JP2003192867A - Thermoplastic elastomer resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an isobutylene-based thermoplastic elastomer resin composition improved in flexibility such as having low hardness and low resilience while retaining the fundamental properties of the thermoplastic elastomer resin composition including mechanical strength, molding processability and appearance, and free from plasticizer bleedout, and to provide various packings made from the composition. <P>SOLUTION: This thermoplastic elastomer resin composition comprises (a) 100 pts.wt. of an isobutylene-based block copolymer composed of a polymer block with isobutylene as the main monomer component and another kind of polymer block with an aromatic vinyl compound as the main monomer component and (b) 5.0-70 pts.wt. of a polyolefin-based polymer. This elastomer composition has a hardness of ≤50 and a resilience of ≤40%. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic elastomer resin composition containing an isobutylene block copolymer and a polyolefin polymer, and more specifically, it is characterized by low hardness and low impact resilience. The present invention relates to a thermoplastic elastomer resin composition useful as a packing.

[0002]

Molded articles made of a thermoplastic resin are widely used for automobile parts, home electric appliance parts, daily necessities, sports goods, toys, industrial parts and the like. Among them, polyolefin resins are used as a wide range of molded products because of their excellent balance between cost, moldability and physical properties.

On the other hand, in recent years, a thermoplastic elastomer, which is a rubber-like soft material and does not require a vulcanization step and has the same moldability as that of a thermoplastic resin, is used for automobile parts, home electric appliance parts, sundries, footwear, It has attracted attention in the field of electric wire coating and packing. At present, various polymers such as polyolefin-based, polyurethane-based, polyester-based, polystyrene-based, and polyvinyl chloride-based polymers have been developed and are commercially available as such thermoplastic elastomers. These thermoplastic elastomers may be used alone, but thermoplastic elastomer resin compositions in which thermoplastic resins and thermoplastic elastomers are variously combined have been studied to meet various needs of users.

In particular, polyolefin resin and styrene-butadiene-block copolymer (SBS) and styrene
A thermoplastic elastomer resin composition comprising a polystyrene-based elastomer such as isoprene-block polymer (SIS) and a softening agent has hardness, flexibility, cushioning property,
It has come to be widely used as a material having a good balance of impact resistance, rubber elasticity, molding processability, and the like.

However, the conventional thermoplastic elastomer resin composition of polyolefin-based resin and polystyrene-based elastomer has a problem that heat stability (heat aging resistance) and weather resistance are not sufficient, and further, a softener. However, there is a problem that low molecular weight components such as lubricants and paraffin oil are contained.

[0006] In order to solve this problem, attempts have hitherto been made to obtain a thermoplastic elastomer resin composition having improved thermal stability by hydrogenating the intramolecular double bond of a block copolymer of styrene and a conjugated diene. Has been done.

For example, Japanese Patent Publication No. 6-88608 discloses a container lid with a liner made of a composition containing liquid paraffin and a propylene resin in a hydrogenated styrene / butadiene block copolymer having a specific MI. In JP-A-2000-239481, a hydrogenated vinyl aromatic / conjugated diene block copolymer having a specific Mn, a propylene-based polymer having a specific MI, and
A resin composition and a liner material containing a propylene-based copolymer having a specific melting point have been proposed. However, even though the conjugated diene block is hydrogenated in these compositions and the like, since it may have a residual double bond in the molecule, problems such as heat stability (heat aging resistance) and weather resistance may occur. In addition, they have high hardness, high impact resilience and insufficient flexibility. On the other hand, addition of a plasticizer or a softening agent was essential to impart flexibility. In order to solve this, it can not have a residual double bond in its molecule, specifically, thermal stability and weather resistance, vibration damping and gas barrier properties, further improved flexibility, and,
There is a demand for an isobutylene / styrene-based thermoplastic elastomer resin composition that does not bleed out of a plasticizer. Regarding these, JP-A-9-87438 discloses a resin composition containing a polyolefin-based resin, an aromatic vinyl / isobutylene block copolymer as a main component, and a closure, and JP-A-11-293083 discloses isobutylene. A thermoplastic resin composition including a block copolymer, a polyolefin resin, and a softening agent has been proposed.
However, these compositions and the like also have high hardness and high impact resilience and insufficient flexibility, and it was necessary to add a plasticizer or a softening agent.

[0008]

The object of the present invention is to maintain the basic properties of the thermoplastic elastomer resin composition such as mechanical strength, moldability, and appearance while maintaining flexibility such as low hardness and low impact resilience. The present invention is to provide an isobutylene-based thermoplastic elastomer resin composition, various packings, and the like, which are characterized by improving the above and not having bleed out of a plasticizer.

[0009]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a thermoplastic elastomer resin composition containing an isobutylene block copolymer and a polyolefin polymer. The present invention has been accomplished by finding that a product solves the above problems.

That is, the present invention relates to (a) 100 wt.% Of an isobutylene block copolymer comprising a polymer block containing isobutylene as a monomer main component and a polymer block containing an aromatic vinyl compound as a monomer main component. Parts, and (b) 5.0 to 70 parts by weight of a polyolefin-based polymer, having a hardness (JIS K6352) of 50 or less and a impact resilience (JIS K6255) of 40% or less. It is a resin composition, and it is preferable that the hardness is 40 or less and the impact resilience is 30% or less. Further, the thermoplastic elastomer resin composition of the present invention may contain 0.1 to 50 parts by weight of an inorganic filler. The component (b) is preferably a polypropylene polymer.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The isobutylene block copolymer which is the component (a) of the present invention comprises a polymer block containing isobutylene as a monomer main component and an aromatic vinyl compound as a monomer main component. There is no particular limitation as long as it has a polymer block, for example, linear, branched, a block copolymer having a star-shaped structure, a diblock copolymer, a triblock copolymer, Any of the multi-block copolymers and the like can be selected, and one or two or more types that meet the requirements of viscoelastic properties, physical properties and molding processability may be selected and used.

A preferred structure of the isobutylene block copolymer of the present invention is a polymer block-isobutylene containing an aromatic vinyl compound as a monomer main component from the viewpoint of physical properties and processability of the resulting composition. Polymer block containing monomer as the main component-Triblock copolymer formed from polymer block containing aromatic vinyl compound as the main component, polymer block containing isobutylene as the main component- Polymer block containing aromatic vinyl compound as monomer main component-triblock copolymer formed from polymer block containing isobutylene as monomer main component, aromatic vinyl compound as monomer main component And a diblock copolymer formed from a polymer block containing isobutylene as a main component, and an aromatic vinyl compound as a monomer. Polymer block as a component - is at least one diblock copolymer formed isobutylene from the polymer block whose monomer major component is selected from the group consisting of star-shaped polymer to be the arm.

The aromatic vinyl compound of the present invention includes:
Styrene, o-, m- or p-methylstyrene, α-methylstyrene, β-methylstyrene, 2,6-dimethylstyrene, 2,4-dimethylstyrene, α-methyl-o
-Methylstyrene, α-methyl-m-methylstyrene,
α-methyl-p-methylstyrene, β-methyl-o-methylstyrene, β-methyl-m-methylstyrene, β-
Methyl-p-methylstyrene, 2,4,6-trimethylstyrene, α-methyl-2,6-dimethylstyrene, α
-Methyl-2,4-dimethylstyrene, β-methyl-
2,6-dimethylstyrene, β-methyl-2,4-dimethylstyrene, o-, m- or p-chlorostyrene,
2,6-dichlorostyrene, 2,4-dichlorostyrene, α-chloro-o-chlorostyrene, α-chloro-m
-Chlorostyrene, α-chloro-p-chlorostyrene,
β-chloro-o-chlorostyrene, β-chloro-m-chlorostyrene, β-chloro-p-chlorostyrene, 2,
4,6-Trichlorostyrene, α-chloro-2,6-dichlorostyrene, α-chloro-2,4-dichlorostyrene, β-chloro-2,6-dichlorostyrene, β-chloro-2,4-dichlorostyrene , O-, m- or pt
-Butylstyrene, o-, m- or p-methoxystyrene, o-, m- or p-chloromethylstyrene, o-,
Examples thereof include m- or p-bromomethylstyrene, styrene derivatives substituted with a silyl group, indene and vinylnaphthalene. These may be used alone or in combination of two or more.

In the polymer block containing an aromatic vinyl compound as a monomer main component of the present invention, the components other than the main component are 40% by weight or less, preferably 20% by weight or less in the block, It is more preferably 5% by weight or less. Specifically, it is not particularly limited as long as it is a cationically polymerizable monomer component, and examples thereof include monomers such as aliphatic olefins, dienes, vinyl ethers, silanes, vinylcarbazole, β-pinene, and acenaphthylene. it can. These may be used alone or in combination of two or more.

Examples of the aliphatic olefinic monomer include ethylene, propylene, 1-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, hexene, cyclohexene, 4-methyl-1-pentene. , Vinylcyclohexane, octene, norbornene and the like.
These may be used alone or in combination of two or more.

Examples of the diene-based monomer include butadiene, isoprene, hexadiene, cyclopentadiene, cyclohexadiene, dicyclopentadiene, divinylbenzene and ethylidene norbornene. These may be used alone or in combination of two or more.

The vinyl ether type monomers include methyl vinyl ether, ethyl vinyl ether, (n-, iso) propyl vinyl ether, (n-, sec-, te).
Examples include rt-, iso) butyl vinyl ether, methyl propenyl ether, ethyl propenyl ether and the like. These may be used alone or in combination of two or more.

As the silane compound, vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-
Examples thereof include divinyl-1,1,3,3-tetramethyldisiloxane, trivinylmethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and the like.
These may be used alone or in combination of two or more.

Further, the block containing the aromatic vinyl compound as the main monomer component of the present invention has an aromatic vinyl compound content of 60 in view of balance with physical properties and polymerization characteristics.
It is preferable that the amount is not less than 80% by weight, preferably not less than 80% by weight, more preferably not less than 95%. As the aromatic vinyl compound, it is preferable to use at least one monomer selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, and indene. From the viewpoint of cost, styrene and α-methyl are preferred. It is particularly preferable to use styrene or a mixture thereof.

The block containing isobutylene as the main monomer component according to the present invention may or may not contain a monomer other than isobutylene. Usually, isobutylene is contained in an amount of 60% by weight or more, preferably 80% by weight. % Or more, and more preferably 95% or more. The monomer other than isobutylene is not particularly limited as long as it is a cationically polymerizable monomer, and examples thereof include the above monomers.

There is no particular limitation on the ratio of the polymer block containing isobutylene as a main monomer component and the polymer block containing an aromatic vinyl compound as a main monomer component,
From the viewpoint of balance between processability and physical properties, the polymer block containing isobutylene as a monomer main component is 98 to 40% by weight, and the polymer block containing an aromatic vinyl compound as a monomer main component is 2 to 60% by weight. It is preferable that the polymer block containing isobutylene as a main monomer component is 95 to 60.
It is particularly preferable that the polymer block containing an aromatic vinyl compound as a monomer main component is 5 to 40% by weight, and the polymer block containing isobutylene as a monomer main component is 90 to 70% by weight. It is particularly preferable that the polymer block containing an aromatic vinyl compound as the main monomer component accounts for 10 to 30% by weight.

The weight average molecular weight of the isobutylene block copolymer is also not particularly limited, but the moldability, processability,
From the viewpoint of physical properties, it is 5000 to 1500000, and 1
It is preferably 0000 to 500000, and 200
Particularly preferably, it is from 00 to 250,000, and 40
It is particularly preferably from 000 to 125,000. The weight average molecular weight of the isobutylene block copolymer is 500.
If it is less than 0, the physical properties are not sufficiently expressed, and
If it exceeds 00, it is disadvantageous in terms of balance among formability, processability and physical properties.

The molecular weight distribution (ratio (Mw / Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn)) is preferably 10 or less, more preferably 5 or less, and more preferably
It is 3 or less.

The block copolymer of the present invention includes an aromatic vinyl-conjugated diene thermoplastic elastomer such as styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer. (SIS), or a styrene-ethylene butylene-styrene block copolymer (S
At least one kind such as EBS) and styrene-ethylene propylene-styrene block copolymer (SEPS) may be contained.

The method for producing the isobutylene block copolymer is not particularly limited. For example, in the presence of a compound represented by the following general formula (1), a monomer containing isobutylene as a main component and isobutylene are added. It is obtained by polymerizing a monomer component which is not the main component. (CR ¹ R ² X) nR ³ (1) [wherein X is a halogen atom, a substituent selected from an alkoxy group having 1 to 6 carbon atoms or an acyloxy group, and R ¹ and R ² are each a hydrogen atom or 1 carbon atom] In the monovalent hydrocarbon group of 1 to 6, R ¹ and R ² may be the same or different, R ³ is a polyvalent aromatic hydrocarbon group or a polyvalent aliphatic hydrocarbon group, and n is 1 Indicates a natural number of ~ 6].

Examples of the halogen atom include chlorine, fluorine, bromine, iodine and the like. The alkoxyl group having 1 to 6 carbon atoms is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, an n- or isopropoxy group, and the like. The acyloxyl group having 1 to 6 carbon atoms is not particularly limited, and examples thereof include an acetyloxy group and a propionyloxy group. The hydrocarbon group having 1 to 6 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n- or isopropyl group and the like.

The compound represented by the above general formula (1) is not open.
It is an initiator and produces carbon cations in the presence of Lewis acids.
Is considered to be the starting point for cationic polymerization. Starting
Examples of compounds of general formula (1) used in the following are:
And the like. (1-Chloro-1-methylethyl) benzene [C₆H_FiveC
(CH₃)₂Cl], 1,4-bis (1-chloro-1-me
Cylethyl) benzene [1,4-Cl (CH ₃)₂CC₆
H_FourC (CH₃)₂Cl], 1,3-bis (1-chloro-
1-methylethyl) benzene [1,3-Cl (CH ₃)₂
CC₆H_FourC (CH₃)₂Cl], 1,3,5-tris (1
-Chloro-1-methylethyl) benzene [1,3,5-
(ClC (CH₃)₂)₃C₆H₃], 1,3-bis (1-
Chlor-1-methylethyl) -5- (tert-butyl)
) Benzene [1,3- (C (CH₃)₂Cl)₂-5-
(C (CH₃)₃) C₆H₃].

Of these, particularly preferred is bis (1
- chloro-1-methylethyl) benzene [C ₆ H ₄ (C
_{(CH 3) 2 Cl) 2} ], tris (1-chloro-1-methylethyl) benzene _{[(ClC (CH 3) 2} ) 3 C 6 H 3]
Is.

Bis (1-chloro-1-methylethyl) benzene is also called bis (α-chloroisopropyl) benzene, bis (2-chloro-2-propyl) benzene or dicumyl chloride, and tris (1- Chlor-1-methylethyl) benzene includes tris (α-chloroisopropyl) benzene and tris (2-chloro-2-).
Propyl) benzene or also called tricumyl chloride.

For polymerizing an isobutylene block copolymer
A Lewis acid catalyst should be allowed to coexist during production.
I can do it. Cationic polymerization as such a Lewis acid
As long as it can be used for_Four, TiBr_Four,
BCl₃, BF₃, BF₃・ OEt ₂, SnCl_Four, SbCl_Five, S
bF_Five, WCl₆, TaCl_Five, VCl_Five, FeCl₃, ZnBr
₂, AlCl₃, AlBr₃Metal halides such as Et;₂A
lCl, EtAlCl ₂Organometallic halides such as
It can be used appropriately. Among them, the ability as a catalyst,
When considering industrial availability, TiCl_Four, BCl
₃, SnCl_FourIs preferred. The amount of Lewis acid used is particularly limited.
Not specified, but the polymerization characteristics or polymerization of the monomers used
It can be set in consideration of the density and the like. Usually a general formula
0.1-100 mol equivalent to the compound represented by (1)
Can be used in an amount of 1 to 50 molar equivalents.
It is a range.

In the polymerization of the isobutylene type block copolymer, an electron donor component may be allowed to coexist if necessary. It is considered that this electron donor component has an effect of stabilizing growing carbon cations during cationic polymerization, and addition of an electron donor produces a polymer having a controlled structure with a narrow molecular weight distribution. The electron donor component that can be used is not particularly limited,
Examples thereof include pyridines, amines, amides, sulfoxides, esters, and metal compounds having an oxygen atom bonded to a metal atom.

Polymerization of the isobutylene block copolymer can be carried out in an organic solvent as the case requires, and the organic solvent can be used without particular limitation as long as it does not substantially inhibit the cationic polymerization. Specifically, methyl chloride,
Halogenated hydrocarbons such as dichloromethane, chloroform, ethyl chloride, dichloroethane, n-propyl chloride, n-butyl chloride, chlorobenzene; alkylbenzenes such as benzene, toluene, xylene, ethylbenzene, propylbenzene, butylbenzene; ethane, propane, butane , Linear amines such as pentane, hexane, heptane, octane, nonane, decane; 2-methylpropane, 2-methylbutane, 2,
Branched aliphatic hydrocarbons such as 3,3-trimethylpentane and 2,2,5-trimethylhexane; cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane and ethylcyclohexane; petroleum fractions were hydropurified Paraffin oil etc. can be mentioned.

These solvents are used singly or in combination of two or more in consideration of the balance between the polymerization characteristics of the monomers constituting the block copolymer and the solubility of the resulting polymer. The amount of the solvent used is such that the concentration of the polymer is 1 to 5 in consideration of the viscosity of the obtained polymer solution and the ease of heat removal.
It is determined to be 0 wt%, preferably 5 to 35 wt%.

In carrying out the actual polymerization, the components are mixed under cooling, for example, at a temperature of -100 ° C or higher and lower than 0 ° C. In order to balance the energy cost and the stability of polymerization, a particularly preferable temperature range is -30 ° C to -80 ° C.

Further, a star-shaped polymer having an arm of a diblock copolymer formed from a polymer block containing an aromatic vinyl compound as a main monomer component and a polymer block containing isobutylene as a main monomer component is used. The production method is not particularly limited, but for example, a monomer containing an aromatic vinyl compound as a main component and a unit amount containing isobutylene as a main component in the presence of a compound having three or more cationic polymerization initiation points. A method for polymerizing a body component, a monomer having an aromatic vinyl compound as a main component and a monomer component having an isobutylene as a main component are polymerized to produce a diblock copolymer, and then a polyfunctional Examples include a method of coupling the above diblock copolymer with a compound as a coupling agent (binding agent).

As the polyfunctional compound, a compound having three or more reactive points (functional groups) capable of coupling per molecule can be used. 2 per molecule
When a compound having three reaction points can be polymerized or reacted to form a polymer and have three or more reaction points (functional groups), it does not prevent use.

Examples of such polyfunctional compounds include 1,3-divinylbenzene, 1,4-divinylbenzene, 1,2-diisopropenylbenzene, 1,3-diisopropenylbenzene, 1,4. -Diisopropenylbenzene, 1,3-divinylnaphthalene, 1,8-divinylnaphthalene, 2,4-divinylbiphenyl, 1,2-
Divinyl aromatic compounds such as divinyl-3,4-dimethylbenzene, 1,3-divinyl-4,5,8-tributylnaphthalene and 2,2'-divinyl-4-ethyl-4'-propylbiphenyl; 2,4-trivinylbenzene, 1,3,5-trivinylnaphthalene, 3,5
Trivinyl aromatic compounds such as 4'-trivinylbiphenyl and 1,5,6-trivinyl-3,7-diethylnaphthalene; cyclohexane diepoxide, 1,4-pentane diepoxide, 1,5-hexane diepoxide, etc. Diepoxide; 2,4-hexane-dione, 2,5-hexane-dione, diketone such as 2,6-heptane-dione; 1,4-butanedial, 1,5-pentanedial, 1,6-hexanedial Dialdehydes such as;
Examples thereof include siloxane compounds and calixarene. These may be used alone or in combination of two or more.

Among these, divinyl aromatic compounds are preferably used from the viewpoints of reactivity, physical properties of the resulting star polymer, and particularly preferred are 1,3-divinylbenzene, 1,4-divinylbenzene, 1, It is at least one selected from the group consisting of 3-diisopropenylbenzene and 1,4-diproisopenylbenzene. The above-mentioned compound is usually commercially available as a mixture with, for example, ethylvinylbenzene, and can be used as it is if the above-mentioned divinylaromatic compound is the main component, and if necessary, purified to increase the purity. You may use.

The excellent heat resistance, oil resistance, heat stability and the like of the isobutylene block copolymer are retained, and molding processability,
Alternatively, the (b) polyolefin-based polymer of the present invention, which is used for improving flexibility during heat resistance or oil resistance, cushioning property, sealing property, and impact resistance, is a homopolymer of ethylene or α-olefin, Alternatively, these random copolymers, block copolymers and mixtures thereof, or random copolymers of ethylene and α-olefins with other unsaturated monomers, block copolymers, graft copolymers and their copolymers. The modified products of the combination can be used alone or in combination of two or more. Specifically, polyethylene, ethylene-propylene copolymer, ethylene-propylene-non-conjugated diene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, ethylene-vinyl acetate. Copolymer, ethylene-vinyl alcohol copolymer, ethylene-ethyl (meth) acrylate copolymer, polyethylene-based polymer such as chlorinated polyethylene, polypropylene, propylene-ethylene random copolymer, propylene-butene-1 random copolymer Polymer, propylene-hexene-1 random copolymer, propylene-4-methyl-1-pentene random copolymer,
Propylene-ethylene block copolymers, polypropylene polymers such as chlorinated polypropylene, polybutene, polyisobutylene, polymethylpentene, (co) polymers of cyclic olefins, oxidation, carboxylic acid (derivatization), glycidylation, oxazolylation , Halogenated, sulfonated,
Examples include various (meth) acrylated polyolefins. Among them, cost, polyethylene polymer from the viewpoint of physical property balance of the thermoplastic elastomer resin composition,
A polypropylene polymer or a mixture thereof can be preferably used.

The excellent heat resistance, oil resistance, heat stability and the like of the isobutylene block copolymer are retained, and molding processability,
Alternatively, in order to improve the flexibility, cushioning property, sealing property, and impact resistance at the time of heat resistance or oil resistance, in particular, the melt flow rate is 10 g / 10 min or more, especially 30 g / 1.
Polypropylene (isotactic or syndiotactic) of 0 min or more, and / or especially a melting point of 135 to 170 ° C., especially 145 to 160
C. (isotactic or syndiotactic) polypropylene is preferred. If the amount of monomers other than propylene is 5% by weight or less, propylene-ethylene copolymer, propylene-butene-1 copolymer, propylene-
An ethylene-butene-1 copolymer or the like can also be used. These copolymers may be random copolymers,
It may be a block copolymer or a mixture of two or more kinds.

The blending amount of the component (b) polyolefin-based polymer is such that the component (a) isobutylene-based block copolymer 10
It is 5.0 to 70 parts by weight, preferably 7.5 to 50 parts by weight, and more preferably 10 to 25 parts by weight with respect to 0 parts by weight. When the amount is less than 5.0 parts by weight, the mechanical strength / molding processability of the obtained thermoplastic elastomer resin composition is lowered, and when it exceeds 70 parts by weight, the rubbery feel of the obtained thermoplastic elastomer resin composition is obtained. Will fall.

In the present invention, the component (b) may contain a component which causes a decomposition reaction mainly by heat treatment in the presence of peroxide,
The properties can be adjusted such that the rubber dispersion in the obtained composition is good and the appearance of the molded product is good. On the other hand, as the component (b), a component which mainly causes a crosslinking reaction by heat treatment in the presence of peroxide may be contained, and the fluidity of the component (b) can be reduced and the characteristics can be adjusted.

Further, a filler may be added to the thermoplastic elastomer resin composition of the present invention for the purpose of improving physical properties or economically. Suitable fillers include
Clay, diatomaceous earth, silica, talc, barium sulfate, calcium carbonate, magnesium carbonate, mica, graphite, aluminum hydroxide, magnesium hydroxide, natural silicic acid, synthetic silicic acid (white carbon), metal oxides (titanium oxide, magnesium oxide) , Zinc oxide) and the like. Of these, calcium carbonate,
Particularly preferred are magnesium oxide, zinc oxide and mica.

Various metal powders such as iron and iron oxide, wood powders, glass powders, ceramics powders, carbon black, granular or powdery solid fillers such as granular or powdery polymers, etc., which are preferably used as a thermal conductivity imparting material, and others Various natural or artificial short fibers, long fibers, and the like can also be exemplified.
Hollow fillers, for example, glass balloons, inorganic hollow fillers such as silica balloons, polyvinylidene fluoride,
Weight reduction can be achieved by blending an organic hollow filler made of a polyvinylidene fluoride copolymer.
To further reduce weight and improve various physical properties such as shock absorption,
It is possible to mix various foaming agents, and it is also possible to mechanically mix the gas at the time of mixing. Thermally expandable microcapsules may be mixed.

The amount of the filler compounded is 0.1 to 5 relative to 100 parts by weight of the component (a) isobutylene block copolymer.
It is 0 parts by weight, preferably 1 to 20 parts by weight. 5
When it exceeds 0 parts by weight, the mechanical strength of the obtained thermoplastic elastomer resin composition is lowered, and the flexibility is deteriorated, which is not preferable.

The optional components will be described below. First,
A small amount of softening agent may be used within a range that does not impair the effects of the present invention, that is, a range that does not bleed out. Usually, a liquid or liquid material at room temperature is preferably used. Further, both hydrophilic and hydrophobic softening agents can be used. Examples of such softening agents include mineral oil-based, vegetable oil-based and synthetic softening agents for rubber or resin. As mineral oils, aromatic, naphthenic, paraffinic process oils and the like, vegetable oils, castor oil, cottonseed oil, linseed oil, rapeseed oil, soybean oil, palm oil, coconut oil, peanut oil, Examples include wood wax, pine oil, olive oil and the like, and examples of synthetic systems include polybutene and low molecular weight polybutadiene. Among these, from the viewpoint of compatibility with the component (a) or the balance of physical properties of the thermoplastic elastomer resin composition, paraffin-based process oil (having a small amount of aromatic ring component) or polybutene is preferably used. These softening agents may be used alone or in combination of two or more in order to obtain the effects of improving the viscosity, moldability and physical properties, appearance and the like.

In the present invention, an organic peroxide may be used as a crosslinking agent or for a decomposition reaction. If necessary, other than organic peroxides, for example, azo compounds, sulfur, organic sulfur compounds, organic nitroso compounds such as aromatic nitroso compounds, oxime compounds,
Examples thereof include metal oxides such as zinc oxide and magnesium oxide, polyamines, compounds such as selenium and tellurium, and resin crosslinking agents such as alkylphenol formaldehyde resins and brominated alkylphenol formaldehyde resins.

In the method for producing the thermoplastic elastomer resin composition of the present invention, a crosslinking aid which is a monomer having an ethylenically unsaturated group can be blended in the treatment with the organic peroxide. Other crosslinking aids can also be used. Other cross-linking aids include, for example, guanidine-based compounds such as diphenylguanidine,
Examples thereof include aldehyde amine compounds, aldehyde ammonium compounds, thiazole compounds, sulfenamide compounds, thiourea compounds, thiuram compounds, and dithiocarbamate compounds.

Furthermore, zinc flower, N, N-m-phenylene bismaleimide, metal halide, organic halide, maleic anhydride, glycidyl methacrylate, and hydroxy may be used together with the above-mentioned crosslinking agent and crosslinking aid, if necessary. It is also possible to use compounds such as propyl methacrylate and stearic acid.

In the thermoplastic elastomer resin composition of the present invention, an aromatic vinyl-conjugated diene-based thermoplastic elastomer, such as styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-, may be added, if desired. Styrene block copolymer (SIS), and at least one of hydrogenated styrene-ethylene butylene-styrene block copolymer (SEBS), styrene-ethylene propylene-styrene block copolymer (SEPS), and the like are blended. May be.

Further, the thermoplastic elastomer resin composition of the present invention may be blended with an antioxidant and / or an ultraviolet absorber, if necessary. In addition to this, other additives such as a flame retardant and an antibacterial agent may be added. Agent, heat stabilizer, light stabilizer,
Colorant, fluidity improver, processing aid (preferably acrylic processing aid), crystal nucleating agent, lubricant, antiblocking agent,
A sealability improving agent, an antistatic agent, etc. can also be added,
These can be used alone or in combination of two or more. Further, as long as the performance of the thermoplastic elastomer resin composition of the present invention is not impaired, various thermoplastic resins such as vinyl aromatic polymers, polyester series, polyamide series, thermoplastic elastomers such as polyurethane series,
You may mix | blend a thermosetting resin, hydrogenated petroleum resin, silicone oil, a silicone type compound, a fluorine type compound, an electron donating compound etc. further.

The method for producing the thermoplastic elastomer resin composition of the present invention is not particularly limited, and known methods can be applied. For example, melt kneading the above-mentioned respective components and optionally an additive component by using a heat kneader, for example, a single-screw extruder, a twin-screw extruder, a roll, a Banbury mixer, a Brabender, a kneader, a high shear type mixer, or the like. Can be manufactured in. The kneading order of each component is not particularly limited, and can be determined according to the equipment used, workability, or the physical properties of the obtained thermoplastic elastomer resin composition.

The thermoplastic elastomer resin composition of the present invention can be molded using a thermoplastic elastomer composition or a molding method and a molding apparatus generally adopted for the thermoplastic resin composition. For example, extrusion molding, injection molding,
Melt molding can be performed by press molding or blow molding.

The thermoplastic elastomer resin composition of the present invention can be suitably used as various packings.

The hardness referred to in the present invention is JIS K 6
352, the value of impact resilience is JIS K 62
The value obtained in accordance with 55.

[0056]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto. Prior to the examples, various measuring methods, evaluation methods and examples will be described.

(Hardness) According to JIS K 6352, a 12.0 mm thick press sheet was used as a test piece.

(Breaking strength) According to JIS K 6251, a test piece was a 2 mm thick press sheet punched into a No. 3 mold with a dumbbell and used. The pulling speed was 500 mm / min.

(Tensile breaking elongation) In conformity with JIS K 6251, a test piece was a 2 mm thick press sheet, and 3 with a dumbbell.
I used it after punching it out into a No. The pulling speed was 500 mm / min.

(Rebound resilience) A 12.0 mm thick press sheet was used as a test piece in accordance with JIS K 6255.

(Bleed out) Test piece is 50 mm × 5
Using a 0 mm x 2 mm thick press sheet, methanol 10
After being immersed in 0 cc in an atmosphere of 25 ° C. for 24 hours, taken out and dried, the weight change was observed. Those with a weight change of 10% or less were marked with ◯, and those with a weight change of 10% or more were marked with x.

The following was used as each component. Component (a-1): Block copolymer (SIBS1) weight average molecular weight 90000. Styrene content 21.5% by weight. Component (a-2): Block copolymer (SIBS2) weight average molecular weight 106000. Styrene content 30% by weight. Hydrogenated isoprene-based block copolymer (SEPS): SEPTON4033 manufactured by Kuraray Co., Ltd. Styrene content 30
weight%. Component (b-1): B manufactured by Random PP Grand Polymer Co., Ltd.
241 (MFR: 0.5 g / 10 minutes) Component (b-2): J70 manufactured by Homo PP Grand Polymer Co., Ltd.
9 W (MFR: 55 g / 10 min) Inorganic filler (CaCO ₃ ): Shiraishi Calcium Co., Softon 3200 Paraffin oil (non-aromatic rubber softening agent): Idemitsu Kosan Diana Process Oil PW-90.

(Production Example: SIBS1) To a 2 L reaction vessel equipped with a stirrer, 525 mL of 1-chlorobutane (dried with molecular sieves), 365 mL of hexane (dried with molecular sieves), and 0.49 g of p-dicumyl chloride were added. It was After cooling the reaction vessel to −70 ° C., 0.93 g of dimethylacetamide and 244 mL of isobutylene were added. Further titanium tetrachloride 6.57
The polymerization was started by adding mL, and the solution was reacted at -70 ° C for 1.5 hours while stirring. Then, 70 g of styrene was added to the reaction solution, the reaction was continued for further 60 minutes, and then the reaction solution was poured into a large amount of water to stop the reaction.

When the separation state of the organic layer and the aqueous layer was visually confirmed, the separability was good, and the separation was easy with a separating funnel. After washing twice with water, after confirming that the aqueous layer is neutral, the organic layer is poured into a large amount of methanol to precipitate the polymer, and the obtained polymer is allowed to stand at 60 ° C. for 24 hours. An isobutylene block copolymer (SIBS1) was obtained by vacuum drying.

The isobutylene block copolymer (SI
GPC analysis of BS1) showed a weight average molecular weight of 90000. The styrene content determined by 1 H-NMR was 21.5% by weight. Similarly, SIBS
2 (weight average molecular weight 106000, styrene content 3
0% by weight) was produced.

(Example 1) SIB as the component (a-1)
90 parts by weight of S1 and random PP as component (b-1)
10 parts by weight of knead was mixed for 15 minutes with a plastomill manufactured by Toyo Seiki Co., Ltd. (rotation speed 100 rpm, temperature 170 ° C.). The obtained kneaded product is pressed at 200 ° C., and the thickness is 2 mm and 12 mm
A thick sheet was made. The 2 mm thick sheet had a smooth surface. In addition, it was flexible enough to be easily bent by hand. On the other hand, the hardness of the 12 mm thick sheet is 3
2, the maximum tensile strength is 11 MPa, the breaking elongation is 660%,
The impact resilience was 16% and the bleed-out was 10% by weight or less. The results are also shown in Table 1.

(Examples 2 to 7) In the same manner as in Example 1, the components (a-1) or (a-2), the components (b-1) or (b-2) and, optionally, the inorganic filler were represented. The mixture was kneaded as in No. 1 and hardness, maximum tensile strength, elongation at break, impact resilience, and bleedout were measured. The results are shown in Table 1.

(Comparative Examples 1 and 2) In the same manner as in Example 1, hydrogenated isoprene-based block copolymer, component (b-1), and optionally paraffin oil were kneaded as shown in Table 1 to obtain hardness,
The maximum tensile strength, elongation at break, impact resilience, and bleedout were measured. The results are shown in Table 1.

(Comparative Example 3) As in Example 1, the component (a
-1) and the component (b-1) are kneaded as shown in Table 1 to obtain the hardness,
The maximum tensile strength, elongation at break, impact resilience, and bleedout were measured. The results are shown in Table 1.

[0070]

[Table 1]

As described above, appearance (surface smoothness), flexibility (flexibility when bent, low hardness, impact resilience) cannot be obtained until the specific amounts of the components (a) and (b) are prepared. Low), mechanical strength (tensile strength, elongation at break), moldability (sheet formability), no bleed-out, etc., and a well-balanced thermoplastic elastomer resin composition can be obtained.

[0072]

The elastomer resin composition obtained by the method of the present invention is rich in flexibility and cushioning property, that is,
It has characteristics such as low hardness and low impact resilience, and has rubber-like characteristics,
Thermoplastic elastomer with well-balanced heat resistance, oil resistance, retort resistance, mechanical strength, moldability, heat stability, weather resistance, vibration damping, gas barrier properties and appearance, and no bleed out of plasticizer. A resin composition is obtained, which is useful in the field of various packings.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J002 BB032 BB052 BB062 BB072                       BB122 BB142 BB152 BB172                       BB182 BB202 BB242 BE032                       BK002 BP022 BP031 CE002                       DA026 DE076 DE106 DE136                       DE146 DE236 DG046 DJ016                       DJ036 DJ046 DJ056 FD016

Claims (4)

[Claims] 1. (a) 100 parts by weight of an isobutylene block copolymer comprising a polymer block containing isobutylene as a monomer main component and a polymer block containing an aromatic vinyl compound as a monomer main component, b) A thermoplastic elastomer resin composition comprising 5.0 to 70 parts by weight of a polyolefin-based polymer, having a hardness of 50 or less and a impact resilience of 40% or less. 2. The thermoplastic elastomer resin composition according to claim 1, wherein the hardness is 40 or less and the impact resilience is 30% or less. 3. The thermoplastic elastomer resin composition according to claim 1, further comprising 0.1 to 50 parts by weight of an inorganic filler. 4. The thermoplastic elastomer resin composition according to claim 1, wherein (b) is a polypropylene polymer.