JPH03177419A - Heat-resistant resin composition for molding - Google Patents

Abstract

PURPOSE:To obtain the subject composition having excellent heat-resistance, moisture-resistance, mechanical properties and sliding property against soft metals such as aluminum by compounding a specific thermosetting resin with a specific composite filler at a specific ratio. CONSTITUTION:The objective composition can be produced by compounding (A) 30-70wt.% of a thermosetting resin composed of (i) preferably 30-80wt.% of a reaction product produced by reacting an unsaturated dicarboxylic acid N,N'-bisimide compound of formula I (R1 is >=2C bivalent group; R2 is bivalent group containing C=C group), an aminophenol of formula II (R3 is H, halogen, etc.) and an aniline compound of formula III (R4 and R5 are H, halogen, etc.) and (ii) preferably 70-20wt.% of an epoxy compound containing >=2 epoxy groups and (B) 30-70wt.% of a composite filler composed of (i) 50-83wt.% of fluororesin powder and (ii) 5-38wt.% of aromatic polyamide powder.

Description

[Detailed Description of the Invention] [Object of the Invention] (Industrial Application Field) The present invention has excellent heat resistance, moisture resistance, and R mechanical properties, and particularly has excellent sliding properties on soft metals such as aluminum and brass. The present invention relates to a heat-resistant resin composition for molding with good properties.

(Conventional technology) Conventionally, it has been used as a base material for molding materials and friction materials with excellent heat resistance.
Asbestos fibers have been used. However, the use of asbestos is now prohibited as it is considered harmful. Carbon fiber, which has good heat resistance and sliding properties, has come to be widely used as an alternative to asbestos fiber.

(Problem to be Solved by the Invention) However, carbon fiber is not effective against hard metals such as steel, and has the drawback that it takes a large amount of abrasion and has poor sliding properties against soft metals such as aluminum and brass. There is.
Furthermore, although phenol resins, epoxy resins, and the like have been the mainstream resins for binders, these resins have poor heat resistance and are limited in their use under high load conditions. A polyimide resin has been proposed as an improved heat-resistant resin, and one in which diaminodiphenylmethane is added to a bismaleimide compound is known. Also known is an addition reaction product of a bismaleimide compound and aminophenol modified with an epoxy resin. The former is a problem in Europe and the United States because it is suspected of being carcinogenic, while the latter is made of aminophenol. The disadvantage is that the reaction time becomes longer. Polyimide resins made by addition-reacting aniline to bismaleimide compounds are known, but they have the drawback of poor wettability with inorganic fillers and the tendency for cracks to occur in molded products.

The present invention was made to eliminate the above-mentioned drawbacks, and aims to provide a heat-resistant resin composition for molding that has excellent heat resistance, moisture resistance, and mechanical properties, and has good sliding properties on soft metals. It is something to do.

[Structure of the Invention] (Measures for Solving the Problem V1) As a result of intensive research to achieve the above object, the present inventors found that the composition described below can achieve the above object, and the present invention This is the completed version. That is, the present invention provides (A) (a) an N,N'-bisimide compound of an unsaturated dicarboxylic acid represented by the general formula (I) (wherein R
+ represents a divalent group having at least 2 carbon atoms, R
2 represents a divalent group containing a double bond between carbon-carbon atoms) (b) Aminophenol represented by the general formula ([1)... (n) (However, in the formula, R3 is a hydrogen atom , )) represents a rogene atom or an alkyl group) (C) Anilines represented by general formula (1)... <
I) reaction product of (R', R' represents a hydrogen atom, halogen atom, alkyl group, -〇CH,, -QC2H5, etc., a group that does not contain active hydrogen) and (d) within one molecule. 30 to 70% by weight of a thermosetting resin whose main component is an epoxy compound having 2 or more E epoxy groups;
B) 30-70% by weight of a composite filler containing (e) 50-83% by weight of 7-carbon resin powder and (f) 5-38% by weight of aromatic polyamide powder. It is a heat-resistant resin composition for molding.

N, N'- of (a) unsaturated dicarboxylic acid which is one of the main components of (A) thermosetting resin used in the present invention
represents a divalent group having at least 2 carbon atoms, R2
each represents a divalent group containing a double bond between carbon-carbon atoms. That is, R1 is a linear or branched alkylene group, a cycloalkylene group having a ring of 5 to 6 carbon atoms, a heterocyclic group containing at least one of oxygen, nitrogen, or sulfur atoms, a benzene group, or a polycarbonate group. Including cyclic aromatic groups, -NHCO--NR'-
Examples include multiple benzene groups and alicyclic groups bonded by -3i R7R8- or -8O7-. However, R', R', and R8 have 1 to 1 carbon atoms.
Indicates 4 alkyl groups, cycloalkyl groups with a ring of 5 to 6 carbon atoms, phenyl groups, etc. Also, as R2, that is, a divalent group containing a double bond between carbon atoms,
Examples include maleic acid residue, citraconic acid residue, and tetrahydrophthalic acid residue. Therefore, the above R
N of an unsaturated dicarboxylic acid satisfying the conditions of 1 and R2,
Specific examples of the N'-bisimide compound include the following, and these can be used alone or in a mixture of two or more. For example, maleic acid NN'-4
, 4'-diphenylmethane bisimide, maleic acid N,
N'-4,4'-diphenyl ether bisimide, maleic acid N, N'-paraphenylene bisimide, maleic acid N, N'-benzidine bisimide, maleic acid N,
N'-methaxylene bismaleimide, malein%N,
N'-1,5-naphthalene bisimide, maleic acid N,
N'-4,4'-diphenylsulfone bisimide, maleic acid N, N'-2,2'-4,4'-dimethylene-cyclohexane-bisimide, maleic acid N, N'
-4,4'-dicyclohexane-methane bisimide, maleic acid N, N'-44'-diphenylcyclohexane bisimide, maleic acid N, N'-4,4'-diphenyl-phenylami-bisimide, maleic acid N,
N'-4,4'-diphenyl-diphenylsilane-bisimide, N maleic acid, N'-44'-diphenylsulfur-bisimide, N maleic acid.

N'-2,2'-(4,4'-diphenyl)propane-
Bisimide, maleic acid N, N'-metaphenylene-bisimide, maleic acid N, N'-3,3'-(N
Examples include N'-metaphenylene-bisbenzamide) bisimide.

As the aminophenol (b) which is a component of the reaction product pond, one having the following general formula is used.

However, in the formula, R3 represents a hydrogen atom, a halogen atom, or an alkyl group, respectively. Specific compounds include the following, and these may be used alone or in a mixture of 2a or more. Examples include 0-aminophenol, aminophenol, p-aminophenol, 2-amino-4-chlorophenol, and 2-amino-4-methylphenol.

As the aniline (C), which is another component of the reaction product, those having the following general formula are used.

However, in the formula, R' and R' are hydrogen atoms, halogen atoms,
Alkyl group, -0CHx, OC2R5, C00CH
, -COOC, H, and other groups that do not contain active hydrogen, specifically aniline, 0-chloroaniline, toluidine, methyl-ρ-aminobenzoic acid ester, etc., in short, nuclear substitution of aniline. Any group that does not contain active hydrogen can be used.

<A) Other main components of the thermosetting resin (d) Epoxy compounds having two or more epoxy groups in one molecule used in the present invention include bisphenol A epoxy resins,
Bisphenol F type epoxy resin, novolac type epoxy resin, polyglycidyl diester resin of polycarboxylic acid, polyglycidyl ether of polyol, urethane-modified epoxy resin, aliphatic or alicyclic polyepoxide obtained by epoxidizing unsaturated compounds, heterocyclic There are engineered boxy resins with polyester resins, epoxy resins with heterocyclic rings, epoxy resins with glycidylated amines, etc., and one or more of these are selected and used.

Next, when obtaining <A> reaction product, (a) N,N'-bisimide compound of unsaturated dicarboxylic acid, <b> amine phenol, (C) blending ratio of anilines and (d
) The blending ratio of the epoxy compound will be explained.

(A) In order to obtain the reaction product, (a) b is added to 1 mole of the N,N'-bisimide compound of the unsaturated dicarboxylic acid.
) amine phenol and (C) aniline [(b)
It is preferable to react 0.1 to 1.0 mol of +(c)1. If the total blending ratio is less than 0.1 mol, the reaction time will be longer and the molecular weight will be lower, resulting in poorer moldability, which is not preferred.

Moreover, if the blending ratio exceeds 1.0, the heat resistance of the resin will deteriorate, which is not preferable. Furthermore, the molar ratio of <C> anilines to (b) aminophenol [(C)/(b)] is 0.
It is preferable that it is 1-9.0.

If this molar ratio is less than 0.1, the aminophenol will be in excess, resulting in poor moisture resistance, which is not preferred.

Moreover, if this molar ratio exceeds 9.0, the wettability of the thermosetting resin with the inorganic filler will be poor, and cracks will occur, which is undesirable.

Dioxane, diglyme, methyl cellosolve, dioxane, diglyme, methyl cellosolve,
The reaction can also be carried out by heating in an inert solvent such as ethyl cellosolve or methyl cellosolve acetate. In the heating reaction under melting, if N,N'-bisimide of unsaturated dicarboxylic acid, aminophenol and anilines are stirred and the temperature is raised, melting can be achieved at around 100°C, and it is possible to melt at around 100°C. If the temperature is maintained, an addition polymerization reaction occurs, and when the desired viscosity is reached, the resin is cooled to room temperature to obtain a solid or viscous liquid resin.

The (A) thermosetting resin can be obtained by blending (d) an epoxy compound with the addition reaction product thus obtained.
The blending ratio of the epoxy compound is preferably 30 to 80% by weight of the addition reactant and 70 to 20% by weight of the epoxy compound. If the addition reaction product is less than 30% by weight, the heat resistance will not be sufficient, and if it exceeds 80% by weight, the heat resistance will be sufficient but the mechanical strength will decrease, which is not preferable.

The combination of the addition reaction product and the epoxy compound does not need to be particularly limited, such as the reaction order, as long as it is within the above range, and no matter how they are mixed, (A) thermosetting provides excellent curability, moldability, and heat resistance. It is possible to obtain a synthetic resin. However, usually, (a) a bisimide compound, (b) an aminophenol, and (C) an aniline are first subjected to an addition reaction to obtain an addition reaction product, and then (d) two or more epoxy groups are present in one molecule. A thermosetting resin (A) is obtained by adding an epoxy compound containing the following.

The composite filler (B) used in the present invention is composed of (e) fluororesin powder, (f) aromatic polyamide powder, etc., and has a particle size of 3.
Preferably, the mesh is 0 or more. Examples of the fluororesin powder (Q) used as the first component include tetrafluoroethylene resin, fluorinated alkoxyethylene resin, fluorinated ethylene propylene ether resin, tetrafluoroethylene hexafluoride propylene copolymer resin, and calcined Teflon. These powders can be used alone or in a mixture of two or more.

Further, as the aromatic polyamide powder (f) used as the second component, for example, Conex (manufactured by Yojinsha, trade name)
can be mentioned. The blending ratio of the fluororesin powder and the aromatic polyamide powder to the filler a is preferably 50 to 83% by weight of the fluororesin powder and 83 to 5% by weight of the aromatic polyamide powder.
If the content is less than 83% by weight or less than 5% by weight of the aromatic polyamide powder, the sliding property will not be affected, and if the content exceeds 83% by weight or 38 doublets 9, the heat resistance will be poor, which is not preferable.

In addition, fillers such as graphite, molybdenum disulfide, and boron nitride, as well as carnauba wax, higher saturated fatty acid esters, stearic acid, zinc stearate, etc., can be added to the composite filler as necessary.

The heat-resistant resin composition for molding of the present invention consists of the above-mentioned thermosetting resin (A) and the composite filler (B), and the blending ratio is 30 to 70% by weight of the thermosetting resin and the composite filler. It consists of 70 to 30% by weight of filler. These blending ratios are not preferable, as if the thermosetting resin is 30% by weight without grooves, workability and moldability are poor, and if it exceeds 70% by weight, a molded product with good mechanical properties and sliding properties cannot be obtained.

The heat-resistant resin composition for molding of the present invention is prepared by mixing a thermosetting resin with a composite filler at room temperature, uniformly dispersing the mixture, heating and kneading it in a mixer, cooling and solidifying it, and grinding it in an appropriate pulverizer. The molded material t1 can be manufactured by crushing it to a size.

This molding material is cured by heating to a temperature of 150 to 250°C, but various additives can be added as necessary to further improve various properties. For example, curability can be improved by adding a known curing catalyst such as an acid anhydride, a boron fluoride complex, a tertiary amine, an imidazole, a quaternary ammonium salt, or a peroxide.

(Function) The heat-resistant resin composition for molding of the present invention is a molding material with good heat resistance, moisture resistance, and mechanical properties by blending and modifying an epoxy resin with a bisimide compound, an amine phenol, and an aniline reactant. This is something that can be obtained. In addition, by using amine phenol and anilines in combination as amino group-containing compounds to be added to the bisimide compound, hygroscopicity due to excess phenolic hydroxyl groups is improved compared to when aminophenol is reacted alone, and it is modified with epoxy resin. By doing so, it is possible to improve the mechanical properties and also improve the heat resistance as a whole.

(Example) Next, the present invention will be specifically explained with reference to Examples.

Examples 1 to 6 N,N'-methylene bismaleimide, aminophenol, anilines, epoxy resin, and 2-ethyl-4-methylimidazole were selected in the weight composition ratio shown in Table 1 and heated. A curable resin was obtained.

A composite filler was added to the obtained thermosetting resin at the weight composition ratio shown in Table 1, and the mixture was uniformly stirred and mixed to produce a heat-resistant molding material.

Comparative Examples 1 to 4 Heat-resistant molding materials were produced in the same manner as in the examples using the composition ratios shown in Table 1.

Book 1: Manufactured by Dow Chemical Company, novolak type epoxy resin, trade name.

Bisphenol A type epoxy resin, product name, manufactured by Nejiel Chemical Co., Ltd.

*3: Manufactured by Mitsui Fluorochemical Co., Ltd., powdered fluororesin, product name.

Ne4: Manufactured by Kitamura Co., Ltd., baked powder fluororesin, trade name.

*5: Manufactured by Yojinsha, aromatic polyamide powder, trade name.

*6: Manufactured by Nippon Graphite Co., Ltd., natural scaly graphite, product name.

*7: Manufactured by Dow Corning, molybdenum disulfide powder, trade name.

The molding materials obtained in Examples 1 to 6 and Comparative Examples 1 to 4 were molded using a pressure molding machine at a temperature of 200 to 220°C.

Pressure 100-300 kp/cI', 1-2 minutes/
Pressure molding under the conditions of
After curing treatment for 15 hours, molded articles for various tests were obtained. Mechanical properties, sliding properties, water absorption, etc. were measured using these, and the results are shown in Table 2. Mechanical properties and water absorption were tested according to JIS-6911. Regarding the sliding properties, a thrust type friction abrasion testing machine was used, and the measurement conditions were 2ca' (outer diameter 25.6φ, inner diameter 20mm).
．． Aluminum (A5052-BD) metal with a sliding area of 0φ cylindrical 3S finish), no lubrication, sliding speed 111/sec, pressurized load 10-50 kg/cn'
(10kg/cumulative load after 10 minutes of operation at c112)
Dynamic friction coefficient and sliding speed of 0.3 cl/
The amount of friction and wear after continuous operation for 24 hours under the condition of pressurized load of 10 kg/cm2 was measured. The present invention showed excellent AM properties and sliding properties, and the effects of the present invention could be confirmed.

*1: Because the coefficient of dynamic friction is extremely large, a! The temperature rise due to friction heat was significant, and the sliding surface had noticeable seizure after measurement.
Amount of wear is large.

*2: The sample was damaged during measurement due to poor mechanical strength.

*3: Operation was stopped midway due to seizure of the M moving surface.

Ne4: The coefficient of dynamic friction is large, highly variable and unstable.

[Effects of the Invention] As is clear from the above explanation and the results shown in Table 2, the high-quality resin composition for molding of the present invention has excellent high-quality resin compositions for molding, excellent high-performance properties, excellent temperature resistance, and mechanical properties, and is suitable for soft metals, etc. It has good sliding properties against other metals, has a small amount of wear, and does not cause cracks in molded products, making it highly reliable.

Claims (1)

[Claims] 1(A) (a) N,N'-bisimide compound of unsaturated dicarboxylic acid represented by the general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are included ▼...(I) ( However, in the formula, R^1 represents a divalent group having at least two carbon atoms and R^2 represents a divalent group containing a double bond between carbon-carbon atoms. Aminophenol represented by (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... (II) (However, in the formula, R^3 represents a hydrogen atom, a halogen atom, or an alkyl group) (c) General formula ( III) Anilines represented by ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(III) (However, R^4 and R^5 are hydrogen atoms, halogen atoms, alkyl groups, -OCH_3, -OC_2H_5, etc.) 30 to 70% by weight of a thermosetting resin whose main components are (d) an epoxy compound having two or more epoxy groups in one molecule; B) (e) 50-83% by weight of fluororesin powder and (f)
A heat-resistant resin composition for molding, comprising 30 to 70% by weight of a composite filler containing 5 to 83% by weight of aromatic polyamide powder.