JP2005179528A - Improved thermoplastic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition excellent in gas/liquid barrier properties, moldability, heat resistance, water vapor barrier properties and impact resistance, and a molding, sheet and film obtained by using the composition. <P>SOLUTION: This thermoplastic resin composition comprises 0.1-20 wt.% copolymer (A) of an olefin and a functional group-containing monomer, 1-50 wt.% polyamide resin (B) and 30-98 wt.% olefinic resin (C), where the resin (B) forms a continuous phase and the resin (C) forms a dispersion phase. The molding, the sheet and the film obtained by using the composition are provided. <P>COPYRIGHT: (C)2005,JPO&amp;NCIPI

Description

  The present invention relates to a thermoplastic resin composition having excellent gas / liquid barrier properties, moldability, heat resistance, water vapor barrier properties, and impact resistance. In particular, the present invention relates to an improved thermoplastic resin composition obtained by blending a polyamide resin, an olefin resin, and a specific compatibilizer in a predetermined ratio, and a molded article, a sheet, and a film obtained therefrom.

Polyamide resins are used in the fields of food packaging materials, food containers and the like because of their excellent chemical resistance and oxygen barrier properties. In addition, since it has excellent chemical resistance and barrier properties such as gasoline and oil, it is widely used in the field of automobile parts.
However, the polyamide resin has a drawback that it has a low melt tension at the molding temperature and is difficult to mold such as a film, a sheet, and a blow.
For this reason, alloying with a polyolefin resin has been studied for the purpose of maintaining the characteristics of the polyamide resin and improving moldability.
In the case of an alloy of a polyamide resin and a polyolefin resin, in order to maximize the characteristics of the polyamide resin, for example, the gas / liquid barrier function, the polyamide resin is a continuous phase (sea) and the polyolefin resin is a dispersed phase ( Island) is most preferable.

An alloy of a polyamide resin having such a phase structure and a polyolefin resin is already known (see Patent Documents 1, 2, 3, and 4).
However, since Patent Document 1 is simply a kneaded polyamide resin and polyolefin resin under specific melt viscosity conditions, the mechanical properties are not sufficient. Further, in Patent Document 2, since it is a composition comprising a polyamide resin having a specific melt viscosity and a dicarboxylic acid-modified polyolefin, all of the problems of poor thermal stability and the composition components are hygroscopic. Therefore, there is a problem that the gas / liquid barrier property is deteriorated.
Further, Patent Documents 3 and 4 have a problem in that since a large amount of polyamide-based resin is a continuous phase, it is difficult to form films, sheets, blows, and the like, and the polyamide composition ratio is high, resulting in high costs.

Japanese Patent Laid-Open No. 3-100024 Japanese Patent Laid-Open No. 7-258541 JP-A-6-234888 Japanese Patent Laid-Open No. 6-234897

  An object of the present invention is to provide a thermoplastic resin composition excellent in gas / liquid barrier property, moldability, heat resistance, water vapor barrier property, and impact resistance, and a molded article, sheet and film obtained therefrom. .

  As a result of intensive studies to achieve this object, the present inventors have found that a thermoplastic resin composition obtained by blending a polyamide resin, an olefinic resin, and a specific compatibilizer in a predetermined ratio is a gas / It has been found that it has excellent liquid barrier properties, moldability, heat resistance, water vapor barrier properties and high impact strength, and has completed the present invention.

  That is, the present invention provides (1) (A) an olefin-functional group-containing monomer copolymer of 0.1 to 20% by weight, (B) a polyamide resin of 1 to 50% by weight, and (C) an olefinic resin, 30 A thermoplastic resin composition characterized by comprising ~ 98% by weight, wherein (B) is a continuous phase and (C) is a dispersed phase, and the ratio of (2) (A), (B), (C) is 1 to 10% by weight, 10 to 40% by weight, and 50 to 85% by weight of the thermoplastic resin composition of (1), and (3) the functional group-containing monomer of (A) is α, The thermoplastic resin composition according to (1) or (2) above, which is a β-unsaturated carboxylic acid and / or a derivative thereof, (4) a functional group-containing monomer of (A) The thermoplastic tree according to any one of (1) to (3) above, which is an α, β-unsaturated dicarboxylic acid anhydride The composition, (5) The thermoplastic resin composition according to any one of (1) to (4), wherein (A) is an ethylene- (meth) acrylic acid ester-maleic anhydride copolymer, (6) ( The average circle-converted particle size of C) is 10 μm or less, the thermoplastic resin composition according to any one of (1) to (5), and (7) any one of (1) to (6). Molded product obtained from thermoplastic resin composition, (8) Sheet obtained from thermoplastic resin composition according to any one of (1) to (6), (9) Said (1) to (6 The film obtained from the thermoplastic resin composition according to any one of the above.

  The thermoplastic composition of the present invention contains a polyamide resin, an olefin resin, and a specific compatibilizer in a predetermined ratio, thereby allowing gas / liquid barrier properties, moldability, heat resistance, water vapor barrier properties, Excellent impact.

  Examples of the olefin component constituting the (A) olefin-functional group-containing monomer copolymer in the composition of the present invention include one or more ethylene hydrocarbons having 2 or more carbon atoms such as ethylene and propylene. Preferred examples of this include ethylene and propylene. As the functional group-containing monomer component, unsaturated carboxylic acid such as (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid and cinnamic acid, unsaturated carboxylic acid anhydride such as maleic anhydride and itaconic anhydride, Examples include epoxy group-containing unsaturated monomers such as glycidyl (meth) acrylate and glycidyl allyl ether. Preferred are (meth) acrylic acid, maleic anhydride, and glycidyl (meth) acrylate. These functional group-containing monomers may be used alone or in combination of two or more.

In addition to the olefin component and the functional group-containing monomer component, a copolymerizable monomer component may be contained as a constituent component. Examples of such copolymerizable monomer components include vinyl aromatic compounds such as styrene, unsaturated carboxylic acid esters such as methyl (meth) acrylate, and unsaturated nitrile compounds such as (meth) acrylonitrile.
Examples of such olefin-functional group-containing monomer copolymers include ethylene- (meth) acrylic acid copolymers, ethylene- (meth) acrylic acid- (meth) acrylic acid ester copolymers, and ethylene-anhydrous. Examples thereof include maleic acid- (meth) acrylic acid (ester) copolymers, and ethylene-maleic anhydride- (meth) acrylic acid ester copolymers are preferable from the viewpoints of moldability and physical properties. These may be used alone or in combination of two or more.

(A) In place of the olefin-functional group-containing monomer copolymer, if a graft-modified polyolefin or the like, for example, a product obtained by adding maleic anhydride or the like to polyolefin or SEBS is used, the thermochromic property of the resin is improved. It may be inferior or appearance troubles may occur due to gas generation during molding.
The proportion of (A) in the composition of the present invention is 0.1 to 20% by weight, preferably 1 to 10% by weight. It is preferable that the ratio of (A) is in this range in terms of impact resistance, molding processability, and barrier properties.

  The (B) polyamide resin in the composition of the present invention is a polyamide-based resin mainly composed of amino acids, lactams, or diamines and dicarboxylic acids. Specific examples of the constituents include ε-caprolactam, enantolactam, ω-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and other amino acids, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodeca Methylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, m-xylylenediamine, p-xylylenediamine, 1,3-bisamino Diamines such as methylcyclohexane, 1,4-bisaminomethylcyclohexane, bis-p-aminocyclohexylmethane, bis-p-aminocyclohexylpropane, isophoronediamine, metaxylylenediamine, adipic acid, suberic acid, azela There are dicarboxylic acids such as inic acid, sebacic acid, dodecanedioic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and dimer acid. These constituent components are used for polymerization alone or in the form of a mixture of two or more, and any of the polyamide homopolymers and copolymers thus obtained can be used in the present invention.

  For example, there are polyamide 66, polyamide 610, polyamide 612, polyamide 46, polyamide MXD (metaxylylenediamine) 6 obtained by polycondensation of diamine and dicarboxylic acid, and polyamide 6 obtained by ring-opening polymerization of lactam. , Polyamide 12 and the like. As polyamide copolymers, polyamide 66/6, polyamide 66/610, polyamide 66/612, polyamide 66 / 6T (T is terephthalic acid component), polyamide 66 / 6I (I is isophthalic acid component), polyamide 6T / 6I Etc. Moreover, the blended material of these polyamide resins is also mentioned. Preferred are polyamide 6, polyamide 66, and polyamide MXD6. These polyamide resins can be produced by a generally known method. Two or more types of polyamide resin (B) may be used in combination.

The proportion of (B) in the composition of the present invention is 1 to 50% by weight, preferably 10 to 40% by weight. It is preferable that the ratio of (B) is in this range in terms of heat resistance, impact resistance, molding processability, and barrier properties.
The (C) olefin resin in the composition of the present invention can be broadly classified into a polyethylene resin, a polypropylene resin, or a mixture of a polyethylene resin and a polypropylene resin.
Examples of the polyethylene resin include high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), a copolymer of (meth) acrylic acid ester and ethylene (EEA, EMMA, etc.) or Examples thereof include a copolymer (EVA) of vinyl acetate monomer and ethylene. However, among these, high-density polyethylene (HDPE), low-density polyethylene (LDPE), and linear low-density polyethylene (LLDPE) are particularly preferable because they are available at low cost. These polyethylene resins may be used alone or in combination of two or more.

When a polyethylene resin is used as the olefin resin, the density is preferably 0.89 g / cm ³ or more and 0.95 g / cm ³ or less from the viewpoint of transparency, and the density is 0.90 g / cm ³ or more and 0.94 g / cm ^3. more desirably ³ or less, it is particularly desirable density 0.91 g / cm ³ or more 0.94 g / cm ³ or less. Even when alone or in combination of two or more, transparency is preferable if the density falls within this range.
Polyethylene having a density of 0.94 to 0.97 g / cm ³ is preferable from the viewpoint of rigidity, chemical resistance, and barrier properties, and among them, the higher the density, the more preferable from the viewpoint of rigidity, chemical resistance, and barrier properties.

When a polypropylene resin is used, the thermoplastic resin composition and the molded product obtained in the present invention are excellent in molding processability such as fluidity, mechanical properties such as rigidity, hinge characteristics and vibration characteristics, and excellent in rigidity.
Examples of the polypropylene-based resin include homopolypropylene, copolymer resins of propylene and other α-olefins such as ethylene, butene-1, pentene-1, and hexene-1 (including blocks and random). .
The (C) olefin resin used in the present invention includes a polyethylene resin and / or a polypropylene resin as described above, and the polyethylene resin is preferable because it has a low-temperature impact property and weather resistance as compared with the polypropylene resin. .

The proportion of (C) in the composition of the present invention is 30 to 98% by weight, preferably 40 to 94% by weight, more preferably 50 to 85% by weight. It is preferable that the ratio of (C) is in this range in terms of heat resistance, impact resistance, molding processability, and barrier properties.
In the composition of the present invention, (B) must form a continuous phase. If (B) is not a continuous phase, the target heat resistance and gas / liquid barrier properties will not be exhibited.
The continuous phase of “(B) is a continuous phase” refers to a phase that is not completely covered with other phases, for example, when it has a two-phase resin phase separation structure.
As for the composition of the present invention, among the phase consisting of (B), the phase not completely covered with the phase consisting of (A), (C) (and other polymers) consists of (B). It is a continuous phase. Formation of the continuous phase comprising (B) can be determined by observation with these electron micrographs (for example, TEM).

In the present invention, (B) is a continuous phase, and the average thickness of the continuous phase is preferably 2 μm or less, more preferably 1 μm or less, and particularly preferably 0.6 μm or less. It is preferable in terms of moldability that the average thickness of the continuous phase is within this range.
In the present invention, (C) is a dispersed phase, and the average circular equivalent particle size of the dispersed phase is preferably 10 μm or less, more preferably 7 μm. It is preferable in terms of impact resistance that the average circular equivalent particle size of the dispersed phase made of (C) is in this range.
The dispersed phase of “(C) is a dispersed phase” refers to a phase that is completely covered with other phases when having a two-phase resin phase separation structure, for example.

With regard to the composition of the present invention, among the phases consisting of (C), the phase completely covered with the phases consisting of (A), (B) (and other polymers) is the dispersed phase consisting of (C) It is.
The formation of the dispersed phase comprising (C) can be determined by observation with these electron micrographs (for example, TEM).
The circle-converted particle size of “(C) average circle-converted particle size” is one of the two-dimensional information of the dispersed phase obtained by the dispersion structure confirmation means in the polymer blend composition in an electron micrograph (for example, TEM). Is obtained, the diameter of a circle having the same area is calculated, and this is used as the circle equivalent particle diameter of the dispersed phase.
The average circle-equivalent particle size of the dispersed phase is determined by the following formula from the circle-equivalent particle size obtained by the above method.
Average circle equivalent particle size = (Σdi ⁴ * ni) / (Σdi ³ * ni)
di: Circle equivalent particle diameter of i-th dispersed phase ni: Number of i-th dispersed phase

In the present invention, the method for controlling the average circular equivalent particle size of the dispersed phase comprising (C) to 10 μm or less is not particularly limited, but the following methods can be used alone or in combination of two or more.
(1) Method of controlling viscosity ratio of (B) and (C) Melt flow rate value (MFRB) of (B) measured according to JISK7210 at a temperature equal to or higher than the melting point of (B) and a load of 2.16 kg. The ratio (MFRB / MFRC) of the melt flow rate value (MFRC) of (C) and (C) is preferably 4000 or less. If it exceeds 4000, the difference in MFR value becomes too large, and it becomes difficult to make the dispersed phase particle size 10 μm or less.

(2) Method of controlling the introduction amount of (A) By increasing the addition amount of (A), the particle size of the dispersed phase tends to be small. However, the relationship between the amount of (A) introduced and the particle size of the dispersed phase differs depending on the composition of (A).
(3) Method of controlling the kneading method As a device for melt-kneading the resin, a single-screw, two-direction twin-screw extruder, two-direction double-screw extruder or the like is usually used. When kneading in the same type of extruder, for example, the same direction twin screw extruder, the kneading becomes stronger as the ratio (L / D) of the total length (L) of the kneading screw to the screw diameter (D) becomes larger. The particle size can be reduced.

In the same-direction twin-screw extruder, normally, two kneading zones are provided. The number of kneading zones is increased, the number of kneading blocks is increased, and the total length of the kneading zones is increased. The particle diameter of the dispersed phase can also be reduced by a technique such as shortening the pitch.
The dispersed phase particle size can also be reduced by increasing the shear rate applied to the resin, such as by increasing the screw speed.
The particle size can also be reduced by methods such as making the mesh in the die portion finer or increasing the number of meshes.

(4) Method of controlling the kneading sequence When the ratio of the MFR values (MFRB / MFRC) of (B) and (C) is in the range of 50 to 2000, (A), (B), (C) are collectively The method of kneading or kneading (B + C) and adding (A) can be raised.
When the MFR ratio exceeds 2000, the method of kneading (A) and (B) in advance and then kneading with (C) is useful. When the MFR ratio is less than 50, (A) and (C) are preliminarily used. A method of kneading with (B) after kneading is useful.

(5) A method of adding an additive for reducing the surface tension of (C) In order to reduce the surface tension at the time of melting in (C), a surfactant such as stearate, N, N-bis (2-hydroxyethyl) ) The particle size can be reduced by adding an antistatic agent such as alkylamine.
(6) Method of selectively adding a plasticizer that lowers the viscosity of (C) Dispersion by adding a plasticizer such as oil having a large plasticizing effect to (C) and a small plasticizing effect of (B) The phase particle size can be reduced.

(7) Inorganic gas filling and kneading method Inorganic gas (nitrogen, carbon dioxide, etc.) having a large plasticizing effect on (C) and a small plasticizing effect on (B) is injected under pressure into the melting zone of the extrusion kneader. Depending on the method, the particle size of (C) can be reduced.
In the present invention, in accordance with JIS K7210, the melt flow rate value (MFRB) of (B) and the melt flow rate value (MFRC) of (C) measured at a load of 2.16 kg or more above the melting point of (B). The ratio (MFRB / MFRC) is preferably 4 or more, more preferably 17 or more, and particularly preferably 50 or more. When the ratio (MFRB / MFRC) of the melt flow rate value (MFRC) satisfies this condition, (B) can be made into a continuous phase.

When the amount of (A) (Wa parts by weight) and the amount of (B) (Wb parts by weight) is 3 <Wb / Wa <100, (B) is the continuous phase, and the thickness of the continuous phase is It can be within the scope of the invention and is preferred. A more preferred range is 3 <Wb / Wa <50, and a particularly preferred range is 3 <Wb / Wa <30.
In the thermoplastic resin composition of the present invention, the crystallization enthalpy (ΔHc1) of the crystalline resin component (B) and the melting enthalpy (ΔHm1) of the crystalline resin component (B) at temperatures exceeding 150 ° C. X = ΔHc1 / ΔHm1 ≧ 0.3 (ΔHc1 and ΔHm1 can be measured by DSC method). Preferably, X ≧ 0.4, more preferably X ≧ 0.5, particularly preferably X ≧ 0.6, and most preferably X ≧ 0.7.
Moreover, in the thermoplastic resin composition of this invention, it is preferable that melting | fusing point of (B) exceeds 150 degreeC. Heat resistance deteriorates that it is 150 degrees C or less. Preferably it is 200 degreeC or more, More preferably, it is 210 degreeC or more.

  Another thermoplastic polymer may be added up to 1 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition of the present invention. Examples of the thermoplastic polymer that can be added include styrene resins (for example, styrene homopolymer, high impact polystyrene, styrene methacrylic acid copolymer, weather resistant resin, AES resin, ASA resin (acrylonitrile-styrene-acrylic rubber). Copolymer)), polyolefin resins, polyamide resins, polyester resins, polyacetal resins, polyphenylene ether resins, acrylic resins and the like, and various compatibilizers can also be used. These may be reinforced with rubber as long as the object of the present invention is not impaired.

Moreover, 1-100 weight part of rubber components may be added with respect to 100 weight part of the thermoplastic resin composition of the present invention.
Examples of rubber components that can be added include styrene butadiene random copolymer, styrene isoprene random copolymer, styrene-isoprene block copolymer, styrene-butadiene block copolymer, hydrogenated styrene-isoprene block copolymer ( SEPS), hydrogenated block copolymers such as hydrogenated styrene-butadiene block copolymer (SEBS), ethylene-α- such as ethylene-propylene copolymer, ethylene-butylene copolymer, ethylene-octene copolymer Examples include olefin copolymers (preferably those based on metallocene catalysts) and the like (polymer structures are not limited), and those modified with reactive functional groups are also included.

  In the thermoplastic resin composition of the present invention, various known ingredients such as calcium carbonate, calcium silicate, apatite, clay, layered silicate, kaolin, talc, silica, diatomaceous earth, mica powder, asbestos, Alumina, barium sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite, glass fiber, glass sphere, shirasu balloon, filler for carbon fiber, carbon black, titanium oxide, zinc oxide, tin oxide, metal fine particle zinc Hua, Bengala, Ultramarine, Bituminous, Azo, Nitroso, Lake, Phthalocyanine, Phenol, Sulfite, Phosphite, Amine, etc. , Foaming agents, antistatic agents, metal soaps, lubricants such as wax, etc. It may be engaged.

In particular, when the filler, especially clay, lamellar viscosity mineral, lamellar silicate, silica fine particles, apatite, etc. are dispersed in the nano order in the phase of the component (B) of the thermoplastic resin composition of the present invention, the gas barrier property is improved. be able to.
The thermoplastic resin composition of the present invention includes injection molding, injection press molding, extrusion molding, blow molding, injection blow molding, stretch blow molding, rotational molding, slush molding, film molding, sheet molding, foam sheet molding, and compression molding. Ordinary molding methods such as these can be used, and multilayer molding with other resins can also be performed.
The sheet, film, and foamed molded article made of the composition of the present invention can be secondarily molded by a known method such as a pressure forming method, a vacuum forming method, a plug assist forming method, or a hot plate contact pressure forming method.

  The thermoplastic resin composition of the present invention can be preferably used as a chemical solution and / or gas transport or storage container and its accessory parts, taking advantage of its excellent gas / liquid barrier properties, impact resistance, and moldability. Examples of chemicals and gases include gasoline fuel tanks and oils because of their excellent gas / liquid barrier properties such as gasoline, methanol, ethanol, isopropyl alcohol, butanol, nitrogen, oxygen, carbon dioxide, methane, propane, and natural gas. Tanks, other chemical storage containers such as bottles for various chemicals such as shampoos, rinses, liquid soaps, etc., or fuel tube connection parts such as valves and fittings attached to the tanks and bottles, hoses, oil tube connection parts, brake hoses It can be usefully used for automobile materials such as connecting parts.

Moreover, the thermoplastic resin composition of the present invention can be usefully used for food packaging materials, food containers, lids thereof, and the like that are excellent in molding processability, heat resistance, oxygen barrier properties, and impact resistance.
Furthermore, the composition of the present invention can be easily recycled by pulverizing the molded product or molded product.
In addition, it is also possible to perform secondary processing and surface treatment such as painting, plating, silica coating, silica alumina coating, etc., on the molded body made of the composition of the present invention.

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
In these Examples and Comparative Examples, test methods and raw materials used for evaluation of various physical properties are as follows.
1. Test Method (1) Barrier Property Based on JIS K7126B, the oxygen transmission coefficient (unit: cm ³ · mm / m ² · 24 h · atm) of an injection molded flat plate of 1 mm was measured (23 ° C., 65% RH).

(2) Observation of continuous phase, dispersed phase, and calculation of average circular equivalent particle size of dispersed phase Cut out a cross section of an Izod test piece and prepare an ultrathin section stained with phosphotungstic acid / ruthenate or ruthenate. Were observed with an electron microscope, and a continuous phase and a dispersed phase were observed. Further, in the electron micrograph, only the dispersed phase particles existing at a magnification of 5000 times and a visual field range of 36 μm × 44 μm were extracted, and the area thereof was determined using software Image Pro Plus Ver4. The diameter of a circle having the same area as the obtained area was calculated and used as the circle-equivalent particle diameter of the dispersed phase. The circle-converted particle diameter of 100 or more dispersed phases was determined, and the average circle-converted particle diameter was determined by the following formula.
Average circle equivalent particle size = (Σdi ⁴ * ni) / (Σdi ³ * ni)
di: Diameter in terms of a circle of the i-th dispersed phase

(3) Impact resistance Based on JIS K7110, an injection molded product having a length of 11.8 mm, a width of 12 mm, and a thickness of 3 mm was obtained. An Izod test piece (notched) was prepared from the obtained molded body and tested (unit: Kg · cm / cm).
(4) Gas generation amount In injection molding at 250 ° C., the amount of gas generated at the time of purging was visually observed, with ○ indicating that the amount of generated gas was small, Δ for slightly increasing amount, and × indicating clearly increasing amount.

2. Raw material [olefin-functional group-containing monomer copolymer]
Ethylene-methacrylic acid copolymer (abbreviated as N0908C in the table. Made by Mitsui DuPont Polychemical Co., Ltd., methacrylic acid content = 9%, melt flow rate 8 g / 10 min (according to JIS K 7210, 230 ° C. , Measured at 2.16 kg load)
Ethylene-acrylic acid ester-anhydride group-containing monomer copolymer (abbreviated as ET182 in the table. Manufactured by Nippon Polyolefin Co., Ltd., maleic anhydride content = 3%, melt flow rate g / 10 min (JIS K 7210 , Measured at 230 ° C and 2.16 kg load)

[Maleic anhydride-modified SEBS]
A twin screw extruder after thoroughly mixing 5000 g of Tough Tech H1052 manufactured by Asahi Kasei Co., Ltd., a hydrogenated styrene butadiene block copolymer, 60 g of maleic anhydride, Perhexa 25B (a radical initiator made by NOF Corporation) and 12 g of ethylbenzene with a Henschel mixer. Was melt kneaded at 200 ° C. and 250 rpm. The amount of maleic anhydride added to the obtained maleic anhydride-modified hydrogenated styrene butadiene block copolymer (abbreviated as M-SEBS in the table) was 0.5% by weight.

[Maleic anhydride-modified polyethylene]
Maleic anhydride-modified polyethylene (abbreviated as L6101M in the table. Adtex L6101M manufactured by Nippon Polyolefin Co., Ltd., melt flow rate 0.7 g / 10 min (measured in accordance with JIS K 7210 at 230 ° C. and 2.16 kg load) Density 0 .92 g / cm ³ (conforming to JIS K7112) was used.
[Polyamide resin]
Polyamide 6 (abbreviated as 1013B in the table. UBE nylon 1013B manufactured by Ube Industries, Ltd., melt flow rate 40 g / 10 min (measured at 230 ° C. and 2.16 kg load according to JIS K 7210)
[Olefin resin]
Polyethylene resin (abbreviated as B872A in the table. Suntech B872A manufactured by Asahi Kasei Corporation, melt flow rate 0.62 g / 10 min, density 0.954 g / cm ³ (according to JIS K 7210, 230 ° C., 2.16 Kg load) Measurement)

[Examples 1-4, Comparative Examples 1-4]
The raw materials are blended at the ratio shown in Table 1, and the same direction rotating twin-screw extruder set at 250 ° C. (40 mmφ, L / D = 48 Kneading element pitch length = 7 mm Kneading part total length = 270 mm Rotational speed = 300 rpm mesh = 60/100/60) and kneaded and pelletized. This composition pellet was injection-molded at 250 ° C. to prepare an Izod test piece and a flat plate, and each evaluation was performed. The results of each evaluation are shown in Table 1.

  The thermoplastic resin composition of the present invention utilizes its excellent gas / liquid barrier properties, impact resistance, and moldability, and stores chemical solutions such as chemical and / or gas chemical bottles, or tanks and bottles thereof. It is used for automobile materials such as valves and fittings, fuel tube connection parts such as hoses, oil tube connection parts, brake hose connection parts, food packaging materials, food containers and their lids, and building materials.

Claims (9)

  (A) Olefin-functional group-containing monomer copolymer 0.1 to 20 wt%, (B) polyamide resin 1 to 50 wt%, and (C) olefin resin 30 to 98 wt%, ) Is a continuous phase, and (C) is a dispersed phase.   The thermoplastic resin composition according to claim 1, wherein the ratio of (A), (B), and (C) is 1 to 10 wt%, 10 to 40 wt%, and 50 to 85 wt%, respectively.   The thermoplastic resin composition according to claim 1 or 2, wherein the functional group-containing monomer (A) is an α, β-unsaturated carboxylic acid and / or a derivative thereof.   The thermoplastic resin composition according to any one of claims 1 to 3, wherein the functional group-containing monomer (A) is an α, β-unsaturated dicarboxylic acid anhydride.   The thermoplastic resin composition according to any one of claims 1 to 4, wherein (A) is an ethylene- (meth) acrylic acid ester-maleic anhydride copolymer.   The thermoplastic resin composition according to any one of claims 1 to 5, wherein the average circle-equivalent particle diameter of (C) is 10 µm or less.   The molded object obtained from the thermoplastic resin composition of any one of Claims 1-6.   The film obtained from the thermoplastic resin composition of any one of Claims 1-6.   The sheet | seat obtained from the thermoplastic resin composition of any one of Claims 1-6.