JPH0410519B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a curable resin composition for sliding materials that has excellent heat resistance properties, mechanical properties, and especially sliding properties. More specifically, it is a composition containing a curable resin, a substantially linear high molecular weight novolak-type substituted phenolic resin, a fibrous filler, and a solid lubricant, and exhibits excellent performance as a sliding molding material. The present invention relates to a curable resin composition for sliding materials that can be used as a sliding material. Curable resins such as various epoxy resins, urethane resins, urea resins, melamine resins, and phenol resins can be made into curable resin compositions by adding curing agents and, if necessary, various fillers and curing them. It is used in various molded products. However, although these curable resin compositions have excellent mechanical properties at relatively low temperatures around room temperature, they have poor thermal deformation temperature, thermal deformation at high temperatures, bending strength, mechanical strength, dimensional stability, etc. Because of their poor heat resistance and mechanical properties, they cannot be used as molded products under heated conditions. In order to improve the heat resistance, mechanical properties, and other properties of these curable resin compositions, resol-type phenolic resins or novolac-type phenolic resins and, if necessary, inorganic fillers such as glass fiber and silica are blended. Many curable resin compositions have been proposed. For example, when the curable resin is an epoxy resin, a curable resin composition prepared by blending the epoxy resin with a novolac type phenol resin and an inorganic filler as necessary is produced by the Japanese Patent Publication No. 32
-9246 publication, 38-11827 publication, 39-3574
Publication No. 39-27769, Publication No. 41-1352,
Publication No. 45-30351, Publication No. 46-38030, Publication No. 48-
No. 8278, No. 48-44958, No. 50-19319, No. 51-20537, No. 51-21679,
No. 51-21839, No. 51-24399, No. 51-
Publication No. 43403, Publication No. 52-3828, Publication No. 52-9480, Publication No. 72293-1983, Publication No. 49-118797, Publication No. 49-118798, Publication No. 50-70497,
No. 50-108400, No. 51-132267, No. 52
-138599 publication, 52-144099 publication, 55-
This is proposed in publications such as Publication No. 29532. In addition, when the curable resin is urethane resin, urea resin, melamine resin, phenolic resin, etc., the same curable resin composition may be prepared by blending a novolak type phenolic resin and, if necessary, an inorganic filler such as glass fiber or silica. Many things have been proposed. but,
All of these compositions have poor heat resistance properties, mechanical properties, and sliding properties, and do not satisfy the performance required as a sliding molding material under heat-resistant conditions. Traditionally, sliding molded products such as bearings, gears, bearings, washers, piston rings, compressor pump vanes, and bushes have been made of metal, but recently these sliding molded products have become lighter, smaller, and more compact. Demand for moldability has become stronger, and molding materials are increasingly being switched from metals to synthetic resins. Synthetic resin compositions for sliding molding materials have wear resistance,
In addition to excellent sliding properties such as dynamic friction coefficient and limit PV value, it is also required to have excellent heat resistance and mechanical properties. Conventionally used synthetic resins for sliding molding materials have been resin compositions made by blending solid lubricants with thermoplastic resins such as polyacetal and polyamide, or thermosetting resins such as phenolic resins. However, all of these resin compositions have poor heat resistance and mechanical properties, as well as poor sliding properties such as abrasion resistance, coefficient of dynamic friction, and limit PV value, so they cannot be used under high temperature conditions or at high speeds and high loads. There were significant restrictions on its use under these conditions. Furthermore, to improve the shortcomings of these conventional synthetic resin sliding molding materials, compositions in which polybismaleimide resin is blended with various fillers and solid lubricants have been proposed, and although they have excellent performance, Since polybismaleimide resins are extremely expensive, there is a demand for the development of synthetic resin compositions for sliding molding materials that are excellent in both performance and economy. Based on this recognition, the present inventors conducted studies with the aim of developing a curable resin composition that has excellent heat resistance, mechanical properties, and sliding properties, and has excellent performance as a sliding molding material. As a result, a resin composition containing a curable resin, a substantially linear high molecular weight novolak-type substituted phenol resin containing difunctional phenol component units as a main component, a fibrous filler, and a solid lubricant has achieved the above object. The present invention was achieved based on the discovery that a sliding molding material with excellent performance could be obtained. According to the present invention, the curable resin composition of the present invention has a thermal deformation temperature, a bending strength at high temperature,
It has excellent heat resistance and mechanical properties such as mechanical strength, impact strength, mechanical strength, and dimensional stability, as well as outstanding sliding properties such as wear resistance, dynamic friction coefficient, and limit PV value, making it suitable for high-temperature conditions. It has the characteristic of being suitable as a heat-resistant sliding molding material used under low-speed, high-speed, and high-load conditions. To summarize the present invention, the present invention consists of (A) a curable resin, (B) a difunctional phenol component as a constituent phenol component, and a number average molecular weight (n).
1,500 or more and a substantially linear high molecular weight novolac-type substituted phenol resin, (C) an organic fibrous filler, and (D) a solid lubricant. The curable resin (A) blended into the curable resin composition for sliding materials of the present invention includes a curable resin that is cured with a curing agent and, if necessary, a curing accelerator;
There are curable resins that are cured by heat. More specifically, various epoxy resins, various urethane resins, urea resins, melamine resins, polybismaleimide resins, ordinary novolac type phenolic resins, ordinary resol type phenolic resins, etc. can be exemplified. Among these curable resins (A), when the present invention is applied to a curable resin that can be cured with a phenolic hydroxyl group-containing compound, the heat resistance and mechanical properties of the resulting curable resin composition are further improved. Therefore, it is preferable. More specifically, among these curable resins (A), when an epoxy resin, a urethane resin, a normal novolac type phenolic resin, or a normal resol type phenolic resin is used, a curable resin composition with further improved performance can be obtained. This is preferable because it provides the following. Furthermore, it is particularly preferable to use an epoxy resin because a curable resin composition with further improved heat resistance and mechanical properties can be obtained. Among the curable resins (A), epoxy resins will be more specifically exemplified. When the curable resin (A) blended into the curable resin composition of the present invention is an epoxy resin, the epoxy resin is a compound containing two or more epoxy groups in one molecule. Specifically, such epoxy resins include:
For example, glycidyl ether-based epoxy resins of polyphenol compounds such as bisphenol A, bisphenol F, and 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane; Glycidyl ether type epoxy resin; Glycidyl ether type epoxy resin of polyhydric phenols such as catechol, resorcinol, hydroquinone, and phloroglucin; Glycidyl ether type of polyhydric alcohols such as ethylene glycol, butanediol, glycerol, erythritol, and polyoxyalkylene glycol Epoxy resin; Novolac type epoxy resin; Alicyclic epoxy resin such as vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene oxide; Ester condensate of polycarboxylic acids such as phthalic acid and cyclohexane-1,2-dicarboxylic acid Polyglycidyl ester-based epoxy resins; polyglycidylamine-based epoxy resins; and methyl epichloro-type epoxy resins. Among these epoxy resins, it is preferable to use glycidyl ether type epoxy resins of polyphenol compounds or novolak type epoxy resins. As a curing agent that may be added as necessary to an epoxy resin composition containing these epoxy resins, any compound generally known as a curing agent for epoxy resins can be used. For example, specifically, chain aliphatic polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylene diamine, and diethylaminopropylamine; cycloaliphatic polyamines; aliphatic polyamine adducts; ketoimines; modified aliphatic polyamine; polyamide amine; aromatic amine; aromatic modified amine; aromatic modified polyamine; tertiary amine curing agent; mercaptan curing agent; acid anhydride curing agent; ethylene-maleic anhydride copolymer Copolymers having acid anhydride groups, such as polymers; compounds having phenolic hydroxyl groups, such as novolak-type or epoxy-type phenolic resin initial condensates;
Compounds such as dicyandiamide and melamine can be mentioned. High molecular weight novolac-type substituted phenolic resin (B) blended into the curable resin composition for sliding materials of the present invention
has a bifunctional phenol component as its constituent phenol component, and has a number average molecular weight [N,N-
It is a substantially linear high molecular weight novolak-type substituted phenol resin which has a value (n) of 1500 or more as measured by vapor pressure osmosis method in a dimethylacetamide solvent. In the present invention, the high molecular weight novolac type substituted phenolic resin (A) (hereinafter sometimes simply referred to as high molecular weight novolac type resin) which is a compounding component may consist entirely of substantially linear novolac repeating units. , or the number average molecular weight is 250 or
A high molecular weight novolak type in which each block of 1200 novolak type repeating units alternately contains chain extending groups consisting of divalent hydrocarbon groups at a ratio of 0.5 to less than 1 mol, particularly 0.6 to less than 1 mol, per mol of said block. It may also be a substituted phenolic resin.
What is important is that this high molecular weight novolak type resin is substantially linear and has a molecular weight of 1,500 or more, preferably in the range of 1,700 to 15,000, particularly preferably in the range of 2,000 to 15,000.
It has a number average molecular weight [n] in the range of 10,000. Here, the number average molecular weight [n] is N,
This is a value measured by vapor pressure osmosis method in N-dimethylacetamide solvent. In addition, "substantially linear" herein means that the polymer chain has a linear structure with a linear or branched structure, and it means that the polymer chain does not substantially contain a network structure (i.e., a gelled product). do. The number average molecular weight of the high molecular weight novolak type resin (B) is in the range of 1500 or more as described above, but as the number average molecular weight of the resin increases, when it is blended into a curable resin, the heat resistance properties and mechanical properties, In particular, it is preferable because a composition with excellent impact strength can be obtained. In addition, the molecular weight distribution of the high molecular weight novolac type resin is such that the content of resin components having a number average molecular weight of 2000 or more is usually 50% by weight or more, preferably 60% by weight or more, and particularly preferably 70% by weight or more.
% by weight or more. Also, number average molecular weight (n)
Ratio of weight average molecular weight (w) to (w/
The molecular weight distribution expressed as n) is preferably in the range from 1.8 to 20, particularly preferably from 2 to 10. Further, the melting point of the high molecular weight novolak type resin is usually in the range of 120°C or higher, preferably 150°C or higher. Further, the high molecular weight novolak type resin is an amorphous or crystalline resin. More specifically, this is the novolak repeating unit constituting the high molecular weight novolak resin (B). (i) The phenol component has the general formula [] (In the formula, two of the three R ¹ are hydrogen atoms, and the remaining one represents an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, a halogen atom, or a hydroxyl group, It preferably represents an alkyl group having 1 to 8 carbon atoms, and more preferably one type of substituent selected from the group consisting of a methyl group, an ethyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, and an octyl group. R represents the same or different groups selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, and a hydroxyl group, and preferably two R One of them is a hydrogen atom, and the remaining one is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, particularly preferably 2
All R's represent a hydrogen atom. ) at least one difunctional phenol component represented by 70 to 100 mol%, preferably 80 to 100 mol%
100 mol%, particularly preferably in the range of 90 to 100 mol%, and the trifunctional phenol component is 0.
30 mol%, preferably 0 to 20 mol%, particularly preferably 0 to 10 mol% (selected so that the total of both phenolic components is 100 mol%). , also configure this. (ii) The aldehyde component has the general formula [] R ² -CHO [] (wherein R ² represents one type of substituent selected from the group consisting of a hydrogen atom, a methyl group, and a halogenated methyl group, and preferably represents a hydrogen atom or a methyl group, particularly preferably a hydrogen atom). In this novolak type repeating unit, the difunctional phenol component has the general formula [ ] in the resin molecule. (In the formula, R ¹ and R each represent the same group as above.) It exists as a hydroxyarylene unit represented by the formula [] at the molecular terminal of the polymer. It exists as a hydroxyaryl unit represented by (wherein R ¹ and R each represent the same group as above). Similarly, the trifunctional phenol component of the resin component also exists as a hydroxyarylene unit in the resin molecule, similar to the above general formula [], and at the molecular end of the resin, hydroxyl as in the above general formula []. Exists as an aryl unit. Further, the aldehyde component constituting the high molecular weight novolak type resin has the general formula [] R ² −CH< [] (wherein R ² is selected from the group consisting of a hydrogen atom, a methyl group, and a halogenated methyl group). It exists as an alkylidene unit represented by one type of substituent. Further, the structure of the novolak type repeating unit is a chain structure in which the hydroxyarylene units and the alkylidene units are alternately arranged. More specifically, the structure of the high molecular weight novolac type resin is such that when the constituent phenol component is only the bifunctional phenol component represented by the general formula [], the resin is linear. However, if the content of trifunctional phenol components increases, it may become branched. The ratio of the aldehyde component to all the phenolic components constituting the high molecular weight novolak type resin is generally in the range of 0.90 to 1.0 mol, preferably 0.93 to 1.0 mol, per 1 mol of the total phenolic components. The high molecular weight novolak type resin usually does not contain a methylol group, but it may contain a trace amount of methylol group, not more than 0.01 molar equivalent per mole of all phenol components. Among the phenolic components constituting the high molecular weight novolak type resin (B), the bifunctional phenol component is represented by the general formula [], and has two active molecules on the benzene nucleus for the substitution reaction. A phenol having a hydrogen atom, specifically an alkyl group having 1 to 8 carbon atoms at the ortho or para position relative to the hydroxyl group in the general formula [],
These are phenols having an aryl group, halogen, or hydroxyl group having 6 to 10 carbon atoms. More specifically, the following ortho isomers or para isomers of phenols can be exemplified. For example, cresol, ethylphenol, n-propylphenol, isopropylphenol, n-butylphenol, sec-butylphenol, tert
- Alkylphenols such as butylphenol, pentylphenol, hexylphenol, heptylphenol, and octylphenol; orthophenols such as halogenated phenols such as fluorophenol, chlorophenol, and bromophenol; and arylphenols such as phenylphenol and tolylphenol. Examples include isomers and para-isomers. In addition, as other bifunctional phenol components represented by the general formula [], 2,3-xylenol, 3,4-xylenol, 2,5-xylenol, 2,5-diethylphenol, 2,5-diisopropyl Examples include phenol, 3,4-dichlorophenol, 2,5-dichlorophenol, and 2-methyl-5-phenylphenol. The bifunctional phenol component constituting the high molecular weight novolac-type substituted phenolic resin is at least one of the above phenol components, and may be a mixture of two or more. The trifunctional phenol component constituting the novolak repeating unit of the high molecular weight novolak resin (B) is a phenol having three active hydrogen atoms for substitution reaction on the benzene nucleus, and specifically is phenol, meta-substituted phenol, and 3,5-substituted phenol. The substituent that these trifunctional phenols have at the meta-position or the 3,5-position is an alkyl group, a halogen, or a hydroxyl group. Among these trifunctional phenols, suitable trifunctional phenols have the general formula [] (In the formula, R represents the same or different substituents selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen, and a hydroxyl group.) More specifically,
Phenol, m-cresol, m-ethylphenol, m-n-propylphenol, m-isopropylphenol, m-n-butylphenol,
m-sec-butylphenol, m-tert-butylphenol, m-pentylphenol, m-hexylphenol, m-heptylphenol, m-
Octylphenol, m-fluorophenol, m
-Meta-substituted phenols such as chlorophenol and resorcin; 3,5-xylenote, 3,5-
Diethylphenol, 3,5-diisopropylphenol, 3,5-dibutylphenol, 3,5
-dipentylphenol, 3,5-dihexylphenol, 3,5-diheptylphenol, 3,
Examples include 3,5-disubstituted phenols such as 5-dioctylphenol, 3,5-difluorophenol, and 3,5-dichlorophenol. The aldehyde component constituting the novolak type repeating unit is an aldehyde component represented by the general formula []. Specific examples of these aldehyde components include formaldehyde, acetaldehyde, monochloroacetaldehyde, dichloroacetaldehyde, and trichloroacetaldehyde. Among these aldehyde components, formaldehyde or acetaldehyde is preferred, and formaldehyde is particularly preferred. These aldehyde components exist in the high molecular weight novolak type substituted phenol resin as alkylidene groups represented by the general formula []. As mentioned above, the high molecular weight novolac type resin (B) blended into the curable resin composition for sliding materials of the present invention is composed only of novolac type repeating units consisting of the phenol component units and aldehyde component units. Furthermore, as mentioned above, each block of the novolak type repeating unit (a) with a number average molecular weight [n] usually in the range of 250 to 1200 has a chain extending group or a bridging group consisting of a divalent hydrocarbon group. (hereinafter sometimes referred to as chain extender component units) may be formed by alternately containing them. The substantially linear high molecular weight novolak type resin (B)
More specifically, this type of resin is composed of a relatively low molecular weight and substantially linear novolak type repeating unit block (a) and a chain extender component unit (b). The novolak type repeating unit block (a) and the chain extender component unit (b) are alternately arranged and connected to increase the molecular weight, and the novolak type repeating unit block (a) is located at the end of the molecule. It is unique in that it is bound. Among this type of high molecular weight novolac type resin, the resin with the simplest molecular structure is a resin in which two molecules of the novolac repeating unit block (a) are connected by one molecule of the chain extender component unit (b). and then a resin in which three molecules of the novolak repeating unit block (a) and two molecules of the chain extender component unit (b) are alternately arranged and connected, and then four molecules of the novolak repeating unit block (a). and a resin in which three molecules of the chain extender component unit (b) are alternately arranged and connected, and similarly, the novolak repeating unit block (a) has n molecules.
A resin in which (n-1) molecules of the chain extender component units (b) are alternately arranged and connected can be exemplified. The high molecular weight novolak type resin blended into the curable resin composition for sliding materials of the present invention has a substantially general formula [ ] Z (-Y _p -Z) - _o Y _p -Z [ ] (In the formula, Z represents a block of substantially linear novolak-type repeating units formed by condensation of the phenolic component and the aldehyde component, and Y represents a chain extender component unit consisting of a divalent hydrocarbon group. p is an integer of 0 or 1, and n is a number of 0 or 1 or more). In the high molecular weight novolak-type resin, when the novolak-type repeating unit blocks are alternately bonded by the chain extender component units, p is 1, and the chain extender consists of only the novolak-type repeating units. p is 0 when it does not substantially (apparently) contain any component units. The chain extender component unit (chain extender group or bridging group) constituting the high molecular weight novolak type resin (B) is a divalent hydrocarbon group as described above, and is further a hydrocarbon group having 1 to 16 carbon atoms. More specifically, an alkylidene group, an alkylene group, a cycloalkylene group, a cycloalkylidene group, an arylalkylidene group, an arylalkylene group, and an arylenebisalkylene group [-R ³ -Ar-R ⁴ -] I can do it. As an alkylidene group,
Examples include methylene group, ethylidene group, propylidene group, butylidene group, and pentylidene group. Specific examples of the alkylene group include ethylene group, propylene group, isopropylene group, butylene group, pentylene group, and hexylene group. Specific examples of the cycloalkylene group include a cyclopentylene group, a cyclohexylene group, and a methylcyclohexylene group. Specific examples of the cycloalkylidene group include a cyclopentylidene group, a cyclohexylidene group, and a methylcyclohexylidene group. Specific examples of the aryl alkylidene group include penzylidene group, o-xylidene group, m-xylidene group, and p-xylidene group. Specific examples of the arylalkylene group include a styrene group, an α-methylstyrene group, and a p-methylstyrene group. Specific examples of the arylene bisalkylene group include o-xylylene group, m-xylylene group, and p-xylylene group. Among these chain extender component units (b), an alkylidene group, an alkylene group, a cycloalkylidene group, a cycloalkylene group, an arylalkylidene group, an arylalkylene group, or an arylenebisalkylylene group is preferable, and in particular It can be an alkylidene group having 1 to 4 carbon atoms, an alkylene group having 2 to 5 carbon atoms, an arylalkylidene group having 7 to 9 carbon atoms, an arylalkylene group having 8 to 10 carbon atoms, or an arylene bisalkylene group having 8 to 10 carbon atoms. preferable. The molecular weight of these chain extender component units (b) is usually in the range of 14 to 200, preferably 14 to 170. The high molecular weight novolak type resin [B] to be incorporated into the curable resin composition for sliding materials of the present invention can be produced, for example, by the following method. That is, (A) (i) is mainly composed of at least one difunctional phenol represented by the general formula [] (wherein R ¹ and R ² each represent the same group as above) Phenols, or (ii) a phenol component mainly consisting of the above difunctional phenols and an aldehyde represented by the general formula [] R ² -CHO [] (wherein R ² represents the same group as above) (B) (i) dimethylolated products of difunctional and trifunctional phenols; (ii) the aforementioned difunctional phenols; A resol-type substituted phenolic resin consisting of a phenol component mainly consisting of phenols and the above aldehyde component and having a number average molecular weight in the range of 250 to 1200, (iii) aldehyde, (iv) ketone, (v) diol and (vi) A chain extender selected from the group consisting of dihalides [wherein, when the reactant (A) is a phenol (i), the chain extender (B) is a resol type substituted phenolic resin (ii) shall be. ] in the presence of an acidic catalyst, at least one of the phenolic components in the final novolac-type substituted phenolic resin is removed.
Until the number average molecular weight of the final novolak-type substituted phenolic resin reaches a range of 1500 or more, with 70 mol% being occupied by the difunctional phenol and measured by vapor pressure osmometry in N,N-dimethylacetamide solvent. Manufactured by condensation. The blending ratio of the substantially linear high molecular weight novolac-type substituted phenolic resin to be blended into the curable resin composition for sliding materials of the present invention is 100% of the curable resin composition of the present invention.
It is usually in the range of 10 to 200 parts by weight, and it is particularly preferable to incorporate it in the range of 30 to 150 parts by weight, since the heat resistance and mechanical properties of the cured resin composition are further improved. The curable resin composition for sliding materials of the present invention contains a fibrous filler (C). Specifically, the fibrous filler (C) blended into the curable composition of the present invention includes inorganic fibers such as glass fibers, asbestos fibers, carbon fibers, and boron fibers, polyterephthaloyl-p
- fully aromatic polyamides such as phenylene diamine, polyterephthaloyl isophthaloyl-p-phenylene diamine, polyisophthaloyl-p-phenylene diamine, polyisophthaloyl-m-phenylene diamine, nylon 66, Polyamide fibers such as nylon 6, nylon 10, and nylon 12, polyamideimide fibers, polybenzimidazole fibers, polyethylene terephthalate, poly-1,4
- Polycondensation type synthetic fibers such as polyester fibers such as butylene terephthalate; addition polymerization type synthetic fibers such as polyvinyl alcohol type synthetic fibers and acrylic fibers such as polyacrylonitrile;
Examples include addition condensation type synthetic fibers such as formaldehyde resin fibers, and natural fibers such as cotton, hemp, flax, wool, and raw silk. It is preferable to mix a synthetic fibrous filler with the fibrous filler, and it is especially preferable to mix a filler made of polycondensed synthetic fibers, and especially a fibrous filler made of wholly aromatic polyamide. It is preferable. The fibrous filler (C) can be used in any of the usual single fiber, stride, and cross shapes. The fiber thickness of these fibrous fillers (C) is
It usually ranges from 3 to 20μ, preferably from 5 to 15μ. In addition, these fibrous materials can be used in either short or long fibrous materials, and the length of the fibrous material can be selected as appropriate depending on the purpose of use. Usually in the range of 0.1 to 1.2 cm, preferably 0.3 to 0.6 cm. The blending ratio of the fibrous filler (C) is usually 5 to 250 parts by weight, preferably 10 parts by weight, based on 100 parts by weight of the total amount of the curable resin (A) and the high molecular weight novolac type phenolic resin (B). The range is from 10 to 100 parts by weight, particularly preferably from 10 to 40 parts by weight.
When the fibrous filler (C) is a cross-like or stride-like material, the curable resin (A) and the high molecular weight novolac type resin (B) are coated with the organic fibrous filler in the form of a varnish. A molded article made of the composition of the present invention can be obtained by impregnating the composition and then molding the impregnated product by heating and curing it. When the fibrous filler (C) is in the form of single fibers or strides, it can be blended by a conventionally known blending method. Specifically, the solid lubricant (D) blended into the curable resin composition for sliding materials of the present invention includes graphite, titanium oxide, molybdenum disulfide, graphite fluoride, fluororesin, lead, etc. I can give an example. Among these solid lubricants, it is preferable to use graphite and fluorocarbon resins because they provide a curable resin composition with even better sliding properties. The blending ratio of the solid lubricant (D) is usually 1 to 100 parts by weight in total of the curable resin (A) and the high molecular weight novolac type phenolic resin (B).
In the range of 50 parts by weight, preferably 3 to 40 parts by weight.
When the amount is particularly preferably in the range of 5 to 20 parts by weight, a curable resin composition with excellent sliding properties can be obtained. The proportion of the solid lubricant (D) to 100 parts by weight of the fibrous filler (C) is usually in the range of 10 to 500 parts by weight, preferably 30 to 300 parts by weight, particularly preferably 50 to 300 parts by weight. When the amount is in the range of 200 parts by weight, a curable resin composition with excellent sliding properties can be obtained. The curable resin composition for sliding materials of the present invention includes the curable resin (A), the substantially linear high molecular weight novolak resin (B), the fibrous filler (C), and the solid lubricant. In addition to (D), an inorganic filler may be added as necessary, and various compounding agents may be added as necessary. For example, when the curable resin is a resin that can be cured with a curing agent, a curing agent, a curing accelerator, a flame retardant, a heat stabilizer, an antioxidant, a lubricant, the inorganic Fillers other than the filler may be added as necessary. Among these combinations,
Regarding the curing agent, even when the high molecular weight novolak type resin (B), which is an essential component of the curable resin composition of the present invention, can serve as a curing agent for the curable resin (A), the high molecular weight novolac type resin (B), which is an essential component of the curable resin composition of the present invention, A curing agent other than the mold resin can be blended as necessary. Also,
When the high molecular weight novolac type resin (B) cannot serve as a curing agent for the curable resin (A), the above-mentioned curing agent is usually blended. These various compounding agents that are added as necessary vary depending on the type of the curable resin and the use of the composition, and conventionally known compounding agents can be used. Further, the proportions of the various compounding agents blended as necessary vary depending on the type of the curable resin and its use, and appropriate amounts are blended. The curable resin composition of the present invention has excellent heat resistance and mechanical properties such as heat distortion temperature, heat distortion at high temperatures, bending strength, mechanical strength, impact strength, and dimensional stability, and has excellent abrasion resistance, coefficient of dynamic friction, It has extremely excellent sliding properties such as limit PV value, and is suitable as a heat-resistant sliding molding material used under high-temperature conditions or high-speed/high-load conditions. For example, the curable resin composition of the present invention is used as a material for sliding molded products such as bearings, gears, bearings, rotating shafts, washers, piston rings, compressor pump vanes, bushes, and pulleys. Next, the curable resin composition for sliding materials of the present invention will be specifically explained with reference to Examples. Table 1 shows the properties of the novolac type phenolic resin used in the Examples and Comparative Examples. A specific example of the method for preparing the curable resin composition used in the Examples and Comparative Examples is shown below. Preparation of curable resin composition [A] 15 g of the novolac-type substituted phenolic resin to be tested shown in Table 2, 25 g of novolac-type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: Epoxidized Phenol Novolak EPPN-201), Fibrous filler listed in Table 2, BF ₃ 2-methylimidazole complex
0.25 g of montanic acid wax, 0.75 g of montan acid wax, and the solid lubricant shown in Table 2 were mixed together and kneaded on a roll at 80°C. After cooling, it was pelletized using a pelletizer and press-molded in a mold at 250° C. at 100 kg/cm ³ (actual pressure) for 20 minutes. After post-curing this at 250°C for 30 minutes, the physical properties of the molded product were measured and the results shown in Table 3 were obtained. Preparation method of curable resin composition [B] 15 g of the novolac-type substituted phenolic resin to be tested shown in Table 2, bisphenol A type epoxy resin (manufactured by Mitsui Petrochemical Epoxy Co., Ltd., trade name)
A mixture consisting of 25 g of EPOMIK R-140), the fibrous filler shown in Table 2, the solid lubricant shown in Table 2, 0.25 g of BF ₃ 2-methylimidazole complex, and 0.75 g of Montanic acid wax was mixed, The mixture was kneaded for 7 minutes on a roll at . After cooling, it was pelletized using a pelletizer and press-molded in a mold at 250°C for 20 minutes at 100 kg/cm ² (actual pressure). This at 250℃ for 30
After post-curing for a minute, the physical properties of the molded product were measured and the results shown in Table 3 were obtained. Examples 1 to 10,
Comparative Examples 1 to 7. The curable resin, curing agent, curing accelerator, novolak resin, fibrous filler, and solid lubricant shown in Table 2 were blended in the proportions shown in Table 2, and the [A]
A curable resin composition was prepared by any of methods [B] and its performance was evaluated, and the results are shown in Table 3.
It was shown to. Note that each performance of the curable resin composition was evaluated in accordance with JIS K6911.

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[Table] (1) Damaged and impossible to measure
(2) P〓20Kg〓cm ² , V〓180cm〓sec

Claims (1)

[Scope of Claims] 1 (A) a curable resin; (B) a bifunctional phenol component as a constituent phenol component, and a number average molecular weight (n);
1,500 or more and a substantially linear high molecular weight novolac-type substituted phenol resin, (C) a fibrous filler, and (D) a solid lubricant.