JPS6253397A - Film-forming hardening oil - Google Patents

Abstract

PURPOSE:A film-forming hardening oil for forming a black film having improved lubricating properties on the surface of a material to be hardened, obtained by blending a mineral base oil with a zinc dialkyldithiophosphate and an alkenylsuccinimide, etc. CONSTITUTION:100pts.wt. mineral base oil is blended with (A) 0.05-10pts.wt. zinc dialkyldithiophosphate and (B) 0.05-30pts.wt. one or more selected from alkenyl- or alkylsuccinimide, boron succinimide and metallic salt of petroleum sulfonic acid, to give the aimed hardening oil. EFFECT:Standing long-term continuous use, having stable cooling performance in hardening.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a quenching oil, and more particularly to a film-forming quenching oil that forms a lubricating film on the surface of an object to be quenched.

[Conventional technology]

As is well known, quenching is a means to increase the hardness of the object to be quenched, and it is also well known that quenching oil is used for this purpose.

Although this quenching oil could impart hardness to the object to be quenched, it could hardly impart lubricity.

However, objects to be hardened, such as bolts, require lubricity, and it is necessary to apply a separate means of imparting lubricity to such objects after quenching with quenching oil. .

Quenching oils that solve these problems have been developed, and for example, as shown in Japanese Patent Publication No. 47-20806, quenching oils have also been developed in which a lubricating film is formed at the same time as quenching. reached.

However, due to recent advances in technology in various fields, quenching oils are increasingly required to have higher performance. There is a strong demand for performance that allows the film to be used stably without deterioration of its properties, and constant cooling performance.

[Object and outline of the present invention]

The purpose of the present invention is to develop a quenching oil that can meet the above demands, and more specifically, to develop a quenching oil that can form a strong and stable film even after long-term continuous use and exhibit stable cooling performance. This object of the present invention is achieved by incorporating two to four specific compounds into a mineral base oil. That is, the present invention comprises blending (A) zinc dialkyldithiophosphate and (B) at least 1 m of an alkenyl or alkyl succinimide, a borated alkenyl succinimide, and a petroleum sulfonic acid metal salt into a mineral base oil. This relates to a film-forming quenching oil.

〔Effect of the invention〕

In the present invention, the specific compounds (A) and (B) above are blended into the mineral base oil, so as shown in the experimental examples below, the quenching oil of the present invention can be used for a long period of time. Even after continuous use, the lubricating film formed on the object to be quenched exhibits extremely stable performance. The cooling performance during quenching is also stable.

In addition, the tough film formed on the object to be quenched is black in color and has excellent lubricity.

[Structure of the invention]

The quenching oil of the present invention basically consists of mineral base oil, (A) zinc dialkyldithiophosphate, preferably 0.05 to 10 parts by weight per 100 parts by weight of mineral base oil, and (B) alkenyl or alkyl succinate. At least one of acid imide, borated succinimide and petroleum sulfonic acid metal salt is preferably the same (0.05 to 30 parts by weight).

Zinc dialkyldithiophosphate used in the present invention is represented by the following general formula.

[However, in the formula, R is the same or different primary or secondary alkyl group having 3 to 12 carbon atoms, or aryl (CH2
-CHCH2) group. ] As the alkyl group of the zinc dialkyldithiophosphate represented by the above general formula (1), primary or secondary alkyl groups are appropriately selected and used depending on the purpose of use.

The alkenyl or haalkyl succinimide used in the present invention has the following general formula (wherein, ma represents an alkyl group or an alkenyl group,
(X represents an integer from θ to lO), and the alkyl group for m usually has about 50 to 200 carbon atoms, preferably about 50 to 100 carbon atoms, and the alkenyl group for k usually has about 50 to 100 carbon atoms. ~2
00, preferably about 50 to 100. Further, a desirable molecular weight is about 800 to 3,500.

The boronated alkenyl succinimide used in the present invention is a boronated alkenyl succinimide, and exists as a dehydrated boric acid polymer bonded as an imide metaborate. It can be easily produced by heating and reacting boron compounds such as boron halides, boron acids, and esters thereof. A preferred boronated alkenyl succinimide has a molecular weight of 8
It is about 50 to 5000.

As the petroleum sulfonic acid metal salt, petroleum sulfonic acid salts of alkaline earth metals can be preferably used, and salts of calcium, magnesium, and barium are particularly preferred. The preferred molecular weight of this petroleum sulfonic acid metal salt is usually 400 to 9.
It is more preferably about 400 to 600 than about 00.

In the present invention, these succinimides, boronated alkenyl succinimides, and petroleum sulfonic acid metal salts are
The amount of one type used is usually 0.05 to 10 parts by weight (per 100 parts by weight of base oil).
It is.

As the mineral oil base oil used in the present invention, any mineral base oil that has been conventionally used for this type of quenching oil can be used, preferably one having a viscosity of 8 to 1000 ast (40 DEG C.).

In the quenching oil of the present invention, base oil, zinc dialkyldithiophosphate (hereinafter simply referred to as zinc thiophosphate), alkenyl or alkylsuccinimide, boronated alkenylsuccinimide, petroleum It is desirable to appropriately select and blend the sulfonic acid metal salt. For example, zinc thiophosphate is used for items with a small heat capacity to be hardened, such as screws, with a secondary alkyl group as R, and for items to be hardened such as ball joints, which have a relatively large heat capacity, It is preferable to use a primary alkyl group as R, and as the quenching oil, various types including zinc thiophosphate can be used, such as cold quenching oil, semi-hot quenching oil, and martemper quenching oil, depending on the field of use. It is preferable to select and use the above compounds.

The quenching oil of the present invention can be blended with various conventionally known additives as required, and specific examples include additives such as antioxidants and pour point depressants.

Experimental examples are given below to make the features of the present invention clearer. However, parts indicate parts by weight.

Experimental Example 1> (i) Preparation of quenching oil and -ψworm 3 process (product of the present invention) Commercially available mineral oil・・・・・・・・・・・・・・・・・・・・・
...94.5 parts (kinematic viscosity at 40°C 426.4 cst
) Zinc thiophosphate・・・・・・・・・・・・・・・
... 1.5 parts (mixture where R is primary and has 4 and 8 carbon atoms) polyisobutenyl succinimide... 4.0 parts (molecular weight 900 to 1100) The above compound in the above specified ratio Quenching oil was prepared by uniformly mixing.

1 piece (comparative example) Quenching oil A with polyisobutenyl succinimide removed.

Penetration upright (product of the present invention) In quenching oil A, the blending amount of polyisobutenyl succinimide was 2.0 parts, and 2.0 parts of calcium stearate was added.
Contains 0 parts.

Ki-no-shiki city knee (comparative example) Quenching oil A using polybutene (molecule (11450) instead of polyisobutenyl succinimide.

Ao no Genmushi (comparative example) Quenching oil A in which trilauryltrithiophosphite was used in place of zinc thiophosphate.

(11) Experimental method Using the experimental furnace shown in Fig. 1, a prescribed test piece 5 was prepared in an argon and helium gas atmosphere using each of the above-mentioned quenching oils.
The quenching oil was quenched and the quenching oil was deteriorated by heat. At this time, the amount of consumption of zinc thiophosphate or trilauryl thiophosphite in the quenching oil was measured every time 10 test pieces were introduced.

The results are shown in FIG. In addition, the test piece was washed with toluene and n-hexano in that order, and after observing the appearance, a commercially available cellophane tape was applied to the surface of the test piece with Tottoh Cellophane Tape 29), and the tape was pulled and peeled off. The presence or absence of film transfer on the surface to which the agent was applied was examined. These results are shown in Tables 1 and 2. However, in Figure 1, (1) is the thermocouple, (2) is the inlet for the mixed gas of argon and hydrogen, (3) is the quenching oil tank, (4) indicates the electric furnace, (5) indicates the outlet for the mixed gas of argon and hydrogen, and A-E in Fig. 2 indicate the corresponding quenching oil A-E. -D was measured by infrared absorption, and quenching oil E was measured by quantitative determination of phosphorus. However, the amount of consumption was expressed by the concentration of each compound present in the quenching oil.

Other experimental conditions were as follows: 0 Furnace heating salinity 2 850°C 0 Amount of quenching oil: 100°C 0 Test piece dimensions: 15φ x 2511 IllQ test piece material: 5UJ-2 0 Test piece heating time: 15 minutes (iii) Discussion of experimental results As is clear from Figure 1, the consumption of zinc thiophosphate in quenching oils A and C (both products of the present invention) is small, but even when zinc thiophosphate is blended, However, it is clearly seen that quenching oil B, which is not used in combination with polyisobutenyl succinimide, has a large consumption amount, and that the synergistic effect of these two types of oil greatly reduces the consumption amount. In addition, even if zinc thiophosphate is used, other compounds other than the present invention are blended (quenching oil D), and even if polyisobutenyl succinimide is used, other compounds are blended without using zinc thiophosphate. It is clearly seen that even when a compound (dilauryl thiophosphite) is used (quenching oil E), the amount of consumption is still large.

Also, from Tables 1 and 2, in both cases, quenching oil A
and C showed good results, but quenching oils B and D
has not obtained good results.

<Experimental example 2> A 3111Ilφ, 40mm nichrome wire coil was heated with N2
Heat to about 800°C in gas. At the same time as turning off the electricity, it is immersed in the quenching oil of No. 11 maintained at about 110±10°C.

After dipping for 60 seconds, pull it out and heat it at the same time to 80℃ in about 60 seconds.
Raise to 0°C. Repeated dipping and pulling and heating to add 80% of quenching oil.
The zinc thiophosphate or trilauryl trithiophosphite that has been subjected to continuous thermal aging for a period of time is then prepared to the original composition of the quenching oil. After conducting a heat deterioration test using the same procedure for a total heat deterioration time of 40 hours, the cooling performance of the new oil and the deteriorated oil was measured using the JIS K2242 cooling performance test method. Figures 3 to 7 show methods for measuring quenching oils A, B, C1D, and H. However, the same quenching oils A to E as in Experimental Example 1 were used.

Figure 3 shows the case of quenching oil A, and similarly, Figure 4 shows the case of quenching oil B, Figure 5 shows the case of quenching oil C1, Figure 6 shows the case of quenching oil D, and Figure 7 shows the case of quenching oil E. The solid lines in each figure show the results for new oil, and the dotted lines show the results for degraded oil.

As is clear from Figures 3 to 7, there is almost no difference between new and deteriorated quenching oils A and C (products of the present invention), and the cooling performance of the deteriorated oil has hardly changed. On the other hand, the difference is large for quenching oils B, D, and E, indicating that the cooling performance of degraded oils is poor.

Experimental Example 3> An actual on-site operation was carried out using quenching oil, and the amount of change in the diameter of the between poles in the ball groove of the ball joint due to heat treatment was measured. The quenching oil used at this time was Experimental Example 1.
quenching oil A and quenching oil E for comparison. The results are shown in FIG. However, the ball joint used is shown in FIG. 9(a), and its ball groove is shown in FIG. 9(b). However, the dotted line in FIG. 8 indicates quenching oil A, and the solid line indicates quenching oil E.

As is clear from Figure 8, the quenching oil A (product of the present invention) is approximately 1
The amount of change in heat treatment hardly changes even after years of use, but for quenching oil E, the amount of change starts to increase after about two months, and has already doubled in amount after about three months.

[Brief explanation of the drawing]

Figure 1 is a schematic diagram of the equipment used to examine the performance of quenching oils, Figure 2 is a graph showing the relationship between the amount of consumption of each quenching oil and the amount of test pieces, and Figures 3- Figure 7 is a graph showing the cooling performance of quenching oil. Moreover, FIG. 8 is a graph showing the relationship between the amount of change in heat treatment of quenching oil and time, and FIG. 9 shows a ball joint. (1)... Thermocouple (2)... Mixed gas of argon and hydrogen (3)...
...Quenching oil tank (4) ...Electric furnace (5) ...Discharge port for mixed gas of argon and hydrogen (
Above) Patent applicant Toyota Motor Corporation Patent applicant Nippon Grease Co., Ltd. Figure 1 Figure 2 Jrj included U 8 dimensions r-1 (Figure 9 (A)

Claims (1)

[Scope of Claims] (1) Mineral base oil, (A) zinc dialkyldithiophosphate, and (B) at least one of an alkenyl or alkyl succinimide, a borated alkenyl succinimide, and a petroleum sulfonic acid metal salt. A film-forming quenching oil made by blending the following. (2) 0.05 to 10 parts by weight of zinc dialkyldithiophosphate, and alkenyl or alkyl succinimide;
Claim 1, characterized in that at least one of boronated succinimide and petroleum sulfonic acid metal salt is blended in an amount of 0.05 to 30 parts by weight based on 100 parts by weight of the base oil. Film-forming quenching oil.