Vibration-damping material, thermoplastic resin composition and molded article

Abstract

A vibration-damping material comprising a polymer (B) having a polymer (b1) having a glass transition temperature of -10°C to 30°C and a polymer (b2) different from the polymer (b1), wherein the polymer (B) has a degree of swelling of a THF-insoluble matter of 900% or more, as measured by the following method. <Method of measuring swelling degree> The polymer (B) is immersed in tetrahydrofuran (THF) for 24 hours, and then the insoluble matter separated by centrifugation is vacuum dried and the weight (weight b) is measured. The obtained THF-insoluble matter is again immersed in THF for 24 hours, after which the weight of the sample swollen with THF (weight c) is measured, and the degree of swelling of the THF-insoluble matter is calculated by the following formula. Swelling degree (%) = c / b x 100

Description

[Technical field]

[0001] The present invention relates to a vibration-damping material that can be blended with a thermoplastic resin composition to provide a molded article having excellent mechanical properties such as fluidity, impact resistance, heat resistance, and rigidity, and molded appearance, as well as high vibration-damping properties, i.e., high vibration damping properties (high logarithmic damping rate) and high resonance suppression effect (low vibration transmissibility). The present invention also relates to a thermoplastic resin composition containing this vibration-damping material, and a molded article obtained by molding this thermoplastic resin composition. [Background technology]

[0002] Thermoplastic resins such as styrene resins, typified by ABS resin, and alloy materials made of styrene resins and other thermoplastic resins, have excellent mechanical properties, physical properties, electrical properties, etc. For this reason, these thermoplastic resins are widely used in the electrical and electronic fields, office automation and home appliances fields, automotive fields, sanitary fields, etc. In recent years, the trend toward lighter and smaller products has led to thinner-walled molded products. As a countermeasure, when obtaining molded products by injection molding, etc., it has become necessary to increase the molding temperature and injection speed. These molding conditions are severe for thermoplastic resins. In addition, when molding with a large molding machine, the resin is likely to remain in the cylinder of the molding machine. As a result, molding defects such as jetting due to deterioration or thermal decomposition of the resin occur, as well as thermal discoloration. Furthermore, there are problems such as poor performance and surface appearance of the molded product obtained.

[0003] It has been confirmed that the effect of improving the thermal stability to a certain extent can be achieved by adding various thermal stability improvers to the thermoplastic resin composition, but in this case, there is a drawback in that the cost increases.

[0004] On the other hand, in recent years, people have come to prefer a healthier and more comfortable living environment, and technologies such as vibration control, vibration prevention, and noise reduction have come to play an even more important role than before. In particular, there is a demand for reducing noise and vibration in the fields of vehicles, home appliances, office automation, and many other fields. For example, there is a demand for materials that reduce the vibration of radiator fans in automobiles, motors in the home appliance field, and optical disks in the office automation field.

[0005] Conventionally, vibration-proof and vibration-damping materials have been made by sandwiching a resin-based or rubber-based material between two metal plates. However, with the recent trend toward lighter and smaller devices, it has become difficult to design products with such structures. For this reason, there is a demand for the materials that form the structures to have high vibration-damping properties.

[0006] However, in general, materials with high rigidity that can be used for structures have low vibration damping properties, and conversely, materials with high vibration damping properties have low rigidity, which is a trade-off between the two. For this reason, it has been difficult to use resin compositions with vibration damping properties as they are as materials for constructing structures.

[0007] As a means to overcome this, Patent Document 1 proposes a combination of a thermoplastic resin and a copolymer having a glass transition temperature of 0°C or higher, which is made of an acrylic acid ester monomer and / or a methacrylic acid ester monomer and another comonomer. Patent Document 2 proposes blending a rubber-like polymer having a specific core-shell structure with a styrene-based resin. However, neither Patent Document 1 nor 2 provides a molded product that has excellent moldability and surface appearance while maintaining vibration damping properties.

[0008] Patent Document 3 proposes a thermoplastic resin composition consisting of a (meth)acrylic acid ester copolymer (a) and another copolymer (b), which has a loss tangent (Tan δ) peak different from the Tg peak of each polymer constituting the composition in a specific temperature range. This thermoplastic resin composition shows improvements in moldability and surface appearance. However, Patent Document 3 does not provide sufficient vibration damping properties.

[0009] Patent Documents 4 to 6 propose to obtain a resin composition with excellent vibration-damping properties by blending an elastomeric block polymer having a specific Tan δ with a rubber-reinforced resin. However, the resin compositions of Patent Documents 4 to 6 do not have sufficient vibration-damping properties, and the surface of the molded article becomes layered and may float or peel off in some cases, resulting in poor molded appearance due to problems such as surface peeling. For this reason, these are not practical for use as molded articles.

[0010] In Patent Documents 1 to 6 and other patent documents, there are many proposals that consider vibration damping as a vibration-damping performance. However, in the past, there has been no proposal about abnormal noises such as "rattling" and "rattling sounds" that are unpleasant elements of vibration, that is, resonance. In other words, a practical vibration-damping material cannot be obtained by only considering vibration damping in the past. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] Japanese Patent Application Publication No. 6-41443 [Patent Document 2] Japanese Patent Application Publication No. 11-349785 [Patent Document 3] JP 2000-212373 A [Patent Document 4] JP 2001-158841 A [Patent Document 5] Japanese Patent Application Publication No. 3-45646 [Patent Document 6] Japanese Patent Application Publication No. 8-3249 Summary of the Invention [Problem to be solved by the invention]

[0012] The present invention aims to provide a vibration-damping material that can be blended with a thermoplastic resin composition to provide a molded article having excellent mechanical properties such as fluidity, impact resistance, heat resistance, and rigidity, and excellent molded appearance, as well as high-level vibration-damping properties, i.e., high vibration damping properties (high logarithmic damping rate) and high resonance suppression effect (low vibration transmissibility); a thermoplastic resin composition containing this vibration-damping material; and a molded article obtained by molding this thermoplastic resin composition. [Means for solving the problem]

[0013] The present inventors have found that a vibration-damping material comprising a polymer (B) having a specific polymer (b1) and a polymer (b2) can solve the above problems, and have completed the present invention.

[0014] That is, the present invention relates to the following.

[0015] [1] A vibration-damping material comprising a polymer (B) having a polymer (b1) having a glass transition temperature of -10°C to 30°C and a polymer (b2) different from the polymer (b1), The polymer (B) is a vibration-damping material having a degree of swelling of the THF-insoluble matter of 900% or more, as measured by the following method. <Method of measuring swelling degree> The polymer (B) is immersed in tetrahydrofuran (THF) for 24 hours, and then the insoluble matter separated by centrifugation is vacuum dried and the weight (weight b) is measured. The obtained THF-insoluble matter is again immersed in THF for 24 hours, after which the weight of the sample swollen with THF (weight c) is measured, and the degree of swelling of the THF-insoluble matter is calculated by the following formula. Swelling degree (%) = c / b x 100

[0016] [2] The vibration damping property-imparting material according to [1], wherein, for the polymer (b1), the temperature (peak temperature) indicating the peak value of the main dispersion of Tanδ measured by the following method is 3°C to 45°C, and the peak intensity, which is the peak value, is 1.900 or more. <Measurement method of Tanδ> Using the polymer (b1), a sheet with a thickness of 1.0 to 1.1 mm is formed by a heat press at a set temperature of 150°C, and a measurement sample is prepared by cutting out a piece with a length of 36 mm × width of 10 mm from the sheet. Using the following dynamic viscoelasticity measuring device, fix both 8 mm portions at both ends of the long side of the measurement sample with a tensile jig, measure Tanδ under the following conditions, and determine the peak temperature and peak intensity. Measuring device: Dynamic viscoelasticity measuring device ("DMA850" manufactured by TA Instruments) Mode: Tensile Frequency: 1 Hz Heating rate: 5°C / min Measurement temperature: -60 to +60°C

[0017] [3] The vibration damping property-imparting material according to [2], wherein, for the polymer (b1), the temperature (peak temperature) indicating the peak value of the main dispersion of Tanδ measured by the Tanδ measurement method is 3°C to 45°C, and the peak intensity, which is the peak value, is 1.950 or more.

[0018] [4] The vibration damping property-imparting material according to any one of [1] to [3], wherein the polymer (B) has a swelling degree of the THF-insoluble content measured by the swelling degree measurement method of 1000% or more.

[0019] [5] The vibration damping property-imparting material according to any one of [1] to [4], wherein the polymer (b1) contains a structural unit derived from an acrylate compound and a structural unit derived from a methacrylate compound.

[0020] [6] The vibration-damping material according to any one of [1] to [5], wherein the polymer (b2) contains one or more structural units selected from the group consisting of structural units derived from a methacrylic acid ester compound, structural units derived from an aromatic vinyl compound, and structural units derived from a vinyl cyanide compound.

[0021] [7] The vibration-damping material according to any one of [1] to [6], wherein the polymer (b2) is bonded to at least a portion of the polymer (b1).

[0022] [8] A thermoplastic resin composition comprising a resin component (A) containing a thermoplastic resin and a vibration-damping material, The thermoplastic resin composition has at least one glass transition temperature in the range of −10° C. to 30° C., The thermoplastic resin composition has a vibration transmissibility (first mode) of 19 times or less, as measured by the following method. <Vibration transmissibility (1st mode)> A test piece measuring 13 mm x 125 mm x 3 mm is molded using the thermoplastic resin composition, and a hole with a diameter of 5 mm is drilled at the center on one side of the test piece, 7 mm from the end, and the test piece is fixed to a vibrator with an M5 bolt. The acceleration a0 [m / sec ] of the excitation point (fixed side of the test piece) when the vibrator is excited with a sweep signal of 10 Hz to 4000 Hz 2 ] and the acceleration a1 [m / sec 2 ] is measured, and the vibration transmissibility is calculated as the value at the resonance point (first mode) using the following formula. Vibration transmissibility [times] = a1 / a0

[0023] [9] The thermoplastic resin composition according to [8], wherein the degree of swelling of the THF-insoluble matter in the thermoplastic resin composition is 900% or more, as measured by the following method. <Method of measuring swelling degree> The thermoplastic resin composition is immersed in tetrahydrofuran (THF) for 24 hours, and then the insoluble matter separated by centrifugation is vacuum dried and the weight (weight b) is measured. The obtained THF-insoluble content was immersed in THF again for 24 hours, and then the weight of the sample swollen with THF (weight c) was measured. The swelling degree of the THF-insoluble content was determined by the following formula. Swelling degree (%) = c / b × 100

[0024]

[10] The vibration damping property-imparting material is a thermoplastic resin composition according to [8] or [9], which contains a polymer (b1) in which the temperature (peak temperature) showing the peak value of the main dispersion of Tanδ measured by the following method is 3°C to 45°C, and the peak strength which is the peak value is 1.900 or more. <Measurement method of Tanδ> Using the polymer (b1), a sheet with a thickness of 1.0 to 1.1 mm was formed by a heat press at a set temperature of 150°C, and a measurement sample was prepared by cutting out a length of 36 mm × width of 10 mm from the sheet. Using the following dynamic viscoelasticity measuring device, both ends of each 8 mm portion of the long side of the measurement sample were fixed with a tensile jig, Tanδ was measured under the following conditions, and the peak temperature and peak strength were determined. Measuring device: Dynamic viscoelasticity measuring device ("DMA850" manufactured by TA Instruments) Mode: Tensile Frequency: 1 Hz Temperature rising rate: 5°C / min Measuring temperature: -60 to +60°C

[0025]

[11] The vibration damping property-imparting material is a polymer (B) having a structural unit derived from an acrylate compound and a structural unit derived from a methacrylate compound, and a polymer (b1) having a glass transition temperature of -10°C to 30°C, and a polymer (b2) containing one or more selected from the group consisting of a structural unit derived from a methacrylate compound, a structural unit derived from an aromatic vinyl compound, and a structural unit derived from a vinyl cyanide compound, The vibration damping property-imparting material, wherein the polymer (b1) has a peak temperature of the main dispersion of Tanδ measured by the following method in the range of 3°C to 45°C, and the peak intensity at the peak value is 1.950 or more, is the thermoplastic resin composition according to any one of [8] to

[10] . <Measurement method of Tanδ> Using the polymer (b1), a sheet with a thickness of 1.0 to 1.1 mm is formed by a heat press at a set temperature of 150°C, and a measurement sample is prepared by cutting out a piece with a length of 36 mm and a width of 10 mm from the sheet. Using the following dynamic viscoelasticity measuring device, fix both 8 mm portions at both ends of the long side of the measurement sample with a tensile jig, measure Tanδ under the following conditions, and determine the peak temperature and peak intensity. Measuring device: Dynamic viscoelasticity measuring device ("DMA850" manufactured by TA Instruments) Mode: Tensile Frequency: 1 Hz Heating rate: 5°C / min Measurement temperature: -60 to +60°C

[0026]

[12] The thermoplastic resin composition according to

[11] , wherein the polymer (B) has a swelling degree of the THF-insoluble content measured by the following method of 1000% or more. <Measurement method of swelling degree> After immersing the polymer (B) in tetrahydrofuran (THF) for 24 hours, the insoluble content separated through a centrifugation operation is vacuum-dried to measure the weight (weight b). After immersing the obtained THF-insoluble content in THF again for 24 hours, measure the weight of the sample swollen with THF (weight c), and determine the swelling degree of the THF-insoluble content by the following formula. Swelling degree (%) = c / b × 100

[0027]

[13] The vibration damping property-imparting material according to

[11] or

[12] , wherein at least a part of the polymer (b1) is bonded to the polymer (b2).

[0028]

[14] The thermoplastic resin composition according to any one of [8] to

[13] , wherein the thermoplastic resin contains an acrylic resin.

[0029]

[15] The thermoplastic resin composition according to any one of [8] to

[14] , wherein the thermoplastic resin comprises one or more resins selected from the group consisting of styrene-based resins, polybutylene terephthalate-based resins, polyamide-based resins, and polycarbonate-based resins.

[0030]

[16] The thermoplastic resin composition according to any one of [8] to

[15] , comprising 90 to 10 parts by weight of the resin component (A) and 10 to 90 parts by mass of the vibration-damping material, the total amount of which is 100 parts by mass.

[0031]

[17] A molded article obtained by molding the thermoplastic resin composition according to any one of [8] to

[16] . Effect of the Invention

[0032] The vibration-damping material of the present invention can provide a thermoplastic resin composition that is excellent in mechanical properties such as fluidity, impact resistance, heat resistance, and rigidity, as well as in molded appearance, and can realize molded articles having high levels of vibration-damping properties, i.e., high vibration damping properties (high logarithmic damping rate) and high resonance suppression effect (low vibration transmissibility). According to the present invention, by using this thermoplastic resin composition, it is possible to provide a molded article which is excellent in mechanical properties such as impact resistance, heat resistance, and rigidity, and in molded appearance, as well as has a high level of vibration damping properties, i.e., high vibration damping properties (high logarithmic damping rate) and a high resonance suppression effect (low vibration transmissibility).

[0033] That is, the vibration-damping material made of the specific polymer (B) according to the present invention not only functions to provide vibration-damping properties, but also effectively maintains the mechanical properties of the molded article obtained and provides a good molded appearance. By blending such a vibration-damping material of the present invention with the resin component (A) containing a thermoplastic resin, it is possible to obtain a thermoplastic resin composition that can provide a molded article having excellent mechanical properties such as fluidity, impact resistance, heat resistance, and rigidity, molded appearance, etc., as well as high vibration-damping properties, i.e., high vibration damping properties (high logarithmic damping rate) and high resonance suppression effect (low vibration transmissibility). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0034] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below with reference to the preferred embodiments.

[0035] In the present invention, "(co)polymerization" means homopolymerization and / or copolymerization. "(Meth)acrylic" means acrylic and / or methacrylic. "(Meth)acrylate" means acrylate and / or methacrylate. The term "structural unit" refers to a structural portion contained in a polymer and derived from a compound (monomer) before polymerization. The content ratio of the structural unit derived from each compound in a polymer corresponds to the content ratio of the compound in the raw material monomer mixture used to produce the polymer.

[0036] [Vibration-damping material] The vibration-damping material of the present invention is a vibration-damping material comprising a polymer (B) (hereinafter, sometimes referred to as "polymer (B) of the present invention") having a polymer (b1) (hereinafter, sometimes referred to as "polymer (b1) of the present invention") having a glass transition temperature of -10°C to 30°C, and a polymer (b2) (hereinafter, sometimes referred to as "polymer (b2) of the present invention") different from the polymer (b1), wherein the polymer (B) is characterized in that the swelling degree of the THF-insoluble matter measured by the following method is 900% or more. <Method of measuring swelling degree> The polymer (B) is immersed in tetrahydrofuran (THF) for 24 hours, and then the insoluble matter separated by centrifugation is vacuum dried and the weight (weight b) is measured. The obtained THF-insoluble matter is again immersed in THF for 24 hours, after which the weight of the sample swollen with THF (weight c) is measured, and the degree of swelling of the THF-insoluble matter is calculated by the following formula. Swelling degree (%) = c / b x 100

[0037] The polymer (B) of the present invention particularly preferably has a swelling degree of the THF-insoluble matter measured by the above-mentioned method for measuring swelling degree of 1000% or more.

[0038] The polymer (b1) of the present invention preferably has a peak temperature of the main dispersion of Tanδ measured by the following method in the range of 3°C to 45°C, and a peak intensity at the peak value of 1.900 or more, particularly preferably 1.950 or more. <Measurement method of Tanδ> Using the polymer (b1), a sheet with a thickness of 1.0 to 1.1 mm is formed by hot pressing at a set temperature of 150°C, and a measurement sample is prepared by cutting out a piece with a length of 36 mm × width of 10 mm from the sheet. Using the following dynamic viscoelasticity measuring device, fix both ends of each 8 mm portion of the long side of the measurement sample with a tensile jig, measure Tanδ under the following conditions, and determine the peak temperature and peak intensity. Measuring device: Dynamic viscoelasticity measuring device ("DMA850" manufactured by TA Instruments) Mode: Tensile Frequency: 1 Hz Temperature rising rate: 5°C / min Measurement temperature: -60 to +60°C

[0039] The polymer (b1) of the present invention preferably contains a structural unit derived from an acrylate compound and a structural unit derived from a methacrylate compound.

[0040] The polymer (b2) of the present invention preferably contains one or more selected from the group consisting of a structural unit derived from a methacrylate compound, a structural unit derived from an aromatic vinyl compound, and a structural unit derived from a vinyl cyanide compound.

[0041] That is, the polymer (B) of the present invention includes a structural unit derived from an acrylate compound (hereinafter, may be simply referred to as "acrylate unit") and a structural unit derived from a methacrylate compound (hereinafter, may be simply referred to as "methacrylate unit"), and a polymer (b1) having a glass transition temperature of -10°C to 30°C, It is preferable that the polymer (B) (hereinafter, may be referred to as "polymer (B) of one embodiment of the present invention") has a polymer (b2) containing one or more selected from the group consisting of a structural unit derived from a methacrylic acid ester compound (methacrylic acid ester unit), a structural unit derived from an aromatic vinyl compound (hereinafter, may be referred to simply as "aromatic vinyl unit"), and a structural unit derived from a vinyl cyanide compound (hereinafter, may be referred to simply as "vinyl cyanide unit").

[0042] In the polymer (B) of the present invention, it is preferable that the polymer (b2) of the present invention is bonded to at least a portion of the polymer (b1).

[0043] [mechanism] When the polymer (b1) contained in the polymer (B) of the present invention has a glass transition temperature of −10° C. to 30° C., vibration can be reduced in the room temperature region. Furthermore, when the temperature (peak temperature) showing the peak value of the main dispersion of Tan δ measured for this polymer (b1) is 3°C to 45°C and the peak value, that is, the peak intensity, is 1.900 or more, particularly 1.950 or more, a more excellent vibration reduction effect and a low vibration transmissibility can be obtained.

[0044] In particular, when the polymer (b1) contained in the polymer (B) of one embodiment of the present invention contains an acrylic acid ester unit and a methacrylic acid ester unit, the vibration can be effectively reduced. This is believed to be because the structural unit of a polar monomer such as methyl methacrylate converts the vibration into heat. Furthermore, when the polymer (b1) containing acrylic acid ester units and methacrylic acid ester units has a glass transition temperature of −10° C. to 30° C., vibration can be reduced in the room temperature region. Furthermore, when the temperature (peak temperature) showing the peak value of the main dispersion of Tan δ measured for this polymer (b1) is 3°C to 45°C and the peak value, that is, the peak intensity, is 1.900 or more, particularly 1.950 or more, a more excellent vibration reduction effect and a low vibration transmissibility can be obtained.

[0045] Furthermore, by containing the polymer (b2) containing the specific structural unit, mechanical properties such as impact resistance can be exhibited.

[0046] Furthermore, when the swelling degree of the THF-insoluble matter of the polymer (B) of the present invention measured by the above-mentioned swelling degree measuring method is 900% or more, particularly 1000% or more, a significantly excellent vibration reducing effect can be obtained. That is, the swelling degree of the polymer (B) of the present invention, which is composed of the polymer (b1) and the polymer (b2), is 900% or more, indicates that the molecular weight between crosslinking points of the polymer (b1) contained in the polymer (B) of the present invention is large and the polymer (b1) is likely to swell. The fact that the polymer (b1) is likely to swell means that the inhibition of molecular chain motion due to crosslinking is small, and a remarkably excellent vibration reducing effect is exhibited.

[0047] [Polymer (B)] The polymer (B) of the present invention is a vibration-damping property-imparting material comprising a polymer (B) having a polymer (b1) having a glass transition temperature of -10°C to 30°C and a polymer (b2) different from the polymer (b1). As long as the swelling degree of the polymer (B) measured by the above-mentioned method is 900% or more, there are no limitations on the structural units of both the polymer (b1) and the polymer (b2), and there are no particular limitations on the existence form of the polymer (b1) and the polymer (b2).

[0048] [Relationship between polymer (b1) and polymer (b2)] The form of existence of the polymer (b1) and the polymer (b2) in the polymer (B) of the present invention is not particularly limited, but it is effective in improving impact resistance and is preferable that the polymer (b1) corresponding to the rubber portion is at least partially bonded to the polymer (b2) corresponding to the resin portion by graft polymerization or the like to form a graft copolymer. In other words, in the polymer (B) of the present invention, it is preferred that at least a part of the polymer (b2) is bonded to at least a part of the polymer (b1) by graft copolymerization or the like. Therefore, the polymer (B) of the present invention is preferably composed of at least a graft copolymer in which at least a part of the polymer (b2) is grafted to at least a part of the polymer (b1), and a (co)polymer constituting the polymer (b2) that is not grafted to the polymer (b1). The polymer (B) of the present invention may further contain the polymer (b1) to which the polymer (b2) is not grafted, and further other components such as additives.

[0049] [Polymer (b1)] <Structural unit> The structural units of the polymer (b1) of the present invention are not particularly limited as long as the polymer (b1) has a glass transition temperature of -10°C to 30°C. However, in view of high vibration damping properties, ease of adjusting the glass transition point, and the like, the polymer (b1) of the present invention is preferably a polymer (b1) having an acrylic acid ester unit and a methacrylic acid ester unit (hereinafter, sometimes referred to as "polymer (b1) of one embodiment of the present invention").

[0050] When the polymer (b1) contains acrylic acid ester units and methacrylic acid ester units, the content ratio of the acrylic acid ester units and the methacrylic acid ester units in the polymer (b1) is adjusted from the viewpoints of adjusting the glass transition temperature and the vibration reducing effect.

[0051] From such a viewpoint, the content of the acrylic ester units in the polymer (b1) of one embodiment of the present invention is preferably 41 to 70 parts by mass and the content of the methacrylic ester units is preferably 59 to 30 parts by mass, and more preferably 46 to 60 parts by mass and 54 to 40 parts by mass of the methacrylic ester units, in a total of 100 parts by mass of the acrylic ester units and the methacrylic ester units.

[0052] The polymer (b1) according to one embodiment of the present invention may contain structural units other than acrylate units and methacrylate units, provided that the object of the present invention is not impaired. Examples of such structural units include structural units derived from a crosslinking agent, which will be described later.

[0053] In one embodiment of the present invention, the polymer (b1) contains a structural unit derived from a crosslinking agent, which improves the appearance such as gloss. However, if the content of the structural unit derived from the crosslinking agent is too high, the degree of swelling of the obtained polymer (B) becomes small, and the effect as a vibration-damping agent is impaired. Therefore, when the polymer (b1) of one embodiment of the present invention contains a structural unit derived from a crosslinking agent, the content thereof is preferably 0.4 parts by mass or less, particularly 0.10 to 0.25 parts by mass, per 100 parts by mass of the polymer (b1).

[0054] The polymer (b1) according to one embodiment of the present invention may contain structural units derived from a vinyl compound other than acrylate units and methacrylate units. Examples of such vinyl compounds include the aromatic vinyl compounds and vinyl cyanide compounds exemplified in the description of the rubber-reinforced styrene-based thermoplastic resin described below. However, from the viewpoint of more effectively obtaining the above-mentioned effects due to the polymer (b1) containing acrylic acid ester units and methacrylic acid ester units, when the polymer (b1) of one embodiment of the present invention contains a structural unit derived from another vinyl compound, the content ratio thereof is preferably 20 parts by mass or less, particularly 0 to 10 parts by mass, per 100 parts by mass of the polymer (b1).

[0055] The acrylic ester compound constituting the acrylic ester unit is preferably an acrylic ester compound in which the alkyl group has a carbon number of 1 to 8. Among them, ethyl acrylate, n-butyl acrylate, and n-ethylhexyl acrylate are preferred, and n-butyl acrylate is more preferred, because they provide excellent impact resistance to the thermoplastic resin composition containing the resulting polymer (B). These alkyl acrylate compounds may be used alone or in combination of two or more. may be used in combination.

[0056] The methacrylic acid ester compound constituting the methacrylic acid ester unit is preferably a methacrylic acid ester compound having an alkyl group with a carbon number of 1 to 8. Among them, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate are preferred, and methyl methacrylate is more preferred, because they provide an excellent vibration reducing effect to the thermoplastic resin composition containing the obtained polymer (B). These methacrylic acid ester compounds may be used alone or in combination of two or more.

[0057] Examples of the crosslinking agent include allyl (meth)acrylate, butylene di(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, polyester di(meth)acrylate, polyurethane di(meth)acrylate, polybutadiene di(meth)acrylate, divinylbenzene, trivinylbenzene, triallyl cyanurate, triallyl isocyanurate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, diallyl dimethyl ammonium chloride, and polyglycerin poly(meth)acrylate. These may be used alone or in combination of two or more.

[0058] <Method for producing polymer (b1)> The polymer (b1) according to one embodiment of the present invention can be produced according to a conventional method using a monomer mixture containing an acrylic acid ester compound, a methacrylic acid ester compound, and, if necessary, a crosslinking agent and other vinyl compounds in the above-mentioned preferred ratio of each structural unit.

[0059] The method for producing the polymer (b1) according to one embodiment of the present invention is not particularly limited, but may include a method of emulsion polymerization of a monomer mixture containing an acrylic acid ester compound, a methacrylic acid ester compound, and, if necessary, a crosslinking agent and other vinyl compounds.

[0060] An example of a method for producing polymer (b1) according to one embodiment of the present invention by emulsion polymerization is a method in which an acrylic acid ester compound, a methacrylic acid ester compound, and optionally a crosslinking agent and other vinyl compounds (hereinafter, these may be referred to as a "raw material monomer mixture") and a radical initiator are added to an aqueous solvent, and copolymerized in the presence of an emulsifier. The radical initiator, the raw material monomer mixture, and the crosslinking agent may be added all at once, in portions, or continuously.

[0061] The emulsifier may be a carboxylic acid-based emulsifier exemplified by alkali metal salts of oleic acid, palmitic acid, stearic acid, rosin acid, and alkali metal salts of alkenyl succinic acid; an anionic emulsifier selected from alkyl sulfates, sodium alkylbenzene sulfonates, sodium alkyl sulfosuccinates, sodium polyoxyethylene nonylphenyl ether sulfate; or the like. Known emulsifiers may be used alone or in combination of two or more kinds.

[0062] The amount of the emulsifier added is preferably 0.01 to 3.0 parts by mass, and more preferably 0.05 to 2.0 parts by mass, per 100 parts by mass of the total raw material monomer mixture, from the viewpoint of controlling the particle size of the polymer (b1).

[0063] The initiator used in the production of the polymer (b1) of one embodiment of the present invention is a radical polymerization initiator for radical polymerization, and there is no particular limitation on the type. Examples of radical polymerization initiators include azo polymerization initiators, photopolymerization initiators, inorganic peroxides, organic peroxides, and redox initiators that combine organic peroxides with transition metals and reducing agents. Among these, azo polymerization initiators, inorganic peroxides, organic peroxides, and redox initiators that can initiate polymerization by heating are preferred. These may be used alone or in combination of two or more.

[0064] Examples of the azo polymerization initiator include 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl)azo]formamide, 4,4'-azobis(4-cyanovaleric acid), dimethyl 2,2'-azobis( 2-methylpropionate), dimethyl 1,1'-azobis(1-cyclohexanecarboxylate), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis(N-cyclohexyl-2-methylpropionamide), 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis(2,4,4-trimethylpentane), and the like.

[0065] Examples of inorganic peroxides include potassium persulfate, sodium persulfate, ammonium persulfate, and hydrogen peroxide.

[0066] Examples of organic peroxides include peroxyester compounds. Specific examples of organic peroxides include α,α'-bis(neodecanoylperoxy)diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate. ester, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy 2-hexylhexanoate, t-butylperoxy 2-hexylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxyisopropylmonocarbonate, t-butylperoxymaleic acid, t-butylperoxy 3,5,5-trimethylhexanoate, t-butylperoxyla urate, 2,5-dimethyl-2,5-bis(m-toluoylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butylperoxyacetate, t-butylperoxy-m-toluoylbenzoate, t-butylperoxybenzoate, bis(t-butylperoxy)isophthalate, 1,1-bis(t-hexyl 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, 2,2-bis(t-butylperoxy)butane, n-butyl 4,4-bis(t-butylperoxy)valerate, 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane, α,Examples of the peroxy group include α'-bis(t-butylperoxide)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, dilauroyl peroxide, diisononanoyl peroxide, t-butyl hydroperoxide, benzoyl peroxide, lauroyl peroxide, dimethylbis(t-butylperoxy)-3-hexyne, bis(t-butylperoxyisopropyl)benzene, bis(t-butylperoxy)trimethylcyclohexane, butyl-bis(t-butylperoxy)valerate, 2-ethylhexaneperoxy acid t-butyl, dibenzoyl peroxide, paramenthane hydroperoxide, and t-butyl peroxybenzoate.

[0067] The redox initiator is preferably a combination of an organic peroxide, ferrous sulfate, a chelating agent, and a reducing agent, such as a combination of cumene hydroperoxide, ferrous sulfate, sodium pyrophosphate, and dextrose, or a combination of t-butyl hydroperoxide, sodium formaldehyde sulfoxylate (Rongalit), ferrous sulfate, and disodium ethylenediaminetetraacetate.

[0068] The amount of the initiator added is usually 5 parts by mass or less, preferably 3 parts by mass or less, for example, 0.001 to 3 parts by mass, based on 100 parts by mass of the total raw material monomer mixture.

[0069] The emulsion polymerization is usually carried out at 40 to 100° C. for about 30 to 600 minutes.

[0070] <Glass transition temperature of polymer (b1)> The glass transition temperature of the polymer (b1) of the present invention is characterized by being in the range of -10°C to +30°C. Even if the glass transition temperature is less than -10°C or exceeds 30°C, an excellent vibration reduction effect cannot be obtained. From the viewpoint of excellent vibration reduction effect, the glass transition temperature of the polymer (b1) is preferably -5°C to +25°C, particularly preferably 0°C to +20°C, more preferably +5°C to +20°C, and most preferably in the range exceeding +5°C and not exceeding +20°C.

[0071] In order to produce the polymer (b1) having a glass transition temperature within the above range, for example, in the polymer (b1) of an embodiment of the present invention, the ratio of the acrylate ester and the methacrylate ester may be adjusted.

[0072] The glass transition temperature of the polymer (b1) is measured by the method described in the Examples section below.

[0073] <Tanδ of polymer (b1)> Regarding the polymer (b1) of the present invention, the temperature (peak temperature) showing the peak value of the main dispersion of Tanδ measured by the following method is 3°C to 45°C, and the peak intensity, which is the peak value, is preferably 1.900 or more. <Measurement method of Tanδ> Using the polymer (b1), a sheet having a thickness of 1.0 to 1.1 mm is formed by a heat press at a set temperature of 150°C, and a measurement sample is prepared by cutting out a length of 36 mm × width of 10 mm from the sheet. Using the following dynamic viscoelasticity measuring device, both ends of each 8 mm portion of the long side of the measurement sample are fixed with a tensile jig, Tanδ is measured under the following conditions, and the peak temperature and peak intensity are determined. Measuring device: Dynamic viscoelasticity measuring device ("DMA850" manufactured by TA Instruments) Mode: Tensile Frequency: 1 Hz Temperature rising rate: 5°C / min Measurement temperature: -60 to +60°C

[0074] If the peak temperature of the polymer (b1) is 3° C. to 45° C., the vibration reducing effect is excellent. From this viewpoint, the peak temperature of the polymer (b1) is more preferably 12° C. to 39° C., and particularly preferably 17° C. to 35° C.

[0075] Furthermore, if the peak intensity of the polymer (b1) is 1.900 or more, the vibration is more effectively reduced. From this viewpoint, the peak intensity of the polymer (b1) is more preferably 1.950 or more, further preferably 2.000 or more, and particularly preferably 2.025 or more. The upper limit of the peak intensity is not particularly limited, but is usually 3 or less.

[0076] To produce a polymer (b1) that satisfies such a peak temperature and peak intensity of Tan δ, it is sufficient to select an optimal monomer constituting the polymer (b1) and adjust the amount of the crosslinking agent.

[0077] <Volume average particle size of polymer (b1)> The shape of the polymer (b1) of the present invention is not particularly limited, but a particulate shape is preferred from the viewpoint of uniformly dispersing the vibration-damping effect. The volume average particle size of the particulate polymer (b1) of the present invention is not particularly limited, but from the viewpoint of the above-mentioned dispersibility, it is preferably in the range of 30 to 500 nm, more preferably in the range of 50 to 400 nm, and even more preferably in the range of 80 to 300 nm.

[0078] Here, the volume average particle size of the polymer (b1) of the present invention can be measured by an optical method before mixing or reacting with the polymer (b2).In addition, after mixing or reacting, or in the case of a thermoplastic resin composition containing the polymer (B) of the present invention further containing the polymer (b1), the polymer (b1) can be dyed with a dyeing agent and then photographed using a transmission electron microscope (TEM), and the obtained image can be subjected to image analysis and measurement. The volume average particle size of the polymer (b1) is specifically measured by the method described in the Examples section below.

[0079] To produce a polymer (b1) having a volume average particle size within the above range, the type and amount of emulsifier used may be adjusted during the production of the polymer (b1).

[0080] [Polymer (b2)] <Structural unit> The structural units constituting the polymer (b2) of the present invention are not particularly limited, but the polymer (b1) of the present invention is preferably a polymer (b2) (hereinafter sometimes referred to as "polymer (b2) of one embodiment of the present invention") containing one or more structural units selected from the group consisting of structural units derived from methacrylic acid ester compounds (methacrylic acid ester units), structural units derived from aromatic vinyl compounds (aromatic vinyl units), and structural units derived from vinyl cyanide compounds (vinyl cyanide units).

[0081] Examples of combinations of structural units contained in the polymer (b2) according to one embodiment of the present invention include the following 1) to 5), but are not limited thereto. 1) Methacrylate ester unit alone 2) Methacrylate units and aromatic vinyl units 3) Methacrylate units and vinyl cyanide units 4) Aromatic vinyl units and vinyl cyanide units 5) Methacrylate units, aromatic vinyl units, and vinyl cyanide units

[0082] Among these, 4) those having aromatic vinyl units and vinyl cyanide units, and 5) those having methacrylic acid ester units, aromatic vinyl units and vinyl cyanide units are preferred from the viewpoint of achieving both vibration reducing effect and physical properties.

[0083] In the case of the combination of 2) above, it is preferable from the viewpoint of vibration reduction effect that the content of the methacrylic acid ester units is 95 to 60 parts by mass and the content of the aromatic vinyl units is 5 to 40 parts by mass per 100 parts by mass of the total of the methacrylic acid ester units and the aromatic vinyl units. In the case of the combination of 3) above, it is preferable from the viewpoint of vibration reduction effect that the content of the methacrylic acid ester units is 95 to 60 parts by mass and the content of the vinyl cyanide units is 5 to 40 parts by mass per 100 parts by mass of the total of the methacrylic acid ester units and the vinyl cyanide units. In the case of the combination of 4) above, it is preferable from the viewpoint of impact resistance that the content of the aromatic vinyl units and the vinyl cyanide units is 95 to 60 parts by mass and the content of the vinyl cyanide units is 5 to 40 parts by mass, based on 100 parts by mass in total. In the case of the combination of 5) above, it is preferable from the viewpoint of vibration reduction effect and impact resistance that the content of the methacrylic acid ester units, the aromatic vinyl units, and the vinyl cyanide units be 60 to 80 parts by mass, the content of the aromatic vinyl units be 35 to 15 parts by mass, and the content of the vinyl cyanide units be 25 to 5 parts by mass, relative to 100 parts by mass in total.

[0084] The polymer (b2) according to one embodiment of the present invention may contain structural units derived from vinyl compounds other than aromatic vinyl units, vinyl cyanide units, and alkyl methacrylate units, within the scope of the present invention. However, in order to more effectively obtain the effects of containing aromatic vinyl units, vinyl cyanide units, and alkyl methacrylate units, the content of structural units derived from other vinyl compounds in 100 parts by mass of the polymer (b2) is preferably 20 parts by mass or less, particularly 0 to 10 parts by mass.

[0085] Examples of aromatic vinyl compounds constituting the aromatic vinyl unit of the polymer (b2) according to one embodiment of the present invention include styrene, α-methylstyrene, o-, m- or p-methylstyrene, vinylxylene, pt-butylstyrene, ethylstyrene, etc. Among these, styrene is preferred from the viewpoint of increasing the impact resistance of the resulting molded article. These aromatic vinyl compounds may be used alone or in combination of two or more.

[0086] Examples of the vinyl cyanide compound constituting the vinyl cyanide unit of the polymer (b2) according to one embodiment of the present invention include acrylonitrile, methacrylonitrile, etc. Among these, acrylonitrile is preferred from the viewpoint of increasing the impact resistance of the resulting molded article. These vinyl cyanide compounds may be used alone or in combination of two or more.

[0087] As the methacrylic acid ester compound constituting the alkyl methacrylate unit of the polymer (b2) according to one embodiment of the present invention, a methacrylic acid ester compound in which the alkyl group has a carbon number of 1 to 8 is preferred. Among them, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate are preferred, and methyl methacrylate is more preferred, because they provide an excellent vibration reducing effect to the thermoplastic resin composition containing the obtained polymer (B). These methacrylic acid ester compounds may be used alone or in combination of two or more.

[0088] Examples of other vinyl compounds constituting the other vinyl compound units include vinyl compounds other than aromatic vinyl compounds, vinyl cyanide compounds, and methacrylic acid ester compounds used in the production of the rubber-reinforced styrene-based thermoplastic resin (A1) described below.

[0089] <Method for producing polymer (b2)> The polymer (b2) according to one embodiment of the present invention can be produced by carrying out polymerization in the presence of the polymer (b1) using a raw material monomer mixture containing one or more of an aromatic vinyl compound, a vinyl cyanide compound and a methacrylic acid ester compound, and other vinyl compounds used as necessary, in the same manner as in the polymerization method of the vinyl monomer (a1) into the rubbery polymer (g) in the rubber-reinforced styrenic thermoplastic resin described below.

[0090] [Polymer (B)] <Content ratio of polymer (b1) and polymer (b2)> The polymer (B) of the present invention, particularly the polymer (B) of an embodiment of the present invention suitable as the polymer (B) of the present invention, as described above, in the presence of the polymer (b1) of an embodiment of the present invention, one or two or more of an aromatic vinyl compound, a vinyl cyanide compound, and a methacrylic acid ester compound constituting the polymer (b2) of an embodiment of the present invention, and other vinyl compounds used as necessary are polymerized. By this method, a polymer (B) which is a graft copolymer in which at least a part of the polymer (b2) is graft copolymerized with at least a part of the polymer (b1) can be obtained. The polymer (B) of the present invention may contain a polymer (b2) that is not graft polymerized to the polymer (b1) or a polymer (b1) that is not graft polymerized to the polymer (b2).

[0091] The preferred content ratios of the polymer (b1) and the polymer (b2) in the polymer (B) of the present invention are as follows. That is, if the content ratio of the polymer (b1) is too high, although the vibration damping property is improved, other mechanical properties may deteriorate or manufacturing difficulties may occur. Conversely, if the content ratio of the polymer (b1) is too low, when mixed with the resin component (A) described later as a vibration damping property-imparting material, there is a possibility that sufficient effects cannot be exhibited in terms of vibration damping property and the like. From such a viewpoint, the ratio of the polymer (b1) and the polymer (b2) contained in the polymer (B) of the present invention is preferably 70 to 20 parts by mass of the polymer (b2) with respect to 30 to 80 parts by mass of the polymer (b1) (however, the total of the polymer (b1) and the polymer (b2) is 100 parts by mass), and more preferably 40 to 70 parts by mass of the polymer (b1) and 60 to 30 parts by mass of the polymer (b2).

[0092] <Swelling degree of THF-insoluble matter> The swelling degree of the THF-insoluble matter of the polymer (B) of the present invention measured by the following method (hereinafter, may be simply referred to as "swelling degree") is 900% or more. <Method for measuring swelling degree> The polymer (B) is immersed in tetrahydrofuran (THF) for 24 hours, and then the insoluble matter separated by centrifugation is vacuum dried and the weight (weight b) is measured. The obtained THF-insoluble matter is again immersed in THF for 24 hours, after which the weight of the sample swollen with THF (weight c) is measured, and the degree of swelling of the THF-insoluble matter is calculated by the following formula. Swelling degree (%) = c / b x 100

[0093] The swelling degree of the polymer (B) of the present invention, which is composed of the polymer (b1) and the polymer (b2), is 900% or more, as described above, indicates that the molecular weight between crosslinking points of the polymer (b1) contained in the polymer (B) of the present invention is large and the polymer (b1) is likely to swell. The fact that the polymer (b1) is likely to swell means that the inhibition of molecular chain motion due to crosslinking is small, and a remarkably excellent vibration reducing effect is exhibited.

[0094] From the viewpoint of vibration reduction effect, the swelling degree of the polymer (B) of the present invention is preferably 1000% or more, more preferably 1200% or more. On the other hand, there is no particular upper limit to the swelling degree of the polymer (B) of the present invention, but in order to improve the appearance, the swelling degree of the polymer (B) of the present invention is preferably 1200 to 3000%.

[0095] To produce a polymer (B) that satisfies such a swelling degree, a crosslinking agent may be omitted in the production of the polymer (b1), or, even if a crosslinking agent is used, the amount of the crosslinking agent may be set to 0.65 parts by mass or less, particularly 0 to 0.55 parts by mass, per 100 parts by mass of the polymer (b1), thereby reducing the crosslinked structure in the polymer (b1).

[0096] <Gel content> The gel content of the polymer (B) of the present invention is preferably 90% or less, particularly 88% or less. If the gel content is 90% or less, the vibration reducing effect is excellent. On the other hand, from the viewpoint of appearance such as gloss, the gel content is preferably 75% or more.

[0097] To produce polymer (B) having such a gel content, the amount of the crosslinking agent during the production of polymer (b1) may be adjusted.

[0098] The gel content of the polymer (B) is measured by the method described in the Examples section below.

[0099] <Molecular weight of acetonitrile soluble matter> The weight average molecular weight of the acetonitrile soluble portion of the polymer (B) of the present invention (hereinafter sometimes referred to as "the molecular weight of the acetonitrile soluble portion") is preferably 50,000 to 80,000, particularly preferably 55,000 to 70,000. When the molecular weight of the acetonitrile soluble portion of the polymer (B) is within the above range, the polymer has excellent impact resistance.

[0100] To produce polymer (B) having such a molecular weight of the acetonitrile soluble portion, the amount of the chain transfer agent during the production of polymer (b2) may be adjusted.

[0101] The molecular weight of the acetonitrile-soluble portion of the polymer (B) is measured by the method described in the Examples section below.

[0102] <Grafting rate> The graft ratio of the polymer (B) of the present invention is preferably 35 to 120%, particularly preferably 40 to 80%. When the graft ratio is equal to or higher than the lower limit, the impact resistance is excellent. On the other hand, when the graft ratio is equal to or lower than the upper limit, sufficient fluidity can be ensured in injection molding.

[0103] To produce polymer (B) having such a graft ratio, the amounts of polymerization initiator and chain transfer agent used during the production of polymer (b2) may be adjusted.

[0104] The graft ratio of the polymer (B) is measured by the method described in the Examples section below.

[0105] [Thermoplastic resin composition] The thermoplastic resin composition of the present invention is a thermoplastic resin composition comprising a resin component (A) containing a thermoplastic resin and a vibration-damping material, and is characterized in that the thermoplastic resin composition has at least one glass transition temperature within a range of -10°C to 30°C, and has a vibration transmissibility (first mode) of 19 times or less as measured by the following method. <Vibration transmissibility (1st mode)> A test piece measuring 13 mm x 125 mm x 3 mm is molded using the thermoplastic resin composition, and a hole with a diameter of 5 mm is drilled at the center on one side of the test piece at a position 7 mm from the end, and the test piece is fixed to a vibrator with an M5 bolt. The acceleration a0 [m / sec ] of the excitation point (fixed side of the test piece) when the vibrator is excited with a sweep signal of 10 Hz to 4000 Hz 2 ] and the acceleration a1 [m / sec 2 ] is measured, and the vibration transmissibility is calculated as the value at the resonance point (first mode) using the following formula. Vibration transmissibility [times] = a1 / a0

[0106] [Physical properties of thermoplastic resin composition] <Glass transition temperature> The thermoplastic resin composition of the present invention is characterized by having at least one glass transition temperature in the range of −10 to 30° C. Hereinafter, the glass transition temperature that the thermoplastic resin composition of the present invention has in the range of −10 to 30° C. may be referred to as a “specific glass transition temperature.”

[0107] A thermoplastic resin composition having a specific glass transition temperature in the range of -10° C. to 30° C. has an excellent vibration reducing effect. From the viewpoint of the vibration reducing effect, the specific glass transition temperature of the thermoplastic resin composition of the present invention is preferably in the range of -5° C. to +25° C., more preferably in the range of 0° C. to +20° C., even more preferably in the range of +5° C. to +20° C., and still more preferably in the range of more than +5° C. to +20° C.

[0108] As long as the thermoplastic resin composition of the present invention has at least one glass transition temperature in the range of -10°C to +30°C, it may have another glass transition temperature in a temperature range other than the range of -10°C to +30°C.

[0109] The specific glass transition temperature of the thermoplastic resin composition of the present invention corresponds to, for example, the glass transition temperature of the polymer (B) of the present invention as a vibration damping property-imparting material preferably used in the thermoplastic resin composition of the present invention, and more specifically, the glass transition temperature of the polymer (b1) in the polymer (B) of the present invention.

[0110] <Vibration transmission rate (primary mode)> The thermoplastic resin composition of the present invention exhibits an excellent vibration reduction effect with a vibration transmission rate (primary mode) measured by the aforementioned method of 19 times or less. From the viewpoint of the vibration reduction effect, this vibration transmission rate is preferably 18 times or less, more preferably 15 times or less, still more preferably 12 times or less, and particularly preferably 10 times or less.

[0111] More specifically, the vibration transmission rate of the thermoplastic resin composition is measured by the method described in the Examples section below.

[0112] <Logarithmic decrement δ> From the viewpoint of vibration reduction, the thermoplastic resin composition of the present invention preferably has a logarithmic decrement δ of 0.20 or more, more preferably 0.25 or more, when measured by the method described in the Examples section below.

[0113] From the viewpoint of vibration damping properties, it is preferable to use the acrylic resin (A3) described below as the resin component (A) in the thermoplastic resin composition of the present invention. In this case, according to a thermoplastic resin composition obtained by mixing the aforementioned vibration damping property-imparting material of the present invention and the acrylic resin (A3) in a range of vibration damping property-imparting material:acrylic resin (A3) = 20:80 to 85:15 (mass ratio), the logarithmic decrement δ is 0.40 to 0.78, and the vibration transmission rate (primary mode) is 11.5 to 7.1, showing good vibration damping properties.

[0114] <Swelling degree of THF-insoluble matter> The thermoplastic resin composition of the present invention preferably has a swelling degree of THF-insoluble matter measured by the following method of 900% or more. <Measurement method of swelling degree> The thermoplastic resin composition is immersed in tetrahydrofuran (THF) for 24 hours, and then the insoluble matter separated by centrifugation is vacuum dried and the weight (weight b) is measured. The obtained THF-insoluble matter is again immersed in THF for 24 hours, after which the weight of the sample swollen with THF (weight c) is measured, and the degree of swelling of the THF-insoluble matter is calculated by the following formula. Swelling degree (%) = c / b x 100

[0115] The swelling degree of the THF-insoluble matter in the thermoplastic resin composition of the present invention is preferably 900% or more, more preferably 1000% or more, and even more preferably 1200% or more, in order to achieve a vibration reducing effect. There is no particular upper limit to the swelling degree of the thermoplastic resin composition, but in order to improve the appearance, it is preferably 1200 to 3000%.

[0116] When the vibration-damping property imparting material contained in the thermoplastic resin composition of the present invention is the polymer (B) of the present invention which is preferably used as a vibration-damping property imparting material, the swelling degree of the THF-insoluble matter in the thermoplastic resin composition of the present invention is usually determined by the swelling degree of the polymer (B) and is measured by the above-mentioned method for measuring swelling degree. Therefore, although the swelling degree of the thermoplastic resin composition itself was not measured in the examples described later, the swelling degree of the polymer (B) contained in the thermoplastic resin composition can be regarded as the swelling degree of the thermoplastic resin composition.

[0117] <Aromatic vinyl compound unit> The thermoplastic resin composition of the present invention preferably contains structural units derived from an aromatic vinyl compound (hereinafter, sometimes referred to as "aromatic vinyl compound units") that are derived from the resin component (A) and / or the vibration-damping agent. The content of the aromatic vinyl compound units in the thermoplastic resin composition of the present invention is preferably 0.5 to 80 mass%, more preferably 1.0 to 70 mass%, and even more preferably 1.5 to 60 mass%. When the content of the aromatic vinyl compound unit in the thermoplastic resin composition of the present invention is equal to or more than the lower limit, the thermoplastic resin composition of the present invention has excellent moldability. When the content of the aromatic vinyl compound unit in the thermoplastic resin composition of the present invention is equal to or more than the lower limit, the vibration-damping agent is uniformly dispersed, and the vibration-damping property is stably expressed. On the other hand, when the content of the aromatic vinyl compound unit in the thermoplastic resin composition of the present invention is equal to or less than the upper limit, the thermoplastic resin composition of the present invention has excellent impact resistance.

[0118] The content of the aromatic vinyl compound unit in the thermoplastic resin composition can be determined by infrared spectroscopy (IR), pyrolysis chromatography, or a combination of these. It can also be calculated by adding up the proportions of the aromatic vinyl compound units contained in the resin component (A) and the vibration-damping material used in the production of the thermoplastic resin composition and the amounts charged as the production raw materials.

[0119] [Vibration-damping material] The vibration-damping property imparting material contained in the thermoplastic resin composition of the present invention preferably contains a polymer (b1) having a temperature (peak temperature) showing a peak value of the main dispersion of Tan δ measured by the method described above in the description of the polymer (b1) of the present invention of 3°C to 45°C and a peak intensity, which is the peak value, of 1.900 or more.

[0120] The vibration-damping material contained in the thermoplastic resin composition of the present invention is preferably a vibration-damping material composed of a polymer (B) having a polymer (b1) which has a structural unit derived from an acrylic acid ester compound and a structural unit derived from a methacrylic acid ester compound and has a glass transition temperature of -10°C to 30°C, and a polymer (b2) which contains one or more structural units selected from the group consisting of a structural unit derived from a methacrylic acid ester compound, a structural unit derived from an aromatic vinyl compound, and a structural unit derived from a vinyl cyanide compound, and the polymer (b1) has a peak temperature of 3°C to 45°C and a peak intensity, which is the peak value, of 1.950 or more.

[0121] The swelling degree of the THF-insoluble matter of the polymer (B) is preferably 1000% or more, and the polymer (b2) is preferably bonded to at least a part of the polymer (b1).

[0122] That is, the vibration-damping agent contained in the thermoplastic resin composition of the present invention is preferably the above-mentioned vibration-damping agent of the present invention, that is, the polymer (B) of the present invention.

[0123] [Content of resin component (A) and vibration-damping material] The thermoplastic resin composition of the present invention may contain only one type of the polymer (B) of the present invention as a vibration-damping property imparting material, or may contain two or more types thereof. The resin component (A) may also contain only one type of thermoplastic resin, or two or more types thereof, selected from the various thermoplastic resins described below.

[0124] The thermoplastic resin composition of the present invention preferably contains 90 to 10 parts by mass of resin component (A) and 10 to 90 parts by mass of vibration-damping material so that the total is 100 parts by mass. When the content of resin component (A) is equal to or less than the above upper limit and the content of vibration-damping material is equal to or more than the above lower limit, the vibration reduction effect is excellent. On the other hand, when the content of resin component (A) is equal to or more than the above lower limit and the content of vibration-damping material is equal to or less than the above upper limit, the inherent characteristics of resin component (A) are fully exhibited. The thermoplastic resin composition of the present invention more preferably contains 80 to 20 parts by mass of resin component (A) and 20 to 80 parts by mass of vibration-damping material relative to a total of 100 parts by mass of resin component (A) and vibration-damping material. The suitable mixing ratio for each thermoplastic resin as the resin component (A) will be described later.

[0125] [Resin component (A)] The thermoplastic resin composition of the present invention contains a thermoplastic resin as the resin component (A).

[0126] Examples of the thermoplastic resin contained as the resin component (A) in the thermoplastic resin composition of the present invention include styrene-based resins, acrylic-based resins, polycarbonate-based resins such as aromatic polycarbonate resins, polyester-based resins such as polybutylene terephthalate resins, polyolefin-based resins, vinyl chloride-based resins, polyamide-based resins, polyacetal-based resins, polyphenylene ether-based resins, and polyarylene sulfide-based resins.

[0127] Examples of styrene-based resins include rubber-reinforced styrene-based resins (A1) containing rubber polymers such as butadiene rubber, butyl acrylate rubber, and ethylene-propylene rubber, and styrene-based resins (A2) that do not contain rubber polymers such as acrylonitrile-styrene copolymers.

[0128] These thermoplastic resins can be used alone or in combination of two or more.

[0129] Among these thermoplastic resins, it is preferable to contain a styrene-based resin (A2) from the viewpoints of moldability, appearance, rigidity, and heat resistance. From the viewpoint of impact resistance, it is preferable that the composition contains a rubber-reinforced styrene-based thermoplastic resin (A1). From the viewpoint of high vibration damping properties, it is preferable to contain an acrylic resin (A3). The resin component (A) according to the present invention does not include the polymer (B) according to the present invention, which is the vibration-damping property imparting material described above.

[0130] When the thermoplastic resin composition of the present invention contains, as the resin component (A), a thermoplastic resin other than the rubber-reinforced styrene-based thermoplastic resin (A1), the styrene-based resin (A2), and the acrylic resin (A3), the content thereof is preferably 50 mass% or less, particularly preferably 30 mass% or less, based on 100 mass% of the resin component (A) including the rubber-reinforced styrene-based thermoplastic resin (A1), the styrene-based resin (A2), the acrylic resin (A3), and other resins.

[0131] <Rubber-reinforced styrene-based thermoplastic resin (A1)> The rubber-reinforced styrene-based thermoplastic resin (A1) contains a rubber polymer portion and a vinyl copolymer portion. The rubber-reinforced styrene-based thermoplastic resin (A1) can be produced by polymerizing a vinyl monomer (a1) such as an aromatic vinyl compound in the presence of a rubber polymer (g).

[0132] Examples of rubber polymers (g) include conjugated diene rubbers such as polybutadiene, polyisoprene, butadiene-styrene copolymers, and butadiene-acrylonitrile copolymers; olefin rubber polymers such as ethylene-α-olefin rubber polymers such as ethylene-propylene copolymers, ethylene-propylene-non-conjugated diene copolymers, ethylene-butene-1 copolymers, and ethylene-butene-1-non-conjugated diene copolymers; acrylic rubbers; silicone rubbers; polyurethane rubbers; silicone-acrylic IPN rubbers; natural rubbers; conjugated diene block copolymers; and hydrogenated conjugated diene block copolymers.

[0133] Among these, in applications where not only vibration damping but also impact resistance is required for indoor use such as interior parts of cars and home appliances, rubbery polymers (g) containing butadiene, such as conjugated diene rubbers such as polybutadiene, butadiene-styrene copolymers, butadiene-acrylonitrile copolymers, are preferred. Among these, rubber-reinforced styrene-based thermoplastic resins (A1) obtained by polymerizing vinyl monomers (a1) containing aromatic vinyl compounds and vinyl cyanide compounds in the presence of butadiene-based rubbery polymers are preferred because they are also effective in terms of impact resistance. That is, the rubber-reinforced styrene-based thermoplastic resin (A1) is preferably a rubber-reinforced styrene-based thermoplastic resin (A1) containing a rubbery polymer portion made of butadiene-based rubber and a vinyl-based copolymer portion containing structural units derived from an aromatic vinyl compound and structural units derived from a vinyl cyanide compound.

[0134] Furthermore, in applications where weather resistance as well as vibration damping is required for outdoor use such as exterior parts of cars and exterior parts of houses, the rubbery polymer (g) is preferably an ethylene-α-olefin rubber, an acrylic rubber, a silicone rubber, or a silicone-acrylic composite rubber. Among these, ethylene-α-olefin rubber, a silicone rubber, or a silicone-acrylic composite rubber is preferred because it is also effective in terms of impact resistance. In particular, a rubber-reinforced styrene-based thermoplastic resin (A1) obtained by polymerizing a vinyl monomer (a1) containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of these rubbery polymers (g) is preferred. That is, the rubber-reinforced styrene-based thermoplastic resin (A1) is preferably a rubber-reinforced styrene-based thermoplastic resin (A1) containing a rubber polymer portion made of ethylene-α-olefin rubber, silicone rubber, or silicone-acrylic composite rubber, and a vinyl copolymer portion containing structural units derived from an aromatic vinyl compound and structural units derived from a vinyl cyanide compound.

[0135] Examples of the aromatic vinyl compound used herein include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, hydroxystyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, pt-butylstyrene, ethylstyrene, vinylnaphthalene, divinylbenzene, 1,1-diphenylstyrene, N,N-diethyl-p-aminoethylstyrene, N,N-diethyl-p-aminoethylstyrene, vinylpyridine, etc., with styrene and α-methylstyrene being preferred, and styrene being particularly preferred. These may be used alone or in combination of two or more.

[0136] Examples of other vinyl monomers copolymerizable with the aromatic vinyl compound include vinyl cyanide compounds, (meth)acrylic acid ester compounds, maleimide compounds, and other various functional group-containing unsaturated compounds. These other vinyl monomers can be used alone or in combination of two or more.

[0137] Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile. These can be used alone or in combination of two or more. Chemical resistance is imparted by using a vinyl cyanide compound. The amount of the vinyl cyanide compound used is usually 0 to 60 mass %, preferably 5 to 50 mass %, based on the total amount of the vinyl monomer (a1).

[0138] Examples of the (meth)acrylic acid ester compound include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, and butyl methacrylate. These can be used alone or in combination of two or more. The use of the (meth)acrylic acid ester compound improves the surface hardness. The amount of the (meth)acrylic acid ester compound used is usually 0 to 80 mass % in the total amount of the vinyl monomer (a1).

[0139] Examples of the maleimide compound include maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-methylmaleimide, and N-benzylmaleimide. These can be used alone or in combination of two or more. In order to introduce maleimide units, maleic anhydride may be copolymerized and then imidized. The use of the maleimide compound imparts heat resistance. The amount of the maleimide compound used is usually 1 to 60 mass % in the total amount of the vinyl monomer (a1).

[0140] The rubber-reinforced styrene-based thermoplastic resin (A1) can be produced by a known polymerization method, for example, emulsion polymerization, bulk polymerization, solution polymerization, suspension polymerization, or a combination of these polymerization methods.

[0141] The rubber-reinforced styrene-based thermoplastic resin (A1) may be used alone or in combination of two or more kinds having different copolymerization compositions, physical properties, and the like.

[0142] <Styrene-based resin (A2)> The styrene-based resin (A2) is a (co)polymer obtained by polymerizing an aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer (a2) copolymerizable with the aromatic vinyl compound. The styrene-based resin (A2) does not include the rubbery polymer (g) described in the explanation of the rubber-reinforced styrene-based thermoplastic resin (A1). That is, the vinyl monomer (a2) may be an aromatic vinyl compound alone, or may be a mixture of an aromatic vinyl compound and another vinyl monomer copolymerizable with the aromatic vinyl compound. As the aromatic vinyl compound and the other vinyl monomer copolymerizable with the aromatic vinyl compound used here, all of those described as the vinyl monomer (a1) in the rubber-reinforced styrene-based thermoplastic resin (A1) can be used. The vinyl monomer (a2) may be the same as or different from the vinyl monomer (a1).

[0143] The content of monomers other than aromatic vinyl compounds in the vinyl monomer (a2) is usually 80% by mass or less, preferably 60% by mass or less, and more preferably 50% by mass or less, when the total amount of the vinyl monomer (a2) is 100% by mass.

[0144] Preferred styrene-based resins (A2) include styrene homopolymers, styrene-acrylonitrile copolymers, α-methylstyrene-acrylonitrile copolymers, α-methylstyrene-styrene-acrylonitrile copolymers, styrene-methyl methacrylate copolymers, styrene-acrylonitrile-methyl methacrylate copolymers, α-methylstyrene-methyl methacrylate copolymers, α-methylstyrene-acrylonitrile-methyl methacrylate copolymers, styrene-maleimide compound copolymers, and copolymers of these with the above-mentioned functional group-containing unsaturated compounds.

[0145] The styrene-based resin (A2) can be produced by known polymerization methods such as emulsion polymerization, bulk polymerization, solution polymerization, suspension polymerization, and combinations of these methods.

[0146] The styrene-based resin (A2) may be used alone or in combination of two or more types having different copolymer compositions, physical properties, and the like.

[0147] <Acrylic resin (A3)> The acrylic resin (A3) is obtained by polymerizing a vinyl monomer containing a (meth)acrylic acid ester monomer or a vinyl monomer mixture by a known method. The vinyl monomer mixture contains a (meth)acrylic acid ester monomer as an essential component, and may contain other vinyl monomers shown below in an amount of 40 mass% or less as necessary.

[0148] Examples of the (meth)acrylic acid ester monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, phenyl (meth)acrylate, etc. These may be used alone or in combination of two or more.

[0149] Examples of vinyl monomers other than the (meth)acrylic acid ester monomer include aromatic vinyl monomers, vinyl cyanide monomers, maleimide monomers, (meth)acrylic acid, etc. The aromatic vinyl monomers and vinyl cyanide monomers can be the same as those contained in the vinyl monomer (a1) described above, and can be used alone or in combination of two or more.

[0150] Examples of the maleimide monomer include N-alkylmaleimides (N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, Ni-propylmaleimide, Nn-butylmaleimide, Ni-butylmaleimide, Nt-butylmaleimide, etc.), N-cycloalkylmaleimides (N-cyclohexylmaleimide, etc.), N-arylmaleimides (N-phenylmaleimide, N-alkyl-substituted phenylmaleimide, N-chlorophenylmaleimide, etc.), etc. These can be used alone or in combination of two or more.

[0151] Among the acrylic resins (A3), specific examples of copolymer resins of methyl methacrylate and methyl acrylate include commercially available products such as "Parapet G" manufactured by Kuraray Co., Ltd., and "Acrypet VH" and "Acrypet MD" manufactured by Mitsubishi Chemical Corporation. Specific examples of polyacrylic resins containing both (meth)acrylic acid ester monomer units and maleimide monomer units include commercially available products such as "Parapet SH-N" manufactured by Kuraray Co., Ltd., and "Polyimilex PML203" manufactured by Nippon Shokubai Co., Ltd.

[0152] These acrylic resins (A3) may be used alone or in combination of two or more.

[0153] <Aromatic polycarbonate resin> Any aromatic polycarbonate resin obtained by a known polymerization method, such as an interfacial polycondensation method between a dihydroxyaryl compound and phosgene, or an ester exchange reaction (melt polycondensation) between a dihydroxyaryl compound and a carbonate compound such as diphenyl carbonate, can be used.

[0154] Examples of the dihydroxyaryl compounds include bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-t-butylphenyl)propane, 2,2-bis(4-hydroxy-3-t-butylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxyphenyl ether, 4,4'-dihydroxyphenyl sulfide, 4,4'-dihydroxyphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, hydroquinone, and resorcin. In addition, there are polyorganosiloxanes terminated with hydroxyaryloxy (see, for example, U.S. Pat. No. 3,419,634). These can be used alone or in combination of two or more. Among these, 2,2-bis(4-hydroxyphenylpropane (bisphenol A) is preferred.

[0155] The viscosity average molecular weight of the aromatic polycarbonate resin is preferably 12,000 to 40,000, more preferably 15,000 to 35,000, and particularly preferably 18,000 to 30,000. The higher the molecular weight, the higher the mechanical strength of the molded article obtained, but the lower the flowability, and the lower the appearance of the molded article tends to be. Two or more aromatic polycarbonate resins having different molecular weights can also be used as the aromatic polycarbonate resin.

[0156] Here, the viscosity average molecular weight of an aromatic polycarbonate resin can usually be calculated by inserting the specific viscosity (ηsp) measured at 20°C and a concentration [0.7 g / 100 ml (methylene chloride)] using methylene chloride as a solvent into the following formula (iii). Viscosity average molecular weight=([η]×8130) 1.205 (iii) Where: [η] = [(ηsp × 1.12 + 1) 1 / 2 -1) / 0.56C. In addition, C indicates the concentration.

[0157] <Polybutylene terephthalate resin> Polybutylene terephthalate resins are generally resins obtained by polycondensation reaction of terephthalic acid and / or its derivatives with 1,4-butanediol and / or its derivatives. As long as the object of the present invention is not impaired, the polybutylene terephthalate resin may also be one obtained by copolymerizing other dicarboxylic acids and / or their derivatives, glycols, etc.

[0158] Examples of copolymerizable dicarboxylic acids include isophthalic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbene dicarboxylic acid, 4,4-biphenyl dicarboxylic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, bisbenzoic acid, bis(p-carboxyphenyl)methane, anthracene dicarboxylic acid, 4,4-diphenyl ether dicarboxylic acid, 4,4-diphenoxyethane dicarboxylic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, and other dicarboxylic acids and derivatives thereof. These copolymerizable dicarboxylic acids and / or derivatives thereof are, for example, appropriately selected from the exemplified ones and used alone or in combination of two or more kinds.

[0159] On the other hand, examples of copolymerizable glycols include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, trans- or cis-2,2,4,4,-tetramethyl-1,3-cyclobutanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A, tetrabromobisphenol A, tetrabromobisphenol A-bis(2-hydroxyethyl ether), etc. These copolymerizable glycols may be appropriately selected from the above-listed ones and used alone or in combination of two or more kinds.

[0160] The polybutylene terephthalate resin used in the present invention preferably has an intrinsic viscosity of 0.7 to 1.50 dl / g, from the viewpoint of sufficiently ensuring the flowability and moldability of the thermoplastic resin composition of the present invention and the impact resistance of the molded article of the present invention molded using this thermoplastic resin composition. Here, the intrinsic viscosity of the polybutylene terephthalate resin is a value measured at 30° C. in a mixed solution of tetrachloroethane and phenol in a 1:1 (mass ratio).

[0161] The thermoplastic resin composition of the present invention using polybutylene terephthalate resin has good chemical resistance, electrical insulation, and abrasion resistance. Therefore, this thermoplastic resin composition can be used for plastic gears, cooling fans for personal computers, etc. Furthermore, by further mixing fillers such as glass fiber and carbon fiber, it can also be applied to the housing of a cooling fan.

[0162] Specific examples of polybutylene terephthalate resins include commercially available products such as "NovaDuran" manufactured by Mitsubishi Chemical Corporation and "Duranex" manufactured by Polyplastics Co., Ltd.

[0163] These polybutylene terephthalate resins may be used alone or in combination of two or more.

[0164] <Polyamide resin> The polyamide resin may be, for example, a polyamide obtained from a diamine and a dicarboxylic acid. Examples of diamines include aliphatic, alicyclic, and aromatic diamines such as ethylenediamine, diaminobutane, hexamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, 1,3- and 1,4-bis(aminomethyl)cyclohexane, bis(p-aminocyclohexyl)methane, metaxylylenediamine, and paraxylylenediamine. These can be used alone or in combination of two or more.

[0165] Examples of dicarboxylic acids include aliphatic, alicyclic, and aromatic dicarboxylic acids such as adipic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, etc. These can be used alone or in combination of two or more.

[0166] Examples of the polyamide resin that can be used include polyamides obtained by ring-opening polymerization of lactams such as ξ-caprolactam and ω-dodecalactam; polyamides obtained from 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and the like; copolymer polyamides thereof; mixed polyamides thereof; and polyamide elastomers having polyamide as a hard segment and polyether as a soft segment. Among these, polycaproamide (nylon 6), polyundecaneamide (nylon 11), polydodecaamide (nylon 12), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon 610), and copolymers thereof are preferred because they are industrially produced at low cost and in large quantities. Examples of copolymers include nylon 6 / 66, nylon 6 / 610, nylon 6 / 12, nylon 66 / 12, and nylon 6 / 66 / 610 / 12. The polyamide resin may be a mixture of these. As the polyamide resin, bis(p-aminocyclohexyl)methane / terephthalic acid / isophthalic acid-based polyamides are also preferred.

[0167] These polyamide resins may be used alone or in combination of two or more.

[0168] The thermoplastic resin composition of the present invention using a polyamide resin has excellent chemical resistance, impact resistance, and abrasion resistance. Therefore, this thermoplastic resin composition can be used for plastic gears and cooling fans. In addition, by further mixing fillers such as glass fiber and carbon fiber, it can be applied to the housing of a cooling fan, etc. In addition, when reinforced with carbon fiber (CFRTP: carbon fiber reinforced thermoplastics / thermoplastic CFRP: Carbon Fiber Reinforced Thermo Plastics), it can be applied to a metal replacement and a housing of a device for preventing malfunction related to robots.

[0169] <Suitable Mixing Ratio of Resin Component (A) and Vibration-Damping Material> In the thermoplastic resin composition of the present invention, when emphasis is placed on improving vibration-damping properties, it is preferable to use an acrylic resin (A3) as the resin component (A). In this case, the mixing ratio of the vibration-damping agent and the acrylic resin (A3) is preferably 10 to 90 mass% for the vibration-damping agent and 90 to 10 mass% for the acrylic resin (A3), with the total being 100 mass%.

[0170] In the thermoplastic resin composition of the present invention, when emphasis is placed on physical properties such as vibration-damping property and heat resistance, it is preferable to use a styrene-based resin (A2) as the resin component (A). In this case, the mixing ratio of the vibration-damping material and the styrene-based resin (A2) is preferably 20 to 80 mass% and 80 to 20 mass% of the styrene-based resin (A2) with respect to a total of 100 mass%.

[0171] In the thermoplastic resin composition of the present invention, when the improvement of vibration-damping properties and impact resistance is particularly important, it is preferable to use a styrene-based resin (A2) and a rubber-reinforced styrene-based thermoplastic resin (A1) as the resin component (A). In this case, the mixing ratio of the vibration-damping material to the styrene-based resin (A2) and the rubber-reinforced styrene-based thermoplastic resin (A1) is preferably 20-70% by mass, 60-10% by mass, and 60-20% by mass, of the total of 100% by mass.

[0172] [Other ingredients] The thermoplastic resin composition of the present invention may contain components other than the resin component (A) and the vibration-damping material, provided that the object of the present invention is not impaired. Other ingredients include the following:

[0173] <Sliding agent> The thermoplastic resin composition of the present invention may contain a sliding property imparting agent. The sliding property imparting agent imparts sliding property to the thermoplastic resin composition. This not only facilitates the assembly of an article made of a molded article obtained from the thermoplastic resin composition of the present invention, but also provides an effect of suppressing the generation of abnormal noises, such as creaking noises, from the article made of such a molded article during use.

[0174] Representative examples of the sliding property imparting agent include low molecular weight polyethylene oxide, ultra-high molecular weight polyethylene, polytetrafluoroethylene, or low molecular weight (for example, number average molecular weight of 10,000 or less) polyolefin wax, silicone oil, etc., as described in JP 2011-137066 A.

[0175] The polyolefin wax is preferably a polyethylene wax having a melting point of 0 to 120° C. When a polyolefin wax having such a melting point or other additives having a melting point of 0 to 120° C. are added to the thermoplastic resin composition of the present invention, the effect of suppressing the generation of abnormal noise such as creaking can be obtained even if the rubber portion of the rubber-reinforced styrene-based thermoplastic resin (A1) does not have a melting point (Tm).

[0176] These lubricity-imparting agents may be used alone or in combination of two or more.

[0177] When a sliding property imparting agent is blended into the thermoplastic resin composition of the present invention, the blending amount is preferably 0.1 to 10 parts by mass per 100 parts by mass of the rubber-reinforced styrene-based thermoplastic resin (A1), or 0.2 to 5 parts by mass per 100 parts by mass of the resin component (A).

[0178] <Other additives> Other additives that can be blended in the thermoplastic resin composition of the present invention include heat aging inhibitors, antioxidants, ultraviolet absorbers, weather resistance agents, fillers such as glass fibers and carbon fibers, antistatic agents, flame retardant agents, antifogging agents, lubricants, antibacterial agents, fungicides, tackifiers, plasticizers, colorants, graphite, carbon black, carbon nanotubes, pigments (including pigments imparted with functionality such as infrared absorption and reflectivity), etc. These may be used alone or in combination of two or more. The amount of these other additives added is usually 0.1 to 30 parts by mass based on 100 parts by mass of the resin component (A).

[0179] [Method of producing thermoplastic resin composition] The thermoplastic resin composition of the present invention can be produced by mixing each component in a predetermined mixing ratio using a tumbler mixer, a Henschel mixer, or the like, and then melt-kneading under appropriate conditions using a kneader such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader, a roll, or a feeder ruder. A preferred kneader is a twin-screw extruder. When kneading each component, the components may be kneaded together or may be kneaded in multiple stages or in separate blends. After kneading using a Banbury mixer or a kneader, the components may be pelletized using an extruder. The melt-kneading temperature is usually 180 to 300°C, and preferably 190 to 280°C.

[0180] [Molded product] The molded article of the present invention can be obtained by molding the thermoplastic resin composition of the present invention by injection molding, extrusion molding such as sheet extrusion and profile extrusion molding, vacuum molding, pressure molding, compression molding, calendar molding, foam molding, blow molding, inflation molding, or the like.

[0181] The thermoplastic resin composition of the present invention can also be used as a material for forming a coating layer on a substrate made of other resins or metals.

[0182] In this case, examples of other resins as constituent materials of the substrate on which a coating layer made of the thermoplastic resin composition of the present invention is formed include rubber-modified thermoplastic resins such as ABS resin and high impact polystyrene resin (HIPS), and thermosetting resins such as phenolic resin and melamine resin.

[0183] The molded article of the present invention can be used in various applications including various industrial applications. For example, the molded article of the present invention is suitable for use in vehicle interior and exterior parts such as engine peripheral parts, trunk floor panels, tire covers, floor boxes, glove boxes, parts around gasoline filler ports, wheel caps, door mirrors, pillars, etc.; building materials and parts such as wall materials and window frames; tableware; toys; home appliance parts such as vacuum cleaner housings, television housings, and air conditioner housings; interior materials; marine parts; electrical equipment housings such as communication device housings, notebook computer housings, mobile terminal housings, and liquid crystal projector housings; road materials such as sound absorbing and soundproofing panels for roads; and the like. EXAMPLES

[0184] The present invention will be described in more detail below with reference to examples. The present invention is not limited to the following examples. In the following, "parts" and "%" are by weight unless otherwise specified.

[0185] 〔raw materials〕 In the following Examples and Comparative Examples, the thermoplastic resin compositions were produced using, as raw materials, resin components produced by the following methods and the following commercially available products.

[0186] [Rubber-reinforced styrene-based thermoplastic resin (A1)] <Production of (A1-1)> In a polymerization vessel equipped with a stirrer, 280 parts of water and 60 parts of polybutadiene latex (solid content equivalent) with a volume average particle size of 0.26 μm and a gel content of 90% as a diene rubber polymer, 0.3 parts of sodium formaldehyde sulfoxylate, 0.0025 parts of ferrous sulfate, and 0.01 parts of disodium ethylenediaminetetraacetate were charged, deoxygenated, and heated to 60° C. while stirring in a nitrogen stream. Then, a monomer mixture consisting of 10 parts of acrylonitrile, 30 parts of styrene, 0.2 parts of t-dodecyl mercaptan, and 0.3 parts of cumene hydroperoxide was continuously added dropwise at 60° C. for 5 hours. After the completion of the dropwise addition, the polymerization temperature was set to 65° C., and stirring was continued for 1 hour, after which the polymerization was terminated to obtain a latex of a graft copolymer. The polymerization conversion rate was 98%. Then, 0.2 parts of 2,2'-methylene-bis(4-ethylene-6-t-butylphenol) was added to the obtained latex, and calcium chloride was added to coagulate it, followed by washing, filtration and drying to obtain a powdery ABS resin (A1-1). The graft ratio of the obtained ABS resin (A1-1) was 40%, and the intrinsic viscosity [η] of the acetone soluble matter was 0.38 dl / g.

[0187] <Production of (A1-2)> A monomer mixture (II) was prepared by mixing 30.4 parts of styrene, 9.6 parts of acrylonitrile, and 0.05 parts of t-butyl mercaptan. 60 parts of polybutyl acrylate rubber polymer latex (based on solid content), 12 parts of water, and 0.36 parts of sodium dodecylbenzenesulfonate were charged into a glass reactor, and the temperature was raised to 70°C under a nitrogen stream while stirring. When the temperature reached 70°C, 52% by mass of an aqueous solution (hereinafter abbreviated as "RED aqueous solution (I)") in which 0.003 parts of tetrasodium ethylenediaminetetraacetate dihydrate, 0.001 parts of ferrous sulfate heptahydrate, and 0.05 parts of sodium formaldehyde sulfoxylate were dissolved in 2 parts of water was charged into the reactor. Immediately after this charging, the entire amount of the monomer mixture (II) and 0.06 parts of t-butyl hydroperoxide were continuously added over a period of 2 hours and 30 minutes to carry out polymerization. 150 minutes after the start of polymerization, the remaining 48 mass% of the RED aqueous solution (I) and 0.03 parts of t-butyl hydroperoxide were charged into the reactor, and the temperature was maintained for 60 minutes, after which the polymerization was terminated to obtain a graft copolymer latex. The graft copolymer latex was coagulated, washed with water, and dried to obtain a powdery graft copolymer (A1-2). The gel content, swelling degree, graft ratio, and molecular weight of acetonitrile soluble matter of the obtained graft copolymer (A1-2) were measured. The results are shown in Table 2A.

[0188] [Styrene-based resin (A2)] <(A2-1)> As the AS resin (A2-1), an acrylonitrile-styrene copolymer was used, which had a ratio of acrylonitrile units and styrene units of 27% and 73%, respectively, a limiting viscosity [η] (in methyl ethyl ketone, 30°C) of 0.47 dl / g, and a glass transition temperature (Tg) of 103°C.

[0189] <Production of (A2-2)> In a reactor equipped with a stirrer, 250 parts of water, 3 parts of sodium laurate, 0.2 parts of t-dodecyl mercaptan, 0.4 parts of sodium formaldehyde sulfoxylate, 0.0025 parts of ferrous sulfate, 0.01 parts of disodium ethylenediaminetetraacetate, and 0.5 parts of cumene hydroperoxide were charged, and the inside of the reactor was deoxygenated. Then, 73 parts of α-methylstyrene were charged while stirring at 60°C in a nitrogen stream. After sufficient emulsification, 17 parts of acrylonitrile, which is a component other than α-methylstyrene, were continuously dropped over 5 hours to carry out copolymerization. The polymerization was terminated when the polymerization conversion rate reached 85.0%. Next, 0.5 parts of cumene hydroperoxide, 0.05 parts of t-dodecyl mercaptan, 0.4 parts of sodium formaldehyde sulfoxylate, 0.0025 parts of ferrous sulfate, and 0.01 parts of disodium ethylenediaminetetraacetate were further charged into the polymerization solution. Then, 2 parts of styrene, 3 parts of acrylonitrile, and 5 parts of methacrylic acid were continuously dropped over 0.5 hours while stirring at 60°C in a nitrogen stream to carry out copolymerization. After the dropwise addition, the mixture was stirred at 60°C for 1.5 hours to terminate the polymerization. The final polymerization conversion rate was 96.0%. The amount of residual monomers in the reactor was 1.4% α-methylstyrene, 0.2% styrene, 1.2% acrylonitrile, and 1.2% methacrylic acid relative to the total amount of monomers used in polymerization. After that, the mixture was solidified with calcium chloride, and then a styrene-based resin (A2-2) having an intrinsic viscosity [η] of 0.31 dL / g was recovered using a vented extruder "DMG40mm" (model name) manufactured by Nippon Placon Co., Ltd.

[0190] <Production of (A2-3)> 15 parts of acrylonitrile, 55 parts of styrene, and 30 parts of N-phenylmaleimide were polymerized by a known continuous solution polymerization to obtain an acrylonitrile-styrene-N-phenylmaleimide terpolymer. This was designated as styrene-based resin (A2-3). The reduced viscosity of the acetone-soluble portion of the styrene-based resin (A2-3) was 0.60 dL / g.

[0191] [Acrylic resin (A3)] <(A3-1)> As the acrylic resin (A3-1), PMMA (Acrypet VH5 (product name)) manufactured by Mitsubishi Chemical Corporation was used.

[0192] [Other resins] As the PC resin (A4-1), an aromatic polycarbonate resin "NOVAREX 7022J (product name)" manufactured by Mitsubishi Engineering Plastics Corporation was used. As the PBT resin (A4-2), a polybutylene terephthalate resin "DURANEX 2006 (product name)" manufactured by Polyplastics Co., Ltd. was used. As the PA resin (A4-3), a nylon 6 resin "CM1021 (product name)" manufactured by Toray Industries, Inc. was used.

[0193] [Vibration-damping material] The vibration-damping materials used were the vibration-damping materials (B-1) to (B-15) of the Examples, which were produced by the methods described below, or the vibration-damping materials (BX-1) to (BX-4), (BX-6), and (BX-7) of the Comparative Examples, as well as the following commercially available vibration-damping materials (BX-8) and (BX-9).

[0194] <Vibration-damping material (BX-8)> Asahi Kasei hydrogenated styrene-butadiene copolymer "S1605" (styrene content: 66%, hydrogenation rate: 95%) <Vibration-damping material (BX-9)> EP-1001, an α-olefin copolymer made by Mitsui Chemicals that has excellent vibration damping and stress relaxation properties

[0195] [Method of measuring polymer] The methods for evaluating various physical properties and characteristics of the polymers in the examples and comparative examples are as follows.

[0196] [Glass transition temperature (Tg)] In accordance with JIS K7121, a DSC curve was measured using a differential scanning calorimeter ("Q200" manufactured by TA Instruments) under the conditions of heating once from -90°C to 50°C (1st run), then cooling to -90°C, and then heating from -90°C to 50°C at 10°C / min (2nd run). The midpoint glass transition temperature of the 2nd run determined from this DSC curve was taken as the glass transition temperature in the present invention.

[0197] [Volume average particle size] The measurement was performed by photon correlation spectroscopy using a Nikkiso Microtrac Model:9230UPA.

[0198] [Tan δ peak intensity · peak temperature] The latex of polymer (b1) was coagulated and dried to obtain a sample of polymer (b1). The sample was then molded into a sheet having a thickness of 1.0 to 1.1 mm using a heat press at a set temperature of 150°C, and cut into a size of 36 mm in length and 10 mm in width to prepare a measurement sample. Using the following dynamic viscoelasticity measuring device, 8 mm portions of both ends of the long sides of the sample were fixed with a tensile jig, and Tan δ was measured under the following conditions to determine the peak temperature and peak strength. Measurement equipment: Dynamic viscoelasticity measuring equipment (TA Instruments "DMA850") Mode: Tensile Frequency: 1Hz Heating rate: 5℃ / min Measurement temperature: -60℃~+60℃

[0199] [Swelling degree of THF insoluble matter] The polymer (B) was immersed in tetrahydrofuran (THF) for 24 hours, and then the insoluble matter separated by centrifugation was vacuum dried and its weight (weight b) was measured. The obtained THF-insoluble matter was immersed again in THF for 24 hours, after which the weight of the sample swollen with THF (weight c) was measured, and the swelling degree of the THF-insoluble matter was calculated by the following formula. Swelling degree (%) = c / b x 100 The swelling degree here refers to the swelling degree of the graft structure contained in the polymer (B). If the graft structure does not have a crosslinked structure, it cannot be obtained as a THF insoluble matter. If the graft structure does not have a crosslinked structure, it dissolves in THF and an accurate swelling degree cannot be obtained. For this reason, when the gel content is 1% or less, the swelling degree is determined to be 3000% or more.

[0200] [Gel content] 1 g of polymer (B) was added to 100 mL of THF, left to stand at room temperature for 48 hours, and then filtered through a 100 mesh wire net (mass W1 gram). The THF insoluble matter and wire net obtained by filtering were vacuum dried at 80° C. for 6 hours and weighed (mass W2 gram). W1 and W2 were substituted into the following formula (i) to obtain the gel content. Gel content = [[W2(g)-W1(g)] / 1(g)] × 100 (i)

[0201] [Grafting rate] 1 g of polymer (B) was added to 20 mL of acetonitrile and shaken for 2 hours using a shaker. The resulting acetonitrile suspension was centrifuged for 60 minutes using a centrifuge (rotation speed: 32,000 rpm) to separate the precipitate (acetonitrile insoluble component) and the acetonitrile solution (acetonitrile soluble component). The precipitate (acetonitrile insoluble component) was dried and its mass (T(g)) was measured, and the graft ratio was calculated using the following formula. In the following formula, T is the mass (g) of the acetonitrile insoluble component of the polymer (B), and S is the mass (g) of the rubber polymer (b1) contained in 1 g of the polymer (B). Graft ratio (mass%) = {(TS) / S} x 100 However, when the polymer (b1) was composed of an aromatic vinyl compound and a conjugated diene, the measurement was carried out using acetone instead of acrylonitrile.

[0202] [Molecular weight of acetonitrile soluble matter] The acetonitrile soluble content obtained in the above evaluation of the graft ratio was measured by gel permeation chromatography under the following conditions: A calibration curve was prepared using standard polystyrene, and the weight average molecular weight in terms of polystyrene was calculated from the relationship between the molecular weight and the retention time. Equipment: Tosoh Corporation "HLC-8320GPC EcoSEC" Column: Tosoh Corporation "TSK-gel-GMH" Solvent: THF Flow rate 0.8mL / min Measurement temperature: 23℃

[0203] [Production of (R-1)] A monomer mixture (I) was prepared by mixing 39.26 parts of n-butyl acrylate (hereinafter abbreviated as "BA"), 20.60 parts of methyl methacrylate (hereinafter abbreviated as "MMA"), and 0.14 parts of allyl methacrylate (hereinafter abbreviated as "AMA") as a crosslinking agent. In a 10L glass reactor equipped with a stirring device, a raw material and auxiliary agent adding device, a thermometer, a heating device, etc., 220 parts of water and 0.1 parts of sodium dodecylbenzenesulfonate as an emulsifier were charged, and the internal temperature was raised to 70°C under a nitrogen stream while stirring. When the temperature reached 70°C, 84% by mass of an aqueous solution (hereinafter abbreviated as "RED aqueous solution (II)") in which 0.01 parts of tetrasodium ethylenediaminetetraacetate dihydrate, 0.002 parts of ferrous sulfate heptahydrate, and 0.3 parts of sodium formaldehyde sulfoxylate were dissolved in 8.5 parts of water was charged into the reactor. Immediately after that, 100 parts of the monomer mixture (I) and 0.2 parts of cumene hydroperoxide were continuously added over a period of 3 hours. One hour after the start of the dropwise addition, an aqueous solution in which 1.6 parts of dodecylbenzenesulfonic acid were dissolved in 20 parts of water was charged into the reactor. Immediately after the continuous addition of the monomer mixture (I) was completed, the remaining 16 mass% of the RED aqueous solution (II) and 0.005 parts of cumene hydroperoxide were charged into the reactor, and the internal temperature of the reactor was maintained at 70° C. for another 30 minutes. Thereafter, the polymerization reaction was terminated to obtain an acrylic rubber polymer (R-1) latex. The polymerization conversion rate at this time was 97%. The volume average particle diameter of the obtained acrylic rubber polymer (R-1) particles, measured by the above-mentioned method, was 150 nm. The acrylic rubber polymer (R-1) latex was dried to obtain a film, and the glass transition temperature (Tg) of the film was measured by the above-mentioned method. In addition, the peak intensity and peak temperature of Tan δ were measured by the above-mentioned method. The results are shown in Table 1A.

[0204] [Production of (R-4)] In a 100-liter stainless steel autoclave equipped with a stirrer and a thermometer, 145 parts of ion-exchanged water, 1.0 parts of disproportionated potassium rosinate, 1.0 parts of potassium oleate, 0.4 parts of sodium formaldehyde sulfoxylate dihydrate, 0.1 parts of anhydrous sodium sulfate, 0.3 parts of tertiary dodecyl mercaptan, 0.5 parts of diisopropylbenzene hydroperoxide, 11.2 parts of 1,3-butadiene (hereinafter abbreviated as "BD"), and 16.8 parts of styrene (hereinafter abbreviated as "ST") were charged, and the internal temperature was raised to 50°C. Then, an aqueous solution consisting of 0.5 parts of sodium pyrophosphate, 0.005 parts of ferrous sulfate heptahydrate, and 5 parts of water was added to initiate polymerization. At a polymerization temperature of 57°C, a mixture consisting of 28.8 parts of 1,3-butadiene and 43.2 parts of styrene was dripped and fed by a pressure pump. Then, when the polymerization conversion rate reached 40%, 0.3 parts of normal dodecyl mercaptan was added to continue the polymerization. After 8 hours, the remaining 1,3-butadiene was removed to obtain a butadiene polymer latex (R-4) having a solid content of 40.2%, a polymerization conversion rate of 97%, and a volume average particle size of 70 nm. The measurement results of the volume average particle size, Tg, Tan δ peak intensity and peak temperature of the butadiene polymer latex (R-4) are shown in Table 1A.

[0205] [Manufacture of (R-2), (R-3), (R-5) to (R-13) and (RX-1) to (RX-4), (RX-6), and (RX-7)] Except for the formulations shown in Tables 1A and 1B, the acrylic rubber polymers (R-2), (R-3), (R-5) to (R-13) and (RX-1) to (RX-4), (RX-6), and (RX-7) were produced in the same manner as (R-1). The measurement results of the volume average particle size, Tg, Tan δ peak intensity and peak temperature of these acrylic rubber polymers are shown in Tables 1A and 1B. In Table 1B, the Tg, the peak intensity of Tan δ, and the peak temperature measured for the vibration-damping material (BX-8) and the vibration-damping material (BX-9) are shown together as the Tg, the peak intensity of Tan δ, and the peak temperature for (RX-8) and (RX-9), respectively.

[0206] [Production of (B-1)] Monomer mixture (II) was prepared by mixing 8.4 parts of ST, 2.8 parts of acrylonitrile (hereinafter abbreviated as "AN"), 28.8 parts of MMA, and 0.05 parts of t-butyl mercaptan. 40 parts of the acrylic rubber polymer (R-1) latex (solid content), 12 parts of water, and 0.36 parts of sodium dodecylbenzenesulfonate were charged into the glass reactor used for producing the acrylic rubber polymer (R-1) latex, and the temperature was raised to 70°C under a nitrogen stream while stirring. When the temperature reached 70°C, 52% by mass of an aqueous solution (RED aqueous solution (I)) in which 0.003 parts of tetrasodium ethylenediaminetetraacetate dihydrate, 0.001 parts of ferrous sulfate heptahydrate, and 0.05 parts of sodium formaldehyde sulfoxylate were dissolved in 2 parts of water was charged into the reactor. Immediately after this charging, the entire amount of the monomer mixture (II) and 0.06 parts of t-butyl hydroperoxide were continuously added over 2 hours and 30 minutes to carry out polymerization. 150 minutes after the start of polymerization, the remaining 48 mass% of the RED aqueous solution (I) and 0.03 parts of t-butyl hydroperoxide were charged into the reactor, and the polymerization was terminated after maintaining the same temperature for 60 minutes to obtain a graft copolymer (B-1) latex. The graft copolymer (B-1) latex was coagulated, washed with water, and dried to obtain a powdered graft copolymer (B-1). The gel content, swelling degree, graft ratio, and molecular weight of acetonitrile soluble matter of the obtained graft copolymer (B-1) were measured. The results are shown in Table 2A.

[0207] [Production of (B-2)~(B-15) and (BX-1)~(BX-4), (BX-6) and (BX-7)] Graft copolymers (B-2) to (B-15), (BX-1) to (BX-4), (BX-6), and (BX-7) were produced in the same manner as graft copolymer (B-1), except that the acrylic rubber polymers (R-2) to (R-13), (RX-1) to (RX-4), (RX-6), and (RX-7) obtained above were used in the formulations shown in Tables 2A and 2B. The gel content, swelling degree, graft ratio, and molecular weight of the acetonitrile-soluble portion of these graft copolymers are shown in Tables 2A and 2B.

[0208] The acrylic rubber polymers (R-1) to (R-13) correspond to the polymer (b1) of the present invention. The graft copolymers (B-1) to (B-15) correspond to the polymer (B) of the present invention in which the polymer (b2) of the present invention is graft-polymerized onto the polymer (b1) of the present invention.

[0209] [Table 1A]

[0210] [Table 1B]

[0211] [Table 2A]

[0212] [Table 2B]

[0213] [Examples 1 to 34, Comparative Examples 1 to 5, 7 to 10] [Production of thermoplastic resin composition] The raw materials shown in Tables 3A to 3F were mixed in the ratios shown in the same tables. The mixture was then melt-kneaded at 250°C using a twin-screw extruder (model name "TEX44, Japan Steel Works") and pelletized. The obtained resin composition was used to carry out the following measurements and evaluations. The results are shown in Tables 3A to 3F. The Charpy impact strength was evaluated for Examples 1, 9, 29, and 32 and Comparative Examples 9 to 10, and the results are shown in Table 4. The (F-1) and (F-2) used in Examples 15 to 17 are as follows. (F-1): Nittobo Glass Fiber Chopped Strand "CSF3PE-331ST" (F-2): Carbon fiber "CFU-HC / HT" manufactured by Nippon Polymer Co., Ltd.

[0214] For the obtained thermoplastic resin composition, the proportion of aromatic vinyl compound (ST) units in the raw materials used and the content of ST units in the thermoplastic resin composition calculated from the blending ratio of the raw materials used are as shown in Tables 3A to 3F.

[0215] [Evaluation method] <Logarithmic decrement δ> A test piece measuring 13mm x 125mm x 3mm was molded, one end of the test piece was fixed at 17mm, and the other end was vibrated so that the initial displacement was 10mm, and a free vibration waveform was obtained with the horizontal axis representing time and the vertical axis representing displacement. The logarithmic damping factor δ was calculated from the following formula. Vibration data was logged using an OROS FFT analyzer "OR34". Logarithmic decrement δ=(1 / m)×ln(αn / αn+m) δ: logarithmic decay rate m: The period to use for the calculation αn: nth amplitude value αn+m: Amplitude value of the n+mth period counting from the period having the nth amplitude value

[0216] <Vibration transmissibility (1st mode)> The vibration transmissibility of the test specimen was measured using a vibration exciter "K2007E01" manufactured by The Modal Shop and an FFT analyzer "OR34" manufactured by OROS. A test piece measuring 13 mm x 125 mm x 3 mm was molded, and a hole with a diameter of 5 mm was drilled at the center 7 mm from the end on one side of the test piece, and the piece was fixed to the vibrator with an M5 bolt. The acceleration a0 [m / sec] at the excitation point (fixed side of the sample) when the vibrator is excited with a sweep signal with a frequency of 10 Hz to 4000 Hz 2 ] and the acceleration a1 [m / sec 2 The sweep signal refers to a signal that changes from a low frequency to a high frequency at a constant speed. The vibration transmissibility was calculated using the following formula. Vibration transmissibility [times] = a1 / a0 Vibration transmissibility means the value at the resonance point (first mode).

[0217] <mvr> The melt volume flow rate was measured in accordance with ISO1133 at a temperature of 220°C or 240°C under a load of 10 kg.

[0218] <Charpy impact strength> The Charpy impact strength (strike direction: edgewise) was measured at a test temperature of 23°C in accordance with ISO179.

[0219] <Tensile yield stress> Measured according to ISO527.

[0220] <Flexural modulus (rigidity)> Measured according to ISO178.

[0221] <Deflection temperature under load> Measurements were performed under a load of 1.8 MPa in accordance with ISO 75.

[0222] <Rockwell hardness> Measured in accordance with ISO2039.

[0223] <Gloss> 100 parts of pellets of each thermoplastic resin composition and 0.8 parts of carbon black were mixed using a Henschel mixer, and the mixture was fed to an extruder heated to 250°C and kneaded to obtain black pellets. The black pellets were injection molded under conditions of a cylinder temperature of 240°C, a mold temperature of 60°C, and an injection rate of 20g / sec to obtain a plate-shaped molded body having a length of 100mm, a width of 100mm, and a thickness of 3mm. Using a "Gloss Meter VG7000" manufactured by Nippon Denshoku Industries Co., Ltd., the reflectance (%) of the surface of the molded body at an incident angle of 60° and a reflection angle of 60° was measured in accordance with ISO2813. The higher the reflectance, the better the surface appearance.

[0224] <Peeling> The pellets of the thermoplastic resin composition obtained by melt kneading were injection molded using a Japan Steel Works J35AD injection molding machine at a cylinder temperature of 250°C, injection pressure of 70 MPa, and mold temperature of 50°C to obtain a molded plate of 55 mm x 80 mm x 2.4 mm thick. This molded plate had a film gate 50 mm wide and 1 mm thick on the short side. This gate cut portion was visually observed to check for the presence (×) or absence (○) of peeling.

[0225] [Table 3A]

[0226] [Table 3B]

[0227] [Table 3C]

[0228] [Table 3D]

[0229] [Table 3E]

[0230] [Table 3F]

[0231] [Table 4]

[0232] From the above results, it can be seen that the thermoplastic resin compositions of the examples, which contain the vibration-damping additive made of the polymer (B) of the present invention, are excellent not only in vibration damping effect but also in resonance suppression effect, have good gloss, are free from the peeling phenomenon that has been a problem in the past, and have excellent appearance. On the other hand, the thermoplastic resin composition of the comparative example in which a (meth)acrylic acid ester-based polymer not satisfying the requirements of the present invention was used as a vibration-damping material was inferior in both vibration reducing effect and resonance suppressing effect. In Comparative Examples 9 and 10, in which a conventional thermoplastic elastomer was used as the vibration-damping material, the logarithmic decrement of the vibration-damping property was insufficient, and in particular the vibration transmissibility indicating resonance was poor, and the peelability was also poor.

[0233] Although the present invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application No. 2024-031500, filed on March 1, 2024, the entirety of which is incorporated by reference.< / mvr>

Claims

1. A vibration-damping material comprising a polymer (B) having a polymer (b1) having a glass transition temperature of -10°C to 30°C and a polymer (b2) different from the polymer (b1), The polymer (b1) is a polymer obtained without using a crosslinking agent or using 0.67 parts by mass or less of a crosslinking agent per 100 parts by mass of the polymer (b1), The vibration-damping material of the polymer (B) has a degree of swelling of the THF-insoluble matter of 900% or more, as measured by the following method. <Method of measuring swelling degree> The polymer (B) is immersed in tetrahydrofuran (THF) for 24 hours, and then the insoluble matter separated by centrifugation is vacuum dried and the weight (weight b) is measured. The resulting THF-insoluble matter is immersed again in THF for 24 hours, after which the weight of the sample swollen with THF (weight c) is measured, and the degree of swelling of the THF-insoluble matter is calculated according to the following formula. Swelling degree (%) = c / b × 100

2. The polymer (b1) has a temperature (peak temperature) showing a peak value of the primary dispersion of Tan δ measured by the following method of 3° C. to 45° C., and the peak intensity of the peak value is 1.900 or more. <Method of measuring Tan δ> The polymer (b1) is molded into a sheet having a thickness of 1.0 to 1.1 mm by a heat press set at a temperature of 150° C., and a measurement sample is prepared by cutting out a piece having a length of 36 mm and a width of 10 mm from the sheet. Using the following dynamic viscoelasticity measuring device, 8 mm portions on both ends of the long sides of the measurement sample are fixed with a tensile jig, Tan δ is measured under the following conditions, and the peak temperature and peak strength are determined. Measuring device: Dynamic viscoelasticity measuring device ("DMA850" manufactured by TA Instruments) Mode: Tensile Frequency: 1Hz Heating rate: 5° C. / min Measurement temperature: -60~+60℃

3. The polymer (b1) has a temperature (peak temperature) showing a peak value of the main dispersion of Tan δ measured by the Tan δ measurement method of 3 ° C. to 45 ° C., and the peak intensity of the peak value is 1.950 or more. The vibration-damping material according to claim 2.

4. 2. The vibration-damping material according to claim 1, wherein the polymer (B) has a swelling degree of the THF-insoluble matter measured by the swelling degree measuring method of 1000% or more.

5. The vibration-damping material according to claim 1 , wherein the polymer (b1) contains a structural unit derived from an acrylic acid ester compound and a structural unit derived from a methacrylic acid ester compound.

6. 2. The vibration-damping material according to claim 1, wherein the polymer (b2) contains one or more structural units selected from the group consisting of structural units derived from a methacrylic acid ester compound, structural units derived from an aromatic vinyl compound, and structural units derived from a vinyl cyanide compound.

7. The vibration-damping material according to claim 1 , wherein the polymer (b2) is bonded to at least a portion of the polymer (b1).

8. A thermoplastic resin composition comprising 10 to 90 parts by mass of the vibration-damping material described in claim 1 and 10 to 90 parts by mass of a resin component (A) containing a thermoplastic resin different from the vibration-damping material, the total amount being 100 parts by mass.

9. A thermoplastic resin composition comprising a resin component (A) containing a thermoplastic resin and a vibration-damping material, The thermoplastic resin composition has at least one glass transition temperature in the range of −10° C. to 30° C., The vibration-damping material is a vibration-damping material comprising a polymer (B) having a polymer (b1) having a glass transition temperature of −10° C. to 30° C. and a polymer (b2) different from the polymer (b1), The polymer (b1) is a polymer obtained without using a crosslinking agent or using 0.67 parts by mass or less of a crosslinking agent per 100 parts by mass of the polymer (b1), The polymer (B) is a vibration-damping material having a degree of swelling of a THF-insoluble matter measured by the following method of 900% or more, The thermoplastic resin composition has a vibration transmissibility (first mode) of 19 times or less as measured by the following method. <Method of measuring swelling degree> The polymer (B) is immersed in tetrahydrofuran (THF) for 24 hours, and then the insoluble matter separated by centrifugation is vacuum dried and the weight (weight b) is measured. The resulting THF-insoluble matter is immersed again in THF for 24 hours, after which the weight of the sample swollen with THF (weight c) is measured, and the degree of swelling of the THF-insoluble matter is calculated according to the following formula. Swelling degree (%) = c / b × 100 <Vibration transmissibility (1st mode)> A test piece of 13 mm x 125 mm x 3 mm is molded using the thermoplastic resin composition, a hole of 5 mm diameter is drilled at the center on one side of the test piece at a position 7 mm from the end, and the test piece is fixed to a vibrator with an M5 bolt. The acceleration a0 [m / sec] at the excitation point (fixed side of the test piece) when the vibrator is excited with a sweep signal having a frequency of 10 Hz to 4000 Hz ２ ] and the acceleration a1 [m / sec] at the measurement point (opposite side of the test piece fixing) ２ ] is measured, and the vibration transmissibility is calculated as the value at the resonance point (first mode) using the following formula. Vibration transmissibility [times] = a1 / a0

10. The thermoplastic resin composition according to claim 9, wherein the degree of swelling of the THF-insoluble matter in the thermoplastic resin composition is 900% or more as measured by the following method. <Method of measuring swelling degree> The thermoplastic resin composition is immersed in tetrahydrofuran (THF) for 24 hours, and then centrifugal separation is performed to separate the insoluble matter, which is then vacuum dried and the weight (weight b) is measured. The resulting THF-insoluble matter is immersed again in THF for 24 hours, after which the weight of the sample swollen with THF (weight c) is measured, and the degree of swelling of the THF-insoluble matter is calculated according to the following formula. Swelling degree (%) = c / b x 100

11. The vibration-damping property imparting material has a temperature (peak temperature) showing a peak value of the main dispersion of Tan δ measured by the following method of 3 ° C. to 45 ° C., and the peak value, which is a peak intensity, is 1.900 or more. The thermoplastic resin composition according to claim 9, comprising a polymer (b1). <Method of measuring Tan δ> The polymer (b1) is molded into a sheet having a thickness of 1.0 to 1.1 mm by a heat press set at a temperature of 150° C., and a measurement sample is prepared by cutting out a piece having a length of 36 mm and a width of 10 mm from the sheet. Using the following dynamic viscoelasticity measuring device, 8 mm portions on both ends of the long sides of the measurement sample are fixed with a tensile jig, Tan δ is measured under the following conditions, and the peak temperature and peak strength are determined. Measuring device: Dynamic viscoelasticity measuring device ("DMA850" manufactured by TA Instruments) Mode: Tensile Frequency: 1Hz Heating rate: 5° C. / min Measurement temperature: -60~+60℃

12. The vibration-damping material is A polymer (b1) having a structural unit derived from an acrylic acid ester compound and a structural unit derived from a methacrylic acid ester compound and having a glass transition temperature of −10° C. to 30° C.; A vibration-damping material comprising a polymer (B) having a polymer (b2) containing one or more structural units selected from the group consisting of a structural unit derived from a methacrylic acid ester compound, a structural unit derived from an aromatic vinyl compound, and a structural unit derived from a vinyl cyanide compound, The polymer (b1) is a vibration-damping material having a temperature (peak temperature) showing a peak value of the main dispersion of Tan δ measured by the following method of 3 ° C. to 45 ° C., and a peak intensity which is the peak value of 1.950 or more. The thermoplastic resin composition according to claim 9. <Method of measuring Tan δ> The polymer (b1) is molded into a sheet having a thickness of 1.0 to 1.1 mm by a heat press set at a temperature of 150° C., and a measurement sample is prepared by cutting out a piece having a length of 36 mm and a width of 10 mm from the sheet. Using the following dynamic viscoelasticity measuring device, 8 mm portions on both ends of the long sides of the measurement sample are fixed with a tensile jig, Tan δ is measured under the following conditions, and the peak temperature and peak strength are determined. Measuring device: Dynamic viscoelasticity measuring device ("DMA850" manufactured by TA Instruments) Mode: Tensile Frequency: 1Hz Heating rate: 5° C. / min Measurement temperature: -60~+60℃

13. The thermoplastic resin composition according to claim 12, wherein the polymer (B) has a degree of swelling of the THF-insoluble matter measured by the following method of 1000% or more. <Method of measuring swelling degree> The polymer (B) is immersed in tetrahydrofuran (THF) for 24 hours, and then the insoluble matter separated by centrifugation is vacuum dried and the weight (weight b) is measured. The resulting THF-insoluble matter is immersed again in THF for 24 hours, after which the weight of the sample swollen with THF (weight c) is measured, and the degree of swelling of the THF-insoluble matter is calculated according to the following formula. Swelling degree (%) = c / b × 100

14. The thermoplastic resin composition according to claim 12, wherein the polymer (b2) is bonded to at least a portion of the polymer (b1).

15. The thermoplastic resin composition according to claim 9 , wherein the thermoplastic resin comprises an acrylic resin.

16. The thermoplastic resin composition according to claim 9, wherein the thermoplastic resin comprises one or more selected from the group consisting of styrene-based resins, polybutylene terephthalate-based resins, polyamide-based resins, and polycarbonate-based resins.

17. The thermoplastic resin composition according to claim 9, comprising 90 to 10 parts by weight of the resin component (A) and 10 to 90 parts by mass of the vibration-damping material, the total amount being 100 parts by mass.

18. A molded article obtained by molding the thermoplastic resin composition according to any one of claims 8 to 17.

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