TW201816147A - Evaporation mask, method for manufacturing the same, and laminated body for evaporation mask and method for manufacturing the same capable of forming high precision large scale evaporation mask with low thermal expansion and warpage suppression - Google Patents

Abstract

The present invention provides an evaporation mask and a method for manufacturing the same, a laminated body for evaporation mask and a method for manufacturing the same, corresponding to high precision of thin film patterns and size increase. An evaporation mask for evaporating a fixed-shape thin film pattern on a evaporated body and comprising a laminated body consisted of a metal layer and a polyimide layer. The metal layer has a plurality of openings, the polyimide layer has a through hole within the opening range of the opening, and has an opening pattern corresponding to the thin film pattern. The polyimide layer is formed of a single layer or multiple layers of polyimide, and the coefficient of thermal expansion of the polyimide layer is 10×10<SP>-6</SP>/K or less in all directions in the plane.

Description

Vapor deposition screen and manufacturing method thereof, and laminate for vapor deposition screen and manufacturing method thereof

The present invention relates to a vapor deposition cover for vapor-depositing a thin film pattern with a fixed shape on an object to be vapor-deposited. For example, the present invention relates to a high-definition, high-definition required for forming an organic electroluminescence (EL) display device. A thin-film pattern vapor deposition mask and a method for manufacturing the same, and a laminate for a vapor deposition mask and a method for manufacturing the same.

For example, an organic EL display device is used as a representative of a large-sized display such as a television, and the organic EL display device is used in a small display such as a mobile phone, a personal computer, a smartphone, or the like. In this organic EL display device, a thin film transistor (hereinafter referred to as a TFT (Thin Film Transistor)) is formed on a vapor-deposited body (a vapor-deposited substrate) containing glass or a resin as a supporting substrate, and then an electrode is sequentially formed, The light-emitting layer and the electrode are finally hermetically sealed with a glass substrate or a multilayer film.

In the past, in the formation of a light-emitting layer and a cathode electrode of an organic EL display device, for example, a vapor deposition cover including only a metal layer formed by arranging a large number of fine openings is used in a region to be vapor-deposited on an object to be vapor-deposited. . At this time, since the openings corresponding to the thin film patterns are usually formed by etching of a metal layer or the like, it is difficult to form the openings with high accuracy. In addition, in order to improve productivity in recent years, it is necessary to increase productivity by increasing the size of an object to be vapor-deposited, or to increase the size of an organic EL display device. Therefore, there is also a demand for increasing the size of an evaporation cover. Continuous improving. However, with such an increase in size, the weight of the vapor deposition cover is also increased, and therefore, it is difficult to perform precise position control and the like.

For this reason, various studies have been performed to solve the problem of the vapor deposition mask formed using a single metal layer. For example, Patent Document 1 discloses a vapor deposition mask in which a metal mask and a resin mask are bonded by an adhesive. In addition, Patent Document 2 discloses a vapor deposition mask in which a resin film that transmits visible light and a metal plate body are surface-bonded. Among them, Patent Document 1 describes that as a material of the resin cover, a material capable of forming a high-definition opening portion by laser processing or the like, a small change in heat or time, and a lightweight material is exemplified as such a material. There are polyimide, polyimide, polyimide, imide, polyester, polyethylene, polyvinyl alcohol, polypropylene, polycarbonate, and polystyrene. In addition, Patent Document 2 discloses that polyimide has high heat resistance and can form openings with high accuracy, which is preferable in this respect. However, none of the specific studies on the characteristics of the resin mask or the specific resin having the same has been disclosed.

Regarding the characteristics of the resin cover, for example, Patent Document 3 discloses that the influence of the thermal expansion coefficient of the resin layer forming the resin cover can be reduced by reducing the thickness to about 10 μm or less. In addition, Patent Document 4 discloses a vapor deposition mask using a polyfluorene film having a thermal expansion coefficient that is different in orthogonal two axes and having anisotropy, and a magnetic metal. However, in the conventional lamination type vapor deposition cover including these Patent Documents 3 and 4, it is difficult to suppress warpage and cause problems in the accuracy of a thin film pattern in a conventional laminated vapor deposition cover in which a resin layer is laminated on a metal layer. Worry. Furthermore, for example, Patent Document 5 discloses a flexible printed wiring board including a polyimide layer and a copper foil-like conductor, and describes that the polyimide layer has a multilayer structure and includes a part of the polyimide layer. Polyimide with low thermal expansion. However, in laminates that require flexibility like a flexible printed wiring board, and laminates that require vapor deposition accuracy like a vapor deposition screen, there are design issues or technical ideas. The difference is that in flexible printed wiring boards, polyimide needs to be flexible, so polyimide containing a soft skeleton is required. In addition, in order to match the thermal expansion coefficient of copper foil, the thermal expansion coefficient is required to be 15´10. ^-6 / K or more. On the other hand, the length of the flexible printed wiring board is several mm to several cm. In contrast, in the vapor deposition cover, high position accuracy is required at a distance of more than 1 m, and therefore, thermal expansion is required to be lower. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2013-163864 [Patent Literature 2] Japanese Patent Laid-Open Publication No. 2013-83704 [Patent Literature 3] Japanese Patent Laid-Open Publication No. 2015-129333 [Patent Literature 4] Japanese Patent Special Publication No. 2014-205870 [Patent Document 5] Japanese Patent Laid-Open No. 8-250860

[Problems to be Solved by the Invention] As for a vapor deposition mask for forming a thin film pattern by vapor deposition, a high-definition thin film pattern is required. For example, the size of display devices such as televisions and digital signages is becoming larger, and the production efficiency of small-sized displays used in smartphones and the like has been improved. Therefore, in the future, the demand for the enlargement of a vapor deposition screen for obtaining a high-definition thin-film pattern is continuously advanced. Therefore, the inventors of the present inventors have made intensive studies on a vapor deposition mask that can obtain a high-definition thin film pattern with high accuracy and can also correspond to an increase in the size of such a thin film pattern. A vapor deposition mask formed by laminating a polyimide layer on a metal layer can suppress warpage, and can form a high-definition thin film pattern corresponding to an increase in size of the vapor deposition mask, thereby completing the present invention.

Therefore, an object of the present invention is to provide a vapor deposition cover that can correspond to high definition and large size of a thin film pattern. In addition, another object of the present invention is to provide a manufacturing method for obtaining such a vapor deposition screen, a laminated body for a vapor deposition screen, and a method for producing the same. [Means for solving problems]

That is, the gist of the present invention is as follows. [1] A vapor deposition hood for vapor deposition to form a fixed-shaped thin film pattern on a vapor-deposited body, the vapor deposition hood is characterized by comprising a laminate of a metal layer and a polyimide layer, The metal layer has a plurality of openings, the polyimide layer has a through hole located in an opening range of the openings, and has an opening pattern corresponding to the thin film pattern, the polyimide The layer is formed of a single layer or multiple layers of polyimide whose thermal expansion coefficient is 10 × 10 ^-6 / K or less in all directions in the plane. [2] The vapor deposition cover according to [1], wherein the polyimide layer is one having an isotropic thermal expansion coefficient in an in-plane direction. [3] The vapor deposition cover according to [1] or [2], wherein the main polyimide forming the polyimide layer is a structural unit represented by the following formula (1) Polyimide precursors made by imidization. [Chemical 1] Wherein R ₁ is a divalent organic group selected from the group represented by the following formula (2), [Chem 2] (R 'are each independently an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group, an aromatic group having 6 to 18 carbon atoms, or a halogen group, and the hydrogen atom of the aromatic group may be a halogen atom or a carbon number 1 -6 alkyl or halogenated alkyl. Z is NH or O), R ₂ is a tetravalent organic group selected from the group represented by the following formula (3), [Chem. 3] R each independently represents a hydrogen atom or a monovalent organic group, and n is a positive integer representing a repeating number. [4] The vapor deposition mask according to [3], wherein the main polyimide forming the polyimide layer is represented by the formula (1) that will contain 60 mol% or more. Polyimide precursors of structural units are formed by imidization. [5] The vapor deposition cover according to [1] or [2], wherein the metal layer is a magnetic body. [6] The vapor deposition cover according to [5], wherein the magnetic body is invar or an invar. [7] The vapor deposition mask according to [1] or [2], wherein the polyimide layer has a light transmittance of 60% or more at a wavelength of 500 nm, and a wavelength of 355 nm and / or a wavelength The transmittance at 308 nm is less than 50%. [8] The vapor deposition mask according to [3], wherein the main polyimide constituting the polyimide layer is a fluorine-containing polyimide or an alicyclic polyimide. [9] The vapor deposition mask according to [1] or [2], wherein the metal layer and the polyimide layer are laminated without interposing an adhesive. [10] The vapor deposition mask according to [1] or [2], wherein the polyimide layer includes multiple layers of polyimide, and the main polyimide forming the polyimide layer The thermal expansion coefficient of the amine is smaller than the thermal expansion coefficient of polyimide other than the main polyimide. [11] The vapor deposition mask according to [1] or [2], wherein the polyimide layer includes a plurality of polyimide, and thermal expansion of the polyimide in contact with the metal layer The coefficient is larger than the thermal expansion coefficients of other polyimide adjacent to the polyimide adjoining the metal layer. [12] The vapor deposition mask according to [1] or [2], wherein the polyimide layer includes a plurality of polyimide, and thermal expansion of the polyimide in contact with the metal layer The coefficient is smaller than the thermal expansion coefficient of other polyimide adjacent to the polyimide adjoining the metal layer. [13] The vapor deposition mask according to [1] or [2], wherein the polyimide layer includes three or more polyimides, forming two outermost polyimide layers on the front surface and the back surface. The thermal expansion coefficient of the imine is larger than the thermal expansion coefficient of the polyimide forming the intermediate layer sandwiched by these outermost polyimides, and any polyimide forming the outermost surface is different from the The metal layers are connected. [14] The vapor deposition cover according to [1] or [2], wherein the polyimide layer is divided into two or more layers in the plane of the metal layer and laminated.

[15] A method for manufacturing a vapor deposition hood, which is used to vapor-deposit a fixed-shape film pattern on a body to be vapor-deposited, and the method for producing the vapor deposition hood is characterized by thermal expansion The polyimide layer having a coefficient of 10 × 10 ^-6 / K or less in all directions in the plane is laminated with the metal layer, and a plurality of openings are formed in the metal layer, or a metal layer having a plurality of openings is formed. After laminating with a polyimide layer having a thermal expansion coefficient of 10 × 10 ^-6 / K or less in all directions in the plane, the polyimide within the opening range in the opening portion of the metal layer is laminated. The layers are penetrated to form an opening pattern corresponding to the thin film pattern. [16] A method for manufacturing a vapor deposition hood, the vapor deposition hood is used to vapor-deposit a fixed-shape film pattern on a body to be vapor-deposited, and the method for manufacturing the vapor deposition hood is characterized by comprising: A liquid composition containing polyimide or a polyimide precursor is coated on a coating substrate and heated to form a thermal expansion coefficient on the coating substrate of 10 × 10 in all directions in a plane. ^-6 / K or less polyimide layer step; laminating a metal layer on the polyimide layer and forming a plurality of openings in the metal layer, or laminating a metal layer having a plurality of openings A step on the polyimide layer; a step of separating the polyimide layer from the coating substrate; and the step of separating the polyimide layer from the opening in the opening portion of the metal layer A step of penetrating the polyimide layer to form an opening pattern corresponding to the thin film pattern. [17] A method for manufacturing a vapor deposition hood, the vapor deposition hood is used to vapor-deposit a fixed-shape film pattern on a body to be vapor-deposited, and the method for manufacturing the vapor deposition hood is characterized by comprising: A step of fixing the metal layer on the fixing member; applying a liquid composition containing polyimide or a polyimide precursor on a surface of the metal layer and heating the liquid to form a polyimide on the metal layer A step of an amine layer; a step of separating the metal layer from the fixing member; a step of forming a plurality of openings in the metal layer; and a step of forming a range of openings in the openings of the metal layer. The step of penetrating the polyimide layer to form an opening pattern corresponding to the thin film pattern. [18] A laminated body for a vapor deposition hood, which is used for vapor deposition of a drape to laminate a metal layer containing a magnetic body and a polyimide layer to form a fixed-shape thin film pattern on the vapor-deposited body. The laminated body for a vapor deposition mask is characterized in that the thermal expansion coefficient of the polyfluorene imide layer is 10 × 10 ^-6 / K or less in all directions in the plane, and the polyfluorine imide layer is composed of A single-layer or multi-layer polyimide is formed, and the main polyimide is obtained by imidating a polyimide precursor having a structural unit represented by the following formula (1). [Chemical 4] Wherein R ₁ is a divalent organic group selected from the group represented by the following formula (2), [Chem. 5] (R 'are each independently an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group, an aromatic group having 6 to 18 carbon atoms, or a halogen group, and the hydrogen atom of the aromatic group may be a halogen atom or a carbon number 1 -6 alkyl or halogenated alkyl. Z is NH or O), R ₂ is a tetravalent organic group selected from the group represented by the following formula (3), [Chem 6] R each independently represents a hydrogen atom or a monovalent organic group, and n is a positive integer representing a repeating number. [19] A method for producing a laminated body for a vapor deposition hood, which is a laminate of a metal layer including a magnetic body and a polyimide layer, and is used for vapor deposition of a vapor deposition hood to be vapor-deposited. A method for producing a fixed-shape thin film pattern is deposited on a plated body by vapor deposition, and the method includes the following steps: applying a liquid composition containing polyimide or a polyimide precursor to the substrate; A step of forming a coating layer on the surface of the metal layer; and a step of heating the coating layer to form a polyimide layer on the metal layer; the liquid composition includes the following formula (1) A polyfluorene imine precursor of the structural unit represented or a polyfluorene imine obtained by fluorinating the polyfluorene imine precursor, so that the polyfluorene imine formed on the metal layer The thermal expansion coefficient of the layer is 10 × 10 ^-6 / K or less in all directions in the plane. [Chemical 7] Wherein R ₁ is a divalent organic group selected from the group represented by the following formula (2), [Chem. 8] (R 'are each independently an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group, an aromatic group having 6 to 18 carbon atoms, or a halogen group, and the hydrogen atom of the aromatic group may be a halogen atom or a carbon number 1 -6 alkyl or halogenated alkyl. Z is NH or O), R ₂ is a tetravalent organic group selected from the group represented by the following formula (3), [Chem 9] R each independently represents a hydrogen atom or a monovalent organic group, and n is a positive integer representing a repeating number. [20] The method for producing a laminate for a vapor deposition mask according to [19], wherein before the step of forming the coating layer on the surface of the metal layer, the method includes fixing the metal layer to a fixed surface. Steps on the component. [Effect of the invention]

According to the present invention, in a vapor deposition cover including a laminated body in which a polyimide layer and a metal layer are laminated, warpage can be suppressed, and a high-definition film can be formed corresponding to an increase in size of the vapor deposition cover. Film pattern. Therefore, according to the vapor deposition cover of the present invention, it is possible to achieve a larger screen of a display device such as an organic EL display device, or to improve the production efficiency of a small display used in a smartphone or the like, and to achieve further high definition. And so on.

Hereinafter, the present invention will be described in detail. In the vapor deposition cover of the present invention, it is assumed that the polyimide layer having an opening pattern corresponding to the film pattern is formed of a single layer or a plurality of polyimide layers, and the coefficient of thermal expansion of the polyimide layer It is 10 × 10 ^-6 / K or less in all directions in the plane. If the coefficient of thermal expansion (CTE) is 10 × 10 ^-6 / K or less, it is possible to reduce the size due to a temperature change in a step with a metal layer having a low thermal expansion property suitable for vapor deposition of a curtain. Therefore, when a laminated body is formed with a metal layer having a plurality of openings, it is flat at normal temperature and its flatness can be maintained when the temperature rises during vapor deposition. The CTE is preferably -10 × 10 ^-6 / K or more and 10 × 10 ^-6 / K or less, more preferably the upper limit of the CTE is 8´10 ^-6 / K or less, and still more preferably 5´10 ^-6 / K the following. In addition, by using such a CTE in all directions in the plane of the polyimide layer, it is possible to suppress the warping of the vapor deposition mask caused by the temperature change in the step, or the temperature unevenness in the vapor deposition mask. The undulations and slacks. Here, the CTE is 10 × 10 ^-6 / K or less in all directions in the plane, and means that the thermal expansion coefficient in the plane includes a direction parallel to one side of the polyimide layer and a direction at a right angle. The state is 10 × 10 ^-6 / K or less in either direction.

In addition, for reasons of increasing the degree of freedom in designing the opening, the vapor deposition cover of the present invention is preferably one in which the polyimide layer is laminated on a metal layer, and the CTE of the polyimide layer is The CTE is 10 × 10 ^-6 / K or less in all directions in the plane, and the CTE has no anisotropy, and includes a CTE that is isotropic in the in-plane direction. Specifically, it is preferable that there is no anisotropy in the orthogonal two axes. The so-called "no anisotropy in the orthogonal two-axis" means that the difference in CTE in the orthogonal two-axis direction is 2´10 ^-6 / K or less. By forming a polyfluorene layer having a CTE that is isotropic in the in-plane direction, it is possible to suppress warpage in any of the longitudinal direction of the opening and the direction intersecting the longitudinal direction, regardless of the thickness of the metal layer. Regardless of the shape of the opening, warpage of the laminate can be suppressed. Further, regarding the CTE of the polyfluorene imide layer, if the CTE is excessively lowered, the polyfluorene imine becomes brittle and has practical problems, etc. Therefore, the lower limit of the CTE is substantially -7´10 ^-6 / K.

In order to form a polyimide layer of such a CTE, it is preferred that the main polyimide forming the polyimide layer is a polyimide precursor having a structural unit represented by the following formula (1). It is more preferable that the fluorinated product is a structural unit represented by formula (1) containing 60 mol% or more, and more preferably a structural unit represented by formula (1) containing 80 mol% or more. Polyimide precursors of structural units are formed by imidization. Here, the "main polyimide" refers to a case where the polyimide layer is a single layer, and refers to a case where the polyimide layer itself includes multiple layers of polyimide. The term "polyimide" refers to the layer with the largest volume fraction. By setting this main polyimide to be a polyimide precursor (polyamidic acid) fluorinated with a structural unit represented by the formula (1), a low thermal expansion polymer can be obtained. For fluorene imine, the CTE of the polyfluorene imide layer is preferably 10 × 10 ^-6 / K or less, which is preferable in this respect. In addition, the polyfluorene imide obtained from a polyfluorene imide precursor having a structural unit represented by the formula (1) exhibits low hygroscopicity as the polyfluorene imine, and therefore, it is possible to suppress the size factor during the process. Changes in the humidity environment are advantageous in this regard. In addition, as for the main polyimide, there is no particular limitation on the remaining polyimide precursors which are different from the general polyimide precursor, and ordinary polyimide precursors can be used. [Chemical 10] Wherein R ₁ is a divalent organic group selected from the group represented by the following formula (2), [Chem. 11] (R 'are each independently an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group, an aromatic group having 6 to 18 carbon atoms, or a halogen group, and the hydrogen atom of the aromatic group may be a halogen atom or a carbon number 1 -6 alkyl or halogenated alkyl. Z is NH or O), R ₂ is a tetravalent organic group selected from the group represented by the following formula (3), [Chem 12] R each independently represents a hydrogen atom or a monovalent organic group, and n is a positive integer representing a repeating number.

In addition, when a polyfluorene imine precursor having a structural unit represented by the formula (1) is subjected to fluorene imidization to form a polyfluorene imine, adhesion may be deteriorated. Therefore, the polyfluorene imide layer may include a plurality of polyfluorene imines, and the layer in contact with the metal layer may be a polyfluorine having a non-low thermal expansion property. That is, a liquid composition containing a polyfluorene imide precursor (or a polyfluorene imine obtained by fluorinating a polyfluorene imine precursor) is applied to a metal layer and heated to form a polyfluorene. In the case of the layer casting method, the first liquid composition containing a polyfluorene imine precursor (or a polyfluorene imine obtained by fluorinating a polyfluorene imine precursor) is applied to the metal layer. After the application, polyimide containing a polyimide precursor having a structural unit represented by formula (1) may be formed by coating thereon. In the case of a lamination method in which a polyimide film is thermocompression-bonded to a metal layer, the polyimide layer may include a plurality of polyimide layers, and a non-low thermal expansion polyimide The polyfluorene imide of the polyfluorene imide precursor of the structural unit represented by the formula (1) [hereinafter, may be simply referred to as the polyfluorene imine of the formula (1)] may be between the metal layer. At this time, the CTE of the non-low thermal expansion polyimide is usually about 50´10 ^-6 / K. Therefore, the thermal expansion coefficient of the polyimide connected to the metal layer is larger than that of other polyimides adjacent to the polyimide. Coefficient of thermal expansion of fluorene imine [that is, polyfluorene imine of formula (1)]. In other words, in the case where the polyimide layer includes multiple layers of polyimide, the thermal expansion coefficient of the main polyimide forming the polyimide layer is preferably smaller than that of polyimide other than the main polyimide. Coefficient of Thermal Expansion of Amine.

In addition, when the polyimide layer is formed in multiple layers, in order to improve the adhesion with the barrier layer or adjust the thermal expansion coefficient of the polyimide layer, a non-low thermal expansion polyimide may be formed in the substrate. The surface of the polyimide layer opposite to the surface of the polyimide layer that is in contact with the metal layer. In this case, the thermal expansion coefficient of the polyimide constituting the surface on the opposite side of the side in contact with the metal layer in the polyimide layer is larger than that of other polyimide adjacent to the polyimide. Coefficient of thermal expansion of imine. The adjustment of the thermal expansion coefficient of the polyimide layer is to use the polyimide to reduce the thermal expansion coefficient of the polyimide adjacent to the polyimide compared to the metal layer. Fine-tune the thermal expansion coefficient.

In addition, in order to improve the adhesion with the metal layer or adjust the thermal expansion coefficient of the polyimide layer, for example, the polyimide layer may include multiple layers of polyimide and the polyimide in contact with the metal layer The coefficient of thermal expansion of is smaller than that of other polyimides adjacent to the polyimide. Alternatively, in order to improve the adhesion with the barrier layer or adjust the thermal expansion coefficient of the polyimide layer, the polyimide layer may include three or more polyimide layers to form the two outermost layers of the surface and the back surface. The thermal expansion coefficient of fluorene imine is larger than that of the polyfluorene imine forming the intermediate layer sandwiched by these outermost polyfluorene imines. In addition, any of the polyfluorene imines forming the outermost surface can be compared with The metal layers are connected.

When the polyfluorene imide layer is formed in a plurality of layers, the number of layers is not particularly limited, and in terms of productivity, two or three layers are preferred. The coating may be simultaneous coating of multiple layers using the same coater, or sequential coating of each layer using different coaters.

In addition, in the vapor deposition cover of the present invention, the adhesion between the metal layer and the polyimide layer is preferably 300 N / m or more. It is more preferably 600 N / m or more. If the adhesion force between the metal layer and the polyimide layer is 300 N / m or more, it is difficult to peel off the metal layer and the polyimide even if the operation of repeatedly forming a thin film pattern on the body to be vapor-deposited Floor. From such a viewpoint, when the polyfluorene imine layer is a polyfluorene imine of the formula (1), it is preferable to form the polyfluorene imine layer by a casting method. On the other hand, when the polyfluorene imide layer is formed by a lamination method, it is preferable that a polyfluorene imide having a non-low thermal expansion property is positioned between the metal layer and the polyfluorene imide layer. In this case, the polyfluorene imide having a non-low thermal expansion property can be regarded as a kind of the polyfluorene imide layer. By setting the polyfluoreneimide layer to the above-mentioned form, the metal layer and the polyfluoreneimide layer can be bonded without interposing an adhesive. However, it is not excluded that an adhesive layer is interposed between the metal layer and the polyimide layer.

That is, in the present invention, the main polyimide forming a polyimide layer refers to a polyimide used to set the overall CTE of the polyimide layer to 10 × 10 ^-6 / K or less, The low thermal expansion polyfluorene imine of the general formula (1) is preferably equivalent to the main polyfluorene imine. As described above, when a polyimide layer is formed from a single layer of polyimide of the formula (1), it goes without saying that the single-layer polyimide becomes the main polyimide. When the layer is formed of a plurality of layers, the CTE of the entire polyimide layer may be set to 10 × 10 ^-6 / K or less by considering the effect of polyimide other than the polyimide of formula (1).

Here, examples of the non-low thermal expansion polyfluorene imine include 4,4'-diaminodiphenyl ether as a diamine, and 1,3-bis (4-aminophenoxy) benzene. , 1,4-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 3,3 ', 4,4 as acid anhydride '-Benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-diphenylphosphonium tetracarboxylic dianhydride, 4,4-oxodiphthalic anhydride, pyromellitic anhydride, 2,3,2 ', 3'-biphenyltetracarboxylic dianhydride and 2,3,3,4-biphenyltetracarboxylic dianhydride are polyimide used as raw materials.

In the present invention, since the CTE of the polyfluorene imide layer is 10 × 10 ^-6 / K or less in all directions in the plane, it is preferred that the polyfluorene imide layer is formed by a casting method. In the case of a lamination method in which a polyimide film is thermocompression-bonded to a metal layer as described above, the polyimide film itself may be formed by a casting method.

In addition, the polyimide layer may be laminated by dividing into two or more layers in the plane of the metal layer. In this case, for example, in the case of the casting method, the liquid composition is divided and applied, and the polyimide layer divided into two or more different types is laminated on the surface of the metal layer. It is effective in suppressing the warpage of the vapor deposition mask including the laminate, and it is also advantageous in terms of weight reduction of the vapor deposition mask.

In addition, the thickness of the polyimide layer is not particularly limited, and is preferably a thickness that can suppress the occurrence of cracks or pinholes, and a thickness that takes the occurrence of vapor deposition shadow into consideration. It is preferably 2 μm to 25 μm. This polyimide layer is required to have characteristics different from the case where transparency is preferably made to transmit visible light and the case where opacity is preferably made not to transmit visible light.

That is, in order to detect a foreign substance or a micro bubble in a polyimide layer, a polyimide layer is required to transmit visible light. The term "transmitting visible light" includes coloring to the extent that the opposite side of the polyimide layer is visible through the polyimide layer in addition to being completely transparent. On the other hand, in order to detect the opening pattern of the polyimide layer, it is required that the polyimide layer does not transmit visible light or has a low transmittance of visible light. Thereby, inspection of an opening pattern can be performed based on the contrast of the shade of the opening pattern. Therefore, what is necessary is just to make a polyimide layer transparent or non-transparent according to the required characteristic.

Polyimide differs depending on the acid anhydride or diamine component constituting the polyimide, and it is usually colored from yellow-brown to dark brown. Therefore, when attention is paid to the detection of defects such as foreign matter or fine air bubbles in the polyimide layer, it is preferable that the main polyimide constituting at least the polyimide layer is a fluorinated polyimide or an alicyclic ring. Polyimide, and make the polyimide layer transparent. Examples of such polyfluorene imine include 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl as a diamine, and cyclobutane-1,2 as an acid anhydride. 3,4-tetracarboxylic dianhydride was used as a starting material for polyimide. With these polyfluorene imines, a CTE of 10 × 10 ^-6 / K or less can be satisfied, and the light transmittance at a wavelength of 500 nm can be set to 60% or more.

On the other hand, in order to improve the contrast of the shade of the opening pattern, the polyimide layer can be made non-transparent. In this case, colored materials such as dyes and pigments can also be added to the polyimide layer. The shape of the colored material component is not particularly limited, as long as a conventionally known shape such as spherical, rod-shaped, and scaly particles is used, and the size is not particularly limited. If the size of the colored material component exceeds 2 μm, Defects such as protrusions caused by the colored material and peeling of the colored material are liable to occur. The lower limit of the size is not particularly limited, and is about 1 nm. In the case where the polyimide layer is a plurality of layers, it is preferable to adopt a configuration in which a colored material is added to the at least one layer, and a colored material is not added to the other layers.

In the present invention, a method for forming an opening pattern by providing a through hole in the polyimide layer is not particularly limited, and examples thereof include applying a photosensitive resist to the surface of the polyimide layer and exposing a predetermined portion. A method of forming through-holes by etching after development; a method of forming through-holes by laser irradiation; a method of forming through-holes by mechanical drill; and the like from the viewpoints of accuracy and productivity, etc. It is advisable to use laser irradiation. When an opening pattern corresponding to a thin film pattern is formed by laser irradiation, if the polyimide layer at a laser wavelength has a high transmittance, a good opening pattern shape may not be obtained. Therefore, the light transmittance of the polyfluorene imine layer at the laser wavelength is preferably 50% or less, preferably 10% or less, and more preferably 0%. Here, as the laser for forming a through hole in the polyfluorene layer and forming an opening pattern by laser irradiation, for example, Ultraviolet-Yttrium aluminum garnet (UV-YAG) laser (wavelength 355 nm), excimer laser (wavelength 308 nm), etc. Among them, UV-YAG laser (wavelength 355 nm) is preferred.

In addition, when the manufacturing process of the vapor deposition mask of this invention includes the process of separating a polyimide layer from a coating base material as mentioned later (henceforth a "laser peeling"), you may irradiate. The general laser used in the formation of the opening pattern is separated. Therefore, if the polyimide layer has a light transmittance of 10% or less with respect to these laser wavelengths such as 308 nm or 355 nm, the separation during the laser peeling can be easily performed, which is preferable in this respect. That is, the laser at the time of forming the opening pattern and the laser at the time of separation may be the same type or different types. When the laser at the time of forming the opening pattern is different from the laser at the time of separation, the polyimide layer is preferably at a wavelength corresponding to one of the wavelength corresponding to the former laser and the wavelength corresponding to the latter laser. The light transmittance is 50% or less. At another wavelength, the light transmittance of the polyimide layer is 10% or less. Here, as these lasers, a known one can be used at the time of formation of the opening pattern and at the time of separation. The UV-YAG laser (wavelength 355 nm) or excimer laser (wavelength 308) which are excellent in working efficiency can be listed. nm) and so on.

In addition, when a polyimide layer is irradiated with laser light and through-holes are provided to form an opening pattern corresponding to a thin film pattern, a reference plate showing a pattern corresponding to the opening pattern to be formed may be prepared, and the reference plate may be disposed on The opening opposite to the laser irradiation side of the polyimide layer is subjected to laser irradiation corresponding to the pattern of the reference plate. In order to detect the pattern of the reference plate through the polyimide layer, the polyimide layer preferably transmits visible light. Therefore, from the viewpoint of improving the pattern detection accuracy of the reference plate, as described above, the transmittance at 500 nm of the polyimide layer is preferably 60% or more, and more preferably 80% or more. The transmittance at 400 nm of the polyfluoreneimide layer is preferably 5% or more, and more preferably 10% or more.

In the formation of the opening pattern by laser irradiation, when a polyimide layer having the above-mentioned optical characteristics is obtained to obtain a good opening pattern, the preferred polyimide contains 60 mol% or more Polyimide of a polyimide precursor of a structural unit represented by the formula (1). As described later, when the light transmission property of the laser wavelength when a polyimide layer is formed on a coating substrate and the polyimide layer is laser-peeled is taken into consideration, a more preferred polyimide is A polyfluorene imide containing a polyfluorene imine precursor containing a structural unit represented by the formula (1) in an amount of 80 mol% or more.

In addition, in the present invention, the material of the metal layer having a plurality of openings is not particularly limited, and the same materials as those used in known vapor deposition covers can be used. Specifically, stainless steel, iron-nickel alloy, aluminum alloy, and the like can be exemplified. Among them, invar steel (or invar alloy), which is an iron-nickel alloy, has less deformation due to heat, and is therefore preferably used. In addition, when a vapor deposition body is vapor-deposited, when a magnet or the like is provided behind the vapor deposition body and the vapor deposition cover is attracted by magnetic force, it is preferable to form a metal layer using a magnetic body. Examples of the metal layer of such a magnetic body include carbon steel, tungsten steel, chrome steel, KS steel, MK steel, NKS steel, and the like, in addition to the iron-nickel alloy including Yin Steel or Yin Steel alloy as described above.

The thickness of the metal layer is not particularly limited, and is preferably a thickness that can suppress cracking or deformation, and a thickness that takes into consideration the occurrence of vapor deposition shadow, and is preferably 2 μm to 100 μm.

FIGS. 1 (1) to 1 (2) show a metal layer 1 having a plurality of openings 1a [FIG. 1 (1)], and a polyimide layer 2 having a through hole 2a [FIG. 1 (2)] As shown in the plan view of FIG. 2 (1) and the cross-sectional view of FIG. 2 (2), the vapor deposition cover 4 including the laminated body formed by stacking these layers has the through hole 2a of the polyimide layer 2 located on the metal layer An opening pattern 3 corresponding to a thin film pattern formed on a vapor-deposited body (not shown) is formed in the opening range of the opening portion 1a of 1.

The method for forming the vapor deposition mask including the above-mentioned laminated body including the metal layer 1 and the polyimide layer 2 is not particularly limited, and examples thereof include a solution containing polyimide or a polyimide precursor. A method for coating a metallic composition (resin solution) on a metal layer and then performing a heat treatment to directly form a polyimide layer on the metal layer; a polyimide film that forms a polyimide layer without interposing an adhesive. A method of direct thermal compression bonding with a metal layer; a method of bonding a metal layer to a polyimide film using an adhesive, an adhesive, etc .; a method of forming a metal layer on the polyimide film by sputtering or plating, etc. Wait. Here, one or both of the openings 1a of the metal layer 1 or the through holes 2a of the polyimide layer may be formed after forming a laminate of the metal layer 1 and the polyimide layer 2, or Either or both of them may be provided before forming the laminate, so that the metal layer 1 and the polyimide layer 2 may be laminated.

That is, as an example of the method for manufacturing the vapor deposition cover of the present invention, a method may be mentioned in which a polyimide layer (polyimide) having a thermal expansion coefficient of 10 × 10 ^-6 / K or less in all directions in a plane is provided. Amine film) is laminated with a metal layer, and a plurality of openings are formed in the metal layer, or a metal layer having a plurality of openings and a coefficient of thermal expansion in all directions in the plane are 10 × 10 ^-6 / K or less. After the fluorene imide layer (polyimide film) is laminated, a polyfluorene imide layer in an opening range in the opening portion of the metal layer is penetrated to provide a through hole, thereby forming an opening pattern corresponding to the film pattern. Furthermore, as described above, the polyimide layer may be formed of a single layer of polyimide, or may be formed of a plurality of layers of polyimide, or may be a polymer divided into two or more layers within the plane of the metal layer.醯 imine layer (the same applies to the following examples).

In addition, the method may further include the step of applying a liquid composition containing polyimide or a polyimide precursor to a coating substrate such as glass or a polyimide film, and heating the substrate to coat the substrate. Forming a polyimide layer having a thermal expansion coefficient of 10 × 10 ^-6 / K or less in all directions in the plane; laminating a metal layer on the polyimide layer and forming a plurality of openings in the metal layer Or a step of laminating a metal layer having a plurality of openings on the polyimide layer; a step of separating the polyimide layer from the coating substrate; and an opening range in the opening of the metal layer A step of forming an opening pattern corresponding to the thin film pattern by providing a polyimide layer inside and penetrating through holes. When forming a laminate of a metal layer and a polyimide layer, from the viewpoint of effectively reducing warpage, the coating substrate preferably has a CTE of 10 × 10 ^-6 / K or less, and more preferably 8´ 10 ^-6 / K or less. In addition, a part of the steps listed here can be changed in order. For example, the step of separating the polyimide layer from the coating substrate may be performed after forming the opening portion of the metal layer or the opening pattern of the polyimide layer. .

Alternatively, the method may include the steps of: fixing a metal layer on a glass substrate or a metal plate, a metal frame, a guide roller, and other fixing members; and coating a liquid composition containing polyimide or a polyimide precursor. A step of forming a polyimide layer on the metal layer by heating on the surface of the metal layer; a step of separating the metal layer from the fixing member; a step of forming a plurality of openings in the metal layer; and a metal layer A step of forming an opening pattern corresponding to the thin film pattern by penetrating the polyfluorene imide layer in the opening range of the opening portion and providing a through hole. By fixing the metal layer to the fixing member in this manner and applying the liquid composition and heating, when a laminate of the metal layer and the polyimide layer is formed, reduction in warpage can be achieved more effectively. From the viewpoint of reducing the warpage, the fixing member preferably has a CTE of 10 × 10 ^-6 / K or less, and more preferably 8´10 ^-6 / K or less. Preferable examples of the fixing member satisfying the preferred CTE include glass, invar, and silicon. In this case, for example, a step of separating the metal layer from the fixing member may be performed after forming the opening portion of the metal layer or the opening pattern of the polyimide layer.

In addition, it may include the following steps: a step of fixing the metal layer to the general fixing member; a step of forming a plurality of openings in the metal layer; and a liquid containing polyimide or a polyimide precursor. A step of coating a metal-like composition on the surface of a metal layer and heating to form a polyimide layer on the metal layer; penetrating the polyimide layer in the opening range of the opening portion of the metal layer to provide a through-hole, thereby A step of forming an opening pattern corresponding to the thin film pattern; and a step of separating the metal layer from the fixing member.

When a metal layer is fixed to these fixing members and a liquid composition is applied to form a polyfluorene layer comprising a plurality of polyfluorene imines, for example, it may include the following steps: The first liquid composition of the fluorene imine precursor is coated on the surface of the metal layer to form a first coating layer, and then a second liquid containing polyfluorene imine or a fluorene imine precursor is coated on the first coating layer. A step of forming a second coating layer by forming the composition, and a step of heating the first coating layer and the second coating layer to form a polyimide layer including a plurality of polyimide on the metal layer. In this case, it is preferable that the second liquid composition contains a polyfluorene imide precursor having a structural unit represented by the previous formula (1) or is obtained by imidizing the polyfluorene imine precursor. And the thermal expansion coefficient of the polyimide layer formed on the metal layer is 10 × 10 ^-6 / K or less in all directions in the plane.

In addition, the heating temperature of the first coating layer and the second coating layer can be appropriately set depending on the structure of the polyimide or polyimide precursor constituting each layer. In addition, depending on the case where the polyfluorene imide precursor is applied and the fluorene imidization is performed by heating, the case where the polyfluorene imine precursor is applied and dried by heating (without the fluorination), the polyimide may be applied The hydrazone is suitably set when it is dried by heating. As an example, the heating temperature may be 200 ° C. or lower, and the heating temperature of the first coating layer may be set lower than the heating temperature of the second coating layer. In addition, the second coating layer may be provided after the hardening (above 300 ° C) of the first coating layer is completed by the imidization, or the second coating layer may be provided only after the first coating layer is dried (below 200 ° C). The coating layer is applied, and thereafter curing of these is completed.

In the present invention, the method of forming the opening portion in the metal layer is not particularly limited, and examples thereof include applying a photosensitive resist to the surface of the metal layer, exposing and developing a predetermined portion, and then forming the opening portion by etching Method of forming an opening by laser irradiation; coating a photosensitive resist on a polyimide layer or other substrate, and exposing and developing a fixed portion, and then performing sputtering, evaporation, and plating And the like to form a metal layer. Among these, it is preferable to form an opening by etching in terms of being able to be processed by a roll and having excellent productivity.

Furthermore, in some examples of the method for manufacturing a vapor deposition hood in the present invention, a metal layer and a polyimide layer are laminated to form a thin film pattern for vapor deposition to form a fixed shape on a vapor-deposited body. Laminate for vapor deposition. In the case of producing the laminated body for vapor deposition hood, it only needs to include the step of applying a first liquid composition containing polyimide or a polyimide precursor to the surface of the metal layer, and After the first coating layer is formed, coating the second liquid composition containing polyimide or a polyimide precursor on the first coating layer to form a second coating layer; and applying the first coating layer to the first coating layer; And heating the second coating layer and the second coating layer to form a polyfluorene imide layer including a plurality of polyfluorene imines on the metal layer. In addition, a step of fixing a metal layer containing a magnetic body to the fixing member may be applied before the step. At this time, the second liquid composition includes a polyfluorene imide precursor having a structural unit represented by the previous formula (1) or a polyfluorene obtained by imidizing the polyfluorene imine precursor. Imine, and the thermal expansion coefficient of the polyfluorene imide layer formed on the metal layer is 10 × 10 ⁻⁶ / K or less in all directions in the plane.

In the present invention, in order to reduce outgassing from polyimide or improve solvent resistance during cleaning of the vapor deposition mask, a barrier layer may be formed on the polyimide surface of the vapor deposition mask or a multilayer polyimide Interlayer, wall surface of the polyimide opening pattern. As the barrier layer, an inorganic oxide, an inorganic nitride, a thin film layer of a metal, or a vapor-deposited layer can be used. In the case of an inorganic oxide and an inorganic nitride, it is preferably formed by a Chemical Vapor Deposition (CVD) method or a Physical Vapor Deposition (PVD) method. When a barrier layer is formed between the layers of a polyimide, it is preferable to apply a liquid composition to the surface of a metal layer, and heat the coating layer to form a polyimide layer, and then form a barrier layer. Further, the liquid composition is coated on the barrier layer and heated.

In the present invention, the object to be vapor-deposited is not particularly limited, and it may be the same as a known supporting substrate, and examples thereof include glass, silicon, metal foil, and resin. In the case of a metal foil, since there is little deformation due to heat, a ferrite-based stainless steel or invar steel can be preferably used. In the case of a resin, polyimide can be preferably used from the viewpoint of less deformation due to heat or heat resistance. [Example]

The raw materials, diamines, anhydrides, and solvents used in the synthesis of the polyamidic acid (polyimide precursor) solution used in the following Synthesis Examples or Examples and Comparative Examples are shown below.

[Diamine] · 4,4'-Diamino-2,2'-bis (trifluoromethyl) biphenyl (TFMB) · 1,4-Phenylenediamine (PPD) · 2,2'- Dimethyl-4,4'-diaminobiphenyl (mTB) · 1,3-bis (4-aminophenoxy) benzene (TPE-R) · 2,2-bis [4- (4- Aminophenoxy) phenyl] propane (BAPP) 5-Amino-2- (4-aminophenyl) benzimidazole (AAPBZI) 5-Amino-2- (4-aminophenyl) ) Benzoxazole (AAPBZO) [anhydride] · pyromellitic anhydride (PMDA) · 2,3,2 ', 3'-biphenyltetracarboxylic dianhydride (BPDA) · cyclobutane-1,2, 3,4-tetracarboxylic dianhydride (CBDA) · 4,4- (hexafluoroisopropylidene) bisphthalic anhydride (6FDA) · 4,4-oxybisphthalic anhydride (ODPA) · 2,3,6,7-naphthalenetetracarboxylic dianhydride (NTCDA) [Solvent] · N, N-dimethylacetamide (DMAc) · N-methyl-2-pyrrolidone (NMP)

＜ Linear expansion coefficient ＞ Using a thermomechanical analysis (TMA) device for a polyimide layer with a size of 3 mm´15 mm, while applying a load of 5.0 g, at a constant heating rate (10 ° C / min) from 30 ° C to 280 The tensile test was performed by heating and cooling in a temperature range of ℃, and the thermal expansion coefficient (ppm / K) was measured based on the change in elongation of the polyimide layer from a temperature change from 250 ° C to 100 ° C.

<Thermal expansion coefficient isotropy> The thermal expansion coefficients were measured three times in a direction parallel to one side of the polyimide layer and in a direction at right angles. The difference between the average values was 2 ppm / K or less. A state of more than 2 ppm / K is set to ×.

<Warpage> A laminate of a metal layer and a polyimide layer was left with the polyimide layer facing up on a horizontal plane, and the average value of the height of the floating from the plane of the four corners of the laminate was set For warping.

<Adhesion> Using a Tensilon tester, the polyimide layer side of the laminated body of a 1 mm wide metal layer and polyimide was fixed to an aluminum plate with a double-sided tape, and the base material was determined to be 180 ° in the direction The force when peeling the polyfluorene imide layer and the metal layer at a speed of 50 mm / min is set to ◎ at 1,000 N / m or more, ○ at less than 1000 N / m, and 600 N / m or more to 600 N / m and 300 N / m or more are set to Δ.

<Polyimide layer opening pattern formation property> Using a UV-YAG laser processing machine (wavelength 355 nm), openings were formed so that the polyimide layer penetrated and the diameter became 50 μm, and a good processed shape was formed. The state of 状态 was evaluated as ○, and the difference from the target machining diameter was ± 5 μm or more, or the state where unevenness was seen on the wall of the machining hole was evaluated as ×.

<Separation of coated substrate> Using an excimer laser processing machine (wavelength 308 nm), a laser beam with a beam size of 14 mm × 1.2 mm and a moving speed of 6 mm / s was irradiated from the support side. A state in which the polyimide layer was completely separated was set to ○, and a state in which the coating substrate and the whole or a part of the polyimide layer were not separated, or a state in which the polyimide layer was discolored was set to ×.

<Transmittance> A polyimide film was produced by etching Yin steel with an iron chloride aqueous solution from a laminate of Yin Steel and polyimide. When polyimide is formed on glass, the polyimide is peeled from the glass to obtain a polyimide film. Shimazu (SHIMADZU) UV-3600 spectrophotometer was used to measure the light transmittance of this polyimide film (50 mm × 50 mm) at 500 nm, 400 nm, 355 nm, and 308 mm. The transmittance of each wavelength is shown in Table 1.

[Synthesis Example 1] (Polyimide precursor solution 1) In a 300 ml separable flask under a nitrogen stream, 8.49 g of TFMB was dissolved in 70 g of DMAc in a solvent. Next, 1.47 g of 6FDA was added to the solution and stirred, then 5.04 g of PMDA was added, 15 g of DMAc was added so that the solid content became 15 wt%, and the polymerization reaction was performed by stirring at room temperature for 6 hours. A viscous, colorless and transparent polyfluorene imine precursor solution 1 was obtained after the reaction.

[Synthesis Example 2] (Polyimide precursor solution 2) In a 200 ml separable flask under a nitrogen stream, 26.3 g of TFMB was dissolved in the solvent DMAc while stirring. Next, 16.9 g of PMDA and 1.8 g of 6FDA were added to the solution. Thereafter, the solution was stirred at room temperature for 6 hours to perform a polymerization reaction. A viscous, colorless and transparent polyfluorene imine precursor solution 2 was obtained after the reaction.

[Synthesis Example 3] (Polyimide precursor solution 3) Under a nitrogen flow, 29.1 g of BAPP was added to a solvent DMAc while stirring in a 500 ml separable flask to dissolve it. Then, BPDA 3.23 g and PMDA 13.6 g were added. Thereafter, the solution was continuously stirred at room temperature for 3 hours to perform a polymerization reaction, thereby obtaining a thick tea brown polyimide precursor solution 3.

[Synthesis Example 4] (Polyimide precursor solution 4) In a 300 ml separable flask under a nitrogen stream, 8.9334 g of TFMB was dissolved in 70 g of DMAc in a solvent. Next, 6.0666 g of PMDA was added to the solution, 15 g of DMAc was added so that the solid content became 15 wt%, and the mixture was stirred at room temperature for 6 hours to perform a polymerization reaction. A viscous, colorless and transparent polyfluorene imine precursor solution 4 was obtained after the reaction.

[Synthesis Example 5] (Polyimide precursor solution 5) Under nitrogen flow, 8.0 g of PPD was added to a solvent DMAc while stirring in a 300 ml separable flask, and the mixture was heated at 50 ° C and dissolved at 50 ° C. Then, BPDA 22.0 g was added. Thereafter, the solution was continuously stirred at room temperature for 3 hours to perform a polymerization reaction, thereby obtaining a thick, tea-brown polyimide precursor solution 5.

[Synthesis Example 6] (Polyimide precursor solution 6) Under a nitrogen stream, mTB 20.3 g and TPE-R 3.1 g were added to a solvent DMAc while stirring in a 500 ml separable flask to dissolve them. Then, PMDA 18.4 g and BPDA 6.2 g were added. Thereafter, the solution was continuously stirred at room temperature for 4 hours to perform a polymerization reaction, thereby obtaining a thick tea-brown polyimide precursor solution 6.

[Synthesis Example 7] (Polyimide precursor solution 7) In a 100 ml separable flask under nitrogen flow, 9.0756 g of TFMB was added to the solvent while stirring while dissolving it. Then, PMDA 4.3 g and CBDA 1.65 g were added. Thereafter, the solution was continuously stirred at room temperature for 4 hours to perform a polymerization reaction, thereby obtaining a thick and transparent polyfluorene imine precursor solution 7.

[Synthesis Example 8] (Polyimide precursor solution 8) Under a nitrogen stream, 18.9 g of TFMB was added to a solvent DMAc while stirring in a 500 ml separable flask to dissolve it. Then, 26.1 g of 6FDA was added. Thereafter, the solution was continuously stirred at room temperature for 5 hours to perform a polymerization reaction, thereby obtaining a thick and transparent polyfluorene imine precursor solution 8.

[Synthesis Example 9] (Polyimide precursor solution 9) 9.34 g of TFMB was added to a solvent NMP while stirring in a 100 ml separable flask under a nitrogen stream to dissolve it. Then, CBDA 5.66 g was added. Thereafter, the solution was continuously stirred at room temperature for 4 hours to perform a polymerization reaction, thereby obtaining a thick and transparent polyfluorene imine precursor solution 9.

[Synthesis Example 10] (Polyimide precursor solution 10) 9.30 g of TFMB was added to a solvent NMP while stirring in a 100 ml separable flask under a nitrogen stream to dissolve it. Then, 0.63 g of PMDA and 5.07 g of CBDA were added. Thereafter, the solution was continuously stirred at room temperature for 4 hours to perform a polymerization reaction, thereby obtaining a thick and transparent polyfluorene imine precursor solution 10.

[Synthesis Example 11] (Polyimide precursor solution 11) In a 100 ml separable flask under a nitrogen stream, 6.3458 g of m-TB was placed and dissolved in 85 g of DMAc. Then, 8.6542 g of BPDA was added to the solution. This solution was heated at 40 ° C. for 10 minutes to dissolve the contents, and then the solution was continuously stirred at room temperature for 24 hours to perform a polymerization reaction, thereby obtaining a thick and transparent polyfluorene imine precursor solution 11.

[Synthesis Example 12 to Synthesis Example 18] (Polyimide precursor solution 12 to Polyimide precursor solution 18) In addition to using the acid anhydride, diamine, and solvent shown in Table 2, it was used as in Synthesis Example 1 The polyfluorene imide precursor solution 12 to the polyfluorene imine precursor solution 18 were obtained in the same manner. The state of the obtained polyfluorene imide precursor solution is shown in Table 2.

[Example 1] Four sides of a sheet-shaped Yin Gang (thickness 100 μm, 100 mm × 100 mm) were fixed to glass (thickness 500 μm, 150 mm × 150 mm) with a heat-resistant tape. In this case, glass is a fixed member. Using an applicator, the polyimide precursor solution 1 was applied to the Yin steel so that the thickness of the polyimide layer after the heat treatment became 10 μm and a polyimide layer was formed in a size of 90 mm × 90 mm. It was heated at 100 ° C for 5 minutes using a hot air oven, and then heated to 360 ° C at 4 ° C / min to perform a heat treatment. After that, the heat-resistant tape was peeled off and the glass was separated to obtain a test laminate (corresponding to the “layer for vapor deposition hood” in the present invention. The same applies hereinafter) to Yin Gang and the polyimide layer. The warpage of the laminate was 0.3 mm.

A dry film resist was laminated on the surface of the obtained laminated body of Yin Gang, the dry film resist was patterned, and along this pattern, Yin Steel was etched with an aqueous solution of ferric chloride to form a 10 mm wide, 30 mm opening in metal layer. In addition, a UV-YAG laser processing machine was used to form an opening pattern in the polyimide layer in the opening so as to form a through hole having a diameter of 50 μm. The characteristics of this laminate are shown in Table 1.

[Example 2] Except that Invar was not fixed to glass, it was carried out in the same manner as in Example 1 to obtain a test laminate of Invar and a polyimide layer. The warpage of this laminate was 0.4 mm. Furthermore, it carried out similarly to Example 1, the opening part was formed in the metal layer, and the through hole (opening pattern) was formed in the polyimide layer. The characteristics of this laminate are shown in Table 1.

[Example 3] An applicator was used to form a polyimide layer having a thickness of 10 μm after heat treatment, and divide the polyimide layer from left to right by 80 mm´35 mm. Except that the fluorene imine precursor solution 1 was applied to Yin Gang, the same procedure as in Example 1 was performed to obtain a test laminate of Yin steel and polyfluorene. At this time, the polyimide layer was not formed at 5 mm inside the four sides of Yin Gang, and the polyimide layer was not formed at a gap of 10 mm between the two polyimide layers formed in two. The warpage of this laminate was 0.1 mm. Furthermore, it carried out similarly to Example 1, the opening part was formed in the metal layer, and the through hole (opening pattern) was formed in the polyimide layer. The characteristics of this laminate are shown in Table 1.

[Example 4] A polyimide precursor solution 2 was applied so that the thickness of the polyimide layer after the heat treatment became 25 μm, and the same procedure was performed as in Example 1 to obtain Yin Gang and Polyimide. A laminate for testing an amine layer. The warpage of the laminate was 0.3 mm. Furthermore, it carried out similarly to Example 1, the opening part was formed in the metal layer, and the through hole (opening pattern) was formed in the polyimide layer. The characteristics of this laminate are shown in Table 1.

[Example 5] A roll-shaped long Yin steel with a thickness of 100 μm, a width of 100 mm, and a length of 30 m was placed in a roll-to-roll heating furnace, and the long Yin steel was drawn out in the longitudinal direction. Using an applicator, the polyimide precursor solution 3 was applied to Yin Steel across the entire width of Yin Steel so that the thickness of the polyimide layer after heat treatment became 2 μm, and it was also continuous in the longitudinal direction. It was applied on the ground, introduced into a heating furnace, and dried at 100 ° C for 5 minutes. Furthermore, the polyimide precursor solution 2 was applied to the polyimide formed on Yin Steel so that the thickness of the polyimide layer after the heat treatment became 25 μm using an applicator in the entire width direction of Yin Steel. The precursor layer is also continuously applied in the lengthwise direction, and is introduced into a heating furnace and heat-treated at 100 ° C, 150 ° C, 200 ° C, 250 ° C, and 350 ° C for 5 minutes, respectively, to obtain a long Yingang steel and polymer A laminate of a sulfonium imine layer. At this time, tension is applied to the invar steel during transportation, and the guide roller in the heating furnace is pressed to fix the invar steel during the heat treatment. In this case, the guide roller is a fixed member. The guide rollers were arranged so as to be in contact with Yin Steel only and not in contact with the polyimide surface. The warp of the test laminate obtained by cutting out the laminate of the long invar and polyimide layer into a size of 100 mm × 100 mm was 0.4 mm. Moreover, it carried out similarly to Example 1, the opening part was formed in the metal layer, and the through hole (opening pattern) was formed in the polyimide layer. The characteristics of this laminate are shown in Table 1. Furthermore, the thermal expansion coefficient of the single-layer polyfluorene imine film obtained by imidizing the polyfluorene imine precursor solution with 3 fluorene was 56 × 10 ^-6 / K, and the polyfluorene imine precursor solution was 2 fluorimine The thermal expansion coefficient of the converted single-layer polyfluoreneimide film was 0.5 × 10 ^-6 / K.

[Example 6] Except that polyimide precursor solution 4 was used for Yin Gang, a test laminate of Yin Gang and polyimide was obtained in the same manner as in Example 1. The warpage of this laminate was 0.1 mm. Furthermore, it carried out similarly to Example 1, the opening part was formed in the metal layer, and the through hole (opening pattern) was formed in the polyimide layer. The characteristics of this laminate are shown in Table 1.

[Example 7] Using an applicator, a polyimide precursor solution 5 was coated on Yin Gang so that the thickness of the polyimide layer after heat treatment was 10 μm, and heated at 100 ° C. using a hot air oven 5 Minutes later, the temperature was raised to 400 ° C. at 1 ° C./min, and heat treatment was performed, except that the same procedure as in Example 1 was performed to obtain a test laminate of Yin Gang and polyimide. The warpage of this laminate was 0.2 mm. Furthermore, it carried out similarly to Example 1, the opening part was formed in the metal layer, and the through hole (opening pattern) was formed in the polyimide layer. The characteristics of this laminate are shown in Table 1.

[Example 8] Using a spin coater, the polyimide precursor solution 2 was applied to the entire thickness of a glass having a thickness of 500 μm and 150 mm by 150 mm so that the thickness of the polyimide layer after the heat treatment was 25 μm. The surface was heated at 100 ° C. for 5 minutes using a nitrogen oven, and then heated to 360 ° C. at 4 ° C./min to perform a heat treatment to form a polyfluoreneimide layer on the glass. In this case, glass is a coating substrate. After masking tape with a width of 10 mm and a length of 30 mm was attached to the polyimide layer, it was sputtered to a thickness of 30 nm of nickel, and each piece of glass was immersed in a plating bath to a thickness of 5 In the μm method, a nickel layer having an opening portion having a width of 10 mm and a length of 30 mm was formed on the polyimide layer. Next, after the masking tape was peeled off, the polyimide layer was separated from the glass by laser lift-off of irradiating excimer laser light (wavelength 308 nm) from the glass side, thereby obtaining a width of 10 mm and a length of 30 mm. A test laminate of a nickel layer and a polyimide layer at the opening portion of the substrate. Then, the polyimide layer in the opening of the nickel layer was penetrated by a UV-YAG laser processing machine with a through hole having a diameter of 50 μm to form an opening pattern. The characteristics of this laminate are shown in Table 1.

[Example 9] The procedure was carried out in the same manner as in Example 8 except that the polyfluorene imine precursor solution 6 was used and a hot air oven was used instead of the nitrogen oven. That is, a polyimide layer is formed on glass, and then a nickel layer having an opening is formed to obtain a test laminate of a nickel layer having an opening and a polyimide layer. Furthermore, the polyimide layer was separated from glass by laser peeling, and an opening pattern was formed in the polyimide layer. The characteristics of this laminate are shown in Table 1.

[Example 10] The procedure was carried out in the same manner as in Example 8 except that the polyfluorene imine precursor solution 7 was used. That is, a polyimide layer is formed on glass, and then a nickel layer having an opening is formed to obtain a test laminate of a nickel layer having an opening and a polyimide layer. Furthermore, the polyimide layer was separated from glass by laser peeling, and an opening pattern was formed in the polyimide layer. The characteristics of this laminate are shown in Table 1.

[Example 11 to Example 18] The procedure was carried out in the same manner as in Example 8 except that the polyfluorene imine precursor solution 11 to the polyfluorene imine precursor solution 18 were used. That is, a polyimide layer is formed on glass, and then a nickel layer having an opening is formed to obtain a test laminate of a nickel layer having an opening and a polyimide layer. Furthermore, the polyimide layer was separated from glass by laser peeling, and an opening pattern was formed in the polyimide layer. Table 1 shows the characteristics of the laminate and the polyfluorene imide used.

[Example 19] A long bar-shaped invar steel having a thickness of 100 μm, a width of 100 mm, and a length of 30 m was placed in a roll-to-roll heating furnace, and the long bar was taken out along the longitudinal direction. The polyfluorene imide precursor solution 3 was applied to Yin Gang using an applicator so that the thickness of the polyfluorine imide layer after the heat treatment became 0.8 μm, and introduced into a heating furnace and dried at 100 ° C. for 5 minutes. Further, the polyimide precursor solution 2 was applied to a polyimide precursor layer formed on Yin Steel using an applicator so that the thickness of the polyimide layer after the heat treatment became 25 μm, and introduced into the heat. Drying was performed in an oven at 100 ° C. for 5 minutes, thereby forming a two-layer polyfluorene imide precursor layer. Furthermore, the polyimide precursor solution 3 was applied to the two-layer polyimide precursor layer using an applicator so that the thickness of the polyimide layer after the heat treatment became 1.2 μm, at 100 ° C. and 150 ° C. Heat treatment was performed at 5 ° C, 200 ° C, 250 ° C, and 350 ° C for 5 minutes, respectively, to obtain a laminate of a long Yin steel and a polyimide layer. At this time, tension is applied to the invar steel during transportation, and the guide roller in the heating furnace is pressed to fix the invar steel during the heat treatment. In this case, the guide roller is a fixed member. The guide rollers were arranged so as to be in contact with Yin Steel only and not in contact with the polyimide surface. The warp of the test laminate obtained by cutting out the laminate of the long invar and polyimide layer into a size of 100 mm × 100 mm was 0.4 mm. Moreover, it carried out similarly to Example 1, the opening part was formed in the metal layer, and the through hole (opening pattern) was formed in the polyimide layer. The characteristics of this laminate are shown in Table 1. Furthermore, the thermal expansion coefficient of the single-layer polyfluorene imine film obtained by imidizing the polyfluorene imine precursor solution with 3 fluorene was 56 × 10 ^-6 / K, and the polyfluorene imine precursor solution was 2 fluorimine The thermal expansion coefficient of the converted single-layer polyfluoreneimide film was 0.5 × 10 ^-6 / K. The characteristics of this laminate are shown in Table 1.

[Comparative Example 1] A laminate of Invar and a polyimide layer was obtained in the same manner as in Example 1 except that the polyimide precursor solution 8 was used. The warpage of this laminate was 1.9 mm. The characteristics of this laminate are shown in Table 1.

[Comparative Example 2] A laminate of Invar and a polyimide layer was obtained in the same manner as in Example 1 except that polyimide precursor solution 3 was used. The warpage of this laminate was 1.4 mm. The characteristics of this laminate are shown in Table 1.

[Comparative Example 3] A polyfluorene imide layer was formed on glass in the same manner as in Example 8 except that the polyfluorene imine precursor solution 9 was used. As a result of laser peeling, the polyimide layer became black and brittle, and a good polyimide film could not be obtained. The characteristics of this laminate are shown in Table 1.

[Comparative Example 4] Except that the polyfluorene imide precursor solution 10 was used, the same procedure as in Example 8 was performed, and as a result, the warpage of the laminate was 1.1 mm. The characteristics of this laminate are shown in Table 1.

[Comparative Example 5] Using an epoxy-based adhesive, a sheet-shaped invar (thickness 100 μm, 100 mm × 100 mm) and a polyimide film (Kapton EN-A, thickness 25 μm, 90 mm × 90 mm) Next, it was held at 120 ° C. for 30 minutes while being pressurized with a batch press to obtain a laminate of polyimide and Yin Gang. The coefficient of thermal expansion of the polyfluoreneimide film is anisotropic, which is 6.2 × 10 ^-6 / K in one direction and 13.0 × 10 ^-6 / K in a direction orthogonal to the same. This laminated body warped in a direction in which the thermal expansion coefficient of polyimide was 13.0 × 10 ^-6 / K, and the warpage was 0.6 mm. The characteristics of this laminate are shown in Table 1.

A dry film resist was laminated on the surface of the obtained laminated body of Yin Gang, and the dry film resist was patterned, and along this pattern, Yin Steel was etched with an aqueous solution of ferric chloride to form a 3 mm wide, 10 mm long metal layer opening. In addition, a UV-YAG laser processing machine was used to form a polyimide in the opening so as to form a through-hole with a diameter of 50 μm. An attempt was made to form an opening pattern. The interface is uneven, and a good opening pattern cannot be formed.

[Table 1]

[Table 2] (Unit: g)

1‧‧‧ metal layer

1a‧‧‧ opening

2‧‧‧Polyimide layer

2a‧‧‧through hole

3‧‧‧ opening pattern

4‧‧‧Evaporation mask

1 (1) to 1 (2) are a metal layer 1 having a plurality of openings 1a [FIG. 1 (1)] and a polyimide layer 2 having a through hole 2a [FIG. 1 (2)] The schematic illustration of the plane. 2 (1) to 2 (2) are plan views showing a vapor deposition mask including a laminate in which a metal layer 1 and a polyimide layer 2 are laminated [FIG. 2 (1)], and the vapor deposition XX 'cross-sectional view of the mask [FIG. 2 (2)] is a schematic explanatory diagram.

Claims (20)

A vapor deposition hood is used for vapor deposition to form a fixed shape thin film pattern on a body to be vapor-deposited. The vapor deposition hood is characterized by comprising a laminate of a metal layer and a polyimide layer, the metal The layer has a plurality of openings. The polyimide layer has through holes located in the opening range of the openings and has an opening pattern corresponding to the film pattern. The polyimide layer is made of a single layer. The polyfluorene imide is formed in one or more layers, and the thermal expansion coefficient of the polyfluorine imide layer is 10 × 10 ⁻⁶ / K or less in all directions in the plane. According to the vapor deposition cover described in item 1 of the scope of the patent application, the polyimide layer is one having an isotropic thermal expansion coefficient in an in-plane direction. The vapor deposition cover according to item 1 or item 2 of the patent application scope, wherein the main polyimide forming the polyimide layer is a structural unit represented by the following formula (1) Polyimide precursor Wherein R ₁ is a divalent organic group selected from the group represented by the following formula (2), R 'are each independently an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group, an aromatic group having 6 to 18 carbon atoms, or a halogen group, and the hydrogen atom of the aromatic group may pass through a halogen atom and 1 to 6 carbon atoms. 6 is substituted by an alkyl group or a halogenated alkyl group; Z is NH or O, and R ₂ is a tetravalent organic group selected from the group represented by the following formula (3), R each independently represents a hydrogen atom or a monovalent organic group, and n is a positive integer representing a repeating number. The vapor deposition mask according to item 3 of the scope of patent application, wherein the main polyimide forming the polyimide layer is represented by the formula (1) that will contain 60 mol% or more. Polyimide precursors of structural units are formed by imidization. The vapor deposition cover according to item 1 or item 2 of the patent application scope, wherein the metal layer is a magnetic body. According to the vapor deposition cover described in item 5 of the patent application scope, wherein the magnetic body is invar or invar alloy. The vapor deposition mask according to item 1 or item 2 of the patent application scope, wherein the polyimide layer has a light transmittance of more than 60% at a wavelength of 500 nm, and a wavelength of 355 nm and / or a wavelength The transmittance at 308 nm is less than 50%. The vapor deposition mask according to item 3 of the scope of the patent application, wherein the main polyimide constituting the polyimide layer is a fluorine-containing polyimide or an alicyclic polyimide. The vapor deposition mask according to item 1 or item 2 of the scope of patent application, wherein the metal layer and the polyimide layer are laminated without interposing an adhesive. The vapor deposition mask according to item 1 or item 2 of the patent application scope, wherein the polyimide layer comprises a plurality of polyimide, and the main polyimide forming the polyimide layer The thermal expansion coefficient of the amine is smaller than the thermal expansion coefficient of polyimide other than the main polyimide. The vapor deposition cover according to item 1 or item 2 of the scope of the patent application, wherein the polyimide layer includes a plurality of polyimide, and thermal expansion of the polyimide connected to the metal layer The coefficient is larger than the thermal expansion coefficients of other polyimide adjacent to the polyimide adjoining the metal layer. The vapor deposition cover according to item 1 or item 2 of the scope of the patent application, wherein the polyimide layer includes a plurality of polyimide, and thermal expansion of the polyimide connected to the metal layer The coefficient is smaller than the thermal expansion coefficient of other polyimide adjacent to the polyimide adjoining the metal layer. The vapor deposition mask according to item 1 or item 2 of the patent application scope, wherein the polyimide layer includes three or more layers of polyimide, forming two outermost layers of polyimide on the surface and the back surface. The thermal expansion coefficient of the imine is larger than the thermal expansion coefficient of the polyimide forming the intermediate layer sandwiched by these outermost polyimides, and any polyimide forming the outermost surface is different from the The metal layers are connected. The vapor deposition cover according to item 1 or item 2 of the patent application scope, wherein the polyimide layer is divided into two or more layers in the plane of the metal layer and laminated. A method for manufacturing a vapor deposition hood is used for vapor deposition to form a fixed-shape thin film pattern on a body to be vapor-deposited. The method for manufacturing the vapor deposition hood is characterized in that the thermal expansion coefficient is on the surface. A polyimide layer having a thickness of 10 × 10 ^-6 / K or less in all directions inside is laminated with a metal layer, and a plurality of openings are formed in the metal layer, or a metal layer having a plurality of openings and a thermal expansion coefficient After the polyimide layer having a thickness of 10 × 10 ^-6 / K or less in all directions in the plane is laminated, the polyimide layer in the opening range in the opening portion of the metal layer is penetrated, Thereby, an opening pattern corresponding to the thin film pattern is formed. A method for manufacturing a vapor deposition hood is used for vapor deposition to form a fixed shape film pattern on a body to be vapor-deposited. The method for manufacturing the vapor deposition hood includes: A liquid composition of an imine or a polyimide precursor is coated on a coating substrate and heated to form a thermal expansion coefficient on the coating substrate of 10 × 10 ^-6 / in all directions in a plane. A step of polyimide layer below K; laminating a metal layer on the polyimide layer and forming a plurality of openings in the metal layer, or laminating a metal layer having a plurality of openings on the metal layer A step on a polyimide layer; a step of separating the polyimide layer from the coating substrate; and the polyimide in an opening range in the opening portion of the metal layer A step of penetrating the amine layer to form an opening pattern corresponding to the thin film pattern. A method for manufacturing a vapor deposition mask is used for vapor deposition to form a fixed shape film pattern on a body to be vapor-deposited. The method for manufacturing the vapor deposition mask is characterized in that: the metal layer is fixed A step on the fixing member; applying a liquid composition containing polyimide or a polyimide precursor to a surface of the metal layer and heating the liquid composition to form a polyimide layer on the metal layer Steps; a step of separating the metal layer from the fixing member; a step of forming a plurality of openings in the metal layer; and the step of making the polycondensation within an opening range in the openings of the metal layer A step of penetrating the imine layer to form an opening pattern corresponding to the thin film pattern. A laminated body for a vapor deposition hood is a laminated metal layer including a magnetic layer and a polyimide layer, and is used for vapor deposition of the drape to form a fixed-shaped thin film pattern on the vapor-deposited body. The laminated body for the vapor deposition hood is characterized in that the thermal expansion coefficient of the polyfluorene imide layer is 10 × 10 ^-6 / K or less in all directions in the plane, and the polyfluorine imide layer is composed of a single layer or A multi-layer polyimide is formed, and the main polyimide is obtained by imidizing a polyimide precursor having a structural unit represented by the following formula (1). Wherein R ₁ is a divalent organic group selected from the group represented by the following formula (2), R 'are each independently an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group, an aromatic group having 6 to 18 carbon atoms, or a halogen group, and the hydrogen atom of the aromatic group may pass through a halogen atom and 1 to 6 carbon atoms. 6 is substituted by an alkyl group or a halogenated alkyl group; Z is NH or O, and R ₂ is a tetravalent organic group selected from the group represented by the following formula (3), R each independently represents a hydrogen atom or a monovalent organic group, and n is a positive integer representing a repeating number. A method for producing a laminated body for a vapor deposition hood is a laminated body for a vapor deposition hood, which is formed by laminating a metal layer containing a magnetic body and a polyimide layer, and is used for vapor deposition on a vapor-deposited body. A method for producing a fixed-shape thin film pattern by vapor deposition, the method comprising: applying a liquid composition containing polyimide or a polyimide precursor to the metal layer; A step of forming a coating layer on the surface of the metal layer; and a step of heating the coating layer to form a polyimide layer on the metal layer; the liquid composition includes a compound represented by the following formula (1) A polyfluorene imine precursor of a structural unit or a polyfluorene imine obtained by fluorinating the polyfluorene imine precursor, so as to thermally expand the polyfluorene imide layer formed on the metal layer The coefficient is 10 × 10 ^-6 / K or less in all directions in the plane, Wherein R ₁ is a divalent organic group selected from the group represented by the following formula (2), R 'are each independently an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group, an aromatic group having 6 to 18 carbon atoms, or a halogen group, and the hydrogen atom of the aromatic group may pass through a halogen atom and 1 to 6 carbon atoms. 6 is substituted by an alkyl group or a halogenated alkyl group; Z is NH or O, and R ₂ is a tetravalent organic group selected from the group represented by the following formula (3), R each independently represents a hydrogen atom or a monovalent organic group, and n is a positive integer representing a repeating number. The method for manufacturing a laminate for vapor deposition hoods according to item 19 of the patent application scope, wherein the step of forming the coating layer on the surface of the metal layer includes fixing the metal layer to a fixed surface. Steps on the component.