JPH1180660A - Lubricating paint - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lubricating paint used for formation of a thermosetting synthetic resin lubricative coating film and which forms a surface layer integral with a substrate and exhibits an excellent low-frictional characteristics. SOLUTION: A lubricating paint is obtained by dissolving 100 pts.wt. epoxy resin, 2-30 pts.wt. reactive silicone oil having an epoxy group and at least W pts.wt. triazine thiol, calculated by the equation, in an organic solvent, and is used for formation of a thermosetting synthetic resin lubricative coating film, provided that E1 is an epoxy equivalent of the epoxy resin used, E2 is an epoxy equivalent of the reactive silicone oil having an epoxy group used, and S is a number of grams of a triazine thiol containing a gram equivalent of a mercapto group -SH.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a lubricating paint for a sliding surface member.

[0002]

With respect to lubricating paints,
i) those used in a wet state by spraying an oil agent with a spray or the like, ii) those used as a dry film by removing the solvent after forming the film, and iii) those used as a cured film by curing the film at room temperature or by heating. There are various things.

[0003] The application examples of i) and ii) are a kind of lubrication application in which a lubricant is supplied to a sliding surface of two sliding members.

In other words, the lubricating coating in these cases is not a sliding member itself but a so-called sliding surface. So if they are exhausted,
The same spraying or the like is performed again to form a lubricating film.

On the contrary, the application example of iii) is different from the above i) and ii). That is, one of the two members sliding or a part of both members,
In other words, the surface layer of the member is formed.

[0006] This surface layer, that is, the film forming the slip surface, has excellent mechanical strength, good adhesion to the substrate,
It is desired not to be damaged by external force, to be easily worn when sliding, or to be peeled off from the substrate.

[0007] Here, the provision of lubricity to the coating and the mechanical strength of the coating and the adhesion to the substrate are contrary to each other.
If lubricity is to be improved, there is a problem that these strengths and performances are necessarily reduced.

The present invention provides a lubricating paint used for forming a lubricating coating of a thermosetting synthetic resin, the lubricating paint having a surface layer formed integrally with a base and exhibiting excellent low friction characteristics. Things.

[0009]

Means for Solving the Problems The present invention has been intensively studied to solve the above problems and problems, and as a result, the reactivity of forming and solidifying a three-dimensional network structure in the presence of a hardening agent. The use of triazine thiol, which has the function of simultaneously curing silicone oil, epoxy resin as a base resin that controls the adhesion to the base, and the ability to simultaneously cure these two components and modify the base surface into a surface suitable for adhesion, is extremely important. It was done by finding it to be effective.

According to the present invention, 100 parts by weight of epoxy resin and reactive silicone oil 2 having epoxy groups
There is provided a lubricating coating material used for forming a thermosetting synthetic resin lubricating film in which about 30 parts by weight and at least W parts by weight of triazinethiol are dissolved in an organic solvent. here,
W is a relational expression, (However, E ₁ is the epoxy equivalent of the epoxy resin used,
E ₂ epoxy equivalent of the reactive silicone oil having an epoxy group used, and S is a value calculated by the number of grams of triazine thiol is) containing a mercapto group -SH 1 gram equivalent. Here, the epoxy equivalent is the number of grams of epoxy resin or reactive silicone oil containing 1 gram equivalent of epoxy group.

That is, the present invention relates to an epoxy resin 10
Thermosetting obtained by dissolving 0 parts by weight, 2 to 30 parts by weight of a reactive silicone oil having an epoxy group, and triazinethiol in an amount sufficient to cause ring-opening polymerization of at least the two epoxy groups of the two components in an organic solvent. Provided is a lubricating paint used for forming a lubricating film of a conductive synthetic resin.

Further, the present invention aims at modifying the above-mentioned synthetic resin lubricating coating, in addition to the above-mentioned component composition, at least one of 2 to 15 parts by weight of an inorganic or organic filler powder and an oil. And a lubricating coating material used for forming a thermosetting synthetic resin lubricating film, wherein at least one of the waxy substance and at least one of 0.5 to 5 parts by weight is dispersed and dissolved in an organic solvent.

Further, the present invention provides a thermosetting synthetic resin lubricating coating formed by replacing a part of triazine thiol in the above-mentioned component composition with a polyamine, an acid anhydride, a phenol resin, a polyamide resin or a mercaptan compound. The present invention provides a lubricating paint used for:

[0014]

DETAILED DESCRIPTION OF THE INVENTION As the epoxy resin of the present invention, a general-purpose epoxy resin can be used. For example, a liquid or solid type epoxy resin "Epicoat (trade name)" of bisphenol A type manufactured by Yuka Shell Epoxy Co., Ltd. can be mentioned. Can be
The epoxy resin forms the base of the synthetic resin lubricating coating of the present invention and also functions as an adhesive with the base.

The reactive silicone oil having an epoxy group is an oily substance having a linear structure. When a curing agent is blended, the epoxy group undergoes ring-opening polymerization and solidifies in a three-dimensional network structure. The three-dimensional network is no longer oily but retains lubricity.

Since the molecular structure forms a net-like structure together with the epoxy resin and they are entangled with each other, they do not squeeze out from the slip surface or break the lubricating film like oily substances.

The reactive silicone oil having an epoxy group includes those having an epoxy group at both ends of polysiloxane and those having an epoxy group in a side chain thereof, and any of them can be used. In particular, those having an epoxy group on the side chain of polysiloxane are preferable. For example, an epoxy-modified silicone oil “KF-102 (trade name)” manufactured by Shin-Etsu Chemical Co., Ltd. may be mentioned.

It has a specific gravity of 0.97 and a viscosity of 4,000.
It is a clear, colorless, viscous oil with 0 centistokes (both at 25 ° C.). By the way, when this is reacted with a curing agent, it becomes a jelly-like semi-solid which has almost no stickiness. This is a three-dimensional network structure.

The effect of the reactive silicone oil having an epoxy group generally starts to be obtained when the amount is about 1 part by weight, but the effect becomes remarkable when the amount is more than 2 parts by weight.

However, when the content is 30 parts by weight, the coating strength is greatly reduced, but it can be used effectively depending on the sliding conditions. The most preferred amount is 5 to 20 parts by weight.

The triazine thiol used in the present invention not only functions as a common curing agent for both the epoxy resin and the reactive silicone oil having an epoxy group, which are constituents of the present invention, but also acts on the substrate. Then, it also has a function of modifying the surface into a surface suitable for adhesion.

The triazine thiol has a structural formula represented by the following formula (1), wherein the substituent R is a mercapto group -SH, a dibutylamino group -N (C ₄ H ₉ ) ₂ , and an anilino group-
A product consisting of NHC ₆ H ₅ is commercially available from Sankyo Chemical Co., Ltd. under the trade name Disnet.

[0023]

Embedded image

Triazine thiol has hitherto been used, in particular, as a crosslinking agent for rubber and vinyl chloride, or as an adhesive between metal and rubber, and also as a surface treatment agent for metal. It is extremely reactive, and is known to react not only with metals but also with functional groups or unsaturated groups such as synthetic resins and rubbers.

In the present invention, R is a dibutylamino group -N
Using (C ₄ H ₉₎ triazine with _2, i.e. 2-dibutylamino-4,6-dithiol -S- triazine to obtain a good result. It can be obtained as an odorless white fine powder having a melting point of 137 ° C. or higher.

The amount of the triazine thiol is such that the two components of the used epoxy resin and the reactive silicone oil having an epoxy group are cured together.

More specifically, the amount depends on the epoxy equivalent E ₁ of the epoxy resin used and the epoxy equivalent E ₂ of the reactive silicone oil having an epoxy group, and the amount of the epoxy resin used is 100 parts by weight. At this time, it must be W parts by weight calculated by the following relational expression.

[0028]

Here, S is the number of grams of triazine thiol containing 1 gram equivalent of mercapto group-SH. For example, as triazine thiol, 2 represented by the following formula (2)
When dibutylamino-4,6-dithiol-S-triazine is used, two mercapto groups per molecule are used.
Since it has SH, it is 量 of the molecular weight 272, that is, 136 grams.

[0030]

Embedded image

E ₁ and E ₂ are different for each brand.

[0032] Incidentally, stocks appear as grade 828 basic liquid type epoxy resin (made by Yuka Shell Epoxy Co., Ltd.) is, E ₁ is shown as 184 to 194. Also, a reactive silicone oil KF-
102 (manufactured by Shin-Etsu Chemical Co., Ltd.) is, E ₂ is shown as 3,600.

Using the above relation, triazinethiol (2-dibutylamino-4.6-
The calculated required amount of dithiol-S-triazine) is about 70 to 75 parts by weight.

This compounding amount is a value indicating the minimum amount required for promoting the curing reaction of the epoxy resin and the reactive silicone oil having an epoxy group of the present invention. Therefore, when the compounding amount is less than this, curing proceeds smoothly. do not do.

Although triazine thiol has a function as a curing agent, it also has other functions as described above. That is, the function is to form a base surface which is preferable for adhesion of the synthetic resin by a reaction with the base of the coating. Microscopically, this means adhesion through the molecular film of triazine thiol on the base. Moreover, the triazine thiol also forms a chemical bond with the synthetic resin used, thus forming an extremely strong film. Furthermore, it has been reported that the triazine thiol also forms a self-bonding between the triazine thiols and forms a molecular film on the base.

Accordingly, from these various viewpoints, the amount of triazine thiol can be considerably large in addition to the amount necessary for curing.

However, as a result of various experiments, triazinethiol having such excellent multifunctionality has some problems. That is a problem that the toughness of the obtained cured film is reduced.

It is not clear whether this is due to the mercapto group -SH or to the length of the molecule of the triazine thiol as a curing agent. It is an effective means to replace a part of the resin with a resin which has been conventionally used as a curing agent for an epoxy resin. For example, a polyamine, an acid anhydride, a phenol resin, a polyamide resin, and a mercaptan compound can be used. Further, a curing accelerator such as a tertiary amine, an imidazole derivative, or a boron fluoride complex salt may be used in combination with these curing agents.

The maximum amount that can be substituted for these curing agents can be up to the amount required to cure almost all of the epoxy resin used.

The polyamines include aliphatic polyamines, alicyclic diamines, aromatic diamines, and those obtained by modifying these. Specific examples include modified aliphatic polyamines “Epicure T (trade name) manufactured by Yuka Shell Epoxy Co., Ltd. Name)",
Modified alicyclic diamine “Epicure 113 (trade name)”,
Modified aromatic diamine “Epicure W (trade name)” may be mentioned.

Examples of the acid anhydride include aliphatic, alicyclic, aromatic, and halogen-based acid anhydrides, and specific examples include “Epicure 134A (trade name)” manufactured by Yuka Shell Epoxy. .

The mercaptan compound is an aliphatic polysulfide polymer having a mercapto group -SH at both ends of a molecular structural formula. Since it does not react with an epoxy resin by itself, the polyamine or tertiary amine is used. It is necessary to use together. Specific examples of the mercaptan-based compound include “Cup Cure 3800 (trade name)” manufactured by Yuka Ciel Epoxy.

In general, unlike triazinethiol, these curing agents do not have the function of reacting with the base to form a preferable surface for adhesion, or have a function of reacting with each other to form a film. Even so, it is necessary to keep this point in mind.

In addition to the above-mentioned three components of the epoxy resin, the reactive silicone oil having an epoxy group, and the triazine thiol, if necessary, a fourth component may include at least one of 2 to 15 parts by weight of the inorganic and organic filler powder. At least one of one and at least one of 0.5 to 5 parts by weight of oil and waxy substance can be blended.

As the inorganic and organic filler powder, graphite,
Examples include inorganic powders such as boron nitride and organic powders such as an ethylene tetrafluoride resin, and 2 parts by weight or more from the viewpoint of the blending effect, and 15 parts by weight or less from the viewpoint of workability of coating film formation. I do.

The inorganic powder is for imparting load resistance and wear resistance to the coating, and the ethylene tetrafluoride resin powder is for supplementing the self-lubricating property of the coating.

The oil and the waxy substance include mineral oil,
Examples thereof include oily substances such as animal and vegetable oils and synthetic lubricating oils, and waxy substances such as petroleum wax, higher fatty acids, salts and esters of higher fatty acids.

Among these fourth components, oils and waxes contribute to imparting self-lubricating properties and lowering friction when mixed with the synthetic resin, but have a positive effect on the mechanical strength of the synthetic resin and its adhesiveness. As for what is not given, it has already been described.

Even if the above-mentioned oil or wax-like substance is blended in an amount of 5 parts by weight or less with the epoxy resin of the present invention, the reactive silicone oil having an epoxy group, and the triazine thiol, the mechanical strength and the adhesiveness are improved. The effect was found to be very slight.

Now, the sliding member having the synthetic resin lubricating film formed by using the lubricating paint according to the present invention exhibits excellent low friction characteristics in sliding contact with the synthetic resin as a member opposed thereto. For example, in sliding contact with a material mainly composed of ethylene tetrafluoride resin, a load of 1
In a heavy load range of 00 to 400 kgf / cm ² , the friction coefficient is extremely low, that is, the dynamic friction coefficient is 0.02 to 0.03.

The blending of the above-described oil and wax as the fourth component has an effect of lowering the dynamic friction coefficient in a light load region. The effect emerges from the 0.5 part by weight formulation.
The upper limit is 5 parts by weight as described above.

Examples of the solvent used for preparing the lubricating coating material include organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, alcohols such as isopropyl alcohol and n-butanol, toluene, and the like. Examples thereof include aromatic hydrocarbon solvents such as xylene, and tetrahydrofuran. These solvents are used alone or as a mixture.

The concentration of the paint is preferably 30 to 40 parts by weight from the viewpoint of handling. The viscosity in this case is about 100 to 200 centistokes at room temperature.

The application of the lubricating paint of the present invention can employ a means for forming a coating film, such as spraying, which is conventionally performed normally.

When the base material used for forming the coating film is a metal, a normal pretreatment is performed. In the case of a material such as a synthetic resin or ceramics, the surface to be adhered should be smooth and clean.

The curing treatment conditions after the formation of the coating film can take various conditions depending on what kind of curing agent is used. As an example, when an alicyclic diamine is used as a curing agent in addition to triazine thiol, after forming a coating film, the solvent is removed by natural drying or pre-drying at 80 ° C. for about 30 minutes. A desired cured film is obtained by baking at 30 ° C. for 30 minutes.

Using a lubricating paint having a solid content of 35 parts by weight, spraying was performed on a steel sheet, and baking and hardening were performed under the above-described conditions, and the thickness of the film obtained was about 30 μm.

If the spraying is carried out with a reduced solid content, a thinner coating can be obtained, and a thicker coating can be obtained by recoating.

Thus, the coating thickness is 5 to 100 μm
Is easily obtained, but as a lubricating film, 10 to 5
A thickness of 0 μm, especially about 20 to 40 μm is desirable.

The coating thus obtained was tightly bound to the substrate, and no peeling of the coating was observed in the Goban test.

The results of determining the adhesive strength of the coating by measuring the compressive shear strength were 30 to 100 kg.
f / cm ^2, which is usually 20 to 30 kgf / cm 2
^{A value of 2} greatly exceeded the range that was said to be acceptable.

This is because the lubricating paint according to the present invention is applied to the surface of the substrate, and in the course of pre-drying and curing, firstly, a reaction with the substrate is caused by triazine thiol. This is considered to be the result of the transfer to the thiol reaction surface and adhesion.

It is also considered that an oil or a waxy substance which causes a decrease in the adhesive strength is prevented from migrating to or covering the adhesive interface.

Therefore, a film is formed in a preferred embodiment in which the silicon component, oil and waxy substance having a network structure are distributed more on the surface side, that is, on the slip surface side of the film.

The lubricating paint of the present invention is applied as a coating to a member requiring slip, such as a bearing used for a bearing, a bridge structure or a building, and forms a slip surface having excellent low friction and wear resistance. I do.

This may be applied to the slip surface on either side of the two members that slide. In other words, the sliding surface on the bearing side or the bearing may be applied to the sliding surface on the bearing plate side, and the mating material opposed thereto, that is, the shaft or slider side in the bearing, the upper shoe or the lower in the bearing. It may be the slip surface of the shoe.

[0067]

[Examples] 1. Sliding member (A) As glass fiber powder, “MF06JB1-2” manufactured by Asahi Fiber Glass Co., Ltd., having a diameter of 10 μm and an average length of 63 μm.
0 (trade name) 15% by weight, as polyimide resin powder, 2% by weight of "P84 (trade name)" manufactured by Lenzing Co., and the remainder from ethylene tetrafluoride resin "Teflon 7AJ (trade name)" manufactured by DuPont-Mitsui Fluorochemicals Co., Ltd. Of a resin composition comprising: The end surface of a rod-shaped object having a diameter of 10 mm and a height of 14 mm was used as a slip surface. (B) A molded article of a resin composition comprising the polyimide resin powder 20% by weight and the balance of the above ethylene tetrafluoride resin. The end surface of a rod-shaped object having a diameter of 10 mm and a height of 14 mm was used as a slip surface.

2. Mating member The components shown in Table 1 and the components shown in Tables 2 and 3 are subjected to shot blasting and degreasing treatment using a plate-shaped carbon steel for machine structure S45C having a width of 40 mm, a length of 280 mm and a thickness of 10 mm as a backing material. Spray lubricating paint in the blending ratio, 80
After pre-drying at 30 ° C for 30 minutes to remove the solvent, 18
Baking was performed at 0 ° C. for 30 minutes to obtain various test pieces having a coating thickness of 30 μm. The test pieces of the comparative examples shown in Table 3 were produced under the same conditions. Each component is given in parts by weight. (Below)

[0069]

[Table 1] 35 parts by weight of solids in lubricating paint. Mineral oil mimics solids. (Below)

[0070]

[Table 2] (Below)

[0071]

[Table 3]

3. Testing machine Combination of a pressurizing unit that can apply a load in the vertical direction by an air cylinder and a movable horizontal support that can push and pull in a horizontal direction in a predetermined mode by a servomotor. A reciprocating motion tester that slides by pushing and pulling horizontally while applying pressure. Maximum vertical load 500kgf Horizontal maximum stroke 30cm Horizontal maximum speed 80cm / sec

4. Test method A sliding member with a diameter of 10 mm and a height of 14 mm
It was gripped over a length of 0 mm, and 4 mm of it was protruded downward and attached to the pressurizing section of the tester. On the other hand, a mating member was attached and fixed to the horizontal support base with a fastener. The test conditions are as follows, and FIG. 1 shows a model of the test speed waveform. (Test conditions) Speed 1 cm / sec to 50 cm / sec Load 20 kgf / cm ^{2 to} 400 kgf / cm ² Test stroke 220 mm Test speed waveform Trapezoidal wave

5. Test results Tables 4, 5 and 6 show that the sliding members (A) and (B) and the mating member having the coatings a to k formed by using the lubricating coating material of the present invention showed slip. Speed 1
cm / sec and a load of 20 to 400 kgf /
It shows a coefficient of kinetic friction when changed in the range of cm ² .

When the amount of the reactive silicone oil KF-102 having an epoxy group exceeds 2 parts by weight, the effect on the friction coefficient is remarkable. However, in cases Ak and Bk in which the amount is 30 parts by weight, the mechanical strength of the coating film begins to decrease. That is, there is a sign that the dynamic friction coefficient increases in the heavy load region.

Accordingly, from the results of this test, the amount of the reactive silicone oil having an epoxy group is from 2 to 30.
It is understood that it is preferable to use 5 parts by weight, particularly 5 to 20 parts by weight. (Below)

[0077]

[Table 4]

[0078]

[Table 5]

[0079]

[Table 6]

Note that Af in Table 4 and Bf and A-
In g and Bg, f and g are fillers arranged as the fourth component and contain 2.5 parts by weight of mineral oil, but in the light load region as compared with other cases not containing mineral oil. It can be seen that the coefficient of friction is low.

Tables 7 and 8 show that the load of each combination of the sliding member (A) and the mating member was 200 kg.
f / cm ² and the sliding speed was 10 to 50 cm /
It shows the dynamic friction coefficient when changed within the range of sec. As the speed increases, the coefficient of kinetic friction rises to the right.

This is observed in both the present invention example and the comparative example, but the tendency of the present invention example was slight. Further, it has a feature that the value of the dynamic friction coefficient is extremely small. (Below)

[0083]

[Table 7]

[0084]

[Table 8]

FIG. 2 shows that the load of the combination of Example Ac of the present invention and the combination of Comparative Example An was 3
Under the conditions of 00 kgf / cm ² and a sliding speed of 1 cm / sec, the load holding time was a dynamic friction coefficient μk and a static friction coefficient μ.
7 is a plot of the effect on s. FIG.
The horizontal axis of is shown on a logarithmic scale.

As is clear from FIG. 2, in the case of the example of the present invention, the values of μs and μk are small, and both values are close to each other, and the effect of the holding time on μs and μk is extremely small. Was.

On the other hand, in the case of the comparative example, the value of μs is as large as 0.1 or more, and the difference between μs and μk is also large. Further, the effect of the retention time on μs and μk is also observed.

If the difference between μs and μk is large, stick-slip is likely to occur at the time of sliding, which also causes sound. In the example of the present invention, such a phenomenon does not occur at all.

The abrasion of the coating was very small, from several tenths to several hundredths, in the case of the present invention as compared with the comparative example.

[Brief description of the drawings]

FIG. 1 shows a model of a test speed waveform of a reciprocating motion testing machine used for a test of the present invention.

FIG. 2 is a graph showing test results.

[Explanation of symbols]

 μs Static friction coefficient μk Dynamic friction coefficient

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09D 161: 06) (C09D 163/00 183: 06 177: 00)

Claims (3)

[Claims] 1. 100 parts by weight of an epoxy resin, 2 to 30 parts by weight of a reactive silicone oil having an epoxy group,
A lubricating paint used for forming a thermosetting synthetic resin lubricating film formed by dissolving at least W parts by weight of triazine thiol calculated by the following relational formula in an organic solvent. Here, E ₁ is the epoxy equivalent of the epoxy resin used, E
₂ is the epoxy equivalent of the reactive silicone oil having epoxy groups used, and S is the number of grams of triazine thiol containing 1 gram equivalent of mercapto group -SH. 2. At least one of 2 to 15 parts by weight of inorganic and organic filler powder, oil and waxy substance 0.5 to 2 parts by weight.
2. The lubricating coating according to claim 1, wherein at least one of the at least one of the five parts by weight is further dispersed and dissolved in an organic solvent to form a thermosetting synthetic resin lubricating coating. 3. The lubricating paint according to claim 1, wherein a part of the W of triazinethiol is replaced by a polyamine, an acid anhydride, a phenol resin, a polyamide resin, or a mercaptan compound.