JP6457370B2 - Pellets and manufacturing method thereof - Google Patents

Description

  The present invention relates to a pellet and a method for producing the pellet.

  Polyphenylene ether is a resin that is suitably used in various applications such as automobiles and OA because it has features such as heat resistance, excellent electrical characteristics, and low specific gravity. However, since polyphenylene ether alone is inferior in moldability, it is often used as an alloy with other resins.

  As such an alloy, it is known that an alloy obtained by adding a small amount of polyphenylene ether to another resin is used as a modifier for a polyolefin resin (particularly, a polypropylene resin) (see Patent Document 1).

  When the modifier containing a small amount of polyphenylene ether described in Patent Document 1 is used for polyolefin resin (especially polypropylene resin), etc., there is a risk of vent-up of the powdered polyphenylene ether from the atmospheric release barrel and dust explosion risk. There was a problem that it was necessary to deal with equipment to suppress it. Further, since the content of polyphenylene ether is small, dispersion of polyphenylene ether in a polyolefin resin or the like may be non-uniform, and sufficient performance may not be exhibited in creep characteristics.

Patent No. 5622905

For the purpose of modifying a resin such as a polyolefin resin, it is sometimes required that another resin contains polyphenylene ether at a high concentration. However, when a composition containing polyphenylene ether at a high concentration is produced, there are problems that black spot foreign substances derived from polyphenylene ether are generated and production efficiency is poor.
In addition, Patent Document 1 describes a resin composition containing polyphenylene ether at a low concentration, which is excellent in appearance and production efficiency, but has not been studied when polyphenylene ether is used at a high concentration.

  This invention is made | formed with respect to such a technical subject, and provides the pellet which contains the polyphenylene ether-type resin excellent in an external appearance with high concentration. In addition, the present invention provides a method for efficiently producing pellets containing a polyphenylene ether-based resin at a high concentration and having an excellent appearance.

  As a result of intensive studies to solve the above problems, the present inventors have found that a pellet containing a polyphenylene ether and a hydrogenated block copolymer having a specific structure and having a black spot foreign matter below a specific amount is advantageous. As a result, the present invention has been completed.

That is, the present invention is as follows.
[1] Total amount of polyphenylene ether resin (I) 80 to 99% by mass, polymer block P mainly composed of vinyl aromatic compound, 1,2-vinyl bond amount and 3,4-vinyl bond amount 1 to 20% by mass of a hydrogenated block copolymer (II) obtained by hydrogenating at least a part of a block copolymer comprising a polymer block Q mainly composed of a conjugated diene compound having a ratio of 50 to 95% , A method for producing pellets produced by melt-kneading a mixture containing a twin-screw extruder,
Regarding the flow direction of the mixture of the twin-screw extruder, the oxygen concentration inside the raw material supply hopper located at the uppermost stream is less than 3% by volume,
The twin-screw extruder has a first kneading zone and a second kneading zone;
There are at least two vents between the first kneading zone and the second kneading zone or downstream of the second kneading zone, and at least one of the vents is an air release vent for degassing. ,
The method for producing pellets, wherein the screw of the first kneading zone does not include a pressure screw element and includes at least one orthogonal screw element.

[2] The method for producing pellets according to [1], wherein the screw of the second kneading zone includes at least one pressure screw element.

[3] The method for producing a pellet according to [1] or [2], wherein the degassing atmosphere release vent portion is filled with an inert gas.

[4] The barrel set temperature from the most upstream barrel in the flow direction of the mixture of the twin-screw extruder to the barrel provided with the degassing atmospheric release vent is 300 ° C. or higher. [3] The method for producing a pellet according to any one of [3].

[5] Total amount of polyphenylene ether resin (I) 80 to 99% by mass, polymer block P mainly composed of vinyl aromatic compound, 1,2-vinyl bond amount and 3,4-vinyl bond amount 1 to 20% by mass of a hydrogenated block copolymer (II) obtained by hydrogenating at least a part of a block copolymer comprising a polymer block Q mainly composed of a conjugated diene compound having a ratio of 50 to 95% , A method for producing pellets produced by melt-kneading a mixture containing a twin-screw extruder,
Regarding the flow direction of the mixture of the twin-screw extruder, the oxygen concentration inside the raw material supply hopper located at the uppermost stream is less than 3% by volume,
The twin-screw extruder has a first kneading zone and a second kneading zone;
There are at least two vents between the first kneading zone and the second kneading zone or downstream of the second kneading zone, and at least one of the vents is an air release vent for degassing. ,
The method for producing pellets, wherein the screw of the second kneading zone includes at least one pressure screw element.

[6] The method for producing pellets according to [5], wherein the vent opening air release vent portion is filled with an inert gas.

[7] The barrel set temperature from the most upstream barrel in the flow direction of the mixture of the twin-screw extruder to the barrel provided with the degassing atmospheric release vent is 300 ° C. or higher. [5] or [6 ] The manufacturing method of the pellet as described in.

[8] Total amount of polyphenylene ether resin (I) 80 to 99% by mass, polymer block P mainly composed of vinyl aromatic compound, 1,2-vinyl bond amount and 3,4-vinyl bond amount 1 to 20% by mass of a hydrogenated block copolymer (II) obtained by hydrogenating at least a part of a block copolymer comprising a polymer block Q mainly composed of a conjugated diene compound having a ratio of 50 to 95% , A method for producing pellets produced by melt-kneading a mixture containing a twin-screw extruder,
Regarding the flow direction of the mixture of the twin-screw extruder, the oxygen concentration inside the raw material supply hopper located at the uppermost stream is less than 3% by volume,
The twin-screw extruder has a first kneading zone and a second kneading zone;
There are at least two vents between the first kneading zone and the second kneading zone or downstream of the second kneading zone, and at least one of the vents is an air release vent for degassing. ,
A method for producing pellets, wherein the degassing atmosphere release vent portion is filled with an inert gas.

[9] The barrel set temperature from the most upstream barrel in the flow direction of the mixture of the twin-screw extruder to the barrel provided with the degassing atmospheric release vent is 300 ° C. or higher. Pellet manufacturing method.

ADVANTAGE OF THE INVENTION According to this invention, the pellet which is excellent in an external appearance and contains polyphenylene ether-type resin in high concentration can be provided. Furthermore, the pellet of the present invention can modify a thermoplastic resin such as polypropylene resin.
Moreover, according to the manufacturing method of this invention, the method of producing efficiently the pellet which is excellent in an external appearance and contains the polyphenylene ether-type resin in high concentration can be provided. Furthermore, the manufacturing method of this invention can manufacture the pellet which can modify | reform thermoplastic resins, such as a polypropylene resin.

FIG. 1 is a schematic view (plan view) showing the shape of a test piece used in the evaluation of the reforming performance of polypropylene resin.

  Hereinafter, a mode for carrying out the present invention (hereinafter also referred to as “the present embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

[pellet]
The pellet of this embodiment contains 80 to 99% by mass of polyphenylene ether resin (I) and 1 to 20% by mass of hydrogenated block copolymer (II), and further, other than component (I) and component (II) The thermoplastic resin (III) and additives (IV) other than the components (I) to (III) may be included.
The pellets of this embodiment are preferably reinforced flame retardant pellets.
In the present specification, the polyphenylene ether resin (I) may be referred to as component (I). Further, the hydrogenated block copolymer (II) may be referred to as component (II).
Hereinafter, it describes about the component of the pellet of this embodiment.

(Polyphenylene ether resin (I))
The polyphenylene ether resin (I) used in the present embodiment is not particularly limited, and examples thereof include polyphenylene ether, modified polyphenylene ether, and mixtures thereof. Component (I) may be used alone or in combination of two or more.

  The reduced viscosity of the polyphenylene ether-based resin (I) is preferably 0.25 dL / g or more, more preferably 0.28 dL / g or more, from the viewpoint of further improving the reforming performance. It is preferably 0.55 dL / g or less, more preferably 0.53 dL / g or less, and particularly preferably 0.50 dL / g or less. The reduced viscosity can be controlled by the polymerization time and the amount of catalyst.

The reduced viscosity (η _red ) was measured using a Uderohde viscometer with a chloroform solution adjusted to 0.5 g / dL at a temperature of 30 ° C., and the specific viscosity η _sp was measured at a concentration c (g / dL). It can be calculated by the following formula.
η _red = η _sp / c

The degree of crosslinking of the polyphenylene ether-based resin (I) is preferably 0 to 0.3% by mass, more preferably 0 to 0.1% by mass, from the viewpoint of reducing black spot foreign matter in the pellet. .
The degree of crosslinking can be measured by the following method.
A mass A (mg) of a polyphenylene ether resin (I) having a mass of about 200 mg is weighed. Next, this test piece is immersed in 20 mL of chloroform and subjected to ultrasonic vibration for 6 hours, and then the soluble and insoluble components are separated by suction filtration. The obtained residue (insoluble matter) is vacuum dried at 100 ° C. for 2 hours, and then the mass B (mg) of the insoluble component is weighed. Based on the obtained mass A and mass B, the degree of crosslinking (unit: mass%) is calculated by the following formula.
Crosslinking degree (% by mass) = 100 × (B / A)

［式中、Ｒ³¹、Ｒ³²、Ｒ³³、及びＲ³⁴は、各々独立して、水素原子、ハロゲン原子、炭素数１〜７の第一級アルキル基、炭素数１〜７の第二級アルキル基、フェニル基、ハロアルキル基、アミノアルキル基、炭化水素オキシ基、及び少なくとも２個の炭素原子がハロゲン原子と酸素原子とを隔てているハロ炭化水素オキシ基からなる群から選択される一価の基である。］ -Polyphenylene ether-
The polyphenylene ether is not particularly limited, and examples thereof include a homopolymer composed of a repeating unit represented by the following formula (1), a copolymer having a repeating unit represented by the following formula (1), and the like. It is done.

[Wherein R ³¹ , R ³² , R ³³ , and R ³⁴ each independently represent a hydrogen atom, a halogen atom, a primary alkyl group having 1 to 7 carbon atoms, or a secondary alkyl group having 1 to 7 carbon atoms. A monovalent group selected from the group consisting of an alkyl group, a phenyl group, a haloalkyl group, an aminoalkyl group, a hydrocarbonoxy group, and a halohydrocarbonoxy group in which at least two carbon atoms separate a halogen atom and an oxygen atom It is the basis of. ]

  Such polyphenylene ether is not particularly limited, and known ones can be used. Specific examples of the polyphenylene ether include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2-methyl- Homopolymers such as 6-phenyl-1,4-phenylene ether) and poly (2,6-dichloro-1,4-phenylene ether); 2,6-dimethylphenol and other phenols (for example, 2,3 , 6-trimethylphenol, 2-methyl-6-butylphenol and the like), and the like, and poly (2,6-dimethyl-1,4-phenylene ether), 2,6 -A copolymer of dimethylphenol and 2,3,6-trimethylphenol is preferred, and poly (2,6-dimethyl-1,4-phenylene ether) is more preferred.

  A method for producing polyphenylene ether is not particularly limited, and a conventionally known method can be used. As a specific example of the method for producing polyphenylene ether, for example, US Pat. No. 3,306,874 produced by oxidative polymerization of 2,6-xylenol using, for example, a complex of cuprous salt and amine as a catalyst. US Pat. No. 3,306,875, US Pat. No. 3,257,357, US Pat. No. 3,257,358, Japanese Patent Publication No. 52-17880, Japanese Patent Laid-Open No. 50-51197, Examples include the method described in JP-A No. 63-152628.

-Modified polyphenylene ether-
The modified polyphenylene ether is not particularly limited, and examples thereof include those obtained by grafting or adding a styrene polymer or a derivative thereof to the above polyphenylene ether. The rate of mass increase due to grafting or addition is not particularly limited, and is preferably 0.01% by mass or more and 10% by mass or less with respect to 100% by mass of the modified polyphenylene ether. Preferably, it is more preferably 7% by mass or less, and particularly preferably 5% by mass or less.

  The method for producing the modified polyphenylene ether is not particularly limited. For example, in the presence or absence of a radical generator, in the molten state, the solution state or the slurry state, under the conditions of 80 to 350 ° C. And a method of reacting the polyphenylene ether with a styrene-based polymer or a derivative thereof.

  When the polyphenylene ether resin (I) used in the present embodiment is a mixture of polyphenylene ether and modified polyphenylene ether, the mixing ratio of the above polyphenylene ether and the above modified polyphenylene ether is particularly limited. Any ratio may be used.

(Hydrogenated block copolymer (II))
The hydrogenated block copolymer (II) used in the present embodiment is not particularly limited, and examples thereof include an unmodified hydrogenated block copolymer, a modified hydrogenated block copolymer, and a mixture thereof. Can be mentioned. Component (II) may be used alone or in combination of two or more.
Component (II) acts as a compatibilizer between the component (I) and another resin such as a polyolefin resin.

  The hydrogenated block copolymer (II) is a polymer block P mainly composed of a vinyl aromatic compound, and the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds is 50 to 95%. At least a part of a block copolymer containing a polymer block Q mainly composed of a certain conjugated diene compound is hydrogenated.

  Hereinafter, the unmodified and modified hydrogenated block copolymers will be described.

-Unmodified hydrogenated block copolymer-
--Polymer block P--mainly composed of vinyl aromatic compounds--
The polymer block P mainly composed of a vinyl aromatic compound is not particularly limited, and examples thereof include a homopolymer block of a vinyl aromatic compound and a copolymer block of a vinyl aromatic compound and a conjugated diene compound. Can be mentioned.
In the polymer block P, “mainly composed of a vinyl aromatic compound” means that the content of the structural unit derived from the vinyl aromatic compound in the polymer block P is more than 50% by mass, The content is preferably 70% by mass or more, more preferably 80% by mass or more, and may be 100% by mass or less.

  The vinyl aromatic compound constituting the polymer block P is not particularly limited, and examples thereof include styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, diphenylethylene, and the like, and styrene is preferable. . The said vinyl aromatic compound may be used individually by 1 type, and may be used together in combination of 2 or more type.

  The number average molecular weight (Mn) of the polymer block P is preferably 15,000 or more, more preferably 20,000 or more, and 25,000 or more from the viewpoint of improving the reforming performance. Is particularly preferred, and preferably 100,000 or less.

  In addition, in this specification, a number average molecular weight (Mn) and a weight average molecular weight (Mw) can be calculated | required by a conventionally well-known method using GPC (Moving bed: Chloroform, Standard substance: Polystyrene).

-Polymer block Q mainly composed of conjugated diene compound-
The polymer block Q mainly composed of a conjugated diene compound is not particularly limited, and examples thereof include a homopolymer block of a conjugated diene compound and a copolymer block of a conjugated diene compound and a vinyl aromatic compound. .
In the polymer block Q, “consisting mainly of a conjugated diene compound” means that the content of the structural unit derived from the conjugated diene compound in the polymer block Q is more than 50% by mass. From the viewpoint of improving fluidity, the content is preferably 70% by mass or more, more preferably 80% by mass or more, and may be 100% by mass or less.

  Examples of the conjugated diene compound constituting the polymer block Q include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and combinations thereof. And combinations thereof, and butadiene is more preferable. The said conjugated diene compound may be used individually by 1 type, and may be used together in combination of 2 or more type.

In the conjugated diene compound, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds is 50% or more from the viewpoint of easily imparting creep resistance to a thermoplastic resin such as polypropylene. 60% or more, more preferably 70% or more, and 95% or less.
“Total amount of 1,2-vinyl bond amount and 3,4-vinyl bond amount” means 1,2-vinyl bond amount, 3,4-vinyl bond amount, 1,4-conjugated bond The ratio of the total amount of 1,2-vinyl bond amount and 3,4-vinyl bond amount to the total amount. The amount of vinyl bonds was measured using an infrared spectrophotometer, and Analytical Chemistry, Volume 21, No. 21. 8, calculated according to the method described in August 1949.

  The number average molecular weight (Mn) of the polymer block Q is preferably 20,000 or more, more preferably 25,000 or more, and more preferably 30,000 or more from the viewpoint of improving the reforming performance. Is particularly preferable, and is preferably 100,000 or less.

  The method for synthesizing the block copolymer including the polymer block P and the polymer block Q is not particularly limited, and examples thereof include known methods such as anionic polymerization.

The block structure of the block copolymer including the polymer block P and the polymer block Q is not particularly limited. For example, the polymer block P is “P”, and the polymer block Q is “Q”. expressed, P-Q, P-Q -P, Q-P-Q-P, (P-Q-) 4 M, include structures such as P-Q-P-Q- P. Here, (PQ-) ₄ M is a reaction residue of a polyfunctional coupling agent such as silicon tetrachloride (M = Si), tin tetrachloride (M = Sn), or a polyfunctional organolithium compound. Initiator residues, etc.

  The molecular structure of the block copolymer including the polymer block P and the polymer block Q is not particularly limited, and examples thereof include linear, branched, radial, or combinations thereof.

  The distribution of units derived from the vinyl aromatic compound in the molecular chain in the polymer block P contained in the block copolymer and the unit derived from the conjugated diene compound in the molecular chain in the polymer block Q are particularly limited. For example, it may be random, tapered (in which the monomer portion is increased or decreased along the molecular chain), partially blocked, or a combination thereof.

  When the block copolymer includes a plurality of polymer blocks P and / or polymer blocks Q, the plurality of polymer blocks P or the plurality of polymer blocks Q have the same structure. It may be a different structure.

The content of the unit derived from the vinyl aromatic compound with respect to the entire block copolymer including the polymer block P and the polymer block Q is determined based on the fluidity and impact resistance of the hydrogenated block copolymer (II). From the viewpoint of improving the appearance and reducing the occurrence of welds, it is preferably 20% by mass or more, more preferably 30% by mass or more, and preferably 95% by mass or less, and 80% by mass. % Or less is more preferable.
In addition, content of the unit derived from a vinyl aromatic compound can be measured using an ultraviolet spectrophotometer.

  The number average molecular weight (Mn) of the block copolymer before hydrogenation is preferably 5,000 or more, more preferably 10,000 or more, particularly preferably 30,000 or more, 1,000,000 or less, more preferably 800,000 or less, and particularly preferably 500,000 or less.

  The molecular weight distribution (Mw / Mn) of the block copolymer before hydrogenation is preferably 10 or less, more preferably 8 or less, and particularly preferably 5 or less.

  The method for hydrogenating the block copolymer is not particularly limited. For example, (1) a supported type in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, diatomaceous earth, or the like. A heterogeneous hydrogenation catalyst, (2) a so-called Ziegler-type hydrogenation catalyst using an organic acid salt such as Ni, Co, Fe, Cr or a transition metal salt such as acetylacetone salt and a reducing agent such as organic aluminum; ) Using a homogeneous hydrogenation catalyst such as so-called organometallic complexes such as organometallic compounds such as Ti, Ru, Rh and Zr, for example, under conditions of a reaction temperature of 0 to 200 ° C. and a hydrogen pressure of 0.1 to 15 MPa. And a method of hydrogenation.

The hydrogenation rate with respect to the conjugated diene compound portion constituting the polymer block Q in the hydrogenated block copolymer (II) is not particularly limited, and is derived from the conjugated diene compound from the viewpoint of increasing the heat resistance of the pellet. The total amount of double bonds is preferably 50% or more, more preferably 80% or more, and particularly preferably 90% or more.
The hydrogenation rate can be measured using a nuclear magnetic resonance apparatus (NMR).

  A production method of the hydrogenated block copolymer (II) is not particularly limited, and a known production method can be used. Specific examples of the known production method include, for example, JP-A-47-11486, JP-A-49-66743, JP-A-50-75651, JP-A-54-126255, JP-A-54-126255. JP 56-10542, JP 56-62847, JP 56-1000084, JP 2-300218, British Patent 1130770, US Pat. No. 3,281,383, US Examples include the methods described in Japanese Patent No. 3639517, British Patent No. 1020720, US Pat. No. 3,333,024, and US Pat. No. 4,501,857.

-Modified hydrogenated block copolymer-
The modified hydrogenated block copolymer is obtained by grafting or adding α, β-unsaturated carboxylic acid or a derivative thereof (for example, acid anhydride, ester, etc.) to the unmodified hydrogenated block copolymer. is there.

  The rate of mass increase due to grafting or addition is not particularly limited, and is preferably 0.01% by mass or more and 100% by mass or less with respect to 100% by mass of the modified hydrogenated block copolymer. It is preferably 7% by mass or less, more preferably 5% by mass or less.

  The method for producing the modified hydrogenated block copolymer is not particularly limited, and for example, in the presence or absence of a radical generator, in a molten state, a solution state or a slurry state, at a temperature of 80 to 350 ° C. And a method of reacting an unmodified hydrogenated block copolymer with an α, β-unsaturated carboxylic acid or a derivative thereof.

(Thermoplastic resin (III) other than component (I) and component (II))
The thermoplastic resin (III) other than the component (I) and the component (II) that is optionally used in the present embodiment is not particularly limited, and examples thereof include polystyrene, syndiotactic polystyrene, and high impact polystyrene. Etc.

(Additives (IV) other than Component (I) to Component (III))
The additive (IV) other than the components (I) to (III) that is optionally used in the present embodiment is not particularly limited. For example, a vinyl aromatic compound-conjugated diene compound block copolymer is used. Polymers; Olefin elastomers; Fluorine polymers; Plasticizers such as low molecular weight polyethylene, epoxidized soybean oil, polyethylene glycol, fatty acid esters; alkyl metal phosphinic acid compounds, melamine pyrophosphates, melamine polyphosphates, phosphate ester compounds, Flame retardants such as ammonium polyphosphate compounds, magnesium hydroxide, aromatic halogen flame retardants, silicone flame retardants, zinc borate, etc .; flame retardant aids such as antimony trioxide; inorganic or organic fillers; carbon black, Titanium oxide, calcium carbonate, mica, kaolin, glass fiber, glass fl Inorganic or organic strengthening agents such as copper, conductive carbon black, talc and wollastonite; antioxidants; metal deactivators; heat stabilizers; weathering (light) improvers; nucleating agents for polyolefins; slips Agents; coloring agents; mold release agents; and the like.

Hereinafter, it describes about the ratio of the component in the pellet of this embodiment.
The content of the component (I) in the pellet of the present embodiment is 80% by mass or more, preferably 85% by mass or more, and 90% by mass with respect to the whole pellet from the viewpoint of improving the reforming performance. More preferably, it is 99% by mass or less, preferably 98% by mass or less, and more preferably 97% by mass or less.

  The content of the component (II) in the pellet of the present embodiment is 1% by mass or more, more preferably 2% by mass or more, from the viewpoint of improving the reforming performance with respect to the whole pellet, and more preferably 3% by mass. % Or more, and from the viewpoint of suppressing peeling from the pellets, it is 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 10% by mass or less.

  The content of each of the component (III) and the component (IV) in the pellet of the present embodiment is not particularly limited as long as the effects of the present invention are not impaired. For example, the pellet total amount (100 parts by mass) Or 0 to 400 parts by mass.

-Number of sunspots-
A black spot foreign material having a major axis exceeding 0.7 mm on the front and back surfaces (total 8 surfaces, total area 36000 mm ² ) of four flat plates formed by molding the pellets of the present invention into a size of 90.0 mm × 50.0 mm × 2.0 mm Is not observed.
Further, the number of black spot foreign substances having a major axis of more than 0.5 mm and not more than 0.7 mm measured on the front and back surfaces of the four flat plates is preferably 5 or less, and more preferably 3 or less.
Further, the number of black spot foreign substances having a major axis of more than 0.3 mm and not more than 0.5 mm measured on the front and back surfaces of the four flat plates is preferably 10 or less, and more preferably 6 or less.
Here, the black spot foreign matter is a black spot foreign matter that is generated due to the progress of crosslinking when the polyphenylene ether-based resin is exposed to high temperature for a long time or is exposed to oxygen at high temperature.
The number of black spot foreign matter can be measured by the method described in “(1) Long diameter and number of black spot foreign matter” in the examples described later. The “major axis” refers to the maximum diameter of a black spot foreign substance in plan view.
In order to bring the number of the foreign substances into the above range, it is necessary to control the manufacturing method as follows.

The pellet of this embodiment can be manufactured by the manufacturing method of the pellet mentioned later.
Since the pellet of this embodiment contains polyphenylene ether at a high concentration, it can impart creep resistance, heat resistance, and the like by mixing with a resin such as polyolefin.

The pellets of this embodiment are suitably used for modifying thermoplastic resins (particularly polyolefin resins) (for example, imparting creep resistance, heat resistance, etc.). It can be used for interior and exterior parts of equipment and other parts.
The automobile parts are not particularly limited, and include, for example, exterior parts such as bumpers, fenders, door panels, various moldings, emblems, engine hoods, wheel caps, roofs, spoilers, various aero parts, instrument panels, consoles, etc. Examples include interior parts such as boxes and trims; secondary battery battery case parts mounted on automobiles, electric cars, hybrid electric cars, etc .; lithium ion secondary battery parts.
Further, the interior / exterior parts of the electrical equipment are not particularly limited, and for example, various computers and peripheral equipment, other office automation equipment, televisions, videos, various disk player cabinets, chassis, refrigerators, air conditioners, liquid crystals Examples include parts used in projectors.
Other parts include electric wires and cables obtained by coating metal conductors or optical fibers, fuel cases for solid methanol batteries, fuel cell water pipes, water cooling tanks, boiler exterior cases, ink jet printer peripheral parts and components , Furniture (chairs, etc.), chassis, water piping, joints, etc.

[Pellet production method]
As a manufacturing method of the pellet of this embodiment, polyphenylene ether-type resin (I) 80-99 mass%, the polymer block P which mainly has a vinyl aromatic compound, 1,2-vinyl bond amount, 3 , 4-vinyl bond amount, and polymer block Q mainly composed of a conjugated diene compound having a content of 50 to 95%, and a hydrogenated block copolymer in which at least a part of the block copolymer is hydrogenated The method of melt-kneading the mixture containing 1-20 mass% of union (II) with a twin-screw extruder is mentioned. In the above production method, it is preferable that the oxygen concentration inside the raw material supply hopper located in the uppermost stream is less than 3% by volume in the flow direction of the mixture of the twin-screw extruder.

  The mixture in the production method of the present embodiment can be produced by mixing the component (I), the component (II), and, if necessary, the component (III) and the component (IV).

  Examples of the apparatus used for melt kneading include a uniaxial or multiaxial kneading extruder, a roll, and a Banbury mixer. Among these, a twin screw extruder is preferable, and a twin screw extruder provided with a decompression device is particularly preferable. Specific examples of the twin screw extruder include a ZSK series manufactured by Coperion, a TEM series manufactured by Toshiba Machine Co., Ltd., and a TEX series manufactured by Nippon Steel Works.

  Examples of the melt-kneading method include a method in which all components are melt-kneaded simultaneously, a method in which a premixed mixture is melt-kneaded, and the like.

In order to eliminate sunspot foreign matter when the pellet is formed, at least one of the following (a) to (h) is used for the screw configuration and vent position when the resin composition is melt-kneaded with a twin-screw extruder. It is preferable to adopt.
(A) The oxygen concentration inside the powder raw material supply collective hopper in the uppermost stream of the twin screw extruder is set to less than 3% by volume.
(B) It has a 1-flight flight screw zone where L / D (screw axial length / screw diameter) = 4.5-20.
(C) On the downstream side of the single flight screw zone, there is a double flight screw zone with L / D = 4-20.
(D) No boost screw element is included downstream of the above-mentioned two-flight flight screw zone (for example, when there are a plurality of two-flight flight screw zones, the most upstream two-flight flight screw zone in the flow direction of the mixture). And having a first kneading zone including two orthogonal screw elements, L / D = 3-8.
(E) It has an atmospheric gas vent or a vacuum vent on the downstream side of the first kneading zone.
(F) A second kneading zone including at least one booster screw element is provided on the downstream side of the atmospheric gas vent or the vacuum vent, and L / D = 3-12.
(G) The atmospheric gas vent portion is filled with an inert gas.
(H) A vacuum vent is provided on the downstream side of the second kneading zone.
The solid conveyance zone, the first kneading zone, the second kneading zone, the single flight screw zone, and the double flight screw zone may be determined in units of barrels.

  Also, from the viewpoint of reducing black spot foreign matter in the obtained pellets, the vent port installed downstream of the first kneading zone is an atmospheric gas vent (atmospheric release vent for degassing), and an inert gas is supplied to this portion. Is preferred.

The barrel temperature setting of the twin-screw extruder can be selected, for example, from a temperature between 250 ° C. and 350 ° C., but from the viewpoint of ensuring stable productivity, from the uppermost stream of the twin-screw extruder to the first kneading zone It is preferable that the set temperature between the vent port installed downstream is 300 ° C. or higher.
Further, in the case of providing an air release vent for venting, from the viewpoint of ensuring stable productivity, a barrel provided with the vent vent for venting from the most upstream barrel in the flow direction of the mixture of the twin-screw extruder. It is preferable that the barrel set temperature is 300 ° C. or higher.

The twin screw extruder preferably has a first kneading zone and a second kneading zone. From the viewpoint of improving productivity, and / or between the first kneading zone and the second kneading zone. A twin-screw extruder having at least two or more vents downstream from the kneading zone and at least one of the vents being an air release vent for degassing is preferable. The degassing atmosphere release vent is preferably filled with an inert gas such as nitrogen from the viewpoint of reducing the black spot foreign matter in the pellet.
Further, as the above twin screw extruder, from the viewpoint of productivity improvement and reduction of sunspot foreign matter, the screw of the first kneading zone does not include a boost screw element and includes at least one orthogonal screw element. An extruder is preferred.
The twin screw extruder is preferably a twin screw extruder in which the screw in the second kneading zone includes at least one pressure screw element from the viewpoint of improving kneading efficiency.

Hereinafter, it describes about suitable embodiment at the time of using extruders, such as multi-screw extruders, such as a single screw extruder and a twin screw extruder.
The type and standard of the extruder are not particularly limited and may be known ones.

  The L / D (barrel effective length / barrel inner diameter) of the extruder is preferably 30 or more, more preferably 40 or more, further preferably 75 or less, and further preferably 60 or less. preferable.

  The screw rotation speed is not particularly limited, and may be usually 100 to 1200 rpm.

  When a liquid raw material is added, it can be added by directly feeding the liquid raw material into the cylinder system using a liquid pump or the like in the extruder cylinder portion. The liquid pump is not particularly limited, and examples thereof include a gear pump and a flange type pump, and a gear pump is preferable. At this time, from the viewpoint of reducing the load applied to the liquid pump and improving the operability of the raw material, the tank for storing the liquid raw material, the piping between the tank and the liquid pump, and between the pump and the extruder cylinder It is preferable that the viscosity of the liquid raw material is reduced by heating a portion that becomes a flow path of the liquid raw material such as a pipe using a heater or the like.

The pellets of this embodiment are optimal for use as a resin modifier. The resin modifier of this invention consists of the pellet of this embodiment, and may contain the other component further.
The resin modifier of this embodiment can modify the properties of the resin by imparting creep resistance, imparting heat resistance, etc. to a thermoplastic resin such as a polyolefin resin such as polypropylene.

  The thermoplastic resin composition of the present invention contains the resin modifier of this embodiment. Furthermore, polyolefin resins such as polypropylene, thermoplastic resins such as polystyrene; block copolymers of vinyl aromatic compounds-conjugated diene compounds, olefin elastomers, antioxidants, metal deactivators, heat stabilizers, flame retardants ( Ammonium polyphosphate compounds, melamine polyphosphate compounds, magnesium hydroxide, aromatic halogen flame retardants, silicone flame retardants, zinc borate, etc.), fluorine polymers, plasticizers (low molecular weight polyethylene, epoxidized soybean oil, Flame retardant aids such as polyethylene glycol and fatty acid esters), antimony trioxide, weathering (light) improvers, polyolefin nucleating agents, slip agents, inorganic or organic fillers and reinforcing agents (GF, GF length) Fiber, CF, CF long fiber, polyacrylonitrile fiber, carbon black, titanium oxide, carbonic acid Calcium, conductive metal fibers, conductive carbon black, etc.), coloring agent, other components such as a releasing agent; may contain.

As for content of the resin modifier with respect to the thermoplastic resin composition whole quantity (100 mass%) of this embodiment, 0.5-50 mass% is preferable.
The thermoplastic resin composition of the present embodiment can be produced, for example, by mixing a thermoplastic resin and the resin modifier of the present embodiment, and melt-kneading them.
According to the thermoplastic resin composition of the present embodiment, since a resin modifier containing a polyphenylene ether resin at a high concentration is used, compared to the case of using a polyphenylene ether resin powder, The explosion of dust from the atmospheric release barrel of the polyphenylene ether resin is unlikely to occur, and the polyphenylene ether resin is uniformly dispersed to easily impart creep resistance.

  The thermoplastic resin composition of this embodiment is excellent in creep resistance. Therefore, it can be used as automobile parts, interior / exterior parts of electrical equipment, other parts, and the like. Examples of the automobile parts, the interior / exterior parts of the electric equipment, and the other parts include those described above.

  EXAMPLES Hereinafter, although an Example is given and embodiment of this invention is described, this invention is not limited to these Examples.

The raw materials used for the pellets of Examples and Comparative Examples are shown below.
-Polyphenylene ether resin (I)-
(Ii): Polyphenylene ether (trade name “XYRON S201A”) having a reduced viscosity (η _{sp /} c: 0.50 g / dL chloroform solution) 0.33 obtained by oxidative polymerization of 2,6-xylenol, Asahi Kasei Chemicals Corporation).
(I-ii): Polyphenylene ether (trade name “XYRON S202A”) having a reduced viscosity (η _{sp /} c: 0.50 g / dL chloroform solution) 0.42 obtained by oxidative polymerization of 2,6-xylenol, Asahi Kasei Chemicals Corporation).
The reduced viscosity was measured under the condition of a temperature of 30 ° C. using a chloroform solution of η _{sp /} c: 0.5 g / dL.

-Hydrogenated block copolymer (II)-
A block copolymer was synthesized using polystyrene (homopolymer) as the polymer block P and polybutadiene (homopolymer) as the polymer block Q. Hydrogenation was performed on the synthesized block copolymer by a known method. The polymer was not modified. The physical properties of the resulting unmodified hydrogenated block copolymer are shown below.
(II-i) QP-Q-P type polystyrene block number average molecular weight (Mn): 41,800,
Number average molecular weight (Mn) of polybutadiene block: 53,200,
Polystyrene content in the block copolymer before hydrogenation: 44%,
Number average molecular weight (Mn) of block copolymer before hydrogenation: 95,000,
Molecular weight distribution (Mw / Mn) of the block copolymer before hydrogenation: 1.06
Total vinyl bond content in the polybutadiene block before hydrogenation (1,2-vinyl bond content): 75%
Hydrogenation rate with respect to the polybutadiene portion constituting the polybutadiene block: 99.9%
(II-x) PQPQ type polystyrene block number average molecular weight (Mn): 46,800,
Number average molecular weight (Mn) of polybutadiene block: 38,000,
Polystyrene content in the block copolymer before hydrogenation: 60%,
Number average molecular weight (Mn) of block copolymer before hydrogenation: 53,500,
Molecular weight distribution (Mw / Mn) of the block copolymer before hydrogenation: 1.20,
Total vinyl bond amount in polybutadiene block before hydrogenation (1,2-vinyl bond amount): 36%,
Hydrogenation rate with respect to the polybutadiene portion constituting the polybutadiene block: 99.9%
The polystyrene content was measured using an ultraviolet spectrophotometer. The number average molecular weight (Mn) was determined by a conventionally known method using GPC (moving layer: chloroform, standard material: polystyrene). The molecular weight distribution (Mw / Mn) is obtained by dividing the weight average molecular weight (Mw) obtained by a conventionally known method using GPC (moving layer: chloroform, standard material: polystyrene) by the number average molecular weight (Mn). Calculated by The total amount of vinyl bonds was measured using an infrared spectrophotometer, and Analytical Chemistry, Volume 21, No. 8, calculated according to the method described in August 1949. The hydrogenation rate was measured using a nuclear magnetic resonance apparatus (NMR).

  The measuring method of the physical property in an Example and a comparative example is shown below.

(1) Major diameter and number of sunspot foreign matter The obtained pellets are supplied to a small injection molding machine (trade name: IS-100GN, manufactured by Toshiba Machine Co., Ltd.) set at a cylinder temperature of 320 ° C., and the mold temperature is 90 ° C., injection. Molding was performed under the condition of a pressure of 60 MPa to obtain a flat test piece of 90.0 mm × 50.0 mm × 2.0 mm. With respect to the four flat plates, a total of eight front and back surfaces of each test piece were visually observed, and the major axis and the number of black spot foreign materials were measured using a scale.
Moreover, the external appearance of the test piece was evaluated according to the following criteria.
◎ (Excellent): There is no black spot foreign material having a major axis of more than 0.7 mm, five or less black spot foreign materials having a major axis of more than 0.5 mm and 0.7 mm or less, and the number of black spot foreign materials having a major axis of more than 0.3 mm and 0.5 mm or less The number was 10 or less.
○ (Good): There was no black spot foreign material with a major axis of more than 0.7 mm, and there were five or less black spot contaminants with a major axis of more than 0.5 mm and less than 0.7 mm. The number was more than 10.
X (defect): There was a black spot foreign material having a major axis exceeding 0.7 mm.

(2) Modification performance of polypropylene resin Production method (a): The obtained pellets were melt-kneaded with homopolypropylene having an MFR of 2.5 g / 10 min measured at 230 ° C. under a load of 2.16 kg, and polyphenylene was obtained. A modified polypropylene having an ether-based resin content of 10% by mass was obtained.
Production method (b): Polyphenylene ether resin powder and hydrogenated block copolymer were added separately without using the pellets of this embodiment, and modified polypropylene having the same composition as production method (a) was added. Obtained.
The pellets of the modified polypropylene obtained by the production method (a) and the production method (b) are supplied to a Toyo Machine Metal Ti-50G2 molding machine set at a cylinder temperature of 245 ° C., and the mold temperature is 60 ° C. and the injection pressure is 65 MPa. Molding was performed under the conditions to obtain a test piece for creep measurement. In addition, as a test piece for creep measurement, a dumbbell molded product (thickness 1 mm) having the shape shown in FIG. 1 was used. The width L _{1 of the} test piece was 65 mm, the width L ₂ was 40 mm, the width L ₃ was 22 mm, and the height H was 10 mm.
The obtained creep measurement test piece was measured using a creep tester (“145-B-PC type” manufactured by Yasuda Seiki Seisakusho Co., Ltd.) with a distance between chucks of 40 mm, a test load corresponding to a stress of 12.25 MPa, and a test temperature. Was measured under the conditions of 80 ° C. and a test time of 165 hours (heat resistance creep resistance test). The heat resistance creep property (creep property) was evaluated by the strain [%] obtained by the following formula. The smaller the numerical value of this strain, the better the creep characteristics.
Strain [%] = (displacement of test piece after 165 hours) / (distance between chucks) × 100

(3) Production efficiency The amount of discharge (kg / h) per unit time discharged from the extruder when producing pellets was recorded, and this value was used as an index of production efficiency. The larger this value, the better the production efficiency.
Further, during the production of the pellets, the presence or absence of the molten resin composition blown out from the air release vent (presence or absence of vent-up) was confirmed. In the absence of vent-up, it was evaluated that it was excellent in safety and production efficiency during production.

  Hereinafter, each example and each comparative example will be described in detail.

(Examples 1-15, Comparative Examples 1-11)
A twin-screw extruder (Toshiba Machine Co., Ltd., TEM-58SS) was used as the melt-kneader used for the production of the pellets of each Example and each Comparative Example. The L / D of the extruder was 54.
The twin screw extruder had 13 barrels and the screw configuration was as shown in Table 1. In addition, the meaning of the symbol which shows the screw structure in Table 1 is as follows.
・ Single flight: Pitch L / D = 1.3
・ Two-flight flight: Pitch L / D = 1.3
・ R1: Kneading disc light (L / D = 1.0)
R2: Kneading disc light (L / D = 0.5)
・ L (pressurization type): Kneading disc left (L / D = 0.5)
N (orthogonal type): kneading disc neutral (L / D = 1.0)
About each Example and each comparative example, the pellet was obtained with the composition and manufacturing conditions which are shown in Table 2 and Table 3. The physical properties of the obtained pellets were measured by the method described above, and the results are shown in Tables 2 and 3.

  As shown in Tables 2 and 3, the pellets of Examples 1 to 15 had fewer black spot foreign matters and were excellent in the reforming performance of the polyolefin resin as compared with the pellets of Comparative Examples 1 to 11.

  In the evaluation of the modification performance of polypropylene resin, the polypropylene modified with the pellets in the production method (a) is highly resistant to creep because the components that improve compatibility with polypropylene are highly finely dispersed in the pellet. Excellent. On the other hand, the polypropylene modified by the production method (b) did not have sufficient dispersibility and was inferior in the creep resistance improving effect.

  According to the present invention, it is possible to provide a pellet containing a polyphenylene ether-based resin at a high concentration, which is optimal for imparting creep resistance to a polyolefin resin to be modified and excellent in appearance after molding, and a method for producing the pellet. .

Claims (9)

The total amount of polyphenylene ether-based resin (I) 80 to 99% by mass, polymer block P mainly composed of vinyl aromatic compound, 1,2-vinyl bond amount and 3,4-vinyl bond amount is 50 to A polymer block Q mainly composed of 95% of a conjugated diene compound, and 1 to 20% by mass of a hydrogenated block copolymer (II) in which at least a part of the block copolymer containing the hydrogenated block copolymer is hydrogenated A method for producing pellets produced by melt-kneading a mixture with a twin-screw extruder,
The flow direction of the mixture of the twin-screw extruder, Ri oxygen concentration der less than 3% by volume of the internal material feed hopper located at the most upstream,
The twin-screw extruder has a first kneading zone and a second kneading zone;
There are at least two vents between the first kneading zone and the second kneading zone or downstream of the second kneading zone, and at least one of the vents is an air release vent for degassing. ,
The method for producing pellets, wherein the screw of the first kneading zone does not include a pressure screw element and includes at least one orthogonal screw element . The manufacturing method of the pellet of Claim 1 in which the screw of the said 2nd kneading | mixing zone contains at least 1 pressure | voltage rise screw element. The manufacturing method of the pellet of Claim 1 or 2 which fills the said air release vent part for degassing with an inert gas. From the most upstream barrel flow direction of the mixture of the twin-screw extruder, the barrel set temperatures of up to barrel the gas vent air opening vent is provided is 300 ° C. or higher, one of claims 1 to 3 1 The manufacturing method of the pellet as described in a term.   The total amount of polyphenylene ether-based resin (I) 80 to 99% by mass, polymer block P mainly composed of vinyl aromatic compound, 1,2-vinyl bond amount and 3,4-vinyl bond amount is 50 to A polymer block Q mainly composed of 95% of a conjugated diene compound, and 1 to 20% by mass of a hydrogenated block copolymer (II) in which at least a part of the block copolymer containing the hydrogenated block copolymer is hydrogenated A method for producing pellets produced by melt-kneading a mixture with a twin-screw extruder,
  Regarding the flow direction of the mixture of the twin-screw extruder, the oxygen concentration inside the raw material supply hopper located at the uppermost stream is less than 3% by volume,
  The twin-screw extruder has a first kneading zone and a second kneading zone;
  There are at least two vents between the first kneading zone and the second kneading zone or downstream of the second kneading zone, and at least one of the vents is an air release vent for degassing. ,
  The method for producing pellets, wherein the screw of the second kneading zone includes at least one pressure screw element.   The manufacturing method of the pellet of Claim 5 which fills the said air release vent part for degassing with an inert gas.   The pellet according to claim 5 or 6, wherein a barrel set temperature from a most upstream barrel in a flow direction of the mixture of the twin-screw extruder to a barrel provided with the degassing atmosphere release vent is 300 ° C or higher. Manufacturing method.   The total amount of polyphenylene ether-based resin (I) 80 to 99% by mass, polymer block P mainly composed of vinyl aromatic compound, 1,2-vinyl bond amount and 3,4-vinyl bond amount is 50 to A polymer block Q mainly composed of 95% of a conjugated diene compound, and 1 to 20% by mass of a hydrogenated block copolymer (II) in which at least a part of the block copolymer containing the hydrogenated block copolymer is hydrogenated A method for producing pellets produced by melt-kneading a mixture with a twin-screw extruder,
  Regarding the flow direction of the mixture of the twin-screw extruder, the oxygen concentration inside the raw material supply hopper located at the uppermost stream is less than 3% by volume,
  The twin-screw extruder has a first kneading zone and a second kneading zone;
  There are at least two vents between the first kneading zone and the second kneading zone or downstream of the second kneading zone, and at least one of the vents is an air release vent for degassing. ,
  A method for producing pellets, wherein the degassing atmosphere release vent portion is filled with an inert gas.   The production of pellets according to claim 8, wherein a barrel set temperature from the most upstream barrel in the flow direction of the mixture of the twin-screw extruder to a barrel provided with the degassing atmosphere release vent is 300 ° C or higher. Method.

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