JPS5940018A - Clutch facing with improved judder resistance and corrosion resistance - Google Patents

Abstract

PURPOSE:To improve the anti-judder property and corrosion resistance of the clutch facing by adjusting the pH of wear resisting powder in the clutch facing. CONSTITUTION:The pH of the wear-resisting powder within the clutch facing is made 6-9 by causing the clutch facing to contain 10-20wt% of a resin for a binder having a gel time at 120 deg.C of 30-300sec. If the resin for the binder has a gel time of 30sec or less at 120 deg.C, it becomes rapidly hardened. Although its judder resistance is excellent, the wear resistance is deteriorated. When the resin has a gel time of 300sec or more, the wear resistance is improved but the judder resistance is deteriorated. If the resin for the binder exceeds 20wt% with respect to the clutch facing, the judder resistance is deteriorated. With 10wt% or less of the resin for the binder, the function thereof is also deteriorated. When the pH of the wear resisting powder is 6 or less, nitric acid ions are vigorously produced, and as a result, rusts are liable to be produced. When the pH of the wear resisting powder exceeds 9, a fixing force is produced between the clutch facing and the partner material.

Description

[Detailed Description of the Invention] The friction material of the present invention, Q! # relates to a clutch facing with improved shudder resistance and rust prevention.

Clutch facing V, asbestos, glass fiber.

Fiber-resistant substances such as potassium titanate P fibers, cotton wool, and polyamide resin fibers, wear-resistant powder made from cured phenolic resins, and other inorganic and organic modifying materials are used as constituent components. A formaldehyde condensation resin such as phenol or melamine was used as a binder, and a molding force of 11 was applied at a temperature of 1120° C. or higher.

Clutch facings manufactured in this way (JTD) are essential parts for automobiles, and must have excellent wear resistance and shudder resistance during driving.Furthermore, during long-term storage, clutch facings However, the facing and the mating material (flywheel or pressure grate) will be in close contact.

Even in such a state, there must be no rust between the clutch facing and the mating material, and smooth latching operation must be possible even when starting use after long-term storage.

However, in actual clutch facings, which are molded products made of composite materials such as those mentioned above, emphasis is placed on shudder resistance. Rust may occur on the molded parts, making it difficult to operate.Of course, to prevent these problems, molded products are treated with a sodium nitrite-based rust preventive agent. Depending on the conditions of use, satisfactory results may not always be obtained.

The present invention has excellent shudder resistance i1. The present inventors have combined the causes of rust on CJ clutch facings with the curing behavior of the binder resin related to shudder resistance. Structure of agent resin and mold generation during clutch facing
ij I studied in detail in relation to the quantity and quantity of the I component /ζ. As a result, the cause of rusting was mainly due to acidic wear-resistant powder.

In addition, shudder resistance depends on the constituent materials of the clutch facing, such as f, & M:-like substances, wear-resistant powder, metal wire, etc., but within the range of industrially producible material rapid ratio, It was confirmed that this greatly depends on the curing behavior of the resin. Furthermore, it was discovered that the curing behavior of the binder resin related to shudder resistance can be determined by measuring the gel time at 120°C.

According to the present invention, at 120℃, the IL time is 30/30
Improvement of jet resistance and rust prevention by containing 10~zo-1) 1% of binder resin of 0 seconds with respect to the clutch facing, and adjusting the pH of the wear-resistant powder in the clutch facing to 6~9. Regarding the clutch facing.

7 The clutch facing of the present invention contains fibrous materials (EL, metal wire, wear-resistant powder, etc.) in addition to the above-mentioned binder resin.
Cone-shaped materials include asbestos, glass fiber, potassium titanate fiber, and polyamide resin fiber.

For the metal wire, carbonated copper, brass, zinc, etc. are used, and for the wear-resistant powder, phenol, alkylphenol, cashew shell oil-based resin (M? compound, etc.) is used. As binder resins, melamine/horizontal human resins, melamine/phenol/pormaldehyde cocondensation resins, etc. are used, and these binder resins have a gel time of 120 °C. However, it is necessary that the gel time is 0 to 300 seconds, and if the gel time is less than 30 seconds, the binder resin will harden quickly and the shudder resistance will be good, but
Abrasion resistance tends to deteriorate and burst fracture strength tends to decrease. Moreover, when the gel time exceeds 300 seconds, the wear resistance is good.

Shudder resistance i'1 deteriorates. Outside this range, especially 300
The reason why the surface 1 shudder property decreases when the time exceeds 2 seconds is not clear, but because the curing of the binder resin is slow, the binder resin flows during molding and the IJ property increases, causing the clutch torque to deteriorate. -・/The binder resin is well impregnated into asbestos during blowfish molding.

The asbestos is fully coated with binder resin.

Therefore, it is presumed that the bare asbeth I. will reduce the effectiveness of removing the binder resin component adhering to the mating material and end the process. This binder resin is in the range of 10 to 20 times the clutch facing, and if it exceeds 20 times, the shudder resistance will be poor, and if it is less than 10 times, it will not function as a clutch facing. Inferior.

The clutch facing of the present invention has wear-resistant powder in the clutch facing with a pl of 16 to 9. If pl:
If less than 6 liters of acidic wear-resistant powder is used, it may be used during the Kujigouf J-Zong manufacturing process or iJ: fi+
, "Treatment of J artificial culm V with an alkaline substance9) Addition of an alkaline substance such as sodium carbonate or magnesia)
pl using an aqueous solution of IIl or these alkaline substances.
l It is said to be in the range of 6 to 9.

Preferably Arca January J after clutch facing manufacture.
It is best to adjust the pH to a range of 6 to 9 by adding substances or using an aqueous solution of these alkaline substances. You can also use 2.

(Needle and wear particles are odor in the clutch facing - CpH
It is sufficient that the pH is within the range of 6 to 9, and it is not necessarily necessary to use the wear-resistant powder at a pH of 6 to 9 in advance.

It is confirmed that the wear-resistant powder in the clutch facing has a pl-16 to 9 by separating the wear-resistant powder in the clutch facing and measuring the pH.

When a sodium nitrite-based rust inhibitor is used at pYr of less than 6, the sodium nitrite undergoes a chemical change, resulting in depletion and the production of some nitrate ions (NO). In such a system, nitrite (IJ) is depleted! Or, by examining the leaves that produce nitrate ions, pT16~
It can be determined whether or not it is within the range of 9. ■1116-9
Within this range, nitrate ion generation is extremely small.

The amount of nitrate ion produced can be measured with an ion/liromatogranoy, etc., and the depletion of nitrite can be confirmed by measuring the content of p-nitrite ion with an ion quamatogranoy.

In the present invention, the wear-resistant powder in the clutch facing is p
If the pH is less than 6, more nitrate ions are produced and rust is likely to occur.If the pH exceeds 9, chemical reactions between alkaline biological materials and asbestos, and alkaline Depending on the properties of the material itself, there is a tendency for adhesive force to occur between the clutch 7 acing and the mating material even if no red rust is formed.

Already known methods can be used to prevent rust on the clutch facing obtained in the present invention.

For example, a method can be used in which the clutch facing is immersed in a sodium nitrite-based rust preventive solution and then dried.

The present invention will be explained below with reference to Examples.

Example 1 Asbestos yarn [stone Ea 80 weight MH%, strength'
/ Nisan oil-based resin cured product (pJ-1 of extracted water: 10
．． 0) Melamine/formaldehyde resin [formaldehyde/
Melamine = 3/1 (mole ratio) 20% by weight resin solution p
H10.5, gel time 90 seconds at 120°C] was impregnated with a solid content of 10% by weight in a mixture of water and methanol solution.
Next, it is dried and heated (150°C).

It was cured for 60 minutes in a mold under pressure (50 Kgf/C1r?). After that, polish the surface and remove the clutch 7 ace! J. Next, this clutch facing (including the clutch facing) was soaked in 1L61 for 1 minute in a rust-preventing aqueous solution containing IJum (Mitsubishi Kasei ll! 10 heavy acid) at 7p℃.
Clutch facing (B) after drying for 1 hour. This Clutch 7 Acing (H) had good shudder performance in II■ when tested on an actual vehicle. Moreover, the rusting force measured by the rusting test method was 0 to 0.01 Kgf/2. The wear-resistant powder 11 was taken out from the clutch facing, heated with 1Qme of water, extracted, and then determined for plI at Tsunebori, and found to be 8.5.

Example 2 Same asbestos yarn as Example 1 with 0.4% glycine
P 111 (, added melamine/formaldehyde resin [formaldehyde/melamine-3/1 (molar ratio),
9118.6 of a 4% resin solution with the addition of 0.4% glycine (0.4% based on the resin solid content), gel time 70 seconds at 120°C]
A mixture of water and methanol solution with a solid content of 20 parts; i
Impregnated with 9%, then dried and heated (150℃)
, pressure (50K9 f/cnr'l) was applied and cured in a mold for 60 minutes.Then, the surface was polished and the clutch 7
Aesing (C) was published. Next, this clutch facing (C) was immersed in a rust-preventing aqueous solution containing 10-weight sodium nitrite (manufactured by Mitsubishi Kasei) for 1 minute, and then dried at 70°C for 1 hour to form the clutch facing (1). ) was obtained. The jagged resistance of Jin's clutch facing (1) in an actual vehicle was extremely good. The rusting force is O~0.
01 K! It was '/cm'. When the pH of the wear-resistant powder was measured in the same manner as in Example 1, the pH was 8.5.

Example 3 Asbestos yarn [80% asbestos, 10% hardened cashew shell oil resin (extract water pI-1: 4.5), 10% cotton and metal wire] with melamine/formaldehydemine = 2.5/1 (molar ratio), pT-1 of a mixed solution of Cassie oil-based resin cured product and melamine formaldehyde resin: 8.7, gel time at 120°C 210 seconds] water and The mixture of methanol solution was impregnated with 10 bites of solids, then dried and heated under high heat (
150℃), pressurized (50Kqf/crr?) l,
and cured in a mold for 60 minutes. After that, the surface is polished,
A clutch facing (El) was obtained. Next, this clutch facing (E) was diluted with sodium carbonate double % (p
The clutch facing (E) was immersed in an aqueous solution containing H11) for 90 minutes, and then the clutch facing (E) was immersed in ion-exchanged water for 90 minutes and washed with water. After washing with water, it was dried at 70° C. for 1 hour to obtain a clutch facing fF).

Next, add this to thorium nitrite (Mitsubishi Kasei 1.□1) 10
The clutch facing (G
) I got it. The shudder resistance of this clutch facing ((1) in an actual vehicle was extremely good.

The rusting force was 0 to 0.01 Kyf/rw'.

When the pH of the wear-resistant powder was measured in the same manner as in Example 1, the pH was 6.8.

Example 4 Adding 0.61 P of phosphoric acid to the same asbestos yarn as in Example
I-1 added melamine/phenol/formaldehyde resin [melamine/phenol = 1/1 (molar ratio)
, formaldehyde/melamine/phenol 2.5/1
(mole ratio), tnf fat solution solution I-17.0 in which phosphoric acid was added at 0.6 TPH and coexisted with wear-resistant powder.

A mixture of water and methanol solution with a gel time of 195 seconds at 120° C. was impregnated with a solid content of 20% by weight.

Next, it was dried, heated (150°C), and pressurized (50°C).
The mixture was cured for 60 minutes in a mold with a paste f/d)l. After that, I polished one surface and installed the clutch face/ring ring. Next, this clutch facing round was immersed for 2 minutes in a rust-preventing aqueous solution containing 10% by weight of nitrous acid (manufactured by Mitsubishi Kasei), and then dried at 70°C for 1 hour. This clutch facing had extremely good shudder resistance when tested on an actual vehicle. When the pH of the wear-resistant powder was measured in the same manner as in Example 1, the pH was 8.5.

Example 5 ゛Asbestos yarn [asbestos 80 weight-utachi, cashew shell oil-based resin cured product (pn-3, o of extracted water) 10! Melamine/phenol/formaldehyde resin [melamine/phenol = t, S/l (molar ratio), formaldehyde/melamine/phenol = 2.5/1 ( molar ratio).

A mixture of water and methanol solution (pH 7, 5, gel time 190 seconds at 120°C of resin solution coexisting with wear-resistant powder) was impregnated with a solid content of 20% by weight, then dried, and this was carried out in the same manner as in Example 1. Molded clutch facing (
J) was obtained. Next, this clutch facing (Jlf sodium carbonate duet-ti and sodium nitrite 10%
The clutch facing (Kl) was obtained by immersing it in an aqueous solution containing for 600 minutes to perform rust prevention treatment, and then drying it at 70° C. for 1 hour.

Clutch facing (H's jitter resistance in actual vehicle was extremely good. Rust force was θ ~ 0.01 Kff
/cn12. When the pH of the wear-resistant powder was measured in the same manner as in Example 1, the pH was 6.5.

Example 6 Glycine 0.4S was added to the same asbestos yarn as in Example 1.
Melamine/phenol/formaldehyde resin added with PHR (melamine/phenol = 4/1 (molar ratio)
, formaldehyde/melamine phenol = 2.75/
1 (molar ratio), glycine 0.41 PH of a resin solution containing wear-resistant powder added with pH 8, 4, gel time at 120°C 60 seconds), impregnated with a solid content of 20% by weight in a mixture of water and methanol solution. This was then dried, molded in the same manner as in Example 1, and further subjected to antirust treatment to obtain a clutch facing (I). The shudder resistance r and j of this clutch facing (L) in an actual vehicle were good.

The rusting force was 0 to 0.01 K417 cm''. When the pH of the IILj wear powder was measured in the same manner as in Example 1, p I-1 was 7.8.

Comparative Example 1 The same asbestos yarn as in Example 1 was coated with melamine/formaldehyde resin [Horno, Artecht/Melamine-2,!
57 molar ratio, pII of the resin solution 8.5.

The proboscis was impregnated with a solid content of 20% by weight using a mixture of water and methanol solution with a gel time of 360 seconds at 120°C.

Next, it is dried, heated (150°C) and pressurized (50°C).
Kpf /CTn2 ) and cured in the mold for 60 minutes. Thereafter, the surface was polished and anti-rust treatment was performed in the same manner as in Example 1 to obtain a clutch facing (goods). The shudder resistance of the clutch facing (N()) on an actual vehicle was good with no shudder occurring.The rusting force was 0~
The pH value of the anti-wear powder was measured in the same manner as in Example 1.
was 8.2.

Comparative Example 2 Same as Example 1: Asbestos Yar/Phosphoric Acid 2.5P I
-1) 1 Added melamine/phenol/formaldehyde resin [melamine/phenol-1,5,/' 1
(mole ratio), formaldehyde/phenol/melamine (mole ratio), phosphoric acid 2.51) 11 '11. pH of added resin solution = 5.9. Gel time 2 at 120°C
5 seconds] Mixing of water and methanol solution 'l = f - Impregnated with 20 @ amount of solid content, then dried, molded in the same manner as in Example 1, and further subjected to anti-corrosion treatment to form a clutch facing. (N) was obtained. This clutch facing (Nl) had good resistance to jitter in an actual vehicle.

The rusting force was 0 to 0.02 K7f/crrt'. However, the abrasion resistance was poor due to significant wear caused by actual vehicles. When the pH of the wear-resistant powder was measured using the same LJ as in Example 1, the pH was 8.0.

Comparative Example 3 Indeed! I&! Melamine/phenol/formaldehyde resin [melamine/phenol = 1/1 (molar ratio), formaldehyde/melamine/phenol = 2.5/1 (molar ratio) on the same asbestos yarn as IJx.

A mixture of water and methanol solution (resin solution coexisting with wear-resistant powder, pH = 9.0, gel time 600 seconds at 120°C) was impregnated with a solid content of 20% by weight S1%, and then dried. Clutch facing (0) was obtained by molding/J[I processing in the same manner as in 1 and further applying anti-corrosion treatment.

This clutch facing (according to the actual vehicle of 01 +nif
The jitteriness was poor due to the occurrence of shudder. The rust resistance was 0 to 0.01 Kr t A-.

When the pH of the wear-resistant powder was measured in the same manner as in Example 1, it was found to be pH 8.1.

Comparative Example 4 The same asbestos yarn as in Example 5 was mixed with melamine/phenol/holt)'-1-tehyde resin [melamine/phenol-2/l (cell ratio), formaldehyde/melami/.
Phenol = 3/1 (molar ratio).

1lff1' p of resin solution coexisting with wear particles) 17.6,1
A mixture of water and methanol solution with a gel time of 90 seconds at 20° C. was impregnated with a solid content of 20% by weight, then dried, and then molded in the same manner as in Example f''111.

Furthermore, a clutch facing (P) was obtained by applying anti-corrosion treatment. The shudder resistance of this clutch facing (■) on an actual vehicle was extremely good. However, the rusting force is 0.02 to 0.05 KyI/Crr? It was defective.

The pH of the wear-resistant powder was measured in the same manner as in Example 1, and the pH was 5.3.

<Method 2 for measuring gel time and pH of resin solution at 120°C Add 40 parts by weight of anti-wear powder to 60 parts by weight M4 parts of resin solids to a mixed solution of water and methanol with a resin solid content of 20% by weight, The sample was stirred and left to stand for 1 hour, and then the pH was measured. After p I-1 measurement, 0.5 while stirring the sample.
cc was sampled, dropped onto a hot plate kept at 120°C, and gel time was measured while stirring.

<Rust test method> Clutch 7 acing was cut into 2.54 cm square pieces with the original thickness, and the pieces were brought into close contact with cast iron FC-25 of the same size.
0.3 Kq f /err? Apply a load of The sample was left in a constant temperature and humidity bath (50°C, 990% RH) for 72 hours, and after being taken out, it was left in the air for 24 hours. Thereafter, the load was removed, and the adhesion force in the shear direction between the clutch facing and cast iron FC-25 was measured using a spring scale-C to determine the rusting force.

As is clear from the comparison between Examples and Comparative Examples.

A clutch facing with good shudder resistance and improved rust prevention can be obtained using a binder resin having a gel time of 30 to 300 seconds at 120°C.

The clutch facing obtained by the present invention has improved shudder resistance and rust prevention without impairing wear characteristics, and is therefore an industrially extremely effective latch facing.

J'-Hangeda 5 Neichi 1l-E-4~ (1"shi'kotsu'September1981' LI I holder' Yamagaku i: tl佼1, thing 1'1 display 1988 special C'1 Application No. 151392-C2 Name of the invention 4 (J, 101 sorting function 0 prevention 'Jj'iM improved Kufuno f-soj, ]〉・ri: 1. l+1id-ta Jru h iii Relationship with I
Name C445) II\γ Kasei Jogyo Co., Ltd. I1 Agent IJ: r9i 160 Nishi-Shinjuku, Shinjuku-ku, Tokyo - Go-chome 1-11-1j → Kasei Toe Co., Ltd. internal phone number Tokyo 34fi3111 (main representative) details -) IT Detailed Explanation of the Invention of 1 Cabinet (:, ? , L
, Chiruno 1 (l' II of extracted water: 9.0)
And, II Stop Shima J0 - 1 Ni

Claims (1)

[Claims] 1. Gel tights at 120℃, bonding resin for 30-300 seconds to clutch facing lO~2
A clutch facing with improved shudder resistance and rust prevention, which contains zero heavy metal and has a pH of 6 to 9 of wear-resistant powder in the clutch facing.