Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
  • C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
  • C08K9/08—Ingredients agglomerated by treatment with a binding agent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/10—Homopolymers or copolymers of propene
  • C08L23/12—Polypropene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2438/00—Living radical polymerisation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/003—Additives being defined by their diameter

Definitions

• the present invention relates to a thermoplastic resin composition and a method for producing the same, an additive for improving the vibration damping property of the thermoplastic resin, and a vibration damping material containing the thermoplastic resin composition.
• vibration countermeasures for various devices have been required, and in particular, they are required in the fields of automobiles, home appliances, precision equipment, and the like.
• a material having high vibration damping property a material obtained by laminating a metal plate and a vibration absorbing material such as rubber or asphalt, or a composite type material such as a vibration damping steel plate in which a vibration absorbing material is sandwiched between metal plates.
• These damping materials retain their shape with a highly rigid metal plate and absorb vibration with a vibration absorbing material.
• alloy-type materials that absorb vibration by converting kinetic energy into thermal energy using twinning and ferromagnetism can be mentioned.
• the composite type material has a limitation in formability because different materials are bonded together, and because a metal steel plate is used, there is a problem that the product itself becomes heavy.
• the alloy type material is heavy because it uses only metal, and its damping performance is insufficient.
• Patent Document 1 describes a polypropylene-based resin in which a reinforcing inorganic filler is blended with a resin component obtained by adding / mixing high-density polyethylene (PE) and an aromatic hydrocarbon resin to crystalline polypropylene (PP).
• PE high-density polyethylene
• PP crystalline polypropylene
• the resin composition is obtained by further adding and mixing a hydrogenated additive of an aromatic vinyl-conjugated diene block copolymer as a resin component.
• a vibration-damping resin molded product characterized by this is disclosed.
• the present invention relates to a new thermoplastic resin composition having excellent vibration damping properties and a method for producing the same, an additive for improving the vibration damping properties of the thermoplastic resin, and a vibration damping material containing the thermoplastic resin composition.
• the present invention relates to the following [1] to [4].
• [1] A thermoplastic resin composition containing a thermoplastic resin and composite particles in which a polymer graft chain is bonded to the particle surface.
• [2] A method for producing a thermoplastic resin composition, which comprises a step of melt-kneading a thermoplastic resin and composite particles in which a polymer graft chain is bonded to the particle surface.
• a method for producing a vibration damping material which comprises a step of melt-kneading a thermoplastic resin and composite particles in which a polymer graft chain is bonded to a particle surface.
• a method for improving the vibration damping property of a thermoplastic resin which uses composite particles in which polymer graft chains are bonded to the particle surface.
• thermoplastic resin composition having excellent vibration damping properties, a method for producing the same, an additive for improving the vibration damping properties of the thermoplastic resin, and a vibration damping material containing the thermoplastic resin composition are provided. can do.
• the present inventors have newly found that the vibration damping property is improved by forming some kind of bond between the elastomer and the filler added to the thermoplastic resin composition and strengthening the interface between them. This mechanism is not clear, but it is presumed that the strain energy in the elastomer can be increased by strengthening the interface between the elastomer and the filler. Further, the present inventors obtained the composite particles in which the elastomer and the filler are bonded by the Grafting from method in which a polymer graft chain corresponding to the elastomer is polymerized from the polymerization initiation point on the surface of the particles used as the filler. It was also newly found that excellent vibration damping properties can be obtained by using the obtained composite particles. It is presumed that this is because the polymer graft chains are bonded to the particle surface at high density by the Grafting from method, so that these interfaces can be remarkably strengthened.
• thermoplastic resin composition contains a thermoplastic resin and composite particles in which polymer graft chains are bonded to the particle surface.
• thermoplastic resin examples include polyolefin resin, polyester resin, polyamide resin, ABS resin, polystyrene resin, polycarbonate resin, vinyl chloride resin, acrylic resin and the like. Of these, from the viewpoint of ease of handling of the obtained resin composition such as moldability, one or more, more preferably polyolefin resin, which consists of a group selected from polyolefin resin, polyamide resin, and ABS resin. One or more, more preferably polypropylene resin, which consists of the selected group.
• the mass average molecular weight of the thermoplastic resin is not particularly limited, but those of 5000 to 500,000 can be used.
• the amount of the thermoplastic resin to be blended in the thermoplastic resin composition of the present invention is preferably 30% by mass or more, more preferably 40% by mass or more, from the viewpoint of obtaining a molded product or a vibration damping material exhibiting a desired elastic modulus. , More preferably 50% by mass or more. On the other hand, from the viewpoint of obtaining a molded product or vibration damping material exhibiting desired vibration damping properties, it is preferably 95% by mass or less, more preferably 80% by mass or less, and further preferably 75% by mass or less. When two or more types of thermoplastic resins are blended, the blending amount is the total amount of the thermoplastic resins.
• a composite particle is one in which a polymer graft chain is bonded to the surface of the particle.
• known fillers can be used, and examples thereof include metal oxides, metal oxide salts, metal hydroxides, metal carbonates, cellulose, and the like, preferably metal oxides, metal oxide salts, and the like.
• it is two or more kinds, and more preferably silica.
• the shape of the particles is not particularly limited, and examples thereof include a plate shape, a granular shape, a needle shape, and a fibrous shape.
• particle refers to particles used in the production of composite particles.
• the polymer graft chain include homopolymers or copolymers such as styrene-based monomers, nitrile-based monomers, (meth) acrylic-based monomers, unsaturated olefins, and conjugated diene-based monomers, and molded bodies exhibiting desired vibration damping properties. From the viewpoint of obtaining a vibration-damping material, one or more homopolymers or copolymers consisting of a group selected from acrylic acid, methacrylic acid, and derivatives thereof, and more preferably from methacrylic acid and its derivatives.
• the bond is preferably a chemical bond, and more preferably a covalent bond, from the viewpoint of obtaining a molded product or vibration damping material exhibiting desired vibration damping properties.
• 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, still more preferably 10 ° C or higher, still more preferably 25 ° C. from the viewpoint of vibration damping. It is °C or more, and from the same viewpoint, it is preferably 80 °C or less, more preferably 50 °C or less, and further preferably 40 °C or less. Further, the polymer graft chain in the composite particle may have a glass transition temperature (Tg) of 2 or more, and may have a Tg other than Tg of ⁇ 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, molecular weight, and molecular weight distribution used in the production of the composite particle. For example, in the case of composite particles, it is known that the graft density increases, and when the polymer chain becomes a stretched chain, Tg increases. In that case, Tg can be controlled by adjusting the graft density. In the temperature range near Tg, the viscoelastic tan ⁇ of the resin becomes maximum, which is effective for the development of vibration damping property. By controlling Tg, the vibration damping property in a desired temperature range can be enhanced.
• the glass transition temperature (Tg) is measured by the method described in Examples below.
• the graft density of the polymer graft chain in the composite particle is preferably 0.001 chain / nm 2 or more, more preferably 0.01 chain / nm 2 or more, still more preferably 0, from the viewpoint of increasing the strain energy in the elastomer. .1 chain / nm 2 or more.
• On the other hand, from the viewpoint of ease of grafting the polymer chain preferably 5 chains / nm 2 or less, more preferably 3 chains / nm 2 or less, still more preferably 1 chain / nm 2 or less, still more preferably 0.3. Chain / nm 2 or less.
• the graft density is measured by the method described in Examples below.
• the 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 from the viewpoint of efficiently increasing the strain energy of the elastomer. From the same viewpoint, it is preferably 1 ⁇ m or less, more preferably 100 nm or less, still more preferably 40 nm or less, still more preferably 15 nm or less.
• the film thickness of the polymer graft chain is calculated by the method described in Examples described later.
• the number average molecular weight of the polymer graft chains in the composite particles is preferably 10,000 or more, more preferably 20,000 or more, still more preferably 30,000 or more, from the viewpoint of controlling the film thickness of the polymer graft chains. .. From the same viewpoint, it is preferably 1,000,000 or less, more preferably 500,000 or less, still more preferably 200,000 or less.
• the number average molecular weight of the polymer graft chain is measured by the method described in Examples described later.
• the amount of the composite particles to be blended in the thermoplastic resin composition of the present invention is preferably 1% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, still more preferably, from the viewpoint of exhibiting vibration damping properties. Is 25% by mass or more.
• it is preferably 75% by mass or less, more preferably 60% by mass or less, still more preferably 55% by mass or less, still more preferably 50% by mass or less. Is.
• the blending amount is the total amount of the composite particles.
• the blending amount of the composite particles in the thermoplastic resin composition of the present invention is preferably 1 part by mass or more, more preferably 20 parts by mass or more, and further, from the viewpoint of exhibiting vibration damping properties, with respect to 100 parts by mass of the thermoplastic resin. It is preferably 30 parts by mass or more, more preferably 40 parts by mass or more. On the other hand, from the viewpoint of obtaining a molded product or vibration damping material exhibiting a desired elastic modulus, it is preferably 300 parts by mass or less, more preferably 200 parts by mass or less, still more preferably 100 parts by mass or less, still more preferably 90 parts by mass or less. Is.
• the content of the polymer graft chain of the composite particles in the thermoplastic resin composition of the present invention is preferably 1 part by mass or more, more preferably 5 parts by mass with respect to 100 parts by mass of the thermoplastic resin from the viewpoint of developing vibration damping properties. It is 10 parts by mass or more, more preferably 10 parts by mass or more. On the other hand, from the viewpoint of obtaining a molded product or a vibration damping material exhibiting a desired elastic modulus, it is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and further preferably 40 parts by mass or less.
• the dispersed particle size of the composite particles in the thermoplastic resin composition of the present invention is preferably 10 nm or more, more preferably 100 nm or more, still more preferably 1 ⁇ m or more from the viewpoint of developing vibration damping properties, and is preferable from the same viewpoint. Is 200 ⁇ m or less, more preferably 100 ⁇ m or less, still more preferably 10 ⁇ m or less.
• the composite particles may exist alone or as an aggregate. The dispersed particle size of the composite particles is measured by the method described in Examples described later.
• Composite particles are obtained by binding a polymer graft chain to the surface of the particles.
• the method of bonding the polymer graft chain to the particle surface is not particularly limited as long as it can graft the polymer chain, but Grafting from polymerizing the polymer graft chain from the polymerization initiation point of the particle surface.
• the method is preferred.
• the polymerization method is not particularly limited, and examples thereof include radical polymerization, anionic polymerization, and cationic polymerization.
• living radical polymerization living anionic polymerization, and living cationic polymerization are preferable from the viewpoint of easy control of the molecular weight and molecular weight distribution of the polymer chain and easy grafting of various copolymers, and are applied to a wide range of monomers.
• Living radical polymerization is more preferable from the viewpoint of being able to do so.
• an atom transfer radical polymerization method ATRP method
• RAFT method a reversible addition cleavage chain transfer polymerization method
• NMP method nitroxide-mediated living radical polymerization method
• a production mode including the following step 2 is exemplified, and if necessary, the following step 1 may be performed.
• the following steps 1 and 2 can be performed under known conditions in living radical polymerization.
• Step 1 Bond the polymerization initiator group to the particle surface
• Step 2 Contact the monomer having the polymerization initiator group on the surface under living radical polymerization conditions
• the particles having a polymerization initiator group on the surface in step 2 are not particularly limited as long as they have a bonding group that binds the particle surface and the polymer chain.
• the polymerization initiator is a living radical polymerization initiator, preferably an atom transfer radical polymerization initiator, more preferably a haloacyl group, still more preferably an ⁇ -haloacyl group, and further, from the viewpoint of bonding a polymer graft chain to the particle surface. It is preferably an ⁇ -bromoacyl group, more preferably a 2-bromoisobutyryl group.
• the compound which is a raw material of the bonding base includes a compound having a group bonded to the particle surface and a polymerization initiating group, a compound having a group bonded to the particle surface or a polymerization initiating group, and the like.
• Step 1 includes a step of introducing an amino group or a hydroxy group on the particle surface and a step of introducing a polymerization initiator group, and from the viewpoint of bonding a polymer graft chain to the particle surface, the amino group or hydroxy is preferably on the particle surface.
• the step of introducing the group there is a step of introducing a polymerization initiator group on the particle surface.
• the compound used in the step of introducing an amino group or a hydroxyl group into the particle surface is a compound having a group bonded to the particle surface and an amino group or a hydroxyl group, and is preferably a silane compound from the viewpoint of availability.
• An aminoalkylsilane compound is preferable, and 3-aminopropyltrimethoxysilane is more preferable.
• the compound used in the step of introducing a polymerization initiating group onto the particle surface is a compound having a polymerization initiating group and a functional group that reacts with an amino group or a hydroxy group, and is preferable from the viewpoint of binding a polymer graft chain to the particle surface.
• Is a haloalkanoic acid derivative more preferably a bromoalkanoic acid derivative, still more preferably a 2-bromo-2-methylpropionic acid derivative, and even more preferably 2-bromoisobutyl bromide.
• step 1 when the particles originally have a polymerization initiation site or are formed as a result of surface treatment by plasma treatment or the like, step 1 is unnecessary because they have polymerization initiation groups.
• Step 1 may be performed when silica, mica, talc, glass filler or the like having no polymerization initiating group is used.
• a silane coupling agent containing no polymerization initiating group may be added to the polymerization initiating group-containing silane coupling agent in step 1 for use.
• a method of dispersing the particles with a dispersion medium is preferable from the viewpoint of not aggregating the particles.
• a monomer constituting a thermoplastic elastomer known as a vibration damping elastomer can be used.
• the monomer constituting such a thermoplastic elastomer include styrene-based monomers, nitrile-based monomers, (meth) acrylic-based monomers, unsaturated olefins, conjugated diene-based monomers, and the like, and other monomers having a specific group in the side chain. Monomers can also be used.
• the particles, the monomer and the composite particle are treated with a dispersion medium from the viewpoint of not aggregating the particles, the monomer and the composite particle.
• a method of dispersing and polymerizing is preferable.
• the composite particles may be arbitrarily purified.
• a method of dispersing the composite particles with a dispersion medium and removing the solvent is preferable from the viewpoint of not aggregating the composite particles. Further, a method of removing the metal catalyst used in the polymerization step is preferable.
• thermoplastic resin composition of the present invention has, as other components other than the above, a chain extender, a plasticizer, an organic crystal nucleating agent, an inorganic crystal nucleating agent, a hydrolysis inhibitor, a flame retardant, an antioxidant, and a hydrocarbon system.
• Blending waxes and anionic surfactants such as lubricants, UV absorbers, antistatic agents, antifogging agents, light stabilizers, pigments, antifungal agents, antibacterial agents, foaming agents, and other polymer materials. Can be done.
• thermoplastic resin composition examples include a production method including a step of melt-kneading the thermoplastic resin and the composite particles in which the polymer graft chain is bonded to the particle surface.
• a known kneader such as a closed kneader, a single-screw or twin-screw extruder, or an open roll type kneader can be used.
• the melt-kneaded product may be dried or cooled according to a known method.
• the raw materials can be uniformly mixed in advance using a Henschel mixer, a super mixer or the like, and then subjected to melt kneading.
• the melt-kneading temperature and melt-kneading time are not unconditionally set depending on the type of raw material used, but are preferably 170 to 240 ° C. and preferably 15 to 900 seconds.
• the amount of the composite particles in which the polymer graft chain is bonded to the particle surface in the step of melt-kneading the composite particles in which the thermoplastic resin and the polymer graft chain are bonded to the particle surface is 100 parts by mass of the thermoplastic resin. From the viewpoint of exhibiting vibration damping properties, it is preferably 1 part by mass or more, more preferably 30 parts by mass or more, still more preferably 40 parts by mass or more, and from the same viewpoint, preferably 200 parts by mass or less, more preferably 100 parts by mass or more. It is less than or equal to parts by mass, more preferably 90 parts by mass or less.
• the additive of the present invention includes composite particles in which polymer graft chains are bonded to the particle surface.
• the additives of the present invention are chain extenders, plasticizers, organic crystal nucleating agents, inorganic crystal nucleating agents, hydrolysis inhibitors, flame retardants, antioxidants, hydrocarbon waxes and lubricants such as anionic surfactants.
• UV absorber, antistatic agent, antifogging agent, light stabilizer, pigment, antifungal agent, antibacterial agent, foaming agent and the like can be arbitrarily contained.
• the additive of the present invention may contain a part of the resin to be melt-kneaded together (for example, 0.1 to 50.0% by mass in the additive).
• the additive of the present invention is used as an additive for improving the vibration damping property of a thermoplastic resin. Therefore, the present invention also discloses a method of using composite particles in which polymer graft chains are bonded to the particle surface for improving the vibration damping property of a thermoplastic resin.
• thermoplastic resin composition of the present invention uses various molding processing methods such as injection molding, extrusion molding, and thermoforming to produce acoustic equipment, electrical products, buildings, industrial equipment, automobile parts, motorcycle members, and containers. It can be suitably used as a vibration damping material used for products such as, or their parts or housings.
• thermoplastic resin composition of the present invention when a part or housing containing the thermoplastic resin composition of the present invention is manufactured by injection molding, pellets of the thermoplastic resin composition of the present invention are filled in an injection molding machine and injected into a mold. It is obtained by molding.
• thermoplastic resin composition of the present invention may be supplied to a cylinder and melt-kneaded as it is, but it is preferable to fill the injection molding machine with the melt-kneaded material in advance.
• molding may be performed according to a known method, and there is no particular limitation.
• the molded product of the thermoplastic resin composition of the present invention can be used for products such as audio equipment, electric products, buildings, industrial equipment, automobile parts, motorcycle members, containers, or vibration damping materials used for their parts or housings. It can be preferably used.
• the application to these can be appropriately set according to the manufacturing method, application location and desired purpose of the parts, housings, devices and devices, and can be used according to the conventional method in the technical field.
• the present invention further discloses the following damping material and a method for producing the same.
• the graft density of the polymer graft chain is preferably 0.001 chain / nm 2 or more, more preferably 0.01 chain / nm 2 or more, and further preferably 0.1 chain / nm 2 or more.
• the listed damping material ⁇ 3>
• the graft density of the polymer graft chain is preferably 5 chains / nm 2 or less, more preferably 3 chains / nm 2 or less, still more preferably 1 chain / nm 2 or less, still more preferably 0.3 chain / nm 2 or less.
• ⁇ 4> Any of ⁇ 1> to ⁇ 3>, wherein the glass transition temperature of the polymer graft chain is preferably -30 ° C or higher, more preferably -10 ° C or higher, still more preferably 10 ° C or higher, still more preferably 25 ° C or higher. Vibration damping material described in Crab. ⁇ 5> The vibration damping material according to any one of ⁇ 1> to ⁇ 4>, wherein the glass transition temperature of the polymer graft chain is preferably 80 ° C. or lower, more preferably 50 ° C. or lower, and further preferably 40 ° C. or lower.
• the film thickness of the polymer graft chain in the composite particle is preferably 1 ⁇ m or less, more preferably 100 nm or less, further preferably 40 nm or less, still more preferably 15 nm or less, according to any one of ⁇ 1> to ⁇ 6>. Vibration damping material.
• ⁇ 8> Described in any one of ⁇ 1> to ⁇ 7>, wherein the number average molecular weight of the polymer graft chains in the composite particles is preferably 10,000 or more, more preferably 20,000 or more, still more preferably 30,000 or more. Vibration damping material.
• the number average molecular weight of the polymer graft chains in the composite particles is preferably 1,000,000 or less, more preferably 500,000 or less, still more preferably 200,000 or less. Vibration damping material described in.
• ⁇ 10> The control according to any one of ⁇ 1> to ⁇ 9>, wherein the dispersed particle size of the composite particles in the thermoplastic resin composition of the present invention is preferably 10 nm or more, more preferably 100 nm or more, still more preferably 1 ⁇ m or more. Shaking material.
• ⁇ 11> The control according to any one of ⁇ 1> to ⁇ 10>, wherein the dispersed particle size of the composite particles in the thermoplastic resin composition of the present invention is preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less, still more preferably 10 ⁇ m or less. Shaking material.
• the amount of the composite particles blended in the vibration damping material is preferably 1 part by mass or more, more preferably 20 parts by mass or more, still more preferably 30 parts by mass or more, still more preferably 40 parts by mass, based on 100 parts by mass of the thermoplastic resin.
• the amount of the composite particles in the damping material is preferably 300 parts by mass or less, more preferably 200 parts by mass or less, still more preferably 100 parts by mass or less, still more preferably 90 parts by mass, based on 100 parts by mass of the thermoplastic resin.
• the blending amount of the composite particles in the vibration damping material is preferably 1% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, still more preferably 25% by mass or more, ⁇ 1> to ⁇ . 13>
• the blending amount of the composite particles in the vibration damping material is preferably 75% by mass or less, more preferably 60% by mass or less, still more preferably 55% by mass or less, still more preferably 50% by mass or less, ⁇ 1> to ⁇ .
• the content of the polymer graft chain of the composite particles in the damping material is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and further preferably 10 parts by mass or more with respect to 100 parts by mass of the thermoplastic resin.
• the content of the polymer graft chain of the composite particles in the damping material is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, still more preferably 40 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin.
• the damping material according to any one of ⁇ 1> to ⁇ 16> is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and further preferably 10 parts by mass or more with respect to 100 parts by mass of the thermoplastic resin.
• the content of the polymer graft chain of the composite particles in the damping material is preferably 100
• the amount of the thermoplastic resin in the vibration damping material is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, according to any one of ⁇ 1> to ⁇ 17>. Vibration damping material. ⁇ 19> The amount of the thermoplastic resin in the vibration damping material is preferably 95% by mass or less, more preferably 80% by mass or less, still more preferably 75% by mass or less, according to any one of ⁇ 1> to ⁇ 18>. Vibration damping material.
• the thermoplastic resin is preferably one or more kinds consisting of a group selected from a polyolefin resin, a polyamide resin, and an ABS resin, more preferably one kind or two or more kinds consisting of a group selected from a polyolefin resin, still more preferably.
• the vibration damping material according to any one of ⁇ 1> to ⁇ 19>, which is a polypropylene resin.
• the particles are one or more, and more preferably silicon oxides such as silica, and mica and talc, which consist of a group selected from metal oxides, metal oxide salts, metal hydroxides and metal carbonates.
• the anti-vibration material according to any one of ⁇ 1> to ⁇ 20>, which is one kind or two or more kinds consisting of a group selected from silicates such as, and more preferably silica.
• the polymer graft chain is preferably a polymer consisting of one or more monomers selected from the group consisting of styrene-based monomers, nitrile-based monomers, (meth) acrylic-based monomers, unsaturated olefins, and conjugated diene-based monomers.
• vibration damping material it is more preferably one or more homopolymers or copolymers consisting of a group selected from acrylic acid, methacrylic acid, and derivatives thereof, and more preferably one or more selected from methacrylic acid and derivatives thereof.
• the vibration damping material according to any one of ⁇ 1> to ⁇ 21>, which is two or more kinds of homopolymers or copolymers, more preferably polybutylmethacrylate.
• a method for producing a vibration damping material which comprises a step of melt-kneading a thermoplastic resin and composite particles in which a polymer graft chain is bonded to a particle surface.
• the method for producing a vibration damping material according to ⁇ 23> which comprises a step of bonding a polymer graft chain to the particle surface.
• the method for producing a vibration damping material according to ⁇ 24> wherein the method of bonding the polymer graft chain to the particle surface is the Grafting from method of polymerizing the polymer graft chain from the polymerization initiation point of the particle surface.
• the polymerization method is preferably radical polymerization, anionic polymerization, or cationic polymerization, more preferably living radical polymerization, living anionic polymerization, or living cationic polymerization, still more preferably living radical polymerization, and further preferably atom transfer radical polymerization.
• ATRP method reversible addition cleavage chain transfer polymerization method
• NMP method living radical polymerization method via nitroxide
• ATRP method atom transfer radical polymerization method
• Step 1 Bonding the polymerization initiator group to the particle surface
• Step 2 Contacting the monomer having the polymerization initiator group on the surface under living radical polymerization conditions
• the polymerization initiator is a living radical polymerization initiator, preferably an atom transfer radical polymerization initiator group, more preferably a haloacyl group, still more preferably an ⁇ -haloacyl group, still more preferably an ⁇ -bromoacyl group, still more preferably 2-bromo.
• the method for producing a vibration-damping material according to ⁇ 27> which is an isobutyryl group.
• Step 1 includes a step of introducing an amino group or a hydroxy group on the particle surface and a step of introducing a polymerization initiating group, preferably after a step of introducing an amino group or a hydroxy group on the particle surface, and then polymerizing on the particle surface.
• the method for producing a vibration damping material according to ⁇ 27> or ⁇ 28> which comprises a step of introducing a starting group.
• the compound used in the step of introducing an amino group or a hydroxyl group into the particle surface is a compound having a group bonded to the particle surface and an amino group or a hydroxyl group, preferably a silane compound, more preferably an aminoalkylsilane compound.
• the method for producing a vibration damping material according to any one of ⁇ 27> to ⁇ 29> which is more preferably 3-aminopropyltrimethoxysilane.
• the compound used in the step of introducing a polymerization initiating group onto the particle surface is a compound having a polymerization initiating group and a functional group that reacts with an amino group or a hydroxy group, preferably a haloalkanoic acid derivative, more preferably a bromoalkanoic acid derivative.
• the method for producing a vibration damping material according to any one of ⁇ 27> to ⁇ 30> which is more preferably a 2-bromo-2-methylpropionic acid derivative, and even more preferably 2-bromoisobutyl bromide.
• the midpoint glass transition temperature Tmg (° C) is the temperature at the intersection of the straight line equidistant from the extended straight line of each baseline in the vertical direction and the curve of the stepwise change part of the glass transition in the DSC thermogram. Asked as.
• ⁇ Number average molecular weight of polymer graft chains in composite particles The number average molecular weight of the polymer graft chains in the composite particles was measured by measuring the number average molecular weight of the polymer chains not bound to the composite particles simultaneously generated in the process of producing the composite particles as the number average molecular weight of the polymer graft chains. ..
• the gel permeation chromatogram uses GMHHR-H + GMHHR-H (cation) as the column and chloroform as the solvent, and the conversion molecular weight standard is set at a flow velocity of 1.0 mL / min and a column temperature of 40 ° C. Measured using polystyrene.
• the graft density (chain / nm 2 ) was calculated by the following formula by measuring the graft amount (W) and the number average molecular weight (Mn) of the graft chains.
• the amount of graft was determined by thermogravimetric loss measurement (TG). More specifically, the temperature was raised from 40 ° C. to 500 ° C. at 10 ° C./min in the atmosphere, and the weight loss rate at that time was measured.
• the number average molecular weight of the graft chains was determined by the gel permeation chromatography (GPC) method shown below.
• Graft density (chain / nm 2 ) Graft amount (g / nm 2 ) / Number of graft chains Average molecular weight x (Avogadro's number)
• ⁇ Film thickness of polymer graft chain in composite particles The film thickness was calculated from the following formula.
• the polymer density the polymer density of the polymer chains not bonded to the composite particles simultaneously generated in the step of producing the composite particles was defined as the polymer density of the polymer graft chains. Measured by the pycnometer method conforming to JIS K 7112
• Step of bringing particles having a polymerization initiator on the surface into contact with a monomer under living radical polymerization conditions In a 500 mL eggplant-shaped flask, a methanol solution containing 40 g of the prepared silica fine particles having a polymerization initiator, 160 mL of methanol and 40 mL of water. , Butyl methacrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added, and nitrogen bubbling was carried out for 1 hour.
• a polymerization initiator prepared in the same step as step a) of preparing composite particles 1 was placed.
• Anisole solution containing 40 g of silica fine particles, 20 mL of anisole, and 60 g of butyl methacrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were added, the temperature was raised to 60 ° C., the mixture was sufficiently stirred, and then nitrogen bubbling was performed for 1 hour.
• silica fine particles were prepared in the same manner as in the composite particles 3 except that the silica fine particles were changed to Nipsil AQ and the polymerization time was changed to 20 minutes.
• thermoplastic resin composition examples 1 to 3, Comparative Example 1 c) Process of melt-kneading composite particles with thermoplastic resin Using a lab plast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.), each component shown in Table 1 is blended in the amount shown in Table 1 at 200 ° C. It was melt-kneaded to obtain a thermoplastic resin composition.
• thermoplastic resin composition was obtained in the same manner as in Examples 1 to 3 except that the formulations shown in Tables 2 and 3 were changed.
• Example 14 Thermoplastics in the same manner as in Examples 1 to 3 except that the composition was changed as shown in Table 3, the melt-kneading temperature was changed to 240 ° C, the melt temperature of press molding was changed to 240 ° C, and the cooling temperature was changed to 80 ° C. A resin composition was obtained.
• 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.
• thermoplastic resin compositions of Example 3 and Comparative Example 1 were injection-molded to form a flat plate test piece (100 mm ⁇ 100 mm ⁇ 2 mm).
• the cylinder temperature was set to 200 ° C. from the nozzle tip side to the fifth unit, 170 ° C. for the remaining one unit, and 45 ° C. under the hopper.
• the mold temperature was set to 50 ° C.
• the vibration test we used a system consisting of Type 3160 for the oscillator, Type 2718 for the amplifier, Type 4810 for the exciter, Type 8001 for the accelerometer, and 4189-A-029 for the sound level meter (all manufactured by B & K). ).
• the vibration level was calculated from the ratio of the vibration acceleration and the vibration force detected by the acceleration sensor in the range of 20 Hz to 12000 Hz.
• the noise level was calculated from the ratio of the sound pressure and the exciting force detected by the sound level meter at the center height of the flat plate of 100 mm.
• the measurement environment was controlled to 20 ° C. or 80 ° C. in a constant temperature bath (PU-3J manufactured by ESPEC). If the value is small, it can be judged that vibration and noise are further reduced.
• thermoplastic resin compositions of Example 3 and Comparative Example 1 were injection-molded, and a plate fan manufactured by FANTEC (PLF125-18, diameter 150 mm, 8 blades).
• FANTEC FANTEC
• a plate fan molded body having the same shape as the above was molded.
• the cylinder temperature was set to 200 ° C. from the nozzle tip side to the fifth unit, 170 ° C. for the remaining one unit, and 45 ° C. under the hopper.
• the mold temperature was set to 50 ° C.
• the vibration test we used a system consisting of Type 3160 for the oscillator, Type 2718 for the amplifier, Type 4810 for the exciter, Type 8001 for the accelerometer, and 4189-A-029 for the sound level meter (all manufactured by B & K). ). After attaching the central part of the plate fan to the contact tip and fixing it to the acceleration sensor, random vibration was applied, and the vibration level was calculated from the ratio of the vibration acceleration and the vibration force detected by the acceleration sensor in the range of 20 Hz to 12000 Hz. The measurement environment was controlled to 80 ° C. in a constant temperature bath (PU-3J manufactured by ESPEC). If the value is small, it can be judged that the vibration is further reduced.
• PU-3J constant temperature bath
• thermoplastic resin composition of Example 3 containing the composite particles in which the polymer graft chain was bonded to the particle surface was added in the same amount in a state where the filler and the elastomer were not bonded, and the thermoplastic resin of Comparative Example 1 was added.
• the loss coefficient was high at both 20 ° C. and 80 ° C., and the vibration damping property was excellent. It was confirmed in Tables 4 and 5 that vibration and noise can be further reduced even in the injection-molded sample.
• Tables 1 to 3 Examples 1, 2, 4 to 13, 16 and 17 containing composite particles in which a polymer graft chain is bonded to the particle surface, and Example 14 using a polyamide resin, ABS. Also in Example 15 using the resin, the loss coefficient was high and the vibration damping property was excellent.
• thermoplastic resin composition of the present invention can be suitably used for products such as audio equipment, electric products, buildings, industrial equipment, automobile parts, motorcycle parts, containers and the like.

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