CN116252424A - Die and method for producing coating film - Google Patents

Abstract

The present invention relates to a die and a method for producing a coating film, and provides a die having excellent adhesion durability of a lyophobic layer and reduced coating streaks, the die comprising: a 1 st outer body including a 1 st front end surface, a 1 st side surface connected to the 1 st front end surface and defining a 1 st discharge port, and a 2 nd side surface connected to the 1 st front end surface at a position opposite to the 1 st side surface; a 2 nd outer body including a 2 nd front end surface, a 1 st side surface facing the 1 st outer body and connected to the 2 nd front end surface, a 3 rd side surface defining a 1 st discharge port or a 2 nd discharge port different from the 1 st discharge port, and a 4 th side surface connected to the 2 nd front end surface at a position opposite to the 3 rd side surface; a metal-containing layer located on at least 1 face selected from the group consisting of a 1 st front end face of a 1 st outer body and a 4 th side face of a 2 nd outer body; and a lyophobic layer located on the metal-containing layer and containing a compound having a perfluoropolyether group.

Description

Die and method for producing coating film

Technical Field

The present invention relates to a die and a method for producing a coating film.

Background

For example, a method of forming a coating film on an object is used in a coating apparatus having a die. In the above method, the die ejects the raw material (e.g., composition) of the coating film.

Patent document 1 discloses a device for producing a coated member in which a coating film is formed on a surface of a member to be coated which moves relatively to a discharge port. The discharge port is formed between the pair of lip tip portions. In the manufacturing apparatus of the coated member, the contact angle of water in the front end portion of the downstream side lip is larger than the contact angle of water in the front end portion of the upstream side lip. In one example of a die used in the apparatus for producing the coated member, the contact angle of water in the tip portion of the downstream lip is increased by coating the waterproof layer of the tip portion of the downstream lip.

Patent document 2 discloses a die coating apparatus used when a transparent conductive layer is formed by applying a coating liquid for forming a transparent conductive layer containing at least a metal material to a transparent substrate. The die coating device comprises a die for discharging the coating liquid for forming the transparent conductive layer, a coating liquid tank for accommodating the coating liquid for forming the transparent conductive layer, and a liquid conveying path for conveying the coating liquid for forming the transparent conductive layer from the coating liquid tank to the die. In the die, a lyophobic region is formed at least on a surface located in a direction opposite to the coating direction.

Patent document 1: japanese patent laid-open No. 2002-248399

Patent document 2: japanese patent laid-open publication 2016-068047

Although a method of reducing or preventing defects of a coating film has been studied in the previous studies on a die, streak-like defects (hereinafter, referred to as "coating streaks") are still observed in a coating film formed using a die in some cases. In addition, for example, the lyophobic layer of the conventional die may be peeled off by various factors such as a solvent. The lyophobic layer is a layer having lyophobicity. In the above-described cases, it is required to improve the adhesion durability of the lyophobic layer of the die while reducing the coating stripes.

Disclosure of Invention

An object of an embodiment of the present invention is to provide a die having excellent adhesion durability of a lyophobic layer and reduced coating streaks. Another embodiment of the present invention is directed to a method for producing a coating film using the die.

The present invention includes the following means.

1 > a die comprising: a 1 st outer body including a 1 st front end surface, a 1 st side surface connected to the 1 st front end surface and defining a 1 st discharge port, and a 2 nd side surface connected to the 1 st front end surface at a position opposite to the 1 st side surface; a 2 nd outer body including a 2 nd front end surface, a 3 rd side surface facing the 1 st side surface of the 1 st outer body and connected to the 2 nd front end surface, and defining the 1 st discharge port or a 2 nd discharge port different from the 1 st discharge port, and a 4 th side surface connected to the 2 nd front end surface at a position opposite to the 3 rd side surface; a metal-containing layer located on at least 1 surface selected from the group consisting of the 1 st front end surface of the 1 st outer body and the 4 th side surface of the 2 nd outer body; and a lyophobic layer which is located on the metal-containing layer and contains a compound having a perfluoropolyether group.

The die according to < 2 > to < 1 >, wherein,

the surface of the metal-containing layer facing the lyophobic layer includes protrusions having a width of 0.01 to 1mm and a height of 0.1 to 1 mm.

The die head described as < 3 > according to < 1 > or < 2 >, wherein,

the slip angle of 0.05mL of water on the lyophobic layer is less than 55 degrees.

A die according to any one of < 1 > to < 3 > wherein,

the 3 rd side surface of the 2 nd outer body defines the 1 st discharge port.

A die according to any one of < 1 > to < 3 > wherein,

the 3 rd side surface of the 2 nd outer body defines the 2 nd discharge port.

A die according to any one of < 1 > to < 5 > wherein,

the metal-containing layer is located on the 1 st front end surface of the 1 st outer body and the 4 th side surface of the 2 nd outer body, respectively.

< 7 > a method for producing a coating film, comprising:

a step of preparing a die according to any one of < 1 > to < 6 >; a kind of electronic device with high-pressure air-conditioning system

And a step of forming a coating film by supplying the composition onto an object using the die.

A method for producing a coating film according to < 8 > to < 7 >, wherein,

25 ℃ and 1s ^-1 The viscosity of the composition at the shear rate is 1 Pa.s to 1,000 Pa.s.

Effects of the invention

According to an embodiment of the present invention, there is provided a die having excellent adhesion durability of a lyophobic layer and reduced coating streaks. According to another embodiment of the present invention, there is provided a method for producing a coating film using the die.

Drawings

Fig. 1 is a schematic perspective view of a die head according to embodiment 1.

Fig. 2 is a schematic cross-sectional view of a die according to embodiment 1 for supplying a coating film raw material to an object.

Fig. 3 is a schematic perspective view of a die according to embodiment 2.

Fig. 4 is a schematic cross-sectional view of a die according to embodiment 2 for supplying a coating film raw material to an object.

Detailed Description

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

In the case where the embodiments of the present invention are described with reference to the drawings, description of the constituent elements and symbols repeated in the drawings may be omitted. Unless otherwise specified, constituent elements denoted by the same reference numerals in the drawings refer to the same constituent elements. The ratio of the dimensions in the drawings does not necessarily represent the ratio of the actual dimensions.

In the present invention, the numerical range indicated by the term "to" means a range in which the numerical values before and after the term "to" are included as a lower limit value and an upper limit value, respectively. In the numerical ranges described in stages in the present invention, the upper limit or the lower limit described in a certain numerical range may be replaced with the upper limit or the lower limit of the numerical range described in other stages. In the numerical ranges described in the present invention, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples.

In the present invention, the amounts of the respective components in the composition, when a plurality of substances corresponding to the respective components are present in the composition, refer to the total amount of the plurality of substances present in the composition unless otherwise specified.

In the present invention, ordinal words (for example, "1 st" and "2 nd") are terms used to distinguish components, and do not limit the number of components and the merits of the components.

In the present invention, "mass%" and "weight%" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning.

In the present invention, a combination of 2 or more preferred modes is a more preferred mode.

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

In the present invention, the term "solid component" means a component other than a solvent. The liquid component other than the solvent is contained in the solid component.

< die >

A die according to an embodiment of the present invention will be described below. The die head comprises a 1 st outer body, a 2 nd outer body, a metal-containing layer, and a lyophobic layer. In the present invention, "1 st outer body" and "2 nd outer body" refer to 2 bodies located at positions away from the center of the die among a plurality of bodies included in the die. For example, in the case where 3 bodies are arranged in a certain direction, 2 bodies located at both ends correspond to "outer bodies", respectively. In the present invention, the body disposed between 2 outer bodies is sometimes referred to as an "inner body". In the present invention, the "lyophobic layer" means a layer having lyophobicity. Examples of the liquid repellency include water repellency and oil repellency. For example, in a method of forming a coating film on an object, a die can supply a raw material (e.g., composition) of the coating film onto the object.

(1 st outer body)

The 1 st outer body includes a 1 st front end face, a 1 st side face, and a 2 nd side face. The 1 st side surface is connected to the 1 st front end surface and defines a 1 st discharge port. The 2 nd side surface is connected to the 1 st front end surface at a position opposite to the 1 st side surface. The 1 st outer body may also include other faces depending on the shape of the object.

The 1 st front end face is an end face located at the front end of the 1 st outer body. For example, in the process of supplying the raw material of the coating film to the object, the 1 st front end face is directed to the object. The shape of the 1 st front end surface as seen in plan view is preferably a quadrangle having 4 interior angles each of which is a right angle. In a quadrilateral with 4 interior angles that are all right angles, the length of side 1 is preferably not equal to the length of side 2 that is orthogonal to side 1. From the viewpoint of the processability of the die, the length of the 1 st front end surface in the direction in which the 1 st outer body and the 2 nd outer body are juxtaposed is preferably 0.01mm to 3mm.

The angle between the 1 st front end face and the 1 st side face is preferably 45 DEG to 135 deg. The angle formed by the front end surface 1 and the side surface 1 can be 45-90 degrees. The connection portion between the 1 st front end face and the 1 st side face may be a curved face. When the connection portion between the 1 st front end surface and the 1 st side surface is a curved surface, the angle between the 1 st front end surface and the 1 st side surface is represented by the angle between the extension line of the 1 st front end surface and the extension line of the 1 st side surface.

The angle between the 1 st front end face and the 2 nd side face is preferably 90 ° to 170 °. The connection portion between the 1 st front end face and the 2 nd side face may be a curved face. When the connecting portion between the 1 st front end face and the 2 nd side face is a curved face, the angle between the 1 st front end face and the 2 nd side face is represented by the angle between the extension line of the 1 st front end face and the extension line of the 2 nd side face.

The 1 st discharge port is an opening for discharging the raw material of the coating film. The discharge opening of the die may be only the 1 st discharge opening. For example, a die having 1 discharge opening is used for monolayer coating. Single-layer coating can form 1 layer coating film on an object. The repetition of single-layer coating can be applied to a method of forming a coating film of 2 or more layers on an object. The die may have more than 2 discharge ports. For example, the die may have two of the 1 st discharge port and the 2 nd discharge port described later. For example, a die having 2 discharge ports is used for multilayer coating. The multilayer coating can form 2 or more coating films on the object.

The 1 st discharge opening is defined by at least the 1 st side surface of the 1 st outer body. The 1 st discharge port may be defined by a 1 st outer body and a 2 nd outer body. Specifically, the 1 st discharge port can be defined by the 1 st side surface of the 1 st outer body and the 3 rd side surface of the 2 nd outer body. The mode of the 2 nd outer body is as follows. On the other hand, in the case where the die further includes another body (i.e., an inner body) between the 1 st outer body and the 2 nd outer body, the 1 st discharge port is preferably defined by the 1 st side surface of the 1 st outer body and the surface of the inner body. The manner of the inner body is as follows.

The 1 st discharge port preferably has a square shape with 4 interior corners each having a right angle in plan view. In a quadrilateral with 4 interior angles that are all right angles, the length of side 1 is preferably not equal to the length of side 2 that is orthogonal to side 1. That is, a quadrangle with 4 interior angles all being right angles is preferably not a square.

The length of the 1 st discharge port (i.e., the size of the opening) in the direction in which the 1 st outer body and the 2 nd outer body are aligned is preferably 0.1mm to 1mm from the viewpoint of making the pressure loss of the raw material of the coating film flowing inside the die toward the 1 st discharge port uniform in the width direction of the coating film.

The 1 st discharge port may communicate with a space for storing or transferring a raw material of the coating film formed inside the die. The space for storing or transferring the raw material of the coating film can be defined by the adjacent 2 bodies.

The 1 st outer body may comprise a recess defining a manifold. The recess may be defined by a plane, a curved surface or a combination of plane and curved surface. The manifold is a space formed inside the die head, and can temporarily store the raw material of the coating film.

Examples of the material of the 1 st outer body include metals. Examples of the metal include stainless steel, cemented carbide (for example, NIPPON TUNGSTEN CO., LTD. Manufactured by NM 15), and ultrafine particle alloy (for example, TF15 manufactured by Mitsubishi Materials Corporation). The material of the 1 st outer body may be a material other than metal. Examples of the material other than metal include ceramics. The front end portion of the 1 st outer body may be formed of a super hard alloy or a super grain alloy, and portions other than the front end portion of the 1 st outer body may be formed of stainless steel. The 1 st outer body may be formed by a combination of a plurality of components.

(2 nd outer body)

The 2 nd outer body includes a 2 nd front end face, a 3 rd side face, and a 4 th side face. The 3 rd side faces the 1 st side of the 1 st outer body and is connected to the 2 nd front end face and defines a 1 st discharge port or a 2 nd discharge port different from the 1 st discharge port. The 3 rd side may define the 1 st discharge port. The 3 rd side may define the 2 nd discharge port. The object of the discharge opening defined by the 3 rd side is determined according to the number of discharge openings included in the die. The 4 th side surface is connected to the 2 nd front end surface at a position opposite to the 3 rd side surface. The 2 nd outer body may also include other faces depending on the shape of the target.

The 2 nd front end face is an end face located at the front end of the 2 nd outer side main body. For example, the 2 nd distal end face is directed to the object in the process of supplying the raw material of the coating film to the object. The shape of the 2 nd front end surface as seen in plan view is preferably a quadrangle having 4 inner corners each at a right angle. In a quadrilateral with 4 interior angles that are all right angles, the length of side 1 is preferably not equal to the length of side 2 that is orthogonal to side 1. That is, a quadrangle with 4 interior angles all being right angles is preferably not a square. From the viewpoint of the processability of the die, the length of the 2 nd distal end face in the direction in which the 1 st outer body and the 2 nd outer body are juxtaposed is preferably 0.01mm to 3mm.

The angle between the 2 nd front end face and the 3 rd side face is preferably 75 to 150 degrees. The connection portion of the 2 nd front end face and the 3 rd side face may be a curved face. When the connecting portion between the 2 nd distal end face and the 3 rd side face is a curved face, the angle between the 2 nd distal end face and the 3 rd side face is represented by the angle between the extension line of the 2 nd distal end face and the extension line of the 3 rd side face.

The angle between the 2 nd front end face and the 4 th side face is preferably 60 DEG to 150 deg. The connection portion of the 2 nd front end face and the 4 th side face may be a curved face. When the connecting portion between the 2 nd distal end face and the 4 th side face is a curved face, the angle between the 2 nd distal end face and the 4 th side face is represented by the angle between the extension line of the 2 nd distal end face and the extension line of the 4 th side face.

The 2 nd discharge port is an opening for discharging the raw material of the coating film. In the case of the die having the 2 nd discharge port, the 2 nd discharge port is defined at least by the 3 rd side surface of the 2 nd outer body. In the case where the die further includes another body (i.e., an inner body) between the 1 st outer body and the 2 nd outer body, the 2 nd discharge port is preferably defined by the 3 rd side surface of the 2 nd outer body and the surface of the inner body. The manner of the inner body is as follows.

The shape of the 2 nd discharge port in plan view is preferably a quadrangle having 4 inner corners each at a right angle. In a quadrilateral with 4 interior angles that are all right angles, the length of side 1 is preferably not equal to the length of side 2 that is orthogonal to side 1.

The length of the 2 nd discharge port (i.e., the size of the opening) in the direction in which the 1 st outer body and the 2 nd outer body are aligned is preferably 0.1mm to 1.0mm from the viewpoint of making the pressure loss of the raw material of the coating film flowing inside the die toward the 2 nd discharge port uniform in the width direction of the coating film.

The 2 nd discharge port may communicate with a space for storing or transferring a raw material of the coating film formed inside the die. The space for storing or transferring the raw material of the coating film can be defined by the adjacent 2 bodies.

The 2 nd outer body may include a recess defining a manifold. The recess may be defined by a plane, a curved surface or a combination of plane and curved surface.

As the material of the 2 nd outer body, for example, metal is cited. Examples of the metal include stainless steel, cemented carbide (for example, NIPPON TUNGSTEN CO., LTD. Manufactured by NM 15), and ultrafine particle alloy (for example, TF15 manufactured by Mitsubishi Materials Corporation). The material of the 2 nd outer body may be a material other than metal. Examples of the material other than metal include ceramics. The front end portion of the 2 nd outer body may be formed of a super hard alloy or a super grain alloy, and portions other than the front end portion of the 2 nd outer body may be formed of stainless steel. The 2 nd outer body may be formed by a combination of a plurality of components.

(containing a Metal layer)

The metal-containing layer is located on at least 1 face selected from the group consisting of the 1 st front face of the 1 st outer body and the 4 th side face of the 2 nd outer body. As will be described later, the metal-containing layer contributes to improvement in adhesion durability of the lyophobic layer.

The metal-containing layer may be located on the 1 st front face of the 1 st outer body or the 4 th side of the 2 nd outer body. The metal-containing layer is preferably located on the 1 st front end face of the 1 st outer body and the 4 th side face of the 2 nd outer body, respectively. That is, the die preferably comprises a metal-containing layer on the 1 st front face of the 1 st outer body and a metal-containing layer on the 4 th side of the 2 nd outer body. The metal-containing layer may be formed in a part or the whole of the object region according to the degree of effect of the object. The metal-containing layer preferably covers the entire area of the 1 st front end face of the 1 st outer body. The metal-containing layer preferably covers the entire area of the area in contact with the raw material of the coating film in the 4 th side face of the 2 nd outer body.

Examples of the metal element contained in the metal-containing layer include Ti, cr, fe, co, ni and Fe. From the viewpoint of surface coatability, the metal-containing layer preferably contains at least 1 metal element selected from the group consisting of Ti, cr, fe, co, ni and Fe, more preferably contains at least 1 metal element selected from the group consisting of Cr and Ni. 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 comprise an alloy. The metal-containing layer may also contain other components.

Regarding the metal-containing layer located between the 1 st front end face of the 1 st outer body and the lyophobic layer or between the 4 th side face of the 2 nd outer body and the lyophobic layer, the surface of the metal-containing layer facing the lyophobic layer preferably contains projections. "surface of the metal-containing layer facing the lyophobic layer" means a surface facing the lyophobic layer among the surfaces of the metal-containing layer. Protrusions formed on the surface of the metal-containing layer facing the lyophobic layer form irregularities on the surface of the lyophobic layer located on the metal-containing layer, thereby improving the lyophobicity of the lyophobic layer. For example, when the surface of the lyophobic layer is in contact with the material of the coating film, the lyophobic property of the lyophobic layer can be greatly improved if the region where the portion in contact with the material of the coating film and the portion not in contact with the material of the coating film coexist is formed by the irregularities formed on the surface of the lyophobic layer. Further, for example, forming a minute uneven structure such as a lotus leaf surface structure promotes the formation of a region where a portion in contact with the raw material of the coating film and a portion not in contact with the raw material of the coating film coexist, and can greatly improve the liquid repellency of the liquid repellent layer. The number of projections may be 1 or 2 or more. The surface of the metal-containing layer facing the lyophobic layer preferably comprises a plurality of protrusions. The width of the projections is preferably 0.01mm to 1mm, more preferably 0.01mm to 0.1mm, from the viewpoint of reducing the coating streaks. When the number of projections is 2 or more, the average value of the widths of the projections is preferably 0.01mm to 1mm, more preferably 0.01mm to 0.1mm. The height of the protrusions is preferably 0.001mm to 1mm, more preferably 0.001mm to 0.05mm, from the viewpoint of reducing the coating streaks. When the number of projections is 2 or more, the average value of the heights of the projections is preferably 0.001mm to 1mm, more preferably 0.001mm to 0.05mm. The ratio of the height of the protrusions to the width of the protrusions is preferably 0.01 to 1. The surface shape of the metal-containing layer was observed by using an optical microscope (for example, optical microscope VHX-5000 manufactured by KEYENCE CORPORATION). The dimensions of the protrusions were measured using an optical microscope (e.g., optical microscope VHX-5000 manufactured by KEYENCE CORPORATION). However, when the characteristic of the surface shape of the metal-containing layer cannot be directly observed or measured, the characteristic of the surface shape of the lyophobic layer located on the metal-containing layer is regarded as the characteristic of the surface shape of the metal-containing layer.

The thickness of the metal-containing layer is preferably 1 μm to 20 μm, more preferably 1 μm to 10 μm, from the viewpoint of adhesion durability of the lyophobic layer. The thickness of the metal-containing layer is expressed by the arithmetic average of the thicknesses measured at 5 sites of the metal-containing layer in cross-sectional view.

Examples of the method for forming the metal-containing layer include electroplating, sputtering, vapor deposition, and electroforming. The method for forming the metal-containing layer is preferably electroplating from the viewpoints of formability of the metal-containing layer and adjustability of the surface shape of the metal-containing layer.

(lyophobic layer)

The lyophobic 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 according to the present invention, it is presumed that the formation of the lyophobic layer on the metal-containing layer contributes to the improvement of adhesion durability of the lyophobic layer. For example, the metal-containing layer located between the 1 st front end surface of the 1 st outer body and the lyophobic layer can improve adhesion between the 1 st front end surface and the lyophobic layer. For example, the metal-containing layer located between the 4 th side surface of the 2 nd outer body and the lyophobic layer can improve adhesion between the 4 th side surface and the lyophobic layer. As a result, the adhesion durability of the lyophobic layer is improved.

In the die according to the present invention, it is assumed that the lyophobicity of the lyophobic layer formed at a specific position contributes to reduction of coating streaks. For example, a stock material discharged from a die toward a target forms a reservoir called a "bead" between the target and the tip of the die. The reinforcing ribs form a three-phase interface outside the die head. Specifically, the three-phase interface is composed of reinforcing ribs, a die head and air. The position of the three-phase interface is not always constant during the discharge of the raw material. In the conventional method for producing a coating film using a die, a complicated behavior of the rib (for example, a change in the position of a three-phase interface) may cause a part of the raw material to separate from the rib. When the raw material separated from the bead and the cured product thereof enter the bead again, coating streaks may occur on the coating film. The more the amount of the material and the cured product thereof that re-enter the bead, the more easily the coating streaks are generated. On the other hand, the lyophobic layer according to the present invention can reduce the adhesion force and resistance of the reinforcing rib to the lyophobic layer. As a result, even if the position of the three-phase interface is changed on the surface of the lyophobic layer by the complicated behavior of the reinforcing rib, the lyophobic layer can reduce or prevent a part of the raw material from being separated from the reinforcing rib. Even if a part of the raw material is separated from the bead, the lyophobic layer can suppress the raw material separated from the bead from remaining on the outside of the die for a long time, and can suppress the occurrence of coating streaks to a minimum. Therefore, it is presumed that the coating streaks are reduced.

The lyophobic layer may be formed at a part or the whole area of the object area according to the degree of effect of the object. The lyophobic layer preferably covers the entire area of the surface of the metal-containing layer facing the lyophobic layer.

Examples of the structural unit of the perfluoropolyether group include- (OCF) ₂ ) _n1 -、-(OC ₂ F ₄ ) _n2 -、-(OC ₃ F ₆ ) _n3 -and- (OC) ₄ F ₈ ) _n4 -. The perfluoropolyether group preferably contains a group 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 -at least 1 structural unit of the group. The perfluoropolyether group may contain a compound 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 -at least 2 building blocks of the group. The perfluoropolyether group may be 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 -at least 2 structural units of the connected structure of the group. - (OC) ₃ F ₆ ) _n3 -and- (OC) ₄ F ₈ ) _n4 The perfluoroalkylene groups in (E) may be linear or branched. - (OC) ₃ F ₆ ) _n3 -and- (OC) ₄ F ₈ ) _n4 The perfluoroalkylene groups in (E) are 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, and still more preferably 30 to 200.

The specific compound is preferably a group having a hydrolyzable group or a group containing a silicon atom bonded to a hydroxyl group, in addition to the perfluoropolyether group. The hydrolyzable group or group containing a silicon atom bonded to a hydroxyl group is preferably a group consisting of-Si (R ^a ) _m (R ^b ) _3-m A group represented by the formula (I). from-Si (R) ^a ) _m (R ^b ) _3-m In the radicals represented, R ^a Represents a hydroxyl group or a hydrolyzable group, R ^b Represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or-Y-Si (R) ^c ) _p (R ^d ) _3-p M represents an integer of 1 to 3. Y represents a 2-valent organic group, R ^c Meaning of (C) and R ^a R has the same meaning as R ^d Meaning of (C) and R ^b P represents an integer of 0 to 3.

Examples of the hydrolyzable group include a group that generates a hydroxyl group by hydrolysis. The hydrolyzable group bonded to the silicon atom is converted into a hydroxyl group by hydrolysis, thereby forming a silanol group (si—oh). Specific examples of the hydrolyzable group include an alkoxy group having 1 to 6 carbon atoms, a cyano group, an acetoxy group, a chlorine atom and an isocyanate group. The hydrolyzable group is preferably an alkoxy group or a cyano group having 1 to 6 carbon atoms (preferably 1 to 4), more preferably an alkoxy group having 1 to 6 carbon atoms (preferably 1 to 4).

Examples of the organic group having a valence of 2 represented by Y include an alkylene group, a group formed by combining an alkylene group with an ether bond (-O-) and a group formed by combining an alkylene group with an arylene group.

Specific examples of the compound include the fluorosilane compounds described in paragraphs 0034 to 0103 of JP-A2015-200884. Specific examples of the compound include compounds represented by formula (1 a), formula (1 b), formula (2 a), formula (2 b), formula (3 a) and formula (3 b) (i.e., perfluoropolyether compounds) described in international publication No. 2018/012344. The contents of these documents are incorporated into the present specification by reference.

The lyophobic layer may be a layer having water repellency. The oleophobic layer can be a layer that has oil repellency. The lyophobic layer may be a layer having water repellency and oil repellency. The lyophobic layer preferably has at least water repellency.

The slip angle of 0.05mL of water relative to the lyophobic layer is preferably 75 ° or less, more preferably 70 ° or less, and further preferably 65 ° or less. The slip angle of 0.05mL of water relative to the lyophobic layer is preferably 60 ° or less, more preferably 55 ° or less, and further preferably 50 ° or less. As the slip angle of water with respect to the lyophobic layer becomes smaller, a part of the raw material is less likely to separate from the reinforcing rib, and the coating streak decreases. The slip angle of 0.05mL of water relative to the lyophobic layer may exceed 0 °. The slip angle of 0.05mL of water relative to the lyophobic layer may be 10 ° or more. The slip angle of 0.05mL of water relative to the lyophobic layer may be 20 ° or more. The slip angle of 0.05mL of water relative to the lyophobic layer may be 30 ° or more. The slip angle of water was measured by a slip method using a contact angle meter at room temperature of 25 ℃ and a relative humidity of 50%. The slip angle of water is represented by the tilt angle of the lyophobic layer when a water drop on the lyophobic layer slips off. Examples of the contact angle measuring instrument include "dropdmaster" (Kyowa Interface Science co., ltd).

From the viewpoint of reduction of the coating streaks and stain resistance, the static contact angle of 0.05mL of water with respect to the lyophobic layer is preferably 60 ° or more, more preferably 70 ° or more, and still more preferably 80 ° or more. The static contact angle of 0.05mL of water with respect to the lyophobic layer may be 100 ° or less. The static contact angle of 0.05mL of water with respect to the lyophobic layer may be 90 ° or less. The static contact angle of water was measured at room temperature of 25℃and relative humidity of 50% using a contact angle measuring instrument. Examples of the contact angle measuring instrument include "dropdmaster" (Kyowa Interface Science co., ltd).

From the viewpoints of reduction of the coating stripes and durability, the thickness of the lyophobic layer is preferably 0.01 μm to 1 μm, more preferably 0.01 μm to 0.1 μm. The thickness of the lyophobic layer is expressed by arithmetic average of thicknesses measured at 5 sites of the lyophobic layer in cross-sectional view.

Examples of the method for forming the lyophobic layer include surface treatment with a specific compound. For example, the lyophobic layer is formed by drying and curing a composition containing a specific compound supplied onto the metal-containing layer. Examples of the method for applying the composition containing the specific compound to the metal-containing layer include brushing, dipping, and spraying.

Examples of the commercial products of the composition containing the specific compound include "fluorine-based ultra-thin film coating MX-031" (surfkogyo corporation), "OPTOOL (registered trademark) DSX" (DAIKIN INDUSTRIES, LTD.), "OPTOOLDSX-E" (DAIKIN INDUSTRIES, LTD.), "OPTOOLUD100" (DAIKIN INDUSTRIES, LTD.), "KY-164" (Shin-Etsu Chemical Co., ltd.) and "KY-108" (Shin-Etsu Chemical Co., ltd.).

The surface to be treated may be subjected to pretreatment prior to the surface treatment with the specific compound. Examples of the pretreatment include an acid treatment, an alkali treatment, a primer treatment, a surface roughening treatment, and a surface modification treatment by plasma.

(other constituent elements)

The die may also contain other components. The other components may be selected from known components of a die according to the purpose.

The die may also include other bodies (i.e., inner bodies) between the 1 st outer body and the 2 nd outer body. The number of the inner body may be 1 or 2 or more. The die may include a 1 st outer body, a 2 nd outer body, and a 1 st inner body between the 1 st outer body and the 2 nd outer body. In a die comprising a 1 st outer body, a 2 nd outer body, and a 1 st inner body between the 1 st outer body and the 2 nd outer body, the 1 st inner body preferably comprises a 5 th side surface defining a 1 st discharge port and a 6 th side surface defining a 2 nd discharge port. That is, the 1 st discharge port can be defined by the 1 st side surface of the 1 st outer body and the 5 th side surface of the 1 st inner body, and the 2 nd discharge port can be defined by the 3 rd side surface of the 2 nd outer body and the 6 th side surface of the 1 st inner body.

The die may further comprise a member located between the adjacent 2 bodies and adjusting the interval of the adjacent 2 bodies. For example, the member for adjusting the interval between the adjacent 2 bodies can adjust the length of the discharge opening (i.e., the size of the opening). For example, the means for adjusting the interval between the adjacent 2 bodies can adjust the size of the space for storing and transferring the raw material of the coating film formed inside the die. The shape of the member for adjusting the interval between the adjacent 2 bodies is not limited. The member for adjusting the interval between the adjacent 2 bodies may be a plate-like member.

The die may also include a member for securing the plurality of bodies. As a member for fixing the plurality of bodies, bolts are exemplified.

(die head according to embodiment 1)

The die according to embodiment 1 will be described below with reference to fig. 1 and 2. Fig. 1 is a schematic perspective view of a die head according to embodiment 1. Fig. 2 is a schematic cross-sectional view of a die according to embodiment 1 for supplying a coating film raw material to an object. In fig. 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.

The die 100 shown in fig. 1 and 2 is an example of a die having a 1 st discharge port.

Die 100 includes an outer body 10, 1 st, and an outer body 20, 2 nd. The 1 st outer body 10 and the 2 nd outer body 20 are aligned along the direction X. That is, the direction X corresponds to the direction in which the 1 st outer body 10 and the 2 nd outer body 20 are aligned. The 1 st outer body 10 and the 2 nd outer body 20 are fixed by bolts (not shown).

The 1 st outer body 10 is disposed further upstream in the direction X than the 2 nd outer body 20. The 1 st outer body 10 has a columnar shape with the direction Y as the longitudinal direction. The 1 st outer main body 10 includes a 1 st front end surface 10A, a 1 st side surface 10B, and a 2 nd side surface 10C.

The 1 st front end surface 10A is an end surface located at the front end of the 1 st outer body 10 in the direction Z. The 1 st front end surface 10A has a rectangular shape with the direction Y as the longitudinal direction in plan view. As shown in fig. 2, the 1 st front end surface 10A faces the object F in the process of supplying the composition L onto the object F. Composition L is a raw material of the coating film.

The 1 st side surface 10B is connected to the 1 st front end surface 10A and defines a 1 st discharge port 30. The 1 st side surface 10B faces the 3 rd side surface 20B of the 2 nd outer body 20.

The 2 nd side surface 10C is connected to the 1 st front end surface 10A at a position opposite to the 1 st side surface 10B. In the front end portion of the die 100, the 2 nd side 10C is inclined with respect to the direction Z. Specifically, the 2 nd side 10C extends to be close to the 1 st side 10B with the direction Z.

The 2 nd outer body 20 is disposed further downstream in the direction X than the 1 st outer body 10. The 2 nd outer body 20 has a columnar shape with the direction Y as the longitudinal direction. The 2 nd outer body 20 includes a 3 rd side surface 20A, a 2 nd front end surface 20B, and a 4 th side surface 20C.

The 2 nd front end surface 20A is an end surface located at the front end of the 2 nd outer body 20 in the direction Z. The shape of the 2 nd distal end surface 20A in plan view is rectangular with the direction Y being the longitudinal direction. As shown in fig. 2, the 2 nd distal end surface 20A is directed toward the object F in the process of supplying the composition L onto the object F.

The 3 rd side surface 20B is connected to the 2 nd front end surface 20A and defines the 1 st discharge port 30. The 3 rd side 20B faces the 1 st side 10B of the 1 st outer body 10.

The 4 th side surface 20C is connected to the 2 nd front end surface 20A at a position opposite to the 3 rd side surface 20B. In the front end portion of the die 100, the 4 th side 20C is inclined with respect to the direction Z. Specifically, the 4 th side 20C extends to be close to the 3 rd side 20B with the direction Z.

The 1 st discharge port 30 is an opening through which the composition L is discharged. The 1 st discharge port 30 is defined by the 1 st side surface 10B of the 1 st outer body 10 and the 3 rd side surface 20B of the 2 nd outer body 20. The 1 st discharge port 30 has a rectangular shape with the direction Y as the longitudinal direction in plan view. The 1 st discharge port 30 communicates with a space formed between the 1 st outer body 10 and the 2 nd outer body 20. The space formed between the 1 st outer body 10 and the 2 nd outer body 20 can store and transfer the composition L.

The manifold 50 is a space formed between the 1 st outer body 10 and the 2 nd outer body 20. The manifold 50 is defined by the recess of the 1 st outer body 10 and the recess of the 2 nd outer body 20. The manifold 50 is capable of temporarily storing the composition L.

Die 100 includes coating layer 20Cz. The coating layer 20Cz is formed on a portion of the 4 th side surface 20C. The coating layer 20Cz includes a metal-containing layer (not shown) and a lyophobic layer (not shown). In the coating layer 20Cz, a metal-containing layer is in contact with the 4 th side 20C, and a lyophobic layer is formed on the metal-containing layer in contact with the 4 th side 20C.

As shown in fig. 2, the die 100 is capable of supplying the composition L onto the object F. Composition L is discharged from discharge port 30 of die 100. The composition L discharged from the discharge port 30 forms a rib B between the object F and the tip of the die 100. The rib B is a reservoir formed by the discharged composition L. The rib B forms a three-phase interface outside the die 100. For example, in fig. 2, three-phase interfaces are formed on the front end face 10A and the coating layer 20Cz, respectively. Even if the position of the three-phase interface varies on the coating layer 20Cz, the lyophobic layer in the coating layer 20Cz can reduce or prevent a part of the raw material from being separated from the reinforcing rib B. Thus, the die 100 can reduce coating stripes. The die 100 may further include a coating layer including a metal-containing layer and a lyophobic layer on the front end surface 10A of the 1 st outer body 10. Forming a coating layer on the front end surface 10A of the 1 st outer body 10 can further reduce coating streaks.

(die head according to embodiment 2)

The die according to embodiment 2 will be described below with reference to fig. 3 and 4. Fig. 3 is a schematic perspective view of a die according to embodiment 2. Fig. 4 is a schematic cross-sectional view of a die according to embodiment 2 for supplying a coating film raw material to an object. In fig. 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.

The structure of the die according to embodiment 2 is different from that of the die according to embodiment 1 in the following matters. The die according to embodiment 2 has a 2 nd discharge port in addition to the 1 st discharge port. The die according to embodiment 2 includes a 1 st inner body in addition to a 1 st outer body and a 2 nd outer body. In the following description, the overlapping matters of the description of the die head according to embodiment 1 will be omitted.

The die 110 shown in fig. 3 and 4 is an example of a die having a 1 st discharge port and a 2 nd discharge port.

Die head 110 includes outer body 10, outer body 20, and inner body 40, 1 st. The 1 st outer body 10, the 2 nd outer body 20, and the 1 st inner body 40 are aligned along the direction X. That is, the direction X corresponds to the direction in which the 1 st outer body 10, the 2 nd outer body 20, and the 1 st inner body 40 are aligned. The 1 st outer body 10, the 2 nd outer body 20, and the 1 st inner body 40 are fixed by bolts (not shown).

The 1 st side surface 10B defines a 1 st discharge port 30a.

Side 20B 3 defines discharge port 30B 2.

The 1 st inner body 40 is located between the 1 st outer body 10 and the 2 nd outer body 20. The 1 st inner body 40 has a columnar shape with the direction Y as the longitudinal direction. The 1 st inner body 40 includes a 3 rd front end surface 40A and a 5 th side surface 40B ₁ Side 6B ₂ 。

The 3 rd front end surface 40A is an end surface located at the front end of the 1 st inner body 40 in the direction Z. The 3 rd front end surface 40A has a rectangular shape as viewed in plan with the direction Y being the longitudinal direction. As shown in FIG. 4, the 3 rd front face 40A is formed by mixing the 1 st composition L ₁ Composition 2L ₂ Toward the object F during the supply to the object F. Composition 1L ₁ Composition 2L ₂ Is a raw material of a coating film.

5 th side 40B ₁ Is connected to the 3 rd front end surface 40A and defines the 1 st discharge port 30A. 5 th side 40B ₁ The 1 st side surface 10B of the 1 st outer body 10.

6 th side 40B ₂ At the 5 th side 40B ₁ And in the opposite position, is connected to the 3 rd front end surface 40A and defines the 2 nd discharge port 30b. 6 th side 40B ₂ And a 3 rd side 20B facing the 2 nd outer body 20.

The 1 st discharge port 30a discharges the 1 st composition L ₁ Is provided. The 1 st discharge port 30a passes through the 1 st side surface 10B of the 1 st outer body 10 and the 5 th side surface 40B of the 1 st inner body 40 ₁ To delineate. The 1 st discharge port 30a communicates with a space formed between the 1 st outer body 10 and the 1 st inner body 40. The 1 st composition L can be stored and transferred in the space formed between the 1 st outer body 10 and the 1 st inner body 40 ₁ 。

The 1 st manifold 50a is a space formed between the 1 st outer body 10 and the 1 st inner body 40. The 1 st manifold 50a is defined by the recess of the 1 st outer body 10 and the recess of the 1 st inner body 40. The 1 st manifold 50a is capable of temporarily storing the 1 st composition L ₁ 。

The 2 nd discharge port 30b discharges the 2 nd composition L ₂ Is provided. The 2 nd discharge port 30B passes through the 3 rd side surface 20B of the 2 nd outer body 20 and the 6 th side surface 40B of the 1 st inner body 40 ₂ To delineate. The 2 nd discharge port 30b communicates with a space formed between the 2 nd outer body 20 and the 1 st inner body 40. The space formed between the 2 nd outer body 20 and the 1 st inner body 40 is capable of storing and transferring the 2 nd composition L ₂ 。

The 2 nd manifold 50b is a space formed between the 2 nd outer body 20 and the 1 st inner body 40. The 2 nd manifold 50b is defined by the recess of the 2 nd outer body 20 and the recess of the 1 st inner body 40. The 2 nd manifold 50b is capable of temporarily storing the 2 nd composition L ₂ 。

As shown in FIG. 4, die 110 is capable of applying composition 1L ₁ Composition 2L ₂ Is supplied to the object F. Composition 1L ₁ Discharge from discharge port 30a of die head 110, composition 2L ₂ And discharged from discharge port 30b of die head 110. Composition 1 st L discharged from discharge port 30a ₁ And the 2 nd composition L discharged from the discharge port 30b ₂ A rib B is formed between object F and the front end of die head 110. The reinforcing rib B is the 1 st composition L discharged by spitting ₁ Composition No. 2L discharged ₂ A liquid storage part is formed. The rib B forms a three-phase interface outside the die head 110. For example, in fig. 4, three-phase interfaces are formed on the front end face 10A and the coating layer 20Cz, respectively. Even if the position of the three-phase interface varies on the coating layer 20Cz, the lyophobic layer in the coating layer 20Cz can reduce or prevent a part of the raw material from being separated from the reinforcing rib B. Thus, the die head 110 can reduce coating stripes. The die head 110 may further include a coating layer including a metal-containing layer and a lyophobic layer on the front end surface 10A of the 1 st outer body 10. Forming a coating layer on the front end surface 10A of the 1 st outer body 10 can further reduce coating streaks.

< coating device >)

A coating apparatus according to an embodiment of the present invention will be described below. The coating device comprises a die head.

The manner of the die is described in the section "die" above. The preferred manner of the die is the same as that described in the above section of "die".

The coating device may also contain other structural elements. The other components may be selected from known components of a coating apparatus including a die according to the purpose. Examples of the other components include a storage container and a liquid feeding device. Examples of the storage container include a storage container for storing a raw material of a coating film. Examples of the liquid feeding device include a liquid feeding device that feeds a raw material of a coating film to a die.

Method for producing coating film

A method for producing a coating film according to one embodiment of the present invention will be described below. The method for producing a coating film includes a step of preparing a die and a step of forming a coating film by supplying the composition onto an object using the die.

The manner of the die is described in the section "die" above. The preferred manner of the die is the same as that described in the above section of "die".

Examples of the object include a base material. The kind of the substrate is not limited. The substrate may be selected from known substrates according to the use. Examples of the substrate include polyester substrates (for example, polyethylene terephthalate and polyethylene naphthalate), cellulose substrates (for example, diacetyl cellulose and triacetyl cellulose (TAC)), polycarbonate substrates, poly (meth) acryl substrates (for example, polymethyl methacrylate), polystyrene substrates (for example, polystyrene and acrylonitrile styrene copolymer), olefin substrates (for example, polyethylene, polypropylene, polyolefin having a cyclic structure, polyolefin having a norbornene structure and ethylene propylene copolymer), polyamide substrates (for example, polyvinyl chloride, nylon and aromatic polyamide), polyimide substrates, polysulfone substrates, polyethersulfone substrates, polyetheretherketone substrates, polyphenylene sulfide substrates, vinyl alcohol substrates, polyvinylidene chloride substrates, polyvinyl butyral substrates, poly (meth) acrylate substrates, polyoxymethylene substrates and epoxy resin substrates. The substrate may be a substrate containing 2 or more polymers. The substrate may be a substrate comprising a conjunct polymer.

From the viewpoint of transport property, the substrate is preferably a polymer film. In the case of using a polymer film as a substrate in the use of an optical film, 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 limited. The substrate may be a long strip of substrate.

The thickness of the substrate is not limited. The thickness of the substrate may be determined in consideration of the use. The thickness of the base material is preferably 5 μm to 300. Mu.m, more preferably 10 μm to 100. Mu.m. The thickness of the substrate is expressed by arithmetic mean of the thicknesses measured at 5 portions of the substrate in cross-sectional view.

The substrate may have a single-layer structure or a multi-layer structure. The substrate may comprise a functional layer. Examples of the functional layer include an adhesive layer, a barrier layer, a refractive index adjusting layer, and an alignment layer. Examples of the barrier layer include a barrier layer against water or oxygen.

The conveying device for the object is not limited. The object conveying device is preferably a backup roller. The support roller is a rotatable member. The object can be conveyed by rotating the support roller. The backup roller can also be conveyed by winding the object. The support roller can be conveyed in a state of stretching the object and can improve coating accuracy.

The support roll may be heated from the viewpoint of promoting drying of the composition and suppressing whitening of the coating film. For example, whitening of a coating film is caused by occurrence of fine dew condensation due to a decrease in the film surface temperature.

The surface temperature of the backup roll is preferably controlled by a temperature control device. The surface temperature of the backup roll is more preferably controlled in accordance with the detected surface temperature and by a temperature control means.

Examples of the temperature control device include a heating device and a cooling device. In the heating device, induction heating, water heating, or oil heating may be used. In the cooling device, cooling based on cooling water may be used.

The diameter of the backup roll is preferably 100mm to 1,000mm, more preferably 100mm to 800mm, even more preferably 200mm to 700mm, from the viewpoints of ease of winding the object, ease of coating by the die, and manufacturing and use of the backup roll.

From the viewpoint of productivity and coatability, the conveyance speed of the object by the support roller is preferably 10 m/min to 100 m/min.

The coating angle of the object with respect to the support roller is preferably 60 ° or more, more preferably 90 ° or more, from the viewpoint of stabilizing the conveyance of the object at the time of coating and reducing the occurrence of uneven thickness of the coating film. The upper limit of the cladding angle may be 180 °. The wrapping angle is a predetermined angle in the conveying direction of the object when the object is in contact with the support roller and in the conveying direction of the object when the object is separated from the support roller.

The kind of the composition is not limited. The composition may be selected from known compositions according to the purpose.

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 according to the present invention can reduce coating streaks even in a method for producing a coating film using a solvent-containing composition.

Examples of the solvent include water and an organic solvent. The organic solvent may be selected from known organic solvents that dissolve or disperse the components contained in the composition. The composition preferably contains water. Examples of the 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 preferably 100% by mass.

When the composition contains water, the water content 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 mass%, more preferably 80 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% by mass to 60% by mass.

At 25 ℃ and 1s ^-1 The viscosity of the composition at the shear rate is preferably 1pa·s to 1,000pa·s, more preferably 1pa·s to 100pa·s. At 25 ℃ and 1s ^-1 The viscosity of the composition at the shear rate of (2) was measured using a cone-plate viscometer.

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

Examples of the inorganic particles include metal particles, semimetal particles, metal compound particles, semimetal compound particles, inorganic pigment particles, mineral particles, and polycrystalline diamond particles. Examples of the metal include alkali metals, alkaline earth metals, transition metals, and alloys thereof. Examples of the semi-metal include silicon. Examples of the metal compound and the semimetal compound include oxides, hydroxides, and nitrides. Examples of the inorganic pigment include carbon black. Examples of the minerals include mica.

Examples of the organic particles include particles of a resin and particles of an organic pigment.

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

In order to impart dispersibility, surface treatment may be applied to the particles. The composite particles may be formed by surface treatment.

The particle size, specific gravity and mode of use of the particles are not limited. The particle diameter, specific gravity and use form of the particles are determined, for example, by the coating film formed from the composition and the conditions under which the coating film is produced.

The composition may comprise 1 or more than 2 particles.

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

Examples of the components of the composition include a binder component, a component contributing to dispersibility of particles, a polymerizable compound, a polymerization initiator, and a component (for example, a surfactant) for improving coating performance.

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 for forming an optically anisotropic layer. Examples of the composition for forming the optically anisotropic layer include a composition containing a polymerizable liquid crystal compound, a polymerization initiator, a leveling agent, and an organic solvent, and having a solid content of 20 to 40 mass%. The optically anisotropic layer-forming composition may also contain other components. Examples of the other components include liquid crystal compounds other than polymerizable liquid crystal compounds, alignment controlling agents, surfactants, tilt angle controlling agents, alignment aids, plasticizers, and crosslinking agents.

The composition may be a composition that forms a polarizing layer. Examples of the composition for forming the polarizing layer include a composition containing a liquid crystalline polymer, a dichroic compound, and an organic solvent for dissolving the liquid crystalline polymer and the dichroic compound, and having a solid content concentration of 1 to 7 mass%. The composition forming the polarizing layer may further contain other components. Examples of the other components include a surface modifier, a polymerization initiator, and various additives.

The composition may be a hard coat layer forming composition. Examples of the composition for forming the hard coat layer include a composition containing a polymerizable compound (preferably a polyfunctional polymerizable compound), inorganic particles (preferably silica particles), a polymerization initiator, and an organic solvent, and having a solid content of 40 to 60 mass%. The hard coat layer-forming composition may also contain other components. Examples of the other components include monomers and various additives.

The composition may be an orientation layer-forming composition. Examples of the composition for forming the alignment layer include a composition containing polyvinyl alcohol (preferably modified polyvinyl alcohol having an acryl group), water, and an organic solvent, and having a solid content of 1 to 10 mass%. The composition for forming the alignment layer may further contain other components. Examples of the other component include a crosslinking agent.

The method for producing a coating film may include a step of drying the composition supplied to the object. That is, the coating film may be formed via drying of the composition. The drying method is not limited. The composition may be dried by heating. The composition may be dried by leaving it in the atmosphere. The composition may be dried by air blowing.

The method for producing a coating film may include a step of curing the composition supplied to the object. That is, the coating film may be formed via curing of the composition. The curing method is not limited. The composition may be cured by heating. The composition may be cured by irradiation with light. The curing of the composition may be performed after drying the composition.

The kind of the coating film is not limited. Examples of the coating film used for the optical film include 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 film may be 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 film was expressed by arithmetic average of the thicknesses measured at 5 sites of the coating film in section observation.

Examples

The present invention will be described in detail with reference to examples. However, the present invention is not limited to the following examples. The matters described in the following examples can be appropriately changed within the scope of the object of the present invention.

Preparation of die 1A

The die 1A including the constituent elements shown in fig. 1 and 2 was manufactured by the following method. The 1 st outer body was fabricated using a cemented carbide (NM 15, NIPPON tunesten co., ltd.) at the front end portion of the 1 st outer body and stainless steel (SUS 630) at a portion other than the front end portion of the 1 st outer body. A 2 nd outer body was fabricated using a cemented carbide (NM 15, NIPPON tunesten co., ltd.) at the front end portion of the 2 nd outer body and stainless steel (SUS 630) at a portion other than the front end portion of the 2 nd outer body. After a metal-containing layer (specifically, a Ni-containing layer) is formed on a portion of the 4 th side surface of the 2 nd outer body by electroless plating, a lyophobic layer is formed on the metal-containing layer by surface treatment using MX-031 (surfkogyo corporation). The thickness of the metal-containing layer in the die 1A and the thickness of the lyophobic layer are shown in table 1.

Features concerning the structure of the die head 1A are shown below.

(1) Length of the 1 st discharge port in the direction of juxtaposition of the 1 st outer body and the 2 nd outer body: 0.5mm

(2) Length of the 1 st front end surface in the parallel direction of the 1 st outer body and the 2 nd outer body: 2mm of

(3) Length of the 2 nd front end surface in the parallel direction of the 1 st outer body and the 2 nd outer body: 2mm of

(4) Angle formed by the 1 st front end surface and the 1 st side surface in the 1 st outer main body: 55 degree

(5) Angle formed by the 1 st front end surface and the 2 nd side surface in the 1 st outer main body: 165 degree

(6) Angle formed by the 2 nd front end surface and the 3 rd side surface in the 2 nd outer main body: 125 °

(7) Angle formed by the 2 nd front end surface and the 4 th side surface in the 2 nd outer main body: 100 degree

Preparation of die 2A

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

Preparation of dies 3A to 7A

Dies 3A to 7A were produced in the same manner as the production method of die 1A except that the Cr-containing layer was formed by sputtering instead of the Ni-containing layer. In the production dies 3A to 7A, the surface shape of the Cr-containing layer (for example, the presence or absence of projections and the size of projections) is controlled mainly by adjustment of the film formation temperature by sputtering. For example, as the film forming temperature becomes lower, it is difficult to form projections or the size of projections becomes smaller. For example, as the film formation temperature becomes higher, the projections are easily formed or the size of the projections is easily increased.

Preparation of die 8A

A die 8A was produced in the same manner as the production method of the die 1A except that the metal-containing layer and the lyophobic layer were not formed.

Preparation of die 9A

SiO-containing formation using a silane coupling agent (KBM-5103, shin-Etsu Chemical Co., ltd.) ₂ The die 9A was produced by the same method as the production method of the die 1A except that the layer was replaced with the Ni-containing layer. SiO-containing of die 9A ₂ The layer is not a metal-containing layer.

Preparation of die 10A

The die 10A was produced by the same method as the production method of the die 1A except that the metal-containing layer was not formed.

Preparation of substrate

As a base material, a long triacetyl cellulose film (TD 40UL, FUJIFILM Corporation, refractive index: 1.48, thickness: 60 μm, length: 1,000m, width: 300 mm) was prepared. Hereinafter, the triacetyl cellulose film is referred to as "TAC film".

< preparation of composition A >

Composition a was prepared by mixing the following ingredients. At 25 ℃ and 1s ^-1 The viscosity of composition A at the shear rate of (2) was 6 Pa.s. The viscosity of composition a was measured using a cone-plate viscometer MCR rheometer MCR72 (Anton Paar Japan k.k.).

The following polymerizable liquid crystal compound L-9:47.50 parts by mass

The following polymerizable liquid crystal compound L-10:47.50 parts by mass

The following polymerizable liquid crystal compound L-3:5.00 parts by mass

The following polymerization initiator PI-1:0.50 part by mass

The following leveling agent T-1 (weight average molecular weight: 10,000): 0.20 part by mass

Methyl ethyl ketone: 50.00 parts by mass

[ chemical formula 1]

In the chemical formula, R ¹ R is R ² One of them represents methyl, R ¹ R is R ² The other of (A) represents a hydrogen atom, R ³ R is R ⁴ One of them represents methyl, R ³ R is R ⁴ And the other of them represents a hydrogen atom. That is, the polymerizable liquid crystal compound L-9 and the polymerizable liquid crystal compound L-10 are each a mixture of positional isomers having different methyl groups.

[ chemical formula 2]

< preparation of composition B >

Composition B was prepared by mixing the following ingredients. At 25 ℃ and 1s ^-1 The viscosity of composition B at the shear rate of (2) was 67 Pa.s. The viscosity of the composition B was measured using a viscometer used for measuring the viscosity of the composition A described above.

Polyvinyl alcohol (CKS-50, saponification degree: 99 mol%, polymerization degree: 300, nippon Synthetic Chemical Industry co., ltd.): 58 parts by mass

CELLOGENPR (DKS co.ltd.): 24 parts by mass

Surfactant (NIHON EMULSION co., ltd., EMALEX 710): 5 parts by mass

Water-dispersible product of ART PEARL (registered trademark) J-7P: 413 parts by mass

The aqueous dispersion of ART PEARLJ-7P was prepared by the following method. To 74 parts by mass of pure water, 3 parts by mass of EMALEX710 (NIHON EMULSION co., ltd., nonionic surfactant) and 3 parts by mass of sodium carboxymethyl cellulose (DKS co.ltd.) were added. To the obtained aqueous solution, 20 parts by mass of ART PEARLJ-7P (Negami Chemical Industrial Co,. Ltd. Silicon dioxide composite crosslinked acrylic resin fine particles) was added, and dispersed at 10,000rpm (revolutions per minute) using an Ace homogenizer (NIHONSEIKI KAISHA LTD.) for 15 minutes, to obtain a water-dispersed product of ART PEARL J-7P (particle concentration: 20 mass%). The true specific gravity of the silica composite crosslinked acrylic resin fine particles in the obtained water dispersion was 1.20, and the average particle diameter of the above particles was 6.5. Mu.m.

Example 1 >

The die 1A is disposed on the support roller. The diameter of the backup roll was 300mm. The 2 nd outer body of the die 1A is disposed further downstream than the 1 st outer body of the die 1A in the conveyance direction of the TAC film. The composition a was supplied onto a TAC film conveyed along the outer peripheral surface of the supporting roller, and a coating film was formed. Specific conditions during the supply of the composition a are shown below. The length of the coating film was 100m, and the width of the coating film was 250mm.

Surface temperature of the backup roll: 60 DEG C

Wrap angle of TAC film with respect to the backup roll: 150 degree

Transport speed of TAC film: 30 m/min

Spacing of the 1 st front end face of the 1 st outer body from the TAC film: 50 μm

Interval between the 2 nd front end face of the 2 nd outer body and the TAC film: 50 μm

Examples 2 to 7 and comparative examples 1 to 3 >, respectively

A coating film was formed in the same manner as in example 1, except that the types of dies were changed as described in table 1.

Examples 8 to 14 and comparative examples 4 to 6 >, respectively

A coating film was formed in the same manner as in example 1, except that the types of dies and the types of compositions were changed as described in table 1.

< evaluation: separation of composition during discharge

A transparent backup roll without a temperature control device was prepared. A camera is provided inside the transparent support roller. The composition was supplied onto a TAC film conveyed along the outer peripheral surface of a transparent support roller. Except for the kind of the die, the kind of the composition and the condition, a transparent supporting roller having no temperature control device was used, the examples and comparative examples described above were used as standards. The behavior of the composition on the 4 th side of the 2 nd outer body during the discharge of the composition from the die was observed using a camera. The separation of the compositions was evaluated according to the following criteria.

A: no composition was observed to separate from the ribs.

B: a composition separated from the ribs was observed. However, it was observed that the composition separated from the rib was returned to the rib without being retained on the 4 th side surface of the 2 nd outer body.

C: a composition separated from the ribs was observed. In addition, the composition separated from the bead was not returned to the bead.

< evaluation: coating stripe >, a coating stripe

The laminate including the coating film and the TAC film was placed on an illumination table. The coating film was irradiated with light from an illumination stage, and the coating film (length: 500mm, width: 250 mm) was observed with naked eyes. The coating stripes were evaluated according to the following criteria.

A: no coating streaks were observed.

B: coating streaks were observed.

< evaluation: sealing durability >, and method for manufacturing the same

The die was immersed in methyl ethyl ketone at room temperature of 25 ℃ for 1 week. The die was removed from the methyl ethyl ketone and the surface of the lyophobic layer was wiped 100 times with BEMCOT (Asahi Kasei Corporation) containing methyl ethyl ketone. The lyophobic layer was visually observed, and the adhesion durability of the lyophobic layer was evaluated according to the following criteria.

A: no peeling of the lyophobic layer was observed.

B: peeling of the lyophobic layer of less than 100 μm square was observed.

C: peeling of the lyophobic layer of 100 μm square or more was observed.

The widths and heights of the projections shown in Table 1 are average values measured by using an optical microscope (VHX-5000, KEYENCE CORPORATION). In table 1, "-" indicated in the column of "width of bump" and "height of bump" indicates that no bump is present.

The "static contact angle of water" described in table 1 represents a static contact angle of 0.05mL of water with respect to the lyophobic layer (but the 4 th side surface of the 2 nd outer body with respect to the die head not containing the lyophobic layer). The static contact angle of water was measured using a contact angle meter (MCA-J2, kyowa Interface Science co., ltd) at room temperature at 25 ℃ and a relative humidity of 50%.

The "water slip angle" described in table 1 indicates a slip angle of 0.05mL of water with respect to the lyophobic layer (but the 4 th side surface of the 2 nd outer body for the die head not containing the lyophobic layer). The slip angle of water was measured using a contact angle meter (MCA-J2, kyowa Interface Science co., ltd) at room temperature at 25 ℃ and a relative humidity of 50%.

Table 1 shows the following: examples 1 to 7 are superior to comparative examples 2 to 3 and examples 8 to 14 are superior to comparative examples 5 to 6 in terms of reduction of coating stripes and adhesion durability of lyophobic layers. Comparison of examples 1 to 7 with comparative example 1 and comparison of examples 8 to 14 with comparative example 4 shows that the lyophobic layer contributes to reduction of coating streaks. Comparison of examples 1 to 7 with comparative examples 2 to 3 and comparison of examples 8 to 14 with comparative examples 5 to 6 shows that the metal-containing layer contributes to improvement of adhesion durability of the lyophobic layer. In addition, table 1 shows that the surface shape of the metal-containing layer has an influence on the surface shape of the lyophobic layer. Specifically, with respect to the projections formed on the surface of the metal-containing layer, the projections are formed on the surface of the lyophobic layer on the metal-containing layer, which contributes to reduction of the coating stripes.

Symbol description

10-1 st outer body, 10A-1 st outer bodyFront end face 1, side face 1 of 10B-1 st outer body, side face 2 of 10C-1 st outer body, side face 20-2 nd outer body, front end face 2 of 20A-2 nd outer body, side face 3 of 20B-2 nd outer body, side face 4 of 20C-2 nd outer body, 20 Cz-coating layer, 30-1 st discharge port, 30A-1 st discharge port, 30B-2 nd discharge port, 40-1 st inner body, 40A-1 st front end face 1 of 1 st inner body, 40B ₁ 5 th side of the 1 st inner body, 40B ₂ -side 6 of the 1 st inner body, 50-manifold, 50 a-1 st manifold, 50B-2 nd manifold, 100-die, 110-die, B-rib, F-object, L-composition, L ₁ -composition 1, L ₂ -composition 2.

Claims (8)

1. A die, comprising:

a 1 st outer body including a 1 st front end surface, a 1 st side surface, and a 2 nd side surface, the 1 st side surface being connected to the 1 st front end surface and defining a 1 st discharge port, the 2 nd side surface being connected to the 1 st front end surface at a position opposite to the 1 st side surface;

a 2 nd outer body including a 2 nd front end surface, a 3 rd side surface, and a 4 th side surface, the 3 rd side surface facing the 1 st side surface of the 1 st outer body and being connected to the 2 nd front end surface and defining the 1 st discharge port or a 2 nd discharge port different from the 1 st discharge port, the 4 th side surface being connected to the 2 nd front end surface at a position opposite to the 3 rd side surface;

A metal-containing layer on at least 1 face selected from the group consisting of the 1 st front end face of the 1 st outer body and the 4 th side face of the 2 nd outer body; a kind of electronic device with high-pressure air-conditioning system

A lyophobic layer located over the metal containing layer and containing a compound having a perfluoropolyether group.

2. The die according to claim 1, wherein,

the surface of the metal-containing layer facing the lyophobic layer includes protrusions having a width of 0.01mm to 1mm and a height of 0.1mm to 1 mm.

3. The die according to claim 1, wherein,

0.05mL of water had a slip angle of 55 DEG or less with respect to the lyophobic layer.

4. The die according to claim 1, wherein,

the 3 rd side surface of the 2 nd outer body defines the 1 st discharge port.

5. The die according to claim 1, wherein,

the 3 rd side surface of the 2 nd outer body defines the 2 nd discharge port.

6. The die according to any one of claims 1 to 5, wherein,

the metal-containing layer is located on the 1 st front end face of the 1 st outer body and the 4 th side face of the 2 nd outer body, respectively.

7. A method for producing a coating film, comprising:

A step of preparing the die according to any one of claims 1 to 6; a kind of electronic device with high-pressure air-conditioning system

And a step of forming a coating film by supplying the composition onto the object using the die.

8. The method for producing a coating film according to claim 7, wherein,

25 ℃ and 1s ^-1 The viscosity of the composition at the shear rate is 1 Pa.s to 1,000 Pa.s.

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