WO2023210111A1 - Resin composition and sliding member using same - Google Patents

Resin composition and sliding member using same Download PDF

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Publication number
WO2023210111A1
WO2023210111A1 PCT/JP2023/005069 JP2023005069W WO2023210111A1 WO 2023210111 A1 WO2023210111 A1 WO 2023210111A1 JP 2023005069 W JP2023005069 W JP 2023005069W WO 2023210111 A1 WO2023210111 A1 WO 2023210111A1
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Prior art keywords
resin composition
mass
parts
resin
biomass
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PCT/JP2023/005069
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French (fr)
Japanese (ja)
Inventor
直樹 赤松
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クラスターテクノロジー株式会社
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Publication of WO2023210111A1 publication Critical patent/WO2023210111A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • 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

Definitions

  • the present invention relates to a resin composition and a sliding member using the same.
  • Some resin compositions constituting resin molded articles have excellent physical properties such as abrasion resistance and friction resistance (hereinafter also referred to as friction/abrasion properties).
  • the resin composition has been used in many sliding members such as bearings since the past by taking advantage of its friction and wear characteristics.
  • Patent Document 1 discloses a resin composition for sliding members using a plant-derived polyethylene resin as a main component as a biomass-derived resin, and mixing this with a petroleum-derived polyethylene resin, a modified polyolefin resin, a plant-derived filler, etc.
  • Patent Document 2 discloses a resin composition for sliding members by mixing a synthetic resin as a main component with lubricating oil, a wood filler, a polyolefin resin, and a compatibilizer as additives, and a resin composition using the same. We are proposing sliding members.
  • Patent Documents 1 and 2 still require the use of petroleum-based resins, and the resulting sliding members cannot be said to have sufficiently satisfactory friction and wear characteristics.
  • the resin compositions described in Patent Documents 1 and 2 still require the use of petroleum-based resins, and the resulting sliding members cannot be said to have sufficiently satisfactory friction and wear characteristics.
  • JP 2021-172705 Publication JP2020-026485A
  • the present invention aims to solve the above-mentioned problems, and its purpose is to provide a material containing biomass-derived resin as a main component and having good friction and wear properties that can be applied to sliding members.
  • An object of the present invention is to provide a resin composition and a sliding member using the same.
  • the present invention contains a biomass-derived polyamide resin, a cellulose filler, and a fatty acid ester, has a flexural modulus of 2000 MPa or more and 12000 MPa or less when measured in accordance with ISO178, and complies with method A described in JIS K7218.
  • a thrust wear test with carbon steel material (S45C) conducted under the conditions of a surface pressure of 0.98 MPa and a sliding speed of 50 cm/sec the maximum friction coefficient was 0.10 or more and 0.35 or less within a 100 minute range immediately after the start of the test. This is a resin composition.
  • the biomass degree in the resin composition of the present invention is 50% or more.
  • the cellulose-based filler is contained as a component of a filler having a content of 45 parts by mass to 100 parts by mass based on 100 parts by mass of the polyamide resin,
  • the content of the cellulose filler is 10 parts by mass to 100 parts by mass based on 100 parts by mass of the polyamide resin,
  • the content of the fatty acid ester corresponds to 15% to 25% by mass of the content of the cellulose filler.
  • the melting point of the polyamide resin is 160°C or more and 260°C or less.
  • the fatty acid ester is an ester of a fatty acid having 12 to 22 carbon atoms and a polyhydric alcohol.
  • the resin composition of the present invention further contains woody carbide.
  • the resin composition of the present invention is further tested with a carbon steel material (S45C) under the conditions of a surface pressure of 0.98 MPa and a sliding speed of 50 cm/sec in accordance with method A described in JIS K7218. It does not melt for 100 minutes in a thrust wear test and has a specific wear amount of 0.1 ⁇ 10 ⁇ 3 mm 3 /N ⁇ km or more and 10 ⁇ 10 ⁇ 3 mm 3 /N ⁇ km or less.
  • S45C carbon steel material
  • the present invention also provides a sliding member containing the above resin composition.
  • a sliding member having excellent friction and wear characteristics can be provided without using underground resources such as petroleum resins and minerals.
  • the resin composition of the present invention is also composed of materials that are relatively easy to obtain, thereby increasing the versatility of the sliding member obtained.
  • the resin composition of the present invention contains a biomass-derived polyamide resin, a cellulose filler, and a fatty acid ester.
  • the biomass from which the polyamide resin is derived is, for example, resource crops such as sugar crops (e.g. sugarcane), oil crops (e.g. rapeseed, castor bean), starch crops (e.g. corn); non-edible parts of agricultural crops (e.g. Plant materials such as rice straw, wheat straw, rice husk, pruned branches), and unused biomass such as forest residue.
  • resource crops such as sugar crops (e.g. sugarcane), oil crops (e.g. rapeseed, castor bean), starch crops (e.g. corn); non-edible parts of agricultural crops (e.g. Plant materials such as rice straw, wheat straw, rice husk, pruned branches), and unused biomass such as forest residue.
  • resource crops such as sugar crops (e.g. sugarcane), oil crops (e.g. rapeseed, castor bean), starch crops (e.g. corn); non-edible parts of agricultural crops (e.g. Plant materials such as rice straw, wheat straw,
  • biomass-derived polyamide resin itself preferably has a biomass degree of 50% or more, more preferably 95% or more, and even more preferably 99% or more.
  • C14 radioactive carbon
  • the content of C14 in plants is approximately the same as that in the atmosphere, while fossil resources such as oil and coal contain almost no C14.
  • the degree of biomass can be calculated as the proportion of the biomass raw material (plant) contained in the sample to be measured by using the content ratio of C14 in the plant serving as the biomass raw material.
  • the biomass content of the biomass-derived polyamide resin is less than 50%, the effect of suppressing the use of mineral resources such as oil and coal will be low, and furthermore, the effect of reducing carbon dioxide emitted during incineration will be limited. become a target.
  • the biomass-derived polyamide resin preferably has a melting point of 160°C or more and 260°C or less, more preferably 178°C or more and 230°C or less. If the melting point of the biomass-derived polyamide resin is lower than 160° C., there is a risk that the sliding member will lack heat resistance when used as a constituent material of the sliding member. If the melting point of the biomass-derived polyamide resin exceeds 260°C, the cellulose filler and fatty acid ester may be significantly decomposed during the preparation and molding of the resin composition, and there is a risk that the sliding properties and mechanical properties will be significantly reduced.
  • biomass-derived polyamide resins examples include polyamide 6 (PA6), polyamide 11 (PA11), polyamide 12 (PA12), polyamide 1010, polyamide 66 (PA66), and polyamide 4/10 (PA4) obtained from the above biomass. /10), polyamide 6/10 (PA6/10), polyamide 6/66 (PA6/66), polyamide 6/12 (PA6/12), and polyamide 6/66/12 (PA6/66/12), and Examples include, but are not limited to, combinations thereof.
  • biomass-derived polyamide resin is preferably biomass-derived polyamide 11 because it is easily available commercially.
  • Biomass-derived polyamide 11 is a condensation polymer of 11-aminoundecanoic acid obtained from castor bean (castor oil), and is commercially available from ARKEMA under the trade name Rilsan® PA11, for example.
  • a cellulose-based filler is a filler containing cellulose as a main component.
  • cellulosic fillers include cellulose fibers, bamboo fibers, ground wood (e.g., wood flour, bamboo flour, etc.), short bamboo fibers (e.g., bamboo flour treated with superheated steam), and microcrystalline cellulose. and combinations thereof, but are not limited to these.
  • the content of the cellulose filler contained in the resin composition is not particularly limited, but is preferably 10 parts by mass to 100 parts by mass, more preferably 15 parts by mass to 95 parts by mass, based on 100 parts by mass of the biomass-derived polyamide resin. Part by mass. If the content of the cellulose filler is less than 10 parts by mass with respect to 100 parts by mass of the polyamide resin, the proportion in the resin composition is too small, and there is a risk that the resulting sliding member will not have sufficient sliding properties. be. If the content of the cellulose filler is more than 100 parts by mass with respect to 100 parts by mass of the polyamide resin, the fluidity may be reduced and the molding of the sliding member may be adversely affected.
  • the cellulose filler may be contained in the resin composition of the present invention as a "filler" by combining with other fillers as necessary.
  • fillers examples include fibrous fillers, particulate fillers, and combinations thereof.
  • fibrous fillers examples include carbon fibers, carbon nanotubes, glass fibers, ceramic fibers, metal fibers, boron fibers, aramid fibers, polyester fibers, aromatic polyamide fibers, and various whiskers (e.g., graphite whiskers, titanium potassium acid whiskers, alumina-based whiskers, silicon carbide whiskers, silicon nitride whiskers, mullite whiskers, magnesia whiskers, magnesium borate whiskers, zinc oxide whiskers, and titanium boride (TiB2) whiskers, and combinations thereof), and combinations thereof.
  • whiskers e.g., graphite whiskers, titanium potassium acid whiskers, alumina-based whiskers, silicon carbide whiskers, silicon nitride whiskers, mullite whiskers, magnesia whiskers, magnesium borate whiskers, zinc oxide whiskers, and titanium boride (TiB2) whiskers, and combinations thereof
  • whiskers e.g., graphite whiskers, titanium potassium acid whiskers, alumina-based whiskers
  • particulate fillers examples include organic fillers, inorganic fillers, and combinations thereof.
  • the shape of the particles may be spherical, needle-like, plate-like, potato-like, coil-like, tube-like, soccer ball-like, or the like.
  • organic fillers include powders of benzoguanamine resin, urea-formalin resin, melamine-formalin resin, polyethersulfone resin, and molded bodies thereof (eg, beads, balloons, etc.).
  • inorganic fillers include silica, alumina, aluminum nitride, carbon, graphite, graphite, zircon, calcium silicate, calcium phosphate, calcium carbonate, magnesium carbonate, silicon carbide, boron nitride, aluminum hydroxide, iron oxide, ferrite, magnetic Iron oxide, zinc oxide, zirconium oxide, magnesium oxide, magnesium sulfate, titanium oxide, potassium titanate, barium titanate, aluminum oxide, calcium sulfate, barium sulfate, forsterite, steatite, spinel, clay, kaolin, dolomite, hydroxy Powders such as apatite, nepheline sinite, cristobalite, wollastonite, diatomaceous earth, talc, zeolite, boehmite, mica, talc, and molybdenum sulfide, and molded bodies thereof (for example, beads, balloons, etc.) are included.
  • a particulate
  • the content of the "filler” that is, the total of the cellulosic filler and the other fillers combined as necessary
  • the content of the It is preferably 45 parts by mass to 100 parts by mass, more preferably 45 parts by mass to 70 parts by mass, per 100 parts by mass of biomass-derived polyamide resin.
  • the content of the filler is less than 45 parts by mass with respect to 100 parts by mass of the polyamide resin, the elastic modulus of the resin composition decreases, and the sliding part of the resulting sliding member and the sliding member itself lack rigidity. There is a risk of If the content of the filler exceeds 100 parts by mass with respect to 100 parts by mass of the polyamide resin, fluidity may decrease, which may adversely affect the molding of the sliding member.
  • Fatty acid esters are generally used as emulsifiers, and are preferably esters of fatty acids having 12 to 22 carbon atoms and polyhydric alcohols.
  • the fatty acid having 12 to 22 carbon atoms that can constitute the fatty acid ester is not particularly limited, but includes, for example, saturated fatty acids having 12 to 22 carbon atoms (for example, lauric acid (C12:0), myristic acid (C14:0), palmitic acid).
  • the polyhydric alcohol is preferably a dihydric alcohol and/or a trihydric alcohol; specific examples include glycerin, propylene glycol, 1,3-butylene glycol, sorbitol, and xylitol, and combinations thereof. .
  • the fatty acid ester is preferably a fatty acid ester derived from biomass in order to increase the degree of biomass of the entire resin composition described below.
  • Biomass-derived fatty acid esters include, for example, biomass-derived vegetable oils such as palm oil, coconut oil, peanut oil, rapeseed oil, mustard oil, corn oil, cottonseed oil, soybean oil, and linseed oil (the above fatty acids having 12 to 22 carbon atoms).
  • Examples include esters (for example, fatty acid methyl esters) obtained by reacting the above-mentioned polyhydric alcohols.
  • fatty acid esters include glycerin monostearate, sorbitan stearate, glycerin monobenenate, glycerin mono-12-hydroxystearate, pentaerythritol furstearate, and dipentaerythritol hexastearate, and combinations thereof. can be mentioned.
  • glycerin monostearate and sorbitan stearate are preferred because they have appropriate dispersibility in the biomass-derived polyamide resin and effectively reduce the coefficient of friction.
  • the content of the fatty acid ester in the resin composition of the present invention is not particularly limited, the above-mentioned cellulose-based It is preferably set based on the content of the filler, specifically, preferably 15% to 25% by mass, more preferably 17% to 22% by mass of the content of the cellulose filler. The corresponding amount is selected.
  • the resin composition of the present invention also contains woody carbide for the purpose of reducing coloration, dimensional change due to water absorption, linear expansion coefficient, and anisotropy of molding shrinkage that causes warping of molded products. It's okay.
  • wood-based charcoal include charcoal and bamboo charcoal, and combinations thereof. Bamboo charcoal is preferred because it is easily available and has relatively stable quality.
  • the content of woody carbide is not particularly limited, but is preferably 10 parts by mass to 100 parts by mass, more preferably 15 parts by mass to 60 parts by mass, based on 100 parts by mass of the biomass-derived polyamide resin.
  • the resin composition of the present invention may also contain other additives as long as they do not inhibit the effects of the present invention obtained by combining the biomass-derived polyamide resin, cellulose filler, and fatty acid ester.
  • additives include lubricating oils, lubricants, flame retardants, colorants and low stress agents, and combinations thereof.
  • a lubricating oil that can be used as another additive can reduce the abrasion properties and increase the sliding properties of the sliding parts made of the resin composition of the present invention.
  • lubricating oils include paraffinic and naphthenic mineral oils such as spindle oil, refrigeration oil, dynamo oil, turbine oil, machine oil, cylinder oil, and gear oil; animal oils such as whale oil; oleic acid, linoleic acid, linolenic acid, etc.
  • Vegetable oils such as linseed oil, tung oil, castor oil, safflower oil, soybean oil, cottonseed oil, coconut oil, rapeseed oil, and jojoba oil, whose main components are unsaturated fatty acids; polybutene, polyisobutylene, 1-octene oligomer, 1- Synthetic hydrocarbon oils such as ⁇ -olefin oligomers such as decene oligomers and ethylene-propylene copolymers or their hydrides; Synthetic ether oils such as polyoxyalkylene glycol oil and polyphenyl ether oil; and combinations thereof. It will be done.
  • lubricants that can be used as other additives are, for example, those commonly used in the field of resin molding.
  • examples of lubricants include hydrocarbon lubricants, higher fatty acid lubricants, higher alcohol lubricants, aliphatic amide lubricants, metal salt lubricants, and ester lubricants, and combinations thereof.
  • hydrocarbon lubricants examples include liquid paraffin, paraffin wax, polyethylene wax, and oxidized polyethylene wax.
  • higher fatty acid-based lubricants include higher fatty acids having 10 or more carbon atoms, preferably 12 or more carbon atoms, such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, arachidic acid, cerotic acid, montanic acid, and melisic acid.
  • Saturated fatty acids such as oleic acid, linoleic acid, linolenic acid, elaidic acid, octadecenoic acid, arachidonic acid, cadreic acid, erucic acid, and parinaric acid; and combinations thereof.
  • Examples of higher alcohol lubricants include stearyl alcohol.
  • aliphatic amide lubricants include saturated higher fatty acid amides such as lauric acid amide, palmitic acid amide, stearic acid amide, and behenic acid amide; Saturated higher fatty acid amides; substituted amides such as N-stearyl stearamide, N-oleyl oleic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide, N-oleyl palmitic acid amide, etc.
  • saturated higher fatty acid amides such as lauric acid amide, palmitic acid amide, stearic acid amide, and behenic acid amide
  • Saturated higher fatty acid amides such as N-stearyl stearamide, N-oleyl oleic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl
  • Methylolamides such as methylolstearamide and methylolbehenic acid amide
  • metal salt lubricants include lead stearate, zinc stearate, calcium stearate, magnesium stearate, aluminum stearate, and barium stearate.
  • ester lubricants include esters of higher fatty acids having 12 to 26 carbon atoms and monoalcohols having 12 to 24 carbon atoms, such as stearyl stearate and behenyl behenate; ethylene glycol mono- or dipalmitinate, ethylene glycol mono- or dipalmitinate; Esters of alkylene diols having 2 to 6 carbon atoms such as distearate, ethylene glycol mono- or dibehenate, ethylene glycol mono- or dimontanate and higher fatty acids having 12 to 26 carbon atoms; glycerin mono-, di- or tripalmitinate, glycerin mono-, di- Or mono-, di- or tristearate, glycerin mono-, di- or tribehenate, glycerin mono-, di- or trimontanate, and other alkanetriols having 3 to 6 carbon atoms (e.g.
  • glycerin and higher fatty acids having 12 to 24 carbon atoms.
  • Triester pentaerythritol mono, di, tri or tetrapalmitinate, pentaerythritol mono, di, tri or tetrastearate, pentaerythritol mono, di, tri or tetrabehenate, pentaerythritol mono, di, tri or tetramontanate etc.
  • Flame retardants that can be used as other additives are, for example, those common in the field of resin molding.
  • flame retardants include halogenated flame retardants, brominated flame retardants, hexabromocyclodecane, bis(dibromopropyl)tetrabromobisphenol A, bis(dibromopropyl)tetrabromobisphenol A, and tris(dibromopropyl)cysocyanurate.
  • Colorants that can be used as other additives are, for example, those commonly used in the field of resin molding.
  • Examples of colorants include dyes (eg, azo, anthraquinone, triphenylmethane), carbon black, red iron, phthalocyanine, and titanium oxide, and combinations thereof.
  • Low stress agents that can be used as other additives are, for example, those common in the field of resin molding.
  • Examples of low stress agents include polybutadiene compounds, acrylonitrile butadiene copolymers, acrylic rubber, isoprene rubber, styrene butadiene copolymers, and silicone compounds (e.g. silicone oil and silicone rubber), ethylene acrylic acid copolymers, ethylene acrylic Included are acid methyl copolymers, ethylene ethyl acrylate copolymers, and combinations thereof.
  • a molded article for example, a core shell, a balloon, etc. that is a combination of these may be used.
  • the content of the other additives mentioned above that may be contained in the resin composition is not particularly limited.
  • An appropriate content can be selected by a person skilled in the art depending on the type and/or combination used.
  • the resin composition of the present invention has the following physical properties by containing the above constituent components.
  • the flexural modulus of the resin composition of the present invention measured in accordance with ISO 178 is from 2,000 MPa to 12,000 MPa, preferably from 2,200 MPa to 10,000 MPa.
  • the flexural modulus of the resulting resin composition is within the range, it can be applied to sliding members with appropriate rigidity.
  • the resin composition of the present invention was tested in a thrust wear test with carbon steel (S45C) conducted under the conditions of a surface pressure of 0.98 MPa and a sliding speed of 50 cm/sec in accordance with method A described in JIS K7218.
  • the maximum friction coefficient is 0.10 or more and 0.35 or less in the range of 100 minutes from immediately after.
  • the maximum friction coefficient of the obtained resin composition is within the range, it is possible to reduce the energy when driving the sliding member, and also to suppress the stick-slip phenomenon.
  • the resin composition of the present invention also has a biomass degree as a whole of preferably 50% or more, more preferably 90% or more, and even more preferably 99% or more.
  • a biomass degree as a whole of preferably 50% or more, more preferably 90% or more, and even more preferably 99% or more.
  • the resin composition of the present invention also melted for 100 minutes in a thrust wear test with carbon steel (S45C) conducted under the conditions of a surface pressure of 0.98 MPa and a sliding speed of 50 cm/sec in accordance with method A described in JIS K7218. It is preferable to have the property that there is no problem. Since the obtained resin composition has the above properties, a sliding member that can be used under high pressure and high speed sliding conditions can be produced.
  • the term "melting" in this specification means that grooves with a depth of at least 1.0 mm are generated in the sliding part of the wear test, and melted material is clearly visually observed as burrs around the sliding part. Point to the state in which you can do it.
  • the resin composition of the present invention preferably exhibits favorable results in a thrust wear test with carbon steel material (S45C) conducted under the conditions of a surface pressure of 0.98 MPa and a sliding speed of 50 cm/sec in accordance with Method A described in JIS K7218.
  • S45C carbon steel material
  • the resin composition of the present invention can be easily prepared using commonly used methods. For example, predetermined amounts of each of the biomass Yura polyamide resin, cellulosic filler and fatty acid ester, and optionally other fillers and/or other additives are mixed in a conventional mixer (e.g., Henschel mixer, super mixer, ball mill, etc.). The resulting mixture can be put into, for example, a single- or twin-screw extruder, melt-kneaded, formed into a strand, and then formed into pellets.
  • a conventional mixer e.g., Henschel mixer, super mixer, ball mill, etc.
  • the resin composition of the present invention is used, for example, as a material for a sliding member that requires sliding friction with a mating material.
  • sliding members include bearings, gears, washers, guide rails, sashes, fasteners, and the like.
  • the sliding member obtained using the resin composition of the present invention has excellent friction and wear characteristics, and has good durability, so that it can be used for a long period of time.
  • the maximum value of the friction coefficient obtained within the range from the start to the end of the test is the "maximum friction coefficient", and the cumulative sliding distance is the “sliding distance”, and if this sliding distance is less than 3 km, that is, the test time is 100 If the time was less than 1 minute, it was judged as "melted”.
  • the wear volume of the test piece at the end of the test was determined from the wear mass, and the value was divided by the product of the load and the sliding distance to calculate the "specific wear amount (mm 3 /N ⁇ km)".
  • Example 1 Preparation of pellet (E1)
  • cellulose filler ARBOCEL (registered trademark) FD00 manufactured by Rettenmeyer Japan Co., Ltd.
  • woody charcoal pulverized bamboo charcoal
  • fatty acid ester glycerin monostearate
  • Example 2 to 6 Preparation of pellets (E2) to (E6)
  • Pellets (E2) to (E6) were prepared in the same manner as in Example 1, except that the amounts of cellulose filler, woody carbide, and fatty acid ester were changed as shown in Table 1, and the above evaluations were performed. Tests (1) and (2) were conducted. The results are shown in Table 1.
  • the short bamboo fibers used in Examples 5 and 6 were superheated steam-treated bamboo powder (manufactured by bamboo Techno Co., Ltd.).
  • pellets (E1) to (E6) produced in Examples 1 to 6 were compared with pellets (C1) to (C5) produced in Comparative Examples 1 to 5. The specific wear amount was suppressed and no melting occurred during the test. From this, it can be seen that the resin compositions constituting the pellets (E1) to (E6) produced in Examples 1 to 6 can withstand high pressure and high speed sliding conditions and have excellent wear resistance. .
  • the present invention it is useful in various technical fields such as, for example, the resin molding field, the electronic/electrical field, the communication machinery field, the automobile parts manufacturing field, the medical equipment manufacturing field, and the semiconductor manufacturing field.

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Abstract

A resin composition according to the present invention contains a biomass-derived polyamide resin, a cellulose-based filler, and a fatty acid ester. The flexural modulus of the resin composition as measured in accordance with ISO 178 is 2000-12000 MPa. The maximum friction coefficient of the resin composition as measured by a thrust friction test with a carbon steel material (S45C) performed at a surface pressure of 0.98 MPa and a sliding speed of 50 cm/sec in accordance with the A-method described in JIS K7218 is 0.10-0.35 in the span of 100 minutes immediately after the start of the test.

Description

樹脂組成物およびそれを用いた摺動部材Resin composition and sliding member using the same
　本発明は、樹脂組成物およびそれを用いた摺動部材に関する。 The present invention relates to a resin composition and a sliding member using the same.
　樹脂成形体を構成する樹脂組成物には、例えば耐摩耗性や耐摩擦性などの優れた物性（以下、摩擦・摩耗特性ともいう）を有するものが存在する。そして、当該樹脂組成物は、その摩擦・摩耗特性を活かして、過去より軸受けなどの多くの摺動部材に利用されている。 Some resin compositions constituting resin molded articles have excellent physical properties such as abrasion resistance and friction resistance (hereinafter also referred to as friction/abrasion properties). The resin composition has been used in many sliding members such as bearings since the past by taking advantage of its friction and wear characteristics.
　一方、昨今の地球温暖化を防止しかつ枯渇資源としての石油の使用量を低減させる観点から、石油系樹脂の全部または一部に代えて、穀類、豆類、イモ類などの植物性材料（バイオマス）を由来とする樹脂の利用が注目されている。 On the other hand, from the perspective of preventing the recent global warming and reducing the amount of petroleum used as a depletable resource, plant materials (biomass) such as grains, beans, and potatoes are being used instead of all or part of petroleum-based resins. ) is attracting attention.
　例えば、特許文献１は、バイオマス由来の樹脂として植物由来ポリエチレン樹脂を主成分に用い、これに石油由来ポリエチレン樹脂、変性ポリオレフィン樹脂、植物由来フィラー等を混合した摺動部材用の樹脂組成物およびそれを用いた摺動部材を提案している。また、特許文献２は、主成分である合成樹脂と、添加剤である潤滑油、木質系フィラー、ポリオレフィン樹脂および相溶化剤とを混合して摺動部材用の樹脂組成物およびそれを用いた摺動部材を提案している。 For example, Patent Document 1 discloses a resin composition for sliding members using a plant-derived polyethylene resin as a main component as a biomass-derived resin, and mixing this with a petroleum-derived polyethylene resin, a modified polyolefin resin, a plant-derived filler, etc. We are proposing a sliding member using Further, Patent Document 2 discloses a resin composition for sliding members by mixing a synthetic resin as a main component with lubricating oil, a wood filler, a polyolefin resin, and a compatibilizer as additives, and a resin composition using the same. We are proposing sliding members.
　しかし、特許文献１および２に記載の樹脂組成物では、依然として石油系樹脂の使用が必要であり、得られる摺動部材も十分満足し得る摩擦摩耗特性を有するとは言い難いものであった。また、石油系樹脂の使用回避に対する世界中の関心や、それを大きく宣言する企業の国際的な注目度の高まりを考えると、石油系樹脂に代わるバイオマス由来の樹脂を用いる、新たな樹脂組成物の開発が所望されている。 However, the resin compositions described in Patent Documents 1 and 2 still require the use of petroleum-based resins, and the resulting sliding members cannot be said to have sufficiently satisfactory friction and wear characteristics. In addition, considering the worldwide interest in avoiding the use of petroleum-based resins and the increasing international attention of companies that make such a big statement, we are considering new resin compositions that use biomass-derived resins to replace petroleum-based resins. development is desired.
特開２０２１－１７２７０５号公報JP 2021-172705 Publication 特開２０２０－０２６４８５号公報JP2020-026485A
　本発明は、上記問題の解決を課題とするものであり、その目的とするところは、バイオマス由来の樹脂を主成分として含有し、かつ摺動部材への応用が可能な良好な摩擦・摩耗特性を有する、樹脂組成物およびそれを用いた摺動部材を提供することにある。 The present invention aims to solve the above-mentioned problems, and its purpose is to provide a material containing biomass-derived resin as a main component and having good friction and wear properties that can be applied to sliding members. An object of the present invention is to provide a resin composition and a sliding member using the same.
　本発明は、バイオマス由来のポリアミド樹脂、セルロース系充填材および脂肪酸エステルを含有し、ＩＳＯ１７８に準拠して測定した曲げ弾性率が２０００ＭＰａ以上１２０００ＭＰａ以下であり、かつＪＩＳ　Ｋ７２１８に記載されたＡ法に準拠した面圧０．９８ＭＰａ、摺動速度５０ｃｍ／秒の条件で行う炭素鋼材（Ｓ４５Ｃ）とのスラスト摩耗試験において、試験開始直後から１００分間の範囲で最大摩擦係数が０．１０以上０．３５以下である、樹脂組成物である。 The present invention contains a biomass-derived polyamide resin, a cellulose filler, and a fatty acid ester, has a flexural modulus of 2000 MPa or more and 12000 MPa or less when measured in accordance with ISO178, and complies with method A described in JIS K7218. In a thrust wear test with carbon steel material (S45C) conducted under the conditions of a surface pressure of 0.98 MPa and a sliding speed of 50 cm/sec, the maximum friction coefficient was 0.10 or more and 0.35 or less within a 100 minute range immediately after the start of the test. This is a resin composition.
　１つの実施形態では、本発明の樹脂組成物におけるバイオマス度は５０％以上である。 In one embodiment, the biomass degree in the resin composition of the present invention is 50% or more.
　１つの実施形態では、上記セルロース系充填材は、上記ポリアミド樹脂１００質量部に対して４５質量部から１００質量部の含有量を有する充填材の構成成分として含有されており、
　該セルロース系充填材の含有量は、該ポリアミド樹脂１００質量部に対して１０質量部から１００質量部であり、
　上記脂肪酸エステルの含有量は、該セルロース系充填材の含有量の１５質量％から２５質量％に相当する。 In one embodiment, the cellulose-based filler is contained as a component of a filler having a content of 45 parts by mass to 100 parts by mass based on 100 parts by mass of the polyamide resin,
The content of the cellulose filler is 10 parts by mass to 100 parts by mass based on 100 parts by mass of the polyamide resin,
The content of the fatty acid ester corresponds to 15% to 25% by mass of the content of the cellulose filler.
　１つの実施形態では、上記ポリアミド樹脂の融点は１６０℃以上２６０℃以下である。 In one embodiment, the melting point of the polyamide resin is 160°C or more and 260°C or less.
　１つの実施形態では、上記脂肪酸エステルは、炭素数１２～２２の脂肪酸と多価アルコールとのエステルである。 In one embodiment, the fatty acid ester is an ester of a fatty acid having 12 to 22 carbon atoms and a polyhydric alcohol.
　１つの実施形態では、本発明の樹脂組成物はさらに木質系炭化物を含有する。 In one embodiment, the resin composition of the present invention further contains woody carbide.
　１つの実施形態では、本発明の樹脂組成物は、さらに、ＪＩＳ　Ｋ７２１８に記載されたＡ法に準拠した面圧０．９８ＭＰａ、摺動速度５０ｃｍ／秒の条件で行う炭素鋼材（Ｓ４５Ｃ）とのスラスト摩耗試験において１００分間溶融することなく、かつ０．１×１０－３ｍｍ３／Ｎ・ｋｍ以上１０×１０－３ｍｍ３／Ｎ・ｋｍ以下の比摩耗量を有する。 In one embodiment, the resin composition of the present invention is further tested with a carbon steel material (S45C) under the conditions of a surface pressure of 0.98 MPa and a sliding speed of 50 cm/sec in accordance with method A described in JIS K7218. It does not melt for 100 minutes in a thrust wear test and has a specific wear amount of 0.1×10 −3 mm 3 /N·km or more and 10×10 −3 mm 3 /N·km or less.
　本発明はまた、上記樹脂組成物を含む、摺動部材である。 The present invention also provides a sliding member containing the above resin composition.
　本発明によれば、石油系樹脂や鉱物などの地下資源を使用することなく、優れた摩擦・摩耗特性を有する摺動部材を提供することができる。本発明の樹脂組成物はまた、比較的入手が容易な材料から構成されており、それにより得られる摺動部材の汎用性が高めることができる。 According to the present invention, a sliding member having excellent friction and wear characteristics can be provided without using underground resources such as petroleum resins and minerals. The resin composition of the present invention is also composed of materials that are relatively easy to obtain, thereby increasing the versatility of the sliding member obtained.
　以下、本発明について詳述する。 Hereinafter, the present invention will be explained in detail.
　本発明の樹脂組成物は、バイオマス由来のポリアミド樹脂、セルロース系充填材および脂肪酸エステルを含有する。 The resin composition of the present invention contains a biomass-derived polyamide resin, a cellulose filler, and a fatty acid ester.
　ポリアミド樹脂の由来となるバイオマスは、例えば、糖質作物（例えばサトウキビ）、油糧作物（例えば、菜種、トウゴマ）、デンプン系作物（例えば、トウモロコシ）などの資源作物；農作物非食用部（例えば、稲わら、麦わら、もみ殻、剪定枝）、林地残材などの非利用系バイオマス；などの植物性材料である。 The biomass from which the polyamide resin is derived is, for example, resource crops such as sugar crops (e.g. sugarcane), oil crops (e.g. rapeseed, castor bean), starch crops (e.g. corn); non-edible parts of agricultural crops (e.g. Plant materials such as rice straw, wheat straw, rice husk, pruned branches), and unused biomass such as forest residue.
　バイオマス由来のポリアミド樹脂は、それ自体が、好ましくは５０％以上、より好ましくは９５％以上、さらにより好ましくは９９％以上のバイオマス度を有する。ここで、本明細書中に用いられる用語「バイオマス度」とは、サンプル中に含まれるバイオマス原料の乾燥重量割合であって、ＡＳＴＭ　Ｄ６８６６、ＩＳＯ１６６２０などに規定されているＡＭＳ法などの方法でＣ１４を定量し、以下のように現在の大気中の二酸化炭素に含まれるＣ１４の量と比較することで算出される。
　バイオマス度（％）＝（サンプル中のＣ１４量／大気中のＣ１４量）×１００ The biomass-derived polyamide resin itself preferably has a biomass degree of 50% or more, more preferably 95% or more, and even more preferably 99% or more. Here, the term "biomass degree" used in this specification is the dry weight percentage of biomass raw material contained in a sample, and is a C14 It is calculated by quantifying C14 and comparing it with the amount of C14 contained in the current atmospheric carbon dioxide as shown below.
Biomass degree (%) = (Amount of C14 in sample/Amount of C14 in the atmosphere) x 100
　大気中の二酸化炭素には、放射性炭素（Ｃ１４）が一定の割合で含まれていることが知られており、このＣ１４の半減期は５７３０年と長く、二酸化炭素を取り込んで成長する。植物ではＣ１４の含有割合はおよそ大気中の割合と同値であり、一方で石油・石炭などの化石資源においては、ほとんど含有されていない。バイオマス度は、こうしたバイオマス原料となる植物中のＣ１４の含有割合を利用して、測定するサンプル中に含まれるバイオマス原料（植物）の割合として算出できる。ここで本発明においては、バイオマス由来のポリアミド樹脂のバイオマス度が５０％を下回ると、石油・石炭などの鉱物資源の使用抑制効果が低くなり、さらに焼却廃棄時に排出する二酸化炭素の削減効果が限定的となる。 It is known that carbon dioxide in the atmosphere contains a certain proportion of radioactive carbon (C14), and this C14 has a long half-life of 5,730 years, and grows by taking in carbon dioxide. The content of C14 in plants is approximately the same as that in the atmosphere, while fossil resources such as oil and coal contain almost no C14. The degree of biomass can be calculated as the proportion of the biomass raw material (plant) contained in the sample to be measured by using the content ratio of C14 in the plant serving as the biomass raw material. In the present invention, if the biomass content of the biomass-derived polyamide resin is less than 50%, the effect of suppressing the use of mineral resources such as oil and coal will be low, and furthermore, the effect of reducing carbon dioxide emitted during incineration will be limited. become a target.
　さらにバイオマス由来のポリアミド樹脂は、好ましくは１６０℃以上２６０℃以下、より好ましくは１７８℃以上２３０℃以下の融点を有する。バイオマス由来のポリアミド樹脂の融点が１６０℃を下回ると、摺動部材の構成材料として使用した際の当該摺動部材の耐熱性が不足するおそれがある。バイオマス由来のポリアミド樹脂の融点が２６０℃を上回ると、樹脂組成物の作製および成形においてセルロース系充填材および脂肪酸エステルが著しく分解し、摺動性および機械的物性が大きく低下するおそれがある。 Furthermore, the biomass-derived polyamide resin preferably has a melting point of 160°C or more and 260°C or less, more preferably 178°C or more and 230°C or less. If the melting point of the biomass-derived polyamide resin is lower than 160° C., there is a risk that the sliding member will lack heat resistance when used as a constituent material of the sliding member. If the melting point of the biomass-derived polyamide resin exceeds 260°C, the cellulose filler and fatty acid ester may be significantly decomposed during the preparation and molding of the resin composition, and there is a risk that the sliding properties and mechanical properties will be significantly reduced.
　バイオマス由来のポリアミド樹脂の例としては、上記バイオマスから得られた、ポリアミド６（ＰＡ６）、ポリアミド１１（ＰＡ１１）、ポリアミド１２（ＰＡ１２）、ポリアミド１０１０、ポリアミド６６（ＰＡ６６）、ポリアミド４／１０（ＰＡ４／１０）、ポリアミド６／１０（ＰＡ６／１０）、ポリアミド６／６６（ＰＡ６／６６）、ポリアミド６／１２（ＰＡ６／１２）、およびポリアミド６／６６／１２（ＰＡ６／６６／１２）、ならびにそれらの組み合わせが挙げられるが、これらに限定されるものではない。 Examples of biomass-derived polyamide resins include polyamide 6 (PA6), polyamide 11 (PA11), polyamide 12 (PA12), polyamide 1010, polyamide 66 (PA66), and polyamide 4/10 (PA4) obtained from the above biomass. /10), polyamide 6/10 (PA6/10), polyamide 6/66 (PA6/66), polyamide 6/12 (PA6/12), and polyamide 6/66/12 (PA6/66/12), and Examples include, but are not limited to, combinations thereof.
　本発明においては、バイオマス由来のポリアミド樹脂は、市販により入手が容易であるとの理由から、バイオマス由来のポリアミド１１が好ましい。バイオマス由来のポリアミド１１は、トウゴマ（ヒマシ油）から得られた１１－アミノウンデカン酸の縮重合体であり、例えば、Ｒｉｌｓａｎ（登録商標）ＰＡ１１の商品名でＡＲＫＥＭＡ社より市販されている。 In the present invention, the biomass-derived polyamide resin is preferably biomass-derived polyamide 11 because it is easily available commercially. Biomass-derived polyamide 11 is a condensation polymer of 11-aminoundecanoic acid obtained from castor bean (castor oil), and is commercially available from ARKEMA under the trade name Rilsan® PA11, for example.
　セルロース系充填材は、セルロースを主成分として含有する充填材である。セルロース系充填材の例としては、セルロースファイバー、竹ファイバー、木質粉砕物（例えば、木粉、竹粉など）、竹短繊維（例えば、過熱水蒸気で処理された竹粉）、および微結晶セルロース、ならびにそれらの組み合わせが挙げられるが、これらに限定されるものではない。 A cellulose-based filler is a filler containing cellulose as a main component. Examples of cellulosic fillers include cellulose fibers, bamboo fibers, ground wood (e.g., wood flour, bamboo flour, etc.), short bamboo fibers (e.g., bamboo flour treated with superheated steam), and microcrystalline cellulose. and combinations thereof, but are not limited to these.
　樹脂組成物に含まれるセルロース系充填材の含有量は特に限定されないが、上記バイオマス由来のポリアミド樹脂１００質量部に対して、好ましくは１０質量部～１００質量部、より好ましくは１５質量部～９５質量部である。当該ポリアミド樹脂１００質量部に対するセルロース系充填材の含有量が１０質量部を下回ると、樹脂組成物中の割合が少なすぎるため、得られる摺動部材について十分な摺動性が得られないおそれがある。当該ポリアミド樹脂１００質量部に対するセルロース系充填材の含有量が１００質量部を上回ると、流動性が低下し、摺動部材の成形に悪影響を及ぼすおそれがある。 The content of the cellulose filler contained in the resin composition is not particularly limited, but is preferably 10 parts by mass to 100 parts by mass, more preferably 15 parts by mass to 95 parts by mass, based on 100 parts by mass of the biomass-derived polyamide resin. Part by mass. If the content of the cellulose filler is less than 10 parts by mass with respect to 100 parts by mass of the polyamide resin, the proportion in the resin composition is too small, and there is a risk that the resulting sliding member will not have sufficient sliding properties. be. If the content of the cellulose filler is more than 100 parts by mass with respect to 100 parts by mass of the polyamide resin, the fluidity may be reduced and the molding of the sliding member may be adversely affected.
　セルロース系充填材は、必要に応じて他の充填材と組み合わせることにより「充填材」として本発明の樹脂組成物中に含有されていてもよい。 The cellulose filler may be contained in the resin composition of the present invention as a "filler" by combining with other fillers as necessary.
　他の充填材としては、例えば、繊維状充填材および粒子状充填材、ならびにそれらの組み合わせが挙げられる。 Examples of other fillers include fibrous fillers, particulate fillers, and combinations thereof.
　繊維状充填材としては、例えば、カーボンファイバー、カーボンナノチューブ、ガラスファイバー、セラミック系ファイバー、金属系ファイバー、ボロンファイバー、アラミド繊維、ポリエステル繊維、芳香族ポリアミド繊維、および各種ウィスカー（例えば、グラファイトウィスカー、チタン酸カリウムウィスカー、アルミナ系ウィスカー、炭化ケイ素ウィスカー、窒化ケイ素ウィスカー、ムライトウィスカー、マグネシアウィスカー、ホウ酸マグネシウムウィスカー、酸化亜鉛ウィスカー、およびホウ化チタン（ＴｉＢ２）ウィスカー、ならびにそれらの組み合わせ）、ならびにそれらの組み合わせが挙げられる。樹脂組成物中でより均一に分散させることができるという理由から、繊維状充填材を用いる場合、その平均繊維長は１μｍ～６ｍｍであることが好ましい。 Examples of fibrous fillers include carbon fibers, carbon nanotubes, glass fibers, ceramic fibers, metal fibers, boron fibers, aramid fibers, polyester fibers, aromatic polyamide fibers, and various whiskers (e.g., graphite whiskers, titanium potassium acid whiskers, alumina-based whiskers, silicon carbide whiskers, silicon nitride whiskers, mullite whiskers, magnesia whiskers, magnesium borate whiskers, zinc oxide whiskers, and titanium boride (TiB2) whiskers, and combinations thereof), and combinations thereof. can be mentioned. When using a fibrous filler, the average fiber length is preferably 1 μm to 6 mm because it can be more uniformly dispersed in the resin composition.
　粒子状充填材としては、例えば、有機充填材および無機充填材、ならびにそれらの組み合わせが挙げられる。粒子の形状としては、球状、針状、板状、いも状、コイル状、チューブ状、サッカーボール形状などであってもよい。有機充填材の例としては、ベンゾグアナミン樹脂、尿素－ホルマリン系樹脂、メラミン－ホルマリン系樹脂、ポリエーテルサルフォン樹脂などの粉体、およびこれらの成形体（例えば、ビーズ、バルーンなど）が挙げられる。無機充填材の例としては、シリカ、アルミナ、窒化アルミニウム、炭素、黒鉛、グラファイト、ジルコン、珪酸カルシウム、リン酸カルシウム、炭酸カルシウム、炭酸マグネシウム、炭化珪素、窒化硼素、水酸化アルミニウム、酸化鉄、フェライト、磁性酸化鉄、酸化亜鉛、酸化ジルコニウム、酸化マグネシウム、硫酸マグネシウム、酸化チタン、チタン酸カリウム、チタン酸バリウム、酸化アルミニウム、硫酸カルシウム、硫酸バリウム、フォステライト、ステアタイト、スピネル、クレー、カオリン、ドロマイト、ヒドロキシアパタイト、ネフェリンサイナイト、クリストバライト、ウォラストナイト、珪藻土、タルク、ゼオライト、ベーマイト、マイカ、タルク、硫化モリブデンなどの粉体、およびこれらの成形体（例えば、ビーズ、バルーンなど）が挙げられる。樹脂組成物中で構造体により均一に分散させることができるという理由から、粒子状充填材を用いる場合、その平均粒子径は５ｎｍ～５００μｍであることが好ましい。 Examples of particulate fillers include organic fillers, inorganic fillers, and combinations thereof. The shape of the particles may be spherical, needle-like, plate-like, potato-like, coil-like, tube-like, soccer ball-like, or the like. Examples of organic fillers include powders of benzoguanamine resin, urea-formalin resin, melamine-formalin resin, polyethersulfone resin, and molded bodies thereof (eg, beads, balloons, etc.). Examples of inorganic fillers include silica, alumina, aluminum nitride, carbon, graphite, graphite, zircon, calcium silicate, calcium phosphate, calcium carbonate, magnesium carbonate, silicon carbide, boron nitride, aluminum hydroxide, iron oxide, ferrite, magnetic Iron oxide, zinc oxide, zirconium oxide, magnesium oxide, magnesium sulfate, titanium oxide, potassium titanate, barium titanate, aluminum oxide, calcium sulfate, barium sulfate, forsterite, steatite, spinel, clay, kaolin, dolomite, hydroxy Powders such as apatite, nepheline sinite, cristobalite, wollastonite, diatomaceous earth, talc, zeolite, boehmite, mica, talc, and molybdenum sulfide, and molded bodies thereof (for example, beads, balloons, etc.) are included. When using a particulate filler, the average particle diameter is preferably 5 nm to 500 μm because it can be more uniformly dispersed in the structure in the resin composition.
　本発明において、樹脂組成物に含有され得る「充填材」（すなわち、上記セルロース系充填材と、必要に応じて組み合わされる上記他の充填材との合計）の含有量は必ずしも限定されないが、上記バイオマス由来のポリアミド樹脂１００質量部に対して、好ましくは４５質量部～１００質量部、より好ましくは４５質量部～７０質量部である。当該ポリアミド樹脂１００質量部に対する充填材の含有量が４５質量部を下回ると、その樹脂組成物の弾性率が低下して、得られる摺動部材の摺動部および摺動部材自体の剛性が不足するおそれがある。当該ポリアミド樹脂１００質量部に対する充填材の含有量が１００質量部を上回ると、流動性が低下し、摺動部材の成形に悪影響を及ぼすおそれがある。 In the present invention, the content of the "filler" (that is, the total of the cellulosic filler and the other fillers combined as necessary) that can be contained in the resin composition is not necessarily limited, but the content of the It is preferably 45 parts by mass to 100 parts by mass, more preferably 45 parts by mass to 70 parts by mass, per 100 parts by mass of biomass-derived polyamide resin. When the content of the filler is less than 45 parts by mass with respect to 100 parts by mass of the polyamide resin, the elastic modulus of the resin composition decreases, and the sliding part of the resulting sliding member and the sliding member itself lack rigidity. There is a risk of If the content of the filler exceeds 100 parts by mass with respect to 100 parts by mass of the polyamide resin, fluidity may decrease, which may adversely affect the molding of the sliding member.
　脂肪酸エステルは一般に乳化剤として使用されるものであり、好ましくは炭素数１２～２２の脂肪酸と多価アルコールとのエステルである。 Fatty acid esters are generally used as emulsifiers, and are preferably esters of fatty acids having 12 to 22 carbon atoms and polyhydric alcohols.
　脂肪酸エステルを構成し得る炭素数１２～２２の脂肪酸としては特に限定されないが、例えば、炭素数１２～２２の飽和脂肪酸（例えば、ラウリン酸（Ｃ１２：０）、ミリスチン酸（Ｃ１４：０）、パルミチン酸（Ｃ１６：０）、ステアリン酸（Ｃ１８：０）、アラキジン酸（Ｃ２０：０）、ベヘン酸（Ｃ２２：０））；炭素数１２～２２の一価飽和脂肪酸（例えば、パルミトオレイン酸（Ｃ１６：１）、オレイン酸（Ｃ１８：１）、エライジン酸（Ｃ１８：１）、パクセン酸（Ｃ１８：１）、エルカ酸（Ｃ２２：１）；および炭素数１２～２２の多価不飽和脂肪酸（例えば、リノール酸（Ｃ１８：２）、γ－リノレン酸（Ｃ１８：３）、α－リノレン酸（Ｃ１８：３）、ジホモ－γ－リノレン酸（Ｃ２０：３）、アラキドン酸（Ｃ２０：４）、エイコサペンタエン酸（Ｃ２０：５）、ドコサヘキサエン酸（Ｃ２２：６））；ならびにそれらの組み合わせが挙げられる。 The fatty acid having 12 to 22 carbon atoms that can constitute the fatty acid ester is not particularly limited, but includes, for example, saturated fatty acids having 12 to 22 carbon atoms (for example, lauric acid (C12:0), myristic acid (C14:0), palmitic acid). acid (C16:0), stearic acid (C18:0), arachidic acid (C20:0), behenic acid (C22:0)); monovalent saturated fatty acids with 12 to 22 carbon atoms (for example, palmitoleic acid ( C16:1), oleic acid (C18:1), elaidic acid (C18:1), paxenoic acid (C18:1), erucic acid (C22:1); and polyunsaturated fatty acids having 12 to 22 carbon atoms ( For example, linoleic acid (C18:2), γ-linolenic acid (C18:3), α-linolenic acid (C18:3), dihomo-γ-linolenic acid (C20:3), arachidonic acid (C20:4), Examples include eicosapentaenoic acid (C20:5), docosahexaenoic acid (C22:6)); and combinations thereof.
　多価アルコールは、好ましくは２価アルコールおよび／または３価アルコールであり、具体的な例としては、グリセリン、プロピレングリコール、１，３－ブチレングリコール、ソルビトール、およびキシリトール、ならびにそれらの組み合わせが挙げられる。 The polyhydric alcohol is preferably a dihydric alcohol and/or a trihydric alcohol; specific examples include glycerin, propylene glycol, 1,3-butylene glycol, sorbitol, and xylitol, and combinations thereof. .
　本発明において脂肪酸エステルは、後述する樹脂組成物全体のバイオマス度を高めるためにバイオマス由来の脂肪酸エステルであることが好ましい。バイオマス由来の脂肪酸エステルは、例えば、パーム油、ヤシ油、落花生油、菜種油、からし菜油、トウモロコシ油、綿実油、大豆油、亜麻仁油などのバイオマス由来の植物油（上記炭素数１２～２２の脂肪酸を含有する）と上記多価アルコールとを反応させて得られるエステル（例えば、脂肪酸メチルエステル）が挙げられる。 In the present invention, the fatty acid ester is preferably a fatty acid ester derived from biomass in order to increase the degree of biomass of the entire resin composition described below. Biomass-derived fatty acid esters include, for example, biomass-derived vegetable oils such as palm oil, coconut oil, peanut oil, rapeseed oil, mustard oil, corn oil, cottonseed oil, soybean oil, and linseed oil (the above fatty acids having 12 to 22 carbon atoms). Examples include esters (for example, fatty acid methyl esters) obtained by reacting the above-mentioned polyhydric alcohols.
　脂肪酸エステルの具体的な例としては、グリセリンモノステアレート、ソルビタンステアレート、グルセリンモノベネネート、グリセリンモノ１２－ヒドロキシステアレート、ペンタエリスリトールフルステアレート、およびジペンタエリスリトールヘキサステアレート、ならびにそれらの組み合わせが挙げられる。特に、上記バイオマス由来のポリアミド樹脂に対して適度な分散性を有し、効果的に摩擦係数を低減するという理由から、グリセリンモノステアレート、ソルビタンステアレートが好ましい。 Specific examples of fatty acid esters include glycerin monostearate, sorbitan stearate, glycerin monobenenate, glycerin mono-12-hydroxystearate, pentaerythritol furstearate, and dipentaerythritol hexastearate, and combinations thereof. can be mentioned. In particular, glycerin monostearate and sorbitan stearate are preferred because they have appropriate dispersibility in the biomass-derived polyamide resin and effectively reduce the coefficient of friction.
　本発明の樹脂組成物における脂肪酸エステルの含有量は、特に限定されないが、セルロース系充填材との相互作用により、当該セルロース系充填材の表面またはその近傍に担持されるという理由から、上記セルロース系充填材の含有量に基づいて設定されることが好ましく、具体的には、上記セルロース系充填材の含有量の好ましくは１５質量％～２５質量％、より好ましくは１７質量％～２２質量％に相当する量が選択される。 Although the content of the fatty acid ester in the resin composition of the present invention is not particularly limited, the above-mentioned cellulose-based It is preferably set based on the content of the filler, specifically, preferably 15% to 25% by mass, more preferably 17% to 22% by mass of the content of the cellulose filler. The corresponding amount is selected.
　本発明の樹脂組成物はまた、着色、吸水による寸法変化の低減、線膨張係数の低減および成形品の反りの原因となる成形収縮の異方性を低減する目的で木質系炭化物を含有していてもよい。木質系炭化物の例としては、木炭および竹炭、ならびにそれらの組み合わせが挙げられる。入手が容易である、品質が比較的安定している等の理由から、竹炭が好ましい。 The resin composition of the present invention also contains woody carbide for the purpose of reducing coloration, dimensional change due to water absorption, linear expansion coefficient, and anisotropy of molding shrinkage that causes warping of molded products. It's okay. Examples of wood-based charcoal include charcoal and bamboo charcoal, and combinations thereof. Bamboo charcoal is preferred because it is easily available and has relatively stable quality.
　木質系炭化物の含有量は、特に限定されないが、上記バイオマス由来のポリアミド樹脂１００質量部に対して、好ましくは１０質量部～１００質量部、より好ましくは１５質量部～６０質量部である。木質系炭化物がこのような含有量の範囲を満たしていることにより、吸水による寸法変化の低減、線膨張係数の低減および成形品の反りの原因となる成形収縮の異方性を低減できる。 The content of woody carbide is not particularly limited, but is preferably 10 parts by mass to 100 parts by mass, more preferably 15 parts by mass to 60 parts by mass, based on 100 parts by mass of the biomass-derived polyamide resin. By satisfying the content range of the woody carbide, it is possible to reduce dimensional changes due to water absorption, reduce the coefficient of linear expansion, and reduce anisotropy of molding shrinkage that causes warping of the molded product.
　本発明の樹脂組成物はまた、上記バイオマス由来のポリアミド樹脂、セルロース系充填材および脂肪酸エステルを組み合わせることによる本発明の効果を阻害しない範囲において、他の添加剤を含有していてもよい。このような他の添加剤の例としては、潤滑油、滑剤、難燃剤、着色剤および低応力剤、ならびにそれらの組み合わせが挙げられる。 The resin composition of the present invention may also contain other additives as long as they do not inhibit the effects of the present invention obtained by combining the biomass-derived polyamide resin, cellulose filler, and fatty acid ester. Examples of such other additives include lubricating oils, lubricants, flame retardants, colorants and low stress agents, and combinations thereof.
　他の添加剤として使用され得る潤滑油は、本発明の樹脂組成物から構成される摺動部の摩耗性を低下させ、かつ摺動性を高めることができる。潤滑油の例としては、スピンドル油、冷凍機油、ダイナモ油、タービン油、マシン油、シリンダー油、ギア油等のパラフィン系およびナフテン系鉱油；鯨油等の動物油；オレイン酸、リノール酸、リノレン酸等の不飽和脂肪酸を主成分とする亜麻仁油、桐油、ヒマシ油、サフラワー油、大豆油、綿実油、ヤシ油、ナタネ油、ホホバ油等の植物油；ポリブテン、ポリイソブチレン、１－オクテンオリゴマー、１－デセンオリゴマーおよびエチレン－プロピレン共重合体等のα－オレフィンオリゴマーまたはその水素化物等の炭化水素系合成油；ポリオキシアルキレングリコール油、ポリフェニルエーテル油等のエーテル系合成油；ならびにそれらの組み合わせが挙げられる。 A lubricating oil that can be used as another additive can reduce the abrasion properties and increase the sliding properties of the sliding parts made of the resin composition of the present invention. Examples of lubricating oils include paraffinic and naphthenic mineral oils such as spindle oil, refrigeration oil, dynamo oil, turbine oil, machine oil, cylinder oil, and gear oil; animal oils such as whale oil; oleic acid, linoleic acid, linolenic acid, etc. Vegetable oils, such as linseed oil, tung oil, castor oil, safflower oil, soybean oil, cottonseed oil, coconut oil, rapeseed oil, and jojoba oil, whose main components are unsaturated fatty acids; polybutene, polyisobutylene, 1-octene oligomer, 1- Synthetic hydrocarbon oils such as α-olefin oligomers such as decene oligomers and ethylene-propylene copolymers or their hydrides; Synthetic ether oils such as polyoxyalkylene glycol oil and polyphenyl ether oil; and combinations thereof. It will be done.
　他の添加剤として使用され得る滑剤は、例えば樹脂成形分野において一般的なものである。滑剤の例としては、炭化水素系滑剤、高級脂肪酸系滑剤、高級アルコール系滑剤、脂肪族アミド系滑剤、金属塩系滑剤、およびエステル系滑剤、ならびにそれらの組み合わせが挙げられる。 The lubricants that can be used as other additives are, for example, those commonly used in the field of resin molding. Examples of lubricants include hydrocarbon lubricants, higher fatty acid lubricants, higher alcohol lubricants, aliphatic amide lubricants, metal salt lubricants, and ester lubricants, and combinations thereof.
　炭化水素系滑剤としては、例えば、流動パラフィン、パラフィンワックス、ポリエチレンワックス、および酸化ポリエチレンワックスが挙げられる。 Examples of hydrocarbon lubricants include liquid paraffin, paraffin wax, polyethylene wax, and oxidized polyethylene wax.
　高級脂肪酸系滑剤としては、例えば、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ベヘニン酸、アラキジン酸、セロチン酸、モンタン酸、メリシン酸などの炭素数１０以上、好ましくは炭素数１２以上の高級飽和脂肪酸；オレイン酸、リノール酸、リノレン酸、エライジン酸、オクタデセン酸、アラキドン酸、カドレイン酸、エルカ酸、パリナリン酸などの炭素数が１２以上の不飽和脂肪酸；ならびにそれらの組み合わせが挙げられる。 Examples of higher fatty acid-based lubricants include higher fatty acids having 10 or more carbon atoms, preferably 12 or more carbon atoms, such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, arachidic acid, cerotic acid, montanic acid, and melisic acid. Saturated fatty acids; unsaturated fatty acids having 12 or more carbon atoms such as oleic acid, linoleic acid, linolenic acid, elaidic acid, octadecenoic acid, arachidonic acid, cadreic acid, erucic acid, and parinaric acid; and combinations thereof.
　高級アルコール系滑剤としては、例えば、ステアリルアルコールが挙げられる。 Examples of higher alcohol lubricants include stearyl alcohol.
　脂肪族アミド系滑剤としては、例えば、ラウリン酸アミド、パルミチン酸アミド、ステアリン酸アミド、ベヘニン酸アミド等の飽和高級脂肪酸アミド；エルカ酸アミド、オレイン酸アミド、ブラシジン酸アミド、エライジン酸アミド等の不飽和高級脂肪酸アミド；Ｎ－ステアリルステアリン酸アミド、Ｎ－オレイルオレイン酸アミド、Ｎ－ステアリルオレイン酸アミド、Ｎ－オレイルステアリン酸アミド、Ｎ－ステアリルエルカ酸アミド、Ｎ－オレイルパルミチン酸アミド等の置換アミド；メチロールステアリン酸アミド、メチロールベヘン酸アミド等のメチロールアミド；メチレンビスステアリン酸アミド、エチレンビスカプリン酸アミド、エチレンビスラウリン酸アミド、エチレンビスステアリン酸アミド（エチレンビスステアリルアミド）、エチレンビスイソステアリン酸アミド、エチレンビスヒドロキシステアリン酸アミド、エチレンビスベヘン酸アミド、ヘキサメチレンビスステアリン酸アミド、ヘキサメチレンビスベヘン酸アミド、ヘキサメチレンビスヒドロキシステアリン酸アミド、Ｎ，Ｎ’－ジステアリルアジピン酸アミド、Ｎ，Ｎ’－ジステアリルセバシン酸アミド等の飽和脂肪酸ビスアミド；エチレンビスオレイン酸アミド、ヘキサメチレンビスオレイン酸アミド、Ｎ，Ｎ’－ジオレイルアジピン酸アミド、Ｎ，Ｎ’－ジオレイルセバシン酸アミド等の不飽和脂肪酸ビスアミド；ならびにそれらの組み合わせが挙げられる。 Examples of aliphatic amide lubricants include saturated higher fatty acid amides such as lauric acid amide, palmitic acid amide, stearic acid amide, and behenic acid amide; Saturated higher fatty acid amides; substituted amides such as N-stearyl stearamide, N-oleyl oleic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide, N-oleyl palmitic acid amide, etc. ; Methylolamides such as methylolstearamide and methylolbehenic acid amide; Methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, ethylene bis stearic acid amide (ethylene bis stearyl amide), ethylene bis isostearic acid amide , ethylene bishydroxystearamide, ethylene bisbehenic acid amide, hexamethylene bisstearic acid amide, hexamethylene bisbehenic acid amide, hexamethylene bishydroxystearic acid amide, N,N'-distearyl adipic acid amide, N,N Saturated fatty acid bisamides such as '-distearylsebacic acid amide; Saturated fatty acid bisamides; as well as combinations thereof.
　金属塩系滑剤としては、例えば、ステアリン酸鉛、ステアリン酸亜鉛、ステアリン酸カルシウム、ステアリン酸マグネシウム、ステアリン酸アルミニウム、およびステアリン酸バリウムが挙げられる。 Examples of metal salt lubricants include lead stearate, zinc stearate, calcium stearate, magnesium stearate, aluminum stearate, and barium stearate.
　エステル系滑剤としては、例えば、ステアリルステアレート、ベヘニルベヘネート等の炭素数１２～２６の高級脂肪酸と炭素数１２～２４のモノアルコールとのエステル；エチレングリコール－モノまたはジパルミチネート、エチレングリコールモノまたはジステアレート、エチレングリコールモノまたはジベヘネート、エチレングリコールモノまたはジモンタネート等の炭素数２～６のアルキレンジオールと炭素数１２～２６の高級脂肪酸とのエステル；グリセリンモノ、ジまたはトリパルミチネート、グリセリンモノ、ジまたはトリステアレート、グリセリンモノ、ジまたはトリベヘネート、グリセリンモノ、ジまたはトリモンタネート等の炭素数３～６のアルカントリオール（例えばグリセリン等）と炭素数１２～２４の高級脂肪酸とのモノ、ジまたはトリエステル；ペンタエリスリトールモノ、ジ、トリまたはテトラパルミチネート、ペンタエリスリトールモノ、ジ、トリまたはテトラステアレート、ペンタエリスリトールモノ、ジ、トリまたはテトラベヘネート、ペンタエリスリトールモノ、ジ、トリまたはテトラモンタネート等のペンタエリスリトールと炭素数１４～２４の高級脂肪酸とのモノ、ジ、トリまたはテトラエステル；ならびにそれらの組み合わせが挙げられる。 Examples of ester lubricants include esters of higher fatty acids having 12 to 26 carbon atoms and monoalcohols having 12 to 24 carbon atoms, such as stearyl stearate and behenyl behenate; ethylene glycol mono- or dipalmitinate, ethylene glycol mono- or dipalmitinate; Esters of alkylene diols having 2 to 6 carbon atoms such as distearate, ethylene glycol mono- or dibehenate, ethylene glycol mono- or dimontanate and higher fatty acids having 12 to 26 carbon atoms; glycerin mono-, di- or tripalmitinate, glycerin mono-, di- Or mono-, di- or tristearate, glycerin mono-, di- or tribehenate, glycerin mono-, di- or trimontanate, and other alkanetriols having 3 to 6 carbon atoms (e.g. glycerin) and higher fatty acids having 12 to 24 carbon atoms. Triester; pentaerythritol mono, di, tri or tetrapalmitinate, pentaerythritol mono, di, tri or tetrastearate, pentaerythritol mono, di, tri or tetrabehenate, pentaerythritol mono, di, tri or tetramontanate etc. mono-, di-, tri- or tetra-esters of pentaerythritol and higher fatty acids having 14 to 24 carbon atoms; and combinations thereof.
　他の添加剤として使用され得る難燃剤は、例えば樹脂成形分野において一般的なものである。難燃剤の例としては、ハロゲン系難燃剤、臭素系難燃剤、ヘキサブロモシクロデカン、ビス（ジブロモプロピル）テトラブロモビスフェノールＡ、ビス（ジブロモプロピル）テトラブロモビスフェノールＡ、トリス（ジブロモプロピル）シソシアヌレート、トリス（トリブロモネオペンチル）ホスフェート、デカブロモジフェニルオキサイド、臭素化エポキシ樹脂、ビス（ペンタブロモ）フェニルエタン、トリス（トリブロモフェノキシ）トリアジン、エチレンビステトラブロモフタルイミド、ポリブロモフェニルインダン、臭素化ポリスチレン、ＴＢＢＰＡポリカーボネート、臭素化フェニレンオキサイド、ポリペンタブロモベンジルアクリレート、塩素系難燃剤、塩素系パラフィン、パークロロシクロペンタデカン、水和金属化合物、水酸化アルミニウム、水酸化マグネシウム、アルミ酸カルシウム、リン系化合物、赤燐、Ｎ系化合物、リン酸アンモン、炭酸アンモン、ホウ酸亜鉛、モリブデン化合物、モリブデン酸亜鉛、錫酸亜鉛、リン系難燃剤、ホスファゼン、リン酸エステル、トリフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、トリメチルホスフェート、トリエチルホスフェート、クレジルジフェニルホスフェート、2-エチルヘキシルジフェニルホスフェート、トリアリルホスフェート、芳香族リン酸エステル、芳香族縮合リン酸エステル、トリスジクロロプロピルホスフェート、トリスβ－クロロプロピルホスフェート、ハロゲンリン酸エステル、ポリリン酸アンモニウム、ポリリンサン塩、含リンポリオール、ポリリン酸アンモニウム、含リンアミン、シリコーン系難燃剤、シリコーンポリマー、トリアジン化合物、メラミン系難燃剤、メラミンシアヌレート、硫酸メラミン、ポリ化リン酸メラミン、グアニジン系難燃剤、グアニジン化合物、スルファミン酸グアニジン、リン酸グアニジン、グアニル尿素系難燃剤、およびリン酸グアニル尿素、ならびにそれらの組み合わせが挙げられる。 Flame retardants that can be used as other additives are, for example, those common in the field of resin molding. Examples of flame retardants include halogenated flame retardants, brominated flame retardants, hexabromocyclodecane, bis(dibromopropyl)tetrabromobisphenol A, bis(dibromopropyl)tetrabromobisphenol A, and tris(dibromopropyl)cysocyanurate. , tris(tribromoneopentyl) phosphate, decabromodiphenyl oxide, brominated epoxy resin, bis(pentabromo)phenylethane, tris(tribromophenoxy)triazine, ethylene bistetrabromophthalimide, polybromophenyl indan, brominated polystyrene, TBBPA polycarbonate, brominated phenylene oxide, polypentabromobenzyl acrylate, chlorinated flame retardant, chlorinated paraffin, perchlorocyclopentadecane, hydrated metal compound, aluminum hydroxide, magnesium hydroxide, calcium aluminate, phosphorus compound, red Phosphorus, N-based compounds, ammonium phosphate, ammonium carbonate, zinc borate, molybdenum compounds, zinc molybdate, zinc stannate, phosphorus flame retardants, phosphazene, phosphoric acid esters, triphenyl phosphate, tricresyl phosphate, tricresyl Nyl phosphate, trimethyl phosphate, triethyl phosphate, cresyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, triallyl phosphate, aromatic phosphate, aromatic condensed phosphate, tris dichloropropyl phosphate, tris β-chloropropyl phosphate, halogen Phosphate ester, ammonium polyphosphate, polyphosphorus salt, phosphorus-containing polyol, ammonium polyphosphate, phosphorus-containing amine, silicone flame retardant, silicone polymer, triazine compound, melamine flame retardant, melamine cyanurate, melamine sulfate, polyphosphoric acid Included are melamine, guanidine flame retardants, guanidine compounds, guanidine sulfamate, guanidine phosphate, guanylurea flame retardants, and guanylurea phosphate, and combinations thereof.
　他の添加剤として使用され得る着色剤は、例えば樹脂成形分野において一般的なものである。着色剤の例としては、染料（例えば、アゾ系、アントラキノン系、トリフェニルメタン系）、カーボンブラック、ベンガラ、フタロシアニン、および酸化チタン、ならびにそれらの組み合わせが挙げられる。 Colorants that can be used as other additives are, for example, those commonly used in the field of resin molding. Examples of colorants include dyes (eg, azo, anthraquinone, triphenylmethane), carbon black, red iron, phthalocyanine, and titanium oxide, and combinations thereof.
　他の添加剤として使用され得る低応力剤は、例えば樹脂成形分野において一般的なものである。低応力剤の例としては、ポリブタジエン化合物、アクリロニトリルブタジエン共重合化合物、アクリルゴム、イソプレンゴム、スチレンブタジエン共重合体、およびシリコーン化合物（例えばシリコーンオイルおよびシリコーンゴム）、エチレンアクリル酸共重合体、エチレンアクリル酸メチルコポリマー、エチレンアクリル酸エチルコポリマー、ならびにそれらの組み合わせが挙げられる。またこれらを組み合わせた成形体（例えば、コアシェル、バルーンなど）でもよい。 Low stress agents that can be used as other additives are, for example, those common in the field of resin molding. Examples of low stress agents include polybutadiene compounds, acrylonitrile butadiene copolymers, acrylic rubber, isoprene rubber, styrene butadiene copolymers, and silicone compounds (e.g. silicone oil and silicone rubber), ethylene acrylic acid copolymers, ethylene acrylic Included are acid methyl copolymers, ethylene ethyl acrylate copolymers, and combinations thereof. Alternatively, a molded article (for example, a core shell, a balloon, etc.) that is a combination of these may be used.
　本発明において、樹脂組成物に含有され得る上記他の添加剤の含有量は特に限定されない。使用されるもの種類および／または組み合わせによって、適切な含有量が当業者によって選択され得る。 In the present invention, the content of the other additives mentioned above that may be contained in the resin composition is not particularly limited. An appropriate content can be selected by a person skilled in the art depending on the type and/or combination used.
　本発明の樹脂組成物は、上記構成成分を含有することにより、以下のような物性を有する。 The resin composition of the present invention has the following physical properties by containing the above constituent components.
　まず、本発明の樹脂組成物における、ＩＳＯ１７８に準拠して測定した曲げ弾性率は２０００ＭＰａ以上１２０００ＭＰａ以下、好ましくは２２００ＭＰａ以下１００００ＭＰａ以下である。得られる樹脂組成物の曲げ弾性率が当該範囲内にあることにより、適度な剛性を有した状態で摺動部材に適用することができる。 First, the flexural modulus of the resin composition of the present invention measured in accordance with ISO 178 is from 2,000 MPa to 12,000 MPa, preferably from 2,200 MPa to 10,000 MPa. When the flexural modulus of the resulting resin composition is within the range, it can be applied to sliding members with appropriate rigidity.
　さらに本発明の樹脂組成物では、ＪＩＳ　Ｋ７２１８に記載されたＡ法に準拠した面圧０．９８ＭＰａ、摺動速度５０ｃｍ／秒の条件で行う炭素鋼材（Ｓ４５Ｃ）とのスラスト摩耗試験において、試験開始直後から１００分間の範囲で最大摩擦係数は０．１０以上０．３５以下である。得られる樹脂組成物の上記最大摩擦係数が当該範囲内にあることにより、摺動部材の駆動時のエネルギーを低減することができる他、スティックスリップ現象を抑制することができる。 Furthermore, the resin composition of the present invention was tested in a thrust wear test with carbon steel (S45C) conducted under the conditions of a surface pressure of 0.98 MPa and a sliding speed of 50 cm/sec in accordance with method A described in JIS K7218. The maximum friction coefficient is 0.10 or more and 0.35 or less in the range of 100 minutes from immediately after. When the maximum friction coefficient of the obtained resin composition is within the range, it is possible to reduce the energy when driving the sliding member, and also to suppress the stick-slip phenomenon.
　本発明の樹脂組成物はまた、組成物全体としてのバイオマス度が好ましくは５０％以上、より好ましくは９０％以上、さらにより好ましくは９９％以上である。組成物自体がこのようなバイオマス度を有していることにより、石油・石炭などの鉱物資源の使用抑制につながり、焼却廃棄時に排出する二酸化炭素の実質的な削減に寄与することができる。 The resin composition of the present invention also has a biomass degree as a whole of preferably 50% or more, more preferably 90% or more, and even more preferably 99% or more. When the composition itself has such a degree of biomass, it leads to a reduction in the use of mineral resources such as petroleum and coal, and can contribute to a substantial reduction in carbon dioxide emitted during incineration and disposal.
　本発明の樹脂組成物はまた、ＪＩＳ　Ｋ７２１８に記載されたＡ法に準拠した面圧０．９８ＭＰａ、摺動速度５０ｃｍ／秒の条件で行う炭素鋼材（Ｓ４５Ｃ）とのスラスト摩耗試験において１００分間溶融することがないという性質を有していることが好ましい。得られる樹脂組成物が当該性質を有していることにより、高圧高速の摺動条件下での使用が可能な摺動部材を作製することができる。ここで、本明細書における用語「溶融」とは摩耗試験の摺動部において少なくとも１．０ｍｍ以上の深さを有する溝が発生し、かつ摺動部周辺に溶融物がバリとして明らかに目視観察できる状態を指して言う。 The resin composition of the present invention also melted for 100 minutes in a thrust wear test with carbon steel (S45C) conducted under the conditions of a surface pressure of 0.98 MPa and a sliding speed of 50 cm/sec in accordance with method A described in JIS K7218. It is preferable to have the property that there is no problem. Since the obtained resin composition has the above properties, a sliding member that can be used under high pressure and high speed sliding conditions can be produced. Here, the term "melting" in this specification means that grooves with a depth of at least 1.0 mm are generated in the sliding part of the wear test, and melted material is clearly visually observed as burrs around the sliding part. Point to the state in which you can do it.
　さらに、本発明の樹脂組成物は、ＪＩＳ　Ｋ７２１８に記載されたＡ法に準拠した面圧０．９８ＭＰａ、摺動速度５０ｃｍ／秒の条件で行う炭素鋼材（Ｓ４５Ｃ）とのスラスト摩耗試験において、好ましくは０．１×１０－３ｍｍ３／Ｎ・ｋｍ以上１０×１０－３ｍｍ３／Ｎ・ｋｍ以下、より好ましくは０．１×１０－３ｍｍ３／Ｎ・ｋｍ以上７．０×１０－３ｍｍ３／Ｎ・ｋｍ以下の比摩耗量を有する。比摩耗量がこのような範囲内にあることにより、当該樹脂組成物は摺動部材とした場合に十分な耐久性を有したものとすることができる。 Furthermore, the resin composition of the present invention preferably exhibits favorable results in a thrust wear test with carbon steel material (S45C) conducted under the conditions of a surface pressure of 0.98 MPa and a sliding speed of 50 cm/sec in accordance with Method A described in JIS K7218. is 0.1×10 −3 mm 3 /N・km or more and 10×10 −3 mm 3 /N・km or less, more preferably 0.1×10 −3 mm 3 /N・km or more and 7.0×10 It has a specific wear amount of -3 mm 3 /N・km or less. When the specific wear amount is within such a range, the resin composition can have sufficient durability when used as a sliding member.
　本発明の樹脂組成物は、一般に用いられている方法を用いて容易に調製することができる。例えば、バイオマス由良のポリアミド樹脂、セルロース系充填材および脂肪酸エステル、必要に応じて他の充填材および／または他の添加剤の各所定量を従来の混合機（例えば、ヘンシェルミキサー、スーパーミキサー、ボールミル、タンブラーミキサー等）で混合し、得られた混合物を例えば一軸または二軸のスクリュー型押出機に投入し、溶融混練してストランドに成形した後、ペレットの形態にすることができる。 The resin composition of the present invention can be easily prepared using commonly used methods. For example, predetermined amounts of each of the biomass Yura polyamide resin, cellulosic filler and fatty acid ester, and optionally other fillers and/or other additives are mixed in a conventional mixer (e.g., Henschel mixer, super mixer, ball mill, etc.). The resulting mixture can be put into, for example, a single- or twin-screw extruder, melt-kneaded, formed into a strand, and then formed into pellets.
　本発明の樹脂組成物は、例えば、相手材との摺動摩擦が求められる摺動部材の材料として用いられる。摺動部材の例としては、軸受け、ギア、ワッシャー、ガイドレール、サッシ、ファスナーなどが挙げられる。本発明の樹脂組成物を用いて得られた摺動部材は、摩擦・摩耗特性に優れており、良好な耐久性を有することによって長期に亘る使用が可能である。 The resin composition of the present invention is used, for example, as a material for a sliding member that requires sliding friction with a mating material. Examples of sliding members include bearings, gears, washers, guide rails, sashes, fasteners, and the like. The sliding member obtained using the resin composition of the present invention has excellent friction and wear characteristics, and has good durability, so that it can be used for a long period of time.
　以下、実施例により本発明をより具体的に説明するが、本発明はこれらの実施例により限定されるものではない。 Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.
　なお、各実施例および比較例で得られたペレット（樹脂組成物）の評価試験を以下のようにして行った。 Note that evaluation tests for the pellets (resin compositions) obtained in each of the Examples and Comparative Examples were conducted as follows.
（評価試験）
（１）曲げ弾性率
　二軸押出機で溶融混練することにより得られたペレット状の樹脂組成物を射出成形機に供給して射出成形し、幅１０ｍｍ、長さ９０ｍｍ、厚さ４ｍｍの試験片を作製し、精密万能試験機（株式会社島津製作所製オートグラフＡＧ－Ｘ）を用いて、ＩＳＯ１７８に準拠して、支点間距離６４ｍｍ、試験速度２ｍｍ／分で三点曲げ試験を行うことにより、曲げ弾性率（ＭＰａ）を測定した。 (Evaluation test)
(1) Flexural modulus A pellet-shaped resin composition obtained by melt-kneading with a twin-screw extruder was fed to an injection molding machine and injection molded to form a test piece with a width of 10 mm, a length of 90 mm, and a thickness of 4 mm. By making a three-point bending test using a precision universal testing machine (Autograph AG-X manufactured by Shimadzu Corporation) in accordance with ISO178, with a distance between fulcrums of 64 mm and a test speed of 2 mm/min, The flexural modulus (MPa) was measured.
（２）スラスト摩耗試験
　得られた樹脂組成物を用いて、射出成形にて得られた一辺が８０ｍｍ、厚さ３ｍｍの成形品（摺動部材に相当するものとして取り扱う）から一辺が３０ｍｍ、厚さ３ｍｍの平板を切り出して試験片とした。この試験片を試験台に固定し、ＪＩＳ　Ｋ７２１８に記載されたＡ法に準拠した炭素鋼材（Ｓ４５Ｃ）の円筒体（内径２０ｍｍ、外径２５．６ｍｍ、接触面積２ｃｍ２）とのスラスト摩耗試験を、摩擦摩耗試験機（株式会社エー・アンド・デイ製　摩擦摩耗試験機ＭＯＤＥＬ　ＥＦＭ－ＩＩＩ－Ｆ）を用いて、面圧０．９８ＭＰａ、摺動速度５０ｃｍ／秒の条件で行い、試験中に急激に温度および摩擦係数が上昇し、摩耗深さが１．０ｍｍを超えて試験片摺動部周辺に溶融物がバリとして明確に発生した時点、または摺動時間１００分、滑り距離として３ｋｍに達した時点で試験終了とした。 (2) Thrust wear test Using the obtained resin composition, a molded product with a side of 80 mm and a thickness of 3 mm obtained by injection molding (handled as equivalent to a sliding member) is molded into a molded product with a side of 30 mm and a thickness of 3 mm. A flat plate with a diameter of 3 mm was cut out to serve as a test piece. This test piece was fixed on a test stand and a thrust wear test was conducted with a carbon steel (S45C) cylindrical body (inner diameter 20 mm, outer diameter 25.6 mm, contact area 2 cm 2 ) in accordance with method A described in JIS K7218. , using a friction and wear tester (Friction and Wear Tester MODEL EFM-III-F manufactured by A&D Co., Ltd.) under the conditions of a surface pressure of 0.98 MPa and a sliding speed of 50 cm/sec. When the temperature and coefficient of friction increase, the wear depth exceeds 1.0 mm, and molten material clearly appears as burrs around the sliding part of the specimen, or the sliding time reaches 100 minutes and the sliding distance reaches 3 km. The test was terminated at that point.
　試験開始から終了までの範囲内で得られた摩擦係数の最大値を「最大摩擦係数」、積算摺動距離を「滑り距離」とし、この滑り距離が３ｋｍに満たないもの、すなわち試験時間が１００分間に満たないものを「溶融した」と判断した。試験終了時の試験片の摩耗体積を摩耗質量から求め、その値を荷重と滑り距離の積で除して「比摩耗量（ｍｍ３／Ｎ・ｋｍ）」を算出した。 The maximum value of the friction coefficient obtained within the range from the start to the end of the test is the "maximum friction coefficient", and the cumulative sliding distance is the "sliding distance", and if this sliding distance is less than 3 km, that is, the test time is 100 If the time was less than 1 minute, it was judged as "melted". The wear volume of the test piece at the end of the test was determined from the wear mass, and the value was divided by the product of the load and the sliding distance to calculate the "specific wear amount (mm 3 /N·km)".
（実施例１：ペレット（Ｅ１）の作製）
　ロッキングミキサーに、セルロース系充填材（レッテンマイヤージャパン株式会社製ＡＲＢＯＣＥＬ（登録商標）ＦＤ００）５５．６質量部、木質系炭化物（竹炭粉砕物）１８．５質量部、および脂肪酸エステル（グリセリンモノステアレート；理研ビタミン株式会社製リケマールＨ－１００）１１．１質量部（使用したセルロース系充填材の含有量の２０．０質量％に相当する）を仕込んで混合し、その混合物をバイオマス由来のポリアミド（ポリアミド１１；ＡＲＫＥＭＡ社製Ｒｉｌｓａｎ（登録商標）ＢＭＮＯ）１００質量部とともに二軸押出機で２３０℃にて溶融混練し、紐状の成形物を成形した後、空冷しながら搬送し、ストランドカッターにて裁断することによりペレット（Ｅ１）を得た。得られたペレット（Ｅ１）について、上記評価試験（１）および（２）を行った。結果を表１に示す。 (Example 1: Preparation of pellet (E1))
In a rocking mixer, 55.6 parts by mass of cellulose filler (ARBOCEL (registered trademark) FD00 manufactured by Rettenmeyer Japan Co., Ltd.), 18.5 parts by mass of woody charcoal (pulverized bamboo charcoal), and fatty acid ester (glycerin monostearate) were placed in a rocking mixer. 11.1 parts by mass (equivalent to 20.0 mass% of the content of the cellulose filler used) (Rikemar H-100 manufactured by Riken Vitamin Co., Ltd.) was charged and mixed, and the mixture was mixed with biomass-derived polyamide ( Polyamide 11; 100 parts by mass of Rilsan (registered trademark) BMNO manufactured by ARKEMA was melt-kneaded at 230°C in a twin-screw extruder to form a string-like molded product, transported while air-cooled, and processed with a strand cutter. Pellets (E1) were obtained by cutting. The above evaluation tests (1) and (2) were conducted on the obtained pellets (E1). The results are shown in Table 1.
（実施例２～６：ペレット（Ｅ２）～（Ｅ６）の作製）
　セルロース系充填材、木質系炭化物および脂肪酸エステルの添加量を表１に記載のように変更したこと以外は実施例１と同様にして、ペレット（Ｅ２）～（Ｅ６）をそれぞれ作成し、上記評価試験（１）および（２）を行った。結果を表１に示す。 (Examples 2 to 6: Preparation of pellets (E2) to (E6))
Pellets (E2) to (E6) were prepared in the same manner as in Example 1, except that the amounts of cellulose filler, woody carbide, and fatty acid ester were changed as shown in Table 1, and the above evaluations were performed. Tests (1) and (2) were conducted. The results are shown in Table 1.
　なお、実施例５および６で使用した竹短繊維には、過熱水蒸気処理竹粉（株式会社バンブーテクノ製）を使用した。 The short bamboo fibers used in Examples 5 and 6 were superheated steam-treated bamboo powder (manufactured by Bamboo Techno Co., Ltd.).
（比較例１～５：ペレット（Ｃ１）～（Ｃ５）の作製）
　セルロース系充填材、木質系炭化物および脂肪酸エステルの添加量を表１に記載のように変更したこと以外は実施例１と同様にして、ペレット（Ｃ１）～（Ｃ５）をそれぞれ作成し、上記評価試験（１）および（２）を行った。結果を表１に示す。 (Comparative Examples 1 to 5: Preparation of pellets (C1) to (C5))
Pellets (C1) to (C5) were prepared in the same manner as in Example 1, except that the amounts of cellulose filler, woody carbide, and fatty acid ester were changed as shown in Table 1, and the above evaluations were performed. Tests (1) and (2) were conducted. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示すように、実施例１～６で作製されたペレット（Ｅ１）～（Ｅ６）はいずれも、比較例１～５で作製されたペレット（Ｃ１）～（Ｃ５）を比較して、比摩耗量が抑えられ、試験中に溶融することもなかった。このことから、実施例１～６で作製されたペレット（Ｅ１）～（Ｅ６）を構成する樹脂組成物は、高圧高速の摺動条件にも耐え、耐摩耗性にも優れていることがわかる。 As shown in Table 1, pellets (E1) to (E6) produced in Examples 1 to 6 were compared with pellets (C1) to (C5) produced in Comparative Examples 1 to 5. The specific wear amount was suppressed and no melting occurred during the test. From this, it can be seen that the resin compositions constituting the pellets (E1) to (E6) produced in Examples 1 to 6 can withstand high pressure and high speed sliding conditions and have excellent wear resistance. .
　本発明によれば、例えば樹脂成形分野、電子・電気分野、通信機械分野、自動車部品製造分野、医療機器製造分野、半導体製造分野等の各種技術分野において有用である。 According to the present invention, it is useful in various technical fields such as, for example, the resin molding field, the electronic/electrical field, the communication machinery field, the automobile parts manufacturing field, the medical equipment manufacturing field, and the semiconductor manufacturing field.

Claims (8)

  1. 　バイオマス由来のポリアミド樹脂、セルロース系充填材および脂肪酸エステルを含有し、ＩＳＯ１７８に準拠して測定した曲げ弾性率が２０００ＭＰａ以上１２０００ＭＰａ以下であり、かつＪＩＳ　Ｋ７２１８に記載されたＡ法に準拠した面圧０．９８ＭＰａ、摺動速度５０ｃｍ／秒の条件で行う炭素鋼材（Ｓ４５Ｃ）とのスラスト摩耗試験において、試験開始直後から１００分間の範囲で最大摩擦係数が０．１０以上０．３５以下である、樹脂組成物。 Contains biomass-derived polyamide resin, cellulose filler, and fatty acid ester, has a flexural modulus of 2,000 MPa or more and 12,000 MPa or less when measured in accordance with ISO178, and has a surface pressure of 0 according to method A described in JIS K7218. In a thrust wear test with carbon steel material (S45C) conducted under the conditions of .98 MPa and a sliding speed of 50 cm/sec, the resin has a maximum friction coefficient of 0.10 or more and 0.35 or less for 100 minutes from the start of the test. Composition.
  2. 　バイオマス度が５０％以上である、請求項１に記載の樹脂組成物。 The resin composition according to claim 1, having a biomass degree of 50% or more.
  3. 　前記セルロース系充填材が、前記ポリアミド樹脂１００質量部に対して４５質量部から１００質量部の含有量を有する充填材の構成成分として含有されており、
    　該セルロース系充填材の含有量が、該ポリアミド樹脂１００質量部に対して１０質量部から１００質量部であり、
    　前記脂肪酸エステルの含有量が、該セルロース系充填材の含有量の１５質量％から２５質量％に相当する、請求項１に記載の樹脂組成物。     The cellulose-based filler is contained as a constituent component of the filler in a content of 45 parts by mass to 100 parts by mass based on 100 parts by mass of the polyamide resin,
    The content of the cellulose filler is 10 parts by mass to 100 parts by mass with respect to 100 parts by mass of the polyamide resin,
    The resin composition according to claim 1, wherein the content of the fatty acid ester corresponds to 15% by mass to 25% by mass of the content of the cellulose filler.
  4. 　前記ポリアミド樹脂の融点が１６０℃以上２６０℃以下である、請求項１に記載の樹脂組成物。 The resin composition according to claim 1, wherein the polyamide resin has a melting point of 160°C or more and 260°C or less.
  5. 　前記脂肪酸エステルが、炭素数１２～２２の脂肪酸と多価アルコールとのエステルである、請求項１に記載の樹脂組成物。 The resin composition according to claim 1, wherein the fatty acid ester is an ester of a fatty acid having 12 to 22 carbon atoms and a polyhydric alcohol.
  6. 　さらに木質系炭化物を含有する、請求項１に記載の樹脂組成物。 The resin composition according to claim 1, further comprising a woody carbide.
  7. 　さらに、ＪＩＳ　Ｋ７２１８に記載されたＡ法に準拠した面圧０．９８ＭＰａ、摺動速度５０ｃｍ／秒の条件で行う炭素鋼材（Ｓ４５Ｃ）とのスラスト摩耗試験において１００分間溶融することなく、かつ０．１×１０－３ｍｍ３／Ｎ・ｋｍ以上１０×１０－３ｍｍ３／Ｎ・ｋｍ以下の比摩耗量を有する、請求項１に記載の樹脂組成物。 Furthermore, in a thrust wear test with carbon steel material (S45C) conducted under the conditions of a surface pressure of 0.98 MPa and a sliding speed of 50 cm/sec in accordance with method A described in JIS K7218, no melting occurred for 100 minutes, and 0. The resin composition according to claim 1, having a specific wear amount of 1×10 −3 mm 3 /N·km or more and 10×10 −3 mm 3 /N·km or less.
  8. 　請求項１から７のいずれかに記載の樹脂組成物を含む、摺動部材。 A sliding member comprising the resin composition according to any one of claims 1 to 7.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008050568A1 (en) * 2006-10-23 2008-05-02 Sony Corporation Resin composition, shaped article and process for producing the same, and electronic equipment
JP2013532757A (en) * 2010-08-06 2013-08-19 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン Composite materials containing natural fibers

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008050568A1 (en) * 2006-10-23 2008-05-02 Sony Corporation Resin composition, shaped article and process for producing the same, and electronic equipment
JP2013532757A (en) * 2010-08-06 2013-08-19 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン Composite materials containing natural fibers

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