JP6949507B2 - Thin-film mask and its manufacturing method, and laminated body for thin-film mask and its manufacturing method - Google Patents

Description

The present invention relates to a thin-film deposition mask for forming a thin-film pattern having a constant shape on an object to be vapor-deposited, and enables the formation of a high-definition thin-film pattern required for, for example, an organic EL display device. The present invention relates to a mask and a method for manufacturing the same, and a laminated body for a vapor-deposited mask and a method for manufacturing the same.

For example, organic EL display devices are used for large displays such as televisions, small displays such as mobile phones, personal computers, and smartphones, lighting, and the like. In this organic EL display device, a thin film transistor (hereinafter referred to as TFT) is formed on a thin-film transistor (hereinafter referred to as TFT) made of glass or resin as a supporting base material, and an electrode, a light emitting layer, and an electrode are sequentially formed. Finally, it is separately airtightly sealed with a glass substrate or a multilayer thin film.

Conventionally, in the formation of a light emitting layer and a cathode electrode of an organic EL display device, a thin-film deposition mask composed of only a metal layer in which a large number of fine openings are arranged, for example, in a region to be vapor-deposited on an object to be deposited. Was used. At that time, in general, since the opening corresponding to the thin film pattern is formed by etching or the like of the metal layer, it is difficult to form the opening with high accuracy. In addition, in order to improve productivity in recent years, it is necessary to improve productivity by increasing the size of the vapor-deposited body and to cope with the increase in the size of the organic EL display device, so there is an increasing demand for larger vapor deposition masks. It's coming. However, there is a problem that precise position control becomes difficult because the weight of the vapor deposition mask increases with such an increase in size.

Therefore, various studies have been made to solve the problem of the vapor deposition mask of the metal layer alone. For example, Patent Document 1 discloses a vapor deposition mask in which a metal mask and a resin mask are bonded with an adhesive. .. Further, 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. Of these, Patent Document 1 describes that as the material for the resin mask, a lightweight material is preferable because a high-definition opening can be formed by laser processing or the like, and the heat and the change with time are small. Examples of such materials include polyimide, polyamide, polyamideimide, polyester, polyethylene, polyvinyl alcohol, polypropylene, polycarbonate, polystyrene and the like. Further, Patent Document 2 discloses that polyimide is preferable in that it has high heat resistance and can form openings with high accuracy. However, in any case, a specific study on the characteristics of the resin mask and a specific resin having the same are not disclosed.

Regarding the characteristics of the resin mask, for example, Patent Document 3 discloses that the influence of the thermal expansion rate of the resin layer forming the resin mask can be reduced by reducing the thickness to about 10 μm or less. Further, Patent Document 4 discloses a vapor deposition mask using an anisotropic polyimide film and a magnetic metal, which have different coefficients of thermal expansion on two orthogonal axes. However, in the conventional laminated type vapor deposition mask in which the resin layer is laminated on the metal layer including these Patent Documents 3 and 4, it is difficult to suppress the warp, and there is a possibility that a problem may occur in the accuracy of the thin film pattern. There is. For example, Patent Document 5 discloses a flexible printed wiring board composed of a polyimide layer and a conductor such as a copper foil. The polyimide layer has a multilayer structure, and a part of the polyimide layer has a low thermal expansion. Although it is stated that it is included, there are design items and technical ideas between a laminate that requires flexibility such as a flexible printed wiring board and a laminate that requires vapor deposition accuracy of a thin film pattern such as a vapor deposition mask. Unlike the flexible printed wiring board, since the polyimide is required to be flexible, it contains a polyimide having a flexible skeleton, and the coefficient of thermal expansion is 15 × 10 in order to match the coefficient of thermal expansion with the copper foil. It is required to be ^{-6 / K or more.} On the other hand, the length of the flexible printed wiring board is several mm to several cm, whereas the vapor deposition mask is required to have high position accuracy at a distance exceeding 1 m, so that lower thermal expansion is required. Will be done.

Japanese Unexamined Patent Publication No. 2013-163864 Japanese Unexamined Patent Publication No. 2013-83704 Japanese Unexamined Patent Publication No. 2015-129333 Japanese Unexamined Patent Publication No. 2014-205870 Japanese Unexamined Patent Publication No. 8-250860

A high-definition thin film pattern is required for a thin film mask used for forming a thin film pattern by vapor deposition. For example, increasing the size of display devices such as televisions and digital signage is a trend, and small displays used in smartphones and the like are pursued to improve production efficiency. Therefore, it is expected that there will be an increasing demand for larger vapor deposition masks for obtaining high-definition thin film patterns. Therefore, the present inventors have diligently studied a thin-film deposition mask that can obtain a high-definition thin film pattern with high accuracy and can cope with such an increase in the size of the thin film pattern. As a result, a predetermined polyimide layer is used as a metal layer. We have found that the laminated vapor deposition mask makes it possible to suppress warpage and form a high-definition thin film pattern while coping with the increase in size of the vapor deposition mask, and completed the present invention.

Therefore, an object of the present invention is to provide a thin-film deposition mask capable of increasing the definition and size of a thin film pattern. Another object of the present invention is to provide a manufacturing method for obtaining such a thin-film deposition mask, and a laminate for the thin-film deposition mask and a method for manufacturing the same.

但し、Ｒ₁は、下記式（２）で表わされる群より選択される２価の有機基であり、

（Ｒ’は各々独立に炭素数１〜６のアルキル基、ハロゲン化アルキル基、炭素数６〜１８の芳香族基、またはハロゲン基であり、前記芳香族基の水素原子はハロゲン原子、炭素数１〜６のアルキル基、又はハロゲン化アルキル基で置換されてもよい。ＺはＮＨ又はＯである。）、
Ｒ₂は、下記式（３）で表わされる群より選択される４価の有機基であり、

Ｒは、各々独立に水素原子又は一価の有機基を示し、ｎは繰り返し数を表す正の整数である。
［４］前記ポリイミド層を形成する主たるポリイミドが、前記式（１）で表される構造単位を６０モル％以上含んだポリイミド前駆体をイミド化したものであることを特徴とする、［３］に記載の蒸着マスク。
［５］前記金属層が磁性体であることを特徴とする、［１］又は［２］に記載の蒸着マスク。
［６］前記磁性体は、インバー又はインバー合金であることを特徴とする、［５］に記載の蒸着マスク。
［７］前記ポリイミド層は、波長５００ｎｍでの光透過率が６０％以上であり、かつ、波長３５５ｎｍ及び／又は波長３０８ｎｍでの光透過率が５０％以下であることを特徴とする、［１］又は［２］に記載の蒸着マスク。
［８］前記ポリイミド層を構成する主たるポリイミドが、含フッ素ポリイミド又は脂環式ポリイミドであることを特徴とする、［３］に記載の蒸着マスク。
［９］前記金属層と前記ポリイミド層とが、接着剤を介すことなく積層されていることを特徴とする、［１］又は［２］に記載の蒸着マスク。
［１０］前記ポリイミド層が複数層のポリイミドからなり、該ポリイミド層を形成する主たるポリイミドの熱膨張係数が、それ以外のポリイミドの熱膨張係数より小さいことを特徴とする、［１］又は［２］に記載の蒸着マスク。
［１１］前記ポリイミド層が複数層のポリイミドからなり、前記金属層に接するポリイミドの熱膨張係数が、当該ポリイミドと隣接する他のポリイミドの熱膨張係数より大きいことを特徴とする、［１］又は［２］に記載の蒸着マスク。
［１２］前記ポリイミド層が複数層のポリイミドからなり、前記金属層に接するポリイミドの熱膨張係数が、当該ポリイミドと隣接する他のポリイミドの熱膨張係数より小さいことを特徴とする、［１］又は［２］に記載の蒸着マスク。
［１３］前記ポリイミド層が３つ以上の複数層のポリイミドからなり、表面と裏面を形成する最表面の２つのポリイミドの熱膨張係数が、これら最表面のポリイミドに挟まれた中間層を形成するポリイミドの熱膨張係数に比べて大きく、また、最表面を形成するいずれか一方のポリイミドが前記金属層に接することを特徴とする、［１］又は［２］に記載の蒸着マスク。
［１４］前記ポリイミド層は、金属層の面内で２以上に分割して積層されていることを特徴とする、［１］又は［２］に記載の蒸着マスク。 That is, the gist of the present invention is as follows.
[1] A thin-film deposition mask for forming a thin-film pattern having a constant shape on a body to be vapor-deposited, which has a metal layer having a plurality of openings and through holes located within the opening range of the openings. It is composed of a laminate with a polyimide layer having an opening pattern corresponding to the thin film pattern.
A vapor deposition mask characterized in that the polyimide layer is formed of a single layer or a plurality of layers of polyimide, and the coefficient of thermal expansion of the polyimide layer is 10 × 10 ^{-6 / K or less in all directions in the plane.}
[2] The vapor deposition mask according to [1], wherein the polyimide layer has an isotropic coefficient of thermal expansion in the in-plane direction.
[3] The method according to [1] or [2], wherein the main polyimide forming the polyimide layer is an imidized polyimide precursor having a structural unit represented by the following formula (1). Vapor deposition mask.

However, R ₁ is a divalent organic group selected from the group represented by the following formula (2).

(R'is independently an alkyl group having 1 to 6 carbon atoms, an alkyl halide group, an aromatic group having 6 to 18 carbon atoms, or a halogen group, and the hydrogen atom of the aromatic group is a halogen atom and a carbon number of carbon atoms. It may be substituted with an alkyl group of 1 to 6 or an alkyl halide group. Z is NH or O),
R ₂ is a tetravalent organic group selected from the group represented by the following formula (3).

R represents a hydrogen atom or a monovalent organic group independently, and n is a positive integer representing the number of repetitions.
[4] The main polyimide forming the polyimide layer is an imidized polyimide precursor containing 60 mol% or more of the structural units represented by the formula (1) [3]. The vapor deposition mask described in.
[5] The vapor deposition mask according to [1] or [2], wherein the metal layer is a magnetic material.
[6] The vapor deposition mask according to [5], wherein the magnetic material is an Invar or an Invar alloy.
[7] The polyimide layer is characterized in that the light transmittance at a wavelength of 500 nm is 60% or more, and the light transmittance at a wavelength of 355 nm and / or a wavelength of 308 nm is 50% or less [1]. ] Or the vapor deposition mask according to [2].
[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 using an adhesive.
[10] The polyimide layer is composed of a plurality of layers of polyimide, and the coefficient of thermal expansion of the main polyimide forming the polyimide layer is smaller than the coefficient of thermal expansion of the other polyimides, [1] or [2]. ] The vapor deposition mask described in.
[11] The polyimide layer is composed of a plurality of layers of polyimide, and the coefficient of thermal expansion of the polyimide in contact with the metal layer is larger than the coefficient of thermal expansion of another polyimide adjacent to the polyimide. [1] The vapor deposition mask according to [2].
[12] The polyimide layer is composed of a plurality of layers of polyimide, and the coefficient of thermal expansion of the polyimide in contact with the metal layer is smaller than the coefficient of thermal expansion of another polyimide adjacent to the polyimide, [1] or The vapor deposition mask according to [2].
[13] The polyimide layer is composed of three or more layers of polyimide, and the coefficient of thermal expansion of the two outermost polyimides forming the front surface and the back surface form an intermediate layer sandwiched between the outermost polyimides. The vapor deposition mask according to [1] or [2], which is larger than the coefficient of thermal expansion of polyimide and is characterized in that one of the polyimides forming the outermost surface is in contact with the metal layer.
[14] The vapor deposition mask according to [1] or [2], wherein the polyimide layer is divided into two or more and laminated in the plane of the metal layer.

但し、Ｒ₁は、下記式（２）で表わされる群より選択される２価の有機基であり、

（Ｒ’は各々独立に炭素数１〜６のアルキル基、ハロゲン化アルキル基、炭素数６〜１８の芳香族基、またはハロゲン基であり、前記芳香族基の水素原子はハロゲン原子、炭素数１〜６のアルキル基、又はハロゲン化アルキル基で置換されてもよい。ＺはＮＨ又はＯである。）、
Ｒ₂は、下記式（３）で表わされる群より選択される４価の有機基であり、

Ｒは、各々独立に水素原子又は一価の有機基を示し、ｎは繰り返し数を表す正の整数である。
［１９］磁性体からなる金属層とポリイミド層とが積層されて、被蒸着体上に一定形状の薄膜パターンを蒸着形成するための蒸着マスク用積層体の製造方法であって、
前記金属層の表面にポリイミド又はポリイミド前駆体を含む液状組成物を塗布して塗布層を形成する工程、及び、
前記塗布層を加熱して、前記金属層上にポリイミド層を形成する工程、
を含み、前記液状組成物が、下記式（１）で表わされる構造単位を有するポリイミド前駆体又は当該ポリイミド前駆体がイミド化したポリイミドを含んで、前記金属層上に形成されたポリイミド層の熱膨張係数が、面内の全ての方向で１０×１０^−６／Ｋ以下にすることを特徴とする蒸着マスク用積層体の製造方法。

但し、Ｒ₁は、下記式（２）で表わされる群より選択される２価の有機基であり、

（Ｒ’は各々独立に炭素数１〜６のアルキル基、ハロゲン化アルキル基、炭素数６〜１８の芳香族基、またはハロゲン基であり、前記芳香族基の水素原子はハロゲン原子、炭素数１〜６のアルキル基、又はハロゲン化アルキル基で置換されてもよい。ＺはＮＨ又はＯである。）、
Ｒ₂は、下記式（３）で表わされる群より選択される４価の有機基であり、

Ｒは、各々独立に水素原子又は一価の有機基を示し、ｎは繰り返し数を表す正の整数である。
［２０］前記金属層の表面に塗布層を形成する工程に先駆けて、固定部材上に金属層を固定する工程を含むことを特徴とする、［１９］に記載の蒸着マスク用積層体の製造方法。 [15] A method for producing a thin-film deposition mask for forming a thin-film pattern having a constant shape on a body to be vapor-deposited, wherein the coefficient of thermal expansion is 10 × 10 ^-6 / K or less in all directions in the plane. The layer and the metal layer are laminated to form a plurality of openings in the metal layer, or the metal layer having a plurality of openings and the coefficient of thermal expansion are 10 × 10 ^-6 / in all directions in the plane. Manufacture of a thin-film deposition mask characterized in that after laminating a polyimide layer having a K or less, the polyimide layer within the opening range in the opening of the metal layer is penetrated to form an opening pattern corresponding to the thin film pattern. Method.
[16] A method for manufacturing a thin-film deposition mask for forming a thin-film pattern having a constant shape on a body to be vapor-deposited.
A liquid composition containing polyimide or a polyimide precursor is applied onto the coated substrate and heated to have a coefficient of thermal expansion of 10 × 10 ^-6 / K or less in all in-plane directions on the coated substrate. The process of forming the polyimide layer, which is
A step of laminating a metal layer on the polyimide layer to form a plurality of openings in the metal layer, or laminating a metal layer having a plurality of openings on the polyimide layer.
A step of separating the polyimide layer and the coating base material, and
A step of forming an opening pattern corresponding to the thin film pattern by penetrating a polyimide layer within the opening range of the opening of the metal layer.
A method for producing a vapor deposition mask, which comprises.
[17] A method for manufacturing a thin-film deposition mask for forming a thin-film pattern having a constant shape on a body to be vapor-deposited.
The process of fixing the metal layer on the fixing member,
A step of applying a liquid composition containing polyimide or a polyimide precursor to the surface of the metal layer and heating to form a polyimide layer on the metal layer.
A step of separating the metal layer and the fixing member,
A step of forming a plurality of openings in the metal layer, and
A step of forming an opening pattern corresponding to the thin film pattern by penetrating a polyimide layer within the opening range of the opening of the metal layer.
A method for producing a vapor deposition mask, which comprises.
[18] A laminated body for a vapor deposition mask for laminating a metal layer made of a magnetic material and a polyimide layer to form a thin film pattern having a constant shape on the body to be vapor-deposited, and thermal expansion of the polyimide layer. ^{The coefficient is 10 × 10 -6} / K or less in all directions in the plane, the polyimide layer is formed from a single layer or a plurality of layers of polyimide, and the main polyimide is represented by the following formula (1). A laminated body for a vapor deposition mask, which is an imidized polyimide precursor having a structural unit.

However, R ₁ is a divalent organic group selected from the group represented by the following formula (2).

(R'is independently an alkyl group having 1 to 6 carbon atoms, an alkyl halide group, an aromatic group having 6 to 18 carbon atoms, or a halogen group, and the hydrogen atom of the aromatic group is a halogen atom and a carbon number of carbon atoms. It may be substituted with an alkyl group of 1 to 6 or an alkyl halide group. Z is NH or O),
R ₂ is a tetravalent organic group selected from the group represented by the following formula (3).

R represents a hydrogen atom or a monovalent organic group independently, and n is a positive integer representing the number of repetitions.
[19] A method for producing a laminated body for a thin-film deposition mask for laminating a metal layer made of a magnetic material and a polyimide layer to form a thin-film pattern having a constant shape on the body to be vapor-deposited.
A step of applying a liquid composition containing polyimide or a polyimide precursor to the surface of the metal layer to form a coating layer, and
A step of heating the coating layer to form a polyimide layer on the metal layer,
The liquid composition contains a polyimide precursor having a structural unit represented by the following formula (1) or a polyimide in which the polyimide precursor is imidized, and the heat of the polyimide layer formed on the metal layer. A method for producing a laminate for a vapor deposition mask, characterized in that the expansion coefficient is 10 × 10 ^{-6 / K or less in all directions in the plane.}

However, R ₁ is a divalent organic group selected from the group represented by the following formula (2).

(R'is independently an alkyl group having 1 to 6 carbon atoms, an alkyl halide group, an aromatic group having 6 to 18 carbon atoms, or a halogen group, and the hydrogen atom of the aromatic group is a halogen atom and a carbon number of carbon atoms. It may be substituted with an alkyl group of 1 to 6 or an alkyl halide group. Z is NH or O),
R ₂ is a tetravalent organic group selected from the group represented by the following formula (3).

R represents a hydrogen atom or a monovalent organic group independently, and n is a positive integer representing the number of repetitions.
[20] The production of the laminated body for a vapor deposition mask according to [19], which comprises a step of fixing the metal layer on the fixing member prior to the step of forming the coating layer on the surface of the metal layer. Method.

According to the present invention, in a vapor deposition mask made of a laminated body in which a polyimide layer and a metal layer are laminated, warpage can be suppressed, and a high-definition thin film pattern can be formed while corresponding to an increase in the size of the vapor deposition mask. Will be. Therefore, according to the vapor deposition mask of the present invention, it is possible to cope with a large screen of a display device such as an organic EL display device, improvement of production efficiency of a small display used in a smartphone or the like, further improvement in definition, and the like. become able to.

FIG. 1 is a schematic plan explanatory view showing a metal layer 1 [FIG. 1 (1)] having a plurality of openings 1a and a polyimide layer 2 [FIG. 1 (2)] having through holes 2a. FIG. 2 is a plan view [FIG. 2 (1)] of a vapor deposition mask composed of a laminated body in which a metal layer 1 and a polyimide layer 2 are laminated, and a cross-sectional view taken along the line XX'of the vapor deposition mask [FIG. 2 (2)). ] Is a schematic explanatory view showing.

Hereinafter, the present invention will be described in detail.
In the vapor deposition mask of the present invention, a polyimide layer having an opening pattern corresponding to a thin film pattern is formed of a single layer or a plurality of layers of polyimide, and the coefficient of thermal expansion of this polyimide layer is 10 × 10 ^{− in all directions in the plane.} Make sure that it is ^{6 / K or less.} If the coefficient of thermal expansion (CTE) is 10 × 10 ^-6 / K or less, the dimensional deviation from the low thermal expansion metal layer suitable for the vapor deposition mask due to temperature changes during the process can be reduced, and thus multiple openings. When the metal layer and the laminate provided with the portions are formed, the flatness can be maintained at room temperature and the flatness can be maintained even when the temperature rises during vapor deposition. Preferably, the CTE is -10 × 10 ^-6 / K or more and 10 × 10 ^-6 / K or less, and more preferably, the upper limit of the CTE is 8 × 10 ^-6 / K or less, further preferably 5 ×. It is 10 ^-6 / K or less. Further, by making such a CTE in all directions in the plane of the polyimide layer, the warp of the vapor deposition mask due to the temperature change during the process and the partial waviness and sagging due to the temperature variation in the vapor deposition mask are suppressed. be able to. Here, the fact that the CTE is 10 × 10 ^-6 / K or less in all the in-plane directions means that thermal expansion occurs in any of the in-plane directions, including the direction parallel to one side of the polyimide layer and the direction perpendicular to the direction. It shall mean a state in which the coefficient is 10 × 10 ^{-6 / K or less.}

^{Further, in the vapor deposition mask in the present invention, the CTE of the polyimide layer is 10 × 10 -6} / K or less in all directions in the plane, and the CTE of the polyimide layer is used because the degree of freedom in designing the opening is increased. It is preferable that a polyimide layer having no anisotropy and having an isotropic CTE in the in-plane direction is laminated on the metal layer. Specifically, it is preferable that there is no anisotropy in the two orthogonal axes. "There is no anisotropy in the orthogonal biaxial" means that the difference in CTE in the orthogonal biaxial directions is 2 × 10 ^-6 / K or less. By using a polyimide layer having an isotropic CTE in the in-plane direction, it is possible to suppress warpage in either the longitudinal direction of the opening or the direction intersecting the longitudinal direction, and the shape of the opening of the metal layer can be adjusted. Therefore, the warp of the laminated body can be suppressed. Regarding the CTE of the polyimide layer, if the CTE is set too low, the polyimide becomes brittle and there is a problem in practical use. Therefore, the actual lower limit of the CTE is −7 × 10 ^-6 / K.

但し、Ｒ₁は、下記式（２）で表わされる群より選択される２価の有機基であり、

（Ｒ’は各々独立に炭素数１〜６のアルキル基、ハロゲン化アルキル基、炭素数６〜１８の芳香族基、またはハロゲン基であり、前記芳香族基の水素原子はハロゲン原子、炭素数１〜６のアルキル基、又はハロゲン化アルキル基で置換されてもよい。ＺはＮＨ又はＯである。）、
Ｒ₂は、下記式（３）で表わされる群より選択される４価の有機基であり、

Ｒは、各々独立に水素原子又は一価の有機基を示し、ｎは繰り返し数を表す正の整数である。 In order to obtain such a CTE polyimide layer, it is preferable that the main polyimide forming the polyimide layer is an imidized polyimide precursor having a structural unit represented by the following formula (1). Preferably, the polyimide precursor containing 60 mol% or more, more preferably 80 mol% or more of the structural unit represented by the formula (1) is imidized. Here, the "main polyimide" refers to the polyimide layer itself when the polyimide layer is a single layer, and refers to the polyimide of the layer having the largest volume fraction when the polyimide layer is composed of a plurality of layers of polyimide. .. By imidizing a polyimide precursor (polyamic acid) having a structural unit represented by the formula (1) in this main polyimide, a polyimide having low thermal expansion can be obtained, and the CTE of the polyimide layer is 10 ×. It is suitable in that it is 10 ^{-6 / K or less.} Further, since the polyimide obtained from the polyimide precursor having the structural unit represented by the formula (1) exhibits low hygroscopicity as the polyimide, the change in dimensions can be suppressed even by the change in the humidity environment during the process. It is also advantageous in terms of points. Regarding the main polyimide, the remaining polyimide precursor different from the general formula (1) for forming the main polyimide is not particularly limited, and a general polyimide precursor can be used.

However, R ₁ is a divalent organic group selected from the group represented by the following formula (2).

(R'is independently an alkyl group having 1 to 6 carbon atoms, an alkyl halide group, an aromatic group having 6 to 18 carbon atoms, or a halogen group, and the hydrogen atom of the aromatic group is a halogen atom and a carbon number of carbon atoms. It may be substituted with an alkyl group of 1 to 6 or an alkyl halide group. Z is NH or O),
R ₂ is a tetravalent organic group selected from the group represented by the following formula (3).

R represents a hydrogen atom or a monovalent organic group independently, and n is a positive integer representing the number of repetitions.

By the way, the polyimide precursor having the structural unit represented by the above formula (1) may be inferior in adhesiveness when imidized into polyimide. Therefore, the polyimide layer may be made of a plurality of polyimide layers, and the layer in contact with the metal layer may be a non-low thermal expansion polyimide. That is, in the case of the casting method in which a liquid composition containing a polyimide precursor (or a polyimide in which the polyimide precursor is imidized) is applied to a metal layer and heated to form a polyimide layer, the polyimide precursor is placed on the metal layer. After applying the first liquid composition containing (or a polyimide in which the polyimide precursor is imidized), a polyimide composed of a polyimide precursor having a structural unit represented by the formula (1) is formed by coating on the first liquid composition. Just do it. In the case of a laminating method in which a polyimide film is thermocompression bonded to a metal layer, the polyimide layer is made of a plurality of layers of polyimide, and a polyimide composed of a polyimide precursor having a structural unit represented by the formula (1) [hereinafter, It may be simply referred to as the polyimide according to the formula (1)] and the non-low thermal expansion polyimide may be located between the metal layer. At that time, since the CTE of the non-low thermal expansion polyimide is generally ^{about 50 × 10 -6} / K, the coefficient of thermal expansion of the polyimide in contact with the metal layer is the other polyimide adjacent to the polyimide [that is, the formula (ie, formula (i.e.)). It is larger than the coefficient of thermal expansion of the polyimide according to 1). In other words, when the polyimide layer is composed of a plurality of polyimide layers, the coefficient of thermal expansion of the main polyimide forming the polyimide layer is preferably smaller than the coefficient of thermal expansion of the other polyimides.

When a plurality of polyimide layers are used, a non-low thermal expansion polyimide is used on the side of the polyimide layer in contact with the metal layer in order to improve the adhesive force with the barrier layer and adjust the coefficient of thermal expansion of the polyimide layer. It may be formed on the surface opposite to the surface. In this case, the coefficient of thermal expansion of the polyimide constituting the surface of the polyimide layer on the side opposite to the surface in contact with the metal layer is larger than the coefficient of thermal expansion of other polyimides adjacent to the polyimide. The adjustment of the coefficient of thermal expansion of the polyimide layer means that when the coefficient of thermal expansion of the polyimide adjacent to the polyimide is smaller than that of the metal layer, the coefficient of thermal expansion of the polyimide is finely adjusted.

Further, in order to improve the adhesive force with the metal layer and adjust the coefficient of thermal expansion of the polyimide layer, for example, the polyimide layer is composed of a plurality of layers of polyimide, and the coefficient of thermal expansion of the polyimide in contact with the metal layer is adjacent to the polyimide. It may be made smaller than the coefficient of thermal expansion of the polyimide of. Alternatively, in order to improve the adhesive force with the barrier layer and adjust the coefficient of thermal expansion of the polyimide layer, the polyimide layer is composed of three or more layers of polyimide, and the two outermost polyimides forming the front surface and the back surface are thermally expanded. The coefficient may be larger than the coefficient of thermal expansion of the polyimide forming the intermediate layer sandwiched between the polyimides on the outermost surface, and one of the polyimides forming the outermost surface may be in contact with the metal layer.

When the number of polyimide layers is a plurality of layers, the number of layers is not particularly limited, but two or three layers are preferable from the viewpoint of productivity. The coating may be a simultaneous coating in which a plurality of layers are coated with the same coater, or a sequential coating in which each layer is coated with a separate coater.

Further, the vapor deposition mask of the present invention preferably has an adhesive force between the metal layer and the polyimide layer of 300 N / m or more. More preferably, it is 600 N / m or more. When the adhesive strength between the metal layer and the polyimide layer is 300 N / m or more, the metal layer and the polyimide layer are difficult to peel off even if the work of repeatedly forming a thin film pattern having a constant shape on the object to be deposited is repeated. From this point of view, when the polyimide layer is the polyimide according to the formula (1), it is preferable to form the polyimide layer by a casting method. On the other hand, when the polyimide layer is formed by the laminating method, it is preferable that the non-low thermal expansion polyimide is located between the metal layer and the polyimide layer. In this case, the non-low thermal expansion polyimide can be regarded as one of the polyimide layers. By adopting the polyimide layer in the above-mentioned form, the metal layer and the polyimide layer can be adhered to each other without using 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 the polyimide layer means a polyimide for reducing the CTE of the entire polyimide layer to 10 × 10 ^-6 / K or less, and is preferably as described above. The low thermal expansion polyimide according to the formula (1) corresponds to this. As described above, when the polyimide layer is formed by a single layer of the polyimide according to the formula (1), this is of course the main polyimide, and when the polyimide layer is formed by a plurality of layers, the formula is used. ^{The CTE of the entire polyimide layer may be set to 10 × 10 -6} / K or less in consideration of the influence of the polyimide other than the polyimide according to (1).

Here, as the non-low thermal expansion polyimide, 4,4'-diaminodiphenyl ether, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2 , 2-Bis [4- (4-aminophenoxy) phenyl] propane, as acid anhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3', 4,4'- Diphenylsulfonetetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid anhydride, pyromellitic anhydride, 2,3,2', 3'-biphenyltetracarboxylic acid dianhydride, 2,3,3', 4 An example is a polyimide made from'-biphenyltetracarboxylic acid dianhydride.

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

Further, the polyimide layer may be divided into two or more and laminated in the plane of the metal layer. At that time, for example, in the case of the casting method, the liquid composition is divided and applied, and different types of polyimide layers divided into two or more are laminated in the plane of the metal layer to form a laminated body. The warpage of the vapor deposition mask can be effectively suppressed, and it is also advantageous in terms of weight reduction of the vapor deposition mask.

The thickness of the polyimide layer is not particularly limited, but it is preferable that the thickness is such that the occurrence of breakage and pinholes can be suppressed, and the thickness is preferably set in consideration of the occurrence of thin-film deposition shadows. It is preferably 2 to 25 μm. The polyimide layer is required to have different characteristics depending on whether it is preferably transparent so that visible light can be transmitted and non-transparent so that visible light is not transmitted.

That is, in order to detect defects such as foreign substances and fine bubbles in the polyimide layer, the polyimide layer is required to transmit visible light. The term "transmitting visible light" includes not only those that are completely transparent but also those that are colored so that the opposite side of the polyimide layer can be visually recognized through the polyimide layer. 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 visible light transmittance. As a result, the aperture pattern can be inspected by the contrast of the shade of the aperture pattern. Therefore, the polyimide layer may be made transparent or non-transparent depending on the required characteristics.

Polyimide varies depending on the acid anhydride and diamine components that compose it, but in general, most polyimides are colored from yellowish brown to brownish brown. Therefore, when the detection of defects such as foreign substances and fine bubbles in the polyimide layer is important, at least the main polyimide constituting the polyimide layer is a fluorine-containing polyimide or an alicyclic polyimide so that the polyimide layer is transparent. It is better to make it. Such polyimides include 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl as a diamine and cyclobutane-1,2,3,4-tetracarboxylic acid dianhydride as an acid anhydride. An example is polyimide made from a product. With these polyimides, ^{a CTE of 10 × 10 -6} / K or less can be satisfied, and the light transmittance at a wavelength of 500 nm can be 60% or more.

On the other hand, in order to increase the contrast of the shade of the opening pattern, the polyimide layer may be made non-transparent, and at that time, a coloring material such as a dye or a pigment may be added to the polyimide layer. The shape of the color material component is not particularly limited, and conventionally known shapes such as spherical, rod-shaped, and scaly particles may be used, and the size is also not particularly limited, but the color material component If the size exceeds 2 μm, defects such as protrusions due to the coloring material and falling off of the coloring material are likely to occur. The lower limit of the size is not particularly limited, but is about 1 nm. When the polyimide layer is a plurality of layers, a coloring material may be added to at least one layer thereof, and no coloring material may be added to the other layers.

In the present invention, the method of forming an opening pattern by providing through holes in the polyimide layer is not particularly limited. For example, a photosensitive resist is applied to the surface of the polyimide layer, a predetermined portion is exposed, and after development, etching is performed. A method of forming a through hole by irradiating a laser, a method of forming a through hole by irradiating a laser, a method of forming a through hole with a mechanical drill, and the like can be mentioned, but from the viewpoint of accuracy and productivity, laser irradiation is preferable. It is better to depend on. When an aperture pattern corresponding to a thin film pattern is formed by laser irradiation, a good aperture pattern shape may not be obtained if the transmittance of the polyimide layer at the wavelength of the laser is high. Therefore, the light transmittance of the polyimide layer at the wavelength of the laser is preferably 50% or less, preferably 10% or less, and more preferably 0%. Here, as a laser used for forming a through hole in the polyimide layer by laser irradiation and forming an opening pattern, for example, a UV-YAG laser (wavelength 355 nm), an excimer laser (wavelength 308 nm), or the like can be used. Of these, a UV-YAG laser (wavelength 355 nm) is preferable.

By the way, when the step of separating the polyimide layer from the coating base material (hereinafter, also referred to as "laser peeling") is included in the manufacturing process of the vapor deposition mask of the present invention as described later, the above-mentioned used in forming the opening pattern. It is also possible to separate by irradiating such a laser. Therefore, when the light transmittance of the polyimide layer with respect to the wavelengths of these lasers such as 308 nm and 355 nm is 10% or less, it is preferable that the separation in the laser peeling can be easily performed. That is, the laser at the time of forming the aperture pattern and the laser at the time of the separation may be of the same type or different types. When the laser at the time of forming the aperture pattern and the laser at the time of separation are different, the light transmittance of the polyimide layer is 50% or less at one of the wavelength corresponding to the former laser and the wavelength corresponding to the latter laser. On the other hand, the light transmittance of the polyimide layer is preferably 10% or less. Here, as these lasers, known lasers can be used both at the time of forming the aperture pattern and at the time of the separation, and preferably, the above-mentioned UV-YAG laser (wavelength 355 nm) or excimer laser (wavelength 355 nm) or excimer laser (wavelength 355 nm) or excimer laser (wavelength 355 nm) having excellent work efficiency are used. Wavelength 308 nm) and the like.

Further, when the polyimide layer is irradiated with a laser to provide through holes and an opening pattern corresponding to the thin film pattern is formed, a reference plate showing a pattern corresponding to the opening pattern to be formed is prepared, and this reference plate is used. It may be arranged on the surface opposite to the laser irradiation side of the polyimide layer and laser irradiation corresponding to the pattern of the reference plate may be performed to form an opening pattern. In order to detect the pattern of the reference plate by transmitting through the polyimide layer, it is preferable that the polyimide layer transmits visible light. Therefore, from the viewpoint of improving the pattern detection accuracy of the reference plate, as described above, the transmittance of the polyimide layer at 500 nm is preferably 60% or more, preferably 80% or more. In addition, the transmittance of the polyimide layer at 400 nm is preferably 5% or more, more preferably 10% or more.

In forming the aperture pattern by laser irradiation, in obtaining a polyimide layer having the above-mentioned optical characteristics so that a good aperture pattern can be obtained, a preferred polyimide is a structural unit represented by the above formula (1). It is a polyimide composed of a polyimide precursor containing 60 mol% or more. As will be described later, a more preferable polyimide is represented by the above formula (1) in consideration of the light transmittance of the laser wavelength when the polyimide layer is formed on the coated substrate and the polyimide layer is laser-peeled. It is a polyimide composed of a polyimide precursor containing 80 mol% or more of structural units.

Further, in the present invention, the material of the metal layer having a plurality of openings is not particularly limited, and the same material as that used in a known vapor deposition mask can be used. Specific examples thereof include stainless steel, iron-nickel alloy, and alumnium alloy. Among them, Invar (or Invar alloy), which is an iron-nickel alloy, is preferably used because it is less deformed by heat. Further, when vapor deposition is performed on the vapor-deposited body, when a magnet or the like is installed behind the vapor-deposited body and the vapor deposition mask is attracted by a magnetic force, it is preferable that the metal layer is formed of the magnetic material. Examples of the metal layer of such a magnetic material include iron-nickel alloys containing Invar or Invar alloys as described above, carbon steel, tungsten steel, chromium steel, KS steel, MK steel, NKS steel and the like. ..

The thickness of the metal layer is not particularly limited, and it is preferable to set the thickness so that breakage and deformation can be suppressed, and the thickness is preferably set in consideration of the generation of thin-film deposition shadow, preferably 2 to 100 μm.

FIG. 1 shows a metal layer 1 [FIG. 1 (1)] having a plurality of openings 1a and a polyimide layer 2 [FIG. 1 (2)] having through holes 2a, and these are laminated. As shown in the plan view of FIG. 2 (1) and the cross-sectional view of FIG. 2 (2), the through hole 2a of the polyimide layer 2 is the opening 1a of the metal layer 1 in the vapor deposition mask 4 made of the laminated body. The opening pattern 3 is located within the opening range of the above and corresponds to the thin film pattern formed on the body to be vapor-deposited (not shown).

The method for forming the vapor deposition mask composed of the laminate of the metal layer 1 and the polyimide layer 2 as described above is not particularly limited, but for example, a liquid composition (resin solution) containing polyimide or a polyimide precursor in the metal layer. A method of directly forming a polyimide layer on a metal layer by heat treatment after coating, a method of directly heat-bonding a polyimide film forming a polyimide layer and a metal layer without using an adhesive, and a metal layer Examples thereof include a method of adhering the polyimide film to the polyimide film with an adhesive, an adhesive, and the like, and a method of forming a metal layer on the polyimide film by sputtering, plating, or the like. Here, with respect to the opening 1a of the metal layer 1 and the through hole 2a of the polyimide layer, one or both of them may be formed after forming a laminate of the metal layer 1 and the polyimide layer 2. , Either one or both may be provided before forming the laminated body so that the metal layer 1 and the polyimide layer 2 are laminated.

That is, as an example of the method for producing a vapor deposition mask according to the present invention, a polyimide layer (polyimide film) having a ^{coefficient of thermal expansion of 10 × 10 -6 / K or less in all in-plane directions is laminated.} , A polyimide layer (polyimide film) in which 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 of 10 × 10 ^{-6 / K or less in all directions in the plane.} ), And then the polyimide layer within the opening range of the opening of the metal layer is penetrated to provide a through hole to form an opening pattern corresponding to the thin film pattern. As described above, the polyimide layer may be formed of a single layer of polyimide, may be formed of a plurality of layers of polyimide, and is further divided into two or more in the plane of the metal layer. It may be a polyimide layer (the same applies to the following examples).

Further, a liquid composition containing polyimide or a polyimide precursor is applied onto a coating base material such as glass or a polyimide film and heated so that the coefficient of thermal expansion on the coating base material is in all directions in the plane. In the step of forming a polyimide layer of 10 × 10 ^-6 / K or less, a metal layer is laminated on the polyimide layer to form a plurality of openings in the metal layer, or a plurality of openings are formed on the polyimide layer. A step of laminating a metal layer having an opening, a step of separating the polyimide layer and the coating base material, and a thin film by penetrating the polyimide layer within the opening range of the opening of the metal layer to provide a through hole. The step of forming the opening pattern corresponding to the pattern may be included. ^{The coating base material preferably has a CTE of 10 × 10 -6} / K or less from the viewpoint of effectively reducing warpage when a laminate of a metal layer and a polyimide layer is formed. More preferably, it is × 10 ^{-6 / K or less.} It is possible to change the order of some of the steps mentioned here. For example, a step of separating the polyimide layer and the coating base material after forming the opening of the metal layer or the opening pattern of the polyimide layer. May be done.

Alternatively, a step of fixing a metal layer on a fixing member such as a glass substrate, a metal plate, a metal frame, or a guide roll, a liquid composition containing polyimide or a polyimide precursor is applied to the surface of the metal layer, and the metal is heated. A step of forming a polyimide layer on a layer, a step of separating a metal layer and a fixing member, a step of forming a plurality of openings in the metal layer, and a step of penetrating the polyimide layer within the opening range of the openings of the metal layer. It may include a step of forming a through hole to form an opening pattern corresponding to the thin film pattern. By fixing the metal layer on the fixing member in this way, applying the liquid composition and heating it, when a laminate of the metal layer and the polyimide layer is formed, the warp can be reduced more effectively. You will be able to plan. From the viewpoint of reducing the warp, the fixing member preferably has a CTE of 10 × 10 ^-6 / K or less, ^{and more preferably 8 × 10 -6} / K or less. Glass, Invar, and silicon are preferably exemplified as the fixing member satisfying this preferable CTE. Also in this case, for example, after forming the opening of the metal layer or the opening pattern of the polyimide layer, the step of separating the metal layer and the fixing member may be performed.

Further, a step of fixing the metal layer on the fixing member as described above, a step of forming a plurality of openings in the metal layer, a liquid composition containing polyimide or a polyimide precursor is applied to the surface of the metal layer, and heating is performed. Then, a step of forming the polyimide layer on the metal layer, a step of penetrating the polyimide layer within the opening range of the opening of the metal layer to provide a through hole, and forming an opening pattern corresponding to the thin film pattern, and A step of separating the metal layer and the fixing member may be included.

When a liquid composition is applied after fixing a metal layer on these fixing members to form a polyimide layer composed of a plurality of layers of polyimide, for example, a first method containing polyimide or a polyimide precursor on the surface of the metal layer. After applying the liquid composition to form the first coating layer, a second liquid composition containing polyimide or a polyimide precursor is applied onto the first coating layer to form a second coating layer. The step of forming and the step of heating the first and second coating layers to form a polyimide layer composed of a plurality of polyimide layers on the metal layer may be included. At that time, preferably, the second liquid composition is formed on the metal layer so as to contain a polyimide precursor having a structural unit represented by the above formula (1) or a polyimide in which the polyimide precursor is imidized. It is preferable that the coefficient of thermal expansion of the obtained polyimide layer is 10 × 10 ^-6 / K or less in all directions in the plane.

Further, the heating temperature of the first and second coating layers can be appropriately set depending on the structure of the polyimide or the polyimide precursor constituting each layer. Further, it can be appropriately set depending on whether the polyimide precursor is applied and imidized by heating, the polyimide precursor is applied and dried by heating (without imidization), or the polyimide is applied and dried by heating. .. As an example, the heating temperature may be set to 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. Further, the second coating layer may be provided after the curing of the first coating layer (300 ° C. or higher) is completed by imidization, or the first coating layer may be dried (200 ° C. or lower) only. After that, a second coating layer may be provided, and then these curings may be completed.

In the present invention, the method for forming an opening in the metal layer is not particularly limited. For example, a photosensitive resist is applied to the surface of the metal layer, a predetermined portion is exposed, and after development, the opening is formed by etching. A method of forming an opening by laser irradiation, a polyimide layer, or a photosensitive resist is applied onto another substrate, a predetermined portion is exposed, and after development, a metal layer is subjected to sputtering, vapor deposition, plating, or the like. A method of forming the above can be mentioned. Among them, since it is possible to process with a roll and it is excellent in productivity, it is preferable to form an opening by etching.

In some examples of the above-mentioned method for producing a vapor-deposited mask according to the present invention, a metal layer and a polyimide layer are laminated to form a thin-film pattern having a constant shape on the body to be vapor-deposited. A laminated body for mask is formed. In the case of producing this thin-film deposition mask laminate, a first liquid composition containing polyimide or a polyimide precursor is applied to the surface of the metal layer to form a first coating layer, and then the first coating is performed. A step of applying a second liquid composition containing polyimide or a polyimide precursor onto the layer to form a second coating layer, and heating the first and second coating layers to form the metal. The step of forming a polyimide layer composed of a plurality of layers of polyimide on the layer may be included. Further, prior to the above step, a step of fixing a metal layer made of a magnetic material on the fixing member may be added. At that time, the second liquid composition was formed on the metal layer containing a polyimide precursor having a structural unit represented by the above formula (1) or a polyimide in which the polyimide precursor was imidized. The coefficient of thermal expansion of the polyimide layer should be 10 × 10 ^-6 / K or less in all in-plane directions.

In the present invention, in order to reduce the outgas generated from the polyimide and improve the solvent resistance during cleaning of the vapor deposition mask, a barrier layer is provided on the polyimide surface of the vapor deposition mask, between the polyimide layers of a plurality of layers, and on the wall surface of the polyimide opening pattern. It may be formed. As the barrier layer, an inorganic oxide, an inorganic nitride, a metal thin film layer or a vapor-deposited layer can be used. In the case of inorganic oxides and inorganic nitrides, it is preferably formed by the CDV method or the PVD method. When forming a barrier layer between layers of a plurality of polyimides, a liquid composition is applied to the surface of the metal layer, the coating layer is heated to form a polyimide layer, then a barrier layer is formed, and further on the barrier layer. It is preferable to apply the liquid composition to the polyimide and heat it.

In the present invention, the material to be vapor-deposited is not particularly limited, and a material similar to a known supporting base material can be used, and glass, silicon, metal foil, and resin are exemplified. In the case of metal foil, ferrite stainless steel and Invar are preferably used because they are less deformed by heat. In the case of resin, polyimide is preferably used from the viewpoint of less deformation due to heat and heat resistance.

The raw materials, diamines, acid anhydrides, and solvents used for the synthesis of the polyamic acid (polyimide precursor) solution used in the following synthesis examples, 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)
[Acid anhydride]
-Pyromellitic anhydride (PMDA)
2,3,2', 3'-biphenyltetracarboxylic dianhydride (BPDA)
-Cyclobutane-1,2,3,4-tetracarboxylic dianhydride (CBDA)
4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA)
4,4'-Oxydiphthalic anhydride (ODPA)
-2,3,6,7-Naphthalenetetracarboxylic dianhydride (NTCDA)
〔solvent〕
-N, N-dimethylacetamide (DMAc)
-N-Methyl-2-pyrrolidone (NMP)

<Coefficient of linear expansion>
A polyimide layer having a size of 3 mm × 15 mm is heated in a temperature range of 30 ° C. to 280 ° C. at a constant temperature rising rate (10 ° C./min) while applying a load of 5.0 g using a thermomechanical analysis (TMA) device. -The temperature was lowered and a tensile test was performed, and the coefficient of thermal expansion (ppm / K) was measured from the change in the amount of elongation of the polyimide layer with respect to the temperature change from 250 ° C. to 100 ° C.

<Coefficient of thermal expansion isotropic>
The coefficient of thermal expansion in the direction parallel to one side of the polyimide layer and the direction perpendicular to one side was measured three times, and the state where the difference between the average values was 2 ppm / K or less was marked with ◯, and the state where the difference was larger than 2 ppm / K was marked with x.

<Warp>
The laminated body of the metal layer and the polyimide layer was allowed to stand on a horizontal plane with the polyimide layer facing up, and the average value of the heights of floating from the flat surfaces at the four corners of the laminated body was taken as the warp.

<Adhesive strength>
Using a Tencilon tester, the metal layer with a width of 1 mm and the polyimide layer side of the polyimide laminate are fixed to the aluminum plate with double-sided tape, and the base material is placed in the 180 ° direction at a speed of 50 mm / min. The force at the time of peeling was determined, and 1000 N / m or more was designated as ⊚, 1000 N / m or more was designated as ◯, 600 N / m or more was designated as ◯, less than 600 N / m, and 300 N / m or more was designated as Δ.

<Aperture pattern forming property of polyimide layer>
Using a UV-YAG laser machine (wavelength 355 nm), openings are formed so that the diameter is 50 μm so as to penetrate the polyimide layer, and the state where a good processed shape is formed is ○, the difference from the target processing diameter. Was ± 5 μm or more, or a state in which irregularities were found on the machined hole wall was evaluated as x.

<Separability of coating base material>
Using an excimer laser processing machine (wavelength 308 nm), a laser with a beam size of 14 mm × 1.2 mm and a moving speed of 6 mm / s was irradiated from the support side, and the state where the coating base material and the polyimide layer were completely separated was ○. The state in which the entire surface or a part of the coating base material and the polyimide layer cannot be separated or the polyimide layer is discolored is marked with x.

<Transmittance>
Invar was removed by etching with an aqueous ferric chloride solution from the laminate of Invar and polyimide to prepare a polyimide film. When the polyimide was formed on the glass, the polyimide was peeled off from the glass to obtain a polyimide film. The light transmittance of this polyimide film (50 mm × 50 mm) at 500 nm, 400 nm, 355 nm, and 308 nm was measured with a SHIMADZU UV-3600 spectrophotometer. The transmittance of each wavelength is shown in Table 1.

[Synthesis Example 1]
(Polyimide precursor solution 1)
Under a nitrogen stream, 8.49 g of TFMB was dissolved in 70 g of DMAc in a 300 ml separable flask. Next, 1.47 g of 6FDA was added to this 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 mixture was stirred at room temperature for 6 hours to carry out a polymerization reaction. After the reaction, a viscous colorless and transparent polyimide precursor solution 1 was obtained.

[Synthesis Example 2]
(Polyimide precursor solution 2)
26.3 g of TFMB was dissolved in the solvent DMAc with stirring in a 200 ml separable flask under a nitrogen stream. Then, 16.9 g of PMDA and 1.8 g of 6FDA were added to this solution. Then, the solution was stirred at room temperature for 6 hours to carry out a polymerization reaction. After the reaction, a viscous colorless and transparent polyimide precursor solution 2 was obtained.

[Synthesis Example 3]
(Polyimide precursor solution 3)
Under a nitrogen stream, 29.1 g of BAPP was added to and dissolved in the solvent DMAc with stirring in a 500 ml separable flask. Then 3.23 g of BPDA and 13.6 g of PMDA were added. Then, the solution was stirred at room temperature for 3 hours to carry out a polymerization reaction to obtain a viscous brown polyimide precursor solution 3.

[Synthesis Example 4]
(Polyimide precursor solution 4)
Under a nitrogen stream, 8.9334 g of TFMB was dissolved in 70 g of DMAc in a 300 ml separable flask. Next, 6.0666 g of PMDA was added to this solution, 15 g of DMAc was added so that the solid content was 15 wt%, and the mixture was stirred at room temperature for 6 hours to carry out a polymerization reaction. After the reaction, a viscous colorless and transparent polyimide precursor solution 4 was obtained.

[Synthesis Example 5]
(Polyimide precursor solution 5)
Under a nitrogen stream, 8.0 g of PPD was added to the solvent DMAc with stirring in a 300 ml separable flask and heated to dissolve at 50 ° C. Then, 22.0 g of BPDA was added. Then, the solution was stirred at room temperature for 3 hours to carry out a polymerization reaction to obtain a viscous brown polyimide precursor solution 5.

[Synthesis Example 6]
(Polyimide precursor solution 6)
Under a nitrogen stream, 20.3 g of mTB and 3.1 g of TPE-R were added to and dissolved in the solvent DMAc with stirring in a 500 ml separable flask. Then PMDA 18.4 and BPDA 6.2 g were added. Then, the solution was stirred at room temperature for 4 hours to carry out a polymerization reaction to obtain a viscous brown polyimide precursor solution 6.

[Synthesis Example 7]
(Polyimide precursor solution 7)
Under a nitrogen stream, 9.0756 g of TFMB was added to and dissolved in the solvent NMP with stirring in a 100 ml separable flask. Then 4.3 g of PMDA and 1.65 g of CBDA were added. Then, the solution was stirred at room temperature for 4 hours to carry out a polymerization reaction to obtain a viscous transparent polyimide precursor solution 7.

[Synthesis Example 8]
(Polyimide precursor solution 8)
Under a nitrogen stream, 18.9 g of TFMB was added to and dissolved in the solvent DMAc with stirring in a 500 ml separable flask. Then 26.1 g of 6 FDA was added. Then, the solution was stirred at room temperature for 5 hours to carry out a polymerization reaction to obtain a viscous transparent polyimide precursor solution 8.

[Synthesis Example 9]
(Polyimide precursor solution 9)
Under a nitrogen stream, 9.34 g of TFMB was added to and dissolved in the solvent NMP with stirring in a 100 ml separable flask. Then 5.66 g of CBDA was added. Then, the solution was stirred at room temperature for 4 hours to carry out a polymerization reaction to obtain a viscous transparent polyimide precursor solution 9.

[Synthesis Example 10]
(Polyimide precursor solution 10)
Under a nitrogen stream, 9.30 g of TFMB was added to and dissolved in the solvent NMP with stirring in a 100 ml separable flask. Then 0.63 g of PMDA and 5.07 g of CBDA were added. Then, the solution was stirred at room temperature for 4 hours to carry out a polymerization reaction to obtain a viscous transparent polyimide precursor solution 10.

[Synthesis Example 11]
(Polyimide precursor solution 11)
Under a nitrogen stream, 6.3458 g of m-TB was placed in a 100 ml separable flask and dissolved in 85 g of DMAc. Then, 8.6542 g of BPDA was added to this solution. This solution was heated at 40 ° C. for 10 minutes to dissolve the contents, and then the solution was stirred at room temperature for 24 hours to carry out a polymerization reaction to obtain a viscous transparent polyimide precursor 11.

[Synthesis Examples 12-18]
(Polyimide precursor solution 12-18)
Polyimide precursor solutions 12 to 18 were obtained in the same manner as in Synthesis Example 1 except that the acid anhydride, diamine and solvent shown in Table 2 were used. The state of the obtained polyimide precursor solution is shown in Table 2.

[Example 1]
The four sides of the sheet-shaped Invar (thickness 100 μm, 100 mm × 100 mm) were fixed to glass (thickness 500 μm, 150 × 150 mm) with heat-resistant tape. In this case, the glass is the fixing member. The polyimide precursor solution 1 is applied onto this inver using an applicator so that the thickness of the polyimide layer after heat treatment becomes 10 μm and the polyimide layer has a size of 90 mm × 90 mm, and a hot air oven is used. After heating at 100 ° C. for 5 minutes, the temperature was raised to 360 ° C. at 4 ° C./min for heat treatment. Then, the heat-resistant tape was peeled off to separate the glass, and a test laminate of Invar and the polyimide layer (corresponding to the “laminate for vapor deposition mask” in the present invention; the same applies hereinafter) was obtained. The warp of this laminated body was 0.3 mm.

A dry film resist is laminated on the Invar surface of the obtained laminate, the dry film resist is patterned, and the Invar is etched with an aqueous ferric chloride solution along the pattern to form a metal layer having a width of 10 mm and a length of 30 mm. An opening was formed. Further, an opening pattern was formed in the polyimide layer in the opening by a UV-YAG laser processing machine so as to form a through hole having a diameter of 50 μm. The characteristics of this laminated body are shown in Table 1.

[Example 2]
A test laminate of Invar and the polyimide layer was obtained in the same manner as in Example 1 except that the Invar was not fixed to the glass. The warp of this laminated body was 0.4 mm. Then, in the same manner as in Example 1, an opening was formed in the metal layer and a through hole (opening pattern) was formed in the polyimide layer. The characteristics of this laminated body are shown in Table 1.

[Example 3]
Except for applying the polyimide precursor solution 1 on the Invar using an applicator so that the thickness of the polyimide layer after heat treatment becomes 10 μm and the polyimide layer is formed in two portions on the left and right in a size of 80 mm × 35 mm. Obtained a test laminate of Invar and polyimide in the same manner as in Example 1. At this time, the polyimide layer was prevented from being formed on the inner side 5 mm of the four sides of the Invar, and the polyimide layer was not formed on the gap 10 mm of the polyimide layer formed by dividing the Invar into two parts. The warp of this laminated body was 0.1 mm. Then, in the same manner as in Example 1, an opening was formed in the metal layer and a through hole (opening pattern) was formed in the polyimide layer. The characteristics of this laminated body are shown in Table 1.

[Example 4]
A test laminate of Invar and the polyimide layer was obtained in the same manner as in Example 1 except that the polyimide precursor solution 2 was applied so that the thickness of the polyimide layer after the heat treatment was 25 μm. The warp of this laminated body was 0.3 mm. Then, in the same manner as in Example 1, an opening was formed in the metal layer and a through hole (opening pattern) was formed in the polyimide layer. The characteristics of this laminated body are shown in Table 1.

[Example 5]
A roll-shaped long Invar having a thickness of 100 μm, a width of 100 mm, and a length of 30 m is mounted on a roll-to-roll heating furnace, and the long Invar is fed out in the longitudinal direction. , The polyimide precursor solution 3 is applied onto the Invar using an applicator in all the width directions of the Invar and continuously in the length direction so that the thickness of the polyimide layer after heat treatment is 2 μm. , It was introduced into a heating furnace and dried at 100 ° C. for 5 minutes. Further, the polyimide precursor solution 2 is applied onto the polyimide precursor layer formed on the Invar using an applicator in all directions in the width direction of the Invar so that the thickness of the polyimide layer after the heat treatment is 25 μm. It is continuously applied in the length direction, introduced into a heating furnace, and heat-treated at 100 ° C., 150 ° C., 200 ° C., 250 ° C., and 350 ° C. for 5 minutes, respectively, and the long Invar and the polyimide layer are laminated. I got a body. At this time, tension was applied to the Invar during transportation and pressed against the guide roll in the heating furnace to fix the Invar during the heat treatment. In this case, the guide roll is a fixing member. The guide roll was arranged so as to contact only the Invar and not the polyimide surface. The warp of the test laminate obtained by cutting out the laminate of the long Invar and the polyimide layer into a size of 100 mm × 100 mm was 0.4 mm. Further, in the same manner as in Example 1, an opening was formed in the metal layer and a through hole (opening pattern) was formed in the polyimide layer. The characteristics of this laminated body are shown in Table 1. The coefficient of thermal expansion of the single-layer polyimide film in which the polyimide precursor solution 3 is imidized is 56 × 10 ^-6 / K, and the coefficient of thermal expansion of the single-layer polyimide film in which the polyimide precursor solution 2 is imidized is 0. It was 5 × 10 ^-6 / K.

[Example 6]
A test laminate of Invar and polyimide was obtained in the same manner as in Example 1 except that the polyimide precursor solution 4 was used on Invar. The warp of this laminated body was 0.1 mm. Then, in the same manner as in Example 1, an opening was formed in the metal layer and a through hole (opening pattern) was formed in the polyimide layer. The characteristics of this laminated body are shown in Table 1.

[Example 7]
The polyimide precursor solution 5 is applied onto the Inver using an applicator so that the thickness of the polyimide layer after heat treatment is 10 μm, heated at 100 ° C. for 5 minutes using a hot air oven, and then up to 400 ° C. 1 A test laminate of Inver and polyimide was obtained in the same manner as in Example 1 except that the temperature was raised at ° C./min and heat treatment was performed. The warp of this laminated body was 0.2 mm. Then, in the same manner as in Example 1, an opening was formed in the metal layer and a through hole (opening pattern) was formed in the polyimide layer. The characteristics of this laminated body are shown in Table 1.

[Example 8]
The polyimide precursor solution 2 is applied to the entire surface of a glass having a thickness of 500 μm and 150 × 150 mm so that the thickness of the polyimide layer after heat treatment is 25 μm using a spin coater, and the temperature is 100 ° C. using a nitrogen oven. After heating for 5 minutes, the temperature was raised to 360 ° C. at 4 ° C./min for heat treatment to form a polyimide layer on the glass. In this case, the glass is the coating base material. A masking tape having a width of 10 mm and a length of 30 mm is attached onto the polyimide layer, and then the nickel is formed to have a thickness of 30 nm by sputtering, and then the glass is immersed in a plating bath to have a thickness of 5 μm. A nickel layer having an opening having a width of 10 mm and a length of 30 mm was formed on the top. Subsequently, after peeling off the masking tape, the polyimide layer was separated from the glass by laser lift-off that irradiates an excimer laser machine (wavelength 308 nm) from the glass side to form a nickel layer having an opening 10 mm wide and 30 mm long. A test laminate of the polyimide layer was obtained. Next, the polyimide layer in the opening of the nickel layer was penetrated by a UV-YAG laser machine through a through hole having a diameter of 50 μm to form an opening pattern. The characteristics of this laminated body are shown in Table 1.

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

[Example 10]
The procedure was the same as in Example 8 except that the polyimide precursor solution 7 was used. That is, after forming the polyimide layer on the glass, a nickel layer having an opening was formed to obtain a test laminate of the nickel layer having an opening and the polyimide layer. Further, the polyimide layer was separated from the glass by laser lift-off, and an opening pattern was formed in the polyimide layer. The characteristics of this laminated body are shown in Table 1.

[Examples 11-18]
The procedure was the same as in Example 8 except that the polyimide precursor solutions 11 to 18 were used. That is, after forming the polyimide layer on the glass, a nickel layer having an opening was formed to obtain a test laminate of the nickel layer having an opening and the polyimide layer. Further, the polyimide layer was separated from the glass by laser lift-off, and an opening pattern was formed in the polyimide layer. Table 1 shows the characteristics of this laminate and the polyimide precursor used.

[Example 19]
A long roll-shaped Invar having a thickness of 100 μm, a width of 100 mm, and a length of 30 m is mounted on a roll-to-roll heating furnace, and the long Invar is fed out in the longitudinal direction. , The polyimide precursor solution 3 is applied onto Invar using an applicator so that the thickness of the polyimide layer after heat treatment is 0.8 μm, introduced into a heating furnace, and dried at 100 ° C. for 5 minutes. rice field. Further, the polyimide precursor solution 2 is applied onto the polyimide precursor layer formed on the inverter using an applicator so that the thickness of the polyimide layer after heat treatment is 25 μm, and is introduced into a heating furnace to be introduced into a heating furnace. And dried at 100 ° C. for 5 minutes to form a two-layer polyimide precursor layer. Further, the polyimide precursor solution 3 is applied onto the two layers of the polyimide precursor layer using an applicator so that the thickness of the polyimide layer after the heat treatment is 1.2 μm, and the temperature is 100 ° C., 150 ° C., 200 ° C. , 250 ° C. and 350 ° C. for 5 minutes, respectively, to obtain a laminate of a long inver and a polyimide layer. At this time, tension was applied to the Invar during transportation and pressed against the guide roll in the heating furnace to fix the Invar during the heat treatment. In this case, the guide roll is a fixing member. The guide roll was arranged so as to contact only the Invar and not the polyimide surface. The warp of the test laminate obtained by cutting out the laminate of the long Invar and the polyimide layer into a size of 100 mm × 100 mm was 0.4 mm. Further, in the same manner as in Example 1, an opening was formed in the metal layer and a through hole (opening pattern) was formed in the polyimide layer. The characteristics of this laminated body are shown in Table 1. The coefficient of thermal expansion of the single-layer polyimide film in which the polyimide precursor solution 3 is imidized is 56 × 10 ^-6 / K, and the coefficient of thermal expansion of the single-layer polyimide film in which the polyimide precursor solution 2 is imidized is 0. It was 5 × 10 ^-6 / K. The characteristics of this laminated body 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 warp of this laminated body was 1.9 mm. The characteristics of this laminated body 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 the polyimide precursor solution 3 was used. The warp of this laminated body was 1.4 mm. The characteristics of this laminated body are shown in Table 1.

[Comparative Example 3]
A polyimide layer was formed on the glass in the same manner as in Example 8 except that the polyimide precursor solution 9 was used. When laser lift-off was performed, the polyimide layer turned black and became brittle, and a good polyimide film could not be obtained. The characteristics of this laminated body are shown in Table 1.

[Comparative Example 4]
When the same procedure as in Example 8 was carried out except that the polyimide precursor solution 10 was used, the warp of this laminated body was 1.1 mm. The characteristics of this laminated body are shown in Table 1.

[Comparative Example 5]
A sheet-shaped inverse (thickness 100 μm, 100 mm × 100 mm) and a polyimide film (Kapton EN-A, thickness 25 μm, 90 mm × 90 mm) are adhered using an epoxy resin adhesive, and 120 while pressurizing with a batch press. The mixture was kept at ° C. for 30 minutes to obtain a laminate of polyimide and Inver. The coefficient of thermal expansion of this polyimide film was anisotropic, one was 6.2 × 10 ^-6 / K, and the direction orthogonal to this was 13.0 × 10 ^-6 / K. This laminated body was warped along the direction in which the coefficient of thermal expansion of polyimide was 13.0 × 10 ^-6 / K, and the warp was 0.6 mm. The characteristics of this laminated body are shown in Table 1.

A dry film resist is laminated on the Invar surface of the obtained laminate, the dry film resist is patterned, and the Invar is etched with an aqueous ferric chloride solution along the pattern to open a metal layer having a width of 3 mm and a length of 10 mm. Formed a part. Further, an attempt was made to form an opening pattern on the polyimide in the opening by using a UV-YAG laser machine so as to form a through hole having a diameter of 50 μm, but unevenness was formed at the interface between the polyimide layer on the wall surface in the through hole and the adhesive. It occurred and a good opening pattern could not be formed.

1: Metal layer, 1a: Aperture, 2: Polyimide layer, 2a: Through hole, 3: Opening pattern, 4: Vapor deposition mask.

Claims (16)

A thin-film deposition mask for forming a thin-film pattern having a constant shape on a body to be vapor-deposited, which has a metal layer having a plurality of openings and through holes located within the opening range of the openings. It consists of a laminate with a polyimide layer having an opening pattern corresponding to the thin film pattern.
The polyimide layer is formed of a single layer or a plurality of layers of polyimide, and the main polyimide forming the polyimide layer is an imidized polyimide precursor having a structural unit represented by the following formula (1). The coefficient of thermal expansion of the polyimide layer is 5 × 10 ^-6 / K or less in all in-plane directions, and the difference in the orthogonal biaxial directions is 2 × 10 ^-6 / K or less in the in-plane direction. isotropic ones der is, also, the deposition mask the metal layer, characterized in Rukoto formed by invar or Invar alloy.

However, R ₁ is a divalent organic group selected from the group represented by the following formula (2).

(R'is independently an alkyl group having 1 to 6 carbon atoms, an alkyl halide group, an aromatic group having 6 to 18 carbon atoms, or a halogen group, and the hydrogen atom of the aromatic group is a halogen atom or a halogen atom. It may be substituted with an alkyl group 1 to 6 or an alkyl halide group),.
R ₂ is a tetravalent organic group selected from the group represented by the following formula (3).

R represents a hydrogen atom or a monovalent organic group independently, and n is a positive integer representing the number of repetitions. The main polyimide forming the polyimide layer, characterized in that the formula (1) structural unit represented by the 60 mol% or more inclusive polyimide precursor is obtained by imidation of claim 1 Vapor deposition mask. The polyimide layer according to claim 1, wherein the polyimide layer has a light transmittance of 60% or more at a wavelength of 500 nm and / or a light transmittance of 50% or less at a wavelength of 355 nm and / or a wavelength of 308 nm. Vapor deposition mask. The vapor deposition mask according to claim 1 , wherein the main polyimide constituting the polyimide layer is a fluorine-containing polyimide or an alicyclic polyimide. The vapor deposition mask according to claim 1, wherein the metal layer and the polyimide layer are laminated without using an adhesive. The vapor deposition mask according to claim 1, wherein the polyimide layer is made of a plurality of layers of polyimide, and the coefficient of thermal expansion of the main polyimide forming the polyimide layer is smaller than the coefficient of thermal expansion of other polyimides. The vapor deposition according to claim 1, wherein the polyimide layer is composed of a plurality of layers of polyimide, and the coefficient of thermal expansion of the polyimide in contact with the metal layer is larger than the coefficient of thermal expansion of another polyimide adjacent to the polyimide. mask. The vapor deposition according to claim 1, wherein the polyimide layer is composed of a plurality of layers of polyimide, and the coefficient of thermal expansion of the polyimide in contact with the metal layer is smaller than the coefficient of thermal expansion of another polyimide adjacent to the polyimide. mask. The polyimide layer is composed of three or more layers of polyimide, and the coefficient of thermal expansion of the two outermost polyimides forming the front surface and the back surface is the heat of the polyimide forming the intermediate layer sandwiched between the outermost polyimides. The vapor deposition mask according to claim 1, wherein the polyimide is larger than the coefficient of expansion and one of the polyimides forming the outermost surface is in contact with the metal layer. The vapor deposition mask according to claim 1, wherein the polyimide layer is divided into two or more and laminated in the plane of the metal layer. A method of manufacturing a deposition mask for depositing a thin film pattern of a predetermined shape on the deposition object, the thermal expansion coefficient is not more than 5 × 10 -6 ^{/ K} in all directions in the plane, perpendicular A polyimide layer having an isotropic coefficient of thermal expansion in the in-plane direction with a biaxial difference of 2 × 10 ^-6 / K or less and a metal layer are laminated to form a plurality of openings in the metal layer. Or, the coefficient of thermal expansion is 5 × ^10-6 / K or less in all directions in the plane with the metal layer having multiple openings, and the difference in the orthogonal biaxial directions is 2 × 10 ^{−. After laminating a polyimide layer having an isotropic coefficient of thermal expansion in the in-plane direction of 6} / K or less, the polyimide layer within the opening range of the opening of the metal layer is penetrated to correspond to the thin film pattern. per to form the opening pattern,
The polyimide layer is formed of a single layer or a plurality of layers of polyimide, and the main polyimide forming the polyimide layer is an imidized polyimide precursor having a structural unit represented by the following formula (1).
A method for producing a thin-film mask, wherein the metal layer is formed of Invar or an Invar alloy.

However, R ₁ is a divalent organic group selected from the group represented by the following formula (2).

(R'is independently an alkyl group having 1 to 6 carbon atoms, an alkyl halide group, an aromatic group having 6 to 18 carbon atoms, or a halogen group, and the hydrogen atom of the aromatic group is a halogen atom or a halogen atom. It may be substituted with an alkyl group 1 to 6 or an alkyl halide group),.
R ₂ is a tetravalent organic group selected from the group represented by the following formula (3).

R represents a hydrogen atom or a monovalent organic group independently, and n is a positive integer representing the number of repetitions. A method for manufacturing a thin-film deposition mask for forming a thin-film pattern having a constant shape on a body to be vapor-deposited.
A liquid composition containing a polyimide precursor having a structural unit represented by the following formula (1) is applied onto the coated substrate and heated, so that the coefficient of thermal expansion is all in-plane on the coated substrate. A polyimide layer having an isotropic coefficient of thermal expansion in the in-plane direction of 5 × 10 ^-6 / K or less in the direction and a difference of 2 × 10 ^{-6 / K or less in the orthogonal biaxial directions is formed.} Process to do,
A metal layer formed of Invar or Invar alloy is laminated on the polyimide layer to form a plurality of openings in the metal layer, or a plurality of openings formed of Invar or Invar alloy on the polyimide layer. The process of laminating metal layers with parts,
A step of separating the polyimide layer and the coating base material, and
A step of forming an opening pattern corresponding to the thin film pattern by penetrating a polyimide layer within the opening range of the opening of the metal layer.
A method for producing a vapor deposition mask, which comprises.

However, R ₁ is a divalent organic group selected from the group represented by the following formula (2).

(R'is independently an alkyl group having 1 to 6 carbon atoms, an alkyl halide group, an aromatic group having 6 to 18 carbon atoms, or a halogen group, and the hydrogen atom of the aromatic group is a halogen atom and a carbon number of carbon atoms. It may be substituted with an alkyl group 1 to 6 or an alkyl halide group),.
R ₂ is a tetravalent organic group selected from the group represented by the following formula (3).

R represents a hydrogen atom or a monovalent organic group independently, and n is a positive integer representing the number of repetitions. A method for manufacturing a thin-film deposition mask for forming a thin-film pattern having a constant shape on a body to be vapor-deposited.
The process of fixing a metal layer formed of Invar or Invar alloy on a fixing member,
A liquid composition containing a polyimide precursor having a structural unit represented by the following formula (1) is applied to the surface of the metal layer and heated to have a coefficient of thermal expansion on the metal layer in all directions in the plane. A step of forming a polyimide layer having an isotropic coefficient of thermal expansion in the in-plane direction of 5 × ^10-6 / K or less and an orthogonal biaxial difference of 2 × ^{10-6 / K or less.} ,
A step of separating the metal layer and the fixing member,
A step of forming a plurality of openings in the metal layer, and
A step of forming an opening pattern corresponding to the thin film pattern by penetrating a polyimide layer within the opening range of the opening of the metal layer.
A method for producing a vapor deposition mask, which comprises.

However, R ₁ is a divalent organic group selected from the group represented by the following formula (2).

(R'is independently an alkyl group having 1 to 6 carbon atoms, an alkyl halide group, an aromatic group having 6 to 18 carbon atoms, or a halogen group, and the hydrogen atom of the aromatic group is a halogen atom or a halogen atom. It may be substituted with an alkyl group 1 to 6 or an alkyl halide group),.
R ₂ is a tetravalent organic group selected from the group represented by the following formula (3).

R represents a hydrogen atom or a monovalent organic group independently, and n is a positive integer representing the number of repetitions. A laminated body for a vapor deposition mask for laminating a metal layer made of a magnetic material and a polyimide layer to form a thin film pattern having a constant shape on the body to be vapor-deposited. It is 5 × ^10-6 / K or less in all in-plane directions, and the difference in the orthogonal biaxial directions is 2 × ^10-6 / K or less, which is isotropic in the in-plane direction. , together with the polyimide layer is formed of a polyimide single layer or plural layers, the principal polyimide state, and are not to imidized polyimide precursor having a structural unit represented by the following formula (1), also, the metal laminate for deposition mask layers are characterized Rukoto formed by invar or Invar alloy.

However, R ₁ is a divalent organic group selected from the group represented by the following formula (2).

(R'is independently an alkyl group having 1 to 6 carbon atoms, an alkyl halide group, an aromatic group having 6 to 18 carbon atoms, or a halogen group, and the hydrogen atom of the aromatic group is a halogen atom or a halogen atom. It may be substituted with an alkyl group 1 to 6 or an alkyl halide group),.
R ₂ is a tetravalent organic group selected from the group represented by the following formula (3).

R represents a hydrogen atom or a monovalent organic group independently, and n is a positive integer representing the number of repetitions. A method for producing a laminated body for a thin-film deposition mask for laminating a metal layer made of a magnetic material and a polyimide layer to form a thin-film pattern having a constant shape on the body to be vapor-deposited.
A step of applying a liquid composition containing a polyimide precursor to the surface of the metal layer to form a coating layer, and
A step of heating the coating layer to form a polyimide layer on the metal layer,
The liquid composition contains a polyimide precursor having a structural unit represented by the following formula (1), and the coefficient of thermal expansion of the polyimide layer formed on the metal layer is in all directions in the plane. Is 5 × 10 ^-6 / K or less, and the difference in the orthogonal biaxial directions is 2 × 10 ^-6 / K or less in the in-plane direction, and the metal layer is inverse. or method of manufacturing a deposition mask stack, wherein Rukoto formed by invar alloy.

However, R ₁ is a divalent organic group selected from the group represented by the following formula (2).

(R'is independently an alkyl group having 1 to 6 carbon atoms, an alkyl halide group, an aromatic group having 6 to 18 carbon atoms, or a halogen group, and the hydrogen atom of the aromatic group is a halogen atom or a halogen atom. It may be substituted with an alkyl group 1 to 6 or an alkyl halide group),.
R ₂ is a tetravalent organic group selected from the group represented by the following formula (3).

R represents a hydrogen atom or a monovalent organic group independently, and n is a positive integer representing the number of repetitions. The method for producing a laminated body for a vapor deposition mask according to claim 15 , further comprising a step of fixing the metal layer on the fixing member prior to the step of forming the coating layer on the surface of the metal layer.

Images