WO2024080062A1 - 熱可塑性樹脂組成物及び成形品 - Google Patents

熱可塑性樹脂組成物及び成形品 Download PDF

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WO2024080062A1
WO2024080062A1 PCT/JP2023/033324 JP2023033324W WO2024080062A1 WO 2024080062 A1 WO2024080062 A1 WO 2024080062A1 JP 2023033324 W JP2023033324 W JP 2023033324W WO 2024080062 A1 WO2024080062 A1 WO 2024080062A1
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Prior art keywords
parts
resin
rubber
vinyl
component
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English (en)
French (fr)
Japanese (ja)
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崇 岩永
宏紀 安藤
成季 田中
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Techno UMG Co Ltd
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Techno UMG Co Ltd
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Priority to US18/993,780 priority Critical patent/US20260022243A1/en
Priority to JP2024516975A priority patent/JP7632746B2/ja
Priority to CN202380060806.7A priority patent/CN119731268A/zh
Priority to EP23877068.9A priority patent/EP4603541A1/en
Publication of WO2024080062A1 publication Critical patent/WO2024080062A1/ja
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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
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • 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
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the present invention relates to a thermoplastic resin composition that contains polyamide made from raw materials derived from biomass (organic resources derived from living organisms such as plants), has good moldability, excellent impact resistance, chemical resistance, and long-term durability, and suppresses the generation of creaking noises (rubbing noises) when it comes into dynamic contact with parts made of the same or different materials.
  • the present invention also relates to a molded article of this thermoplastic resin composition.
  • Thermoplastic resin compositions are widely used as molding materials for parts of vehicles, office automation equipment, home appliances, electric and electronic equipment, building materials, and the like.
  • polyamide resins have excellent mechanical strength, chemical resistance, abrasion resistance, and other characteristics, and are therefore used in many applications, such as automobiles, industrial products such as electrical/electronic/machine parts, and sports/leisure products.
  • polyamide resins have the disadvantages of poor paintability and impact resistance.
  • polyamide resins have the problem of being prone to water absorption and large dimensional changes due to their chemical structure. Therefore, many studies have been conducted in the past to improve these disadvantages.
  • a rubber-modified nylon composition has been proposed in which a carboxylic acid group-containing copolymer obtained by copolymerizing an unsaturated carboxylic acid with styrene or acrylonitrile is used as a compatibilizer, and ABS resin is blended with a polyamide resin (see Patent Document 1).
  • thermoplastic resin composition has been proposed in which glass fiber or carbon fiber is blended into a composition containing polyamide resin and ABS resin (see Patent Document 2).
  • This thermoplastic resin composition has excellent impact resistance, dimensional stability, rigidity, and heat resistance, making it a molding material with a good balance of performance.
  • thermoplastic resin parts used in these fields there are some that are used in combination with other parts, such as thermoplastic resin parts made of the same or different material as thermoplastic resin composition X, cured resin parts, or inorganic material parts made of metal or inorganic compounds.
  • thermoplastic resin parts and other parts are placed in contact with each other, or these parts are placed at a predetermined interval (see Patent Documents 3 and 4).
  • thermoplastic resin parts are adjacent to each other (simply in contact with each other, or in contact with each other with a part of an adhesive portion, or in contact with each other with a predetermined interval), it is known that one or both of them move or deform due to vibration, rotation, twisting, sliding, impact, etc., and come into dynamic contact, generating a creaking sound (rubbing sound). It is said that this creaking sound is a sound caused by the stick-slip phenomenon that occurs when two objects rub against each other.
  • the stick-slip phenomenon is said to be a phenomenon different from the conventionally known sliding phenomenon between objects.
  • the stick-slip phenomenon is understood as a phenomenon in which frictional force fluctuates greatly periodically, as shown in FIG. 1. Specifically, the stick-slip phenomenon occurs as shown in FIG. 2. That is, when an object M connected by a spring is placed on a drive stage moving at a drive speed V as shown in the model of FIG. 2(a), the object M first moves to the right as shown in FIG. 2(b) together with the stage moving at the drive speed V due to the action of static frictional force. Then, when the force of the spring trying to return the object M to its original position becomes equal to this static frictional force, the object M starts to slip in the direction opposite to the drive speed V.
  • the object M is subjected to a kinetic frictional force, and the slipping stops at the point in FIG. 2(c) where the force of the spring and this kinetic frictional force become equal. That is, the object M adheres to the drive stage and moves again in the same direction as the drive speed V (FIG. 2(d)). This is called the stick-slip phenomenon. As shown in FIG. 1, it is said that when the difference ⁇ between the static friction coefficient ⁇ s and the friction coefficient ⁇ l at the lower end of the sawtooth waveform is large, creaking noise is likely to occur.
  • the dynamic friction coefficient is an intermediate value between ⁇ s and ⁇ l.
  • creaking noise is a major cause of loss of comfort and quietness in the interior of a car, an office, or a house. For this reason, there is a strong demand for suppression or reduction of the occurrence of creaking noise.
  • Patent Document 3 discloses a thermoplastic resin composition which contains a rubber-reinforced aromatic vinyl resin (A, B), a crystalline thermoplastic resin (C) and a fibrous or layered filler (D), and which has a melting point measured in accordance with JIS K7121-1987 in the range of 0 to 100° C. and 170 to 280° C. and a flexural modulus of elasticity of 3,000 MPa or more.
  • Patent Document 4 discloses an automobile interior part made of a thermoplastic resin composition that is 100% by mass of the above (A), (B) and (C) components, and comprises a rubber-reinforced styrene-based resin (A1) obtained by polymerizing a vinyl-based monomer (b) consisting of an aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer copolymerizable with the aromatic vinyl compound in the presence of a rubber-based polymer (a) consisting of a conjugated diene-based rubber-based polymer (a-1) and/or an acrylic rubber-based polymer (a-2). ...
  • A1 rubber-reinforced styrene-based resin
  • thermoplastic resin composition containing a polyamide resin as the main component and further containing an inorganic filler is known (see Patent Document 5).
  • polyamide resins such as polyamide 6 are prone to moisture absorption and dimensional changes, making it difficult to maintain long-term suppression or reduction of squeak noise.
  • biomass is an organic compound produced by photosynthesis from carbon dioxide and water.
  • biomass is a so-called carbon-neutral raw material, which turns back into carbon dioxide and water (the amount of carbon dioxide emitted and absorbed in the environment is the same, so the increase of carbon dioxide, a greenhouse gas, can be suppressed).
  • biomass plastics made from these biomass raw materials has progressed rapidly. Attempts are also being made to produce polyamide, a general-purpose polymer material, from these biomass raw materials.
  • the object of the present invention is to provide a thermoplastic resin composition containing a biomass-derived polyamide that has good moldability, excellent impact resistance, chemical resistance, and long-term durability, and suppresses the generation of creaking noises (rubbing noises) when in dynamic contact with parts made of the same or different materials.
  • the present inventors have found that by blending a biomass-derived polyamide (A) with a rubber-reinforced vinyl graft resin (B), an aromatic vinyl copolymer resin (C), and an acid-modified vinyl resin (D) in predetermined ratios, it is possible to obtain a product with good moldability, excellent impact resistance, chemical resistance, and long-term durability, while also significantly reducing the generation of the above-mentioned creaking noise.
  • the present invention relates to the following.
  • thermoplastic resin composition comprising a polyamide (A) at least a part of which is derived from biomass, a rubber-reinforced vinyl graft resin (B), an aromatic vinyl copolymer resin (C), and an acid-modified vinyl resin (D),
  • a thermoplastic resin composition comprising, per 100 parts by mass in total of polyamide (A), rubber-reinforced vinyl-based graft resin (B), aromatic vinyl-based copolymer resin (C) and acid-modified vinyl-based resin (D), 20 to 70 parts by mass of polyamide (A), 5 to 45 parts by mass of rubber-reinforced vinyl-based graft resin (B), 10 to 75 parts by mass in total of aromatic vinyl-based copolymer resin (C) and acid-modified vinyl-based resin (D), and 0.1 to 40 parts by mass of acid-modified vinyl-based resin (D).
  • the rubber-reinforced vinyl-based graft resin (B) comprises a rubber polymer (b) portion and a resin (m) portion containing a structural unit derived from a vinyl-based monomer grafted to the rubber polymer (b); 2.
  • thermoplastic resin composition of the present invention it is possible to provide a molded article which contains a biomass-derived polyamide, has good moldability, and is excellent in impact resistance, chemical resistance, and long-term durability, and which suppresses the generation of creaking noises (rubbing noises) when in dynamic contact with parts made of the same or different materials.
  • thermoplastic resin composition of the present invention further contains a reinforced vinyl graft resin using a specific ethylene- ⁇ -olefin rubber polymer, it is possible to obtain a molded article in which the generation of creaking noise (rubbing noise) is suppressed for a long period of time.
  • FIG. 1 is an explanatory diagram of the stick-slip phenomenon.
  • 2(a), (b), (c), and (d) are model diagrams of the stick-slip phenomenon.
  • FIG. 3 is a schematic cross-sectional view showing an example of a contact state between components.
  • FIG. 4 is a schematic cross-sectional view showing another example of the contact mode.
  • FIG. 5 is a schematic cross-sectional view showing another example of the contact mode.
  • FIG. 6 is a schematic cross-sectional view showing another example of the contact mode.
  • FIG. 7 is a schematic cross-sectional view showing another example of the contact mode.
  • FIG. 8 is a schematic cross-sectional view showing another example of the contact mode.
  • 9(A), (B), and (C) are schematic diagrams showing other contact modes, where Fig.
  • FIG. 10 is a schematic perspective view of the part 20 of FIG. 11(A), (B), and (C) are schematic diagrams showing other contact modes, where Fig. 11(A) is a plan view, Fig. 11(B) is a side view, and Fig. 11(C) is a cross-sectional view taken along line CC of Fig. 11(A).
  • FIG. 12(A), (B), and (C) are schematic diagrams showing other contact modes, where (A) is a plan view, (B) is a side view, and (C) is a cross-sectional view taken along line CC in (A).
  • FIG. 13 is a schematic perspective view of a part used in another contact mode in FIG.
  • Figures 14(A), (B) and (C) are schematic diagrams showing other contact modes, where Figure 14(A) is a bottom view, Figure 14(B) is a cross-sectional view taken along line B-B in Figure 14(A), and Figure 14(C) is a cross-sectional view taken along line CC in Figure 14(A).
  • thermoplastic resin composition and molded article of the present invention.
  • (meth)acrylic means acrylic and/or methacrylic.
  • (meth)acrylate means acrylate and/or methacrylate.
  • (meth)acryloyl means acryloyl and/or methacryloyl.
  • (Co)polymer means a homopolymer and/or a copolymer.
  • the thermoplastic resin composition of the present invention is a thermoplastic resin composition comprising polyamide (A), at least a part of which is derived from biomass as a raw material, a rubber-reinforced vinyl-based graft resin (B), an aromatic vinyl-based copolymer resin (C), and an acid-modified vinyl-based resin (D), characterized in that, per 100 parts by mass in total of the polyamide (A), the rubber-reinforced vinyl-based graft resin (B), the aromatic vinyl-based copolymer resin (C), and the acid-modified vinyl-based resin (D), the composition contains 20 to 70 parts by mass of polyamide (A), 5 to 45 parts by mass of the rubber-reinforced vinyl-based graft resin (B), 10 to 75 parts by mass in total of the aromatic vinyl-based copolymer resin (C) and the acid-modified vinyl-based resin (D), and 0.1 to 40 parts by mass of the acid-modified vinyl-based resin (D).
  • polyamide (A) polyamide
  • B
  • biomass-derived polyamide (A) may be referred to simply as “polyamide (A)” or “component (A).”
  • Rubber-reinforced vinyl graft resin (B), aromatic vinyl copolymer resin (C), and acid-modified vinyl resin (D) may be referred to as “component (B),” “component (C),” and “component (D),” respectively.
  • Component (B) according to the present invention differs from components (C) and (D) in that component (B) contains a rubber polymer portion, whereas components (C) and (D) do not contain a rubber polymer portion.
  • Components (C) and (D) differ in that component (D) contains acid-modified groups consisting of carboxy groups and/or acid anhydride groups, whereas component (C) does not contain these acid-modified groups.
  • a graft copolymer (B-1) is produced in which a resin containing a structural unit derived from a vinyl-based monomer is chemically bonded to a rubber-like polymer (b), and a resin (B-2) containing a structural unit derived from a vinyl-based monomer that exists in a free state without being bonded to the rubber-like polymer (b).
  • the graft copolymer (B-1) thus produced is defined as the rubber-reinforced vinyl graft resin (B) of component (B), and the resin (B-2) which is not grafted to the rubber polymer produced at the same time is defined as component (C) or component (D).
  • component (B) the resin (B-2) which is not grafted to the rubber polymer produced at the same time is defined as component (C) or component (D).
  • Component (B) can be distinguished from components (C) and/or (D) by solvent separation using acetone.
  • the reaction product during the production of rubber-reinforced vinyl graft resin (B) is put into acetone, shaken, and then centrifuged for solid-liquid separation to obtain an acetone-insoluble fraction, which corresponds to component (B).
  • the acetone-soluble fraction corresponds to components (C) and/or (D).
  • the components (C) and (D) according to the present invention may be used in the production of a thermoplastic resin composition as acetone-soluble components produced during the production of component (B), or components (C) and (D) produced separately from the production of component (B) may be used, or both of these may be used.
  • Polyamide (A) is a resin having an acid amide bond (-CO-NH-) in the main chain.
  • Polyamide (A) can be produced by a conventional method, that is, by polymerization of lactam or amino acid having a ring structure, or by condensation polymerization of dicarboxylic acid and diamine. Therefore, as polyamide (A), homopolyamide, copolyamide, etc. can be used.
  • the polyamide (A) used in the present invention is, for example, polyamide 11, polyamide 610, polyamide 1010, polyamide 410, polyamide MXD10 resin, polyamide 11-6T copolymer resin, etc., and is a polyamide that uses a monomer derived from biomass as at least a part of the raw material.
  • a particularly preferred polyamide (A) is polyamide 11.
  • Polyamide 11 is a polyamide having a structure in which monomers having 11 carbon atoms are bonded via amide bonds.
  • Polyamide 11 is usually obtained by using aminoundecanoic acid or undecane lactam as a monomer.
  • aminoundecanoic acid is a monomer obtained from castor oil, and is therefore desirable from the viewpoint of carbon neutrality.
  • the content of the structural units derived from these monomers having 11 carbon atoms is preferably 50 mol % or more, more preferably 80 mol % or more, and may be 100 mol % of the total structural units of polyamide 11.
  • Polyamide 11 is usually produced by the ring-opening polymerization of the above-mentioned undecane lactam.
  • the polyamide 11 obtained by the ring-opening polymerization is usually subjected to removal of the lactam monomer with hot water, followed by drying and melt extrusion in an extruder.
  • Polyamide 610 is a polyamide resin having a structure in which a diamine having six carbon atoms and a dicarboxylic acid having ten carbon atoms are polymerized. Usually, hexamethylenediamine and sebacic acid are used. Of these, sebacic acid is a monomer obtained from castor oil, and is therefore desirable from the viewpoint of carbon neutrality.
  • the total content of the structural units derived from a monomer having six carbon atoms and the structural units derived from a monomer having ten carbon atoms is preferably 50 mol% or more, more preferably 80 mol% or more, and may be 100 mol% of the total structural units of polyamide 610.
  • Polyamide 1010 is a polyamide resin having a structure in which a diamine having 10 carbon atoms and a dicarboxylic acid having 10 carbon atoms are polymerized.
  • 1,10-decanediamine (decamethylenediamine) and sebacic acid are used. Decamethylenediamine and sebacic acid are monomers obtained from castor oil, and are therefore desirable from the viewpoint of carbon neutrality.
  • the total content of the structural units derived from these monomers having 10 carbon atoms and the structural units derived from monomers having 10 carbon atoms is preferably 50 mol% or more, more preferably 80 mol% or more, and may be 100 mol% of the total structural units of polyamide 1010.
  • Polyamide 410 is a polyamide resin having a structure in which a diamine having four carbon atoms and a dicarboxylic acid having ten carbon atoms are polymerized. Usually, tetramethylenediamine and sebacic acid are used. Sebacic acid is a monomer obtained from castor oil, and is therefore desirable from the viewpoint of carbon neutrality.
  • the total content of the constituent units derived from these monomers having four carbon atoms and the constituent units derived from monomers having ten carbon atoms is preferably 50 mol% or more, more preferably 80 mol% or more, and may be 100 mol% of the total constituent units of polyamide 410.
  • the ends of the polyamide (A) may be blocked with a carboxylic acid, an amine, or the like.
  • carboxylic acid include aliphatic monocarboxylic acids such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid.
  • amine include aliphatic primary amines such as hexylamine, octylamine, decylamine, laurylamine, myristylamine, palmitylamine, stearylamine, and behenylamine.
  • the plant-based content of polyamide (A) as determined by ASTM 6866 (measurement of radioactive carbon 14C content) is preferably 50% or more, and more preferably 80 to 100%.
  • the melting point of polyamide (A) according to JIS K7121-1987 is preferably 160°C or higher, more preferably 170°C or higher, from the viewpoint of ease of mixing with rubber-reinforced vinyl graft resin (B), aromatic vinyl copolymer resin (C), and acid-modified vinyl resin (D).
  • thermoplastic resin composition of the present invention may contain only one type of polyamide (A), or may contain two or more types.
  • the rubber-reinforced vinyl-based graft resin (B) comprises a rubber polymer (b) portion and a resin (m) portion containing a structural unit derived from a vinyl-based monomer grafted to the rubber polymer (b), and the rubber polymer (b) and the resin (m) portion are chemically bonded to each other.
  • the rubber polymer (b) in the rubber-reinforced vinyl graft resin (B) include ethylene/ ⁇ -olefin rubber polymer (b1), diene rubber polymer (b2), acrylic rubber polymer (b3), silicone rubber polymer (b4), etc.
  • the rubber-reinforced vinyl-based graft resin (B) is preferably a graft resin obtained by polymerizing a vinyl-based monomer in the presence of an ethylene- ⁇ -olefin-based rubbery polymer and/or a diene-based rubbery polymer (b2), particularly an ethylene- ⁇ -olefin-based rubbery polymer (b1).
  • the weight average particle size of the rubber polymer (b) constituting the rubber-reinforced vinyl graft resin (B) is preferably 0.20 to 0.70 ⁇ m, more preferably 0.23 to 0.60 ⁇ m, and even more preferably 0.25 to 0.50 ⁇ m.
  • a thermoplastic resin composition having excellent impact resistance and suppression of creaking noise (rubbing noise) can be obtained.
  • a thermoplastic resin composition having excellent chemical resistance can be obtained.
  • the average particle size of the rubber polymer (b) is a value measured by the following measurement method 1 or measurement method 2.
  • ⁇ Method 1 for measuring average particle size The weight average particle size and number average particle size are determined using a Microtrac (manufactured by Nikkiso Co., Ltd., "Nanotrac UPA-EX150" dynamic light scattering method) as a measuring device and pure water as a measuring solvent.
  • This measuring method is mainly used for measuring the average particle size of the rubber polymer (b) in the rubber-reinforced vinyl graft resin (B) prepared by emulsion polymerization. Incidentally, it has been confirmed by image analysis using an electron microscope that the average particle size of the rubber polymer (b) dispersed in the latex is equivalent to the average particle size of the rubber polymer (b) in the thermoplastic resin composition.
  • the particle size of the rubber polymer (b) in the thermoplastic resin composition is measured by image analysis of a transmission electron microscope photograph of the thermoplastic resin composition to determine the weight average particle size (volume average particle size) and number average particle size.
  • This method is mainly used for measuring the average particle size of the rubber polymer (b) in the rubber-reinforced vinyl graft resin (B) prepared by solution polymerization.
  • the ethylene/ ⁇ -olefin rubber polymer (b1) is a copolymer containing structural units derived from ethylene and structural units derived from an ⁇ -olefin.
  • the ⁇ -olefin include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, and 1-eicosene.
  • These ⁇ -olefins can be used alone or in combination of two or more.
  • the number of carbon atoms of the ⁇ -olefin is preferably 3 to 20, more preferably 3 to 12, and even more preferably 3 to 8, from the viewpoint of the appearance and impact resistance of a molded article obtained using the thermoplastic resin composition of the present invention.
  • the content ratios of the structural units derived from ethylene and the structural units derived from the ⁇ -olefins constituting the ethylene- ⁇ -olefin rubber polymer (b1) are preferably 5 to 95 mass% of the structural units derived from ethylene and 5 to 95 mass% of the structural units derived from the ⁇ -olefins, more preferably 50 to 95 mass% of the structural units derived from ethylene and 5 to 50 mass% of the structural units derived from the ⁇ -olefins, and even more preferably 60 to 95 mass% of the structural units derived from ethylene and 5 to 40 mass% of the structural units derived from the ⁇ -olefins, when the sum of the two is taken as 100 mass%, in order to obtain a molded product that has good moldability, excellent impact resistance, chemical resistance, and long-term durability, and that suppresses the generation of creaking noises (rubbing noises) when it comes into dynamic contact with parts made of the same or other materials.
  • the preferred ethylene- ⁇ -olefin rubbery polymer (b1) is an ethylene- ⁇ -olefin copolymer having a melting point in the range of 0 to 100°C as measured according to JIS K7121-1987, and to that extent may have structural units derived from other monomers.
  • examples of other monomers include non-conjugated diene compounds such as alkenylnorbornenes, cyclic dienes, and aliphatic dienes.
  • the structural units derived from other monomers may be used alone or in combination of two or more.
  • the upper limit of the content of structural units derived from non-conjugated diene compounds is preferably 10% by mass, more preferably 5% by mass, and even more preferably 3% by mass, when the total amount of structural units constituting the ethylene- ⁇ -olefin rubbery polymer (b1) is taken as 100% by mass.
  • the melting point of the ethylene- ⁇ -olefin rubber polymer (b1) is more preferably 10 to 90° C., and even more preferably 20 to 80° C., in order to obtain a molded product which has good moldability, impact resistance, chemical resistance, and which suppresses the generation of creaking noise (rubbing noise) when dynamically contacted with a part made of the same or another material.
  • the melting point of the ethylene- ⁇ -olefin rubber polymer (b1) being in the range of 0 to 100° C. means that this rubber polymer has crystallinity.
  • the ethylene/ ⁇ -olefin rubber polymer (b1) is preferably an ethylene/ ⁇ -olefin copolymer comprising structural units derived from ethylene and structural units derived from an ⁇ -olefin, since the effects of the present invention can be sufficiently obtained.
  • the ethylene/ ⁇ -olefin rubber polymer (b1) in particular, an ethylene/propylene copolymer, an ethylene/1-butene copolymer, or an ethylene/1-octene copolymer is preferred, with an ethylene/propylene copolymer being particularly preferred.
  • These ethylene/ ⁇ -olefin rubber polymers (b1) can be used alone or in combination of two or more kinds.
  • diene rubber polymer (b2) examples include homopolymers such as polybutadiene and polyisoprene, butadiene copolymers such as styrene-butadiene copolymer, styrene-butadiene-styrene copolymer, acrylonitrile-styrene-butadiene copolymer, and acrylonitrile-butadiene copolymer, and isoprene copolymers such as styrene-isoprene copolymer, styrene-isoprene-styrene copolymer, and acrylonitrile-styrene-isoprene copolymer, etc.
  • the diene rubbery polymer (b2) may be a crosslinked polymer or a non-crosslinked polymer. These diene rubbery polymers (b2) may be used alone or in combination of two or more kinds.
  • the acrylic rubber polymer (b3) is not particularly limited, but is preferably a (co)polymer of a (meth)acrylic acid alkyl ester compound having an alkyl group with 1 to 8 carbon atoms, or a copolymer of this (meth)acrylic acid alkyl ester compound and a vinyl monomer copolymerizable therewith.
  • acrylic acid alkyl ester compound used herein in which the alkyl group has 1 to 8 carbon atoms, include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, i-butyl acrylate, amyl acrylate, hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, etc.
  • methacrylic acid alkyl ester compound examples include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, amyl methacrylate, hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, and cyclohexyl methacrylate.
  • n-butyl acrylate and 2-ethylhexyl acrylate are preferred, with n-butyl acrylate being particularly preferred. These may be used alone or in combination of two or more.
  • acrylic rubber polymers (b3) can be used alone or in combination of two or more.
  • the silicone rubber polymer (b4) is not particularly limited, but is preferably a polyorganosiloxane having a vinyl polymerizable functional group, and from the viewpoint of color development, a silicone/acrylic composite rubber is preferred.
  • a silicone/acrylic composite rubber a silicone/acrylic composite rubber in which polyorganosiloxane and an alkyl (meth)acrylate polymer are composited is preferable.
  • the silicone/acrylic composite rubber can be produced, for example, according to the method described in JP 2016-125006 A.
  • silicone rubber polymers (b4) can be used alone or in combination of two or more.
  • the vinyl monomer forming the resin (m) portion of the rubber-reinforced vinyl graft resin (B) is not particularly limited, but mainly includes aromatic vinyl compounds, vinyl cyanide compounds, (meth)acrylic acid ester compounds, maleimide compounds, vinyl monomers that provide structural units with carboxy groups, vinyl monomers that provide acid anhydride groups, vinyl monomers with other functional groups, etc. Among these, it is preferable to include aromatic vinyl compounds and vinyl cyanide compounds.
  • the aromatic vinyl compound is not particularly limited as long as it is a compound having at least one vinyl bond and at least one aromatic ring.
  • aromatic vinyl compounds include styrene, ⁇ -methylstyrene, o-methylstyrene, p-methylstyrene, ⁇ -methylstyrene, ethylstyrene, p-tert-butylstyrene, vinyltoluene, vinylxylene, vinylnaphthalene, and the like. Of these, styrene and ⁇ -methylstyrene are preferred, with styrene being particularly preferred. These can be used alone or in combination of two or more.
  • the vinyl cyanide compounds include acrylonitrile, methacrylonitrile, ethacrylonitrile, ⁇ -ethylacrylonitrile, ⁇ -isopropylacrylonitrile, etc. Among these, acrylonitrile is preferred. These can be used alone or in combination of two or more.
  • the above (meth)acrylic acid ester compounds include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, hexyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, etc. These can be used alone or in combination of two or more.
  • maleimide-based compound examples include maleimide, N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-dodecylmaleimide, N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-(2,6-diethylphenyl)maleimide, N-benzylmaleimide, N-naphthylmaleimide, N-cyclohexylmaleimide, etc. These can be used alone or in combination of two or more.
  • a method can be applied in which an unsaturated dicarboxylic acid anhydride is copolymerized with maleic anhydride, followed by imidization.
  • Vinyl monomers that provide structural units having a carboxyl group include (meth)acrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, etc. Of these, methacrylic acid is preferred. These can be used alone or in combination of two or more.
  • Vinyl monomers (unsaturated acid anhydrides) that provide structural units having an acid anhydride group include maleic anhydride, itaconic anhydride, citraconic anhydride, etc. These can be used alone or in combination of two or more.
  • vinyl monomers having at least one functional group selected from a hydroxy group, an amino group, an epoxy group, and an oxazoline group can also be used.
  • vinyl monomers having a hydroxy group include (meth)acrylic acid esters having a hydroxy group such as hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate; o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy- ⁇ -methylstyrene, m-hydroxy- ⁇ -methylstyrene, p -hydroxy- ⁇ -methylstyrene, 2-hydroxymethyl- ⁇ -methylstyrene, 3-hydroxymethyl- ⁇ -methylstyrene, 4-hydroxymethyl- ⁇ - ⁇ -
  • Vinyl monomers having an amino group include aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminomethyl acrylate, diethylaminomethyl acrylate, 2-dimethylaminoethyl acrylate, aminoethyl methacrylate, propylaminoethyl methacrylate, dimethylaminomethyl methacrylate, diethylaminomethyl methacrylate, 2-dimethylaminoethyl methacrylate, phenylaminoethyl methacrylate, p-aminostyrene, N-vinyldiethylamine, N-acetylvinylamine, acrylamine, methacrylamine, N-methylacrylamine, etc. These can be used alone or in combination of two or more.
  • vinyl monomers epoxy group-containing unsaturated compounds
  • examples of vinyl monomers (epoxy group-containing unsaturated compounds) that provide structural units having epoxy groups include glycidyl (meth)acrylate, 3,4-oxycyclohexyl (meth)acrylate, vinyl glycidyl ether, allyl glycidyl ether, and methallyl glycidyl ether. These can be used alone or in combination of two or more.
  • Vinyl monomers having an oxazoline group include vinyl oxazoline, 4-methyl-2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 2-vinyl-4,4-dimethyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 4-methyl-2-isopropenyl-2-oxazoline, 5-methyl-2-isopropenyl-2-oxazoline, 2-isopropenyl-4,4-dimethyl-2-oxazoline, etc. These can be used alone or in combination of two or more.
  • the resin (m) portion is preferably a resin (m1) portion containing a structural unit derived from an aromatic vinyl compound and a structural unit derived from a vinyl cyanide compound, or a resin (m2) portion containing a structural unit derived from a vinyl monomer that provides a structural unit derived from an aromatic vinyl compound, a structural unit derived from a vinyl cyanide compound, and a structural unit having a carboxy group, i.e., a structural unit derived from a carboxy group-containing unsaturated compound and/or an unsaturated acid anhydride, and more preferably a resin (m1) portion containing a structural unit derived from an aromatic vinyl compound and a structural unit derived from a vinyl cyanide compound.
  • the lower limit of the proportion of the total amount of structural units derived from aromatic vinyl compounds and structural units derived from vinyl cyanide compounds in a total of 100% by mass of structural units derived from vinyl monomers forming the resin (m) portion is preferably 50% by mass, more preferably 70% by mass, and even more preferably 90% by mass, from the viewpoint of the appearance and impact resistance of a molded article obtained using the thermoplastic resin composition of the present invention.
  • the content ratio of the structural units derived from aromatic vinyl compounds and the structural units derived from vinyl cyanide compounds contained in the resin (m1) part is preferably 50 to 95 mass% of structural units derived from aromatic vinyl compounds and 5 to 50 mass% of structural units derived from vinyl cyanide compounds, more preferably 60 to 85 mass% of structural units derived from aromatic vinyl compounds and 15 to 40 mass% of structural units derived from vinyl cyanide compounds, and even more preferably 65 to 80 mass% of structural units derived from aromatic vinyl compounds and 20 to 35 mass% of structural units derived from vinyl cyanide compounds, from the viewpoint of the appearance, impact resistance, and color tone of a molded article obtained using the thermoplastic resin composition of the present invention.
  • the content of the structural unit derived from the carboxyl-containing unsaturated compound and/or an unsaturated acid anhydride is preferably 0.1 to 20% by mass, more preferably 1 to 20% by mass, and even more preferably 2 to 8% by mass, based on the total 100% by mass of the structural units derived from the vinyl monomers forming the resin (m2).
  • the content ratio of the structural units derived from an aromatic vinyl compound and the structural units derived from a vinyl cyanide compound in the resin (m2) part is preferably the same as that in the resin (m1) part.
  • the rubber-reinforced vinyl graft resin (B) contains a rubber-like polymer (b) part and a resin (m) part in a proportion that, when the total of the two is taken as 100% by mass, is 100% by mass, because it provides a molded product that has good moldability, excellent impact resistance, chemical resistance, and long-term durability, and suppresses the generation of creaking noises (rubbing noises) when in dynamic contact with parts made of the same or different materials. Therefore, the rubber-like polymer (b) part and the resin (m) part are preferably 20 to 90% by mass and 10 to 80% by mass, more preferably 25 to 84% by mass and 16 to 75% by mass, and even more preferably 30 to 77% by mass and 23 to 70% by mass, respectively.
  • the graft ratio of the rubber-reinforced vinyl graft resin (B) of component (B) is usually 10 to 150%, preferably 15 to 120%, more preferably 20 to 100%, and particularly preferably 30 to 80%.
  • the graft ratio of component (B) is within the above range, the impact resistance and moldability of the resulting thermoplastic resin composition are further improved.
  • S represents the mass (g) of the insoluble matter obtained by adding 1 g of component (B) or a mixture of component (B) and component (C) and/or component (D) obtained by the above-mentioned production method by graft polymerization to 20 mL of acetone, shaking the mixture for 2 hours using a shaker at 25° C., and then centrifuging the mixture for 60 minutes using a centrifuge (rotation speed: 23,000 rpm) at 5° C. to separate the insoluble matter from the soluble matter.
  • T is the mass (g) of the rubber polymer (b) contained in 1 g of the component (B).
  • the mass of the rubber polymer (b) can be obtained by a method of calculation from the polymerization recipe and the polymerization conversion rate, or by a method of determination by infrared absorption spectroscopy (IR), pyrolysis gas chromatography, CHN elemental analysis, or the like.
  • the graft ratio of component (B) can be adjusted by appropriately selecting, for example, the type and amount of chain transfer agent used in the graft polymerization when producing component (B), the type and amount of polymerization initiator used, the method and time of addition of the monomer components during polymerization, the polymerization temperature, etc.
  • thermoplastic resin composition of the present invention may contain only one type of rubber-reinforced vinyl graft resin (B), or may contain two or more types of resins differing in the type, composition, physical properties, etc. of structural units.
  • the rubber polymer (b) of the rubber-reinforced vinyl-based graft resin (B) may be an ethylene/ ⁇ -olefin-based rubber polymer (b1), a diene-based rubber polymer (b2), an acrylic-based rubber polymer (b3), a silicone-based rubber polymer (b4), etc.
  • the rubber-reinforced vinyl-based graft resin (B) may be a graft resin containing an ethylene/ ⁇ -olefin-based rubber polymer (b1) as the rubber polymer (b), a graft resin containing a diene-based rubber polymer (b2) as the rubber polymer (b), a graft resin containing an acrylic-based rubber polymer (b3) as the rubber polymer (b), a graft resin containing a silicone-based rubber polymer (b4) as the rubber polymer (b), etc., and two or more of these may be used in combination.
  • a rubber-reinforced vinyl graft resin (B) containing an ethylene- ⁇ -olefin rubber polymer (b1) as the rubber polymer (b) alone.
  • the rubber-reinforced vinyl graft resin (B) can be produced, for example, by graft polymerizing a vinyl monomer consisting of an aromatic vinyl compound and, if desired, another vinyl compound copolymerizable with the aromatic vinyl compound, in the presence of a rubber polymer (b) such as an ethylene- ⁇ -olefin rubber polymer (b1) having a melting point (Tm) of 0 to 100°C.
  • a rubber polymer (b) such as an ethylene- ⁇ -olefin rubber polymer (b1) having a melting point (Tm) of 0 to 100°C.
  • the polymerization method in this production method is not particularly limited as long as the graft copolymer component (B) is obtained, and known methods can be applied.
  • the polymerization method emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a combination of these can be used. In these polymerization methods, known polymerization initiators, chain transfer agents (mole
  • a mixed product is obtained from the above-mentioned component (B), which is a graft copolymer (B-1) in which a (co)polymer of vinyl monomers is graft-polymerized to a rubber polymer (b), and the above-mentioned component (C) and/or component (D), which is a (co)polymer resin (B-2) in which vinyl monomers are not graft-polymerized to a rubber polymer (b).
  • the mixed product may also contain a rubber polymer (b) to which the (co)polymer is not graft-polymerized.
  • thermoplastic resin composition of the present invention contains components (B), (C), and (D) as essential components.
  • the thermoplastic resin composition of the present invention contains both the above-mentioned components (B), (C), and (D) as essential components. Therefore, the mixed product of the above-mentioned component (B) and the component (C) and/or the component (D) manufactured as described above can be used as it is as the raw material of the thermoplastic resin composition of the present invention as the component (B), the component (C), and/or the component (D).
  • the graft copolymer (B-1) which is the component (B) can be separated from the mixed product of the component (B) and the resin (B-2) which is the component (C) and/or the component (D) by solvent separation using acetone. Specifically, the mixed product of the component (B) and the component (C) and/or the component (D) is put into acetone, shaken, and then centrifuged, whereby the component (B) is obtained as an acetone insoluble matter, and the component (C) and/or the component (D) is obtained as an acetone soluble matter.
  • the raw material of component (B) in the thermoplastic resin composition of the present invention can be an acetone insoluble matter separated by the acetone separation from the mixed product of the component (B) and the component (C) and/or the component (D).
  • the raw material of component (C) and/or the component (D) in the thermoplastic resin composition of the present invention can be an acetone soluble matter separated by the acetone separation from the mixed product of the component (B) and the component (C) and/or the component (D).
  • the above-mentioned components (B), (C) and (D) may be a mixture produced by mixing the separated components (B) and (C) and/or (D).
  • the aromatic vinyl copolymer resin (C) is a copolymer having structural units derived from vinyl monomers including at least an aromatic vinyl compound.
  • the aromatic vinyl copolymer resin (C) preferably has the same structural unit composition as the resin (m1) portion described above, including structural units derived from an aromatic vinyl compound and structural units derived from a vinyl cyanide compound.
  • the aromatic vinyl copolymer resin (C) may be one produced as resin (B-2) during the production of component (B), or may be one obtained by copolymerizing a vinyl monomer containing an aromatic vinyl compound separately from this resin (B-2) without using a rubber polymer, or may contain both.
  • component (C) produced as resin (B-2) during the production of component (B) and component (C) produced separately without using a rubber polymer are used, the vinyl monomer compositions and physical properties of these components may be different or the same.
  • the intrinsic viscosity (in methyl ethyl ketone, 30°C) of component (C) in the thermoplastic resin composition of the present invention is usually 0.1 to 1.5 dL/g, preferably 0.15 to 1.2 dL/g, and more preferably 0.15 to 1.0 dL/g. When the intrinsic viscosity is within the above range, the impact resistance and moldability of the thermoplastic resin composition of the present invention are improved.
  • the intrinsic viscosity [ ⁇ ] of component (C) and component (D) described below was measured by the following method. First, the acetone-soluble portion of component (C) or component (D), or the mixed product of component (B) and component (C) and/or component (D), is dissolved in methyl ethyl ketone to prepare five solutions with different concentrations. The reduced viscosity of each solution is measured at 30° C. using an Ubbelohde viscometer, and the intrinsic viscosity [ ⁇ ] (dL/g) is calculated from the results.
  • thermoplastic resin composition of the present invention may contain only one type of component (C), or may contain two or more types that differ in the type, composition, physical properties, etc. of structural units.
  • the acid-modified vinyl resin (D) is a copolymer having at least an acid-modified group, i.e., a structural unit derived from a vinyl monomer having a carboxyl group and/or an acid anhydride group.
  • the acid-modified vinyl resin (D) preferably has a structural unit composition similar to that of the resin (m2) part described above, including a structural unit derived from an aromatic vinyl compound, a structural unit derived from a vinyl cyanide compound, and a structural unit derived from a carboxyl group-containing unsaturated compound and/or an unsaturated acid anhydride.
  • the acid-modified vinyl resin (D) may be one produced as resin (B-2) during the production of component (B), or may be one obtained by copolymerizing a vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound, and a carboxyl group-containing unsaturated compound and/or an unsaturated acid anhydride, without using a rubber polymer, separately from this resin (B-2), or may contain both.
  • component (D) produced as resin (B-2) during the production of component (B) and component (D) produced separately without using a rubber polymer are used, the vinyl monomer compositions and physical properties of these components may be different or the same.
  • the intrinsic viscosity (in methyl ethyl ketone, 30°C) of component (D) in the thermoplastic resin composition of the present invention is usually 0.1 to 1.5 dL/g, preferably 0.15 to 1.2 dL/g, and more preferably 0.15 to 1.0 dL/g. When the intrinsic viscosity is within the above range, the impact resistance and moldability of the thermoplastic resin composition of the present invention are improved.
  • thermoplastic resin composition of the present invention may contain only one type of component (D), or may contain two or more types that differ in the type, composition, physical properties, etc. of structural units.
  • the content of component (A) in the thermoplastic resin composition of the present invention is 20 to 70 parts by mass, preferably 25 to 65 parts by mass, and more preferably 30 to 60 parts by mass, per 100 parts by mass of the total of components (A), (B), (C), and (D). If the content of component (A) is equal to or higher than the lower limit, the impact resistance, chemical resistance, and squeak noise reduction effect due to the inclusion of component (A) are excellent. In addition, the carbon neutral effect can be improved by including biomass-derived polyamide (A). If the content of component (A) is equal to or lower than the upper limit, the contents of other components (B) to (D) can be secured, resulting in excellent long-term durability.
  • the content of component (B) in the thermoplastic resin composition of the present invention is 5 to 45 parts by mass, preferably 7 to 40 parts by mass, and more preferably 10 to 35 parts by mass, per 100 parts by mass of the total of components (A), (B), (C), and (D).
  • the content of component (B) is equal to or higher than the lower limit, the impact resistance and squeak noise reduction effect due to the inclusion of component (B) are excellent.
  • the content of component (B) is equal to or lower than the upper limit, the contents of other components (A), (C), and (D) can be secured, and excellent chemical resistance can be obtained.
  • the respective contents in the thermoplastic resin composition of the present invention are, from the viewpoint of reducing squeak noise, 5 to 30 parts by mass of the rubber-reinforced vinyl graft resin (B) containing an ethylene- ⁇ -olefin rubber polymer (b1) and 20 parts by mass of the diene rubber polymer (b2) per 100 parts by mass of the total of components (A), (B), (C) and (D).
  • the amount of the rubber-reinforced vinyl graft resin (B) containing the ene-based rubber polymer (b2) is preferably 30 to 1 part by mass, more preferably 10 to 30 parts by mass of the rubber-reinforced vinyl graft resin (B) containing the ethylene- ⁇ -olefin-based rubber polymer (b1), and 20 to 1 part by mass of the rubber-reinforced vinyl graft resin (B) containing the diene-based rubber polymer (b2), and even more preferably 10 to 30 parts by mass of the rubber-reinforced vinyl graft resin (B) containing the ethylene- ⁇ -olefin-based rubber polymer (b1), and 10 to 1 part by mass of the rubber-reinforced vinyl graft resin (B) containing the diene-based rubber polymer (b2).
  • the weight average particle size of the rubber polymer (b) of the component (B) used in the present invention is preferably 0.20 to 0.70 ⁇ m, particularly 0.23 to 0.60 ⁇ m, and especially 0.25 to 0.50 ⁇ m.
  • Component (B) may contain a rubber-reinforced vinyl-based graft resin (B) containing a rubber polymer (b) outside the above range of weight-average particle size, but if the rubber-reinforced vinyl-based graft resin (B) containing a rubber polymer (b) having a weight-average particle size of less than 0.15 ⁇ m is contained, the impact resistance and the effect of suppressing the generation of creaking noise (rubbing noise) of the obtained thermoplastic resin composition tend to be inferior.
  • thermoplastic resin composition of the present invention contains a rubber-reinforced vinyl graft resin (B) containing a rubber polymer (b) having a weight average particle size of less than 0.15 ⁇ m, the content thereof is preferably 45 parts by mass or less, particularly 30 parts by mass or less, and especially 0 to 20 parts by mass, per 100 parts by mass of the total of components (A), (B), (C) and (D).
  • component (B) of the total mass 100% of component (B), it is preferable that 30% by mass or more, particularly 50% by mass or more, and especially 70 to 100% by mass is a rubber-reinforced vinyl graft resin (B) containing a rubber polymer (b) having a weight average particle size of 0.20 to 0.70 ⁇ m.
  • the total content of component (C) and component (D) in the thermoplastic resin composition of the present invention is 20 to 65 parts by mass, preferably 25 to 60 parts by mass, and more preferably 30 to 55 parts by mass, per 100 parts by mass of the total of component (A), component (B), component (C), and component (D).
  • the total content of components (C) and (D) is equal to or greater than the lower limit, the impact resistance and long-term durability are excellent due to the inclusion of components (C) and (D).
  • the total content of components (C) and (D) is equal to or less than the upper limit, the contents of other components (A) and (B) can be ensured, resulting in excellent impact resistance and chemical resistance.
  • the content of component (D) in the thermoplastic resin composition of the present invention is 0.1 to 40 parts by mass, preferably 2 to 38 parts by mass, and more preferably 5 to 36 parts by mass, per 100 parts by mass of the total of components (A), (B), (C), and (D).
  • Component (D) is effective in suppressing hydrolysis of component (A) and improving the compatibility of component (A) with components (B) and (C). If the content of component (D) is equal to or greater than the lower limit, a thermoplastic resin composition having excellent effects due to component (D), impact resistance, long-term durability, and suppression of squeak noise can be obtained. If the content of component (D) is too high, the components (D) react with each other, deteriorating the moldability and molded appearance of the thermoplastic resin composition. For this reason, the content of component (D) is set to equal to or less than the upper limit.
  • the content of only component (C) is less than 45 parts by mass, particularly less than 40 parts by mass, and especially less than 35 parts by mass, per 100 parts by mass of the total of components (A) and (B) (C) and (D).
  • component (B) resin (B-2) is produced together with the aforementioned graft copolymer (B-1), and depending on the type of vinyl monomer used in the production of component (B), it may not be possible to determine whether it corresponds to component (C) or component (D). Normally, if the vinyl monomer used in the production of component (B) contains the aforementioned carboxy-containing unsaturated compound and/or unsaturated acid anhydride, resin (B-2) can be considered as component (D). If it does not contain a carboxy-containing unsaturated compound and/or unsaturated acid anhydride, resin (B-2) is considered as component (C).
  • the content of the aforementioned rubbery polymer (b) derived from component (B) and contained in the thermoplastic resin composition of the present invention is preferably 5 to 80 parts by mass, more preferably 10 to 70 parts by mass, even more preferably 15 to 65 parts by mass, and particularly preferably 20 to 60 parts by mass, per 100 parts by mass of the total of components (B), (C), and (D).
  • the content of the rubbery polymer (b) is within the above range, the mechanical strength and squeak noise reduction effect of the molded article made from the thermoplastic resin composition of the present invention are further improved.
  • the content of the rubber-reinforced vinyl graft resin (B) containing the rubber polymer (b) having a weight average particle diameter of 0.20 to 0.07 ⁇ m in the above-mentioned rubber-reinforced vinyl graft resin (B) it is preferable that 30 mass % or more, particularly 50 mass % or more, and especially 70 to 100 mass % of the total amount of the rubber polymer (b) contained in the thermoplastic resin composition of the present invention is a rubber polymer (b) having a weight average particle diameter of 0.20 to 0.70 ⁇ m.
  • the rubber polymer (b) having a weight average particle diameter of less than 0.15 ⁇ m is preferably 70% by mass or less, particularly 50% by mass or less, and even more preferably 0 to 30% by mass, of the total amount of the rubber polymer (b) contained in the thermoplastic resin composition of the present invention (100% by mass).
  • the melt volume rate (MVR) of the thermoplastic resin composition of the present invention is preferably 10 to 70 cm 3 /10 min, particularly 15 to 60 cm 3 /10 min, and especially 20 to 50 cm 3 /10 min under conditions of 240°C and 98 N.
  • MVR melt volume rate
  • the MVR of the thermoplastic resin composition of the present invention is measured by the method described in the Examples section below.
  • the plant-derived content of the thermoplastic resin composition of the present invention is preferably 20% or more, more preferably 25% or more, and even more preferably 30% or more from the viewpoint of carbon neutrality.
  • the plant-based content of the thermoplastic resin composition of the present invention is determined as a percentage obtained by multiplying the mass proportion of the biomass-derived polyamide (A) in the thermoplastic resin composition by the plant-based content of the biomass-derived polyamide (A).
  • the thermoplastic resin composition of the present invention preferably has an abnormal noise risk index of 5 or less, more preferably 3 or less, measured under conditions of a temperature of 23°C, a humidity of 50% RH, a load of 5N, and a speed of 1 mm/sec.
  • an abnormal noise risk index of 3 or less is acceptable.
  • Such a preferable abnormal noise risk index can be satisfied by appropriately adjusting the blending amounts of components (A) to (D), etc.
  • thermoplastic resin composition of the present invention can be obtained by mixing component (A), component (B), component (C), and component (D) and other components as desired in a desired blending ratio and melt-kneading.
  • component (B) is produced by graft polymerization
  • component (C) and/or component (D) are also produced, so a mixture of component (B) and component (C) and/or component (D) is obtained.
  • the mixture of component (B) and component (C) and/or component (D) can be used as a raw material as it is.
  • component (C) and/or component (D) produced separately from component (B) can be additionally mixed into the mixture.
  • Component (C) and/or component (D) produced during the production of component (B) may have the same or different physical properties such as copolymerization composition and intrinsic viscosity as component (C) and/or component (D) produced separately from the production of component (B).
  • components (A) to (D) that can be blended into the thermoplastic resin composition of the present invention include nucleating agents, lubricants, heat stabilizers, antioxidants, UV absorbers, anti-aging agents, plasticizers, antibacterial agents, colorants, fillers, etc. These components can be blended to the extent that they do not impair the purpose of the present invention.
  • the filler to be used is preferably in the form of fibers or layers.
  • fibrous fillers include inorganic fibers such as glass fibers and ceramic whiskers, and organic fibers such as carbon fibers and aramid fibers.
  • layer-like fillers include scaly or flat fillers, such as montmorillonite, hectorite, vermiculite, saponite, and glass flakes.
  • the content of the filler is preferably 5 to 50 parts by mass, more preferably 8 to 35 parts by mass, and particularly preferably 10 to 25 parts by mass, per 100 parts by mass of the total of components (A), (B), (C), and (D).
  • the content of the filler is within the above range, the rigidity of the resulting molded product is superior, which is preferable.
  • thermoplastic resin composition of the present invention may contain other thermoplastic resins other than components (A) to (D) as necessary, to the extent that the object of the present invention is not impaired.
  • other thermoplastic resins include polyvinyl chloride, polymethyl methacrylate resin, polycarbonate (PC) resin, polylactic acid resin, polystyrene resin, high-impact polystyrene resin, ASA resin, etc.
  • Polyamide resins that are not derived from biomass may also be blended. These may be used alone or in combination of two or more.
  • thermoplastic resins other than components (A) to (D) are blended with the thermoplastic resin composition of the present invention, from the viewpoint of effectively obtaining the effects of the present invention by using components (A) to (D) in a specified ratio, it is preferable that the content of the thermoplastic resin other than components (A) to (D) is 50 parts by mass or less per 100 parts by mass of the total of components (A) to (D) and the other thermoplastic resin.
  • thermoplastic resin composition of the present invention can be produced by mixing the components in a predetermined mixing ratio using a tumbler mixer, Henschel mixer, or the like, and then melt-kneading the components under appropriate conditions using a kneading machine such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader, a roll, a feeder ruder, etc.
  • a preferred kneading machine is a twin-screw extruder.
  • the components may be pelletized with an extruder.
  • fibrous ones are preferably fed from the middle of the extruder by a side feeder in order to prevent them from being cut during kneading.
  • the melt-kneading temperature is usually from 200 to 300°C, preferably from 220 to 280°C.
  • the molded article obtained by molding the thermoplastic resin composition of the present invention can be used as at least one component of an article that includes at least two components that come into contact with each other, thereby preventing the article from generating creaking noise.
  • an article that includes at least two parts that are in contact with each other, and at least one of the parts is a molded article made of the thermoplastic resin composition of the present invention.
  • the article of the present invention it is preferable that two or more parts are molded articles made of the thermoplastic resin composition of the present invention, and it is particularly preferable that all of the parts are molded articles made of the thermoplastic resin composition of the present invention.
  • thermoplastic resin composition of the present invention There are no limitations on the method for producing the above molded article or part from the thermoplastic resin composition of the present invention. Examples include injection molding, injection compression molding, gas-assisted molding, press molding, blow molding, and profile extrusion molding. Other examples include known methods such as film and sheet molding, such as calendar molding and T-die extrusion molding.
  • thermoplastic resin composition of the present invention is suitable as a molding material for an article in which at least two of the parts of the article are in constant or intermittent contact with each other, and when an external force such as vibration, twisting, or impact is applied to the article, the contacting parts move or collide slightly with each other.
  • the contacting manner of such contacting parts may be any of surface contact, line contact, point contact, etc., and may be partially bonded.
  • Specific examples include an article in which one surface of part 10 and one surface of part 20 are butted together and bonded together as shown in Figure 3; an article in which a portion of part 10 is in contact with and fitted into a recess formed in part 20 as shown in Figures 4 to 8; and the like.
  • Specific examples of articles in which parts are in contact with each other in a fitted state include the following (1) to (4).
  • the two parts in the article of the present invention do not need to fit snugly together. As shown in Figure 8, they may fit together with a certain amount of gap or play, and may be articles that repeatedly come into and out of contact with each other when an external force such as vibration, twisting, or impact is applied to the article.
  • FIG. 9(A) to (C) Examples of articles having the above-mentioned contact portions in a composite manner include articles as shown in Figures 9(A) to (C).
  • part 10 is a box-shaped part consisting of a rectangular parallelepiped with the bottom surface all open.
  • Part 20 is a molded product having the same shape as part 10 and with a rectangular opening formed in the center of the top surface.
  • part 20 can be fitted into part 10.
  • the outer peripheral surface of part 20 and the inner peripheral surface of part 10 are in contact with each other, and when subjected to an external force such as vibration, the two are slightly deformed and repeatedly come into and out of contact.
  • part 20 has projections 30 on opposing outer surfaces. As shown in Fig. 9(A) to (C), part 10 has holes on two opposing side surfaces for accommodating projections 30 of part 20. When part 10 is mated with part 20, projections 30 snap-fit into the holes, preventing the two parts from easily coming apart.
  • thermoplastic resin composition of the present invention By molding at least one of parts 10 and 20 with the thermoplastic resin composition of the present invention, it is possible to prevent the generation of creaking noises, for example, even when an external force is applied in the direction of the arrow in Figure 9 (C).
  • the direction of the external force is not limited to the direction in Figure 9 (C), and even when an external force is applied from another direction, the generation of creaking noises is prevented when at least one of parts 10 and 20 is molded with the thermoplastic resin composition of the present invention.
  • the cross-sectional shape of protrusion 30 and the shape of the hole in part 10 in Figures 9 (A) to (C) can also be changed to change the configuration so that both parts are press-fitted.
  • Figures 11(A)-(C) show the same embodiment as the article of Figures 9(A)-(C), except that instead of protrusions 30 and holes that snap-fit into them, parts 10 and 20 are bonded to parts of the inner and outer surfaces of parts 10 and 20 using adhesive 31. Instead of adhesive 31, parts 10 and 20 can also be welded to each other by laser welding or the like. This method is convenient when both parts are thermoplastic resin molded products. In particular, for laser welding, it is preferable to combine a part made of a transparent thermoplastic resin that transmits laser light with a part made of a thermoplastic resin that absorbs laser light. Specific products include instruments such as in-vehicle speedometers, lighting, etc.
  • Figures 12(A) to (C) show the same configuration as the article in Figures 9(A) to (C), except that holes are drilled at opposing positions on opposing sides of parts 10 and 20, and the two parts are secured together by fastening bolts and nuts 33 through these two holes.
  • parts 10 and 20 may be secured together using screws, pins, rivets, bushings, brackets, hinges, nails, etc.
  • an article such as that shown in Figs. 14(A)-(C) is suitable for molding with the thermoplastic resin composition of the present invention, and includes a part 18 having a rectangular plate-like body with cylindrical shafts 19 protruding outward in the longitudinal direction from both ends, and a frame-like part 28 into which the shaft 19 of part 18 is inserted to support part 18 so that it can rotate around the shaft 19.
  • the article when a frame-like part 28 has multiple openings 29, the article can be suitably used as a device that adjusts the amount and direction of air flow depending on the angle of the part 18.
  • Examples of such devices include air outlets for home and car air conditioners, air purifiers, fans, etc.
  • the generation of creaking noise can be significantly reduced.
  • the other article may also be a molded article made from the thermoplastic resin composition of the present invention.
  • Materials that may be used to make parts made of materials other than the thermoplastic resin composition of the present invention include various thermoplastic resins, thermosetting resins, rubber, organic materials, inorganic materials, and metal materials.
  • Thermoplastic resins constituting parts made of materials other than the thermoplastic resin composition of the present invention include, for example, polyvinyl chloride, polyethylene, polypropylene, AS resin, ABS resin, AES resin, ASA resin, polymethyl methacrylate resin, polystyrene resin, impact-resistant polystyrene resin, ethylene-vinyl acetate (EVA) resin, polyamide (PA) resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate (PC) resin, polylactic acid resin, PC/ABS resin, PC/AES resin, PA/ABS resin, PA/AES resin, etc. These can be used alone or in combination of two or more.
  • thermosetting resins constituting parts made of materials other than the thermoplastic resin composition of the present invention include phenolic resins, epoxy resins, urea resins, melamine resins, unsaturated polyester resins, etc. These can be used alone or in combination of two or more.
  • Rubbers constituting parts made of materials other than the thermoplastic resin composition of the present invention include chloroprene rubber, polybutadiene rubber, ethylene-propylene rubber, various synthetic rubbers such as SEBS, SBS, and SIS, and natural rubber. These can be used alone or in combination of two or more.
  • organic materials constituting parts made of materials other than the thermoplastic resin composition of the present invention include insulation board, MDF (medium density fiberboard), hardboard, particleboard, lumber core, LVL (laminated veneer lumber), OSB (oriented structural board), PSL (parallel board), WB (wafer board), hard fiberboard, soft fiberboard, lumber core plywood, board core plywood, special core plywood, veneer core plywood, laminated sheets and boards of paper impregnated with tap resin, boards made by mixing adhesive with fine pieces and linear pieces of crushed (used) paper and heating and compressing them, various types of wood, etc. These can be used alone or in combination of two or more types.
  • Inorganic materials constituting parts made of materials other than the thermoplastic resin composition of the present invention include, for example, calcium silicate board, flexible board, homocement board, gypsum board, sheathing gypsum board, reinforced gypsum board, gypsum lath board, decorative gypsum board, composite gypsum board, various ceramics, glass, etc. These can be used alone or in combination of two or more kinds.
  • Metal materials constituting parts made of materials other than the thermoplastic resin composition of the present invention include iron, aluminum, copper, various alloys, etc. These can be used alone or in combination of two or more kinds.
  • thermoplastic resins thermosetting resins, and rubber are preferred, and ABS resin, AES resin, PC resin, ABS resin, PC/AES resin, and polymethyl methacrylate resin are particularly preferred.
  • the article of the present invention can be suitably used as an automobile part, an office machine part, a housing part, a home appliance part, etc.
  • thermoplastic resin composition of the present invention When an automobile part is molded from the thermoplastic resin composition of the present invention, it is possible to significantly reduce the generation of creaking noise, for example, even when the part repeatedly comes into contact with and out of contact with other parts due to vibrations while the vehicle is running.
  • thermoplastic resin composition of the present invention contains a diene rubber, it has excellent fracture properties at low temperatures and is therefore particularly suitable for use in automobile interior parts.
  • Examples of such automobile parts include door trims, door linings, pillar garnishes, consoles, door pockets, ventilators, ducts, air conditioner blades, valve shutters, louvers, meter visors, instrument panel upper garnishes, instrument panel lower garnishes, A/T indicators, on-off switches (slide parts, slide plates), grill front defrosters, grill side defrosters, lid clusters, cover installers, masks (mask switches, mask radios, etc.), glove boxes, pockets (pocket decks, pocket cards, etc.), steering wheel horn pads, switch parts, exterior parts for car navigation systems, etc.
  • the material can be particularly suitably used as ventilators, air conditioner blades, valve shutters, louvers, switch parts, exterior parts for car navigation systems, etc.
  • thermoplastic resin composition of the present invention When office equipment parts are molded from the thermoplastic resin composition of the present invention, it is possible to significantly reduce the generation of creaking noises, even when the parts repeatedly come into contact with other parts due to, for example, vibrations during operation of the equipment or opening and closing of desk drawers.
  • housing components are molded from the thermoplastic resin composition of the present invention, for example, when a door or sliding door is opened and closed and the component comes into contact with and out of contact with other components, it is possible to significantly reduce the generation of creaking noises.
  • thermoplastic resin composition of the present invention When a home appliance part is molded from the thermoplastic resin composition of the present invention, it is possible to significantly reduce the generation of squeaking noises, even when the part repeatedly comes into contact with other parts due to vibrations during operation of the appliance.
  • home appliance parts include exterior parts such as cases and housings, interior parts, parts around switches, and moving parts.
  • the molded product of the present invention not only reduces the generation of creaking noise, but also has a pleasant feel and high rigidity, making it particularly suitable for use as parts for electrical or electronic devices, optical devices, lighting devices, office equipment, or home appliances, automotive interior parts, and residential interior parts.
  • it is particularly suitable for parts of vehicles such as automobiles that may be touched by the hands, such as grips such as assist grips, as well as parts such as handles and doorknobs, and for portable items.
  • Electrical or electronic equipment and optical equipment parts include housings and covers for cameras such as digital video cameras and still cameras, which are often touched by hand, and housings and covers for handheld computers, mobile phones, personal digital assistants, etc.
  • Lighting equipment parts include ceiling light panels, covers, connectors, and parts around switches.
  • Parts for office equipment include exterior parts such as cases and housings, interior parts, parts around switches, moving parts, desk lock parts, desk drawers, copier paper trays, etc.
  • Home appliance parts include exterior parts such as cases and housings, interior parts, parts around switches, moving parts, etc.
  • Automobile interior parts include, for example, grips such as doorknobs, handles, and assist grips, as well as door trim, door linings, pillar garnishes, consoles, console boxes, center panels, door pockets, ventilators, ducts, air conditioners, meter visors, instrument panel upper garnishes, instrument panel lower garnishes, A/T indicators, on/off switches (slide parts, slide plates), switch bezels, grill front defrosters, grill side defrosters, lid clusters, cover installers, masks (mask switches, mask radios, etc.), glove boxes, pockets (pocket decks, pocket cards, etc.), steering wheel horn pads, switch parts, exterior parts for car navigation systems, etc.
  • grips such as doorknobs, handles, and assist grips
  • door trim door linings
  • pillar garnishes consoles, console boxes, center panels, door pockets, ventilators, ducts, air conditioners, meter visors, instrument panel upper garnishes, instrument panel lower garnishes
  • Home interior parts include doorknobs, shelf doors, chair dampers, movable parts for folding table legs, door opening and closing dampers, sliding door rails, curtain rails, etc.
  • MVR Melt Volume Rate
  • thermoplastic resin composition was injection molded using a Toshiba Machine injection molding machine "IS-170FA" (product name) at a cylinder temperature of 250°C, injection pressure of 80 MPa, and mold temperature of 60°C to obtain a molded specimen having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm.
  • the V-notched Charpy impact strength (kJ/m 2 ) of this specimen was measured in accordance with ISO test method 179 at measurement temperatures of 23°C and -30°C, with a specimen thickness of 4 mm.
  • thermoplastic resin composition was injection molded using a Toshiba Machine injection molding machine "IS-170FA" (trade name) under conditions of a cylinder temperature of 250 ° C., an injection pressure of 50 MPa, and a mold temperature of 60 ° C.
  • a molded product having a length of 150 mm, a width of 100 mm, and a thickness of 4 mm was obtained. From the molded product, a length of 60 mm, a width of 100 mm, a thickness of 4 mm, and a length of 50 mm, a width of 25 mm, and a thickness of 4 mm were cut out with a disk saw.
  • test pieces were chamfered with sandpaper having a grit size of #100, and then fine burrs were removed with a cutter knife to obtain two test pieces for squeak noise evaluation, one large and one small.
  • the above-mentioned evaluation test pieces were left in an oven tank adjusted to 80° C. ⁇ 5° C. for 300 hours, and then cooled at 25° C. for 24 hours to obtain heat-aged evaluation test pieces.
  • the two heat-aged test pieces one large and one small, were set in a ZIEGLER stick-slip tester "SSP-02" and rubbed together three times with an amplitude of 20 mm under conditions of a temperature of 23° C., humidity of 50% RH, load of 5 N, and speed of 1 mm/sec, to measure the abnormal noise risk index.
  • This test method is performed by thermal aging, so it is also possible to evaluate the sustainability of the squeak noise reduction effect.
  • thermoplastic resin compositions are either the following commercially available products or those produced according to the following Production Examples.
  • Polyamide (A) As the polyamide (A), the following commercially available product was used. PA11: “Rilsan BMNO” manufactured by Arkema (Polyamide 11, plant-based content: 100%, melting point: 190°C) PA1010: “Vestamid Terra DS22” manufactured by Daicel-Evonik Co., Ltd. (Polyamide 1010, vegetable content: 100%, melting point: 200°C) PA610: “Rilsan SMVO” manufactured by Arkema (Polyamide 610, vegetable content: 62%, melting point: 225°C)
  • the internal temperature was cooled to 100°C, and 0.2 parts of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenol)-propionate and 0.02 parts of dimethyl silicone oil; KF-96-100cSt (product name: manufactured by Shin-Etsu Silicones Co., Ltd.) were added, after which the reaction mixture was removed from the autoclave, and unreacted materials and the solvent were removed by steam distillation. The volatile matter was then substantially degassed using a 40 mm ⁇ vented extruder (cylinder temperature 220°C, vacuum degree 760 mmHg) and pelletized.
  • KF-96-100cSt product name: manufactured by Shin-Etsu Silicones Co., Ltd.
  • ethylene- ⁇ -olefin rubber-reinforced aromatic vinyl resin (B1) (a mixture of component (B1), which is a rubber-reinforced vinyl graft resin (B), and component (C1), which is an aromatic vinyl copolymer resin (C))
  • the content of the ethylene- ⁇ -olefin rubber polymer was 30% (calculated from the polymerization conversion rate)
  • the acetone insoluble matter was 47%
  • the acetone soluble matter was 53%
  • the graft ratio was 55%
  • the intrinsic viscosity [ ⁇ ] of the acetone soluble matter was 0.33 dL/g
  • the melting point measured according to JIS K7121-1987 was 40°C.
  • weight average particle diameter (volume average particle diameter) and number average particle diameter of the ethylene- ⁇ -olefin rubber polymer in the solution polymerization system were 0.45 ⁇ m and 0.35 ⁇ m, respectively.
  • ⁇ Production Example 2 Production of Mixture Product of Component (B2) and Component (C2)> 100 parts of ethylene-propylene copolymer similar to that used in Production Example 1, 20 parts of maleic anhydride-modified polyethylene (Mitsui Chemicals, Inc., "Mitsui Hiwax 2203A", mass average molecular weight: 2,700, acid value: 30 mg/g) as an acid-modified olefin polymer, and 5 parts of potassium tallow fatty acid (a mixture of potassium oleate, potassium stearate, and potassium palmitate) as an anionic emulsifier were mixed.
  • maleic anhydride-modified polyethylene Mitsubishi Chemicals, Inc., "Mitsui Hiwax 2203A", mass average molecular weight: 2,700, acid value: 30 mg/g
  • potassium tallow fatty acid a mixture of potassium oleate, potassium stearate, and potassium palmitate
  • the solid discharged from the tip of the twin-screw extruder was then poured into 80°C warm water and continuously dispersed therein, diluting the solid concentration to about 40% to obtain an aqueous dispersion of an olefin resin.
  • the particle size of the ethylene- ⁇ -olefin rubber polymer in the obtained olefin resin was determined by the above-mentioned Measurement Method 1 (dynamic light scattering method) and found to be 0.40 ⁇ m in weight average particle size (0.26 ⁇ m in number average particle size).
  • An olefin resin aqueous dispersion (60 parts as solids of ethylene-propylene copolymer) was placed in a stainless steel polymerization tank equipped with a stirrer, ion-exchanged water was added to the olefin resin aqueous dispersion so that the solids concentration was 30%, 0.006 parts of ferrous sulfate, 0.3 parts of sodium pyrophosphate, 0.35 parts of fructose, and 1.0 parts of potassium tallow fatty acid (a mixture of potassium oleate, potassium stearate, and potassium palmitate) were added, and the temperature was set to 80°C.
  • the ethylene- ⁇ -olefin rubber-reinforced aromatic vinyl resin (B2) (a mixture of component (B2), which is rubber-reinforced vinyl graft resin (B), and component (C2), which is aromatic vinyl copolymer resin (C))
  • the ethylene- ⁇ -olefin rubber polymer content was 60% (calculated from the polymerization conversion rate), the acetone insoluble content was 84%, the acetone soluble content was 16%, the graft ratio was 40%, the intrinsic viscosity [ ⁇ ] of the acetone soluble content was 0.37 dL/g, and the melting point measured according to JIS K7121-1987 was 42°C.
  • the polybutadiene rubber content was 40% (measured using pyrolysis gas chromatography), the acetone insoluble content was 67%, the acetone soluble content was 33%, the graft ratio was 68%, the intrinsic viscosity [ ⁇ ] of the acetone soluble content was 0.45 dL/g, and no melting point was observed when measured according to JIS K7121-1987.
  • the obtained butadiene rubber-reinforced aromatic vinyl resin (B4) (a mixture of component (B4) which is a rubber-reinforced vinyl graft resin (B) and component (D4) which is an acid-modified vinyl resin (D)) had a polybutadiene rubber content of 40% (measured using pyrolysis gas chromatography), an acetone insoluble content of 52%, an acetone soluble content of 48%, a graft ratio of 30%, an intrinsic viscosity [ ⁇ ] of the acetone soluble content of 0.56 dL/g, and no melting point was observed as measured according to JIS K7121-1987.
  • ⁇ Production Example 5 Production of a mixed product of component (B5) and component (C5)>
  • 75 parts of ion-exchanged water, 0.5 parts of potassium rosinate, 0.1 parts of t-dodecyl mercaptan, 40 parts (solids) of polybutadiene rubber latex (weight average particle size: 0.10 ⁇ m, number average particle size: 0.08 ⁇ m, gel content: 85%), 15 parts of styrene, and 5 parts of acrylonitrile were charged in a nitrogen stream, and the temperature was raised with stirring.
  • the polybutadiene rubber content was 40% (measured using pyrolysis gas chromatography), the acetone insoluble content was 67%, the acetone soluble content was 33%, the graft ratio was 68%, the intrinsic viscosity [ ⁇ ] of the acetone soluble content was 0.45 dL/g, and no melting point was observed when measured according to JIS K7121-1987.
  • Glass fiber Owens Corning glass fiber "MA FT698" (product name) (fibrous, fiber length 3 mm, fiber diameter 13 ⁇ m) was used.
  • PA6 "Novamid 1015" (product name) polyamide resin manufactured by Mitsubishi Engineering Plastics Corporation (polyamide 6, plant-derived content: 0%, melting point: 225°C) was used.
  • Examples 1 to 30, Comparative Examples 1 to 9 The components shown in Tables 1 to 5 were mixed in the blending ratios shown in Tables 1 to 5 using a Henschel mixer, and then the mixture was melt-kneaded using a twin-screw extruder (manufactured by Japan Steel Works, Ltd., TEX44 ⁇ , barrel set temperature 250° C.) and pelletized to obtain a thermoplastic resin composition.
  • the thermoplastic resin composition thus obtained was subjected to the above-mentioned measurements and evaluations, and the results are shown in Tables 1 to 5.
  • Tables 1 to 5 also show the plant-based content of the produced thermoplastic resin compositions.
  • Examples 1 to 30 were within the range of the requirements of the present invention, they had good moldability and were excellent in impact resistance, chemical resistance, long-term durability, and squeak noise suppression.
  • Comparative Examples 1 and 2 which did not contain polyamide (A), were inferior in long-term durability and squeak noise suppression.
  • Comparative Examples 3 and 4 in which the blending amount of polyamide (A) was outside the range of the present invention, were inferior in any one of impact resistance, chemical resistance and long-term durability.
  • Comparative Examples 5 and 6 in which the amount of rubber-reinforced vinyl resin (B) was outside the range of the present invention, were inferior in any one of impact resistance, chemical resistance, and squeak noise suppression.
  • Comparative Examples 7 and 8 the blending amount of the acid-modified vinyl resin (D) was outside the range of the present invention, and therefore, the moldability, impact resistance, and squeak noise suppression were poor.
  • Comparison of Example 26 and Comparative Example 9 shows that even when a filler such as glass fiber is added, the incorporation of polyamide (A) can provide excellent impact resistance and long-term durability.
  • Examples 27 to 30 are examples using a rubber-reinforced aromatic vinyl resin (B5) containing a rubber-like polymer (b) having a small particle size of 0.10 ⁇ m in weight average particle size as the rubber-reinforced vinyl graft resin (B), but the Charpy impact strength and abnormal sound risk index are inferior to other examples not using the rubber-reinforced aromatic vinyl resin (B5) containing such a small particle size rubber-like polymer (b). This tendency is also evident in Example 27, which used a very small amount of rubber-reinforced aromatic vinyl resin (B5).
  • thermoplastic resin composition of the present invention has excellent moldability and can be suitably used as a molding material for molded products that require impact resistance, chemical resistance, long-term durability, and suppression of squeaking noise.

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JPH0784549B2 (ja) 1985-05-10 1995-09-13 モンサント カンパニ− ゴム変性ナイロン組成物
JP2002212383A (ja) 2001-01-17 2002-07-31 Toray Ind Inc 熱可塑性樹脂組成物
JP2008214585A (ja) * 2007-03-07 2008-09-18 Nippon A & L Kk 環境対応型熱可塑性樹脂組成物
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JP2022165619A (ja) 2021-04-20 2022-11-01 文化シヤッター株式会社 開閉装置

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