JPH1160754A - Biaxially oriented film and laminated film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin film excellent in durability, wear resistance and resistance to Gelbo properties by using a specific aliphatic polyketone as an essential constituent, and allowing the polyketone to include a specified amount of inorganic and/or organic particles having a particle diameter within a specific range. SOLUTION: This biaxially oriented film is obtained by using a polymer formed out of constituents consisting essentially of an aliphatic polyketone containing >=80 mol.%, preferably >=90 mol.%, especially preferably 95 mol.% constituent unit of the formula [(r) is H or methyl, preferably H; R is H or a 1-4C alkyl, preferably H or methyl], and including 0.001-10 wt.% inorganic and/or organic particles having 0.01-10 μm, preferably 0.01-5 μm, especially preferably 0.01-3 μm particle diameter expressed in terms of weight ratio. Preferably, the thickness fluctuation of the film is <20%, preferably <10% especially preferably <5%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a biaxially stretched film and a laminated film, and more particularly, to a biaxially stretched film using a novel resin and having excellent durability, abrasion resistance and gelling property. It relates to a laminated film.

[0002]

2. Description of the Related Art At present, various films are commercially available, and applications utilizing various characteristics are being developed. For example, polyolefin films such as polypropylene films are mainly used as packaging materials, taking advantage of appropriate mechanical strength, flexibility, cost performance, water resistance, recyclability, and the like. Polyester films such as polyethylene terephthalate have excellent mechanical properties, surface properties, water resistance, and the like, and are being developed in various fields including magnetic materials and industrial materials.

[0003] However, these films each have disadvantages, and polyolefin films are inferior in mechanical properties and inferior in durability, impact resistance and abrasion resistance as compared with engineering plastic films. Polyester films are inferior in flexibility and thus deteriorate in properties due to bending or the like (deterioration in gelling properties), and recently, the problem of recyclability is particularly noticed particularly in packaging applications such as bottles.

In recent years, various studies have been made, and aliphatic polyketones, resins produced from carbon monoxide and olefins, have been developed. Although it is a polyolefin, it is excellent in various properties such as mechanical properties and impact resistance, and is considered to be advantageous from the point of recyclability because it is a polyolefin, so it is expected to be developed for various applications. In particular, the use in fuel tanks and the like is being considered in the automobile industry. Various studies have been made on behalf of this, but the center of the study is on molded articles, and studies on films have not been made.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the conventional film and to improve the durability and durability of the film.
An object of the present invention is to provide a novel resin film having excellent wear resistance and gelling property.

[0006]

In order to achieve the above object, the present invention provides a film containing an aliphatic polyketone containing a structural unit represented by the following general formula as a main component and having a particle diameter of 0. It comprises a biaxially stretched film containing 0.001 to 10% by weight of inorganic and / or organic particles of 0.01 to 10 μm.

[0007]

Embedded image

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, it is necessary to use an aliphatic polyketone containing a structural unit represented by the following general formula.

[0009]

Embedded image In the formula, r is hydrogen or a methyl group, and hydrogen is preferable. R is hydrogen, a methyl group, an ethyl group, an propyl group, or other alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen or methyl group. The content of the structural unit in the aliphatic polyketone is preferably 80 mol% or more, more preferably 90 mol% or more, and particularly preferably 95 mol% or more. As such an aliphatic polyketone, a commercially available product can be used, and for example, "Calilon" manufactured by Shell Chemical Company, "Ketonex" manufactured by BP Chemical Company, etc. can be used.

In the present invention, it is necessary to contain inorganic and / or organic particles from the viewpoint of the handleability of the film. Generally, in polyolefin films, hydrocarbon-based or fatty acid amide-based lubricants are often added in order to improve the handleability of the film,
These may bleed out to the film surface and adversely affect the film properties. However, in the present invention, the use of inorganic and / or organic particles has little adverse effect on the film properties.

Examples of the material of the inorganic particles that can be used in the present invention include calcium carbonate, titanium oxide,
Examples include silicon oxide, calcium fluoride, lithium fluoride, alumina, barium sulfate, zirconia, mica, talc, kaolinite, and calcium phosphate. As the material of the organic particles, for example, polyimide, polyamide imide, polymethyl methacrylate, formaldehyde resin, phenol resin, polystyrene, polysilsesquioxane so-called silicone resin, having only one aliphatic unsaturated bond in the molecule Monovinyl compound and 2 in the molecule
And vinyl-based cross-linked polymers which are copolymers with a compound having two or more aliphatic unsaturated bonds.

The inorganic and / or organic particles used in the present invention must have a particle size of 0.01 to 10 μm. Preferably, it is 0.01 to 5 μm, particularly preferably 0.01 to 3 μm. Outside this range, the handleability, abrasion resistance and durability of the film may deteriorate. The particle size was 1000 using a transmission microscope or the like.
The particle diameter is obtained by taking a photograph of a film cross section of 0 to 100000 times and calculating the number average. Regarding the particle diameter ratio, which is the ratio of the major axis to the minor axis of the particles, in the present invention, the particle diameter ratio of the inorganic and / or organic particles is preferably in the range of 1 to 1.2. The closer the particle size ratio is to 1, the closer the particle is to a spherical shape. More preferably, it is 1 to 1.1.

The amount of the inorganic and / or organic particles of the present invention must be 0.001 to 10% by weight. Preferably, it is 0.01-5%, more preferably 0.01-3%. If it is less than 0.001%, the film surface may be poor in slipperiness and the handleability of the film may be poor. If it exceeds 10%, the transparency may be deteriorated.

In the present invention, the inorganic and / or organic particles may be added at the time of production of an aliphatic polyketone, for example, during polymerization, or particles may be added to a polymerized aliphatic polyketone resin to prepare a high-particle concentration master pellet. Alternatively, the film may be formed after blending particles and resin pellets using a stirrer or the like immediately before film formation.

The present invention is a film containing the above-mentioned aliphatic polyketone as a main component, and it is necessary that the film is a biaxially stretched film. By biaxially stretching, film thickness unevenness and mechanical properties are improved. Film 2
The fact that the film is axially stretched can be confirmed by analyzing the orientation state of the film. As a specific method, a refractive index method, a total reflection Raman spectrum method, a total reflection infrared spectrum method, or the like is preferably used.

In the present invention, the thickness unevenness of the film is preferably less than 20%, more preferably less than 10%, particularly preferably less than 5%. When the thickness unevenness is within the above range, durability and abrasion resistance are improved.

Although the thickness of the film is not particularly limited,
0.1 to 500 μm is preferable, 1 to 200 μm is more preferable, and 5 to 100 μm is particularly preferable.

The present invention relates to a film containing an aliphatic polyketone as a main component, and the main component indicates that the weight of the aliphatic polyketone is 70% or more based on all components of the film. As long as the durability, abrasion resistance, gelling property and transparency are not impaired, various additives may be contained in a weight ratio of 30% or less. As various additives,
Antioxidants, weathering agents, heat stabilizers, lubricants, nucleating agents, ultraviolet absorbers, coloring agents and the like.

The biaxially stretched film may be laminated with another resin. Other resins are not particularly limited, but include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene-2,6-naphthalate, polyamides such as nylon 6, nylon 12, polyvinyl chloride, and ethylene acetate. Vinyl copolymer or saponified product thereof, polystyrene, polycarbonate, polysulfone, polyphenylene oxide, polyphenylene sulfide, aromatic polyamide, polyimide, polyamideimide, cellulose, cellulose acetate, polyvinylidene chloride, polyacrylonitrile, polyvinyl alcohol, etc. It is preferable that a polymer is used and laminated with polypropylene or polyethylene terephthalate in terms of mechanical properties and gelling properties. Arbitrariness.

On the other hand, for applications requiring gas barrier properties, it is preferable to laminate polyethylene naphthalate and ethylene vinyl alcohol. Lamination method is not particularly limited, a melt co-extrusion method for laminating inside or outside the die using a plurality of extruders, extrusion lamination, heat lamination, dry lamination, lamination methods such as wet lamination, gravure coating, reverse coating, Spray coat, kiss coat, comma coat, die coat,
A coating method such as a knife coat, an air knife coat or a metaling bar coat is used.

Next, a typical method for producing the biaxially stretched film of the present invention will be described, but the present invention is not limited thereto.

First, a predetermined amount of inorganic and / or organic particles is added to an aliphatic polyketone pellet as a raw material, mixed with a stirrer, sufficiently dried in a vacuum, supplied to an extruder, and heated to a temperature of 240 to 280 ° C. And then extruded through a slit die. This is wound around a metal drum and cooled and solidified into a sheet to obtain an unstretched film.

Next, the unstretched film is biaxially stretched. At this time, the total stretching ratio is obtained by multiplying the stretching ratio (longitudinal stretching) in the longitudinal direction of the film and the stretching ratio (lateral stretching) in the width direction of the film. Is preferably at least 2 times, more preferably at least 3 times. The stretching method is not particularly limited, and a sequential stretching method of performing longitudinal stretching-lateral stretching, transverse stretching-longitudinal stretching, an inflation method, and a simultaneous biaxial stretching method using a vertical and horizontal simultaneous biaxial stretching type tenter are used. Further, longitudinal stretching and / or transverse stretching may be further performed. The stretching temperature of the film is 80 ° C.
Preferably, the temperature is 200 ° C. The temperature is more preferably 100 to 150 ° C. It is preferable that the film be biaxially stretched in this range, since a uniform film having a small thickness unevenness and a good appearance can be obtained.

Next, this film is heat-treated. The relaxation heat treatment is preferably performed at a temperature of 150 ° C. to 230 ° C. for a time of 0.5 to 60 seconds.

Further, in order to improve the mechanical properties, gelling properties and interlayer adhesion of the laminated film, the aliphatic polyketone may be used as a layer laminated on the film of the present invention in an amount of 0.1 to 20.
It is preferable to use one containing the compound by weight. Particularly preferably, the composition contains 1 to 15% by weight of an aliphatic polyketone. 0.1 ~ 2 aliphatic polyketone
The layer containing 0% by weight is in the form of a film and may be laminated and laminated on the film of the present invention, or may be coated and laminated on the film of the present invention. It may be something.

[0026]

[Characteristic evaluation method] The characteristic evaluation method used in the present invention is as follows.
It is as follows.

(1) Particle Size and Particle Size Ratio A biaxially stretched film is cut perpendicularly to the film surface to form an ultra-thin section having a thickness of about 0.1 μm. ~ 1000
Observation was performed at a magnification of 00 times. The particle diameter of at least 200 particles was measured as an area equivalent diameter from a screen or a photograph, and the number average particle diameter of the area equivalent diameter was calculated to be the particle diameter.
Further, the major axis and the minor axis of each particle were measured, and the average value was determined as the particle diameter ratio.

(2) Content of Particles Calculate from the amount of particles added to the aliphatic polyketone as a film raw material, or dissolve the film in a solvent that does not dissolve the particles, and centrifuge the particles obtained from the resin. The weight ratio to the total weight of the film was defined as the amount of particles added.

(3) Uneven thickness Thickness tester KG6 manufactured by Anritsu Corporation
01A and the electronic micrometer K306C,
The thickness of a film sampled 30 mm in width and 1 m in the vertical and horizontal directions of the film is continuously measured. The transport speed of the film was 2 m / min. From the maximum thickness value Tmax (μm) and minimum value Tmin (μm) at 1 m length, R = Tmax−Tmin is determined, and from the average thickness Tave (μm) at 1 m length, the thickness unevenness (%) = R / Tave × 100. As the thickness unevenness in the vertical and horizontal directions is determined,
The average value was regarded as uneven thickness.

(4) Durability The film was placed in a 1 m square frame, the appearance of the film after the earth and sand was dropped from above 50 cm was observed, and the durability of the film was determined as follows.

A: The film has no defects such as holes or tears. B: The film is slightly scratched, but there is no problem in use. C: The film has defects such as holes or tears. (5) Abrasion resistance Steel wool The film was rubbed while lightly pressing # 0000 on the film surface, and the degree of scratching was evaluated according to the following criteria.

○: scarcely scratched △: slight scratching but no problem ×: considerable scratching (6) Gelbo property The gelbo tester was set so that the ambient temperature was 5 ° C, and the gelbo was repeated 1000 times. The number of pinholes was compared for the film samples (280 mm × 180 mm) that were performed (the number of ink-permeable portions on the filter paper was counted).

[0033]

【Example】

Example 1 "Carillon" (manufactured by Shell Chemical Co., Ltd.) was used as an aliphatic polyketone, and silica particles (particle diameter 1.2 μm, particle diameter ratio 1.0) were used as inorganic and / or organic particles in a weight ratio of 0.08. %, And then 6% using a rotary vacuum dryer.
After drying at 0 ° C. for 3 hours, the mixture was fed to an extruder, melted at 260 ° C., discharged from a die onto a sheet, and cooled and solidified on a casting drum to obtain an unstretched film. While holding the unstretched film with a clip, the film is guided to a simultaneous biaxial stretching type tenter to make a total stretch ratio (longitudinal stretch ratio × lateral stretch ratio) of 6 at 120 ° C., and then heat-treated at 150 ° C. for 4 seconds to obtain a film. Was. The obtained film had a thickness of 20 μm and a thickness unevenness of 4%. Table 1 shows the properties of the obtained film.

Example 2 A film was obtained in the same manner as in Example 1 except that the stretching temperature was 130 ° C. and the total stretching ratio was 7 times. Table 1 shows the obtained characteristics.

Example 3 The unstretched film obtained in Example 1 was stretched 2.5 times in the longitudinal direction at 110 ° C. by a stretching roll and 12 times in the transverse direction in a tenter.
After successively biaxially stretching 2.5 times at 0 ° C., heat treatment was performed at 150 ° C. for 4 seconds to obtain a film. The obtained film had a thickness of 20 μm and a thickness unevenness of 5%. Table 1 shows the properties of the obtained film.

Example 4 A film was obtained in the same manner as in Example 3, except that both the longitudinal stretching and the transverse stretching were changed to twice at 105 ° C. The thickness of the obtained film was 25 μm, the thickness unevenness was 16%, and other characteristics are shown in Table 1.

Example 6 Ethylene vinyl alcohol and an aliphatic polyketone were mixed at 10% by weight (A layer), and the aliphatic polyketone (B
Layer) and melt-extruded to obtain a film by a tubular method. The thickness of the obtained film is 30μ.
m (lamination ratio A: B = 5: 1), and the thickness unevenness is 18%.
Met. The abrasion resistance was ○.

Example 7 5% by weight of polyethylene naphthalate and an aliphatic polyketone were mixed, laminated with the aliphatic polyketone of Example 1, and melt-extruded. The film was axially stretched and heat-set at 190 ° C. The thickness of the obtained film was 20 μm, and the thickness unevenness was 11%.
Met. The abrasion resistance was ○.

Comparative Example 1 A film having a thickness of 30 μm was obtained in the same manner as in Example 1 except that longitudinal stretching and transverse stretching were not performed. Table 1 shows the properties of the obtained film.

COMPARATIVE EXAMPLE 2 Polyethylene terephthalate was dried at 160 ° C. for 2 hours using a rotary vacuum drier, and then supplied to an extruder.
C. and melted on a sheet from a die. The sheet is cooled and solidified on a casting drum,
The film was longitudinally stretched three times at 00 ° C., horizontally stretched three times at 110 ° C. in a tenter, and then heat-treated at 220 ° C. for 4 seconds to obtain a film. The obtained film has a thickness of 20 μm and a thickness unevenness of 2 μm.
% And other properties are shown in Table 1.

[0041]

[Table 1] Example 5 "Carilon" (manufactured by Shell Chemical Co., Ltd.) was used as an aliphatic polyketone, and silica particles (particle diameter 1.2 μm, particle diameter ratio 1.0) were used as inorganic and / or organic particles in a weight ratio of 0.08. %, And then 6% using a rotary vacuum dryer.
After drying at 0 ° C. for 3 hours, it was supplied to an extruder and melted at 260 ° C. Feed the polypropylene resin to another extruder,
Melted at 60 ° C. In the three-layer forming die, they are merged in a die (thickness ratio 1/1/1) into an aliphatic polyketone layer / polypropylene layer / aliphatic polyketone layer, discharged onto a sheet, and cooled and solidified on a casting drum. Then, an unstretched film was obtained. The unstretched film is guided by a simultaneous biaxial stretching type tenter while holding the unstretched film with a clip, and after a total stretching ratio (longitudinal stretching ratio × lateral stretching ratio) of 6 times at 140 ° C., 15
Heat treatment was performed at 0 ° C. for 4 seconds to obtain a laminated film. The obtained film had a thickness of 30 μm and thickness unevenness of 6%. Durability: 、, abrasion resistance: 、, gelbo property: 4, and films excellent in each property were obtained.

[0042]

According to the present invention, it is possible to solve the problems of the conventional film and to provide a novel resin film having excellent durability, abrasion resistance and gelling property.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 73/00 C08L 73/00 // B29K 61:00 105: 16 B29L 7:00

Claims (10)

[Claims] 1. A film mainly composed of an aliphatic polyketone containing a structural unit represented by the following general formula, wherein inorganic and / or organic particles having a particle diameter of 0.01 to 10 μm are contained in a weight ratio of 0.1 to 0.1 μm. A biaxially stretched film characterized by containing 001 to 10%. Embedded image 2. The biaxially stretched film according to claim 1, which contains 0.01 to 5% of inorganic particles having a particle size of 0.01 to 3 μm. 3. The biaxially stretched film according to claim 1, wherein the thickness unevenness of the biaxially stretched film is less than 20%. 4. The method according to claim 1, wherein the particle size ratio of the inorganic and / or organic particles is 1 to 5.
The biaxially stretched film according to any one of claims 1 to 3, which is 1.2. 5. A laminated film comprising one or more layers of the biaxially stretched film according to claim 1. 6. A laminated film, wherein the biaxially stretched film according to claim 1 is laminated with polypropylene. 7. A laminated film, wherein the biaxially stretched film according to claim 1 is laminated with polyethylene terephthalate. 8. A laminated film, wherein the biaxially stretched film according to claim 1 is laminated with polyethylene naphthalate. 9. A laminated film, wherein the biaxially stretched film according to claim 1 is laminated with ethylene vinyl alcohol. 10. An aliphatic polyketone of 0.1 to 20% by weight.
The laminated film according to any one of claims 5 to 9, wherein a layer containing the biaxially stretched film according to any one of claims 1 to 4 is laminated.