JPH02266905A - Manufacture of sliding parts by monomer-casting method - Google Patents

Abstract

PURPOSE:To produce the sliding parts excellent in durability by a method in which the casting material of a specified composition is injected into the clearance between a bearing and a shaft, and then resin lining is formed on the surface of the shaft or the bearing by polymerizing and curing it. CONSTITUTION:The casting material containing the composition of (A) and (B) is injected into the clearance between the bearing 1 of an outer spline and the inner spline shaft 2 fitted into said bearing 1 and supported rotatably or freely reciprocatably, and then said material is polymerized and cured. Consequently, resin lining 3 is formed on the surface of the shaft or the bearing. Here, the composition A is the omega-lactam liquid containing the polymerizing catalyst of the compound of alkali metal or alkali earth metal, and the composition B is the omega-lactam liquid containing at least two end groups of lactam shown by the formula (I) and at least one lactam polymerization initiator containing elastomer skeleton derived from telechelic polyamine containing at least two amino groups of primary or secondary one.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a sliding component consisting of shafts and their bearings that fit into each other, such as a journal and a journal bearing, a spline shaft and its bearings, etc. . More specifically, the present invention relates to a method of manufacturing a sliding component in which a resin lining is formed on the surface of a shaft or bearing by a monomer casting method.

[Conventional technology]

A so-called cash processing method has been proposed in the past, in which a low-viscosity monomer or polymer is injected into the clearance between the bearing and the shaft, polymerized and hardened, and the surface of the bearing is lined with resin (Japanese Unexamined Patent Application Publication No. 60/1999). In these cash processing methods, an ω-lactam melt containing a polymerization catalyst and an ω-lactam melt containing a polymerization initiator are simultaneously processed into cash. It is injected or injected into a mold and reacted within the mold to form a resin lining. Conventionally, as the above-mentioned polymerization initiators, lactam anions and acyllactams have been disclosed in JP-A-60-178013, and JP-A-63-212518 has disclosed formulas [wherein A is halogen]. Represents an atom or! (wherein Y represents C2-C11 alkylene),
a is an integer of 1.2 or 3, b is an integer of 2 or more, R1 represents an alkylene group, an aralkyl group, an alkyloxy group, an aryloxy group, a halogen group or an aralkyloxy group, R3 represents a divalent or higher group selected from a hydrocarbon group and a hydrocarbon having an ether bond, and Z represents (1) a polyether having a minimum molecular weight of 2,000, (2) a minimum molecular weight of 2,000. represents a polyester segment having a polyether segment, or (3) a hydrocarbon having a minimum molecular weight t, ooo.

On the other hand, various kinds of lactam polymerization initiators are known in addition to those mentioned above.
No. 28 contains the formula [wherein Q is a lactam residue having a C2-C8 alkylene group and is bonded to carbonyl via the nitrogen atom of the lactam; A is an aliphatic or aromatic a hydrocarbyl group or a hydrocarbyl ether 1; when ring 0, n is 0 or 1 and p is 1; when ring 1, i is in the range from 1 to 3 and p=n. ]; A lactam characterized by containing at least two lactam end groups represented by the formula and an elastic skeleton derived from a telechelic polyamine containing at least two primary or secondary amine 7 groups. A polymerization initiator is disclosed.

[Problem to be solved by the invention]

Sliding parts obtained by applying a resin lining using the monomer casting method are used by injecting grease into the clearance between the shaft and the bearing on which the resin lining is formed.

When sliding parts obtained by the above conventional method are injected with general-purpose grease and used at high temperatures (100°C or higher),
The drawback was that the polyamide resin lining deteriorated. As the resin deteriorates, cracks occur in the polyamide resin, causing separation of the polyamide resin and the resin from the bearing surface, and depending on the area where the sliding parts are applied, an increase in vibration noise or sliding This also leads to an increase in the sliding resistance.

The present invention is intended to solve the above-mentioned problems, and its purpose is to select a polymerization catalyst and a polymerization initiator to be used in lining polyamide resin, thereby making it possible to perform lining under high temperature atmosphere. Another object of the present invention is to provide a method for manufacturing a sliding component with excellent durability, which can prevent deterioration of polyamide resin and decrease in adhesive strength with a metal interface even under conditions where grease is present.

[Means to solve the problem]

That is, the gist of the present invention is to provide a casting material containing the following compositions (A> and (B)) in the clearance between a bearing and a shaft that is fitted into the bearing and is supported so as to freely rotate or reciprocate. A method for manufacturing a sliding part, which comprises forming a resin lining on the surface of the shaft or bearing by injecting and polymerizing and curing: (A) ω containing a polymerization catalyst of an alkali metal or alkaline earth metal compound; -Lactam liquid: (B) A lactam terminal group represented by the following formula and/or -Nu-S-Qp (wherein, Q is a lactam residue having an alkylene group from 03 to C, and the lactam C, P via the nitrogen atom of
mana is bonded to S, A is an aliphatic or aromatic hydrocarbyl group or hydrocarbyl ether group, gu is 0 or 1, when - is O, n is O or 1, p is 1 and when - is 1, n is within the range of 1 to 3, p=n, and RI represents an alkyl group, an aralkyl group, an alkyloxy group, an aryloxy group, a halogen group, or an aralkyloxy group. ) and an elastic skeleton derived from a telechelic polyamine containing at least two primary or secondary amino groups, and at least one lactam polymerization initiator containing: The purpose of the present invention is to provide a lactam liquid.

The sliding parts that are the object of the present invention are firstly connected to a shaft such as a round shaft or a square shaft using a suitable bearing (herein, bearings include not only individual or separate bearings but also bearings that are integrated with the main body of the device). ) is fitted into the ω-lactam solution, i.e., the casting material (A), which is supported rotatably or reciprocally in the axial direction, and then contains the required amount of a polymerization catalyst of an alkali or alkaline earth metal compound, i.e., a casting material (A); An ω-lactam solution containing a polymerization initiator, i.e., a low viscosity solution obtained by mixing and stirring the casting material (B) etc., is injected into the clearance between the bearing and the shaft, or these solutions are first poured into the internal space of the bearing. The resin lining is formed on the surface of the shaft or bearing by pouring an appropriate amount of the solution and then fitting the shaft into the bearing to uniformly spread the solution in the clearance and polymerize and harden it by heating. That is, it is a cash processing method in which a resin lining is directly formed in the clearance between the shaft and bearing that are currently fitted. In this case, it is difficult to remove the resin lining after polymerization, so it is preferable to apply an appropriate seal to the bearing in advance, except for the part (bearing surface) where the bearing function (bearing surface) is desired. In order for the polymerization reaction to proceed uniformly and smoothly, it is preferable to preheat the shaft and bearing before injection of the solution and maintain it at a temperature suitable for polymerization. Additionally, by applying an appropriate primer to the bearing surface of the bearing and an appropriate mold release agent to the shaft, the resin lining can be firmly fixed onto the bearing surface. If you wish, you can apply a primer to the shaft and a release agent to the bearing.

The present invention will be explained in detail below.

(ω-lactam) As the ω-caprolactam used in the present invention, γ-
Butyrolactam, δ-valerolactam, ε-caprolactam, ω-enantholactam, ω-capryllactam,
Examples include ω-undecanolactam and ω-laurinlactam. These ω-lactams may be used alone or in combination of two or more.

(Polymerization catalyst) The polymerization catalyst for the alkali metal or alkaline earth metal compound contained in the casting material (A) used in the present invention is selected from those used in known anionic polymerization of ω-lactams. be able to. Specific examples thereof include alkali metals, alkaline earth metals, their hydrides, oxides, hydroxides, carbonates, alkyl compounds, arylated metals, alkoxides, Grignard compounds, and the above metals or metal compounds. -Reaction products with lactams, such as sodium salts, potassium salts, and magnesium halide salts of ω-lactams. The amount of alkaline polymerization catalyst used is 0.01 based on the total ω-lactam.
-15, or 20 mol% or more.

(Polymerization initiator) The lactam polymerization initiator according to the present invention has the following formula: -Nfl
-C-A--fc-)-nQGl, -N
H-P-Qp device and/or (wherein Q is a lactam residue having a C5-O8 alkylene group, and C, P
or bonded to S, A is an aliphatic or aromatic prodrocarbyl group or hydrocarbyl ether group, the ugliness is O or 1, when - is 0, n is 0 or 1, p is 1, when - is 1, n is within the range of 1 to 3, p=n, and R1 is an alkyl group, an aralkyl group, an alkyloxy group, an aryloxy group, a halogen group, or an aralkyloxy group ) and an elastic skeleton derived from a telechelic polyamine containing at least two primary or secondary amino groups.

More specifically, the initiator has the formula A polyvalent group derived from a telechelic polyamine containing at least two primary or secondary amino groups selected from the group consisting of, t is at least 1, A, Q, -1n , R+ and p are as defined above.)

This initiator can be produced by the reaction of an acyllactam monomer having at least two acyllactam groups with a telechelic polyamine.

According to the method of the present invention, a polyamide-polyether block copolymer can be obtained as a lining resin, but in order to produce a block copolymer with excellent properties, it is necessary to , at least 90 mol% of the amino groups of the polyamine, more preferably 95
It is advisable to convert a mole % of the lactam end groups into lactam end groups; this can be done by preforming the initiator or
Alternatively, the initiator may be generated on-site before being placed under lactam polymerization conditions.

The number average molecular weight of the lactam polymerization initiator is about 500 to about 1
5. Goo preferably about t, ooo to about 10,000 are advantageous. Preferred lactam polymerization initiators are derived from polyether polyamines and polyhydrocarbon polyamines and have at least about t, ooo, preferably about 2
, Goo ~ about 6. It has a molecular weight of Goo. All molecular weights referred to herein, unless otherwise specified, refer to number average molecular weights as determined by methods known in the art.

The initiator according to the invention can be obtained by carrying out the following steps sequentially, which proceed at ambient temperature.

a) complexing the acid halide group of the polyfunctional acid halide with a tertiary amine; b) complexing at least one but not all of the 11-formed acid halide groups with the formula It is a fullkylene group at C. ) to replace the halogen with a lactam residue to produce a halogenated ammonium salt; g) at least 90 mol% of the remaining complexed acid halide groups are converted into polyfunctional reacting with a primary amine to form an amide group, and d) removing the ammonium halide salt, the acid halide groups are advantageously present in a slight excess of the stoichiometric amount relative to the amino groups. be. In this method, the acid halide group reacts with the amino group of the polyamine to form an amide bond and a substituted ammonium halide byproduct. 1 of this reaction
Examples are: That is, (lactam polymerization initiator) + (HXNRa) (in the formula,
X is chlorine or bromine, :NR, is a tertiary amine:
Z, Q, A and are as previously described; and ≧dx. ) Certain polyfunctional acid halides may contain more than one acid halide group after reaction with the lactam monomer in step b) to form the initiator, in which case the polyfunctional acid halide The acid halide is
Two or more telechelic polyamines can be coupled by removing two molecules of substituted ammonium halide per coupling reaction.

The initiator is a non-interfering solvent such as cyclohexane,
Preferably it is produced in the presence of toluene, tetrahydrofuran or acetone.

The initiator can also be produced at elevated temperatures, e.g. from 30 to 150<0>C, depending on the nature of the solvent used. If a solvent is used, the solvent used can be removed by distillation after the initiator has been formed.

Telechelic polyamine has a number average molecular number of approximately 300.
~to,000 are advantageous, preferably at least about 500, more preferably at least to,o
It belongs to oo. And while polylactam segments produced by addition polymerization of lactam monomers to initiators provide hard, crystalline segments, this telechelic polyamine provides soft, elastic segments to nylon block copolymers. selected to give a backbone.

The soft segment, when incorporated into the nylon block copolymer, contributes to a glass transition temperature, T8, of about 0°C or less, preferably about -25°C or less. The glass transition temperature can be easily measured by the scanning speed 10-b method under a nitrogen atmosphere.

Such segments include telechelic polyamines selected from the group consisting of polyoxyalkylene polyamines, oxyalkylene copolymer polyamines, polyalkadiene polyamines, alkadiene copolymer polyamines, polyalkene polyamines, alkene copolymer polyamines, and combinations thereof. It is advantageous to be guided.

The amount of elastomer segments in the nylon block copolymers produced by the process of the invention varies depending on the properties desired, but can vary from 10 to 90% by weight of the copolymer.

Examples of suitable polymeric hydrocarbon polyamines are polybutadiene diamine, polybutadiene polyamine and butadiene-acrylonitrile copolymer polyamine.

Examples of suitable polyether polyamines are poly(oxybutylene) diamine, poly(oxyethylene) diamine,
poly(oxypropylene)diamine, poly(oxypropylene)triamine, poly(oxypropylene)tetramine, and combinations thereof, such as at least two
It is a block copolymer of poly(oxypropylene) and poly(oxyethylene) functionalized with two amino groups. A preferred polyether polyamine is poly(oxypropylene) triamine having a number average molecular weight of at least about 5.000.

Telechelic polyamines are disclosed in U.S. Pat.
It can be produced from telechelic polyols by replacing the hydroxyl groups of the telechelic polyols with amino groups according to the methods described in No. 728 and No. 3,236,896. Due to the method of production of these compounds, it is expected that some residual hydroxyl groups will be present. Alternatively, nitrile-containing polymers can be amine-functionalized by reduction of their nitrile groups, and formyl-containing polymers can be amine-functionalized by reductive amination of their formyl groups.

A polyfunctional acid halide that can be suitably used for producing a lactam polymerization initiator is represented by the following formula.

(In the formula, - is O or 1, when the argument is 0, n is 0 or 1 and p=l, when n is 1, n is pmn in the range of 1 to 3, and X is It is chlorine or bromine. A is an aliphatic or aromatic hydrocarbyl group or a hydrocarbyl ether group. R3 is an alkyl group, an aralkyl group, an alkyloxy group, an aryloxy group, a halogen group or an aralkyloxy group. Preferred groups as )A represented by A are paraphenylene or metaphenylene and -+CH*)-x (where X is within the range of 3 to 8), and more preferred are paraphenylene or metaphenylene. and mixtures thereof,
Other preferred diacid halides, which yield nylon block copolymers with excellent physical properties, contain oxalyl groups, where -=0 and n=1.

Suitable lactams for reaction with the complexed acid halide are those having C3 to C11 alkylene groups, preferably those having C3 or C1 alkylene groups, based on their reactivity and availability. , that is, 2-
Pyrrolidinone or ε-caprolactam.

A third compound that can be used to complex polyfunctional acid halides.
Examples of class amines include trialkylamines, pyridine and alkyl-substituted pyridines, quinoline, and other substituted amines having substituents that do not substantially interfere with the function of the amine as a complexing agent and with the formation of the lactam polymerization initiator M. It is. Preferably, the ammonium salt and excess tertiary amine are removed after initiator formation.

The lactam polymerization initiator is preferably prepared by reacting one equivalent of a telechelic polyamine, based on the number of amino groups, with one equivalent of an acid halide, based on the number of acid halide groups. If a polymeric lactam initiator with a backbone containing alternating and soft segments is desired, a polyfunctional acid halide is reacted to combine with two or more telechelic polyamines. In this case, the equivalent ratio of telechelic polyamine to acid halide is less than 1:1 (for example, if the telechelic polyamine is trifunctional and the difunctional acid halide is added to the two polyamines) When coupling, it is advantageous to use an equivalent ratio of 1:3 to obtain a polymeric tetrafunctional initiator. It is preferable to follow the molecular weight regulations discussed in Section 1-a.

The lactam polymerization initiator can be reacted with a lactam monomer, preferably ε-caprolactam, in the presence of a lactam polymerization catalyst to form a nylon block copolymer having soft segments and hard segments;
The hard segment is then represented by the formula % where q is from about 4 to about 300 and Y is as defined above, and the hard and soft segments are:
They are joined by an amide bond of the formula: (where A, Y, Y, n, and p are as defined above).

This block copolymer contains substantially no ester bonds between the hard and soft segments and has better hydrolytic and thermal stability than those containing such ester bonds. There is.

The weight average molecular weight of the resulting nylon block copolymer can vary within a wide range, but is approximately ts, oo
Advantageously, the range is from about 100 to about 100. The molecular weight depends on the molar ratio of lactam monomer and lactam polymerization initiator.

The concentration of the initiator or the activated N-lactam groups present during the polymerization of the lactam monomer, provided by the lactam polymerization initiator, influences the overall reaction rate. activation N
- the total amount of lactam groups, i.e. the number of equivalents of initiator groups, is
It may vary depending on the functionality and/or concentration of initiator present in the mixture. Generally, the functionality of the initiator or
The number of activated N-lactam groups per molecule is at least 2.
, preferably from about 2 to about 10, and more preferably from about 3 to about 6. Generally, the amount of lactam polymerization initiator used is at least 0.1 mol%, more preferably from 0.25 to 1.0 mol% of the total number of moles of caprolactam monomer used.

ε- in the presence of a suitable catalyst using a lactam polymerization initiator
When reacting with caprolactam monomer to produce a nylon-6 block copolymer, the resulting block copolymer generally consists of a lactam polymerization initiator with polyamide chains having repeating units of the general formula %. On the other hand, nylon-6 block copolymers are made essentially from ε-caprolactam, but other lactam monomers can also be included so long as the reaction rate or degree of polymerization of the caprolactam addition is not substantially impaired.

(Other compounded materials) In the present invention, other additives such as plasticizers, blowing agents, dyes and pigments, antioxidants, internal mold release agents, etc. may not be added unless they substantially inhibit the polymerization reaction. Can be blended.

〔Example〕

Next, the present invention will be explained in more detail based on examples.

In addition, in the following examples, evaluation of appearance and evaluation of resin deterioration were performed as follows.

Outside of sliding parts: Grease (Autorex A made by Idemitsu Petrochemicals) was injected into the clearance between the shaft and bearing of a single moving part molded based on the example described below, and
After leaving the bearing for ooo hours, the shaft and bearing were slid 10,000 times, and then the shaft was removed from the bearing and visually observed to see if any cracks had formed in the resin lining the bearing. The evaluation display was as follows.

0: No cracks occurred at all. ×: Cracks occurred. Evaluation of resin deterioration: 3Ofll dumbbells of ^STN D-638-72 type ■ were cut out from a flat molded product molded based on the example described below, and subjected to this test. Coat the piece with the specified grease (
It was immersed in Autorex A) manufactured by Idemitsu Petrochemical. In this state, after leaving it open for 100 hours at 120℃,
Tensile elongation was measured according to STHD-838-72.

1 Seed 5-” 11th! 1 and 2, (1) shows the bearing of the outer spline, (2) shows the shaft of the inner spline fitted in the bearing (1) and supported for reciprocating movement, and (3) shows the shaft of the inner spline fitted in the bearing (1). ) shows the resin lining made of polyamide resin formed on the bearing surface (4), and (5) and (6) are centering centers.

For the sliding parts of this example, first, a primer is applied to the bearing (1) and a mold release agent is applied to the shaft, and then the bearing (1) and the shaft (2) are preheated to 130 to 160°C. held. After that, equal amounts of the following casting material (A) and casting material (B) are mixed to form a clearance (7) between the bearing (1) and the shaft (2).
(approximately 0.2 s+m) and polymerized and cured at 130 to 160°C to form a resin lining (3) on the bearing surface (4) of the bearing (1). The appearance of the obtained sliding parts after deterioration was evaluated.

In addition, the following casting material (A) and casting material (B) are also available.
) were weighed and mixed, and immediately heated to 140°C with an electric heater, 220cm long and 180m wide.
g, poured into a flat plate forming mold having a cavity with a depth of 3 mm, and held at 140° C. for 5 minutes. The resulting molded product was evaluated for resin deterioration.

Casting material (A) ε-caprolactam 291 g Bromagnesium caprolactam 84 g Casting material (B) ε-caprolactam 1672 Polymerization initiator having the following chemical structure 167 g (However, in the formula, Z represents polypropylene oxide with a molecular weight of approximately 5,000. represent,
) Table 1 regarding appearance of sliding parts and resin deterioration evaluation results
Shown below.

1 Seed-1 A bearing was lined with resin in the same manner as in Example 1, except that the following polymerization initiator was used as the polymerization initiator contained in the casting material (A).

Resin lining of a bearing was performed in the same manner as in Example 1, except that the following materials were used.

(However, 2 in the formula represents polypropylene oxide with a molecular weight of about 5,000.) Table 1 shows the appearance of the sliding parts and the evaluation results of resin deterioration.

A bearing was lined with resin in the same manner as in Example 1, except that the following polymerization initiator was used as the polymerization initiator contained in the casting material (A).

(However, 2 in the formula represents polypropylene oxide with a molecular weight of about s, ooo.) Table 1 shows the appearance of the sliding parts and the results of evaluating the deterioration of the resin.

Resin lining of a bearing was performed in the same manner as in Example 1, except that the following polymerization initiator was used as the polymerization initiator contained in the casting material (A).

(However, in the formula, Z represents polypropylene oxide with a molecular weight of approximately 5.0.) Table 1 shows the appearance of the sliding parts and the results of evaluating the deterioration of the resin.

Plate 11 Table 1 shows the appearance of sliding parts and the evaluation results of resin deterioration using the polymerization initiator contained in the casting material (A) (representing an oxide block copolymer).

As can be seen from Table 1, when a bearing is lined with a resin using the casting material (B) in which a polymerization initiator is selected according to the present invention, the lining does not deteriorate or break even in a long-term sliding test at high temperatures. It can be seen that this did not occur and there was no physical deterioration of the resin itself.

Table 1

[Brief explanation of drawings]

FIG. 1 is a sectional view showing a sliding component manufactured according to an embodiment of the present invention. FIG. 2 is a plan view showing the sliding component of FIG. 1. 1: Bearing of outer spline 2: Shaft of inner spline 3: II fat silicon lining: Inner surface of bearing 5 and (6): Center for centering 7; Clearance [Effect of the invention] As explained above, the present invention has the following advantages: Sliding parts made using the monomer molding method have excellent grease resistance and are extremely precise sliding parts without any rattling, which is a conventional feature, and have extremely high industrial utility value. Patent applicant: Mitsubishi Monsando Kasei Co., Ltd.
Toyota Motor Corporation Patent Attorney Teru Sowado: ゛・−,′□(1)η
, J.

Claims (1)

[Claims] The following (A) and (B) are required for the clearance between the bearing and the shaft that fits into the bearing and is supported so as to freely rotate or reciprocate.
A method for producing a sliding part, which comprises forming a resin lining on the surface of the shaft or the bearing by injecting and polymerizing and curing a casting material having the composition: (A) an alkali metal or an alkaline earth metal; ω-lactam liquid containing a compound polymerization catalyst; (B) Lactam end group represented by the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ mathematical formulas, chemical formulas,
There are tables, etc.▼ and/or▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Q is a lactam residue having an alkylene group of C_3 to C_1_1, and C, P or bonded to S, A is an aliphatic or aromatic hydrocarbyl group or hydrocarbyl ether group, m is 0 or 1, and when m is 0, n is 0 or 1, and p is 1. Yes, when m is 1, n is 1 to
3, p=n, and R_1 is an alkyl group, an aralkyl group, an alkyloxy group, an aryloxy group,
Represents a halogen group or an aralkyloxy group. ) and an elastomer skeleton derived from a telechelic polyamine containing at least two primary or secondary amino groups; thing.