JPH0297543A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in adhesion to a polyolefin adhesive layer and stability during melt molding by mixing an ethylene/vinyl acetate copolymer saponificate with a specified phosphate, a substituted phenol derivative and an organophosphite compound. CONSTITUTION:An ethylene/vinyl acetate copolymer saponificate (A) of an ethylene content of 20-60mol% and a degree of saponification of the vinyl acrtate component >=95mol% is mixed with a mixture (B) of an alkali metal secondary or tertiary phosphate (e.g., dipotassium phosphate) with, optionally, an alkali metal carboxylate, 0.001-5-wt.%, based on component A, substituted phenol (C) [e.g., 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)-benzene] and 0.001-5wt.%, based on component A, organophosphite compound (D) [e.g., bis(2,6-di-t-butylphenyl)pentaerythritol diphosphite] to obtain a resin composition containing 15-250ppm alkali metal and 5-5000ppm phosphorus based on component A.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is directed to an unsaturated carboxylic acid-modified polyolefin adhesive layer that is commonly used when laminating a polyolefin layer and an edgeless vinyl acetate copolymer saponified layer. The present invention relates to a saponified ethylene-vinyl acetate copolymer composition that exhibits good adhesive strength and excellent stability during melt molding.

[Prior Art] A two or three or more layer laminate having a laminated structure of a polyolefin layer and a saponified ethylene-vinyl acetate copolymer layer has good water resistance of polyolefin and a saponified ethylene-vinyl acetate copolymer layer. Since the combined saponified product has a good combination of excellent oxygen barrier properties and oil and solvent resistance, it is expected to be used in a variety of applications including food packaging films, sheets, bags, and containers. However, polyolefin and saponified ethylene-vinyl acetate copolymer do not have sufficient adhesion to each other, so even when these resins are laminated by simultaneous melt extrusion or melt coating, delamination occurs, making it difficult to put them into practical use as side soles. There is a problem that it cannot be provided.

Therefore, a method is proposed in which at least one layer of a laminate consisting of a polyolefin layer/saponified ethylene-vinyl acetate copolymer layer is blended with a resin constituting the other layer. Methods of blending adhesion-imparting resins such as polymers, ethylene-acrylic acid ester copolymers, saponified ethylene-hinyl acetate copolymers with a high ionomer ethylene content, and unsaturated polycarboxylic acid grafted polyolefins have been proposed. However, these methods tend to impair the inherent oxygen barrier properties and oil and solvent resistance of saponified ethylene-vinyl acetate copolymers, and when blended with polyolefins, they tend to impair transparency and surface smoothness. Moreover, the desired effect of improving adhesion may not always be achieved.

[Problems to be Solved by the Invention] In order to avoid such drawbacks, various studies have been conducted, including methods of interposing an adhesive layer between the polyolefin layer and the saponified ethylene-vinyl acetate copolymer layer to improve interlayer adhesion. There is. A typical example of the adhesive layer llh is an unsaturated carphonic acid-modified polyolefin (for example, JP-A-51-112887). In this method, the polyolefin layer and the saponified ethylene-vinyl acetate copolymer layer are blend-modified. Since it exists without being oxidized, its original properties are preserved, but it feels like it is still one step away from being fully satisfied in practical terms.

Furthermore, from the viewpoint of melt molding, saponified ethylene-vinyl acetate copolymer does not necessarily have sufficient long-run processability, and when molding is continued for a long time, the melt viscosity tends to fluctuate, especially viscosity increases, and it is difficult to stably mold the product. There is a tendency for it to be difficult to manufacture.

[Means for Solving the Problems] The present inventors have conducted extensive research on improving interlayer adhesion using an adhesive layer interposition method, and have found that the ethylene content is 20 to 60 mol%, and the degree of saponification of the vinyl acetate component is 95 mol%. % or more of the saponified vinyl acetate copolymer, a secondary or tertiary phosphate of an alkali metal, a substituted phenol derivative and a
The composition containing a phosphorous acid compound exhibits remarkable adhesion to the unsaturated carboxylic acid-modified polyolefin adhesive layer, and the melt viscosity converges to a nearly constant range after long-term molding. The present inventors have discovered that this material has extremely excellent long-run workability, and have completed the present invention.

In the present invention, as mentioned above, the second or third alkali metal
It is characterized by the fact that it contains phosphate, and in the past, various acids and salts have been added to improve the thermal stability of saponified vinyl acetate copolymer. However, there is no evidence that secondary or tertiary phosphates of alkali metals have been used as in the present invention, and furthermore, there has been no attempt to use such a field to improve adhesion with a specific adhesive layer. It was first achieved through invention.

Moreover, in the present application, the combined use of a substituted phenol derivative and an organic phosphorous acid compound improves molding processability.

Hereinafter, the composition of the present invention will be explained in detail.

Saponified ethylene-vinyl acetate copolymer targeted by the present invention (ethylene content: 20 to 60 mol%, preferably 2
5 to 55 mol%, degree of saponification of vinyl acetate component 95 mol%
That's all.

If the ethylene content is less than 20 mol %, the oxygen barrier properties at high humidity will decrease, while if it is 60 mol % or more, physical properties such as oxygen barrier properties and printability will decrease. Furthermore, if the degree of saponification is less than 95 mol%, oxygen barrier properties and moisture resistance will decrease.

In addition, the saponified copolymer further contains small amounts of propylene, isobutyne, α-octene, α-dodecene, α-octadecene, α-olefin, unsaturated carboxylic acid or its salt, partial alkyl ester, complete alkyl ester, nitrile, It may contain a comonomer such as an amide, anhydride, unsaturated sulfonic acid or a salt thereof as a copolymerization component.

Impregnation of secondary or tertiary phosphate of alkali metal is ethylene-hinyl acetate (20-50% for saponified polymer).
o ppm is appropriate. Finally, in the resin composition,
15 to 250 ppm of alkali metal to saponified product
It seems that it contains 5 to 5000 ppm of phosphorus;
Must do.

If the alkali metal or phosphorus content is below the lower limit, the effect of improving interlayer adhesion is poor, if the alkali metal content is above the upper limit, the molded product will be colored, and if the phosphorus content is above the upper limit, the formation of stains on the film will become noticeable.

Normally, a secondary or tertiary alkali metal linoate is used alone in order to make the alkali metal content within the above range, but in the present invention, a part of it is converted into an alkali metal carboxylate. There is no problem with replacing it.

Depending on the yA production method of the composition, the interlayer adhesion may be improved more by using a secondary or tertiary phosphate salt and a carboxylic acid salt in combination.

When a carboxylic acid salt is used in combination, the amount added must not deviate from the above-mentioned range after the alkali metal is contained.

Among alkali metal carboxylates, carboxylic acids such as acetic acid and propionic acid have a p Ka (at 25°C) of 35 to
It is a polymeric acid such as a saponified ethylene-vinyl acetate copolymer impregnated with about 6 or more carboquinol, and the alkali metal is sodium, potassium, lithium, etc. The most practical are sodium acetate or potassium acetate. Of course, two or more of the above carboxylic acid salts may be used in combination.

The composition of the present invention further contains a substituted phenol derivative and an organic phosphorous acid compound.

Substituted phenol derivatives include 2.5-butylhydride [J quinone, 2.6-butyl-p-cresol, 4.4'-thiohis-(6-L-butylphenol), 2.2'- Medile sea bis (4-methyl-6
-[butylphenol), tetrakis-[methylene-3
(3°, 5゛-]-]L dithi-4゛-hydroquine phenylpropionate comethane, oftadenol-3-(
3'5'-di-butyl-14'-hydroquinphenyl)bu[1 bionate, 4,4'-thiohis-(6-t
-butylphenol), N,N'-hexamedylcehis(3,5-)[-butyl-4-hydroquino-hydrononamide), 135-trimedel-2,4,6 tris(
3,5-No-L-butylene-4-hydroquinobenzyl)benzene, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, tetrakis[methylene(3,5-di- Examples include t-butyl-4-hydroquinohydrocinnamate]methane, pentaerythyl-tetrakis[3-(3,5-di[-butyl-4-hydroxyphenyl)propionate], and the like.

Examples of organic phosphite compounds include triarylphosphites such as triphenyl phosphite, tris (p-nonylphenyl) phosphite, and tris (2,4-nonylphenyl) phosphite, nophenylisooctyl phosphite, Monoalkyl diphenyl phosphites such as diphenyl isode/ruphosphite, alkylaryl phosphites such as noalkyl monophenyl phosphites such as phenyl diisooctyl phosphite and phenylnoisodenorphosphite, and triisooctyl phosphite. , trialkylphosphites such as tristearylphosphite, and other tetrakis(2,4-diL-
butylphenyl)-4,4°-biphenylenephosphonite, bis(2,4-di-butylphenyl)pentaerythritol-di-phosphite, his(2,6-)t
Examples include -butyl-methylphenyl)pentaerythritol-di-phosphite.

Substituted phenol derivatives and i v! i+ and the phosphoric acid compound are added in proportions of 0001 to 5% by weight and 0.001 to 5% by weight, respectively, based on the saponified ethylene-vinyl acetate copolymer. Such an addition m results in falsification of long-run properties.

Finally, the resin composition contains 115-250 ppm of alkali metal and 5-5000 ppm of phosphorus based on the saponified material.
Preferably, 20 to 1,000 ppm of light must be contained.

If the alkali metal or phosphorus content is below the lower limit, the effect of improving interlayer adhesion will be poor; if the alkali metal content is above the upper limit, the molded product will be colored, and if the phosphorus content is above the 2nd limit, the formation of stains on the film will be noticeable. .

There are no particular limitations on the method for producing the resin composition, and in short, ethylene-
In the saponified vinyl acetate copolymer, alkali metal secondary
Alternatively, a tertiary phosphate or, if necessary, an alkali metal carboxylate, a substituted phenol derivative, and a phosphorous acid compound may be contained.

A common method is to mix the salt into powder, pellets, or granules of saponified ethylene-vinyl acetate copolymer. The mixing means adds the above-mentioned additive to the saponified material in the form of any color such as powder, solution, or dispersion.

In addition, the additives are not necessarily limited to the above-mentioned method, but may be added at any stage during the production of saponified ethylene-vinyl acetate copolymer, that is, during polymerization, saponification, post-treatment, and drying. This is possible by making sure that it is contained in a predetermined amount.

The composition obtained in this way has a wide range of uses such as molded products, adhesives, and paints.The composition of the present invention is often used for molded products, and can be melted and mixed into pellets, films, sheets, containers, etc. Senii ([, molded into rods, tubes, various molded products, etc.)

These pulverized products (when reusing recovered materials, etc.) or pellets are often used for melt molding again. It is also possible to uniaxially or biaxially stretch the obtained film or sheet. As the melt-kneading method, extrusion molding (T-die extrusion, inflation extrusion, blow molding, melt spinning, profile extrusion, etc.) and injection molding are mainly employed. The melt-kneading temperature is often selected from a range of 170 to 270°C. The above-mentioned injection molding method includes two-color molding, inno-ex-combination molding, etc., and molded products with good dimensional accuracy can be obtained. During such molding, two saponified ethylene-vinyl acetate copolymers with various ethylene contents and degrees of saponification are used.
Of course, it is possible to use more than one species in combination. In addition, in melt molding, in addition to the saponified ethylene-vinyl acetate copolymer, plasticizers (polyhydric alcohols, etc.), stabilizers, surfactants, crosslinking substances (epoxy compounds, polyvalent metal salts, inorganic or organic polybasic acids or salts thereof), fillers, colorants, fibers as reinforcing agents (glass fibers, carbon fibers, etc.), etc. can be blended in appropriate amounts. In addition, other thermoplastic resins can be blended in appropriate amounts, and such other thermoplastic resins include polyolefins (polyethylene, polypropylene, ethylene-propylene copolymers, ethylene-propylene-diene copolymers, ethylene and carbon atoms). 4 or more”-α
- copolymers with olefins, ethylene-vinyl acetate copolymers, ethylene-acrylic acid ester copolymers, ionomer polybutenes, polypenteno, etc.) or polyolefins, polyamides, and polyolefins obtained by graft-modifying these with unsaturated carboxylic acids or derivatives thereof. Examples include vinyl chloride, polyvinylidene chloride, polyester, polystyrene, polyacrylonitrile, polyurethane, polyacetal, polycarbonate, and melt-moldable polyvinyl alcohol resin. When extrusion molding is used as a melt-kneading method, it is not only necessary to mold only the saponified ethylene-vinyl acetate copolymer, but also to melt-knead the thermoplastic resin separately and use a compiling adapter or die. They are often joined together and coextruded inside the die or outside the die. Moreover, the composition of the saponified ethylene-hinyl acetate co-merchandising material can be extrusion coated onto a plastic film, metal foil, or base film such as Ginato. In the case of coextrusion, other thermoplastic resins such as those mentioned above in the case of thermoplastic resin compounding are used, and in the case of extrusion coating, cellophane, polypropylene, polyamide, and polyester are used as plastic active materials. , films and sheets of polyacetal, polycarbonate, polystyrene, polyvinyl chloride, etc. (these may be -axially or biaxially stretched, and one or both sides may be coated with polyvinylidene chloride resin); Examples include laminate films.

The composition of the present invention can best exhibit its characteristics because the polyolefin layer (Δ)/unsaturated carboxylic acid-modified polyolefin adhesive layer (B)/saponified ethylene-vinyl acetate copolymer layer (C) has a basic groove structure. This is the case when manufacturing a laminate.

In the present invention, examples of the polyolefin layer (A) include low-density, medium-density, and high-density polyethylene, ionomers, edylenopropylene copolymer, crystalline polypropylene, polybutene, and the like.

The adhesive layer (B) is a modified polyolefin resin obtained by grafting an unsaturated carboxylic acid compound to a polyolefin resin in an amount of about 001 to 25% by weight. Here, the polyolefin resin refers to polyethylene, polypropylene, and ethylene-vinyl acetate copolymer. Unsaturated carboxylic acid compounds include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid, or their alkyl esters, acrylic acid amide, maleic acid diamide, and fumaric acid N and N. - Not only unsaturated carboxylic acids such as noamide, maleic imide, maleic anhydride, zinc acrylate, ammonium acrylate, and sodium methacrylate, but also their anhydrides, alkyl esters, amides,
Contains imide, salt, etc. Grafting is a method in which polyolefin resin is mixed with an unsaturated carboxylic acid compound and a radical generator, and then melted and reacted. A method of carrying out a grafting reaction by dissolving i13 or dissolving it and adding thereto an unsaturated carboxylic acid compound, a radical generator, and if necessary a small amount of radically polymerizable 7-mer, and other methods using ionizing radiation or ultraviolet irradiation. , well-known lazy crafting methods are used, such as methods that utilize oxygen, ozone, heat, and shearing force.

Polyolefin layer (A), adhesive layer (B) and ethylene-
A multilayer structure consisting of a vinyl acetate copolymer layer (C) can be obtained by simultaneously melt-extruding (A), (B) and (C) and contacting them inside or outside the goo, or by the method of (C) film. Melt-coat (I3) on the film and then melt-coat (A), or (C) film with (Δ) and ([1)
A method of melt-coating (A) with (B) and then melt-coating (C) at the same time, or a method of melt-coating (B) and (C) on a film of (A) at the same time. A method of melt coating at the same time, a method of stacking (C) on the (B) side of a two-layer film consisting of (A) and (B), applying pressure and laminating, or a method of laminating a two-layer film consisting of (13) and (C). A method of laminating (A) on the (B) side of the layer film by heating and pressing, a two-layer film consisting of (A)/(B> and (B)
)/(C) and (B) are stacked so that they are in contact with each other, and the two-layer films are laminated by heating and pressing. Moreover, it is not limited to the three-layer structure consisting of (A)/(B')/(C), but also (A)/(B)/(C)/(B)/(A)(c)/(B
)/(A)/(B)/(c)(A)/(B)/(C
) / (B ) / (A / (B) / (c) and other multilayer structures, (Δ) / (B) / (C) are the basic structures, and on top of this are resin films, paper, and aluminum. Structures with added foil or the like can also be created.

[Function] Since the composition of the present invention has good adhesion to unsaturated carboxylic acid-modified polyolefins, it is possible to advantageously produce multilayer structures with good long-run properties using them, and such multilayer structures Things include food, luxury items, seasonings, medicines,
Films and sheets for packaging industrial chemicals, aroma-containing substances, etc.
Suitable for use as bags and containers.

[Example] Next, the composition of the present invention will be specifically explained by giving examples. Below, "%" and "part" are based on Tamamushi standards unless otherwise specified. Note that all water used was ion-exchanged water.

Example 1 Ethylene-Ill'1. containing 140 mol% ethylene. 1,000 parts of a 40% methanol solution of acid vinyl copolymer was placed in a pressure reactor and heated to 110° C. with stirring. Subsequently, 40 parts of a 6% methanol solution of sodium hydroxide and 2,500 parts of methanol were continuously charged, and a saponification reaction was carried out for 25 hours while distilling by-product methyl acetate and excess methanol from the system to remove the vinyl acetate component. A saponified ethylene-vinyl acetate copolymer having a saponification degree of 990 mol% was obtained.

Adding 450 parts of 30% water-containing methanol to the saponified liquid and distilling off excess methanol U, resin concentration 39%
A water/methanol (composition ratio 3/7) solution was prepared.

A water/methanol mixture of the saponified ethylene-vinyl acetate copolymer at a temperature of 50° C. was poured into the water/methanol mixture through a nozzle with a 4 mra hole diameter. ! Water/methasol (mixing ratio 9/1) coagulation liquid pig (il
I O (lnm, length 1000mm, depth 100mm
) and extrude it into strands.

After the coagulation is completed, the strand I-shaped material is passed through a take-up roller (linear speed 2 m/min) attached to the end of the coagulation liquid tank, and
A white, porous pellet with a diameter of 4 mm and a length of 4 mm was produced by cutting the I-shita.

Next, 100 parts of the pellet was immersed in 300 parts of 3% acetic acid aqueous solution, stirred at 30° C. for 1 hour, and washed twice.

After separating the slurry, the obtained pellets were mixed with 300 parts of IJ water to form a slurry, and the slurry was washed three times with stirring at 30° C. for 1 hour, and then separated.

Furthermore, the pellet was immersed in 200 parts of 0.015% dipotassium hydrogen phosphate aqueous solution and stirred at 30° C. for 4 hours.

The slurry was filtered and dried.

To the saponified product, 0.1% of 1.3.5-)lynchyl-2,4,6)lis(3,5-1-t-butyl-4-hydroquinobenzyl)benzene and bis(2,6- (di-t-butylphenyl)pentaerythritol-di-phosphite
0.01% was added to each.

The composition thus obtained contained a saponified ethylene-vinyl acetate copolymer with an ethylene content of 440 mol% and a degree of saponification of 99.0%, and a potassium metal content of 155 p with respect to the saponified product.
pm, sodium metal content 2 ppm, phosphorus content 1
The composition was 30 ppm.

The method for quantifying alkali metals and the method for quantifying phosphorus are as follows.

(Alkali metal) A dried sample of 809 was accurately weighed, and about 109 of it was placed in a platinum evaporating dish with a constant weight, and carbonized with an electric heater. Next, I heated it with a gas burner and baked it until there was no smoke.

The platinum evaporation dish was placed in an electric furnace at about 400°C, most of it covered with a magnetic crucible lid, and the stomach was gradually heated to 700°C.

It was held at 700°C for 3 hours to completely incinerate it.

Special grade hydrochloric acid 2IIIl in a platinum crucible! and 31+1 liters of pure water were added and heated with an electric heater to dissolve. 50ml of the above solution
The sample was poured into a volumetric flask with pure water, and further pure water was added up to the marked line to prepare a sample for atomic absorption spectrometry.

Atomic absorbance was measured using a separately prepared standard solution (alkali metal 1 ppm, hydrochloric acid 0.5N) as a control solution.
The amount of sodium metal was determined from the ratio of absorbance.

The measurement conditions are as follows.

Equipment: Hitachi 180-30 atomic absorption/tip spectrophotometer Wavelength: 589. Onm (sodium) 766.5n
w (potassium) Frame: Acetylene-air (determination of phosphorus) Molybdenum blue (ascorbic acid) spectrophotometry according to JIS K-0102 was used.

However, the samples were prepared according to the following procedure.

1. Accurately weigh 1 g of the sample and put it into a 300 ml Kjeldahl flask. 2. Add 5 ml of pure water and gradually drop in about 15 ml of concentrated sulfuric acid. 3. Heat the Kjeldahl flask with a heater and add water until just before drying. Remove the sulfuric acid 4. After cooling, add about 5 ml of concentrated sulfuric acid, cover the mouth of the Kjeldahl flask with a funnel, and heat it again. 5. After white smoke begins to fill the Kjeldahl flask, gradually add a few drops of concentrated sulfuric acid. In addition, the inside of the Kjeldahl flask is NO.
After the mixture turns brown with the X gas, stop adding nitric acid and continue heating until white smoke appears. Repeat the operation of dropping nitric acid under heating several times 6. After the solution in the Kjeldahl flask becomes colorless to yellow-green and transparent, stop dropping the nitric acid and expel the remaining nitric acid and residual water in the solution 7. Kjeldahl flask Remove the funnel covering the mouth of the funnel and expel the sulfuric acid by igniting heat until the remaining volume is 2 to 3 ml.
Manufacture of laminate (A) Low-density polyethylene with density 0, 9249/cc, melt index 3.0 (B) Edgeless vinyl acetate copolymer with vinyl acetate content 9% Modified ethylene-vinyl acetate copolymer (C) with 0.6% maleic anhydride grafted onto it. It is supplied to an extruder (Flufflight screw) and melted and kneaded.
The molten resin was bonded to the shell in a gooey at 0°C, extruded through a gouey (Goui I + 400 + nm), and cooled to 50°C at a film take-up speed of 5 m/min. A three-layer laminate with a7 torsion was obtained.

Outer layer (A) 407z Intermediate layer ([3) 30μ Inner layer (C) 30ti A test piece of 15 mm inside and approximately 300 mm in length was cut from this film in the MD direction, and the same test piece was aged while peeling approximately 501 pieces at a time. Changes in adhesive force between (B) and (c) were tracked.

As a control example I, a saponified product of vinyl acetate co-merchandising, which was not treated with dipotassium hydrogen phosphate (C
) The same experiment was performed except that it was used as These results are shown in Table 1. In addition, as a control example 2, a composition in which neither a substituted phenol derivative nor an organic phosphorous acid compound was used, as a control example 3, a composition in which only a substituted phenol derivative was used, and as a control example 4, (f Experiments were conducted using only acid compounds.

The results are shown in Table 1. 4-0 No. 1712 (t'F-) Melt ratio 1y ratio is the melt viscosity (η,...
η4.4. ηso) was measured and expressed as a ratio to the melt viscosity (η5) when maintained at the same temperature for 5 minutes. [Measurement conditions: Koka type flow tester nozzle I mmX I Om+n, load 10 to 97 cm”) (Note) The delamination strength was determined by leaving the above test piece in a 20°C 165% R11 atmosphere for a specified period of time. Using Autograph S-100 type, distance between chucks 30 mm% tensile speed 300 mm/
The measurement was performed by performing T-shaped peeling at min.

The same experiment as in Example I was conducted using the following as the adhesive layer (B). The results are shown in Table 2.

Note that the values in parentheses are the values when the use of secondary phosphate is omitted.

Actual example 2 Contains vinyl acetate! lt8・76 Z) Ethylene-hinyl acetate jti 11t (4) modified polyurethane vinyl acetate with 13% grafted furyic anhydride 11% maleinoic acid
Grafted modified polyester resin Example 1 Acetic acid heel content: n 36% polyester/-hinyl acetate J
(The polymer was modified with 7 g of 21 parts of acrylic acid.

Hinyl acetate copolymer Example 5 Vinyl acetate containing UIt 28%]) - Tireno Hinyl acetate co-mercury grafted with c1tonic acid 03% t+f dimodified ethylene vinyl acetate co-mercure Table 2 Example 6- 12. Comparative Examples 5 to 8 The saponified ethylene vinyl acetate (polymer saponified pellet) washed with acetic acid aqueous solution and water in Example 1 was then separated by tI and dried.

After spraying 0.3 parts of an aqueous solution containing a prescribed amount of salt as shown in Table 3 onto 100 parts of the pellets, the pellets were re-pelletized under the following conditions, mixed and dried at the same time to produce a resin composition, and treated in the same manner as on the same side. A laminate was obtained.

Extruder 10m1φ (with head) Suririko Dalmage type Rotation speed 80rpm Norinder Maximum temperature: 220°C Heno F' 7! ! IJ mouth ・210℃♀
＋'jri is shown in Table 3. Simo 4-0 ((1, substituted] J-nol derivative, FJI phosphorus compound) used is as follows. Examples 13 to 14 In place of the saponified ethylene-vinyl acetate copolymer in Example 1, a saponified product with an ethylene content of 30 mol% and a saponification degree of 995 mol% (Example 13), an ethylene content of 44 mol%, and a saponification degree Example except that 990 mol% saponified product (Example 14) was used! conducted the same experiment.

However, as a substituted fer derivative, 113 in Example ■3
-Tris(2-methyl-4-hydroquine-5-t-butylphenyl)butane was used at 0.2%, and in Example 14 it was 10%, and as the organic phosphorous acid compound in Example 13, bis(2,4 -di-t-butylphenyl)pentaerythritol-nophosphite 02%, in Example 14 1
．． 0% of each was used.

The peel strength (g/15mm) between (B) and (C) was 1300 (after 1 hour) for the implementation f@I I3 and 1350 (after 1 hour).
1 day later), 1450 (3 days later), Example +4 was 950
(1 hour later), 990 (1 day later), 1040 (3 days later)
Met.

ηto/η6. η4o/η6. η6°/η is 1.1 in Example 13, respectively! , 1.1.2, Example 14 is 1
．． 1, l 1.1.1.

[Effects] The saponified ethylene-vinyl acetate copolymer composition of the present invention exhibits good adhesion to unsaturated carboxylic acid-modified polyolefins and has excellent viscosity stability during melt molding.

Patent applicant Nippon Gosei Kagaku Kogyo Co., Ltd. Six points of the invention: Resin composition supplementer 1999 7JJ31 5. Contents of amendment (1) "Sodium" and "alkali" at the end of page 18 of the specification No corrections.

2) r(10), 1 of comparative example 6 in Table 3 on page 27 of the specification calendar
Correct 4-ru to r(20)J.

of

Claims (1)

[Claims] A saponified ethylene-vinyl acetate copolymer having an ethylene content of 20 to 60 mol% and a degree of saponification of the vinyl acetate component of 95 mol% or more is added with an alkali metal secondary or tertiary phosphate, a substituted phenol derivative, and an organic substituent. Contains a phosphoric acid compound, and the ratio of alkali metal to saponified product is 15 to 250.
ppm, a resin composition in which the proportion of phosphorus is 5 to 5000 ppm.