JP2000063683A - Resin composition and its multilayered structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin compsn. which is free of the occurrence of such a gel or hard spot as formed by agglomeration of a colorant even in scrap return or in a long-time melt molding process and is excellent in melt moldability. SOLUTION: This compsn. comprises a thermoplastic resin (A), a saponified ethylene-vinyl acetate copolymer (B), a colorant (C), and a higher fatty acid metal salt (D). Based on 100 pts.wt. ingredient A, the content of ingredient B is 0.5-25 pts.wt., and that of ingredient C, 0.01-10 pts.wt. Based on 100 pts.wt. sum of ingredients A, B, and C, the content of ingredient D is 0.001-10 pts.wt.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a composition having improved long-run property during melt molding, that is, a thermoplastic resin (A), a saponified ethylene-vinyl acetate copolymer (B).
The present invention relates to a resin composition comprising (hereinafter abbreviated as EVOH), a colorant (C) and a higher fatty acid metal salt (D), and further relates to a multilayer structure using the same.

[0002]

2. Description of the Related Art Conventionally, various molded products have been obtained by melt molding a mixture of a thermoplastic resin typified by a polyolefin resin such as polyethylene and polypropylene and EVOH. To obtain the physical properties that cannot be obtained by each, thermoplastic resin and EVO
It is roughly classified into two types: scraps and ends of products generated during the manufacturing of a laminated structure with H, and reuse (scrap return or regrind) by collecting defective products. The industrial utility is more remarkable when the implementation is limited to the industrial scale.

[0003]

However, a laminated structure such as a sheet or film made of the thermoplastic resin and EVOH as described above is formed, and the scrap composition is melt-formed as a regrind layer to form a film, sheet or the like. In the case of producing a laminated structure of, the composition causes gelation at the time of molding, or a heat-colored resin called charring or carbonized resin adheres to the inside of the extruder and is continuously melt-molded for a long period of time. However, there is a problem that the so-called long-run property is inferior. Further, the gelled product at the time of melting and the phase-separated foreign matter of the thermoplastic resin and EVOH are often mixed in the molded product, which is a major cause of defects of the molded product including generation of fish eyes in film molding, Inevitable deterioration of product quality.

In particular, in recent years, a coloring agent has been blended with a thermoplastic resin for the purpose of improving the appearance and diversification of a laminated structure to increase the commercial value. Melt molding of a resin composition comprising a thermoplastic resin, EVOH and a colorant, in which the structure is recovered and reused, is carried out. In the melt molding operation, the colorant aggregates within a short time. Such dark gels and lumps will start to appear on the molded product, which will increase with time, making long-run molding difficult and reducing productivity. The product value of the obtained product is significantly reduced.

Therefore, in the present invention, under such a background, even when the laminated structure containing the coloring agent is repeatedly scrap-returned or melt-processed for a long period of time, gel or lumps like aggregation of the coloring agent are generated. It is an object of the present invention to provide a resin composition having excellent melt moldability and a multilayer structure thereof.

JP-A-3-72541 discloses that polyolefin, EVOH having an ethylene content of 20 to 65 mol% and a saponification degree of 96 mol% or more, titanium oxide, talc,
At least one inorganic substance selected from calcium carbonate, mica, and water-absorbing inorganic substance, and ethylene content 68 to 9
A resin composition comprising 8 mol% of EVOH having a saponification degree of 20 mol% or more, excellent compatibility, and effective for regrinding has been proposed, which has the effect of reducing the appearance of the obtained molded product and phase-separated foreign matter. Although it is recognized to some extent, the above problems due to the addition of the colorant have not been studied at all, and the inventors of the present invention have studied in detail about such points, and still gels and spots are generated, and particularly It has been found that the resin composition is not yet satisfactory when used as a regrind layer.

[0007]

[Means for Solving the Problems] Therefore, as a result of intensive studies in view of the above circumstances, the present inventors have found that the thermoplastic resin (A), EVOH (B), colorant (C) and high-grade resin The content of the EVOH (B) is 0.5 to 25 parts by weight and the content of the colorant (C) is 0 based on 100 parts by weight of the thermoplastic resin (A), which is composed of the fatty acid metal salt (D). .0
1 to 10 parts by weight, and the content of the higher fatty acid metal salt (D) is 0.001 with respect to 100 parts by weight of the total amount of the thermoplastic resin (A), EVOH (B) and colorant (C). ~ 1
The present invention has been completed by finding that a resin composition of 0 parts by weight meets the above object.

In the present invention, the thermoplastic resin (A),
The hydrotalcite-based compound (E) was added in an amount of 0.001 per 100 parts by weight of the total amount of EVOH (B) and colorant (C).
When the resin composition contains 10 to 10 parts by weight, the effect of the present invention is remarkably exhibited.

The resin composition of the present invention has great utility value not only as a single layer but also as a laminate. For example, thermoplastic resin layer / resin composition layer of the present invention / adhesive resin layer / EVOH.
Layer, thermoplastic resin layer / resin composition layer of the present invention / adhesive resin layer / EVOH layer / adhesive resin layer / thermoplastic resin layer / thermoplastic resin layer / resin composition layer of the present invention / adhesive resin layer / EVO
It is useful for a multilayer structure having a structure such as H layer / adhesive resin layer / resin composition layer of the present invention / thermoplastic resin layer.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below. The thermoplastic resin (A) of the present invention is not particularly limited,
Polyolefin resin, polyamide resin, polyester resin, polyether resin, polyurethane resin,
Polycarbonate resins and the like can be mentioned, but polyolefin resins are preferably used. These may be used alone or in combination of two kinds. The polyolefin-based resin is not particularly limited, but by using a polyolefin-based resin which is produced using a Ziegler type catalyst and contains chlorine due to the catalyst of 1 to 300 ppm, preferably 3 to 150 ppm, The effect of the present invention can be more remarkably obtained.

Examples of such polyolefin resins include high density, medium density and low density polyethylenes, homopolymers such as polypropylene, polybutene and polypentene, ethylene-propylene copolymers, 1-butene mainly containing ethylene or propylene, 1-Hexene etc. with 2 to 2 carbon atoms
Copolymers with about 0 α-olefins, and olefin-vinyl acetate copolymers having a composition relatively close to that of polyolefins having an olefin content such as ethylene or propylene of 90 mol% or more, olefin- (meth) acryl One or two or more kinds of acid ester copolymers and ionomer resins modified with metal ions, or homopolymers or copolymers of the above polyolefin resins graft-modified with unsaturated carboxylic acids or the like can be arbitrarily used. Is. Among them, especially the melt index (MI) is 0.
1 to 15 g / 10 minutes (190 ° C., 2160 g) polyethylene resin, or 0.1 to 12 g / 10 minutes (230
The problem of resin pressure rise is likely to occur when a polypropylene resin at 2 ° C., 2160 g) is used, and the effects of the present invention are also excellent.

The EVOH (B) used in the present invention has an ethylene content of 10 to 70 mol%, preferably 20.
˜60 mol%, the degree of saponification of vinyl acetate portion is 90 mol% or more, preferably 95 mol% or more. When the ethylene content is less than 10 mol%, the thermal stability is poor and the melt moldability is deteriorated, and when the ethylene content is more than 70 mol%, the oxygen barrier property is deteriorated, resulting in poor practicability. Also, the degree of saponification of the vinyl acetate portion is 90 mol%
If it is less than 1, the thermal stability is poor and the physical properties such as oxygen barrier property, oil resistance and water resistance are inferior, so that it is not practical.

The EVOH (B) is, in addition to ethylene and vinyl acetate (or saponified vinyl alcohol), unsaturated carboxylic acid or ester or salt thereof, unsaturated sulfonic acid or salt thereof, (meth) acrylamide, (Meta)
A small amount of about 10 mol% or less of the third component such as acrylonitrile, propylene, butene, α-octene, α-olefin such as α-octadecene, vinyl ester other than vinyl acetate, and the like may be contained.

The colorant (C) is not particularly limited, but various organic pigments and inorganic pigments are adopted. Organic pigments include azo pigments, quinacridone pigments, phthalocyanine pigments, atine pigments, nitro pigments, isoindolinone pigments, architectural dye pigments, nitroso pigments, acidic dye lakes, basic dye pigments. Lakes and the like are mentioned, and one or more of these are used. Inorganic pigments include titanium oxide, zinc sulfide, lead pigments, cadmium pigments, rouge, cobalt pigments, ultramarine blue, navy blue, barium sulfate, calcium carbonate, kaolin clay, silica powder, talc, alumina white, antimony oxide. , Carbon black, acetylene black, barium chromate, titanium yellow, iron oxide, antimony red, manganese purple, chrome green, zinc green, emerald green,
Examples thereof include zinc silicate, zinc sulfide, calcium sulfide, strontium sulfide, calcium tungstate, and metal powders such as aluminum and copper, and one or more of these may be used. Above all, organic pigments such as azo pigments, quinacridone pigments and phthalocyanine pigments, and zinc sulfide, lead pigments, cadmium pigments, cobalt pigments, ultramarine blue and dark blue inorganic pigments are preferably used.

The higher fatty acid metal salt (D) is not particularly limited, but higher fatty acid metal salts having 8 or more carbon atoms are preferable, and examples thereof include lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecyl acid,
Alkali metal salts such as sodium salts and potassium salts of higher fatty acids such as stearic acid, hydroxystearic acid, nonadecanoic acid, oleic acid, capric acid, behenic acid and linoleic acid, alkaline earth salts such as magnesium salts, calcium salts and barium salts. Examples thereof include metal salts and zinc metal salts.
Among these, stearic acid, hydroxystearic acid,
Metal salts of oleic acid and lauric acid are particularly remarkable in terms of effects.

In the present invention, the above-mentioned thermoplastic resins (A), E
It consists of VOH (B), colorant (C) and higher fatty acid metal salt (D). Regarding the content of each component,
EVOH to 100 parts by weight of the thermoplastic resin (A)
The content of (B) is 0.5 to 25 parts by weight, preferably 1 to
20 parts by weight, more preferably 2 to 15 parts by weight, and the content of the colorant (C) is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, more preferably 0.1 to 2 parts by weight. Parts by weight.

If the content of EVOH (B) is less than 0.5 part by weight, the gas barrier property of the laminated structure will be insufficient, and if it exceeds 25 parts by weight, gels or lumps like agglomeration of the colorant will be generated. Is difficult to control, and the appearance of the molded product deteriorates. The content of the colorant (C) is 0.
If it is less than 01 parts by weight, the coloring property of the laminated structure will be reduced and the commercial value will be reduced, and if it exceeds 10 parts by weight, it will be difficult to suppress the generation of gel or lumps such as agglomeration of the colorant, and further molding The appearance of the product also deteriorates.

Further, the content of the higher fatty acid metal salt (D) is 0.001-1 with respect to 100 parts by weight of the total amount of the thermoplastic resin (A), EVOH (B) and colorant (C).
It is 0 part by weight, preferably 0.005 to 5 parts by weight, and more preferably 0.01 to 1 part by weight. When the content of the higher fatty acid metal salt (D) is less than 0.001 part by weight, it is difficult to suppress the generation of gel or lumps such that the colorant is aggregated, and when it exceeds 10 parts by weight, the appearance of the molded product is It will deteriorate and the commercial value will decrease.

Further, in the present invention, it is preferable to contain a hydrotalcite compound (E) in addition to the above components (A) to (D). By containing such a hydrotalcite compound (E), The melt moldability of the present invention is further improved. Hydrotalcite-based compound (E)
Are, for example, 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, z are positive numbers, with a compound represented by a is 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 2 and the like can be mentioned. Also, not limited to the above, for example, Mg ₂ Al
(OH) ₉ · 3H ₂ O, which has a chemical formula such as CO ₃ or HPO _{4 in} which a part of OH is not substituted, or which is free of water of crystallization (a = 0) The same effect can be expected. Of these, M is Mg and E is CO ₃
The compounds that are the most effective.

Further, the hydrotalcite compound (E)
It is also possible to use a hydrotalcite-based solid solution represented by the following general formula. [[(M ₁ ²⁺ ) _{y 1} (M ₂ ²⁺ ) _{y 2} ] _1-x M _x ³⁺ (OH) ₂ A ^n- _{x / n}
MH ₂ O] (wherein M ₁ ²⁺ is at least one metal selected from Mg, Ca, Sr and Ba, and M ₂ ²⁺ is Zn, Cd, Pb, Sn.
A metal selected from the following, M _x ³⁺ is a trivalent metal, A ⁿ⁻ is an n-valent anion, x, y1, y2 and m are each 0 <x ≦ 0.5,
0.5 <y1 <1, y1 + y2 = 1, 0 ≦ m <2 positive number)

In the above general formula, M ₁ ²⁺ is M
g and Ca are preferable, M ₂ ²⁺ is preferably Zn and Cd, and M _x ³⁺ is Al, Bi, In, Sb, B,
Although Ga, Ti, etc. can be illustrated, Al is practical.
As A ^n- , CO ₃ ²⁻ , OH ⁻ , HCO ₃ ⁻ , salicylate ion, citrate ion, tartrate ion, NO ₃ ⁻ ,
^{I -, (OOC-COO)} 2-, ClO 4-, CH 3 CO
O ⁻ , CO ₃ ²⁻ , (OOCHC = CHCOO) ²⁻ , [Fe
(CN) ₆ ] ^4- , and CO ₃ ²⁻ and OH ⁻ are useful.

Specific examples of such hydrotalcite-based solid solution
As a practical example, [Mg₀.₇₅ Zn_0.25]_0.67 Al_0.33(OH)₂(C
O₃)_0.165・ 0.45H₂O, [Mg₀.₇₉ Zn_0.21]_0.7 Al_0.3(OH)₂(CO₃)
_0.15, [Mg_1/7 Ca_3/7 Zn_3/7]_0.7 Al_0.3(OH)₂(O
OCHC = CHCOO) _0.15・ 0.41H₂O, [Mg_6/7 Cd_1/7]_0.7 Al_0.3(OH)₂(CH₃CO
O)_0.3・ 0.34H₂O, [Mg_5/7 Pd_2/7]_0.7 Al_0.30(OH)₂(CO₃)
_0.15・ 0.52H₂O, [Mg₀.₇₄ Zn_0.26]_0.68 Al_0.32(OH)₂(C
O₃)_0.16, [Mg₀.₅₆ Zn_0.44]_0.68 Al_0.32(OH)₂(C
O₃)_0.16・ 0.2H₂O, [Mg₀.₈₁ Zn_0.19]_0.74 Al_0.26(OH)₂(C
O₃)_0.13, [Mg₀.₇₅ Zn_0.25]_0.8 Al_0.20(OH)₂(CO₃)
_0.10・ 0.16H₂O, [Mg₀.₇₁ Zn_0.29]_0.7 Al_0.30(OH)₂(NO₃)
_0.30, [Mg₀.₇₁ Zn_0.29]_0.7 Al_0.30(OH)₂(OOC
HC = CHCOO)_0.15, [Mg₀.₁₄ Ca_0.57 Zn_0.28]_0.7 Al_0.30(OH)₂.
₃・ 0.25H₂O Etc., [Mg₀.₇₅ Zn_0.25]_0.67 Al_0.33(OH)₂(C
O₃)_0.165・ 0.45H₂O, [Mg₀.₇₉ Zn_0.21]_0.7 Al_0.3(OH)₂(CO₃)
_0.15, [Mg_6/7 Cd_1/7]_0.7 Al_0.3(OH)₂(CH₃CO
O)_0.3・ 0.34H₂O, [Mg_5/7 Pd_2/7]_0.7 Al_0.30(OH)₂(CO₃)
_0.15・ 0.52H₂O Is preferably used.

The hydrotalcite compound (E)
Content of 0.001 with respect to 100 parts by weight of the total amount of the thermoplastic resin (A), EVOH (B) and colorant (C).
10 to 10 parts by weight is preferable, and further 0.005
It is preferably from 5 to 5 parts by weight, particularly from 0.01 to 1 part by weight. If the content of the hydrotalcite-based compound (E) is less than 0.001 part by weight, the suppression of the generation of gels or lumps such as agglomerated colorants may be insufficient.
If it exceeds 10 parts by weight, the appearance of the molded article is deteriorated and the commercial value is lowered, which is not preferable.

The resin composition of the present invention has the above-mentioned (A).
To (D) or (A) to (E) are mixed, but the mixing method is not particularly limited, and (A) to (E) may be mixed at once, or any two components may be mixed. After blending, the remaining components may be blended one by one, and any of them may be appropriately selected and used. Above all, it is particularly preferable to preliminarily blend the higher fatty acid metal salt (D) and / or the hydrotalcite compound (E) into the thermoplastic resin (A) because the generation of foreign matter such as gel of the molded article can be suppressed. preferable.

The mixing means may be of any type. For example, the thermoplastic resin (A) and the higher fatty acid metal salt (D), or the thermoplastic resin (A) and the higher fatty acid metal salt (D) and the hydrotalcite compound (E) are mixed with a Henschel mixer or a tumbler. Alternatively, after melt mixing with an extruder or the like, the colorant (C) is melt mixed and further EV
A method of melt mixing OH (B), and further EVOH (B)
A layered structure composed of a mixture of a thermoplastic resin (A), a colorant (C), and a higher fatty acid metal salt (D) (further a hydrotalcite compound (E)). Examples of the method include melt mixing. In the latter method, crushed products (so-called regrind) such as scraps, edges, and defective products that are usually generated during the production of the above laminated structure.
And a method of melt mixing.

The resin composition of the present invention thus obtained is
Used for various melt-molded products. In the production of such a melt-molded product, the temperature condition during melt-molding is about 160-
A temperature of 280 ° C is desirable. Further, it is preferable that at least one screen pack is used for melt molding with an extruder, and the opening of the screen is 50 μm or more, and further 100 to 400 μm is a point that the melt moldability is stable. Is preferred.

Upon molding, if necessary, reinforcing materials such as glass fibers and carbon fibers, low molecular weight polyethylene, low molecular weight polypropylene, paraffin, higher fatty acid amide type, epoxy type lubricants, inorganic fillers, antioxidants, and ultraviolet absorbers. Known additives such as agents, antibacterial agents, and foaming agents may be appropriately blended.

As the melt molding method, an arbitrary 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 span method.

The shape of the molded article obtained by the method of the present invention is arbitrary, and it may be a film, sheet, tape, bottle,
Not only tubes, tanks, hoses, pipes, filaments, modified cross-section extrudates, etc., but it is also important to make a multilayer structure having at least one layer of the resin composition of the present invention, as the counterpart resin when laminating, Polyolefin resin, polyamide resin such as EVOH, nylon-6, nylon-6,6, vinylidene chloride resin, styrene resin, polyester resin and the like are often used. Of course, ordinary thermoplastic resins other than the above, such as polycarbonate, vinyl chloride resin, acrylic resin, vinyl ester resin, polyester elastomer, polyurethane elastomer, chlorinated polyethylene, and chlorinated polypropylene may be used. The thermoplastic resin and EVOH are the above-mentioned thermoplastic resin (A) and EVOH.
The same thing as (B) can be used.

The specific layer structure of the multilayer structure is as follows: thermoplastic resin layer / resin composition layer of the present invention / adhesive resin layer / E
VOH layer, thermoplastic resin layer / resin composition layer of the present invention / adhesive resin layer / EVOH layer / adhesive resin layer / thermoplastic resin layer,
Thermoplastic resin layer / resin composition layer of the present invention / adhesive resin layer /
EVOH layer / adhesive resin layer / resin composition layer of the present invention / thermoplastic resin layer and further resin composition layer / adhesive resin layer / EVOH layer of the present invention, resin composition layer / adhesive resin layer / E of the present invention
VOH layer / adhesive resin layer / EVOH layer, resin composition layer / adhesive resin layer / EVOH layer / adhesive resin layer / thermoplastic resin layer of the present invention, resin composition layer / adhesive resin layer / EVOH of the present invention
Layer / adhesive resin layer / resin composition layer / thermoplastic resin layer of the present invention.

As the adhesive resin used in such an adhesive resin layer, a known adhesive can be used, for example, a density 0.86 modified with an unsaturated carboxylic acid or an anhydride thereof.
It is preferably an ethylene-α-olefin copolymer of 0.95 g / cm ^{3 or} less, and can be obtained by copolymerizing or graft-modifying a resin similar to the above polyolefin resin with an unsaturated carboxylic acid or an anhydride thereof. Of course, the modification also includes a blend of an unmodified ethylene-α-olefin copolymer and an unsaturated carboxylic acid or an anhydride thereof. As the unsaturated carboxylic acid or its anhydride, maleic acid,
Examples thereof include maleic anhydride, fumaric acid, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, citraconic acid, hexahydrophthalic anhydride, and the like, and maleic anhydride is preferably used.

The amount of unsaturated carboxylic acid or its anhydride contained in the ethylene-α-olefin copolymer at this time is preferably 0.001 to 10% by weight, more preferably 0.01 to 5% by weight. is there. If the content is too small, the adhesive strength will be decreased, and conversely, if it is too large, a crosslinking reaction will occur, resulting in poor moldability, which is not preferable. It is also possible to mix such adhesive resins in adjacent layers.

The multilayer structure of the present invention is not limited to a sheet or a film, but can be formed into a pipe or a pipe by the above coextrusion molding method, coinjection molding method, coextrusion inflation molding method or blow molding method.
It can be formed into a tubular shape or a container such as a tank or a bottle, and further, the multilayer structure can be heated again to about 100 to 150 ° C. and stretched by a blow stretching method or the like. Further, each layer (other than the resin composition layer of the present invention) of the multilayer structure of the present invention contains an antioxidant, a lubricant, an antistatic agent, a plasticizer, a colorant, in order to improve molding processability, physical properties and the like.
Ultraviolet absorbers, antibacterial agents, inorganic / organic fillers and the like may be added within a range that does not impair the effects of the present invention.

[0034]

EXAMPLES 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 Resin (A)] A1; polypropylene (MI = 0.8 g / 10 minutes, density 0.90 g / cm ³ , chlorine content 110 ppm) A2; maleic anhydride modified polypropylene (MI = 1.
0g / 10 minutes, density 0.89g / cm ³ , chlorine content 80
ppm) A3; high-density polyethylene (MI = 6.0 g / 10 minutes, density 0.952 g / cm ³ , chlorine content 15 ppm) The above MI is 230 ° C. (polypropylene), 19
It represents the melt flow index at 0 ° C. (polyethylene) under a load of 2160 g.

[EVOH (B)] B1; ethylene content 38 mol%, saponification degree 99.6 mol%, MI = 3.5 g / 10 min B2; ethylene content 27 mol%, saponification degree 99.5 Mol%, MI = 6 g / 10 min B3; ethylene content 40 mol%, saponification degree 98.7 mol%, MI = 8 g / 10 min. The above MI is the melt flow index at 210 ° C. and 2160 g load. Represents

[Colorant (C)] C1; Cadmium red (red inorganic pigment) C2: Zinc sulfide (white inorganic pigment) C3: Ultramarine (blue inorganic pigment)

[Higher fatty acid metal salt (D)] D1; calcium stearate (manufactured by NOF Corporation) D2; 12-magnesium hydroxystearate (manufactured by Eishin Kasei)

[0038] [hydrotalcite compound (E)] E1;. Mg 4 5 Al 2 (OH) 13 CO 3 · 3.5H 2 O E2; [. Mg 0 75 Zn 0.25] 0.67 Al 0.33 (OH)
₂ (CO ₃ ) _0.165・ 0.45H ₂ O

[Adhesive resin] F1; Modified polyolefin resin (trade name: Modic AP P512 (manufactured by Mitsubishi Chemical Corporation))

Examples 1 to 3, Comparative Examples 1 to 4 Thermoplastic resins (A), EVOH (B), as shown in Table 1,
The colorant (C), higher fatty acid metal salt (D), and hydrotalcite compound (E) were melt-mixed by a single-screw extruder and melt-molded to obtain a sheet. The molding conditions are as follows. Molding conditions Extruder: 40 mm diameter single screw extruder Screw: L / D = 28 Compression ratio 3.5 Screen pack: Use 2 sheets with opening 120 μm Day: Coat hanger type Extrusion temperature: Cylinder tip 240 ° C Die 230 ° C. Screw rotation speed: 40 rpm The operation of crushing the obtained sheet and forming the sheet again under the same conditions was repeated 10 times, and the appearance of the sheet obtained at the 1st, 5th and 10th times was visually observed. Then, the following evaluation criteria were evaluated.

Appearance O: Almost no streaks and rough surface are observed. Δ: Some streaks and rough surface are observed. X: Many streaks and rough skin are observed. The number of gel foreign matters having a diameter of 0.4 mm or more per 100 cm ² (10 cm × 10 cm) of the gel sheet was measured and evaluated according to the following criteria. ◯: 2 or less Δ: 3 to 10 × ... 11 or more The respective results are shown in Table 2.

[0042]

(Table 1) (A) (B) (C) (D) (E) (Blending amount) (Blending amount) (Blending amount) (Blending amount) (Blending amount) Example 1 A1 A2 B2 C1 D2 E1 (93 ) (7) (5) (0.4) (0.2) (0.2) 〃 2 A3 B3 C2 C3 D1 E2 (100) (10) (0.2) (0.2) (0.3) (0.1) 〃 3 A1 A2 B1 C3 D1 − −− (86) (14) (13.5) (0.3) (0.5) Comparative Example 1 A1 A2 B1 C3 D1 −−− (86) (14) (55) (0.3) (0.5) 〃 2 A1 A2 B1 C3 D1 −−− (86) (14) (13.5) (20) (0.5) 〃 3 A1 A2 B1 C3 −−−−−− (86) (14) (13.5) (0.3) 〃 4 A1 A2 B1 C3 D1 − --- (86) (14) (13.5) (0.3) (15) Note) The blending amounts of (B) and (C) are based on 100 parts of (A), and the blending amount of (D) is (A). , (B), and (C) based on 100 parts in total.

[0043]

[Table 2] 1st 5th 10th appearance Gel appearance Gel appearance Gel Example 1 ○ ○ ○ ○ ○ ○ 〃 2 ○ ○ ○ ○ ○ ○ 〃 3 ○ ○ ○ ○ △ △ Comparative Example 1 ○ △ × × × × 〃 2 ○ × △ × △ × 〃 3 △ △ × × × × 〃 4 × ○ × ○ × △

Example 4 0.5 part of the colorant (C1) and 0.5 part of the higher fatty acid metal salt (D1) per 100 parts of the polyolefin resin (A1).
Parts, and a resin composition (a) obtained by melt-mixing 0.5 part of a hydrotalcite compound (E2) with a single-screw extruder, resin composition (a) layer / resin composition ( A) layer / adhesive resin (F1) layer / EVOH (B1) layer / adhesive resin (F
1) layer / resin composition (a) layer (thickness = 100 μm / 40
0 μm / 100 μm / 100 μm / 100 μm / 500
A multilayer structure having a structure of (μm) was produced under the following conditions by using a 4-layer 6-layer feed block die.

Molding condition Extruder 65 mm diameter extruder (for resin composition (A) layer) 65 mm diameter extruder (for resin composition (A) or (A) layer) 30 mm diameter extruder (adhesive resin (F1) Layer) 30 mm diameter extruder (for EVOH (B1) layer) Extrusion temperature C1 C2 C3 C4 AD FB Die (° C.) 200 230 230 230 210 220 220 220 230 200 200 230 230 230 210 220 220 220 230 200 200 230 --- --- 220 220 230 230 200 230 --- --- 220 220 220 230 screw rotation speed 20 rpm, 25 rpm, 10 rpm, 15 rpm die width 650 mm extrusion rate 24 kg / hr take-up speed 0.33 m / min roll temperature 80 ° C.

The resin composition (a) obtained by crushing the multilayer structure obtained above into about 1 to 5 mm square is used as the above-mentioned layer again under the same conditions as the multilayer structure, resin composition (a) layer / resin composition. (A) layer / adhesive resin (F1) layer / EVOH (B1) layer / adhesive resin (F1) layer / resin composition (a) layer (thickness = 1
00 μm / 400 μm / 100 μm / 100 μm / 10
0 μm / 500 μm). This operation is repeated 10 times (scrap return), and the multilayer structure obtained in the 1st, 5th, and 10th times is used to mold a cup with a vacuum / pressure molding machine under the following conditions. did. The EVOH content in the resin composition (a) layer of the first multilayer structure was about 10 parts, and the EVOH content of the fifth and tenth cycles was about 15 parts. The content of the colorant is about 0.4 parts for the first time and about 0.3 for the fifth time and the tenth time.
Parts, about 0.4 parts for higher fatty acid metal salts, about 0.3 parts for the 5th and 10th times, and about 0.4 parts for the first time, about 0.3 parts for the 5th and 10th times. It was

Molding condition Heater temperature 450 ° C. above and below Laminate surface temperature 160 ° C. Cup shape Mouth portion: 9 × 9 cm, bottom portion: 8 × 8 c
m, depth; 6.5 cm The appearance of the obtained cup was evaluated according to the following procedure.

(Appearance) The appearance of the obtained cup was visually observed and evaluated according to the following criteria. a --- The surface smoothness is good, and there are no streaks or gel foreign matters. b --- There are some streaks and no gel foreign matter. c --- There are many streaks on the whole and there are no gel foreign matters. d --- Overall there are many streaks and some gel foreign matter. e --- There are many streaks and gel foreign matters as a whole.

Example 5 In Example 4, 100 parts of the polyolefin resin (A1) as the resin composition (a) was added to the colorant (C3).
Other than using a resin composition obtained by melt-mixing 0.3 part, 0.8 part of higher fatty acid metal salt (D1), and 0.3 part of hydrotalcite compound (E1) with a single-screw extruder. Was performed in the same manner and evaluated in the same manner.

Example 6 In Example 4, the structure of the multilayer structure was changed to resin composition (A) layer / resin composition (A) layer / adhesive resin (F1) layer /
EVOH (B1) layer / adhesive resin (F1) layer / resin composition (a) layer / resin composition (a) layer = 200 μm / 200 μ
m / 100 μm / 100 μm / 100 μm / 200 μm
The same evaluation was performed in the same manner except that the thickness was set to / 400 μm.

Comparative Example 5 In the same manner as in Example 4, except that only the mixture of the polyolefin resin (A1) and the colorant (C1) of Example 4 was used as the resin composition (A), the same evaluation was performed. Did.

Comparative Example 6 In the same manner as in Example 4, except that only the mixture of the polyolefin resin (A1) and the colorant (C1) of Example 5 was used as the resin composition (A), the same evaluation was carried out. Did. The respective results are shown in Table 3.

[0053]

[Table 3] Note) The above number represents the number of scrap returns.

[0054]

The resin composition of the present invention contains the above-mentioned components (A) to (D), preferably components (A) to (E) in a specific amount, and therefore is excellent in appearance and heat resistance. Along with repeated scrap returns and long-term melt molding processing, it is a resin composition with excellent melt moldability that does not generate foreign substances called gels and lumps such as aggregates of colorants, and is used as various multilayer structures. It is useful for packaging films, containers, bottles / bottles, food trays, sheets, and various equipment parts.

Continued front page    F-term (reference) 4F100 AA11A AA21A AC10A AC10H                       AH00A AH08A AK01A AK01B                       AK01C AK01E AK69A AK69D                       AT00B BA01 BA04 BA05                       BA06 BA07 BA10B BA10D                       BA10E BA13 CA13A GB15                       JB16A JB16B JB16E JJ03                       JL01 JL11C YY00A                 4J002 AA011 BB001 BB031 BB051                       BB061 BB071 BB121 BB141                       BB151 BB171 BB231 BE032                       BN051 CL001 DE096 DE116                       DE136 DE156 DE288 DG026                       EG027 EG037 EG047 EQ016                       EU026 EU036 FD010 FD096                       FD170 GF00

Claims (7)

[Claims] 1. A thermoplastic resin (A), a saponified ethylene-vinyl acetate copolymer (B), a colorant (C) and a higher fatty acid metal salt (D), and a thermoplastic resin (A).
The content of the saponified ethylene-vinyl acetate copolymer (B) is 0.5 to 25 parts by weight, and the content of the colorant (C) is 0.01 to 10 parts by weight with respect to 100 parts by weight, Further, the content of the higher fatty acid metal salt (D) is the thermoplastic resin (A),
0.001 to 1 with respect to 100 parts by weight of the total amount of the saponified ethylene-vinyl acetate copolymer (B) and the colorant (C).
A resin composition comprising 0 parts by weight. 2. A thermoplastic resin (A), ethylene-
The hydrotalcite-based compound (E) is contained in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the total amount of the saponified vinyl acetate copolymer (B) and the colorant (C). The resin composition according to claim 1. 3. The resin composition according to claim 1, wherein the colorant (C) contains at least one organic pigment selected from azo pigments, quinacridone pigments and phthalocyanine pigments. 4. The colorant (C) contains at least one inorganic pigment selected from titanium oxide, zinc sulfide, lead pigments, cadmium pigments, red iron oxide, cobalt pigments, ultramarine blue and dark blue. The resin composition according to claim 1 or 2, wherein 5. A multilayer structure comprising at least one layer of the resin composition according to claim 1. 6. The multilayer structure according to claim 5, having a structure of thermoplastic resin layer / resin composition layer / adhesive resin layer / saponified ethylene-vinyl acetate copolymer layer. 7. The thermoplastic resin layer / resin composition layer / adhesive resin layer / ethylene-vinyl acetate copolymer saponification layer / adhesive resin layer / thermoplastic resin layer. The described multilayer structure.