JPH08325389A - Polyalcohol film and its laminated film - Google Patents

Abstract

PURPOSE: To improve the high-speed bag productivity, thermal filling and sealing properties, film formability, film appearance, adhesion and gas barrier properties of a polyalcohol film. CONSTITUTION: This polyalcohol film comprises a polyalcohol, prepared by reducing a polyketone comprising a carbon monoxide-ethylenic copolymer and having 0.3-3.0dl/g intrinsic viscosity and 110-180 deg.C melting point and has 10<8> to 10<11> dyne/cm dynamic elastic modulus at 75 deg.C and 5×10<-12> cc.cm/ cm<2> .sec.cmHg oxygen permeation coefficient at 20 deg.C an 75% RH. Furthermore, the laminated film has the film.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyalcohol film excellent in high-speed bag-making property, heat-filling sealing property, film-forming property, film appearance, adhesive property and gas barrier property, and a laminated film thereof.

[0002]

2. Description of the Related Art Films made of polyalcohols obtained by reducing polyketones are disclosed in JP-A-5-339367, JP-A-6-226925 or JP-A-6-26925.
It is known from, for example, Japanese Patent No. 255057. That is,
In JP-A-5-339367, an ethylene-carbon monoxide random copolymer is treated with an ether (eg, 1,3-dioxolane) or water using a mixed solvent of the ether and water or an alcohol (eg, methanol). It is described that a polyalcohol is additionally obtained, and that the obtained polyalcohol has excellent gas barrier properties and is therefore useful as a food packaging material. Further, in JP-A-6-226925 and JP-A-6-255057, ethylene-
Multilayer stretched film consisting of carbon monoxide alternating copolymer hydrogenated material layer and polyolefin layer (JP-A-6-226925)
No.) and an ethylene-carbon monoxide alternating copolymer hydrogenated layer and a polyester layer (JP-A-6-255057), and all of these films are heat-shrinkable films. It is described as being useful.

[0003]

However, the conventionally known polyalcohol film is inferior in high-speed bag-making property, heat-filling sealing property, film-forming property, film appearance, adhesiveness and gas barrier property, and is practically used as a packaging film. The improvement is necessary to offer.

[0004]

[Means for Solving the Problems] The above-mentioned problems are obtained by reducing a polyketone comprising a carbon monoxide-ethylene alternating copolymer and having an intrinsic viscosity of 0.3 to 3.0 dl / g and a melting point of 11
It is composed of polyalcohol at 0 to 180 ° C., has a dynamic elastic modulus at 75 ° C. of 10 ⁸ to 10 ¹¹ dyne / cm ² , and an oxygen permeability coefficient of 5 × 10 at 20 ° C. and 75% RH.
^The problem is solved by providing a film of ^-12 cc · cm / cm ² · sec · cmHg or less and a laminated film using the film.

In the present invention, polyalcohol is a polyalcohol obtained by reducing a polyketone composed of a carbon monoxide-ethylene alternating copolymer, and particularly 80% of the repeating unit represented by the formula (I) is used. Polyalcohol containing the above,
It is preferable in terms of gas barrier properties, mechanical properties, and moldability. The content of the repeating unit is more preferably 90% or more, particularly preferably 95% or more, and most preferably 97% or more.

[0006]

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The above-mentioned polyketone is a carbon monoxide-ethylene alternating copolymer, and the carbon monoxide-ethylene alternating copolymer is obtained by copolymerizing carbon monoxide and ethylene. Representative examples include those obtained by copolymerizing carbon monoxide and ethylene as a main component with an unsaturated compound other than ethylene. Here, as the unsaturated compound other than ethylene, an olefin having 3 to 12 carbon atoms, a diene having 4 to 12 carbon atoms, a vinyl ester,
Examples thereof include aliphatic unsaturated carboxylic acid, aliphatic unsaturated carboxylic acid salt and aliphatic unsaturated carboxylic acid ester. As the carbon monoxide-ethylene copolymer, there are a random copolymer and an alternating copolymer, but in the present invention, it is limited to the alternating copolymer from the viewpoint that the effects of the present invention are sufficiently exhibited.

Examples of the olefin having 3 to 12 carbon atoms include propylene, butene-1, isobutene, pentene-
1,4-methylpentene-1, hexene-1, octene-1, dodecene-1, styrene and the like can be mentioned, but propylene, olefin having 4 to 8 carbon atoms, or propylene and olefin having 4 to 8 carbon atoms. A combination system with is preferred. Examples of the diene having 4 to 12 carbon atoms include butadiene, isoprene, 1,5-hexadiene, 1,7-octadiene and 1,9-decadiene. Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl pivalate and the like. Also,
Examples of the aliphatic unsaturated carboxylic acid, its salt and its ester include acrylic acid, methacrylic acid, maleic anhydride,
Maleic acid, itaconic acid, acrylic acid ester, methacrylic acid ester, maleic acid monoester, maleic acid diester, fumaric acid monoester, fumaric acid diester, itaconic acid monoester, itaconic acid diester (as these esters, methyl ester, ethyl ester Alkyl ester such as ester), acrylate,
Examples thereof include maleic acid salts and itaconic acid salts (these salts include monovalent or divalent metal salts).

The ethylene-carbon monoxide alternating copolymer can be produced by a known method, for example, JP-A-59-19.
7427, JP-A-61-191226, JP-A-62-162
Although the method described in No. 232434 and the like can be mentioned, the method is not particularly limited thereto.

Next, as a method for reducing the carbonyl group in the above polyketone to obtain a polyalcohol, a method for reducing a part or all of the carbonyl group in the polyketone with hydrogen or the like, for example, JP-A-2-232228. , JP-A-5-339367 and JP-A-6-49203, and further, a method of treating a part or all of carbonyl groups in a polyketone with a metal hydrogen compound to reduce, for example, JP-A-1- Examples include the method described in No. 204929. The above-mentioned polyalcohol film having the characteristics of the present invention is not obtained by using any reducing condition, but is obtained by adopting the condition as described in Examples described later. This is fully supported by the examples and comparative examples described below. Further, the above-mentioned properties of the polyalcohol of the present invention are affected not only by reducing conditions but also by production conditions such as stretching and heat treatment of a polyalcohol film described later, and therefore it is important to appropriately select these conditions.

Next, the means for solving the above problems in the present invention will be described in detail. The packaging film is generally used by making a single-layer film or a laminated film into a bag, and at the time of bag making, a heat-sealing method (including an impulse-sealing method, a fusion-sealing method, and a melt-sealing method) and ultrasonic waves. A bag is made by sealing by a sealing method or a high frequency sealing method.

Each of the above-mentioned sealing methods is a method of sealing by internal heat generation of the polymer due to external heating or a load of external energy such as ultrasonic waves, high frequencies, etc., but all of them are methods of sealing by softening or melting the polymer by heat. Is. Since the packaging film is required to have high-speed bag-making properties in order to improve productivity, the sealing temperature must be high in order to obtain sufficient sealing strength in a short time.

From this point of view, in the case of sealing with a polyalcohol film, in particular, in the case of sealing with such a sealant layer in a laminated film of a polyalcohol film and a sealant made of another polymer, the melting point of polyalcohol is too low. At the time of sealing, the polyalcohol softens or melts, and a sealing failure occurs due to the thinning of the polyalcohol layer due to the pressure applied at the time of sealing. Further, when the elastic modulus of the polyalcohol film decreases due to heat during sealing, darts are generated on the sealing surface during high-speed sealing, resulting in poor sealing and deterioration of the appearance of the sealing surface, making it unusable for practical use.

Therefore, in order to improve the high-speed bag-making property, the melting point of the polyalcohol is 110 to 180 ° C., preferably 1
15 to 170 ° C., more preferably 120 to 160 ° C., and the dynamic elastic modulus of the polyalcohol film at 75 ° C. is 10 ⁸ to 10 ¹¹ dyne / cm ² , preferably 5 × 10 ^{8 to} 7 × 10. ^It is preferable to specify ¹⁰ dyne / cm ² , and more preferably 10 ^{9 to} 5 × 10 ¹⁰ dyne / cm ² .

If the melting point of the polyalcohol falls below the above temperature, the heat generated during the sealing causes the polyalcohol layer to become thin, resulting in defective sealing. If the melting point exceeds the above temperature, gel or fish
Eyes and streaks tend to occur.

If the dynamic modulus of elasticity of the polyalcohol film at 75 ° C. is less than the above range, darts are generated on the sealing surface during bag making at high speed, resulting in poor appearance of the sealing surface and poor sealing. Further, when the dynamic elastic modulus exceeds the above range, it is necessary to increase the sealing pressure, and various troubles due to the increase of the sealing pressure, such as a displacement of the sealing surface, deterioration of appearance, thinning of the polyalcohol layer, and sealing strength. It causes defects. In the present invention, it is particularly important to set the dynamic elastic modulus within the above specific range.

The melting point of the polyalcohol is largely determined by the basic structure of the polymer. To raise the melting point for the purpose of the present invention, the polyalcohol is reacted with a specific compound. For example, a method of reacting vinyltrimethoxysilane, vinyldimethylmethoxysilane, or the like with a polyalcohol can be exemplified. On the contrary, in order to lower the melting point of polyalcohol, it is easily produced by copolymerizing carbon monoxide with a comonomer other than ethylene during polymerization of polyketone, for example, olefin having 3 or more carbon atoms such as propylene, and then reducing. can do.

The dynamic elastic modulus of the polyalcohol film at 75 ° C. can be increased by a method of crosslinking the polyalcohol with a boron compound such as boric acid or a method of stretching and heat-treating the polyalcohol film. The dynamic elastic modulus can be reduced by copolymerization with an olefin having 3 or more carbon atoms such as propylene. As a particularly preferable method, a method of forming a tetrahydrofuran (THF) ring in polyalcohol and controlling the amount thereof is recommended.

The bag made by forming the packaging film is sealed and circulated after filling the contents, but when the viscous contents are filled, the contents are packed for the purpose of improving the high-speed filling and sealing property. The method of heating, reducing the viscosity, filling, and sealing is adopted.

From this point of view, if the dynamic elastic modulus in the vicinity of the filling temperature of the polyalcohol film is too low, when filling and sealing the heated contents, darts are generated on the sealing surface in the filling and sealing machine, resulting in poor sealing, This will deteriorate the appearance of the seal surface and cause leakage of the contents.

If the dynamic elastic modulus near the filling temperature is too large, it is necessary to increase the sealing pressure, and various troubles associated with the increase of the sealing pressure, such as displacement of the sealing surface, deterioration of appearance, thinning of the polyalcohol layer, It causes poor sealing strength. For the purpose of improving the heat-filling sealing property, it is important to adjust the dynamic elastic modulus of the polyalcohol film at 75 ° C. to 10 ⁸ to 10 ¹¹ dyne / cm ² .

When the film is formed, particularly when it is formed at a high speed for the purpose of improving productivity, the film has good film forming property, that is, the neck-in and its variation are small and the thickness unevenness is small during the film formation. Is required. Further, it is required that the film surface has few fish eyes, gels, streaks, and wood grain patterns, that is, the film surface appearance is beautiful. It goes without saying that a film having poor film-forming properties and a poor film surface appearance cannot be put to practical use at all.

In order to improve the film forming property of polyalcohol and the film surface appearance, the intrinsic viscosity of polyalcohol is 0.3 to 3.0 dl / g, preferably 0.5 to 2.
5 dl / g, more preferably 0.7 to 2.0 dl / g, and the melting point of the polyalcohol is 110 ° C to 180 ° C.
℃, preferably 115-170 ℃, more preferably 12
It is better to specify 0 to 160 ° C.

When the intrinsic viscosity of the polyalcohol falls below the above value, neck-in during high-speed film formation and its fluctuation or thickness unevenness increase, and a wood grain pattern is likely to occur on the film. On the other hand, when the intrinsic viscosity exceeds the above value, the load on the extruder during film formation increases, high-speed film formation becomes difficult, and streaks are likely to occur on the film. When the melting point is lower than the above value, the unevenness of the thickness of the film is increased and the high-speed bag-making property is poor, and when the melting point is higher than the above value, gel, fish eyes and streaks are likely to occur.

When a polyalcohol is coextruded with another polymer to produce a laminated film, the polyalcohol and the other polymer are multilayer coextruded through an adhesive polyolefin modified with an unsaturated carboxylic acid or an anhydride thereof. In the case of producing a laminated film by compounding a polyalcohol film and a film of another polymer via an adhesive such as a urethane-isocyanate adhesive, or a polyalcohol film with a urethane-isocyanate adhesive. When an anchor coat (AC) agent is applied and then another polymer is extrusion coated to produce a laminated film, or after the AC agent is applied to a film of another polymer, extrusion coating is performed with a polyalcohol to form a laminate. Layers in each case when producing the film It adhesion is good is required.

In particular, in the case of high-speed bag-making or heat-filling seal, there is a problem that the temperature of the polyalcohol film rises and the interlaminar adhesive strength of the laminated film containing the polyalcohol film decreases, so high-speed bag-making or heat-filling seal. In this case, it is necessary to improve the interlaminar adhesive strength at the time of temperature rise such as heat filling. Thus, in order to improve the interlayer adhesive force, particularly the interlayer adhesive force at the time of temperature rise, it is improved by specifying the dynamic elastic modulus at 75 ° C. of the polyalcohol film as described above. The reason for this is not necessarily clear, but if the dynamic elastic modulus is too large with respect to deformation due to external stress, stress concentrates between layers, causing delamination,
On the contrary, if the dynamic elastic modulus is too small, the stress concentrates on the polyalcohol, which is weak in strength, and the reinforcing effect of stacking is lost,
It is considered that the polyalcohol layer is destroyed and peeling occurs.

Therefore, 7 of the polyalcohol film
Even if the dynamic elastic modulus at 5 ° C. exceeds or falls below the above range, sufficient interlayer adhesive strength, particularly sufficient interlayer adhesive strength at the time of temperature rise cannot be obtained. Furthermore, the dynamic elastic modulus of the polyalcohol film at 75 ° C. is specified within the above range, and the polyalcohol film has a T represented by the formula (II) and the formula (III).
0.01 to 10 mol% of HF ring, preferably 0.03 to
By including 5 mol%, more preferably 0.05 to 3 mol%, the synergistic effect of the interlayer adhesion, especially the layer indirect contact with the polyolefin modified with the unsaturated carboxylic acid or its anhydride at the time of temperature rise. The adhesion, the interlaminar adhesive strength of the coextruded film with polyamide at the time of heating, or the interlayer adhesive strength of the urethane-isocyanate adhesive and the AC agent at the time of heating is further improved. The THF ring in the present invention means a 5-membered ring having an ether bond represented by the formulas (II) and (III), and the content of the THF ring means the total amount thereof.

When the content of the THF ring is below the above value,
When the synergistic effect of the interlayer adhesive force is not exhibited, and when the content of the THF ring exceeds the above value, not only high-speed bag-making property and heat-filling sealing property are deteriorated but also gas barrier property is significantly deteriorated. . As a method for incorporating such a THF ring into a polyalcohol, when a polyketone is reduced, an alcohol is produced from the ketone, and such an alcohol reacts with the ketone remaining in the polymer to form a compound of the formula (II)
And a method of forming a THF ring represented by the formula (III) or the like is industrially advantageous.

[0029]

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[0030]

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Thus, the formation of such a THF ring can be appropriately controlled by the selection of the solvent during the reduction of the polyketone and the reduction reaction temperature. That is, by using a solvent having a low solubility of polyketone, and by setting the reduction reaction temperature high, it is possible to increase the formation of the THF ring in the polyalcohol, and conversely use a solvent having a high solubility of polyketone, and By setting the reduction reaction temperature low, the formation of the THF ring in the polyalcohol can be suppressed as much as possible. Incidentally, the content of the THF ring in the polyalcohol can be determined by a method known per se such as NMR spectrum analysis,
It can be easily analyzed and quantified.

The packaging material is required to have a gas barrier property. In the present invention, the oxygen permeability coefficient at 20 ° C. and 75% RH (unit: cc · cm / cm ² · sec · c
mHg) is 5 × 10 ⁻¹² or less, preferably 1.5 × 10
^-12 or less, more preferably 1.0 × 10 ^-12 or less. When the oxygen permeability coefficient exceeds the above value, it is impossible to prevent the oxidative deterioration of the contents, the emission of the aroma components of the contents out of the bag, and the transfer of the odorous components outside the bag to the contents. Oxygen permeability coefficient of the polyalcohol film, in addition to the method of adjusting the type and content of the comonomer in the polyalcohol, the method of adjusting the content of the THF ring,
A method for adjusting the cooling conditions during the polyalcohol film formation, a method for adjusting the heat treatment conditions, a method for adjusting the stretching conditions, and the like are appropriately selected, and if necessary, such methods can be easily combined by appropriately combining them. You can

In the present invention, the production conditions such as stretching and heat treatment for obtaining the polyalcohol film having the above-mentioned characteristics include, for example, stretching conditions of 1.5 to 10 times in the longitudinal and transverse directions, preferably 2 to 10 times. With a draw ratio of 5 times,
Biaxial stretching is preferably carried out at a temperature of 50 ° C. to the melting point, preferably 70 ° C. to (melting point −3 ° C.), and the method of stretching in the water-containing state is particularly preferred for uniform stretching. The heat treatment conditions after stretching are 70 ° C to (melting point -3 ° C),
Suitably at a temperature of 80 ° C. to (melting point −5 ° C.) for 1 second to 3
It is preferable that the dry heat treatment is performed for a minute, preferably 3 to 30 seconds. Representative examples of these are shown in Examples described later.
A method of heat treatment after stretching is preferable, but a method of only heat treatment can be adopted. In the present invention, the polyalcohol film includes a so-called film-like material having a thickness of 100 μm or less and a sheet-shaped material having a thickness of 100 μm or more.

In the polyalcohol film of the present invention, various additives such as slip agents, antistatic agents, colorants, and heat stabilizers can be added to the polyalcohol film within a range that does not impair the effects of the present invention. It is also possible to appropriately add an antioxidant, a plasticizer, a hydrotalcite, a recovering agent such as higher fatty acid salt, an ultraviolet absorber and the like.

The polyalcohol film according to the present invention may have a moisture-resistant thermoplastic resin layer laminated on at least one surface. As the moisture-resistant thermoplastic resin layer, polyolefin resin, polyester resin, polystyrene resin, polyamide resin, polycarbonate resin, polyvinyl chloride resin and polyvinylidene chloride resin, polyacetal resin, polyurethane resin, ethylene −
Examples include vinyl alcohol copolymer resins. Here, as the polyolefin, polyethylene (high, medium,
Low density polyethylene, linear low density polyethylene), ethylene-propylene copolymer, polypropylene, ionomer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, etc. are exemplified. To be done. Examples of polyesters include polyethylene terephthalate and polybutylene terephthalate. Among these moisture resistant thermoplastic resins, polyolefin resins, polyester resins, polystyrene resins and polyamide resins are preferred.

The laminated film is formed by a known method such as coextrusion or extrusion coating, and scraps of these formed products can be reused.

When a laminated film is obtained, it is often preferable to interpose an adhesive resin layer between the polyalcohol film layer of the present invention and the moisture-resistant thermoplastic resin layer because both layers can be firmly adhered. The adhesive resin is not particularly limited as long as it can firmly bond both layers, but an unsaturated carboxylic acid or its anhydride (maleic anhydride, etc.) is used as an olefin polymer or copolymer. Polymer [polyethylene {low-density polyethylene, linear low-density polyethylene (LLDPE), ultra-low-density polyethylene (SLDPE)}, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer,
Grafted with ethylene- (meth) acrylic acid ester (methyl ester or ethyl ester) copolymer, polypropylene, etc.], acid anhydride (maleic anhydride, etc.) modified product of hydrogenated styrene-butadiene copolymer, liquid butadiene Diene polymer acid anhydride modified products such as acid anhydride modified products and ethylene-propylene-diene copolymer acid anhydride modified products are preferably used.

The layer structure of the laminated film is as follows: film layer / moisture-resistant thermoplastic resin layer, film layer / moisture-resistant thermoplastic resin layer / film layer, moisture-resistant thermoplastic resin layer / film layer / moisture-resistant thermoplastic resin layer. , Moisture resistant thermoplastic resin layer /
A film layer / scrap recovery layer / moisture-resistant thermoplastic resin layer, a moisture-resistant thermoplastic resin layer / scrap recovery layer / film layer / scrap recovery layer / moisture-resistant thermoplastic resin layer, or at least one of these layers The adhesive resin layer may be included. Here, the film means the polyalcohol film of the present invention.

By using the laminated film as described above, the high-speed bag-making property and the heat-filling sealing property of the polyalcohol film are further improved, and the water resistance and the moisture resistance of the polyalcohol film are significantly improved.

Thus, the polyalcohol film and the laminated film thereof according to the present invention are directly subjected to bag-making, or subjected to heat molding such as vacuum forming and pressure forming, as a bag or container for packaging, as a food or a drug. It is preferably used for packaging pharmaceuticals, oils and fats, drinking water, cosmetics and the like. It can also be used in retort containers, bag-in-boxes, agricultural films, etc.

[0041]

EXAMPLES The present invention will now be described in detail with reference to Examples, but the method of measuring characteristic values and the method of evaluation are as follows.

Method for Measuring Characteristic Values (1) Intrinsic Viscosity A solution of water-containing phenol [water / phenol = 15/85 (weight)] was measured using an Ostwald viscometer to measure 3
It was measured at 0 ° C. (2) Melting point Differential scanning calorimeter (DSC) R manufactured by Seiko Instruments Inc.
Using DC220 / SSC5200H type, heating rate 10
Measure at ° C / min. In addition, indium and lead were used for temperature calibration. (3) Dynamic elastic modulus RHEOVIBRON DDV manufactured by Orientec Co., Ltd.
Using -II-EA type, frequency 110H _Z, heating rate 3 ° C.
/ Min and the dynamic elastic modulus at a temperature of 75 ° C. was determined. (4) Oxygen permeability coefficient MODERN CONTROLS, INC. It was measured according to JIS K7126 under the conditions of 20 ° C. and 75% RH using an oxygen permeability measuring device MOCONOX-TRAN10 / 50 type.

Evaluation Method (1) High-speed bag-making property A high-speed automatic bag-making machine HSE-500A manufactured by Seibu Machine Co., Ltd. was used and a three-sided sealed bag (1
50 × 230 mm) was made at a bag making speed of 80 bags / min. (2) Heat-filling sealability Ketchup heated to 75 ° C using a high-speed automatic filling and packaging machine KS313 type manufactured by Komatsu Ltd. has a sealing temperature of 180.
It was filled at a rate of 120 bags / min at ℃ (bag size 68 × 8
5 mm).

(3) Film-forming property and film surface (3-1) Single-layer film film-forming 720 mm of polyalcohol using a 60 mmφ extruder.
The film was extruded from the width T die at a temperature 30 ° C. higher than the melting point of the polyalcohol, and a film having a thickness of 30 μ was formed at a take-up speed of 150 m / min. The film-forming property was judged from the situation during film formation, that is, neck-in, neck-in fluctuation, thickness variation, and the like. The film surface condition was judged by the presence or absence of fish eyes, gels, streaks, and wood grain patterns. (3-2) Formation of Coextrusion Laminated Film Using two 60 mmφ extruders, polyalcohol and a polymer other than polyalcohol were respectively charged into the extruder, and the two resins were fed by Cloeren. Allow them to meet at a block, 2 from a 720 mm wide T-die
Of the melting points of the seed polymers, extruded at a temperature 30 ° C. higher than the higher melting point, at a take-up speed of 150 m / min, polyalcohol 30 μ / polymers other than polyalcohol 30 μ
A laminated film having a total thickness of 60 μ is formed, and the (3-
The film-forming property and the film surface of the film were determined according to the item 1).

(4) Interlayer Adhesion The laminated film was cut into a width of 15 mm to prepare a test piece,
Using an Autograph AG-500A type manufactured by Shimadzu Corp., it was determined by the peel strength when a T-type peeled a test piece whose humidity was controlled at 20 ° C. and 65% RH at a peeling speed of 250 mm / min. (4-1) Coextrusion Laminated Film The laminated film described in the item (3-2) was used as a sample. (4-2) Dry Laminated Laminated Film Takeda Pharmaceutical Co., Ltd. urethane-isocyanate adhesive for dry lamination Takelac A-385 (main component) / on specific films other than polyalcohol films
Takenate A-10 (curing agent) was applied to a solid content of 3 g / m ² with a dry laminator using ethyl acetate as a diluent, and a polyalcohol film was dry-laminated to prepare a laminated film, which was used as a sample.

(5) Food storability A package containing the ketchup prepared for the evaluation of the heat filling and sealing property in the above item (2) at 35 ° C. and 75% R
It was put in a constant temperature and humidity chamber of H for 60 days, and judged by the degree of deterioration of hue of ketchup with time.

The evaluation result is displayed as follows. ◎… Extremely good ○… Good △… Slightly bad ×… Poor

Example 1 A polyketone composed of a carbon monoxide-ethylene alternating copolymer (CO ratio 50 mol%) was supported on α-alumina in a mixed solvent of 1,3-dioxolane / methanol = 10/90 (weight). 110 kg / cm 2 of hydrogen at room temperature in an autoclave using a ruthenium catalyst (supported amount: 7% by weight).
After pressurizing ² G, heat it at 150 ° C for 4 hours to reduce it and convert it to 1
00% polyalcohol (PAL) was obtained. The obtained polyalcohol is formed into a film based on the item (3-1) to form a film having a thickness of 30 μm, and the film is formed with a tenter at 100 ° C.
Heat treatment was performed for 10 seconds. The characteristic values and the evaluation results of the polyalcohol film are shown in Tables 1 and 2.

Example 2 A biaxially oriented polypropylene film (OPP, Tocello OPU) was formed on one surface of the polyalcohol film obtained in Example 1.
Laminated on the basis of the method described in the item (4-2) using the corona-treated surface of (-1, 20 μ) as a laminated surface. Then, on the polyalcohol surface of such a laminated film, a linear low-density polyethylene (LL) is used as a sealant.
DPE, Tocello TUX-TC, 60μ) (4-2)
By laminating according to the method described in the section 1, a three-layer laminated film was prepared. The symbol "//" in the table means that they were bonded with a urethane-isocyanate adhesive.

Example 3 Carbon monoxide-ethylene-propylene alternating copolymer (CO
Using a palladium catalyst in which a polyketone composed of a ratio of 50 mol% and a propylene ratio of 2 mol% was supported on α-alumina in cyclohexanol (carrying amount: 5% by weight), hydrogen was injected at room temperature at 100 kg / cm ² G in an autoclave. After that, it is heated at 110 ° C for 5 hours to reduce the conversion rate to 100%.
Was obtained. This polyalcohol and maleic anhydride-modified linear low-density polyethylene having a melting point of 120 ° C. Admer NF505 (M manufactured by Mitsui Petrochemical Co., Ltd.
-PO) was used to prepare a coextrusion laminated film based on the above item (3-2). The dynamic modulus of elasticity of the polyalcohol film is the same as that of Admer NF505, MI3.
5 (190 ° C, ASTM D1238), density 0.92
A coextruded laminated film was prepared under the same conditions by replacing with unmodified linear low density polyethylene which has the same MI, density and melting point as Admer NF505 of g / cm ³ and a melting point of 120 ° C., but is not modified with maleic anhydride. Then, the polyalcohol film portion was peeled off and taken out, and the measurement was carried out.

Example 4 The polyalcohol described in Example 1 and the nylon-6 Ube Industries 1013B (NY) having a melting point of 220 ° C. were coextruded and co-extruded according to the above item (3-2) except that the thickness was changed. An extruded laminated film was created. After immersing such a laminated film in water, it was simultaneously biaxially stretched at 85 ° C. in the lengthwise direction and three times in the widthwise direction with a tenter, and heat-treated at 120 ° C. for 8 seconds. The dynamic elastic modulus of polyalcohol was measured by immersing a biaxially stretched film having a NY / PAL structure in trifluoroethanol and then peeling off the PAL film. According to Example 2, linear low-density polyethylene was laminated on the polyalcohol surface of the laminated biaxially stretched film to prepare a three-layer laminated film. The structure of the laminated film is NY (30μ) / PA
It was L (30μ) // LLDPE (60μ).

Example 5 The polyalcohol described in Example 3 was collected at a take-up speed of 20 m /
In a minute, a film is formed according to the item (3-1), and the thickness is 270 μm.
A PAL single layer film was prepared. After the film was immersed in water, it was simultaneously biaxially stretched at 80 ° C. in the lengthwise and widthwise directions by a tenter, and heat-treated at 110 ° C. for 5 seconds. Table 1 shows the evaluation results of the obtained biaxially stretched PAL film having a thickness of 30 μm.
It shows in Table 2.

Example 6 A polyketone comprising a carbon monoxide-ethylene alternating copolymer (CO ratio of 50 mol%) was methanol / water = 80/20.
Using a mixed solvent (by weight) and a Raney cobalt catalyst, hydrogen was injected under pressure of 100 kg / cm ² G at room temperature in an autoclave, and then heated until the internal temperature reached 160 ° C. After that, hydrogen was additionally injected to make the total pressure 150 kg / cm ² G, 1
The mixture was heated and reduced at 35 ° C. for 10 hours to obtain a polyalcohol (PAL) having a conversion rate of 100%. The obtained polyalcohol was formed into a film at a take-up speed of 20 m / min according to the above item (3-1) to prepare a PAL single-layer film having a thickness of 270 μm.
The film was biaxially stretched at 110 ° C. in the lengthwise and widthwise directions of 3 times in a tenter, and heat-treated at 120 ° C. for 10 seconds.
The evaluation results of the obtained biaxially stretched PAL film having a thickness of 30 μ are shown in Tables 1 and 2.

Example 7 The biaxially stretched polyalcohol film obtained in Example 6 was laminated in the same manner as in Example 2 to prepare a three-layer laminated film.

Comparative Example 1 Carbon monoxide-ethylene-propylene alternating copolymer (CO
Using a polyketone composed of a ratio of 50 mol% and a propylene ratio of 10 mol%), the reduction reaction solvent is changed to methanol,
Moreover, a polyalcohol was prepared in the same manner as in Example 3 except that the reduction reaction temperature was raised to 170 ° C.
A film was formed based on the item 1). (However, heat treatment is not performed.)

Comparative Example 2 Using the polyalcohol film obtained in Comparative Example 1, a three-layer laminated film was prepared according to Example 2.

Comparative Example 3 Using a polyketone composed of a carbon monoxide-ethylene alternating copolymer (CO ratio of 50 mol%), a polyalcohol was prepared in the same manner as in Comparative Example 1 to prepare a polyalcohol. The film was formed based on (However, heat treatment is not performed.)

Comparative Example 4 CO ratio 47 mol% Reduced viscosity η _{sp / c} = 1.10 dl / g
(Concentration 0.5 g / dl, measured with m-cresol solution)
Carbon monoxide-ethylene random copolymer, 5% -ruthenium / α-alumina catalyst powder as a catalyst, and 1,3-dioxolane as a solvent were charged in an autoclave, and hydrogen was injected at room temperature to 100 kg / cm ² , Thirteen
The mixture was heated and reduced at 0 ° C. for 3 hours to obtain a polyalcohol.
The obtained polyalcohol was formed into a film in the same manner as in Example 1 to form a film having a thickness of 30 μm. However, no heat treatment was performed. The characteristic values and the evaluation results of the polyalcohol film are shown in Tables 1 and 2.

[0059]

[Table 1]

[0060]

[Table 2]

[0061]

EFFECTS OF THE INVENTION According to the present invention, a film excellent in high-speed bag-making property, heat-filling-sealing property, film-forming property, film appearance, adhesiveness, gas barrier property and a laminated film thereof can be obtained.

Claims (3)

[Claims] 1. An intrinsic viscosity of 0.3 to 10 obtained by reducing a polyketone composed of a carbon monoxide-ethylene alternating copolymer.
It is made of polyalcohol having a melting point of 110 to 180 ° C. and a dynamic elastic modulus at 75 ° C. of 10 ⁸ to 10 ° C.
The oxygen permeation coefficient at ¹¹ dyne / cm ² at 20 ° C. and 75% RH is 5 × 10 ⁻¹² cc · cm / cm ² · se.
A film of c · cmHg or less. 2. The film according to claim 1, wherein the polyalcohol is a polyalcohol containing 0.01 to 10 mol% of tetrahydrofuran rings. 3. A laminated film having a moisture-resistant thermoplastic resin layer on at least one surface of the film according to claim 1.