JP2000327872A - Resin composition and laminated body thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition of a saponified product of an ethylene-vinyl acetate copolymer excellent in long-run melt molding properties, appearances and the like and further excellent in low odor properties and interlaminar adhesion properties when laminated and to provide a laminated body thereof. SOLUTION: The title resin composition comprises a saponified product (A) of an ethylene-vinyl acetate copolymer having an ethylene content of 20-60 mole %, a saponification degree of at least 90 mole %, a melt index(MI), measured at 210 deg.C and a load of 2,160 g, of 0.1-100 g/10 min, acetic acid (B) and magnesium acetate and calcium acetate (C), wherein the content of (B) is not more than 0.05 pt.wt. and the content of (C) is 0.001-0.02 pt.wt. in terms of the metal, each based on 100 pts.wt. of (A).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a saponified ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVOH).
With respect to the resin composition of the present invention and a laminate using the same, more specifically, it is excellent in long-run property at the time of melt molding, fish eyes, stripes, coloring and the like are excellent in appearance, and the odor is reduced when the laminate is formed. The present invention also relates to a resin composition having excellent interlayer adhesion and a laminate using the same.

[0002]

2. Description of the Related Art In general, EVOH is excellent in transparency, gas barrier property, fragrance retention, solvent resistance, oil resistance and the like. It is used after being formed into materials, films and sheets of packaging materials for agricultural chemicals, containers such as bottles, and the like. In such molding, usually, melt molding is performed, and by such molding, it is processed into a shape such as a film shape, a sheet shape, a bottle shape, a cup shape, a tube shape, a pipe shape, and is provided for practical use. (Long-run moldability, appearance of molded product, etc.) are very important, and in general, a substrate such as a polyolefin resin and an adhesive layer are provided to impart mechanical strength, moisture resistance, heat sealability, and the like. Are coextruded to form a laminate, and low odor and interlayer adhesion of the laminate are also important. That is, the appearance of the molded article (molded article without fish eyes or stripes), long run property during melt molding (a molded article without fish eyes or stripes can be obtained even during long-time molding), It is necessary to sufficiently satisfy odor and interlayer adhesion.

In order to improve the thermal stability of EVOH, Japanese Patent Application Laid-Open No. 51-91988 discloses
It has been proposed that a sodium or potassium salt of an acid whose pKa satisfies a specific condition is contained. JP-A-56-41204 discloses that EVOH contains calcium acetate or magnesium acetate and a specific organic acid. It has been proposed in Japanese Patent Application Laid-Open No. 66662/1987 that an EVOH containing a specific metal salt and two kinds of acidic substances and having a specific viscosity behavior is disclosed.
JP-A-80954 describes an EVOH containing a polymerization degree controlling agent and having a change in viscosity average polymerization degree during heat treatment satisfying a specific conditional expression.

[0004]

However, according to a detailed study by the present inventor, according to Japanese Patent Application Laid-Open Nos. 51-91988, 56-41204, and 7-809.
It has been found that there is still room for a new improvement in the long-run formability of each of the disclosed techniques of JP-A-54-54, and the long-run moldability of the disclosed technique of JP-A-64-66262 is considerably improved. Although,
It has also been found that there is room for new improvement in the odor and interlayer adhesion of the laminate, and new improvements are desired.

[0005]

Accordingly, the present inventor has conducted intensive studies in view of the present situation, and as a result, has found that when the ethylene content is 20 to 60 mol% and the saponification degree is 90 mol% or more, the melt index ( MI) (210 ° C., load 2160
g) contains 0.1 to 100 g / 10 min of EVOH (A), acetic acid (B), magnesium acetate and calcium acetate (C), and the content of (B) is (A) 1
The content of (C) is 0.001 part by weight or less based on 100 parts by weight of (A) in terms of metal.
0.02 parts by weight of the resin composition can solve the above-mentioned problems, and the weight reduction rate when held at a temperature 70 ° C. higher than the melting point of EVOH (A) for 1 hour is 10% by weight or less. In some cases, and in the relationship between the heating time at a temperature 40 ° C. higher than the melting point of (A) and the apparent melt viscosity at a shear rate of 100 sec ^−1, the apparent melt viscosity keeps increasing for up to one hour, and the apparent melt after one hour The heating time and shear rate at a temperature where the viscosity is in the range of 1.05 to 2 times the apparent melt viscosity after 5 minutes and 70 ° C. higher than the melting point of (A).
In relation to the apparent melt viscosity in sec- ^1, the apparent melt viscosity shows a maximum value within one hour, and the apparent melt viscosity after one hour is 0.05 to 0.05% of the apparent melt viscosity after five minutes.
When the ratio is 1.5 times, it is found that the operation and effect of the present invention is remarkable, and the present invention has been completed.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The EVOH (A) of the present invention has an ethylene content of 2
Those having 0 to 60 mol% (more preferably 25 to 55 mol%) and a saponification degree of 90 mol% or more (furthermore, 95 mol% or more) are used. The gas barrier properties and melt-molding properties of the resin deteriorate, whereas if it exceeds 60 mol%, sufficient gas barrier properties cannot be obtained, and if the saponification degree is less than 90 mol%, the gas barrier properties, heat stability and moisture resistance And the like, and the object of the present invention cannot be achieved. EVOH (A) has a melt index (MI) (210 ° C., load 2160 g) of 0.1 to
If the melt index is less than 100 g / 10 min (more preferably 0.5 to 50 g / 10 min) and the melt index is smaller than the above range, the inside of the extruder will be in a high torque state at the time of molding and extrusion processing will be difficult. If it is larger than the range,
The mechanical strength of the molded product is insufficient.

The EVOH (A) is obtained by saponifying an ethylene-vinyl acetate copolymer, and the ethylene-vinyl acetate copolymer can be produced by any known polymerization method, for example, suspension polymerization, emulsion polymerization. , A solution polymerization or the like, and saponification of an ethylene-vinyl acetate copolymer can be carried out by a known method. If EVOH is used in a small amount, other comonomers such as α-olefin, unsaturated carboxylic acid compound, unsaturated sulfonic acid compound, (meth) acrylonitrile, (meth) acrylamide, vinyl ether, vinyl silane compound, vinyl chloride and styrene And may be "copolymerized". Also, "post-modified" such as urethanization, acetalization, and cyanoethylation may be used as long as the gist of the present invention is not impaired.

[0008] The content of acetic acid (B) contained in the above EVOH (A) is 0.0% with respect to 100 parts by weight of (A).
Not more than 5 parts by weight, more preferably 0.0005 to 0.0
3 parts by weight, particularly preferably 0.0005 to 0.01 parts by weight, and when the content of (B) exceeds 0.05 parts by weight, the long-run property is reduced and the object of the present invention can be achieved. Can not. The method of causing (B) to be contained in (A) is not particularly limited, and a method of directly blending (B) with (A), dissolving (B) in a solvent such as water, and then adding (A)
, Method of dipping (A) in solution of (B), method of blending (B) with (A) in molten state, addition of solution of (B) to water / alcohol solution of (A) Thereafter, a method of drying the (porous) precipitate by depositing it in a coagulation bath, and a method of impregnating the porous precipitate of the water / alcohol solution of (A) in the solution of (B) and then drying it However, from the viewpoint of dispersing (B) more uniformly and efficiently, the following method is suitably used.

The content of magnesium acetate and calcium acetate (C) contained in the EVOH (A) is 0.001 to 0 with respect to 100 parts by weight of (A) in terms of metal of magnesium and calcium. 0.02 parts by weight, more preferably 0.0015 to 0.015 parts by weight, particularly preferably 0.002 to 0.01 parts by weight. When the content of (C) is less than 0.001 part by weight, long run properties are obtained. If the content exceeds 0.02 parts by weight, the coloring and the odor of the laminate become remarkable, and the interlayer adhesion is reduced, so that the object of the present invention cannot be achieved. The method for containing (C) in (A) is not particularly limited, and the same containing method as in the above (B) can be adopted. In addition, in the adjustment of the above (B), it is also possible to adjust at the time of the production of EVOH. For example, the amount of acetic acid (B) added for the purpose of neutralizing the alkali used in the saponification step is dried. It is also possible to make adjustments by using.

In the present invention, the above-mentioned EVOH
By adding a specific amount of acetic acid (B), magnesium acetate and calcium acetate (C) to (A), the desired resin composition can be obtained for the first time. As described above, the object of the present invention cannot be achieved.

[0011] Thus, the resin composition of the present invention is obtained.
Heating time and shear rate at a temperature of 70 ° C. higher than the melting point of EVOH (A) for 1 hour when the weight loss rate is 10% by weight or less, or at a temperature 40 ° C. higher than the melting point of (A) In relation to the apparent melt viscosity at 100 sec ^-1 (hereinafter the same unless otherwise specified), the apparent melt viscosity always keeps increasing up to 1 hour, and the apparent melt viscosity after 1 hour becomes less than the apparent melt viscosity after 5 minutes. The heating time at a temperature 70 ° C. higher than the melting point of (A) and a shear rate of 100 sec ⁻¹ (hereinafter, referred to as
In the case of the apparent melt viscosity, the apparent melt viscosity shows a maximum value within 1 hour, and the apparent melt viscosity after 1 hour is 0.1% of the apparent melt viscosity after 5 minutes.
When it is in the range of from 0.5 to 1.5 times, the effect of the present invention can be remarkably obtained, which is preferable.

In the former case, if the weight reduction ratio exceeds 10% by weight, the odor and the interlayer adhesion of the laminate tend to be particularly deteriorated. In the latter case, in the relation between the heating time at a temperature 40 ° C. higher than the melting point of (A) and the apparent melt viscosity, if the apparent melt viscosity does not always increase until 1 hour, the odor of the laminate and the interlayer adhesion When the apparent melt viscosity after 1 hour exceeds twice the apparent melt viscosity after 5 minutes, the long-run moldability tends to be insufficient, and is 70 ° C. higher than the melting point of (A). In the relationship between the heating time at the temperature and the apparent melt viscosity, if the viscosity increases after 1 hour, the long-run moldability becomes insufficient, and the apparent melt viscosity after 1 hour is 0.05% of the apparent melt viscosity after 5 minutes. If the ratio is less than 1.5 times, the odor of the laminate and the interlayer adhesion deteriorate, and if it exceeds 1.5 times, the long-run moldability tends to be insufficient.

The method of controlling the weight loss rate and the viscosity behavior is not particularly limited, but it is important to keep the heat history before obtaining the resin composition small, and in particular, the temperature, time, oxygen, It is effective to adjust the concentration and the like. The above weight loss rate (%)
Is a value calculated by the following equation. Weight reduction rate (%) = [(weight before heating−weight after heating) / (weight before heating)] × 100 When two or more EVOHs are used, the EVOH component having the largest blending weight ratio (blending) When the weight ratio is 50/50, the melting point of the EVOH component having the highest melting point) is
As the melting point of H (A), the weight loss rate at a temperature 70 ° C. higher than that may be calculated.

The resin composition of the present invention may further contain, if necessary, additives such as a plasticizer, a heat stabilizer, an ultraviolet absorber, an antioxidant, a coloring agent, an antibacterial agent, a filler and other resins. It is also possible to use In particular, a hydrotalcite-based compound, a hindered phenol-based, a hindered amine-based heat stabilizer, and a metal salt of a higher aliphatic carboxylic acid can also be added as a gel generation inhibitor. Also, EVOH
As (A), two or more different EVOHs can be used. In this case, EVs having ethylene contents different by 5 mol% or more and / or saponification degrees differing by 1 mol% or more are used.
The use of the OH blend is useful because the stretchability at the time of high stretching and the secondary workability such as vacuum pressure forming and deep drawing are improved while maintaining gas barrier properties.

The resin composition of the present invention thus obtained is
It is often used for molded products, and pellets by melt molding etc.
It is formed into films, sheets, containers, fibers, rods, tubes, various molded products, and the like, and is often subjected to melt molding again using crushed products (such as when reused products) or pellets are used. As the melt molding method, extrusion molding methods (T-die extrusion, inflation extrusion, blow molding, melt spinning,
Injection molding is mainly employed. The melt molding temperature is often selected from the range of 150 to 250 ° C.

The resin composition obtained by the present invention can be used for a molded product as described above, and particularly as a laminate comprising a thermoplastic resin layer laminated on at least one surface of a layer made of the resin composition. It is preferably used, and a laminate suitable for practical use is obtained. Since the laminate uses the EVOH composition of the present invention, it has not only excellent gas barrier properties and transparency, but also excellent interlayer adhesion at the time of high stretching and at the time of secondary processing such as vacuum pressure forming or deep drawing. It shows an excellent effect.

In producing the laminate, another substrate is laminated on one or both sides of the layer of the EVOH composition obtained in the present invention. The lamination method is, for example, a film of the composition. A method of melt-extruding a thermoplastic resin into a sheet, a method of melt-extruding the composition on a substrate such as a thermoplastic resin, a method of co-extruding the resin composition with another thermoplastic resin, and A method of laminating a film or sheet of the EVOH composition obtained by the present invention with a film or sheet of another substrate using a known adhesive such as an organic titanium compound, an isocyanate compound, a polyester compound, or a polyurethane compound. Is mentioned.

In the case of coextrusion, the mating resin may be a linear low-density polyethylene, low-density polyethylene, medium-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ionomer, ethylene-propylene copolymer, ethylene -Acrylic vinegar ester copolymer, polypropylene, propylene-α-olefin (C 4-20
Α-olefins) copolymers, polyolefins such as polybutenes and polypentenes, or polyolefins in a broad sense, such as homo- or copolymers of these olefins, or graft-modified homo- or copolymers of these olefins with unsaturated carboxylic acids or esters thereof Resin, polyester, polyamide, copolymerized polyamide, polyvinyl chloride, polyvinylidene chloride, acrylic resin, polystyrene, vinyl ester resin,
Examples thereof include polyester elastomer, polyurethane elastomer, chlorinated polyethylene, and chlorinated polypropylene. Saponified ethylene-vinyl acetate copolymer can also be coextruded. Among these, polypropylene, polyamide, polyethylene, ethylene-vinyl acetate copolymer, polystyrene, and PET are preferably used from the viewpoint of ease of coextrusion film formation and practicality of film physical properties (particularly strength).

Further, a molded product such as a film or a sheet is once obtained from the resin composition obtained by the present invention, and another substrate is extrusion-coated thereon, or a film or sheet of another substrate is bonded to an adhesive. In the case of laminating using, any substrate (paper, metal foil, uniaxially or biaxially stretched plastic film or sheet, woven fabric, nonwoven fabric, metal flocculent, woody, etc.) other than the above-mentioned thermoplastic resin can be used. is there. The layer structure of the laminate is such that the layer of the resin composition obtained in the present invention is a (a ₁ , a ₂ ,...)
.), Another substrate, for example, a thermoplastic resin layer b (b ₁ ,
b ₂ ,...), in the case of a film, sheet, or bottle, not only a two-layer structure of a / b but also b / a /
b, a / b / a, a 1 / a 2 / b, a / b 1 / b 2, b 2 /
_{b 1 / a / b 1 /} b 2 , etc. are possible any combination,
In the filament form, a and b are bimetal type, core (a)-
Any combination such as a sheath (b) type, a core (b) -sheath (a) type, or an eccentric core-sheath type is possible.

In the case of coextrusion, a may be blended with b and b may be blended with a, or at least one of a and b may be blended with a resin for improving the adhesion between the two layers. In the present invention, the laminate is used as it is in various shapes, but it is also preferable to perform a stretching treatment in order to further improve the physical properties of the laminate, breaking, pinholes, cracks,
Since it exhibits an effect of excellent stretchability and interlayer adhesion without delamination or the like, it is a very excellent laminate.

The stretching may be any of uniaxial stretching and biaxial stretching, and it is better to perform stretching at the highest possible magnification. In the present invention, a stretched film or a stretched sheet free from pinholes, cracks, stretch unevenness, delamination and the like during stretching can be obtained.

The stretching method includes a roll stretching method, a tenter stretching method, a tubular stretching method, a stretching blow method, and the like.
Of the deep drawing, vacuum forming and the like, those having a high stretching ratio can be employed. In the case of biaxial stretching, any of a simultaneous biaxial stretching method and a sequential biaxial stretching method can be adopted. Stretching temperature is 80
To 170 ° C, preferably about 100 to 160 ° C.

After completion of the stretching, heat setting is performed. The heat setting can be performed by a well-known means, and heat treatment is performed at 80 to 170 ° C., preferably 100 to 160 ° C. for about 2 to 600 seconds while keeping the stretched film in a tensioned state. The obtained stretched film should be subjected to cooling, rolling, printing, dry laminating, solution or melt coating, bag making, deep squeezing, box processing, tube processing, split processing, etc. as necessary. Can be.

The shape of the thus obtained laminate may be any shape, and examples thereof include a film, a sheet, a tape, a bottle, a pipe, a filament, and an extrudate having a modified cross section. Further, the obtained laminate is heat-treated, cooled, rolled, printed, dry-laminated,
Solution or melt coating processing, bag making processing, deep drawing processing, box processing, tube processing, split processing, and the like can be performed. The films, sheets, containers and the like obtained as described above are useful as various packaging materials for foods, pharmaceuticals, industrial chemicals, agricultural chemicals and the like.

[0025]

The present invention will be specifically described below with reference to examples. In the examples, "parts" and "%" are based on weight unless otherwise specified. Example 1 Ethylene content 35 mol%, saponification degree 99.5 mol%,
MI 8 g / 10 min (210 ° C., load 2160 g), porous precipitate of water / methanol solution after saponification of EVOH (A) having a melting point of 178 ° C. (100 parts water per 100 parts EVOH (A)) After washing with 0.5% acetic acid aqueous solution,
It was poured into an aqueous solution containing 0.1% acetic acid (B), 0.03% magnesium acetate and 0.02% calcium acetate (C), and stirred at 30 ° C. for 5 hours.
After drying at 110 ° C. for 8 hours under a nitrogen stream of 5% or less, acetic acid (B), magnesium acetate (C), and calcium acetate (C) were added to 100 parts by weight of EVOH (A), respectively. An EVOH composition of the present invention containing 0.015 parts by weight, 0.0035 parts by weight (as magnesium), and 0.002 parts by weight (as calcium) was obtained.

The obtained resin composition was heated at 248 ° C. (melting point 17
(At 8 ° C. + 70 ° C.) for 1 hour (left standing), the weight loss rate was 1.3%. 218 ° C. (mp 178
(+ 40 ° C.) for 1 hour, but the apparent melt viscosity continued to rise, and the apparent melt viscosity after 1 hour was 1200 Pa
· Apparent melt viscosity after 5 minutes in sec (780 Pa · sec
c) 1.5 times and 248 ° C. (mp 178 ° C. + 70
° C), the heating was continued for 1 hour or more (3 hours), but within 1 hour, the apparent melt viscosity showed a maximum value and decreased. The apparent melt viscosity after 1 hour was 59 Pa · sec for 5 minutes. After the apparent melt viscosity (490 Pa · sec) of 0.
It was 12 times.

Next, the obtained EVOH composition was supplied to a single-screw extruder equipped with a T die, and a thickness of 40 mm was obtained under the following conditions.
A μm EVOH film was molded, and the appearance and long-run property were evaluated in the following manner. [Film forming conditions by single screw extruder] Screw inner diameter 40 mm L / D 28 Screw compression ratio 3.2 T die Coat hanger type Die width 450 mm Extrusion temperature C1: 200 ° C, H: 220 ° C C2: 220 ° C, D: 220 C3: 220C, C4: 220C

(Appearance) The film (1) immediately after molding
(0 cm × 10 cm), the appearance of streaks, fish eyes and coloring was visually observed and evaluated as follows. Streaks ○ --- No streaks were observed. △ −−− Slight streaks were observed, but practical use was possible. × −−− Many streaks occurred, and practical use was not possible. Fisheye ◎ −−− 0 to 3 ○ −−− 4 to 10 pieces △ −−− 11 to 50 pieces × −−− 51 or more Coloring ○ −−− Coloring was not recognized △ −−− Coloring was slightly recognized but practically usable × −−− Significant coloring, not practical

(Long run property)
The test was carried out for consecutive days, and the formed film at that time was visually observed for the increase in streaks, gels, fish eyes, and coloring, and evaluated as follows. ○ −−− No increase was observed △ −−− Although a slight increase was observed, continuous operation was possible × −−− A remarkable increase was observed and continuous operation was not possible In addition, the obtained EVOH composition Was used to form a multilayer film having a layer structure of polypropylene layer / adhesive resin layer / EVOH composition layer / adhesive resin layer / polypropylene layer with a feed block 5-layer T-die. In addition, the structure of the film is such that the polypropylene layers of both outer layers (the MI of polypropylene is 1.2 g / 10 min) are 100
μm, the adhesive resin layer (the adhesive resin is maleic anhydride-modified polypropylene, and its MI is 2.6 g / 10 min)
The thickness of the EVOH composition layer was 5 μm, and the thickness of the intermediate layer was 50 μm.
About such a multilayer laminated film, the odor and interlayer adhesiveness were evaluated as follows.

(Odor) The obtained multilayer film was subjected to an odor of 3
It was confirmed by 0 panelists and evaluated as follows. ○ −−− All 30 persons judged that odor was not recognized △ −−− 5 or more of 30 persons felt odor, but judged that it was practically usable × −−− All 30 persons were remarkable Feels odor and is judged to be unusable for practical use

(Interlayer adhesion) EV of the above multilayer film
The adhesive strength between the OH layer and the adhesive layer was determined by an autograph as 20
It measured by the T-peel method at 300 degreeC and the tensile speed of 300 mm / min, and evaluated as follows. ○ −−− 700 g / 15 mm or more △ −−− 300 to less than 700 g / 15 mm × −−− Less than 300 g / 15 mm

Example 2 Ethylene content 40 mol%, saponification degree 99 mol%, MI
3 g / 10 min (210 ° C., load 2160 g), melting point 17
EVOH (A) at 0 ° C. was added to 0.05% acetic acid (B), 0.1%
It was poured into an aqueous solution containing 015% magnesium acetate and 0.04% calcium acetate (C), stirred at 35 ° C for 3 hours, and then heated at 110 ° C in a nitrogen stream having an oxygen concentration of 0.5% or less. After drying for 8 hours, the EVOH (A) 100
Acetic acid (B), magnesium acetate (C) based on parts by weight
And calcium acetate (C) in an amount of 0.006 parts by weight, 0.0015 parts by weight (converted to magnesium), 0.1 parts by weight, respectively.
An EVOH composition containing 0045 parts by weight (calculated) was obtained and evaluated in the same manner as in Example 1. In addition, when the obtained resin composition was held (rested) at 240 ° C. (melting point 170 ° C. + 70 ° C.) for 1 hour, the weight loss rate was 2.2%. Further, at 210 ° C. (melting point 170 ° C. + 40 ° C.), 1
Although heating was continued for an hour, the apparent melt viscosity continued to rise, and the apparent melt viscosity after 1 hour was 1.2 times the apparent melt viscosity after 5 minutes (1800 Pa · sec) at 2200 Pa · sec and 240 ° C. (170 ° C. + 70 ° C.), the heating was continued for 1 hour or more (5 hours), but within 1 hour, the apparent melt viscosity showed a maximum value and decreased, and after 1 hour, the apparent melt viscosity was 200 Pa · sec. Was 0.2 times the apparent melt viscosity (990 Pa · sec) after 5 minutes. The film forming conditions were as follows.

[Film forming conditions by single screw extruder] Screw inner diameter 40 mm L / D 28 Screw compression ratio 3.2 T die Coat hanger type Die width 450 mm Extrusion temperature C1: 180 ° C, H: 210 ° C C2: 200 ° C, D: 210 ° C C3: 210 ° C, C4: 210 ° C

Example 3 In Example 2, as EVOH (A), ethylene content was 32 mol%, saponification degree was 99.5 mol%, and MI was 12 g.
/ 10 minutes (210 ° C, load 2160g), melting point 183 ° C
A mixture of EVOH (A1) and EVOH (A2) having an ethylene content of 42 mol%, a saponification degree of 99.6 mol%, MI of 15 g / 10 min (210 ° C., load of 2160 g) and a melting point of 167 ° C. A weight ratio of 70/30) was used in the same manner as above, with respect to 100 parts by weight of EVOH (A).
Acetic acid (B), magnesium acetate (C) and calcium acetate (C) were each added in an amount of 0.006 parts by weight and 0.001 part by weight.
An EVOH composition containing 5 parts by weight (in terms of magnesium) and 0.0045 parts by weight (in terms of calcium) was obtained and similarly evaluated. In addition, the obtained resin composition was heated at 253 ° C.
(The melting point was 183 ° C. + 70 ° C.), and the weight loss rate after holding (leaving) for 1 hour was 2.6%. 223 ° C
(Melting point: 183 ° C. + 40 ° C.), heating was continued for 1 hour, but the apparent melt viscosity continued to rise, and the apparent melt viscosity after 1 hour was 790 Pa · sec, and the apparent melt viscosity after 5 minutes (520
Pa · sec) and 253 ° C (melting point 18
(3 ° C. + 70 ° C.), the heating was continued for 1 hour or more (3 hours), but within 1 hour, the apparent melt viscosity showed a maximum value and decreased, and after 1 hour, the apparent melt viscosity was 35 Pa
The apparent melt viscosity after 5 minutes in sec (230 Pa
0.15 times of c). The film forming conditions were as follows.

[Film forming conditions by single-screw extruder] Screw inner diameter 40 mm L / D 28 Screw compression ratio 3.7 T die Coat hanger type Die width 450 mm Extrusion temperature C1: 200 ° C, H: 220 ° C C2: 220 ° C, D: 220 ° C C3: 225 ° C, C4: 225 ° C

Example 4 In Example 2, as EVOH (A), ethylene content was 32 mol%, saponification degree was 99.5 mol%, and MI was 12 g.
/ 10 minutes (210 ° C, load 2160g), melting point 183 ° C
EVOH (A1) and ethylene content 47 mol%, saponification degree 97 mol%, MI 15 g / 10 min (210 ° C., load 2
160 g) and a mixture of EVOH (A2) having a melting point of 142 ° C. (the mixing weight ratio of A1 / A2 is 80/20). ), Magnesium acetate (C) and calcium acetate (C) in an amount of 0.006 parts by weight, 0.0015 parts by weight, respectively.
An EVOH composition containing parts by weight (in terms of magnesium) and 0.0045 parts by weight (in terms of calcium) was obtained and similarly evaluated. In addition, when the obtained resin composition was held (rested) at 253 ° C. (melting point: 183 ° C. + 70 ° C.) for 1 hour, the weight loss rate was 2.6%. Heating was continued at 223 ° C. (melting point: 183 ° C. + 40 ° C.) for 1 hour, but the apparent melt viscosity continued to rise, and the apparent melt viscosity after 1 hour was 820.
Apparent melt viscosity after 5 minutes in Pa · sec (540Pa ·
sec) and 253 ° C (melting point: 183 ° C +
(70 ° C.) for more than one hour (3 hours).
Within a period of time, the apparent melt viscosity shows a maximum value and decreases, while the apparent melt viscosity after one hour is 50 Pa · sec.
c was 0.2 times the apparent melt viscosity (240 Pa · sec) after 5 minutes. The film forming conditions were the same as in Example 3.

COMPARATIVE EXAMPLE 1 The procedure of Example 1 was repeated except that the amount of acetic acid (B) in the aqueous solution was changed to 1%, and acetic acid (B) and magnesium acetate (100 parts by weight) were added to 100 parts by weight of EVOH (A). C) and 0.09 parts by weight of calcium acetate (C), respectively.
An EVOH composition containing 0035 parts by weight (in terms of magnesium) and 0.002 parts by weight (in terms of calcium) was obtained.
Evaluation was performed similarly.

Comparative Example 2 In Example 1, magnesium acetate (C) in an aqueous solution was used.
And acetic acid (B), magnesium acetate (C), and calcium acetate (C) were added to 100 parts by weight of EVOH (A) except that the amount of calcium acetate (C) was 0.005%. 0.01 parts by weight,
0.0003 parts by weight (magnesium conversion), 0.000
An EVOH composition containing 4 parts by weight (calculated as calcium) was obtained and similarly evaluated.

Comparative Example 3 In Example 1, magnesium acetate (C) in an aqueous solution was used.
And the amount of calcium acetate (C) was 0.1% and 0.15%, respectively.
Acetic acid (B), magnesium acetate (C), and calcium acetate (C) were added to 100 parts by weight, respectively.
1 part by weight, 0.01 part by weight (calculated as magnesium), 0.1 part by weight.
An EVOH composition containing 015 parts by weight (calcium equivalent) was obtained and similarly evaluated. Table 1 shows the evaluation results of the examples and comparative examples.

[Table 1]Appearance Long run property Odor Interlayer adhesion  Example 1 ○ ◎ ○ ○ ○ ○ 〃 2 ○ ◎ ○ ○ ○ ○ 〃 3 ○ ◎ ○ ○ ○ ○４ 4 ○ ◎ ○ ○ ○ ○ Comparative Example 1 △ ○ ○ × ○ ○ 〃 2 ○ ◎ ○ × ○ △３ 3 ○ ◎ △ ○ × ×

[0041]

According to the present invention, since the EVOH composition contains acetic acid, magnesium acetate and / or magnesium acetate in a specific amount, it has an excellent long-run property at the time of melt molding, and has little fish eyes, streaks, and coloring, A molded article having excellent appearance is obtained, and the odor is reduced even when the molded article is formed into a laminate, and the interlayer adhesion of the laminate after secondary processing such as stretching or deep drawing. And can be used as various laminates, and is very useful for applications such as films, sheets, tubes, bags, containers, and the like for packaging foods, pharmaceuticals, agricultural chemicals, and industrial chemicals.

Claims (5)

[Claims] 1. A melt index (MI) having an ethylene content of 20 to 60 mol% and a saponification degree of 90 mol% or more.
(210 ° C., load 2160 g) is 0.1 to 100 g / 1.
0 minute saponified ethylene-vinyl acetate copolymer (A),
It comprises acetic acid (B), magnesium acetate and calcium acetate (C), and the content of (B) is (A) 1
The content of (C) is 0.001 part by weight or less based on 100 parts by weight of (A) in terms of metal.
To 0.02 parts by weight. 2. The method according to claim 1, wherein the weight loss rate of the saponified ethylene-vinyl acetate copolymer (A) after holding at a temperature 70 ° C. higher than the melting point for 1 hour is 10% by weight or less. Resin composition. 3. In the relationship between the heating time at a temperature 40 ° C. higher than the melting point of (A) and the apparent melt viscosity at a shear rate of 100 sec ^−1, the apparent melt viscosity always keeps increasing up to 1 hour, and after 1 hour, (A) the apparent melt viscosity is in the range of 1.05 to 2 times the apparent melt viscosity after 5 minutes, and
Heating time at a temperature 70 ° C. higher than the melting point of
In relation to the apparent melt viscosity at ⁰ sec ^-1 , 1
The apparent melt viscosity shows a maximum value within 1 hour, and the apparent melt viscosity after 1 hour is 0.05 to 0.05% of the apparent melt viscosity after 5 minutes.
3. The resin composition according to claim 1, wherein the ratio is 1.5 times. 4. A laminate comprising a layer made of the resin composition according to claim 1 and a thermoplastic resin layer laminated on at least one surface of the layer. 5. The laminate according to claim 4, wherein the thermoplastic resin is a polyolefin resin or a polystyrene resin.