JP3267743B2 - Composition for sliding members - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for a sliding member using a heat-resistant synthetic resin as a binder, and more particularly to a composition for a sliding member used for a portion which is slid under lubrication in oil. The sliding member obtained by using the composition for a sliding member is suitably used, for example, for a skirt portion of a piston of an engine.

[0002]

2. Description of the Related Art Conventionally, as a proposal for improving the sliding characteristics of a sliding member using a heat-resistant synthetic resin as a binder, a mineral Mo has been proposed.
Solid lubricants such as S ₂ , PTFE, and C (graphite) are blended. For example, (1) PT
FE blended to reduce wear (Japanese Patent Application Laid-Open No. 54-16 / 1979)
2014), (2) Mineral MoS _{2 in} epoxy resin
(JP-A-57-39916),
(3) An epoxy resin blended with C (graphite) (JP-A-59-190455), and (4) a polyamideimide blended with the mineral MoS ₂ (JP-A-63).
-125821).

As a proposal for improving the sliding characteristics of a magnetic recording medium, (5) a magnetic layer in which a ferromagnetic powder is dispersed in a binder has a general formula:

[0004]

Embedded image

(Where R is an alkyl group having 1 to 20 carbon atoms) containing an organic molybdenum compound (JP-A-60-195729);

[0006]

Embedded image

(Where R is an alkyl group having 1 to 20 carbon atoms) containing an organic molybdenum compound (JP-A-60-195731);

[0008]

Embedded image

[0009] (wherein, R represents an alkyl group having 1 to 20 carbon atoms) is known which contains an organic molybdenum compound represented by (JP 60-19573 2 No.).

[0010]

However, the above (1) to (1)
Minerals MoS ₂ , PTFE, C in each proposal of (4)
Solid lubricants such as (graphite) are commercially available having a particle size of, for example, 10 to 30 μm for mineral MoS ₂ and 5 for PTFE.
It is relatively large, such as 10 μm to 10 μm, and tends to be non-uniformly dispersed in the liquid when it is simultaneously dissolved in a solvent together with a binder serving as a matrix.

For this reason, if a coated sliding member is manufactured by coating the base material with such a composition, local absence of the solid lubricant occurs on the sliding surface, and the local frictional force increases. It also becomes the starting point of the occurrence of wear and peeling. Thus, the non-uniform dispersion of the solid lubricant not only impairs the wear characteristics and the seizure characteristics, but also does not reduce the friction characteristics for the mixing ratio of the solid lubricant, and causes variations in these characteristics. . In the worst case, there is a possibility that the coat sliding member is broken.

When a molded sliding member is manufactured using such a composition, for example, when an external force such as a bending stress or a tensile stress is applied, the solid lubricant dispersed non-uniformly in the molded sliding member. May cause stress concentration in the resulting material, and there is a possibility that the molded sliding portion agent is broken. Of course, means for reducing the particle size of the solid lubricant in the coated sliding member and the molded sliding member as much as possible can be considered. However, in order to reduce the particle size of the solid lubricant, a sand mill, a roll mill, a homogenizer, etc. , The minerals MoS ₂ , PTFE, C (graphite), etc. are reduced to about 1 to 4 μm, but still cannot be sufficiently dispersed uniformly in the solvent together with the binder.

On the other hand, the magnetic layer containing the organic molybdenum compound of formulas 1 to 3 in each of the above-mentioned proposals (5) to (7) constitutes a magnetic recording medium such as a magnetic tape, and its sliding characteristics are also dry. Under relatively light load under conditions.
Therefore, the proposals (5) to (7) cannot be directly applied to a sliding member under oil lubrication. The present invention has been made in view of the above circumstances, and it is possible to produce a sliding member that reliably exhibits excellent wear characteristics, seizure characteristics, and friction characteristics under lubrication in oil and does not easily break. An object is to provide a composition for a sliding member.

[0014]

Composition for sliding member of the present invention, in order to solve the problem] is a composition of a sliding member used in the site to be slid under lubrication oil, a binder containing Epoxy resins When,
It is characterized in that it has a powdery organic molybdenum compound in a distributed normal temperature to the binder. From The binder containing Epoxy resins, for example, other possible to epoxy alone (EP) resin as a binder, under the purpose of strengthening the binder, the EP resin and xylene resin and a vinyl resin and a polyimide (PI) resin Resin mixture as a binder, EP resin and phenol (P
F) A resin mixture of a resin and a silicon resin can be used as a binder, and a resin mixture of an EP resin and an amino resin can be used as a binder for the purpose of accelerating curing.

The organic molybdenum compound in the form of powder at room temperature includes

[0016]

Embedded image

(Where R is an alkyl group and X is O or S) powdery ones at room temperature can be employed. Specifically, "Sakura Lube 500" and "Sakura Lube 600" manufactured by Asahi Denka Kogyo KK can be used. It is preferable that the organic molybdenum compound in a powder form at room temperature is 0.01 to 40% by weight in the coating film. Powdery organic molybdenum compound at room temperature is
0 . If the content is less than 01 wt%, Mo is unlikely to be present on the sliding surface, and the binder serving as a matrix easily controls the sliding surface. Therefore, the friction does not decrease, the shearing force on the sliding surface is large, and seizure occurs early. . Further, in the coated sliding member, the coated layer is easily peeled from the base material. Conversely, if the amount of the organic molybdenum compound in a powder form exceeds 40 wt% at room temperature, the strength of the binder serving as a matrix is significantly reduced, and the wear characteristics are deteriorated. As a result, although MoS ₂ is generated by the sliding, the sliding surface is actively worn, so that the roughness increases, and as a result, the friction coefficient increases and the seizure surface pressure decreases.

[0018] When producing a composition for a sliding member of the present invention, to obtain a binder containing Epoxy resins are dissolved in a solvent, the composition mixed powdery organic molybdenum compound at room temperature in the solution The composition can be coated on a base material and the coated layer can be cured by heating.

[0019]

The present inventors have conducted intensive studies for the above purpose, and as a result, as an organic molybdenum compound, in addition to a powdery one, a liquid one is commercially available. It has been found that the shape-like material has a lower coefficient of friction, a smaller amount of wear, and a higher seizure surface pressure. Here, in the sliding member containing the organic molybdenum compound, Mo in the molecules of the organic molybdenum compound on the sliding surface and S in the same molecule are activated by heat during sliding, and Mo is generated by an intermolecular reaction.
To generate the S _2. Since the generated MoS ₂ adheres to the sliding member and the surface of the mating material, the frictional force is reduced, the friction coefficient is reduced, and accordingly, the wear resistance and the seizure surface pressure are improved. Here, under lubrication in oil, S in the lubricating oil is also MoS ₂
Involved in the generation of For this reason, in the sliding member manufactured using the composition for a sliding member of the present invention, more effective improvement in the sliding characteristics can be obtained.

[0020] Then, adopting those containing Epoxy resins as a binder, powdered at room temperature in the binder
If it caused to disperse the organic molybdenum compound, and found that the powdery <br/> organic molybdenum compound are uniformly dispersed. At this time, the powdery organic molybdenum compound,
Epoxy resins with hardly heating since the intermolecular reaction does not occur to both be dispersed, while easily obtained improvement in sliding properties due to the powdery organic molybdenum compounds,
If ask dispersed in a binder in consisting Epoxy resins other than the resin easily occurs intermolecular reaction to both was also found that the improvement in the sliding characteristics due to powdery organic molybdenum compound is obtained hardly. Thus, the present invention has been completed.

[0021]

【Example】

(1) Embodiments 1 to 1 in which the present invention is applied to a coated sliding member
18 will be described together with Comparative Examples 1 to 48 with reference to the drawings. First, as organic molybdenum compounds, "Sakura Lube 230" and "Sakura Lube 3" manufactured by Asahi Denka Kogyo KK
00 "," Sakura Lube 474 "," Sakura Lube 700 "," Sakura Lube 500 ", and" Sakura Lube 600 ".

Among them, "Sakura Lube 500" and "Sakura Lube 600" are powdered at normal temperature.
On the other hand, “Sakura Lube 230”, “Sakura Lube 30”
"0", "Sakura Lube 474" and "Sakura Lube 70"
"0" is a liquid at normal temperature and has solubility with methyl ethyl ketone or polyglycol monoethyl ether acetate which dissolves the binder.

Here, "Sakura Lube 230",
"Sakura Lube 500" and "Sakura Lube 600"
Is molybdenum dithiocarbamate (Mo-DTC), as shown in the above chemical formula 4. "Sakura Lube 300"
Is molybdenum dithiophosphate (Mo-DTP) as shown in the following chemical formula 5. "Sakura Lube 47
“4” is molybdenum phosphate as shown in the following formula (where R is an alkyl group, x, y, z ≦
3). “Sakura Lube 700” is a molybdenum amine complex as shown in the following Chemical Formula 7 (where,
R is an alkyl group, x, y, z ≦ 3).

[0024]

Embedded image

[0025]

Embedded image

[0026]

Embedded image

As the binder, EP resin ("Epiclon 850", manufactured by Dainippon Ink and Chemicals, Inc.) and xylene resin (manufactured by Mitsubishi Gas Chemical Company, "Nicanol DL")
-15 "), vinyl resin (manufactured by Sekisui Chemical Co., Ltd.," S-LEC BL-2 "), PI (manufactured by Mitsubishi Gas Chemical Co., Ltd.)
“BIM-450”), silicon resin (“KP-282”, manufactured by Shin-Etsu Chemical Co., Ltd.), amino resin (“Beckamine P-138”, manufactured by Dainippon Ink and Chemicals, Inc.)
PF (Hoechst Japan K.K., “Phenodur”
PR401 "), polyamideimide (PAI) (HI-400", manufactured by Hitachi Chemical Co., Ltd.), polyurethane (PU) ("Barnock M5350", manufactured by Dainippon Ink and Chemicals, Inc.), polyesteramide (Dainippon) "Beccosol ER-3400" manufactured by Ink Chemical Industry Co., Ltd.)
Prepare

Using methyl ethyl ketone, propylene glycol methyl ether acetate or N-methyl-2-pyrrolidone as a solvent, each binder is prepared as shown in Tables 1-4. In Tables 1 to 4, the binder composed of the resin mixture was obtained by weight ratio.

[0029]

[Table 1]

[0030]

[Table 2]

[0031]

[Table 3]

[0032]

[Table 4]

As shown in Tables 1 to 4, the above organic molybdenum compound is mixed to prepare a composition. The composition is coated on a base material with a thickness of 10 μm by spraying.
Heat and cure at 80 ° C for 2 hours. Thus, Examples 1 to
18 and the coated sliding members of Comparative Examples 1 to 46 are obtained.

Further, as Comparative Examples 47 and 48, coated sliding members in which the mineral MoS ₂ or the minerals MoS ₂ and PTFE are mixed as shown in Table 4 in a binder made of EP resin are obtained. The friction coefficient, abrasion loss (μm) and baking surface pressure (MPa) of each of the obtained coated sliding members are measured. At this time, in the coated sliding members of Examples 1 to 18,
And S powdered S or lubricating oil in Mo and the molecules in the molecule of the organic molybdenum compound is activated by heat at the time of sliding at room temperature, to produce a MoS ₂ by intermolecular reaction. Since the generated MoS ₂ adheres to the coated sliding member and the surface of the mating member, the frictional force is reduced, the friction coefficient is reduced, and accordingly, the wear resistance and the seizure surface pressure are improved.

Here, the friction coefficient was determined by a thrust type testing machine, slip speed: 60 m / min, surface pressure: 9.8 MPa, mating material: gray cast iron FC25, lubricating oil: under the lubrication of mineral oil without additives It is. The amount of wear was as follows: a sliding speed of 5 m / min with a ring-on-block type testing machine, and a surface pressure of 0.5 MP.
a, mating material: gray cast iron FC25, test time: 5 minutes, lubricating oil: under the lubrication of mineral oil without additives. The baking surface pressure was determined by the sliding speed of a thrust type testing machine: 60 m /
Min, partner material: gray cast iron FC25, lubricating oil: under the lubrication of mineral oil without additives, when the surface pressure is increased at a certain period,
This is the surface pressure at which seizure occurred. The results are also shown in Tables 1 to 4.

FIG. 1 shows an EPMA analysis result of the sliding surface of the coated sliding member of Example 2, and FIG. 2 shows an EPMA analysis result of the sliding surface of the coated sliding member of Comparative Example 47. 1 and 2 show the distribution of Mo on each sliding surface. From FIG. 2, if formulated with mineral MoS ₂ in EP resin, easily dispersed while mineral MoS ₂ is secondary aggregation,
It can be seen that Mo is difficult to be uniformly dispersed on the sliding surface.
On the other hand, FIG. 1 shows that EP resin is powdered at room temperature.
By blending the organic molybdenum compound of
It can be seen that o is uniformly dispersed. Therefore, E
The composition obtained by blending a powdery organic molybdenum compound at room temperature to P resin, even when producing a coated sliding member, hardly result in an increase in localized friction, it can be seen that hardly occurs variation in the characteristics. And it is also understood that the coat sliding member is hardly broken.

Further, powdery organic molybdenum compound at room temperature is difficult to heat generated from the intermolecular reaction does not occur to both be dispersed with E P resins, the sliding characteristics due to the powdery organic molybdenum compound An improvement was obtained. However, if dispersed in the binder in comprising the powdery organic molybdenum compound from only a resin other than E P resins, reaction becomes coated sliding member of the black makes it was found that the sliding properties are impaired. This, if dispersed in the binder in comprising the powdery organic molybdenum compound from only a resin other than E P resins is believed to be because prone to intermolecular reaction to both.

Therefore, also from Tables 1-4, Example 1
It can be seen that the coated sliding members of Nos. To 18 have a lower friction coefficient, a smaller amount of wear, and a higher seizure surface pressure than those of Comparative Example 47. Also, from Tables 1 to 4, the coated sliding members of Comparative Examples 1 to 4 and the like employing a liquid as the organic molybdenum compound were also more oily than those of Comparative Example 5 and the like containing no organic molybdenum compound. Under lubrication, the coefficient of friction is low, the amount of wear is small, and the seizure surface pressure is high.
It turns out that there is a certain effect. However, at room temperature
Embodiment employing a powdery organic molybdenum compound have Example 1
Coated sliding members such as Nos. 1 to 4 have a remarkably low coefficient of friction, a small amount of abrasion, and a high seizure surface pressure, as compared with those of Comparative Examples 1 to 4 using the liquid organic molybdenum compound. You can see that. (2) As in Examples 5 and 6, EP is used as the binder.
A resin mixture of a resin, a xylene resin, a vinyl resin and PI, and at room temperature, a powdery organic molybdenum compound “Sakura Lube 500” is used, and 0 to 40 (wt.
%) Coated sliding members having variously changed mixing ratios up to the above are obtained. With respect to these coated sliding members, the coefficient of friction, the amount of wear (μm), and the baking surface pressure (MPa) are measured. The results are shown in FIG.

[0039] From FIG. 3, the powdery molybdenum <br/> emission compounds in room temperature, relative to the total 100 wt%, including the binder, it can be seen that 0.01～40Wt% is preferred. (3) Embodiments 19 to 19 in which the present invention is embodied in a molded sliding member
22 will be described together with Comparative Examples 49 to 76. Room temperature
A powdery organic molybdenum compound of the same type as described above is prepared.

As the binder, EP resin (same as above), PI (manufactured by Toshiba Chemical Co., Ltd., "Imidalloy KI")
R "), PF (manufactured by Toshiba Chemical Corporation," KM-96 "
0 "), polyamide 12 (Ube Industries, Ltd.," 302
4U "), polyamide 66 (Polyplastics Co., Ltd.)
Manufactured by "1000"), polyetheretherketone (P
EEK) (manufactured by Sumitomo Chemical Co., Ltd., “GK344
0 "), polyacetal (POM) (manufactured by Polyplastics Co., Ltd.," M-90 "), polyphenylene sulfide (PPS) (manufactured by Dainippon Ink and Chemicals, Inc.," R-
4)) is prepared.

Each binder is prepared using methyl ethyl ketone, propylene glycol methyl ether acetate or N-methyl-2-pyrrolidone as a solvent. Normal temperature as shown in Tables 5 and 6 for the total 100 wt% including each binder
The composition is prepared under various conditions in which the amount of the powdery organic molybdenum compound is varied. Table 5 shows such compositions.
It is molded into a predetermined shape under the conditions shown in Nos. Here, in the casting method, 170 ° C. × 10 under a pressure of 150 kgf / cm ^2.
The molding is performed at 230 ° C. for 3 hours. Also,
In the injection molding, the injection pressure of 780 kgf / cm ² , 75
The holding pressure is 0 kgf / cm ² . However, if the cylinder temperature is 300 ° C or more during injection molding, the powder
Since the organic molybdenum compound of may be decomposed,
The heating was not performed at 300 ° C. or more for 10 minutes or more. Thus, the molded sliding members of Examples 19 to 22 and Comparative Examples 49 to 76 are obtained.

[0042]

[Table 5]

[0043]

[Table 6]

The friction coefficient, abrasion amount (μm) and surface pressure (MPa) of each of the obtained molded sliding members are measured in the same manner as described above. The results are also shown in Tables 5 and 6. From Tables 5 and 6, it can be seen that the same results as in the coated sliding member can be obtained in the molded sliding member. In addition, EP resin powder at room temperature
When a molded sliding member is manufactured from a composition in which an organic molybdenum compound is blended, stress concentration hardly occurs in the molded sliding member even when an external force such as bending stress or tensile stress is applied. It is also expected that the members are less likely to break.

[0045]

As described above in detail, the sliding member composition of the present invention, since the dispersed powdery organic molybdenum compound in a binder containing Epoxy resins, under lubrication in oil, excellent It is possible to manufacture a sliding member that reliably exhibits wear characteristics, seizure characteristics, and friction characteristics and is less likely to break.

[Brief description of the drawings]

FIG. 1 is a 500 × EPMA photograph showing a particle structure on a sliding surface of a coated sliding member of Example 2.

FIG. 2 is a 500 × EPMA photograph showing a particle structure on a sliding surface of a coated sliding member of Comparative Example 47.

FIG. 3 is a graph showing a relationship between a Mo compounding ratio and a friction coefficient, a wear amount, and a seizure surface pressure.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C10M 139: 00) C10M 139: 00) Z C10N 10:12 C10N 10:12 30:06 30:06 40:02 40:02 50 : 08 50:08 (72) Inventor Yoshiyuki Hirokawa 3-69-3 Kogocho, Yokosuka City, Kanagawa Prefecture (72) Inventor Isao Tomura 1007-2, Hikotomicho, Hikone City, Shiga Prefecture (72) Inventor, Masahiro Nagasaki 883 Kadayamacho, Hikone City, Shiga Prefecture (56) References JP-A-57-39916 (JP, A) JP-A-2-212633 (JP, A) JP-A-61-73723 (JP, A) JP-A-60 JP-A-195729 (JP, A) JP-A-60-195731 (JP, A) JP-A-50-62204 (JP, A) JP-A-50-62206 (JP, A) (58) Fields investigated (Int. . ^7, DB name) C10M 169/04 F16J 1/02 F16J 1/04

Claims (1)

(57) [Claims] 1. A composition of the sliding member used in the site to be slid under lubrication oil, a binder containing Epoxy resins, powdered in has been cold dispersed in the binder < A composition for a sliding member, comprising: an organic molybdenum compound.