KR20140106396A - Casting die, diehead and method of manufacturing film - Google Patents

Abstract

Provided are a flow casting die, a die head manufacturing method and a film manufacturing method capable of suppressing the generation of cracks when a DLC film is formed on a base of a die head. A flow casting die is equipped with a die head (82) that is coupled and detached to and from an outlet of a dope. The die head (82) has a base (85), an underlayer (9.2) and a DLC film (86). The base is constituted of stainless steel, and the underlayer (92) is constituted of tungsten carbide (WC). The DLC film is formed on the underlayer (92). A combination of a linear expansion coefficient, a length (LY) of a longitudinal direction of the die head (82) and a heating temperature in a vapor phase forming method is determined such that stress applied on the underlayer (92), which is calculated from external force due to heat expansion deformation of the base (85) and the underlayer (92), wherein the stress is less than rupture stress. The underlayer (92) and the DLC film (86) are formed on the basis of this combination.

Description

[0001] CASTING DIE, DIEHEAD AND METHOD OF MANUFACTURING FILM [0002]

The present invention relates to a flexible die, a method of manufacturing a die head, and a method of manufacturing a film.

A light-transmitting polymer film (hereinafter referred to as a film) is lightweight and easy to mold, and thus is used in many fields as an optical film. Among them, a cellulose ester film using cellulose acylate or the like is used as an optical film (a polarizing plate protective film or a retardation film, etc.) of a liquid crystal display device in addition to a photo sensitive film.

As a main production method of a film, a solution casting method is known. In the solution film-forming method, a flexible film forming step, a flexible film drying step, a peeling step and a wet film drying step are sequentially performed. In the flexible film forming step, a polymer solution containing a polymer and a solvent (hereinafter referred to as a dope) is flowed out using a flexible die, and a flexible film is formed on the moving support. In the flexible film drying step, the solvent is evaporated from the flexible film or the flexible film is cooled until the flexible film becomes self-supporting and transportable. In the peeling step, the coarse film that has undergone the coarse film drying step is peeled from the support to form a wet film. In the wet film drying step, the solvent is evaporated from the wet film to form a film.

The flexible die has a pair of lip plates juxtaposed in the moving direction of the support, a pair of side plates covering both side ends of the pair of lip plates, and a flow path surrounded by the pair of lip plates and the pair of side plates. In the cross section orthogonal to the flow direction of the dope, the flow path is formed in a slit shape. The slit is formed as a rectangle having a long side extending in the moving direction of the support body and a long side extending in the direction (width direction) perpendicular to the moving direction of the support body. The lip plate or the side plate is formed of stainless steel having a low coefficient of thermal expansion and low solubility with respect to a solvent used for dope. The stainless steel is, for example, SUS316L or the like.

The flexible die drains the dope from the outlet of the flow path toward the moving support. As a result, a bead is formed between the distal end of the lip plate and the support. When the beads become unstable in the process of forming a flexible film, a thickness deviation occurs in the flexible film. Thus, the bead is stabilized by sharpening the tip of the lip plate, which is the starting point of the bead formation.

However, since SUS316L has relatively Vickers hardness of about Hv 180, it is very difficult to sharpen the front end portion by machining. As a result, a super hard layer harder than SUS316L is provided at the tip of the lip plate, and the super hard layer is subjected to predetermined machining to sharpen the tip of the lip plate. As a super hard layer, for example, a tungsten carbide (WC) layer is known as disclosed in Japanese Patent Application Laid-Open No. 2003-200097.

The preferable shape of the tip of the lip plate is changed according to the production conditions of the film. Due to this, the lip plate is divided into a lip plate body constituting the inlet of the oil passage and a front end portion constituting the outlet of the oil passage (hereinafter referred to as a die head), and the die head is detachably provided on the lip body. By selecting and using such a die head, it becomes easy to manufacture and manufacture a variety of films in one production line.

However, when the flexible film forming process is continuously performed for a long time, the tungsten carbide layer provided on the die head is corroded. Corrosion of the tungsten carbide layer is caused by elution of the binder metal (cobalt atom, etc.). If a flexible die is used in a state in which the tungsten carbide layer is corroded, a tungsten carbide layer is peeled off and a breakdown occurs in the surface of the film due to the peeling. Therefore, every time the flexible film forming process is performed for a predetermined time, the process for forming a flexible film is stopped to replace the die head with a new one, and the production efficiency of the film is lowered.

From this background, a stable DLC (Diamond Like Carbon) film is formed on the die head, as described in Japanese Patent Application Laid-Open No. H04-148442, which has a longer life than the tungsten carbide layer. In addition, as the size of a liquid crystal display device is increased, the demand for wide optical films is rapidly increasing. In order to manufacture a wide optical film, the gap between the pair of side plates must be made larger than in the prior art, and the length of the lip body and the die head must be increased. If this die head is lengthened, the amount of bending of the die head generated at the time of forming the DLC film increases. It is difficult to mount the die head with the warp to the lip board main body. Thus, in Japanese Patent Application Laid-Open No. H04-148442, the DLC film is formed at a heating temperature of not less than 130 占 폚 and not more than 200 占 폚, thereby suppressing the deflection of the die head to a certain range.

However, when a die head having a DLC film on its surface and suppressing warpage is attached to a dope outlet of a flexible die and a solution is formed thereon, no breakage occurs on the surface of the film immediately after the start of film formation. However, It is known that a stripe failure occurs, and a countermeasure has been demanded. Such stripe failure can be prevented by using a flexible die having a long exit shape corresponding to the widening of the film.

Accordingly, it is an object of the present invention to provide a flexible die, a die head, and a manufacturing method of a film corresponding to the widening of a film.

The cause of the stripe failure was examined. It was found that a fine crack occurred in the DLC film or the underlayer, and a stripe failure occurred due to peeling of the DLC film due to cracking or cracking. Based on this finding, it was found that fine cracks were generated due to thermal expansion deformation occurring between the base layer and the base when the DLC film was formed.

The flexible die for discharging the dope with the support of the present invention has a detachable die head at the dope outlet and the die head comprises a base, a base layer, a DLC film, a base and an underlayer, The length of the die head in the longitudinal direction, and the heating temperature at the time of forming the DLC film, and the dope includes a polymer and a solvent. The base is made of stainless steel. The base layer is formed on the base and is formed of a super hard material. The DLC film is formed on the base layer by the vapor phase film formation method. Here,? 1 is the stress acting on the underlayer due to the thermal expansion deformation of the base and the underlayer due to the temperature rise at the time of forming the DLC film, and? 2 is the fracture stress of the underlayer.

(1) acting on the ground layer when the compressive force acting on the base is PB, the tensile force acting on the ground layer is PL, and the cross sectional area of the ground layer on the cross section perpendicular to the longitudinal direction of the die head is AL, It is preferable that? 1 = (PB-PL) / AL.

The length LY of the die head is 1500 mm or more when the length in the longitudinal direction is LY and the maximum length in the cross section orthogonal to the longitudinal direction is LW, 70 占 퐉 or more and 130 占 퐉 or less, and the thickness of the DLC film is preferably 0.7 占 퐉 or more and 2 占 퐉 or less.

It is preferable that the base is formed of any one of SUS316L, SUS329J1 and SUS630, and the base layer is formed of tungsten carbide.

It is preferable that the hardness difference between the base layer and the DLC film is within 500 Hv.

The hardness of the DLC film is preferably 1300 Hv or more.

The gas phase film formation method is preferably any one of ionization deposition, ion plating, and plasma CVD.

The method for producing a film of the present invention comprises a flexible film forming step, a flexible film drying step, a peeling step, and a wet film drying step. The flexible film forming step forms a flexible film made of dope by discharging the dope from the flexible die with the support. The dope includes a polymer and a solvent. The flexible die has a detachable die head at the dope outlet. The die head has a base, a base layer and a DLC film. The base is made of stainless steel. The base layer is formed on the base. The underlayer is formed of a super hard material. The DLC film is formed on the base layer by the vapor phase film formation method. The die head has a combination of coefficient of linear expansion between the base and the underlayer,? 1 is less than? 2, a length in the longitudinal direction of the die head, and a heating temperature at the time of forming the DLC film. The flexible film drying step evaporates the solvent from the flexible film until the flexible film is self-supporting and transportable. In the peeling step, the flexible film is peeled from the support to form a wet film. The wet film drying step evaporates the solvent from the wet film to form a film. Here,? 1 is the stress acting on the underlayer due to the thermal expansion deformation of the base and the underlayer due to the temperature rise at the time of forming the DLC film, and? 2 is the fracture stress of the underlayer.

A method of manufacturing a die head according to the present invention includes a step of forming a base layer (step A), a step of forming a DLC film (step B), and a step of determining a crack preventing conforming condition (step C) Elongated column body mounted to the dope outlet of the outgoing flexible die, the dope including polymer and solvent. Step A forms a base layer on the base made of stainless steel. The underlayer is formed of a super hard material. In the step B, a DLC film is formed on the base layer by a vapor deposition method. Step C determines the combination of the coefficient of linear expansion between the base and the base layer, the length in the longitudinal direction of the die head, and the heating temperature in the vapor phase film forming method before the step A is performed. The C step is determined by the above combination in which? 1 is less than? 2. Here,? 1 is the stress acting on the base layer due to the thermal expansion deformation of the base and the underlayer in the B step, and? 2 is the fracture stress of the base layer.

According to the present invention, when the DLC film is formed on the ground layer, generation of cracks in the ground layer and the DLC film is suppressed, and a die head made of a DLC film without cracks is obtained. By using the flexible die having such a die head, the peeling of the DLC film due to the crack is eliminated. In addition, since the low friction characteristic due to the DLC film is partially lowered due to the peeling, dope solids are generated and grow at the die head outlet of this lowered portion. However, since peeling is not caused, Growth is inhibited. Therefore, in order to remove the dope solids, the number of times of cleaning the die head can be greatly reduced by stopping the softening, and the product loss due to the interruption of the softening is reduced, and the film can be continuously and stably produced. This effect can be obtained also for widening of the film.

The above objects and advantages will be readily apparent to those skilled in the art by reading the detailed description of the preferred embodiments with reference to the accompanying drawings.
1 is a side view showing an outline of an example of a solution film-forming equipment.
2 is a perspective view showing an outline of an example of a flexible die, a flexible drum, and the like in a flexible chamber.
3 is a partial cross-sectional view showing an outline of an example of the distal end portion of the flexible die.
4 is a perspective view showing an outline of an example of a flexible die.
5 is an exploded perspective view of the flexible die.
6 is a perspective view showing an outline of an example of a flow path provided in a flexible die.
7 is a cross-sectional view showing an example of the outline of the flow path.
8 is a perspective view showing an outline of an example of a lip plate having a lip plate main body and a die head.
9 is an exploded perspective view of the lip plate.
10 is a cross-sectional view showing an example of the outline of the die head.
11 is a cross-sectional view schematically showing the tip portion of the lip plate constituting the outlet.
12 is a cross-sectional view showing an example of the outline of the base and foundation layer.
13 is a cross-sectional view showing an outline of an example of a DLC film forming apparatus.
14 is a perspective view showing an example of the outline of a die head mounted on a fixture.
15 is an exploded perspective view of a fixture and a die head.
16 is a flowchart showing a manufacturing method of a die head.

(Solution deposition equipment)

1 showing an example of a solution film-forming apparatus, the solution film-forming apparatus 10 has a flexible chamber 12, a pin tenter 13, a drying chamber 15, a cooling chamber 16 and a winding chamber 17. In the flexible chamber 12, a flexible die 21, a flexible drum 22, a decompression chamber 23, and a peeling roller 24 are provided.

2, the flexible drum 22 has a drive shaft 22a arranged horizontally and a drum main body 22b fixed to the drive shaft 22a. The driving shaft 22a is connected to a driving device (not shown). The flexible drum 22 is preferably made of stainless steel and more preferably made of SUS316L in view of having sufficient corrosion resistance and strength.

As shown in Fig. 3, the flexible die 21 has a flow passage 29 therein. An outlet 29o of the flow path 29 is opened at the lower end portion of the flexible die 21. The flexible die 21 is arranged so that the outlet 29o is close to the circumferential surface 22c of the flexible drum 22. Details of the flexible die 21 will be described later. By the rotation of the flexible drum 22, the circumferential surface 22c moves in the X direction at a predetermined speed in the vicinity of the outlet 29o. The X direction indicates the rotation direction of the flexible drum 22, the Y direction indicates the direction orthogonal to the X direction (the width direction of the flexible film 34), the Z direction indicates the XY plane including the X direction and the Y direction (The height direction of the flexible die 21).

A dope 28 is sent to the flow path 29 of the flexible die 21. The dope 28 flows out the dope 28 from the outlet 29o toward the circumferential surface 22c. The bead 33 is formed by the dope 28 from the outlet 29o to the circumferential surface 22c. The dope 28 reaching the circumferential surface 22c is stretched in the X direction on the circumferential surface 22c, resulting in a strip-shaped flexible film 34. [ In this manner, a flexible film forming process for forming the flexible film 34 by the flexible die 21 and the flexible drum 22 is performed.

The decompression chamber 23 is arranged on the upstream side of the flexible die 21 in the X direction. By the control of a controller (not shown), the decompression chamber 23 sucks the gas on the upstream side of the bead 33 in the X direction. By the suction of this gas, the pressure on the upstream side of the bead 33 becomes lower than the pressure on the downstream side of the bead 33. It is possible to suck the accompanying wind which is generated in accordance with the movement of the circumferential surface 22c by the decompression chamber 23 and flows in the X direction in the vicinity of the circumferential surface 22c. Therefore, the vibration of the bead 33 due to collision with the accompanying wind is suppressed. Further, the length of the bead 33 is shortened by suction, and the vibration of the bead 33 is suppressed corresponding to the shortened length.

A temperature regulating device 32 is connected to the flexible drum 22. The temperature regulating device 32 incorporates a temperature regulating section for regulating the temperature of the heat transfer medium. The temperature regulating device 32 circulates the heat transfer medium adjusted to a desired temperature between the temperature regulating portion and the flow path provided in the flexible drum 22. [ By circulating the heat transfer medium, the temperature of the peripheral surface 22c of the flexible drum 22 can be maintained at a desired temperature. The solution film-forming equipment 10 is provided with a condensing device for condensing the solvent contained in the atmosphere in the flexible chamber 12 and a recovery device for recovering the condensed solvent. The solvent contained in the atmosphere in the flexible chamber 12 Is maintained in a constant range. Thus, in the flexible drum 22, a flexible film drying process for evaporating the solvent from the flexible film 34 is performed.

The peeling roller 24 is disposed on the downstream side of the flexible die 21 in the X direction. The peeling roller 24 peels the flexible film 34 formed on the circumferential surface 22c and performs a peeling process using the wet film 35. The wet film (35) is guided to the downstream side of the flexible chamber (12).

1, a pin tenter 13, a drying chamber 15, a cooling chamber 16, and a winding chamber 17 are arranged in this order in the downstream of the flexible chamber 12. And has a passage portion 40 between the flexible chamber 12 and the pin tenter 13. A plurality of support rollers 41 are arranged in the passing portion 40. The support roller 41 is rotated by a motor (not shown). The support roller 41 supports the wet film 35 and guides it to the pin tenter 13. However, the number of the support rollers 41 of the passing portion 40 is not limited to two but may be one or more. The support roller 41 may be a free roller.

The pin tenter 13 has a pair of annular chains, a pulley, and a dry air feeder. The annular chain has a plurality of pins mounted at a constant pitch. The plurality of fins support both ends of the wet film 35 in the width direction. The ring chain runs circulatingly around the pulleys. The dry wind supplier supplies dry wind to the wet film 35 supported by the fins. A brush is installed at the entrance of the pin tenter 13. The brush presses both side portions of the wet film 35 to penetrate the pin into the wet film 35. The wet film 35 supported on both sides by the pin is conveyed by the circulating running of the annular chain. During this conveyance, the solvent is evaporated from the wet film 35 by the contact with the drying wind to become the film 45. In this manner, a wet film drying process is performed in which the solvent is evaporated from the wet film 35 to the film 45 from the passage portion 40 to the pin tenter 13.

A side slitter 47 is provided between the pin tenter 13 and the drying chamber 15. The side slitter 47 cuts both side portions of the film, from which the through holes are left by the pins, from the center portion. The cut side portions are sent to a crusher (all not shown) through a cut blower, finely cut, and reused as raw materials for dope and the like.

The drying chamber (15) has a plurality of rollers (49). The film 45 is wound on the roller 49 and transported. The temperature and humidity of the atmosphere in the drying chamber 15 are controlled by an air conditioner (not shown). In the drying chamber 15, drying of the film 45 is performed. The adsorption / recovery device 52 is connected to the drying chamber 15. The adsorption recovery device (52) recovers the solvent evaporated from the film (45) by adsorption.

The cooling chamber 16 cools the film 45 until the temperature of the film 45 becomes approximately room temperature. A null bar 54, a nulling roller 55 and a side slitter 56 are provided in this order from the upstream side of the cooling chamber 16 and the winding chamber 17. The static electricity removing bar 54 performs a static eliminating process for removing electricity from the charged film 45. [ The knurling imparting roller 55 imparts a knurling for winding to both side portions of the film 45. [ The side slitter 56 cuts both side portions of the film 45 so as to leave the knurling on the product film side.

The winding chamber (17) has a winder (63). The winder (63) winds the film (45) around the winding core (62) and winds it in a roll shape. The press roller 61 presses the film 45 toward the core 62 side.

4, the flexible die 21 has a pair of side plates 71 made of stainless steel (such as SUS316 or SUS316L) and a pair of lip plates 72. As shown in Fig. The pair of lip plates 72 are brought into close contact with each other. As shown in Fig. 5, a flow path forming surface 72a is formed on the contact surface of the lip plate 72, and a flow path 29 is formed by the flow path forming surface 72a as shown in Fig. The pair of side plates 71 are mounted so as to cover both end surfaces 72b of the lip plate 72. [ Both ends of the flow path 29 are closed by the side plate 71.

6, the flow path 29 includes an inlet 29a, a manifold 29b, and a slit flow path 29c. The inlet 29i opens at the top of the flexible die 21, To the outlet (dope outlet) 29o. The inlet flow passage 29a sends the dope 28 introduced from the inlet 29i to the manifold 29b. The manifold 29b relaxes the deformation of the polymer molecules contained in the dope 28 while diffusing the dope 28 in the Y direction and then sends the dope 28 to the slit flow path 29c. The slit flow path 29c sends the dope 28 toward the outlet 29o.

As shown in Fig. 7, the slit flow path 29c is formed in an elongated rectangular shape in the cross section on the XY plane perpendicular to the flow direction (Z direction) of the dope 28 in the flow path 29. [ A pair of long sides in the cross section of the slit flow path 29c is formed of the flow path forming surface 72a and the short side is formed of the flow path forming surface 71a.

8 and 9, the lip plate 72 is divided into a lip plate main body 81 made of stainless steel (such as SUS316 or SUS316L) and a die head 82. As shown in Fig. The die head 82 is an elongated rectangular body having a substantially wedge-shaped cross section along the XZ plane in the Y direction. The die head 82 is detachably attached to the lip body 81 by a mounting screw 97. As a result, the die head 82 is detachably provided at the outlet 29o of the flexible die 21. [ The dividing position of the lip plate main body 81 and the die head 82 is halfway of the slit flow path 29c in the flow path forming surface 72a.

(Die head)

As shown in Fig. 10, the die head 82 has a base 85, a base layer 92, and a DLC film 86. As shown in Fig. As shown in Fig. 9, the base 85 is made of stainless steel (SUS316 or SUS316L or the like) and is formed into a long rectangular prism whose cross section along the XZ plane is substantially wedge-shaped. The base 85 has, for example, four mounting holes 95 at regular intervals in the Y direction. 11, a screw hole 96 is formed in the lip plate main body 81 at a position corresponding to the mounting hole 95. As shown in Fig. The die head 82 is detachably fastened to the lip main body 81 by attaching the mounting screw 97 to the screw hole 96 through the mounting hole 95. [

12, the base layer 92 is formed on the surface of the lower front end portion 85a of the base 85. As shown in Fig. The surface of the base layer 92 is sharply formed toward the Z direction and has a flow path surface 92a for forming the flow path 29 and an exposed surface 92b exposed to the outside.

As the material for forming the ground layer 92, super hard materials such as tungsten carbide (WC), Al ₂ O ₃ , TiN, and Cr ₂ O ₃ can be mentioned, but WC is particularly preferable. Examples of the WC include WC-Ni-based, WC-TiC-based, WC-TaC-based, and the like, to which cobalt is added as a binder metal, all of which can be used in the present invention. The base layer 92 can be formed, for example, by spraying. The thickness of the base layer 92 is preferably in the range of 50 占 퐉 to 200 占 퐉, for example, and more preferably 70 占 퐉 to 130 占 퐉.

However, in the drawings, the base layer 92 and the DLC film 86 are exaggerated relative to other members in view of the relationship shown.

The base layer 92 is formed, for example, as follows. First, the base layer formation area is concavely provided on the pointed portion of the wedge-shaped base 85. Next, the foundation layer 92 is formed in the foundation layer formation area. After forming the base layer 92, the base layer 92 is formed by machining such as polishing without stepping with the base 85. The base layer forming step is thus carried out.

9 and 12, when the maximum length of the die head 82 in the XY plane is LW and the length of the die head 82 in the Y direction is LY, LY / LW) is 50 or more and 400 or less, that is, 50 · LW · LY · 400 · LW. LY is preferably 1500 mm or more, more preferably 2000 mm or more.

The mounting hole 95 penetrates the base 85 in the Z direction. A plurality of mounting holes 95 are formed apart from each other in the Y direction. At a position corresponding to the mounting hole 95, a screw hole 96 is formed in the lip plate main body 81. However, in Fig. 12, the display of the DLC film 86 is omitted in order to avoid the redundancy in the drawing.

The Vickers hardness Hv of the base layer 92 is larger than the Vickers hardness Hv of the base 85. [ The Vickers hardness Hv of the underlayer 92 is smaller than the Vickers hardness Hv of the DLC film 86. [ The Vickers hardness (Hv) of the ground layer 92 is preferably 150 Hv or more. The Vickers hardness (Hv) of the DLC film 86 is preferably 1000 Hv or more and 2500 Hv or less. The Vickers hardness difference (Hv2-Hv1 described later) between the base layer 92 and the DLC film 86 is preferably 500 Hv or less, although it will be described later in detail. The Vickers hardness (Hv) is a value converted from an indentation hardness (Oliver & Pharr calculation method) of ISO 14577. However, in the following description, the Vickers hardness may be referred to as " hardness " and the Vickers hardness difference may be referred to as " hardness difference ".

(DLC film)

As shown in Fig. 10, the DLC film 86 is formed on the entire surface of the base 85. As shown in Fig. In this embodiment, however, since the upper end face 85b of the base 85 shown in Fig. 10 is mounted in close contact with the fixture 106 as shown in Fig. 14, a DLC film 86 are not formed. The DLC film 86 is formed by a known vapor phase film formation method. The heating temperature T of the base 85 in the process is preferably 130 ° C or more and 300 ° C or less in order to reduce the deflection amount of the die head 82 after the treatment. This? T will be described later. As the gas phase film forming method, specifically, there are plasma CVD, ion plating, ionization deposition and the like, among which ionization deposition is preferable. The thickness d of the DLC film 86 is preferably in the range of, for example, 0.7 μm or more and 2 μm or less, more preferably 1 μm or more and 2 μm or less.

13, a DLC film forming apparatus 99 for forming a DLC film by ionization deposition is provided with a reflector 101, a filament 102, an anode 103, and a target electrode (not shown) 104), and a gas introduction pipe (105). The reflector 101 is formed in a cylindrical shape having, for example, a bottom portion. The anode 103 is installed in the reflector 101 in a state of being electrically insulated from the reflector 101. [ The plasma source 107 is constituted by the three-electrode structure of the filament 102, the anode 103, and the reflector 101. A gas introduction pipe 105 is connected to the reflector 101. A reaction gas 108 such as a hydrocarbon gas is sent from the gas introduction pipe 105 to the reflector 101. A base 85 is attached to the target electrode 104 through a fixing member 106. The power source unit 109 has a reflector power source 109a, a filament power source 109b, an anode power source 109c, and a target power source 109d. These power sources 109a to 109d apply a predetermined voltage to the reflector 101, the filament 102, the anode 103 and the target electrode 104 to be connected.

As shown in Figs. 14 and 15, the stainless steel fixture 106 includes a fixing plate 110 having a foot plate 111 at right angles to both sides, a fixing plate 110 having a size of, for example, M6 (Japanese Industrial Standards And a fixing bolt 112 of a standard size. The fixing plate 110 is formed with the screw holes 115 arranged in a spaced apart relation in the Y direction. The base 85 is fastened to the fastener 106 by mounting the fastening bolt 112 to the screw hole 115 through the mounting hole 95.

As shown in FIG. 13, the reaction gas 108 is introduced into the inner space of the reflector 101 from the gas introduction pipe 105. Plasma is generated around the anode 103 by DC arc discharge. Hydrocarbon ions are generated from the reaction gas 108 by this plasma. The generated hydrocarbon ions are directed to the target electrode 104. Since the base 85 is attached to the target electrode 104, the hydrocarbon ions collide with the base 85, and the DLC film 86 is formed on the base 85. Thus, in the DLC film forming apparatus 99, a DLC film forming step for forming the DLC film 86 on the base 85 is performed by ionization deposition.

By ionization deposition, the base 85 is heated to a predetermined temperature. A plurality of the plasma sources 107 are arranged in the longitudinal direction in accordance with the length of the die head 82 to form the DIC film 86 on the elongated and elongated shape like the die head 82, Lt; RTI ID = 0.0 > length. ≪ / RTI > As a result, the length of the elongated thinner, such as the die head 82, increases as the length of the plasma generator 107 increases, and the number of electrodes increases accordingly. Therefore, the processing temperature in the DLC film- .

When the hardness of the DLC film 86 is adjusted, for example, in the ionization deposition method, the following procedure is performed. First, a hydrocarbon gas is used as a raw material, and carbon ions C ⁺ are generated by vaporization such as plasma. By applying a negative (-) voltage to the base 85, carbon ions collide with the base 85 to form a DLC film 86. (Sp3 bond) and the graphite film (Sp2 bond) constituting the DLC film 86 depend on the impact energy of the carbon ions generated in the base 85 when the carbon ions collide with the base 85. [ The mixing ratio changes. In the DLC film 86, the more the Sp3 bond is, the harder the film becomes, and the more the Sp2 bond is, the more the film having low friction tends to be obtained. By using this tendency, the DLC film 86 having desired characteristics can be formed by controlling the cathode voltage and the like on the base 85.

After ionization deposition, it is cooled to room temperature. In this process of heating and cooling, the base 85 is warped. As a result, the surface of the fixing plate 110 is coated with fluorine. A fluorine film having lower friction than the forming material of the base 85 (for example, SUS316L) is formed on the surface of the fixing plate 110 and ionization deposition is performed while the base 85 is fixed through the fluorine film having low friction, The DLC film 86 (see FIG. 10) can be formed on the base 85 while suppressing the warpage of the base 85.

However, it is preferable that the fastening torque of the fastening bolt 112 (see Fig. 15) is reduced from the Y-direction center portion toward the Y-direction both end portions. For example, the tightening torque of the center fixing bolt 112 in the Y-direction central portion is 10 N · m, and the tightening torque of the end fixing bolt 112 in the Y-direction end portion is 3 N · m. The tightening torque of the fixing bolt 112 between the center fixing bolt 112 and the end fixing bolt 112 is 5 N · m. The end of the base 85 is easily moved so that the DLC film 86 (also referred to as a " bottom ") is formed on the base 85 while the warpage and cracks of the base 85 are more reliably suppressed. 10) can be formed.

Since the base 85 and the base layer 92 are different in material, the coefficient of linear expansion? 1 of the base 85 and the coefficient of linear expansion? 2 of the base layer 92 are different. When the DLC film 86 is formed by the relationship between the difference (? 1 -? 2) between the two and the heating temperature at the time of forming the DLC film (the processing temperature in the DLC film forming process - room temperature) 85), the elongation of the two is different and thermal expansion and deformation occur. The thermal expansion deformation is a deformation caused by thermal expansion of the base 85 and the base layer 92. When the stress? 1 received by the underlayer 92 due to the thermal expansion deformation exceeds 820 MPa of the WC breaking stress? 2, for example, the underlayer 92 is broken and the underlayer 92 and the underlayer Cracks are generated in the DLC film 86 formed on the substrate 92. [ The generation of this crack lowers the yield of the die head 82 (the number of good products / the number of fabrics produced without occurrence of cracks) and the production efficiency is lowered. In addition, due to a slight crack that has been overlooked in the past, peeling of the DLC film 86 occurs at the time of use for a long time, and a streak defect occurs in the film at the time of solution deposition.

Thus, as shown in FIG. 16, the die head 82 is manufactured through the determination step 121 of the crack preventing adaptation condition, the base layer forming step 122, and the DLC film forming step 123. In the determination step 121 of the crack preventive compliance condition, the coefficient of linear expansion of the base 85 and the base layer 92, the length LY of the die head 82 in the longitudinal direction (Y direction) The stress acting on the foundation layer 92 from the external force due to the thermal expansion deformation of the base 85 and the foundation layer 92 due to the temperature rise at the time of forming the DLC film, that is, the thermal expansion deformation Lt; / RTI > acting on the foundation layer 92 is found. When the stress? 1 becomes 820 MPa or more, which is the fracture stress? 2 of the foundation layer 92, it is judged that a crack occurs in this combination. When the obtained stress? 1 is less than 820 MPa, it is judged that no crack occurs. The external force described above is a force generated by the compressive force PB acting on the base 85 and the tensile force PL acting on the foundation layer 92 and applied to each of them in the longitudinal direction. Specifically, it is calculated by PB-PL.

The compressive force acting on the base 85 is denoted by PB and the tensile force acting on the base layer 92 is denoted by PL and the stress applied to the base layer 92 is a cross section perpendicular to the longitudinal direction of the die head (PB-PL) / AL, where AL is the sectional area of the foundation layer 92 in the cross section of the base layer 92. [

The compressive force PB acting on the base 85 is obtained as follows. First, the strain? B is obtained from? B =? LYB / LY from the elongation amount? LYB according to the heating temperature of the base 85 and the length LY of the base. Next, the strain? B is multiplied by the Young's modulus EB of the base 85 to obtain a normal stress? B (? B =? B 占 EB). The compressive force PB (PB =? B 占 AB) is obtained by multiplying the obtained normal stress? B by the cross sectional area AB in the cross section along the XZ plane. In the same manner, the tensile force PL of the foundation layer 92 is obtained. First, strain εL is calculated from σL = ΔLYL / LY from the elongation ΔLYL according to the heating temperature of the base layer 92 and the length LY of the base. Next, the strain epsilon L of the base layer 92 is multiplied by the Young's modulus EL to determine the normal stress? L (? L =? L EL). The tensile force PL (PL =? L? AL) is obtained by multiplying the obtained normal stress? L by the sectional area AL. Here,? LYB is obtained by subtracting the length of the base 85 in the Y direction from the length in the Y direction under the heating temperature and before heating (in a non-heated state, that is, at room temperature). ? LYL is obtained by subtracting the length of the base layer 92 in the Y direction from the length in the Y direction under the heating temperature before heating (in the non-heated state, that is, at room temperature).

However, as the length LY of the base 85, which is the object, becomes longer, it is necessary to increase the number of the reflectors 101. As a result, as the number of reflectors 101 increases, the number of electrodes increases. Since the vacuum plasma discharge is performed by this electrode, an increase in the electrode leads to an increase in the processing temperature. As described above, the processing temperature in the DLC film forming step 123 rises by increasing the reflector 101 in accordance with the length LY of the base 85. Therefore, the heating temperature in the DLC film forming step 123 may be determined in advance by experiment, or may be determined on the basis of the processing history data so far.

In addition to the method of obtaining the crack prevention condition, the table calculation software (for example, Excel manufactured by Microsoft Corporation) may be used. In this case, the length (LY) in the longitudinal direction of the base 85 to be used, the linear expansion coefficient (?) Of the base 85 and the base layer 92, The numerical values of the heating temperature T at the time of formation, the Young's modulus E and the sectional area A and the fracture stress? 2 of the foundation layer 92 are numerically inputted to calculate the elongation Numerical values after the calculation are displayed in the columns of the stress (?), The external force (F) at that time, and tensile stress (? 1) generated in the base layer (92) by the thermal expansion deformation. The obtained stress? 1 is compared with the fracture stress? 2 (= 820 MPa) of the foundation layer 92 to determine that the value of the combination is appropriate when? 1 <? 2, Quot; suitability &quot; if appropriate, and &quot; unsuitable &quot; if unsuitable. By using the table calculation software as described above, it is possible to automatically determine whether or not the entered numerical value falls within the crack preventive conforming condition by inputting the numerical data or the dimensional data by the material of the die head to be made.

[Table 1]

In the case where a combination satisfying the condition of no crack is obtained by the step 121 of determining the crack preventing adaptation condition, the underlayer 92 is first formed by the underlayer forming step 122 under this condition, Next, by forming the DLC film 86 by the DLC film forming step 123, the die head 82 free from cracks can be surely obtained.

However, instead of performing the numerical calculation by the table calculation software, an application having a comparison judgment and a data input guidance function added thereto may be incorporated in the PC, although not shown. In this case, the function of calculating the stress (? 1) based on the input guidance function of each condition, the inputted numerical value of each condition, and the calculated stress? 1 are compared with the fracture stress? A cracking occurrence alarm is sounded when the stress? 1 is equal to or higher than the breaking stress? 2 by the comparison determination, and when the stress? 1 is less than the breaking stress? 2, The application is configured to give the PC a re-input function for re-entering the condition.

It is also possible to use an application combining table calculation software. In this case, the calculated stress (? 1) and the fracture stress (? 2) are compared with each other in addition to the tabular input guide shown in Table 1, and it is determined that the combination of the respective conditions is a favorable condition Display. When? 1?? 2, the number in each column is displayed by flashing, and it is required to change the numerical value. In this case, when a satisfactory condition is obtained in the direction of increasing the numerical value, the symbols ↑ and ▲ are assigned to the numerical value, and when the appropriate condition is obtained in the numerical value decreasing direction, Can be easily performed. In place of the numerical value input, it is also possible to automatically calculate whether to enter the acceptable condition by changing the numerical value to some extent, and to change the color to display the numerical value or to display it adjacent to the inputted numerical value. At this time, it is also possible to fix one condition value and automatically calculate another value by varying the value.

The hardness difference between the base layer 92 and the DLC film 86 is set to 500 Hv or less, preferably 200 Hv or less, more preferably 100 Hv or less. Experimental results show that the adhesion of the DLC film 86 to the underlayer 92 improves when the difference in hardness between the both is within a certain range, such as 500 Hv or less. This is considered to be due to the fact that, when the difference in the hardness of the interface between the two is large, a difference occurs in the amount of deformation and the adhesion is lowered. If the difference in hardness exceeds a predetermined value, a flexible undercoat such as SUS is first concaved, so that the DLC film 86 can not follow the change of the base, resulting in cracking.

However, the range of forming the DLC film 86 may be the entire surface of the base 85 or a part of the front end portion.

In the above embodiment, the flexible die 21 is configured by a combination of the pair of side plates 71 and the pair of lip plates 72, but the present invention is not limited thereto. For example, the side plate 71 may be omitted And the flow path 29 is formed only by the lip plate 72. Further, the flexible die may be configured to include other members besides the side plate 71 and the lip plate 72.

In the above embodiment, the flexible film 34 is cooled in order to allow the flexible film 34 to freely move and be conveyed. However, the present invention is not limited to this, and the flexible film 34 may be supplied with a drying air to evaporate the solvent, It may be brought into a state in which it can stand alone and be conveyed.

Although the flexible drum 22 is used as the support in the above embodiment, a flexible band may be used instead. In the case of using a flexible band, a flexible band is placed between a pair of drums, and the drum is rotated to circulate the flexible band.

In the present invention, it is possible to perform a simultaneous laminated shared lamination in which two or more types of dope are simultaneously shared and fused when the dope is flexible, or a laminated shared laminate in which a plurality of dods are laminated successively and sequentially. However, both shared lines may be combined. In the case of carrying out the simultaneous stacking and stacking, a flexible die equipped with a feed block may be used, or a multi-pocket flexible die may be used.

In the solution casting facility 10 of the present invention, the width of the film as a product is preferably 600 mm or more, more preferably 1400 mm or more and 2500 mm or less. However, it is effective even when the width of the film is larger than 2500 mm. The film thickness of the film is preferably 15 占 퐉 or more and 80 占 퐉 or less. The polymer to be a raw material of the polymer film is not particularly limited, and examples thereof include cellulose acylate and a ring-shaped polyolefin.

The acyl group used in the cellulose acylate of the present invention may be only one type, or two or more kinds of acyl groups may be used. When two or more kinds of acyl groups are used, one of them is preferably an acetyl group. It is preferable that the ratio of the esterification of the hydroxyl group of cellulose with carboxylic acid, that is, the degree of substitution of the acyl group satisfies all of the following formulas (I) to (III). In the following formulas (I) to (III), A and B represent substitution degrees of an acyl group, A represents an acetyl group substitution degree, and B represents an acyl group substitution of 3 to 22 carbon atoms . It is also preferable that 90 mass% or more of triacetyl cellulose (TAC) is particles having a diameter of 0.1 mm to 4 mm.

(I) 2.0? A + B? 3.0

(II) 1.0? A? 3.0

(III) 0? B? 2.9

The total substitution degree (A + B) of the acyl group is more preferably 2.20 or more and 2.90 or less, and particularly preferably 2.40 or more and 2.88 or less. The substitution degree (B) of the acyl group having 3 to 22 carbon atoms is more preferably 0.30 or more, and particularly preferably 0.5 or more.

Details of the cellulose acylate are described in paragraph [0195] of Japanese Patent Laid-Open Publication No. 2005-104148. These descriptions are also applicable to the present invention. The additives such as a solvent and a plasticizer, a deterioration inhibitor, an ultraviolet absorber (UV), an optically anisotropic control agent, a retardation control agent, a dye, a matting agent, a releasing agent and a peeling promoter are also disclosed in the same Japanese Patent Application Publication No. 2005-104148 Are described in detail in the paragraph [0516].

[Example]

(Experiment 1)

The DLC film 86 was formed on the base 85 shown in Fig. 12 by the ionization deposition method in the DLC film forming apparatus 99 shown in Fig. 13 to obtain the die head 82 (see Fig. 10). The base 85 was made of SUS316L as a whole and the base layer 85 of WC-Co system was provided at the lower end portion 85a. The base layer 92 was formed by WC spraying, and its hardness (Hv) was 1500 and its coefficient of linear expansion was 8 占^0-6 / 占 폚. The coefficient of linear expansion of the base layer 85 was 16 × 10 ^-6 / ° C. and the difference in coefficient of linear expansion between the base layer 92 and the base 85 was 8 × 10 ^-6 / ° C. The length LX was 20 mm, the length LY was 2000 mm, the length LZ was 20 mm, and the maximum length LW in the cross section on the XY plane was 28 mm with respect to the base 85. The base 85 was fixed to the target electrode 104 by using a fixture 106 (see Figs. 14 and 15) in which a fluorine film was formed on the surface of the fixing plate 110 made of stainless steel (SUS316L). The heating temperature? T of the base 85 in the cured film forming step was 180 占 폚. The thickness d of the DLC film 86 was 1.6 mu m and the hardness Hv was 2000 Hv. The hardness difference between the base layer 92 and the DLC film 86 was 500 Hv.

(Experiments 2 to 11)

In Experiments 2 to 11, the DLC film 86 was formed on the base 85 in the same manner as Experiment 1 except for the conditions shown in Table 2, and the die head 82 was obtained.

[Table 2]

In Table 2, the length LY (mm) of the base 85 in Experiments 1 to 11, the material of the base 85, the coefficient of linear expansion? 1, the material of the base layer 92, the coefficient of linear expansion? The hardness Hv1 of the DLC film 86, the hardness Hv2 of the DLC film 86, and the heating temperature? T (占 폚). The hardness represents Vickers hardness (Hv).

In Experiment 2, the length (LY) of the base 85 was set to 2200 mm, which was longer than Experiment 1 by 700 mm. Thus, the same conditions as in Experiment 1 were used except that the heating temperature (? T) in the DLC film forming step was 60 占 폚 higher than Experiment 1 and 240 占 폚. The hardness difference between the base layer 92 and the DLC film 86 was 500 Hv, which was the same as in Experiment 1. [

In Experiment 3, the length (LY) of the base 85 was set to 2700 mm, and the material was changed to SUS329J1. Thereby, the coefficient of linear expansion? 1 of the base 85 was 12 占^0-6 / 占 폚 and the heating temperature? T of the DLC film forming process was 90 占 폚 higher than that of Experiment 1 and became 270 占 폚 , And the same conditions as in Experiment 1 were used. The hardness difference between the base layer 92 and the DLC film 86 was 500 Hv, which was the same as in Experiment 1. [

In Experiment 4, the length (LY) of the base 85 was set to 3000 mm, and the material was changed to SUS630. Thereby, the coefficient of linear expansion? 1 of the base 85 was 12 占^0-6 / 占 폚 and the heating temperature? T of the DLC film forming process was 105 占 폚 higher than that of Experiment 1 and became 285 占 폚 , And the same conditions as in Experiment 1 were used. The hardness difference between the base layer 92 and the DLC film 86 was 500 Hv, which was the same as in Experiment 1. [

In Experiment 5, the length (LY) of the base 85 was set at 1800 mm, which is longer than Experiment 1 by 300 mm. Thus, the heating temperature (? T) in the DLC film forming step was 20 占 폚 higher than that in Experiment 1 to 200 占 폚, and the hardness of the obtained DLC film was 1700 Hv. The hardness difference between the undercoat layer 92 and the DLC film 86 was 200 Hv, which is lower than that of Experiment 1.

In Experiment 6, the length (LY) of the base 85 was set at 1700 mm, which is longer than Experiment 1 by 200 mm. Thereby, the heating temperature (? T) of the DLC film forming step was 20 占 폚 higher than that of Experiment 1 and became 200 占 폚, and the hardness of the obtained DLC film was 1400 Hv. The hardness difference between the base layer 92 and the DLC film 86 was -100 Hv lower than that of Experiment 1. [

In Experiment 7, the length LY of the base 85 was set to 3000 mm, and the length was 1500 mm longer than that of Experiment 1. [ Thus, the same conditions as those in Experiment 1 were employed except that the heating temperature (? T) in the DLC film forming step was 105 ° C higher than that of Experiment 1 and became 285 ° C. The hardness difference between the base layer 92 and the DLC film 86 was 500 Hv, which was the same as in Experiment 1. [

In Experiment 8, the length (LY) of the base 85 was set at 1800 mm, which is longer than Experiment 1 by 300 mm. Thereby, the same conditions as in Experiment 1 were obtained except that the heating temperature (? T) in the DLC film forming step was 20 占 폚 higher than Experiment 1 and became 200 占 폚 and the hardness of the obtained DLC film 86 was 1100 Hv. The hardness difference between the base layer 92 and the DLC film 86 was -400 Hv, which is lower than that of Experiment 1. [

Experiment 9 was carried out under the same conditions as in Experiment 1 except that the heating temperature (? T) in the DLC film forming step was set to 170 占 폚 and the hardness of the obtained DLC film was set to 2700 Hv. The hardness difference between the base layer 92 and the DLC film 86 was 1200 Hv, which is higher than that of Experiment 1. [

Experiment 10 was performed under the same conditions as Experiment 5 except that the base layer 92 was not formed on the base 85 and the DLC film 86 was directly formed on the base 85. [

Experiment 11 was carried out under the same conditions as in Experiment 10 except that the base of SUS316L of Experiment 10 was replaced with a base of nickel-based super hard material (WC-Ni).

(evaluation)

The die head 82 obtained in Experiments 1 to 11 was subjected to the following evaluations. In Table 2, the numbers indicated in the evaluation items indicate the numbers assigned to the following evaluation items.

1. DLC film crack

The presence or absence of cracks in the DLC film 86 was examined. The presence or absence of cracks and the length of cracks were determined by observing magnification 100 times with an enlarged lens using a microscope VH-900 manufactured by KEYENCE CORPORATION. The evaluation was made based on the presence or absence of cracks and the length based on the following criteria.

A: No crack occurred.

B: There is a crack, and the length is 100 μm or less.

C: There is a crack, and its length is larger than 100 탆.

2. Deflection of the die head

And the amount of warpage W was measured with respect to the die head 82. First, the die head 82 is disposed on the pedestal such that the curved portion is downward. The largest amount of the gap between the die head 82 and the pedestal was defined as the amount of warpage W. The bending amount (W) was evaluated based on the following criteria.

A: W is 5 탆 or less.

B: W is greater than 5 탆 and not greater than 15 탆.

C: W is larger than 15 탆.

3. Friction Wear Strength of DLC Film

The DLC film 86 was subjected to a frictional wear test. After this test, the DLC film 86 was visually observed, and the strength of the DLC film 86 was evaluated based on the following criteria. The order of friction wear test is as follows. A friction and wear test (JIS R 1613-1993) was performed using a tribometer (ball-on-disk type) manufactured by CSM Instruments. First, a test piece (50 mm x 20 mm x 10 mm) with a part of the die head 82 cut out was fixed on a rotating table and the rotating table was rotated at a predetermined rotating speed. Next, as a tip of the die head 82, a disk ball (test piece) made of Al ₂ O ₃ having a ball shape (diameter 6.35 mm) at the position of the DLC film 86, which is 3.0 mm away from the center of rotation, Was pressed to a predetermined load (5.0 N). The speed of the DLC film 86 at the pressing position was 0.1 m / sec. And the die head 82 was rotated at 20,000 revolutions / hour while the disk balls were pressed. Thereafter, the amount of wear of the DLC film 86 by the disk balls was measured by a surface roughness meter (SURFCOM 2000DX3) manufactured by TOKYO SEIMITSU CO., LTD. The evaluation was made based on the following criteria according to the wear amount.

A: The wear amount is "0" and there is no wear.

B: The wear amount is 100 nm or less.

C: Wear amount is larger than 100 nm.

4. Evaluation of adhesion of DLC film

The DLC film 86 was subjected to a scratch test to evaluate the adhesion of the DLC film 86. For the scratch test, Revetest (scratch tester) manufactured by CSM Instruments was used. (N2-3962) having a radius of curvature of 200 mu m, and evaluated under the following conditions. First, the DLC film 86 is scratched at a moving speed of 10 mm / min while applying a load of 100 N / min to the DLC film 86 with diamond indenter. When the DLC film 86 is broken during this scratching, the object to be scratched is changed from the DLC film 86 to the WC film of the base film 92. At this time, the frictional coefficient of the WC film is 0.4, while the frictional coefficient of the DLC film 86 is 0.1, and the change in frictional resistance is detected. When the variation of the frictional resistance exceeds a predetermined value, it is detected that the DLC film 86 is broken. The critical load of delamination in which the DLC film 86 was broken was defined as adhesion.

When a slight time loss occurs when the friction coefficient is calculated from the load by the scratch tester, the accurate adhesion (stress in which the DLC film 86 is broken) is not obtained. Therefore, when the DLC film 86 is broken, the acoustic wave emitted at the time of breakage is detected by an AE (acoustic) sensor, and the time at which the DLC film 86 is destroyed is accurately recorded, . However, the initial load was 0.9 N, the load was 100 N / min, the moving speed was 10.0 mm / min, and the sensitivity of the AE sensor was 9. In practice, however, the adhesion of the DLC film 86 is stable without detachment of the DLC film 86 when the evaluation method is 30 N or more. Were evaluated on the basis of the following criteria according to the adhesion.

A: The adhesion is over 30N.

B: Adhesion is more than 20N and not more than 30N.

C: Adhesion is 20N or less.

In Experiments 1, 3 and 4, cracks, warps, and strengths were "A" and adhesion was "B". In Experiment 2, the strength was &quot; A &quot;, and the crack, warpage, and adhesion were &quot; B &quot;. In Experiment 5, cracks, warpage, strength, and adhesion were all "A". In Experiment 6, cracks, warpage, adhesion were "A" and strength was "B". In Experiment 7, the cracks and warps were "C", the strength was "A", and the adhesion was "B". In Experiment 8, cracks, warpage, adhesion were "A" and strength was "C". In Experiments 9 and 10, cracks, warpage, and strength were "A" and adhesion was "C". In Experiment 11, cracks, warpage, strength, and adhesion were all "A".

When the SUS316L is used as the material of the base 85, in the case of Experiment 1 in which the base length LY is 1500 mm, the crack length, the warpage, and the strength are all "A" The evaluation tends to be lowered. For example, the base length LY is as long as 2200 mm (Experiment 2), and the evaluation of the ground, the warpage and the crack is lowered to "B", and a crack of 100 μm or less is generated. When the base length LY is longer than 3000 mm (Experiment 7), only the evaluation of the strength becomes "A", the evaluation of the bending and crack becomes "C", and the evaluation of the adhesion becomes "B" .

In Experiments 3 and 4, the material of the base was changed from SUS316L to SUS329J1 or SUS630. In this case, even if the base length LY is as long as 2700 mm or 3000 mm, a die head having cracks, warpage, and strength of "A"

Experiment 5 was the same as Experiment 1 except that the base length LY was 300 mm longer and became 1800 mm and the heating temperature of the DLC film 86 was 200 ° C and the hardness Hv2 was 1700, In this case, the hardness difference (Hv2-Hv1) between the DLC layer and the ground layer 92 was 200, and a die head having cracks, warps, strengths, and adhesion forces of "A" was obtained.

Experiment 6 was carried out under the same conditions as Experiment 1 except that the base length LY was increased by 200 mm to 1700 mm and the heating temperature of the DLC film 86 was 200 ° C and the hardness Hv2 was 1400 to be. In this case, the hardness difference (Hv2-Hv1) between the DLC layer and the foundation layer 92 was -100, and a die head with cracks, warpage, adhesion strength "A" and strength "B" was obtained.

Experiment 7 is a die head under the same conditions as Experiment 4 except that the material is changed to SUS316L for Experiment 4. [ In this case, a die head in which the crack and warpage were C, the strength was A, and the adhesion was B was obtained. There is a problem in that durability is deteriorated when the film is used as a film forming die because cracks and warpage are C. There is a drawback that a film is formed on the surface of the film formed due to the peeling of the foundation layer 92.

Experiment 8 is a die head under the same conditions as Experiment 5 except that the hardness (Hv2) of the DLC film 86 was 1100 for Experiment 5. In this case, the hardness difference (Hv2-Hv1) between the base layer 92 and the DLC film 86 was -400, cracks, warpage, and adhesion were A, and a die head with strength C was obtained . Since the strength is C, there is a problem in durability when it is used as a die for film formation.

Experiment 9 is a die head which is the same as Experiment 1 except that the hardness (Hv2) of the DLC film 86 is 2700 and the heating temperature is 170 占 폚. In this case, the hardness difference (Hv2-Hv1) between the base layer 92 and the DLC film 86 became 1200, and the crack, warpage, and strength became A, and the die head with the adhesion C was obtained. Since the adhesive force is C, there is a problem in durability when it is used as a die for film formation.

Experiment 10 is a die head under the same conditions as Experiment 5 except that the base layer 92 is not formed on the base 85 and the DLC film 86 is directly formed on the base. In Experiment 10, it was found that the hardness difference 1800 between the DLC film 86 and the member in contact with the DLC film 86 was lower than that in Experiment 5, because the adhesion was C and decreased.

Experiment 11 was a die head under the same conditions as Experiment 10 except that the base of SUS316L of Experiment 10 was replaced with a base of nickel-based super hard material. In this Experiment 11, it was found that the hardness difference between the DLC film 86 and the member in contact with the DLC film 86 was 600, and the adhesion was A as compared with the case of Experiment 10.

As in Experiment 11, since no base layer is formed and the base itself is constituted by an ultra-hard material, stress due to thermal expansion deformation of the base and ground layer does not occur at the time of forming the DLC film, There is no possibility that cracks are generated in the substrate 86 or the adhesion of the DLC film 86 due to cracks is lowered. Thereby, the durability of the flexible die is enhanced, and the occurrence of the stripe failure can be suppressed.

Next, Table 3 shows the results of calculation by the numerical calculation table as to whether or not the conditions in each experiment are appropriate.

[Table 3]

From the results shown in Table 3, it can be seen that the determination result of the conformity condition coincides with the evaluation of cracks in Experiments 1 to 9. Therefore, when the die head is manufactured, it is possible to confirm whether cracks have occurred before manufacturing by combining the materials used, the mechanical characteristics and the lengths depending on the materials, and there is no case of lowering the yield. In addition, since the generation of cracks is eliminated, peeling of the DLC film 86 due to aging use due to minute cracks is eliminated, and a film free from occurrence of stripe failure can be efficiently produced.

Claims (11)

A flexible die having a detachable die head at a dope outlet to drain the dope to a support,
Wherein the dope comprises a polymer and a solvent,
The die head includes:
A base made of stainless steel;
A ground layer formed on the base;
A DLC film formed on the base layer by a vapor deposition method; And
a combination of respective linear expansion coefficients of the base and the ground layer, a length in the longitudinal direction of the die head, and a heating temperature at the time of forming the DLC film, wherein? 1 is less than? 2,
The base layer is formed of an ultra hard material,
From here,
? 1: stress acting on the underlayer due to thermal expansion deformation of the base and the underlayer due to temperature rise at the time of forming the DLC film,
and? 2 is the breaking stress of the underlying layer. The method according to claim 1,
The compressive force acting on the base is denoted by PB, the tensile force acting on the base layer is denoted by PL, and the sectional area of the base layer on the cross section orthogonal to the longitudinal direction of the die head is denoted by AL. (? 1) is obtained by? 1 = (PB-PL) / AL. 3. The method of claim 2,
Wherein the die head has a length LY of LY and a length LY of 50 LW or more and a length LY of 1500 mm or more when a maximum length in a cross section orthogonal to the length direction is LW, Wherein the thickness of the DLC film is not less than 70 占 퐉 and not more than 130 占 퐉 and the thickness of the DLC film is not less than 0.7 占 퐉 and not more than 2 占 퐉. 4. The method according to any one of claims 1 to 3,
Wherein the base is formed of one of SUS316L, SUS329J1, and SUS630, and the base layer is formed of tungsten carbide. 4. The method according to any one of claims 1 to 3,
Wherein the difference in hardness between the underlying layer and the DLC film is within 500 Hv. 6. The method of claim 5,
Wherein the hardness of the DLC film is 1300 Hv or more. 4. The method according to any one of claims 1 to 3,
Wherein the vapor phase film formation method is any one of ionization deposition, ion plating, and plasma CVD. A method for producing a film,
A step of forming a flexible film composed of the dope by discharging the dope from the flexible die as a support,
Evaporating the solvent from the flexible film until the flexible film is self-supporting and transportable;
Peeling the flexible film from the support to form a wet film; And
And evaporating the solvent from the wet film to form a film,
Wherein the dope comprises a polymer and a solvent, the flexible die having a separable die head at a dope outlet, the die head having a base, a ground layer and a DLC film, the base being made of stainless steel, Wherein the base layer is formed of an ultra hard material and the DLC film is formed on the base layer by a vapor phase deposition method and the die head is made of a material having a? Layer, the length of the die head in the longitudinal direction, and the heating temperature at the time of forming the DLC film,
From here,
? 1: stress acting on the underlayer due to thermal expansion deformation of the base and the underlayer due to temperature rise at the time of forming the DLC film,
and? 2 is the breaking stress of the underlying layer. A method for manufacturing a die head of an elongated column body mounted on a dope outlet of a flexible die for discharging the dope,
Wherein the dope comprises a polymer and a solvent,
(A) forming a base layer on a base made of stainless steel;
(B) forming a DLC film on the base layer by a vapor deposition method; And
(C) a step of determining, before the step A, a combination of respective linear expansion coefficients of the base and the ground layer, a length of the die head in the longitudinal direction, and a heating temperature in the vapor phase film forming method,
The base layer is formed of an ultra hard material,
lt; / RTI &gt; is determined to be less than sigma 2,
From here,
? 1: stress acting on the base layer due to thermal expansion deformation of the base and the base layer in the B step,
and? 2 is the breaking stress of the underlying layer. 10. The method of claim 9,
Wherein when the compressive force acting on the base is PB, the tensile force acting on the base layer is PL, and the cross sectional area of the base layer on the cross section orthogonal to the longitudinal direction of the die head is AL, stress acting on the base layer (? 1) is obtained by? 1 = (PB-PL) / AL. 10. The method of claim 9,
Wherein the vapor phase film formation method is any one of ionization deposition, ion plating, and plasma CVD.

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