JPH101570A - Resin composition and its production and use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition which is scarcely influenced by repeated heat history occurring when scraps are returned by mixing a polyolefin resin with a saponified ethylene/vinyl acetate copolymer, a hydrotalcite compound, a higher fatty acid and a phosphoric acid. SOLUTION: This composition comprises a polyolefin resin (A), a saponified ethylene/vinyl acetate copolymer (B), a hydrotalcite compound (C), an 8C or higher fatty acid (D) and a phosphoric acid and/or an alkali (alkaline earth) metal hydrogenphosphate (E). The composition is produced by preparing a composition (I) prepared by mixing components B and E with each other and a composition (II) prepared by mixing components C and D with each other and melt-blending component A and compositions (I) and (II). A multifunctional laminate is formed by using at least one layer made from the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a polyolefin resin and an ethylene-vinyl acetate copolymer having improved long-run properties during melt molding and improved heat resistance (retention of physical properties against repeated thermal histories during regrind). The present invention relates to a resin composition mainly comprising a compound (hereinafter abbreviated as EVOH), a production method thereof, and a use thereof.

[0002]

2. Description of the Related Art Conventionally, various molded products have been obtained by melt-molding a mixture of a polyolefin-based resin such as polyethylene and polypropylene and EVOH. Obtaining physical properties, and scraps and edges generated during the production of a laminated structure of a polyolefin-based resin and EVOH, or recycling (scrap return or regrind) by collecting defective products. You. The industrial utility is more pronounced when implemented only on an industrial scale.
However, when a molded product of a film or a sheet is to be produced by melt molding or the like using the resin mixture as described above, the composition may cause gelation at the time of molding, or may be a heat-colored resin called carbonized or carbonized. There is a problem that the resin adheres to the inside of the extruder and cannot be melt-molded continuously for a long period of time, that is, the so-called long-run property is poor. Further, since the gelled product at the time of melting is often mixed into the molded product, it becomes a major cause of defects of the molded product such as generation of fish eyes in film molding, for example, and the quality of the product is inevitably degraded.

[0003] Such a problem has a particularly significant significance in the reuse of waste products in the production of a laminated structure of a polyolefin resin and EVOH as described above. That is, recently, polyolefin resins and EVOH are rarely used alone in applications such as films, sheets, containers, and bottles for packaging. Resin and EV
Two layers of OH with an adhesive resin layer interposed as necessary
It is often used as a laminated structure having four or more layers, and the production of such a laminated structure usually involves a large amount of scraps and edges of the structure, and furthermore, the occurrence of defective products. It is necessary to recycle.

[0004] Of course, such a long-run property may cause a problem even when EVOH or polyolefin-based resin is used alone, but it is a peculiar phenomenon that occurs remarkably when both coexist. The gelled material is very often clogged in the screen mesh,
Alternatively, the extruder must be disassembled and the screen mesh or the screw must be cleaned each time the resin melt adheres to the screw, so that a very troublesome operation is required.

[0005] As an attempt to improve the above disadvantages, Japanese Patent Application Laid-Open
-199040 discloses that polyolefin-based resins and E
It is disclosed that a salt or oxide containing at least one element selected from Group I, Group II, and Group III of the periodic table coexists in a mixture of VOH. According to the description of the examples in the publication, it is recommended that the above salt or oxide is first blended in advance with EVOH, and after sufficient kneading, a polyolefin resin is blended and melt molded. It is not always possible to obtain satisfactory results by the method, and the effect of improving long-run property can only be achieved by continuous melt molding for at most about 48 hours. In the case of melt-molding on an industrial scale, continuous operation is required for a longer period. Needless to say, it is as advantageous as possible. In order to solve the above-mentioned problems, the present applicant has melt-blended a specific amount of a hydrotalcite-based compound to a specific polyolefin-based resin in advance, and then melt-blended EVOH. 179530).

[0006]

However, in such a method for manufacturing a molded product, although the long-run moldability is sufficiently improved, the performance change of the resin composition due to the repeated heat history at the time of the scrap return (foreign matter) Generation, decrease in strength, etc.) are not sufficiently considered, and a resin composition which is less affected by heat history is desired.

[0007]

[Means for Solving the Problems] Accordingly, the present inventor has proposed:
In view of the above circumstances, as a result of intensive studies, polyolefin resin (A), EVOH (B), hydrotalcite compound (C), higher fatty acid having 8 or more carbon atoms (D) and phosphoric acid and / or It has been found that a resin composition comprising a hydrogen phosphate (E) of an alkali (earth) metal is less affected by repeated thermal histories at the time of scrap return and can maintain good physical properties, thereby completing the present invention. Reached.

Further, in producing the above resin composition, a composition (I) in which EVOH (B) and phosphoric acid and / or an alkali (earth) metal hydrogen phosphate (E) are mixed in advance, and Composition (II) in which a talcite compound (C) and a higher fatty acid having 8 or more carbon atoms (D) are mixed.
After preparing (A), (A), (I) and (II) are melt-mixed to obtain a good resin composition aimed at by the present invention, and the resin composition of the present invention is a polyolefin-based resin composition. Resin (a) layer / resin composition layer of the present invention / adhesive resin layer / EVOH (b) layer, polyolefin resin (a)
Layer / resin composition layer of the present invention / adhesive resin layer / EVOH
(B) layer / adhesive resin layer / polyolefin resin (a)
Layer, polyolefin resin (a) layer / resin composition layer of the present invention / adhesive resin layer / EVOH (b) layer / adhesive resin layer / resin composition layer of the present invention / polyolefin resin (a)
The inventors have found that the present invention is also useful for a laminate having a structure such as a layer, and have completed the present invention.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. Although the polyolefin resin (A) of the present invention is not particularly limited, it is produced using a Ziegler type catalyst and contains 1 to 300 ppm, preferably 3 to 150 ppm of chlorine originating from the catalyst. By using a resin, the effect of the present invention can be more remarkably obtained. Such polyolefin resin (A)
Examples of high-density, medium-density, low-density polyethylene, polypropylene, polybutene, homopolymers such as polypentene, ethylene-propylene copolymer, mainly ethylene or propylene 1-butene, 1-hexene and the like carbon number A copolymer with about 2 to 20 α-olefins,
Furthermore, the content of olefin such as ethylene or propylene is 9
Olefin-vinyl acetate copolymer having a composition relatively close to polyolefin of 0 mol% or more, olefin-
A (meth) acrylic acid ester copolymer or the like, or a homopolymer or a copolymer of the above-mentioned polyolefin resin obtained by graft modification with an unsaturated carboxylic acid or the like can be used singly or in combination of two or more. Of these, especially 210 ° C,
The melt index (MI) at 2160 g is 0.2.
1-15 g / 10 min polyethylene resin or 0.2-
When the polypropylene resin is used at 12 g / 10 minutes, the problem of gelation easily occurs, and the effect of the present invention is excellent.

The EVOH (B) used in the present invention has an ethylene content of 20 to 80 mol%, preferably 25 to 7 mol%.
0 mol%, saponification degree of vinyl acetate part 90 mol% or more,
Preferably, those having a composition of 95 mol% or more are mentioned. If the ethylene content is less than 20 mol%, the thermal stability is poor, and the melt moldability is reduced. If the ethylene content is more than 80 mol%, the oxygen barrier property is reduced, so that the practicality is poor.
On the other hand, if the saponification degree of the vinyl acetate portion is less than 90 mol%, the thermal stability is poor and the physical properties such as oxygen barrier property, oil resistance, water resistance and the like are inferior. EVOH is ethylene and vinyl acetate (or saponified vinyl alcohol), as well as unsaturated carboxylic acids or their esters or salts, unsaturated sulfonic acids or their salts, (meth) acrylamide, (meth) acrylonitrile, propylene, A third component such as an α-olefin such as butene, α-octene and α-octadecene, and a vinyl ester other than vinyl acetate may be contained in a small amount of about 10 mol% or less.

The above-mentioned polyolefin resin (A)
And the hydrotalcite-based compound (C) blended with EVOH (B) are represented by the general formula: MxAly (OH) _{2x + 3y-2z} (E) z
AH ₂ O (where M is Mg, Ca or Zn, E is CO ₃ or H
PO _4, x, y, z are positive numbers, a is a compound represented by 0 or a positive number), _{specifically, Mg 4. 5 Al 2 (} OH) 13 CO 3 · 3.5H 2
_{O, Mg 5 Al 2 (OH} ) 14 CO 3 · 4H 2 O, Mg 6 Al 2 (OH)
₁₆ CO ₃ .4H ₂ O, Mg ₈ Al ₂ (OH) ₂₀ CO ₃ .5H ₂ O,
Mg ₁₀ Al ₂ (OH) ₂₂ (CO ₃ ) ₂ .4H ₂ O, Mg ₆ Al ₂ (OH)
_{16 HPO 4 · 4H 2 O,} Ca 6 Al 2 (OH) 16 CO 3 · 4H
₂ O, Zn ₆ Al ₆ (OH) ₁₆ CO ₃ .4H ₂ O and the like. Further, not limited to the above _{example, Mg 2 Al (OH) 9} · 3H 2
The same effect can be expected even if the chemical formula is not clearly shown as in the case where a part of OH in O is replaced by CO ₃ or HPO ₄ , or even if the crystallization water is removed (a = 0). .
In particular, among these, compounds in which M is Mg and E is CO ₃ show the most remarkable effects.

Further, a hydrotalcite compound (C)
It is also possible to use a hydrotalcite-based solid solution represented by the following general formula. ^{_{[[(M 1 2+) y1 (M}} 2 2+) y2 ] ^{_{1-x M x 3+ (OH}} ) 2 A n- x / n
_{· MH 2 O] (M 1} 2+ in the formula is Mg, Ca, at least one metal selected from Sr and Ba, M ₂ ²⁺ is Zn, Cd, Pb, Sn
M _x ³⁺ is a trivalent metal, A ⁿ⁻ _{x / n} is an n-valent anion, and x, y 1, y 2, and m are each 0 <x ≦ 0.
5,0.5 <y1 <1, y1 + y2 = In 1, 0 ≦ m <positive number represented by 2) the general formula, Mg, Ca is preferable as M ₁ ^2+, M ₂ as the ²⁺ Zn , Cd, and M _x ³⁺
Examples thereof include Al, Bi, In, Sb, B, Ga, and Ti, but Al is practical. Further, A as the ^{_{n-, CO 3 2-, OH -}} , HCO 3 -, salicylate, citrate, ^{_{tartrate, NO 3 -, I -,}} (OOC
—COO) ²⁻ , ClO ⁴⁻ , CH ₃ COO ⁻ , CO ₃ ²⁻ ,
(OOCHC = CHCOO) ^2- , [Fe (CN) ₆ ] ^4- , and CO ₃ ^2- or OH ^- is useful.

[0013] Specific examples of such hydrotalcite solid _{solution, [Mg 0. 75 Zn 0.25} ] 0.67 Al 0.33
_{(OH) 2 (CO 3)} 0.165 · 0.45H 2 O, [Mg 0. 79 Zn
_0.21 ] _0.7 Al _0.3 (OH) ₂ (CO ₃ ) _0.15 , [Mg _1/7
Ca _3/7 Zn _3/7 ] _0.7 Al _0.3 (OH) ₂ (OOCHC =
CHCOO) _0.15 · 0.41 H ₂ O, [Mg _6/7 Cd _1/7 ]
_0.7 Al _0.3 (OH) ₂ (CH ₃ COO) _0.3 · 0.34 H ₂ O,
[Mg _5/7 Pd _2/7 ] _0.7 Al _0.30 (OH) ₂ (CO ₃ )
_{0.15 · 0.52H 2 O, [Mg} 0. 74 Zn 0.26] 0.68 Al
_{0.32 (OH) 2 (CO 3} ) 0.16, [Mg 0. 56 Zn 0.44]
_0.68 Al _0.32 (OH) ₂ (CO ₃ ) _0.16 · 0.2 H ₂ O, [M
_{g 0. 81 Zn 0.19] 0.74} Al 0.26 (OH) 2 (CO 3)
_{0.13, [Mg 0. 75 Zn} 0.25] 0.8 Al 0.20 (OH)
_{2 (CO 3) 0.10 · 0.16H} 2 O, [Mg 0. 71 Zn 0.29]
_{0.7 Al 0.30 (OH) 2 (} NO 3) 0.30, [Mg 0. 71 Zn
_0.29 ] _0.7 Al _0.30 (OH) ₂ (OOCHC = CHCO
_{O) 0.15, [Mg 0.} 14 Ca 0.57 Zn 0.28] 0.7 Al
_{0.30 (OH) 2. 3 ·} 0.25H 2 O , and the like, [Mg _{0. 75}
Zn _0.25 ] _0.67 Al _0.33 (OH) ₂ (CO ₃ ) _0.165・ 0.4
_{5H 2 O, [Mg 0.} 79 Zn 0.21] 0.7 Al 0.3 (OH)
₂ (CO ₃ ) _0.15 , [Mg _6/7 Cd _1/7 ] _0.7 Al _0.3 (O
H) ₂ (CH ₃ COO) _0.3 · 0.34 H ₂ O, [Mg _5/7 Pd
_2/7 ] _0.7 Al _0.30 (OH) ₂ (CO ₃ ) _0.15・ 0.52H ₂ O
Is preferably used.

The hydrotalcite-based compound (C)
Is the total amount of polyolefin resin (A) and saponified ethylene-vinyl acetate copolymer (B) (A +
B) The amount is preferably 0.00001 to 10 parts by weight, more preferably 0.0001 to 1 part by weight, per 100 parts by weight. When the amount is less than 0.00001 part by weight, the effect of the addition is poor. On the contrary, when the amount exceeds 10 parts by weight, the physical properties of the molded product, particularly transparency, surface smoothness, flexibility, impact resistance, etc., are significantly reduced. Is not preferred. In the present invention, a higher fatty acid (D) having 8 or more carbon atoms and a hydrogen phosphate (E) of phosphoric acid or an alkali (earth) metal are further added to the resin composition comprising (A) to (C). The higher fatty acids having 8 or more carbon atoms (D) include lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, and oleic acid. , Higher fatty acids such as capric acid, behenic acid, linoleic acid and the like, alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as magnesium salt, calcium salt and barium salt, and zinc metal salt etc. used. Among these, stearic acid, oleic acid, lauric acid or metal salts thereof are particularly remarkable in terms of effect.

The amount of the higher fatty acid having 8 or more carbon atoms (D) is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 8 parts by weight, per 100 parts by weight of the hydrotalcite-based compound (C). Parts by weight are preferred. If the amount is less than 0.1 part by weight, heat resistance (retention of physical properties against repeated thermal histories at the time of regrind) becomes insufficient, and if it exceeds 10 parts by weight, the mechanical strength of the molded product decreases. Is not preferred. Examples of the phosphoric acid or the hydrogen phosphate of an alkali (earth) metal (E) include disodium hydrogen phosphate,
Alkali metal hydrogen phosphate such as sodium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, magnesium hydrogen phosphate, magnesium dihydrogen phosphate, calcium monohydrogen phosphate, calcium dihydrogen phosphate, etc. And alkaline earth metal hydrogen phosphates. Specific examples thereof include disodium hydrogen phosphate, dipotassium hydrogen phosphate,
Magnesium dihydrogen phosphate, dicalcium hydrogen phosphate,
Phosphoric acid is preferably used.

The amount of the phosphoric acid and / or alkali (earth) metal hydrogen phosphate (E) to be added is ethylene-
0.0001 to 0.05 part by weight (1 to 50 parts by weight) of phosphoric acid group per 100 parts by weight of the saponified vinyl acetate copolymer (B).
0 ppm), more preferably 0.0005 to 0.03
Part by weight (5-300 ppm) is preferred. If the amount is less than 0.0001 parts by weight (1 ppm), the heat resistance (retention of physical properties against repeated thermal history during regrind) becomes insufficient, and conversely 0.05 parts by weight (500 pp).
When the value exceeds m), the long-run processability is undesirably reduced.

The resin composition of the present invention comprises the above-mentioned (A)
To (E), and the method of compounding is not particularly limited. However, in order to remarkably obtain the effects of the present invention, EVOH (B) and phosphoric acid and / or alkali (earth) metal are required in advance. Composition (I) mixed with hydrogen phosphate (E)
And a composition (II) in which a hydrotalcite-based compound (C) and a higher fatty acid having 8 or more carbon atoms (D) are mixed in advance, and then (A), (I) and (II) are melt-mixed. A method for obtaining the resin composition of the present invention is preferable, and a method in which (A) and (II) are melt-mixed in advance and then (I) is melt-mixed is preferable.

The mixing means may be in any mode. For example, in mixing EVOH (B) with phosphoric acid and / or alkali (earth) metal hydrogen phosphate (E), phosphoric acid and / or alkali (earth) metal hydrogen phosphate (E) Is dissolved in a solvent (eg, water) to form a solution, and then the solution is impregnated with EVOH (B), or EVOH (B) is mixed with a phosphoric acid and / or an alkali (earth) metal hydrogen phosphate (E). ) Is directly melt-blended or dry-blended, and the method of obtaining the composition (I) by the former method of impregnation can be suitably used. On the other hand, a composition (II) in which a hydrotalcite-based compound (C) and a higher fatty acid having 8 or more carbon atoms (D) are similarly mixed with a Henschel mixer or a tumbler to obtain a composition (II), Polyolefin resin (A)
A method of melt-mixing the pellets and powders of the above, and further melt-mixing the composition (I), and further comprising a step of mixing the layer comprising the composition (I) with the mixture of the composition (II) and the polyolefin resin (A). And a method of melt-mixing two or more laminated structures again. The latter method includes, for example, a method of melting and mixing crushed products (so-called regrind) such as dust, edges, and defective products which are usually generated during the production of the laminate structure.

The resin composition of the present invention thus obtained is
Used for various melt molded products. In the production of such a melt-formed product, the temperature condition during melt-molding is about 160 to
The temperature is desirably 280 ° C. When molding, known materials such as reinforcing materials such as glass fiber and carbon fiber, lubricants such as low molecular weight polyethylene, low molecular weight polypropylene, paraffin, ethylene bisamide type, epoxy type, fillers, coloring agents, stabilizers, foaming agents, etc. May be appropriately compounded. In addition, polyolefin resins (A) and E
VOH (B) may be preliminarily blended with an appropriate amount of a modifying thermoplastic resin such as polyamide, polyester, polyvinyl chloride, or polyacrylic resin.

As the melt molding method, any molding method such as an injection molding method, a compression molding method, and an extrusion molding method can be adopted. Among these, examples of the extrusion molding method include a T-die method, a hollow molding method, a pipe extrusion method, a linear extrusion method, a profile die extrusion method, an inflation method, and a melt spun method. The shape of the molded product obtained by the method of the present invention is arbitrary, and the film, sheet, tape, bottle, pipe, filament,
Not only the extruded product having an irregular cross-section but also a laminate of the resin and another resin is important. As the mating resin for lamination, polyolefin resin (a), EVOH (b), nylon-6, nylon- Polyamide resins such as 6,6 and vinylidene chloride resins are often used. Of course, other ordinary thermoplastic resins, such as polycarbonate, vinyl chloride resin, acrylic resin, styrene resin, vinyl ester resin, polyester resin and polyester elastomer, polyurethane elastomer, chlorinated polyethylene, chlorinated polypropylene There is nothing wrong with it. Such polyolefin resin (a) and EVOH
(B) shows the polyolefin resin (A) and EV
The same thing as OH (B) can be used.

The specific layer structure of the laminate is as follows: polyolefin resin (a) layer / resin composition layer of the present invention / adhesive resin layer / EVOH (b) layer, polyolefin resin (a) layer / Inventive resin composition layer / adhesive resin layer / EV
OH (b) layer / adhesive resin layer / polyolefin resin (a) layer, polyolefin resin (a) layer / resin composition layer of the present invention / adhesive resin layer / EVOH (b) layer / adhesive resin layer / Resin composition layer of the present invention / Polyolefin-based resin (a) layer and further resin composition layer of the present invention / Adhesive resin layer / EVOH (b) layer, Resin composition layer of the present invention / Adhesive resin layer / EVOH (b) layer / adhesive resin layer / EVOH
(B) layer, resin composition layer of the present invention / adhesive resin layer / EV
OH (b) layer / adhesive resin layer / polyolefin resin (a) layer, resin composition layer of the present invention / adhesive resin layer / EV
OH (b) layer / adhesive resin layer / resin composition layer of the present invention /
And a polyolefin-based resin (a) layer.

As the adhesive resin used for the adhesive resin layer, a known adhesive can be used, for example, a resin having a density of 0.1 modified with an unsaturated carboxylic acid or an anhydride thereof.
An ethylene-α-olefin copolymer of 86 to 0.95 g / cm ³ is preferable, and the polyolefin resin (A
Alternatively, it can be obtained by copolymerizing or graft-modifying the same resin as in a) with an unsaturated carboxylic acid or an anhydride thereof. Of course, the unmodified ethylene-α-olefin copolymer Also included are blends of acids or anhydrides. Examples of unsaturated carboxylic acids or anhydrides thereof include maleic acid, maleic anhydride, fumaric acid, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, citraconic acid, hexahydrophthalic anhydride and the like. Is preferably used. The amount of the unsaturated carboxylic acid or anhydride contained in the ethylene-α-olefin copolymer at this time is 0.001 to 10% by weight.
And more preferably 0.01 to 5% by weight. If the content in the modified product is small, the adhesive strength decreases, and if it is too large, a crosslinking reaction occurs, and moldability deteriorates, which is not preferable. It is also possible to mix such an adhesive resin in an adjacent layer.

The laminate of the present invention can be produced not only in the form of a sheet or a film, but also in the form of a pipe, a tube or a tank or a bottle by the above-mentioned coextrusion molding method, co-injection molding method, co-extrusion inflation molding method or blow molding method. The laminated structure can be heated again to about 100 to 150 ° C. and stretched by a blow stretching method or the like. Further, in each layer of the laminate of the present invention, an antioxidant, a lubricant, an antistatic agent, a plasticizer, a coloring agent, an ultraviolet absorber, an inorganic / organic filler, and the like for improving moldability, physical properties, and the like. It can be added within a range that does not inhibit the effects of the present invention.

[0024]

The present invention will be specifically described below with reference to examples. In the examples, “parts” and “%” mean on a weight basis unless otherwise specified. The following resins and compounds were prepared. [Polyolefin-based resin (A or a)] A1: polypropylene (MI = 0.8 g / 10 min, density 0.90 g / cm ³ , chlorine content 110 ppm) A2; high-density polyethylene (MI = 6.0 g / 10 min) , Density 0.952 g / cm ³ , chlorine content 15 ppm) A3; linear low density polyethylene (MI = 1.0 g / 10
Min, density 0.923g / cm ³ , chlorine content 30pp
m) The above MI is 230 ° C. (A1) or 190 ° C. (A
2, A3) and a melt flow index under a load of 2160 g.

[EVOH (B or b)] B1: ethylene content 32 mol%, degree of saponification 99.6 mol%, MI = 4.0 g / 10 min B2: ethylene content 38 mol%, saponification degree 99 B3: ethylene content 29 mol%, degree of saponification 99.6 mol%, MI = 8.0 g / 10 min. The above MI is 210 ° C., 2160 g. Shows the melt flow index under load.

[0026] [hydrotalcite compound (C)] C1;. Mg 4 5 Al 2 (OH) 13 CO 3 · 3.5H 2 O C2; Ca 6 Al 2 (OH) 16 CO 3 · 4H 2 O C3; _{[Mg 0. 75 Zn 0.25]} 0.67 Al 0.33 (OH)
₂ (CO ₃ ) _0.165 · 0.45 H ₂ O [C8 or higher fatty acid (D)] D1; Stearic acid D2; Oleic acid

[Phosphoric acid or hydrogen phosphate of alkaline (earth) metal (E)] E1; calcium dihydrogen phosphate E2; phosphoric acid E3; disodium hydrogen phosphate [adhesive resin] F1; Resin (trade name: Admer Q)
F500, manufactured by Mitsui Petrochemical Industry Co., Ltd.)

Example 1 Alkaline (earth) metal hydrogen phosphate (E1) 0.5
% Aqueous solution was impregnated with 100 parts of EVOH (B1) to obtain a resin composition (I) containing a phosphate compound (E1) in an amount of 50 ppm in terms of phosphate groups. On the other hand, 100 parts of a hydrotalcite-based compound (C1) and 2 parts of a higher fatty acid (D1) having 8 or more carbon atoms (20,000 ppm based on the hydrotalcite-based compound) were mixed by a tumbler to obtain a composition (II). . Next, the polyolefin resin (A1)
After 100 parts and 0.1 part of the above composition (II) are melt-mixed with a twin screw extruder, 5 parts of the resin composition (I) are further melt-mixed to obtain the resin composition (III) of the present invention. Obtained.

Using this resin composition (III), a film was formed under the following forming conditions, and the occurrence of fish eyes and the film strength were evaluated. In addition, in order to examine whether or not the performance was deteriorated based on the heat history, the operation of pulverizing the formed film and again forming the film under the same conditions was repeated 10 times and evaluated.

Further, the occurrence of fish eyes
Is 100cm^TwoThe diameter generated per hit is 0.2mm or less
The number of the above items was checked and evaluated as follows. ◎; 0-5 pieces / 100cm^Two  ○; 6 to 10 pieces / 100cm^Two △ 11-50 pieces / 100cm^Two ×; 51 to 200 pieces / 100 cm^Two XX: 201 or more / 100cm^Two Further, regarding film strength, JIS K 6758
The film strength at break was measured according to
Was.

Examples 2 to 6 and Comparative Examples 1 to 2 Resin compositions (III) were prepared according to the formulations shown in Tables 1 and 2 in the same manner as in Example 1, and were similarly evaluated. Table 3 shows the evaluation results of Examples 1 to 6 and Comparative Examples 1 and 2.

Table 1 Resin composition (I) Resin composition (II) (B) Component (E) Component (C) Component (D) Component type Mixing amount Type Mixing amount Type Mixing amount Type Mixing amount Example 1 B1 100 E1 0.012 (50) C1 100 D1 2〃2 B2 100 E2 0.021 (200) C1 100 D14４3 B1 100 E3 0.004 (30) C2 100 D1 1〃4 B3 100 E2 0.012 (120) C1 100 D2 2〃5B1 100 E1 0.012 (50) C1 100 D2 3 〃 6 B1 100 E1 0.012 (50) C3 100 D1 2 Comparative Example 1 B1 100 E1 0.012 (50) Use of C1 only 2 Use of B1 only C1 100 D12 2 ) The amount represents parts by weight, and the value in parentheses of the component (E) represents the content (ppm) in terms of phosphate group relative to the component (B).

[0032]

Table 2 Resin composition (III) (A) component Resin composition (I) Resin composition (II) Type Mixing amount Mixing amount Mixing amount Example 1 A1 100 5 0.1 〃 2 A2 100 5 0.05 〃 3 A1 100 8 0.2 〃 4 A1 100 10 0.25 ５ 5 A3 1005 0.07 ６ 6 A1 100 5 0.1 Comparative Example 1 A1 100 5 0.1 〃 2 A1 100 5 0.1 Note ) Mixing amounts represent parts by weight.

[0033]

[Table 3] Fish eye generation film strength (kg / cm ² ) 1st 5th 10th 1st 5th 10th 10th Example 1 ◎ ◎ ◎ 380 370 360 360 2 ◎ ◎ ○ 310 300 300 ３ 3 ◎ ◎ ◎ 360 360 360 〃 4 ◎ ○ ○ 350 340 340 ５ 5 ◎ ◎ ◎ 300 300 290 〃 6 ◎ 380 360 360 Comparative Example 1 ○ × ３ 380 340 160 〃 2 ○ × × × 380 300 80

Example 7 Using the compositions (I) to (III) obtained in Example 1, a blend of the polyolefin resin (A1) and the composition (II) (the blending weight ratio is 100/0. 1) Layer / Blend of polyolefin resin (A1) and composition (II) (blending weight ratio is 100 / 0.1) Layer / Adhesive resin (F1)
Layer / composition (I) layer / adhesive resin (F1) layer / blend of polyolefin resin (A1) and composition (II) (blend weight ratio 100 / 0.1) layer / polyolefin resin (A1) ) And composition (II) (blending weight ratio is 100 / 0.1) layer (thickness = 100 μm / 400)
μm / 50 μm / 100 μm / 50 μm / 400 μm /
(500 μm) was manufactured under the following conditions using four types of seven-layer feed block dies.

Molding conditions Extruder 65 mm diameter extruder (for blended layer of polyolefin resin (A1) and composition (II)) 65 mm diameter extruder (same as above or for resin composition (III) layer) 30 mm diameter extruder Extruder (for adhesive resin (F1) layer) 30 mm diameter extruder (for composition (I) layer) Extrusion temperature C1 C2 C3 C4 AD FB Die (° C.) 200 230 230 230 210 220 220 230 230 200 230 230 230 220 220 220 230 200 230 −−−−−−− 220 220 230 230 200 230 −−−−−−− 220 220 230 230 Screw rotation speed 20 rpm, 25 rpm, 10 rpm, 15 rpm Die width 650 mm Extrusion amount 24 kg / hr Taking speed 0.33 m / min Roll temperature 80 ° C

A dry blend of 80 parts by weight of the above-obtained laminate obtained by grinding to about 1 to 5 mm square and 20 parts by weight of the blend of the polyolefin resin (A1) and the composition (II) ( The resin composition (III)) is again used as the above-mentioned layer under the same conditions and the laminate polyolefin resin (A)
Blend of 1) and composition (II) (the blend weight ratio is 1
00 / 0.1) layer / resin composition (III) layer / adhesive resin (F1) layer / composition (I) layer / adhesive resin (F1) layer /
Resin composition (III) layer / polyolefin resin (A1)
Of the composition (II) (the blending weight ratio is 100
/0.1) layer /, thickness is 100 μm / 400 μm / 50
μm / 100μm / 50μm / 400μm / 500μ
m) was prepared. With this as the first time, such an operation is performed 10 times.
This was repeated (scrap return), and a cup was formed by a vacuum pressure molding machine under the following conditions using the laminates obtained at the first, fifth, and tenth times. The EVOH content in the resin composition (III) layer of the first laminate was about 6%, and the EVOH content in the fifth and tenth times was about 10%.
%Met.

Molding conditions Heater temperature Upper and lower 450 ° C. Laminate surface temperature 160 ° C. Cup shape Mouth: 9 × 9 cm, bottom: 8 × 8c
m, depth: 6.5 cm The appearance and impact resistance of the obtained cup were evaluated in the following manner. (Appearance) The appearance of the obtained cup was visually observed and evaluated according to the following criteria. ◎ −−− Good surface smoothness and no streaks and foreign matter ○ −−− Slightly streaks and no foreign matter △ −−− Overall many streaks and no foreign matter × −−− Overall many streaks and slight foreign matter ×× −−− Overall, many streaks and foreign matter

(Impact Resistance) The obtained cup was filled with ethylene glycol, and PP / LLDPE was used as a lid material.
(Thickness = 60 μm / 120 μm) After heat-sealing with a film and sealing, drop it from the bottom of the cup to the concrete surface from a height of 2 m at 0 ° C., visually observe the damage status of the cup, and evaluate according to the following criteria. did. ◎ −−− No change ○ −−− Slight whitening, no leakage of contents △ −−− Small cracks, no leakage of contents × −−− Cracks, slight leakage of contents ×× −−− Cup destruction

Example 8 In Example 7, the composition (I) was prepared by mixing 100 parts of B2 with E
2 was performed in the same manner except that a mixture of 0.021 parts was used.
Evaluation was performed in the same manner. Example 9 In Example 7, the configuration of the laminate was changed to ////
/ = 100 μm / 400 μm / 50 μm / 100 μm
The evaluation was performed in the same manner except that / 50 μm / 500 μm was used.

Comparative Example 3 The procedure of Example 7 was repeated except that the composition (II) of Comparative Example 1 was used as the composition (II). Comparative Example 4 The procedure of Example 7 was repeated except that the composition (I) of Comparative Example 2 was used as the composition (I). Table 4 shows the evaluation results of Examples 7 to 9 and Comparative Examples 3 and 4.

[0041]

TABLE 4 Appearance impact 1st 5th 10th 1st 5th 10th Embodiment 7 ◎ ◎ ○ ◎ ◎ ◎ 〃 8 ◎ ◎ ○ ◎ ◎ ○ 〃 9 ◎ ○ ○ ◎ ○ ○ Comparative Example 3 ◎ × × △ × × ４ 4 △ × × × × × × Note) The above number indicates the number of scrap returns.

[0042]

Since the resin composition of the present invention contains the components (A) to (E) as described above, it has excellent long-run formability and is not easily affected by repeated thermal histories during scrap return. It can be used as various laminates, and is useful for packaging films, containers, bottles and bottles, food trays, sheets, various equipment parts, and the like.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C08K 3/32 KEE C08K 3/32 KEE 5/09 KEP 5/09 KEP C08L 23/26 LDM C08L 23 / 26 LDM // B29C 47/00 B29C 47/00

Claims (11)

[Claims] 1. Polyolefin resin (A), saponified ethylene-vinyl acetate copolymer (B), hydrotalcite compound (C), higher fatty acid having 8 or more carbon atoms (D)
And a phosphoric acid and / or a hydrogen phosphate (E) of an alkali (earth) metal. 2. The composition according to claim 1, wherein the polyolefin resin (A) is 1 to 30.
2. The resin composition according to claim 1, which contains 0 ppm of chlorine. 3. The resin composition according to claim 1, wherein the hydrotalcite compound (C) is a compound represented by the following general formula. MxAly (OH) _{2x + 3y-2z} (E) z · aH ₂ O (where M is Mg, Ca or Zn, E is CO ₃ or HPO ₄ , x,
y and z are positive numbers, a is 0 or positive number) 4. The resin composition according to claim 1, wherein the hydrotalcite-based compound (C) is a hydrotalcite-based solid solution represented by the following general formula. ^{_{[[(M 1 2+) y1 (M}} 2 2+) y2 ] ^{_{1-x M x 3+ (OH}} ) 2 A n- x / n
_{· MH 2 O] (M 1} 2+ in the formula is Mg, Ca, at least one metal selected from Sr and Ba, M ₂ ²⁺ is Zn, Cd, Pb, Sn
M _x ³⁺ is a trivalent metal, A ⁿ⁻ _{x / n} is an n-valent anion, and x, y 1, y 2, and m are each 0 <x ≦ 0.
5, 0.5 <y1 <1, y1 + y2 = 1, positive number represented by 0 ≦ m <2) 5. The compounding amount of the hydrotalcite compound (C) is a total amount (A + B) of the polyolefin resin (A) and the saponified ethylene-vinyl acetate copolymer (B) of 10
0.00001 to 10 parts by weight based on 0 parts by weight, and the compounding amount of the higher fatty acid having 8 or more carbon atoms (D) is 0.1 to 10 parts by weight based on 100 parts by weight of the hydrotalcite-based compound (C).
In terms of parts by weight, the amount of phosphoric acid and / or the hydrogen phosphate of an alkali (earth) metal (E) is 0 based on 100 parts by weight of the saponified ethylene-vinyl acetate copolymer (B). The resin composition according to any one of claims 1 to 4, wherein the amount is 0.0001 to 0.005 parts by weight. 6. A method for producing the resin composition according to claim 1, wherein the saponified ethylene-vinyl acetate copolymer (B) and phosphoric acid and / or phosphoric acid of an alkali (earth) metal are used in advance. Composition (I) mixed with hydrogen salt (E)
And a hydrotalcite-based compound (C) and a carbon number of 8
A method for producing a resin composition, comprising: preparing a composition (II) in which the above higher fatty acid (D) is mixed, and then melt-mixing (A), (I) and (II). 7. The method for producing a resin composition according to claim 6, wherein (A) and (II) are previously melt-mixed, and then (I) is further melt-mixed. 8. A laminate comprising at least one layer of the resin composition according to claim 1. 9. The laminate according to claim 8, having a structure of a polyolefin-based resin (a) layer / resin composition layer / adhesive layer / saponified ethylene-vinyl acetate copolymer (b) layer. 10. The composition of the polyolefin resin (a) layer / resin composition layer / adhesive layer / saponified ethylene-vinyl acetate copolymer (b) layer / adhesive layer / polyolefin resin (a) layer The laminate according to claim 8, which has: 11. Polyolefin resin (a) layer / resin composition layer / adhesive layer / saponified ethylene-vinyl acetate copolymer (b) layer / adhesive layer / resin composition layer / polyolefin resin (a) 9. The laminate according to claim 8, having a layer structure.