Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
  • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
  • C08L81/02—Polythioethers; Polythioether-ethers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
  • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
  • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols

Definitions

• the present invention relates to a resin composition which has excellent mechanical properties, such as tensile strength and flexural modulus and is suitable for use in sliding molded parts, specifically to a resin composition obtained by adding a thermoplastic phenolic resin and all-aromatic polyamide particles or fibers to a thermoplastic resin matrix.
• thermoplastic resins such as polyamides
• thermoset resins such as phenolic resins
• aromatic polyamide particles are disclosed in International Laid Open WO 093/04300, Japanese Patent Laid Open H 2-163163, Japanese Patent Laid Open H 2-185563, and so on.
• Japanese Patent Laid Open H 4-283262 proposes incorporating, in a matrix resin, surface-modified aromatic polyamide particles obtained by the graft-wise addition of organics to the surface of the aromatic polyamide particles.
• aromatic polyamide particles Although the addition of aromatic polyamide particles to these thermoplastic resins improves the sliding properties of the molded articles therefrom, mechanical properties, such as tensile strength and flexural modulus, are disadvantageously reduced.
• Surface modified aromatic polyamide particles may suppress the reduction in mechanical properties to some extent, but the work of surface modifying aromatic polyamide particles itself is cumbersome, making this approach not necessarily a highly productive method.
• the present invention aims to provide a resin composition which has excellent mechanical properties such as tensile strength and flexural modulus and friction characteristics, and is suitable to be molded into sliding parts.
• the present inventors discovered that the decrease in mechanical properties affected by the addition of aromatic polyamide particles is related to the quality of the adhesion between the aromatic polyamide particles and the matrix resin, and found that the adhesion may be improved by adding a thermoplastic phenolic resin, which has led to the completion of this invention.
• the present invention is a resin composition comprising
• thermoplastic phenolic resin in this invention is a polycondensate of a phenolic compound and formaldehyde, preferably an oligomer or polymer obtained by polycondensing in the presence of an acid catalyst.
• Phenolic compounds include phenol, alkyl phenols, such as cresol, butylphenol, octylphenol, naphthol, resorcinol, hydroquinone, hydroxybenzoic acid, and the like.
• a polyvinylphenol which is a polymer of p-vinylphenol can also be suitably used.
• thermoplastic phenolic resin used should have a number average molecular weight, in general, of up to 150,000, preferably 200-10,000. Too small an amount of addition of a thermoplastic phenolic resin will fail to improve the adhesion between the all-aromatic polyamide particles or fibers and the matrix resin, which is not preferred, nor is the use of too large an amount which considerably decreases the elongation of the molded articles therefrom.
• the suitable amount of addition of the thermoplastic phenolic resin is 0.1-30.0% by weight based on the total resin weight.
• the matrix resin in this invention is a thermoplastic resin which is compatible or semi-compatible with the phenolic resin.
• Whether it is compatible or semi-compatible is judged by the clarity of the melt obtained by melt mixing the matrix resin with the phenolic resin, the shift in the glass transition temperature (Tg) or melt temperature (Mp) according to a differential scanning calorimetric measurement (DSC), the change in the peak temperature position of the dissipation factor (tan delta) by dynamic viscoelastic measurement (DMA), and the like.
• Tg glass transition temperature
• Mp melt temperature
• DSC differential scanning calorimetric measurement
• DMA dynamic viscoelastic measurement
• the matrix resin and the thermoplastic phenolic resin are judged to be compatible or semi-compatible if the mix melt is clear or semi-clear, or if there is a shift in the glass transition temperature (Tg) or the melt temperature (Mp) peak of a mixture of the matrix resin with the thermoplastic phenolic resin by DSC, from that of the DSC data of the matrix resin alone, or if there is change in the dissipation factor (tan delta) peak temperature as measured by DMA of a mixture compared to the matrix resin alone.
• Tg glass transition temperature
• Mp melt temperature
• thermoplastic resins include thermoplastic resins having functional groups, such as esters, nitriles, amides, ketones, ethers, sulfides, sulfones, carbonates, urethanes, and the like, such as styrene acrylonitrile copolymer resin (SAN), methyl methacrylate resin (PMMA), polycaprolactone resin (PCL), styrene-maleic anhydride copolymer resin (S/MANH), imidated methyl methacrylate resin (EVIM-MMA), polycarbonate resin (PC), polyarylate resin (PAR), polysulfone resin, polyphenyleneoxide (PPO), semi-aromatic polyamide resin (6T/6I), polyamide resins (nylon 6, nylon 612), polyethylene terephthalate resin (PET), polybutylene terephthalate resin (PBT), liquid crystalline polymer resin (LCP), polyphenylene sulfide resin (PPS), polyacetal resin (PO
• the amount of the matrix resin added is 99.8-30.0% by weight based on the total resin weight.
• the all-aromatic polyamides in this invention are polymers essentially comprising the following repeating units:
• para-all- aromatic polyamides specifically para-aromatic polycarbon amides in which ARi and AR 2 are the same or different divalent para-oriented aromatic groups.
• the para-oriented aromatic groups include substituted or unsubstituted aromatic groups including 1,4-phenylene, 4,4'-biphenylene, 2,6-naphthalene, 1,5-naphthalene. Suitable substituents are, for example, chloro, lower alkyl, and methoxy groups.
• Para-oriented all-aromatic polyamides include para-oriented copolymers from two or more para-oriented monomers containing a small amount of a comonomer of the same aromatic in which both an acid and amine functional group are present together.
• All aromatic polyamides preferably used in this invention are obtained by polymerizing an aromatic amine at least 80 mole % of which is paraphenylene diamine and an aromatic dicarboxylic halide, at least 80 mole % of which is a terephthaloyl halide in an amide solvent, preferably at temperatures not higher than 60°C.
• the preferred amide solvents include N-methyl pyrrolidone, dimethylacetamide, tetramethylurea containing an alkali metal halide.
• the most suitable all-aromatic polyamide in this invention is a poly-p-phenylene terephthalamide.
• All aromatic polyamide fibers which are used in this invention have diameters of not more than 30 microns or particles having a particle size of not more than 500 microns.
• all-aromatic polyamide particles are used, where too large a particle size will give molded articles with reduced mechanical properties which cannot be prevented even by adding a thermoplastic phenolic resin.
• the preferred all-aromatic polyamide particles have a 1-50 micron particle size. It is not preferred to add too small an amount of the all-aromatic polyamide particles or fibers because no expected improvement on sliding properties is obtained, while using too large an amount will decrease the mechanical properties.
• the preferred amount of addition of all-aromatic polyamide particles or fibers are 0.1-40% by weight based on the total resin.
• the resin composition of this invention may, in addition to the above components, be compounded with a variety of additives which are normally added, such as a stabilizer, a nucleating agent, an antistatic agent, a flame retardant, a colorant, a lubricant, and the like. It is also permissible to add a filler, such as glass fiber, inorganic powder, talc, or the like. Methods known in the art can be used for manufacturing the resin composition of this invention.
• kneading each component in a molder such as an extruder
• a method of mechanically kneading using a kneader or the like
• a method of mixing each component in a suitable good solvent at the same time or dissolving each component individually, followed by mixing and removing the solvent or a combination of two or more of these methods, and the like.
• thermoplastic phenolic resin is compatible or semi-compatible and improves the adhesion of the matrix resin to all-aromatic polyamide particles or fibers which are added to impart sliding properties to the matrix resin. Therefore, the addition of a thermoplastic phenolic resin, along with the all-aromatic polyamide particles or fibers into the matrix resin will uniformly disperse the all-aromatic polyamide particles or fibers in the matrix resin, thereby improving the mechanical properties of the molded articles without reducing sliding properties.
• Example 1 Compatibilitv of Thermoplastic Phenolic Resins and Matrix Resins
• the compatibility or semi-compatibility of each matrix resin with a Novolak resin was judged by observing the clarity of a melt mixture of the Novolak resin with each matrix resin, or measuring any shift in the glass transition temperature (Tg) or melt temperature (Mp) on DSC, or a change in the temperature position of the peak temperature position of the dissipating factor (tan delta) on DMA.
• Table 1 shows thermoplastic resins which are compatible or semi-compatible with the thermoplastic phenolic resin.
• Tg, MP, and tan delta represent mixtures of thermoplastic resin itself/Novolak.
• the first number is for the resin itself and the second number after the/ is the Novolak mixture.
• Example 2 Measurement of Mechanical Properties Each component was melt kneaded using a twin screw extruder
• Tables 2-4 show the compositions of pellets produced and the results of measurement of the mechanical properties.
• Example 1 Example 2 Example 3 Example 4
• Example 5 Example 6 Example 1 Example 2
• PBT Polybutylene terephthalate
• KEVLAR All-aromatic polyamide particles
• the tensile strength and flexural modulus are shown to be improved in all the examples of this invention. It is also noted that increasing the Kevlar content from Examples 4 and 6 reduces the tensile strength, but improves the flexural modulus.
• Novolak Resin 1.5 3.0 Kevlar (40 micrometers) 15.0 15.0 10.0
• PPS Polyphenylene sulfide
• Kevlar (40 micrometers) 10.0 10.0 - -
• Kevlar 120 micrometers
• Kevlar (200 micrometers) ⁇ ⁇ 10.0
• Kevlar (40 micrometers) - 10.0 - -
• Kevlar 120 micrometers
• Kevlar (200 micrometers) " _. 10.0
• the tensile strength and flexural modulus are also improved when nylon 66 is used as the matrix resin, as in the cases where PBT and PPS were used.
• Examples 13 and 15 show that the smaller the Kevlar particle size, the more significant the improvement in tensile strength and the less reduction in elongation and impact strength.
• the present invention which comprises adding all-aromatic polyamide particles or fibers along with a thermoplastic phenolic resin into a matrix resin improves mechanical properties without adversely affecting the sliding properties of the molded articles therefrom.

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• Chemical & Material Sciences (AREA)
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• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Materials Engineering (AREA)
• Compositions Of Macromolecular Compounds (AREA)
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Citations (8)

• 1995
  • 1995-05-12 JP JP11450995A patent/JP3665383B2/ja not_active Expired - Fee Related
• 1996
  • 1996-05-13 WO PCT/US1996/006825 patent/WO1996035742A1/en active Application Filing

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