JP2020152810A - Thermoplastic polymer composition, fiber and vibration-damping material - Google Patents

Abstract

To provide a thermoplastic polymer composition capable of obtaining a molding which is excellent in molding workability such as melt-spinning, and is excellent in heat resistance and vibration-damping property.SOLUTION: A thermoplastic polymer composition contains a conjugated diene-based polymer (A), a thermoplastic resin (B) and an aliphatic hydrocarbon resin (C), in which when the total content of the component (A), the component (B) and the component (C) is 100 pts.mass, a content ratio of the component (A) is 10-80 pts.mass, a content ratio of the component (B) is 10-65 pts.mass, and a content ratio of the component (C) is 1-39 pts.mass.SELECTED DRAWING: None

Description

The present invention relates to a thermoplastic polymer composition, and a fiber and a damping material composed of a molded product of the composition.

Conventionally, various vibration damping materials and soundproofing materials have been used in the fields of building materials such as houses, the fields of transportation such as automobiles, ships and aircraft, and the fields of machinery, electricity and electronics. Generally, as the material of these vibration damping materials and soundproofing materials, those made of asphalt-based, synthetic rubber-based, and synthetic resin-based materials are used.

Most asphalt-based products are made by blending rubber or thermoplastic elastomer with asphalt, but they have high adhesiveness and low heat resistance, and it is difficult to uniformly disperse rubber and thermoplastic elastomer in asphalt. There are problems such as difficulty. In addition, synthetic rubber has a problem in processability because it requires a complicated compounding and vulcanization process, and it is also difficult to make it into a fiber. As a synthetic resin system, vinyl chloride resin is widely used. For vinyl chloride resin, the hardness and mechanical properties can be set in a wide range by adjusting the amount of plasticizer and filler added, and a material with excellent flexibility, vibration damping, abrasion resistance, and scratch resistance can be used. Can be provided. However, due to concerns about weight reduction of materials and the high burden on the environment during incineration and decomposition of the resin in recent years, there is an increasing demand for replacing vinyl chloride resin with other materials.

In response to such demands, a technique of using a thermoplastic elastomer and a technique of using a mixture of a thermoplastic elastomer and a thermoplastic resin have been studied (see, for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 2003-238617

However, it has been difficult to apply the technique using a thermoplastic elastomer to automobile applications and the like where the temperature becomes high due to insufficient heat resistance. Further, in the technique of using a mixture of a thermoplastic elastomer and a thermoplastic resin, since the compatibility between the conventional thermoplastic elastomer and the thermoplastic resin is low, disconnection is likely to occur in melt spinning, and the application to fibers Was limited.

Therefore, some aspects of the present invention provide a thermoplastic polymer composition capable of obtaining a molded product having excellent molding processability such as melt spinning and excellent heat resistance and vibration damping property. In addition, some aspects of the present invention provide fibers with excellent heat resistance and vibration damping properties. Further, some aspects of the present invention provide a damping material having excellent heat resistance and damping properties.

The present invention has been made to solve at least a part of the above-mentioned problems, and can be realized as any of the following aspects.

One aspect of the thermoplastic polymer composition according to the present invention is
Containing a conjugated diene polymer (A), a thermoplastic resin (B), and an alicyclic hydrocarbon resin (C), the component (A), the component (B), and the component (C) When the total amount of the components (A) is 100 parts by mass, the content ratio of the component (A) is 10 to 80 parts by mass, the content ratio of the component (B) is 10 to 65 parts by mass, and the component (C). ) Is 1 to 39 parts by mass.

In one aspect of the thermoplastic polymer composition,
The conjugated diene-based polymer (A) can be one containing a block having a repeating unit derived from an aromatic alkenyl compound and hydrogenated.

In any aspect of the thermoplastic polymer composition
The content ratio of the repeating unit derived from the aromatic alkenyl compound in the conjugated diene polymer (A) can be 40% by mass or less.

In any aspect of the thermoplastic polymer composition
The aromatic alkenyl compound can be styrene.

In any aspect of the thermoplastic polymer composition
The thermoplastic resin (B) can be a propylene-based resin.

In any aspect of the thermoplastic polymer composition
The alicyclic hydrocarbon resin (C) can be an alicyclic saturated hydrocarbon resin having a softening point of 100 ° C. or higher.

In any aspect of the thermoplastic polymer composition
The melt flow rate (MFR) under the conditions of 230 ° C. and a load of 21 N can be 10 to 70 g / 10 minutes.

One aspect of the fiber according to the present invention is
It comprises a molded product of the thermoplastic polymer composition of any of the above embodiments.

One aspect of the damping material according to the present invention is
It comprises a molded product of the thermoplastic polymer composition of any of the above embodiments.

According to the thermopolymer composition according to the present invention, a molded product (for example, a fiber or a vibration damping material) having excellent molding processability such as melt spinning and excellent heat resistance and vibration damping property can be obtained.

Hereinafter, preferred embodiments according to the present invention will be described in detail. It should be noted that the present invention is not limited to the embodiments described below, and should be understood to include various modifications implemented without changing the gist of the present invention.

In the present specification, the numerical range described by using "~" means that the numerical values described before and after "~" are included as the lower limit value and the upper limit value.

In the present specification, the conjugated diene polymer (A) is referred to as "component (A)", the thermoplastic resin (B) is referred to as "component (B)", and the alicyclic hydrocarbon resin (C) is used. May be abbreviated as "component (C)" and the antioxidant (D) may be abbreviated as "component (D)".

1. 1. Thermoplastic Polymer Composition The thermoplastic polymer composition according to the embodiment of the present invention includes a conjugated diene polymer (A), a thermoplastic resin (B), and an alicyclic hydrocarbon resin (C). , Contain. Hereinafter, each component contained in the thermoplastic polymer composition according to the present embodiment will be described.

1.1. Conjugated diene polymer (A)
The thermoplastic polymer composition according to this embodiment contains a conjugated diene-based polymer (A). Since the component (A) has good compatibility with the component (B) and the component (C), it is considered that the component (A) exhibits good processability in a molding process such as melt spinning. Further, in the molded product obtained by molding the thermoplastic polymer composition according to the present embodiment, the component (A) can improve tan δ, which is an index of vibration damping property.

Component (A) contains a repeating unit derived from a conjugated diene compound. Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 2-methylpropene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-octadien, and 1, , 3-Hexadiene, 1,3-Cyclohexadiene, 4,5-diethyl-1,3-octadien, 3-butyl-1,3-octadiene, milsen, farnesene, chloroprene and the like. Among these, 1,3-butadiene and isoprene are preferable. These conjugated diene compounds may be used alone or in combination of two or more.

The component (A) may have a repeating unit derived from a compound other than the conjugated diene compound. As such a compound, an aromatic alkenyl compound is preferable.

Specific examples of the aromatic alkenyl compound include styrene, tert-butyl styrene, α-methyl styrene, p-methyl styrene, divinyl benzene, 1,1-diphenyl styrene and the like. Of these, styrene is particularly preferable. These aromatic alkenyl compounds may be used alone or in combination of two or more.

When the component (A) has a repeating unit derived from the conjugated diene compound and a repeating unit derived from the aromatic alkenyl compound, the content ratio of the repeating unit derived from the aromatic alkenyl compound in the component (A) is 40. It is preferably 1% by mass or less, and more preferably 35% by mass or less. Further, the content ratio of the repeating unit derived from the aromatic alkenyl compound in the component (A) is preferably 1% by mass or more, more preferably 5% by mass or more, and 10% by mass or more. Is particularly preferable. When the content ratio of the repeating unit derived from the aromatic alkenyl compound in the component (A) is within the above range, the moldability of melt spinning and the like is further improved. The content ratio of the repeating unit derived from the aromatic alkenyl compound in the component (A) can be measured by ^{1 1} H-NMR.

The component (A) is preferably a block-type copolymer in order to enhance compatibility with the component (B). Examples of the polymer block include the following polymer blocks A to D.

A block: A polymer block derived from an aromatic alkenyl compound and having a repeating unit amount of 80% by mass or more.
B block: A polymer block derived from a conjugated diene compound having a repeating unit amount of 80% by mass or more and a vinyl bond content of less than 30 mol%.
C block: A polymer block having a repeating unit amount derived from a conjugated diene compound of 80% by mass or more and a vinyl bond content of 30 mol% or more and 90 mol% or less.
D block: A random copolymer block of a repetition derived from a conjugated diene compound and a repetition derived from an aromatic alkenyl compound, which is a polymer block other than the above A to C.

The "vinyl bond content" in the present invention is a repetition derived from a conjugated diene compound incorporated in a polymer before hydrogenation in the form of 1,2, 3,4 and 1,4 bonds. Of the units, it is the total ratio (based on mol%) of the units incorporated in 1, 2 bonds and 3, 4 bonds. The vinyl bond content (1,2 bond content and 3,4 bond content) can be calculated by an infrared absorption spectrum method (Morero method).

When the component (A) has the above C block, the entanglement and compatibility of the molecules with the component (C) are improved, so that the molding processability of melt spinning and the like can be improved and the fiber breakage can be suppressed. become. Further, when the C block is hydrogenated, the entanglement and compatibility of the molecule with the component (C) are remarkably improved, which is more preferable.

Further, the component (A) preferably contains a block having a repeating unit derived from an aromatic alkenyl compound and is hydrogenated. When the component (A) contains a block having a repeating unit derived from an aromatic alkenyl compound, the entanglement and compatibility of the molecule with the component (C) are improved. Further, since the component (A) is hydrogenated, the molecular entanglement and compatibility with the component (B) are improved. As a result, the entanglement and compatibility of the molecules of the three components (A), (B) and (C) are remarkably improved, and it is considered that good processability is exhibited in molding such as melt spinning. ..

The hydrogenation rate of the component (A) is preferably 60% or more, more preferably 80% or more of a double bond such as a vinyl bond. The hydrogenation rate can be measured by ^{1 1} H-NMR.

The component (A) may have at least one functional group selected from the group consisting of an amino group, a carboxy group, an oxazoline group and an acid anhydride structure. In the present specification, the "amino group" refers to a primary amino group (-NH ₂ ), a secondary amino group (-NHR, where R is a hydrocarbon group) and a tertiary amino group (-NRR', where R). , R'refers to any one of the hydrocarbon groups). As used herein, the term "carboxy group" is a concept that includes not only -COOH but also -COOM (M is a monovalent metal ion). Specific examples of the "acid anhydride structure" include acetic anhydride structure, propionic anhydride structure, oxalic anhydride structure, succinic anhydride structure, phthalic anhydride structure, maleic anhydride structure, and benzoic anhydride structure. The object structure can be mentioned. The amino group, carboxy group, oxazoline group and acid anhydride structure may each be protected by a protecting group.

When the component (A) has at least one functional group selected from the group consisting of an amino group, a carboxy group, an oxazoline group and an acid anhydride structure, an amino group, a carboxy group, an oxazoline group and an acid per molecular chain The total amount of the anhydride structure is preferably 0.1 or more, more preferably 0.3 or more, and particularly preferably 0.5 or more. When the total amount of the amino group, carboxy group, oxazoline group and acid anhydride structure per molecular chain of the component (A) is within the above range, the compatibility with the component (B) is improved. It is considered that good processability is exhibited in the molding process.

The weight average molecular weight (Mw) of the component (A) is preferably 10,000 or more, more preferably 20,000 or more and 3 million or less, and particularly preferably 30,000 or more and 2 million or less. The weight average molecular weight (Mw) is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

The melt flow rate (MFR) of the component (A) measured at 230 ° C. and a load of 21 N is preferably 10 to 70 g / 10 minutes, more preferably 15 to 60 g / 10 minutes, and 18 It is particularly preferably ~ 55 g / 10 minutes. When the MFR measured at 230 ° C. and a load of 21 N is within the above range, the load at the time of molding tends to be small and the moldability of melt spinning or the like tends to be good, which is preferable. The melt flow rate (MFR) can be determined by measuring with a load of 230 ° C. and 21 N according to the test method described in "JIS K 7210-1: 2014".

The content ratio of the component (A) in the thermoplastic polymer composition according to the present embodiment is 10 to 80 when the total amount of the component (A), the component (B) and the component (C) is 100 parts by mass. It is parts by mass, preferably 15 to 80 parts by mass, more preferably 20 to 80 parts by mass, and particularly preferably 25 to 75 parts by mass. When the content ratio of the component (A) in the thermoplastic polymer composition according to the present embodiment is within the above range, tan δ, which is an index of vibration damping property, is improved in the molded product obtained by molding the composition. It can be made easier.

The component (A) can be produced, for example, according to the method described in Japanese Patent No. 5402112, Japanese Patent No. 4840140, International Publication No. 2003/029299, International Publication No. 2014/014502, and the like. Further, as the component (A), a commercially available product can also be used. Examples of commercially available products of the component (A) include product names "DR8600", "DR1321", and "DR8913" manufactured by JSR Corporation; product names "Tough Tech M1913" and "Tough Tech MP10" manufactured by Asahi Kasei Chemicals Co., Ltd. Be done.

1.2. Thermoplastic resin (B)
The thermoplastic polymer composition according to the present embodiment contains a thermoplastic resin (B). Examples of the component (B) include olefin resins; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polylactic acid; acrylic resins; styrene resins such as polystyrene, AS resin, and ABS resin; nylon 6, nylon 6. , 6, Nylon 12, Semi-aromatic polyamide (Nylon 6T, Nylon 6I, Nylon 9T), Polyamide such as modified polyamide; Polycarbonate, Polyacetal, Fluororesin, Modified polyphenylene ether, Polyphenylene sulfide, Polyester elastomer, Polyallylate, Liquid crystal polymer (Whole aromatic type, semi-aromatic type), polysulfone, polyethersulfone, polyether ether ketone, polyetherimide, polyamideimide, polyimide, polyurethane resin and the like can be mentioned. These components (B) may be used alone or in combination of two or more.

Among these components (B), an olefin resin is preferable from the viewpoint of improving compatibility with the component (A). Examples of the olefin-based resin include homopolymers of α-olefins having about 2 to 8 carbon atoms such as ethylene, propylene and 1-butene; these α-olefins and ethylene, propylene, 1-butene and 3-methyl. -1-butene, 1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 1-hexene, 4-methyl-1-hexene, 1-hexene, 1-octene, 1-decene , 1-octadecene and other binary or ternary copolymers with other α-olefins having about 2 to 18 carbon atoms can be mentioned.

Specific examples of the olefin resin include an ethylene homopolymer, an ethylene-propylene copolymer, an ethylene-1-butene copolymer, an ethylene-propylene-1-butene copolymer, and an ethylene-4-methyl-1. Ethylene resins such as −pentene copolymers, ethylene-1-hexene copolymers, ethylene-1-heptene copolymers, ethylene-1-octene copolymers; propylene homopolymers, propylene-ethylene copolymers, A propylene resin such as a propylene-ethylene-1-butene copolymer; a 1-butene resin such as a 1-butene homopolymer, a 1-butene-ethylene copolymer, a 1-butene-propylene copolymer; Examples thereof include 4-methyl-1-pentene-based resins such as methyl-1-pentene homopolymers and 4-methyl-1-pentene-ethylene copolymers.

These olefin resins may be used alone or in combination of two or more. Among these, ethylene-based resins and propylene-based resins are preferable, propylene-based resins are more preferable, and propylene homopolymers are particularly preferable. In particular, the component (A) is a C block (that is, a polymer block having a repeating unit amount derived from a conjugated diene compound of 80% by mass or more and a vinyl bond content of 30 mol% or more and 90 mol% or less). In the case of the block polymer having the propylene resin, the propylene resin is preferable in that the compatibility with the component (A) is particularly good. In this case, the vinyl bond content of the C block is more preferably 50 mol% or more and 90 mol% or less. Further, when the component (A) is hydrogenated, compatibility with the propylene resin and molecular entanglement are remarkably improved, which is preferable.

The weight average molecular weight (Mw) of the component (B) is preferably 5,000 or more and 1 million or less in order to suppress disconnection in molding processing such as melt spinning. Further, the molecular weight distribution (Mw / Mn = weight average molecular weight / number average molecular weight) of the component (B) is preferably 1 or more and 10 or less.

The content ratio of the component (B) in the thermoplastic polymer composition according to the present embodiment is 10 to 65 when the total amount of the component (A), the component (B) and the component (C) is 100 parts by mass. It is parts by mass, preferably 12 to 65 parts by mass, more preferably 15 to 65 parts by mass, and particularly preferably 20 to 60 parts by mass. When the content ratio of the component (B) in the thermoplastic polymer composition according to the present embodiment is within the above range, tan δ, which is an index of vibration damping property, is improved in the molded product obtained by molding the composition. It can be made easier.

1.3. Alicyclic hydrocarbon resin (C)
The thermoplastic polymer composition according to this embodiment contains an alicyclic hydrocarbon resin (C). The component (C) has very good compatibility with the component (A). It was found that the addition of the component (C) dramatically improves the workability in molding processes such as melt spinning. In addition, the component (C) has the effect of increasing the glass transition temperature (Tg) of the component (A), and the Tg of the thermoplastic polymer composition according to the present embodiment can be increased to around room temperature. As a result, in the molded product obtained by molding the thermoplastic polymer composition according to the present embodiment, heat resistance can be imparted and tan δ, which is an index of vibration damping property, can be further improved.

The component (C) is preferably a hydrogenated alicyclic saturated hydrocarbon resin. By using the hydrogenated alicyclic saturated hydrocarbon resin as the component (C), the entanglement and compatibility of the molecules with the component (A) and the component (B) are remarkably improved, and molding, particularly melting. It is considered that good processability is exhibited in spinning. Further, by adding the component (C), the heat resistance of the molded product obtained by molding the thermoplastic polymer composition according to the present embodiment is also improved.

The softening point of the component (C) is preferably 100 to 150 ° C., more preferably 105 to 145 ° C., and particularly preferably 110 to 140 ° C. When the softening point of the component (C) is within the above range, the Tg of the thermoplastic polymer composition according to the present embodiment can be increased to around room temperature, and in the molded product obtained by molding the composition. , Heat resistance is imparted, and tan δ, which is an index of vibration damping property, can be further improved. The softening point of the component (C) can be measured according to "JIS K2207 6.4 softening point test method (ring ball method)".

The component (C) requires a petroleum resin obtained by (co) polymerizing C5 (aliphatic), C9 (aromatic), C5 / C9, dicyclopentadiene (DCPD), etc. It can be obtained by hydrogenating accordingly.

As the component (C), a commercially available product can also be used. For example, "Arcon" series manufactured by Arakawa Chemical Industry Co., Ltd., "Quinton (registered trademark) 1000" series manufactured by Nippon Zeon Corporation, and JXTG Energy Co., Ltd. "T-REZ H" series, "Neopolymer" series and the like.

The content ratio of the component (C) in the thermoplastic polymer composition according to the present embodiment is 1 to 39 when the total amount of the component (A), the component (B) and the component (C) is 100 parts by mass. It is parts by mass, preferably 3 to 38 parts by mass, more preferably 5 to 35 parts by mass, and particularly preferably 10 to 30 parts by mass. When the content ratio of the component (C) in the thermoplastic polymer composition according to the present embodiment is within the above range, the processability is dramatically improved in molding processing such as melt spinning, and the composition can be molded. In the molded product, heat resistance is imparted, and tan δ, which is an index of vibration damping property, can be easily improved.

1.4. Anti-aging agent (D)
The thermoplastic polymer composition according to the present embodiment may contain an antiaging agent (D). By containing the component (D) in the thermoplastic polymer composition according to the present embodiment, thermal decomposition is suppressed and molding at a high temperature can be withstood, and in the molded product obtained by molding the composition. , Heat resistance may be improved.

The component (D) includes hindered amine compounds, hydroquinone compounds, hindered phenol compounds, sulfur-containing compounds, phosphorus-containing compounds, naphthylamine compounds, diphenylamine compounds, p-phenylenediamine compounds, quinoline compounds, and hydroquinone derivatives. Systematic compounds, monophenolic compounds, bisphenol compounds, trisphenol compounds, polyphenol compounds, thiobisphenol compounds, hindered phenol compounds, phosphite ester compounds, imidazole compounds, nickel dithiocarbamate compounds, Examples include phosphoric acid compounds. These components (D) may be used alone or in combination of two or more.

As the component (D), a commercially available product can also be used, and for example, trade names “ADEKA STAB AO-60”, “ADEKA STAB 2112”, “ADEKA STAB AO-412S” and the like manufactured by ADEKA can be used.

The content ratio of the component (D) in the thermoplastic polymer composition according to the present embodiment is preferably 0 when the total amount of the component (A), the component (B) and the component (C) is 100 parts by mass. It is 0.01 to 10 parts by mass, more preferably 0.02 to 8 parts by mass. When the content ratio of the component (D) in the thermoplastic polymer composition according to the present embodiment is within the above range, thermal decomposition is suppressed and molding at a high temperature can be withstood, and the composition can be obtained by molding. In the molded product, the heat resistance may be improved.

1.5. Other Components The thermoplastic polymer composition according to the present embodiment may contain other components other than the above components. Other components include moisture, metal atoms, antioxidants, weather resistant agents, light stabilizers, heat stabilizers, UV absorbers, antibacterial / antifungal agents, deodorants, conductivity imparting agents, dispersants, softeners. , Plasticizers, crosslinkers, co-crosslinkers, vulcanizers, vulcanization aids, foaming agents, foaming aids, colorants, flame retardants, nucleating agents, neutralizers, lubricants, antiblocking agents, dispersants, Examples thereof include fluidity improvers, mold release agents, fillers, inorganic fibers, organic fibers and the like.

1.6. Melt flow rate (MFR) of the composition
The melt flow rate (MFR) of the thermoplastic polymer composition according to the present embodiment measured at 230 ° C. and a load of 21 N is preferably 10 to 100 g / 10 minutes, preferably 10 to 8 minutes.
It is more preferably 0 g / 10 minutes, and particularly preferably 10 to 70 g / 10 minutes. When the MFR measured at 230 ° C. and a load of 21 N is within the above range, the load at the time of molding tends to be small and the moldability of melt spinning or the like tends to be good, which is preferable. The melt flow rate (MFR) can be determined by measuring with a load of 230 ° C. and 21 N according to the test method described in "JIS K 7210-1: 2014".

1.7. Method for Producing Composition The thermoplastic polymer composition according to the present embodiment is produced by mixing or melt-kneading the component (A), the component (B), the component (C), and other components as necessary. can do. The method for producing the composition is not particularly limited, and a known method can be used. For example, it is possible to perform dry blending with various mixers, and a general mixer such as a Banbury mixer, a single-screw screw extruder, a twin-screw screw extruder, a kneader, a multi-screw screw extruder, or a roll is used. A melt-kneading method, a method of dissolving or dispersing and mixing each component, and then heating and removing the solvent are used. In the present embodiment, the melt kneading method using an extruder is preferable from the viewpoint of productivity and good kneading property. The shape of the obtained composition is not particularly limited, and examples thereof include pellets, sheets, strands, and chips. Further, after melt-kneading, it can be directly molded.

2. 2. Molded article The molded article according to the embodiment of the present invention is obtained by molding the above-mentioned thermoplastic polymer composition. As a molding method, a known method can be applied, and for example, a method such as injection molding, extrusion molding, hollow molding, foam molding, press molding, melt spinning and the like can be applied.

Among the molded products according to the present embodiment, fibers obtained by molding the above-mentioned thermoplastic polymer composition by melt spinning are preferable. The above-mentioned thermoplastic polymer composition is extremely excellent in molding processability in melt spinning, and disconnection is unlikely to occur. Examples of the fiber manufacturing method include a method in which the above-mentioned thermoplastic polymer composition melted at a high temperature is discharged from a discharge hole of a spinneret, cooled and solidified, and then spun oil or the like is applied to wind the fiber at high speed. Be done.

Further, as the molded product according to the present embodiment, a foam molded product produced by using the above-mentioned thermoplastic polymer composition is also suitable. When a foamed molded product is obtained by using the above-mentioned thermoplastic polymer composition, the molding method includes a chemical method, a physical method, and the like, and each of the foaming agents such as an inorganic foaming agent and an organic foaming agent. The addition can disperse bubbles inside the material. By using a foam molded product, it is possible to reduce the weight, improve the flexibility, improve the design, and the like. Examples of the inorganic foaming agent include sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, ammonium nitrite, azide compound, sodium hydride, metal powder and the like. Examples of the organic foaming agent include azodicarbonamide, azobisformamide, azobisisobutyronitrile, barium azodicarboxylic acid and the like.

The molded body according to the present embodiment makes use of its characteristics, for example, automobile materials such as automobile interior materials, sound absorbing materials, soundproofing materials, outer panels, housings for household electric appliances, home appliances, packaging materials, building materials, etc. It is suitably used for vibration insulation of civil engineering materials, fishery materials, other industrial materials, information equipment, video equipment, etc.

3. 3. Examples Hereinafter, specific examples of the present invention will be described, but the present invention is not limited to these examples. In addition, "%" in the following production examples, examples and comparative examples is based on mass unless otherwise specified.

3.1. Example 1
3.1.1. Preparation of pellets Pentaerythritol tetrakis [3- (3) as an anti-aging agent (D) with respect to a total of 100 parts by mass of the type, component (A), component (B) and component (C) shown in Table 1. 3,5-Di-tert-butyl-4-hydroxyphenyl) propionate] (trade name "ADEKA STAB AO-60", manufactured by ADEKA) 0.1 parts by mass and tris (2,4-di-tert-butylphenyl) ) Phosphite (trade name "ADEKA STUB 2112", manufactured by ADEKA) was added in an amount of 0.1 part by mass. Next, this mixture is supplied to a twin-screw extruder "KTX30" (model name) manufactured by Kobe Steel, Ltd., melt-kneaded under the conditions of a cylinder temperature of 210 ° C., a screw rotation speed of 300 rpm, and a discharge of 30 kg / h, and has a diameter of 2 mm. , A columnar pellet having a length of 4 mm was obtained.

The produced undried pellets are dried using a dryer (trade name "parallel flow batch dryer", manufactured by Satake Chemical Machinery Co., Ltd.) under the condition of a drying temperature of 60 ° C. until the water content reaches 150 ppm. , The obtained pellets were subjected to molding.

3.1.2. Preparation of molded product (press sheet)
Using the pellets prepared above, a press sheet having a thickness of 1 mm was prepared by a press manufactured by Iwaki Kogyo Co., Ltd. (model IPS37).

3.1.3. Fabrication of molded product (molten spinning)
The pellets produced above are supplied to a multifilament manufacturing apparatus manufactured by Musashino Kikai Co., Ltd., and drawn through a die with a diameter of 0.3 mm and 24 holes under the conditions of a cylinder temperature of 230 ° C., a nozzle temperature of 260 ° C. Fibers were made by winding with a roll.

3.2. Examples 2-9 and Comparative Examples 1-4
In the preparation of the pellet of Example 1, the same as that of Example 1 except that the types and mass parts of the component (A), the component (B) and the component (C) were changed as shown in Table 1. Pellets and molded bodies (press sheets, fibers) were produced.

3.3. Evaluation of Thermoplastic Polymer Composition (1) MFR (Fluidity)
The pellet prepared above was supplied to SemiAutoMeltIndexer3A (model name) manufactured by Toyo Seiki Seisakusho Co., Ltd., and measured under the conditions of a temperature of 230 ° C. and a load of 21N.

(2) Storage elastic modulus E'(heat resistance)
From the press sheet formed above, a strip-shaped test piece having a width of 2 mm and a length of 5 cm was punched out using a punching blade. The obtained strip-shaped test piece was attached to a tensile jig of the viscoelasticity measuring device RSA-GII (model) manufactured by TA Instruments, and the temperature was raised from -70 ° C to 200 ° C under a frequency of 1 Hz and a strain of 0.05%. While measuring the viscoelasticity, the storage elastic modulus E'(MPa) at 150 ° C. was determined. When the storage elastic modulus E'(MPa) at 150 ° C. can be measured, it is judged to be good and is described as "A" in Table 1, and when the test piece melts before reaching 150 ° C., it cannot be measured and is considered defective. Judgment was made and described as "B" in Table 1.

(3) Loss tangent tan δ (vibration damping property)
From the press sheet formed above, a strip-shaped test piece having a width of 2 mm and a length of 5 cm was punched out using a punching blade. The obtained strip-shaped test piece was attached to a tensile jig of the viscoelasticity measuring device RSA-GII (model) manufactured by TA Instruments, and the viscoelasticity at 23 ° C. under a frequency of 1 Hz and a strain of 0.05% was measured. The loss tangent tan δ (without unit) at 23 ° C. was determined.
When the loss tangent tan δ (without unit) at 23 ° C. is 0.10 or more, it is judged as good and described as “A” in Table 1, and when it is less than 0.10, it is judged as defective and “B” in Table 1. ".

(4) Melt spinnability (molding processability)
In the production of the above-mentioned molded product (melt spinning), it is judged that it is good if the molded product can be wound without disconnection for 10 minutes or more after the start of winding, and is described as "A" in Table 1, and the disconnection occurs in less than 10 minutes. When it occurred, it was judged to be defective and "B" was described in Table 1.

(5) Average Fiber Diameter In the production of the above-mentioned molded product (melt spinning), the wound fibers were observed at 30 points with a KEYENCE DIGITAL MICROSCOPE VHX-900 (model), and the average fiber diameter (μm) was determined. ..

3.4. Evaluation Results Table 1 below shows the composition of the thermoplastic polymer compositions prepared in each Example and Comparative Example, and the evaluation results.

In Table 1 above, the abbreviations for each component are as follows.
<Conjugated diene polymer (A)>
-A1: JSR Co., Ltd., hydrogenated conjugated diene block polymer (SEBS block polymer), trade name "DR8600", styrene content 15 parts by mass, vinyl bond content 80 mol%, block content 90% or more-A2: Made by JSR Co., Ltd., hydrogenated conjugated diene block polymer (SEBS block polymer), trade name "DR1321", styrene content 10 parts by mass, vinyl bond content 70 mol%, block content 90% or more ・ A3: JSR Co., Ltd. Manufactured, hydrogenated conjugated diene polymer (SEBS block polymer), trade name "DR8913", styrene content 35 parts by mass, vinyl bond content 70 mol%, block content 90% or more <thermoplastic resin (B)>
-B1: Made by Japan Polypropylene Corporation, polypropylene "Novatec MA04A" (trade name), propylene homopolymer ・ B2: manufactured by SunAllomer Ltd., polypropylene "PLB00A" (trade name), propylene homopolymer <Alicyclic hydrocarbon resin ( C)>
・ C1: "ARKON P-125" (trade name) manufactured by Arakawa Chemical Industry Co., Ltd., softening point 125 ° C.
-C2: Arakawa Chemical Industry Co., Ltd., "ARKON P-140" (trade name), softening point 140 ° C.
<Anti-aging agent (D)>
-D1: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] manufactured by ADEKA, "ADEKA STAB AO-60" (trade name)
-D2: Tris (2,4-di-tert-butylphenyl) phosphite manufactured by ADEKA, "ADEKA STAB 2112" (trade name)

From the evaluation results in Table 1 above, according to the thermoplastic polymer compositions of Examples 1 to 9, a molded product having excellent molding processability (molten spinnability) and excellent heat resistance and vibration damping properties can be obtained. I understand.

The thermoplastic polymer composition of Comparative Example 1 does not contain the component (C). Therefore, the molded product obtained by molding the thermoplastic polymer composition of Comparative Example 1 is inferior in vibration damping property to the molded product obtained by molding the thermoplastic polymer composition of each example. A tendency was observed.

In the thermoplastic polymer composition of Comparative Example 2, the content ratio of the component (B) exceeds the specified amount. Therefore, the molded product obtained by molding the thermoplastic polymer composition of Comparative Example 2 is inferior in vibration damping property to the molded product obtained by molding the thermoplastic polymer composition of each example. A tendency was observed.

In the thermoplastic polymer composition of Comparative Example 3, the content ratio of the component (A) exceeds the specified amount, the content ratio of the component (B) is less than the specified amount, and the content ratio of the component (C) is specified. Less than the amount. Therefore, the thermoplastic polymer composition of Comparative Example 3 has poor molding processability (molten spinnability), and the heat resistance of the molded product obtained by molding the thermoplastic polymer composition of Comparative Example 3 is measured. I couldn't.

The thermoplastic polymer composition of Comparative Example 4 does not contain the component (B). Therefore, the heat resistance of the molded product obtained by molding the thermoplastic polymer composition of Comparative Example 4 could not be measured.

The present invention is not limited to the above embodiment, and various modifications are possible. The present invention includes substantially the same configurations as those described in the embodiments (eg, configurations with the same function, method and result, or configurations with the same purpose and effect). The present invention also includes a configuration in which a non-essential part of the configuration described in the above embodiment is replaced with another configuration. Further, the present invention also includes a configuration that exhibits the same action and effect as the configuration described in the above embodiment, or a configuration that can achieve the same object. Further, the present invention also includes a configuration in which a known technique is added to the configuration described in the above embodiment.

Claims (9)

Containing a conjugated diene polymer (A), a thermoplastic resin (B), and an alicyclic hydrocarbon resin (C),
When the total amount of the component (A), the component (B) and the component (C) is 100 parts by mass, the content ratio of the component (A) is 10 to 80 parts by mass, and the component (B). ) Is 10 to 65 parts by mass, and the content of the component (C) is 1 to 39 parts by mass, a thermoplastic polymer composition. The thermoplastic polymer according to claim 1, wherein the conjugated diene-based polymer (A) contains a block having a repeating unit derived from an aromatic alkenyl compound and is hydrogenated. Composition. The thermoplastic polymer according to claim 1 or 2, wherein the content ratio of the repeating unit derived from the aromatic alkenyl compound in the conjugated diene polymer (A) is 40% by mass or less. Composition. The thermoplastic polymer composition according to claim 2 or 3, wherein the aromatic alkenyl compound is styrene. The thermoplastic polymer composition according to any one of claims 1 to 4, wherein the thermoplastic resin (B) is a propylene-based resin. The thermoplastic according to any one of claims 1 to 5, wherein the alicyclic hydrocarbon resin (C) is an alicyclic saturated hydrocarbon resin having a softening point of 100 ° C. or higher. Polymer composition. The thermoplastic polymer composition according to any one of claims 1 to 6, wherein the melt flow rate (MFR) under the condition of 230 ° C. and a load of 21 N is 10 to 70 g / 10 minutes. .. A fiber comprising a molded product of the thermoplastic polymer composition according to any one of claims 1 to 7. A vibration damping material comprising a molded product of the thermoplastic polymer composition according to any one of claims 1 to 7.