JPH0339211A - Manufacture of sliding parts with monomer casting method - Google Patents

Abstract

PURPOSE:To improve grease resistance by eliminating unsteadiness of sliding parts, by a method wherein a casting material of a specific composition is cast into a clearance between a beating and shaft, which is fitted in the bearing and supported turnably or reciprocatably, and cured through polymerization. CONSTITUTION:A casting material is prepared by compounding an omega-lactam liquid matter containing an alkaline metal or a polymerization catalyst of an alkaline earth metal compound with an omega-lactam liquid matter containing a lactam polymerization initiator represented by a formula I (wherein Z, Q, (t) and (p) show respectively polypropylene oxide polyol, a lactam residue having a C3-C11 alkylene group, at least 1 and 0 or 1). The foregoing casting material is cast into a clearance between a bearing and a shaft, which is fitted in the bearing and supported turnably or reciprocatably, cured through polymerization, a resin lining is formed on the surfaces of the shaft and the bearing and sliding parts are manufactured.

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]

The so-called cash processing method, in which a low-viscosity monomer or prepolymer is injected into the clearance between the bearing and the shaft, polymerized and hardened, and the surface of the bearing is lined with resin, has been proposed for some time (Japanese Patent Laid-Open Publication No. 80-178013 and JP-A No. 63-212518), 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. 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 acyl lactams have been disclosed in JP-A-80-178013, and JP-A-63212518 has disclosed the formula % (formula %) [wherein A represents a halogen atom, or N-C=0 (wherein, Y represents C1-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, R2 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 approximately 2,000, (2> having a minimum molecular weight of approximately 2,000) (3) represents a hydrocarbon having a minimum molecular weight of 1,000. A polymerization initiator is disclosed.

On the other hand, various kinds of lactam polymerization initiators are known in addition to those mentioned above.
No. 23 contains the formula [wherein Q is a lactam residue having a C3 to C1 alkylene group, and is bonded to carbonyl via the nitrogen atom of the lactam; A is an aliphatic or aromatic is a hydrocarbyl group or a hydrocarbyl ether group;
Zeng is O or 1; when Peng is 0, n is O or 1
In this case, p is 1, and when - is 1, n is within the range of 1 to 3, and p=n. ] ; Lactam polymerization characterized by containing at least two lactam terminal groups represented by the above and an elastic skeleton derived from a telechelic polyamine containing at least two primary or secondary amino groups. An 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.

The sliding parts obtained by the above-mentioned conventional method had the disadvantage that when general-purpose grease was injected and used at high temperatures (100° C. or higher), the polyamide resin lining deteriorated. As the deterioration of the vI4 resin progresses, cracks occur in the polyamide resin, causing peeling of the polyamide resin and the resin from the bearing surface, and depending on the area where the sliding parts are applied, vibration noise may increase or sliding may occur. This also leads to an increase in sliding resistance during movement.

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 supported so as to freely rotate or reciprocate. forming a resin lining on the surface of the shaft or the bearing by injecting and polymerizing and curing;
Manufacturing method for sliding parts: (A) ω-lactam liquid containing a polymerization catalyst of an alkali metal or alkaline earth metal compound; (B) a lactam polymerization initiator represented by the following formula or OZMo0-5- Qp)t (wherein, Z is polyproblene oxide polyol, A
is an aliphatic or aromatic hydrocarbyl group, Q is a lactam residue having a C3-C1 alkylene group, t is at least 1, is O or 1, and -
is O, n is 0 or 1, p is 1, and - is 1
In this case, 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. ) An ω-lactam liquid containing at least one of the following.

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 H(A), which is supported rotatably or reciprocally in the axial direction, and then contains a required amount of a polymerization catalyst of an alkali or alkaline earth metal compound, that is, a casting material H(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 area where the bearing function is desired (bearing surface). 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 a suitable primer to the bearing surface of the bearing and a suitable mold release agent to the shaft, the resin lining can be firmly fixed onto the bearing surface. If you want to apply a resin lining to the shaft, you can also apply a primer to the shaft and a release agent to the bearing.

The present invention will be explained in detail below.

(ω-lactam) The ω-lactam used in the present invention includes γ-lactam.
Butyrolactam, δ-valerolactam, e-caprolactam, ω-enantholactam, ω-caaryllactam,
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. Specific examples include alkali metals, alkaline earth metals, their hydrides, oxides, hydroxides, carbonates, alkyl compounds, aryl compounds, alkoxides, Grignard compounds, and the above metals or metals. Examples of reaction products between compounds and ω-lactams include sodium salts, potassium salts, magnesium halide salts, etc. of ω-lactams.The amount of the alkaline polymerization catalyst used is 0.1 to 10% of the total ω-lactams.
-15, or 20 mol% or more.

(Polymerization amount initiator) The lactam polymerization initiator according to the present invention has the following formula or
O word Z-(:2 o-5-qp)t (wherein 2 is polypropylene oxide polyol, A
is an aliphatic or aromatic hydrocarbyl group, Q is a lactam residue with a C3-C0 alkylene group, t is at least 1, the ring is O or 1, and -
is O, n is O or 1, p is 1, and - is 1
In this case, n is within the range of 1 to 3, p=n, and R6 is an alkyl group, an aralkyl group, an alkyloxy group, an aryloxy group, a halogen group, or an aralkyloxy group. ) The initiator can be produced by the reaction of an acyllactam monomer having at least two acyllactam groups with a telechelic polyproblene oxide polyol. In order to produce block copolymers with outstanding properties, at least 90 mole percent, and more preferably 95 mole percent, of the hydroxyl groups of the polypropylene oxide polyol are converted to lactam end groups prior to substantial lactam polymerization. This can be done either by preforming the initiator or by creating the initiator in situ before being subjected to the lactam polymerization conditions.

The number average molecular weight of the lactam polymerization initiator is about 500 to about 1
5,000, preferably about 1,000 to about 10,000, are advantageous. Preferred lactam polymerization initiators have a molecular weight of at least about 1,000, preferably from about 2,000 to about e
, ooo molecular weight. All molecular weights herein refer to number average molecular weights as measured by methods known in the art, unless otherwise specified.

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

a) a step of complexing the acid halide group of the polyfunctional acid halide with a tertiary amine; b) complexing at least one but not all of the ig-formed acid halide groups with the formula % formula % (in the formula, Y is a C1-C11 alkylene group.) A step of reacting with a lactam monomer represented by C1 to C11 to replace the halogen with a lactam residue to produce a halogenated ammonium salt; C) remaining complexed acid halide group; a step of reacting at least 90 mol% of the ammonium halide with a polyfunctional secondary hydroxyl group to form a carboxyl group, and d> a step of removing the ammonium halide salt.

Advantageously, the acid halide groups are present in a slight excess of the stoichiometric amount relative to the hydroxyl groups. In this method, the acid halide groups react with the hydroxyl groups of the polyproblene oxide polyol to form an ester linkage and a 1m ammonium halide byproduct.

An example of this reaction is as follows. That is, (lactam polymerization initiator) + (HX N R3) (wherein, X
is chlorine or bromine, :NR, is a tertiary amine; Z
, Q, A, and x are as described above; and K>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 contains 2 substituted ammonium halides per coupling reaction.
Molecules can be removed to couple two or more telechelic polyproblene oxide polyols.

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.

Advantageously, the telechelic polyproblene oxide polyol has a number average molecular weight of about 300 to 10,000, preferably at least about 500, and more preferably at least i,ooo. And while the polylactam segments produced by addition polymerization of lactam monomers to the initiator provide hard, crystalline segments, this telechelic polypropylene oxide polyol gives the nylon block copolymer soft, elastic properties. chosen to give the main chain of body segments.

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

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 fin is O, n is O or 1 and p=l, when the waterfall is 1, it is nG, and in the range from tl to 3, it is p"n, and X is chlorine or bromine.

A is an aliphatic or aromatic hydrocarbyl group or hydrocarbyl ether group. R3 represents an alkyl group, an aralkyl group, an alkyloxy group, an aryloxy group, a halogen group, or an aralkyloxy group.) Preferred groups as A are paraphenylene or metaphenylene and 1+c H2h x (where x is 3 ~8), and more preferred are paraphenylene or metaphenylene and mixtures thereof, which yield nylon block copolymers with outstanding physical properties, and other preferred diacid halides. contains an oxalyl group where the amount=0 and n=1.

Suitable lactams for reaction with the complexed acid halide are those having C3 to C8 alkylene groups, preferably those having C3 or C5 alkylene groups, based on their reactivity and availability. , namely 2-pyrrolidinone or ε-caprolactam.

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

The lactam polymerization initiator is preferably prepared by reacting 1 equivalent of telechelic polypropylene oxide polyol based on the number of hydroxyl groups with 1 equivalent of acid halide based on the number of acid halide groups. If a polymeric lactam initiator with a backbone containing alternating segments and soft segments is desired, a polyfunctional acid halide can be reacted to combine with two or more telechelic polypropylene oxide polyols. I am made to do so. In this case, the equivalent ratio of telechelic polypropylene oxide polyol to acid halide is 1
: Less than 1 is selected.

For example, if the telechelic polypropylene oxide polyol is trifunctional and a difunctional acid halide is added to couple the two polypropylene oxide polyols, to obtain a polymeric tetrafunctional initiator, It is advantageous to use an equivalence ratio of 1:3. The above description of the soft segment preferably follows the molecular weight definitions generally discussed for the telechelic polypropylene oxide polyols.

The weight average molecular weight of the resulting nylon block copolymer can vary within a wide range, but is approximately 18.00.
The zero molecular weight, which is advantageously within the range of 0 to about 100,000, depends, in part, on the molar ratio of lactam monomer to 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. In general, the functionality of the initiator or ■
The number of activated N-lactam groups per molecular weight 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 a nylon-6 block copolymer is produced by reacting with caprolactam monomer, 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, the nylon-6 block copolymer is made essentially from ε-caprolactam, but other lactam monomers can also be included as long as the reaction rate or degree of caprolactam polymerization is not substantially impaired.

(Other compounded materials) Furthermore, in the present invention, other additives such as plasticizers, blowing agents, dyes and pigments, antioxidants, internal mold release agents, etc. may be compounded as long as they do not substantially inhibit the polymerization reaction. be able to.

〔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.

Appearance of sliding parts: Grease (Autorex hole manufactured by Idemitsu Petrochemical Co., Ltd.) was injected into the clearance between the shaft and the bearing of the sliding part molded based on the example described below, and placed in an oven at 120°C for 2 hours.
After being left for 40 hours, the shaft and bearing were slid 10,000 times, and then the shaft was removed from the bearing, and the resin lining the bearing was visually inspected to see if any cracks had formed. The evaluation display was as follows.

○: No cracks occurred at all ×: Cracks occurred Evaluation of resin deterioration: Thirty dumbbells of ^STM D-638-72 type ■ were cut out from a flat molded product molded based on the example described below. The test piece was immersed in the specified grease (Autorex hole manufactured by Idemitsu Petrochemical Co., Ltd.). After leaving this state in an oven at 120℃ for 240 hours, ^STM
Tensile elongation was measured according to D-638-72.

In Figures 1 and 2, (1) shows the bearing of the outer spline, and (2) shows the shaft of the inner spline that fits into the bearing (1) and is supported for reciprocating movement. , also (3
) indicates the resin lining made of polyamide resin formed on the bearing surface (4) of the bearing (1), (5) and (
6) is a centering center.

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, and the clearance between the bearing (1) and the shaft (2) is
(approximately 0.2 mm) and polymerized and hardened at 130 to 160°C to form the resin lining (3) on the bearing surface (1) of the bearing (1).
4> Formed on top. The appearance of the obtained store moving 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 using an electric heater.
The mixture was poured into a flat plate forming mold having a cavity 3 cm deep, and held at 140°C for 5 minutes. The resulting molded product was evaluated for resin deterioration.

Casting material (A) ε-caprolactam 291g Brommagnesium caprolactam 84g Casting material (B) ε-caprolactam 167g Polymerization initiator having the following chemical structure #I 187゜ (However, in the formula, Z is the molecular weight s, ooo Representing polypropylene oxide) Group 1 regarding the appearance of sliding parts and resin deterioration evaluation results
Shown below.

Movement [ As a 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, in the formula, Z represents polypropylene oxide with a molecular weight of about 5,000.) The appearance of the sliding parts and the evaluation results of resin deterioration are shown in Group 1.

``! Ui&J-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).

Cii (CL)S <In the formula, Z represents polypropylene oxide with a molecular weight of about 5,000.> The appearance of the sliding parts and the evaluation results of resin deterioration are shown in Group 1.

Table 10L-A Bearings were lined with resin in the same manner as in Example 1, except that the following polymerization initiators were used as the polymerization initiators contained in the casting material (A).

(However, in the formula, Z represents polypropylene oxide having a molecular weight of about 5,000.) The results of evaluating the deterioration of the outer shell of the sliding part and the resin are shown in Group 1.

Resin lining of a bearing was carried out 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).

(In the formula, Z represents a copolymer in which the terminals of polypropylene oxide having a molecular weight of about 5000 are blocked with polyethylene oxide.) The appearance of the opening parts and the results of evaluating the deterioration of the resin are shown in Group 1.

As can be seen from Group 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 [Effects of the Invention] As explained above, the sliding parts produced by the monomer molding method of the present invention have excellent grease resistance and are extremely accurate with no rattling, which is a conventional feature. It is a sliding part, and its industrial value is extremely large.

[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 parts of FIG. 5. 1: Outer spline bearing 2: Inner spline shaft 3: 1M fat lining): Inner surface of bearing 5 and (6): Centering center (7; Clearance

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; Omega-lactam liquid containing compound polymerization catalyst; (B) Lactam polymerization initiator represented by the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, Z is polypropylene oxide polyol, A
is an aliphatic or aromatic hydrocarbyl group, Q is a lactam residue having an alkylene group from C_3 to C_1_1, t is at least 1, m is 0 or 1, and when m is 0, n is 0 or 1, p is 1, when m is 1, n is within the range of 1 to 3, p = n, and R_1 is an alkyl group, an aralkyl group, an alkyloxy group, an aryloxy group , a halogen group or an aralkyloxy group. ) An ω-lactam liquid containing at least one of the following.