WO2010018681A1 - 樹脂組成物 - Google Patents
樹脂組成物 Download PDFInfo
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- WO2010018681A1 WO2010018681A1 PCT/JP2009/003834 JP2009003834W WO2010018681A1 WO 2010018681 A1 WO2010018681 A1 WO 2010018681A1 JP 2009003834 W JP2009003834 W JP 2009003834W WO 2010018681 A1 WO2010018681 A1 WO 2010018681A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/343—Polycarboxylic acids having at least three carboxylic acid groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/14—Polyamide-imides
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- 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
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- 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
- C08L81/04—Polysulfides
Definitions
- the present invention relates to a novel resin composition containing an aromatic polyamideimide resin and a polyarylene sulfide resin which are excellent in sliding properties, mechanical strength, toughness, and fluidity at the time of melting.
- Aromatic polyamide-imide resin (hereinafter abbreviated as “PAI resin”) is a plastic material having excellent heat resistance, mechanical strength, electrical properties, chemical resistance, and self-lubricating properties.
- PAI resins are inferior in melt fluidity, most PAI resins are often difficult to injection mold. Therefore, when molding a PAI resin, the PAI resin is molded by a compression molding method, or a precursor of the PAI resin is injection molded, and then a long-term post-cure reaction is performed on the injection molded body. The present condition is using a thing as a molded object.
- a polyarylene sulfide resin represented by a polyphenylene sulfide resin (hereinafter abbreviated as “PPS resin”) is excellent in heat resistance, electrical characteristics, and solvent resistance. In particular, it is characterized by excellent melt fluidity. Further, it is known that a PAS resin is imparted with excellent mechanical strength, rigidity and dimensional stability by reinforcing the PAS resin using a filler or the like. However, since the PAS resin has a relatively low glass transition temperature, its use is limited in applications where excellent slidability is required at a high temperature of 100 ° C. or higher.
- Patent Document 1 In order to improve the disadvantages of these PAI resins and PAS resins, in Patent Document 1 below, by combining the PAI resin and PAS resin synthesized by reducing the water content in the reaction system during synthesis, heat resistance, It has been proposed to obtain a resin composition having excellent mechanical strength and fluidity.
- a PAI resin synthesized with a water content of 20 to 30 ppm in the reaction system is used.
- an object of the present invention is to provide a resin composition having good fluidity upon melting, sliding properties, toughness, and mechanical strength, a method for producing the same, and a molded body.
- this invention relates to the manufacturing method of the resin composition shown below, the molded object which consists of this composition, and a resin composition.
- An aromatic polyamideimide resin obtained by reacting an aromatic tricarboxylic acid anhydride and diisocyanate in a reaction system with a water content of 100 to 5000 ppm, which is N, N-dimethylacetamide at 30 ° C.
- a resin composition comprising an aromatic polyamideimide resin (A) having a reduced viscosity of 0.15 to 0.40 dl / g and a polyarylene sulfide resin (B).
- a method for producing a resin composition comprising an aromatic polyamideimide resin (A) and a polyarylene sulfide resin (B), wherein the aromatic polyamideimide resin (A) is treated with an aromatic tricarboxylic acid anhydride.
- the water content in the reaction system is 100 to 5000 ppm
- the reduced viscosity in N, N-dimethylacetamide at 30 ° C. is 0.15 to 0.40 dl / g.
- the blending ratio of the aromatic polyamideimide resin (A) is 5 to 60% by weight;
- the resin composition of the present invention has excellent fluidity at melting, sliding properties, toughness, and mechanical strength, and can be molded for various uses.
- the PAI resin as the component (A) is represented by the following general formula.
- Ar 1 is a bivalent aromatic group having 6 to 18 carbon atoms, a divalent alicyclic hydrocarbon group having 5 to 14 carbon atoms
- Ar 2 is a trivalent aromatic group having 6 to 18 carbon atoms
- n Represents an integer of 4 to 400
- Ar 1 include the following, but a mixture of two or more types can also be used.
- Ar 2 include the following, but a mixture of two or more types can also be used.
- the polymerization reaction of the PAI resin in the present invention is an isocyanate method in which an aromatic tricarboxylic acid anhydride and an aromatic diisocyanate are polymerized (for example, Japanese Patent Publication No. 44-19274).
- the PAI resin obtained by the above method is preferable because it has a high rate of imide ring formation in the molecule and is excellent in sliding properties, toughness, and mechanical strength after being combined with the PAS resin.
- N-alkylpyrrolidone such as N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), acetonitrile, tetrahydrofuran, diglyme, cyclohexanone, Aprotic polar solvents such as 1,4-dioxane are preferred because high molecular weight polymers are easily obtained.
- NMP NMP
- DMF N-dimethylformamide
- DMAC N-dimethylacetamide
- acetonitrile tetrahydrofuran
- diglyme diglyme
- cyclohexanone cyclohexanone
- Aprotic polar solvents such as 1,4-dioxane are preferred because high molecular weight polymers are easily obtained.
- Particularly preferred solvents are NMP, DMF and DMAC. These solvents may be used alone or in combination of two or more.
- a nonpolar solvent that is compatible with the aprotic polar solvent may be mixed and used.
- aromatic hydrocarbons such as toluene, xylene and solvent naphtha can be used.
- the ratio of the nonpolar solvent in the mixed solvent is preferably 30% by weight or less.
- the water content in the system during polymerization of the PAI resin is 100 to 5000 ppm, preferably 500 to 5000 ppm, and most preferably 600 to 3000 ppm.
- the reduced viscosity of the PAI resin of the present invention is a value measured when the concentration of the PAI resin is 1 g / dl in DMAC at 30 ° C., and is 0.15 to 0.40 dl / g, preferably 0.17. To 0.40 dl / g, particularly preferably 0.20 to 0.40 dl / g, most preferably 0.25 to 0.40 dl / g.
- the PAS resin as the component (B) used in the resin composition of the present invention is an arylene represented by the formula [—Ar—S—] (where —Ar— is an arylene group). It is an aromatic polymer whose main constituent is a sulfide repeating unit.
- the PAS resin can contain other structural units as necessary.
- the PAS resin used in the present invention is a polymer containing the above repeating unit in an amount of usually 50 mol% or more, preferably 70 mol% or more, more preferably 90 mol% or more.
- arylene group examples include a p-phenylene group, an m-phenylene group, a substituted phenylene group (the substituent is preferably an alkyl group having 1 to 6 carbon atoms, or a phenyl group), p, p′-di Examples thereof include a phenylene sulfone group, p, p′-biphenylene group, p, p′-diphenylenecarbonyl group, and naphthylene group.
- PAS resin a homopolymer having mainly the same arylene group can be preferably used, but a copolymer containing two or more arylene groups can also be used from the viewpoint of processability and heat resistance.
- a PPS resin having a repeating unit of p-phenylene sulfide as a main constituent element is particularly preferable because of excellent processability and industrial availability.
- polyarylene ketone sulfide, polyarylene ketone ketone sulfide, and the like can be used.
- the copolymer examples include a random or block copolymer having a repeating unit of p-phenylene sulfide and a repeating unit of m-phenylene sulfide, a random or block copolymer having a repeating unit of phenylene sulfide and a repeating unit of arylene ketone sulfide, and phenylene sulfide. And a random or block copolymer having a repeating unit of arylene ketone ketone sulfide and a random or block copolymer having a repeating unit of phenylene sulfide and a repeating unit of arylene sulfone sulfide.
- PAS resins are preferably crystalline polymers.
- the PAS resin is preferably a linear polymer from the viewpoint of toughness and strength.
- Such a PAS resin can be obtained by a known method (for example, Japanese Patent Publication No. 63-33775) in which an alkali metal sulfide and a dihalogen-substituted aromatic compound are subjected to a polymerization reaction in a polar solvent.
- alkali metal sulfide examples include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, and cesium sulfide.
- Sodium sulfide produced by reacting NaSH and NaOH in the reaction system can also be used.
- dihalogen-substituted aromatic compound examples include p-dichlorobenzene, m-dichlorobenzene, 2,5-dichlorotoluene, p-dibromobenzene, 2,6-dichloronaphthalene, 1-methoxy2,5-dichlorobenzene, 4 , 4'-dichlorobiphenyl, 3,5-dichlorobenzoic acid, p, p'-dichlorodiphenyl ether, 4,4'-dichlorodiphenyl sulfone, 4,4'-dichlorodiphenyl sulfoxide, 4,4'-dichlorodiphenyl ketone, etc. Can be mentioned. These can be used alone or in combination of two or more.
- a small amount of a polyhalogen-substituted aromatic compound having 3 or more halogen substituents per molecule can be used in combination.
- Preferred examples of the polyhalogen-substituted aromatic compound include 1,2,3-trichlorobenzene, 1,2,3-tribromobenzene, 1,2,4-trichlorobenzene, 1,2,4-tribromobenzene, Mention may be made of trihalogen-substituted aromatic compounds such as 1,3,5-trichlorobenzene, 1,3,5-tribromobenzene, 1,3-dichloro-5-bromobenzene, and alkyl-substituted products thereof.
- 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene, and 1,2,3-trichlorobenzene are more preferable from the viewpoints of economy, reactivity, and physical properties.
- a polymerization solvent is used for the purpose of allowing the polymerization reaction to proceed stably.
- a polymerization solvent N-alkylpyrrolidone such as N-methyl-2-pyrrolidone, aprotic organic amide solvent represented by 1,3-dialkyl-2-imidazolidinone, tetraalkylurea, hexaalkylphosphoric triamide and the like
- N-alkylpyrrolidone such as N-methyl-2-pyrrolidone
- aprotic organic amide solvent represented by 1,3-dialkyl-2-imidazolidinone, tetraalkylurea, hexaalkylphosphoric triamide and the like
- One or more of these solvents can be used.
- the PAS resin used in the present invention has a melt viscosity of usually 10 to 600 Pa ⁇ s measured at a temperature of 310 ° C. and a shear rate of 1200 / sec, and has more sufficient physical properties such as mechanical strength and toughness, and more sufficiently. From the viewpoint of ensuring a good melt fluidity, it is preferably 50 to 550 Pa ⁇ s, more preferably 70 to 550 Pa ⁇ s. When two or more kinds of PAS resins having different melt viscosities are blended and used, it is preferable that the melt viscosity of the blend is in the above range. Further, it is particularly desirable that the PAS resin has a melt viscosity of 100 Pa ⁇ s or more from the viewpoint of mechanical strength, toughness, and the like.
- the PAS resin used in the present invention can be washed after the completion of polymerization, and is further treated with an aqueous solution containing an acid such as hydrochloric acid or acetic acid, or a water-organic solvent mixed solution, It is preferable to use one that has been treated with an aqueous ammonium salt solution such as ammonium.
- an aqueous ammonium salt solution such as ammonium.
- the PAS resin used in the present invention is preferably a granular material having an average particle diameter of 100 ⁇ m or more. If the average particle size of the PAS resin is too small, the feed amount is limited during melt extrusion by the extruder, so the residence time of the resin composition in the extruder becomes long, and problems such as deterioration of the resin composition occur. May occur. Further, it is not desirable in terms of manufacturing efficiency.
- the blending ratio of the PAI resin and the PAS resin in the resin composition of the present invention is usually as follows when the total of the PAI resin and the PAS resin is 100% by weight with respect to the total of the PAI resin and the PAS resin. It becomes. That is, the blending ratio of the PAI resin is 5 to 60% by weight, and the blending ratio of the PAS resin is 95 to 40% by weight.
- the blending ratio of the PAI resin is preferably 10% by weight or more, more preferably 15% by weight or more, further preferably 20% by weight or more, and most preferably 30% by weight or more.
- the blending ratio of the PAI resin is preferably 55% by weight or less, more preferably 50% by weight or less.
- the blending ratio of the PAI resin is more than 60% by weight, melt kneading is difficult, and when it is less than 5% by weight, the heat resistance and sliding characteristics tend to be less improved.
- slidability can be improved more as compared with the case where the compounding ratio of a PAI resin is 20 weight% or more compared with less than 20 weight%.
- the resin composition used in the present invention is produced by melt-kneading PAI resin and PAS resin.
- the melt kneading temperature is 250 to 400 ° C, preferably 280 to 360 ° C.
- the kneading method can be performed with an extruder, a kneader, a Banbury mixer, a mixing roll, or the like, but a preferable method is a method using a twin screw extruder.
- a filler In the resin composition used in the present invention, a filler, a pigment, a lubricant, a plasticizer, a stabilizer, an ultraviolet ray agent, a flame retardant, an additive for a flame retardant aid, other resins, etc. are appropriately used as desired. You may mix.
- fillers examples include glass beads, wollastonite, mica, talc, kaolin, silicon dioxide, clay, asbestos, calcium carbonate, magnesium hydroxide, silica, diatomaceous earth, graphite, carborundum, and molybdenum disulfide.
- Mineral fillers such as glass fiber, milled fiber, carbon fiber, potassium titanate fiber, boron fiber, silicon carbide fiber, and the like.
- the filler can be blended in an amount of 1 to 70% by weight of the resin composition.
- Preferred fillers are glass fiber, milled fiber, carbon fiber, and potassium titanate fiber, and those treated with a silane coupling agent such as urethane or amino can also be suitably used.
- Examples of the pigment include carbon black, titanium oxide, zinc sulfide, and zinc oxide.
- lubricant examples include mineral oil, silicon oil, ethylene wax, polypropylene wax, montanic acid amide, or metal salts such as sodium stearate and sodium montanate.
- plasticizer examples include commonly used silane compounds and phthalic acid compounds such as dimethyl phthalate and dioctyl phthalate.
- phthalic acid compounds such as dimethyl phthalate and dioctyl phthalate.
- ultraviolet absorbers, colorants, and the like can be used.
- Flame retardants include phosphoric esters such as triphenyl phosphate, brominated compounds such as decabromobiphenyl, pentabromotoluene, brominated epoxy resins, nitrogen-containing phosphorus compounds such as melamine derivatives, magnesium hydroxide, Metal hydroxides such as aluminum hydroxide. Flame retardant aids may be used, examples of which include compounds such as antimony, boron and zinc.
- polyesters such as epoxy resin, phenoxy resin, polyethylene terephthalate, polybutylene terephthalate, fluororesins such as tetrafluoroethylene, polyphenylene ether, polysulfone, polycarbonate, polyether ketone, polyether Aromatic resins such as imide, polythioetherketone, and polyetheretherketone are listed.
- the molded body of the resin composition of the present invention has a plate shape, a rod shape, a spherical shape, a sheet shape, a film shape, a hollow shape, a gas fine dispersion shape, a foam shape, a fiber shape, a pellet shape, etc.
- a molding method of these molded bodies it is possible to mold by a known method such as injection molding, sheet molding, blow molding, injection blow molding, inflation molding, press molding, extrusion molding, foam molding, film molding and the like. Secondary processing molding methods such as pressure forming and vacuum forming can also be used.
- the resin composition of the present invention has good fluidity at the time of melting, sliding properties, toughness, and mechanical strength, and is particularly useful for applications such as slide bearings, rolling bearings, gears, and cams.
- Example 1 50 parts by weight of PAI resin produced in Synthesis Example 1 and 50 parts by weight of PAS resin (trade name DIC-PPS-LR300G, manufactured by Dainippon Ink & Chemicals, Inc.) were blended, and this resin composition was biaxially extruded.
- the mixture was melt kneaded at 320 ° C. using a machine to produce pellets (resin composition).
- This pellet was injection molded at a cylinder temperature of 340 ° C. and a mold temperature of 140 ° C. using an injection molding machine (IS-100F3 manufactured by Toshiba Machine Co., Ltd.), and a ring having an outer diameter of 26 mm ⁇ inner diameter of 20 mm ⁇ height of 15 mm.
- a test specimen was obtained.
- the amount of sliding wear was measured.
- the sliding wear amount was measured using a friction wear tester (Suzuki type friction wear tester EFM-III-EN manufactured by Orientec Co., Ltd.), a test temperature of 100 ° C., a test speed of 1000 mm / sec, and a counterpart material SUS304.
- the test time was 24 hours and the test load was 10 kgf.
- the results are shown in Table 1. Further, the pellet was injection molded to obtain a JIS dumbbell test piece. And about this dumbbell test piece, the tensile strength and the tensile elongation were measured.
- Tensile strength and tensile elongation are measured using a tensile tester (Autograph AG-5000B manufactured by Shimadzu Corporation) under the conditions of a measurement temperature of 23 ° C., a test speed of 20 mm / min, and a distance between gripping jigs of 100 mm. It was. The results are shown in Table 1.
- the tensile strength is a parameter for evaluating the mechanical strength of the resin composition
- the tensile elongation is a parameter for evaluating the toughness of the resin composition.
- the fluidity at the time of melting was measured using the pellets obtained as described above.
- the melt fluidity is measured using a melt fluidity measuring device (Capillograph 1B, manufactured by Toyo Seiki Seisakusho Co., Ltd.) under the conditions of a capillary length of 10 mm, a capillary diameter of 1.0 mm, a shear rate of 1000 sec ⁇ 1 , and a test temperature of 320 ° C. Went under.
- a melt fluidity measuring device Capillograph 1B, manufactured by Toyo Seiki Seisakusho Co., Ltd.
- Example 2 A resin composition was produced in the same manner as in Example 1 except that the PAI of Synthesis Example 2 was used as the PAI, and the sliding wear amount, tensile strength, tensile elongation, and fluidity during melting were evaluated. The results are shown in Table 1.
- Example 3 A resin composition was produced in the same manner as in Example 1 except that the PAI of Synthesis Example 3 was used as the PAI, and the sliding wear amount, tensile strength, tensile elongation, and fluidity at the time of melting were evaluated. The results are shown in Table 1.
- Example 4 A resin composition was produced in the same manner as in Example 1 except that the blending ratios of PAI and PAS were as shown in Table 1, and the sliding wear amount, tensile strength, tensile elongation, and fluidity during melting were evaluated. . The results are shown in Table 1.
- Example 5 A resin composition was produced in the same manner as in Example 2 except that the blending ratios of PAI and PAS were as shown in Table 1, and the sliding wear amount, tensile strength, tensile elongation, and fluidity during melting were evaluated. . The results are shown in Table 1.
- Example 6 A resin composition was produced in the same manner as in Example 3 except that the blending ratios of PAI and PAS were as shown in Table 1, respectively, and the sliding wear amount, tensile strength, tensile elongation, and melting time were The fluidity was evaluated. The results are shown in Table 1.
- Example 3 A resin composition was produced in the same manner as in Example 1 except that the PAI of Synthesis Example 7 was used as the PAI, and the sliding wear amount, tensile strength, tensile elongation, and fluidity during melting were evaluated. The results are shown in Table 1.
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Abstract
Description
本発明の目的は、上記した欠点を鑑み、良好な溶融時流動性、摺動特性、靭性、機械的強度を有する樹脂組成物、その製造方法及び成形体を提供するものである。
(1)芳香族トリカルボン酸無水物とジイソシアネートを重合させる反応において、反応系中の水分含有量を100~5000ppmとして得られた芳香族ポリアミドイミド樹脂であって、30℃におけるN,N―ジメチルアセトアミド中での還元粘度が0.15~0.40dl/gである芳香族ポリアミドイミド樹脂(A)と、ポリアリーレンスルフィド樹脂(B)とを含有する樹脂組成物。
(2)芳香族ポリアミドイミド樹脂(A)及びポリアリーレンスルフィド樹脂(B)の合計を100重量%とした場合に、芳香族ポリアミドイミド樹脂(A)の配合率が5~60重量%であり、ポリアリーレンスルフィド樹脂(B)の配合率が95~40重量%である(1)に記載の樹脂組成物。
(3)反応系中の水分含有量が500~5000ppmである(1)又は(2)に記載の樹脂組成物。
(4)芳香族ポリアミドイミド樹脂(A)の還元粘度が0.25~0.40dl/gである(1)~(3)のいずれかに記載の樹脂組成物。
(5)上記(1)~(4)のいずれかに記載の樹脂組成物からなる成形体。
(6)芳香族ポリアミドイミド樹脂(A)と、ポリアリーレンスルフィド樹脂(B)とを含有する樹脂組成物の製造方法であって、前記芳香族ポリアミドイミド樹脂(A)を、芳香族トリカルボン酸無水物とジイソシアネートを重合させる反応において、反応系中の水分含有量を100~5000ppmとし、30℃におけるN,N―ジメチルアセトアミド中での還元粘度が0.15~0.40dl/gとなるように製造する樹脂組成物の製造方法。
(7)芳香族ポリアミドイミド樹脂(A)及びポリアリーレンスルフィド樹脂(B)の合計を100重量%とした場合に、芳香族ポリアミドイミド樹脂(A)の配合率が5~60重量%、ポリアリーレンスルフィド樹脂(B)の配合率が95~40重量%となるように樹脂組成物を製造する(6)に記載の樹脂組成物の製造方法。
(8)芳香族トリカルボン酸無水物とジイソシアネートを重合させる反応において、反応系中の水分含有量を500~5000ppmとする(6)又は(7)に記載の樹脂組成物の製造方法。
(Ar1は炭素数6~18の2価の芳香族基、炭素数5~14の2価の脂環式炭化水素基、Ar2は炭素数6~18の3価の芳香族基、nは4~400の整数を表す)
なお、PAI樹脂の配合率は好ましくは10重量%以上、より好ましくは15重量%以上、さらに好ましくは20重量%以上、最も好ましくは30重量%以上である。またPAI樹脂の配合率は好ましくは55重量%以下、より好ましくは50重量%以下である。
PAI樹脂の配合率が60重量%より多いと溶融混練が難しく、5重量%より少ないと耐熱性、摺動特性の向上が少ない傾向がある。なお、PAI樹脂の配合率が20重量%以上であると、20重量%未満である場合に比べて摺動性をより向上させることができる。
水分含有量15ppmのN-メチルピロリドン3000gを、5リットルの攪拌機、温度計、先端に塩化カルシウムを充填した乾燥管を装着した還流冷却器を備えた反応器に仕込んだ。ここに無水トリメリット酸555g(50モル%)、次いで2,4-トリレンジイソシアネート503g(50モル%)、さらに純水2.955gを加えた。そして、カールフィッシャー水分計を使用し、系内水分含有量を測定したところ、純水添加後の系内水分含有量は1000ppmであった。最初、室温から30分を要して内容物温度を120℃とし、この温度に保ったまま8時間重合反応を継続した。重合反応終了後N-メチルピロリドンの2倍容量のメタノール中に強力な攪拌下で重合液を滴下し、ポリマーを析出させた。析出したポリマーを吸引ろ別し、さらにメタノールでよく洗浄し、200℃で減圧乾燥を行い、PAI樹脂を得た。このPAI樹脂について、30℃のN,N-ジメチルアセトアミド溶媒中でPAI樹脂の濃度を1g/dlとし、還元粘度を測定したところ、還元粘度は0.35dl/gであった。
純水0.555gを加え純水添加後の系内水分含有量を200ppmとしたこと以外は、合成例1と同様にしてPAI樹脂を得た。このPAI樹脂について、合成例1と同様にして還元粘度を測定したところ、還元粘度は0.32dl/gであった。
純水14.955gを加え純水添加後の系内水分含有量を5000ppmとしたこと以外は、合成例1と同様にしてPAI樹脂を得た。このPAI樹脂について、合成例1と同様にして還元粘度を測定したところ、還元粘度は0.38dl/gであった。
純水0.105gを加え純水添加後の系内水分含有量を50ppmとしたこと以外は、合成例1と同様にしてPAI樹脂を得た。このPAI樹脂について、合成例1と同様にして還元粘度を測定したところ、還元粘度は0.24dl/gであった。
純水23.955gを加え純水添加後の系内水分含有量を8000ppmとしたこと以外は、合成例1と同様にしてPAI樹脂を得た。このPAI樹脂について、合成例1と同様にして還元粘度を測定したところ、還元粘度は0.45dl/gであった。
内容物の温度を120℃に保持したまま重合反応を継続した時間を2時間としたこと以外は、合成例1と同様にしてPAI樹脂を得た。このPAI樹脂について、合成例1と同様にして還元粘度を測定したところ、還元粘度は0.13dl/gであった。
内容物の温度を120℃に保持したまま重合反応を継続した時間を24時間としたこと以外は、合成例1と同様にしてPAI樹脂を得た。このPAI樹脂について、合成例1と同様にして還元粘度を測定したところ、還元粘度は0.50dl/gであった。
合成例1で製造したPAI樹脂50重量部とPAS樹脂(大日本インキ化学工業(株)製、商品名DIC-PPS-LR300G)50重量部とをブレンドし、この樹脂組成物を、2軸押出機を用いて320℃で溶融混錬し、ペレット(樹脂組成物)を製造した。
このペレットを、射出成形機(東芝機械(株)製IS-100F3)を使用して、シリンダ温度340℃、金型温度140℃で射出成形し、外径26mm×内径20mm×高さ15mmのリング状試験片を得た。
このリング状試験片を用いて摺動摩耗量の測定を行った。摺動摩耗量の測定は、摩擦摩耗試験機((株)オリエンテック製 鈴木式摩擦摩耗試験機 EFM-III-EN)を使用して、試験温度100℃、試験速度1000mm/sec、相手材SUS304、試験時間24時間、試験荷重10kgfの条件下で行った。結果を表1に示す。
さらに、上記ペレットを射出成形してJISダンベル試験片を得た。そして、このダンベル試験片について、引張強度および引張伸びの測定を行った。引張強度および引張伸びの測定は、引張試験機((株)島津製作所製 オートグラフ AG-5000B)を用い、測定温度23℃、試験速度20mm/min、つかみ治具間距離100mmの条件下で行った。結果を表1に示す。なお、引張強度は、樹脂組成物の機械的強度を評価するためのパラメータであり、引張伸びは、樹脂組成物の靱性を評価するためのパラメータである。
また、上記のようにして得られたペレットを用いて溶融時流動性の測定を行った。溶融時流動性の測定は、溶融時流動性測定装置((株) 東洋精機製作所製 キャピログラフ1B)を用い、キャピラリー長10mm、キャピラリー径1.0mm、シェアレート1000sec-1、試験温度320℃の条件下で行った。結果を表1に示す。
PAIとして、合成例2のPAIを用いたこと以外は、実施例1と同様にして樹脂組成物を製造し、摺動摩耗量、引張強度、引張伸び及び溶融時流動性を評価した。結果を表1に示す。
PAIとして、合成例3のPAIを用いたこと以外は、実施例1と同様にして樹脂組成物を製造し、摺動摩耗量、引張強度、引張伸び及び溶融時流動性を評価した。結果を表1に示す。
PAI及びPASの配合率をそれぞれ表1に示す通りとしたこと以外は実施例1と同様にして樹脂組成物を製造し、摺動摩耗量、引張強度、引張伸び及び溶融時流動性を評価した。結果を表1に示す。
PAI及びPASの配合率をそれぞれ表1に示す通りとしたこと以外は実施例2と同様にして樹脂組成物を製造し、摺動摩耗量、引張強度、引張伸び及び溶融時流動性を評価した。結果を表1に示す。
PAIとして、合成例5のPAIを用いたこと以外は、実施例1と同様にして樹脂組成物を製造し、摺動摩耗量、引張強度、引張伸び及び溶融時流動性を評価した。結果を表1に示す。
PAIとして、合成例6のPAIを用いたこと以外は、実施例1と同様にして樹脂組成物を製造し、摺動摩耗量、引張強度、引張伸び及び溶融時流動性を評価した。結果を表1に示す。
PAIとして、合成例7のPAIを用いたこと以外は、実施例1と同様にして樹脂組成物を製造し、摺動摩耗量、引張強度、引張伸び及び溶融時流動性を評価した。結果を表1に示す。
PAIとして、合成例5のPAIを用い、PAI及びPASの配合率をそれぞれ表1に示す通りとしたこと以外は実施例1と同様にして樹脂組成物を製造し、摺動摩耗量、引張強度、引張伸び及び溶融時流動性を評価した。結果を表1に示す。
Claims (8)
- (1)芳香族トリカルボン酸無水物とジイソシアネートを重合させる反応において、反応系中の水分含有量を100~5000ppmとして得られた芳香族ポリアミドイミド樹脂であって、30℃におけるN,N―ジメチルアセトアミド中での還元粘度が、0.15~0.40dl/gである芳香族ポリアミドイミド樹脂(A)と、
(2)ポリアリーレンスルフィド樹脂(B)とを含有する樹脂組成物。 - 芳香族ポリアミドイミド樹脂(A)及びポリアリーレンスルフィド樹脂(B)の合計を100重量%とした場合に、芳香族ポリアミドイミド樹脂(A)の配合率が5~60重量%であり、ポリアリーレンスルフィド樹脂(B)の配合率が95~40重量%である請求項1に記載の樹脂組成物。
- 反応系中の水分含有量が500~5000ppmである請求項1又は2に記載の樹脂組成物。
- 芳香族ポリアミドイミド樹脂(A)の還元粘度が0.25~0.40dl/gである請求項1~3のいずれか一項記載の樹脂組成物。
- 請求項1~4のいずれか一項に記載の樹脂組成物からなる成形体。
- (1)芳香族ポリアミドイミド樹脂(A)と、
(2)ポリアリーレンスルフィド樹脂(B)とを含有する樹脂組成物の製造方法であって、
前記芳香族ポリアミドイミド樹脂(A)を、
芳香族トリカルボン酸無水物とジイソシアネートを重合させる反応において、反応系中の水分含有量を100~5000ppmとし、30℃におけるN,N―ジメチルアセトアミド中での還元粘度が0.15~0.40dl/gとなるように製造する樹脂組成物の製造方法。 - 芳香族ポリアミドイミド樹脂(A)及びポリアリーレンスルフィド樹脂(B)の合計を100重量%とした場合に、芳香族ポリアミドイミド樹脂(A)の配合率が5~60重量%、ポリアリーレンスルフィド樹脂(B)の配合率が95~40重量%となるように樹脂組成物を製造する請求項6に記載の樹脂組成物の製造方法。
- 芳香族トリカルボン酸無水物とジイソシアネートを重合させる反応において、反応系中の水分含有量を500~5000ppmとする請求項6又は7に記載の樹脂組成物の製造方法。
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CN2009801308089A CN102112553A (zh) | 2008-08-11 | 2009-08-10 | 树脂组合物 |
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