JPH1036571A - Functional thermoplastic elastomer composition and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition to which functional characteristics are imparted, for example, adhesion, antistatic properties, impermeability, ultraviolet absorption and biocompatibility. SOLUTION: (A) A thermoplastic elastomer composition at a weight ratio of 10/90-80/20 the thermoplastic resin component/the elastomer component is blended with (B) an incompatible functional resin material having Δ SP>1 so that the following formula is satisfied and the volume fraction of the component (B) is adjusted to 1-40%: the formula: α=(ϕA/ϕB)μ(ηB/ηA)<1.0 where ϕA: the elastomer volume fraction in the thermoplastic elastomer composition in which the elastomer is dispersed; ηA: the viscosity when they are melt-kneaded; ϕB: the volume fraction of the functional resin in the thermoplastic elastomer composition; ηB: the viscosity when they are melt-kneaded.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a rubber-like elastic function inherent in a thermoplastic composition comprising a thermoplastic resin component as a continuous phase, an elastomer component constituting a dispersed phase, and at least a part thereof being crosslinked. In addition, a functional thermoplastic elastomer composition further provided with desired functions (adhesion, antistatic property, anti-permeability, ultraviolet absorption, biocompatibility, etc.), a method for producing the same, and the functionality The present invention relates to a hose and a pneumatic tire using a thermoplastic elastomer composition.

[0002]

2. Description of the Related Art A thermoplastic elastomer composition in which a thermoplastic resin component is used as a continuous phase, an elastomer component is used as a dispersed phase, and at least a part of the elastomer component is cross-linked (vulcanized) is generally used. It is known that the composition has a rubber elasticity function due to the cross-linked elastomer component, and is a thermoplastic resin component forming a continuous phase. I have. That is, the thermoplastic elastomer composition having the dispersed structure has a feature that it can be molded by the same processing technique as that for plastics while maintaining the properties of the vulcanized rubber.

[0003] The elastomer composition has the following basic advantages as compared with vulcanized rubber. No vulcanization step is required. Recycling of products and scrap generated during molding is possible. Lightening is possible. Above all, in particular, the heat is obtained by crosslinking (vulcanizing) the elastomer component forming the dispersed phase and at least part or all of the thermoplastic resin forming the continuous phase during kneading, that is, dynamically crosslinking (vulcanizing). The plastic elastomer composition can provide a product excellent in mechanical physical properties, compression set resistance and oil resistance, etc., especially as a rubber elastic body. , Medical equipment, general industrial materials, etc.

[0004] The present inventors have previously described the above-mentioned thermoplastic elastomer.
Regarding the tomer composition, as a polymer composition for tires
Excellent balance between air permeability and flexibility, and tires
Air permeability coefficient that can be used to reduce the weight of
Is 25 × 10^-12cc ・ cm / cm ^Two・ Sec ・ Year less than cmHg
Specified amount of thermoplastic resin with over 500MPa and air permeation
Coefficient is 25 × 10^-12cc ・ cm / cm^Two・ Sec ・ cmHg
With a specific amount of the elastomer component having a
25 × 10^-12cc ・ cm / c
m^Two・ Sec ・ cmHg or less and Young's modulus is 1 ~ 500MPa
And filed an application for a tire polymer composition (Japanese Patent Application
-8394).

[0005] However, the composition of this application has an excellent function as a polymer composition for tires, but when it is used as an air permeation preventing layer such as an inner liner layer of a pneumatic tire, the composition is not suitable. There is a problem that the adhesiveness to the rubber layer is not sufficient only with the thermoplastic elastomer composition.

Further, the present applicant has been studying to improve the air permeation preventing property of the polymer composition for a tire to a more efficient one, and has studied a blend of at least two kinds of incompatible thermoplastic resins. In the process of extrusion molding, one thermoplastic resin component in the thermoplastic resin is incompatible with each other, so that it does not finely disperse due to shear stress at the time of extrusion molding, but is oriented and dispersed in a flat shape to form air integrally. A thermoplastic resin composition for a tire constituting an anti-permeation layer was presented and filed (Japanese Patent Application No. 7-55929).

However, when the above-mentioned thermoplastic resin composition is used as an air-permeation preventing layer of a pneumatic tire, a sufficient air-permeation-preventing property can be obtained because it is a thermoplastic resin composition. However, there is a problem that it is not always enough to control sufficient flexibility and durability against bending fatigue, and that the thermoplastic resin composition alone does not have sufficient adhesiveness to a rubber layer.

Further, the present inventors have satisfied various characteristics required for a low-permeability hose for reducing gas permeation of low-molecular components such as refrigerants, and have a low permeation weight that is lightweight and does not require a vulcanization step. respect thermoplastic elastomer composition for sex hose, a specific amount of para-alkylstyrene and C ₄ -C ₇ rubber component and a specific thermoplastic resin comprising a halide of a copolymer of isomonoolefin consisting component copolymer (Japanese Patent Application No. Hei 7-286168).

When the thermoplastic elastomer composition for a low-permeability hose is used for a part of an inner tube or an outer tube of a hose, the composition has good gas permeation preventing properties and good flexibility. Yes, it is satisfactory for performance such as drastic improvement in weight reduction, but similarly, if the thermoplastic elastomer alone is used, if it has a reinforcing layer or, if necessary, a multilayer structure with other rubber materials, the adhesiveness will be poor. There is a problem that it is not enough.

That is, as described above, a thermoplastic elastomer composition having a thermoplastic resin component as a continuous layer and an elastomer component as a dispersion layer has rubber elasticity,
Thermoplastic elastomer compositions that are flexible and capable of thermoplastic processing, and that can further control air permeability or gas permeability are known, and also have an integrated gas permeation preventing property. Although a thermoplastic resin composition for forming a layer inside the layer is also known, a layer having rubber elasticity and capable of thermoplastic processing, and having a necessary function such as integral bonding is used. A thermoplastic elastomer composition formed outside the layer has not yet been obtained.

[0011]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has been made in response to industrial needs.
In addition to the original properties of various thermoplastic elastomer compositions, various functionalities (adhesion, antistatic, anti-permeation,
UV protection, biocompatibility, etc.) is intended to provide a functionalized thermoplastic elastomer composition imparted, while maintaining the performance of the thermoplastic elastomer material, a small amount of functionalized thermoplastic resin component It is another object of the present invention to provide a method for producing a composition having the above functions by simply blending with an existing apparatus by blending. It is another object of the present invention to provide a hose and a pneumatic tire using a thermoplastic elastomer composition having the above-mentioned function.

[0012]

According to the present invention, the blending weight ratio of the elastomer component constituting the dispersed phase to the thermoplastic resin component constituting the continuous phase is from 10/90 to 80 /.
In the thermoplastic composition (A) in which the elastomer component of No. 20 is dispersed, the difference of the value (SP value) of the compatibility parameter (SP value) with the thermoplastic resin component of (A) is more than 1.0. Functional thermoplastic elastomer composition in which the functional resin component (B) is blended and the following formula (1) is satisfied, and the volume fraction relative to the total amount of (B) and (A) is controlled to 1 to 40%. Is provided.

(Equation 3) Here, φ _A : volume fraction of the thermoplastic elastomer composition component φ _B : volume fraction of the functional thermoplastic resin component η _A : melt viscosity of the thermoplastic elastomer composition component during melt-kneading η _B : function Viscosity during melt-kneading of reactive thermoplastic resin components

According to the present invention, the compatibilizer component (C) is further added to the functional thermoplastic elastomer composition in an amount of 0.5 to 0.5% based on the total amount of the components (A) and (B) in the functional thermoplastic elastomer composition. 10
Provided is a functional thermoplastic elastomer composition which is added by weight%.

Further, according to the present invention, a thermoplastic elastomer composition (A) in which the mixing weight ratio of the elastomer component constituting the dispersed phase to the thermoplastic resin component constituting the continuous phase is 10/90 to 80/20. ), And then the incompatible functional thermoplastic resin component (B) in which the difference of the compatibility parameter value (ΔSP value) with the thermoplastic resin component (A) is more than 1.0 ) Is melt-kneaded under conditions satisfying the following expression (1), and the volume fraction of (B) is 1 to 40 with respect to the total amount of (B) and (A).
%, And then applying a shearing stress to a sheet or tube to form a functional thermoplastic elastomer composition in which the functional thermoplastic resin component is arranged at the surface. .

(Equation 4) Here, φ _A : volume fraction of the thermoplastic elastomer composition component φ _B : volume fraction of the functional thermoplastic resin component η _A : melt viscosity of the thermoplastic elastomer composition component during melt-kneading η _B : function Viscosity during melt-kneading of reactive thermoplastic resin components

Further, according to the present invention, (B)
An adhesive thermoplastic elastomer composition in which an adhesive thermoplastic resin component is blended as a functional thermoplastic resin component is provided, and the adhesive thermoplastic elastomer composition is connected to a hose outer tubing material adjacent to a reinforcing layer. Hose used for at least one of a tube inner layer material, an inner tube outer layer material, and (when the reinforcing layer is a multilayer) a reinforcing layer, and the adhesive thermoplastic elastomer composition used as an air permeation preventing layer for a tire A pneumatic tire is provided.

The thermoplastic resin used for the thermoplastic resin component in the thermoplastic elastomer composition in which the elastomer blended as the component (A) is dispersed in the functional thermoplastic elastomer composition according to the present invention is air. Transmission coefficient is 2
5 × 10 ^-12 cc · cm / cm ² · sec · cmHg or less, preferably 0.1 × 10 ^-12 to 10 × 10 ^-12 cc · cm / cm ² · se
c · cmHg, HFC-134a Freon gas permeability coefficient is 5 mg · mm / 24h · cm ² or less, and Young's modulus is 5
Any thermoplastic resin having a pressure of at least 00 MPa, preferably 500 to 3000 MPa can be used, and the compounding amount thereof is 15% by weight or more, preferably 20 to 85%, based on the total weight of the thermoplastic resin component and the polymer component including the elastomer component.
% By weight.

As such a thermoplastic resin, for example, the following thermoplastic resins, and these or any thermoplastic resin mixtures containing these can be exemplified.
Further, it may be a thermoplastic resin component containing an antioxidant, a heat resistance preventing agent, a stabilizer, a processing aid, a pigment, a dye, and the like.

A polyamide resin (for example, nylon 6
(N6), nylon 66 (N66), nylon 46 (N
46), nylon 11 (N11), nylon 12 (N1
2), nylon 610 (N610), nylon 612
(N612), nylon 6/66 copolymer (N6 / 6
6), nylon 6/66/610 copolymer (N6 / 66
/ 610), nylon MXD6, nylon 6T, nylon 6 / 6T copolymer, nylon 66 / PP copolymer, nylon 66 / PPS copolymer), polyester resin (for example, polybutylene terephthalate (PBT), polyethylene terephthalate) (PET), polyethylene isophthalate (PEI), polybutylene terephthalate / tetramethylene glycol copolymer, PET / PEI
Copolymer, polyarylate (PAR), polybutylene naphthalate (PBN), liquid crystal polyester, aromatic polyester such as polyoxyalkylenediimide diacid / polybutylene terephthalate copolymer), polynitrile resin (for example, polyacrylonitrile ( PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, methacrylonitrile / styrene / butadiene copolymer), poly (meth) acrylate-based resin (for example, poly Methyl methacrylate (PMMA), polyethyl methacrylate), polyvinyl resins (eg, vinyl acetate, polyvinyl alcohol (PVA), vinyl alcohol / ethylene copolymer (EVOH), polyvinylidene chloride (PV
DC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymer, vinylidene chloride / methyl acrylate copolymer), cellulosic resin (eg, cellulose acetate, cellulose acetate butyrate), fluororesin (eg, Vinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polychlorofluoroethylene (PCT)
FE), tetrafluoroethylene / ethylene copolymer (E
TFE)) and imide-based resins (for example, aromatic polyimide (PI)).

As described above, these thermoplastic resins are particularly
Use a constant air (gas) permeability coefficient, Young's modulus and
I have to. Flexible with a Young's modulus of 500MPa or less
And the air permeability coefficient is 25 × 10^-12cc ・ cm / cm^Two・
sec ・ cmHg or less, or HFC134a CFC gas permeation
Coefficient is 5mg ・ mm / 24h ・ cm^TwoThe following materials are industrial
Has not yet been developed and has an air permeability coefficient of 25
× 10^-12cc ・ cm / cm ^Two・ Sec ・ cmHg
Is HFC134a fluorocarbon gas permeability coefficient of 5mg · mm / 24
h ・ cm^TwoExceeds the functional thermoplastic composition for tires
Air permeation resistance and gas permeation resistance composition for hoses
The aforementioned air or gas permeability decreases,
Air permeation prevention layer or hose gas permeation prevention layer
Stop functioning. Furthermore, these thermoplastic resins
Gas permeation resistance similarly when the blending amount is less than 10% by weight
To prevent air (gas) permeation of tires and hoses
It is not preferable because it cannot be used as a layer.

The elastomer component in the thermoplastic elastomer composition containing the elastomer component forming the dispersed phase to be blended as the component (A) with the functional thermoplastic elastomer composition according to the present invention has an air permeability coefficient of 25 ×. 10
^-12 cc · cm / cm ² · sec · cmHg, gas permeability coefficient of more than 5 mg · mm / 24 h · cm ² , and any elastomer having a Young's modulus of 500 MPa or less, or any blend thereof, or elastomer thereof Reinforcing agents, fillers, crosslinkers, softeners, antioxidants, which are generally compounded with elastomers to improve the dispersibility and heat resistance of
An elastomer composition to which a necessary amount of a compounding agent such as a processing aid is added. The compounding amount is based on the total weight of the total amount of the component (A) constituting the functional thermoplastic elastomer composition constituting the air or gas permeation preventing layer. 10% by weight or more, preferably 10%
~ 85% by weight.

The elastomer constituting such an elastomer component is not particularly limited as long as it has the above air or gas permeability coefficient and Young's modulus.
For example, the following can be mentioned.

Diene rubbers and hydrogenated products thereof (for example, NR, IR, epoxidized natural rubber, SBR, BR
(High cis BR and low cis BR), NBR, hydrogenated NB
R, hydrogenated SBR), olefin rubber (eg, ethylene propylene rubber (EPDM, EPM), maleic acid-modified ethylene propylene rubber (M-EPM)), butyl rubber (IIR), isobutylene and aromatic vinyl or diene monomer. Polymer, acrylic rubber (ACM), ionomer), halogen-containing rubber (for example, Br-IIR,
CI-IIR, bromide of isobutylene paramethylstyrene copolymer (Br-IPMS), chloroprene rubber (CR), hydrin rubber (CHC, CHR), chlorosulfonated polyethylene (CSM), chlorinated polyethylene (CM), maleic acid Modified chlorinated polyethylene (MC
M)), silicone rubber (eg, methyl vinyl silicone rubber, dimethyl silicone rubber, methyl phenyl vinyl silicone rubber), sulfur-containing rubber (eg, polysulfide rubber), fluorine rubber (eg, vinylidene fluoride rubber, fluorine-containing vinyl ether rubber) , A tetrafluoroethylene-propylene rubber, a fluorine-containing silicon rubber, a fluorine-containing phosphazene rubber), a thermoplastic elastomer (for example, a styrene-based elastomer, an olefin-based elastomer, a polyester-based elastomer, a urethane-based elastomer, and a polyamide-based elastomer). Can be mentioned.

The functional thermoplastic resin component to be blended as the component (B) in the functional thermoplastic elastomer composition according to the present invention has an adhesive property, an antistatic property, an anti-penetration property as a structure of the thermoplastic resin. Any substance can be used as long as it has an active substituent that contributes to ultraviolet protection and biocompatibility. However, the value of the compatibility parameter (SP value) of this functional resin material with respect to the thermoplastic elastomer composition (A) in which the elastomer component to be mixed with the functional thermoplastic elastomer of the present invention is dispersed is (A). If the difference between the two is not incompatible with each other, the dispersion state is effectively flattened at the time of molding by applying a shearing stress as described below, and the dispersion state is arranged around the layer. The functional thermoplastic resin component cannot be used effectively, and if the formula (1) satisfies the condition of α <1.0, the functional thermoplastic resin component is contained in the component (A). It is necessary for finely dispersing as a dispersed phase. Furthermore, the volume fraction of the functional thermoplastic resin material (B) in the functional thermoplastic elastomer composition is 1 to 40%.
It is blended so that Here, the SP value is determined by calculation from the chemical structures of the thermoplastic resin component, the elastomer component, and the functional thermoplastic resin component to be used, and is based on the known atomic group contribution method, Small's formula, Hoftizer-V
It is assumed to have been obtained by the expression of an Krevelen.

As described above, the functional thermoplastic elastomer composition of the present invention is a blend of chemically incompatible polymers having basically a compatibility parameter value (SP value) of more than 1.0. Therefore, if these are used alone, the interface strength between the two polymers is weak, and if properties such as mechanical strength or high durability fatigue are particularly required, the desired mechanical properties such as elongation are not exhibited. It is desirable to add. As such a compatibilizer, generally, (A)
A copolymer having a structure of both or one of the thermoplastic resin component and the functional thermoplastic resin component contained in the component, or an epoxy group or a carbonyl group capable of reacting with the thermoplastic resin component or the functional thermoplastic resin component , Halogen group,
The copolymer may have a structure having an amino group, an oxazoline group, a hydroxyl group, or the like. These may be selected depending on the type of both resin components to be blended,
Those which can be generally used include polyolefins such as styrene / ethylene / butylene block copolymer (SEBS) and its maleic acid-modified product, EPDM, EPDM / styrene or EPDM / acrylonitrile graft copolymer and its maleic acid-modified product, and the like. Modified polyolefin-based thermoplastic resin components, styrene / maleic acid copolymers, reactive phenoxy, and the like can be given. The compounding amount of the compatibilizer is 0.5 to 0.5 to the total amount of the component (A) and the component (B) in the functional thermoplastic elastomer component.
It is 10% by weight, preferably 1.0 to 10% by weight.

The process for producing a functional thermoplastic elastomer composition according to the present invention comprises a thermoplastic resin component constituting a continuous phase and an elastomer component constituting a dispersed phase in a predetermined ratio, preferably crosslinking (vulcanization) during kneading. That is, a thermoplastic elastomer composition (A) produced by finely kneading an elastomer component dynamically crosslinked (vulcanized) under a relatively high shear stress, for example, in a twin-screw kneading extruder, is produced. Then, this is blended with a predetermined functional thermoplastic resin (B) in a uniaxial thermoplastic resin kneading extruder under a relatively low shear rate condition. More specifically, the component (B) is unevenly distributed to the outside within a range satisfying the conditions of the melt viscosity and the volume fraction of (A) and (B) using a normal T-shaped die or a tubing die formed into a tube shape. Thin film, Over preparative like material, plate-like material, and is characterized in that shaping the stick-shaped material and tubular material. Here, the relatively high shear stress conditions during biaxial kneading are as follows:
The shear rate is 1000 to 7500 sec ^-1 , and the condition of relatively low shear stress in a single screw extruder or the like is preferably ^{1 to} less than 1000 sec ^-1 at a shear rate. In the extruded product, the functional thermoplastic resin component is added to the surface by its rheological flow behavior as long as the difference between the condition of the formula (1) and the SP value is satisfied. It will be arranged unevenly.

The compatibilizer component (C) is simultaneously kneaded with the previously prepared thermoplastic elastomer composition (A) and the functional thermoplastic elastomer component (B) at the time of kneading under the above-mentioned low shear stress conditions. The bonding force at the interface between the components (A) and (B) may be improved, or a relatively high shear stress such as biaxial kneading of the thermoplastic resin component and the elastomer component of the thermoplastic elastomer composition (A). The same effect can also be obtained by adding and dispersing simultaneously or separately with the thermoplastic elastomer component at the time of kneading under. That is, in the present invention, by adding the component (C) in an amount of 0.5 to 10% by weight based on the total amount of the components (A) and (B), the properties of the thermoplastic elastomer composition itself are not impaired. Furthermore, not only the functional thermoplastic resin component has the function possessed integrally, but also in the present invention, the functional thermoplastic resin component takes a dispersed structure unevenly distributed, a small amount of function Even if the amount of the thermoplastic resin component is mixed, the function can be effectively and fully exerted.

In the production of an adhesive thermoplastic elastomer composition using an adhesive thermoplastic resin as the functional thermoplastic resin component in the present invention, it is necessary to first produce the thermoplastic elastomer composition of the component (A). In a method for producing the composition, the thermoplastic resin component and the elastomer component (an unvulcanized product excluding a vulcanizing (crosslinking) agent) are melt-kneaded by a twin-screw kneading extruder or the like, and a continuous phase (matrix) is formed. The elastomer component is dispersed as a disperse phase (domain) in the thermoplastic resin that forms At this time, when the elastomer component is cross-linked (vulcanized), a vulcanizing agent and, if necessary, a vulcanizing aid are added under kneading to dynamically vulcanize the elastomer component. The various additives (excluding the vulcanizing agent) to the thermoplastic resin or the elastomer component may be added during the kneading, but may be mixed before the kneading. The conditions for the melt-kneading at this time may be at least the temperature at which the thermoplastic resin component melts, and the shear rate during kneading is preferably 1000 to 7500 sec ^-1 . The kneading time is preferably from 30 seconds to 10 minutes, and when a crosslinking (vulcanizing) agent is added, the vulcanizing time after the addition is preferably from 15 seconds to 5 minutes.

The elastomer composition according to the present invention may further contain a filler (calcium carbonate, titanium oxide, alumina, etc.), a reinforcing agent such as carbon black and white carbon, a softener, A plasticizer, a processing aid, a pigment, a dye, an antioxidant, and the like can be arbitrarily added as long as the requirement for the air permeability or gas permeability is not impaired. Further, the elastomer component,
The elastomer component can also be dynamically vulcanized during mixing with the thermoplastic resin. Vulcanizing agent, vulcanizing aid, vulcanizing conditions (temperature, time) for dynamically vulcanizing elastomer components
Etc. may be appropriately determined according to the composition of the elastomer component to be added, and are not particularly limited.

As the vulcanizing agent, a general rubber vulcanizing agent (crosslinking agent) can be used. Specifically, examples of the sulfur-based vulcanizing agent include powdered sulfur, precipitated sulfur, highly dispersible sulfur, surface-treated sulfur, insoluble sulfur, dimorpholine disulfide, and alkylphenol disulfide. About 4 phr (parts by weight per 100 parts by weight of the elastomer component (polymer)).

The organic peroxide-based vulcanizing agents include:
Benzoyl peroxide, t-butyl hydroperoxide, 2,4-bichlorobenzoyl peroxide,
Examples thereof include 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and 2,5-dimethylhexane-2,5-di (peroxylbenzoate).
About 1 to 20 phr can be used. Further, examples of the phenol resin-based vulcanizing agent include brominated alkylphenol resins and mixed cross-linking systems containing a halogen donor such as tin chloride and chloroprene and an alkylphenol resin. Can be. In addition, zinc white (about 5 phr), magnesium oxide (about 4 phr), litharge (about 10 to 20 phr), p-quinone dioxime, p-dibenzoylquinone dioxime, tetrachloro-p-benzoquinone, poly-
Examples thereof include p-dinitrosobenzene (about 2 to 10 phr) and methylene dianiline (about 0.2 to 10 phr).

[0031] If necessary, a vulcanization accelerator may be added. Examples of the vulcanization accelerator include general vulcanization accelerators such as aldehyde / ammonia, guanidine, thiazole, sulfenamide, thiuram, dithioate, and thiourea, for example, About 2 phr can be used. Specifically, hexamethylenetetramine or the like is used as the aldehyde / ammonia-based vulcanization accelerator, diphenylguanidine is used as the guanidine-based vulcanization accelerator, and dibenzothiazyl disulfide (or the like) is used as the thiazole-based vulcanization accelerator. DM), 2-mercaptobenzothiazole and its Zn salt, cyclohexylamine salt, etc., as sulfenamide-based vulcanization accelerators, cyclohexylbenzothiazylsulfenamide (CBS), N-oxydiethylenebenzothiazyl-2- Examples of thiuram-based vulcanization accelerators such as sulfenamide, Nt-butyl-2-benzothiazolesulfenamide, 2- (thymopolynyldithio) benzothiazole and the like include tetramethylthiuram disulfide (TMTD), tetraethyl Thiuram disulfide, tetrame Le monosulfide (TMTM), dipentamethylenethiuram tetrasulfide and the like, as the dithio acid salt-based vulcanization accelerator,
Zn-dimethyldithiocarbamate, Zn-diethyldithiocarbamate, Zn-di-n-butyldithiocarbamate, Zn-ethylphenyldithiocarbamate, T
e-diethyldithiocarbamate, Cu-dimethyldithiocarbamate, Fe-dimethyldithiocarbamate,
Examples of thiourea-based vulcanization accelerators such as pipecoline pipecolyl dithiocarbamate include ethylene thiourea and diethyl thiourea. As a vulcanization accelerating auxiliary, a general rubber auxiliary may be used in combination, for example, zinc white (about 5 phr), stearic acid, oleic acid and Zn salt thereof (about 2 to 4 phr). Etc. can be used.

The thermoplastic elastomer composition prepared by the above method is then used as it is, or
After being extruded into a single pellet by a screw kneading extruder, it is charged into a single screw extruder, and simultaneously, the adhesive thermoplastic resin component is mixed separately or in a blended state. After being kneaded under the proper kneading conditions,
It is oriented and extruded by a constant shear stress from a T-die for seating or a pin for tubing attached to the tip, a tubing die having a die structure,
It is extruded into a desired shape (thin film, sheet, plate, rod, hollow tube, etc.). The kneading time in the single-screw kneading extruder is preferably 30 seconds to 10 minutes.

In the molded product thus obtained, at least a part of the elastomer component is dispersed as a dispersed phase (domain) in the continuous phase (matrix) of the thermoplastic resin component, and the adhesive resin component is formed in the surface region. The structure is concentrated and unevenly distributed. The compatibilizer component (C), which is added as necessary, has a structure in which the interface between the thermoplastic resin component and the adhesive resin component is reinforced and arranged. The strength is also improved so that it can be used suitably. By taking the dispersion structure in such a state, it is possible to obtain a molded article having not only the above-mentioned basic properties and advantages of the thermoplastic elastomer composition itself in which the elastomer is dispersed, but also excellent adhesiveness and mechanical properties. When a molded article made of the adhesive thermoplastic elastomer composition is formed into a thin film, the molded article is used as an air permeation preventing layer such as an inner liner of a pneumatic tire, and an inner pipe or an outer pipe of a low permeability hose. It can be effectively used for a gas permeation prevention layer of a tube, etc., and is a molded product excellent in adhesiveness obtained by extruding or melting the adhesive thermoplastic elastomer composition into a rod or a predetermined shape. Taking advantage of this feature, it can be used as packing for various window frames and upper members of packing, or as molded packing material for joining members of automobile lamps. It is possible to use to.

An example of a method for manufacturing a pneumatic tire having an air permeation preventing layer comprising a thin film of the adhesive thermoplastic elastomer composition according to one embodiment of the present invention, wherein an inner liner layer is disposed inside a carcass layer To explain, the adhesive thermoplastic elastomer composition previously obtained by the method of the present invention is extruded into a thin film of a predetermined width and thickness from a single screw extruder having a T-shaped head-structured sheeting die at the tip. And stick it on a cylinder for tire building. The members used for normal tire production, such as a carcass layer, a belt layer, and a tread layer made of unvulcanized rubber, are sequentially laminated thereon, and the drum is pulled out to obtain a green tire. Next, by heating and vulcanizing the green tire according to a conventional method, a desired lightweight pneumatic tire can be manufactured. In addition, also when providing an air permeation prevention layer on the outer peripheral surface of a carcass layer, it can be performed according to this.

In the manufacture of the pneumatic tire, the adhesive thermoplastic resin has an adhesive property because it is unevenly arranged on the surface, and therefore, an adhesive is used as in the prior art, or Complicated treatment such as using the air permeation preventing layer separately by extrusion molding the adhesiveness-imparting layer, or forming a laminate of the air permeation preventing layer and the adhesiveness-imparting layer before use. Since no process is required, it is extremely advantageous in terms of manufacturing cost and workability.

The method for producing a gas-permeable low-pressure hose made of the adhesive thermoplastic elastomer composition according to one embodiment of the present invention may be applied to the case where the hose is used as it is for an inner tube or outer tube of a hose, or as a sheet-like material. The gas permeation prevention layer is used as the inner tube inner layer, and any configuration utilizing its adhesiveness and gas permeation prevention properties, such as an inner tube outer layer made of a rubber composition, a reinforcing layer, and a low permeability hose made of an outer tube, is possible. is there. An example of the case of a low-permeability hose consisting of a rubber composition, an inner tube outer layer, a reinforcing layer, and an outer tube is described below. On the mandrel, the adhesive thermoplastic elastomer composition obtained by the method of the present invention, the gas permeation prevention layer of the inner tube inner layer is extruded from a resin extruder having a crosshead structure, and further using a rubber extruder. Extruding the rubber outer tube outer layer, braiding the reinforcing yarn appropriately using a braiding machine thereon to form a fiber reinforcing layer, and further forming the rubber outer tube on the rubber cross head structure in the same manner. What is necessary is just to extrusion-mold with the rubber extruder which has. Thereafter, the rubber layer is vulcanized using a vulcanizer or the like, and after cooling, the mandrel is finally pulled out to obtain the low permeability hose of the present invention. Although the mandrel is used in the method of manufacturing the hose, the low permeability hose of the present invention may be manufactured without using a mandrel unless particularly strict dimensional accuracy is required.

In manufacturing the hose, the inner layer of the inner tube as the gas permeation preventing layer is in a phase state in which the adhesive resin material component is unevenly distributed on the surface portion. As described above, there is no need to apply an adhesive to the outer layer again, and it is sufficient to simply extrude the outer layer of the inner tube as it is, thereby simplifying the production.

[0038]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples, but it goes without saying that the present invention is not limited to the following Examples.

Preparation of Thermoplastic Elastomer Composition (A) A thermoplastic resin component having the composition shown in the following composition table (I):
A thermoplastic elastomer composition (A) was prepared using an elastomer component and a vulcanization system. First, the elastomer component was kneaded with a rubber Banbury mixer in the ratio shown in the composition table (I), then sheeted out with a rubber roll to a thickness of 2 mm, and then pelletized with a rubber pelletizer, followed by thermoplastic thermoplastics shown below. It was used for producing an elastomer composition. 2
At a relatively high shear rate of 50 rotations, an exemplary polypropylene resin which is a thermoplastic resin component is charged from the first inlet using a biaxial kneading extruder having a diameter of 44 mm, and allowed to melt while kneading. Pellets of the above-mentioned elastomer component were continuously charged from the inlet of No. 2 so as to have a composition ratio shown in the mixing table- (I), and kneaded so that the elastomer component was finely dispersed in the polypropylene resin. Then, the vulcanization system of the indicated mixing ratio is added from the third input port to the thermoplastic resin component and the elastomer component while similarly kneading so as to have the composition ratio shown in the mixing table (I). Then, it was extruded into a strand form from the tip of a twin-screw kneading extruder, cooled in a water bath, pelletized with a resin pelletizer, and kneaded with a functional resin material.

[0040]

[Table 1]

Preparation of Functional Thermoplastic Elastomer Composition The thermoplastic elastomer composition pellets obtained above and the modified polyester-based adhesive resin pellets shown in Table I below were used as the functional thermoplastic resin components, and Table II
Were blended at the weight ratio shown in Table 1. Using the blended pellets, using a single-screw kneading extruder having a diameter of 40 mm, the mixture was melt-kneaded at 40 rpm under a relatively low shearing rate. Thereafter, the strand was extruded into a strand from a die attached to the tip of a single-screw kneading extruder, and the strand was water-cooled, pelletized with a resin pelletizer, and subjected to measurement of compression set.

Preparation of a thin layer sheet When a thin layer sheet was prepared, a film having a thickness of 150 μm and a width of 350 mm was prepared using a T-die mounted on the tip of the single screw kneading extruder. Measurement of film air permeability coefficient, CFC gas permeability coefficient, elongation at break and peel strength test with rubber or fiber material to be laminated,
An evaluation was performed.

Preparation of Tire 1 of the functional thermoplastic elastomer composition obtained above
Using a film having a thickness of 50 μm, the tire is wound around a tire forming drum, and a tire member such as a carcass, a side belt, a tread or the like coated with a rubber of the following Formula II is laminated thereon, and the green tire is inflated. And
(FIG. 1) The green tire was vulcanized under pressure at 180 ° for 10 minutes using a vulcanizer to obtain a tire having a tire size of 165SR13.

Formulation of rubber composition (II) parts by weight Natural rubber RSS # 3 80 SBR 20 Nippol 1502 FEF carbon black 50 HTC # 100 manufactured by Zeon Corporation Stearic acid 2 beads stearic acid NY Nippon Oil & Fats manufactured by Chubu Carbon Co., Ltd. Co., Ltd. ZnO 3 No. 3 Zinc flower Sulfur 3 Powder sulfur Karuizawa Refinery Vulcanization accelerator (BBS) 1 Nt-butyl-2-benzothiazylsulfenamide aroma oil 2 Desolex 3 Showa Shell Sekiyu KK Made

On the other hand, as a comparative example, a green tire having an inner liner layer of about 0.5 mm made of unvulcanized butyl rubber was formed through a tie rubber having a thickness of about 0.7 mm on the inner surface of the green tire. The tire was cured by vulcanization (size 165SR13). The composition of the inner liner layer and the results of the long-term durability test of the obtained pneumatic tire are shown in Tables V and VI below.

Preparation of Rubber Hose Using the pellets of the functional thermoplastic elastomer composition obtained above, using a single-screw extruder for resin having a crosshead structure, the thermoplastic elastomer composition was previously released with a release agent. Was coated on a nylon 11 mandrel having an outer diameter of 11 mm and extruded into a tube having an inner diameter of 12 mm and a thickness of 150 μm. Thereafter, the nylon 11 was extruded using a rubber extruder having a crosshead structure. On a member obtained by coating the functional thermoplastic elastomer composition on the mandrel of No. 1, a brominated butyl rubber composition comprising the following uncured rubber compound III was extruded to a thickness of 2.0 mm. On the molding, further using a braiding machine, RF
L-dip treated polyester fiber (Toray,
Tetron, 1550d / 2) reinforcing yarn was braided to form a reinforcing layer. Using a rubber extruder having a crosshead structure, the unvulcanized brominated butyl rubber composition of rubber compound III was further extruded to a thickness of 1.5 mm on the reinforcing layer to form an outer tube. (FIG. 2) The unvulcanized hose structure was wound up twice with a wrapping tape of nylon cloth, and the hose was vulcanized under pressure at 153 ° for 60 minutes in a vulcanizing can. After vulcanization, the wrapping tape was removed, and the mandrel was pulled out to obtain a test hose.

Formulation of rubber composition (III) parts by weight bromine butyl rubber 100 exon bromobutyl 2244 carbon black HAF 30 manufactured by Exxon Chemical Co., Ltd. ZnO 3 zinc flower No. 3 manufactured by Tokai Carbon Co., Ltd. DM 1 Noxeller DM Ouchi Shinko Chemical Stearic acid 1 Beads stearic acid NY manufactured by NOF Corporation

On the other hand, as a comparative example, a rubber hose having the above-mentioned hose structure and having no functional thermoplastic elastomer composition having a thickness of 150 μm according to the present invention in the inner layer of the inner tube was prepared with the same dimensions except for the film. Similarly, the impulse durability of the hose was measured. The composition and properties of the resulting hose are shown in Tables III, IV and VI of the latter stage.

Only the functional thermoplastic elastomer composition
Using the pellets of the adhesive thermoplastic elastomer obtained based on the thermoplastic elastomer composition comprising the acrylic rubber / polyester thermoplastic resin and the EPDM / polypropylene thermoplastic resin obtained above. ,
Using a resin extruder having a crosshead structure, a 2.0 mm thick mandrel of the same material and dimensions as the rubber hose was used.
The inner tube was extruded with a mm, and a reinforcing fiber of polyester fiber (Tetron, 1550d / 2, manufactured by Toray Co., Ltd.) not subjected to dip treatment was braided on the molded product using a braiding machine to form a reinforcing layer. . On the reinforcing layer, using a resin extruder, the functional (adhesive) resin composition shown in Table IV was extruded to a thickness of 1.5 mm as an outer tube material, and then the mandrel was pulled out. To evaluate the durability of the hose and the adhesive strength between the inner and outer tubes and the reinforcing layer. Table IV shows the results.
Shown in

The evaluation method used in the following examples is as follows.

In the measurement of the melt viscosity, the melt viscosity refers to the melt viscosity of any component at the time of kneading, and the melt viscosity of each polymer material is determined by the temperature, shear rate (sec ^-1 ) and shear rate. Any temperature in the molten state that generally flows through the capillary, due to stress dependence,
In particular, the stress and shear rate of the polymer material in the temperature range at the time of kneading are measured, and the melt viscosity is measured by the following equation (2).

(Equation 5) The melt viscosity was measured using a capillary rheometer Capillograph 1C manufactured by Toyo Seiki Co., Ltd.

Peel strength test This was in accordance with JIS K6256 "Test method for adhesion of vulcanized rubber". (Test method = Evaluation method I) E of Examples 1 to 7 and Comparative examples 1 to 4
In the case of a functional thermoplastic elastomer composition based on a PDM / PP-based or acrylic rubber / copolyester-based thermoplastic elastomer composition, the compositions of Examples and Comparative Examples were prepared in order to impart adhesion to a reinforcing layer. The sheet is formed with a T-die as described above, and the sheet is made of polyester plain woven canvas (made of Tetoron 1550d / 2, manufactured by Toray Industries, Inc.).
And heat-sealed with a press (press temperature: 200 ° C., press time: 1 minute, press pressure: 1-2 kg / cm ³ ). The obtained laminate was cut into a 25 mm wide × 150 mm long tank shape, and a 180 ° peel test was performed at a peel speed of 50 mm / min. (Test method II) In case of rubber laminate of hose and tire,
Since adhesion with the rubber composition becomes a problem, an adhesion peel test with the following rubber was conducted. Using the compositions of Example 8 and Comparative Example 5, a film having a thickness of 150 μm similarly molded with a T-die was used. On the other hand, the rubber composition (II) (carcass rubber composition for tires) or (III) (rubber composition for hoses) previously kneaded with a Banbury mixer was sheeted out to a thickness of 2.3 mm with a rubber roll. The adhesive sample of the carcass rubber for tire (II) and the film is
The adhesive sample with the rubber composition for hoses (III) was vulcanized by pressure at 185 ° C. for 15 minutes at 185 ° C. for 15 minutes, and subjected to 180 ° peel test under the same conditions as above. Was served.

Measurement of Elongation at Break (E _B %) Using the above-mentioned T-die-formed film, a test piece punched in a dumbbell shape along the flow direction was used in accordance with JIS K62.
51 was measured.

Measurement of Compression Set (C-set) Using the pellets of the uniaxial kneader as described above for the samples of Examples and Comparative Examples, in accordance with JIS K6262,
Using a mold for forming a compression set sample, forming the sample into a predetermined shape at a temperature 40 ° C. higher than the melting temperature of the functional thermoplastic elastomer composition, and using a compression set sample of a predetermined size obtained after cooling, 25% % Compression ratio, 100 ° C, 7
The compression set after 2 hours was measured.

Impulse test of hose A rubber hose having a thin layer of the inner layer of the functional plastic resin prepared above and a hose made of only the functional thermoplastic resin were fitted with metal fittings at both ends. Was subjected to an impulse durability test. Test conditions: The test was performed according to SAEJ188 type 1. (Oil: Auto multi oil (light emission, 120 ° C)) Apply a pulse of 1 million times at a pressure of 210 kgf / cm ² , and confirm that there are no abnormalities such as missing metal parts and body breakage.

Long-term running durability test of tire 165SR13 steel radial tire (rim 13 × 4
1 / 2-J), air pressure 200kPa, 1500cc class passenger car, equivalent load (65kg /
) And drive 50,000 km on the actual road. After running, the tire is removed from the rim, and the liner layer on the inner surface of the tire is visually observed. If the liner layer has cracks, wrinkles, peeling, or the like, it is judged as rejected, and if not, it is judged as passed.

Examples 1 to 5 and Comparative Examples 1 to 3 The base thermoplastic elastomer composition (A) used in Examples 1 to 5 and Comparative Examples 1 to 3 prepared as described above, and the functionality ( The viscosity and physical properties of the (adhesive) thermoplastic resin component are shown in Table I. Test pieces used in each test were prepared from the functional (adhesive) thermoplastic elastomer composition having a predetermined weight ratio of each polymer in Table I. Created as
The test results are shown in Table II.

[0058]

[Table 2]

[0059]

[Table 3]

From the results in Table II, it can be seen from Examples 1 to 5 of the present invention.
5, those satisfying the requirements regarding the difference (ΔSP) of the value of the compatibility parameter, the value of the formula (1) and the volume fraction of the functional thermoplastic resin material (adhesive thermoplastic resin material) specified in the present invention. It can be seen that, since the added adhesive thermoplastic resin component is coordinated to the surface portion by molding, good adhesion can be obtained with the reinforcing yarn even though the bonding treatment is not performed. On the other hand, even in the same blending system of ΔSP, when the α value is larger than 1.0, the adhesive thermoplastic resin component cannot be completely coordinated on the surface (Comparative Example 1). Even if the small condition is satisfied, when ΔSP is smaller than 1 and the compatibility is too good, coordination cannot be completed similarly (Comparative Examples 2 and 3), and sufficient functionality (adhesiveness) cannot be imparted. You can see that. Further, as a more preferred embodiment, in order to obtain a functional (adhesive) thermoplastic elastomer composition having good physical properties while maintaining good adhesive strength, the above-mentioned requirements must be satisfied. It is also clear that it is preferable to add an olefin-based thermoplastic resin as a compatibilizer (as is clear from a comparison between Examples 1 and 2 and Examples 3 and 4).

Examples 6 and 7 and Comparative Example 4 An ACM / COPE thermoplastic resin as shown in Table III below was prepared in the same manner as in the thermoplastic elastomer composition, except that 3 parts of stearic acid and 5 parts of butanetetracarboxylic acid were used. An elastomer composition was prepared. Using this composition as an inner tube, a hose consisting of only the functional thermoplastic elastomer composition was prepared by the method described in the above-mentioned production method. Table IV shows the results of the adhesive strength and the hose impulse durability of the obtained hose.

[0062]

[Table 4]

[0063]

[Table 5]

As is clear from comparison of the results of Examples 6 and 7 and the comparative example, an olefin-based adhesive resin as a compatibilizer which is chemically compatible in this combination is added to the outer tube material of the hose structure. When not added, the adhesiveness can be secured and good, but the physical properties are relatively weak and the durability tends to decrease due to the outer tube breaking, and the target of 200,000 times of the impulse durability condition is cleared. However, it also tends to decrease (Example 7). On the other hand, even if a compatibilizer is used, the adhesive resin is not unevenly distributed on the surface due to the relationship of ΔSP value or α value, and the adhesive force cannot be obtained. It turns out that it is bad and cannot be used (Comparative Example 4). In comparison with these, Example 6
Indicate that the results of the adhesive strength and the impulse durability test are extremely good.

Example 8 and Comparative Example 5 The above-mentioned thermoplastic elastomer compositions (A) and (B)
The thermoplastic elastomer composition (C) used in this example was prepared in the same manner as described above using the composition shown in Table V. In this case, as a dynamic vulcanization system for the modified butyl elastomer, 0.5 parts by weight of zinc white, 2.0 parts by weight of stearic acid and 1.0 part by weight of zinc stearate are added to 100 parts by weight of the elastomer, and A functional (adhesive) thermoplastic elastomer composition was prepared in the manner described above using a polyolefin-based adhesive resin having the properties shown in Table V below as a functional resin material. Then, as described above, 150
A film having a thickness of μm was prepared and used as an air permeation prevention layer in the inner liner layer.
3 tires. Table VI shows the material properties and the long-term durability evaluation results as a tire. Further, a hose having a thin layer of a functional (adhesive) thermoplastic elastomer composition in the innermost layer was prepared by the above-mentioned method using the compositions shown in the following Example 8 and Comparative Example 5. The hose was subjected to an impulse durability test. The results are also shown in Table VI.

[0066]

[Table 6]

[0067]

[Table 7]

As is clear from the results in Table VI above, even in a combination different from the conventional one such as the modified IIR / N11 / polyolefin adhesive resin, as long as both the predetermined conditions of the ΔSP value and the α value are satisfied, It can be seen that due to the uneven distribution of the adhesive resin material on the surface of the film layer, good adhesion to the rubber composition was obtained, and good results were also obtained in tire and hose durability tests.

[0069]

As described above, according to the present invention,
A small amount of a functional (adhesive, antistatic, anti-permeant, ultraviolet-absorbing, biocompatible, etc.) resin material is added to the thermoplastic elastomer composition in which the elastomer is dispersed by a predetermined ΔSP value, α value and By kneading so as to satisfy the volume fraction value of the functional resin material and extruding with a resin extruder, the thermoplastic elastomer composition in which the elastomer is dispersed retains various properties inherent in the thermoplastic elastomer composition. A functional thermoplastic elastomer composition having the same functional characteristics as described above can be obtained, and the equipment and work required for obtaining the functional thermoplastic elastomer composition can be extremely simple. This can be used effectively instead of technology.

[Brief description of the drawings]

FIG. 1 is a meridional cross-sectional view showing a structure of a pneumatic tire using a functional thermoplastic elastomer composition of the present invention for an inner liner layer.

FIG. 2 is a cross-sectional view of a hose in which the functional thermoplastic elastomer composition of the present invention is used for an outer tube material of a hose or an inner tube inner layer or an inner tube outer layer.

Claims (6)

[Claims] 1. A thermoplastic elastomer composition (A) in which an elastomer component having a blending ratio of the elastomer component constituting the dispersed phase to the thermoplastic resin component constituting the continuous phase is from 10/90 to 80/20 is dispersed. The value (S) of the compatibility parameter for the thermoplastic resin component of (A)
(P value) is more than 1.0, the incompatible functional thermoplastic resin component (B) is blended and the following formula (1) is satisfied, and the total amount of (B) and (A) is satisfied. Volume fraction for
A functional thermoplastic elastomer composition controlled to 0%. (Equation 1) Here, φ _A : volume fraction of the thermoplastic elastomer composition component φ _B : volume fraction of the functional thermoplastic resin component η _A : melt viscosity of the thermoplastic elastomer composition component during melt-kneading η _B : function Viscosity during melt-kneading of reactive thermoplastic resin components 2. Compatibilizer component (C) is further added in an amount of 0.5 to 10% by weight based on the total amount of component (A) and component (B) in the functional thermoplastic elastomer composition. The functional thermoplastic elastomer composition according to claim 1. 3. The adhesive thermoplastic elastomer composition according to claim 1, wherein the functional thermoplastic resin component (B) is an adhesive thermoplastic resin component. 4. A hose using the adhesive thermoplastic elastomer composition according to claim 3 for at least one of a hose outer tube material, an inner tube inner layer material, an inner tube outer layer material, and a reinforcing layer adjacent to a reinforcing layer. . 5. A pneumatic tire using the adhesive thermoplastic elastomer composition according to claim 3 for an air permeation preventing layer. 6. A thermoplastic elastomer composition (A) in which the blending weight ratio of the elastomer component constituting the dispersed phase to the thermoplastic resin component constituting the continuous phase is from 10/90 to 80/20, is then prepared. , The value of the compatibility parameter (SP) for the thermoplastic resin component (A)
Value) is melt-kneaded under conditions that satisfy the following formula (1), and the sum of (B) and (A) A functional thermoplastic elastomer composition in which the volume fraction of (B) with respect to the amount is controlled to 1 to 40%, and then the sheet is formed into a sheet or a tube so that the functional thermoplastic resin component is disposed on the surface. Manufacturing method. (Equation 2) Here, φ _A : volume fraction of the thermoplastic elastomer composition component φ _B : volume fraction of the functional thermoplastic resin component η _A : melt viscosity of the thermoplastic elastomer composition component during melt-kneading η _B : function Viscosity during melt-kneading of reactive thermoplastic resin components