Thermoplastic resin composition

Abstract

The present invention relates to a thermoplastic resin composition comprising a thermoplastic resin and composite particles having a high molecular grafted chain bound to the surface of the particles. The thermoplastic resin composition of the present invention can be suitably used for products such as acoustic equipment, electrical products, buildings, industrial equipment, automobile members, two-wheeled vehicle members, containers, and the like.

Description

[0001] This application is a divisional application of the patent application for invention with international application No. PCT / JP2020 / 021118, Chinese application No. 202080037309.1, and the invention name of "Thermoplastic resin composition", the international application date of which is May 28, 2020. TECHNICAL FIELD

[0002] The present application relates to a novel thermoplastic resin composition having excellent vibration damping properties, a method for producing the same, an additive for improving the vibration damping properties of a thermoplastic resin, and a vibration damping material containing the thermoplastic resin composition. BACKGROUND

[0003] In recent years, vibration countermeasures for various devices have been increasingly required, and in particular, in the fields of automobiles, home electric appliances, precision devices, and the like, vibration countermeasures have become necessary. In general, as a material having high vibration damping properties, a composite material such as a material in which a metal plate and a rubber, pitch, or the like are attached, or a vibration damping steel sheet in which a vibration absorbing raw material is sandwiched with a metal plate can be cited. These vibration damping materials maintain the shape using a metal plate having high rigidity, and absorb vibration using a vibration absorbing raw material. In addition, only with respect to metals, an alloy material that absorbs vibration by converting kinetic energy into heat energy using twinning and ferromagnetism can be cited. However, the composite material is limited in terms of formability because different raw materials are attached, and there is a problem in that the product itself becomes heavy because a metal steel plate is used. In addition, the alloy material is also heavy because only a metal is used, and furthermore, the vibration damping performance is insufficient.

[0004] In view of such prior art, a functional resin composition having a vibration suppressing function has been proposed. For example, a vibration damping resin molded article is disclosed in Patent Literature 1, which is formed of a polypropylene-based resin composition in which a reinforcing inorganic filler is compounded in a resin component in which high-density polyethylene (PE) and an aromatic hydrocarbon resin are added / mixed in a crystalline polypropylene (PP), and is characterized in that a hydrogenated product of an aromatic vinyl-conjugated diene block copolymer is added / mixed as a resin component.

[0005] PRIOR ART DOCUMENTS

[0006] PATENT LITERATURE

[0007] Patent Literature 1: Japanese Patent Application Laid-Open No. 5-331329 SUMMARY

[0008] PROBLEMS TO BE SOLVED BY THE INVENTION

[0009] The present application relates to a novel thermoplastic resin composition having excellent vibration damping properties, a method for producing the same, an additive for improving the vibration damping properties of a thermoplastic resin, and a vibration damping material containing the thermoplastic resin composition.

[0010] Means for solving the problem

[0011] The present application relates to the following [1] to [4].

[0012] [1] A thermoplastic resin composition comprising a thermoplastic resin and a composite particle having a polymer graft chain bound to the surface of a particle.

[0013] [2] A method for producing a thermoplastic resin composition, comprising a step of melt-kneading a thermoplastic resin and a composite particle having a polymer graft chain bound to the surface of a particle.

[0014] [3] An additive for improving the vibration-damping property of a thermoplastic resin, comprising a composite particle having a polymer graft chain bound to the surface of a particle.

[0015] [4] A vibration-damping material comprising the thermoplastic resin composition described in [1] containing a thermoplastic resin and a composite particle having a polymer graft chain bound to the surface of a particle.

[0016] [5] A vibration-damping material comprising a thermoplastic resin and a composite particle having a polymer graft chain bound to the surface of a particle.

[0017] [6] A method for producing a vibration-damping material, comprising a step of melt-kneading a thermoplastic resin and a composite particle having a polymer graft chain bound to the surface of a particle.

[0018] [7] Use of a composite particle having a polymer graft chain bound to the surface of a particle for improving the vibration-damping property of a thermoplastic resin.

[0019] [8] A method for improving the vibration-damping property of a thermoplastic resin, using a composite particle having a polymer graft chain bound to the surface of a particle.

[0020] Effects of the Invention

[0021] According to the present application, it is possible to provide a new thermoplastic resin composition having excellent vibration-damping property, a method for producing the same, an additive for improving the vibration-damping property of a thermoplastic resin, and a vibration-damping material containing the thermoplastic resin composition. DETAILED DESCRIPTION

[0022] The present inventors have newly found that by strengthening the interface between an elastomer added in a thermoplastic resin composition and a filler by causing some kind of bonding therebetween, the vibration damping property is improved. The mechanism is not clear, but it is presumed that by strengthening the interface between the elastomer and the filler, the strain energy in the elastomer can be increased. In addition, the present inventors have also newly found that as the composite particles in which the elastomer and the filler are bonded, composite particles obtained by a grafting from method in which a polymer graft chain equivalent to the elastomer is grafted from the surface of a particle used as the filler, starting from a polymerization initiation point on the surface, are used, whereby excellent vibration damping property can be obtained. It is presumed that this is because by the grafting from method, the polymer graft chain is bonded to the surface of the particle at high density, whereby the interface thereof can be significantly strengthened.

[0023] [Thermoplastic resin composition]

[0024] The thermoplastic resin composition of the present application contains a thermoplastic resin and a composite particle in which a polymer graft chain is bonded to the surface of a particle.

[0025] [Thermoplastic resin]

[0026] As the thermoplastic resin, polyolefin resin, polyester resin, polyamide resin, ABS resin, polystyrene resin, polycarbonate resin, vinyl chloride resin, acrylic resin, etc. can be exemplified. Among these, from the viewpoint of moldability, etc., and ease of handling of the obtained resin composition, one or two or more kinds selected from the group consisting of polyolefin resin, polyamide resin and ABS resin are preferable, one or two or more kinds selected from the group consisting of polyolefin resin are more preferable, and polypropylene resin is further preferable.

[0027] The weight average molecular weight of the thermoplastic resin is not particularly limited, and a molecular weight of 5000 to 500000, etc. can be used.

[0028] As the compounding amount of the thermoplastic resin in the thermoplastic resin composition of the present application, from the viewpoint of obtaining a molded body, a vibration damping material that exhibits the desired modulus of elasticity, 30 mass% or more is preferable, 40 mass% or more is more preferable, and 50 mass% or more is further preferable. On the other hand, from the viewpoint of obtaining a molded body, a vibration damping material that exhibits the desired vibration damping property, 95 mass% or less is preferable, 80 mass% or less is more preferable, and 75 mass% or less is further preferable. When two or more kinds of thermoplastic resins are compounded, the compounding amount is the total amount of the thermoplastic resins.

[0029] [Composite particle]

[0030] The composite particle is a particle in which a polymer graft chain is bound to the surface of the particle. As the particle, a publicly known filler can be used, and examples thereof include metal oxides, metal oxide salts, metal hydroxides, metal carbonates, celluloses, and the like, and preferably one or two or more selected from the group consisting of metal oxides, metal oxide salts, metal hydroxides, and metal carbonates, more preferably one or two or more selected from the group consisting of silicon oxides such as silica and silicates such as mica and talc, and further preferably silica. The shape of the particle is not particularly limited, and examples thereof include plate-like, granular, needle-like, fibrous, and the like. In the present specification, the case where only "particle" is described refers to a particle used in the production of the composite particle. As the polymer graft chain, examples thereof include homopolymers or copolymers of styrene monomers, nitrile monomers, (meth)acrylic acid monomers, unsaturated olefins, conjugated diene monomers, and the like, and from the viewpoint of obtaining a molded body or a damping material that exhibits a desired damping property, preferably one or two or more selected from the group consisting of acrylic acid, methacrylic acid, and derivatives thereof, more preferably one or two or more selected from the group consisting of methacrylic acid and derivatives thereof, and further preferably polybutyl methacrylic acid. From the viewpoint of obtaining a molded body or a damping material that exhibits a desired damping property, the bond is preferably a chemical bond, and more preferably a covalent bond.

[0031] From the viewpoint of exhibiting a damping property, the glass transition temperature (Tg) of the polymer graft chain in the composite particle is preferably -30°C or higher, more preferably -10°C or higher, further preferably 10°C or higher, and further preferably 25°C or higher, and from the same viewpoint, is preferably 80°C or lower, more preferably 50°C or lower, and further preferably 40°C or lower. In addition, the glass transition temperature (Tg) of the polymer graft chain in the composite particle can be two or more, or can be a Tg other than -30°C or higher and 80°C or lower. The glass transition temperature (Tg) of the polymer graft chain in the composite particle can be controlled by the monomer, the molecular weight, and the molecular weight distribution used in the production of the composite particle. It is known that, for example, in the case of a composite particle, when the graft density increases and the polymer chain becomes an extended chain, the Tg increases. In this case, the Tg can be controlled by adjusting the graft density. In the temperature region around the Tg, the tan δ of the viscoelasticity of the resin becomes maximum, which is effective in exhibiting a damping property, and by controlling the Tg, the damping property in the desired temperature region can be improved. The glass transition temperature (Tg) is measured by the method described in the Examples below.

[0032] From the viewpoint of increasing the strain energy in the elastomer, the graft density of the polymer graft chain in the composite particle is preferably 0.001 chain / nm 2 More preferably, 0.01 chain / nm 2 Further preferably, 0.1 chain / nm2 That's all. On the other hand, from the viewpoint of ease of polymer chain grafting, 5 chains / nm is preferred. 2 Below, 3 chains / nm is preferred. 2 The following is further preferred: 1 chain / nm 2 Hereinafter, 0.3 chains / nm is further preferred. 2 The grafting density was determined using the methods described in the examples below.

[0033] From the viewpoint of efficiently increasing the strain energy in the elastomer, the film thickness of the polymer grafted chains in the composite particles is preferably 1 nm or more, more preferably 3 nm or more, and even more preferably 5 nm or more. Furthermore, from the same viewpoint, it is preferably 1 μm or less, more preferably 100 nm or less, even more preferably 40 nm or less, and even more preferably 15 nm or less. The film thickness of the polymer grafted chains is calculated using the method described in the examples below.

[0034] From the viewpoint of controlling the film thickness of the polymer grafted chains, the number-average molecular weight of the polymer grafted chains in the composite particles is preferably 10,000 or more, more preferably 20,000 or more, and even more preferably 30,000 or more. Furthermore, from the same viewpoint, it is preferably 1,000,000 or less, more preferably 500,000 or less, and even more preferably 200,000 or less. The number-average molecular weight of the polymer grafted chains is determined by the method described in the examples below.

[0035] From the viewpoint of exhibiting damping properties, the amount of composite particles in the thermoplastic resin composition of the present invention is preferably 1% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and even more preferably 25% by mass or more. On the other hand, from the viewpoint of obtaining a molded article or damping material that exhibits the desired elastic modulus, it is preferably 75% by mass or less, more preferably 60% by mass or less, even more preferably 55% by mass or less, and even more preferably 50% by mass or less. The amount of composite particles contained in the case of two or more types is the total amount of composite particles.

[0036] From the viewpoint of exhibiting a damping property, the content of the composite particles in the thermoplastic resin composition of the present application is preferably 1 part by mass or more, more preferably 20 parts by mass or more, further preferably 30 parts by mass or more, further preferably 40 parts by mass or more, relative to 100 parts by mass of the thermoplastic resin. On the other hand, from the viewpoint of obtaining a molded body, a damping material that exhibits a desired elastic modulus, it is preferably 300 parts by mass or less, more preferably 200 parts by mass or less, further preferably 100 parts by mass or less, further preferably 90 parts by mass or less. From the viewpoint of exhibiting a damping property, the content of the high molecular graft chain of the composite particles in the thermoplastic resin composition of the present application is preferably 1 part by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, relative to 100 parts by mass of the thermoplastic resin. On the other hand, from the viewpoint of obtaining a molded body, a damping material that exhibits a desired elastic modulus, it is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, further preferably 40 parts by mass or less.

[0037] From the viewpoint of exhibiting a damping property, the dispersed particle diameter of the composite particles in the thermoplastic resin composition of the present application is preferably 10 nm or more, more preferably 100 nm or more, further preferably 1 μm or more, and from the same viewpoint, it is preferably 200 μm or less, more preferably 100 μm or less, further preferably 10 μm or less. The composite particles can exist alone or in an aggregate. The dispersed particle diameter of the composite particles is measured by the method described in the Examples below.

[0038] [Method for producing composite particles]

[0039] The composite particles are obtained by allowing the high molecular graft chain to bind to the surface of the particles. The method for allowing the high molecular graft chain to bind to the surface of the particles is not particularly limited as long as it is a method that enables grafting of the high molecular chain, but a surface grafting method in which the high molecular graft chain is polymerized from the polymerization starting point on the surface of the particles is preferred. The polymerization method is not particularly limited, and radical polymerization, anionic polymerization, cationic polymerization, and the like can be mentioned. Among these, from the viewpoint of ease of control of the molecular weight and the molecular weight distribution of the high molecular chain and the ease of grafting of various copolymers, radical polymerization, anionic polymerization, cationic polymerization are preferred, and from the viewpoint of applicability to a wide range of monomers, radical polymerization is further preferred. As the radical polymerization method, an atom transfer radical polymerization method (ATRP method), a reversible addition fragmentation chain transfer polymerization method (RAFT method), a nitrogen oxide stable radical polymerization method (NMP method), and the like can be used, and from the same viewpoint, the atom transfer radical polymerization method (ATRP method) is preferred.

[0040] More specifically, as the production method of the composite particle, examples include the production method of the following process 2, and the following process 1 can also be performed as necessary. The following process 1 and process 2 can be performed under known conditions of living radical polymerization.

[0041] Process 1: Process of binding a polymerization starting group to the surface of a particle

[0042] Process 2: Process of contacting a particle having a polymerization starting group on the surface with a monomer under living radical polymerization conditions

[0043] The particle having a polymerization starting group on the surface in process 2 is not particularly limited as long as it has a binding group that binds the surface of the particle to a polymer chain. From the viewpoint of binding a polymer graft chain to the surface of the particle, the polymerization starting group is a living radical polymerization starting group, preferably an atom transfer radical polymerization starting group, more preferably a haloacyl group, further preferably an α-haloacyl group, further preferably an α-bromoacyl group, further preferably a 2-bromoisobutyryl group. The compound of the raw material that becomes the binding group portion is a compound having a group that binds to the surface of the particle and a polymerization starting group, a compound having a group that binds to the surface of the particle or a polymerization starting group, or the like. Process 1 has a process of introducing an amino group or a hydroxyl group to the surface of the particle and a process of introducing a polymerization starting group, and from the viewpoint of binding a polymer graft chain to the surface of the particle, it is preferable to have, after the process of introducing an amino group or a hydroxyl group to the surface of the particle, a process of introducing a polymerization starting group to the surface of the particle. The compound used in the process of introducing an amino group or a hydroxyl group to the surface of the particle is a compound having a group that binds to the surface of the particle and an amino group or a hydroxyl group, and from the viewpoint of ease of obtaining, it is preferable to be a silane compound, more preferable to be an aminoalkylsilane compound, further preferable to be 3-aminopropyltrimethoxysilane. The compound used in the process of introducing a polymerization starting group to the surface of the particle is a compound having a polymerization starting group and a functional group that reacts with an amino group or a hydroxyl group, and from the viewpoint of binding a polymer graft chain to the surface of the particle, it is preferable to be a haloalkanoic acid derivative, more preferable to be a bromoalkanoic acid derivative, further preferable to be a 2-bromo-2-methylpropionic acid derivative, further preferable to be 2-bromoisobutyryl bromide. As the particle, for example, in the case of originally having a polymerization starting site, in the case of forming a polymerization starting site as a result of surface treatment by plasma treatment or the like, or the like, since it has a polymerization starting group, process 1 is not required, and in the case of using silica, mica, talc, glass filler, or the like that does not have a polymerization starting group, process 1 can be performed. Note that, from the viewpoint of adjusting the graft density, in process 1, a silane coupling agent that does not contain a polymerization starting group can be added to a silane coupling agent that contains a polymerization starting group and used. In the process of binding a polymerization starting group to the surface of a particle in process 1, from the viewpoint of not causing the particles to agglomerate, it is preferable to use a method of dispersing the particles with a dispersion medium.

[0044] As the vibration-damping elastomer, the monomer in Step 2 can use a publicly known monomer constituting a thermoplastic elastomer. As such a monomer constituting a thermoplastic elastomer, a styrene-based monomer, a nitrile-based monomer, a (meth)acrylic acid-based monomer, an unsaturated olefin, a conjugated diene-based monomer, etc. can be listed, and a monomer having a specific group in other side chains can be used. In the step of Step 2 in which the particles having a polymerization initiation group on the surface are contacted with the monomer under the active radical polymerization conditions, from the viewpoint of not causing the particles, the monomer, and the composite particles to agglomerate, a method in which the particles, the monomer, and the composite particles are dispersed and polymerized with a dispersion medium is preferred.

[0045] In addition, after polymerization, the composite particles can be arbitrarily purified. In the purification step of the composite particles, from the viewpoint of not causing the composite particles to agglomerate, a method in which the polymer is dispersed and the solvent is removed with a dispersion medium is preferred. A method in which a metal catalyst used in the polymerization step is removed is further preferred.

[0046] As the other components other than the above, the thermoplastic resin composition of the present application can incorporate a chain extender, a plasticizer, an organic crystal nucleating agent, an inorganic crystal nucleating agent, a hydrolysis inhibitor, a flame retardant, an antioxidant, a lubricant as a hydrocarbon-based wax, an anionic surfactant, an ultraviolet absorber, an antistatic agent, an antifog agent, a light stabilizer, a pigment, a mold inhibitor, an antibacterial agent, a foaming agent, other polymer materials, etc.

[0047] [Method for producing thermoplastic resin composition]

[0048] As the method for producing the thermoplastic resin composition of the present application, a production method including a step of melt-kneading a thermoplastic resin and composite particles having a polymer graft chain bound to the surface of a particle can be listed. In the melt-kneading, a publicly known kneader such as a closed kneader, a single-screw or twin-screw extruder, an open roll-type kneader, etc. can be used. After the melt-kneading, the melt-kneaded product can be dried or cooled according to a publicly known method. In addition, as the raw material, it is also possible to uniformly mix in advance using a Henschel mixer, a super mixer, etc. and then supply to the melt-kneading. The melt-kneading temperature and the melt-kneading time cannot be determined depending on the kind of the raw material used, and are preferably 170 to 240°C and 15 to 900 seconds.

[0049] From the viewpoint of vibration damping performance, the amount of the composite particles having the polymer graft chain bound to the surface of the particles added in the step of melt-mixing the thermoplastic resin with the composite particles having the polymer graft chain bound to the surface of the particles is preferably 1 part by mass or more, more preferably 30 parts by mass or more, and further preferably 40 parts by mass or more, relative to 100 parts by mass of the thermoplastic resin, and is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, and further preferably 90 parts by mass or less, from the same viewpoint.

[0050] [Additive]

[0051] The additive of the present application contains the composite particles having the polymer graft chain bound to the surface of the particles. The additive of the present application can arbitrarily contain a chain extender, a plasticizer, an organic crystal nucleating agent, an inorganic crystal nucleating agent, a hydrolysis inhibitor, a flame retardant, an antioxidant, a lubricant as a hydrocarbon-based wax, an anionic surfactant, an ultraviolet absorber, an antistatic agent, an antifog agent, a light stabilizer, a pigment, a mold inhibitor, an antibacterial agent, a blowing agent, and the like. In the additive of the present application, a part of the resin to be melt-mixed together (for example, 0.1 to 50.0% by mass in the additive) can also be contained. The additive of the present application can be used as an additive for improving the vibration damping performance of a thermoplastic resin. Therefore, in the present application, a method for improving the vibration damping performance of a thermoplastic resin using the composite particles having the polymer graft chain bound to the surface of the particles is also disclosed.

[0052] [Vibration damping material]

[0053] The thermoplastic resin composition of the present application can be suitably used as a vibration damping material used in products such as acoustic equipment, electrical products, buildings, industrial equipment, automobile members, two-wheeled vehicle members, containers, or the like, or parts or frames thereof, by using various molding processes such as injection molding, extrusion molding, thermoforming, and the like.

[0054] For example, in the case of manufacturing a part or a frame containing the thermoplastic resin composition of the present application by injection molding, a pellet of the thermoplastic resin composition of the present application is filled in an injection molding machine, injected into a mold, and molded.

[0055] As the injection molding, a publicly known injection molding machine can be used. For example, an injection molding machine having a cylinder and a screw inserted through the inside thereof as main constituent elements [J75E-D, J110AD-180H (manufactured by Nissei Machine Inc.), and the like] can be cited. Note that the raw material of the thermoplastic resin composition of the present application can be directly melt-mixed by being supplied to the cylinder, but it is preferable to fill the raw material that has been previously melt-mixed into the injection molding machine.

[0056] In addition, in the case where a molding method other than injection molding is used, the molding can be performed according to a publicly known method without particular limitation.

[0057] The molded body of the thermoplastic resin composition of the present application can be suitably used as a damping material or the like used in a product such as an acoustic device, an electrical product, a building, an industrial device, an automobile member, a two-wheeled vehicle member, a container, or the like, or a part or a frame thereof. In the application thereof, it can be appropriately set according to the manufacturing method of the part, the frame, the device, and the equipment, the application position, and the desired purpose, and can be used according to a conventional method in the technical field.

[0058] With respect to the above-described embodiments, the present application also discloses the following damping material and a manufacturing method thereof.

[0059] <1>

[0060] A damping material including a thermoplastic resin and a composite particle in which a polymer graft chain is bound to the surface of a particle.

[0061] <2>

[0062] The damping material according to <1>, in which the graft density of the polymer graft chain is preferably 0.001 chain / nm 2 More preferably, 0.01 chain / nm 2 Further preferably, 0.1 chain / nm 2 or more.

[0063] <3>

[0064] The damping material according to <1> or <2>, in which the graft density of the polymer graft chain is preferably 5 chain / nm 2 More preferably, 3 chain / nm 2 Further preferably, 1 chain / nm 2 Further preferably, 0.3 chain / nm 2 or more.

[0065] <4>

[0066] The damping material according to any one of <1> to <3>, in which the glass transition temperature of the polymer graft chain is preferably -30°C or higher, more preferably -10°C or higher, further preferably 10°C or higher, further preferably 25°C or higher.

[0067] <5>

[0068] The damping material according to any one of <1> to <4>, in which the glass transition temperature of the polymer graft chain is preferably 80°C or lower, more preferably 50°C or lower, further preferably 40°C or lower.

[0069] <6>

[0070] The damping material according to any one of <1> to <5>, wherein a film thickness of the polymer graft chain in the composite particle is preferably 1 nm or more, more preferably 3 nm or more, and further preferably 5 nm or more.

[0071] <7>

[0072] The damping material according to any one of <1> to <6>, wherein a film thickness of the polymer graft chain in the composite particle is preferably 1 μm or less, more preferably 100 nm or less, further preferably 40 nm or less, and further preferably 15 nm or less.

[0073] <8>

[0074] The damping material according to any one of <1> to <7>, wherein a number average molecular weight of the polymer graft chain in the composite particle is preferably 10,000 or more, more preferably 20,000 or more, and further preferably 30,000 or more.

[0075] <9>

[0076] The damping material according to any one of <1> to <8>, wherein a number average molecular weight of the polymer graft chain in the composite particle is preferably 1,000,000 or less, more preferably 500,000 or less, and further preferably 200,000 or less.

[0077] <10>

[0078] The damping material according to any one of <1> to <9>, wherein a dispersed particle diameter of the composite particle in the thermoplastic resin composition of the present application is preferably 10 nm or more, more preferably 100 nm or more, and further preferably 1 μm or more.

[0079] <11>

[0080] The damping material according to any one of <1> to <10>, wherein a dispersed particle diameter of the composite particle in the thermoplastic resin composition of the present application is preferably 200 μm or less, more preferably 100 μm or less, and further preferably 10 μm or less.

[0081] <12>

[0082] The damping material according to any one of <1> to <11>, wherein a compounding amount of the composite particle in the damping material is preferably 1 part by mass or more, more preferably 20 parts by mass or more, further preferably 30 parts by mass or more, and further preferably 40 parts by mass or more, with respect to 100 parts by mass of the thermoplastic resin.

[0083] <13>

[0084] The vibration damping material according to any one of <1> to <12>, wherein the content of the composite particles in the vibration damping material is preferably 300 parts by mass or less, more preferably 200 parts by mass or less, further preferably 100 parts by mass or less, further preferably 90 parts by mass or less, relative to 100 parts by mass of the thermoplastic resin.

[0085] <14>

[0086] The vibration damping material according to any one of <1> to <13>, wherein the content of the composite particles in the vibration damping material is preferably 1% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, further preferably 25% by mass or more.

[0087] <15>

[0088] The vibration damping material according to any one of <1> to <14>, wherein the content of the composite particles in the vibration damping material is preferably 75% by mass or less, more preferably 60% by mass or less, further preferably 55% by mass or less, further preferably 50% by mass or less.

[0089] <16>

[0090] The vibration damping material according to any one of <1> to <15>, wherein the content of the polymer graft chain of the composite particles in the vibration damping material is preferably 1 part by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, relative to 100 parts by mass of the thermoplastic resin.

[0091] <17>

[0092] The vibration damping material according to any one of <1> to <16>, wherein the content of the polymer graft chain of the composite particles in the vibration damping material is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, further preferably 40 parts by mass or less, relative to 100 parts by mass of the thermoplastic resin.

[0093] <18>

[0094] The vibration damping material according to any one of <1> to <17>, wherein the content of the thermoplastic resin in the vibration damping material is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more.

[0095] <19>

[0096] The vibration damping material according to any one of <1> to <18>, wherein the content of the thermoplastic resin in the vibration damping material is preferably 95 mass% or less, more preferably 80 mass% or less, and further preferably 75 mass% or less.

[0097] <20>

[0098] The vibration damping material according to any one of <1> to <19>, wherein the thermoplastic resin is preferably one or two or more selected from the group consisting of polyolefin resin, polyamide resin, and ABS resin, more preferably one or two or more selected from the group consisting of polyolefin resin, and further preferably polypropylene resin.

[0099] <21>

[0100] The vibration damping material according to any one of <1> to <20>, wherein the particle is one or two or more selected from the group consisting of metal oxide, metal oxide salt, metal hydroxide, and metal carbonate, more preferably one or two or more selected from the group consisting of silicon oxide such as silica, and silicate such as mica and talc, and further preferably silica.

[0101] <22>

[0102] The vibration damping material according to any one of <1> to <21>, wherein the high-molecular graft chain is preferably a polymer formed from one or two or more monomers selected from the group consisting of styrene-based monomer, nitrile-based monomer, (meth)acrylic acid-based monomer, unsaturated olefin, and conjugated diene-based monomer, more preferably a homopolymer or copolymer of one or two or more selected from the group consisting of acrylic acid, methacrylic acid, and derivatives thereof, further preferably a homopolymer or copolymer of one or two or more selected from the group consisting of methacrylic acid and derivatives thereof, and further preferably polybutyl methacrylate.

[0103] <23>

[0104] A method for producing a vibration damping material, comprising a step of melt-kneading a thermoplastic resin and a composite particle in which a high-molecular graft chain is bound to the surface of a particle.

[0105] <24>

[0106] The method for producing a vibration damping material according to <23>, comprising a step of binding a high-molecular graft chain to the surface of a particle.

[0107] <25>

[0108] The method for producing a vibration damping material according to <24>, wherein the method for binding a high-molecular graft chain to the surface of a particle is a surface grafting method in which a high-molecular graft chain is polymerized from a polymerization starting point on the surface of a particle.

[0109] <26>

[0110] The method for producing a damping material according to <25>, wherein the polymerization method is preferably radical polymerization, anionic polymerization, or cationic polymerization, more preferably living radical polymerization, living anionic polymerization, or living cationic polymerization, further preferably living radical polymerization, further preferably atom transfer radical polymerization (ATRP method), reversible addition fragmentation chain transfer polymerization (RAFT method), or nitroxide-mediated polymerization (NMP method), further preferably atom transfer radical polymerization (ATRP method).

[0111] <27>

[0112] The method for producing a damping material according to any one of <24> to <26>, wherein the method for binding the high molecular graft chain to the particle surface includes the following process 1 and process 2.

[0113] Process 1: Process for binding a polymerization initiation group to the particle surface

[0114] Process 2: Process for contacting the particle having the polymerization initiation group on the surface with a monomer under living radical polymerization conditions

[0115] <28>

[0116] The method for producing a damping material according to <27>, wherein the polymerization initiation group is a living radical polymerization initiation group, preferably an atom transfer radical polymerization initiation group, more preferably a haloacyl group, further preferably an α-haloacyl group, further preferably an α-bromoacyl group, further preferably 2-bromoisobutyryl.

[0117] <29>

[0118] The method for producing a damping material according to <27> or <28>, wherein process 1 has a process for introducing an amino group or a hydroxyl group to the particle surface and a process for introducing a polymerization initiation group, preferably has a process for introducing a polymerization initiation group to the particle surface after the process for introducing an amino group or a hydroxyl group to the particle surface.

[0119] <30>

[0120] The method for producing a damping material according to any one of <27> to <29>, wherein the compound used in the process for introducing an amino group or a hydroxyl group to the particle surface is a compound having a group to be bound to the particle surface and an amino group or a hydroxyl group, preferably a silane compound, more preferably an aminoalkylsilane compound, further preferably 3-aminopropyltrimethoxysilane.

[0121] <31>

[0122] The method for producing a damping material according to any one of <27> to <30>, wherein the compound used in the step of introducing a polymerization initiation group to the surface of the particle is a compound having a functional group that reacts with the polymerization initiation group and an amino group or a hydroxyl group, preferably a haloalkanoic acid derivative, more preferably a bromoalkanoic acid derivative, further preferably a 2-bromo-2-methylpropionic acid derivative, further preferably 2-bromoisobutyryl bromide.

[0123] Examples

[0124] Hereinafter, the present application will be specifically described according to examples, but the present application is not limited to these examples.

[0125] Glass transition temperature of polymer graft chain in composite particle

[0126] Determined by the method of JIS K 7121. Using a differential scanning calorimeter (Hitachi High-Technologies DSC7020), the heat capacity was determined by raising the composite particle from 40°C to 200°C at 10°C / minute. The midpoint glass transition temperature Tmg (°C) was calculated as the temperature of the intersection of the straight line equidistant from the extension of each baseline in the DSC thermogram and the curve of the phase change portion of the glass transition.

[0127] Number average molecular weight of polymer graft chain in composite particle

[0128] Regarding the number average molecular weight of the polymer graft chain in the composite particle, the number average molecular weight of the polymer chain not combined with the composite particle, which is simultaneously generated in the process of producing the composite particle, was determined as the number average molecular weight of the polymer graft chain. In gel permeation chromatography (GPC), using GMHHR-H+GMHHR-H (cation) for the chromatography column, chloroform for the solvent, at a flow rate of 1.0 mL / minute, a column temperature of 40°C, using polystyrene as the conversion molecular weight standard, the above number average molecular weight was determined.

[0129] Graft density of polymer graft chain in composite particle

[0130] The graft amount (W) and the number average molecular weight of the graft chain (Mn) were determined, and the graft density (chains / nm 2 ) was calculated by the following formula. Note that the graft amount was calculated by thermogravimetric loss measurement (TG). More specifically, the weight reduction rate at the time was determined by raising the temperature from 40°C to 500°C at 10°C / minute in the atmosphere. The number average molecular weight of the graft chain was calculated by the gel permeation chromatography (GPC) method shown below.

[0131] Graft density (chains / nm 2 ) = graft amount (g / nm 2) x (Avogadro's number)

[0132] Film thickness of polymer graft chain in composite particle

[0133] The film thickness was calculated by the following equation. As for the polymer density, the polymer density of the polymer chain not combined with the composite particle, which was simultaneously produced in the process of producing the composite particle, was used as the polymer density of the polymer graft chain. It was measured by the specific gravity bottle method based on JIS K7112.

[0134] [Equation 1]

[0135]

[0136] Dispersed particle diameter of composite particle

[0137] The composite particles in the thermoplastic resin composition were observed for the cross section of a test piece of the thermoplastic resin using a scanning electron microscope (SEM). From the image observed by the scanning electron microscope, 30 cross sections of the composite particles were selected, and the respective major axes were visually read and averaged to be the dispersed particle diameter.

[0138] Conditions

[0139] Apparatus: Field emission scanning electron microscope (S-4000, manufactured by Hitachi, Ltd.)

[0140] Acceleration rate: 10 kV

[0141] Beam spot diameter: 8 mm

[0142] Magnification: 400x to 5,000x

[0143] [Preparation of composite particle 1]

[0144] a) Process of binding polymerization initiation group to surface of particle

[0145] a-1) Introduction of amino group to surface of silica fine particle

[0146] Silica fine particles (SILFIL NSS-3N, manufactured by Tokuyama Corp., average particle diameter 120 nm) 40 g and 3-aminopropyltrimethoxysilane (KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 g were added to ethanol 200 mL. This mixture was stirred at room temperature for 12 hours. Thereafter, the silica fine particles were recovered by washing with ethanol using a centrifugal separator, and then heated at 110°C for 1 hour to obtain silica fine particles to which an amino group was introduced.

[0147] a-2) Introduction of polymerization initiation group to surface of silica fine particle to which an amino group was introduced

[0148] In a 500 mL eggplant flask, the above amino-introduced silica fine particles 40 g, anhydrous THF 200 mL, anhydrous triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) 1 mL, 2-bromoisobutyryl bromide (BIBB, manufactured by Tokyo Chemical Industry Co., Ltd.) 1 mL were added, and stirred at room temperature for 2 hours. After that, the amino-introduced silica fine particles into which 2-bromoisobutyryl bromide was introduced as a polymerization initiator were recovered with a centrifugal separator, and then stored as a methanol solution of the silica fine particles into which a polymerization initiator was introduced.

[0149] b) a step of bringing the particles having a polymerization initiator group on the surface into contact with a monomer under active radical polymerization conditions

[0150] In a 500 mL eggplant flask, a methanol solution of the prepared silica fine particles 40 g containing silica fine particles having a polymerization initiator group, methanol 160 mL, water 40 mL, butyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 35 g were added, and nitrogen bubbling was performed for 1 hour. After that, a methanol solution in which Cu(II)Br (manufactured by Tokyo Chemical Industry Co., Ltd.) 11 mg, pentamethyldiethylene triamine (manufactured by Tokyo Chemical Industry Co., Ltd.) 90 mg were stirred in advance in methanol 2 mL was injected. After sufficient stirring, an aqueous solution of ascorbic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 90 mg was injected, and the polymerization was initiated. After that, it was warmed to 40°C, and stirred for 4 hours. After that, the silica fine particles to which polybutyl methacrylate was grafted were recovered with methanol and a centrifugal separator. The content of the polymer graft chain was 35.5 mass%.

[0151] [Preparation of composite particles 2]

[0152] b) a step of bringing the particles having a polymerization initiator group on the surface into contact with a monomer under active radical polymerization conditions

[0153] In a 500 mL eggplant flask, a benzylic ether solution of the silica fine particles 40 g having a polymerization initiator group prepared in the same procedure as in the step a) of the preparation of the composite particles 1, benzylic ether 20 mL, butyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 60 g were added, and warmed to 60°C, and after sufficient stirring, nitrogen bubbling was performed for 1 hour. After that, a benzylic ether solution in which Cu(I)Br (manufactured by Tokyo Chemical Industry Co., Ltd.) 144 mg, pentamethyldiethylene triamine (manufactured by Tokyo Chemical Industry Co., Ltd.) 346 mg were stirred in advance in benzylic ether 2 mL was injected, and the polymerization was initiated. After that, it was stirred for 10 hours. After that, it was dispersed in chloroform, washed with methanol and aqueous ammonia, and the solvent was dried to obtain silica fine particles to which polybutyl methacrylate was grafted. The content of the polymer graft chain was 32.0 mass%.

[0154] [Preparation of composite particles 3]

[0155] The amount of the silica fine particles was changed to 6 g, the amount of anisole was changed to 60 mL, the amount of butyl methacrylate was changed to 180 g, the polymerization temperature was changed to 80°C, the amount of Cu(I)Br stirred in 2 mL of anisole was changed to 431 mg, the amount of pentamethyldiethylenetriamine was changed to 1040 mg, the polymerization time was changed to 5 minutes, and otherwise, it was produced in the same manner as the composite particle 2.

[0156] [Production of composite particle 4]

[0157] It was produced in the same manner as the composite particle 3 except that the polymerization time was changed to 15 minutes.

[0158] [Production of composite particle 5]

[0159] It was produced in the same manner as the composite particle 3 except that the polymerization time was changed to 30 minutes.

[0160] [Production of composite particle 6]

[0161] The amount of the silica fine particles was changed to 20 g, the amount of anisole was changed to 3 mL, the amount of butyl methacrylate was changed to 100 g, the polymerization temperature was changed to 80°C, and otherwise, it was produced in the same manner as the composite particle 2.

[0162] [Production of composite particle 7]

[0163] It was produced in the same manner as the composite particle 3 except that the silica fine particles were changed to Nipsil AQ and the polymerization time was changed to 20 minutes.

[0164] [Production of composite particle 8]

[0165] It was produced in the same manner as the composite particle 3 except that the silica fine particles were changed to mica fine particles A-21S and the polymerization time was changed to 20 minutes.

[0166] [Production of composite particle 9]

[0167] The amount of the silica fine particles was changed to 12 g, the amount of Cu(I)Br was changed to 861 mg, the amount of pentamethyldiethylenetriamine was changed to 2080 mg, the polymerization time was changed to 10 minutes, and butyl methacrylate was changed to hexyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), and otherwise, it was produced in the same manner as the composite particle 3.

[0168] [Production of thermoplastic resin composition]

[0169] Examples 1 to 3, Comparative Example 1

[0170] c) a step of melt-kneading the composite particle with a thermoplastic resin

[0171] Using Labo Plastomill (manufactured by Toyo Precision Machine Works), each component described in Table 1 was compounded in an amount described in Table 1, and melt-kneaded at 200°C to obtain a thermoplastic resin composition.

[0172] Examples 4 to 13, Comparative Examples 15 to 17

[0173] A thermoplastic resin composition was obtained in the same manner as in Examples 1 to 3 except that compounding described in Tables 2 and 3 was changed.

[0174] Example 14

[0175] A thermoplastic resin composition was obtained in the same manner as in Examples 1 to 3 except that compounding shown in Table 3 was changed, the melt-kneading temperature was changed to 240°C, the melt temperature for press molding was changed to 240°C, and the cooling temperature was changed to 80°C.

[0176] Loss Coefficient

[0177] Using an automatic press molding machine (manufactured by Toyo Precision Machine Works), a test piece (127 mm x 12.7 mm x 1.6 mm) for loss coefficient was molded after being melted at 200°C and cooled at 30°C. For the test piece, the loss coefficient was calculated from the peak of the secondary resonance of the frequency response function measured by the central excitation method using the half-width method based on JIS K7391. A system composed of an oscillator Type 3160, an amplifier Type 2718, an exciter Type 4810, and an acceleration sensor Type 8001 (all manufactured by B&K) was used, and a loss coefficient measuring software MS18143 was used. The measurement environment was controlled by a thermostat (manufactured by Espec, PU-3J), and the measurement was performed in a temperature range of 0°C to 80°C. The results at 20°C and 80°C are shown in Tables 1 to 3.

[0178] [Table 1]

[0179]

[0180] [Table 2]

[0181]

[0182] [Table 3]

[0183]

[0184] Details of each component shown in Tables 1 to 3 are as follows.

[0185] Polypropylene: MA03 (manufactured by Japan Polypropylene Corporation)

[0186] PBMA: Polybutyl methacrylate (manufactured by Sigma-Aldrich)

[0187] GF: T-480 (manufactured by Nitto Boseki)

[0188] SiO2of composite particle 7: Nipsil AQ (manufactured by Tosoh Silica)

[0189] Mica of composite particle 8: A-21S (manufactured by Yamaguchi Mica)

[0190] Polyamide: Amilan CM1017 (manufactured by Toray)

[0191] ABS: Toyolac 7000-314 (manufactured by Toray)

[0192] The thermoplastic resin compositions of Example 3 and Comparative Example 1 were injection molded, and the following flat plate vibration test, fan vibration test and fan rotation noise test were carried out. The results are shown in Tables 4 and 5.

[0193] < Flat plate vibration test >

[0194] Using an injection molding machine (J11AD-180H manufactured by Nippon Steel), the thermoplastic resin compositions of Example 3 and Comparative Example 1 were injection molded to form a flat plate test piece (100 mm x 100 mm x 2 mm). The cylinder temperature was set to 200°C from the front end of the nozzle to the 5th unit, and the remaining 1 unit was set to 170°C, and the hopper below was set to 45°C. The mold temperature was set to 50°C. In the vibration test, a system composed of a shaker of Type 3160, an amplifier of Type 2718, an exciter of Type 4810, an acceleration sensor of Type 8001, and a noise meter of 4189-A-029 (all manufactured by B&K) was used. The central portion of the flat plate formed was mounted on the conductive nozzle and fixed to the acceleration sensor, and then random excitation was applied, and the vibration level was calculated from the ratio of the vibration acceleration detected by the acceleration sensor to the excitation force in the range of 20 Hz to 12000 Hz. In addition, the noise level was calculated from the ratio of the sound pressure detected by the noise meter to the excitation force at a height of 100 mm from the center of the flat plate. The measurement environment was controlled to be 20°C or 80°C in a thermostat (PU-3J manufactured by Espec). If the value is small, it can be judged that the vibration and noise are further reduced.

[0195] < Fan vibration test >

[0196] A flat fan molded body was injection molded using an injection molding machine (SE180D, Sumitomo Heavy Industries, Ltd.) using the thermoplastic resin composition of Example 3 and Comparative Example 1, in the same shape as a flat fan (PLF125-18, diameter 150 mm, 8 blades) of Funtec Co. The barrel temperature was set to 200°C from the nozzle tip side to the 5th unit, and 170°C for the remaining 1 unit, and 45°C below the hopper. The mold temperature was set to 50°C. In the vibration test, a system composed of a shaker of Type 3160, an amplifier of Type 2718, an exciter of Type 4810, an acceleration sensor of Type 8001, and a noise meter of 4189-A-029 (all of B&K Co.) was used. The central portion of the flat fan was mounted on a conductive nozzle and fixed to the acceleration sensor, and then random excitation was applied, and the vibration level was calculated from the ratio of the vibration acceleration detected by the acceleration sensor to the excitation force in the range of 20 Hz to 12,000 Hz. The measurement environment was controlled to 80°C in a thermostat (PU-3J, Espec Co.). The smaller the value, the more the vibration was judged to be reduced.

[0197] < Fan rotation noise test >

[0198] The same flat fan molded body as described above was used. The fan molded body was mounted on the rotating shaft of a motor (AC motor, Kusatsu Electric Co.) and rotated at each rotation speed. The noise generated at that time was collected at a position 100 mm laterally and 200 mm below the fan using a noise meter (4189-A-029, B&K Co.), and FFT analysis was performed. The measurement time was 60 seconds, the average number of times was 358 times per frequency, and the frequency weighting characteristic was analyzed with A characteristic. The measurement environment was controlled to 80°C in a thermostat (PU-3J, Espec Co.). In the FFT analysis of the fan noise at each rotation speed, the frequency and the noise level corresponding to the peak of the rotation noise of F = 2NZ / 60 were measured. The smaller the value, the more the rotation noise was judged to be reduced.

[0199] [Table 4]

[0200]

[0201] [Table 5]

[0202]

[0203] As shown in Table 1, the thermoplastic resin composition of Example 3 containing the composite particles having the polymer graft chain bound to the surface of the particles has a high loss factor at any temperature of 20°C and 80°C, and is excellent in vibration damping property, as compared with the thermoplastic resin composition of Comparative Example 1 to which the same amount of the filler is added without being bound to the elastomer. This confirms that the vibration and noise can be further reduced in the injection-molded sample in Tables 4 and 5. In addition, as shown in Tables 1 to 3, the thermoplastic resin compositions of Examples 1, 2, 4 to 13, 16, 17, Example 14 using a polyamide resin, and Example 15 using an ABS resin, each containing the composite particles having the polymer graft chain bound to the surface of the particles, also have a high loss factor and are excellent in vibration damping property.

[0204] Industrial applicability

[0205] The thermoplastic resin composition of the present application can be suitably used for products such as acoustic equipment, electric products, buildings, industrial equipment, automobile members, two-wheeled vehicle members, containers, and the like.

Claims

1. A thermoplastic resin composition comprising a thermoplastic resin and a composite particle in which a high molecular graft chain is bound to a particle surface, The grafting density of the polymer grafting chains is 0.001 chains / nm 2 The grafting density of the polymer grafting chains is 0.001 chains / nm 2 In the following, the content of the high molecular graft chain of the composite particle is 1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin, the film thickness of the high molecular graft chain in the composite particle calculated from the following formula is 1 nm or more and 1 μm or less, 。 2. A thermoplastic resin composition comprising a thermoplastic resin and a composite particle in which a high molecular graft chain is bound to a particle surface, The grafting density of the polymer grafting chains is 0.001 chains / nm 2 The grafting density of the polymer grafting chains is 0.001 chains / nm 2 In the following, the film thickness of the high molecular graft chain in the composite particle calculated from the following formula is 1 nm or more and 1 μm or less, 。 3. The thermoplastic resin composition according to claim 1 or 2, wherein, the glass transition temperature of the high molecular graft chain is -30°C or more and 80°C or less.

4. The thermoplastic resin composition according to claim 1 or 2, wherein, the glass transition temperature of the high molecular graft chain is -10°C or more and 40°C or less.

5. The thermoplastic resin composition according to claim 1 or 2, wherein, the film thickness of the high molecular graft chain in the composite particle calculated from the following formula is 5 nm or more and 15 nm or less, 。 6. The thermoplastic resin composition according to claim 1 or 2, wherein, the number average molecular weight of the high molecular graft chain in the composite particle is 10,000 or more and 1,000,000 or less.

7. The thermoplastic resin composition according to claim 1 or 2, wherein, the number average molecular weight of the high molecular graft chain in the composite particle is 30,000 or more and 200,000 or less.

8. The thermoplastic resin composition according to claim 1 or 2, wherein, the dispersed particle diameter of the composite particle is 10 nm or more and 200 μm or less.

9. The thermoplastic resin composition according to claim 1 or 2, wherein, the dispersed particle diameter of the composite particle is 1 μm or more and 10 μm or less.

10. The thermoplastic resin composition according to claim 1 or 2, wherein, the blending amount of the composite particle is 1 part by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin.

11. The thermoplastic resin composition according to claim 1 or 2, wherein, the blending amount of the composite particle is 20 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin.

12. The thermoplastic resin composition according to claim 1 or 2, wherein, the blending amount of the composite particle is 40 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin.

13. The thermoplastic resin composition according to claim 1 or 2, wherein, the blending amount of the composite particle is 1 mass% or more and 75 mass% or less.

14. The thermoplastic resin composition according to claim 1 or 2, wherein, the blending amount of the composite particle is 25 mass% or more and 50 mass% or less.

15. The thermoplastic resin composition according to claim 1 or 2, wherein, the content of the high molecular graft chain of the composite particle is 10 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin.

16. The thermoplastic resin composition according to claim 1 or 2, wherein, the blending amount of the thermoplastic resin is 30 mass% or more and 95 mass% or less.

17. The thermoplastic resin composition according to claim 1 or 2, wherein, the blending amount of the thermoplastic resin is 50 mass% or more and 75 mass% or less.

18. The thermoplastic resin composition according to claim 1 or 2, wherein, The grafting density of the polymer grafting chains is 0.1 chains / nm 2 above and 0.37 chains / nm 2 below.

19. The thermoplastic resin composition according to claim 1 or 2, wherein, the thermoplastic resin is one or more selected from the group consisting of a polyolefin resin, a polyamide resin and an ABS resin.

20. The thermoplastic resin composition according to claim 1 or 2, wherein, the high molecular graft chain is a polymer formed from one or two or more monomers selected from the group consisting of a styrene monomer, a nitrile monomer, a (meth)acrylic acid monomer, an unsaturated olefin and a conjugated diene monomer.

21. A method for producing a thermoplastic resin composition, which is a method for producing the thermoplastic resin composition described in claim 1 or 2, which includes a step of binding a high molecular graft chain to a particle surface and a step of melt-kneading a thermoplastic resin and a composite particle in which a high molecular graft chain is bound to a particle surface, the step of binding a high molecular graft chain to a particle surface is a surface grafting method in which a high molecular graft chain is polymerized from a polymerization starting point on the surface of a particle, and includes the following step 1 and step 2, step 1: a step of binding a polymerization starting group to a particle surface; Step 2: a step of contacting the particles having a polymerization initiation group on the surface with a monomer under a living radical polymerization condition.

22. The method for producing a thermoplastic resin composition according to claim 21, further comprising a shaping process.

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