. kinetic viscosity: 60 mm 2 /s
• Base oil 2-3 mineral oil, 40° C. kinetic viscosity: 200 mm 2 /s
• Petroleum resin 2 partially hydrogenated aliphatic-aromatic copolymerized petroleum resin, softening point: 110° C., number average molecular weight: 760
• ⁇ -Olefin copolymer ⁇ -olefin copolymer, 100° C. kinetic viscosity: 2,000 mm 2 /s
• the heat treatment oil composition of Example 2 has a short 300° C. number of second, and thus has a cooling capability equivalent to the No. 1 oil of Class 2 of JIS K2242:2012. It is also confirmed that the heat treatment oil composition of Example 2 has small values for the ellipticity 3 ⁇ and the taper distortion 3 ⁇ , and thus can suppress the fluctuation in distortion in mass quenching. It is further confirmed that the heat treatment oil composition of Example 2 can suppress the deterioration of the capability (i.e., the increase of the characteristic time, the increase of the 300° C. number of second, and the decrease of the kinetic viscosity) with the lapse of time in the repeated heat treatment.
• the capability i.e., the increase of the characteristic time, the increase of the 300° C. number of second, and the decrease of the kinetic viscosity
• the heat treatment oil composition of Example 2 shows good values for the characteristic time and the 300° C. number of second in the initial stage, and thus can retain the good capability over a prolonged period of time, i.e., in the initial stage and after the repeated use.
• the heat treatment oil composition of the embodiment is capable of reducing the fluctuation in cooling capability among components subjected to mass quenching while retaining a cooling capability equivalent to the No. 1 oil of Class 2 of JIS K2242:2012, and is capable of suppressing deterioration in cooling capability thereof with the lapse of time under repetition of the heat treatment of the metal material. Therefore, the heat treatment oil composition of the embodiment is favorably used as a heat treatment oil for heat treatments, such as quenching, annealing, and tempering, of an alloy steel, such as a carbon steel, a nickel-manganese steel, a chromium-molybdenum steel, and a manganese steel, and particularly favorably used as a heat treatment oil for quenching.
• an alloy steel such as a carbon steel, a nickel-manganese steel, a chromium-molybdenum steel, and a manganese steel

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