JP3518022B2 - Thermoplastic elastomer composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to wear resistance, slip resistance,
A thermoplastic elastomer composition having excellent mechanical strength, stretchability, moldability, molding appearance, and lightness, a top lift,
Footwear bottom materials such as sports shoes, food applications, daily sundries applications, ski equipment, exercise equipment, toys applications, car interior materials such as car mat materials, civil engineering sheets, waterproofing sheets and other civil engineering / construction applications, home appliance applications, AV Equipment applications, O. A
・ For office equipment, hose / tube materials, textile applications, medical equipment applications, chemical / mining and industrial materials, packaging / transportation materials, agricultural / livestock / fisheries materials, etc., particularly thermoplastic elastomer compositions useful as footwear sole materials .

[0002]

2. Description of the Related Art Conventionally, a polyamide resin or a thermoplastic polyurethane resin having excellent wear resistance has been used for footwear bottom materials such as top lifts, soccer shoes, and baseball shoes. However, these resins are expensive and have a problem of deterioration of physical properties due to hydrolysis. Further, the thermoplastic polyurethane resin has a problem that it is very difficult to mold. Therefore, the advent of inexpensive alternative materials having excellent wear resistance and moldability is desired.

[0003]

The present invention has been made against the background of the above-mentioned problems of the prior art, and has the following features: wear resistance, slip resistance, mechanical strength, stretchability, moldability, molding appearance, and lightness. An object is to provide an excellent thermoplastic elastomer composition.

[0004]

The present invention provides (a) 1, 2
-65% to 80 % by weight of 1,2-polybutadiene having a bond amount of 70% or more and a crystallinity of 5 to 50%, (b) 10 to 30% by weight of a polyolefin resin, and (c) a conjugated diene polymer. 1 to 15% by weight of a hydrogenated diene-based polymer having a number average molecular weight of 50,000 to 700,000 in which the double bond of the conjugated diene portion is saturated by 80% or more [however, (a) + (b)).
+ (C) = 100% by weight] as a main component.

The (a) 1,2-polybutadiene of the present invention has a 1,2-bond content of 70% or more, preferably 85% or more. If it is less than 70%, the rubber-like properties will be enhanced, resulting in poor moldability. Also, (a) 1,2-
Polybutadiene has a crystallinity of 5 to 50%, preferably 20 to 50%. When the crystallinity is in this range, the balance of physical properties such as mechanical strength, stretchability and molding heat stability is excellent. The intrinsic viscosity [η] of (a) 1,2-polybutadiene is preferably 0.5 dl / g or more, more preferably 0.7 to 3 dl / g. Within this range, the balance of physical properties such as moldability, mechanical strength and stretchability is excellent.

The content of (a) 1,2-polybutadiene in the composition of the present invention is 65 to 8 in the components (a) to (c).
0 % by weight, and if less than 65% by weight, slip resistance is poor,
On the other hand, mechanical strength exceeding 80 % by weight and abrasion resistance are poor.

Next, the polyolefin resin used as the component (b) used in the present invention is a resin obtained by polymerizing one or more monoolefins by either a high pressure method or a low pressure method. . This polyolefin resin may be a homopolymer or a copolymer obtained by polymerizing the following monomers.

In the component (b), preferable copolymerizable monomers include, for example, ethylene, and linear α such as propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1. -Olefins,
4-methylpentene-1,2-methylpropene-1,3
-Methylpentene-1,5-methylhexene-1,4-
Branched α-olefins such as methylhexene-1,4,4-dimethylpentene-1, monocarboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid and crotonic acid,
Dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid and citraconic acid and their monoesters, acrylic or methacrylic acid esters such as methyl methacrylate, methyl acrylate and ethyl acrylate, vinyls of saturated carboxylic acids such as vinyl acetate and vinyl propionate Aromatic vinyl compounds such as esters, styrene, α-methylstyrene and p-methylstyrene, maleic anhydride, itaconic anhydride, citraconic anhydride, aconitic anhydride, and acid anhydrides such as acrylonitrile and methacrylonitrile. -Unsaturated nitrile, 1,4-hexadiene, dicyclopentadiene, diene monomer such as ethylidene norbornene, acrylamide, methacrylamide, maleimide and the like are used. These other copolymerizable monomers may be used alone or in combination of two or more kinds. The amount of these copolymerization components is preferably 20% by weight or less, more preferably 10% by weight or less. There is no particular limitation on the form of the copolymer when these are copolymerized, for example, random type, block type,
Any of a graft type and a mixed type thereof may be used.

As the homopolymer used as the component (b), polyethylene, polypropylene, polybutene-
1, and preferred copolymers include propylene-ethylene copolymer and propylene-butene-1.
Copolymer, butene-1-ethylene copolymer, propylene-ethylene-butene-1 copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer,
Ethylene-ethyl methacrylate copolymer, ethylene-
Examples thereof include a methyl acrylate copolymer, an ethylene-methyl methacrylate copolymer, an ethylene-n-butyl acrylate copolymer and the like. These (b) polyolefin resins can be used alone or in combination of two or more.

The melt flow rate (MFR) (AST) of the (b) polyolefin resin used in the present invention is
MD 1238, 230 ° C., 2.16 kg load) is preferably 0.01 to 100 g / 10 minutes, more preferably 0.1 to 80 g / 10 minutes.

The blending amount of the (b) polyolefin resin in the composition of the present invention is 10 to 30 in the components (a) to (c).
If it is less than 10 % by weight, the abrasion resistance is inferior, and if it exceeds 30 % by weight, the slip resistance is inferior.

Next, the component (C) used in the present invention is
The double bond of the conjugated diene portion of the conjugated diene polymer is 80
% Or more, preferably 90% or more, more preferably 95
% Hydrogenated diene polymer having a number average molecular weight of 50,000 to 700,000, preferably 100,000 to 600,000. If the hydrogenation rate is less than 80%, the mechanical strength, heat resistance and weather resistance will be poor. When the number average molecular weight is less than 50,000, the hydrogenated diene-based polymer obtained is easily blocked when pelletized, and when blended with another resin, mechanical strength and molding appearance are poor. If it exceeds 10,000, the moldability will be poor.

Examples of the component (c) include a homopolymer of a conjugated diene, a random copolymer of a conjugated diene and an aromatic vinyl compound, a block composed of a polymer block of an aromatic vinyl compound and a polymer block of a conjugated diene. Examples thereof include hydrogenated products of diene-based polymers such as copolymers and block copolymers composed of a polymer block of an aromatic vinyl compound and a copolymer block of an aromatic vinyl compound / conjugated diene.

The component (C) is preferably at least one hydrogenated diene polymer selected from the group (C-1), (C-2) and (C-3) below. By using, it is possible to obtain a thermoplastic elastomer composition having further excellent mechanical strength, stretchability and moldability.

(C-1): (A) -consisting of an aromatic vinyl compound polymer block (A) and a conjugated diene polymer or a random copolymer block of an aromatic vinyl compound and a conjugated diene (B). (B) or (A)-
(B)-(A) block copolymer, or (A)-(B) -consisting of a tapered block (C) in which an aromatic vinyl compound and an aromatic vinyl compound consisting of a conjugated diene are gradually increased.
In the block copolymer (C), the ratio of the aromatic vinyl compound / conjugated diene in all the monomers constituting the component (C-1) is 5/95 by weight.
60/40, the bonding amount of the aromatic vinyl compound in the block (A) and the block (C) optionally formed is (C-1).
3 to 50% by weight of all the monomers constituting the component, and the amount of the aromatic vinyl compound in the block (A) bonded is at least 3% by weight or more of all the monomers constituting the component (C-1), and the block (B Block copolymer or a block copolymer unit thereof in which the amount of 1,2- and 3,4-bonds in the conjugated diene moiety in () is more than 20% (hereinafter, also referred to as "1,2-bond amount"). Is a block copolymer in which the polymer molecular chain is extended or branched via a coupling agent residue,
Hydrogenated diene polymer having a number average molecular weight of 50,000 to 700,000 in which the double bond of the conjugated diene portion is saturated by 80% or more.

(C-2): A polymer block (D) mainly containing an aromatic vinyl compound and a polymer block (E) mainly containing a conjugated diene, and the 1,2-bond content is less than 25%. A (D)-(E)-(F) block copolymer comprising a polybutadiene polymer block (F), wherein the content of the block (D) is 5 to 60% by weight, and the content of the block (E) is 30. ~ 90 wt% and the content of the block (F) is 5 to 60 wt% [however,
(D) + (E) + (F) = 100 wt%], or the block copolymer unit has a polymer molecular chain extended or branched via a coupling agent residue. The block copolymer was hydrogenated, and the double bond of the conjugated diene moiety was saturated by 80% or more, and the number average molecular weight was 5
A hydrogenated diene polymer having a viscosity of 10,000 to 700,000.

(C-3): a polybutadiene polymer block (G) having a 1,2-bond content of less than 25%, and a polymer containing a conjugated diene as a main component and a conjugated diene moiety of 1,
2-a polymer block (H) having a bond amount of 25% or more, (G)-(H) or (G)-
The (H)-(G) block copolymer, or the block copolymer in which the block copolymer unit has a polymer molecular chain extended or branched via a coupling agent residue, is hydrogenated to give a conjugated diene. A hydrogenated diene polymer having a number average molecular weight of 50,000 to 700,000, in which a double bond in a portion is saturated by 80% or more.

The explanation of the component (c) of the present invention will be given below with reference to the above-mentioned hydrogenated diene polymers (c-1), (c-2) and (c).
3) will be described as an example.

Component (C-1): Preferred aromatic vinyl compounds constituting the component (C-1) are styrene and t
-Butyl styrene, α-methyl styrene, p-methyl styrene, divinyl benzene, N, N-dimethyl-p-aminoethyl styrene, N, N-diethyl-p-aminoethyl styrene, vinyl pyridine and the like are mentioned, and more preferable. Are styrene and α-methylstyrene, and these can be used alone or in combination of two or more. Preferred conjugated dienes constituting the component (C-1) include 1,3-butadiene, isoprene and 2,3-
Dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene,
Examples thereof include 3-butyl-1,3-octadiene and chloroprene, more preferably 1,3-butadiene, isoprene and 1,3-pentadiene, and most preferably 1,3-butadiene.

Block (A) in component (C-1)
Is a polymer block mainly composed of an aromatic vinyl compound, and other copolymerizable vinyl compound may be copolymerized preferably at 10% by weight or less, more preferably at 5% by weight or less.

The preferred weight ratio of aromatic vinyl compound / conjugated diene in all the monomers in component (c-1) is 5
/ 95-60 / 40, more preferably 7 / 93-50
/ 50. When the amount of the aromatic vinyl compound is less than 5% by weight (the conjugated diene exceeds 95% by weight), the mechanical strength, moldability and heat resistance are poor, and when the obtained hydrogenated diene polymer is pelletized, blocking occurs. Easier to do. On the other hand, when the amount of the aromatic vinyl compound exceeds 60% by weight (the conjugated diene is less than 40% by weight), it becomes resin-like and the slip resistance, stretchability and low temperature properties are poor.

The preferable amount of the aromatic vinyl compound in the block (A) and the block (C) optionally formed is 3 to 50% by weight based on the total monomers constituting the component (C-1). , More preferably 5 to 40% by weight,
It is particularly preferably 5 to 30% by weight. When the amount of the aromatic vinyl compound bonded is less than 3% by weight of all monomers,
The heat resistance and mechanical strength are inferior, and when the obtained hydrogenated diene polymer is pelletized, it is easy to block, and when blended with other components, the moldability is inferior, while when it exceeds 50% by weight. , Slip resistance, moldability and low temperature properties are poor. In addition, the preferable binding amount of the aromatic vinyl compound in the block (A) is 3% by weight or more, and more preferably 5 to 30% by weight based on the total monomers constituting the component (C-1).
If it is less than 3% by weight, mechanical strength, moldability, and heat resistance are poor when blended with other components.

Furthermore, the preferred vinyl bond content of the conjugated diene moiety before hydrogenation in the block (B) is 20%.
Over 40%, more preferably 40% or more, particularly preferably 60% or more. If it is 20% or less, the effect of improving the softness when blended with the (b) polyolefin resin decreases. The hydrogenation rate of the double bond of the conjugated diene portion of the component (C-1) is 80% or more, preferably 90%.
Or more, More preferably, it is 95% or more. If it is less than 80%, heat resistance, weather resistance and mechanical strength are poor, which is not preferable.

The content of the blocks (A), (B) and (C) in the block copolymer constituting the component (C-1) is preferably 3 to 50% by weight of the block (A), more preferably. 4-40% by weight, block (B) 30-97% by weight, more preferably 35-94% by weight, block (C) 0-50% by weight, more preferably 2-40% by weight [where (A) + (B) + (C) = 100% by weight]
Is. The preferred number average molecular weight of the blocks (A), (B) and (C) is 1,500 to 35 in the block (A).
10,000, more preferably 4,000 to 240,0
00, block (B) 15,000 to 679,000,
More preferably 35,000 to 564,000, block (C) 0 to 350,000, and more preferably 2,
It is in the range of 000 to 240,000.

The number average molecular weight of the hydrogenated diene polymer as the component (C-1) is 50,000 to 700,000, preferably 100,000 to 60.
In many cases. If it is less than 50,000, blocking may easily occur when the obtained hydrogenated diene polymer is pelletized.
Mechanical strength decreases, while if it exceeds 700,000, fluidity,
Moldability is poor, which is not preferable. The (c-1) hydrogenated diene polymer of the present invention can be obtained, for example, by the method disclosed in JP-A-3-72512, page 4, upper right column, line 13 to page 6, lower left column, line 1. You can

The hydrogenated diene-based polymer (c-1) of the present invention is (A)-(B) or (A)-(B)-(A),
Alternatively, a block copolymer having an (A)-(B)-(C) block structure but having a polymer molecular chain extended or branched, as represented by the following general formula, is obtained by adding a coupling agent. It may be a combination. [(A)-(B)] l-X, [(A)-(B)-(A)] l-X, or [(A)-(B)-(C)] l-X [wherein , (A), (B) and (C) are the same as above. l is 2
~ 4, X represents a coupling agent residue. ]

As the coupling agent at this time, for example, diethyl adipate, divinylbenzene, tetrachlorosilane, butyltrichlorosilane, methyldichlorosilane, tetrachlorotin, butyltrichlorotin, dimethylchlorosilane, tetrachlorogermanium, 1,2-
Examples include dibromoethane, 1,4-chloromethylbenzene, bis (trichlorosilyl) ethane, epoxidized linseed oil, tolylene diisocyanate, 1,2,4-benzenetriisocyanate.

Component (C-2): The aromatic vinyl compound and conjugated diene used in the component (C-2) are the same as those described in the above (C-1).
1) The same as that used for the component. Here, the block (D) constituting the hydrogenated diene-based polymer of the component (C-2) is a polymer block mainly containing an aromatic vinyl compound, and specifically, a homopolymer of an aromatic vinyl compound. Alternatively, a copolymer block with a conjugated diene containing 90% by weight or more of an aromatic vinyl compound in the block (D), and a polymer block in which 80% or more of the conjugated diene portion is hydrogenated is preferable. When the content of the aromatic vinyl compound in the block (D) is less than 90% by weight, mechanical strength and weather resistance are deteriorated. The content of the block (D) in the component (C-2) is preferably 5 to 60% by weight, more preferably 5 to 60% by weight.
When it is less than 5% by weight, heat resistance and mechanical strength are poor, and when it exceeds 60% by weight, moldability is poor. The preferred number average molecular weight of the block (D) is 2,0.
It is from 00 to 420,000.

Further, (C-2) the block (E) constituting the hydrogenated diene polymer is a conjugated diene polymer block,
Alternatively, it is an aromatic vinyl compound-conjugated diene copolymer block. The preferred content of block (E) is 30-
It is 90% by weight, and more preferably 35 to 90% by weight. If it is less than 30% by weight, the flexibility is lowered, while if it exceeds 90% by weight, the moldability and mechanical strength are lowered.

The 1,2-bond content of the conjugated diene moiety before hydrogenation contained in the block (E) is preferably 25 to 95%, more preferably 30 to 90%. In the conjugated diene polymer block before hydrogenation that becomes the block (E), for example, when the conjugated diene is butadiene, when the 1,2-bond content is less than 25%, a polyethylene chain is generated when hydrogenated, and a rubber is obtained. However, if it exceeds 95%, the glass transition temperature becomes high when hydrogenated, and the rubbery property is lost, which is not preferable. The amount of the aromatic vinyl compound that may be contained in the block (E) is preferably 35% by weight or less, more preferably 30% by weight or less, and particularly preferably 25% by weight of the monomer constituting the block (E). % Or less, 35
If it exceeds 5% by weight, the glass transition temperature of the block (E) rises, resulting in poor low temperature properties. Further, the preferred number average molecular weight of the block (E) is 15,000 to 630,000,
More preferably, it is a conjugated diene polymer block having a molecular weight of 35,000 to 420,000 and having 80% or more hydrogenated double bonds in the conjugated diene moiety.

Further, (c-2) the preferred 1,2-bond content of the polybutadiene before hydrogenation in the block (F) constituting the hydrogenated diene polymer is less than 25%, more preferably 20% or less. Is. This 1,2-bond amount is 2
If it is more than 5%, the resinous property is lost after hydrogenation,
Further, the properties of the thermoplastic elastomer as a block copolymer are lost. The content of the block (F) is preferably 5 to 60% by weight, more preferably 5 to 50% by weight.
Is. If the content of the block (F) is less than 5% by weight, the mechanical strength will decrease, while if it exceeds 60% by weight, the flexibility will be poor. Further, the preferred number average molecular weight of the block (F) is 2,500 to 420,000, and is a polybutadiene polymer block in which 80% or more of the double bonds of the butadiene portion of the polybutadiene block are hydrogenated.

The number average molecular weight of the hydrogenated diene polymer (c-2) of the present invention is 50,000 to 700,000, preferably 100,000 to 6.
If it is less than 50,000, the mechanical strength and heat resistance of the resulting composition will decrease, while if it exceeds 700,000, the fluidity and moldability will decrease. The (c-2) hydrogenated diene-based polymer used in the present invention can be obtained by, for example, the method disclosed in JP-A-2-133406, page 4, lower left column, line 13 to page 5, lower left column, line 10. Can be obtained by

The hydrogenated diene-based polymer (c-2) of the present invention has a (D)-(E)-(F) block structure.
It may be a block copolymer in which the polymer molecular chain is extended or branched as shown by the following general formula by adding a coupling agent. [(D)-(E)-(F)] m-Y or [(D)-(E)-(F)] Y [(D)-(E)] [wherein (D), ( E) and (F) are the same as above. m is 2
~ 4, Y represents a coupling agent residue. The coupling agent at this time is the same as that used in the above-mentioned component (C-1).

Component (C-3): The aromatic vinyl compound and the conjugated diene used in the component (C-3) are the same as those described in the above (C).
1) The same as that used for the component. Here, the hydrogenated diene-based polymer which is the component (C-3) used in the present invention is mainly composed of a polybutadiene polymer block (G) having a 1,2-bond content of less than 25% and a conjugated diene. And the amount of 1,2-bonds in the conjugated diene moiety is 2
5% or more of the polymer block (H),
(G)-(H) or (G)-(H)-(G) block copolymer, or the polymer chain of the block copolymer unit is extended or branched via a coupling agent residue. It is a hydrogenated diene-based polymer having a number average molecular weight of 50,000 to 700,000, in which a double bond of a conjugated diene portion is saturated by 80% or more by hydrogenating a block copolymer.

The block (G) in the component (C-3) becomes a crystalline polymer block having a structure similar to that of ordinary low density polyethylene by hydrogenation. The preferred 1,2-bond content of the polybutadiene in the block (G) before hydrogenation is less than 25%, more preferably 20% or less, particularly preferably 15% or less, and 25% or more hydrogenated. After that, the melting point of the crystal is remarkably lowered, and the mechanical strength is poor.

The block (H) is mainly composed of a conjugated diene, specifically, a conjugated diene homopolymer block or an aromatic vinyl compound-conjugated diene copolymer block. In the case of butadiene, it becomes a rubber-like ethylene-butene-1 copolymer block or a polymer block showing a structure similar to that of the aromatic vinyl compound-ethylene-butene-1 copolymer.

The amount of the aromatic vinyl compound which may be contained in the block (H) is preferably 35% by weight or less, more preferably 30% by weight or less, and particularly preferably 30% by weight or less of the monomer constituting the block (H). Is 25% by weight or less, and if it exceeds 35% by weight, the glass transition temperature of the block (H) rises and the low temperature characteristics are deteriorated. In addition, preferred 1, of the conjugated diene portion of the block (H) before hydrogenation
The 2-bond amount and the like are 25% or more, more preferably 25 to 95%, and particularly preferably 35 to 85%.
If it is less than 25%, hydrogenation causes a crystalline structure derived from a polyethylene chain, for example, when the conjugated diene is butadiene, and becomes a resin-like property, resulting in poor flexibility.

Further, the preferable weight ratio of the block (G) / (H) in the component (C-3) is usually 5/9.
5 to 90/10, more preferably 10/90 to 80 /
Twenty. When the amount of the block (G) is less than 5% by weight [the amount of the block (H) exceeds 95% by weight], the crystalline polymer block is insufficient and the mechanical strength is poor. On the other hand, the block (G) exceeds 90% by weight [block (H) is 10
If it is less than wt%, the slip resistance is poor.

The hydrogenated diene polymer (c-3) used in the present invention has at least 80%, preferably 90% or more of the double bonds of the conjugated diene moieties of the block (G) and the block (H), Particularly preferably, it is necessary that 95% or more is hydrogenated and saturated, and if it is less than 80%, the weather resistance and mechanical strength are poor. The preferred number average molecular weight of the block (G) is 2,500 to 630,000,
More preferably, it is 10,000 to 480,000. The preferred number average molecular weight of the block (H) is
5,000 to 665,000, more preferably 20,
000 to 540,000. The number average molecular weight of the hydrogenated diene-based polymer (c-3) of the present invention is 50,000 to 700,000, preferably 100,000 to 600,000, and if it is less than 50,000, the mechanical strength and heat resistance of the obtained composition are high. On the other hand, when it exceeds 700,000, the fluidity and moldability are deteriorated. The hydrogenated diene-based polymer (C-3) used in the present invention is described in, for example, JP-A 3-1.
No. 28957, page 4, lower right column, line 8 to page 6, lower left column, line 7 can be obtained.

The hydrogenated diene polymer (c-3) of the present invention has a (G)-(H) or (G)-(H)-(G) block structure, but a coupling agent is added. As a result, a block copolymer in which the polymer molecular chain is extended or branched as represented by the following general formula may be used. [(G)-(H)] n-Z or [(G)-(H)-(G)] n- Z [wherein (G) and (H) are the same as above. n represents an integer of 2 to 4, and Z represents a coupling agent residue. The coupling agent at this time is the same as that used in the above-mentioned component (C-1).

The hydrogenated diene polymer (c) used in the present invention may be modified with a functional group, and may be a group of acid anhydride group, carboxyl group, hydroxyl group, amino group, isocyanate group and epoxy group. The unsaturated compound having at least one functional group selected from the above can be used for modification with a kneader, a mixer, an extruder or the like.

The content of the hydrogenated diene polymer (c) of the present invention is 1 to 15 % by weight in the components (a) to (c).
If it is less than 1% by weight, the stretchability is poor, while if it exceeds 15 % by weight, the moldability and the molded appearance are poor.

The thermoplastic elastomer composition of the present invention comprises
If necessary, crosslinking such as sulfur crosslinking, peroxide crosslinking, metal ion crosslinking, silane crosslinking, and resin crosslinking can be performed by a conventionally known method.

The thermoplastic elastomer composition of the present invention has, in addition to the components (a), (b), and (c) described above, abrasion resistance, slip resistance, mechanical strength, and stretching depending on the application. sex,
Antioxidant in an amount that does not interfere with moldability and molding appearance,
Weathering agents, metal deactivators, ultraviolet absorbers, light stabilizers, bleed / bloom inhibitors, sealability improvers, crystal nucleating agents, flame retardants, lubricants, antistatic agents, antibacterial / antifungal agents, dispersions Agent,
Softeners, plasticizers, viscosity modifiers, coloring inhibitors, foaming agents, foaming aids, titanium oxide, colorants such as carbon black,
Metal powder such as ferrite, glass fiber, inorganic fiber such as metal fiber, organic fiber such as carbon fiber and aramid fiber,
Composite fibers, inorganic whiskers such as potassium titanate whiskers, glass beads, glass balloons, glass flakes, asbestos, mica, calcium carbonate, talc, silica, calcium silicate, hydrotalcite, kaolin, diatomaceous earth, graphite, pumice stone, evo Fillers such as powders, cotton flocs, cork powders, barium sulfate, fluororesins, polymer beads or mixtures thereof, or other rubbery polymers such as SBR, NBR, BR
[However, the component (a) of the present invention is excluded], NR, IR,
AR, CR, IIR and, if necessary, thermoplastic resins other than the above-mentioned components (a) to (c), such as diene resins, polyvinyl chloride resins, polycarbonate resins, polyacetal resins, polyamide resins, polyesters. Resins, polyether resins, polysulfones, polyphenylene sulfides, POMs, etc. can be appropriately added.

The composition of the present invention is melt-kneaded by a conventionally known kneading machine such as an extruder, a kneader or a Banbury mixer, or a kneading machine combining these, and is dry blended by an injection molding machine. Can be obtained. In order to produce the composition of the present invention, each component may be mixed at once, or any component may be premixed in advance and then the remaining components may be added and mixed. The most preferable mixing device is a single-screw or twin-screw extruder, which allows continuous and efficient kneading and pelletization.

The composition of the present invention can be molded practically by a conventionally known method such as injection molding, extrusion molding, blow molding, compression molding, vacuum molding, slush molding, foam molding , lamination molding, calender molding and the like. It can be processed into a product. Further, if necessary, processing such as foaming, powdering, drawing, adhesion, printing, painting, and plating can be performed.

Preferred embodiments of the thermoplastic elastomer composition of the present invention are as follows. (A) A thermoplastic elastomer composition in which 1,2-polybutadiene has a 1,2-bond content of 85% or more and a crystallinity of 20 to 50%. (B) A thermoplastic elastomer composition in which the polyolefin resin is at least one selected from the group consisting of polyethylene, polypropylene and polybutene-1. (C) The conjugated diene constituting the hydrogenated diene polymer is
A thermoplastic elastomer composition which is 1,3-butadiene. (C) A thermoplastic elastomer composition in which the aromatic vinyl compound constituting the hydrogenated diene polymer is styrene.

[0048]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the examples as long as the gist of the invention is not exceeded. In the examples, parts and% are by weight unless otherwise specified. In addition, various measurements in the examples were based on the following methods.

(1) The hydrogenated diene polymer was analyzed by infrared analysis based on the absorption of a phenyl group having an aromatic vinyl compound binding amount of 679 cm ^-1 . (2) 1,2-of the conjugated diene portion of the hydrogenated diene polymer
The amount of binding was calculated by the Hampton method using the infrared analysis method. (3) Number average molecular weight of hydrogenated diene polymer It was determined in terms of polystyrene using gel permeation chromatography (GPC) at 135 ° C. using trichlorobenzene as a solvent. (4) Hydrogenation rate of hydrogenated diene-based polymer (hydrogenation rate) Using tetrachloroethylene as a solvent, 100 MHz, ¹ H-N
It was calculated from the MR spectrum.

(5) Abrasion resistance DIN abrasion test method; conforming to JIS K6369, DI
The N wear value was measured and judged according to the following criteria. ◯: Excellent in wear resistance (DIN wear value is less than 100 cc). B: Good wear resistance (DIN wear value of 100 cc or more
Less than 200 cc). X: Wear resistance is poor (DIN wear value is 200 cc or more).

(6) Slip resistance Using a friction angle tester manufactured by Toyo Seiki Co., Ltd., the static friction angle was measured and judged according to the following criteria. ◯: Excellent in slip resistance (coefficient of static friction of 0.8 or more). Δ: Good slip resistance (coefficient of static friction of 0.5 or more to 0.
Less than 8). X: Inferior in slip resistance (coefficient of static friction is less than 0.5).

(7) Mechanical Strength The breaking strength was measured according to JIS K6301 and judged according to the following criteria. ◯: excellent mechanical strength (breaking strength 150 kg / cm
² or more). Δ: Good mechanical strength (breaking strength 100 kg / cm ²
Or more but less than ~150kg / cm ^2). X: poor mechanical strength (breaking strength 100 kg / cm ²
Less than).

(8) Stretchability The elongation at break was measured according to JIS K6301 and judged according to the following criteria. ◯: Excellent in stretchability (elongation at break is 500% or more). Δ: Good stretchability (breaking elongation of 200% to 500%
Less than). X: Poor stretchability (breaking elongation less than 200%).

(9) Formability 15 × 15 × 2 of film gate according to the following criteria
Injection molding was performed using a mm sheet mold, and the moldability was evaluated from the appearance of the obtained molded product. ◯: A molded product with a good appearance can be obtained under a wide range of molding conditions. Δ: A molded product having a good appearance can be obtained under limited molding conditions. X: Poor appearance, such as having flow marks, bleeding and blooming, rough surface, and strong surface tackiness, is difficult to correct depending on molding conditions.

(10) Lightness The specific gravity was determined by the buoyancy method and the following criteria. ○: Specific gravity is less than 0.95 Δ: Specific gravity is 0.95 or more and 1 or less X: Specific gravity exceeds 1.

Reference Example Various components used in the formulation of Examples and Comparative Examples are as follows. 1,2-Polybutadiene (P-1 to 2 ) P-1; RB820 [Nippon Synthetic Rubber Co., Ltd., syndiotactic 1,2-polybutadiene, 1,2-bond amount =
92%, crystallinity = 25%] P-2; RB830 [Nippon Synthetic Rubber Co., Ltd., syndiotactic 1,2-polybutadiene, 1,2-bonding amount =
93%, crystallinity = 29%]

Polyolefin resin (Q-1 to 4 ) Q-1: Polypropylene [Tosoh Corp., propylene-ethylene random copolymer, J6200G] Q-2: Polyethylene [Mitsubishi Petrochemical Co., Ltd., low Density polyethylene, YK-30] Q-3; Polyethylene [Nippon Oil Co., Ltd., high-density polyethylene, E780 (C)] Q-4; Polybutene-1 [Mitsui Petrochemical Industry Co., Ltd.,
Beaulon M7000]

Hydrogenated diene-based polymers (R-1 to 8 ) Hydrogenated diene-based polymers (R-1 to 8) are prototype polymers manufactured by Nippon Synthetic Rubber Co., Ltd. The microstructure, number average molecular weight, and hydrogenation ratio of are as shown in Tables 1 to 3.

Polyamide Resin (S-1 ) S-1; Nylon 12 [Daicel KK, Daiamide L2121] Thermoplastic Polyurethane Resin (T-1 to 2 ) T-1; TPU [Takeda Bardish Urethane Industry Co., Ltd. )
Manufactured by Elastollan S90A50] T-2; TPU [Takeda Birdiche Urethane Industry Co., Ltd.
Manufactured by Elastollan S98A50]

Examples 1 to 12 and Comparative Examples 1 to 8 The formulations shown in Tables 4 to 6 were mixed using a Henschel mixer, and further using a single screw extruder (40 mmφ).
The mixture was kneaded at a kneading temperature of 120 to 170 ° C., melt-extruded and pelletized. The obtained pellets were sheet-molded by an injection molding machine to prepare test pieces used for various measurements. The results are shown in Tables 4-6. As is clear from Tables 4 to 5, the elastomer composition of the present invention is superior in moldability and lightness as compared with Comparative Examples 1 to 3 shown in Table 6, and has wear resistance, slip resistance, and mechanical properties. Strength and stretchability are the same. On the other hand, in Comparative Examples 4 to 8 shown in Table 6, since the compounding ratio is outside the range of the present invention, the balance of physical properties of wear resistance, slip resistance and moldability is poor.

[0061]

[Table 1]

[0062]

[Table 2]

[0063]

[Table 3]

[0064]

[Table 4]

[0065]

[Table 5]

[0066]

[Table 6]

[0067]

INDUSTRIAL APPLICABILITY The thermoplastic elastomer composition of the present invention has essentially the excellent physical properties of the thermoplastic elastomer composition, and has abrasion resistance, slip resistance, mechanical strength, stretchability, moldability, and molding. Excellent appearance and light weight. The thermoplastic elastomer composition of the present invention is a material having the above-mentioned excellent properties, and is used for foot lifts such as top lifts and sports shoes, food applications, daily sundries applications, ski equipment, exercise equipment, toy applications. , Automotive interior applications such as car mat materials, civil engineering sheets, waterproofing sheets and other civil engineering / construction applications, home appliance applications, AV equipment applications, O.I. A. It can be used for office equipment, hoses / tubes, textiles, medical equipment, chemical / mining industry materials, packaging / transportation materials, agricultural / livestock / fisheries materials, etc. is there.

Continuation of front page (56) References JP-A-4-270745 (JP, A) JP-A-4-189870 (JP, A) JP-A-59-155478 (JP, A) (58) Fields investigated (Int .Cl. ⁷ , DB name) C08L 9/00-9/10 C08L 23/00-23/36

Claims (6)

(57) [Claims] 1. (a) 1,2-Polybutadiene 65 having a 1,2-bond content of 70% or more and a crystallinity of 5-50%.
~ 80 wt%, (b) Polyolefin resin 10 to 30
%, And (c) 1 to 15% by weight of hydrogenated diene polymer having a number average molecular weight of 50,000 to 700,000, in which the double bond of the conjugated diene portion of the conjugated diene polymer is saturated by 80% or more.
A thermoplastic elastomer composition containing [(a) + (b) + (c) = 100% by weight] as a main component. 2. The thermoplastic elastomer composition according to claim 1, wherein the component (a) has a 1,2-bond content of 85% or more and a crystallinity of 20 to 50%. 3. The thermoplastic elastomer composition according to claim 1, wherein the component (b) is at least one selected from the group consisting of polyethylene, polypropylene and polybutene-1. 4. A homopolymer in which component (c) is a conjugated diene,
Random copolymer of conjugated diene and aromatic vinyl compound, block copolymer consisting of polymer block of aromatic vinyl compound and polymer block of conjugated diene, and polymer block of aromatic vinyl compound and aromatic vinyl The thermoplastic elastomer composition according to any one of claims 1 to 3, which is at least one hydrogenated product selected from the group of block copolymers consisting of a compound / copolymer of conjugated diene. 5. The conjugated diene constituting the component (C) is 1,
The thermoplastic elastomer composition according to any one of claims 1 to 4, which is 3-butadiene. 6. The thermoplastic elastomer composition according to claim 4 or 5, wherein the aromatic vinyl compound constituting the component (c) is aromatic styrene.