JP2003155419A - Resin composition and its molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition which excels in transparency, heat sealability, gas barrier properties, recycling properties, and mold processing properties. SOLUTION: The resin composition comprises (A) 0.1-20 pts.wt. thermoplastic polymer having a functional group (f), (B) 1-70 pts.wt. crystalline resin containing a polymer chain having a component which reacts with the functional group (f) at the terminal, and (C) 10-98.9 pts.wt. olefin based resin, and the component (C) is a continuous phase; the enthalpy (ΔHc1) of crystallization of the crystalline resin component of the component (B) having a crystallization initiation temperature of >150 deg.C and the enthalpy (ΔHm1) of fusion of the crystalline resin component of the component (B) meet the formulae: X=ΔHc1/ΔHm1 and 0<=X<=0.7; and the melting point of the crystalline resin component of the component (B) is >150 deg.C.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition which is excellent in transparency, heat sealability, gas barrier property, recyclability and molding processability. More specifically, it relates to a resin composition comprising a thermoplastic polymer, a crystalline resin and an olefin resin, which is excellent in transparency, heat sealability, gas barrier properties, recyclability, and moldability, a molded product, and a container.

[0002]

2. Description of the Related Art A method of enhancing the functions of resin materials by mixing two or more kinds of resins and diversifying the functions are general goods, packaging materials, and home appliances.
Widely used in industrial fields such as A material and automobile material. In particular, a polyamide resin is a resin having excellent heat resistance, oil resistance, and gas barrier properties, and it is actively blended with other resins. For example, "Polymer alloy application note, edited by Takashi Inoue (published by Kogyo Kogyo)" introduces polypropylene / polyamide alloy, polyphenylene ether / polyamide alloy, acrylonitrile butadiene styrene copolymer (ABS) / polyamide alloy, etc. It has been reported that it has been put to practical use as a material.

[0003] These are materials which have the drawbacks of water absorption of the polyamide resin improved by taking advantage of the characteristics of the polyamide resin and the partner resin and by alloying with the polyolefin resin. For food packaging materials that require gas barrier properties, a method of laminating several kinds of resins is used as a method of imparting functionality, instead of the alloy method. For example, JP-A-55-16313
Japanese Patent Publication No. 4 discloses a three-layer container in which the outer layer is polyethylene, the intermediate layer is adhesive polyethylene, and the inner layer is nylon, and the gas permeation amount is small. In addition, Japanese Patent Laid-Open No. 61-10
Japanese Patent No. 4952 discloses a multi-layer plastic fuel tank which uses a high-density polyethylene as an outer layer and a polyamide layer as an innermost layer or an intermediate layer and is excellent in gasoline permeation prevention performance.

However, these are multi-layered molded products, which are economically disadvantageous in that the equipment cost is higher than that of a single-layer manufacturing facility, and the molded products are multi-layered products and therefore cannot be recycled (the laminated products are different in each layer). Since it is a mixture of, it cannot be returned to the process of each layer). In order to solve these drawbacks, it is required that the characteristics of the multi-layer molded product be exhibited in the single-layer molded product.
In order to express the gas barrier property of a multilayer molded product in a single-layer molded product, it is known to disperse a polyamide resin which imparts a gas barrier property in a layered manner in an olefin resin.
56036, "Polymer, 40, 244 (199
1) ”.

However, it is difficult to stretch the polyamide resin which is the dispersion layer into a layer by stretching and stretching, and it is difficult for the polyamide resin having a high crystallization temperature to be stretched. In a process such as extrusion foaming that foams in the process of being foamed, the polyamide-based resin having a high crystallization temperature is crystallized in the cooling process before being sufficiently stretched or foamed, and the expected polyamide-based resin is satisfied. In addition to not being able to obtain a layered dispersion form, it has a drawback in terms of molding processability that a large draw ratio and foaming ratio cannot be achieved due to crystallization.

Further, when molding is carried out in a temperature range where crystallization does not occur during the stretching or foaming deformation process, the melt tension is too low, so that the molten composition does not drip when it comes out of the die, or foam cells are not formed. Had a problem. In addition, there is a single layer film of polyamide resin, but this has the drawback that the gas barrier property changes due to water absorption, and the drawback that heat sealing is difficult, and in order to improve these drawbacks, lamination with olefin resin Or alloy is required.

As described above, there are proposals for materials for single-layer moldings which are excellent in gas barrier properties and recyclability, but these solve the problem of poor moldability and workability due to the high crystallization temperature of polyamide. However, at present, for example, there is no composition having excellent gas barrier properties and recyclability. Polyamide resin excellent in gas barrier property is alloyed with olefin resin excellent in heat sealing property and water vapor barrier property, and has advantages of polyamide resin and olefin resin, and also has excellent transparency, recyclability,
A material that enables a single-layer molded body with excellent molding processability is an epoch-making technology that expands the range of material selection, and the advent of that technology is highly anticipated.

[0008]

An object of the present invention is to provide a resin composition which is excellent in transparency, heat sealability, gas barrier property, recyclability and molding processability.

[0009]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have surprisingly found that in a resin composition of a thermoplastic polymer, a crystalline resin and an olefin resin. It was discovered that crystallization of the crystalline resin was significantly delayed, and that it had an extremely excellent effect on molding processability, which was impossible to achieve because molding process was difficult until now, transparency, heat sealing property. A resin composition having excellent gas barrier properties, recyclability, and moldability has been completed.

(A) 0.1 to 20 parts by weight of a thermoplastic polymer having a functional group (f) (B) Crystallinity containing a polymer chain having a component reactive with the functional group (f) at the end Resin 1 part by weight or more and 70 parts by weight or less (C) Olefin-based resin 10 parts by weight or more and 98.9 parts by weight or less, component (C) is a continuous phase, and has a crystallization start temperature at a temperature above 150 ° C. The crystallization enthalpy (ΔHc1) of the crystalline resin component (B) and the melting enthalpy (ΔHm1) of the crystalline resin component (B) satisfy the following formula: X = ΔHc1 / ΔHm1 0 ≦ X ≦ 0.7 ( A resin composition having a melting point of the crystalline resin component of B) above 150 ° C.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. As the functional group (f) of the thermoplastic polymer having the functional group (f) (A) in the present invention, an amino group (—N
H ₂ ), a carboxyl group (-COOH), a hydroxyl group (-OH), an unsaturated dicarboxylic acid anhydride group, an epoxy group, an isocyanate group, a mercapto group, an oxazoline group, and the like, and these functional groups are those of a thermoplastic polymer. Introduced by grafting to the polymer chain, copolymerization into the polymer chain of the thermoplastic polymer using a polymerizable monomer containing these functional groups, or introduction by a method of bonding to the polymer chain end of the thermoplastic polymer. It

There is no limitation on the method for producing the thermoplastic polymer having the functional group (f) (A). Examples of the radical-reactive unsaturated monomer having a functional group (f) include methacrylic acid, acrylic acid, itaconic acid, maleic acid, fumaric acid,
Unsaturated carboxylic acid monomers such as cinnamic acid, 2-norbornene-5,6-dicarboxylic acid, maleic anhydride, itaconic anhydride, ethylmaleic anhydride, methylitaconic anhydride, chloromaleic anhydride, 2-norbornene- Examples thereof include unsaturated dicarboxylic acid anhydride monomers such as 5,6-dicarboxylic acid anhydride and epoxy group-containing unsaturated monomers such as glycidyl acrylate, glycidyl methacrylate and glycidyl allyl ether. Of these, unsaturated carboxylic acid monomers and unsaturated dicarboxylic acid anhydride monomers are preferable.

The method of introducing a functional group into a thermoplastic polymer is as follows:
A method of copolymerizing the radical-reactive unsaturated monomer and another monomer constituting the thermoplastic polymer by a general polymerization method, the thermoplastic polymer and the radical-reactive unsaturated monomer. A method of melt-kneading the body and the presence of a radical initiator,
There is a method of bonding to the living end of ionic polymerization. As long as it is a thermoplastic polymer having a functional group (f), the kind of the thermoplastic polymer is not particularly limited, but (A) the functional group (f)
Examples of the monomer constituting the thermoplastic polymer having: o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, in addition to styrene,
Nucleoalkyl-substituted styrenes such as ethyl styrene and p-tert-butyl styrene, vinyl aromatic compound monomers such as α-methyl styrene and α-alkyl substituted styrenes such as α-methyl-p-methyl styrene, methyl methacrylate, cyclohexyl Unsaturated carboxylic acid alkyl ester monomers such as alkyl methacrylate such as methacrylate, methylphenyl methacrylate, isopropyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl methacrylate, acrylonitrile, methacryloyl Unsaturated nitrile monomer such as nitrile, ethylene, carbon number 3 to 2
0-α-olefins (as α-olefins having 3 to 20 carbon atoms, for example, propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1, heptene-1, octene-1, nonene -1, decene-1, undecene-1, dodecene-1 and the like), butadiene, isoprene, 1,3-cyclohexadiene, 1,
Examples thereof include conjugated diene compound monomers such as 3-pentadiene and 2,3-dimethyl-1,3-butadiene.

As the thermoplastic polymer of the thermoplastic polymer having the functional group (f) (A), these monomers may be used alone, or two or more of them may be in the form of solution, lump, suspension, emulsification, anion, coordination. Thermoplastic polymer obtained by polymerizing by an ordinary polymerization method such as anion or condensation polymerization and further introducing a functional group (f), a polyphenylene ether resin having a functional group (f), a polyacetal resin, polyethylene terephthalate, polyethylene naphthalate. Examples thereof include polyester resins such as polyvinyl alcohol and polyvinyl alcohol resins such as ethylene vinyl alcohol, and polycarbonate resins such as polycarbonate. The structure may be linear, branched, block, random, or any other structure. Specific examples include styrene butadiene block copolymer, styrene butadiene random copolymer, styrene isoprene block copolymer, styrene isoprene random copolymer, hydrogenated styrene butadiene block copolymer, hydrogenated styrene butadiene random copolymer. , Hydrogenated styrene isoprene block copolymer, hydrogenated styrene isoprene random copolymer, ethylene propylene copolymer, ethylene butylene copolymer, ethylene styrene copolymer, maleic anhydride modified product, styrene methacrylic acid copolymer , Styrene-maleic anhydride copolymer, maleic anhydride-modified polypropylene, maleic anhydride-modified polyethylene, and the like. Two or more kinds of (A) thermoplastic polymers may be used in combination. Preferred are maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, and maleic anhydride-modified hydrogenated styrene-butadiene block copolymer.

The content ratio of the functional group-containing monomer in the thermoplastic polymer (A) having the functional group (f) is preferably 0.001% by weight to 30% by weight, more preferably 0.
It is from 01 to 14% by weight, particularly preferably from 0.02 to 10% by weight. 0.001% by weight
If it is less than the above, the reaction with the component (B) is not performed, the adhesion at the interface is insufficient, and the interface phase is broken during stretching and foaming,
It is not preferable because the appearance of the molded product is deteriorated and the strength of the resulting molded product is lowered, and the transparency is also deteriorated. If it exceeds 30% by weight, it becomes difficult to control side reactions such as gelation of the thermoplastic polymer, and the thermoplasticity of the thermoplastic polymer decreases, resulting in deterioration of moldability and appearance of the resulting composition molded article. It is not preferable because it deteriorates. The amount of functional group (f) is IR
Method, titration method and the like.

The functional group (f) is added to the terminal (B) in the present invention.
As the crystalline resin containing a polymer chain having a reactive component, amino (-NH _2), carboxyl group (-COO
H), hydroxyl group (-OH), unsaturated dicarboxylic acid anhydride group,
A crystalline resin including a polymer chain having an epoxy group, an isocyanate group, a mercapto group, an oxazoline group, or the like can be given, and a typical example thereof is a polyamide resin.

The polyamide resin is a polyamide resin containing amino acids, lactams, or diamines and dicarboxylic acids as main constituents. Specific examples of the constituent components are ε-caprolactam, enantolactam, ω-
Amino acids such as aminocaproic acid, 11-aminoundecaic acid and 12-aminododecanoic acid, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4 -Trimethylhexamethylenediamine, 5-methylnonamethylenediamine, m-xylylenediamine, p-xylylenediamine, 1,3-bisaminomethylcyclohexane, 1,4
-Diaminos such as bisaminomethylcyclohexane, bis-p-aminocyclohexylmethane, bis-p-aminocyclohexylpropane, isophoronediamine, metaxylylenediamine, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1 , 4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, dimer acid and the like. These constituents are subjected to polymerization in the form of a single kind or a mixture of two or more kinds, and any of the polyamide homopolymers and copolymers thus obtained can be used in the present invention.
For example, polyamide 66, polyamide 610, and polyamide 61 obtained by polycondensation of diamine and dicarboxylic acid.
2, polyamide 46, polyamide 1212, polyamide MXD6 and the like, and also polyamide 6, polyamide 12 and the like obtained by ring-opening polymerization of lactam. As the polyamide copolymer, polyamide 66/6, polyamide 66/610, polyamide 66/612, polyamide 66 / 6T (T is a terephthalic acid component), polyamide 66 / 6I (I is an isophthalic acid component), polyamide 6T.
/ 6I etc. are mentioned. Moreover, the blended product of these polyamide resins is also mentioned. Polyamide 6 and polyamide MXD6 are preferred.

The method for producing these polyamide resins may be a generally known method. In the case of polyamide, a melt polymerization method is generally carried out, but batch polymerization or continuous polymerization may be used. These polyamide resins have an amino group and / or a carboxyl group at the terminal, and this is a component that reacts with the functional group (f). Further, (B) the crystalline resin may be used in combination of two or more kinds. Next, the (C) olefin resin in the present invention will be described.

The olefin resin can be roughly classified into polyethylene resin, polypropylene resin or a mixture of polyethylene resin and polypropylene resin. As the polyethylene resin, high density polyethylene (HDPE), low density polyethylene (LDP)
E), linear low-density polyethylene (LLDPE), copolymer of acrylic vinyl monomer and ethylene (EE
A, EMMA, etc.) or a copolymer (EVA) of vinyl acetate monomer and ethylene. However, among these, high density polyethylene (HD
PE), low-density polyethylene (LDPE) and linear low-density polyethylene (LLDPE) are particularly preferable because they are available at low cost. These polyethylene-based resins may be used alone or in combination of two or more.

Polyethylene resin to olefin resin
When used, density 0.89 g / m²0.95 g / m or more²
The following is preferable from the viewpoint of transparency, and the density is 0.90.
g / m²0.94 g / m or more²More preferably:
Fresh, density 0.91g / m ²0.94 g / m or more²Below
It is especially preferred that there is. Can be used alone or in combination
Even if combined, if the density falls within this range, transparency is preferred.
I'll get better. As a polypropylene resin, homopoly
Propylene, propylene and ethylene, butene-1, pen
Coexistence with other α-olefins such as ten-1, hexene-1
To list polymerized resin (including block and random)
You can

The olefin resin used in the present invention comprises a polyethylene resin and / or a polypropylene resin as described above, but the polypropylene resin is preferable because it has higher heat resistance than the polyethylene resin. Among them, homopolypropylene resin has the highest heat resistance and is more preferable. In the 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 a temperature above 150 ° C. Must be met. X = ΔHc1 / ΔHm1 0 ≦ X ≦ 0.7 If the value of X exceeds 0.7, stretching and foam molding become difficult and the moldability deteriorates. Further, even if molding is possible, heat sealability and transparency are obtained. Inferior to. A preferred range is 0 or more and 0.5 or less, a more preferred range is 0 or more and 0.3 or less, and a particularly preferred range is 0 or more and 0.2 or less.

In the present invention, the component (C) must be a continuous phase. When the component (B) takes a continuous phase, the crystalline resin component (B) used is crystallized at a temperature exceeding 150 ° C., which makes molding processing difficult (stretching or foaming is not possible) and heat sealability is deteriorated. To do. Even if the component (B) is a dispersed phase, dispersed particles having a particle size of 9.5 μm or more are
It is presumed that the crystalline resin component (B) is likely to crystallize in the particles at a temperature exceeding 150 ° C., which may deteriorate the moldability. 9. In the total volume of the component (B),
The ratio of the total volume of dispersed particles of 5 μm or more is preferably 70% or less, and more preferably all of the dispersed particles are less than 9.5 μm. These forms can be observed by an electron micrograph.

The resin composition of the present invention can be obtained by melt mixing using an extruder having strong kneading. Both shear kneading and extension kneading are acceptable as long as the kneading is strong, but a co-rotating twin-screw extruder is preferable, and a counter-rotating twin-screw extruder or a single-screw extruder having a low kneading effect is not desirable. When the kneading effect is low, the crystalline resin component (B) does not form a continuous phase or the value of X does not become small. The melting and mixing temperature is preferably equal to or higher than the crystal melting end temperature of the crystalline resin (B) used as the material, and more preferably equal to or higher than (crystal melting end temperature + 20 ° C.). When the temperature is lower than this temperature, the value of X does not become small and the crystal component may remain, which may deteriorate the moldability. The resin composition of the present invention can be obtained by using an extruder with strong kneading and adjusting the temperature appropriately.

By using the resin composition of the present invention, it is possible to prevent the crystalline resin from being crystallized even at a low temperature at which they are foamed or stretched, for example, to obtain a molded article which could not be molded until now. At the same time, since the crystalline resin is stretched and foamed before being crystallized, the crystalline resin can be linear, plate-shaped, or continuous-phased. When the resin composition of the present invention is molded, it is preferable that the crystals of the crystalline resin (B) are completely melted in the resin melting portion of the molding machine, and higher is more preferable. When the temperature is lower than this temperature, the crystalline component remains, which deteriorates the moldability.

However, if the temperature is too high, it is difficult to cool when foaming or stretching continuously after melting, which is not desirable, and in a facility having a low cooling capacity, the melt viscosity is low, and thus foaming or stretching may be difficult. . The desirable crystal melting end temperature of the crystalline resin component (B) is more than 150 ° C. and less than 280 ° C., a more desirable range is more than 150 ° C. and less than 270 ° C., and a particularly desirable range is more than 150 ° C. 26
The temperature is lower than 5 ° C., and it is desirable to once melt at a crystal melting end temperature or higher in this range during sheet molding or foam molding. After melting, used at any cooling rate (B)
Crystallize below the crystallization temperature of the crystalline resin.

Further, after melting, in the temperature range below the crystallization temperature of the crystalline resin (B) used and above the lowered crystallization temperature, it does not crystallize even if it stays in the molding machine or kneading machine. For example, if the crystalline resin is crystallized due to a long residence time in the T-die of a sheet molding machine or the like, the appearance of a sheet molded article or the like will be significantly deteriorated and subsequent cleaning will be significantly difficult. Further, the cooling zone of the foaming extruder or the like has a complicated structure in order to improve cooling efficiency, and has a structure in which retention easily occurs. If crystallization occurs due to retention in the cooling zone, cooling efficiency is significantly reduced.
As described above, the resin composition of the present invention also has a characteristic that it does not crystallize during heat retention at a normal molding processing temperature, and is extremely excellent in moldability.

In addition, the crystallization start temperature of the composition at 150 ° C. or lower is preferably lower than 140 ° C. from the viewpoint of moldability. If this temperature is low, the temperature range in which foaming or stretch molding is possible is widened, which is preferable. The lower the crystallization temperature of the component (C) or the lower crystallization temperature of the component (B), the wider the temperature range in which foaming or stretch molding is possible (preferably easier molding). In this case, the crystallization start temperature of the composition at 150 ° C. or lower is preferably 150 ° C. or lower, more preferably the crystallization start temperature of the composition at 150 ° C. or lower is 140 ° C. or lower, and the composition It is particularly preferable that the crystallization start temperature at 150 ° C. or lower is 130 ° C. or lower.

A method of continuously stretching and foam-molding the resin composition of the present invention after melting at a temperature above the melting end temperature and at a temperature above the crystallization start temperature at a temperature below 150 ° C. It is preferable as a method for obtaining a stretched film molded product and a foamed sheet molded product having good transparency, heat sealability, gas barrier property, recyclability, and moldability. The "stretching" used in the present specification can be realized by any method such as a roll method and / or a tenter method or an inflation method, regardless of the means.

In foaming, stretching, or secondary molding using these sheets, the melt viscosity behavior of the (C) olefin resin and the melt viscosity behavior of the composition which are continuous phases are important. We have found that the melt viscosity of the resin composition of the present invention is (C)
It may be found that the moldability may be too low compared to the components, and the moldability (primary moldability, secondary moldability) may deteriorate.
It has been discovered that there is an optimum viscosity range for the composition in terms of moldability. That is, in the present invention, JIS K
According to 7210 (melting point of crystalline resin (B) in the composition + 30 ° C or higher), melt flow rate (MI1) of the composition according to claim 1 measured with a load of 2.16 (C) ) Melt flow rate of olefin resin (MI
It is preferable that the relationship of 2) satisfies the following formula. 0.001 <(MI1 / MI2) <2.5

If the value of (MI1 / MI2) is 0.001 or less, the viscosity of the composition becomes too higher than that of the olefin resin (C), and the fluidity at the time of melting is lowered too much. It is not preferable in terms of workability, and when it is 2.5 or more, the viscosity becomes too low, stretching is not performed, stable bubbles cannot be formed during inflation, and stable formation of foam cells becomes difficult. In the secondary molding, a problem that the sheet sags occurs, which is not preferable in terms of molding processability, and it becomes difficult to develop a good heat seal property derived from the (C) olefin resin, resulting in heat seal property. Take More preferable range is 0.001
<(MI1 / MI2) <2, and a particularly preferable range is 0.
005 <(MI1 / MI2) <1.5.

Further, in the resin composition of the present invention,
The melting point of the crystalline resin component (B) must exceed 150 ° C. If it is 150 ° C or lower, the heat resistance deteriorates.
The temperature is preferably 200 ° C. or higher, more preferably 21.
It is 0 ° C or higher. The resin composition of the present invention comprises (A) a thermoplastic polymer having a functional group (f) in an amount of 0.1 part by weight or more and 20 parts by weight or less (B) a polymer chain having a component reactive with the functional group (f) at the end. The amount of the (A) thermoplastic polymer having a functional group (f) is 0.1 to 70 parts by weight and not more than 70 parts by weight of the (C) olefin resin and not more than 98.9 parts by weight.
When it is less than 1 part by weight, the transparency is deteriorated, and when it exceeds 20 parts by weight, the transparency and the appearance of the molded product are deteriorated.

When the amount of the crystalline resin (B) is less than 1 part by weight, the characteristics of the crystalline resin used are impaired (for example, in the case of polyamide resin, the gas barrier property is deteriorated),
If the amount exceeds 70 parts by weight, the crystallization temperature is high, and therefore it must be molded at a temperature above the crystallization temperature, and since the melt viscosity becomes too low, foaming and stretching cannot be performed, which is not preferable in terms of molding processability. However, the heat sealability also deteriorates.

The preferred range is 0.1 part by weight or more and 20 parts by weight or less of (A) a thermoplastic polymer having a functional group (f), and (B) a polymer chain having a component reactive with the functional group (f) at the terminal. Containing crystalline resin 5 parts by weight or more and 60 parts by weight or less (C) Olefin resin 20 parts by weight or more and 94.9 parts by weight or less More preferred range is (A) 0.1 part by weight of thermoplastic polymer having functional group (f) Part or more and 20 parts by weight or less (B) crystalline resin containing a polymer chain having a component reactive with the functional group (f) at the end 6 parts by weight or more and 55 parts by weight or less (C) olefin resin 25 parts by weight or more 93. 9 parts by weight or less Particularly preferred range is (A) thermoplastic polymer having functional group (f) 0.1 part by weight or more and 15 parts by weight or less (B) Polymer having component reactive with functional group (f) at terminal 10 parts by weight or more of a crystalline resin containing a chain 55 The following amounts portion (C) olefin-based resin 30 parts by weight or more 89.9 or less parts by weight.

The resin composition of the present invention may contain 1 to 500 parts by weight of another thermoplastic polymer with respect to 100 parts by weight. As the thermoplastic polymer that can be added, a styrene resin (for example, styrene homopolymer,
High-impact polystyrene, styrene-methacrylic acid copolymer, weather resistant resin AES resin, ASA resin (acrylonitrile-styrene-acrylic rubber copolymer)
Etc.), polyolefin-based resins, polyamide-based resins, polyester-based resins, polyacetal-based resins, polyphenylene ether-based resins, acrylic-based 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.

The resin composition of the present invention may contain a rubber component in an amount of 1 to 500 parts by weight per 100 parts by weight. As the rubber component that can be added, a styrene-butadiene random copolymer, a styrene-isoprene random copolymer, a styrene-isoprene block copolymer, a styrene-butadiene block copolymer, a hydrogenated styrene-isoprene block copolymer ( SEP
S), hydrogenated block copolymers such as hydrogenated styrene-butadiene block copolymer (SEBS), ethylene-propylene copolymer, ethylene-butylene copolymer,
Examples thereof include ethylene-α-olefin copolymers such as ethylene-octene copolymers (preferably those using a metallocene catalyst) (regardless of polymer structure), and those modified with a reactive functional group are also included.

In the resin composition of the present invention, various compounding agents known per se, such as calcium carbonate, calcium silicate, apatite, clay, layered silicate, kaolin, talc, silica, diatomaceous earth, mica powder, Fillers such as asbestos, alumina, barium sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite, glass fiber, glass sphere, silas balloon, carbon fiber, carbon black, titanium oxide, zinc oxide, tin oxide, metal Fine particles, zinc white, red iron oxide, ultramarine blue, dark blue, azo pigment, nitroso pigment, lake pigment, phthalocyanine pigment, phenol-based, sulfite-based, phosphite-based, heat-resistant stabilizer such as amine-based, antioxidant,
A light stabilizer, a UV absorber, a foaming agent, an antistatic agent, a metal soap, a lubricant such as wax, and the like can be added.

In particular, when the above-mentioned filler, especially clay, layered clay mineral, layered silicate, silica fine particles, apatite, etc. are dispersed in the crystalline resin phase (B) of the resin composition of the present invention in nano order, the resin composition However, the gas barrier property can be improved. The resin composition of the present invention is an injection-molded article,
It can be used as a molded product obtained by an ordinary molding method such as an extrusion molded product, a blow molded product, a film molded product, a foamed sheet molded product, a compression molded product, or it can be used by being multi-layer molded with another resin.

Sheets, films and foamed molded articles using the resin composition of the present invention are subjected to secondary molding by a known method such as a pressure molding method, a vacuum molding method, a plug assist molding method and a hot plate contact pressure molding method. can do. Further, the resin composition of the present invention can be particularly useful for food packaging materials having excellent gas barrier properties, food containers, foam sheets used for building materials, and the like, window frames, sash frames, sills, outer wall materials, Flooring,
Building materials such as interior materials, exterior materials, decoration materials, deck materials, fence materials, terrace materials; pipes, gutters, various structural materials, furniture, office equipment, machine parts, housings for various devices, automobile materials, road signs It is also usefully used for.

[0039]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In addition, in these Examples and Comparative Examples, the test methods and raw materials used for evaluation of various physical properties are as follows. 1. Test method (1) Measurement of crystallization temperature, singulation temperature, melting point, melting end temperature Using a differential scanning calorimeter (DSC: Perkin Elmer Pyris 1), in accordance with JIS K7121, heating rate, cooling rate 50K / Measured in minutes. Resin composition,
Put the components (B) and (C) in an aluminum pan. After that, it was installed in the apparatus, and once the temperature was raised above the melting end temperature of the crystalline component (250 ° C. for the system using PA6), the temperature was lowered.
The temperature was raised and the measurement was performed. As shown in FIGS. 1 and 2, crystallization start temperature, melting point, melting end temperature, and enthalpies were determined.

(2) Transparency According to ASTM-D1003, the film was dipped in paraffin oil and Haze was measured. (3) Two heat-sealable films were stacked and heat-sealed under the conditions of a sealing temperature: 120 ° C., a sealing pressure: 2.0 Kg / cm ² , and a sealing time: 2 seconds. 180 degree peel strength of the obtained heat-sealed film (pulling speed 300 mm /
Min) was measured in an atmosphere of 23 ° C., and the judgment was made as follows. Those with a peel strength of 1.0 (Kg / 15mm width) or more are ○. Those with a peel strength of less than 1.0 (Kg / 15mm width) are ×.

(4) Gas Barrier Property In accordance with ISO 2556-1974, the oxygen permeability of the resin sheet was measured using a gas permeability measuring device (MTC3 manufactured by Toyo Seiki Seisaku-sho, Ltd.). The results are shown in Table 3. (5) Molding workability Inflation molding was performed, and those that could be molded under the conditions of the examples were marked with ◯, and those that could not be molded were marked with x. (6) Recyclability A part of the blown blown film was molded again and the physical properties were compared. (7) Measurement of Morphology Tungstophosphoric acid was used to dye the polyamide resin component in the resin pellet, and an electron micrograph was measured.

2. Raw Material [(A) Thermoplastic Polymer Having Functional Group (f)] 5000 g Toughtech H1052 manufactured by Asahi Kasei Corporation which is a hydrogenated styrene butadiene block copolymer, 60 g maleic anhydride, Perhexa 25B (radical initiator manufactured by NOF Corporation) ), And 12 g of ethylbenzene are thoroughly mixed with a Henschel mixer, and then mixed with a twin-screw extruder to 200
Melt kneading was performed at 250 ° C. at 250 ° C. The amount of maleic anhydride in the obtained maleic anhydride-modified hydrogenated styrene butadiene block copolymer (H1) was 0.5% by weight.

[(B) Crystalline Resin] Polyamide 6 (PA6): Novamid 1007J manufactured by Mitsubishi Engineering-Plastics Co., Ltd. (crystallization start temperature is 185 ° C., crystal melting end temperature is 226 ° C.), 10
13C (crystallization start temperature is 185 ° C., melting end temperature of crystals is 229 ° C.) was used. [(C) Olefin Resin] Polyethylene Resin (PE): Low Density Polyethylene, Suntech F2206 (JIS K manufactured by Asahi Kasei Corporation)
According to 7210, melt flow rate measured at 250 ° C., 2.16 Kg load, 2.5 g / 10 min, density 0.9
21 g / m ² ), F2225.4 (JIS K7210)
Melt flow rate 12.1 g / 10 minutes, density 0.923 g measured at 250 ° C. under a load of 2.16 Kg
/ M ² ) was used.

[0044]

Examples 1 to 6 and Comparative Examples 1 to 2 The blends having the compositions shown in Table 1 were mixed in a co-rotating twin screw extruder (40 ° C) set at 270 ° C.
mmφ, L / D = 47), melted and kneaded, and then extruded into a strand and pelletized. Next, the composition pellets were put into an extruder set at 250 ° C., and a circular die set at 210 ° C. (lip thickness 1 mm, diameter 100 m
m) was used for inflation molding. The obtained cylindrical film has a diameter of 382 mm and a thickness of 70 μm.
Was adjusted so that a film was obtained.

[0045]

Example 7 Example 2 The obtained formed film (cylindrical film) was flattened (width 600 mm), both ends were cut (one end 50 mm), and the cut film was used.
The compounded pellets of (1) were put into a molding machine extrusion machine (cut film / combined pellets of Example 2: 1/5 weight ratio), and inflation molding was performed in the same manner as in Example 2. The results are shown in Table 1.

[0046]

[Table 1]

[Explanation of FIGS. 1, 2, and 3] [FIG. 1] Embodiment 4
(ACT208 (F2225.4 / M1943 / 1013J: 40/10/50)) DSC measurement result. The temperature shown as the crystallization start temperature of 150 ° C. or lower is the crystallization start temperature of the low temperature component of the crystallization components of (B). [FIG. 2] (ON34 (F2206 / M1943 / 1007J: 50/10/4) of Example 6
0)) DSC measurement result. The component indicated as ΔHc1 is a component of the crystallized component (B) that was not lowered in temperature. [Fig. 3] Example 5 (ON32 (F2206 / M1943 / 1007J: 60/10/3
0)) An electron micrograph showing the magnification of the cross section of the resin pellet. The portion dyed black is the component (B). The white portion is the (C) olefin resin and has a continuous phase.

[0048]

EFFECT OF THE INVENTION The resin composition of the present invention can provide a material excellent in transparency, heat sealing property, gas barrier property, recyclability and molding processability which has not been provided so far.

[Brief description of drawings]

FIG. 1 is a diagram showing a relationship between Heat Flow Endo Up and temperature.

FIG. 2 is a diagram showing a relationship between Heat Flow Endo Up and temperature.

FIG. 3 is an electron micrograph.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification symbol FI theme code (reference) C08L 23/00 C08L 77/02 77/02 B65D 1/00 AF term (reference) 3E033 BA14 BA21 BB02 CA16 FA02 FA03 FA04 3E086 AB01 BA02 BA15 BA16 BA33 BB01 BB22 BB51 BB90 CA01 CA32 CA33 CA34 CA35 DA08 4F071 AA04 AA10 AA12X AA14 AA15 AA18 AA22X AA54 AA75 ABB ABB BB07 A01 AO AA AO AA AO AA AAF AH AA AAF AA AH AA AAF AA AH AA AAF AA AH BB04Y BB06Y BB07Y BB21W BC04W BC05W BC07W BE02W BP01W CB00W CF06W CF08W CG00W CH07W CL01X CL02X CL03X CL05X FD010 FD170 GG00 GL00 4J031 AA12 AA13 AA15 AA19 AA20 AA23 AA29 AA38 AA49 AA52 AA53 AA55 AB01 AC03 AC04 AC07 AC08 AC09 AC11 AD01 AE03 AF11 AF17

Claims (11)

[Claims] 1. A thermoplastic polymer having (A) a functional group (f) in an amount of 0.1 part by weight or more and 20 parts by weight or less (B) containing a polymer chain having a component reactive with the functional group (f) at the end. Crystalline resin 1 part by weight or more and 70 parts by weight or less (C) Olefin-based resin 10 parts by weight or more and 98.9 parts by weight or less, the component (C) is a continuous phase, and the crystallization start temperature exceeds 150 ° C. The crystallization enthalpy (ΔHc1) of the crystalline resin component of (B) and the enthalpy of fusion (ΔHm1) of the crystalline resin component of (B) satisfy the following formula, and X = ΔHc1 / ΔHm1 0 ≦ X ≦ 0. 7 A resin composition in which the melting point of the crystalline resin component (B) exceeds 150 ° C. 2. In accordance with JIS K7210 (melting point of crystalline resin (B) in composition + 30 ° C. or higher), 2.16
The melt flow rate (MI1) of the composition according to claim 1 measured with a Kg load and the melt flow rate (MI2) of the (C) olefinic resin to be used satisfy the following formula: Composition. 0.001 <(MI1 / MI2) <2.5 3. The resin composition according to claim 1, wherein the thermoplastic polymer (A) having a functional group (f) is a hydrogenated block copolymer modified with maleic anhydride. 4. The resin composition according to claim 1, wherein the thermoplastic polymer (A) having a functional group (f) is an olefin elastomer modified with maleic anhydride. 5. The composition according to claim 1 or 2, wherein the composition has a crystallization initiation temperature at a temperature of 150 ° C. or lower of less than 140 ° C. 6. The (C) olefin resin has a density of 0.91.
The composition as claimed in claim 1 and 2 and 3 and 4 and 5 and 6 and 7, characterized in that a g / m ² or more 0.94 g / m ² or less of the polyethylene resin. 7. The composition according to claim 1, wherein (B) the crystalline resin is polyamide 6. 8. The composition according to claim 1, after being melted at a temperature equal to or higher than a melting end temperature, continuously stretch-molded at a temperature higher than a crystallization start temperature at a temperature of 150 ° C. or lower. A stretched film molded product of the composition according to claim 1. 9. The composition according to claim 1, after being melted at a temperature equal to or higher than a melting end temperature, continuously foam-molded at a temperature higher than a crystallization start temperature at a temperature of 150 ° C. or lower. A foamed sheet molded article of the composition according to claim 1. 10. A package using the molded body according to claim 9. 11. A container formed by secondary molding using the molded article according to claim 9.