JPH1143573A - Resin composition and laminate thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a saponified ethylene-vinyl acetate copolymer composition which is excellent in long-run property and appearance during melt molding and further has excellent interlayer adhesion when formed into a laminate. Providing the laminate. SOLUTION: An ethylene-vinyl acetate copolymer saponified product (A) having an ethylene content of 20 to 60 mol% and a saponification degree of 90 mol% or more, a boron compound (B), an acetic acid (C) and a phosphoric acid compound (D), and the content of (B) is 0.1% based on 100 parts by weight of (A) in terms of boron.
001 to 1 part by weight, the content of (C) is 0.05 parts by weight or less based on 100 parts by weight of (A), and the content of (D) is 0 based on 100 parts by weight of (A) in terms of phosphate. .0005-
0.05 parts by weight of a resin composition and a laminate thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a saponified ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVOH).
The resin composition and the laminate using the same, more specifically, a resin composition having excellent long-run property during melt molding, having less fish eyes and stripes, having excellent appearance, and having excellent interlayer adhesion when formed into a laminate. TECHNICAL FIELD The present invention relates to a product 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. (Moldability) is very important, and is generally co-extruded with a base material such as a polyolefin resin via an adhesive layer in order to impart mechanical strength, moisture resistance, heat sealability, and the like. It is a laminate, and the interlayer adhesion of the laminate is also important. That is, the appearance of the molded product (molded product without fish eyes or stripes),
It is necessary to sufficiently satisfy the long run property at the time of melt molding (a molded article free of fish eyes and streaks is obtained even during long time molding), interlayer adhesion, and the like. It has been proposed to incorporate a boron compound into EVOH in order to improve the interlayer adhesion (JP-A-59-192564).
The present applicant has also proposed a molding method of a composition in which boron or a salt thereof is blended with EVOH in order to improve the melt moldability (Japanese Patent Application Laid-Open No. 55-12108).

[0003]

However, the technique disclosed in Japanese Patent Application Laid-Open No. Sho 59-192564 and the method disclosed in Japanese Patent Application Laid-Open No.
In the technology disclosed in -12108, the appearance of the molded product and the long-run property during melt molding are not sufficiently considered, and a new improvement in interlayer adhesion is desired.

[0004]

Accordingly, the present inventor has conducted intensive studies in view of the present situation, and as a result, has found that the ethylene content is 20 to 60 mol% and the saponification degree is 90 mol% or more.
It contains VOH (A), boron compound (B), acetic acid (C) and phosphoric acid compound (D), and the content of (B) is 0.1% based on 100 parts by weight of boron (A). 00
1 to 1 part by weight, the content of (C) is 0.05 parts by weight or less based on 100 parts by weight of (A), and the content of (D) is 0 based on 100 parts by weight of (A) in terms of phosphate group. .0005-0.
It has been found that a resin composition having a weight of 05 solves such a problem, and the present invention has been completed. The content of (B) to (D) can be measured by the following method. (B): The resin composition was alkali-melted, and the amount of boron was determined by IPC emission spectroscopy. (C): The resin composition was extracted with hot water, and the extract was neutralized and titrated with alkali to determine the amount of acetic acid. Quantitative (D): The resin composition is extracted with warm dilute sulfuric acid, and the phosphate group is quantified by a spectrophotometric method (molybdenum blue) (JIS K
0102)

[0005]

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 0.5 to
The melt index is preferably 100 g / 10 min (more preferably 1 to 50 g / 10 min). If 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 this range, the mechanical strength of the molded product is insufficient, which is not preferable.

The EVOH (A) is obtained by saponification of 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.

As the boron compound (B) contained in the above EVOH (A), boric acid or a metal salt thereof, for example, calcium borate, cobalt borate, zinc borate (zinc tetraborate, zinc metaborate, etc.) ), Potassium aluminum borate, ammonium borate (ammonium metaborate, ammonium tetraborate, ammonium pentaborate,
Cadmium borate (cadmium orthoborate, cadmium tetraborate, etc.), potassium borate (potassium metaborate, potassium tetraborate, potassium pentaborate, potassium hexaborate, potassium octaborate, etc.) ), Silver borate (silver metaborate, silver tetraborate, etc.), copper borate (cupric borate, copper metaborate, copper tetraborate, etc.),
Sodium borate (sodium metaborate, sodium diborate, sodium tetraborate, sodium pentaborate,
Sodium hexaborate, sodium octaborate, etc.), lead borate (lead metaborate, lead hexaborate, etc.), nickel borate (nickel orthoborate, nickel diborate, nickel tetraborate, nickel octaborate, etc.) ), Barium borate (barium orthoborate, barium metaborate, barium diborate, barium tetraborate, etc.), bismuth borate, magnesium borate (magnesium orthoborate, magnesium diborate, magnesium metaborate, tetraborate) Trimagnesium, pentamagnesium tetraborate, etc.), manganese borate (manganese borate, manganese metaborate, manganese tetraborate, etc.), lithium borate (lithium metaborate, lithium tetraborate, lithium pentaborate, etc.) ), Borax, carnite, inyoite, stones,
Examples thereof include borate minerals such as suyanite and ziberite, and preferably borax, boric acid, and sodium borate (sodium metaborate, sodium diborate, sodium tetraborate, sodium pentaborate, hexaborate). Sodium octarate, etc.) are used.

The content of (B) is 0.001 to 1 part by weight based on 100 parts by weight of (A) in terms of boron.
The content of (B) is more preferably 0.001 to 0.5 part by weight, particularly preferably 0.002 to 0.1 part by weight, and the content of (B) is less than 0.001 part by weight in terms of boron. In contrast, when the content exceeds 1% by weight, gels and fish eyes frequently occur, and the object of the present invention cannot be achieved. 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 acetic acid (C) contained in the EVOH (A) is 0.05 parts by weight or less, more preferably 0.0005 to 5 parts by weight, per 100 parts by weight of (A).
0.03 parts by weight, particularly preferably 0.0005 to 0.0
If the content of (C) exceeds 1 part by weight and the content of (C) exceeds 0.05 part by weight, the long run property is reduced, and 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 (B) above can be employed.

Further, the phosphate compound (D) contained in the EVOH (A) includes sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate,
Dipotassium hydrogen phosphate, tripotassium phosphate, calcium monohydrogen phosphate, calcium dihydrogen phosphate, tricalcium phosphate, magnesium phosphate, magnesium hydrogen phosphate, magnesium dihydrogen phosphate, zinc hydrogen phosphate, phosphoric acid Examples thereof include barium hydrogen and manganese hydrogen phosphate, and sodium dihydrogen phosphate, potassium dihydrogen phosphate, calcium dihydrogen phosphate, and magnesium dihydrogen phosphate are preferably used, and the content of (D) Is 0.0005 to 0.0 with respect to 100 parts by weight of (A) in terms of phosphate group.
5 parts by weight, more preferably 0.001 to 0.04 parts by weight, particularly preferably 0.002 to 0.03 parts by weight, and the content of (D) is less than 0.0005 parts by weight in terms of phosphate group. In this case, the long-run property and the interlayer adhesion are reduced, and if it exceeds 0.05 parts by weight, the appearance of the molded product is reduced,
The object of the present invention cannot be achieved. The method for causing (A) to contain (D) is not particularly limited, and the same method for containing (D) as described above can be employed.

In the present invention, the above-mentioned EVOH
By adding a specific amount of the boron compound (B), the acetic acid (C), and the phosphoric acid compound (D) to (A), a target resin composition can be obtained for the first time, and these conditions are not satisfied. In such a case, the object of the present invention cannot be achieved as described above. In the resin composition of the present invention as described above, further, 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 are used. It is also possible. 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.
Further, as the EVOH (A), two or more different EVOs are used.
H can also be used, in which case the ethylene content differs by 5 mol% or more and / or the saponification degree is 1 mol%.
By using a blend of different EVOHs,
This is useful because the stretchability during high stretching and the secondary workability such as vacuum pressure forming and deep drawing can be further improved while maintaining gas barrier properties.

[0012] 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 is particularly used 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 manufacturing 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 -Acrylate copolymer, polypropylene, propylene-α-olefin (having 4 to 20 carbon atoms)
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 sheet is once obtained from the resin composition obtained by the present invention, and another substrate is extrusion-coated thereon, or the 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 co-extrusion, 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 which improves 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 either uniaxial stretching or biaxial stretching, and it is preferable to perform stretching at the highest possible magnification in terms of physical properties. 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 laminate thus obtained may be arbitrary, 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.

[0022]

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%,
E of MI 20g / 10min (210 ° C, load 2160g)
After washing the porous precipitate of the water / methanol solution after saponification of VOH (A) (containing 100 parts of water with respect to 100 parts of EVOH (A)) with a 0.5% aqueous acetic acid solution and further washing with water Into an aqueous solution containing 0.2% boric acid (B), 0.1% acetic acid (C) and 0.015% sodium dihydrogen phosphate (D), and stirred at 30 ° C. for 5 hours. After doing
After drying at 110 ° C. for 8 hours, the EVOH (A) 100
Parts by weight of boric acid (B), acetic acid (C) and sodium dihydrogen phosphate (D) were 0.03 parts by weight (in terms of boron), 0.009 parts by weight and 0.01 parts by weight (phosphorous). An EVOH composition of the present invention containing (in terms of acid radical) was obtained.

Next, the obtained EVOH composition was supplied to a single-screw extruder equipped with a T die, and a thickness of 12 mm was obtained under the following conditions.
A 0 μm EVOH film was molded, and the appearance and long run properties were evaluated in the following manner. (Film forming condition 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 C3: 220C, C4: 220C

(Appearance) The film (1)
(0 cm × 10 cm), the appearance of streaks and fish eyes was visually observed and evaluated as follows. Streaks---No streaks were observed.----Streaks were slightly observed, but there was no problem in practical use.----Streaks occurred frequently and could not be used practically. Fisheye ◎---0 to 3 ○ −−− 4 to 10 △ −−− 11 to 50 × −−− 51 or more

(Long run property)
Performed for consecutive days, for the molded film at that time, streak, gel, visually observe the increase in fisheye,
The evaluation was as follows. ○ --- No increase was observed. △ --- A slight increase was observed. × --- A remarkable increase was observed. In addition, using the obtained EVOH composition, a feed block 5-layer T-die was used. Then, a film was formed so as to have a layer structure of polypropylene layer / adhesive resin layer / EVOH composition layer / adhesive resin layer / polypropylene layer to prepare a multilayer laminated film. 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.
With respect to such a multilayer laminated film, stretch unevenness and interlayer adhesion were evaluated as follows.

(Stretching unevenness) The above multilayer structure was 8 cm ×
The sample was sampled at 8 cm, the sample was preheated at 150 ° C. for 1 minute, and successively biaxially stretched at a stretching speed of 100 mm / sec in the order of 3 times in the longitudinal direction and 3 times in the transverse direction (stretching ratio: 9 times). The evaluation was performed according to the following criteria based on the change in appearance of the obtained stretched film. ◎ −−− No streaks were observed at all. ○ −−− Although small streaks were slightly observed, there was no problem in practical use. △ −−− One or two large streaks were generated. Limited to use × −−− Three or more large streaks are generated and cannot be used in practice

(Interlayer Adhesion) The adhesion strength between the EVOH layer and the adhesive layer of the stretched film of the multilayer structure was measured by an autograph at 20 ° C. and a tensile speed of 300 mm / min by the T-peel method. It evaluated as follows. ○ −−− 1000 g / 15 mm or more △ −−− 300 to less than 1000 g / 15 mm × −−− Less than 300 g / 15 mm

Example 2 In Example 1, the ethylene content was 40 mol%, the saponification degree was 99 mol%, and MI was 30 g / 10 min (210 ° C., load 2
160 g) of EVOH (A), except that it was treated with an aqueous solution containing 0.2% boric acid (B), 0.1% acetic acid (C) and 0.007% calcium dihydrogen phosphate Is carried out in the same manner, and with respect to 100 parts by weight of EVOH (A), 0.02 parts by weight (in terms of boron) of boric acid (B), acetic acid (C) and calcium dihydrogen phosphate (D) are added. An EVOH composition containing 008 parts by weight and 0.005 parts by weight (in terms of phosphate group) was obtained and evaluated in the same manner as in Example 1.

Example 3 In Example 1, 0.5% boric acid (B), 0.1%
Of acetic acid (C) and an aqueous solution containing 0.018% of magnesium dihydrogen phosphate (D) in the same manner as described above, with respect to 100 parts by weight of EVOH (A), boric acid (B), Acetic acid (C) and magnesium dihydrogen phosphate (D) were each added in an amount of 0.07 parts by weight (in terms of boron),
008 parts by weight and 0.015 parts by weight (in terms of phosphate group)
An EVOH composition was obtained and evaluated similarly.

Example 4 In Example 2, 0.1% boric acid (B), 0.05%
% Of acetic acid (C) and an aqueous solution containing 0.01% of potassium dihydrogen phosphate (D). , Acetic acid (C) and potassium dihydrogen phosphate (D)
Are 0.009 parts by weight (converted to boron) and 0.009 parts by weight, respectively.
An EVOH composition containing 5 parts by weight and 0.008 parts by weight (in terms of phosphate group) was obtained and evaluated in the same manner.

Example 5 In Example 2, as EVOH (A), ethylene content was 30 mol%, saponification degree was 99.5 mol%, and MI was 20 g.
EVOH (A) for 10 minutes (210 ° C., load 2160 g)
1) and ethylene content of 42 mol%, saponification degree of 99.6 mol%, MI of 15 g / 10 min (210 ° C., load of 2160
g), except that a mixture of EVOH (A2) (mixing weight ratio of A1 / A2 is 70/30) was used.
(A) 100 parts by weight of boric acid (B), acetic acid (C) and dicalcium phosphate (D) in an amount of 0.1 part each.
An EVOH composition containing 018 parts by weight (in terms of boron), 0.008 parts by weight, and 0.005 parts by weight (in terms of phosphate groups) was obtained and similarly evaluated.

Example 6 In Example 1, as EVOH (A), ethylene content was 30 mol%, saponification degree was 99.5 mol%, and MI was 20 g.
EVOH (A) for 10 minutes (210 ° C., load 2160 g)
1) and ethylene content 47 mol%, saponification degree 97 mol%, MI 35 g / 10 min (210 ° C., load 2160 g)
Of EVOH (A2) (A1 / A2 mixture weight ratio of 80
/ 20), except that EVOH (A) was used.
Boric acid (B), acetic acid (C) and sodium dihydrogen phosphate (D) were added to each of 0.029 parts by weight based on 100 parts by weight.
Parts by weight (in terms of boron), 0.009 parts by weight and 0.0
An EVOH composition containing 11 parts by weight (in terms of phosphate group) was obtained and evaluated in the same manner.

Comparative Example 1 In Example 1, the amount of boric acid (B) in the aqueous solution was reduced to 0.0
EVOH (A) 10
With respect to 0 parts by weight, boric acid (B), acetic acid (C) and sodium dihydrogen phosphate (D) were respectively 0.0005 parts by weight (in terms of boron), 0.009 parts by weight and 0.01 part by weight.
An EVOH composition containing parts by weight (in terms of phosphate groups) was obtained and evaluated in the same manner.

Comparative Example 2 The procedure of Example 1 was repeated, except that the amount of boric acid (B) in the aqueous solution was changed to 3%. The amount of boric acid (B) and acetic acid was 100 parts by weight of EVOH (A). An EVOH composition containing 1.3 parts by weight (in terms of boron), 0.009 parts by weight and 0.01 part by weight (in terms of phosphate radical) of (C) and sodium dihydrogen phosphate (D), respectively, was obtained. Was evaluated.

Comparative Example 3 The procedure of Example 1 was repeated, except that the amount of acetic acid (C) in the aqueous solution was changed to 1%, with respect to 100 parts by weight of EVOH (A), boric acid (B) and acetic acid ( An EVOH composition containing 0.03 parts by weight (in terms of boron), 0.08 parts by weight and 0.01 part by weight (in terms of phosphate radical) of C) and sodium dihydrogen phosphate (D), respectively, was obtained. An evaluation was performed.

Comparative Example 4 The procedure of Example 1 was repeated except that the amount of sodium dihydrogen phosphate (D) in the aqueous solution was 0.0005%.
With respect to 100 parts by weight of EVOH (A), boric acid (B),
E containing 0.03 parts by weight (in terms of boron), 0.009 parts by weight and 0.0003 parts by weight (in terms of phosphate radical) of acetic acid (C) and sodium dihydrogen phosphate (D), respectively.
A VOH composition was obtained and evaluated similarly.

Comparative Example 5 EVO was performed in the same manner as in Example 1 except that the amount of sodium dihydrogen phosphate (D) in the aqueous solution was changed to 0.1%.
With respect to 100 parts by weight of H (A), boric acid (B), acetic acid (C) and sodium dihydrogen phosphate (D) were added in an amount of 0.03 part by weight (in terms of boron), 0.009 part by weight, and 0.1 part by weight, respectively. An EVOH composition containing 08 parts by weight (in terms of phosphate groups) was obtained and evaluated in the same manner. Table 1 shows the evaluation results of the examples and comparative examples.

[0038]

[Table 1]Appearance Long run properties Uneven stretchability Interlayer adhesion  Example 1 ○ ◎ ○ ○ ○ 〃 2 ○ ◎ ○ ◎ ○ 〃 3 ○ ◎ ○ ○ ○ 〃 4 ○ ◎ ○ ◎ ○ 〃 5 ○ ◎ ○ ◎ ○６ 6 ○ ◎ ○ ◎ ○ Comparative Example 1 ○ ◎ ○ × × 〃 2 △ × △ △ ○ 〃 3 ○ ○ × ○ ○ 〃 4 ○ × × × △ △〃 5 × × ○ × ○

[0039]

According to the present invention, since the EVOH composition contains a specific amount of a boron compound, an acetic acid and a phosphoric acid compound, it has an excellent long-run property at the time of melt molding, has less fish eyes, and has an excellent appearance. In addition, the molded article is obtained, and the molded article is formed into a laminate, and after the secondary processing such as stretching or deep drawing, the laminate has excellent interlayer adhesion, and can be formed into various laminates. It is very useful for applications such as films, sheets, tubes, bags, containers and the like for packaging pharmaceuticals, agricultural chemicals and industrial chemicals, and can be suitably used particularly for secondary processed products involving stretching.

Claims (4)

[Claims] 1. A saponified ethylene-vinyl acetate copolymer (A) having an ethylene content of 20 to 60 mol% and a saponification degree of 90 mol% or more, a boron compound (B), acetic acid (C) and phosphoric acid Compound (D) is contained, and the content of (B) is 0.1% based on 100 parts by weight of (A) in terms of boron.
001 to 1 part by weight, the content of (C) is 0.05 parts by weight or less based on 100 parts by weight of (A), and the content of (D) is 0 based on 100 parts by weight of (A) in terms of phosphate. .0005-
A resin composition characterized by being 0.05 part by weight. 2. The phosphoric acid compound (D) is at least one selected from sodium dihydrogen phosphate, potassium dihydrogen phosphate, calcium dihydrogen phosphate, and magnesium dihydrogen phosphate. 2. The resin composition according to 1. 3. 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. 4. The laminate according to claim 3, wherein the thermoplastic resin is a polyolefin resin.