JP2019131671A - Manufacturing method of thermoplastic elastomer composition - Google Patents

Abstract

To provide a thermoplastic elastomer composition excellent in moldability, flexibility, compressive permanent set resistance under high temperature, gas barrier property, steam barrier property, bleeding resistance, molding appearance, sealing property by melting and mixing raw materials of Components (A) to (D) in an extruder.SOLUTION: Component (A), Component (B) and a part of Component (C) and Component (D) are supplied from a first raw material supply port in most upstream side of an extruder, and remaining part of Component (D) is supplied from other raw material supply port arranged in a downstream side than the first raw material supply port. Component (A): a vinyl aromatic compound-conjugated diene/isobutylene-block copolymer, or a hydrogenated article thereof. Component (B): a dynamic heat treated article of a mixture containing (a) an isobutylene polymer, (b) polyolefin, (c) polybutene, and (d) a hydroxyl group-containing compound. Component (C): a polyolefin resin. Component (D): a curing agent.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing a thermoplastic elastomer composition. Specifically, thermoplastic elastomers used in various molded products such as automobiles, home appliances, electrical equipment, medical equipment, packaging materials, stationery and miscellaneous goods, and various members such as grips, tubes, packings, gaskets, films, sheets, etc. The present invention relates to a method for producing a composition.

Conventionally, rubbers obtained by blending a rubber such as natural rubber or synthetic rubber with a crosslinking agent or a reinforcing material and crosslinking under high temperature and high pressure have been used as the polymer material having elasticity. However, such rubbers require a process of crosslinking and molding for a long time under high temperature and pressure, and are inferior in processability. In addition, since the crosslinked rubber does not exhibit thermoplasticity, it is generally impossible to perform recycle molding like a thermoplastic resin.
In recent years, thermoplastic elastomers have been developed that can easily produce molded articles using general-purpose molding techniques such as injection molding and extrusion molding as in the case of ordinary thermoplastic resins.

  In Patent Document 1, an isobutylene polymer having an alkenyl group at the terminal, a resin component comprising a polyethylene resin and / or a polypropylene resin, and an inorganic filler, preferably a softening agent, are melt-kneaded, and then a hydrosilyl group-containing polysiloxane And then melt-kneading, or melt-kneading an isobutylene polymer having an alkenyl group at the terminal and an inorganic filler hydrosilyl group-containing polysiloxane, and then adding a resin component comprising a polyethylene resin and / or a polypropylene resin, and A process for producing a thermoplastic elastomer composition having improved compression set properties, compression set properties, tensile properties and fluidity by dynamically cross-linking an isobutylene polymer with a hydrosilyl group-containing polysiloxane by melt-kneading. It is disclosed.

  Patent Document 2 discloses hydrogen of a block copolymer Z having two or more polymer blocks X containing styrene units as main constituent units and one or more polymer blocks Y containing butadiene units as main constituent units. An additive, a softening agent having a weight average molecular weight of 160 to 400,000, a block polymer having a styrene unit content of 20 to 70% by mass, 100 parts by mass, and a kinematic viscosity at 40 ° C. of 50 to 500 cSt Medical container stopper having 100 to 300 parts by mass, 1 to 50 parts by mass of propylene polymer C having a flexural modulus of 1000 to 3000 MPa, and 5 to 80 parts by mass of cross-linked product R of isobutylene polymer Q having a reactive group A body elastomer composition is disclosed.

  In Patent Document 3, a crosslinkable elastomer, a softening agent, a softening retention agent, and if necessary, a crosslinking agent and a crosslinking aid are added and mixed without melting to form a master batch (MB). A process for producing a softener-containing elastomer composition is disclosed in which melt-kneading and dynamic crosslinking are performed, and if necessary, a softener is added during the melt-kneading.

  Patent Document 4 discloses that when a crosslinkable elastomer, a thermoplastic resin, a softener, a softener retainer, and a crosslinker are melt-kneaded and dynamically cross-linked, the softener is divided into a plurality of feed supply sections. A process for producing an elastomer composition to be fed is disclosed.

JP 2006-152030 A JP 2010-227285 A JP 2000-143819 A JP 2000-143820 A

  Among the above conventional techniques, the thermoplastic elastomer composition obtained by the method for producing a thermoplastic elastomer composition described in Patent Document 1 has a low melt fluidity, and the surface of the molded body tends to be rough when molded. In addition, there was a concern that the surface became sticky due to bleed-out of the softener.

  When the thermoplastic elastomer composition described in Patent Document 2 is produced by the production method described herein, the dispersibility of the cross-linked product R of the isobutylene polymer Q having a reactive group with low melt flowability is maintained. As a result, the surface of the molded body is likely to be rough, and there is a concern that the molded appearance and the sealing performance may be deteriorated.

  Moreover, although the compounding composition of the raw material component used and the thermoplastic elastomer composition obtained differs from patent document 1 and patent document 2, the manufacturing method of the softener containing elastomer composition of patent document 3 which improved the manufacturing process According to Japanese Patent Application Laid-Open No. H11-260260, it is said that the reduction in mechanical properties of the manufactured product can be suppressed by reducing the load caused by blending the main raw material and the softener in advance and adding and kneading. No mention is made of improving the dispersibility of raw materials with low melt fluidity as described in.

  Also, Patent Document 4 differs from Patent Document 1 and Patent Document 2 in the raw material components used and the blended composition of the resulting thermoplastic elastomer composition. It is said to reduce the mechanical properties of the manufactured product by reducing the load by introducing and kneading from the feed supply part of the place, but here also about improving the dispersibility of raw materials with low melt fluidity Not mentioned.

  Accordingly, an object of the present invention is to improve the dispersibility of raw material components having low melt flowability when producing thermoplastic elastomers by melt kneading the raw materials of specific components (A) to (D) in an extruder. In addition to excellent moldability and flexibility and high compression set resistance, gas barrier properties, water vapor barrier properties, and bleed resistance even at high temperatures, the molded product has less surface roughness, and has a molded appearance and sealability. An object of the present invention is to provide a method for producing a thermoplastic elastomer composition that does not affect the deterioration of the temperature.

In the present invention, as a result of intensive studies to solve the above-mentioned problems, the softener supply is divided and supplied from a plurality of locations including the raw material supply port under the extruder hopper, and further, the distribution of the softener is appropriately distributed. By optimizing the load applied to each kneading part in the extruder, the raw material with low melt fluidity can be advanced without accompanying deterioration in quality such as mechanical properties or excessive load applied to the extruder. It was found that the above problems can be solved.
That is, the gist of the present invention resides in the following [1] to [3].

[1] A method for producing a thermoplastic elastomer composition by supplying the following component (A), component (B), component (C), and component (D) to an extruder and melt-kneading in the extruder. Then, as the extruder, an extruder having two or more raw material supply ports whose arrangement positions are different in the extrusion direction is used. Component (A), component (B), component (C) and component (D) 1 or 2 or more provided from the first raw material supply port on the most upstream side of the extruder, and the remainder of the component (D) is provided downstream of the first raw material supply port A method for producing a thermoplastic elastomer composition, characterized in that the thermoplastic elastomer composition is fed to the extruder from another raw material feed port.
Component (A): a block copolymer having a polymer block derived from a vinyl aromatic compound and a polymer block derived from at least one selected from conjugated diene and isobutylene, and hydrogenating the block copolymer At least one block copolymer component (B): (a) an isobutylene polymer having a reactive group, (b) a polyolefin, (c) a polybutene, and (d) a hydrosilyl group. A dynamic heat-treated product of a mixture containing a containing compound. However, (b) polyolefin is at least 1 sort (s) selected from the group which consists of a polyethylene-type resin and a polypropylene-type resin, (c) The number average molecular weights of polybutene are 700-100,000, a) Component (C): Polyolefin resin with a content of (b) polyolefin of 5 to 30 parts by mass and a content of polybutene of 5 to 100 parts by mass with respect to 100 parts by mass of the isobutylene polymer having a reactive group Ingredient (D): Softener

[2] The method for producing a thermoplastic elastomer composition according to [1], wherein the first raw material supply port is installed under a hopper that supplies the raw material to the extruder.

[3] When the amount of the component (D) supplied from the first raw material supply port is D1, and the total amount of the component (D) supplied to the extruder is Dx, D1 / Dx is 0.8. The method for producing a thermoplastic elastomer composition according to [1] or [2], which is as follows.

  According to the present invention, from specific components (A) to (D), it has excellent moldability and flexibility, and has high compression set resistance even at high temperatures, durability, gas barrier properties, water vapor barrier properties, In addition, it is possible to produce a thermoplastic elastomer composition that is not only excellent in bleed resistance but also has little surface roughness of the molded body and does not affect the molding appearance or the deterioration of sealing properties.

It is a schematic diagram explaining an example of a structure of the extruder suitable for implementation of this invention.

  Embodiments of the present invention will be described in detail below, but the present invention is not limited to the following descriptions, and can be arbitrarily modified and implemented without departing from the gist of the present invention. In addition, in this specification, when expressing by putting a numerical value or a physical-property value before and behind using "-", it shall use as what includes the value before and behind.

The method for producing the thermoplastic elastomer composition of the present invention comprises supplying the following component (A), component (B), component (C), and component (D) to an extruder, and melt-kneading in the extruder. A method for producing a thermoplastic elastomer composition, wherein as the extruder, an extruder having two or more raw material supply ports with different arrangement positions in the extrusion direction is used, and component (A), component (B), And the component (C) and a part of the component (D) are supplied from the first raw material supply port on the most upstream side of the extruder, and the remainder of the component (D) is supplied from the first raw material supply port. It is characterized in that it is supplied to the extruder from one or more other raw material supply ports provided on the downstream side, that is, the softening agent of component (D) is dividedly fed.
Component (A): a block copolymer having a polymer block derived from a vinyl aromatic compound and a polymer block derived from at least one selected from conjugated diene and isobutylene, and hydrogenating the block copolymer At least one block copolymer component (B): (a) an isobutylene polymer having a reactive group, (b) a polyolefin, (c) a polybutene, and (d) a hydrosilyl group. A dynamic heat-treated product of a mixture containing a containing compound. However, (b) polyolefin is at least 1 sort (s) selected from the group which consists of a polyethylene-type resin and a polypropylene-type resin, (c) The number average molecular weights of polybutene are 700-100,000, a) Component (C): Polyolefin resin with a content of (b) polyolefin of 5 to 30 parts by mass and a content of polybutene of 5 to 100 parts by mass with respect to 100 parts by mass of the isobutylene polymer having a reactive group Ingredient (D): Softener

[mechanism]
According to the present invention, the supply of the softening agent of component (D) is supplied from a plurality of locations including the raw material supply port under the hopper of the extruder, and further, the supply distribution is appropriately performed in the extruder. By optimizing the load on each kneading part, the component (B), which is a raw material with low melt fluidity, is highly uniform without deteriorating the quality of mechanical properties and increasing the excessive load on the extruder. Can be dispersed.

On the other hand, when the total amount of the softening agent of component (D) is mixed with other components and supplied from the first raw material supply port under the hopper of the extruder, the softening agent lowers the melt viscosity of the mixture, and the melt flow It becomes difficult to apply the kneading to disperse the components having low properties.
On the other hand, if the softener is not supplied from the first raw material supply port from below the hopper and is supplied only from the middle portion of the cylinder of the extruder, the raw material supplied from the first raw material supply port below the extruder hopper is Since the softener is not included, the cylinder from the first raw material supply port to the softener feed section is kneaded with the raw material having a high melt viscosity, and therefore a load is applied to the extruder (extruder torque is reduced). If it is significant, production will stop. That is, since the extruder is designed to be interlocked to stop when the normal torque exceeds a certain value to prevent failure, the operation is stopped due to the torque increase of the extruder.
In addition, when such a large load is applied, the raw material becomes excessively kneaded, and there is a concern that mechanical properties such as tensile strength and elongation of the product are lowered.

  According to the present invention, by dividing feed of the softener of component (D) and optimizing the kneading of raw materials, it is possible to reduce flaws by uniform dispersion without deteriorating mechanical properties and the like, and high quality thermoplasticity An elastomer composition can be obtained.

[Method for producing thermoplastic elastomer composition]
The method for producing the thermoplastic elastomer composition of the present invention is obtained by supplying components (A) to (D) described below and other components used as necessary to an extruder, and melt-kneading the thermoplastic elastomer composition. Is produced by dividing and feeding the softener of component (D).

  Specifically, as shown in FIG. 1, using an extruder 1 having two or more raw material supply ports with different arrangement positions in the extrusion direction, the component (A), component (B), component (C) and Without melting part of the component (D), for example, a raw material mixture obtained by mixing at 100 ° C. or less is charged from the hopper 13 to the raw material supply port of the extruder, and the remainder of the component (D) is placed downstream of the extruder. The component (D) is dividedly fed so as to be supplied to

  The extruder 10 in FIG. 1 has a raw material charging hopper 13 at the uppermost stream portion of a cylinder 12, and a first raw material supply port 14A is provided at the lower portion of the hopper. The second raw material supply port 14B is provided on the downstream side in the extrusion direction of the cylinder 12 from the first raw material supply port 14A. 15 is a vent port and 16 is a die. 1, 2, 3, 4,..., N-2, n-1, and n are cylinder blocks, and the extruder 1 is provided with n cylinder blocks.

The extruder 10 shown in FIG. 1 has two raw material supply ports, but the component (D) may be divided and fed at three or more locations using an extruder having three or more raw material supply ports. .
Further, the component (A), the component (B), and the component (C) may be divided and fed in the same manner as the component (D).

In the present invention, the first raw material supply port 14A of the extruder is preferably provided at the lower portion of the hopper 13 as shown in FIG.
Further, if the second raw material supply port 14B is too close to the first raw material supply port 14A, the above-described effects by dividing and feeding the component (D) cannot be sufficiently obtained, and are separated too much. If so, the remainder of the component (D) supplied from the second raw material supply port 14B may not be sufficiently melt kneaded with other components. Accordingly, the second raw material supply port 14B is positioned in a region where two or more cylinder blocks are downstream from the first raw material supply port 14A below the hopper 13 of the extruder 10 and one or more cylinder blocks are upstream from the vent port 15. It is preferable that the third raw material supply port and the fourth raw material supply port are also provided in this region.

In addition, in order to reliably obtain the above-described effect by feeding the component (D) in a divided manner, the amount of the component (D) supplied from the first raw material supply port 14A is set to D1, the total amount supplied to the extruder. When the amount of component (D) (in FIG. 1, the amount of all components (D) supplied from both first raw material supply port 14A and second raw material supply port 14B) is Dx, D1 / Dx is 0. It is preferable to feed the component (D) in a divided manner so that it becomes 0.8 or less, for example, 0.15 to 0.75.
When D1 / Dx exceeds 0.8, the kneading load applied to the extruder is reduced due to the influence of the softener component (D) to be blended, so that mechanical properties are deteriorated due to excessive kneading, hue is deteriorated, burnt contamination, etc. However, it is not preferable because sufficient kneading strength sufficient to disperse the component (B) having low melt fluidity cannot be obtained. However, if D1 / Dx is too small, the kneading load applied to the extruder becomes too large. Therefore, D1 / Dx is preferably equal to or greater than the above lower limit.

  Thus, the manufacturing method of the thermoplastic elastomer composition of this invention can be performed in accordance with a conventional method except dividing-feeding a component (D).

In order to efficiently produce the thermoplastic elastomer composition, it is preferable to use a continuous kneader such as a single screw extruder or a twin screw extruder as the extruder, and particularly a twin screw extruder having a high kneading performance is used. It is more preferable. As the rotation direction of the extruder screw, either the same direction type or the different direction type can be used, and the number of grooves can be any of the 2-row type and 3-row type.
Further, these extruders are provided with at least two raw material supply ports, a vent port, a cylinder provided with a die, and two screws provided with one or more raw material kneading sections. Those having a structure in which a liquid substance or a powdery substance can be added into the extruder cylinder from the raw material supply ports at more than one place are preferable.

  The melt kneading temperature is not particularly limited as long as it is a temperature at which all components are uniformly dispersed and kneaded, but is preferably melt kneaded at about 120 to 220 ° C. as the cylinder temperature of the extruder.

[Thermoplastic elastomer composition]
Below, each component used for manufacture of a thermoplastic elastomer composition in this invention is demonstrated.
Hereinafter, the thermoplastic elastomer composition produced in the present invention may be referred to as “the thermoplastic elastomer composition of the present invention”.

<Component (A)>
The component (A) used in the present invention is a polymer derived from at least one selected from a polymer block derived from a vinyl aromatic compound (hereinafter sometimes referred to as “block P”), a conjugated diene, and isobutylene. A block copolymer having a block (hereinafter sometimes referred to as “block Q”), and at least one block copolymer in the group consisting of a block copolymer obtained by hydrogenating the block copolymer It is a coalescence.

  The monomeric vinyl aromatic compound constituting the block P is not particularly limited, but styrene derivatives such as styrene and α-methylstyrene are preferable. Of these, styrene is the main component. The block P may contain a monomer other than the vinyl aromatic compound as a raw material. Here, “mainly” in the present invention means 50% by mass or more.

  Examples of the monomer other than the vinyl aromatic compound include ethylene and α-olefin. Moreover, when the block P contains monomers other than the said vinyl aromatic compound as a raw material, the content is less than 50 mass%, Preferably it is 40 mass% or less. When the content of monomers other than vinyl aromatic compounds is within this range, heat resistance and compression set tend to be good.

  Block Q is derived from conjugated dienes and / or isobutylene. The monomeric conjugated diene that can be used in the block Q is not particularly limited, but is preferably mainly composed of butadiene and / or isoprene, and more preferably butadiene and isoprene. The block Q may contain monomers other than conjugated dienes and isobutylene as raw materials.

  Examples of the monomers other than the conjugated diene and / or isobutylene include styrene. Moreover, when the block Q contains monomers other than the said conjugated diene and / or isobutylene as a raw material, the content is less than 50 mass%, Preferably it is 40 mass% or less. When the content of the monomer other than the conjugated diene and / or isobutylene is within this range, bleeding out tends to be suppressed.

The block copolymer of component (A) may be a hydrogenated block copolymer obtained by hydrogenating a block copolymer having the block P and the block Q. More specifically, it may be a hydrogenated block copolymer obtained by hydrogenating double bonds of the block copolymer block Q. In the block copolymer of component (A), the number of blocks P and blocks Q is not particularly limited, but preferably has at least two blocks P and at least one block Q. Although the hydrogenation rate of the block Q is not specifically limited, Preferably it is 80-100 mass%, More preferably, it is 90-100 mass%. By hydrogenating the block Q in the above range, the adhesive properties of the thermoplastic elastomer composition obtained are lowered, the elastic properties are increased, and the durability tends to be excellent. Here, the hydrogenation rate can be measured by ¹³ C-NMR.

  When the conjugated diene monomer constituting the block Q is butadiene, the butadiene in the microstructure can take a 1,4-addition structure and a 1,2-addition structure. In particular, the block Q is hydrogenated. When it is a derivative and is mainly composed of butadiene, the 1,4-addition structure of butadiene in the block Q microstructure is preferably 20 to 100% by mass.

  When the conjugated diene of the monomer constituting the block Q is isoprene, the isoprene in the microstructure can take a 1,2-addition structure, a 1,4-addition structure, and a 3,4-addition structure. Similarly, in particular, when the block Q is a hydrogenated derivative and the block Q is composed of isoprene, the 1,4-addition structure of isoprene in the microstructure of the block Q is 30 to 100% by mass. Is preferred.

  Further, when the block Q is a hydrogenated derivative and the conjugated diene monomer constituting the block Q contains butadiene and isoprene, the 1,4-addition structure of butadiene and isoprene in the microstructure of the block Q is These are preferably 20 to 100% by mass and 30 to 100% by mass, respectively.

In any case, by setting the ratio of the 1,4-addition structure within the above range, the adhesive property of the obtained thermoplastic elastomer composition tends to decrease and the elastic property tends to increase. The ratio of 1,4-addition structure (hereinafter sometimes referred to as “1,4-microstructure ratio”) can be measured by ¹³ C-NMR.

  The component (A) in the present invention is not particularly limited as long as it has a structure having a block P and a block Q, and may be any of linear, branched, radial, etc., but the following formula (1) or ( The case where it is a block copolymer represented by 2) is preferable. Furthermore, the block copolymer represented by the following formula (1) or (2) is more preferably a hydrogenated block copolymer obtained by hydrogenation. When the copolymer represented by the following formula (1) or (2) is a hydrogenated block copolymer, the thermal stability is improved.

P- (QP) _m (1)
(PQ) _n (2)
(In the formula, P represents block P, Q represents block Q, m represents an integer of 1 to 5, and n represents an integer of 2 to 5.)

  In formula (1) or (2), m and n are preferably larger in terms of lowering the order-disorder transition temperature as a rubbery polymer, but smaller in terms of ease of production and cost. Good.

  When component (A) is a hydrogenated block copolymer represented by formula (1) or (2) and block Q is composed of butadiene, 1,4-addition of butadiene in the microstructure of block Q The structure is preferably 20 to 100% by mass. Similarly, when the block Q is composed of isoprene, the 1,4-addition structure of isoprene in the microstructure of the block Q is preferably 30 to 100% by mass. Similarly, when the block Q is composed of butadiene and isoprene, the 1,4-addition structure of butadiene and isoprene in the microstructure of the block Q may be 20 to 100% by mass and 30 to 100% by mass, respectively. preferable. In any case, by setting the 1,4-microstructure ratio in the above range, the adhesive properties of the obtained thermoplastic elastomer composition tend to be lowered and the elastic properties tend to be increased.

  The component (A) block copolymer and / or hydrogenated block copolymer (hereinafter sometimes referred to as “(hydrogenated) block copolymer”) is excellent in rubber elasticity, so that the formula (2 The (hydrogenated) block copolymer represented by formula (1) is more preferable than the (hydrogenated) block copolymer represented by formula (1), and m is 3 or less. A (hydrogenated) block copolymer is more preferred, and a (hydrogenated) block copolymer represented by the formula (1) in which m is 2 or less is further preferred, and a formula (1) in which m is 1. (Hydrogenated) block copolymers are most preferred.

  The weight ratio of the block P and the block Q constituting the component (A) is arbitrary, but the block P is more in view of the mechanical strength and the heat fusion strength of the thermoplastic elastomer composition used in the present invention. On the other hand, it is preferable that the number of blocks P is small in terms of flexibility, profile extrusion moldability, and bleed-out suppression.

  The weight ratio of the block P in the component (A) is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and preferably 80% by mass or less, more preferably It is 75 mass% or less, More preferably, it is 70 mass% or less.

  The method for producing component (A) in the present invention is not particularly limited as long as the above structure and physical properties can be obtained. Specifically, for example, it can be obtained by performing block polymerization in an inert solvent using a lithium catalyst or the like by the method described in Japanese Patent Publication No. 40-23798. The block copolymer may be hydrogenated (hydrogenated), for example, as described in JP-B-42-8704, JP-B-43-6636, JP-A-59-133203, and JP-A-60-79005. Can be carried out in an inert solvent in the presence of a hydrogenation catalyst. In this hydrogenation treatment, 50% or more of the olefinic double bonds in the polymer block are preferably hydrogenated, more preferably 80% or more are hydrogenated, and in the polymer block It is preferable that 25% or less of the aromatic unsaturated bond is hydrogenated.

  The number average molecular weight (Mn) of the component (A) in the present invention is not particularly limited, but is preferably 90,000 or more, more preferably 140,000 or more, further preferably 180,000 or more, and preferably 450. , 000 or less, more preferably 410,000 or less, and still more preferably 360,000 or less. When the number average molecular weight of the component (A) is within the above range, moldability and heat resistance tend to be good.

  The weight average molecular weight (Mw) of the component (A) is not particularly limited, but is preferably in the range of 100,000 to 500,000. That is, the weight average molecular weight is preferably 100,000 or more, more preferably 150,000 or more, further preferably 200,000 or more, preferably 500,000 or less, more preferably 450,000 or less, Preferably it is 400,000 or less. There exists a tendency for a moldability and heat resistance to become favorable that the weight average molecular weight of a component (A) is in the said range.

  In addition, in this invention, the weight average molecular weight (Mw) and number average molecular weight (Mn) of a component (A) are the polystyrene conversion values calculated | required by the measurement by a gel permeation chromatography (GPC), The measurement conditions are the following. It is as follows.

(Measurement condition)
Equipment: “HLC-8120GPC” manufactured by Tosoh Corporation
Column: “TSKgel Super HM-M” manufactured by Tosoh Corporation
Detector: Differential refractive index detector (RI detector / built-in)
Solvent: Chloroform Temperature: 40 ° C
Flow rate: 0.5 mL / min Injection volume: 20 μL
Concentration: 0.1% by mass
Calibration data: Monodisperse polystyrene Calibration method: Polystyrene conversion

The block copolymer of the component (A) can be obtained as a commercially available product, and the corresponding product can be appropriately selected from commercially available products.
Commercially available hydrogenated block copolymers include “Clayton (registered trademark) -G series”, “Clayton (registered trademark) -A series” manufactured by Kraton Polymer, “Septon (registered trademark) series” manufactured by Kuraray, Some grades of “Hibler (registered trademark) series”, “Tuftec (registered trademark) series” manufactured by Asahi Kasei Corporation, and the like.
Commercially available products of non-hydrogenated block copolymers include “Clayton (registered trademark) -D series” manufactured by Kraton Polymer Co., Ltd., some grades of “Hylar (registered trademark) series” manufactured by Kuraray Co., Ltd., “ And “Tuffprene (registered trademark) series”.

The thermoplastic elastomer composition of the present invention may contain only one type of component (A), or may contain two or more types having different polymer block compositions and physical properties.
In particular, by using a combination of two or more different molecular weights of the above-mentioned block polymer, contents, types and / or addition structures of the respective monomer constituents constituting the polymer block Q, the heat resistance , Sealing property, moldability and the like can be imparted in a balanced manner, which is preferable.

<Component (B)>
In the present invention, component (B) is a dynamic heat-treated product of a mixture containing (a) an isobutylene polymer having a reactive group, (b) polyolefin, (c) polybutene, and (d) a hydrosilyl group-containing compound. Specifically, (a) 100 parts by mass of an isobutylene polymer having a reactive group is 5 to 30 masses of polyolefin which is at least one selected from the group consisting of (b) a polyethylene resin and a polypropylene resin. And (c) in the presence of 5 to 100 parts by mass of polybutene having a number average molecular weight of 700 to 100,000, (d) a composition formed by crosslinking during melt kneading with a hydrosilyl group-containing compound.

((A) Isobutylene polymer having a reactive group)
(A) The isobutylene-based polymer having a reactive group (hereinafter sometimes referred to as “component (a)”) is capable of forming a crosslinked product by crosslinking by having a reactive group, The reactive group is not particularly limited as long as it has activity for the crosslinking reaction by the later-described (d) hydrosilyl group-containing compound which is a crosslinking agent, and an alkenyl group having a carbon-carbon double bond. In addition, from the viewpoint of reaction activity, the isobutylene polymer of component (a) preferably has a reactive group at the terminal. That is, (a) the isobutylene polymer having a reactive group is preferably an isobutylene polymer having an alkenyl group at the terminal. Specific examples of the alkenyl group of the reactive group include a chain alkenyl group such as a vinyl group, an allyl group, a methylvinyl group, a propenyl group, a butenyl group, a pentenyl group, and a hexenyl group, a cyclopropenyl group, a cyclobutenyl group, and a cyclopentenyl group. And cycloalkenyl groups such as a cyclohexenyl group, and from the viewpoint of steric hindrance, an allyl group is preferred.

  The amount of the reactive group such as an alkenyl group contained in the component (a) can be arbitrarily selected depending on the required properties, but at least 0.2 reactive groups per molecule from the viewpoint of the properties after crosslinking. That is, the reactive group content of the component (a) is preferably 0.2 / mol or more, and the reactive group content is 1.0 or more per molecule (1.0 / Mol or more), more preferably 1.5 or more (1.5 / mol or more) per molecule. If the amount of reactive groups is less than 0.2 per molecule, the crosslinking reaction may not proceed sufficiently. Although there is no restriction | limiting in particular in the upper limit of this reactive group amount, Usually, it is 5 pieces / mol or less. Here, the amount of reactive groups such as alkenyl groups can be determined by 1H-NMR analysis.

  The (a) component isobutylene polymer is a polymer having an isobutylene unit content of more than 50% by mass with respect to all monomer units. The type of the isobutylene polymer is not particularly limited, and any of an isobutylene homopolymer, an isobutylene random copolymer, an isobutylene block copolymer, and the like can be used.

  When the isobutylene polymer is an isobutylene copolymer, the monomers copolymerized with isobutylene are ethylene, propylene, 2-methylpropylene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4 Examples thereof include one or more of methyl-1-pentene, 1-octene, styrene and the like.

  The content of isobutylene units in the isobutylene polymer is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more. As the content of isobutylene units is larger than the above lower limit value, the compatibility with (c) polybutene tends to improve, so the isobutylene polymer is an isobutylene homopolymer with an isobutylene unit content of 100% by mass. Most preferred. In addition, content of the isobutylene unit of an isobutylene-type polymer can be calculated | required by an infrared spectroscopy.

  The weight average molecular weight of the isobutylene polymer is preferably 5,000 to 500,000, particularly 10,000 to 200,000. When the weight average molecular weight of the isobutylene-based polymer is not less than the above lower limit, mechanical characteristics and the like tend to be sufficiently expressed, and when it is not more than the above upper limit, melt kneadability and crosslinking reactivity tend to be excellent.

  Here, the weight average molecular weight of the isobutylene polymer is a value in terms of polystyrene measured by GPC.

  As a method for introducing an alkenyl group at the end of an isobutylene polymer, a polymer having a functional group such as a hydroxyl group as disclosed in JP-A-3-152164 and JP-A-7-304909 is not suitable. Examples thereof include a method of introducing an unsaturated group into a polymer by reacting a compound having a saturated group. In order to introduce an unsaturated group into a polymer having a halogen atom, a method of performing a Friedel-Crafts reaction with alkenylphenyl ether, a method of performing a substitution reaction with allyltrimethylsilane in the presence of a Lewis acid, various phenols, etc. And a method of performing the above-mentioned alkenyl group introduction reaction after introducing a hydroxyl group by performing a Friedel-Crafts reaction. Among these, those in which an allyl group is introduced at the terminal by a substitution reaction of allyltrimethylsilane and chlorine are preferable from the viewpoint of reactivity.

  As the component (a), only one type may be used, or two or more types of different reactive groups, isobutylene polymer monomer compositions, mass average molecular weights, and the like may be used in combination.

((B) Polyolefin))
(B) Polyolefin (hereinafter sometimes referred to as “component (b)”) is selected from the group consisting of polyethylene resins and polypropylene resins, and component (b) is component (a). In addition to functioning as a crosslinking reaction field, the thermoplastic elastomer in the present invention has a function of imparting molding fluidity, heat resistance, and mechanical strength.

  The polyethylene-based resin is a polyolefin resin having an ethylene unit content of more than 50% by mass with respect to all monomer units.

  The type of the polyethylene resin is not particularly limited, and any of an ethylene homopolymer, an ethylene random copolymer, an ethylene block copolymer, and the like can be used.

  When the polyethylene resin is an ethylene copolymer, the monomers copolymerized with ethylene include propylene, 1-butene, 2-methylpropylene, 1-pentene, 3-methyl-1-butene, 1-hexene, One type or two or more types such as 4-methyl-1-pentene and 1-octene can be exemplified.

  The polypropylene resin is a polyolefin resin having a propylene unit content of more than 50% by mass with respect to all monomer units.

  The type of the polypropylene resin is not particularly limited, and any of a propylene homopolymer, a propylene random copolymer, a propylene block copolymer, and the like can be used.

  When the polypropylene resin is a propylene copolymer, the monomers copolymerized with propylene include ethylene, 1-butene, 2-methylpropylene, 1-pentene, 3-methyl-1-butene, 1-hexene, One type or two or more types such as 4-methyl-1-pentene and 1-octene can be exemplified.

  The content of propylene units in the polypropylene resin is preferably 60% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more. When the content of the propylene unit is not less than the above lower limit, the crystallinity of the composition is improved and the heat resistance of the molded product tends to be good. On the other hand, there is no restriction | limiting in particular about the upper limit of content of the propylene unit in a polypropylene-type resin, and it is 100 mass% or less normally. In addition, content of the propylene unit of polypropylene resin can be calculated | required by an infrared spectroscopy.

  Preferred polyethylene-based resins include high-density polyethylene, low-density polyethylene, and linear low-density polyethylene, which are preferable. Examples of the polypropylene resin include homopolypropylene, random polypropylene, and block polypropylene. As the component (b), it is preferable to use a polypropylene resin from the viewpoint of heat resistance.

  Although it does not specifically limit as a melt flow rate (MFR) of (b) component, In the case of a polyethylene-type resin, according to JISK7210, as MFR measured on the conditions of the measurement temperature of 190 degreeC and the measurement load of 21.2N, 0. It is preferably 1 to 100 g / 10 minutes, more preferably 0.5 to 50 g / 10 minutes, and particularly preferably 1 to 30 g / 10 minutes. In the case of polypropylene resin, the MFR measured under the conditions of a measurement temperature of 230 ° C. and a measurement load of 21.2 N according to JIS K7210 is preferably 0.1 to 100 g / 10 minutes, and preferably 0.5 to 50 g. / 10 min is more preferable, and 1 to 30 g / 10 min is particularly preferable. In any case, it is preferable from the viewpoint of molding fluidity that the MFR is not less than the above lower limit, and it is preferable from the viewpoint of improving the dispersibility of the isobutylene polymer during dynamic heat treatment when it is not more than the upper limit.

  As the component (b), only one type may be used, or two or more types having different resin types and physical properties may be used in combination.

  (B) A component uses 5-30 mass parts with respect to 100 mass parts of (a) component. When the amount of the component (b) is less than 5 parts by mass, not only the effects such as sufficient molding fluidity by using the component (b) can be obtained, but also the dispersion of the component (a) becomes insufficient. ) Dynamic heat treatment of components may not proceed uniformly. When the amount of the component (b) is more than 30 parts by mass, the amount of the component exposed to the increase in the resin temperature due to the dynamic heat treatment is increased, so that the composition as a whole is liable to be thermally deteriorated, resulting in discoloration and stickiness of the resulting composition. Occurrence, generation of low molecular weight components, generation of foreign matters such as burns may occur, flexibility may be impaired, and sufficient sealing properties may not be obtained in the obtained thermoplastic elastomer composition. The component (b) is preferably used in an amount of 6 to 25 parts by mass, more preferably 7 to 20 parts by mass with respect to 100 parts by mass of the component (a).

((C) polybutene)
(C) Polybutene having a number average molecular weight of 700 to 100,000 (hereinafter sometimes referred to as “component (c)”) functions as a softening agent for imparting flexibility and molding fluidity. is there.

  When the number average molecular weight of the polybutene as the component (c) is less than 700, bleed out is observed. The number average molecular weight of the (c) component polybutene is preferably 800 to 100,000, more preferably 850 to 80,000.

  Here, the number average molecular weight of polybutene is a value in terms of polystyrene measured by GPC.

  (C) A component uses 5-100 mass parts with respect to 100 mass parts of (a) component. When the amount of the component (c) is less than 5 parts by mass, the above-described effect due to the use of the component (c) cannot be sufficiently obtained, and when the amount is more than 100 parts by mass, there is a fear of bleeding out. The component (c) is preferably used in an amount of 10 to 80 parts by mass, more preferably 20 to 70 parts by mass with respect to 100 parts by mass of the component (a).

((D) hydroxyl group-containing compound)
(D) A hydroxyl group-containing compound (hereinafter sometimes referred to as “component (d)”) functions as a crosslinking agent for component (a).

Although there is no restriction | limiting in particular in the hydrosilyl group containing compound of (d) component, Hydrosilyl group containing polysiloxane is preferable and various things can be used. Among them, a hydrosilyl group-containing polysiloxane having 3 or more hydrosilyl groups and 3 to 500 siloxane units is preferred, and a hydrosilyl group polysiloxane having 3 or more hydrosilyl groups and 10 to 200 siloxane units. Siloxane is more preferable, and hydrosilyl group polysiloxane having 3 or more hydrosilyl groups and 20 to 100 siloxane units is particularly preferable. When the number of hydrosilyl groups is less than 3, sufficient growth of the network due to crosslinking tends not to be achieved and optimum rubber elasticity tends to be not obtained. When the number of siloxane units exceeds 500, the viscosity of the polysiloxane is high (a) There is a tendency that the dispersibility in the component is lowered and the progress of the crosslinking reaction becomes insufficient. The polysiloxane unit mentioned here refers to a partial structure represented by the following general formula (I), (II), or (III).
[Si (R ¹ ) ₂ O] (I)
[Si (H) (R ² ) O] (II)
[Si (R ² ) (R ³ ) O] (III)
(In the above formula, R ¹ and R ² represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R ³ represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group.)

  As the hydrosilyl group-containing polysiloxane, one or more of a chain polysiloxane represented by the following general formula (IV) or (V) and a cyclic polysiloxane represented by the following general formula (VI) are used. be able to.

(In the above formulas (IV) to (VI), R ¹ and R ² represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R ³ represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group. B Is an integer satisfying 3 ≦ b, a, b, c is 3 ≦ a + b + c ≦ 500. E is an integer satisfying 3 ≦ e, and d, e, f is an integer satisfying d + e + f ≦ 500.)

  The component (d), the hydrosilyl group-containing compound, can be used in any proportion, but from the viewpoint of crosslinking speed, the amount of hydrosilyl group relative to the reactive group such as the alkenyl group (a) (hydrosilyl group / reactive group) ) Is preferably used in a molar ratio of 0.5 to 10, and more preferably 1 to 5. When this molar ratio is less than 0.5, crosslinking tends to be insufficient, and when it is more than 10, a large amount of active hydrosilyl groups remain even after crosslinking, so that volatile matter tends to be generated. .

(Hydrosilylation catalyst)
The crosslinking reaction between the component (a) and the component (d) proceeds by mixing and heating the two components, but it is preferable to add a hydrosilylation catalyst in order to advance the reaction more rapidly. Such hydrosilylation catalyst is not particularly limited, and examples thereof include radical generators such as organic peroxides and azo compounds, and transition metal catalysts.

  The radical generator is not particularly limited, and examples thereof include di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di ( t-butylperoxy) -3-hexyne, dicumyl peroxide, t-butylcumyl peroxide, dialkyl peroxides such as α, α′-bis (t-butylperoxy) isopropylbenzene, benzoyl peroxide, p-chlorobenzoyl peroxide, m-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diacyl peroxides such as lauroyl peroxide, peracid esters such as t-butyl perbenzoate, diisopropyl percarbonate, di-2-ethylhexyl percarbonate Peroxydicarbonate such as 1,1 Examples thereof include peroxyketals such as -di (t-butylperoxy) cyclohexane and 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane.

Also, it is not particularly limited as a transition metal catalyst, for example, platinum simple substance, alumina, silica, carbon black or the like dispersed in a platinum solid, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, ketone, etc. And a platinum-olefin complex and a platinum (0) -dialkenyltetramethyldisiloxane complex. Examples of the catalyst other than platinum _{compounds, RhCl (PPh 3) 3,} RhCl 3, RuCl 3, IrCl 3, FeCl 3, AlCl 3, PdCl 2 · H 2 O, NiCl 2, TiCl 4 and the like (here "Ph" represents "phenyl group". These catalysts may be used alone or in combination of two or more. Of these, platinum vinylsiloxane is preferred in terms of crosslinking efficiency.

Although there is no restriction | limiting in particular as a hydrosilylation catalyst amount, It is good to use in the range of 10 ^{< -1} > ^-10 <^-8> mol with respect to 1 mol of reactive groups of (a) component, Preferably it is 10 ^<-3 > ^-10 <^-6>. It is good to use in the range of mole. When the amount of the catalyst is not less than the above lower limit, there is a tendency that the crosslinking proceeds sufficiently, and when it is not more than the above upper limit, heat generation is suppressed and the crosslinking reaction tends to be sufficiently controlled.

(Production method of component (B))
Component (B) is obtained by subjecting a mixture containing (a) component, (b) component, (c) component and (d) component, and other components such as the aforementioned hydrosilylation catalyst as necessary, to dynamic heat treatment. By this dynamic heat treatment, the cross-linking reaction in which the (a) component is cross-linked by the (d) component proceeds in the presence of the (b) and (c) components to become a cross-linked product.

  In the present invention, “dynamic heat treatment” means kneading in a molten state or a semi-molten state. This dynamic heat treatment is preferably performed by melt kneading, and there is no particular limitation on the heat kneading apparatus for that purpose. For example, a single screw extruder, twin screw extruder, roll, Banbury mixer, Brabender, kneader, high A shearing type mixer etc. are mentioned. Moreover, as the order of the addition, after the component (b) is melted, the component (a) is added to the melted component (b) and component (c), and if necessary, other components are added, A method is preferred in which after uniform mixing, the crosslinking reaction of component (d) and a hydrosilylation catalyst are added to advance the crosslinking reaction. The hydrosilylation catalyst may be mixed with the liquid component (c) and added.

  The temperature for melt kneading during the dynamic heat treatment is preferably 130 to 240 ° C. If this temperature is 130 ° C. or higher, the component (b) is sufficiently melted and tends to be uniformly kneaded. If this temperature is 240 degrees C or less, the thermal decomposition of (a) component can be suppressed. The melt kneading time is usually about 1 to 10 minutes.

  In the thermoplastic elastomer composition of the present invention, the above-mentioned (a) isobutylene polymer having a reactive group is at least one selected from the group consisting of a predetermined amount of (b) a polyethylene resin and a polypropylene resin. The effect of component (B) obtained by dynamic heat treatment with (d) hydrosilyl group-containing compound in the presence of polyolefin as seed and (c) polybutene having a number average molecular weight of 700 to 100,000 is assuredly obtained. In the above, the component (B) is composed of (a) component, (b) component, (c) component, (d) component and the above-mentioned hydrosilylation catalyst used as necessary in total by dynamic heat treatment. (B) is preferably blended so as to be contained in the raw material mixture for producing 50% by mass or more, particularly 60% by mass or more, especially 80 to 100% by mass. It is preferably blended.

  The crosslinked elastomer used for the component (B) can be obtained as a commercial product. Examples of the commercially available products include “Sibster (registered trademark) series” manufactured by Kaneka Corporation, and the products can be appropriately selected from these and used.

  The thermoplastic elastomer composition of the present invention may contain only one type of component (B), and contains two or more types of components (a) to (d) with different types and blends. There may be.

<Ingredient (C)>
The component (C) is selected from the group consisting of polyethylene resins and polypropylene resins, and has a function of imparting molding fluidity, heat resistance, and mechanical strength to the thermoplastic elastomer in the present invention.

  The polyethylene-based resin is a polyolefin resin having an ethylene unit content of more than 50% by mass with respect to all monomer units.

  The type of the polyethylene resin is not particularly limited, and any of an ethylene homopolymer, an ethylene random copolymer, an ethylene block copolymer, and the like can be used.

  When the polyethylene resin is an ethylene copolymer, the monomers copolymerized with ethylene include propylene, 1-butene, 2-methylpropylene, 1-pentene, 3-methyl-1-butene, 1-hexene, One type or two or more types such as 4-methyl-1-pentene and 1-octene can be exemplified.

  The polypropylene resin is a polyolefin resin having a propylene unit content of more than 50% by mass with respect to all monomer units.

  The type of the polypropylene resin is not particularly limited, and any of a propylene homopolymer, a propylene random copolymer, a propylene block copolymer, and the like can be used. Moreover, in order to improve moldability, a modified polypropylene can also be used.

  When the polypropylene resin is a propylene copolymer, the monomers copolymerized with propylene include ethylene, 1-butene, 2-methylpropylene, 1-pentene, 3-methyl-1-butene, 1-hexene, One type or two or more types such as 4-methyl-1-pentene and 1-octene can be exemplified.

  The modified polypropylene is preferably a propylene-based (co) polymer having a branched structure or a propylene-based (co) polymer having a high molecular weight component. Examples of such propylene-based (co) polymers include linear propylene homopolymers, propylene homopolymers, block copolymers, and random copolymers that are irradiated with radiation on linear polypropylene resins. Examples thereof include a crystalline propylene (co) polymer obtained by melt-mixing a polypropylene resin, a diene compound, and a radical polymerization initiator. Among these, modified polypropylene graft-modified with a diene compound is particularly preferable.

  Examples of the diene compound used in the modified polypropylene include diene compounds such as butadiene, isoprene, 1,3-heptadiene, 2,3-dimethylbutadiene, and 2,5-dimethyl-2,4-hexadiene. These compounds may be used alone or in any combination and ratio of two or more. Among these, butadiene and isoprene are preferable, and isoprene is particularly preferable.

  The content of propylene units in the polypropylene resin is preferably 60% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more. When the content of the propylene unit is not less than the above lower limit, the crystallinity of the thermoplastic elastomer composition is improved, and the resulting molded article tends to have good heat resistance. On the other hand, there is no restriction | limiting in particular about the upper limit of content of the propylene unit in a polypropylene-type resin, and it is 100 mass% or less normally.

  In addition, content of the ethylene unit of polyethylene-type resin and content of the propylene unit of polypropylene-type resin can be calculated | required by infrared spectroscopy.

  Although it does not specifically limit as a melt flow rate (MFR) of a component (C), In the case of a polyethylene-type resin, according to JISK7210, as MFR measured on the conditions of the measurement temperature of 190 degreeC and the measurement load of 21.2N, 0. It is preferably 1 to 100 g / 10 minutes, more preferably 0.5 to 50 g / 10 minutes, and particularly preferably 1 to 30 g / 10 minutes. In the case of a polypropylene resin, the MFR measured under the conditions of a measurement temperature of 230 ° C. and a measurement load of 21.2 N according to JIS K7210 is preferably 0.1 to 100 g / 10 minutes, preferably 0.5 to 80 g. / 10 min is more preferable, and 1 to 70 g / 10 min is particularly preferable. In any case, it is preferable from the viewpoint of molding fluidity that MFR is not less than the above lower limit, and it is preferable from the viewpoint of improving dispersibility of each component if it is not more than the above upper limit.

  The polyolefin resin used for the component (C) can be obtained as a commercial product. Examples of the polyethylene resin include “Novatech (registered trademark) HD series”, “Novatech (registered trademark) LL series”, “Novatech (registered trademark) LD series”, and “Kernel (registered trademark) series” manufactured by Japan Polyethylene Corporation. Examples of the polypropylene-based resin include “Novatech (registered trademark) PP series”, “Wintech (registered trademark) series”, “Wellnex (registered trademark) series” manufactured by Nippon Polypro Co., Ltd. Applicable products can be appropriately selected from these and used.

  The thermoplastic elastomer composition of the present invention may contain only one type of component (C), or may contain two or more types having different monomer compositions and physical properties.

<Component (D)>
The softening agent for component (D) used in the thermoplastic elastomer composition of the present invention is preferably a hydrocarbon rubber softening agent. Component (D) softens the thermoplastic elastomer composition, improves flexibility, elasticity, processability, and fluidity, and contributes to improving the appearance and the like of the resulting molded article.

  As the softener for hydrocarbon rubber, in addition to mineral oil softener and synthetic resin softener, vinyl polymer having low polymerization degree (olefin polymer, diene compound polymer, liquid at room temperature (20 ° C.), Acrylic polymer, etc.). In addition, the hydrocarbon rubber softening agent may be used alone, or two or more may be used in any combination and ratio.

  The kinematic viscosity at 40 ° C. of the hydrocarbon rubber softener is not particularly limited, but is preferably 500 cSt or less, and particularly preferably 50 to 450 cSt.

  The hydrocarbon rubber softener of component (D) can be obtained as a commercial product. Examples of the commercially available products include “Diana (registered trademark) process oil PW series” manufactured by Idemitsu Kosan Co., Ltd., “Lucanto (registered trademark) series” manufactured by Mitsui Chemicals, and “Nisseki polybutene (manufactured by JX Nippon Oil & Energy Corporation) (Registered trademark) HV series "and the like, and the appropriate products can be appropriately selected from these and used.

  The thermoplastic elastomer composition of the present invention may contain only one type of component (D), or may contain two or more types in any combination and in any ratio.

<Use ratio of components (A) to (D)>
In the method for producing the thermoplastic elastomer composition of the present invention, the ratio of the component (A) in the total 100 parts by mass of the components (A) to (D) is 5 to 80 parts by mass, particularly 10 to 50 parts by mass. It is preferable to use the component (A) for. If the ratio of a component (A) is more than the said minimum, the moldability of a product will become favorable. Moreover, since it does not impair the heat resistant fall of a product if it is below the said upper limit, it is preferable.

  Moreover, it is preferable to use a component (B) so that the ratio of the component (B) in a total of 100 mass parts of components (A)-(D) may be 3-60 mass parts, especially 5-50 mass parts. If the ratio of the component (B) is equal to or higher than the above lower limit, a quality improvement effect by blending the component (B) such as compression set or gas barrier property can be expected. This is preferable because the resulting formability does not deteriorate.

  Moreover, it is preferable to use a component (C) so that the ratio of the component (C) in a total of 100 mass parts of components (A)-(D) may be 3-50 mass parts, especially 5-40 mass parts. If the ratio of a component (C) is more than the said minimum, the fluidity required for the shaping | molding of a product can be provided, and if it is below the said upper limit, it is preferable at the point of hardness and rubber elasticity.

  Moreover, it is preferable to use a component (D) so that the ratio of the component (D) in a total of 100 mass parts of components (A)-(D) may be 5-70 mass parts, especially 10-60 mass parts. If the ratio of the component (D) is not less than the above lower limit, flexibility necessary for the product and fluidity necessary for molding can be imparted, and if it is not more than the above upper limit, the bleed of the component (D) after molding. This is preferable because there is no concern about the out.

<Other ingredients>
In the thermoplastic elastomer composition of the present invention, in addition to the above-mentioned components (A) to (D), other components can be blended as necessary within a range not impairing the effects of the present invention.

  Examples of other components include resins such as thermoplastic resins and elastomers other than the above-described components (A), (B), and (C), fillers, antioxidants, thermal stabilizers, and light stabilizers. UV absorbers, neutralizers, lubricants, antifogging agents, antiblocking agents, dispersants, colorants, flame retardants, flame retardant aids, antistatic agents, conductivity enhancers, metal deactivators, molecular weight adjustment And various additives such as agents, crystal nucleating agents, impact modifiers, pigments, compatibilizers, tackifiers, antibacterial agents, fungicides, and fluorescent brighteners. Any of these may be used alone or in combination.

  Examples of the thermoplastic resin other than the above components (A), (B) and (C) include, for example, polyphenylene ether resins; polyamide resins such as nylon 6, nylon 66, nylon 11, etc .; polyethylene terephthalate, polybutylene Polyester resins such as terephthalate; polyoxymethylene resins such as polyoxymethylene homopolymers and polyoxymethylene copolymers; acrylic / methacrylic resins such as polymethyl methacrylate resins, ethylene-vinyl acetate copolymers, polyurethane resins, Polycarbonate resin, polyvinyl chloride resin, polyolefin resin (but excluding those corresponding to component (C)) and the like. Examples of elastomers other than component (A), component (B) and component (C) include ethylene / propylene copolymer rubber (EPM), ethylene / propylene / non-conjugated diene copolymer rubber (EPDM), ethylene / propylene copolymer rubber (EPDM), and ethylene / propylene copolymer rubber (EPDM). Olefin elastomers such as butene copolymer rubber (EBM), ethylene / propylene / butene copolymer rubbers; polyvinyl chloride elastomers and polybutadiene elastomers; styrenes such as styrene / butadiene copolymer rubbers and styrene / isoprene copolymer rubbers Elastomers (excluding those corresponding to the components (A) and (B)); polyester elastomers, those hydrogenated or acid anhydrides that have been modified to introduce polar functional groups, Furthermore, other monomers may be grafted, random and / or block copolymerized. It is. These components may be used alone or in combination of two or more in any ratio.

  Fillers are roughly classified into organic fillers and inorganic fillers. Examples of the organic filler include naturally occurring polymers such as starch, cellulose fine particles, wood flour, okara, fir husk, bran, and modified products thereof. Inorganic fillers include talc, calcium carbonate, zinc carbonate, wollastonite, silica, alumina, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, glass balloon, carbon Black, zinc oxide, antimony trioxide, zeolite, hydrotalcite, metal fiber, metal whisker, ceramic whisker, potassium titanate, boron nitride, graphite, carbon fiber, glass fiber, mica, metal soap, titanium dioxide, etc. . When using a filler, it is normally used by 0.1-50 mass parts with respect to 100 mass parts in total of a component (A)-a component (D).

  Examples of the heat stabilizer and the antioxidant include hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, alkali metal halides, and the like. When using a heat stabilizer and antioxidant, it is normally used in the range of 0.01-3 mass parts with respect to a total of 100 mass parts of the above-mentioned component (A) -component (D).

  Examples of the lubricant include silicone oil, fatty acid amide, fatty acid glyceride and the like. When using a lubricant, it is normally used in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass in total of the above components (A) to (D).

<Application>
The thermoplastic elastomer composition of the present invention has excellent moldability and flexibility, has high compression set resistance even at high temperatures, and has excellent gas barrier properties, water vapor barrier properties, bleed resistance, molded appearance, and sealing properties. It is suitably used for various molded products such as automobiles, home appliances, electrical equipment, medical equipment, packaging materials, stationery and miscellaneous goods, and various members such as grips, tubes, packings, gaskets, films and sheets.

  Hereinafter, although the specific aspect of this invention is demonstrated in detail using an Example, this invention is not limited by a following example, unless the summary is exceeded. In addition, the value of various manufacturing conditions and evaluation results in the following examples has a meaning as a preferable value of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-described upper limit or lower limit value. A range defined by a combination of values of the following examples or values of the examples may be used.

[material]
The materials used in Examples and Comparative Examples are shown below.

(Ingredient (A))
A-1: “Septon (registered trademark) J3341” manufactured by Kuraray Co., Ltd.
Hydrogenated product of styrene-isoprene-butadiene-styrene block copolymer Weight average molecular weight (Mw): 340,000
Number average molecular weight (Mn): 230,000
Styrene unit content: 40% by mass
1,4-microstructure ratio of isoprene: 94%
1,4-microstructure ratio of butadiene: 93%
A-2: “Hibler (registered trademark) 7135” manufactured by Kuraray Co., Ltd.
Hydrogenated product of styrene-isoprene-styrene block copolymer Weight average molecular weight: 280,000
Number average molecular weight (Mn): 140,000
Styrene unit content: 33% by mass
1,4-microstructure ratio: 41%
A-3: “Clayton (registered trademark) A1535HU” manufactured by Kraton Polymer Co., Ltd.
Hydrogenated product of styrene-butadiene-styrene block copolymer Weight average molecular weight (Mw): 270,000
Number average molecular weight (Mn): 250,000
Styrene unit content: 58% by mass
1,4-microstructure ratio: 70%

(Ingredient (B))
B: “Sibustar (registered trademark) P1140B” manufactured by Kaneka Corporation
(A) Polyisobutylene having an allyl group (weight average molecular weight: 50,000): 100 parts by mass, (b1) component: polypropylene (MFR (JIS-K7210 (230 ° C., 21.2 N load) = 7 g / 10 min) 11 parts by mass, (c) component: 40 parts by mass of polybutene (number average molecular weight = 960), and (d) component: (CH ₃ ) ₃ SiO— [Si (H) (CH ₃ ) O] ₄₈ —Si (CH ₃ ) Hydrosilyl group-containing polysiloxane represented by ₃

<Ingredient (C)>
C: Kaneka's isoprene-grafted modified polypropylene “039N”
Modified polypropylene obtained by grafting isoprene to polypropylene homopolymer MFR (JIS K7210 (230 ° C., load 21.2 N): 60 g / 10 min. Propylene unit content: 99% by mass or more

<Component (D)>
D: “Diana (registered trademark) process oil PW90” manufactured by Idemitsu Kosan Co., Ltd.
Paraffinic oil Kinematic viscosity at 40 ° C: 95.5 cSt

<Other ingredients>
Filler (E) "Microace (registered trademark) K-1" (talc) manufactured by Nippon Talc
Antioxidant (F): “Irganox (registered trademark) 1330” (hindered phenol antioxidant) manufactured by BASF Japan
Lubricant (G): “SH200-100CS” manufactured by Toray Dow Corning (silicone oil, kinematic viscosity (25 ° C.): 100 cSt)

[Examples 1 to 3]
In the formulation shown in Table 1, components (A-1, A-2, A-3), component (B), component (C), part of component (D), filler (E), antioxidant (F) and the lubricant (G) were mixed without melting. These blended products are supplied from the first raw material supply port installed under the hopper of the same-direction twin screw extruder (“TEX-30α” manufactured by Nippon Steel Works, cylinder diameter: 32 mm), and the remaining components (D ) Is added directly to the extruder from the second raw material supply port provided in the middle of the extruder cylinder, and the total supply rate from both raw material supply ports is 20 kg / hr. The mixture was melt kneaded at an elevated temperature to produce a thermoplastic elastomer composition. In Table 1, the amount of the softening agent component (D) supplied from the first raw material supply port blended with other raw materials and installed under the hopper is set to D1, directly from the second raw material supply port to the extruder. The amount of the softener component (D) added is described as D2. The ratio of D1 to be supplied and the total softener component (D) amount Dx (Dx is the sum of D1 and D2) is also shown in Table 1.

  The extruder has a total of 13 cylinder blocks, the first raw material supply port at the bottom of the hopper in the first cylinder block, the second raw material supply port at the 10th cylinder block, and the vent at the 12th cylinder block. The one having a mouth was used.

The resulting thermoplastic elastomer composition was molded into a sheet using an injection molding machine (“IS130GN-5A” manufactured by Toshiba Machine Co., Ltd.). The injection molding conditions were resin temperature: 180-240 ° C., injection time: 2-20 seconds, mold temperature: 20-60 ° C., cooling time: 10-50 seconds.
The following (1) to (4) were evaluated using the obtained injection-molded sheet (thickness 2 mm). These evaluation results are shown in Table-1.

(1) Flexibility (Duro hardness A)
The hardness (type A durometer) was measured based on ISO7619-1. (2) Compression set The compression set was measured based on ISO815.
(3) Tensile fracture strength Based on ISO527, the tensile fracture strength was measured.
(4) Tensile fracture elongation The tensile fracture elongation was measured based on ISO527.

Further, 1 g of the obtained thermoplastic elastomer composition was sandwiched between transparent PET films, and the press sheet was formed by the following pressing procedure 1) → 2) → 3), and the obtained press sheet was placed in 5 cm × 5 cm (25 cm ² ). By counting the number of gels having a diameter of 0.5 mm or more, the appearance of the molded body and the surface roughness index were obtained. These results are shown in Table-1.
Pressing procedure 1) Pressing temperature 200 ° C., pressurizing for 3 minutes without pressure 2) Pressing temperature 200 ° C., pressurizing for 3 minutes at 8 MPa Pressing procedure 3) Pressurizing to 10 MPa and cooling for 3 minutes

[Comparative Examples 1 and 2]
In Example 1, the thermoplastic elastomer composition was produced in the same manner except that the raw material composition was as shown in Table 1, and all the softener components (D) were supplied from the first raw material supply port. Evaluation was performed and the results are shown in Table 1.

  From Table 1, it can be confirmed that the number of gels generated in Examples 1, 2, and 3 is significantly smaller than the number of gels derived from the component (B) generated in Comparative Examples 1 and 2. Moreover, also about the tensile breaking strength of Example 1, 2, 3, and the tensile breaking elongation, all have shown the value higher than the comparative examples 1 and 2, and highly disperse | distributed the component (B) with low fluidity | liquidity. It can be confirmed that the mechanical properties are also improved.

DESCRIPTION OF SYMBOLS 10 Extruder 12 Cylinder 13 Hopper 14A 1st raw material supply port 14B 2nd raw material supply port 15 Vent port 16 Dice

Claims (3)

A method for producing a thermoplastic elastomer composition by supplying the following component (A), component (B), component (C), and component (D) to an extruder and melt-kneading in the extruder: As the extruder, an extruder having two or more raw material supply ports with different arrangement positions in the extrusion direction is used.
Component (A), component (B), component (C), and part of component (D) are supplied from the most upstream first raw material supply port of the extruder, and the remainder of component (D) Is supplied to the extruder from one or more other raw material supply ports provided on the downstream side of the first raw material supply port.
Component (A): a block copolymer having a polymer block derived from a vinyl aromatic compound and a polymer block derived from at least one selected from conjugated diene and isobutylene, and hydrogenating the block copolymer At least one block copolymer component (B): (a) an isobutylene polymer having a reactive group, (b) a polyolefin, (c) a polybutene, and (d) a hydrosilyl group. A dynamic heat-treated product of a mixture containing a containing compound. However, (b) polyolefin is at least 1 sort (s) selected from the group which consists of a polyethylene-type resin and a polypropylene-type resin, (c) The number average molecular weights of polybutene are 700-100,000, a) Component (C): Polyolefin resin with a content of (b) polyolefin of 5 to 30 parts by mass and a content of polybutene of 5 to 100 parts by mass with respect to 100 parts by mass of the isobutylene polymer having a reactive group Ingredient (D): Softener   The manufacturing method of the thermoplastic-elastomer composition of Claim 1 with which the said 1st raw material supply port is installed under the hopper which supplies a raw material to the said extruder.   When the amount of the component (D) supplied from the first raw material supply port is D1, and the total amount of the component (D) supplied to the extruder is Dx, D1 / Dx is 0.8 or less. The manufacturing method of the thermoplastic-elastomer composition of Claim 1 or 2.

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