JPH0733925A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition which has good compatibility and a low gel fraction and can give a film of good appearance. CONSTITUTION:The composition comprises an ethylene/vinyl alcohol copolymer and an olefin polymer terminated with a functional group selected from among a carboxyl group, a group of a carboxylic acid derivative, a silicon-containing group, an epoxy group, a sulfonate group and a phosphonate group.

Description

Detailed Description of the Invention

The present invention relates to a resin composition having excellent compatibility.

[0002]

2. Description of the Related Art Conventionally, an ethylene-vinyl alcohol polymer (hereinafter abbreviated as EVOH) alone has insufficient flexibility and mechanical properties, and in order to improve it, a blend with an olefin polymer is used. Is being attempted.
However, since the ethylene-vinyl alcohol-based copolymer and the olefin-based polymer have poor compatibility, a simple blend may reduce the mechanical properties, transparency, uniformity, etc. of the film and may not be suitable for use. Many. As a method for improving the compatibility, an unsaturated carboxylic acid derivative compound, an unsaturated silane compound, an unsaturated epoxy compound or the like is graft-polymerized with a peroxide as a catalyst to a reactive functional group in an olefin polymer. It is known to introduce. (For example, JP-A-55-155042, JP-A-SHO-5
0-155042, JP-A-61-155412, JP-A-3-88837).

[0003]

However, in a blend of a polyolefin having a reactive functional group in the side chain and EVOH with the polyolefin, particularly when the amount of the reactive functional group is large, the functional group of the side chain of the polyolefin and the EVOH are mixed. Often, the hydroxyl groups of the side chains react to cause gelation and impair the appearance of the film. Therefore, an object of the present invention is to provide a resin composition having good compatibility, less gel, and good film appearance by suppressing unnecessary crosslinking.

The above object is to achieve ethylene-vinyl alcohol.
-Based copolymer (A) and an olefin-based polymer (B) having at a terminal a functional group selected from the group consisting of a carboxyl group, a carboxylic acid derivative group, a silicon-containing group, an epoxy group, a sulfonate group and a phosphonate group. It is achieved by providing a resin composition containing

EVOH used in the present invention is ethylene-
It is a saponified product of vinyl ester copolymer, and the content of ethylene units is not particularly limited, but is selected in the range of 10 to 70 mol%, preferably 15 to 60 mol%, and further 20 to
60 mol% is preferable, and optimally 25-55 mol%. The degree of saponification of the vinyl ester unit of EVOH is selected from the range of 90 to 100 mol% and 95 to 1
00 mol% is preferable, and 99-100 mol% is more preferable. When the degree of saponification is low, crystallization is lowered, the gas barrier property is lowered, and the thermal stability at the time of melting may be deteriorated. Therefore, the degree of saponification is preferably high. Here, vinyl acetate may be mentioned as a typical example of vinyl ester, but in addition, vinyl propionate, vinyl pivalate,
Also included are vinyl esters such as vinyl valerate, vinyl caprate, vinyl benzoate and the like. These vinyl esters may be used alone or in combination of two or more.
Further, EVOH may be used by mixing EVOH having different ethylene content, saponification degree, or polymerization degree.

[0006] EVOH may contain other copolymerization components within a range not impairing the object of the present invention. Here, other components include olefinic monomers such as propylene, 1-butene and isobutene; acrylamide copolymers such as acrylamide, N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide; methacrylamide. , N-methyl methacrylamide, N-ethyl methacrylamide, N, N-dimethyl methacrylamide and other methacrylamide copolymers; methyl vinyl ether
Ter, t-butyl vinyl ether, dodecyl vinyl ether
Vinyl ether type monomers such as ter; allyl alcohol;
Vinyltrimethoxysilane; N-vinyl-2-pyrrolidone and the like can be mentioned.

The EVOH used in the present invention preferably has a degree of polymerization of 85% by weight of phenol and 15% by weight of water.
The intrinsic viscosity at 30 ° C. in the mixed solvent is preferably 0.1 to 5 deciliters / g (hereinafter abbreviated as dl / g), and more preferably 0.2 to 2 dl / g.

An olefin-based polymer (B) having a functional group selected from the group consisting of a carboxyl group, a carboxylic acid derivative group, a silicon-containing group, an epoxy group, a sulfonate group and a phosphonate group for use in the present invention; Is an olefin polymer having a functional group selected from the group consisting of a carboxyl group, a carboxylic acid derivative group, a functional group containing a silicon atom, an epoxy group, a sulfonate group, and a phosphonate group at one or both ends.

In the present invention, examples of the carboxyl group and the carboxylic acid derivative group include a carboxyl group, a carboxylic acid metal base represented by the following general formula (I), and a cyclic carboxylic acid anhydride group represented by the following general formula (II). Is mentioned. In the present invention, examples of the silicon-containing group include a silyl ether derivative group represented by the following general formula (III). In the present invention, the epoxy group is represented by the following general formula (IV). The sulfonate group in the present invention is represented by the following general formula (V). In the present invention, the phosphonate group is represented by the following general formula (VI) and the following general formula (VII).

[0010]

[Chemical 1]

[0011]

[Chemical 2]

[0012]

[Chemical 3]

[0013]

[Chemical 4]

[0014]

[Chemical 5]

[0015]

[Chemical 6]

[0016]

[Chemical 7]

(In the formula, n represents 1 or 2. M represents an alkali metal, an alkaline earth metal or zinc. At least one of X, Y and Z represents an alkoxyl group, and the rest are methyl group and ethyl. Represents an aliphatic hydrocarbon group such as a group or a propyl group, or an aromatic hydrocarbon group.
↑ 1, R ↑ 2 and R ↑ 3 represent a hydrogen atom or a lower alkyl group. )

The general formula (I) and the general formulas (V) to (VI)
Specific examples of the metal salt of carboxylic acid group, sulfonic acid group, or phosphonic acid group represented by I) include sodium salt,
Examples thereof include alkali metal salts such as potassium salts; alkaline earth metal salts such as magnesium and calcium salts, and zinc salts.

Specific examples of the substituents R ↑ 1, R ↑ 2 and R ↑ 3 in the cyclic carboxylic acid anhydride group represented by the general formula (II) include lower fatty acids such as methyl group, ethyl group and propyl group. Group hydrocarbon groups and hydrogen atoms are included. Among these, particularly preferable examples include the case where R ↑ 1, R ↑ 2 and R ↑ 3 are all hydrogen atoms.

Specific examples of the substituents X, Y and Z in the silyl ether derivative group represented by the general formula (III) include alkoxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group; methyl group, ethyl group. Group, propyl group, butyl group and other aliphatic hydrocarbon groups; phenyl group and other aromatic hydrocarbon groups. As a particularly preferable example, R ↑ 1, R
When ↑ 2 and R ↑ 3 are all methoxy groups, R ↑ 1,
When R ↑ 2 and R ↑ 3 are all ethoxy groups, R ↑
1, the case where R ↑ 2 is a methoxy group and R ↑ 3 is a methyl group.

[0021] It is preferable that the functional group is present substantially only at one end or both ends of the polyolefin polymer. The amount of the functional group is 0.0001 to 1 meq /
g (milliequivalent / g) is preferable, and 0.001 to 0.
The range of 1 meq / g is preferable.

An olefin polymer (B) having a functional group selected from the group consisting of a carboxylic acid derivative group, a silicon-containing functional group, an epoxy group, a sulfonate group, and a phosphonate group used in the present invention is formed. Specific examples of the monomer unit include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1
-Heptene, 1-octene, 1-nonene, 1-decene, etc., and the olefin polymer (B) of the present invention is a homopolymer of one monomer selected from the above olefin monomers. Alternatively, a copolymer of the above-mentioned olefinic monomer (random copolymer, block copolymer) or a copolymer containing a monomer other than the above-mentioned monomer as a copolymerization component (random copolymer, block) Copolymer), but the content of the olefinic monomer in the polymer is 50.
It is preferably at least wt%, more preferably at least 80 wt%. As the component other than the olefin-based monomer,
Acrylic ester monomers such as methyl acrylate, ethyl acrylate, butyl acrylate; Methacrylic acid ester monomers such as methyl methacrylate, ethyl methacrylate, butyl methacrylate; vinyl acetate, vinyl pivalate, etc. Vinyl ester-based monomers: vinyl chloride, vinylidene chloride, vinyl fluoride and the like.

Among the base polymers of the olefin copolymer (B) composed of the above-mentioned monomers, particularly ethylene polymers (ultra low density polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, Linear low-density polyethylene, ethylene vinyl acetate-copolymer, ethylene-acrylic acid ester copolymer, ethylene-propylene copolymer, etc.) and propylene-based copolymer are preferable.

A preferred melt index (MI) of the olefin polymer (B) used in the present invention (190)
Value measured under a load of 2160 g) is 0.01 to 10
00 g / 10 minutes is preferable, and 0.1-100 g / 10 minutes is more preferable.

Next, a carboxylic acid derivative group used in the present invention,
A typical method for producing the olefin polymer (B) having a functional group selected from the group consisting of a silicon-containing functional group, an epoxy group, a sulfonate group, and a phosphonate group at the end will be described. The olefin polymer (B) having a functional group selected from the group consisting of a carboxylic acid derivative group, a silicon-containing functional group, an epoxy group, a sulfonate group, and a phosphonate group at the end has a double bond at the end. It is obtained by converting the terminal double bond of the polyolefin having a functional group.

As a typical method for producing an olefin polymer having a double bond as a raw material, 1) a method utilizing a small amount of double bond at the terminal of an ordinary olefin polymer;
2) A method for producing an olefin polymer having a double bond at a terminal by thermally decomposing an ordinary olefin polymer under anoxic conditions; Regarding 1), a known production method of an olefin polymer can be used, but particularly, a production method using a metallocene polymerization catalyst as a polymerization catalyst without using hydrogen as a chain transfer agent (for example, DE403039).
9) is preferred. Regarding 2), it can be obtained by a known method (for example, US2835659, 3087922) by thermally decomposing an olefin-based polymer at a temperature of 300 ° C to 500 ° C under oxygen-free conditions such as a nitrogen atmosphere and a vacuum condition.

The olefin polymer having a carboxyl group at the terminal is converted into a polyolefin having a double bond at the terminal in a hydrocarbon solvent such as benzene, toluene or xylene in the presence of an azo or peroxide radical initiator. It is obtained by adding a carboxylic acid having a thiol group such as thioglycolic acid and 2-mercaptopropionic acid. Further, the olefin polymer having a carboxylate group at the terminal neutralizes the olefin polymer having a carboxyl group at the terminal with a metal hydroxide such as sodium hydroxide, sodium carbonate, potassium hydroxide, or a metal carbonate. Obtained by

The olefin polymer having a carboxylic acid anhydride group at the terminal is an olefin polymer having a double bond at the terminal and an unsaturated carboxylic acid anhydride such as maleic acid anhydride, citraconic acid anhydride or itaconic acid anhydride. It can be obtained by reacting a substance with heat.

The olefin-based polymer having a silicon-containing functional group at its terminal is trimethoxylized to a polyolefin having a double bond at the terminal in a hydrocarbon-based solvent such as benzene, toluene or xylene in the presence of hexachloroplatinic acid or a radical initiator. It can be obtained by adding a silane compound having a silicon-hydrogen bond such as silane, triethoxysilane and dimethoxymethylsilane.

The polyolefin having a sulfonate group at the terminal is added with thioacetic acid to the polyolefin having a double bond at the terminal in the presence of a radical initiator, and further reacted with methanol in the presence of an alkali catalyst to give a thiol group at the terminal. It can be obtained by obtaining a polyolefin having the same and further oxidizing it with sodium hypochlorite or the like.

The olefin polymer having an epoxy group at the terminal can be obtained by reacting an olefin polymer having a double bond at the terminal with a peracid such as peracetic acid or m-chloroperbenzoic acid.

The olefinic polymer having a phosphonic acid group at the terminal is reacted with an olefinic acid dialkyl ester having a double bond at the terminal in the presence of a radical initiator to give a phosphonic acid dialkyl ester group at the terminal. After obtaining the olefin-based polymer having, it is obtained by reacting with hydrogen chloride and further neutralizing.

The resin composition of the present invention is the EVOH described above.
(A) and an olefin polymer (B) having a functional group selected from the group consisting of a carboxylic acid derivative group, a silicon-containing functional group, an epoxy group, a sulfonate group, and a phosphonate group at the terminal, and a component (A) The weight mixing ratio of the component (B) and component (B) is preferably 99: 1 to 1:99, and more preferably 95: 5 to 5:99. When the characteristics of component (A), such as gas barrier property and solvent resistance, are desired to be more strongly exerted, (A) :( B) is preferably 95: 5 to 50:50, and component (B) is preferably When it is desired to exert the characteristics such as hot water resistance and mechanical properties more strongly, (A) :( B) is preferably 5:95 to 50:50. When a propylene-based polymer is used as the base polymer of the component (B), as will be apparent from Examples described later,
Since the hot water resistance is improved, it is extremely useful in fields requiring hot water resistance, such as packaging materials for retorts. Further, when an ethylene polymer is used as the base polymer of the component (B), impact resistance is improved as will be apparent from the examples described later, and therefore, a field in which impact resistance is required. It is useful as a packaging material for bottles, tubes, cups, pouches, etc.

The resin composition of the present invention can be easily molded by a known melt molding method (T-die extrusion, inflation extrusion, blow molding, injection molding, press molding).
It can be formed into an arbitrary molded article such as a film, a sheet, a tube, a bottle, a fiber, a rod and a tube.

Further, the resin composition of the present invention is a multilayer structure having an EVOH layer and a thermoplastic resin (polyolefin etc.) layer, for example, a multilayer structure composed of EVOH layer / thermoplastic resin layer, thermoplastic resin layer / Film, sheet, tue from multi-layer structure consisting of EVOH layer / thermoplastic resin layer
It also includes a mode in which the component (B) used in the present invention is blended with scraps generated during the production of bu, bottles and the like. Further, the resin composition of the present invention, other thermoplastic resin,
For example, the olefin polymer of the base polymer of the component (B), further polyester (polyethylene ethylene terephthalate, polybutylene terephthalate, etc.), polyamide, polycarbonate, polyvinyl chloride, It is preferably used as a multilayer structure with polyurethane, polyacetal, EVOH or the like. The multilayer structure is molded by a known method such as co-extrusion, co-injection, extrusion coating, and scraps of these molded products can be reused, and when the scraps are reused, the resin of the present invention can be used. The composition can be blended in the scrap, or the component (B) used in the present invention can be blended in the scrap.

When a multilayer structure is obtained, it is often preferable to interpose an adhesive resin layer between the resin composition layer of the present invention and the thermoplastic resin layer because both layers can be firmly adhered. The adhesive resin is not particularly limited as long as it can firmly bond both layers, but an unsaturated carboxylic acid or its anhydride (maleic anhydride, etc.) is used as an olefin polymer or copolymer. Polymer [Polyethylene {Low density polyethylene, Linear low density polyethylene (LLDPE), Ultra low density polyethylene (SLDP
E)}, ethylene-vinyl acetate copolymer, ethylene-
(Meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester (methyl ester or ethyl ester) copolymer, polypropylene, etc.) grafted, hydrogenated styrene-butadiene copolymer acid anhydride (example A maleic anhydride) modified product, an acid anhydride modified product of liquid butadiene, and an acid anhydride modified product of an ethylene-propylene-diene copolymer are preferably used.

The layer structure of the multilayer structure is as follows: resin composition layer / thermoplastic resin layer, resin composition layer / thermoplastic resin layer /
Resin composition layer, thermoplastic resin layer / resin composition layer / thermoplastic resin layer, thermoplastic resin layer / resin composition layer / scrap recovery layer / thermoplastic resin layer, thermoplastic resin layer / scrap recovery layer / resin composition Examples include a material layer / scrap recovery layer / thermoplastic resin layer, or a layer in which the above-mentioned adhesive resin layer is interposed between at least one of these layers.

A molded product and a multilayer structure obtained from the above-mentioned resin composition of the present invention are foods which are required to have gas barrier properties.
It is particularly useful as a packaging material for medicines, medical equipment, clothing and the like.

[0039]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In addition, in the following synthesis examples and examples, unless otherwise specified, a ratio means a weight ratio and “%” means “% by weight”. Unless otherwise specified, the melt index (hereinafter abbreviated as MI) is 2160 at a load of 190 ° C.
It is measured by g. The intrinsic viscosity is phenol 8
It has an intrinsic viscosity at 30 ° C. in a mixed solvent of 5% by weight and 15% by weight of water (hereinafter abbreviated as hydrous phenol).
The amount of double bonds in the polyolefin was determined by 270 MHz 1H-NMR using heavy paraxylene as a solvent. The contents of sodium, phosphorus and sulfur in the polyolefin were measured by X-ray fluorescence analysis. The amount of trimethoxysilyl group in the polyolefin was measured by NMR.

Synthesis Example 1 Synthesis of polypropylene having a double bond at the end: 200 g of polypropylene {MI (230 ° C., load 2160 g) 0.3 g / 10 minutes} was charged in a separable flask and the bath temperature was 250 ° C. under vacuum. After heating for 1 hour, the bath temperature was further raised to 340 ° C. and then heating was performed for 2 hours. After cooling, the polypropylene was taken out and pulverized to obtain a polypropylene having a double bond amount of 0.031 meq / g and MI of 80 g / 10 min.

Synthesis Example 2 Synthesis of polypropylene having a carboxylic acid anhydride group at its end: A separable flask equipped with a condenser and a stirrer was charged with 20 parts by weight of the polypropylene obtained in Synthesis Example 1 and 50 parts by weight of maleic anhydride. , After nitrogen substitution, 2
The reaction was carried out at 10 ° C for 4 hours. The obtained polymer was washed well with cetone and dried to give a maleic anhydride group amount of 0.026 meq / g, MI 80 g / 10.
Minute polypropylene was obtained.

Synthesis Example 3 Synthesis of low-density polyethylene having a double bond at the terminal: A segment-type 25φ twin-screw extruder (D / L = 25) having a nitrogen-sealed feeder and a vent was used, and low-density polyethylene (MI = (0.3 g / 10 min) with a screw rotation speed of 200 rpm, a screw part temperature of 390 ° C., a die temperature of 270 ° C., and a discharge rate of 1.2 Kg / h, to give a double bond amount of 0.03 meq / g, MI10 g / g.
A polyethylene having a double bond at the end of 10 minutes was obtained.

Synthesis Example 4 Synthesis of low-density polyethylene having carboxylate group at the end: Polyethylene 100 having double bond at the end of Synthesis Example 3 in a separable flask having a stirrer and a condenser.
By weight, 20 parts by weight of 3-mercaptopropionic acid and 200 parts by weight of xylene were charged, and the atmosphere was replaced with nitrogen. 1
After heating to 30 ° C., 20 parts by weight of a separately prepared 3% azobisisobutyronitrile / xylene solution was added dropwise. After cooling the reaction solution, the gel polyethylene was thoroughly washed with acetone, neutralized with a 0.2% sodium hydroxide / methanol solution, washed with methanol, and dried to give a sodium content of 0.55% and MI of 7 g. / 1
A polyolefin having a carboxylate group at the 0-minute end was obtained.

Synthesis Example 5 Synthesis of low-density polyethylene having a phosphonate group at the end: Polyethylene 100 having a double bond at the end of Synthesis Example 3 in a separable flask having a stirrer and a condenser.
By weight, 25 parts by weight of phosphonic acid dimethyl ester and 200 parts by weight of xylene were charged, and nitrogen substitution was carried out. 1
After heating to 30 ° C., 20 parts by weight of a separately prepared xylene solution of 3% azobisisobutyronitrile was added dropwise. After cooling the reaction solution, the gel polyethylene was thoroughly washed with acetone and further dried. The polyethylene having a phosphonic acid dimethyl ester group thus obtained was heated in a hydrogen chloride atmosphere at 100 ° C. for 1 hour, neutralized with a 0.2% sodium hydroxide methanol solution, and then washed well with methanol and distilled water. By further drying, a low density polyethylene having a phosphorus content of 0.75% and a phosphonate group at the end of MI 5 g / 10 min was obtained.

Synthesis Example 6 Synthesis of low-density polyethylene having trimethoxysilyl group at the end: 100 parts by weight of polyethylene having a double bond at the end of Synthesis Example 3 in a separable flask having a stirrer and a condenser, dimethyl phosphonate 25 parts by weight of ester and 200 parts by weight of xylene were charged and nitrogen substitution was carried out. After heating to 130 ° C., 20 parts by weight of a separately prepared 3% azobisisobutyronitrile / xylene solution was added dropwise.
After cooling the reaction solution, the gel polyethylene was thoroughly washed with acetone and further dried. Obtained by this,
By heating polyethylene having a phosphonic acid dimethyl ester group in a hydrogen chloride atmosphere at 100 ° C. for 1 hour, neutralizing it with a 0.2% sodium hydroxide methanol solution, washing it well with methanol and distilled water, and further drying it. A low density polyethylene having a phosphorus content of 0.75% and a phosphonate group at the end of MI 5 g / 10 min was obtained.

Synthesis Example 7 Synthesis of low-density polyethylene having a sulfonate group at the end: Polyethylene 100 having a double bond at the end of Synthesis Example 3 in a separable flask having a stirrer and a condenser.
Parts by weight, 10 parts by weight of thioacetic acid and 200 parts by weight of xylene were charged, and the atmosphere was replaced with nitrogen. After heating to 100 ° C., 20 parts by weight of a separately prepared xylene solution of 3% azobisisobutyronitrile was added dropwise. After cooling the reaction solution, the gel polyethylene was thoroughly washed with acetone and further dried. 90 parts by weight of the obtained polymer and 200 parts by weight of a 1% sodium hydroxide methanol solution were placed in a flask equipped with a condenser, and after nitrogen substitution, the mixture was heated at 60 ° C. for 2 hours.
The polymer obtained was washed with distilled water, then immersed in 200 parts by weight of a 2% aqueous solution of sodium hypochlorite for 1 day, thoroughly washed with water and methanol, and dried to give a sulfur content of 0.7% and MI of 6 g / 10. A low density polyethylene having a sulfonate group at the end of the minute was obtained.

Synthesis Example 8 Synthesis of polypropylene having an epoxy group at the terminal: Synthesis Example 1 in which a separable flask having a stirring group was separately ground.
20 parts by weight of polypropylene having a double bond at the terminal of
100 parts by weight of a methylene chloride solution of 1% m-chloroperbenzoic acid was charged, and the mixture was stirred at room temperature for 1 day. After completion of the reaction, the polymer was thoroughly washed with acetone and further dried to give an epoxy group content of 0.025 meq / Kg and MI of 80 g.
A polypropylene having an epoxy group at the end of / 10 minutes was obtained.

Example 1 Carboxylic anhydride group-based polypropylene 5 at the end of Synthesis Example 2
Melt kneading was performed under the following conditions, using 45 parts by weight of EVAL (registered trademark) -F104 manufactured by Kuraray (ethylene content: 32 mol%, intrinsic viscosity at 30 ° C. in water-containing phenol: 0.95 dl / g). It was Machine used: Plastograph Rotor shape: Roller type Rotational speed: 80 rpm Kneading temperature: 220 ° C. Kneading time: 10 minutes By hot pressing the resin composition obtained by the above method at 220 ° C. The film was 100 micron thick. This film was broken in liquid nitrogen, the fracture surface was extracted with xylene at 140 ° C., and the fracture surface was observed with a scanning electron microscope. As a result, the average dispersed particle diameter of polypropylene was 0.8 μm, and the haze of this press film was 20%. 1 piece of this film piece under pressure condition
When the film was treated with hot water at 10 ° C. for 30 minutes, the shape of the film was hardly changed.

Comparative Example 1 In the same manner as in Example 1 except that 5 parts by weight of polypropylene having a carboxylic acid anhydride group at the end was replaced with 5 parts by weight of polypropylene having a double bond at the end of Synthesis Example 1. When a film was obtained, the average dispersed particle diameter of unmodified polypropylene in the film was 5 μm, and the haze of the film was 4
It was 0%, and both dispersibility and transparency were poor. Again 1
It was partially deformed by the hot water treatment at 10 ° C.

Comparative Example 2 Only EVAL (registered trademark) -F101 manufactured by Kuraray Co., Ltd.
After hot pressing at 0 ° C., hot water treatment was performed under the same conditions as in Example 1. As a result, the material was completely deformed by heat and could not be retained in its original shape.

Example 2 A film was prepared in the same manner as in Example 1 except that 5 parts by weight of polypropylene having an epoxy group at the end of Synthesis Example 8 was used instead of 5 parts by weight of a polypropylene having a carboxylic acid anhydride group at the end. As a result, the average dispersed particle diameter of the unmodified polypropylene in the film was 1 μm, and the haze of the film was 25%.

Example 3 10 parts by weight of a low-density polyethylene having a carboxylic acid anhydride group at the end of Synthesis Example 4 and EVAL (registered trademark) -F10 manufactured by Kuraray Co., Ltd.
1 (Ethylene content 32 mol%, 30 ° C in water-containing phenol)
Melt kneading was performed under the following conditions using 90 parts by weight of the intrinsic viscosity of 1.1 dl / g). Machine used: Labo Plastomill (25φ) Screw: Strong kneading type Rotational speed: 120 rpm Kneading temperature: 220 ° C. Discharge rate: 1 Kg / h The resin composition obtained by the above method is formed into an extruded film having a thickness of 50 microns. Filmed This film was broken in liquid nitrogen, the fracture surface was extracted with xylene at 140 ° C., and the fracture surface was observed with a scanning electron microscope. As a result, the average dispersed particle diameter of polypropylene is 0.5 μm,
The haze of this film was 6%. The film had few spots and the film surface was in a good condition. Further, the notched Izod impact strength of a sample piece obtained by molding the above composition with a small injection molding machine was measured according to the method of JIS K7120, and it was 13 Kgfcm / cm ↑ 2.

Comparative Example 3 Instead of 10 parts by weight of low-density polyethylene having a carboxylic group at the end of Synthesis Example 4, an ethylene-acrylic acid-sodium acrylate copolymer (acrylic acid content 0.2 mol%, sodium acrylate) was used. Content 0.8 mol%, MI5
g / 10 min) and the other tests were carried out in the same manner as in Example 3. The average dispersed particle diameter was 0.7 μm, and the haze of this extruded film was 10%. The film had many lumps, and the state of the film surface was poor. Notched Iz of a sample piece formed by molding this composition with a small injection molding machine
The od impact strength was 10 Kgfcm / cm ↑ 2.

Comparative Example 4 In place of 10 parts by weight of low-density polyethylene having a carboxylic acid group at the end of Synthesis Example 4, low-density polyethylene having a double bond at the end of Synthesis Example 3 was used, and otherwise, Example 3 was used.
When tested in the same manner as above, the average dispersed particle diameter is 4 μm.
The haze of this film was 25%. A notched Izod impact strength of a sample piece molded from this composition with a small injection molding machine was 3 Kgfcm / cm ↑ 2.

Comparative Example 5 Notched Izo of a sample piece injection-molded in the same manner as in Example 3 using only EVAL (registered trademark) -F101 manufactured by Kuraray.
The d impact strength was 2.1 Kgfcm / cm ↑ 2.

Example 4 In place of 10 parts by weight of low-density polyethylene having a carboxylic acid group at the end of Synthesis Example 4, low-density polyethylene having a phosphonate group at the end of Synthesis Example 5 was used, and otherwise the same as in Example 3. The average dispersed particle diameter was 0.5 μm, and the haze of this film was 5%.
The gel of this film was small and the state of the film surface was good. A notched Izod impact strength of a sample piece molded from this composition with a small injection molding machine was 13 Kgfcm / cm.
↑ It was 2.

Example 5 In place of 10 parts by weight of the polyolefin having a carboxyl group at the terminal of Synthesis Example 4, the low density polyethylene having a trimethoxysilyl group of Synthesis Example 6 was used, and other tests were performed in the same manner as in Example 3. As a result, the average dispersed particle diameter is 1 μm.
The haze of this film was 12%. The gel of this film was small and the state of the film surface was good. A notched Izod impact strength of a sample piece molded from this composition with a small injection molding machine was 6 Kgfcm / cm ↑ 2.

Example 6 In place of 10 parts by weight of the low-density polyethylene having a carboxylic acid group at the end of Synthesis Example 4, the low-density polyethylene having a sulfonate group of Synthesis Example 7 was used.
When tested in the same manner as above, the average dispersed particle diameter is 0.5 μm.
m, the haze of this extruded film was 7%. The film had few spots and the film surface was in a good condition. A notched Izod impact strength of a sample piece molded from this composition with a small injection molding machine was 12 Kgfcm / cm.
↑ It was 2.

[Procedure amendment]

[Submission date] October 20, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0059

[Correction method] Change

[Correction content]

[0059]

EFFECT OF THE INVENTION According to the present invention, a resin composition having a good compatibility, a small amount of gel and a good appearance can be obtained.

Claims (1)

[Claims] 1. An ethylene-vinyl alcohol copolymer (A) and a terminal functional group selected from the group consisting of a carboxyl group, a carboxylic acid derivative group, a silicon-containing group, an epoxy group, a sulfonate group and a phosphonate group. A resin composition comprising the olefin-based polymer (B) described in 1.