JP2005232353A - Improved thermoplastic resin molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin molded article, especially a thermoplastic resin sheet, film and a packaging container, a packaging material or the like obtained therefrom, excellent in gas/liquid barrier property, moldability, heat resistance, water vapor barrier property, impact resistance and adhesivity. <P>SOLUTION: This thermoplastic resin molded article, especially a sheet or film thereof, contains (A) 0.1-20 wt.% thermoplastic polymer having a functional group, (B) 1-50 wt.% polyamide resin and (C) 30-98 wt.% olefinic resin, characterized in that (B) and (C) are coexisting on the surface of at least one surface of the molded article. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a thermoplastic resin molded article having excellent gas / liquid barrier properties, moldability, heat resistance, water vapor barrier properties, impact resistance, and excellent adhesion, such as a thermoplastic resin sheet and a film. In particular, a thermoplastic resin sheet having a specific phase structure obtained by blending a polyamide resin, an olefinic resin, and a specific compatibilizer at a predetermined ratio, a film, and a packaging container, a packaging material obtained therefrom, etc. About.

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 Furthermore, in the case of a resin composition in which a polyamide resin forms a continuous phase (sea), for example, since the surface of the sheet or film is a polyamide resin, a high temperature is required for bonding with other materials. In addition, there are problems such as poor adhesion to resins with low polarity such as polyolefin resins.

  An object of the present invention is to provide a thermoplastic resin molded article having excellent gas / liquid barrier properties, moldability, heat resistance, water vapor barrier properties, impact resistance and excellent adhesiveness, in particular, a thermoplastic resin sheet, a film, and The present invention relates to packaging containers and packaging materials obtained therefrom.

As a result of intensive studies to achieve this object, the present inventor has obtained a thermoplastic resin having a specific phase structure obtained by blending a polyamide resin, an olefinic resin, and a specific compatibilizer in a predetermined ratio. The present inventors have found that molded articles such as sheets and films are excellent in gas / liquid barrier properties, moldability, heat resistance, water vapor barrier properties, impact resistance, and adhesiveness, and have completed the present invention.
That is, the present invention includes (1) (A) 0.1 to 20% by weight of a thermoplastic polymer having a functional group, (B) 1 to 50% by weight of a polyamide resin, and (C) 30 to 98% by weight of an olefin resin. A thermoplastic resin molded body characterized in that (B) and (C) are mixed on at least one surface of the molded body,

(2) The thermoplastic resin molded article according to (1) above, wherein (B) forms a continuous phase and (C) forms a dispersed phase in a portion other than the surface,
(3) The ratio of (A), (B), and (C) is 1 to 10% by weight, 10 to 40% by weight, and 50 to 85% by weight, respectively, according to (1) or (2) above Thermoplastic resin moldings,
(4) The thermoplastic resin molded article according to any one of (1) to (3), wherein (A) is a copolymer of an olefin and a functional group-containing monomer.
(5) The thermoplastic resin molded article according to any one of (1) to (4), wherein the functional group-containing monomer is an α, β-unsaturated carboxylic acid and / or a derivative thereof.
(6) The thermoplastic resin molded article according to any one of (1) to (5), wherein (A) is a copolymer of ethylene, (meth) acrylic acid ester and maleic anhydride,
(7) The thermoplastic resin molded article according to any one of the above (1) to (6), wherein the average circular equivalent particle diameter of (C) is 10 μm or less.

(8) The thermoplastic resin molded body according to any one of (1) to (7), wherein the thermoplastic resin molded body is a thermoplastic resin sheet,
(9) The thermoplastic resin molded body according to any one of (1) to (7), wherein the thermoplastic resin molded body is a thermoplastic resin film,
(10) A packaging container obtained from the thermoplastic resin molded article according to any one of (1) to (9) above,
(11) A packaging material obtained from the thermoplastic resin molded article according to any one of (1) to (9) above,
(12) The thermoplastic resin sheet according to (8) above is a thermoplastic resin sheet that is a sheet for automobile ceilings.

  The thermoplastic resin molded body of the present invention, in particular, a thermoplastic resin sheet and a film are blended in a predetermined ratio of a polyamide resin, an olefin resin, and a specific compatibilizer, and have a specific phase structure. Excellent gas / liquid barrier properties, moldability, heat resistance, water vapor barrier properties, impact resistance, and adhesiveness.

As the functional group of the thermoplastic polymer having a functional group (A) in the present invention, an amino group (—NH ₂ ), a carboxyl group (—COOH), a hydroxyl group (—OH), an unsaturated dicarboxylic anhydride group, an epoxy Group, isocyanate group, mercapto group, oxazoline group and the like (hereinafter referred to as functional group (f)).
The method of introducing the functional group (f) into the thermoplastic polymer is not particularly limited, but the thermoplastic polymer and the compound having the functional group (f) are melt-kneaded in the presence of a radical initiator to perform graft modification. There are a method, a method of copolymerizing a compound having a functional group (f), a method of bonding a compound having a functional group (f) to an ionic polymerization living terminal, and the like.

  Specific examples of (A) in the present invention include polyolefin resins, styrene butadiene block copolymers, styrene butadiene random copolymers, styrene isoprene block copolymers, styrene isoprene random copolymers, hydrogenated styrene butadiene block copolymers. Hydrogenated styrene conjugated diene random copolymer such as polymer, hydrogenated styrene conjugated diene block copolymer such as hydrogenated styrene isoprene block copolymer, hydrogenated styrene butadiene random copolymer, hydrogenated styrene isoprene random copolymer, etc. Thermoplastic polymers such as polymers, ethylene propylene copolymers, ethylene butylene copolymers, ethylene styrene copolymers, unsaturated carboxylic acid monomers such as maleic anhydride, or epoxy groups such as glycidyl (meth) acrylate Bad Graft-modified with sum monomers, styrene methacrylic acid copolymer, styrene maleic anhydride copolymer, ethylene- (meth) acrylic acid (ester) copolymer, ethylene-maleic anhydride- (meth) acrylic A compound having a functional group (f) such as an acid (ester) copolymer, an ethylene-glycidyl (meth) acrylate copolymer, and an ethylene-glycidyl (meth) acrylate- (meth) acrylic acid (ester) copolymer The thing etc. which superposed | polymerized are mentioned, These are used individually or in mixture.

A preferred example of (A) in the present invention includes a copolymer of an olefin and a functional group-containing monomer. Here, examples of the olefin component include one or more ethylene-based 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, cinnamic acid, unsaturated carboxylic acid anhydride such as maleic anhydride, 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 a copolymer of an olefin and a functional group-containing monomer include, for example, an ethylene- (meth) acrylic acid copolymer, an ethylene- (meth) acrylic acid- (meth) acrylic acid ester copolymer, an ethylene- Examples thereof include maleic anhydride- (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.

When a copolymer of olefin and functional group-containing monomer is used as (A), compared with the case of using a graft-modified type, appearance trouble occurs due to thermal discoloration of the resin and gas generation during molding. Less preferred.
The proportion of (A) in the present invention is 0.1 to 20% by weight, preferably 1 to 20% by weight, more 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 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.
Examples of the (C) olefin resin in the present invention include 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 desirably 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. 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 viewpoints of rigidity, chemical resistance, and barrier properties, and among them, the higher the density, the more preferable from the viewpoints of rigidity, chemical resistance, and barrier properties.

When a polypropylene resin is used as the olefin resin, the thermoplastic resin composition obtained in the present invention and the molded product thereof are excellent in molding processability such as fluidity, mechanical properties such as rigidity, hinge characteristics, and vibration characteristics. Excellent 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 present invention is 30 to 98% by weight, preferably 40 to 94% by weight, and 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.
(B) and (C) must be mixed on the surface of at least one surface of the thermoplastic resin molded article of the present invention, particularly the thermoplastic resin sheet and film, and the other part is (B). The continuous phase (C) preferably forms a dispersed phase. At least on one surface, if (B) and (C) are not mixed, excellent adhesiveness cannot be expressed. Further, in other parts, it is preferable that (B) forms a continuous phase and (C) forms a dispersed phase in order to express target heat resistance and gas / liquid barrier properties.

Here, “mixed” refers to a state in which the surface of the thermoplastic resin molded body is not composed of only one of the components (B) and (C), but both components are present.
“Continuous phase” means, for example, a phase that is not completely covered by another phase when it has a two-phase resin phase separation structure, and “dispersed phase” is completely covered by another phase. It refers to the phase that is.
In the thermoplastic sheet and film of the present invention, (B) and (C) are mixed on the surface, and (B) forms a continuous phase and (C) forms a dispersed phase in other portions. It can be judged by observation with these electron micrographs (for example, TEM).

Further, the average thickness of the continuous phase (B) in the thermoplastic resin molded body of the present invention, particularly the thermoplastic resin sheet and the portion other than the surface of the film, is preferably 0.01 μm or more and 2 μm or less, more preferably. It is 0.01 μm or more and 1 μm or less, and particularly preferably 0.01 μm or more and 0.6 μm or less. It is preferable in terms of moldability that the average thickness of the continuous phase comprising (B) is in this range. The thickness of the continuous phase is a transmission electron micrograph (magnification of 10,000 times) of the molded body, and is shown in FIG. As shown in Fig. 5, draw a straight line parallel to the minor axis direction of the dispersed phase, measure the width of the continuous phase portion intersecting the straight line, draw a plurality of straight lines in parallel at 5 μm intervals, and measure 50 or more thicknesses The average is taken to be the average thickness of the continuous phase. When the thickness of the continuous phase is thin and it is difficult to measure, it is preferable to use a photograph with a magnification of 50000 or more and measure 25 or more at 2.5 μm intervals.

The average circular-equivalent particle diameter of the dispersed phase (C) in a portion other than the surface of the thermoplastic resin molded body of the present invention, particularly the thermoplastic resin sheet or film, is preferably 0.1 μm or more and 10 μm or less, more preferably 0.8. 1 μm or more and 7 μm or less. 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 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: i-th disperse phase circle-converted particle diameter ni: number of i-th disperse phase In the present invention, the method for controlling the average circle-converted particle size of the disperse phase comprising (C) to 10 μm or less is not particularly limited. However, 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 4000 or less in view of the fact that the difference in MFR value becomes too large and it becomes difficult to make the dispersed phase particle size 10 μm or less. Preferably there is.
(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 and 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 higher than the melting point of (B). The ratio (MFRB / MFRC) is preferably 4 or more and 4000 or less, more preferably 17 or more and 3000 or less, and particularly preferably 50 or more and 2000 or less. 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.

Further, in the thermoplastic resin molded article of the present invention, particularly the thermoplastic resin sheet and film, the crystallization enthalpy (ΔHc1) of the crystalline resin component (B) and the crystallinity of (B) at a temperature exceeding 150 ° C. The relationship of the melting enthalpy (ΔHm1) of the resin component is 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 molding of this invention, especially a thermoplastic resin sheet | seat and a film, it is preferable from a heat resistant viewpoint that melting | fusing point of (B) exceeds 150 degreeC. Preferably it is 200 degreeC or more, More preferably, it is 210 degreeC or more and 300 degrees C or less.

In the present invention, 1 to 100 parts by weight of another thermoplastic polymer may be added to 100 parts by weight of the thermoplastic resin composition as a raw material for the thermoplastic resin sheet and film. Examples of thermoplastic polymers that can be added include styrene resins (for example, styrene homopolymers, high impact polystyrene, styrene methacrylic acid copolymers, weather resistant resins such as AES resins and ASA resins), polyolefin resins, Examples include polyamide resins, polyester resins, polyacetal resins, polyphenylene ether resins, acrylic resins, and various compatibilizers. These may be reinforced with rubber as long as the object of the present invention is not impaired.
In addition, the rubber component may be added in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition as a raw material of the thermoplastic resin molded body, particularly the thermoplastic resin sheet and film 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 addition, the thermoplastic resin molded article, particularly the thermoplastic resin sheet and film in the present invention may contain various compounding agents known per se, 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 ball, shirasu balloon, filler such as carbon fiber, carbon black, titanium oxide, Zinc oxide, tin oxide, metal fine zinc oxide, bengara, ultramarine, bitumen, azo pigment, nitroso pigment, lake pigment, phthalocyanine pigment, phenol-based, sulfite-based, phosphite-based, amine-based heat stabilizer, antioxidant Agent, light stabilizer, ultraviolet absorber, foaming agent, antistatic agent, Genus soap, lubricant such as wax, and the like may be blended.

In particular, the above-mentioned fillers, particularly clay, lamellar viscosity minerals, lamellar silicates, silica fine particles, apatite, etc. are in the nano order in the phase of the component (B) of the thermoplastic resin molded body of the present invention, particularly the thermoplastic resin sheet, film When dispersed, the gas barrier properties can be improved.
The thermoplastic resin sheet and film of the present invention can be produced by a generally known method. In the case of an unstretched sheet, for example, a method of extruding a molten resin using a T-die is common. In the case of a stretched sheet, a method of stretching by a tenter method after extruding a molten resin from a T-die can be employed. Among these, a sequential biaxial method in which a sheet extruded from a T-die is stretched in one direction depending on the speed ratio of the roll group and then stretched in a vertical direction with a tenter, or a method of simultaneous biaxial stretching with a tenter is preferable.

The thermoplastic resin sheet and film of the present invention can be secondarily formed 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 sheet or film of the present invention is preferably used as a chemical and / or gas transport or storage container and its accessory parts, taking advantage of its excellent gas / liquid barrier properties, impact resistance, moldability, and adhesion. I can do it. For example, gasoline / methanol, ethanol, isopropyl alcohol, butanol, nitrogen, oxygen, carbon dioxide, methane, propane, natural gas, etc. Chemical liquid storage containers such as various chemical bottles such as rinsing, liquid soap, etc., or tanks, valves and fittings attached to the bottles, fuel tube connection parts such as hoses, oil tube connection parts, brake hose connection parts, etc. It can be usefully used as a material.

Further, the thermoplastic resin molded article of the present invention, in particular, a thermoplastic resin sheet and film, is useful for food packaging materials, food containers and lids thereof excellent in molding processability, heat resistance, oxygen barrier properties and impact resistance. Can be used.
Furthermore, the thermoplastic resin molded body of the present invention, particularly the thermoplastic resin sheet and film, can be easily recycled by being pulverized and formed. In that case, the thermoplastic resin sheet and film of the present invention can be re-formed.
In addition, the thermoplastic resin molded body of the present invention, particularly the thermoplastic sheet and film, can be subjected to secondary processing, surface treatment, and the like, if necessary.

In addition, the thermoplastic sheet and film of the present invention are excellent in moldability, heat resistance, gas / liquid barrier properties, water vapor barrier properties, and impact resistance, and are optimal as sheets for automobile ceiling materials. As a specific example of the use of the sheet for automobile ceiling material, the thickness of the present invention having a thickness of about 0.05 to 0.5 mm is provided between the nonwoven fabric of the automobile interior ceiling and the ceiling structure molded body (glass fiber reinforced polypropylene molded body). Examples thereof include a method in which a glass fiber mat sandwiched between a thermoplastic resin sheet and a film is interposed and thermally bonded.
In general, a thick sheet is defined as “sheet”, and a thin sheet is defined as “film”. However, a sheet having a thickness of 0.1 mm or more is often defined as “sheet”, and a film having a thickness of approximately 100 μm or less is defined as “film”. Often defined.

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) in compliance with barrier properties JIS K7126B, sheet, oxygen permeability coefficient of the film ^{(unit: cm 3 · mm / m 2} · 24h · atm) was measured (23 ℃, 65% RH) . Further, the water vapor transmission coefficient (unit: g · mm / m ² · 24 h · atm) of the sheet was measured according to JIS K7129B (40 ° C., 90% RH).

(2) Observation of electron microscope and calculation of average circular equivalent particle diameter of dispersed phase After embedding film and sheet with epoxy, cut out a section of sheet parallel to extrusion direction, phosphotungstic acid dyeing / ruthenium acid dyeing, or ruthenic acid Stained ultrathin sections were prepared, and the surface and other portions were observed using a transmission electron microscope. 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 was determined using the 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: Circle equivalent particle diameter of i-th dispersed phase ni: Number of i-th dispersed phase

(3) Adhesiveness Sheets, films and low-density polyethylene film (thickness 20 μm) are bonded together under the following heat-sealing conditions with low-density polyethylene facing down, and the non-adhesive part is pulled by hand to qualitatively determine the adhesive strength Judged to.
Heat sealing conditions: apparatus; FI-300-10 (manufactured by Fuji Impulse Co., Ltd.),
Heating time adjustment knob; scale 8
Adhesive strength: Peel; x, No peel; ○
(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 [Thermoplastic polymer having functional group (A)]
Ethylene-acrylic acid ester-anhydride group-containing monomer copolymer (abbreviated as ET182 in the table. Made by Nippon Polyolefin Co., Ltd., methacrylic acid content = 9%, melt flow rate 8 g / 10 min (JIS K 7210 Measured at 230 ° C. and 2.16 kg load))).
Maleic anhydride-modified SEBS (abbreviated as M-SEBS in the table) After thoroughly mixing 5000 g of Tuftec H1052 manufactured by Asahi Kasei Co., Ltd. A maleic anhydride-modified hydrogenated styrene butadiene block copolymer having a maleic anhydride addition amount of 0.5% by weight obtained by melt-kneading at 200 ° C. and 250 rpm using a twin screw extruder.

[Polyamide resin (B)]
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 (C)]
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 to 5, Comparative Example 1]
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. The obtained pellets were sufficiently dried, then supplied to an extruder set at a maximum temperature of 260 ° C., extruded from a T-die, and a sheet having a predetermined thickness was obtained at a roll temperature of 50 ° C. The evaluation results of the sheet are shown in Table 1. In addition, a gas generation test was carried out using an injection molding machine for the pellets. The results are shown in Table 1. Moreover, the electron micrograph (10000 time multiplication factor) containing the surface part of Example 3 is shown in FIG.

[Comparative Examples 2 and 3]
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. The obtained pellets were sufficiently dried and then supplied to an extruder set at a maximum temperature of 260 ° C. and extruded from a ring die having a diameter of 60 mmφ and a slit width of 2 mm to obtain a film having a predetermined thickness. The evaluation results of the film are shown in Table 1. In addition, a gas generation test was carried out using an injection molding machine for the pellets. The results are shown in Table 1. Moreover, the electron micrograph (10000-times multiplication factor) containing the surface part of the comparative example 3 is shown in FIG.

  The present invention relates to a thermoplastic resin sheet, a film excellent in gas / liquid barrier properties, moldability, heat resistance, water vapor barrier properties, impact resistance, and excellent adhesiveness, and a packaging container, packaging material and the like obtained therefrom. . In particular, a thermoplastic resin sheet having a specific phase structure obtained by blending a polyamide resin, an olefinic resin, and a specific compatibilizer at a predetermined ratio, a film, and a packaging container, a packaging material obtained therefrom, etc. About.

It is a schematic diagram of the electron micrograph containing the sheet | seat of Examples 1-5, and the surface part of a film. The black part is (C) and the white part is (B). (B) and (C) are mixed on the surface. It is a schematic diagram of the electron micrograph of the sheet | seat of Examples 1-5, and the center part (other than surface part) of a film. The black part is (C) and the white part is (B). (B) forms a continuous phase and (C) forms a dispersed phase. It is a schematic diagram of the electron micrograph containing the sheet | seat of Comparative Examples 2 and 3, and the surface part of a film. The black part is (C) and the white part is (B). Only (B) is present on the surface. 3 is an electron micrograph (magnification 10,000 times) including a surface portion of Example 3. FIG. 6 is an electron micrograph (magnification 10,000 times) including a surface portion of Comparative Example 3.

Claims (12)

(A) In a thermoplastic resin molded body containing 0.1 to 20% by weight of a thermoplastic polymer having a functional group, (B) 1 to 50% by weight of a polyamide resin, and (C) 30 to 98% by weight of an olefin resin. (B) and (C) are mixed on at least one surface of the molded body. The thermoplastic resin molded article according to claim 1, wherein (B) forms a continuous phase and (C) forms a dispersed phase in a portion other than the surface. The thermoplastic resin molded article according to claim 1 or 2, 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 molded article according to any one of claims 1 to 3, wherein (A) is a copolymer of an olefin and a functional group-containing monomer. The thermoplastic resin molded article according to any one of claims 1 to 4, wherein the functional group-containing monomer is an α, β-unsaturated carboxylic acid and / or a derivative thereof. The thermoplastic resin molded article according to any one of claims 1 to 5, wherein (A) is a copolymer of ethylene, (meth) acrylic acid ester and maleic anhydride. The average circle-converted particle diameter of (C) is 10 µm or less, The thermoplastic resin molded article according to any one of claims 1 to 6. The thermoplastic resin molded body according to any one of claims 1 to 7, wherein the thermoplastic resin molded body is a thermoplastic resin sheet. The thermoplastic resin molded body according to any one of claims 1 to 7, wherein the thermoplastic resin molded body is a thermoplastic resin film. The packaging container obtained from the thermoplastic resin molding of any one of Claims 1-9. The packaging material obtained from the thermoplastic resin molding of any one of Claims 1-9. A thermoplastic resin sheet, wherein the thermoplastic resin sheet according to claim 8 is an automobile ceiling sheet.

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