JP2005112990A - Thermoplastic resin composition and molded form thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition excellent in gas/liquid-barrier tendency, moldability, heat resistance, water vapor-barrier tendency and impact resistance, and to provide a molded form thereof. <P>SOLUTION: The thermoplastic resin composition comprises (A) 0.1-25 wt.% of an acid-modified styrene-based copolymer hydrogenated product, (B) 1-50 wt.% of a polyamide resin and (C) 30-98 wt.% of an olefin resin. In this thermoplastic resin composition, the component B stands in continuous phase whose mean thickness is &le;2,000 nm. <P>COPYRIGHT: (C)2005,JPO&amp;NCIPI

Description

The present invention relates to a thermoplastic resin composition having excellent gas / liquid barrier properties, molding processability, heat resistance and impact resistance, and a molded product thereof. In particular, the present invention relates to a thermoplastic resin composition having a specific phase structure obtained by blending a polyamide resin, an olefin resin, and a specific compatibilizer in a predetermined ratio, and a molded product thereof.
The gas / liquid barrier property in the present invention refers to a barrier property other than water vapor. Specifically, it refers to barrier properties against oxygen, nonpolar solvents such as gasoline and oil and their vapor, barrier properties against organic solvents such as ethyl alcohol and methyl ethyl ketone, and their vapor.
The thermoplastic resin composition and molded product thereof according to the present invention have a unique morphology in which the morphology is small when (B) is a continuous phase (sea) and (C) is a dispersed phase (island) when observed with an electron microscope. The present invention relates to a thermoplastic resin composition having a phase structure and a molded body thereof.

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 that it is inferior in thermal stability and the constituent components of the composition are hygroscopic. There was a problem that the gas / liquid barrier property 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, molding processability and heat resistance, and particularly excellent in impact resistance, and a molded product thereof.

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 olefin resin, and a specific compatibilizing agent in a predetermined ratio is a gas / liquid. It has been found that it has excellent barrier properties, molding processability, heat resistance and high impact strength, and has completed the present invention.
That is, the present invention comprises (1) (A) 0.1 to 25% by weight of an acid-modified hydrogenated block copolymer, (B) 1 to 50% by weight of a polyamide resin, and (C) 30 to 98% by weight of an olefin resin. %, The thermoplastic resin composition, wherein (B) is a continuous phase, and the average thickness of the continuous phase is 2000 nm or less,

(2) (A) mainly comprises at least one olefin compound hydrogenated to such an extent that the degree of unsaturation of at least one vinyl aromatic compound polymer block S and the conjugated diene compound portion does not exceed 20%. A block copolymer having a vinyl aromatic compound content of 10 to 60% by weight and a molecular unit containing a carboxylic acid group or a derivative thereof is 100% by weight of the block copolymer. A thermoplastic resin composition which is a modified block copolymer bonded to 0.05 to 10 parts by weight per part,
(3) The ratio of (A), (B), (C) is 0.1 to 15% by weight, 10 to 40% by weight, 45 to 85% by weight, respectively (1) to (2) the thermoplastic resin composition,
(4) A molded article comprising the thermoplastic resin composition according to any one of (1) to (3).

  The thermoplastic composition of the present invention and the molded product thereof include a polyamide resin, an olefinic resin, and a specific compatibilizing agent in a predetermined ratio, whereby a gas / liquid barrier property, moldability, heat resistance, and impact resistance. Excellent in properties.

The (A) acid-modified hydrogenated block copolymer in the composition of the present invention is obtained by modifying a styrene copolymer hydrogenated product with an unsaturated carboxylic acid or a derivative thereof.
Examples of the styrene copolymer hydrogenated product include hydrogenated products such as vinyl aromatic-conjugated diene block copolymers and vinyl aromatic-conjugated diene random copolymers. In particular, a hydrogenated vinyl aromatic-conjugated diene block copolymer is preferred.
The hydrogenated styrenic copolymer used in the present invention is composed of a block S mainly composed of a vinyl aromatic compound and an olefin hydrogenated to such an extent that the unsaturation of the conjugated diene compound portion does not exceed 20%. And a polymer E mainly composed of a compound.

  The polymer block S mainly composed of a vinyl aromatic compound has a weight ratio in which the weight ratio of the vinyl aromatic compound to the conjugated diene compound is 100/0 to 51/49, preferably 100/0 to 70/30. When a vinyl aromatic compound and a conjugated diene compound are copolymerized, the distribution of the conjugated diene compound in this block is random, tapered (in which the monomer component increases or decreases along the molecular chain), and part It can be either in block form or any combination thereof.

  The polymer block E mainly composed of a conjugated diene compound has a composition ratio in which the weight ratio of the vinyl aromatic compound to the conjugated diene compound is 0/100 to 49/51, preferably 0/100 to 30/70. When the polymer block is a copolymer of a conjugated diene compound and a vinyl aromatic compound, the distribution of the vinyl aromatic compound in this block is random, tapered (in which the monomer component increases or decreases along the molecular chain), It may be partly in block form or any combination thereof. As the vinyl aromatic compound provided here, one or more of styrene, α-methylstyrene, alkylstyrene such as p-methylstyrene and p-tertiarybutylstyrene, paramethoxystyrene, vinylnaphthalene, and the like may be used. Among them, styrene and p-methylstyrene are particularly preferable.

As the conjugated diene compound, one or more of butadiene, isoprene, piperylene, methylpentadiene, phenylbutadiene, 3,4-dimethyl-1,3-hexadiene, 4,5-diethyl-1,3-octadiene, etc. Two or more types are selected, and butadiene and / or isoprene are particularly preferable.
The content of the vinyl aromatic compound is preferably 10 to 60% by weight, and if it exceeds 60% by weight, the vinyl aromatic compound itself becomes resinous and the impact resistance of the composition is low. The molecular structure of the block copolymer may be any of linear, branched, radial, or a combination thereof. Each of the polymer block S mainly composed of a vinyl aromatic compound or the block E mainly composed of a conjugated diene may have the same structure, the monomer component content, the distribution in the molecular chain, the block Each structure such as molecular weight and microstructure may be different.

  Examples of the method for producing the block copolymer include the methods described in Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-14979, Japanese Patent Publication No. 49-36957, and the like. These use organolithium compounds as anionic polymerization initiators in hydrocarbon solvents, ether compounds such as diethyl ether and tetrahydrofuran as vinylating agents, triethylamine, N, N, N ′, N′-tetramethylethylenediamine and the like. Tertiary amine, a method of block copolymerizing a vinyl aromatic compound and a conjugated diene compound using a polyfunctional compound such as epoxidized soybean oil or silicon tetrachloride as a coupling agent, if necessary, It is obtained as a block copolymer having a branched or radial structure. In the present invention, any polymer obtained by any polymerization method can be used as long as it is as described above.

  A hydrogenated styrene block copolymer can be obtained by hydrogenating the above styrene block copolymer by a known method, for example, the method described in JP-B-42-8704. In the present invention, it is preferable to hydrogenate 80% or more of the conjugated diene moiety. The higher the ratio of hydrogenation, the better the compatibility with the polyolefin resin composition and the less the composition is susceptible to thermal degradation, so that an excellent composition can be obtained. The hydrogenation rate can be analyzed by instrumental analysis using a nuclear magnetic resonance apparatus (NMR).

  The hydrogenated styrenic copolymer is then modified by an addition reaction with at least one modifier selected from unsaturated carboxylic acids and derivatives thereof, and the acid-modified hydrogenated block copolymer used in the present invention. A polymer is obtained. Examples of the unsaturated carboxylic acid and its derivatives as modifiers are maleic acid, maleic anhydride, maleic acid ester, maleic acid amide, maleic acid imide, fumaric acid, fumaric acid ester, fumaric acid amide, fumaric acid imide, itacone Acid, itaconic anhydride, itaconic acid ester, itaconic acid amide, itaconic acid imide, halogenated maleic acid, halogenated maleic anhydride, halogenated maleic acid ester, halogenated maleic acid amide, halogenated maleic acid imide, cis-4 -Cyclohexene-1,2-dicarboxylic acid, anhydrous cis-4-cyclohexene-1,2-dicarboxylic acid, cis-4-cyclohexene-1,2-dicarboxylic acid ester, cis-4-cyclohexene-1,2-dicarboxylic acid Amido, cis-4-cyclohexene-1,2-dicar Acid imide, endo-cis-bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic acid, anhydrous endo-cis-bicyclo (2,2,1) -5-heptene-2,3- Dicarboxylic acid, endo-cis-bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic acid ester, endo-cis-bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic acid Acid amide, endo-cis-bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic imide, acrylic acid, acrylic acid ester, acrylic acid amide, methacrylic acid, methacrylic acid ester, methacrylic acid amide, etc. Is mentioned. These can be used not only by 1 type but by mixing 2 or more types. Among these, unsaturated dicarboxylic acids or derivatives thereof are preferable, and maleic anhydride is particularly preferable.

  The acid-modified hydrogenated block copolymer can be obtained by adding the above modifier to a hydrogenated styrene copolymer of a substrate in a solution state or a molten state with or without using a radical initiator. The method for producing these acid-modified hydrogenated block copolymers is not particularly limited in the present invention, but the obtained acid-modified hydrogenated block copolymer contains an undesirable component such as a gel or its melt viscosity. A manufacturing method in which the processability is remarkably increased and the workability is deteriorated is not preferable. As a preferred method, for example, a method of reacting the hydrogenation product of the styrene copolymer of the substrate with the above modifier in the presence of a radical initiator in an extruder may be mentioned.

The amount of the molecular unit containing the carboxylic acid group or derivative group thereof contained in the acid-modified hydrogenated block copolymer, that is, the amount of the unsaturated carboxylic acid or derivative thereof added is the same as the acid-modified hydrogenated block copolymer used in the present invention. The average value of the whole polymer is 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight per 100 parts by weight of the hydrogenated styrene copolymer of the base. When the molecular unit containing the carboxylic acid group or its derivative group is less than 0.05 parts by weight, the improvement effect is hardly recognized as compared with the unmodified styrene copolymer hydrogenated product, and the amount exceeds 10 parts by weight. However, the improvement effect is not remarkable as compared with the case of less than it.
The content of molecular units containing a carboxylic acid group or a derivative group thereof in the acid-modified hydrogenated block copolymer can be easily grasped by a method such as infrared spectrophotometry or titration. Further, in the present invention, an unmodified styrenic copolymer within a range in which the amount of the unsaturated carboxylic acid or its derivative added in the acid-modified hydrogenated block copolymer used satisfies the above range as an overall average value. A hydrogenated product may be contained. Two or more kinds of the (A) acid-modified hydrogenated block copolymer component obtained as described above may be used in combination.

Preferable examples include maleic anhydride-modified styrene conjugated diene block copolymer hydrogenation products.
The proportion of (A) in the composition of the present invention is 0.1 to 25% by weight, preferably 0.1 to 15% by weight. When the amount is less than 0.1% by weight, the impact resistance of the resulting molded article, which may result in insufficient adhesion at the interface based on the reaction with (B) or chemical interaction such as hydrogen bonding, may be reduced. Absent. On the other hand, when it exceeds 25% by weight, compatibilization of (B) and (C) of the composition comprising (A), (B) and (C) proceeds excessively, or (A) and (B ) Reaction or chemical interaction such as hydrogen bonding proceeds and the melt viscosity of (A) + (B) becomes high, and it becomes difficult for (B) to form a continuous phase. The composition molded article may be inferior in gasoline permeability resistance, which is not preferable.
In addition, it is not preferable to use a graft-modified type polyolefin or the like, for example, a product obtained by adding maleic anhydride or the like to a polyolefin, instead of (A), because the impact resistance of the molded composition may be inferior.
(A) can be present in the phases (B) and (C) and in the interfacial phases (B) and (C).

  The (B) polyamide resin in the composition of the present invention is a polyamide resin mainly composed of amino acids, lactams, or diamines and dicarboxylic acids. Specific examples of the constituent components include ε-caprolactam, enantolactam, ω-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and other amino acids, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, and dodecamethylene. Diamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, m-xylylenediamine, p-xylylenediamine, 1,3-bisaminomethyl Diamines such as cyclohexane, 1,4-bisaminomethylcyclohexane, bis-p-aminocyclohexylmethane, bis-p-aminocyclohexylpropane, isophoronediamine, metaxylylenediamine, adipic acid, suberic acid, and azelai There are dicarboxylic acids such as 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 1212, polyamide MXD (metaxylylenediamine) 6 obtained by polycondensation of diamine and dicarboxylic acid, and also obtained by ring-opening polymerization of lactam. Examples thereof include polyamide 6 and polyamide 12. 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 and polyamide MXD6.

These polyamide resins can be produced by a generally known method. In the case of polyamide, a melt polymerization method is generally carried out, but it may be batch polymerization or continuous polymerization. These polyamide-based resins have an amino group and / or a carboxyl group at the terminal, and this is a component that reacts with a functional group comprising a carboxylic acid group or a derivative thereof in (A).
Further, two or more kinds of the polyamide-based resin (B) may be used in combination.
The amount of (B) in the composition of the present invention is 1 to 50% by weight, preferably 10 to 40% by weight. If it is less than 1 part by weight, the heat resistance and gas / liquid barrier property may be inferior. If it exceeds 50 parts by weight, formability of a film, sheet, blow or the like may become difficult, which is not preferable.

As the (C) olefin resin in the composition of the present invention, a polyethylene resin, a polypropylene resin, or a mixture of a polyethylene resin and a polypropylene resin can be roughly used.
Polyethylene resins include high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), copolymers of acrylic vinyl monomers and ethylene (EEA, EMMA, etc.) or vinyl acetate. A copolymer of monomers and ethylene (EVA) can be used. 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.
Further, 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, the thermoplastic resin composition and the molded body obtained in the present invention are excellent in molding processability such as fluidity, mechanical properties such as rigidity, hinge characteristics, vibration characteristics, and 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 polypropylene resin is preferable because it has higher heat resistance than the polyethylene resin. Of these, homopolypropylene resins and block copolymerized polypropylene have the highest heat resistance and are more preferable. Moreover, when the phase which consists of (C) olefin resin exists in a thermoplastic resin composition and the molded object surface, water vapor | steam barrier property will be improved further and it is desirable.

The amount of (C) in the composition of the present invention is 30 to 98% by weight, preferably 45 to 85% by weight. If it is less than 30 parts by weight, moldability may be difficult, and if it exceeds 98 parts by weight, heat resistance and gas / liquid barrier properties are deteriorated.
In the present invention, (B) must be a continuous phase. If (B) is not a continuous phase, the target heat resistance and gas barrier properties are not 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 two-phase separation. In the context of the present invention, a phase that is not completely covered by a phase consisting of (A), (C) (and other polymers) (excluding the thermoplastic resin composition and the surface of the molded body thereof) is (B) It is a continuous phase.
The formation of the continuous phase comprising (B) can be determined from these electron micrographs (for example, TEM).

Moreover, in this invention, (B) is a continuous phase and the average thickness of a continuous phase must be 2000 nm or less. Preferably it is 1000 nm or less, More preferably, it is 600 nm or less. When the average thickness of the continuous phase exceeds 2000 nm, the water vapor barrier property is deteriorated, and the melt tension is lowered. Deformability deteriorates due to difficulties.
Moreover, in this invention, it is preferable that (B) is a continuous phase, the average thickness of a continuous phase is 2000 nm or less, and the continuous phase part whose thickness is 1000 nm or less is 40% or more. If the continuous phase portion having a thickness of 1000 nm or less is less than 40%, the moldability is deteriorated. Preferably it is 50% or more, more preferably 60% or more, and particularly preferably 70% or more. Moreover, in this invention, it is preferable that the average thickness of the continuous phase part whose thickness is 1000 nm or less is 600 nm or less. If the average thickness of the continuous phase portion having a thickness of 1000 nm or less exceeds 600 nm, the moldability deteriorates. More preferably, it is 500 nm or less, Especially preferably, it is 400 nm or less.

In the present invention, the melt flow rate value (MFRB) of (B) and the melt flow rate of (C) measured according to JIS K7210, melting point of (B) + 30 ° C. to 100 ° C., 2.16 kg load The ratio of the value (MFRC) (MFRB / MFRC) is preferably 4 or more. If it is less than 4, it is not preferable because it becomes difficult to make (B) the continuous phase and make the thickness of the continuous phase within the scope of the present invention. More preferably, it is 17 or more, and particularly preferably 50 or more.
In addition, when the amount of (A) (Wa parts by weight) and the amount of (B) (Wb parts by weight) satisfy the following formula, (B) is a continuous phase, and the thickness of the continuous phase is within the scope of the present invention. This is preferable.
3 <Wb / Wa <100,
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 and the molded product thereof, the crystallization enthalpy (ΔHc1) of (B) and the melting enthalpy (ΔHm1) of (B) satisfy the following formula at a temperature exceeding 150 ° C. (ΔHc1 and ΔHm1 can be measured by DSC method).
X = ΔHc1 / ΔHm1
Usually, 0.3 ≦ X, but 0.4 ≦ X is preferable, and 0.5 ≦ X is more preferable. From the viewpoint of heat resistance, the value of X is preferably 0.5 or more, more preferably 0.6 or more, and particularly preferably 0.7 or more.

Moreover, in the thermoplastic resin composition and its molded object 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.
The thermoplastic resin composition and molded product thereof according to the present invention may have other thermoplastic polymers added to 1 to 100 parts by weight with respect to (A) + (B) + (C) = 100 parts by weight. good. 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, the thermoplastic resin composition of this invention and its molded object may add 1-100 weight part of rubber components with respect to (A) + (B) + (C) = 100 weight part.
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.

  Further, the thermoplastic resin composition and the molded body thereof according to the present invention include 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 sphere, Shirasu balloon, Filler such as carbon fiber, Carbon black, Titanium oxide, Zinc oxide, Tin oxide , Metal fine particles zinc white, bengara, ultramarine, bitumen, azo pigment, nitroso pigment, lake pigment, phthalocyanine pigment, phenolic, sulfite, phosphite, amine, etc. heat stabilizer, antioxidant, light stabilizer , UV absorber, foaming agent, antistatic agent, metal soap, wax, etc. Lubricant, or the like may be blended.

In particular, when the thermoplastic resin composition of the present invention and the molded product (B) thereof are dispersed in the nano-order, the above-mentioned fillers, especially clay, lamellar viscosity minerals, lamellar silicates, silica fine particles, apatite, etc., improve the gas barrier properties. can do.
The thermoplastic resin composition of the present invention comprises (A) + (B) + (C), and if necessary, the other thermoplastic polymer and / or the above various compounding agents are added to these, and an extruder or the like. It can be obtained by melt mixing with a conventional apparatus.
The molded body made of 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, and foam sheet. It can be obtained by ordinary molding methods such as molding and compression molding, and can be multilayer molded with other resins.

  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.

Further, 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 molded product of the present invention can be easily recycled by pulverizing the molded product or molded product. The molded article of the present invention can be subjected to secondary processing such as painting, plating, silica coating, silica alumina coating, and surface treatment.

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) Gasoline permeability According to JIS Z0208, a gasoline permeability test (cup method: 60 ° C) of commercial gasoline was performed, and the permeability after 100 hours was measured. Can be determined.

(2) Heat resistance RHEOLOGY CO. , LTD DVE-V4 FT Rheospectr was used to measure the temperature dependence of E ′. The ratio of the melting end temperature (Tmc) of the component (C) to E ′ (30) at 30 ° C. + E ′ (Tmc + 10) at 10 ° C., E ′ (Tmc + 10) / E ′ (30), was determined. It can be determined that the lower the value, the worse the heat resistance.
(3) Impact resistance Based on JIS K7110, an injection molded article 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) Observation of continuous phase A cross section of a molded article for an Izod test piece was cut out and stained with phosphotungstic acid / ruthenic acid or ruthenium acid, an ultrathin section was prepared, and an electron micrograph was measured. The thickness of the polyamide-based resin component that is a continuous phase was measured from the obtained electron micrograph, and the average thickness of the continuous phase was determined.
(5) Measurement of the thickness of the continuous phase In a transmission electron micrograph of the molded body (magnification 5000 times, measurement field range width 36 μm × length 44 μm), a straight line is drawn parallel to the short piece of the photograph as illustrated in FIG. It was. The thickness of the continuous phase portion intersecting with the straight line was measured. Further, a plurality of straight lines were drawn in parallel with the straight line at intervals of 6 μm, and the thickness of the continuous phase portion that intersected the straight line was measured. As the thickness of the continuous phase portion, 90 or more thicknesses were measured. In Example 1, 68 were those having a thickness of 1 μm or less, and 46 were over 1 μm (a total of 114 measured). The average thickness of all (114 pieces) was 1062 nm. The average thickness of 1 μm or less (68 pieces) was 386 nm.
The same measurement was performed in other examples and comparative examples.

2. Raw materials [(A) acid-modified hydrogenated block copolymer]
A hydrogenated styrene butadiene block copolymer having a vinyl aromatic content of 20% and a hydrogenation rate of 80% or more, modified with maleic anhydride and having a maleic anhydride content of 0.4% by weight (H1 in the table) (Abbreviation)
A hydrogenated styrene butadiene block copolymer having a vinyl aromatic content of 40% and a hydrogenation rate of 80% or more modified with maleic anhydride and having a maleic anhydride content of 1.5% by weight (in the table, H2 (Abbreviation)
A hydrogenated styrene butadiene block copolymer having a vinyl aromatic content of 30% and a hydrogenation rate of 80% or more modified with maleic anhydride and having a maleic anhydride content of 0.1% by weight (in the table, H3 and (Abbreviation)

[(B) Polyamide resin]
Polyamide 6 (abbreviated as 1007J in the table. Novamid 1007J manufactured by Mitsubishi Engineering Plastics Co., Ltd., melt flow rate 200 g / 10 min (measured according to JIS K7210 at 250 ° C. and 2.16 Kg (0.212 N) load))
Polyamide 6 (abbreviated as 1013B in the table. UBE nylon 1013B manufactured by Ube Industries, Ltd. 1013B melt flow rate 40 g / 10 min (measured in accordance with JIS K7210 at 250 ° C. and 2.16 Kg load)

[(C) Olefin resin]
Polyolefin resin (abbreviated as J751 in the table, Suntec J751 manufactured by Asahi Kasei Corporation, melt flow rate 3.0 g / 10 min, density 0.952 g / cm ³ (measured at 250 ° C., 2.16 kg load according to JIS K7210) ))
Polyolefin resin (abbreviated as B161 in the table, Suntech B161 manufactured by Asahi Kasei Corporation, melt flow rate 2.0 g / 10 min, density 0.966 g / cm ³ (measured at 250 ° C., 2.16 Kg load according to JIS K7210) ))
Polyolefin resin (abbreviated as B872A in the table, Suntech B872A manufactured by Asahi Kasei Corporation, melt flow rate 0.8 g / 10 min, density 0.959 g / cm ³ (measured at 250 ° C., 2.16 Kg load according to JIS K7210) ))
Polyolefin resin (abbreviated as F184 in the table, Suntec F184 manufactured by Asahi Kasei Corporation, melt flow rate 0.1 g / 10 min, density 0.954 g / cm ³ (measured in accordance with JIS K7210 at 250 ° C., 2.16 Kg load) ))

[Modified olefin elastomer]
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 (JIS K7210), density 0.92 g / cm ³ (JIS K7112))
Acid-modified polyolefin composition (abbreviated as HB030 in the table, Admer HB030 manufactured by Mitsui Chemicals, Ltd., melt flow rate 0.2 g / 10 min (ASTM D1238 190 ° C.), density 0.95 g / cm ³ (ASTM D1505))

[Examples 1-7 and Comparative Examples 1-6]
A composition having the composition shown in Table 1 was subjected to a co-rotating twin screw extruder set at 260 ° C. (45 mmφ, L / D = 30, pitch length of kneading elements = 9 mm, kneading part total length = 180 mm, rotation speed = 200 rpm. ), And then extruded into a strand shape and pelletized.
The obtained composition pellets were put into an injection molding machine set at 250 ° C., Izod test pieces and flat plates were prepared, and each evaluation was performed. The results are shown in Table 1.

  The thermoplastic resin composition and molded product thereof according to the present invention, taking advantage of its excellent gas / liquid barrier properties, impact resistance, and moldability, are used for storing chemical solutions such as chemical solutions and / or bottles for various drugs such as gases, or the like. Used in tanks, valves and fittings attached to bottles, fuel tube connection parts such as hoses, oil tube connection parts, brake hose connection parts, and other automotive materials, food packaging materials, food containers and their lids, building materials, etc. .

2 is an electron micrograph showing the particle structure of the molded body of Example 1. FIG. The portion dyed black by the phosphotungstic acid staining method is the component (B) that is a continuous phase.

Claims (4)

  (A) Acid-modified hydrogenated block copolymer 0.1 to 25% by weight, (B) polyamide resin 1 to 50% by weight, and (C) olefin resin 30 to 98% by weight. (B) is a continuous phase, The average thickness of a continuous phase is 2000 nm or less, The thermoplastic resin composition characterized by the above-mentioned.   (A) according to claim 1, wherein at least one olefin hydrogenated to such an extent that the degree of unsaturation of at least one vinyl aromatic compound polymer block S and the conjugated diene compound portion does not exceed 20%. A block copolymer having a vinyl aromatic compound content of 10 to 60% by weight, and a molecular unit containing a carboxylic acid group or a derivative thereof, The thermoplastic resin composition according to claim 1, which is a modified block copolymer bonded to 0.05 to 10 parts by weight per 100 parts by weight of the combined body.   The ratios of (A), (B), and (C) are 0.1 to 15% by weight, 10 to 40% by weight, and 45 to 85% by weight, respectively. Plastic resin composition   A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 3.

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