WO2017033701A1

WO2017033701A1 - Method for producing resin film

Info

Publication number: WO2017033701A1
Application number: PCT/JP2016/072941
Authority: WO
Inventors: 正澤里; 洪太永岡; 睦松本
Original assignee: デンカ株式会社
Priority date: 2015-08-26
Filing date: 2016-08-04
Publication date: 2017-03-02
Also published as: TW201718730A; TWI712637B; JPWO2017033701A1; JP6762945B2

Abstract

[Problem] To provide a method for producing a resin film that contains an ethylene-chlorotrifluoroethylene copolymer and has excellent transparency and appearance. To additionally provide a method for producing a multilayer film and a method for producing an outdoor waterproof film, each of which uses this resin film. [Solution] A resin film having excellent transparency and appearance is able to be obtained by melting and kneading a resin composition, which contains an ethylene-chlorotrifluoroethylene copolymer, by an extruder provided with a T-die under specific conditions, and subsequently subjecting the resulting resin composition to casting with use of a cooling roll. The extruder is provided with a breaker plate between the front end portion of a screw and the T-die; the breaker plate is provided with a screen mesh; the aperture ratio of the breaker plate is 40-60%; the minimum opening of the screen mesh is 0.03-0.1 mm; and the temperature of the resin composition at the front end portion of the ejection port of the T-die is higher than the surface temperature of the cooling roll by 110-280°C.

Description

Manufacturing method of resin film

The present invention is a method for producing a resin film using a resin composition containing an ethylene-chlorotrifluoroethylene copolymer, and the resin film obtained thereby is laminated with a base material containing a thermoplastic resin. The present invention relates to a laminated film manufacturing method and an outdoor waterproof film manufacturing method.

Ethylene-chlorotrifluoroethylene copolymer (ECTFE) is weather resistant, chemical resistant, stain resistant, water repellency, insulation, low friction, electrical insulation, low moisture absorption, water vapor barrier property, low Because of its excellent chemical permeability, flame retardancy, and fire spread resistance, it is used for structural parts of semiconductor manufacturing equipment and various corrosion-resistant lining materials. Moreover, since ECTFE can be extrusion-molded and film-forming is also possible, it is used for various uses, such as a surface protection film and a member film for solar cells.

Generally, in order to obtain a film having excellent transparency, a molding process is required in which the resin temperature is rapidly cooled from a state higher than the crystallization temperature to suppress crystallization. However, ECTFE is known to have a maximum melting point of 242 ° C and a crystallization temperature of 222 ° C by adjusting the composition ratio of ethylene and chlorotrifluoroethylene. It is easy to crystallize at the time of molding, and the transparency of the film becomes difficult to express. In order to obtain excellent transparency, it is preferable to set the resin temperature as high as possible when melted and kneaded by an extruder and extruded from the die outlet. However, when the resin temperature is set too high, it is known that, on the contrary, the deterioration of the resin easily proceeds and the color changes to brown or black.

On the other hand, a film using ECTFE has a high quality requirement that does not contain discontinuous physical unevenness or hue unevenness as much as possible, which is called a defect, such as foreign matter, fish eye, gel, and contamination. ing. For this reason, further efforts to reduce the occurrence of defects are required.
JP 2013-237730 A Special table 2013-500856 gazette JP 2011-176192 A

The main causes of defects are coloring due to decomposition or deterioration of ECTFE, gelation, carbonization, mixing of components other than ECTFE, and the like. As an approach to reduce the occurrence of these defects, there is a means for making the mesh of the screen mesh arranged downstream of the screw tip of the extruder finer. However, if the opening is made too fine, it will lead to the retention and deterioration of the molten resin, making it difficult to suppress the occurrence of defects, and toxic corrosive properties such as hydrogen chloride and hydrogen fluoride. This is not preferable because it increases the risk of gas generation.

Furthermore, in the production of a film, after a part of the produced film is pulverized or granulated to be a recycled raw material, it is generally mixed with an unused raw material at an arbitrary ratio to improve the yield. ing. In this case, since ECTFE that has received a thermal history once exposed to the molten environment receives the thermal history again, there is a high possibility that a decrease in transparency due to deterioration of the resin or a defect will occur. Under such circumstances, even when the mesh of the screen mesh is made finer, the development of an ECTFE film with excellent transparency and excellent appearance without defects such as fish eye, gel, and contamination is difficult to cause resin retention. Was desired.

In view of the above problems and actual conditions, an object of the present invention is to provide a method for producing a resin film containing an ethylene-chlorotrifluoroethylene copolymer excellent in transparency and appearance. Furthermore, it aims at providing the manufacturing method of the laminated | multilayer film and outdoor waterproofing film using this resin film.

In the process of carrying out earnest research, the present inventor, when producing a resin film from a resin composition containing ECTFE, has an aperture ratio of a breaker plate, an opening of a screen mesh, a resin temperature at a T die discharge port, and a T die. By making the difference from the surface temperature of the cooling roll (first cooling roll) that receives the resin discharged from the discharge port within a specific range, ethylene-chlorotrifluoro is prevented while preventing the resin composition from rising in temperature and mixing in foreign matter. The present inventors have found that crystallization of an ethylene copolymer can be suppressed and have completed the present invention.

The present invention for solving the above-described problems is constituted as follows.
(1) In the present invention, a resin composition containing an ethylene-chlorotrifluoroethylene copolymer is melt-kneaded with an extruder equipped with a T-die, and then subjected to a casting treatment using at least one cooling roll. The extruder includes a breaker plate between a screw tip and the T die, the breaker plate includes a screen mesh, and the opening ratio of the breaker plate is 40% to 60%. %, The minimum mesh opening of the screen mesh is 0.03 mm to 0.1 mm, and the temperature of the resin composition at the discharge port of the T die is 110 ° C. to the surface temperature of the first cooling roll. It is a manufacturing method of the resin film which is 280 degreeC high temperature.
(2) In the present invention, the casting process is performed using the first cooling roll and the touch roll, and a part of the surface of the first cooling roll is in contact with a part of the surface of the touch roll. The distance between the discharge port tip of the T die and the end of the T die on the surface where the first cooling roll surface and the touch roll surface are in contact is 400 mm or less. It can be set as a manufacturing method.
(3) In the present invention, the method for producing a resin film according to (1) or (2), wherein the temperature of the resin composition at the discharge port of the T die is 240 ° C. to 300 ° C. .
(4) In the present invention, the resin composition contains a heat stabilizer, and the content of the heat stabilizer in the resin composition is 0.1% by mass to 5% by mass. It can be set as the manufacturing method of the resin film as described in any one of (3).
(5) In the present invention, the resin composition contains an ultraviolet absorber, and the content of the ultraviolet absorber in the resin composition is 0.1% by mass to 5% by mass. It can be set as the manufacturing method of the resin film as described in any one of (4).
(6) In the present invention, a recycling raw material comprising a resin film prepared using a resin composition containing an ethylene-chlorotrifluoroethylene copolymer as the resin composition, The method for producing a resin film according to any one of (1) to (5), which is contained at 40% by mass.
(7) The present invention relates to a resin film in which an ethylene-chlorotrifluoroethylene copolymer-containing resin composition is melt-kneaded with an extruder equipped with a T die and then cast using at least one cooling roll. And forming the first surface of the obtained resin film in one or more reformed gases selected from nitrogen gas, oxygen gas, hydrogen gas, carbon dioxide gas, rare gas element gas and hydrocarbon gas A step of surface modification by corona treatment or plasma treatment, and a step of laminating a base material containing a thermoplastic resin on the first surface of the surface-modified resin film by vacuum lamination. In the step of forming a film, the extruder includes a breaker plate between a screw tip and the T die, and the breaker plate The breaker plate has an opening ratio of 40% to 60%, the minimum opening of the screen mesh is 0.03 mm to 0.1 mm, and the resin composition at the discharge port of the T die This is a method for producing a laminated film, wherein the temperature is 110 ° C. to 280 ° C. higher than the surface temperature of the first cooling roll.
(8) The present invention relates to a resin film obtained by melt-kneading a resin composition containing an ethylene-chlorotrifluoroethylene copolymer in an extruder equipped with a T-die and then casting using at least one cooling roll. And forming the first surface of the obtained resin film in one or more reformed gases selected from nitrogen gas, oxygen gas, hydrogen gas, carbon dioxide gas, rare gas element gas and hydrocarbon gas A step of surface modification by corona treatment or plasma treatment, and a step of laminating a base material containing a thermoplastic resin on the first surface of the surface-modified resin film by vacuum lamination. In the step of forming a film, the extruder includes a breaker plate between a screw tip and the T die, and the breaker plate The breaker plate has an opening ratio of 40% to 60%, the minimum opening of the screen mesh is 0.03 mm to 0.1 mm, and the resin composition at the discharge port of the T die A method for producing an outdoor waterproof film, wherein the temperature is 110 ° C. to 280 ° C. higher than the surface temperature of the first cooling roll.

According to the present invention, a method for producing a resin film containing an ethylene-chlorotrifluoroethylene copolymer having excellent transparency and appearance can be provided. Furthermore, the manufacturing method of the laminated | multilayer film and outdoor waterproofing film using this resin film can be provided. The resin film obtained by the production method of the present invention is excellent in transparency and appearance.

It is a schematic diagram which shows the structure of an extruder, T die | dye, a 1st cooling roll, and a touch roll. It is the schematic diagram which expanded the structure of T die | dye, a 1st cooling roll, and a touch roll.

Hereinafter, embodiments for carrying out the present invention will be described in detail. Note that the present invention is not limited to the embodiments described below.

[Production method of resin film]
The resin film production method of the present embodiment is obtained by melt-kneading a resin composition containing an ethylene-chlorotrifluoroethylene copolymer in an extruder equipped with a T die, and then performing a casting treatment using a cooling roll. Forming a film.
<Resin composition>
The resin composition contains an ethylene-chlorotrifluoroethylene copolymer (hereinafter also referred to as “ECTFE”). As the ethylene-chlorotrifluoroethylene copolymer, a copolymer comprising ethylene (hereinafter also referred to as “Et”) and chlorotrifluoroethylene (also referred to as “ethylene trifluorinated chloride”, hereinafter also referred to as “CTFE”). In addition to the polymer, in addition to the above monomers, (perfluorohexyl) ethylene, (perfluorobutyl) ethylene, (perfluorooctyl) ethylene, [4 (heptafluoroisopropyl) perfluorobutyl] ethylene, perfluoroalkyl vinyl ether, etc. The copolymer used as the third monomer can be used. The monomer ratio (molar ratio) in the copolymerization of Et and CTFE is not particularly limited, but the monomer ratio is Et / CTFE = 40 / 60-60 in order to impart heat resistance to the resin film. / 40 is preferable.

As the resin composition, ECTFE having an arbitrary Et / CTFE ratio (molar ratio) may be used alone, or at least one kind of ECTFE having different Et / CTFE ratios may be mixed and used. Moreover, resin other than ECTFE can be added in the range which does not inhibit the effect of the resin film of this invention.

The resin composition can contain a heat stabilizer as necessary. Examples of heat stabilizers include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, metal soaps, organotin compounds, epoxy compounds, β-diketones, perchloric acid metal salts, hydrotalcite, etc. Of these, phenol-based antioxidants, phosphorus-based antioxidants, and metal soaps are preferable in terms of transparency. As a method for adding the heat stabilizer, one previously added in the granulating step of the ECTFE raw material to be used may be used, or when manufacturing a resin film, an ECTFE raw material to which no heat stabilizer is added and A heat stabilizer and a melt stabilizer can also be contained. The addition amount of the antioxidant is preferably 0.001% by mass to 5% by mass in the total resin composition, and more preferably 0.1% by mass to 1.0% by mass. If it is less than 0.001% by mass, sufficient thermal stability cannot be obtained, and if it exceeds 5% by mass, the transparency or color tone may be deteriorated.

An ultraviolet absorber can be added to the resin composition as necessary. Examples of the UV absorber include organic UV absorbers such as benzotriazole UV absorbers, benzophenone UV absorbers and triazine UV absorbers, hindered amine stabilizers (HALS), and the like. Of these, triazine-based ultraviolet absorbers are preferable, and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- [2- (2- (4) is particularly preferable in terms of compatibility with ECTFE. 2-Ethylhexanoyloxy) ethoxy] phenol is preferred. As a method for adding the ultraviolet absorber, one previously added in the granulation step of the ECTFE raw material to be used may be used, or when the resin film is produced, the ECTFE raw material to which the ultraviolet absorber is not added and the ultraviolet ray are added. It is also possible to melt and mix the absorbent. The addition amount of the ultraviolet absorber is preferably 0.001% by mass to 5% by mass, and more preferably 0.1% by mass to 1.0% by mass. If the amount is less than 0.001% by mass, the effect of a sufficient ultraviolet absorber cannot be obtained, and if it exceeds 5% by mass, transparency or color tone may be deteriorated.

In the resin composition, a part of the broken material of the resin film produced by the method described later can be added to the resin composition as a recycle raw material within a range that does not impair the effects of the present invention. The addition ratio of the resin film broken material is preferably 1% by mass to 40% by mass in the resin composition. In addition, the resin composition has plasticizers, lubricants, antistatic agents, antifogging agents, droplets, hydrophilic agents, liquid repellents, etc., as long as the transparency, color tone, heat resistance, film appearance, etc. are not practically impaired. Can be added. As a method for adding these additives, the resin composition may be kneaded, or may be applied to the surface of the resin film after producing the resin film.

<Resin film forming process>
The resin film is obtained by melt-kneading the resin composition with an extruder equipped with a T die and then casting with a cooling roll. The “casting process” is a process for forming a film by a so-called casting method. For example, a resin melted by an extruder is extruded from a linear slit (discharge port) provided in a die, and the molten film is formed. The process which forms a winding film, cooling and extending | stretching with a cooling roll. In the following description, “resin composition” may be abbreviated as “resin”.

FIG. 1 is a schematic diagram showing an example of a resin film forming process of the present embodiment. In the present embodiment, the resin composition is melt-kneaded with a screw in a heated cylinder (not shown) provided in the extruder 1, and then passed through a T die 3 connected through a single pipe 2, and is discharged from a discharge port 4. Discharge molten resin. Thereafter, the molten resin is cast using the first cooling roll 5 and the touch roll 6 to obtain the resin film 10. The “first cooling roll” is a cooling roll provided closest to the discharge port 4 of the T die 3 and is a casting roll that cools and stretches the discharged resin.

As the extruder, a single screw type, a twin screw type, a tandem type or the like can be used as a general one, but a single screw is used because it does not give excessive shear to the resin and does not stay in the system. A screw type extruder is preferred.

The screw of the extruder is not particularly limited as long as the specification is sufficient to plasticize and homogenize the resin and does not cause resin deterioration due to excessive shearing. As a screw which can be used suitably, a full flight type screw is preferable. The full flight type screw preferably has a compression ratio of 1.3 to 3.0, and the ratio of the screw length L to the screw diameter D (L / D) is preferably 20 to 40, more preferably 2. 0 to 3.0 and L / D is 25 to 35.

The extruder includes a breaker plate between the screw tip and the T die. The breaker plate may be provided, for example, at the tip flange portion of the cylinder in the extruder so as to cross the inner hole of the cylinder and to go directly to the flow path of the molten resin. The breaker plate has a plurality of through-holes through which the molten resin passes at the center. The opening ratio of the breaker plate is 40% to 60%, preferably 42% to 58%. By setting the opening ratio of the breaker plate to 40% or more, it is possible to suppress back pressure to the resin and to prevent the resin from staying in the extruder. Further, by setting the aperture ratio to 60% or less, the number of defects of the film (number of fish eyes, gels, contaminants, etc.) can be stably kept low for a long time. The opening ratio means the area of the part where the resin through-hole is formed with respect to the entire area including the resin through-hole with reference to the part exposed to the resin circulation part of the extruder.

More preferably, the minimum diameter of the resin through hole of the breaker plate is 3.7 mm to 6.0 mm. “Minimum diameter” refers to the smallest diameter of each through hole. By setting the minimum diameter of the resin through hole to 3.7 mm or more, the back pressure on the resin can be suppressed and the resin staying in the extruder can be suppressed. Further, by setting the minimum diameter of the resin through hole to 6.0 mm or less, the number of defects of the film can be stably kept low for a long time.

The breaker plate has a screen mesh. For example, one or more screen meshes may be provided in contact with the surface on the upstream side (screw tip side) of the breaker plate. The screen mesh disposed on the breaker plate is preferably a combination of two or more screen meshes having different openings. As the screen mesh, a screen mesh having the same mesh opening can be used in combination. In general, it is preferable to arrange a screen mesh having a large mesh size and a screen mesh having a small mesh size in this order from the upstream side (near the screw) to the downstream side (breaker plate opening side) of the resin flow part. Furthermore, it is preferable to dispose a mesh coarser than the mesh downstream of the mesh having the smallest mesh size for the purpose of preventing the mesh from being broken by the resin pressure. In this embodiment, the minimum mesh opening of the screen mesh is 0.03 mm to 0.1 mm, and preferably 0.03 mm to 0.7 mm. By setting the minimum mesh size of the screen mesh to 0.03 mm or more, it is possible to suppress deterioration due to resin retention and shear heat generation. In addition, by setting the minimum mesh size of the screen mesh to 0.1 mm or less, it is possible to reduce contamination, degraded raw materials, and the like mixed in the resin. The screen mesh having a large opening serves to remove coarse defects, and the opening is preferably 0.15 mm to 0.6 mm. Furthermore, for the purpose of preventing the screen mesh from being broken by the resin pressure, a coarse screen mesh having a larger opening may be introduced downstream of the screen mesh having the smallest opening. It is preferable that the screen mesh is disposed 10 to 100 mm downstream from the tip of the screw.

The resin temperature at the T-die discharge port is preferably maintained at 240 ° C. to 300 ° C., although it depends on the melting point of ECTFE used. When the resin temperature exceeds 300 ° C., ECTFE is likely to be decomposed, which may easily lead to a change in color tone and generation of defects due to degradation of the resin. On the other hand, if the resin temperature is less than 240 ° C., a decrease in fluidity accompanying an increase in the viscosity of the resin occurs, which may promote excessive shearing and retention in the extruder.

The resin plasticized according to the above-described method is extruded from a T-die into a sheet shape, and then taken out while being cast between a temperature-controlled first cooling roll and a rubber touch roll. It can be adjusted to a predetermined thickness by being pulled while contacting the cooling roll. Here, since the touch roll is in contact with or pressed against the first cooling roll, a part of the surface of the touch roll is in contact with the surface of the cooling roll. The thickness of the resin can be adjusted to a desired thickness by adjusting the pressure applied to and the take-up speed of the first cooling roll and the touch roll.

The cooling roll includes at least one cooling roll and may include a plurality of rolls. As described above, the cooling roll provided closest to the discharge port of the T die is the first cooling roll. The resin temperature at the T die discharge port is + 110 ° C. to + 280 ° C. higher than the surface temperature of the first cooling roll, and preferably + 120 ° C. to + 250 ° C. higher. If the temperature difference between the resin temperature at the discharge port of the T-die and the surface temperature of the cooling roll is less than + 110 ° C., ECTFE will crystallize and the transparency of the resin film will deteriorate, or the film to the cooling roll will be produced during resin film production Since adhesion occurs, it is not preferable. On the other hand, if the temperature difference exceeds + 280 ° C., the number of defects due to the deterioration of the resin and the deterioration of the film appearance tend to occur, which is not preferable. The resin temperature at the T die discharge port can be obtained, for example, by measuring the temperature of the resin passing through the lip outlet of the T die using a contact thermometer or the like. The surface temperature of the first cooling roll can be obtained, for example, by measuring the surface temperature of the first cooling roll using a contact thermometer or the like.

The distance from the T-die discharge port to the surface where the first cooling roll surface and the touch roll surface are in contact plays an important role in controlling the crystallinity of the resin film. 1 and 2 show configurations of the T die, the first cooling roll, and the touch roll. As shown in FIGS. 1 and 2, on the surface 7 where the surface of the first cooling roll 5 and the surface of the touch roll 6 are in contact, the point 8 at the highest position of the surface 7 in contact (the first cooling roll and the touch roll in the rotating state are Or the contact point between the cooling roll surface and the touch roll surface may be abbreviated as “contact”, and the distance from the T-die discharge port 4 to the contact 8 (shortest distance) ) 9 may be abbreviated as “air gap”. That is, the air gap is when the T-die discharge port and the contact surface of the first cooling roll surface and the touch roll surface are in a vertical position (for example, the contact surface is positioned below the T-die discharge port in the vertical direction). , That is, in the case of downward discharge) means the shortest vertical distance between the T-die discharge port and the contact, and when the T-die discharge port and the contact surface are arranged at positions different from vertical , T means the linear distance connecting the die outlet and the contact.

The distance (shortest distance) of the air gap is preferably 400 mm or less, and more preferably 100 mm to 300 mm or less. If the distance of the air gap exceeds 400 mm, crystallization proceeds before reaching the first cooling roll, and a good transparent resin film may not be obtained.

The resin film can be obtained by slitting the end of the cooled film to an arbitrary film width and then winding the film with an appropriate tension that does not cause the film to be tightened or wound.

The thickness of the resin film is preferably 0.001 mm to 0.5 mm, and more preferably 0.01 mm to 0.3 mm. If the thickness of the resin film is less than 0.001 mm, tearing may easily occur during film production, and it may be difficult to control the thickness of the film. Moreover, when thickness exceeds 0.5 mm, the nonuniformity of a cooling rate will arise easily in the thickness direction of a film, and transparency will deteriorate easily.

As one of the measures representing the transparency of a resin film, the total light transmittance can be mentioned. The resin film obtained by the production method of the present embodiment preferably has a total light transmittance of 92% or more, more preferably 93% or more, measured by a haze meter. If it is less than 92%, it may be difficult to apply to uses where a reduction in designability when a resin film is laminated on a substrate or a high light collection efficiency is required.

The resin film obtained by the production method of the present embodiment can be suitably used as various waterproof films used outdoors, taking advantage of the water vapor barrier property, chemical resistance, antifouling property, and weather resistance of ECTFE. Examples of applications used outdoors include membrane materials in buildings such as sports facilities, metal steel sheet coating materials such as road signs, concrete waterproof sheets, etc. Can be suitably used. In particular, since the resin film of the present embodiment described above is excellent in transparency and appearance, it is suitable as a surface protective film for other resin sheets and inorganic materials. In particular, since it contains ECTFE excellent in weather resistance and water vapor barrier properties, it is suitable for use as an outdoor waterproof film.

[Method for producing laminated film and method for producing outdoor waterproof film]
When forming a laminated film using the above-described resin film as a surface protective film, an adhesive surface (first surface of the resin film) is provided so as to provide adhesion to an object to be protected (hereinafter referred to as “base material”). ) Is preferably surface-modified. In the case of a laminated film or an outdoor waterproof film, a resin film forming step comprising the above-described resin film manufacturing method, a step of surface-modifying the first surface of the obtained resin film, and a surface-modified resin film And laminating a base material containing a thermoplastic resin on the first surface.

(Surface modification process)
Examples of the surface modification method include a method of treating the first surface of the resin film with corona treatment or plasma treatment. The “first surface” refers to either one or both of the front and back surfaces of a resin film that can be an adhesive surface. As a method of corona treatment and plasma treatment, the resin film may be processed in-line downstream of the process of the cooling roll, or after the resin film is manufactured, it may be processed off-line with corona treatment equipment or plasma treatment equipment. Good.

The amount of discharge related to the corona treatment is not particularly limited, but is preferably 30 W · min / m ² or more, more preferably 50 W · min for the purpose of obtaining suitable adhesion to the substrate. / M ² or more. If it is less than 30 W · min / m ² , a sufficient surface modification effect of the resin film cannot be obtained, and the adhesion to the substrate may be insufficient. About the upper limit of discharge amount, it can set suitably in the range by which the external appearance of a resin film is not impaired.

The surface modification effect obtained by the plasma treatment varies depending on the type of gas to be present, but examples of the modified gas that can be suitably used for the resin film of the present embodiment include nitrogen, oxygen, hydrogen, carbon dioxide, and argon. And hydrocarbon-based gas. As an example of a more preferable processing gas for the purpose of obtaining adhesiveness to the substrate, a rare gas element gas component such as argon gas and a hydrocarbon-based gas can be given. These process gases may be used alone or in combination of two or more. As a general plasma processing method, there are a remote plasma method and a direct plasma method, and the resin film of this embodiment can be suitably used for any of the processing methods. The direct plasma method is more preferable for the purpose of reducing surface roughness and enabling surface treatment at a low cost.

(Substrate lamination process)
As a method of laminating a substrate on a resin film whose surface has been modified by corona treatment or plasma treatment, a method of laminating a resin film on the surface of a substrate softened by heat can be employed.

As another surface modification method of the resin film, an adhesive resin having adhesiveness to both the resin film and the substrate is applied to the adhesive surface (first surface) of the surface-modified resin film, and heat is applied. A method of softening the resin film and laminating the surface of the substrate can be suitably employed.

The main adhesive resins that can be used in the coating include ethylene-vinyl acetate copolymer (EVA), acrylate resins, isocyanate resins, epoxy resins, urethane resins, silicone resins, polyolefin resins, ionomers. Resins etc. are mentioned, At least 1 or more types can be selected and used according to the objective and a use. These adhesive resins are also used as sealing resins.

Examples of the substrate include films and sheet-like flat plate shapes, and those having a three-dimensional shape such as a rectangular parallelepiped, a prism, a pyramid, a cylinder, and a cone. The kind of base material is not specifically limited, Resin, glass, etc. can be mentioned. Examples of the resin include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polycarbonate (PC), polymethyl methacrylate (PMMA), styrene-butadiene copolymer (SBC), and ethylene-vinyl acetate copolymer ( EVA), polyimide (PI), polyphenylene sulfide (PPS), aramid, polypropylene (PP), polyethylene (PE), polylactic acid (PLA), polyvinyl chloride (PVC), silicone resin, alicyclic acrylic resin, cycloolefin A thermoplastic resin such as resin (COP) or triacetyl cellulose (TAC) can be used. As glass, soft glass, hard glass, or quartz glass can be used. Among these, a thermoplastic resin is preferable from the viewpoint of adhesion to a resin film, and an ethylene-vinyl acetate copolymer is particularly preferable from the viewpoint of adhesion and transparency.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

The raw materials used in Examples and Comparative Examples are described below.
[ECTFE]
ECTFE1: “Halar ECTFE 500LC” manufactured by Solvay, melting point 242 ° C., MFR 18 g / 10 min (ASTM D1238 275 ° C./2.16 kg load)
ECTFE2: “Halar ECTFE 350LC” manufactured by Solvay, melting point 242 ° C., MFR 4.0 g / 10 min (ASTM D1238 275 ° C./2.16 kg load)
ECTFE3: “Halar ECTFE XPH802B (700HC)” manufactured by Solvay, melting point 202 ° C., MFR 9.0 g / 10 min (ASTM D1238 275 ° C./2.16 kg load)
[Antioxidant]
* "ADEKA STAB 593" manufactured by ADEKA: Mixture of zinc stearate and calcium stearate [UV absorber]
“LA-46” manufactured by ADEKA: 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- [2- (2-ethylhexanoyloxy) ethoxy] phenol

The resin film of an Example and a comparative example was formed using the following apparatus.
[Extruder]
・ “VS65-25 single screw horizontal extruder” manufactured by Tanabe Plastic Industry Co., Ltd., hopper type [screw]
・ Screw configuration: Full flight type screw ・ Screw diameter: 65 mm
-Screw length (L) / screw diameter (D) ratio: 25
・ Compression ratio: 2.5

[Screen mesh]
Tables 1 and 2 show the screen mesh configurations and aperture values used in Examples and Comparative Examples. The material of the screen mesh was SUS304, and was installed 20 mm downstream from the screw tip. The screen mesh has a three-layer structure that is continuous on the screw side, the center side, and the T die side.

[Breaker plate]
Tables 1 and 2 show the aperture ratios of the breaker plates used in the examples and comparative examples. In addition, SUS304 was used for the material of a breaker plate, and it installed with the form adjacent to the process downstream of the said screen mesh.

[T die]
The specifications of the T-die used in the examples and comparative examples are shown below.
-Die specification: Coat hanger method / downward discharge type, hard chrome plating on the inner surface-Lip width: 1050mm
[roll]
・ Model: Touch roll type Linear pressure 25-30kgf / cm
・ Roll specifications:
First cooling roll 260mm in diameter
Hard chrome plating finish after surface hardening and polishing Surface roughness: 0.2S (maximum height of convex part)
Chiller water circulation system Touch roll Diameter 260mm
Surface mirror finish white mirror roll Surface roughness: (maximum height of convex part) Ry 3.2 μm, (arithmetic mean roughness) Ra 0.05 μm
・ The shortest distance (air gap) from the T-die discharge port to the highest position on the surface where the first cooling roll surface and the touch roll surface are in contact: 100 to 250 mm

Example 1
After drying pellets of ECTFE1 (Halar ECTFE 500LC) at 80 ° C. for 4 hours, the set temperature of the breaker plate part and the T die was set to 280 ° C. using the above-described extruder, and melt-kneaded. As the screen mesh, meshes of 0.18 mm, 0.075 mm, and 0.18 mm were used from the upstream side to the downstream side of the resin flow part. The air gap was 120 mm. The resin temperature at the T-die discharge port was 280 ° C., and the surface temperature of the first cooling roll was 60 ° C. The thickness of the obtained resin film was 0.025 m. The results are shown in Table 1.

<Resin temperature at T-die outlet>
The resin temperature at the T-die outlet is measured using a contact-type thermometer (DIGITAL SURFACE THERMOMETER, model number: HL-200, manufactured by Anritsu Keiki Co., Ltd.), and the temperature of the resin passing through the lip outlet of the T-die is measured. The measured value.

<Transparency of resin film>
The transparency of the resin film was evaluated by using a Haze Meter “NDH7000” manufactured by Nippon Denshoku Industries Co., Ltd., based on the total light transmittance and the haze value. In the evaluation, a sample cut out from any five points from the TD direction of the resin film was used, and its arithmetic average value was adopted.
Excellent: Haze value of less than 4% Good: Haze value of 4% or more, less than 7% Possible: Haze value of 7% or more, less than 20% Defect: Haze value of 20% or more

<Defects of resin film (appearance)>
The number of defects (foreign matter, fish eye, gel) of 0.7 mm or more contained in a film area of 1000 m ² was measured using an in-line defect detector equipped in the film production facility. The number of defects in the resin film was determined based on the following criteria.
Excellent: Less than 50 Good: 50 or more, less than 80 Possible: 80 or more, less than 100 Poor: 100 or more

<Weather resistance>
The obtained resin film was dried using a xenon arc weatherometer Ci4000 (light source xenon lamp) manufactured by Toyo Seiki Seisakusho Co., Ltd., with an irradiation intensity of 80 W / m ² , a black panel temperature of 85 ° C., a relative humidity of 50%, and drying for 102 minutes. The resin film was irradiated with ultraviolet rays for 2000 hours with a water spray cycle of 18 minutes, and the total light transmittance and hue change (Δb) of the obtained resin film were measured.
The hue (Δb) was measured by using “Color Cute i” manufactured by Suga Test Instruments Co., Ltd., and the change in b value with respect to before ultraviolet irradiation was measured as Δb. Regarding the weather resistance, the performance was determined according to the following criteria for the measured Δb value.
Excellent: Less than 0.3 Good: 0.3 or more, less than 0.6 Possible: 0.7 or more, less than 0.9 Poor: 1.0 or more

<Dampproof>
The moisture resistance of the resin film was measured at a temperature of 40 ° C. and a relative humidity of 90% using an L-80-5000 type water vapor permeability meter manufactured by Lyssy. The moisture resistance of the resin film was determined based on the following criteria.
Excellent: Less than 1.0 Good: 1.0 or more, less than 5.0 Possible: 5.0 or more, less than 10.0 Poor: 10.0 or more

<Surface coating on substrate with resin film>
The resin film was plasma-treated in an argon environment by a remote plasma method to a wetness index of 44 mN / m, and then the plasma-treated surface was pressure-bonded to an EVA resin sheet having a thickness of 0.4 mm at 150 ° C. for 30 minutes and vacuum laminated. . The performance of the base material after lamination was judged according to the following criteria. An atmospheric pressure plasma surface treatment apparatus was used for the plasma treatment.
Good: Macroscopic appearance deterioration such as defects such as delamination and discoloration of molded product is not recognized.
Defect: Delamination is observed, or a macroscopic appearance deterioration such as a defect such as discoloration of a molded product is recognized.

(Examples 2 to 9)
Under the conditions shown in Table 1, resin films were prepared and subjected to various evaluations. The recycled resin films used in Examples 2 to 4 and Examples 6 to 9 are obtained by blending the resin film produced in the same Example with the raw material for the resin composition.

(Comparative Examples 1 to 9)
Under the conditions shown in Table 2, resin films were prepared and subjected to various evaluations. In Comparative Examples 7 to 9, polyvinylidene fluoride (PVDF) was used as the resin composition.

From the results of Examples 1 to 9 and Comparative Examples 1 to 9, it can be seen that the resin film of this embodiment has excellent transparency and a small number of defects. By using the film of this embodiment, it can be suitably used for various protective films that require design properties and outdoor waterproof films.

1 Extruder 2 Single tube 3 T die 4 T die discharge port 5 First cooling roll 6 Touch roll 7 Contact surface 8 between the first cooling roll surface and the touch roll surface 8 Position 9 Shortest distance to the highest position on the surface where the surface of the first cooling roll and the surface of the touch roll contact 10 Resin

Claims

A step of forming a resin film by melt-kneading a resin composition containing an ethylene-chlorotrifluoroethylene copolymer with an extruder equipped with a T-die and casting using at least one cooling roll; ,
The extruder includes a breaker plate between a screw tip and the T die,
The breaker plate comprises a screen mesh,
The opening ratio of the breaker plate is 40% to 60%, and the minimum mesh opening of the screen mesh is 0.03 mm to 0.1 mm;
The method for producing a resin film, wherein the temperature of the resin composition at the discharge port of the T die is 110 ° C. to 280 ° C. higher than the surface temperature of the first cooling roll.
The casting process is performed using the first cooling roll and the touch roll,
A part of the surface of the first cooling roll is in contact with a part of the surface of the touch roll,
2. The resin film production according to claim 1, wherein a distance between a discharge port front end portion of the T die and an end portion on the T die side in a surface where the first cooling roll surface and the touch roll surface are in contact is 400 mm or less. Method.
The method for producing a resin film according to claim 1 or 2, wherein the temperature of the resin composition at the discharge port of the T-die is 240 ° C to 300 ° C.
4. The resin composition according to claim 1, wherein the resin composition contains a heat stabilizer, and the content of the heat stabilizer in the resin composition is 0.1% by mass to 5% by mass. The manufacturing method of the resin film of description.
5. The resin composition according to claim 1, wherein the resin composition contains an ultraviolet absorber, and the content of the ultraviolet absorber in the resin composition is 0.1% by mass to 5% by mass. The manufacturing method of the resin film of description.
The resin composition contains 1% by mass to 40% by mass of a recycled material composed of a resin film produced using a resin composition containing an ethylene-chlorotrifluoroethylene copolymer. The manufacturing method of the resin film as described in any one of Claim 1 to 5.
A step of forming a resin film by melt-kneading a resin composition containing an ethylene-chlorotrifluoroethylene copolymer with an extruder equipped with a T-die and casting using at least one cooling roll;
The first surface of the obtained resin film is subjected to corona treatment or plasma treatment in one or more reformed gases selected from nitrogen gas, oxygen gas, hydrogen gas, carbon dioxide gas, rare gas element gas and hydrocarbon gas. A step of surface modification;
Laminating a base material containing a thermoplastic resin on the first surface of the surface-modified resin film by vacuum lamination,
In the step of forming the resin film, the extruder includes a breaker plate between a screw tip and the T die, and the breaker plate includes a screen mesh,
The opening ratio of the breaker plate is 40% to 60%, and the minimum mesh opening of the screen mesh is 0.03 mm to 0.1 mm;
The method for producing a laminated film, wherein the temperature of the resin composition at the discharge port of the T die is 110 ° C. to 280 ° C. higher than the surface temperature of the first cooling roll.
A step of forming a resin film by melt-kneading a resin composition containing an ethylene-chlorotrifluoroethylene copolymer with an extruder equipped with a T-die and casting using at least one cooling roll;
The first surface of the obtained resin film is subjected to corona treatment or plasma treatment in one or more reformed gases selected from nitrogen gas, oxygen gas, hydrogen gas, carbon dioxide gas, rare gas element gas and hydrocarbon gas. A step of surface modification;
Laminating a base material containing a thermoplastic resin on the first surface of the surface-modified resin film by vacuum lamination,
In the step of forming the resin film, the extruder includes a breaker plate between a screw tip and the T die, and the breaker plate includes a screen mesh,
The opening ratio of the breaker plate is 40% to 60%, and the minimum mesh opening of the screen mesh is 0.03 mm to 0.1 mm;
The method for producing an outdoor waterproof film, wherein the temperature of the resin composition at the discharge port of the T die is 110 ° C. to 280 ° C. higher than the surface temperature of the first cooling roll.