TW201718730A - Method for producing resin film - Google Patents

Abstract

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. 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 DEG C.

Description

Method for producing resin film

The present invention relates to a method for producing a resin film using a resin composition containing an ethylene-chlorotrifluoroethylene copolymer, and a method for producing a laminated film obtained by laminating a resin film obtained therefrom and a substrate containing a thermoplastic resin. A method of manufacturing an outdoor waterproof film.

Ethylene-chlorotrifluoroethylene copolymer (ECTFE) is low in hygroscopicity and water vapor barrier in addition to weather resistance, chemical resistance, stain resistance, water repellency, insulation, low friction and electrical insulation. It is excellent in low-penetration, flame-retardant, and burn-resistant, and is therefore used in structural parts of semiconductor manufacturing equipment, various corrosion-resistant lining materials, and the like. Further, since the ECTFE can be extruded or formed into a film, it can be used for various applications such as a surface protective film and a member film for a solar cell.

In general, in order to obtain a film having excellent transparency, it is necessary to rapidly cool the temperature of the resin from a state higher than the crystallization temperature to suppress crystallization. However, it is known that ECTFE is adjusted by the composition ratio of ethylene and chlorotrifluoroethylene, and the maximum melting point is 242 ° C, and the crystallization temperature is 222 ° C. Since the crystallization temperature is close to the melting point, it is easily crystallized during extrusion molding. The transparency of the film is difficult to display. Further, in order to obtain excellent transparency, it is melted and kneaded in an extruder, and the resin temperature at the time of extrusion from the die exit is preferably set as high as possible. However, it is known that when the resin temperature is excessively set at a high temperature, deterioration of the resin proceeds easily, and discoloration becomes brown or black.

On the other hand, in the film using ECTFE, the quality requirements such as physical irregularities or unevenness of hue which are discontinuous for the average thickness of the film, such as foreign matter called a defect, fish eyes, gel, and contamination, are not contained as much as possible. Raise. Therefore, a further collocation method that can reduce the occurrence of defects is required.

Patent Document 1 Japanese Patent Laid-Open Publication No. 2013-237730

Patent Document 2 Japanese Special Report 2013-500856

Patent Document 3 Japanese Patent Laid-Open Publication No. 2011-176192

The cause of the defect is mainly coloring, gelation, carbonization, and mixing of components other than ECTFE due to decomposition or deterioration of ECTFE. As a means for reducing the occurrence of such defects, there is a means for reducing the aperture of the screen disposed downstream of the screw front end portion of the extruder. However, when the pore diameter is excessively narrowed, it is associated with the retention or deterioration of the molten resin, and it is difficult to obtain the effect of suppressing the occurrence of defects, and the risk of toxic and corrosive gas such as hydrogen chloride or hydrogen fluoride is increased. .

Further, in the production of the film, a part of the produced film is pulverized or granulated to be a recycled raw material, and then blended at an arbitrary ratio in the unused raw material, and the matching method for improving the yield is generally performed. By. At this time, the ECTFE which has been exposed to heat in a molten environment is subjected to thermal experience again, and the possibility of deterioration of transparency or occurrence of defects due to deterioration of the resin is high. In such a situation When it is desired to reduce the pore size of the screen, it is expected that the retention of the resin is less likely to occur, and there is no defect such as fish eyes, gel, or contamination, and the ECTFE film having excellent appearance and excellent transparency is developed.

The present invention has been made in view of the above problems and actual circumstances, and an object of the invention is to provide a method for producing a resin film containing an ethylene-chlorotrifluoroethylene copolymer which is excellent in transparency and appearance. Further, another object is to provide a method for producing a laminated film using the resin film and an outdoor waterproof film.

The inventors of the present invention found that when a resin film is formed from a resin composition containing ECTFE, the aperture ratio of the breaker plate, the pore diameter of the sieve, and the T-die spit are found in the process of intensive research. The difference between the resin temperature of the outlet and the surface temperature of the cooling roll (first cooling roll) of the resin discharged from the T-die discharge port is within a specific range, and it is possible to suppress the temperature rise of the resin composition or the incorporation of foreign matter. The crystallization of the ethylene-chlorotrifluoroethylene copolymer finally completed the present invention.

The present invention for solving the above problems is constituted by the following.

(1) The present invention relates to a method for producing a resin film comprising: a resin composition containing an ethylene-chlorotrifluoroethylene copolymer, which is melt-kneaded by an extruder having a T die, and then at least one cooling is used. a step of forming a resin film by forming a resin film between the front end portion of the screw and the T-die, wherein the porous plate is provided with a screen, and the aperture ratio of the porous plate is 40% to 60. %, the minimum pore diameter of the screen is 0.03 mm to 0.1 mm, and the temperature of the resin composition of the discharge port of the T die is higher than the surface temperature of the first cooling roll by 110 ° C to 280 ° C.

(2) The method for producing a resin film according to (1), wherein the casting treatment is performed by using the first cooling roll and a touch roll, and the surface of the first cooling roll a portion is in contact with a portion of a surface of the contact roller, and a distance between a tip end portion of the discharge port of the T die and an end portion of the T die side in a surface in contact with a surface of the first cooling roller and a surface of the contact roller is 400 mm. the following.

(3) The method for producing a resin film according to (1) or (2), wherein the temperature of the resin composition of the discharge port of the T-die is 240 to 300 °C.

(4) The method for producing a resin film according to any one of the above aspects of the present invention, wherein the resin composition contains a thermal stabilizer, and the thermal stabilizer in the resin composition The content is from 0.1% by mass to 5% by mass.

(5) The method for producing a resin film according to any one of the above aspects of the present invention, wherein the resin composition contains an ultraviolet absorber, and the ultraviolet absorber in the resin composition The content is from 0.1% by mass to 5% by mass.

(6) The method for producing a resin film according to any one of the above aspects of the present invention, wherein the resin composition is contained in the resin composition in an amount of 1% by mass to 40% by mass. A recycled raw material comprising a resin film produced using a resin composition containing an ethylene-chlorotrifluoroethylene copolymer.

(7) The present invention relates to a method for producing a laminated film comprising: a resin composition containing an ethylene-chlorotrifluoroethylene copolymer, which is melt-kneaded by an extruder having a T die, and at least one is used. Cooling roller a step of forming a resin film by casting; the first side of the obtained resin film is borrowed from one or more modified gases selected from nitrogen, oxygen, hydrogen, 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 substrate containing a thermoplastic resin by vacuum lamination on the first side of the surface-modified resin film; In the step of the resin film, the extruder includes a porous plate between the tip end portion of the screw and the T die, and the porous plate includes a mesh, and the opening ratio of the porous plate is 40% to 60%. The minimum pore diameter is 0.03 mm to 0.1 mm, and the temperature of the resin composition of the discharge port of the T die is higher than the surface temperature of the first cooling roll by 110 ° C to 280 ° C.

(8) The present invention relates to a method for producing an outdoor waterproof film, comprising: a resin composition containing an ethylene-chlorotrifluoroethylene copolymer, which is melt-kneaded by an extruder having a T-die, and then used at least 1 a step of forming a resin film by casting a cooling roll; and modifying the first side of the obtained resin film with at least one selected from nitrogen, oxygen, hydrogen, carbon dioxide gas, rare gas element gas, and hydrocarbon gas a step of surface modification by corona treatment or plasma treatment in a gas; and a step of laminating a substrate containing a thermoplastic resin by vacuum lamination on the first surface of the surface-modified resin film In the step of forming a resin film, the extruder includes a porous plate between the tip end portion of the screw and the T die, and the porous plate has a mesh, and the opening ratio of the porous plate is 40% to 60%. The minimum pore diameter of the screen is 0.03 mm to 0.1 mm, and the foregoing resin group of the discharge port of the T die is The temperature of the product is higher than the surface temperature of the first cooling roll by a temperature of 110 ° C to 280 ° C.

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

1‧‧‧Extrusion machine

2‧‧‧Single tube

3‧‧‧T die

4‧‧‧T die spit

5‧‧‧First cooling roller

6‧‧‧Contact roller

7‧‧‧Contact surface of the surface of the first chill roll and the surface of the contact roll

8‧‧‧The highest position of the surface of the first chill roll that is in contact with the surface of the contact roll

9‧‧‧The shortest distance from the highest position in the surface of the first chill roll that is in contact with the surface of the contact roll

10‧‧‧Resin

Fig. 1 is a schematic view showing the constitution of an extruder, a T die, a first cooling roll, and a contact roll.

Fig. 2 is a schematic view showing the configuration of an enlarged T die, a first cooling roll, and a contact roll.

[Formation of the Invention]

Hereinafter, the form of carrying out the invention will be described in detail. Further, the present invention is not limited to the embodiments described below.

[Method for Producing Resin Film]

In the method for producing a resin film of the present embodiment, a resin composition containing an ethylene-chlorotrifluoroethylene copolymer is melt-kneaded in an extruder equipped with a T-die, and then cast by a cooling roll to form a resin composition. The step of the resin film.

<Resin composition>

The resin composition contains an ethylene-chlorotrifluoroethylene copolymer (hereinafter also referred to as "ECTFE"). As an ethylene-chlorotrifluoroethylene copolymer, in addition to use In addition to the copolymer of ethylene (hereinafter also referred to as "Et") and chlorotrifluoroethylene (alias "chlorotrifluoroethylene", hereinafter also referred to as "CTFE"), the above monomers may be used in addition ( Perfluorohexyl)ethylene, (perfluorobutyl)ethylene, (perfluorooctyl)ethylene, [4 (heptafluoroisopropyl)perfluorobutyl]ethylene, perfluoroalkyl vinyl ether, etc. as the third Copolymer of body. The monomer ratio (mole ratio) in the copolymerization of Et and CTFE is not particularly limited, but in order to impart heat resistance to the resin film, the monomer is preferably Et/CTFE=40/60 to 60/40.

As the resin composition, ECTFE having an arbitrary Et/CTFE ratio (mole ratio) may be used alone, or at least one type of different Et/CTFE ratio ECTFE may be used in combination. Further, a resin other than ECTFE may be added to the extent that the effect of the resin film of the present invention is not impaired.

In the resin composition, a heat stabilizer may be contained as needed. Examples of the thermal stabilizer include a phenolic antioxidant, a phosphorus antioxidant, a sulfur antioxidant, a metal soap, an organotin compound, an epoxy compound, a β-diketone, a metal perchlorate, and a hydrotalcite. Among these, a phenolic antioxidant, a phosphorus antioxidant, and a metal soap are preferable in terms of transparency. As a method of adding the heat stabilizer, it may be added in advance in the granulation step of the ECTFE raw material to be used, or the ECTFE raw material to which the thermal stabilizer is not added and the heat stabilizer may be melt-mixed at the time of producing the resin film. Make it contain. The amount of the antioxidant added is preferably 0.001% by mass to 5% by mass, and more preferably 0.1% by mass to 1.0% by mass based on the total of the resin composition. When the amount is less than 0.001% by mass, sufficient thermal stability cannot be obtained, and if it exceeds 5% by mass, transparency or color tone may be deteriorated.

In the resin composition, an ultraviolet absorber may be added as needed. Examples of the ultraviolet absorber include a benzotriazole-based ultraviolet absorber, a diphenylketone-based ultraviolet absorber, and three It is an organic ultraviolet absorber, such as a UV absorber, and a hindered amine stabilizer (HALS). Among these, preferably three It is a UV absorber, especially at the point of compatibility with ECTFE, preferably 2-(4,6-diphenyl-1,3,5-three 2-yl)-5-[2-(2-ethylhexyloxy)ethoxy]phenol. As a method of adding the ultraviolet absorber, it may be used in advance in the granulation step of the ECTFE raw material to be used, or the ECTFE raw material to which the ultraviolet absorber is not added may be melt-mixed with the ultraviolet absorbent when the resin film is produced. Make it contain. The amount of the ultraviolet absorber added is preferably 0.001% by mass to 5% by mass, more preferably 0.1% by mass to 1.0% by mass. When the amount is less than 0.001% by mass, a sufficient effect of the ultraviolet absorber is not obtained, and when it exceeds 5% by mass, transparency or color tone may be deteriorated.

In the resin composition, a part of the scrap material of the resin film produced by the method described later can be added to the resin composition as a raw material for recycling without departing from the effects of the present invention. The addition ratio of the resin film material is preferably from 1% by mass to 40% by mass in the resin composition. Further, in the resin composition, a plasticizer, a slip agent, an antistatic agent, an antifogging agent, a drip agent, and a hydrophilic substance may be added in a range that does not impair transparency, color tone, heat resistance, film appearance, and the like in practical use. Agent, liquid dispensing agent, etc. The method of adding such an additive may be applied to the surface of the resin film after the resin composition is kneaded, after the resin film is produced.

<Step of Forming Resin Film>

In the resin film, the resin composition is melt-kneaded in an extruder equipped with a T-die, and then cast by a cooling roll. The term "casting treatment" refers to a process of 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. The molten film is cooled and extended on a cooling roll, and is wound up to form a film. In addition, in the following description, "resin composition" is also simply referred to as "resin".

Fig. 1 is a schematic view showing an example of a procedure for forming a resin film of the present embodiment. In the present embodiment, the resin composition is melt-kneaded by a screw in a heated cylinder (not shown) provided in the extruder 1, and then passed through a T-die connected via a single tube 2. In the head 3, the molten resin is discharged from the discharge port 4. Then, the molten resin is cast by the first cooling roll 5 and the contact roll 6, and the resin film 10 is obtained. Further, 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 extends the discharged resin.

As the extruder, a uniaxial screw type, a twin-shaft screw type, a tandem type, or the like can be generally used, but in order not to give excessive shear to the resin, and it is difficult to stay in the system, a single-axis screw type is preferable. Extruder.

The screw of the extruder is not particularly limited as long as it is a resin which is sufficiently plasticized and homogenized and does not cause excessive resin shearing. As the screw which can be suitably used, a full flighted screw is preferable. The full-thread type screw preferably has a compression ratio of 1.3 to 3.0, and the ratio of the length L of the screw to the diameter D of the screw (L/D) is 20 to 40, and the compression ratio is preferably 2.0 to 3.0, and the L/D is 25 ~35.

The extruder has a perforated plate between the tip end portion of the screw and the T die. The perforated plate is provided, for example, in the flange portion of the front end of the barrel in the extruder so as to cross the inner hole of the barrel and go straight to the flow path of the molten resin. The perforated plate forms a plurality of through holes through which the molten resin passes in the center portion. The aperture ratio of the porous plate is 40% to 60%, preferably 42% to 58%. Since the aperture ratio of the porous plate is set to 40% or more, the back pressure to the resin can be suppressed, and the retention of the resin in the extruder can be suppressed. Moreover, since the aperture ratio is made 60% or less, the number of defects (fish eyes, gel, contamination, etc.) of the film can be kept stable for a long period of time. In addition, the aperture ratio means the area of the portion in which the resin through-hole is formed with respect to the entire area including the resin through-hole, based on the portion exposed in the resin flow portion of the extruder.

The minimum diameter of the resin through-hole of the perforated plate is preferably from 3.7 mm to 6.0 mm. The so-called "minimum diameter" refers to the smallest of the diameters of the through holes. Since the minimum diameter of the resin through-hole is set to 3.7 mm or more, the back pressure to the resin can be suppressed, and the retention of the resin in the extruder can be suppressed. Further, since the minimum diameter of the resin through-hole is set to 6.0 mm or less, the number of defects of the film can be kept stable for a long period of time.

The perforated plate is provided with a screen. For example, the screen may be attached to the upstream side (the front end side of the screw) of the perforated plate, and may have one or two or more sheets. The screen disposed on the perforated plate is preferably a combination of two or more screens having different pore diameters. The screen can also be used with a screen of the same aperture. In general, it is preferable to arrange from the upstream side (the vicinity of the screw side) of the resin flow-through portion to the downstream side (the opening side of the porous plate) in the order of a screen having a large pore diameter and a screen having a small pore diameter. Furthermore, downstream of the mesh with the smallest aperture to prevent resin pressure For the purpose of damage to the mesh, it is preferable to configure a mesh that is thicker than the mesh. In the present embodiment, the minimum aperture of the screen is 0.03 mm to 0.1 mm, more preferably 0.03 mm to 0.7 mm. Since the minimum pore diameter of the screen is set to 0.03 mm or more, deterioration due to retention of the resin and shear heat generation can be suppressed. In addition, since the minimum pore diameter of the screen is set to 0.1 mm or less, contamination contaminated with the resin, deterioration of the raw material, and the like can be reduced. The screen with a large aperture has the role of removing coarse defects, and the aperture is preferably 0.15 mm to 0.6 mm. Further, in order to prevent the screen from being damaged by the resin pressure, a coarse screen having a larger opening diameter can be introduced on the downstream side of the screen having the smallest aperture. The arrangement position of the screen is preferably provided on the downstream side of 10 mm to 100 mm from the tip end portion of the screw.

The resin temperature of the T die discharge port depends on the melting point of the ECTFE used, but is preferably maintained at 240 ° C to 300 ° C. When the resin temperature exceeds 300 ° C, the ECTFE is easily decomposed, and as the decomposition of the resin deteriorates, the color tone or the defect may easily occur. Further, when the resin temperature is lower than 240 ° C, the viscosity of the resin increases, and the fluidity is lowered, which contributes to excessive shearing and retention in the extruder.

The resin which can be plasticized according to the above method can be pulled between the temperature-adjusted first cooling roll and the rubber contact roll after casting, and then contacted with a plurality of sides after being extruded into a sheet shape from the T die. The chill roll is drawn while being drawn to a specified thickness. Here, since the contact roller system is in a state of being in contact with the first cooling roller or being pressed, a part of the surface of the contact roller is in contact with the surface of the cooling roller, and the contact roller can be adjusted by the pressure sensor. Pressure applied to the resin The force, and the thickness of the resin is adjusted to a desired thickness by adjusting the pulling speed of the first cooling roll and the contact roll.

The cooling roll has at least one cooling roll and may have 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 of the T die discharge port is such that the surface temperature of the first cooling roll is from +110 ° C to +280 ° C, preferably from +120 ° C to +250 ° C. When the temperature difference between the resin temperature of the discharge port of the T die and the surface temperature of the cooling roll is less than +110 ° C, crystallization of ECTFE occurs, and the transparency of the resin film is deteriorated, and adhesion of the film to the cooling roll occurs during production of the resin film. Not suitable. Further, if the temperature difference is higher than +280 ° C, the increase in the number of defects due to deterioration of the resin or the deterioration of the appearance of the film tends to occur, which is not preferable. The resin temperature of the T die discharge port can be measured, for example, by using a contact thermometer or the like, and measuring the temperature of the resin passing through the lip outlet of the T die. 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 discharge port of the T die to the surface of the surface of the first cooling roll which is in contact with the surface of the contact roller plays an important role in controlling the crystallinity of the resin film. In the first and second figures, the configuration of the T die, the first cooling roller, and the contact roller is shown. As shown in Figs. 1 and 2, in the surface 7 where the surface of the first cooling roller 5 is in contact with the surface of the contact roller 6, there is a point 8 which will be at the highest position of the contact surface 7 (the first cooling roller in a rotating state) The point at which the contact roller is initially contacted, or the end portion of the T-die side in the surface where the surface of the chill roll is in contact with the surface of the contact roller, referred to as the "contact", may be from the T-die discharge port 4 to the contact point. Distance up to 8 (shortest distance) 9 The case of "air gap". That is, the so-called air gap, when the contact surface of the T-die discharge port and the surface of the first cooling roll and the surface of the contact roll is in a vertical position (for example, when the contact surface is located on the lower side in the vertical direction of the discharge port of the T die, When the bottom is spit out, it means the shortest distance between the T-die discharge port and the joint in the vertical direction. When the T-die discharge port and the contact surface are arranged at different positions, it means connecting the T-mode. The straight line distance between the head spout and the joint.

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

After the end portion of the cooled film is slit to have an arbitrary film width, the film is wound up and wound up at an appropriate tension without occurrence of winding deviation, whereby a resin film can be obtained.

The thickness of the resin film is preferably from 0.001 mm to 0.5 mm, more preferably from 0.01 mm to 0.3 mm. When the thickness of the resin film is less than 0.001 mm, it may be easily broken during the production of the film, or the thickness control of the film may become difficult. Moreover, when the thickness exceeds 0.5 mm, unevenness in cooling rate is likely to occur in the thickness direction of the film, and transparency is likely to be deteriorated.

One of the dimensions indicating the transparency of the resin film is the total light transmittance. The resin film obtained by the production method of the present embodiment has a total light transmittance of the film measured by a haze meter of preferably 92% or more, more preferably 93% or more. When it is less than 92%, the pattern design property when the resin film is laminated on the substrate is lowered, or it is difficult to apply it to applications requiring high light collection efficiency.

The resin film obtained by the production method of the present embodiment is excellent in water vapor barrier property, chemical resistance, antifouling property, and weather resistance of ECTFE, and is applicable as various waterproof films used outdoors. As an example of the use of the outdoor use, it is applicable to various types of applications requiring the above-described characteristics, such as a film material of a construction such as a sports facility, a coating material of a metal steel plate as an example of a road sign, and a water stop sheet of concrete. In particular, the resin film of the above-described embodiment is excellent in transparency and appearance, and can be suitably used as a surface protective film of another resin sheet or inorganic material. In particular, it is suitable for use as an outdoor waterproof film because it contains ECTFE excellent in weather resistance or water vapor barrier property.

[Method for Producing Laminate Film and Method for Producing Outdoor Waterproof Film]

When the laminated film is formed by using the above-mentioned resin film as a surface protective film, it is preferable to apply a surface modification to the adhesive surface (the first surface of the resin film) in order to impart adhesion to the protected body (hereinafter referred to as "substrate"). quality. When the laminated film or the outdoor waterproof film is formed, the resin film may be formed by the method for producing the resin film, and the first surface of the obtained resin film may be surface-modified, and the surface may be subjected to surface modification. A step of laminating a substrate containing a thermoplastic resin on the first side of the modified resin film.

(surface modification step)

Examples of the surface modification method include a method in which the first surface of the resin film is subjected to corona treatment or plasma treatment. In addition, the "first surface" means the surface of either or both of the surface of the resin film which can be a bonding surface. As a method of corona treatment and plasma treatment, When the resin film is produced, it is processed in-line downstream of the chill roll process, or after the resin film is manufactured, it is processed offline by a corona treatment device or a plasma processor device.

The discharge amount of the corona treatment is not particularly limited, so as to obtain a suitable adhesion to the substrate, preferably 30 W. Min / m ² or more, more preferably 50W. Min/m ² or more. Less than 30W. At the time of min/m ² , a sufficient surface modification effect of the resin film is not obtained, and the adhesion to the substrate may be insufficient. The upper limit of the discharge amount can be appropriately set within a range that does not impair the appearance of the resin film.

The surface modification effect by the plasma treatment is various depending on the type of the gas to be present, but examples of the reforming gas applicable to the resin film of the present embodiment include nitrogen, oxygen, and hydrogen. , carbon dioxide, argon, hydrocarbon gas. For the purpose of obtaining the adhesion to the substrate, a rare gas element gas component such as argon gas or a hydrocarbon-based gas may be mentioned as an example of a more preferable processing gas. These treatment gas systems may be used alone or in combination of two or more. As a general plasma processing method, a far-end plasma method or a direct plasma method can be used. The resin film of the present embodiment can be applied to any of the treatment methods, but the gas during plasma treatment can be reduced. The amount of use makes it possible to achieve low-cost surface treatment, and is more preferably a direct plasma method.

(Step of laminating the substrate)

As a method of laminating a substrate on a resin film surface-modified by corona treatment or plasma treatment, a method of laminating a resin film on a surface of a substrate softened by heat may be employed.

As another method of modifying the surface of the resin film, it is preferable to apply a bonding resin having an adhesive property to both the resin film and the substrate on the adhesive surface (first surface) of the surface-modified resin film. A method of softening a resin film by heat, laminating a surface of a substrate, or the like.

Examples of the main binder resin that can be used for the coating include an ethylene-vinyl acetate copolymer (EVA), an acrylate resin, an isocyanate resin, an epoxy resin, a urethane resin, an anthracene resin, and a polyolefin system. A resin, an ionic polymer resin, or the like can be used by selecting at least one type or more depending on the purpose and use. These subsequent resins can also be used as a sealing resin.

Examples of the substrate include those having a flat plate shape or a sheet shape, or a three-dimensional shape such as a rectangular parallelepiped, a corner post, a pyramid, a cylinder, or a cone. The type of the substrate is not particularly limited, and examples thereof include a resin and glass. Examples of the resin include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polycarbonate (PC), and polymethyl methacrylate (PMMA). Styrene-butadiene copolymer (SBC), ethylene-vinyl acetate copolymer (EVA), polyimine (PI), polyphenylene sulfide (PPS), aromatic polyamine, polypropylene (PP), A thermoplastic resin such as polyethylene (PE), polylactic acid (PLA), polyvinyl chloride (PVC), polyoxyxylene resin, alicyclic acrylic resin, cycloolefin resin (COP), or triacetyl cellulose (TAC). As the glass, soft glass, hard glass, or quartz glass can be used. Among these, in the point of adhesion to the resin film, a thermoplastic resin is preferable, and in particular, in the point of adhesion or transparency, an ethylene-vinyl acetate copolymer is preferable.

Example

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

The materials used in the 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 Co., Ltd., melting point 202 ° C, MFR 9.0 g/10 min (ASTM D1238 275 ° C / 2.16 kg load)

[Antioxidants]

. "ADK STAB 593" manufactured by ADEKA Co., Ltd.: a mixture of zinc stearate and calcium stearate

[UV absorber]

. "LA-46" made by ADEKA: 2-(4,6-diphenyl-1,3,5-three -2-yl)-5-[2-(2-ethylhexyloxy)ethoxy]phenol

The resin films of the examples and the comparative examples were formed using the following apparatus.

[extruder]

. "VS65-25 single-axis horizontal extrusion machine" manufactured by Tanabe Plastics Co., Ltd., hopper type

[screw]

. Screw configuration: full threaded screw

. Screw diameter: 65mm

. Screw length (L) / screw diameter (D) ratio: 25

. Compression ratio: 2.5

[Screen]

Tables 1 and 2 show the constitution and pore diameter values of the sieves used in the examples and comparative examples. The material of the screen is SUS304, which is placed 20 mm downstream from the front end of the screw. Further, the configuration of the screen is a three-layer structure that is continuous on the screw side, the center side, and the T die side.

[Multiwell plate]

The aperture ratios of the perforated plates used in the examples and comparative examples are shown in Tables 1 and 2. Further, SUS304 is used as the material of the perforated plate, and is disposed in a form adjacent to the downstream of the screen.

[T die]

The specifications of the T die used in the examples and comparative examples are shown below.

. Die specifications: hanger style / bottom spit type, hard chrome plating on the inside

. Lip width: 1050mm

[roller]

. Type: contact roller type line pressure 25~30kgf/cm

. Roll specification: first cooling roller

260mm in diameter

Hard chrome plating after surface hardening

Surface roughness: 0.2S (maximum height of the convex part)

Cooling water circulation

Contact roller

260mm in diameter

Surface mirror processing white mirror roller

Surface roughness: (maximum height of convex part) Ry3.2μm, (arithmetic mean roughness) Ra0.05μm

. The shortest distance (air gap) from the discharge point of the T die to the highest position in the surface of the first cooling roll that contacts the surface of the contact roll: 100~250mm

(Example 1)

After the pellet of ECTFE1 (Halar ECTFE 500LC) was dried at 80 ° C for 4 hours, the above-mentioned extruder was used, and the set temperature of the perforated plate portion and the T die was 280 ° C, and melt kneading was carried out. The screen was a mesh of 0.18 mm, 0.075 mm, and 0.18 mm from the upstream side to the downstream side of the resin circulation portion. Also, the air gap is 120 mm. The resin temperature of 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.

<The temperature of the resin at the T die discharge port>

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

<Transparency of Resin Film>

The transparency of the resin film was evaluated by the Haze Meter "NDH7000" manufactured by Nippon Denshoku Industries Co., Ltd., and the total light transmittance and the haze value were evaluated. In the evaluation, the TD direction from the resin film was used, and the sample cut out from any five points was used, and the arithmetic mean value was used.

Excellent: fog value is less than 4%

Good: fog value is 4% or more and less than 7%

Can: fog value of 7% or more, less than 20%

Bad: fog value is more than 20%

<Defect of resin film (appearance)>

The number of defects (foreign matter, fisheye, gel) of 0.7 mm or more contained in the film area of 1000 m ² was measured using a defect detector equipped in a line of a film manufacturing facility. The number of defects in the resin film was judged by the following criteria.

Excellent: less than 50

Good: 50 or more, less than 80

Available: 80 or more, less than 100

Bad: more than 100

<Weather resistance>

For the obtained resin film, a neoconducting arc lamp weathering tester Ci4000 (light source xenon lamp) manufactured by Toyo Seiki Co., Ltd. was used, and the irradiation intensity was 80 W/m ² , the black panel temperature was 85 ° C, the relative humidity was 50%, and the drying was performed for 102 minutes. The total light transmittance and the hue change (Δb) of the obtained resin film were measured by a period of 18 minutes, ultraviolet irradiation for 2000 hours.

For the measurement of the hue (Δb), "Colour Cute i" manufactured by SUGA Test Machine Co., Ltd. was used, and the change in the b value before the ultraviolet irradiation was measured, and it was regarded as Δb. The weather resistance is judged by the following criteria for the measured Δb value.

Excellent: less than 0.3

Good: 0.3 or more, less than 0.6

Can be: 0.7 or more, less than 0.9

Bad: 1.0 or more

<moisture resistance>

The moisture resistance of the resin film was measured using a L-80-5000 type water vapor permeability meter manufactured by Lyssy Co., Ltd., and the temperature was 40 ° C and a relative humidity of 90%. The moisture resistance of the resin film was judged by the following criteria.

Excellent: less than 1.0

Good: 1.0 or more, less than 5.0

Available: 5.0 or more, less than 10.0

Bad: 10.0 or more

<Resin film is coated on the surface of the substrate>

The resin film was plasma-treated in an argon atmosphere to a wetness index of 44 mN/m, and the EVA resin sheet having a plasma-treated surface and a thickness of 0.4 mm was pressed at 150 ° C for 30 minutes to carry out vacuum lamination. on The laminated substrate was judged by the following criteria. In the plasma treatment, an atmospheric piezoelectric slurry surface treatment device is used.

Good: The macroscopic appearance such as defects such as interlayer peeling and discoloration of the molded article is not deteriorated.

Poor: The macroscopic appearance of defects such as discoloration of the molded article or the like of the molded article is deteriorated.

(Examples 2 to 9)

A resin film was produced under the conditions shown in Table 1, and various evaluations were carried out. Further, the regenerated resin films used in Examples 2 to 4 and Examples 6 to 9 were obtained by blending the resin film produced in the same example with the raw material for the resin composition.

(Comparative examples 1 to 9)

A resin film was produced under the conditions shown in Table 2, and various evaluations were performed. Further, 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 is understood that the resin film of the present embodiment is a film which is excellent in transparency and has a small number of defects. By using the film of the present embodiment, it is possible to apply to various protective films and outdoor waterproof films which require design design.

1‧‧‧Extrusion machine

2‧‧‧Single tube

3‧‧‧T die

4‧‧‧T die spit

5‧‧‧First cooling roller

6‧‧‧Contact roller

7‧‧‧Contact surface of the surface of the first chill roll and the surface of the contact roll

10‧‧‧Resin

Claims (8)

A method for producing a resin film, which comprises melt-kneading a resin composition containing an ethylene-chlorotrifluoroethylene copolymer and extruding it with an extruder having a T-die, and then performing a casting process using at least one cooling roll. a step of forming a resin film, the extruder having a breaker plate between the front end portion of the screw and the T die, the porous plate having a sieve, the aperture ratio of the porous plate being 40% to 60%, The minimum pore size of the screen is 0.03 mm to 0.1 mm, and the temperature of the resin composition at the discharge port of the T die is higher than the surface temperature of the first cooling roll by 110 ° C to 280 ° C. The method for producing a resin film according to claim 1, wherein the casting treatment is performed using the first cooling roller and the contact roller, a portion of a surface of the first cooling roller is in contact with a portion of a surface of the contact roller, the T mold The distance between the tip end portion of the discharge port of the head and the end portion on the side of the T die on the surface in contact with the surface of the first cooling roller and the surface of the contact roller is 400 mm or less. The method for producing a resin film according to claim 1 or 2, wherein a temperature of the resin composition of the discharge port of the T die is 240 ° C to 300 ° C. The method for producing a resin film according to any one of claims 1 to 3, wherein the resin composition contains a heat stabilizer, and the content of the heat stabilizer in the resin composition is from 0.1% by mass to 5% by mass. The method for producing a resin film according to any one of claims 1 to 4, wherein the resin composition contains an ultraviolet absorber, and the content of the ultraviolet absorber in the resin composition is from 0.1% by mass to 5% by mass. The method for producing a resin film according to any one of claims 1 to 5, wherein the resin composition contains 1% by mass to 40% by mass of the resin composition containing the ethylene-chlorotrifluoroethylene copolymer. A raw material for recycling a resin film produced from a resin composition. A method for producing a laminated film comprising: casting a resin composition containing an ethylene-chlorotrifluoroethylene copolymer, extruding and kneading it with an extruder having a T die, and then performing casting treatment using at least one cooling roll; And forming a resin film, the first side of the obtained resin film is in a modified gas selected from nitrogen, oxygen, hydrogen, carbon dioxide gas, rare gas element gas and hydrocarbon gas, by corona a step of surface modification by treatment or plasma treatment, and a step of laminating a substrate containing a thermoplastic resin by vacuum lamination on the first side of the surface-modified resin film; and the step of forming the resin film The extruder has a perforated plate between the front end portion of the screw and the T die, the perforated plate is provided with a screen, the aperture ratio of the perforated plate is 40% to 60%, and the minimum aperture of the sieve is 0.03. The temperature of the resin composition of the discharge port of the T die is mm to 0.1 mm higher than the surface temperature of the first cooling roll by 110 ° C to 280 ° C. A method for producing an outdoor waterproof film, comprising: a resin composition containing an ethylene-chlorotrifluoroethylene copolymer, which is melt-kneaded by an extruder having a T-die, and then cast using at least one cooling roll; And forming a resin film, the first side of the obtained resin film is in one or more modified gases selected from nitrogen, oxygen, hydrogen, carbon dioxide gas, rare gas element gas and hydrocarbon gas, by electricity a step of surface modification by halo treatment or plasma treatment, and a step of laminating a substrate containing a thermoplastic resin by vacuum lamination on the first side of the surface-modified resin film; and forming a resin film In the step, the extruder has a porous plate between the front end portion of the screw and the T die, the porous plate is provided with a screen, and the opening ratio of the porous plate is 40% to 60%, and the minimum pore diameter of the sieve is 0.03 mm to 0.1 mm, the temperature of the resin composition of the discharge port of the T die is higher than the surface temperature of the first cooling roll by a temperature of 110 ° C to 280 ° C.