JP2000263711A - Laminate - Google Patents

Abstract

(57) [Problem] To provide a laminate excellent in appearance, thermal stability (at the time of regrind), and the like. SOLUTION: A saponified ethylene-vinyl acetate copolymer in which the relationship between the heating time measured by a Koka type flow tester and the discharge speed and the relationship between the time measured by a plastograph and the torque satisfy specific conditions. A laminate comprising a layer containing:

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate comprising a layer containing a saponified ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVOH).
The present invention relates to a laminate having excellent thermal stability (at the time of regrind).

[0002]

2. Description of the Related Art In general, EVOH is excellent in transparency, gas barrier property, fragrance retention, solvent resistance, oil resistance and the like.
It is used by being molded into films or sheets of industrial chemical packaging materials, agricultural chemical packaging materials, etc., or containers such as bottles, etc., and in its implementation, it may be used as a laminate with various thermoplastic resin layers. In many cases, the appearance is also a large required performance. For the purpose of improving such performance, Japanese Patent Application Laid-Open No. 64-64843 discloses a relationship between a heating temperature and a discharge speed at at least one point of 10 to 80 ° C. higher than the melting point of EVOH in a Koka flow tester. The discharge speed does not substantially increase at least up to 15 minutes, and the discharge speed in an arbitrary heating time within 2 hours after 15 minutes is 1/10 of the discharge speed after 15 minutes.
It exhibits flow characteristics such that the discharge speed at any heating time within 2 hours and within 10 hours is at least once within a range of 2 to 50 times the discharge speed after 15 minutes. A laminate using EVOH has been proposed.

[0003]

However, the present inventor has conducted detailed studies on the flow characteristics of the EVOH, and as a result, it has been found that the discharge speed at any heating time within 10 hours after 2 hours is at least once 15 minutes. Later discharge speed 2
It has been found that the flow characteristics as in the range of up to 50 times cause a problem in the thermal stability, and the laminate using such EVOH has a workability when subjected to a reuse treatment such as recycling or regrind. And it is difficult to obtain a good laminate, and improvement is desired.

[0004]

In view of this situation, the present inventor has conducted further intensive studies on the flow characteristics of EVOH. As a result, the present inventors have found that the melting point measured by a DSC (differential scanning calorimeter) is 10 times lower than the melting point. At least one of ~ 80 ° C higher temperature
In the relationship between the heating temperature and the discharge speed in the Koka type flow tester at the point, the discharge speed in an arbitrary heating time within 15 minutes and within 2 hours is 0.1% of the discharge speed after 15 minutes.
The discharge speed at any heating time within 10 hours after 2 hours is less than twice the discharge speed after 15 minutes, and 3 times lower than the melting point measured by DSC.
In relation to the time and torque measured by a torque detection type rheometer at at least one point at a temperature higher by 0 to 60 ° C., the torque value at any heating time within 1 to 2 hours and within 20 minutes is the maximum torque value. 1/6 to 5
The present inventors have found that a laminate using EVOH in the range of / 6 can solve the above-mentioned problems and is excellent in appearance and thermal stability (at the time of regrind). The invention has been completed.

The melting point is a value indicated by a main endothermic peak temperature measured by a DSC (differential scanning calorimeter; heating rate: 10 ° C./min). The discharge speed measured by a Koka flow tester is 1 mm in diameter. 10k using a 10mm long nozzle
The measurement was carried out under a load of g / cm ² , and the measurement time was a time including a preheating time of 5 minutes. In addition, the relationship between time and torque is measured using a torque detection type rheometer. As such a torque detection type rheometer, for example, `` Plasticorder '' manufactured by Brabender and `` Toyo Seiki Seisakusho '' Labo Plastmill "and the like. The measurement is carried out using a measuring mixer having a chamber capacity of 60 cc and a roller-type blade. As the roller-type blade, "Plastic coder" is used for "roller mixer W50", and "Laboplast mill" is used for "roller". Shape blade R60B "is used. In the measurement, 55 g of a sample (filling rate: 90 to 100% by volume) was charged from the supply port under air, the lid was sealed with a load of 7 kg, and the rotation speed was increased to 50 rpm within 30 seconds after preheating for 5 minutes. 60
The torque value at the time of kneading is detected.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The EVOH used in the present invention is, as described above, at least one point at a temperature higher than the melting point measured by DSC at 10 to 80 ° C. in the Koka type flow tester and the discharge speed, from 15 minutes to 2 hours. The discharge speed at an arbitrary heating time within the range of 0.1 to 0.1 of the discharge speed after 15 minutes.
The discharge speed at any heating time within 10 hours after 2 hours is 2 times the discharge speed after 15 minutes.
Less than 30 times and 30 ° C above the melting point measured by DSC.
In the relationship between the time and the torque measured by the torque detection type rheometer at at least one point at a temperature higher by ６０60 ° C., the maximum value of the torque that appears within 20 minutes at any heating time within 1 hour to 2 hours. 1/6 ~
It has specific flow characteristics in the range of 5/6 (further 1/3 to 2/3), and satisfies such conditions.
There is no particular limitation as long as it is VOH, but in general, a specific process is required for ordinary EVOH.

The specific processing method will be described later,
The EVOH to be treated is not particularly limited, but has an ethylene content of 20 to 60 mol% (further 25 to 55 mol%) and a saponification degree of 90 mol% or more (furthermore, 95 mol%
When the ethylene content is less than 20 mol%, the gas barrier properties and melt moldability at high humidity are reduced, and when it exceeds 60 mol%, sufficient gas barrier properties cannot be obtained. If the saponification degree is less than 90 mol%, the gas barrier properties, thermal stability, moisture resistance, etc. are undesirably reduced. In addition, the melt index (MI) of the EVOH (210)
° C, load 2160 g) is preferably 1 to 100 g / 10 min (more preferably 3 to 50 g / 10 min), and if the melt index is smaller than this range, the inside of the extruder will be in a high torque state during molding. Extrusion becomes difficult, and if it is larger than this range, the mechanical strength of the molded product is insufficient, which is not preferable.

The EVOH is obtained by saponifying an ethylene-vinyl acetate copolymer, and the ethylene-vinyl acetate copolymer can be produced by any known polymerization method, for example, solution polymerization,
It is produced by suspension polymerization, emulsion polymerization, or the like, and saponification of an ethylene-vinyl acetate copolymer can also be performed by a known method.

In the present invention, a copolymerizable ethylenically unsaturated monomer may be copolymerized as long as the effects of the present invention are not impaired. Examples of such a monomer include propylene and 1-butene. , Olefins such as isobutene, acrylic acid, methacrylic acid, crotonic acid, (anhydrous) phthalic acid,
Unsaturated acids such as (anhydride) maleic acid and (anhydride) itaconic acid or salts thereof, mono- or dialkyl esters having 1 to 18 carbon atoms, acrylamide, 1 to 1 carbon atoms
8, acrylamides such as N-alkylacrylamide, N, N-dimethylacrylamide, 2-acrylamidopropanesulfonic acid or a salt thereof, acrylamidopropyldimethylamine or an acid salt thereof or a quaternary salt thereof, methacrylamide, having 1 to 18 carbon atoms Methacrylamides such as N-alkylmethacrylamide, N, N-dimethylmethacrylamide, 2-methacrylamidopropanesulfonic acid or a salt thereof, methacrylamidopropyldimethylamine or an acid salt thereof or a quaternary salt thereof, N-vinylpyrrolidone , N-vinylformamide, N-vinylamides such as N-vinylacetamide,
Vinyl cyanides such as acrylonitrile and methacrylonitrile, vinyl ethers such as alkyl vinyl ethers having 1 to 18 carbon atoms, hydroxyalkyl vinyl ethers and alkoxyalkyl vinyl ethers, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and vinyl bromide And vinylsilanes such as trimethoxyvinylsilane, allyl acetate, allyl chloride, allyl alcohol, dimethylallyl alcohol, trimethyl- (3-acrylamido-3-dimethylpropyl)-
Ammonium chloride, acrylamido-2-methylpropanesulfonic acid and the like.

In imparting the flow characteristics as described in the present invention to the EVOH as described above, the EVOH is not particularly limited.
It is possible to apply a treatment such as attaching a higher fatty acid salt to the surface of OH, or impregnating with water containing a large amount of an alkaline earth metal such as calcium or magnesium. It is preferable to attach, and such a method is described below, but is not limited to this method.

Examples of such higher fatty acid salts include salts of fatty acids having 8 or more carbon atoms. Specifically, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, Alkaline metal salts such as sodium and potassium salts of higher fatty acids such as nonadecanoic acid, oleic acid, capric acid, behenic acid and linoleic acid, alkaline earth metal salts such as magnesium salt, calcium salt and barium salt, and zinc metal Salts and the like can be mentioned. Of these, divalent metal salts of stearic acid, oleic acid, and lauric acid (magnesium salts, calcium salts, zinc salts) are preferably used.

There is no particular limitation on the attachment of the higher fatty acid salt to the surface of the EVOH,
It is only necessary that the higher fatty acid salt adhere to the surface of the OH (pellet), and EVOH (pellet) having a water content of 1 to 5% by weight.
Method of blending higher fatty acid salt with liquor, heated EVO
A method of blending a higher fatty acid salt melted in H (pellet), a method of blending a higher fatty acid salt in EVOH (pellet) mixed with a small amount of silicone oil, and a higher fatty acid in EVOH (pellet) containing a liquid plasticizer Examples of the method include a method of blending a salt and a method of blending a higher fatty acid salt dissolved in a small amount of a solvent with EVOH (pellet).

The method will be described more specifically, but is not limited thereto. In attaching the higher fatty acid salt to the surface of the EVOH, the water content is adjusted to 1 to 5% by weight in order to improve the adhesion of the higher fatty acid salt.
(More preferably, 2 to 3% by weight). If the water content is less than 1% by weight, the higher fatty acid salt falls off and the adhesion (attachment) becomes uneven, and on the contrary, it exceeds 5% by weight. And the higher fatty acid salt is aggregated, and the adhesion (attachment) is not uniform even at this time, which is not preferable. In addition, a device such as a rocking mixer, a ribbon blender, and a super mixer can be used for blending.

Thus, the higher fatty acid salt is attached to the surface of the EVOH (pellet).
30 to 300 ppm (more preferably 50 to 2 ppm) with respect to EVOH
It is preferably 50 ppm, especially 100 to 200 ppm). When the amount is less than 30 ppm, long-run moldability is deteriorated. On the other hand, when the amount exceeds 300 ppm, generation of gas due to decomposition is extremely undesirable.

Thus, E satisfying the flow characteristics of the present invention
VOH can be obtained. First, the EVOH has a relationship between the heating temperature and the discharge speed in the Koka flow tester at at least one point at a temperature 10 to 80 ° C. higher than the melting point measured by DSC. The discharge speed in an arbitrary heating time within 2 hours after the minute is within the range of 0.1 to 50 times the discharge speed after 15 minutes. On the other hand, if it exceeds 50, molding becomes difficult due to severe viscosity reduction, and the object of the present invention cannot be achieved.
If the discharge speed is less than twice the discharge speed after 5 minutes, and if the magnification is twice or more, the generation of gas due to decomposition becomes remarkable, and the object of the present invention cannot be achieved. In the relationship between the time and the torque measured by the torque detection type rheometer at at least one point at a temperature higher by ６０60 ° C., the maximum value of the torque that appears within 20 minutes at any heating time within 1 hour to 2 hours. If the ratio is less than 1/6, the viscosity is so severe that it is difficult to mold, and if the ratio is more than 5/6, the ratio is less than 1/6. The long-run formability becomes poor, and the object of the present invention cannot be achieved even at this time. That is, the object of the present invention can be achieved only when all of the above specific flow characteristics are satisfied.

In the present invention, since it has the specific flow characteristics as described above, the effect of adding a lubricant is large, and a remarkable effect can be expected such as the effect of suppressing the fluctuation of motor torque during extrusion molding by the addition of the lubricant. . Examples of such a lubricant include ethylene bis stearamide, ethylene bis oleamide, ethylene bis erucamide, ethylene bis lauric amide, m-xylylene bis stearamide, p
Amide-based lubricants such as phenylene bisstearamide, erucamide, oleamide, stearamide, behenic amide, methyl laurate, methyl myristate, methyl palmitate, methyl stearate, methyl stearate, methyl oleate, erucic acid Fatty acid methyl ester lubricants such as methyl and methyl behenate, butyl laurate, butyl stearate, isopropyl myristate, isopropyl palmitate, octyl palmitate, palm FA
Monoester lubricants such as octyl ester, octyl stearate, lauryl laurate, stearyl stearate, behenyl behenate, cetyl myristate, fatty acid triglyceride lubricant, higher alcohol lubricant,
Higher fatty acid-based lubricants, monoglyceride-based lubricants, ester wax-based lubricants, polyethylene wax-based lubricants, and the like can be given, and the added amount is preferably 50 to 2000 ppm, more preferably 100 to 1000 ppm. It is also preferable to add an antioxidant. As such an antioxidant, pentaerythrityl-tetrakis [3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate],
Triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6-
(4-hydroxy-3,5-di-t-butylanilino)
-1,3,5-triazine, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N'hexamethylenebis (3,5 -Di-t-butyl-4-hydroxy-hydrocinnamamide), octadecyl-3- (3,5-di-
(tert-butyl-4-hydroxyphenyl) propionate, 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-
Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris-
(3,5-di-t-butyl-4-hydroxybenzyl)
-Isocyanurate, octylated diphenylamine,
2,4-bis [(octylthio) methyl] -O-cresol, isooctyl-3- (3,5-di-t-butyl-
4-hydroxyphenyl) propionate, tris (2,4-di-t-butylphenyl) phosphite, and the like, and the added amount thereof is 30 to 4000 pp.
m, more preferably 50 to 2000 ppm.

The EVOH of the present invention may further contain a plasticizer, a slip agent, an anti-blocking agent,
Additives such as a heat stabilizer, an ultraviolet absorber, an antistatic agent, a surfactant, a coloring agent, an antibacterial agent, a filler, and other resins can also be blended. In particular, hydrotalcite-based compounds, hindered phenol-based compounds,
A hindered amine-based heat stabilizer may be added. In addition, as long as the effects of the present invention are not impaired, two or more types of EVOH having different structures and molecular weights can be used, and an acid component (acetic acid, phosphoric acid, boric acid, etc.) can be added. is there.

The laminate of the present invention has an EVOH having the specific flow characteristics as described above (hereinafter referred to as f-EVOH).
And at least one layer containing f-EVOH, specifically, a laminate in which the layer containing f-EVOH is any one of an intermediate layer, an innermost layer, and an outermost layer.
The layer containing EVOH may be a layer of only f-EVOH or a layer of a blend of f-EVOH and other EVOH. Further, the intermediate layer does not mean only the middle layer (central portion) of the laminate, but means that the laminate has at least one layer on both sides, and furthermore, the innermost layer and the outermost layer are Means a layer exposed on the surface when made into a laminate, especially in containers and the like,
With respect to those that can be distinguished from the inside and the outside, the innermost layer means a layer arranged to be exposed inside and the outermost layer means a layer arranged to be exposed to the outside.

Specifically, the layer containing f-EVOH is a (a ₁ , a ₂ ,...), And the other layers are b (b ₁ , b ₂ ,.
・), Not only the two-layer structure of a / b but also b / a
/ B, a / b / a , a 1 / a 2 / b, a / b 1 / b 2, b 2
/ B ₁ / a / b ₁ / b ₂ , a ₁ / b ₁ / a ₂ / b _{2 and the} like. / B, b ₂ / b ₁ / a / b ₁ /
a / b ₁ / b ₂ , a ₁ / b ₁ / a ₂ / b ₂ are required to further have a stain-preventing performance such as wallpaper for packaging applications such as liquids where b ₂ is a fragrance required. A / b, a ₁ /
A layer configuration of a ₂ / b is useful. In the filament form, any combination of a and b such as a bimetal type, a core (a) -sheath (b) type, a core (b) -sheath (a) type, or an eccentric core-sheath type is possible.

As the resin used for the other layer (b), a thermoplastic resin is used. Specifically, linear low-density polyethylene, low-density polyethylene, medium-density polyethylene, high-density polyethylene, ethylene-acetic acid Vinyl copolymer, ionomer, ethylene-propylene copolymer,
Ethylene-acrylate copolymer, polypropylene, propylene-α-olefin (α having 4 to 20 carbon atoms)
-Olefins) Copolymers, homo- or copolymers of olefins such as polybutene and polypentene, and blends thereof, homo- or copolymers of these olefins, and blends obtained by graft-modifying the olefins with unsaturated carboxylic acids or esters thereof. Polyolefin resin, polyester, polyamide, copolymerized polyamide, polyvinyl chloride, polyvinylidene chloride, acrylic resin, polystyrene, vinyl ester resin, polyester elastomer, polyurethane elastomer, chlorinated polyethylene, in a broad sense
Chlorinated polypropylene, aromatic or aliphatic polyketone,
Polyalcohol, EVOH, etc., among which, ease of co-extrusion film formation, film properties (particularly strength)
From the viewpoint of practicality, polypropylene, polyamide, polyethylene, ethylene-vinyl acetate copolymer, polystyrene, PET, and PEN are preferably used.

If necessary, an adhesive resin can be used between a and b. Various resins can be used as the resin, and depending on the type of resin b, Although it cannot be said unconditionally, a carboxyl group-containing modification obtained by chemically bonding an unsaturated carboxylic acid or an anhydride thereof to an olefin polymer (the above-mentioned broad polyolefin) by an addition reaction, a graft reaction or the like. Olefin polymers can be mentioned, and specifically, maleic anhydride graft-modified polyethylene, maleic anhydride graft-modified polypropylene, maleic anhydride graft-modified ethylene-ethyl acrylate copolymer,
Suitable examples include one or a mixture of two or more selected from maleic anhydride graft-modified ethylene-vinyl acetate copolymer, maleic anhydride graft-modified ethylene-vinyl acetate copolymer, and the like. It is also possible to blend f-EVOH and other EVOHs with the adhesive resin, and further, a resin of the b layer. Although the thickness of each layer of the laminate cannot be unconditionally determined depending on the layer configuration, the type of b, the application, and the like, the layer a is usually 1 to 200 μm (more preferably 3 to 15 μm).
0 μm), and the layer b is 5 to 1000 μm (further 10 to 50 μm).
0 μm), the adhesive resin layer is 1 to 200 μm (and 3 to
150 μm).

In manufacturing the laminate, f-EV
Another substrate is laminated on one or both sides of the layer of OH or a blend thereof. As a lamination method, for example, a thermoplastic resin is melt-extruded into a film or sheet of the f-EVOH or a blend thereof. A method of melt-extruding the f-EVOH or a blend thereof on a substrate such as a thermoplastic resin, a method of co-extruding the f-EVOH or a blend thereof and a thermoplastic resin, and a method of coextruding the f-EVOH or a blend thereof. EV
A method of dry laminating a film or sheet of OH or a blend thereof with a film or sheet of a thermoplastic resin using a known adhesive such as an organic titanium compound, an isocyanate compound, a polyester compound, or a polyurethane compound may be used.

Further, a molded product such as a film or a sheet is once obtained from f-EVOH or a blend thereof, and another substrate is extrusion-coated thereon, or the other substrate film, sheet, or the like is formed using an adhesive. In the case of lamination, any substrate (paper, metal foil, uniaxially or biaxially stretched plastic film or sheet, woven fabric, nonwoven fabric, metal flocculent, woody, etc.) other than the above-mentioned thermoplastic resin can be used.

The laminate of the present invention may be stretched. In such stretching, a heat stretching treatment is usually carried out. Means the operation of uniformly forming a parison-shaped laminate into cups, trays, tubes, bottles, and films by means of chucks, plugs, vacuum force, pneumatic force, blow, and the like. It may be any of axial stretching, and it is better to perform stretching at the highest possible ratio in terms of physical properties, and does not generate pinholes, cracks, stretching unevenness, uneven thickness, delamination, etc. during stretching, and has excellent gas barrier properties. A molded product is obtained.

As the stretching method, any of a roll stretching method, a tenter stretching method, a tubular stretching method, a stretch blow method, a vacuum pressurization molding, and the like having a high stretching ratio can be employed. In the case of biaxial stretching, any of a simultaneous biaxial stretching method and a sequential biaxial stretching method can be adopted. The stretching temperature is 60 to 170 ° C,
Preferably, it is selected from the range of about 80 to 160 ° C.

After completion of the stretching, it is also preferable to carry out heat setting. Heat setting can be carried out by known means,
80-170 while keeping the stretched film under tension.
The heat treatment is performed at a temperature of 100 ° C., preferably 100 to 160 ° C. for about 2 to 600 seconds. Also, when used for heat shrink packaging of raw meat, processed meat, cheese, etc., the product film is not heat-set after stretching, and the raw meat, processed meat, cheese, etc. are stored in the film, 50-130 ° C, preferably 7
At 0 to 120 ° C, heat treatment is performed for about 2 to 300 seconds,
The film is heat-shrinked and tightly packaged.

The shape of the laminate of the present invention may be any shape as described above, and examples thereof include a film, a sheet, a tape, a bottle, a pipe, a filament, and an extrudate having a modified cross section. The laminate is subjected to heat treatment, cooling treatment, rolling treatment, printing treatment, dry laminating treatment, solution or melt coating treatment, bag making processing, deep drawing processing, box processing, tube processing, split processing, etc., as necessary. It is useful as various packaging materials for foods, pharmaceuticals, industrial chemicals, agricultural chemicals and the like.

[0028]

The present invention will be specifically described below with reference to examples. In the Examples, “parts” and “%” are based on weight unless otherwise specified.

Example 1 EVOH having a water content of 0.1% [ethylene content 35 mol%, saponification degree 99.6 mol%, MI 10 g / 10 min (2
10 ° C., load 2160 g)] 2 parts of water was added to 100 parts of pellets, and the mixture was blended for 10 minutes with a rocking mixer.
EVOH pellets with a water content of 2% were obtained. Next, 100 parts of the obtained EVOH pellets were separately charged into a rocking mixer, and 100 parts of magnesium stearate were further charged and blended to obtain EVOH pellets having 94 ppm of magnesium stearate adhered to the surface of the EVOH pellets.
A pellet was obtained. The amount of magnesium stearate deposited was calculated from the amount of Mg obtained by atomic absorption spectrometry. Further, it was dried for 10 hours in a dryer at 100 ° C., and had a water content of 0.3
%.

The obtained EVOH pellets (f-EVO
H) is determined by DSC (“Pyr manufactured by PerkinElmer”).
is 1 DSC ”differential scanning calorimeter
When measured at 0 ° C./min), it was 181 ° C. In addition, the measurement value of the two-point piston position (3 mm, 7 mm) with a load value of 10 kg / cm ² using a 1 mm Φ × 10 mm L nozzle with a Koka type flow tester (“Flow Tester CFT-500C Model” manufactured by Shimadzu Corporation) 2)
After 15 minutes at 61 ° C. (melting point + 80 ° C.), after 1 hour,
After 2 hours and 4 hours (all including preheating time of 5 minutes), the discharge speed (measurement results are summarized in Table 1) and the torque detection type rheometer ("Plasticorder P" manufactured by Brabender)
LE331, using "Roller Mixer W50E" and "Quick Loading Chute"
After 55 g of the OH pellets were charged from the “quick loading chute”, the mixture was preheated under a load of 7 kg for 5 minutes, and then, after 15 seconds, the rotation speed was increased to 50 rpm and the kneading time was 231 ° C. (melting point +50) at 60 rpm. 2)
The maximum value of the torque value within 0 minutes and the torque value after 1 hour and 2 hours (measurement results are described in Table 2) were measured, and the flow characteristics of the present invention were satisfied.

Next, using a three-type, five-layer co-extrusion T-die film forming apparatus, the f-EVOH obtained above and a thermoplastic resin (polypropylene, MI at 190 ° C. under a load of 2160 g, 2.4 g / 10 min. ), Adhesive resin (“MODIC-APP523” manufactured by Mitsubishi Chemical Corporation, 2 at 190 ° C.)
When the MI under a load of 160 g is 2.5 g / 10 min), the thermoplastic resin layer (20 μm thick) / adhesive resin layer (5
A laminate having a structure of (μm thickness) / resin composition layer (5 μm thickness) / adhesive resin layer (5 μm thickness) / thermoplastic resin layer (25 μm thickness) was obtained. In addition, the said film-forming conditions were as follows.

[Film forming conditions of single screw extruder for EVOH] Screw inner diameter 32 mm L / D 28 Extrusion temperature C1: 180 ° C H: 240 ° C C2: 230 ° C C3: 240 ° C C4: 240 ° C

[Film forming condition of single screw extruder for thermoplastic resin] Screw inner diameter 40 mm L / D 28 Extrusion temperature C1: 180 ° C H: 240 ° C C2: 220 ° C C3: 240 ° C C4: 240 ° C

[Film forming condition of single-screw extruder for adhesive resin] Screw inner diameter 32 mm L / D 24 Extrusion temperature C1: 180 ° C H: 240 ° C C2: 220 ° C C3: 240 ° C

[Die setting conditions] T-die Feed block 5-layer die Die width 450 mm Set temperature 240 ° C

With respect to the obtained laminate, the appearance and the thermal stability at the time of regride were evaluated in the following manner.

(Appearance) The appearance of the obtained film was visually observed and evaluated as follows. ○ −−− No streaks were observed even after 6 hours. △ −−− Streaks occurred in less than 6 hours after 3 hours × −−− Streaks occurred in less than 3 hours (thermal stability: during regrind). After the obtained film was pulverized by a pulverizer, the film was again supplied to a twin-screw extruder, and pelletized under the following conditions to obtain re-granulated pellets.

[Granulation conditions by twin-screw extruder] Screw inner diameter 30 mm L / D 30 Screw rotation speed 120 rpm Extrusion temperature C1: 180 ° C H: 220 ° C C2: 210 ° C D: 220 ° C C3: 220 ° C C4: 220 ° C C5: 220 ° C

Forty parts of the obtained re-granulated pellets were blended with 60 parts of a thermoplastic resin (polypropylene, MI at 190 ° C. under a load of 2160 g under a load of 2.4 g / 10 minutes) to give pellets for a regrind layer. F-EVOH, a thermoplastic resin (polypropylene, MI under a load of 2160 g at 190 ° C. under a load of 2160 g: 2.4 g / 10 min), and an adhesive resin (manufactured by Mitsubishi Chemical Corporation) “MODIC-AP P523”, MI under a load of 2160 g at 190 ° C. is 2.5 g / 10 min),
In the above-mentioned pellets for re-glide, the thermoplastic resin layer (4
60 μm) / adhesive resin layer (30 μm) / resin composition layer (100 μm) / adhesive resin layer (30 μm) / regrind layer (690 μm) / thermoplastic resin layer (230 μm)
Was obtained.

The obtained laminate was cut with a razor, and an iodine potassium iodide ethanol solution (dilute tincture tincture manufactured by All Japan Drug Co., Ltd.) was applied to the cross section. The cross section of the sheet was observed with an optical microscope and evaluated as follows. did. The number of samples was set to 10, and comprehensively evaluated. ○---EVOH is uniformly dispersed in the regrind layer.---EVOH is aggregated in the regrind layer.

Example 2 In the preparation of f-EVOH of Example 1, EVOH pellets (melting point: 181 ° C.) to which 75 ppm of the magnesium stearate was attached were obtained with the input amount of magnesium stearate being 80 parts, and the water content was 0%. After adjusting to 3%, erucamide 150 ppm as a lubricant and pentaerythrityl-tetrakis [3- [3-
(3,5-di-t-butyl-4-hydroxyphenyl)] propione was added in the same manner except that 100 ppm was added, and the discharge speed of the obtained f-EVOH (measurement results are summarized in Table 1) And torque values (measurement results are shown in Table 2
Were collectively measured in the same manner, but they satisfied the flow characteristics of the present invention. Evaluation was performed in the same manner as in Example 1 using the obtained f-EVOH.

Example 3 In the preparation of f-EVOH of Example 1, 40 parts of magnesium acetate was added instead of magnesium stearate, and EVO to which 36 ppm of the magnesium acetate had adhered.
H pellets (melting point: 181 ° C.) were obtained and adjusted to a water content of 0.3%.
m and ethylenebisstearamide were added in the same manner except that 100 ppm was added, and the discharge speed of the obtained f-EVOH (measurement results are summarized in Table 1) and torque value (measurement results are summarized in Table 2) ) Was measured in the same manner, but it satisfied the flow characteristics of the present invention. The obtained f-
Evaluation was performed in the same manner as in Example 1 using EVOH.

Example 4 In the preparation of f-EVOH in Example 1, 350 parts of zinc laurate was added instead of magnesium stearate, and EV containing 310 ppm of the zinc laurate was added.
Obtained OH pellets (melting point 181 ° C), water content 0.3%
, And the same procedure as above was carried out except that 150 ppm of ethylenebisstearamide was further added as a lubricant. The discharge speed of the obtained f-EVOH (measurement results are summarized in Table 1) and the torque value (measurement results) Were collectively shown in Table 2), but they satisfied the flow characteristics of the present invention. Evaluation was performed in the same manner as in Example 1 using the obtained f-EVOH.

Example 5 In the preparation of f-EVOH of Example 1, calcium stearate was replaced with magnesium stearate by 22%.
0 parts, and the calcium stearate is 208 pp.
to obtain EVOH pellets (melting point: 181 ° C.)
After adjusting to a water content of 0.3%, 100 ppm of ethylenebisstearamide as a lubricant and N, N'hexamethylenebis (3,5-dibutyl-4) as an antioxidant were further added.
-Hydroxy-hydroxy namamide) was performed in the same manner except that 500 ppm was added, and the discharge speed of the obtained f-EVOH (measurement results are summarized in Table 1) and torque value (measurement results are summarized in Table 2) ) Was measured in the same manner, but it satisfied the flow characteristics of the present invention. Evaluation was performed in the same manner as in Example 1 using the obtained f-EVOH.

Example 6 In the preparation of f-EVOH of Example 1, the water content was 0.1
% EVOH, ethylene content 45 mol%, degree of saponification 99.6 mol%, MI 10 g / 10 min (210 ° C.,
EVOH to which 91 ppm of magnesium stearate was adhered in the same manner except that a load of 2160 g) was used.
After obtaining pellets (melting point 162 ° C.) and adjusting the water content to 0.3%, ethylene bissteramide 1 was further used as a lubricant.
00 ppm and amorphous silica 5 as an antiblocking agent
The same procedure was performed except that 0 ppm was added, and the obtained f-
EVOH discharge speed (measurement results are summarized in Table 1)
The torque and the torque value (measurement results are summarized in Table 2) were measured in the same manner, but they satisfied the flow characteristics of the present invention. Evaluation was performed in the same manner as in Example 1 using the obtained f-EVOH.

Example 7 In the preparation of f-EVOH of Example 1, the water content was 0.1
% EVOH, ethylene content 35 mol%, degree of saponification 98.6 mol%, MI 10 g / 10 min (210 ° C.,
An EVOH pellet (melting point: 172 ° C.) with 89 pm of magnesium stearate was obtained in the same manner except that a powder having a load of 2160 g) was used, and after adjusting the water content to 0.3%, ethylene bissteramide was further used as a lubricant. 10
0 ppm amorphous silica 50 as antiblocking agent
The resulting f-E was obtained in the same manner except that ppm was added.
The VOH discharge speed (measurement results are summarized in Table 1) and the torque value (measurement results are summarized in Table 2) were measured in the same manner, but they satisfied the flow characteristics of the present invention. Evaluation was performed in the same manner as in Example 1 using the obtained f-EVOH.

Example 8 In the preparation of f-EVOH of Example 1, the water content was 0.1
% EVOH pellets, the same procedure was followed except that EVOH pellets having a water content of 5% were obtained.
° C) and adjusted to a water content of 0.3%, and the same procedure was carried out except that 100 ppm of ethylenebissteroamide as a lubricant and 50 ppm of amorphous silica as an antiblocking agent were further added. The discharge speed (measurement results are summarized in Table 1) and the torque value (measurement results are summarized in Table 2) were measured in the same manner, and they satisfied the flow characteristics of the present invention. The obtained fE
Evaluation was performed in the same manner as in Example 1 using VOH.

Example 9 In the preparation of f-EVOH of Example 1, the water content was 0.1
% EVOH pellets were heated to 150 ° C., and melted magnesium stearate was sprayed, and the same procedure was carried out except that the magnesium stearate was adhered to obtain EVOH pellets (melting point: 181 ° C.) having 98 ppm of magnesium stearate attached thereto. After adjusting to 0.3%, the same procedure was performed except that 100 ppm of ethylenebissteroamide was further added as a lubricant, and the discharge rate of the obtained f-EVOH (measurement results are shown in Table 1).
And the torque values (measurement results are summarized in Table 2) were measured in the same manner, but they satisfied the flow characteristics of the present invention. Using the obtained f-EVOH,
Evaluation was performed in the same manner as in Example 1.

Example 10 Using the f-EVOH obtained in Example 1, a three-layer, three-layer co-extrusion T-die film forming apparatus was used to form a resin composition (15 μm).
m) / adhesive resin (10 μm) / thermoplastic resin (40 μm)
The evaluation was performed in the same manner except that a laminate having the layer configuration m) was obtained. The extruder setting conditions were the same, and the T-die setting conditions were as follows.

[Die setting conditions] T-die Multi-manifold three-layer die Die width 450 mm Set temperature 240 ° C

Comparative Example 1 EVOH pellets of Example 1 having a water content of 0.1% (melting point 1
(81 ° C.) was changed to f-EVOH, a laminate was obtained in the same manner as in Example 1, and the evaluation was performed in the same manner. The discharge speed of the EVOH pellets (measurement results are summarized in Table 1;
The measurement temperature was 261 ° C.) and the torque value (measurement results are summarized in Table 2; the measurement temperature was 231 ° C.), but they did not satisfy the flow characteristics of the present invention.

Comparative Example 2 100 parts of the EVOH pellets having a water content of 0.1% of Example 1 and 0.012 parts of magnesium stearate were charged into a single screw extruder, and melt-kneaded at 240 ° C. to obtain magnesium stearate. An EVOH composition (melting point: 181 ° C.) containing 105 ppm was obtained, and 100 ppm of ethylenebisstearamide was further added as a lubricant. As in Example 1, the discharge speed (measurement results are summarized in Table 1; the measurement temperature was 2
61 ° C.) and torque value (measurement results are described in Table 2; measurement temperature is 231 ° C.), but did not satisfy the flow characteristics of the present invention. Such EVOH
Using the pellets, a laminate was produced in the same manner as in Comparative Example 1, and was similarly evaluated. Table 3 summarizes the evaluation results of the examples and the comparative examples.

[0053]

Table 1 Measurement temperature discharge rate ^{(cm 3 / sec) (℃} ) 4 hours after 15 minutes after 1 hour after 2 hours Example ^{1 261 1.4 × 10 -2 3.7 ×} 10 -2 (2.6) 2.6 × 10 - ^{2 (1.9) 1. 7 ×} 10 -2 (1.9) 〃 ^{2 261 1.3 × 10 -2 3.5 ×} 10 -2 (2.7) 2.4 × 10 -2 (1.8) 1.4 × 10 -2 (1.1) 〃 3 261 1.5 × 10 ^-2 4.1 × 10 ^-2 (2.7) 2.4 × 10 ^-2 (1.6) 1.7 × 10 ^-2 (1.1) ４ 4 261 1.4 × 10 ^-2 3.6 × 10 ^-2 (2.6) 2.4 × 10 ^-2 ( 1.7) 1.7 × 10 ^-2 (1.2) ５ 5 261 1.6 × 10 ^-2 4.2 × 10 ^-2 (2.6) 3.0 × 10 ^-2 (1.9) 1.5 × 10 ^-2 (0.9) ６ 6 242 1.3 × 10 ^-2 3.5 × 10 ^-2 (2.7) 2.4 × 10 ^-2 (1.8) 1.4 × 10 ^-2 (1.1) ７ 7 252 1.5 × 10 ^-2 4.1 × 10 ^-2 (2.7) 2.4 × 10 ^-2 (1.6) 1.7 × ^10-2 (1.1) 〃 ^{8 261 1.3 × 10 -2 3.5 ×} 10 -2 (2.7) 2.4 × 10 -2 (1.8) 1.4 × 10 -2 (1.1) 〃 ^{9 261 1.5 × 10 -2 4.1 ×} 10 - ² (2.7) 2.4 × 10 ^-2 (1.6) 1.7 × 10 ^-2 (1.1) 〃 10 261 1.4 × 10 ^-2 3.7 × 10 ^-2 (2.6) 2.6 × 10 ^-2 (1.9) 1.7 × 10 ^-2 ( 1.9) Comparative Example 1 261 1.0 × 10 ^-2 9.7 × 10 ^-2 (1.0) 2.7 × 10 ^-2 (0.5) 2 .3 × 10 ^-2 (0.5) 〃2 261 1.5 × 10 ^-2 4.1 × 10 ^-2 (2.7) 2.4 × 10 ^-2 (1.6) 1.7 × 10 ^-2 (1.1) Note) Numbers in () The ratio with the measured value after 15 minutes is shown.

[0054]

Table 1 Measured temperature torque value (Nm) (° C) Maximum value After 1 hour After 2 hours Example 1 231 5.5 [11 minutes] 2.6 (0.5) 2.2 (0.4) 〃 2 231 4 [12 minutes] 3.8 (0.7) 3.7 (0.7) 〃 3 231 5.7 [12 minutes] 2.8 (0.5) 2.5 (0.4) 〃 4 231 5.3 [10 minutes] 2 2.4 (0.9) 2.1 (0.4) ５ 5 231 5.5 [12 minutes] 2.8 (0.5) 2.5 (0.5) ６ 6 212 5.4 [12 minutes] 3.8 (0.7) 3 0.7 (0.7) ７ 7 222 5.4 [12 minutes] 3.8 (0.7) 3.7 (0.7) ８ 8 231 5.4 [12 minutes] 3.8 (0.7) 3.7 (0.7) 〃 9 231 5.4 [12 minutes] 3.8 (0.7) 3.7 (0.7) 〃 10 231 5.5 [11 minutes] 2.6 (0.5) 2.2 (0.4) Comparative Example 1 231 7.0 [18 min] 6.6 (0.9) 6.6 (0.9) 〃 2 231 2.2 [17 min] 0 (0) 0 (0) Note) [], when the maximum value In numbers in () represents the ratio between the measurement value after 15 minutes.

[0055]

[Table 3]

[0056]

Since the laminate of the present invention has at least one layer containing EVOH exhibiting specific flow characteristics, it is excellent in appearance, thermal stability (at the time of regride), and the like. The body is very useful for applications such as films, sheets, tubes, bags, containers and the like for packaging foods, pharmaceuticals, agricultural chemicals, and industrial chemicals.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] April 19, 2000 (2004.1.
9)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0029

[Correction method] Change

[Correction contents]

Example 1 EVOH having a water content of 0.1% [ethylene content 35 mol%, degree of saponification 99.6 mol%, MI 10 g / 10 min (2
10 ° C., load 2160 g)] 2 parts of water was added to 100 parts of pellets, and the mixture was blended for 10 minutes with a rocking mixer.
EVOH pellets with a water content of 2% were obtained. Next, 100 parts of the obtained EVOH pellets were separately charged into a rocking mixer, and further 100 ppm of magnesium stearate was added.
And blended, EVOH pellets with 94 ppm of magnesium stearate adhered to the surface of the EVOH pellets
OH pellets were obtained. The amount of magnesium stearate deposited was calculated from the amount of Mg obtained by atomic absorption spectrometry. Further, it was dried with a dryer at 100 ° C. for 10 hours to adjust the water content to 0.3%.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0041

[Correction method] Change

[Correction contents]

Example 2 In the preparation of f-EVOH in Example 1, EVOH pellets (melting point: 181 ° C.) having 75 ppm of magnesium stearate attached thereto were obtained at an input amount of magnesium stearate of 80 ppm , and a water content of 0% was obtained. After adjusting to 3%, erucamide 150 ppm as a lubricant and pentaerythrityl-tetrakis [3- [3-
(3,5-di-t-butyl-4-hydroxyphenyl)] propione was added in the same manner except that 100 ppm was added, and the discharge speed of the obtained f-EVOH (measurement results are summarized in Table 1) And torque values (measurement results are shown in Table 2
Were collectively measured in the same manner, but they satisfied the flow characteristics of the present invention. Evaluation was performed in the same manner as in Example 1 using the obtained f-EVOH.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0042

[Correction method] Change

[Correction contents]

Example 3 In the preparation of f-EVOH of Example 1, 40 ppm of magnesium acetate was used instead of magnesium stearate.
E was charged with 36 ppm of the magnesium acetate.
VOH pellets (melting point 181 ° C.) were obtained with a water content of 0.3
%, And then erucamide 150 as a lubricant.
ppm and 100 ppm of ethylenebisstearamide were added in the same manner, and the discharge speed of the obtained f-EVOH (measurement results are summarized in Table 1) and torque value (measurement results are summarized in Table 2) ) Was measured in the same manner, but it satisfied the flow characteristics of the present invention. Evaluation was performed in the same manner as in Example 1 using the obtained f-EVOH.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction contents]

Example 4 In the preparation of f-EVOH of Example 1, 350 pp of zinc laurate was used instead of magnesium stearate.
m , and EVOH pellets (melting point: 181 ° C.) having 310 ppm of the zinc laurate attached thereto were obtained.
After adjusting to 3%, the same procedure was repeated except that 150 ppm of ethylenebisstearamide was further added as a lubricant.
The discharge speed (measurement results are summarized in Table 1) and the torque value (measurement results are summarized in Table 2) of the obtained f-EVOH were measured in the same manner, but those satisfying the flow characteristics of the present invention. Met. Evaluation was performed in the same manner as in Example 1 using the obtained f-EVOH.

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0044

[Correction method] Change

[Correction contents]

Example 5 In the preparation of f-EVOH of Example 1, calcium stearate was replaced with magnesium stearate by 22%.
0 ppm, the calcium stearate was 208
After obtaining EVOH pellets (melting point: 181 ° C.) to which ppm was attached and adjusting the water content to 0.3%, ethylene bisstearamide (100 ppm) was further used as a lubricant and N, N′hexamethylenebis (3,5) was used as an antioxidant. -Di-butyl-
4-hydroxy - except for adding hydroxy raw bromide) 500Pp m is performed in the same manner, the discharge rate of the resulting f-EVOH (measurement results are summarized in Table 1) and the torque value (measurement results in Table 2 (Collectively described) were measured in the same manner, but they satisfied the flow characteristics of the present invention. Evaluation was performed in the same manner as in Example 1 using the obtained f-EVOH.

Claims (3)

[Claims] 1. A relationship between a heating temperature and a discharge speed in a Koka type flow tester at at least one point of a temperature higher by 10 to 80 ° C. than a melting point measured by a DSC (differential scanning calorimeter) after 15 minutes. The discharge speed in an arbitrary heating time within 2 hours is 0.1 to 5 of the discharge speed after 15 minutes.
The discharge speed in any heating time within 10 hours after 2 hours is less than twice the discharge speed after 15 minutes, and is 30 to less than the melting point measured by DSC.
In relation to time and torque measured by a torque detection type rheometer at at least one point at a temperature 60 ° C. higher,
The torque value in an arbitrary heating time within 1 hour to 2 hours is 1/6 to 5/6 of the maximum torque value appearing within 20 minutes.
A laminate comprising at least one layer containing a saponified ethylene-vinyl acetate copolymer in the range of 1. 2. The layer containing a saponified ethylene-vinyl acetate copolymer as an intermediate layer.
The laminate according to the above. 3. The laminate according to claim 1, wherein the layer containing the saponified ethylene-vinyl acetate copolymer is either the innermost layer or the outermost layer.