JPH10315394A - Coat-formed film and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve barrier properties, prevent cracks, and prevent performance deterioration in the case of providing on an uneven film surface by providing a coat of specified thickness composed of polymonochloro-para- xylylene or poly-para-xylylene resin on at least one side of a plastic base film. SOLUTION: On at least one side of a base film 2 composed of plastic, a coat 3 of 0.02-120 μm thickness composed of polymonochloro-para-xylylene or poly-para-xylylene resin is provided. As a result, the film is given barrier properties, and resistance to chemicals of the film surface is improved. The base film 2 is composed of single or multi-ply lamination composed of olefin resin, vinylidene chloride resin, polyester resin, or the like. Alternatingly, a film precoated with anchor coat 4 on the surface, where the coat 3 is formed, can be used for the base film 3. Polyethelene-imine, organic titanium, isocyanate, or the like is, used for the anchor coat agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thin film layer for improving physical properties of a single film material and a technique for forming the thin film layer.

[0002]

2. Description of the Related Art Various films have their own physical properties, but may be subjected to a secondary method in order to improve the physical properties. For example, in the packaging field, as a packaging material having gas barrier properties, a packaging material in which an aluminum foil is laminated on a base film has been conventionally used. Although such packaging materials exhibit stable gas barrier properties, there is a problem that aluminum (hereinafter abbreviated as aluminum) foil as a barrier layer is not suitable for incineration, so that disposal after use is not easy. Was. Also, in terms of recycling of packaging materials, separation and peeling were difficult due to lamination with aluminum foil, making recycling difficult. Further, since aluminum foil is laminated, transparency cannot be obtained, and it cannot be used for heating by a microwave oven. In addition, formation of a barrier layer by coating with polyvinylidene chloride or the like is a commonly used method. However, the coating film of the vinylidene chloride or the like causes stress cracks due to the bending of the film, and therefore, a predetermined barrier performance is reduced. Had an effect. In addition to aluminum or SiO _x barrier layer, such as the polyvinylidene chloride, but may form a barrier layer by vapor deposition layer such as aluminum oxide, again, the barrier layer also part destruction of the film due to flexing or impact In some cases, resulting in a decrease in barrier properties. In addition, the substrate film having irregularities on the surface, that is, the coating or the metal or inorganic oxide vapor deposited layer on the embossed substrate film surface, due to the irregularities, the thickness of the coating film is not constant, Accordingly, the barrier properties and the like may be reduced.

[0003]

SUMMARY OF THE INVENTION A barrier layer which has improved barrier properties, does not generate cracks even when subjected to a force such as bending, and has no deterioration in performance when provided on a film surface having irregularities. Provide a film and its manufacturing technology.

[0004]

[MEANS FOR SOLVING PROBLEMS] A coating film made of polymonochloroparaxylylene or polyparaxylylene resin is coated on at least one surface of a plastic base material film at 0.02 μm.
~ 120μm is a film formed with a coating film provided in a thickness, irregularities are formed on at least one surface of the substrate film, it is a film formed the coating film on the surface on which the irregularities are formed. Including. Further, a coating film made of a resin of polymonochloroparaxylylene or polyparaxylylene is provided on at least one surface of a base film made of plastic by a CVD method to a thickness of 0.02 μm to 120 μm to form a coating film. A method of manufacturing a film, comprising forming the base film on at least one side thereof with irregularities, and forming the coating film on the surface on which the irregularities are formed.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a film on which a coating film of polymonochloroparaxylylene resin or polyparaxylylene resin (hereinafter collectively referred to as polyparaxylylene resin, etc.) is formed, and the above coating film. That is, it is formed by a CVD method. By providing a layer of polyparaxylylene resin or the like on the film substrate, a barrier property is imparted to the film, and the chemical resistance of the film surface is improved. Further, by forming a coating film of the polyparaxylylene resin or the like by a CVD method, a coating film having a constant film thickness, flexibility, and excellent heat resistance and cold resistance can be obtained. FIG. 1 is a cross-sectional view (a) showing an embodiment of a film on which a coating film of the present invention is formed, and a cross-sectional view (b) in the case where another resin layer is provided. FIG. 2 is a cross-sectional view (a) showing another embodiment of the film on which the coating film of the present invention is formed, and a cross-sectional view (b) in the case where another resin layer is provided. FIG.
1 is a conceptual diagram of a CVD apparatus used for forming a coating film of the present invention.

In the present invention, the base film 2 on which the coating film 3 of the polyparaxylylene resin is formed includes olefin resins such as polyethylene and ethylene copolymers, polypropylene and propylene copolymers, and polyvinyl chloride. -Based resin, vinylidene chloride-based resin such as vinylidene chloride-vinyl chloride copolymer, polyimide resin, polycarbonate resin, polyester-based resin such as polyethylene terephthalate, and single- or multi-layered resin such as fluororesin such as polytetrafluoroethylene. Films. These base films may be unstretched, or uniaxially or biaxially stretched,
A coated film or the like in which these base films are further coated with another resin such as a vinylidene chloride-based resin may be used. Further, as shown in FIG. 1A, the base film 2 may be a film in which an anchor coat 4 is previously applied to a surface on which a coating film 3 such as a polyparaxylylene resin is formed. The anchor coat 4 is intended to more firmly adhere the coating film 3 such as polyparaxylylene resin to the base film 2 and is provided on the base film 2 or the material of the base film 2. It is selected according to the material such as the coat layer. Specific examples of the anchor coating agent include polyethyleneimine-based, organic titanium-based, and isocyanate-based anchor coating agents 4 and the like.

In the present invention, the coating film formed on the base film 2 is a polymonochloroparaxylylene resin or a polyparaxylylene resin as described above. The polymonochloroparaxylylene resin has excellent barrier properties against water vapor or various gases, that is, excellent gas barrier properties.
Further, the polyparaxylylene resin is also excellent in the above-mentioned water vapor or gas barrier properties, and has good flexibility of the coating film and good permeability to extremely fine portions, so that a uniform film thickness can be secured. Both types have good water repellency and chemical resistance as coating films, and are excellent in electrical properties such as insulating properties. Each of the coating films is colorless and transparent.

[0008] The coating film 3 of the polyparaxylylene resin or the like according to the present invention can be formed by a CVD method as described later. The thickness of the coating ranges from 0.02 μm to 120 μm
And more preferably 0.05 μm to 80 μm. If the thickness of the coating film is less than 0.02 μm, the desired effect of improving the barrier properties of the film is not exhibited. Also, even if the thickness of the coating film exceeds 120 μm, the efficiency for forming the coating film is poor,
Further, no remarkable effect as the thickness of the coating film is shown as the effect of the coating film.

[0009] Film 1 on which a coating film according to the present invention is formed
Is a coating film 3 made of polyparaxylylene resin formed at the same time as leveling the surface of the base film evenly.
Also exhibit high moisture-proof and gas-barrier properties. Further, since the coating film 3 has heat resistance, it is possible to supply a packaging material having a coating film which is not destroyed even in retort sterilization or the like. In addition, since the coating film is transparent, the contents are visible, and the coating film can be used as a packaging material for food or the like heated by a microwave oven.

The surface of the base film 2 may be made uneven to improve the slipperiness. When the film is used, slipperiness with a metal or plastic surface may be desired when the film is used. For this reason, the irregularities 7 may be formed on the film surface by embossing or the like. The unevenness provided on the film surface reduces the contact area between the film and the other surface, thereby improving the slipperiness. When the film is embossed by pressing using a metal or the like having an uneven surface, that is, by the so-called hot press method, the thickness of the film becomes thin and the gas barrier property in the thin part is reduced. May occur. For the above purpose, by forming a coating film such as polyparaxylylene resin of the present invention on a film provided with unevenness on the surface, despite the existence of the unevenness on the film surface,
A coating film having a constant thickness can be formed following the uneven shape. In the formation of a coating film by a conventional coating method or a coating film by vapor deposition or the like, it has been difficult to form a stable coating film at a concave portion or a boundary portion of unevenness. The coating film such as resin
Along with the method of forming a coating film described below, following the shape of the surface of the film, it is formed at a constant film thickness at any part, so that the film having excellent physical properties as a film on which the obtained coating film is formed It can be. For example, FIG.
As shown in (a), a polyparaxylylene resin or the like can be provided on a surface having irregularities. Although a film having irregularities formed on the surface may show a decrease in barrier properties, the film is formed by forming a coating film 3 such as polyparaxylylene resin on the irregular surface according to the present invention. The barrier property of the material film main body can be prevented from being lowered, and the film can be covered by the barrier property. By forming a coating film on the uneven surface, the moisture-proof property, the barrier property, and the like are improved while maintaining the characteristics of slipperiness due to the unevenness.
In the formation of the coating film of the polyparaxylylene resin 3 or the like according to the present invention, a uniform coating can be formed even on the concave portions on the concave and convex surface, and the gas barrier property can be ensured. Without this, a stable film can be supplied.

FIG. 3 is a conceptual diagram for explaining a CVD apparatus used in forming a coating film of polyparaxylylene resin or the like according to the present invention. In forming a coating film of polyparaxylylene resin or the like, first, a raw material obtained by winding the base film 2 is prepared, and the pressure reducing unit 12 of the PCVD apparatus 11 is prepared.
Raw material supply roll 13 in (hereinafter referred to as a chamber)
And set on the take-up roll 14. In this case, the film is set so that a polyparaxylylene resin or the like adheres to the vapor deposition layer of the film. When the polyparaxylylene resin 3 is adhered onto the base film 2 by the method of the present invention, a single-wafer batch method is also possible, but in consideration of mass productivity and product stability, a rolled film Is preferred. When a coating film 3 such as a polyparaxylylene resin is formed on the base film 2, the raw material diparaxylylene (DP
X, dimer) is volatilized by the raw material volatilizing and supplying device 21 maintained at 1 torr and 150 to 170 ° C., and then the volatile components are introduced into the thermal decomposition chamber 24 from the raw material supplying nozzle. In a pyrolysis chamber, the diparaxylylene is decomposed in an atmosphere of 0.5 torr and 660 to 690 ° C. to form a radical paraxylylene, cooled to room temperature, and introduced into the chamber. The pressure in the chamber 12 is reduced to 0.1 torr by a vacuum pump. In the chamber 12, the radical paraxylylene polymerizes and adheres to the surface of the running base film to form a coating film made of a high molecular weight polyparaxylylene (PPX) resin. At this time, if necessary, the plasma P can be generated to improve the adhesion to the base film. Thereafter, the film is cooled and deodorized in a high vacuum state, and the film on which the coating film is formed is wound up to stabilize the coating film. Then, the pressure in the chamber is returned to normal pressure, and the film is taken out from the chamber.

The composition of the film to be formed is a polyparaxylylene resin, and when monochloroparaxylylene is used as a raw material, the composition of the film to be formed is a polymonochloroparaxylylene resin. It is transparent.

As described above, in the process of forming the coating film 3 of the polyparaxylylene resin, the base film is unwound from the supply roll 13 of the base film 2 set in the chamber 12 and is taken up by the take-up roll 14. When the base film 2 is run at a constant speed, the radical para-xylylene introduced into the chamber 12 polymerizes and adheres on the film surface to form a coating film. The film is characterized in that it is a film having a uniform thickness. In this case, depending on the type of the base film, if the adhesion is poor, the electrode plate and the plasma P
The coating film can be formed therein. The properties of the coating film such as the polyparaxylylene resin are mainly determined by the composition and thickness of the film. As the thickness of the film, a good film can be formed by optimizing the degree of vacuum in the chamber, the running speed of the film, the electric power at the time of plasma generation, and the like as parameters of the preparation conditions. The degree of vacuum in the chamber when the polyparaxylylene resin or the like adheres to the surface of the film is preferably 0.05 to 1.5 torr. The running speed of the film is 5 to 200 m / min, preferably 10 to 100 m / min. The degree of vacuum and the running speed of the film are set according to the thickness of the coating film to be formed. The thickness of the coating film such as polyparaxylylene resin formed on the film is 0.02 to 120 μm, preferably 0.05 to 80 μm.

When the plasma CVD method is used, the plasma is excited at a low temperature to further activate the radical para-xylylene and exhibit an effect of improving the adhesion to the adherend.

The film on which the coating film of the present invention is formed may be used alone or as a composite material laminated with another film. For example, FIG.
(B) As shown in FIG.
A polyparaxylylene resin 3 is formed by the CVD method of the present invention, and a laminated resin layer 6 having a heat sealing property is provided on the polyparaxylylene resin layer 3 with an adhesive 5 interposed therebetween, so that the heat sealing property is improved. It can be a packaging material. In addition, although not shown, various other films can be laminated on the coating surface side of the polyparaxylylene resin or the like according to the purpose of use. In laminating the film on which the coating film of the present invention is formed and another film, an adhesive may be applied to the film on which the coating film is formed, and the film may be laminated by dry lamination with the other film, A method of laminating the thermoplastic resin as an adhesive layer while melt-extruding the thermoplastic resin, that is, a method of so-called sandwich lamination may be used. Further, as the laminated resin layer to be laminated on the film on which the coating film of the present invention is formed, various resins or films can be selected depending on the application, and the thickness is also 10 to 10.
It can be about 00 μm.

The film on which the coating film of the present invention is formed can be used for various applications requiring a barrier property.
Specific examples thereof include containers for packaging contents requiring barrier properties, such as a goebel top type or brick type paper container, a paper cup container, an inner bag of a bag-in-box, a pouch, a laminate tube,
Laminated sheets and the like used for vacuum forming and the like can be mentioned, and they can be used as bags for forming these packaging containers or as materials for forming.

[0017]

【Example】

Example 1 A polyparaxylylene resin was formed on a polyester film by CVD at a thickness of 25 μm. Specifically, a 12 μm-thick polyethylene terephthalate film was used as a substrate film for the raw material, and the raw material was set on a supply roll of the apparatus of the present invention. And
When the film is wound up by the winding roll, it is brought into close contact with the electrode drum in the chamber. The pressure in the chamber was reduced by 0.1 tprr. Next, the raw material diparaxylylene DPX, dimer) is taken out from the raw material volatilization supply device 21 and
At 180 ° C., and the volatile components are removed from the pyrolysis chamber 2
Then, the mixture was decomposed by heating in an atmosphere of 0.5 torr and 670 ° C. to produce radical para-xylene, which was introduced into the chamber 12. In the chamber 12, the radical para-xylene was formed by depositing polyparaxylylene as a coating film on the surface of the base film by a vapor phase vapor deposition polymerization method. A polyethylene terephthalate film was run in the chamber at a running speed of 30 m / min, and a polyparaxylylene resin was adhered on the polyethylene terephthalate film. At this time, the degree of vacuum of the chamber was kept at 0.08 torr. The thickness of the polyparaxylylene resin formed at this time was 20 ± 2 μm. A film of linear low-density polyethylene of 40 μm was dry-laminated using an isocyanate-based adhesive on a surface of the obtained film on which no coating film was formed, on which no coating film was formed, to obtain a composite film.

Comparative Example 1 As a comparative example, an SiO _x film was formed on a 12 μm-thick polyethylene terephthalate by an ordinary vapor deposition method. The film thickness of the vapor deposition layer was 800 mm as observed with a transmission electron microscope. Of the resulting film,
Linear low-density polyethylene on the surface where no evaporation layer is formed
A 40 μm film was dry-laminated using an isocyanate-based adhesive to form a composite film. <Comparative experiment> From the films of Example 1 and Comparative example 1,
Make a four-sided seal bag with an inner dimension of 110 mm width and 150 mm length (seal width is 7 mm width in both length and width), fill with 120 cm ³ of water, and
After storing 20 bags each in a predetermined size cardboard, set the following conditions and put it on a vibration tester, then unpack the bags,
A sample was prepared in a flat state, and the oxygen permeability was measured. Table 1 shows the results of the measurement of the oxygen permeability. The oxygen permeability test was measured according to JIS K 7126. [OXYTRAN 2/20 manufactured by MOCON was used for the measurement. Vibration test conditions According to method B of JIS Z 032, vibration was performed in the vertical direction at a frequency of 10 C / S and an acceleration of 1 G for one hour.

[0019]

[Table 1]

[0020]

According to the present invention, a coating film of a polyparaxylylene resin or the like is coated on at least one surface of a plastic base film at a rate of 0.02.
Physical properties of the substrate film, for example, the effect of improving the barrier properties is exhibited by the film formed with the coating film of the present invention provided in a thickness of μm to 120 μm, and further, the coating film is subjected to stress such as bending that the film receives. Also, since no crack is generated in the coating film, the barrier property is stably maintained. Further, even when a coating film of a polyparaxylylene resin or the like is provided on the uneven surface of the base film having unevenness, the coating film has a uniform thickness following the unevenness of the base film surface. Since it can be formed, there is no decrease in barrier properties due to unevenness and the like, and in this case, there is little decrease in barrier properties due to stress due to bending or the like that the film undergoes and exhibits excellent properties such as preservation of contents. . In addition to the improvement in the barrier properties described above, it exhibits excellent electrical properties such as water repellency, chemical resistance and electrical insulation, so that various plastic films can be used for many applications. The coating of the polyparaxylylene resin or the like can be stably applied by providing the coating using the CVD method.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing an example of a film on which a coating film of the present invention is formed, and FIG.

FIG. 2 is a cross-sectional view showing another embodiment of a film on which a coating film of the present invention is formed, and FIG. 2B is a cross-sectional view showing a case where another resin layer is further laminated.

FIG. 3 is a conceptual diagram of a CVD apparatus used to form a coating film of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Film which formed coating film 2 Base film 3 Polyparaxylylene resin etc. or its coating film 4 Anchor coating agent 5 Adhesive layer 6 Laminated resin layer 7 Irregularities 11 CVD apparatus 12 Chamber 13 Supply roll 14 Take-up roll 15 Cooling Electrode drum 16 Guide roll 17 Power supply 18 Vacuum pump 19 Raw material supply nozzle 21 Raw material volatile supply device 23 Electrode plate P Plasma

Claims (4)

[Claims] A coating film made of polymonochloroparaxylylene or polyparaxylylene resin is coated on at least one surface of a plastic base film at 0.02 μm to 120 μm.
m. A film having a coating film formed thereon having a thickness of m. 2. The film according to claim 1, wherein the base film has irregularities formed on at least one surface, and the coating film is formed on the surface on which the irregularities are formed. . 3. A coating film made of polymonochloroparaxylylene or polyparaxylylene resin on at least one surface of a plastic base film by a CVD method.
A method for producing a film having a coating film, wherein the film is provided with a thickness of from 02 μm to 120 μm. 4. The film according to claim 3, wherein the base film has irregularities formed on at least one surface, and the coating film is formed on the surface on which the irregularities are formed. Production method.