JPH1112398A - Resin composition and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition excellent in durability, thermal contraction followability, solvent resistance and oxygen penetration resistance, and to provide its use. SOLUTION: This resin composition comprises (A) an ethylene-vinyl acetate copolymer saponification product having an ethylene content of 20-60 mol.% and a vinyl acetate component saponification degree of >=90 mol.%, (B) a thermoplastic resin having a tensile breaking elongation of >=700% measured according to JIS K7113 or JIS K6760, (C) a phenolic compound and (D) a phosphorus compound or an amine compound. Therein, the components A and B are contained in a (A)/(B) weight ratio of 97/3 to 70/30, and the components (C) and (D) are contained in amounts of 0.05-5 pts.wt., respectively, per 100 pts.wt. of the total amount of the components (A) and (B). A laminated product contains the resin composition as at least one layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition having excellent durability, resistance to oxygen permeation, ability to follow heat shrinkage, resistance to solvents and flexibility, and a laminate using the composition.

[0002]

2. Description of the Related Art Conventionally, iron and copper pipes have been frequently used as hot water pipes used for central heating by a hot water circulation method, particularly for floor heating equipment. However, recently, resin compositions such as polyethylene, polypropylene, and polybutene have been used instead of iron pipes in terms of cost and construction. However, in the case of such a resin pipe, corrosion may be observed in a metal part such as a heat exchanger or a pump. It is believed to be due to. As such a solution, JP-A-61-83035 discloses that
A pipe composed of a layer structure of water-crosslinked polyolefin / saponified ethylene-vinyl acetate copolymer / water-crosslinked polyolefin is described. Japanese Patent Publication No. H8-19293 discloses that a specific hinder is added to a saponified ethylene-vinyl acetate polymer. A resin composition containing an amide having a dophenol group is described. JP-A-2-74341 discloses a saponified ethylene-vinyl acetate polymer, a substituted phenol derivative and an organic phosphorous acid compound or a thioether compound. A hot water circulation pipe having a laminated structure having at least one layer of a composition containing at least one of the above is described.

[0003]

SUMMARY OF THE INVENTION However, Japanese Unexamined Patent Publication No.
According to the technique disclosed in Japanese Patent Publication No. 1-83035, saponified ethylene-vinyl acetate copolymer cannot follow shrinkage of water-crosslinked polyolefin in extremely bent portions or in portions where temperature changes are severe, and cracks during long-term use. However, pipes made of a polyolefin-based resin / laminate of the resin composition using the resin composition disclosed in Japanese Patent Publication No. H8-19293 and the technique disclosed in Japanese Patent Application Laid-Open No. 2-74341 are disadvantageous. Although the improvement of the durability of the pipe is seen, it has been found by the study of the present inventor that crack generation due to heat shrinkage may not be suppressed, and further detailed examination reveals that the mechanical strength is unstable. , There is room for improvement, excellent oxygen permeability to solve these issues,
There has been a demand for a resin composition which is excellent in durability, followability of heat shrinkage, solvent resistance, and flexibility and is useful for pipes as described above.

[0004]

The present inventor has conducted intensive studies in view of the above circumstances. As a result, the present inventors have found that an ethylene content of 20 to 60 mol% and a saponification degree of a vinyl acetate component of 90 mol% or more are obtained. -Saponified vinyl acetate copolymer (A), JIS K 7113 or JIS K 676
The thermoplastic resin (B), the phenolic compound (C), the phosphorus compound or the amine compound (D) having a tensile breaking elongation of 700% or more measured according to 0
(B) = 97-70 / 3-30 (weight ratio), [(A) +
(B)] The resin composition in which each of (C) and (D) is 0.05 to 5 parts by weight with respect to 100 parts by weight has durability,
It has been found that the oxygen permeation resistance, the heat shrinkage following property, the solvent resistance are excellent, and the laminate using the composition overcomes the above-mentioned disadvantages and is useful for the above-mentioned applications, and has completed the present invention. .

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the resin composition of the present invention will be specifically described. The saponified ethylene-vinyl acetate copolymer (A) used in the present invention has an ethylene content of 20 to 60 mol%, preferably 25 to 47 mol%, and a degree of saponification of the vinyl acetate component of 90 mol% or more, preferably More than 95 mol% is used. If the ethylene content is less than 20 mol%, the water resistance decreases, while if it exceeds 60 mol%, the oxygen permeability decreases. Also, the saponification degree of the vinyl acetate component is 9
If it is less than 0 mol%, the oxygen barrier properties and the moisture resistance will decrease. Among the saponified products (A), the melt flow index (MFI) measured at 210 ° C. under a load of 2160 g is 0.5 to 50 g / 10 min, preferably 1 to 35 g / min.
10 min, more preferably 2 to 15 g / 10 min is suitably used in terms of mechanical strength.

The saponified copolymer (A) may further comprise a small amount of an α-olefin such as propylene, isobutene, α-octene, α-dodecene, α-octadecene, an unsaturated carboxylic acid or a salt thereof, or a partial alkyl. Comonomers such as esters, full alkyl esters, nitriles, amides, anhydrides, unsaturated sulfonic acids or salts thereof may be included.

[0007] The thermoplastic resin (B) used in the present invention is J
Tensile elongation at break measured according to IS K 7113 or JIS K 6760 (JIS K 6760 for polyethylene, JIS K 7113 otherwise)
The tensile elongation at break is preferably 800 to 1800%, more preferably 900% or more.
~ 1500%. If the tensile elongation at break is less than 700%, the flexibility of the mixture of (A) and (B) becomes insufficient, which is inappropriate. Note that the tensile elongation at break of the present invention was determined by using a No. 2 test piece as a tumbler shape and a tensile speed of 50 mm / mi.
The value measured at n is adopted.

The thermoplastic resin (B) is not particularly limited as long as it satisfies the above-mentioned tensile elongation at break. Specific examples of the type of resin include polyolefin resin, polyamide resin, polyester resin, and the like. Examples thereof include ionomers, and preferably, polyester resins and polyolefin resins are used.

Such polyester resins include one or more acid components such as aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, and aliphatic dicarboxylic acids such as adipic acid and sebacic acid, and 1,6-hexane. Diol, 1,
It is produced by polycondensing a glycol component such as an alkylene glycol having 2 to 6 carbon atoms such as 4-butanediol, ethylene glycol and propylene glycol.

The polyester resin preferably has a glass transition temperature (Tg) of -150 to 25 ° C. measured by a differential scanning calorimeter (heating rate of 10 ° C./min), more preferably -80 to -10. ° C. Further, the heat of crystal fusion (ΔH) measured by a differential scanning calorimeter (heating temperature: 20 ° C./min)
u) is preferably 30 J / g or less, and more preferably 10 to 20 J / g.
/ G.

The glass transition temperature (Tg) and the heat of crystal fusion (ΔHu) of the polyester resin can be controlled by the composition of the polyester resin. That is, the glass transition temperature (Tg) can be controlled by the mixing ratio of the aromatic acid and the aliphatic acid,
The glass transition temperature (Tg) can be lowered by increasing the ratio of the aliphatic acid, and the heat of crystal fusion (ΔHu) can be lowered by increasing the amount of the raw material that breaks the crystallinity (for example, phthalic acid). However, it is not limited to these.

As the phenolic compound (C), 2,
5-di-t-butylhydroquinone, 2,6-di-t-
Butyl-p-cresol, 4,4′-thiobis- (6-
t-butylphenol), 2,2'-methylene-bis (4-methyl-6-t-butylphenol), tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-
4'-hydroxyphenyl) propionate] methane,
4,4′-thiobis- (6-t-butylphenol),
N, N'-hexamethylene-bis (3,5-di-tert-butyl-4'-hydroxy-hydrocinnamide), 1,
3,5-trimethyl-2,4,6 tris (3,5-di-
t-butyl-4-hydroxybenzyl) benzene, pentaerythrityl-tetrakis [3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate, triethylene glycol-bis [3- (3-t-butyl-
5-methyl-4-hydroxyphenyl) propionate], and when α is the ratio of molecular weight / melting point (° C.), α is 4.0 ≦ α ≦ 10.
0, specifically, N, N′-hexamethylene-bis (3,5-di-t-butyl-4′-hydroxy-hydrocinnamide) (α = 4.0), penta Erythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (α =
9.4), triethylene glycol-bis [3- (3-
t-butyl-5-methyl-4-hydroxyphenyl) propionate] (α = 7.4) is preferably used, and α <
In the case of 4.0 or α> 10.0, the dispersibility is poor and the mechanical properties are sometimes reduced, which is not preferable.

As the phosphorus compound or the amine compound (D), triphenyl phosphite, tris (p-nonylphenyl) phosphite, tris (2,4-di-t-
Trialkyl phosphites such as butylphenyl) phosphite, monoalkyl diphenyl phosphites such as diphenyl isooctyl phosphite and diphenyl isodecyl phosphite, and dialkyl monophenyl phosphites such as phenyl diisooctyl phosphite and phenyl diisodecyl phosphite And phosphorus-based compounds such as trialkyl phosphites such as alkylaryl phosphites, triisooctyl phosphites and tristearyl phosphites, and bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite. , 2, 4
-Bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, N, N-diphenyl-p-phenylenediamine, N-phenyl- Amine compounds such as N′-isopropyl-p-phenylenediamine and N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine; among them, the ratio of molecular weight / melting point (° C.) is β Is preferably 3.0 ≦ β ≦ 7.0, specifically, tris (2,4-di-t-butylphenyl) phosphite (β = 3.5), bis (2,4-di-
(t-butylphenyl) pentaerythritol di-phosphite (β = 3.7), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino)- 1,3,5-triazine (β = 6.
2) is preferably used, when β <3.0 or β> 7.0.
The case (1) is not preferable because the dispersibility is poor and the mechanical strength is sometimes poor.

[0014] The resin composition of the present invention comprises the above (A) to
(D), but such (A),
The mixing ratio of (B), (C) and (D) is (A) /
(B) = 97-70 / 3-30 (weight ratio), preferably 95-80 / 5-20 (weight ratio). If the ratio of (A) is larger than (A) / (B) = 97/3 (weight ratio), mechanical properties cannot be satisfied due to insufficient flexibility, and (A) / ( B) = 70/30 (weight ratio)
If the proportion of (A) is smaller, the compatibility is poor, so that sufficient flexibility cannot be exhibited, which is not suitable.

It is also necessary that each of (C) and (D) is 0.05 to 5 parts by weight, preferably 0.05 to 5 parts by weight, per 100 parts by weight of [(A) + (B)]. 1 part by weight. If (C) or (D) is less than 0.05 part by weight, the heat resistance becomes insufficient, and if it exceeds 5 parts by weight, the dispersibility is reduced, and the mechanical properties are insufficient, which is not suitable.

As a method for producing the resin composition comprising the above (A) to (D), a method of blending (A) to (D) with an extruder is suitably used. Examples of the blend include melt blending using a single screw extruder or twin screw extruder, and melt blending using a twin screw extruder is preferably used. Further, the resin composition by melt molding method, pellets,
Molded products such as films, sheets, pipes, tubes and the like can also be formed by extrusion molding (T-
Die extrusion, inflation extrusion, blow molding, melt spinning, profile extrusion, etc.) are mainly employed. The melt molding temperature is in the range of 170 to 270 ° C.

In melt molding, two or more saponified ethylene-vinyl acetate copolymers having different ethylene contents and saponification degrees can be used in combination. During melt molding, additives other than (C) and (D), stabilizers, surfactants, and crosslinkable substances (epoxy compounds, polyvalent metal salts, inorganic or organic polybasic acids or salts thereof) are reinforced. An appropriate amount of fiber (glass fiber, carbon fiber, etc.) hydrotalcite or the like as a material can be mixed.

The resin composition of the present invention is not limited to the production of a resin molded article having only a single layer of the resin composition as described above, but may be a laminate having at least one molded article such as a film or sheet of the present invention. Often used for practical use. In producing the laminate, a film obtained from the resin composition of the present invention, one or both sides of a layer of a resin molded product such as a sheet is laminated with another substrate, as a laminating method, For example, a method in which a thermoplastic resin is melt-extruded into the molded product (film, sheet, etc.), and conversely, the composition or the molded product (pellet, etc.) is formed on a substrate such as a thermoplastic resin.
, A method of co-extruding the composition or molded product with another thermoplastic resin, and a method of further forming the resin molded product obtained by the present invention and another base film or sheet with an organic titanium compound. And a method of laminating using a known adhesive such as an isocyanate compound or a polyester compound.

In the case of co-extrusion, the mating resin includes linear low-density polyethylene, low-density polyethylene, medium-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ionomer, ethylene-propylene copolymer, ethylene -Acrylate copolymer, polypropylene, propylene-α-olefin (having 4 to 20 carbon atoms)
Of α-olefin) copolymers, homo- or copolymers of olefin resins such as polybutene and polypentene, and graft-modified homo- or copolymers of these olefin resins with unsaturated carboxylic acids or esters thereof. Polyolefin resin, polyester, polyamide,
Copolymerized polyamide, polyvinyl chloride, polyvinylidene chloride, acrylic resin, styrene resin, vinyl ester resin, polyester elastomer, polyurethane elastomer, chlorinated polyethylene, chlorinated polypropylene, and the like. Saponified ethylene-vinyl acetate copolymer can also be coextruded.

The layer structure of the laminate is such that a layer of the composition obtained in the present invention is A (A ₁ , A ₂ ...), And another substrate, for example, a thermoplastic resin layer is B (B ₁ , B 2). when a ₂ ...), film, sheet, if the bottle shape, not only the double layer structure of a / B, B / a / B, a / B / a, a 1 / a 2 /
Any combination such as B, A / B ₁ / B ₂ , B ₂ / B ₁ / A / B ₁ / B ₂ is possible.

In the case of co-extrusion, A may be blended with B, B may be blended with A, or at least one of A and B may be blended with a resin for improving the adhesion between the two layers. The shape of the laminate may be any, such as a film, a sheet,
Examples include tapes, bottles, pipes, filaments, extrudates of irregular cross-section, and the like. For example, to produce a multilayer film, T-die extrusion, inflation extrusion, or the like is employed. For example, when the layer configuration is a polyolefin-based resin layer / adhesive layer / resin composition layer of the present invention / adhesive layer / polyolefin-based resin layer, ethylene-acetic acid is obtained by using a three-type five-layer coextrusion apparatus. When a saponified vinyl copolymer layer / adhesive layer / polyolefin-based resin layer is used, coextrusion from a die set at a temperature of 180 to 250 ° C. is performed by using three types and three layers of the apparatus, followed by chill rolls or the like. After cooling, a five-layer or three-layer laminated film can be obtained.

In the present invention, it is particularly useful to use a multilayer tube or a multilayer pipe, and such multilayer applications will be described more specifically. In order to produce a multilayer pipe from the resin composition of the present invention, a coextrusion method, an extrusion coating method and the like are used. When producing a multi-layer pipe by a co-extrusion method, for example, when producing a multi-layer pipe of (inside) a polyolefin-based resin layer / adhesive layer / resin composition layer of the present invention (outside), three types of three-layer co-extrusion Using a molding machine, temperature 180-
Co-extrude at 250 ° C.

In order to produce a multi-layer pipe having practical mechanical strength, a method of crosslinking a polyolefin resin layer is generally employed. Examples of the crosslinking method include a thermal crosslinking method, a water crosslinking method, and a radiation crosslinking method. The thermal crosslinking method is a method of crosslinking by reacting with a peroxide in an extruder. Examples of the peroxide used include ketone peroxide, diacyl peroxide, hydroperoxide, dialkyl peroxide, and alkyl peroxide. Esters and the like. In the water crosslinking method, a polyolefin resin having an alkoxysilyl group that causes a condensation reaction by hydrolysis is used. The functional group forms a siloxane bridge —Si (OR) ₂ —O—Si (OR) ₂ — by hydrolysis. Specifically, cross-linking can be performed by treating the polyolefin-based resin side of a multilayer pipe manufactured using a water-crosslinkable polyolefin-based resin with water, hot water, or steam.

The radiation crosslinking is carried out by irradiating ionizing radiation such as electron beam, γ-ray and β-ray. Specifically, the polyolefin resin portion of the multilayer pipe is irradiated with radiation to crosslink. On the other hand, the extrusion coating method is a method in which an extruder is used to coat a substrate pipe that has been manufactured in advance, and various methods are used depending on the layer structure. For example, when manufacturing a multilayer pipe of (inside) polyolefin-based resin layer / adhesive layer / resin composition layer of the present invention (outside), a method of coextrusion-coating a polyolefin-based resin pipe via an adhesive and an adhesive resin And a tandem type in which the resin composition of the present invention is sequentially extrusion-coated. By utilizing a plurality of extruders, a multilayer pipe having an arbitrary configuration can be manufactured. Also in this case, in order to give the practical strength of the multilayer pipe, it is usual to use a polyolefin pipe which has been crosslinked in advance by the above-mentioned method. In addition, the multilayer pipe of the present invention has, besides the above-mentioned layer constitution, (inside) a polyolefin resin layer / adhesive layer / polyamide resin / resin composition layer of the present invention (outside), (inside) polyolefin resin layer / A layer structure such as an adhesive layer / a polyolefin-based resin layer / the resin composition layer (outside) of the present invention can be adopted, and at this time, it can be produced in the same manner as described above. Also, a multilayer tube can be manufactured according to the above.

The above-mentioned multilayer pipe and multilayer tube are used for circulating hot or hot water, for transporting fuel, for transporting ink, and for transporting solvent. When used for circulation of hot water or hot water, the layer structure is (inside) polyolefin resin layer / adhesive layer / resin composition layer of the present invention (outside), (inside) polyolefin resin layer / adhesive layer / book. The resin composition layer / adhesive layer / polyolefin resin layer (outside) of the present invention is preferable, and the outer diameter is preferably 10 to 50 mm and the thickness is preferably 1 to 5 mm. The thickness of each layer is 1000 to 1000 for the polyolefin resin layer.
5000 μm, the adhesive layer is preferably 10-500 μm, and the resin composition layer of the present invention is preferably about 10-500 μm. In this case, the temperature of hot water or hot water is 40 to 95 ° C, usually 50 to 90 ° C.

When used for transporting fuel, the layer structure is (inside) polyolefin resin layer / adhesive layer / resin composition layer of the present invention (outside), (inside) polyolefin resin layer / adhesive layer / The resin composition layer / adhesive layer / polyolefin-based resin layer (outside) of the present invention, (inside) the resin composition layer / adhesive layer / polyolefin-based resin layer (outside) of the present invention are preferable, and the outer diameter is 10 Preferably, the thickness is 1 to 5 mm. The thickness of each layer is 1000-5000 μm for the polyolefin-based resin layer and 10-
500 μm, the resin composition layer of the present invention is 10 to 500 μm
The degree is preferred.

When used for transporting ink, the layer structure is (inside) polyolefin resin layer / adhesive layer /
Resin composition layer of the present invention (outside), (inside) polyolefin resin layer / adhesive layer / resin composition layer of the present invention / adhesive layer / polyolefin resin layer (outside), (inside) resin of the present invention The composition layer / adhesive layer / polyolefin-based resin layer (outside) is preferable, and the outer diameter is preferably 2 to 10 mm, and the thickness is preferably 0.05 to 2 mm. The thickness of each layer is 45-2000 μm for the polyolefin-based resin layer and 2-2 for the adhesive layer.
The thickness of the resin composition layer of the present invention is preferably about 2 to 200 μm.

Pipes for transporting solvents and fuel are useful for piping (flexible tubing) for fuels such as gasoline for automobiles or for solvents such as washer fluids, and pipes for transporting ink are ink tubing (flexible tubing) for printers and the like. ) Is useful.

Further, in the present invention, when a resin molded product such as a film or a sheet is extrusion-coated with another substrate, or when a film or a sheet of another substrate is laminated with an adhesive, a thermoplastic resin is used. In addition, any substrate (paper, metal foil, uniaxially or biaxially stretched plastic film or sheet, woven fabric, nonwoven fabric, metal cotton strip, wood surface, etc.) can be used.

[0030]

The present invention will be described below in more detail with reference to examples. Unless otherwise specified, “parts” indicates “parts by weight” and “%” indicates “% by weight”.

Example 1 A polyester (B) was obtained by reacting 60 parts of terephthalic acid, 40 parts of adipic acid and 100 parts of 1,4-butanediol. JIS K711 for polyester (B)
The tensile elongation at break, measured according to 3, was 1200%, the glass transition temperature (Tg) was -25 ° C., and the heat of crystal fusion (ΔHu) was 1
It was 3 J / g. Next, an ethylene content of 32 mol%, a saponification degree of 99.8 mol%, and a melt flow index (MFI) of 3 g / 10 min (2
90 ° C., 2160 g) of a saponified ethylene-vinyl acetate copolymer (A), N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide) [ "Irganox 1" manufactured by Ciba Geigy
098 "] (C) 0.3 part and tris (2,4-di-t-
Butylphenyl) phosphite (manufactured by Ciba-Geigy Corporation,
(Irgafos 168)) (D) Composition consisting of 0.3 part [(A) / (B) = 90/10, [(A) + (B)]
(C) and (D) are each 0.3 parts for 100 parts], and the twin-screw extruder 30 mmφ, L / D =
30, temperature of supply section 210 ° C, temperature of compression section and measurement section 2
The mixture was melt-mixed at 30 ° C. at a discharge rate of 7.0 kg / hr.

The obtained resin composition was evaluated as follows,
Table 3 shows the results. (A) Tensile breaking elongation From the obtained resin composition, length 50 mm, width 15 mm,
A test piece having a thickness of 100 μm was prepared, and the tensile speed was 50 mm.
The tensile elongation at break (%) was measured five times at room temperature at / min, and the average value (%), the maximum value (%), and the minimum value (%) were determined.

(B) Durability From the obtained resin composition, a length of 50 mm, a width of 15 mm,
A test piece having a thickness of 100 μm was aged at several points in the range of 130 to 150 ° C., and the tensile elongation at break was 2% of the original length.
The time at which the tensile elongation at 90 ° C. was 25% of the original length was determined by the Arrhenius method by calculating the time (year) by plotting the temperature at 5% and then plotting the temperature and the time.

(C) Oxygen permeability Using a three-layer, three-layer coextrusion apparatus, the outer layer is the above resin composition, the intermediate layer is carboxylic acid-modified polyethylene (460H, manufactured by Mitsubishi Kasei Corporation), and the inner layer is high-density polyethylene. (Mitsubishi Kasei Co., Ltd., JV070) F [outer layer / middle layer / inner layer = 80 μm
/ 160 μm / 1760 μm] by a co-extrusion method, one end of a 100 cm long multilayer pipe is sealed with a mixed epoxy adhesive, and the other end is an oxygen permeation measuring device (OXTRAN 10/50, manufactured by MOCON). ) And a heat treatment in a thermostat at 150 ° C. for 30 hours.

(D) Following heat shrinkage The multilayer pipe obtained above is cut into a length of 500 mm.
Installed in a thermostat with a fixed jig so that it can be bent into an L-shape, the temperature is repeatedly changed between 5 ° C and 95 ° C at 16 cycles / day, and the number of cycles at which cracks are completely generated at the bent part Was measured and evaluated as follows. ○ ・ ・ ・> 5000 cycles △ ・ ・ ・ 2000-5000 cycles × ・ ・ ・ <2000 cycles

(E) Solvent resistance A single-layer film (10 cm × 10 cm × 100 μm) was prepared from the resin composition obtained in the present invention using an extruder.
The rate of change in weight when immersed in gasoline, toluene, methyl ethyl ketone, and ethyl acetate at 23 ° C. for 7 days was measured, and evaluated as follows. ○: Less than 0.1% for all solvents ×: 0.1% or more for at least one solvent

Examples 2 to 13 and Comparative Examples 1 to 7 Resin compositions according to Example 1 using the components (A), (B), (C) and (D) shown in Tables 1 and 2. Was manufactured.
The obtained resin composition was evaluated in the same manner as in Example 1, and the results are shown in Table 3.

(Table 1) (A) (B) (A) / (B) Ethylene saponified MFI Type Elongation rupture Tg ΔHu Compounding ratio Content Elongation (° C) (J / G) (Weight ratio) (mol%) ( (Mol%) (g / 10min) (%) Example 1 32 99.8 3.0 1200 -25 13 90/10 Example 2 32 99.8 3.0 1200 -25 13 70/30 Example 3 44 99.8 12.0 1200 -25 13 90/10 Example 4 32 99.8 3.0 1000 ----90/10 Example 5 32 99.8 3.0 850 ----90/10 Example 6 32 99.8 3.0 900 ----90/10 Example 7 32 99.8 3.0 950 -25 13 90/10 Example 8 32 99.8 3.0 1200 -25 13 90/10 Example 9 32 99.8 3.0 1200 -20 15 90/10 Example 10 32 99.8 3.0 1200 -25 13 90/10 Example 11 32 99.8 3.0 1200 -25 13 90/10 Example 12 32 99.8 3.0 1200 -25 13 90/10 Example 13 32 99.8 3.0 1200 -25 13 90/10 Comparative Example 1 32 99.8 3.0 1200 -25 13 99/1 Comparative Example 2 32 99.8 3.0 1200 -25 13 65/35 Comparative Example 3 32 99.8 3.0 1200 -25 13 90/10 Comparative Example 4 32 99.8 3.0 1200 -25 13 90/10 Comparative Example 5 32 99.8 3.0 1200 -25 13 90 / 10 Comparative Example 6 32 99.8 3.0 1200 -25 13 90/1 Comparative Example 7 32 99.8 3.0 600 -25 13 90/10 : Polyester (consisting of 60 parts of terephthalic acid, 40 parts of adipic acid, and 100 parts of 1,4-butanediol): EP rubber ("EP01P" manufactured by Nippon Synthetic Rubber Co., Ltd.) )): EVA (manufactured by DuPont-Mitsui Polychemicals, “P-2805”): LLDPE (manufactured by Mitsubishi Polyethylene, “UF240”)

[0038]

(C) (D) Type Addition amount α * Type Addition amount β * (parts) (parts) Example 1 0.3 4.0 0.3 3.5 Example 2 0.3 4.0 0.3 3.5 Example 3 0.3 4.0 0.3 3.5 Example 4 0.3 4.0 0.3 3.5 Example 5 0.3 4.0 0.3 3. 5 Example 6 0.3 4.0 0.3 3.5 Example 7 0.3 4.0 0.3 3.5 Example 8 0.3 4.0 0.3 6.0 Example 90 3.3 5.9 0.3 3.5 Example 10 0.3 3.0 0.3 3.5 Example 11 0.3 10.0 0.3 3.5 Example 12 0.3 4.0 0.3 2.0 Example 13 0.3 4.0 0.3 8.0 Comparative Example 1 0.3 4.0 0.3 3.5 Comparative Example 2 0.3 4.0 0.3 3. 5 Comparative Example 3 0.03 4.0 0.3 3.5 Comparative Example 4 0.3 4.0 0.03 3.5 Comparative Example 5 6.0 4.0 0.3 3.5 Comparative Example 6 0.3 4.0 6.0 3.5 Comparative Example 7 0.3 4.0 0.3 3.5 * α = (C ) / Melting point of (C) (° C.) β = molecular weight of (D) / melting point of (D) (° C.): N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy) --- Hydrocinnamamide) ("Irganox 1098", manufactured by Ciba Geigy): 3,9-bis [1,1-dimethyl-2- @ β- (3-t-butyl-4-hydroxy-5-) [Methylphenyl) propionyloxydiethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane (Adeka Chemical Co., Ltd., "Adeka Stab AO-80"): Tris (2,4-di-t-) Butylphenyl) phosphite (“Irganophos 168” manufactured by Ciba-Geigy): amine-based compound ( "ADK STAB LA-57" manufactured by Asahi Denka Co., Ltd.)

[0039]

[Table 3](A) Tensile elongation at break(B)(C) (D) (e) Average value Minimum value Maximum value Initial value After 30 days Heat shrinkage Solvent resistant (%) (%) (%) ^{(Year) (cc / m 2 · 24hr} ) conformability properties Example 1 312 287 321 58 0.0002 0.0003 ○ Example 2 347 320 355 62 0.0003 0.0004 ○ Example 3 420 411 429 52 0.0002 0.0003 ○ Example 4 343 320 354 53 0.0002 0.0002 ○ Example 5 308 288 322 58 0.0002 0.0003 ○ ○ Example 6 290 274 311 54 0.0002 0.0003 ○ ○ Example 7 336 308 352 63 0.0002 0.0003 ○ ○ Example 8 325 306 343 50 0.0002 0.0003 0.003 ○ ○ Example 9 288 281 290 56 0.0002 0.0003 ○ ○ Example 10 237 211 301 45 0.0002 0.0004 ○ ○ Example 11 301 263 352 41 0.0002 0.0005 ○ ○ Example 12 313 251 353 46 0.0002 0.0005 ○ ○Example 13 291 255 342 40 0.0002 0.0005 ○ ○ Comparative Example 1 154 98 228 36 0.0002 0.0012 × ○ Comparative Example 2 211 71 281 27 0.0003 0.0024 △ ○ Comparative Example 3 295 285 302 39 0.0002 0.0008 ○ ○ Comparative Example 4 301 290 307 28 0.0002 0.0006 ○ ○ Comparative Example 5 241 211 275 36 0.0002 0.0005 ○ × Comparative Example 6 253 208 306 41 0.0002 0.0006 ○ ×Comparative Example 7 206 107 281 45 0.0002 0.0006 × ○

[0040]

The resin composition of the present invention comprises a saponified ethylene-vinyl acetate copolymer (A), a thermoplastic resin (B),
Since it contains a phenolic compound (C), a phosphorus compound or an amine compound (D) at a specific composition ratio, it has excellent durability, heat shrinkage followability, solvent resistance, and oxygen permeability resistance. The laminate having at least one layer of the product is also useful for applications such as tubes and pipes for circulating hot or hot water, for transporting fuel, for transporting ink, and for transporting solvent.

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Claims (6)

[Claims] 1. Ethylene having an ethylene content of 20 to 60 mol% and a saponification degree of a vinyl acetate component of 90 mol% or more.
Saponified vinyl acetate copolymer (A), JISK 7113
Alternatively, a thermoplastic resin (B), a phenol compound (C), a phosphorus compound or an amine compound (D) having a tensile elongation at break of 700% or more measured according to JIS K 6760.
(A) / (B) = 97-70 / 3-3
0 (weight ratio), (C) and (D) are each 0.05 to 5 parts by weight based on 100 parts by weight of [(A) + (B)]. 2. JIS K 7113 or JIS K
The thermoplastic resin (B) having a tensile elongation at break of 700% or more measured according to 6760 has a glass transition temperature (Tg) of -15.
The resin composition according to claim 1, wherein the resin composition is a thermoplastic polyester having a temperature of 0 to 25C and a heat of crystal fusion (? Hu) of 30 J / g or less. 3. The resin composition according to claim 1, wherein the phenolic compound (C) and the phosphorus compound or the amine compound (D) satisfy the following conditions. 4.0 ≦ α ≦ 10.0 [α represents the molecular weight of (C) / melting point (° C.)]. 3.0 ≦ β ≦ 7.0 [where β represents the molecular weight of (D) / melting point (° C.)]. ] 4. A laminate comprising at least one layer of the resin composition according to claim 1. 5. The laminate according to claim 4, wherein the laminate is a multilayer tube or a multilayer pipe. 6. The multi-layer tube or multi-layer pipe according to claim 5, wherein the multi-layer tube or multi-layer pipe is a multi-layer tube or multi-layer pipe for hot water or hot water circulation, fuel transport, ink transport, and solvent transport. Laminate.