JPH09278952A - Resin composition, its production and use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition excellent in long-run moldability, hardly being influenced by a heat history in recovery of scrap, by blending a polyolefin- based resin with a saponified substance of an ethylene-vinyl acetate copolymer and specific three kinds of components. SOLUTION: This resin composition comprises (A) a polyolefin-based resin (preferably a polyethylene resin having 0.1-15g/10 minutes melt index at 210 deg.C by 2,160g or a polypropylene-based resin having 0.2-12g/10 minutes melt index), (B) a saponified substance of an ethylene-vinyl acetate copolymer, (C) a hydrotalcite-based compound, (D) a >=8C fatty acid (preferably stearic acid or oleic acid) and (E) a <=7C fatty acid metal salt (preferably sodium acetate, calcium acetate, etc.). A saponified substance of an ethylene-vinyl acetate copolymer having 25-70mol% ethylene content and >=95mol% degree of saponification is preferable as the component B. A compound of the formula (M is Mg; E is CO3 ; (x), (y) and (z) are each a positive number; (a) is 0 or a positive number) is preferable as the component C.

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, although the long-run formability is sufficiently improved by such a method, the performance change of the resin composition due to repeated heat history at the time of scrap return (for example, generation of foreign matter, deterioration of strength, etc.). Is not sufficiently taken into consideration, and a resin composition that is less affected by such heat history is desired.

[0007]

Therefore, the present inventor has
As a result of earnest studies in view of the above circumstances, polyolefin resin (A), EVOH (B), hydrotalcite compound (C), higher fatty acid (D) having 8 or more carbon atoms and 7 or less carbon atoms It was found that the resin composition comprising the lower fatty acid metal salt (E) is not affected by repeated heat history at the time of scrap return and can maintain good physical properties, and completed the present invention.

Further, in producing the above resin composition, a composition (I) in which EVOH (B) and a lower fatty acid metal salt (E) having a carbon number of 7 or less are mixed in advance and a hydrotalcite compound (C) is previously mixed. And a higher fatty acid (D) having 8 or more carbon atoms are mixed to prepare a composition (II),
By melt-mixing (I) and (II), a good resin composition aimed at by the present invention can be obtained, and the resin composition of the present invention comprises a polyolefin resin (a) layer / the present invention. Resin composition layer / 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 / adhesive resin layer / E of the present invention
It was also found that it is useful for a laminate having a constitution of VOH (b) layer / adhesive resin layer / resin composition layer of the present invention / polyolefin resin (a) layer, and the present invention has been completed. .

[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. Also, not limited to the above, for 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
A metal selected from M _x ^3+, a trivalent metal, A ^n- _{x / n} is an n-valent anion, and x, y1, y2 and m are 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, the higher fatty acid (D) having 8 or more carbon atoms and the lower fatty acid metal salt (E) having 7 or less carbon atoms are further added to the resin composition comprising (A) to (C). Examples of the higher fatty acid (D) having 8 or more carbon atoms include lauric acid, tridecyl acid, myristic acid, pentadecyl acid, palmitic acid, heptadecyl acid, stearic acid, nonadecanoic acid, oleic acid, capric acid, and behenin. In addition to higher fatty acids such as acids and linoleic acids and their alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as magnesium salts, calcium salts and barium salts, zinc metal salts and the like are also 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. Also, a lower fatty acid metal salt having 7 or less carbon atoms (E)
Examples thereof include alkali or alkaline earth metal salts, specifically, sodium salts such as acetic acid, propionic acid and butyric acid, alkali metal salts such as potassium salts and magnesium salts, calcium salts, alkaline earth salts such as barium salts. Examples of the metal salts include sodium acetate, magnesium acetate, and calcium acetate.

The amount of the lower fatty acid metal salt having a carbon number of 7 or less (E) is 0.000 in terms of metal based on 100 parts by weight of the saponified ethylene-vinyl acetate copolymer (B).
5 to 0.05 parts by weight (5 to 500 ppm) is preferable,
Furthermore, 0.002-0.03 parts by weight (20-300 pp
m) is preferred. If the blending amount is less than 0.0005 parts by weight (5 ppm), the heat resistance (retention of physical properties against repeated thermal history during regrind) becomes insufficient, and conversely, if it exceeds 0.05 parts by weight (500 ppm), Long run processability is deteriorated, which is not preferable.

The resin composition of the present invention comprises the above-mentioned (A)
~ (E) are mixed, and the mixing method is not particularly limited, but in order to obtain the effect of the present invention remarkably, EVOH (B) and a lower fatty acid metal salt having 7 or less carbon atoms (E ) Is mixed with a hydrotalcite compound (C) and a higher fatty acid (D) having 8 or more carbon atoms (D) to prepare a composition (II), and then (A), (I) And (II) are melt-mixed to obtain the resin composition of the present invention. Further, (A) and (II) are melt-mixed in advance and then (I) is melt-mixed.

The mixing means may be in any mode. For example, EVOH (B) and a lower fatty acid metal salt having 7 or less carbon atoms (E) are mixed with a Henschel mixer, a tumbler, etc., and then melt-kneaded with an extruder to obtain a pelletized composition (I), or EVOH Examples include a method in which the water-containing pellet (B) and the lower fatty acid metal salt (E) having 7 or less carbon atoms are mixed in water and then dried. 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), A method of melt-mixing pellets and powders of the polyolefin resin (A), and further melt-mixing the composition (I). Further, a layer comprising the composition (I), the composition (II) and the polyolefin resin A method in which two or more laminate structures of the layer composed of the mixture of (A) are melt-mixed again, and the like. 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 unsaturated carboxylic acid or its anhydride contained in the ethylene-α-olefin copolymer at this time is 0.001 to 10% by weight.
Is preferable, and more preferably 0.01 to 5% by weight. If the content in the modified product is small, the adhesive strength will be lowered, and conversely, if the content is large, a crosslinking reaction will occur and moldability will be poor, such being undesirable. 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, "part" and "%" mean 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

[Lower fatty acid metal salt having 7 or less carbon atoms (E)] E1; Magnesium acetate E2; Sodium acetate [Adhesive resin] F1; Modified polyolefin resin (trade name: Admer Q
F500, manufactured by Mitsui Petrochemical Industry Co., Ltd.)

Example 1 100 parts of EVOH (B1) and 0.024 part of a lower fatty acid metal salt (E1) having 7 or less carbon atoms (40 ppm in terms of magnesium based on EVOH) were melt mixed and pelletized. A resin composition (I) having a shape of a circle was obtained. 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). . Then, 100 parts of the polyolefin-based resin (A1) and 0.1 part of the above composition (II) are melt-mixed with a twin-screw extruder, and then the resin composition (I) is further mixed.
Five parts were melt mixed to obtain a resin composition (III) of the present invention.

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.

The generation of fish eyes was evaluated as follows by examining the number of fish eyes having a diameter of 0.2 mm or more per 100 cm ² . a; 0 to 5 pieces / 100 cm ² b; 6 to 10 pieces / 100 cm ² c; 11 to 50 pieces / 100 cm ² d; 51 to 200 pieces / 100 cm ² e; 201 pieces or more / 100 cm ² , JIS K 6758
And 6760, the film strength at break was measured.

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) Component (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 0.024 (40) C1 100 D1 2 〃 2 B2 100 E2 0.071 (200) C1 100 D1 4 〃 3 B1 100 E1 0.030 (50) C2 100 D1 1 〃 4 B3 100 E2 0.043 (120) C1 100 B5 D2 2 〃 100 E1 0.024 (40) C1 100 D2 3 〃 6 B1 100 E1 0.024 (40) C3 100 D1 2 Comparative Example 1 B1 5 E1 0.024 (40) C1 only 〃 2 B1 only C1 100 D1 2 Note) Mixed The amount represents parts by weight, and the value in parentheses of the component (E) represents the content (ppm) in terms of metal 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] Generation of Fish Eyes Film Strength (kg / cm ² ) 1st 5th 10th 1st 5th 10th Example 1 a a b 380 380 370 〃 2 a a a 300 300 300 〃 3 a a b 360 350 350 350 a 340 b 350 340 330 330 5 a a 280 280 270 〃 6 a ab 380 370 370 Comparative Example 1 a b d 380 320 140 〃 2 a b 380 e

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. a ---- Surface smoothness is good and there are no streaks and foreign substances b ---- Slightly streaks and no foreign substances c ------ Overall streaks and no foreign substances d ------ Overall streaks and slightly foreign substances e-- −− Overall there are many streaks and foreign substances

(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. a ---- No change b ---- Slightly whitening, no content leakage c ---- Small cracks, no content leakage d ---- Cracks, some content leakage e --- Cup Destruction

Example 8 In Example 7, the composition (I) was prepared by mixing 100 parts of B2 with E
The same procedure was followed except that 2 was a mixture of 0.071 parts,
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 same evaluation as in Example 7 was performed 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 Example 7 a a a a a a 〃 8 a a b a a b 〃 9 a b b a a b Comparative Example 3 a bee ac e 〃 4 ac e ad e Note) The above number represents 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.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location C08L 29/04 LDM C08L 29/04 LDM

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 lower fatty acid metal salt (E) having 7 or less carbon atoms, a resin composition. 2. The polyolefin resin (A) is 1 to 30.
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 (wherein 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
A metal selected from M _x ^3+, a trivalent metal, A ⁿ⁻ _{x / n} is an n-valent anion, and x, y 1, y 2 and m are 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 parts by weight, the amount of the lower fatty acid metal salt (E) having a carbon number of 7 or less is such that the saponified ethylene-vinyl acetate copolymer (B) 1
0.0005 to 0.05 in terms of metal based on 00 parts by weight
It is a weight part, The resin composition in any one of Claims 1-4 characterized by the above-mentioned. 6. In producing the resin composition according to claim 1, a saponified ethylene-vinyl acetate copolymer (B) and a lower fatty acid metal salt (E) having 7 or less carbon atoms are mixed in advance. Composition (I) and hydrotalcite compound (C) and higher fatty acid (C) having 8 or more carbon atoms in advance
After the composition (II) is prepared by mixing
And a method for producing a resin composition, which comprises melt-mixing (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.