JP2023085992A - Die head and coated film manufacturing method - Google Patents

Abstract

To provide a die head whose liquid repellent layer has excellent adhesion durability, which can reduce coating stripes, and application thereof.SOLUTION: A die head and application thereof include: a first outer main body that includes a first tip surface, a first side surface linked to the first tip surface to define a first discharge port and a second side surface linked to the first tip surface at a position at the opposite side of the first side surface; a second outer main body that includes a second tip surface, a third side surface linked to the second tip surface while pointing to the first side surface of the first outer main body to define the first discharge port or a second discharge port different from the first discharge port, and a fourth side surface linked to the second tip surface, at a position at the opposite side of the third side surface; a metal-containing layer positioned on at least one surface selected from a group constituted of the first tip surface of the first outer main body and the fourth side surface of the second outer main body; and a liquid repellent layer, positioned on the metal-containing layer, which includes a chemical compound having a perfluoropolyether group.SELECTED DRAWING: Figure 1

Description

The present disclosure relates to die heads and methods of making coatings.

A coating device with a die head is used, for example, in a method of forming a coating film on an object. In the methods as described above, the die head dispenses the raw material (eg, composition) of the coating film.

Patent Literature 1 listed below discloses a coating member manufacturing apparatus that forms a coating film on the surface of a member to be coated that moves relative to an ejection port. A discharge port is formed between a pair of lip tip portions. In the applicator member manufacturing apparatus, the contact angle of water at the tip of the downstream lip is larger than the contact angle of water at the tip of the upstream lip. In an example of a die used in an applicator member manufacturing apparatus, the contact angle of water at the tip of the downstream lip is increased by the water-repellent layer covering the tip of the downstream lip.

Patent Literature 2 below discloses a die coater used for forming a transparent conductive layer by coating a transparent conductive layer-forming coating liquid containing at least a metal material on a transparent base material. The die coater includes a die head that discharges a transparent conductive layer-forming coating liquid, a coating liquid tank that stores the transparent conductive layer-forming coating liquid, and a transparent conductive layer-forming coating liquid that is sent from the coating liquid tank to the die head. and a liquid feeding path for liquid. In the die head, a liquid-repellent area is formed at least on the surface located in the direction opposite to the coating direction.

JP-A-2002-248399 JP 2016-068047 A

Although methods for reducing or preventing coating film defects have been investigated in previous studies on die heads, streak-like defects (hereinafter referred to as "coating streaks") still occur in coating films formed using a die head. is sometimes observed. Further, for example, the liquid-repellent layer of conventional die heads may come off due to various factors such as solvents. The liquid repellent layer is a layer having liquid repellency. Due to the circumstances described above, it is desired to improve the adhesion durability of the liquid-repellent layer of the die head while reducing coating streaks.

An object of one embodiment of the present disclosure is to provide a die head that has excellent adhesion durability of a liquid-repellent layer and reduces coating streaks. Another embodiment of the present disclosure aims to provide a coating film manufacturing method using the die head.

The present disclosure includes the following aspects.
<1> The first tip surface is connected to the first tip surface, and the first side surface defining the first ejection port is connected to the first tip surface at a position opposite to the first side surface. a first outer body including a second side surface; a second distal end surface; and a second distal end surface facing the first lateral surface of the first outer body and connected to the second distal end surface. a second outer body including a third side defining a second outlet different from the first outlet, and a fourth side opposite the third side and connected to the second tip side; a metal-containing layer positioned on at least one surface selected from the group consisting of the first tip surface of the first outer body and the fourth side surface of the second outer body; a liquid-repellent layer comprising a compound having a perfluoropolyether group located thereon.
<2> The die head according to <1>, wherein the surface of the metal-containing layer facing the liquid-repellent layer includes protrusions having a width of 0.01 mm to 1 mm and a height of 0.1 mm to 1 mm.
<3> The die head according to <1> or <2>, wherein the falling angle of 0.05 mL of water with respect to the liquid-repellent layer is 55° or less.
<4> The die head according to any one of <1> to <3>, wherein the third side surface of the second outer body defines the first outlet.
<5> The die head according to any one of <1> to <3>, wherein the third side surface of the second outer body defines the second outlet.
<6> Any one of <1> to <5>, wherein the metal-containing layer is positioned on each of the first tip surface of the first outer body and the fourth side surface of the second outer body. Die head described in one.
<7> Preparing the die head according to any one of <1> to <6>, supplying the composition onto an object using the die head to form a coating film, A method for producing a coating film comprising.
<8> The method for producing a coating film according to <7>, wherein the viscosity of the composition at 25° C. and a shear rate of 1 s ⁻¹ is 1 Pa·s to 1,000 Pa·s.

According to an embodiment of the present disclosure, a die head is provided that has excellent adhesion durability of a liquid-repellent layer and reduces coating streaks. According to another embodiment of the present disclosure, a coating film manufacturing method using the above die head is provided.

FIG. 1 is a schematic perspective view of a die head according to the first embodiment. FIG. FIG. 2 is a schematic cross-sectional view of a die head according to a first embodiment feeding raw materials for a coating film onto an object. FIG. 3 is a schematic perspective view of a die head according to the second embodiment. FIG. 4 is a schematic cross-sectional view of a die head according to a second embodiment feeding raw materials for a coating film onto an object.

Hereinafter, embodiments of the present disclosure will be described in detail. The present disclosure is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the purpose of the present disclosure.

When the embodiments of the present disclosure are described with reference to the drawings, descriptions of overlapping components and reference numerals in the drawings may be omitted. Components shown with the same reference numerals in the drawings mean the same components unless otherwise specified. The dimensional ratios in the drawings do not necessarily represent the actual dimensional ratios.

In the present disclosure, a numerical range indicated using "to" indicates a range including the numerical values described before and after "to" as lower and upper limits, respectively. In the numerical ranges described step by step in the present disclosure, upper or lower limits described in a certain numerical range may be replaced with upper or lower limits of other numerical ranges described step by step. In addition, in the numerical ranges described in the present disclosure, upper or lower limits described in a certain numerical range may be replaced with values shown in Examples.

In the present disclosure, the amount of each component in the composition means the total amount of the multiple substances present in the composition unless otherwise specified when there are multiple substances corresponding to each component in the composition. .

In the present disclosure, ordinal numbers (e.g., “first” and “second”) are terms used to distinguish between components and do not limit the number of components or the relative superiority of components.

In the present disclosure, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous.

In the present disclosure, a combination of two or more preferred aspects is a more preferred aspect.

In the present disclosure, "(meth)acrylic" means acrylic, methacrylic or both acrylic and methacrylic.

In the present disclosure, "solid content" means components other than solvent. Liquid components other than the solvent are included in the solid content.

<Die head>
A die head according to one aspect of the present disclosure will be described below. The die head includes a first outer body, a second outer body, a metal-containing layer, and a liquid repellent layer. In this disclosure, "first outer body" and "second outer body" refer to the two bodies farther from the center of the die head among the bodies included in the die head. For example, when three main bodies are arranged along a certain direction, each of the two main bodies positioned at both ends corresponds to the "outer main body". In this disclosure, a body that is positioned between two outer bodies is sometimes referred to as an "inner body." In the present disclosure, "liquid-repellent layer" means a layer having liquid repellency. Liquid repellency includes, for example, water repellency and oil repellency. For example, in a method of forming a coating on an object, a die head can deliver the raw material (eg, composition) of the coating onto the object.

(first outer body)
The first outer body includes a first distal surface, a first side surface, and a second side surface. The first side surface is connected to the first tip surface and defines a first outlet. The second side surface is connected to the first tip surface at a position opposite to the first side surface. The first outer body may further include other surfaces depending on the desired shape.

The first distal surface is an end surface located at the distal end of the first outer body. For example, in the process of dispensing a coating material onto an object, the first leading edge face is directed toward the object. It is preferable that the shape of the first tip surface observed in a plan view is a quadrilateral in which all four interior angles are right angles. In a quadrilateral in which all four interior angles are right angles, the length of the first side is preferably unequal to the length of the second side perpendicular to the first side. From the standpoint of workability of the die head, the length of the first tip surface in the parallel direction of the first outer body and the second outer body is preferably 0.01 mm to 3 mm.

The angle formed by the first tip surface and the first side surface is preferably 45° to 135°. The angle formed by the first tip surface and the first side surface may be 45° to 90°. A curved surface may be sufficient as the connection part of a 1st front-end|tip surface and a 1st side surface. When the connection portion between the first tip surface and the first side surface is a curved surface, the angle formed by the first tip surface and the first side surface is the angle formed by the extension line of the first tip surface and the extension line of the first side surface. represented by

The angle formed by the first tip surface and the second side surface is preferably 90° to 170°. A curved surface may be sufficient as the connection part of a 1st front-end|tip surface and a 2nd side surface. When the connection portion between the first tip surface and the second side surface is a curved surface, the angle formed by the first tip surface and the second side surface is the angle formed by the extension line of the first tip surface and the extension line of the second side surface. represented by

The first ejection port is an opening through which the raw material of the coating film is ejected. The ejection port of the die head may be only the first ejection port. For example, a die head with one outlet is used for single layer coating. Single layer coating can form a single layer of coating on an object. Repetition of single layer application may be applied to the method of forming two or more layers of coating on an object. The die head may have two or more outlets. For example, the die head may have both a first outlet and a second outlet, which will be described later. For example, a die head with two outlets is used for multilayer coating. Multilayer coating can form two or more coating layers on an object.

A first outlet is defined by at least the first side of the first outer body. The first outlet may be defined by a first outer body and a second outer body. Specifically, the first outlet may be defined by a first side of the first outer body and a third side of the second outer body. Aspects of the second outer body are as described below. On the other hand, if the die head further includes another body (i.e., inner body) between the first outer body and the second outer body, the first outlet is defined by the first side of the first outer body and the inner body. is preferably defined by a surface. Aspects of the inner body are as described below.

The shape of the first ejection port observed in a plan view is preferably a quadrilateral with all four interior angles being right angles. In a quadrilateral in which all four interior angles are right angles, the length of the first side is preferably unequal to the length of the second side perpendicular to the first side. That is, it is preferable that a quadrilateral whose four interior angles are all right angles is not a square.

From the viewpoint of uniforming the pressure loss of the raw material of the coating film flowing through the inside of the die head toward the first discharge port in the width direction of the coating film, the first discharge port in the parallel direction of the first outer body and the second outer body The length (ie the size of the opening) is preferably between 0.1 mm and 1 mm.

The first discharge port may communicate with a space formed inside the die head for storing and transferring the raw material of the coating film. A space for storing and transporting the raw material of the coating may be defined by two adjacent bodies.

The first outer body may include a recess defining a manifold. The recesses may be defined by flat surfaces, curved surfaces, or a combination of flat and curved surfaces. A manifold is a space formed inside the die head, and can temporarily store raw materials for the coating film.

Materials for the first outer body include, for example, metal. Examples of metals include stainless steel, cemented carbide (eg, NM15 manufactured by Nippon Tungsten Co., Ltd.), and ultrafine grain alloys (eg, TF15 manufactured by Mitsubishi Materials Corporation). The material of the first outer body may be a material other than metal. Examples of materials other than metals include ceramics. The tip portion of the first outer body may be made of cemented carbide or micro-grain alloy, and the portion of the first outer body other than the tip portion may be made of stainless steel. The first outer body may be formed by a combination of multiple members.

(second outer body)
The second outer body includes a second distal surface, a third side surface, and a fourth side surface. The third side faces the first side of the first outer body and joins the second distal surface to define the first outlet or a second outlet different from the first outlet. The third side may define a first outlet. The third side may define a second outlet. The target of the outlet defined by the third side is determined according to the number of outlets included in the die head. The fourth side surface is connected to the second tip surface at a position opposite to the third side surface. The second outer body may further include other surfaces depending on the desired shape.

The second distal end surface is an end surface located at the distal end of the second outer body. For example, in the process of dispensing a coating material onto an object, the second leading edge face is directed toward the object. It is preferable that the shape of the second distal end surface observed in a plan view is a quadrilateral in which all four interior angles are right angles. In a quadrilateral in which all four interior angles are right angles, the length of the first side is preferably unequal to the length of the second side perpendicular to the first side. That is, it is preferable that a quadrilateral whose four interior angles are all right angles is not a square. From the standpoint of workability of the die head, the length of the second tip surface in the parallel direction of the first outer body and the second outer body is preferably 0.01 mm to 3 mm.

The angle formed by the second tip surface and the third side surface is preferably 75° to 150°. A curved surface may be sufficient as the connection part of a 2nd front-end|tip surface and a 3rd side surface. When the connection portion between the second tip surface and the third side surface is a curved surface, the angle formed by the second tip surface and the third side surface is the angle formed by the extension line of the second tip surface and the extension line of the third side surface. represented by

The angle formed by the second tip surface and the fourth side surface is preferably 60° to 150°. A curved surface may be sufficient as the connection part of a 2nd front-end|tip surface and a 4th side surface. When the connection portion between the second tip surface and the fourth side surface is a curved surface, the angle formed by the second tip surface and the fourth side surface is the angle formed by the extension line of the second tip surface and the extension line of the fourth side surface. represented by

A 2nd ejection port is an opening which ejects the raw material of a coating film. If the die head has a second outlet, the second outlet is defined by at least the third side of the second outer body. If the die head further includes another body (i.e., an inner body) between the first outer body and the second outer body, the second outlet is formed between the third side of the second outer body and the surface of the inner body. is preferably defined by Aspects of the inner body are as described below.

It is preferable that the shape of the second ejection port observed in a plan view is a quadrilateral in which all four interior angles are right angles. In a quadrilateral in which all four interior angles are right angles, the length of the first side is preferably unequal to the length of the second side perpendicular to the first side.

From the viewpoint of uniforming the pressure loss of the raw material of the coating film flowing through the inside of the die head toward the second discharge port in the width direction of the coating film, the second discharge port in the parallel direction of the first outer body and the second outer body The length (that is, the size of the opening) is preferably 0.1 mm to 1.0 mm.

The second outlet may communicate with a space formed inside the die head for storing and transporting the raw material of the coating film. A space for storing and transporting the raw material of the coating may be defined by two adjacent bodies.

The second outer body may include a recess defining a manifold. The recesses may be defined by flat surfaces, curved surfaces, or a combination of flat and curved surfaces.

Materials for the second outer body include, for example, metal. Examples of metals include stainless steel, cemented carbide (eg, NM15 manufactured by Nippon Tungsten Co., Ltd.), and ultrafine grain alloys (eg, TF15 manufactured by Mitsubishi Materials Corporation). The material of the second outer body may be a material other than metal. Examples of materials other than metals include ceramics. The tip portion of the second outer body may be made of cemented carbide or micro-grain alloy, and the portion of the second outer body other than the tip portion may be made of stainless steel. The second outer body may be formed by a combination of multiple members.

(Metal-containing layer)
The metal-containing layer is located on at least one surface selected from the group consisting of the first distal surface of the first outer body and the fourth side surface of the second outer body. As will be described later, the metal-containing layer contributes to improving the adhesion durability of the liquid-repellent layer.

The metal-containing layer may be located on the first distal surface of the first outer body or the fourth side surface of the second outer body. A metal-containing layer is preferably located on each of the first distal surface of the first outer body and the fourth side surface of the second outer body. That is, the die head preferably includes a metal-containing layer overlying the first distal surface of the first outer body and a metal-containing layer overlying the fourth side surface of the second outer body. The metal-containing layer may be formed over part or all of the target area, depending on the extent of the desired effect. The metal-containing layer preferably covers the entire first distal surface of the first outer body. The metal-containing layer preferably covers the entire fourth side surface of the second outer body that contacts the raw material of the coating.

Examples of metal elements contained in the metal-containing layer include Ti, Cr, Fe, Co, Ni and Fe. From the viewpoint of surface coverage, the metal-containing layer preferably contains at least one metal element selected from the group consisting of Ti, Cr, Fe, Co, Ni and Fe, and is selected from the group consisting of Cr and Ni. It is more preferable to contain at least one metal element. The metal-containing layer may be a Cr-containing layer. The metal-containing layer may be a Ni-containing layer. The metal-containing layer may contain an alloy. The metal-containing layer may further contain other components.

With respect to the metal-containing layer located between the first tip surface of the first outer body and the liquid-repellent layer or between the fourth side surface of the second outer body and the liquid-repellent layer, the surface of the metal-containing layer facing the liquid-repellent layer preferably includes protrusions. “The surface of the metal-containing layer facing the liquid-repellent layer” means the surface of the metal-containing layer facing the liquid-repellent layer. The protrusions formed on the surface of the metal-containing layer facing the liquid-repellent layer can improve the liquid repellency of the liquid-repellent layer by forming unevenness on the surface of the liquid-repellent layer located on the metal-containing layer. For example, when the surface of the liquid-repellent layer comes into contact with the raw material of the coating film, the unevenness formed on the surface of the liquid-repellent layer makes the part in contact with the raw material of the coating film and the part not in contact with the raw material of the coating film. When a region in which both are mixed is formed, the liquid repellency of the liquid repellent layer can be greatly improved. Furthermore, for example, the formation of a fine concave-convex structure such as the surface structure of a lotus leaf leads to the formation of a region in which a portion that is in contact with the raw material of the coating film and a portion that is not in contact with the raw material of the coating film are mixed. It is possible to greatly improve the liquid repellency of the liquid repellent layer. The number of projections may be one or two or more. The surface of the metal-containing layer facing the liquid-repellent layer preferably includes a plurality of protrusions. From the viewpoint of reducing coating streaks, the width of the protrusions is preferably 0.01 mm to 1 mm, more preferably 0.01 mm to 0.1 mm. When the number of projections is two or more, the average width of the projections is preferably 0.01 mm to 1 mm, more preferably 0.01 mm to 0.1 mm. From the viewpoint of reducing coating streaks, the height of the protrusions is preferably 0.001 mm to 1 mm, more preferably 0.001 mm to 0.05 mm. When the number of projections is two or more, the average height of the projections is preferably 0.001 mm to 1 mm, more preferably 0.001 mm to 0.05 mm. The ratio of the height of the protrusion to the width of the protrusion is preferably 0.01-1. The surface shape of the metal-containing layer is observed using an optical microscope (for example, optical microscope VHX-5000 manufactured by Keyence Corporation). The dimensions of the protrusions are measured using an optical microscope (for example, an optical microscope VHX-5000 manufactured by Keyence Corporation). However, when the surface shape feature of the metal-containing layer cannot be directly observed or measured, the surface shape feature of the liquid-repellent layer located on the metal-containing layer is regarded as the surface shape feature of the metal-containing layer.

From the viewpoint of adhesion durability of the liquid-repellent layer, the thickness of the metal-containing layer is preferably 1 μm to 20 μm, more preferably 1 μm to 10 μm. The thickness of the metal-containing layer is represented by the arithmetic mean of the thicknesses measured at five locations of the metal-containing layer in cross-sectional observation.

Examples of methods for forming the metal-containing layer include plating, sputtering, vapor deposition, and electroforming. From the viewpoint of formability of the metal-containing layer and adjustability of the surface shape of the metal-containing layer, the method of forming the metal-containing layer is preferably plating.

(Liquid-repellent layer)
The liquid-repellent layer is located on the metal-containing layer and contains a compound having a perfluoropolyether group (hereinafter sometimes referred to as "specific compound").

In the die head according to the present disclosure, it is presumed that the formation of the liquid-repellent layer on the metal-containing layer contributes to the improvement of the adhesion durability of the liquid-repellent layer. For example, a metal-containing layer positioned between the first tip surface of the first outer body and the liquid-repellent layer can improve adhesion between the first tip surface and the liquid-repellent layer. For example, a metal-containing layer positioned between the fourth side surface of the second outer body and the liquid-repellent layer can improve adhesion between the fourth side surface and the liquid-repellent layer. As a result, the adhesion durability of the liquid-repellent layer is improved.

Furthermore, in the die head according to the present disclosure, it is presumed that the liquid repellency of the liquid repellent layer formed at specific positions contributes to the reduction of coating streaks. For example, raw material discharged from a die head toward an object forms a puddle called a "bead" between the object and the tip of the die head. The beads form a three-phase interface at the outer surface of the die head. Specifically, the three-phase interface is composed of a bead, a die head, and air. The position of the three-phase boundary is not always constant during the process of discharging the raw material. In conventional methods of manufacturing coatings using a die head, complex bead behavior (eg, changes in the position of the three-phase interface) can cause some raw material to separate from the bead. When the raw material separated from the bead and the solidified material thereof are reintroduced into the bead, coating streaks may occur in the coating film. Coating streaks are more likely to occur as the amount of the raw material and its solidified material retaken into the bead increases. On the other hand, the liquid-repellent layer according to the present disclosure can reduce the adhesion and resistance of beads to the liquid-repellent layer. As a result, the liquid-repellent layer can reduce or prevent separation of a portion of the raw material from the beads even if the position of the three-phase interface changes on the surface of the liquid-repellent layer due to the complex behavior of the beads. Even if part of the raw material is separated from the bead, the liquid-repellent layer prevents the raw material separated from the bead from staying on the outer surface of the die head for a long time, and can minimize the occurrence of coating streaks. Therefore, it is estimated that coating streaks are reduced.

The liquid-repellent layer may be formed on part or all of the target area depending on the degree of the desired effect. The liquid-repellent layer preferably covers the entire surface of the metal-containing layer facing the liquid-repellent layer.

Constituent units of the perfluoropolyether group include, for example, -(OCF ₂ ) _n1 -, -(OC ₂ F ₄ ) _n2 -, -(OC ₃ F ₆ ) _n3 - and -(OC ₄ F ₈ ) _n4 - is mentioned. The perfluoropolyether group is selected from the group consisting of -(OCF ₂ ) _n1 -, -(OC ₂ F ₄ ) _n2 -, -(OC ₃ F ₆ ) _n3 - and -(OC ₄ F ₈ ) _n4 - It preferably contains at least one structural unit. The perfluoropolyether group is selected from the group consisting of -(OCF ₂ ) _n1 -, -(OC ₂ F ₄ ) _n2 -, -(OC ₃ F ₆ ) _n3 - and -(OC ₄ F ₈ ) _n4 - may contain at least two constitutional units. The perfluoropolyether group is selected from the group consisting of -(OCF ₂ ) _n1 -, -(OC ₂ F ₄ ) _n2 -, -(OC ₃ F ₆ ) _n3 - and -(OC ₄ F ₈ ) _n4 - may contain a structural unit having a structure in which at least two of The perfluoroalkylene group in -(OC ₃ F ₆ ) _n3 - and -(OC ₄ F ₈ ) _n4 - may be linear or branched. The perfluoroalkylene group in -(OC ₃ F ₆ ) _n3 - and -(OC ₄ F ₈ ) _n4 - is preferably linear. n1 to n4 each independently represent an integer of 1 or more. n1 to n4 are each independently preferably 2 or more, more preferably 20 to 200, even more preferably 30 to 200.

The specific compound preferably has, in addition to the perfluoropolyether group, a hydrolyzable group or a group containing a silicon atom bonded to a hydroxy group. A hydrolyzable group or a group containing a silicon atom bonded to a hydroxy group is preferably a group represented by —Si(R ^a ) _m (R ^b ) _3-m . In the group represented by —Si(R ^a ) _m (R ^b ) _3-m , R ^a represents a hydroxy group or a hydrolyzable group, and R ^b is a hydrogen atom having 1 to 22 carbon atoms. represents an alkyl group or -Y-Si(R ^c ) _p (R ^d ) _3-p , and m represents an integer of 1-3; Y represents a divalent organic group, R ^c has the same definition as R ^a , R ^d has the same definition as R ^b , and p represents an integer of 0-3.

Hydrolyzable groups include, for example, groups that give hydroxy groups upon hydrolysis. A silanol group (Si—OH) is formed by converting a hydrolyzable group attached to a silicon atom into a hydroxy group by hydrolysis. Specific hydrolyzable groups include, for example, alkoxy groups having 1 to 6 carbon atoms, cyano groups, acetoxy groups, chlorine atoms and isocyanate groups. The hydrolyzable group is preferably an alkoxy group or a cyano group having 1 to 6 carbon atoms (preferably 1 to 4), and an alkoxy group having 1 to 6 carbon atoms (preferably 1 to 4). It is more preferable to have

Examples of the divalent organic group represented by Y include an alkylene group, a group in which an alkylene group and an ether bond (--O--) are combined, and a group in which an alkylene group and an arylene group are combined.

Specific compounds include, for example, fluorine-containing silane compounds described in paragraphs 0034 to 0103 of JP-A-2015-200884. As the specific compound, for example, represented by formula (1a), formula (1b), formula (2a), formula (2b), formula (3a) or formula (3b) described in WO 2018/012344 compounds (that is, perfluoropolyether compounds). The contents of these documents are incorporated herein by reference.

The liquid repellent layer may be a layer having water repellency. The liquid repellent layer may be a layer having oil repellency. The liquid repellent layer may be a layer having water repellency and oil repellency. The liquid-repellent layer preferably has at least water repellency.

The falling angle of 0.05 mL of water with respect to the liquid-repellent layer is preferably 75° or less, more preferably 70° or less, and even more preferably 65° or less. Furthermore, the falling angle of 0.05 mL of water with respect to the liquid-repellent layer is preferably 60° or less, more preferably 55° or less, and even more preferably 50° or less. As the falling angle of water with respect to the liquid-repellent layer becomes smaller, it becomes more difficult for a part of the raw material to separate from the bead, and coating streaks are reduced. The falling angle of 0.05 mL of water with respect to the liquid-repellent layer may be greater than 0°. The falling angle of 0.05 mL of water with respect to the liquid-repellent layer may be 10° or more. The falling angle of 0.05 mL of water with respect to the liquid-repellent layer may be 20° or more. The falling angle of 0.05 mL of water with respect to the liquid-repellent layer may be 30° or more. The falling angle of water is measured by a sliding method using a contact angle meter under an environment of room temperature of 25° C. and relative humidity of 50%. The falling angle of water is represented by the angle of inclination of the liquid-repellent layer when a water droplet located on the liquid-repellent layer slides down. Examples of the contact angle meter include "DropMaster" (Kyowa Interface Science Co., Ltd.).

From the viewpoint of reducing coating streaks and antifouling properties, the static contact angle of 0.05 mL of water on the liquid-repellent layer is preferably 60° or more, more preferably 70° or more, and 80° or more. is more preferable. A static contact angle of 0.05 mL of water to the liquid-repellent layer may be 100° or less. A static contact angle of 0.05 mL of water to the liquid-repellent layer may be 90° or less. The static contact angle of water is measured using a contact angle meter under an environment of room temperature of 25° C. and relative humidity of 50%. Examples of the contact angle meter include "DropMaster" (Kyowa Interface Science Co., Ltd.).

The thickness of the liquid-repellent layer is preferably 0.01 μm to 1 μm, more preferably 0.01 μm to 0.1 μm, from the viewpoints of reduction of coating streaks and durability. The thickness of the liquid-repellent layer is represented by the arithmetic mean of the thicknesses measured at five points of the liquid-repellent layer in cross-sectional observation.

Examples of methods for forming the liquid-repellent layer include surface treatment using a specific compound. For example, the liquid-repellent layer is formed by drying and curing a composition containing a specific compound supplied on the metal-containing layer. Methods of supplying the composition containing the specific compound onto the metal-containing layer include, for example, brush coating, dip coating and spray coating.

Commercially available products of compositions containing specific compounds include, for example, "Fluorine-based ultra-thin coat MX-031" (Surf Industry Co., Ltd.), "Optool (registered trademark) DSX" (Daikin Industries, Ltd.), "Optool DSX- E" (Daikin Industries, Ltd.), "Optool UD100" (Daikin Industries, Ltd.), "KY-164" (Shin-Etsu Chemical Co., Ltd.) and "KY-108" (Shin-Etsu Chemical Co., Ltd.).

Prior to the surface treatment using the specific compound, the surface to be treated may be pretreated. Pretreatment includes, for example, acid treatment, alkali treatment, primer treatment, surface roughening treatment, and surface modification treatment with plasma.

(other components)
The die head may further include other components. Other components may be selected from known die head components depending on the purpose.

The die head may further include another body (ie, inner body) between the first outer body and the second outer body. The number of inner bodies may be one or more. The die head may include a first outer body, a second outer body, and a first inner body between the first outer body and the second outer body. A die head comprising a first outer body, a second outer body, and a first inner body between the first outer body and the second outer body, wherein the first inner body defines a first outlet. It preferably includes five sides and a sixth side defining a second outlet. That is, the first outlet is defined by the first side of the first outer body and the fifth side of the first inner body, and the second outlet is defined by the third side of the second outer body and the first inner body. and a sixth side of the body.

The die head may further include a member positioned between two adjacent bodies for adjusting the spacing between the two adjacent bodies. For example, the member that adjusts the spacing between two adjacent bodies can adjust the length of the outlet (ie, the size of the opening). For example, the member for adjusting the distance between two adjacent bodies can adjust the size of the space formed inside the die head for storing and transporting the raw material of the coating film. The shape of the member that adjusts the distance between two adjacent bodies is not limited. A plate-like member may be used as the member for adjusting the interval between two adjacent bodies.

The die head may further include members securing the plurality of bodies. For example, a bolt may be used as the member for fixing the plurality of main bodies.

(Die head according to the first embodiment)
A die head according to a first embodiment will be described below with reference to FIGS. 1 and 2. FIG. FIG. 1 is a schematic perspective view of a die head according to the first embodiment. FIG. FIG. 2 is a schematic cross-sectional view of a die head according to a first embodiment feeding raw materials for a coating film onto an object. 1 and 2, the direction X is orthogonal to the direction Y, the direction X is orthogonal to the direction Z, and the direction Y is orthogonal to the direction Z. FIG.

A die head 100 shown in FIGS. 1 and 2 is an example of a die head having a first ejection port.

Die head 100 includes a first outer body 10 and a second outer body 20 . The first outer body 10 and the second outer body 20 are aligned along the direction X. As shown in FIG. That is, the direction X corresponds to the parallel direction of the first outer body 10 and the second outer body 20 . The first outer body 10 and the second outer body 20 are fixed by bolts (not shown).

The first outer body 10 is arranged in direction X upstream of the second outer body 20 . The shape of the first outer body 10 is columnar with the direction Y as its longitudinal direction. The first outer body 10 includes a first distal surface 10A, a first side surface 10B and a second side surface 10C.

The first tip surface 10A is an end surface located at the tip of the first outer body 10 in the Z direction. The shape of the first distal end surface 10A observed in plan view is a rectangle with the direction Y as the longitudinal direction. As shown in FIG. 2, the first distal end surface 10A is directed toward the object F in the process of dispensing the composition L onto the object F. As shown in FIG. Composition L is the raw material for the coating film.

The first side surface 10B is connected to the first tip surface 10A and defines the first ejection port 30. As shown in FIG. The first side 10B faces the third side 20B of the second outer body 20 .

The second side surface 10C is connected to the first tip surface 10A at a position opposite to the first side surface 10B. 10 C of 2nd side surfaces incline with respect to the direction Z in the front-end|tip part of the die head 100. As shown in FIG. Specifically, the second side surface 10C extends closer to the first side surface 10B in the Z direction.

The second outer body 20 is arranged in the direction X downstream of the first outer body 10 . The shape of the second outer body 20 is columnar with the direction Y as its longitudinal direction. The second outer body 20 includes a third side surface 20A, a second distal surface 20B, and a fourth side surface 20C.

The second tip surface 20A is an end surface positioned at the tip of the second outer body 20 in the Z direction. The shape of the second distal end surface 20A observed in plan view is a rectangle with the direction Y as the longitudinal direction. As shown in FIG. 2, the second tip surface 20A is directed toward the object F in the process of dispensing the composition L onto the object F. As shown in FIG.

The third side surface 20B is connected to the second tip surface 20A and defines the first ejection port 30. As shown in FIG. The third side 20B faces the first side 10B of the first outer body 10 .

The fourth side surface 20C is connected to the second tip surface 20A at a position opposite to the third side surface 20B. 20 C of 4th side surfaces incline with respect to the direction Z in the front-end|tip part of the die head 100. As shown in FIG. Specifically, the fourth side surface 20C extends closer to the third side surface 20B in the Z direction.

The first ejection port 30 is an opening through which the composition L is ejected. The first outlet 30 is defined by the first side 10B of the first outer body 10 and the third side 20B of the second outer body 20 . The shape of the first ejection port 30 observed in plan view is a rectangle having the direction Y as its longitudinal direction. The first outlet 30 communicates with the space formed between the first outer body 10 and the second outer body 20 . A space formed between the first outer body 10 and the second outer body 20 can store and transfer the composition L.

Manifold 50 is a space formed between first outer body 10 and second outer body 20 . Manifold 50 is defined by a recess in first outer body 10 and a recess in second outer body 20 . Manifold 50 can temporarily store composition L.

The die head 100 includes a coating layer 20Cz. The covering layer 20Cz is formed on part of the fourth side surface 20C. The coating layer 20Cz includes a metal-containing layer (not shown) and a liquid-repellent layer (not shown). In the coating layer 20Cz, the metal-containing layer is in contact with the fourth side surface 20C, and the liquid-repellent layer is formed on the metal-containing layer in contact with the fourth side surface 20C.

A die head 100 can dispense a composition L onto an object F, as shown in FIG. The composition L is ejected from the ejection port 30 of the die head 100 . The composition L ejected from the ejection port 30 forms a bead B between the object F and the tip of the die head 100 . The bead B is a liquid pool formed by the ejected composition L. As shown in FIG. Bead B forms a three-phase interface at the outer surface of die head 100 . For example, in FIG. 2, a three-phase interface is formed on each of tip surface 10A and coating layer 20Cz. Even if the position of the three-phase interface changes on the coating layer 20Cz, the liquid-repellent layer in the coating layer 20Cz can reduce or prevent separation of a part of the raw material from the bead B. Therefore, the die head 100 can reduce coating streaks. The die head 100 may further include a coating layer including a metal-containing layer and a liquid-repellent layer on the distal end surface 10A of the first outer body 10 . Forming a coating layer on the tip surface 10A of the first outer body 10 can further reduce coating streaks.

(Die head according to the second embodiment)
The die head according to the second embodiment will be described below with reference to FIGS. 3 and 4. FIG. FIG. 3 is a schematic perspective view of a die head according to the second embodiment. FIG. 4 is a schematic cross-sectional view of a die head according to a second embodiment feeding raw materials for a coating film onto an object. 3 and 4, the direction X is orthogonal to the direction Y, the direction X is orthogonal to the direction Z, and the direction Y is orthogonal to the direction Z. FIG.

The configuration of the die head according to the second embodiment differs from that of the die head according to the first embodiment in the following respects. A die head according to the second embodiment has a second ejection port in addition to the first ejection port. A second embodiment of the die head includes a first inner body in addition to a first outer body and a second outer body. In the following description, matters overlapping with the description of the die head according to the first embodiment are omitted.

The die head 110 shown in FIGS. 3 and 4 is an example of a die head having first and second outlets.

Die head 110 includes a first outer body 10 , a second outer body 20 and a first inner body 40 . The first outer body 10, the second outer body 20 and the first inner body 40 are aligned along the direction X. As shown in FIG. That is, the direction X corresponds to the parallel direction of the first outer body 10 , the second outer body 20 and the first inner body 40 . The first outer body 10, the second outer body 20 and the first inner body 40 are fixed by bolts (not shown).

The first side surface 10B defines the first ejection port 30a.

The third side surface 20B defines a second outlet 30b.

The first inner body 40 is located between the first outer body 10 and the second outer body 20 . The shape of the first inner main body 40 is columnar with the direction Y as its longitudinal direction. The first inner body 40 includes a third distal side 40A, a fifth side _40B1 , and a sixth side _40B2 .

The third tip surface 40A is an end surface located at the tip of the first inner main body 40 in the Z direction. The shape of the third distal end face 40A observed in plan view is a rectangle with the direction Y as the longitudinal direction. As shown in FIG. 4, the third tip surface 40A is directed toward the object F in the process of dispensing the first composition _L1 and the second composition _L2 onto the object F. As shown in FIG. The first composition L ₁ and the second composition L ₂ are raw materials for the coating film.

The fifth side surface _40B1 is connected to the third tip surface 40A and defines the first ejection port 30a. The fifth side 40B ₁ faces the first side 10B of the first outer body 10 .

The sixth side surface 40B- ₂ is connected to the third tip surface 40A at a position opposite to the fifth side surface 40B _-1 , and defines the second outlet 30b. The sixth side _40B2 faces the third side 20B of the second outer body 20 .

The first ejection port 30a is an opening through which the first composition _L1 is ejected. The first outlet 30 a is defined by the first side 10 B of the first outer body 10 and the fifth side 40 B ₁ of the first inner body 40 . The first outlet 30a communicates with the space formed between the first outer body 10 and the first inner body 40 . A space formed between the first outer body 10 and the first inner body 40 can store and transport the first composition _L1 .

The first manifold 50 a is a space formed between the first outer body 10 and the first inner body 40 . The first manifold 50 a is defined by a recess in the first outer body 10 and a recess in the first inner body 40 . The first manifold 50a can temporarily store the first composition _L1 .

The second ejection port 30b is an opening through which the second composition _L2 is ejected. The second outlet 30 b is defined by the third side 20 B of the second outer body 20 and the sixth side 40 B ₂ of the first inner body 40 . The second outlet 30 b communicates with the space formed between the second outer body 20 and the first inner body 40 . A space formed between the second outer body 20 and the first inner body 40 can store and transport the second composition _L2 .

The second manifold 50 b is a space formed between the second outer body 20 and the first inner body 40 . The second manifold 50 b is defined by a recess in the second outer body 20 and a recess in the first inner body 40 . The second manifold 50b can temporarily store the second composition _L2 .

As shown in FIG. 4, a die head 110 can apply a first composition _L1 and a second composition _L2 onto a workpiece F. As shown in FIG. The first composition L ₁ is ejected from the ejection port 30 a of the die head 110 and the second composition L ₂ is ejected from the ejection port 30 b of the die head 110 . The first composition L ₁ ejected from the ejection port 30 a and the second composition L ₂ ejected from the ejection port 30 b form a bead B between the object F and the tip of the die head 110 . The bead B is a liquid pool formed by the ejected first composition _L1 and the ejected second composition _L2 . Bead B forms a three-phase interface at the outer surface of die head 110 . For example, in FIG. 4, a three-phase interface is formed on each of tip surface 10A and coating layer 20Cz. Even if the position of the three-phase interface changes on the coating layer 20Cz, the liquid-repellent layer in the coating layer 20Cz can reduce or prevent separation of a part of the raw material from the bead B. Therefore, the die head 110 can reduce coating streaks. The die head 110 may further include a coating layer including a metal-containing layer and a liquid-repellent layer on the distal end surface 10A of the first outer body 10 . Forming a coating layer on the tip surface 10A of the first outer body 10 can further reduce coating streaks.

<Coating device>
Hereinafter, a coating device according to one aspect of the present disclosure will be described. The coating device includes a die head.

Embodiments of the die head are described in the "Die Head" section above. Preferred embodiments of the die head are the same as the preferred embodiments of the die head described in the "Die Head" section above.

The coating device may further include other components. Other components may be selected from known coating apparatus components including a die head according to the purpose. Other components include, for example, a reservoir and a liquid delivery device. Examples of the storage container include a storage container for storing the raw material of the coating film. Examples of the liquid feeding device include a liquid feeding device that supplies the raw material of the coating film to the die head.

<Method for producing coating film>
Hereinafter, a method for manufacturing a coating film according to one aspect of the present disclosure will be described. A method of making a coating includes providing a die head and using the die head to dispense a composition onto an object to form a coating.

Embodiments of the die head are described in the "Die Head" section above. Preferred embodiments of the die head are the same as the preferred embodiments of the die head described in the "Die Head" section above.

Examples of the target include a base material. The type of base material is not limited. The substrate may be selected from known substrates depending on the application. Substrates include, for example, polyester-based substrates (e.g., polyethylene terephthalate and polyethylene naphthalate), cellulose-based substrates (e.g., diacetylcellulose and triacetylcellulose (TAC)), polycarbonate-based substrates, and poly(meth)acryl. base material (e.g., polymethyl methacrylate), polystyrene base material (e.g., polystyrene and acrylonitrile styrene copolymer), olefin base material (e.g., polyethylene, polypropylene, polyolefin having a cyclic structure, polyolefin having a norbornene structure and ethylene propylene copolymer), polyamide-based substrates (e.g., polyvinyl chloride, nylon and aromatic polyamide), polyimide-based substrates, polysulfone-based substrates, polyethersulfone-based substrates, polyetheretherketone-based substrates, Examples include polyphenylene sulfide-based substrates, vinyl alcohol-based substrates, polyvinylidene chloride-based substrates, polyvinyl butyral-based substrates, poly(meth)acrylate-based substrates, polyoxymethylene-based substrates, and epoxy resin-based substrates. The substrate may be a substrate comprising two or more polymers. The substrate may be a substrate comprising blended polymers.

From the viewpoint of transportability, the substrate is preferably a polymer film. When a polymer film is used as a substrate in optical film applications, the polymer film is preferably an optically isotropic polymer film.

In the application of the optical film, the light transmittance of the substrate is preferably 80% or more.

The shape of the substrate is not restricted. The substrate may be an elongated substrate.

The thickness of the substrate is not limited. The thickness of the substrate may be determined in consideration of the application. The thickness of the substrate is preferably 5 μm to 300 μm, more preferably 10 μm to 100 μm. The thickness of the substrate is represented by the arithmetic mean of the thicknesses measured at five locations on the substrate in cross-sectional observation.

The substrate may have a single layer structure or a multilayer structure. The substrate may contain a functional layer. Functional layers include, for example, adhesive layers, barrier layers, refractive index adjusting layers and alignment layers. Barrier layers include, for example, barrier layers against water or oxygen.

The transportation means of the object is not restricted. It is preferable that the means for conveying the object is a backup roller. A backup roller is a rotatable member. The object can be conveyed by rotating the backup roller. The backup roller can also be conveyed by winding the object. The backup roller can convey the object in a stretched state, and can improve the coating accuracy.

From the viewpoint of promoting drying of the composition and suppressing whitening of the coating film, the backup roller may be heated. For example, the whitening of the coating film is caused by the occurrence of fine dew condensation caused by a decrease in film surface temperature.

The surface temperature of the backup roller is preferably controlled by temperature control means. More preferably, the surface temperature of the backup roller is controlled by temperature control means based on the detected surface temperature.

Examples of temperature control means include heating means and cooling means. In the heating means, induction heating, water heating or oil heating may be used. Cooling by cooling water may be used in the cooling means.

The diameter of the backup roller is preferably 100 mm to 1,000 mm, more preferably 100 mm to 800 mm, from the viewpoints of easiness of wrapping the object, easiness of coating with a die head, and manufacturing cost of the backup roller. , 200 mm to 700 mm.

From the viewpoint of productivity and coating properties, the transfer speed of the object by the backup roller is preferably 10 m/min to 100 m/min.

From the viewpoint of stabilizing the conveyance of the object during coating and reducing the occurrence of unevenness in the thickness of the coating film, the wrap angle of the object with respect to the backup roller is preferably 60° or more, and is preferably 90° or more. more preferred. The upper limit of the wrap angle may be 180°. The wrap angle is an angle defined by the direction in which the object is conveyed when the object contacts the backup roller and the direction in which the object is conveyed when the object separates from the backup roller.

The type of composition is not limited. The composition may be selected from known compositions depending on the application.

The composition may contain a solvent. In general, the use of a solvent-containing composition tends to cause coating streaks. On the other hand, the die head according to the present disclosure can reduce coating streaks even in a coating film manufacturing method using a composition containing a solvent.

Examples of solvents include water and organic solvents. The organic solvent may be selected from known organic solvents that dissolve or disperse the ingredients contained in the composition. The composition preferably contains water. Examples of water include natural water, purified water, distilled water, ion-exchanged water, pure water, and ultrapure water.

When the composition contains water, the proportion of water in the solvent contained in the composition is preferably 90% by mass or more, more preferably 95% by mass or more, and particularly 100% by mass. preferable.

When the composition contains water, the content of water in the composition is preferably 40% by mass or more, more preferably 50% by mass or more, relative to the total mass of the composition. The water content in the composition is preferably less than 100% by mass, more preferably 80% by mass or less, relative to the total mass of the composition.

The solid content concentration of the composition is preferably less than 70% by mass, more preferably 30% to 60% by mass.

The viscosity of the composition at 25° C. and a shear rate of 1 s ⁻¹ is preferably 1 Pa·s to 1,000 Pa·s, more preferably 1 Pa·s to 100 Pa·s. The viscosity of the composition at 25° C. and a shear rate of 1 s ⁻¹ is measured using a cone and plate viscometer.

The composition may include particles. Examples of particles include inorganic particles, organic particles, and composite particles of an inorganic substance and an organic substance.

Inorganic particles include, for example, metal particles, metalloid particles, metal compound particles, metalloid compound particles, inorganic pigment particles, mineral particles, and polycrystalline diamond particles. Examples of metals include alkali metals, alkaline earth metals, transition metals and alloys thereof. Semimetals include, for example, silicon. Metal compounds and metalloid compounds include, for example, oxides, hydroxides and nitrides. Examples of inorganic pigments include carbon black. Minerals include, for example, mica.

Examples of organic particles include resin particles and organic pigment particles.

Examples of composite particles of an inorganic substance and an organic substance include composite particles in which inorganic particles are dispersed in a matrix of an organic substance, composite particles in which the periphery of an organic particle is coated with an inorganic substance, and composite particles in which an inorganic substance is surrounded by an organic substance. and coated composite particles.

The particles may be surface-treated to impart dispersibility. Composite particles may be formed by surface treatment.

The particle size, specific gravity and usage form of the particles are not limited. The particle size, specific gravity and usage form of the particles are determined, for example, according to the coating film formed from the composition and the conditions for producing the coating film.

The composition may contain one or more particles.

The content of particles in the composition is not limited. The content of the particles in the composition is determined, for example, according to the purpose of adding the particles, the coating film formed from the coating liquid, and the conditions for producing the coating film.

The components of the composition also include, for example, a binder component, a component that contributes to dispersibility of particles, a polymerizable compound, a polymerization initiator, and a component that enhances coating performance (eg, surfactant).

The composition may be a curable composition comprising a polymerizable compound or a crosslinkable compound. The composition may be a non-curable composition.

The composition may be a composition that forms an optically anisotropic layer. The composition forming the optically anisotropic layer contains, for example, a polymerizable liquid crystal compound, a polymerization initiator, a leveling agent, and an organic solvent, and has a solid concentration of 20% to 40% by mass. compositions. The composition forming the optically anisotropic layer may further contain other components. Other components include, for example, liquid crystal compounds other than polymerizable liquid crystal compounds, alignment control agents, surfactants, tilt angle control agents, alignment aids, plasticizers and cross-linking agents.

The composition may be a composition that forms a polarizing layer. The composition that forms the polarizing layer includes, for example, a liquid crystalline polymer, a dichroic compound, and an organic solvent that dissolves the liquid crystalline polymer and the dichroic compound, and has a solid concentration of 1% by mass. Compositions that are ˜7% by weight are included. The composition forming the polarizing layer may further contain other components. Other components include, for example, interfacial modifiers, polymerization initiators and various additives.

The composition may be a composition that forms a hard coat layer. The composition forming the hard coat layer includes, for example, a polymerizable compound (preferably a polyfunctional polymerizable compound), inorganic particles (preferably silica particles), a polymerization initiator, and an organic solvent, A composition having a solid content concentration of 40% to 60% by mass may be mentioned. The composition forming the hard coat layer may further contain other components. Other components include, for example, monomers and various additives.

The composition may be a composition that forms an alignment layer. The composition for forming the alignment layer includes, for example, polyvinyl alcohol (preferably modified polyvinyl alcohol having an acryloyl group), water, and an organic solvent, and has a solid content concentration of 1% by mass to 10% by mass. compositions. The composition forming the alignment layer may further contain other components. Other components include, for example, cross-linking agents.

The method of making the coating may include drying the composition dispensed onto the object. That is, the coating film may be formed through drying of the composition. A drying method is not limited. The composition may be dried by heating. The composition may be dried by being left in the atmosphere. The composition may be dried by blowing air.

A method of making a coating may include curing a composition dispensed onto an object. That is, the coating film may be formed through curing of the composition. The curing method is not restricted. The composition may be cured by heating. The composition may be cured by irradiation with light. Curing of the composition may be carried out after drying the composition.

The type of coating film is not limited. Coating films used in optical films include, for example, a hard coat layer, an optically anisotropic layer, a polarizing layer and a refractive index adjusting layer.

The thickness of the coating film is not limited. The thickness of the coating may be from 0.1 μm to 100 μm. The thickness of the coating film is preferably 5 μm or less, more preferably 0.1 μm to 5 μm. The thickness of the coating is represented by the arithmetic mean of the thicknesses measured at five locations on the coating in cross-sectional observation.

EXAMPLES The present disclosure will be described in detail below with reference to examples. However, the present disclosure is not limited to the following examples. Matters described in the following examples may be changed as appropriate within the scope of the purpose of the present disclosure.

<Preparation of die head 1A>
A die head 1A including the components shown in FIGS. 1 and 2 was produced by the following method. A first outer body was fabricated using cemented carbide (NM15, Nippon Tungsten Co., Ltd.) for the tip portion of the first outer body and stainless steel (SUS630) for the portion other than the tip portion of the first outer body. A second outer body was fabricated using cemented carbide (NM15, Nippon Tungsten Co., Ltd.) for the tip portion of the second outer body and stainless steel (SUS630) for the portion other than the tip portion of the second outer body. After forming a metal-containing layer (specifically, a Ni-containing layer) on a portion of the fourth side surface of the second outer body by electroless plating, surface treatment using MX-031 (Surf Industry Co., Ltd.) to form a liquid-repellent layer on the metal-containing layer. Table 1 shows the thickness of the metal-containing layer and the thickness of the liquid-repellent layer in the die head 1A.

The structural features of the die head 1A are shown below.
(1) Length of the first outlet in the parallel direction of the first outer body and the second outer body: 0.5 mm
(2) Length of the first tip surface in the parallel direction of the first outer body and the second outer body: 2 mm
(3) Length of the second tip surface in the parallel direction of the first outer body and the second outer body: 2 mm
(4) The angle between the first tip surface and the first side surface of the first outer body: 55°
(5) The angle between the first tip surface and the second side surface of the first outer body: 165°
(6) The angle formed by the second tip surface and the third side surface of the second outer body: 125°
(7) The angle formed by the second tip surface and the fourth side surface of the second outer body: 100°

<Preparation of die head 2A>
A die head 2A was fabricated in the same manner as the die head 1A except that a Cr-containing layer was formed by vapor deposition instead of the Ni-containing layer.

<Preparation of die heads 3A to 7A>
Die heads 3A to 7A were fabricated in the same manner as die head 1A, except that a Cr-containing layer was formed by sputtering instead of the Ni-containing layer. In manufacturing the die heads 3A to 7A, the surface shape of the Cr-containing layer (for example, the presence or absence of protrusions and the dimensions of the protrusions) was controlled mainly by adjusting the deposition temperature of sputtering. For example, as the film formation temperature decreases, it is difficult to form protrusions, or the size of protrusions tends to decrease. For example, as the film formation temperature increases, protrusions are likely to be formed, or the dimensions of the protrusions are likely to increase.

<Preparation of die head 8A>
A die head 8A was produced by the same method as the production method of the die head 1A, except that the metal-containing layer and the liquid-repellent layer were not formed.

<Preparation of die head 9A>
Die head 9A was produced by the same method as that of die head 1A, except that a silane coupling agent (KBM-5103, Shin-Etsu Chemical Co., Ltd.) was used instead of the Ni-containing layer to form a SiO ₂ -containing layer. . The _SiO2- containing layer of die head 9A is not a metal-containing layer.

<Preparation of die head 10A>
A die head 10A was fabricated by the same method as the die head 1A fabrication method, except that no metal-containing layer was formed.

<Preparation of base material>
A long triacetyl cellulose film (TD40UL, Fuji Film Co., Ltd., refractive index: 1.48, thickness: 60 μm, length: 1,000 m, width: 300 mm) was prepared as a substrate. Hereinafter, the triacetyl cellulose film is referred to as "TAC film".

<Preparation of composition A>
Composition A was prepared by mixing the following ingredients. The viscosity of Composition A at 25° C. and a shear rate of 1 s ⁻¹ is 6 Pa·s. The viscosity of composition A was measured using a cone plate viscometer MCR rheometer MCR72 (Anton Paar Japan Co., Ltd.).
- The following polymerizable liquid crystal compound L-9: 47.50 parts by weight - The following polymerizable liquid crystal compound L-10: 47.50 parts by weight - The following polymerizable liquid crystal compound L-3: 5.00 parts by weight - Below Polymerization initiator PI-1: 0.50 parts by mass The following leveling agent T-1 (weight average molecular weight: 10,000): 0.20 parts by mass Methyl ethyl ketone: 50.00 parts by mass

In the above chemical formula, one of R ¹ and R ² represents a methyl group, the other of R ¹ and R ² represents a hydrogen atom, one of R ³ and R ⁴ represents a methyl group, and the other of R ³ and R ⁴ represents a hydrogen atom. That is, each of the polymerizable liquid crystal compound L-9 and the polymerizable liquid crystal compound L-10 is a mixture of positional isomers having different positions of methyl groups.

<Preparation of composition B>
Composition B was prepared by mixing the following ingredients. The viscosity of Composition B at 25° C. and a shear rate of 1 s ⁻¹ is 67 Pa·s. The viscosity of Composition B was measured using the viscometer used to measure the viscosity of Composition A previously described.
・ Polyvinyl alcohol (CKS-50, degree of saponification: 99 mol%, degree of polymerization: 300, Nippon Synthetic Chemical Industry Co., Ltd.): 58 parts by mass ・ Cellogen PR (Daiichi Kogyo Seiyaku Co., Ltd.): 24 parts by mass ・ Surfactant Agent (Nippon Emulsion Co., Ltd., Emarex 710): 5 parts by mass Artpearl (registered trademark) J-7P aqueous dispersion: 413 parts by mass

An aqueous dispersion of Artpearl J-7P was prepared by the following method. To 74 parts by mass of pure water were added 3 parts by mass of Emarex 710 (Nippon Emulsion Co., Ltd., nonionic surfactant) and 3 parts by mass of carboxymethylcellulose sodium (Daiichi Kogyo Seiyaku Co., Ltd.). 20 parts by mass of Artpearl J-7P (Negami Kogyo Co., Ltd., silica composite crosslinked acrylic resin fine particles) was added to the resulting aqueous solution, and the mixture was spun at 10,000 rpm (revolutions per minute) using an Ace homogenizer (Nippon Seiki Seisakusho Co., Ltd.). ) for 15 minutes to obtain an aqueous dispersion of Artpearl J-7P (particle concentration: 20% by mass). The true specific gravity of the silica composite crosslinked acrylic resin fine particles in the obtained aqueous dispersion is 1.20, and the average particle size of the particles is 6.5 μm.

<Example 1>
Die head 1A was placed over the backup roller. The diameter of the backup roller is 300 mm. The second outer body of the die head 1A is arranged downstream of the first outer body of the die head 1A in the transport direction of the TAC film. Composition A was supplied onto the TAC film conveyed along the outer peripheral surface of the backup roller to form a coating film. Specific conditions in the supply process of composition A are shown below. The length of the coating is 100 m and the width of the coating is 250 mm.
・Surface temperature of backup roller: 60°C
・Lapping angle of TAC film with respect to backup roller: 150°
・Conveyance speed of TAC film: 30 m/min ・Gap between the first tip surface of the first outer body and the TAC film: 50 μm
・Gap between the second tip surface of the second outer body and the TAC film: 50 μm

<Examples 2 to 7 and Comparative Examples 1 to 3>
A coating film was formed by the same procedure as in Example 1, except that the type of die head was changed according to Table 1.

<Examples 8 to 14 and Comparative Examples 4 to 6>
A coating film was formed by the same procedure as in Example 1, except that the type of die head and the type of composition were changed according to Table 1.

<Evaluation: Separation of Composition in Dispensing Process>
A transparent back-up roller was provided with no means of temperature control. A camera is provided inside the transparent backup roller. The composition was fed onto a TAC film that was transported along the outer peripheral surface of a transparent backup roller. The type of die head, the type of composition, and the conditions were the same as in the above-described Examples and Comparative Examples, except that a transparent backup roller without temperature control means was used. A camera was used to observe the behavior of the composition on the fourth side of the second outer body during the process of the die head dispensing the composition. Composition separation was evaluated according to the following criteria.
A: No composition separated from the beads is observed.
B: A composition separated from the beads is observed. However, it is observed that the composition separated from the bead does not stay on the fourth side of the second outer body and returns to the bead.
C: A composition separated from the beads is observed. Furthermore, the composition separated from the beads is not observed to return to the beads.

<Evaluation: Coating Streaks>
The laminate containing the coating and TAC film was placed on a light table. Light emitted from a light table was applied to the coating film, and the coating film (length: 500 mm, width: 250 mm) was visually observed. Coating streaks were evaluated according to the following criteria.
A: No coating streak is observed.
B: Coating streaks are observed.

<Evaluation: Adhesion durability>
The die head was immersed in methyl ethyl ketone at room temperature of 25° C. for one week. The die head was removed from the methyl ethyl ketone, and the surface of the liquid-repellent layer was rubbed 100 times with Bemcot (Asahi Kasei Corporation) containing methyl ethyl ketone. The liquid-repellent layer was visually observed, and the adhesion durability of the liquid-repellent layer was evaluated according to the following criteria.
A: No peeling of the liquid-repellent layer is observed.
B: Peeling of the liquid-repellent layer of less than 100 μm square is observed.
C: Peeling of the liquid-repellent layer of 100 μm square or more is observed.

The width and height of the protrusions listed in Table 1 are average values measured using an optical microscope (VHX-5000, Keyence Corporation). "-" written in the column of "Width of projection" and the column of "Height of projection" in Table 1 indicates that there is no projection.

The "static contact angle of water" listed in Table 1 is the static contact angle of 0.05 mL of water on the liquid-repellent layer (except for the fourth side of the second outer body for die heads that do not include a liquid-repellent layer). represents an angle. The static contact angle of water was measured using a contact angle meter (MCA-J2, Kyowa Interface Science Co., Ltd.) under an environment of room temperature of 25° C. and relative humidity of 50%.

The "falling angle of water" listed in Table 1 represents the falling angle of 0.05 mL of water against the liquid repellent layer (except for the fourth side of the second outer body for die heads that do not include a liquid repellent layer). The falling angle of water was measured using a contact angle meter (MCA-J2, Kyowa Interface Science Co., Ltd.) under an environment of room temperature of 25° C. and relative humidity of 50%.

Table 1 shows that Examples 1 to 7 are superior to Comparative Examples 2 to 3 in terms of reduction of coating streaks and adhesion durability of the liquid-repellent layer, and that Examples 1 to 7 are superior to Comparative Examples 5 and 6. 8 to 14 are superior. A comparison between Examples 1 to 7 and Comparative Example 1 and a comparison between Examples 8 to 14 and Comparative Example 4 show that the liquid-repellent layer contributes to the reduction of coating streaks. The comparison between Examples 1-7 and Comparative Examples 2-3 and the comparison between Examples 8-14 and Comparative Examples 5-6 show that the metal-containing layer contributes to the improvement of the adhesion durability of the liquid-repellent layer. is shown. Furthermore, Table 1 shows that the surface shape of the metal-containing layer affects the surface shape of the liquid-repellent layer. Specifically, the protrusions formed on the surface of the metal-containing layer form protrusions on the surface of the liquid-repellent layer located on the metal-containing layer, contributing to the reduction of coating streaks.

10: First Outer Body 10A: First Tip Surface of First Outer Body 10B: First Side of First Outer Body 10C: Second Side of First Outer Body 20: Second Outer Body 20A: Second Outer Body Second tip surface 20B: Third side surface of second outer body 20C: Fourth side surface of second outer body 20Cz: Coating layer 30: First outlet 30a: First outlet 30b: Second outlet 40: First outlet Inner main body 40A: First tip surface of first inner main body _40B1 : Fifth side surface of first inner main body _40B2 : Sixth side surface of first inner main body 50: Manifold 50a: First manifold 50b: Second manifold 100: Die head 110: Die head B: Bead F: Object L: Composition _L1 : First composition _L2 : Second composition

Claims (8)

a first tip surface, a first side surface that is connected to the first tip surface and defines a first outlet, and a second side surface that is connected to the first tip surface at a position opposite to the first side surface; and a first outer body comprising
a second distal end surface facing the first side of the first outer body and connected to the second distal surface to define the first outlet or a second outlet different from the first outlet; a second outer body including a third side surface and a fourth side surface opposite the third side surface and connected to the second distal surface;
a metal-containing layer positioned on at least one surface selected from the group consisting of the first distal surface of the first outer body and the fourth side surface of the second outer body;
a liquid-repellent layer located on the metal-containing layer and containing a compound having a perfluoropolyether group;
including die head. The die head of claim 1, wherein the surface of the metal-containing layer facing the liquid-repellent layer comprises protrusions having a width of 0.01 mm to 1 mm and a height of 0.1 mm to 1 mm. The die head according to claim 1 or 2, wherein the falling angle of 0.05 mL of water with respect to the liquid-repellent layer is 55° or less. The die head of any one of claims 1-3, wherein the third side of the second outer body defines the first outlet. The die head of any one of claims 1-3, wherein the third side of the second outer body defines the second outlet. 6. The metal-containing layer of any one of claims 1-5, wherein the metal-containing layer is located on each of the first distal surface of the first outer body and the fourth side surface of the second outer body. die head. Preparing the die head according to any one of claims 1 to 6;
supplying a composition onto an object using the die head to form a coating;
A method for producing a coating film comprising. The method for producing a coating film according to claim 7, wherein the viscosity of the composition at 25°C and a shear rate of 1 s ^-1 is from 1 Pa·s to 1,000 Pa·s.

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