JP2019157269A - Vapor deposition mask, polyamide for forming vapor deposition mask, laminate for forming vapor deposition mask and method of producing vapor deposition mask - Google Patents

Abstract

To suppress the occurrence of warpage in a laminate such as a vapor deposition mask.SOLUTION: A vapor deposition mask is provided with a metal layer having a plurality of openings, and a single or a plurality of polyimide layers laminated on the metal layer and having a through-hole located within an opening range of the opening. The metal layer of the vapor deposition mask has a thermal expansion coefficient (CTE) of 5 ppm/K or more and 15 ppm/K or less. The polyimide layer has a thermal expansion coefficient (CTE) of ±5 ppm/K with respect to the thermal expansion coefficient of the metal layer, and a tensile elastic modulus of 4.5 GPa or and less than 8 GPa. The metal layer is preferably formed by a semiadditive process.SELECTED DRAWING: None

Description

  The present invention relates to a vapor deposition mask for vapor-depositing a thin film pattern having a predetermined shape on a vapor-deposited body, a polyamic acid and a laminate used for forming the vapor deposition mask, and a method for producing the vapor deposition mask.

  In a small electronic device such as a smartphone, the display has been improved in definition. In addition, liquid crystal displays have been mainstream until now, but it is expected that some of them will be replaced with organic EL displays in the future. An organic EL display is formed by forming a thin film transistor (hereinafter referred to as TFT) on a deposition target (deposition substrate) made of glass or resin as a supporting base material, and then forming an electrode, a light emitting layer, and an electrode in order. It is made by hermetically sealing with a glass substrate or a multilayer thin film. And in the formation of the light emitting layer and the cathode electrode by vapor deposition, vapor deposition is performed on the deposition target using a vapor deposition mask.

  As the vapor deposition mask, an FMM (fine metal mask) made of a metal foil having a low coefficient of thermal expansion (CTE) formed by arranging a large number of fine through openings is used. In addition, in order to achieve high definition patterning using a vapor deposition mask, a change from FMM to FHM (fine hybrid mask), which is a vapor deposition mask having a structure in which a metal layer and a resin layer are laminated, is being studied. However, in FHM, due to the difference in thermal expansion coefficient between the metal layer and the resin layer, the accuracy of the thin film pattern by vapor deposition tends to decrease or warpage occurs. Therefore, as a basic design for manufacturing a laminate in which a metal layer and a resin layer are laminated like FHM, control is performed so that the CTE of the resin layer is close to the CTE of the metal layer.

  In Patent Document 1, regarding a laminate used for a semiconductor package application, in order to realize a high elastic modulus and low CTE comparable to that of a metal, as a raw material monomer for polyimide, a polyimide composed of paraphenylenediamine and pyromellitic dianhydride is used. Biaxially stretching a copolymer polyimide formed by molecularly bonding a block component and a random component of a copolymer polyimide composed of 4,4′-diaminodiphenyl ether and an acid dianhydride such as pyromellitic dianhydride Molding techniques have been proposed.

  In Patent Document 2, in order to suppress the occurrence of dimensional change in the COF production process using the semi-additive method, as the main raw material of the polyimide film, paraphenylenediamine is used as an aromatic diamine component, and While using merit acid dianhydride and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, the coefficient of thermal expansion αMD in the machine conveying direction (MD) is 2.0 ppm / ° C. or more and 10.0 ppm / ° C. Hereinafter, the coefficient of thermal expansion αTD in the width direction (TD) is set to −2.0 ppm / ° C. or more and 3.5 ppm / ° C. or less, and is further controlled to satisfy the relationship of | αMD | ≧ | αTD | × 2.0. Has been proposed.

Japanese Patent No. 4009918 JP 2006-132744 A

  As described above, in the prior art, the CTE of a resin layer is controlled in a laminate in which a metal layer and a resin layer are laminated. In particular, from the viewpoint of suppressing warpage, it is considered preferable to make the CTE of the resin layer as close as possible to the CTE of the metal layer. However, since the CTE of the resin layer is greatly affected by the thermal history during the manufacture of the laminate and its processing, in the actual manufacturing process, it is naturally limited to approximate the CTE of the resin layer to the CTE of the metal layer. Therefore, countermeasures against warping are an important issue.

  Therefore, an object of the present invention is to effectively suppress the occurrence of warpage in a laminated body such as a vapor deposition mask.

The vapor deposition mask of this invention is for vapor-depositing and forming the thin film pattern of a fixed shape on a to-be-deposited body.
This vapor deposition mask has a metal layer having a plurality of openings, and is laminated on the metal layer, and has a through hole located within the opening range of the opening, and the through hole corresponds to the thin film pattern. A single layer or a plurality of polyimide layers forming an opening pattern.
And the vapor deposition mask of this invention has the thermal expansion coefficient (CTE) of the said metal layer in the range of 5 ppm / K or more and 15 ppm / K or less,
The thermal expansion coefficient (CTE) of the polyimide layer is within a range of ± 5 ppm / K with respect to the thermal expansion coefficient (CTE) of the metal layer, and the tensile elastic modulus of the polyimide layer is 4.5 GPa or more and 8 GPa. Within the range of less than.

  In the vapor deposition mask of the present invention, the difference between the thermal expansion coefficient (CTE-MD) in the longitudinal (MD) direction of the polyimide layer and the thermal expansion coefficient (CTE-TD) in the width (TD) direction is ± 2. It may be 5 ppm / K or less.

In the vapor deposition mask of the present invention, the polyimide constituting the polyimide layer contains an acid anhydride residue derived from an acid anhydride component and a diamine residue derived from a diamine component. May be.
And 50 mol parts or more of acid anhydride residues derived from pyromellitic dianhydride may be contained with respect to 100 mol parts in total of the acid anhydride residues.
Moreover, the diamine residue derived from the diamine compound represented by the following general formula (1) with respect to a total of 100 mol parts of the diamine residues is within the range of 50 mol parts to 90 mol parts, and You may contain the diamine residue induced | guided | derived from the at least 1 sort (s) of diamine compound represented by Formula (a)-(d) in the range of 10 to 50 mol parts.

  In the general formula (1), the substituent Y independently represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group or an alkenyl group having 2 to 3 carbon atoms which may be independently substituted with a halogen atom, and p and q are independently Represents an integer of 0 to 4.

In the general formulas (a) to (d), the substituent R ₁ independently represents a monovalent hydrocarbon group or alkoxy group having 1 to 4 carbon atoms, and the linking group A is independently —O—, —S—, _{-CO -, - SO -, -} SO 2 -, - COO -, - CH 2 -, - C (CH 3) 2 -, - NH- or -CONH- indicates the linking group B is a single bond or -C (CH ₃ ) ₂ —, and n1 independently represents an integer of 0-4.

  Moreover, as for the vapor deposition mask of this invention, the said polyimide layer may consist of a single layer.

  In the vapor deposition mask of the present invention, the metal layer may contain a nickel element as a main component.

  The polyamic acid for forming a vapor deposition mask of the present invention is a polyamic acid for forming a vapor deposition mask used for forming the polyimide layer in the vapor deposition mask.

  The polyamic acid for forming a vapor deposition mask of the present invention may contain an acid anhydride residue derived from an acid anhydride component and a diamine residue derived from a diamine component. And 50 mol parts or more of acid anhydride residues derived from pyromellitic dianhydride may be contained with respect to 100 mol parts in total of the acid anhydride residues. Moreover, the diamine residue derived from the diamine compound represented by the general formula (1) with respect to a total of 100 mol parts of the diamine residues is within the range of 50 mol parts to 90 mol parts, and the above general You may contain the diamine residue induced | guided | derived from the at least 1 sort (s) of diamine compound represented by Formula (a)-(d) in the range of 10 to 50 mol parts.

The laminated body for vapor deposition mask formation of this invention is used for formation of the vapor deposition mask for carrying out vapor deposition formation of the thin film pattern of a fixed shape on a to-be-deposited body.
And the laminated body for vapor deposition mask formation of this invention is the following.
A metal layer,
A single layer or multiple layers of polyimide layer laminated on the metal layer;
It has.
The laminate for forming a vapor deposition mask of the present invention has a coefficient of thermal expansion (CTE) of the metal layer in the range of 5 ppm / K or more and 15 ppm / K or less,
The thermal expansion coefficient (CTE) of the polyimide layer is within a range of ± 5 ppm / K with respect to the thermal expansion coefficient (CTE) of the metal layer, and the tensile elastic modulus of the polyimide layer is 4.5 GPa or more and 8 GPa. Within the range of less than.

  Moreover, the laminated body for vapor deposition mask formation of this invention is the difference of the thermal expansion coefficient (CTE-MD) of the longitudinal (MD) direction of the said polyimide layer, and the thermal expansion coefficient (CTE-TD) of the width (TD) direction. May be ± 2.5 ppm / K or less.

Moreover, the laminated body for vapor deposition mask formation of this invention contains the acid anhydride residue induced | guided | derived from an acid anhydride component, and the diamine residue induced | guided | derived from a diamine component in the polyimide which comprises the said polyimide layer. You may do.
And 50 mol parts or more of acid anhydride residues derived from pyromellitic dianhydride may be contained with respect to 100 mol parts in total of the acid anhydride residues.
Moreover, the diamine residue derived from the diamine compound represented by the general formula (1) with respect to a total of 100 mol parts of the diamine residues is within the range of 50 mol parts to 90 mol parts, and the above general You may contain the diamine residue induced | guided | derived from the at least 1 sort (s) of diamine compound represented by Formula (a)-(d) in the range of 10 to 50 mol parts.

  Moreover, as for the laminated body for vapor deposition mask formation of this invention, the said polyimide layer may consist of a single layer.

  Moreover, the laminated body for vapor deposition mask formation of this invention WHEREIN: The said metal layer may contain a nickel element as a main component.

The manufacturing method of the vapor deposition mask of this invention is a method of manufacturing the vapor deposition mask for carrying out vapor deposition formation of the thin film pattern of a fixed shape on a to-be-deposited body. The method for producing a vapor deposition mask of the present invention includes the following steps I to III;
I) A step of forming a single layer or a plurality of polyimide layers by applying a polyamic acid solution on a supporting substrate and then heat-treating to obtain a first laminate,
II) forming a metal layer having a plurality of openings on the first laminated body to obtain a second laminated body;
III) forming a plurality of through holes in the polyimide layer in a range overlapping the opening of the metal layer, and forming an opening pattern corresponding to the thin film pattern;
Is included.
And the manufacturing method of the vapor deposition mask of this invention is in the range whose thermal expansion coefficient (CTE) of the said metal layer is 5 ppm / K or more and 15 ppm / K or less,
The thermal expansion coefficient (CTE) of the polyimide layer is within a range of ± 5 ppm / K with respect to the thermal expansion coefficient (CTE) of the metal layer, and the tensile elastic modulus of the polyimide layer is 4.5 GPa or more and 8 GPa. Within the range of less than.

  Moreover, the manufacturing method of the vapor deposition mask of this invention has the difference of the thermal expansion coefficient (CTE-MD) of the longitudinal (MD) direction of the said polyimide layer, and the thermal expansion coefficient (CTE-TD) of a width | variety (TD) direction. It may be ± 2.5 ppm / K or less.

Further, in the method for producing a vapor deposition mask of the present invention, the polyamic acid used in Step I includes an acid anhydride residue derived from an acid anhydride component and a diamine residue derived from a diamine component. You may do.
And 50 mol parts or more of acid anhydride residues derived from pyromellitic dianhydride may be contained with respect to 100 mol parts in total of the acid anhydride residues.
With respect to a total of 100 mol parts of the diamine residues, the diamine residues derived from the diamine compound represented by the general formula (1) are within the range of 50 mol parts to 90 mol parts, and the general formula ( You may contain the diamine residue induced | guided | derived from the at least 1 sort (s) of diamine compound represented by a)-(d) in 10 mol part or more and 50 mol part or less.

  Moreover, in the manufacturing method of the vapor deposition mask of this invention, the said process II may form the said metal layer by a semi-additive construction method.

  ADVANTAGE OF THE INVENTION According to this invention, the curvature of the laminated body of the structure where the polyimide layer and the metal layer were laminated | stacked can be suppressed effectively. This laminated body is useful as, for example, a vapor deposition mask, and can improve the production efficiency of a display device such as an organic EL display device, and can further cope with higher definition.

[Vapor deposition mask]
A vapor deposition mask according to an embodiment of the present invention is for vapor-depositing a thin film pattern having a predetermined shape on a vapor deposition target, and a metal layer having a plurality of openings and laminated on the metal layer. A single layer or a plurality of polyimide layers. Moreover, the polyimide layer has a through hole located within the opening range of the opening of the metal layer. The through hole forms an opening pattern corresponding to the thin film pattern.

<Metal layer>
The metal layer on the other side on which the polyimide layer is laminated has a CTE in the range of 5 ppm / K to 15 ppm / K, and preferably in the range of 10 ppm / K to 15 ppm / K. Examples of the material of the metal layer in which the CTE is in the above range include metals such as nickel, iron, stainless steel, titanium, and alloys thereof, and preferably a metal containing nickel element as a main component. Here, the “main component” means that the content of the nickel element is the highest among all the elements contained in the metal layer, and preferably means that the nickel element is contained by 50% by weight or more. . Among these, nickel having a CTE of about 13 ppm / K or an alloy thereof is preferable. In addition, as long as CTE is in the said range, content, such as nickel, will not ask | require an alloy.

<Polyimide layer>
The polyimide layer has a CTE within a range of ± 5 ppm / K and preferably within a range of ± 3 ppm / K with respect to the CTE of the metal layer. When the CTE difference between the polyimide layer and the metal layer is within the range of ± 5 ppm / K, internal stress is less likely to occur between the metal layer and, in the case of a deposition mask, the opening in the polyimide layer with the metal layer. This is advantageous because the position accuracy of the portion can be maintained and large warpage can be suppressed. Moreover, if the CTE difference between the polyimide layer and the metal layer is within a range of ± 5 ppm / K, the occurrence of warpage can be effectively suppressed by controlling the tensile elastic modulus described below. When the CTE difference exceeds ± 5 ppm / K, the effect of suppressing warpage by controlling the tensile elastic modulus cannot be sufficiently obtained.

  The polyimide layer has a tensile modulus of 4.5 GPa or more and less than 8 GPa, and preferably 5 GPa or more and 7 GPa or less. When the tensile modulus of the polyimide layer is 8 GPa or more, the flexibility becomes low, so the stress difference between the heat-treated metal layer and the polyimide layer due to the CTE difference cannot be absorbed and the occurrence of warpage is effectively suppressed. It becomes difficult to do. On the other hand, if the tensile elastic modulus of the polyimide layer is less than 4.5 GPa, the flexibility of the polyimide layer becomes too high and it becomes difficult to control the CTE. For example, when the laminate is used as a vapor deposition mask, recycling is not possible. For this reason, when solvent washing is repeated, the film is deformed, and the pattern accuracy during deposition may be lowered.

  Further, the polyimide layer has a difference between the thermal expansion coefficient (CTE-MD) in the longitudinal (MD) direction and the thermal expansion coefficient (CTE-TD) in the width (TD) direction of ± 2.5 ppm / K or less. It is preferable that it is ± 1.5 ppm / K or less. If the difference between CTE-MD and CTE-TD is within the above range, the dimensional change in the MD direction and the TD direction can be suppressed, and the accuracy of the thin film pattern by vapor deposition can be maintained when used as a vapor deposition mask. . In particular, by forming the polyimide layer by a casting method, it becomes difficult to produce a difference in the orientation of the polymer chains in the MD direction and the TD direction, so that in-plane dimensional variations can be suppressed. In addition, CTE of a polyimide layer is synonymous with each of CTE-MD and CTE-TD. Therefore, when the range of CTE is prescribed | regulated about a polyimide layer, it means that both CTE-MD and CTE-TD satisfy | fill the said range.

  Further, the glass transition temperature (Tg) of the polyimide layer is not particularly limited, but is preferably set to 300 ° C. or higher when improving the dimensional accuracy at high temperature. When improving the adhesive strength, it is preferable that it is less than 300 degreeC.

[Laminated body for vapor deposition mask formation]
The laminate for forming a vapor deposition mask of the present embodiment is used for forming the vapor deposition mask. The laminated body for vapor deposition mask formation of this Embodiment is equipped with the metal layer and the single layer or multiple layers of polyimide layer laminated | stacked on the said metal layer. Although the metal layer in the laminated body for vapor deposition mask formation may be the same structure as the metal layer in the said vapor deposition mask, it may have the said opening part and does not need to have it. Moreover, the polyimide layer in the laminated body for vapor deposition mask formation may be the same structure as the polyimide layer in the said vapor deposition mask except the point which does not have the said through-hole.

[Polyamide acid]
The polyamic acid of this Embodiment is used in order to form the polyimide layer laminated | stacked on a metal layer. More specifically, polyamic acid is used for forming a polyimide layer in a laminate having a metal layer and a polyimide layer laminated on the metal layer. Here, examples of the laminated body include the vapor deposition mask and the laminated body for forming a vapor deposition mask. The polyamic acid of the present embodiment is particularly preferably used as a material for forming a polyimide layer in FHM by a casting method. Note that the “polyimide layer” includes a polyimide layer in the laminate or includes a “polyimide film” for forming the polyimide layer.

  The polyamic acid of the present embodiment contains an acid anhydride residue derived from an acid anhydride component and a diamine residue derived from a diamine component. Since this polyamic acid is generally produced by reacting an acid anhydride and a diamine, a specific example of the polyamic acid can be understood by explaining the acid anhydride and the diamine. Hereinafter, the preferred polyamic acid will be described using an acid anhydride and a diamine.

(Raw material monomer)
Acid anhydride component:
The polyamic acid used in the present embodiment is preferably produced using PMDA as the main raw material monomer. PMDA can control the orientation of molecules in polyimide compared to other general acid anhydride components, and has the effect of suppressing the coefficient of thermal expansion (CTE) and improving the glass transition temperature (Tg). . From such a viewpoint, the amount of PMDA is preferably 50 mol parts or more, for example, in the range of 50 mol parts to 100 mol parts, more preferably 75 mol parts to 100 mols, relative to 100 mol parts of the acid anhydride component of the raw material monomer. It is good to use within the range of the part. When the charged amount of PMDA is less than 50 mol parts with respect to 100 mol parts of the total acid anhydride component of the raw material, the molecular orientation is lowered and it is difficult to achieve low CTE.

  The acid anhydride component that can be used in addition to PMDA can be appropriately selected from acid dianhydrides generally used as raw materials for polyamic acid / polyimide, but aromatic tetracarboxylic dianhydrides are preferred. . As an aromatic tetracarboxylic dianhydride, for example, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA), 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 4,4′-oxydiphthalic anhydride, 2,3 ′, 3,4′-biphenyltetracarboxylic dianhydride, 2, 2 ', 3,3'-, 2,3,3', 4'- or 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,3', 3,4'-diphenyl ether tetra Carboxylic dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, 3,3 ″, 4,4 ″-, 2,3,3 ″, 4 ″-or 2,2 '', 3,3 ''-p-terphenyltetracarboxylic dianhydride, 2,2-bis (2,3- or 3,4-dicarboxyphenyl) -propane dianhydride, bis (2,3 -Or 3.4-Dicarboxypheny ) Methane dianhydride, bis (2,3- or 3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3- or 3,4-dicarboxyphenyl) ethane dianhydride, 1,2,7,8-, 1,2,6,7- or 1,2,9,10-phenanthrene-tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride 2,2-bis (3,4-dicarboxyphenyl) tetrafluoropropane dianhydride, 2,3,5,6-cyclohexane dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7 -Hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 2,6- or 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid 2,3,4,7- (or 1,4,5,8-) tetrachloronaphthalene-1,4,5,8- (or 2,3,6,7-) tetracarboxylic dianhydride 2,3,8,9-, 3,4,9,10-, 4,5,10,11- or 5,6,11,12-perylene-tetracarboxylic dianhydride, cyclopentane-1, 2,3,4-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, thiophene-2 , 3,4,5-tetracarboxylic dianhydride, 4,4′-bis (2,3-dicarboxyphenoxy) diphenylmethane dianhydride, and the like.

Diamine component:
The polyamic acid used in the present embodiment is preferably produced using a diamine compound having a biphenyl skeleton as the main raw material monomer in the diamine component. That is, with respect to 100 mol parts of the diamine component of the raw material monomer, the diamine compound represented by the following general formula (1) is preferably within the range of 50 mol parts to 90 mol parts, more preferably 50 mol parts to 80 mols. It is good to use within the range below a part. In addition, at least one diamine compound represented by the following general formulas (a) to (d) is preferably in the range of 10 to 50 mole parts, more preferably in the range of 20 to 50 mole parts. It is good to use within.

In the general formula (1), the substituent Y independently represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group, or an alkenyl group having 2 to 3 carbon atoms which may be independently substituted with a halogen atom, and p and q are Independently represents an integer of 0-4.
In the general formulas (a) to (d), the substituent R ₁ independently represents a monovalent hydrocarbon group or alkoxy group having 1 to 4 carbon atoms, and the linking group A is independently —O—, — S—, —CO—, —SO—, —SO ₂ —, —COO—, —CH ₂ —, —C (CH ₃ ) ₂ —, —NH— or —CONH—, wherein the linking group B is a single bond or -C _{(CH 3) 2} - indicates, n1 is an integer of independently 0-4. Here, “independently” means that in one or more of the above formulas (a) to (d), the linking group A, the group R ₁ and the integer n1 may be the same or different. Means good.
In the present invention, the “diamine compound” may have hydrogen atoms in the two terminal amino groups substituted, for example, —NR ₃ R ₄ (where R ₃ and R ₄ are independently an alkyl group). Meaning an arbitrary substituent such as

  The diamine compound represented by the general formula (1) is a diamine compound having a biphenyl skeleton (meaning a diamine compound composed of two aromatic rings, not including those having three or more aromatic rings. The same applies hereinafter. ). A diamine compound having a biphenyl skeleton easily forms an ordered structure and contributes to a low CTE of the polyimide layer. Preferable specific examples of the diamine compound having a biphenyl skeleton include 2,2′-dimethyl-4,4′-diaminobiphenyl (m-TB), 2,2′-diethyl-4,4′-diaminobiphenyl (m- EB), 2,2'-diethoxy-4,4'-diaminobiphenyl (m-EOB), 2,2'-dipropoxy-4,4'-diaminobiphenyl (m-POB), 2,2'-n- Propyl-4,4′-diaminobiphenyl (m-NPB), 2,2′-divinyl-4,4′-diaminobiphenyl (VAB), 4,4′-diaminobiphenyl, 4,4′-diamino-2, Examples thereof include diamine compounds such as 2′-bis (trifluoromethyl) biphenyl (TFMB). Among these, 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB) is particularly preferable because it is easy to form an ordered structure and has a large effect on lowering CTE.

  On the other hand, since the diamine compounds represented by the general formulas (a) to (d) have a highly flexible molecular structure, they have the effect of increasing the flexibility of the polyimide layer and suppressing the tensile elastic modulus low. . Therefore, by using within the above range, even if there is a CTE difference between the metal layer and the polyimide layer, the stress can be relaxed and the occurrence of warpage can be effectively suppressed. When the total amount of the diamine compounds represented by the general formulas (a) to (d) is less than 10 mol parts with respect to the total 100 mol parts of the diamine compounds, the elastic modulus of the polyimide layer increases, and the metal layer and the polyimide layer On the other hand, when the total amount exceeds 50 mole parts, the CTE becomes too large and the difference in the CTE of the metal layer increases, both of which cause warpage. .

In the general formula (a), preferable examples of the group R ₁ include an alkyl group having 1 to 4 carbon atoms, or an alkoxy group or alkenyl group having 1 to 3 carbon atoms. Examples of the diamine compound represented by the formula (a) include m-phenylenediamine (m-PDA), 2,4-diethyl-6-methyl-1,3-benzenediamine, and 4,6-diethyl-2- Examples include methyl-1,3-phenylenediamine and 2,4-diaminotoluene.

In the general formula (b), preferred examples of the group R ₁ include an alkyl group having 1 to 4 carbon atoms, or an alkoxy group or alkenyl group having 1 to 3 carbon atoms. In the general formula (b), preferred examples of the linking group A include —O—, —S—, —CH ₂ —, —SO ₂ —, and —CO—. Preferable specific examples of the diamine compound represented by the general formula (b) include 4,4′-diaminodiphenyl ether (4,4′-DAPE), 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether ( 3,4′-DAPE), 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 3,3′-diaminodiphenylpropane, 3,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylsulfone, 3,3'- Diaminodiphenyl sulfone, 4,4′-diaminobenzophenone, 3,4′-diaminobenzophenone, 3,3′-dia Diamine compounds such as Roh benzophenone.

In the general formula (c), preferred examples of the group R ₁ include an alkyl group having 1 to 4 carbon atoms, or an alkoxy group or alkenyl group having 1 to 3 carbon atoms. In the general formula (c), preferred examples of the linking group A include —O—, —S—, —CH ₂ —, —SO ₂ —, and —CO—. Preferable specific examples of the diamine compound represented by the general formula (c) include 1,3-bis (4-aminophenoxy) benzene (TPE-R), 1,4-bis (4-aminophenoxy) benzene (TPE). -Q), 1,3-bis (3-aminophenoxy) benzene (APB), bis (4-aminophenoxy) -2,5-di-tert-butylbenzene (DTBAB), 4,4-bis (4- Aminophenoxy) benzophenone (BAPK), 1,3-bis [2- (4-aminophenyl) -2-propyl] benzene 1,4-bis [2- (4-aminophenyl) -2-propyl] benzene, etc. A diamine compound is mentioned.

In the general formula (d), preferred examples of the group R ₁ include an alkyl group having 1 to 4 carbon atoms, or an alkoxy group or alkenyl group having 1 to 3 carbon atoms. In the general formula (d), preferred examples of the linking group A include —O—, —S—, —CH ₂ —, —SO ₂ —, and —CO—. Preferable examples of the linking group B include a single bond or —C (CH ₃ ) ₂ —. Preferable specific examples of the diamine compound represented by the general formula (d) include 4,4′-bis (4-aminophenoxy) biphenyl (BAPB), 2,2′-bis [4- (4-aminophenoxy). And diamine compounds such as phenyl] propane (BAPP).

  Since the diamine compound represented by the general formulas (b) to (d) has 2 to 4 benzene rings, at least one terminal group bonded to the benzene ring is used to suppress an increase in CTE. Is preferably in the para position. Therefore, as a preferable embodiment, at least one diamine compound represented by the following general formulas (a1) to (d1) is included in a range of 10 to 50 parts by mole with respect to 100 parts by mole of the diamine compound. It is good to contain. The general formula (a1) is the general formula (a), the general formula (b1) is the general formula (b), the general formula (c1) is the general formula (c), and the general formula (d1) is the general formula ( d) respectively.

In the general formulas (a1) to (d1), the substituent R ₁ independently represents a monovalent hydrocarbon group or alkoxy group having 1 to 4 carbon atoms, and the linking group A is independently —O—, —S—, A divalent group selected from —CO—, —SO—, —SO ₂ —, —COO—, —CH ₂ —, —C (CH ₃ ) ₂ —, —NH— or —CONH—, and a linking group; B represents a single bond or a divalent group selected from —C (CH ₃ ) ₂ —, and n1 independently represents an integer of 0 to 4.

  In addition, as a diamine component that can be used in addition to the diamine compound represented by the general formula (1) and the diamine compounds represented by the general formulas (a) to (d), it is generally used as a raw material for polyamic acid / polyimide. Examples of the diamine compound are aromatic diamine compounds. Examples of the aromatic diamine compound include p-phenylenediamine (p-PDA), bis [4- (3-aminophenoxy) phenyl] ether, and 2,2-bis- [4- (4-aminophenoxy) phenyl]. Hexafluoropropane, 2,2-bis- [4- (3-aminophenoxy) phenyl] hexafluoropropane, 4,4'-methylenedi-o-toluidine, 4,4'-methylenedi-2,6-xylidine, 3 , 3′-diaminodiphenylethane, 3,3′-diaminobiphenyl, 3,3 ″ -diamino-p-terphenyl, 4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisaniline, 4,4 '-[1,3-phenylenebis (1-methylethylidene)] bisaniline, bis (p-aminocyclohexyl) methane, bis (p-β-amino-t-butylphenyl) ether, bis (p-β -Methyl-δ-aminopentyl) benzene, p-bis (2-methyl-4-aminopentyl) , P-bis (1,1-dimethyl-5-aminopentyl) benzene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,4-bis (β-amino-t-butyl) toluene, m -Xylene-2,5-diamine, p-xylene-2,5-diamine, m-xylylenediamine, p-xylylenediamine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,5-diamino 1,3,4-oxadiazole, piperazine and the like.

  The particularly preferred polyamic acid of the present embodiment preferably contains 50 mol% or more of a structural unit represented by the following general formula (2).

  In the general formula (2), the substituent Y represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group or an alkenyl group having 2 to 3 carbon atoms which may be independently substituted with a halogen atom, and p and q are independently Represents an integer of 0 to 4.

  For example, it is preferable that the structural unit represented by the general formula (2) is included in the range of 50 to 80 parts by mole with respect to 100 parts by mole of the structural unit constituting the polyamic acid. Here, the “structural unit (unit)” means a unit in which one diamine residue and one acid anhydride residue are linked through an amide bond. The structural unit represented by the general formula (2) includes both a residue derived from a diamine compound having a biphenyl skeleton and a residue derived from pyromellitic dianhydride (PMDA) (PMDA residue). Therefore, it contributes to lower CTE of the polyimide layer. When the structural unit represented by the general formula (2) is less than 50 mole parts with respect to 100 mole parts of the polyamic acid structural unit, it is difficult to achieve low CTE by controlling the in-plane orientation of polyimide, and the resin composition Since the ratio of the aromatic ring inside decreases, the transmittance of excimer laser (308 nm) or UV-YAG laser (355 nm) increases, and the processing shape at the time of laser processing tends to deteriorate. On the other hand, if the structural unit represented by the general formula (2) exceeds 80 mole parts with respect to 100 mole parts of the structural unit of polyamic acid, the elastic modulus of polyimide tends to increase.

  In the polyamic acid used in the present embodiment, the structural unit represented by the general formula (2) may be present in the homopolymer or as a structural unit of the copolymer. In the case of a copolymer having a plurality of structural units, it may exist as a block copolymer or a random copolymer. Depending on the type of substituent, there may be a plurality of types of structural units represented by the general formula (2), but there may be one type or two or more types.

  As described above, the polyamic acid of this embodiment is used to increase the flexibility of the polyimide layer and the tensile modulus of elasticity by increasing the acid anhydride residue and diamine residue for suppressing the CTE of the polyimide layer low. Since the diamine residue is contained at a predetermined ratio, the CTE of the polyimide layer is controlled within a range of ± 5 ppm / K with respect to the metal layer within the range of CTE of 5 ppm / K or more and 15 ppm / K or less, The tensile elastic modulus can be controlled within a range of 4.5 GPa or more and less than 8 GPa. And by making the tensile elastic modulus of the polyimide layer within the above range, if the CTE difference between the metal layer and the polyimide layer is within the range of ± 5 ppm / K, the stress difference after the heat treatment can be relaxed, so that the warping is effective. Can be suppressed.

  By selecting the types of acid anhydride residues and diamine residues, and the molar ratios when applying two or more acid anhydride residues and diamine residues, the thermal expansion coefficient and tensile elasticity of polyimide are selected. The rate, glass transition temperature, etc. can be controlled.

  For example, the weight average molecular weight of the polyimide is preferably in the range of 10,000 to 400,000, and more preferably in the range of 50,000 to 350,000. When the weight average molecular weight is less than 10,000, the strength of the polyimide layer tends to be reduced and it tends to become brittle. On the other hand, when the weight average molecular weight exceeds 400,000, the viscosity increases excessively, and defects such as film thickness unevenness and streaks tend to occur during the coating operation.

(Synthesis of polyamide acid and polyimide)
In general, a polyimide can be produced by reacting an acid anhydride component and a diamine component in a solvent to form a polyamic acid and then ring-closing with heating. For example, it is a polyimide precursor by dissolving an acid anhydride component and a diamine component in an approximately equimolar amount in an organic solvent and stirring and polymerizing at a temperature in the range of 0 to 100 ° C. for 30 minutes to 24 hours. A polyamic acid is obtained. In the reaction, the reaction components are dissolved so that the precursor to be produced is in the range of 5 to 30% by weight, preferably in the range of 10 to 20% by weight in the organic solvent. Examples of the organic solvent used in the polymerization reaction include N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N, N-diethylacetamide, N-methyl-2-pyrrolidone (NMP), 2 -Butanone, dimethyl sulfoxide (DMSO), hexamethylphosphoramide, N-methylcaprolactam, dimethyl sulfate, cyclohexanone, dioxane, tetrahydrofuran, diglyme, triglyme, cresol and the like. Two or more of these solvents can be used in combination, and further, aromatic hydrocarbons such as xylene and toluene can be used in combination. In addition, the amount of such organic solvent used is not particularly limited, but it should be adjusted so that the concentration of the polyamic acid solution obtained by the polymerization reaction is about 5 to 30% by weight. Is preferred.

  The synthesized polyamic acid is usually advantageously used as a reaction solvent solution, but can be concentrated, diluted or replaced with another organic solvent as necessary. Moreover, since polyamic acid is generally excellent in solvent solubility, it is advantageously used. The viscosity of the polyamic acid solution is preferably in the range of 500 cps to 100,000 cps. If it is out of this range, defects such as uneven thickness and streaks are likely to occur in the film during coating by a coater or the like. The method for synthesizing the polyimide by imidizing the polyamic acid is not particularly limited, and for example, a heat treatment such as heating in the solvent at a temperature within the range of 80 to 400 ° C. for 1 to 24 hours is suitably employed. Is done.

<Solvent>
Moreover, it is preferable to use the polyamic acid of this Embodiment as a polyamic-acid composition in the state of the varnish containing a solvent. Examples of the solvent include the organic solvents exemplified above for use in the polymerization reaction of polyamic acid. A solvent can also be used 1 type or in combination of 2 or more types.

<Optional component>
The polyamic acid composition can contain optional components such as a flame retardant and a filler as long as the effects of the invention are not impaired.

[Method of manufacturing vapor deposition mask]
The manufacturing method of the vapor deposition mask of this Embodiment is the method of forming the polyimide layer by imidating the polyamic acid after apply | coating the said polyamic-acid composition to the surface of arbitrary support base materials, and forming a coating film. (Casting method) is preferably included. The polyimide layer formed by the casting method has an advantage in that in-plane dimensional variation is small because a difference in the orientation of polymer chains in the longitudinal direction (MD direction) and the width direction (TD direction) is less likely to occur. .

  Hereinafter, a method for producing a vapor deposition mask having a metal layer and a polyimide layer laminated on the metal layer by a combination of a casting method and a semi-additive method will be specifically described.

The manufacturing method of the vapor deposition mask of this Embodiment can include the following processes (1)-(9).
Step (1):
Step (1) is a step of obtaining a polyamic acid composition. In this step, first, as described above, the polyamic acid is synthesized by reacting the raw material diamine component and acid anhydride component in an appropriate solvent. The polyamic acid is used as a polyamic acid composition in a solution containing a solvent.

Step (2):
Step (2) is a step of applying the polyamic acid composition obtained in step (1) to the surface of an arbitrary support substrate to form a coating film. Examples of the supporting base material include a glass substrate, a metal foil, and a resin film.

  The coating film can be formed by applying a solution-like polyamic acid composition directly on a supporting substrate and then drying. The application method is not particularly limited, and can be applied by a coater such as a comma, a die, a knife, a lip, a spin, or a slit.

  The polyimide layer can be composed of multiple layers by repeating the application and drying of the polyamic acid composition. However, in order to facilitate the control of CTE and tensile modulus, it should be composed of a single layer. Is preferred.

Step (3):
Step (3) is a step of forming a polyimide layer by heat-treating the coating film to imidize it. The imidization method is not particularly limited, and for example, heat treatment such as heating for a time within a range of 1 to 200 minutes under a temperature condition within a range of 80 to 400 ° C. is suitably employed. By the heat treatment, the polyamic acid in the coating film is imidized to form polyimide.

  Although there is no restriction | limiting in particular about the thickness of a polyimide layer, It is good to set it as the thickness which can suppress generation | occurrence | production of a fracture | rupture and a pinhole, and it is good to set it as the thickness which considered generation | occurrence | production of the vapor deposition shadow. Preferably it is 2-25 micrometers.

Step (4):
A seed layer made of a metal such as palladium, nickel, a nickel-chromium alloy, a nickel-phosphorus alloy, a nickel-boron alloy, or a nickel-copper alloy is formed on the surface of the polyimide layer. The method for forming the seed layer is not particularly limited, and can be formed by a method such as electroless plating, sputtering, or ion plating. If necessary, as a pretreatment for forming the seed layer, for example, a modification treatment of the polyimide layer by plasma treatment or alkali treatment may be performed.

Step (5):
A resist is applied to the surface of the seed layer, and is exposed and developed by a photolithography technique to form a resist pattern having a predetermined shape.

Step (6):
A metal layer is formed by embedding metal in the opening of the patterned resist. The method for forming the metal layer is not particularly limited, and can be performed by a method such as electroplating. The material of the metal member to be the metal layer is not particularly limited as long as the CTE is in the range of 5 ppm / K to 15 ppm / K, and may be used for a known vapor deposition mask, but nickel and nickel alloys are preferable. .

  Although there is no restriction | limiting in particular in the thickness of a metal layer, While being able to suppress a fracture | rupture and a deformation | transformation, it is good to set it as the thickness which considered generation | occurrence | production of a vapor deposition shadow, Preferably it is 2-100 micrometers.

Step (7):
By peeling off the resist and removing the seed layer by etching, a laminate including a metal layer patterned on the polyimide layer is obtained. A polyimide layer is exposed at the bottom of the opening of the patterned metal layer of the laminate.

Step (8):
For the polyimide layer of the laminate obtained in the step (7), a plurality of through-opening patterns are processed preferably in a width narrower than the opening width in correspondence with the opening range. This through-opening pattern corresponds to a thin film pattern formed by vapor deposition on the deposition target.

  A method for forming an opening pattern by providing a through opening in a polyimide layer is not particularly limited, and examples thereof include a method of forming a through opening by irradiating a laser, a method of forming a through opening with a mechanical drill, and the like. . Laser irradiation is preferable from the viewpoint of accuracy and productivity. When an opening pattern corresponding to a thin film pattern is formed by laser irradiation, a good opening pattern shape may not be obtained if the transmittance of the polyimide layer at the laser wavelength is high. Therefore, the light transmittance of the polyimide layer at the wavelength of the laser should be 50% or less, preferably 10% or less, more preferably 0%. Here, as a laser used for forming a through-opening in a polyimide layer by laser irradiation, for example, a UV-YAG laser (wavelength 355 nm), an excimer laser (wavelength 308 nm), or the like can be used. Among these, a UV-YAG laser (wavelength 355 nm) is preferable.

Step (9):
By peeling the supporting substrate, a vapor deposition mask having a polyimide layer and a metal layer is obtained. The method for peeling the supporting substrate is not particularly limited, and can be performed by a method such as a laser lift-off method. In addition, peeling of a support base material can also be implemented after a process (7) and before a process (8).

  As described above, a vapor deposition mask having a polyimide layer and a metal layer can be manufactured.

<Action>
In a laminate in which a metal layer and a resin layer are laminated, in order to suppress warpage, it is desirable to make the CTE of the resin layer as close as possible to the CTE of the metal layer, and to match them if possible. However, in an actual manufacturing process, it is often difficult to approximate the CTE of the resin layer to the CTE of the metal layer. Therefore, in the present invention, paying attention to the tensile elastic modulus of the resin layer, even if a CTE difference inevitably occurs between the metal layer and the resin layer, the resin is controlled while controlling the CTE difference within a certain range. The elastic modulus of the layer was reduced. That is, even when it is difficult to approximate the CTE in a laminate of different materials having a relatively large difference in elastic modulus, such as a laminate of a metal layer and a resin layer, By reducing the elastic modulus, the followability to the metal layer is increased, so that the stress is relaxed and the warpage can be effectively suppressed.
Therefore, the CTE range of the metal layer in the present invention, the CTE range of the resin layer for suppressing warpage, and the tensile elastic modulus range are the metal species constituting the metal layer, the thickness of the metal layer, and the tensile strength of the metal layer. Various settings can be made according to the elastic modulus, the resin type constituting the resin layer, and the thickness of the resin layer.

  The features of the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to the examples. In the following examples, various measurements and evaluations are as follows unless otherwise specified.

[Measurement of viscosity]
The viscosity was measured at 25 ° C. using an E-type viscometer (manufactured by Brookfield, trade name: DV-II + Pro). The number of revolutions was set so that the torque was 10% to 90%, and after 2 minutes from the start of measurement, the value when the viscosity was stabilized was read.

[Measurement of coefficient of thermal expansion (CTE)]
Using a thermomechanical analyzer (manufactured by Bruker, trade name: 4000SA), a polyimide film having a size of 3 mm × 20 mm was heated from 30 ° C. to 250 ° C. at a constant heating rate while applying a load of 5.0 g. Furthermore, after maintaining at that temperature for 10 minutes, it was cooled at a rate of 5 ° C./minute, and an average thermal expansion coefficient (thermal expansion coefficient) from 250 ° C. to 100 ° C. was determined. In addition, the measurement was implemented about the longitudinal direction (MD direction) and the width direction (TD direction).

[Measurement of elastic modulus of film]
The elastic modulus of the film was obtained by performing a tensile test at 50 mm / min using a tension tester (Orientec Tensilon) on a polyimide film cut to a width of 12.7 mm and a length of 127 mm to obtain the film elastic modulus at 25 ° C. It was.

[Measurement of glass transition temperature (Tg)]
Glass transition temperature is a rate of temperature increase from 30 ° C. to 400 ° C. using a polyimide film having a size of 5 mm × 20 mm, using a dynamic viscoelasticity measuring device (DMA: manufactured by UBM, trade name: E4000F). Measurement was performed at 4 ° C./min and a frequency of 11 Hz, and the temperature at which the change in elastic modulus (tan δ) was maximum was taken as the glass transition temperature.

[Measurement of warpage]
The laminated body was warped by adjusting a sample of 50 mm × 50 mm size at 23 ° C. and 50% humidity for 20 hours, and then leaving the sample at the center of the sample so that the convex surface of the sample was in contact with the flat surface. The presence or absence of lifting from the stationary surface was visually observed, and when there was lifting even at one place, it was judged as “warping”, and when the lifting was 10 mm or less, it was determined as “no warping”.

(Laser lift off; LLO)
A laminate of a polyimide layer and a glass substrate is irradiated with a laser having a beam size of 14 mm × 1.2 mm and a moving speed of 6 mm / s from the support substrate (glass substrate) side using an excimer laser processing machine (wavelength 308 nm). The glass substrate and the polyimide layer were completely separated (the peeling range was determined with a cutter, and the polyimide film was naturally peeled from the glass substrate after one cut was made). At this time, the laser irradiation energy density was 110 (mJ / cm ² ).

Abbreviations used in Examples and Comparative Examples indicate the following compounds.
m-PDA: metaphenylenediamine p-PDA: paraphenylenediamine 3,4′-DAPE: 3,4′-diaminodiphenyl ether 4,4′-DAPE: 4,4′-diaminodiphenyl ether m-TB: 2,2 ′ -Dimethyl-4,4'-diaminobiphenyl TPE-R: 1,3-bis (4-aminophenoxy) benzene TPE-Q: 1,4-bis (4-aminophenoxy) benzene APB: 1,3-bis ( 3-aminophenoxy) benzene BAPB: 1,4-bis (4-aminophenoxy) biphenyl PMDA: pyromellitic dianhydride s-BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride DMAc : N, N-dimethylacetamide

(Synthesis Example 1)
Under a nitrogen stream, 4.338 g of m-PDA (0.0401 mol) and 8.515 g of m-TB (0.0401 mol) were added to a 300 ml separable flask so that the solid concentration was 15% by weight. ) And 170.0 g of DMAc were added and dissolved by stirring at room temperature. Next, after adding 17.148 g of PMDA (0.0786 mol), stirring was continued at room temperature for 3 hours to conduct a polymerization reaction to prepare a polyamic acid solution a having a viscosity of 8900 cP.

(Synthesis Example 2)
Under a nitrogen stream, 7.188 g of 4,4′-DAPE (0.0359 mol), 7.621 g of m-TB (0) were added to a 300 ml separable flask so that the solid concentration was 15% by weight. 0.0359 mol) and 170.0 g of DMAc were added and dissolved by stirring at room temperature. Next, after 15.191 g of PMDA (0.0696 mol) was added, stirring was continued at room temperature for 3 hours to conduct a polymerization reaction to prepare a polyamic acid solution b, and the viscosity was 10800 cP.

(Synthesis Example 3)
Under a nitrogen stream, in a 300 ml separable flask, 9.453 g of TPE-Q (0.0323 mol), 6.865 g of m-TB (0.0323 mol) so that the solid content concentration becomes 15% by weight. ) And 170.0 g of DMAc were added and dissolved by stirring at room temperature. Next, after 13.683 g of PMDA (0.0627 mol) was added, stirring was continued at room temperature for 3 hours to carry out a polymerization reaction to prepare a polyamic acid solution c, and the viscosity was 11200 cP.

(Synthesis Example 4)
Under a nitrogen stream, 9.408 g of TPE-R (0.0322 mol) and 6.832 g of m-TB (0.0322 mol) were added to a 300 ml separable flask so that the solid concentration was 15% by weight. ) And 170.0 g of DMAc were added and dissolved by stirring at room temperature. Next, after adding 13.759 g of PMDA (0.0631 mol), stirring was continued at room temperature for 3 hours to conduct a polymerization reaction to prepare a polyamic acid solution d, and the viscosity was 8900 cP.

(Synthesis Example 5)
Under a nitrogen stream, 3.679 g of TPE-R (0.0126 mol), 10.686 g of m-TB (0.0503 mol) in a 300 ml separable flask so that the solid content concentration becomes 15% by weight. ) And 170.0 g of DMAc were added and dissolved by stirring at room temperature. Next, 6.656 g of PMDA (0.0305 mol) and 8.979 g of s-BPDA (0.0305 mol) were added, and then the polymerization reaction was continued for 3 hours at room temperature to obtain a polyamic acid solution e And the viscosity was 13100 cP.

(Synthesis Example 6)
Under a nitrogen stream, in a 300 ml separable flask, 6.760 g of APB (0.0231 mol), 9.117 g of m-TB (0.0430 mol) and a solid concentration of 15 wt% and 170.0 g of DMAc was added and dissolved by stirring at room temperature. Next, after adding 14.123 g of PMDA (0.0648 mol), the polymerization reaction was carried out by continuing the stirring at room temperature for 3 hours to prepare a polyamic acid solution f, and the viscosity was 6900 cP.

(Synthesis Example 7)
Under a nitrogen stream, 8.048 g BAPB (0.0218 mol), 8.612 g m-TB (0.0406 mol) and a solids concentration of 15% by weight in a 300 ml separable flask and 170.0 g of DMAc was added and dissolved by stirring at room temperature. Next, after adding 13.341 g of PMDA (0.0612 mol), stirring was continued at room temperature for 3 hours to conduct a polymerization reaction to prepare a polyamic acid solution g, and the viscosity was 13700 cP.

(Synthesis Example 8)
Under a nitrogen stream, in a 300 ml separable flask, 6.568 g of 3,4'-DAPE (0.0328 mol), 6.963 g of m-TB (0 0.0328 mol) and 170.0 g of DMAc were added and dissolved by stirring at room temperature. Next, 7.011 g of PMDA (0.0321 mol) and 9.458 g of s-BPDA (0.0321 mol) were added, and the polymerization reaction was continued by stirring at room temperature for 3 hours to obtain a polyamic acid solution h. And the viscosity was 8600 cP.

(Synthesis Example 9)
Under a nitrogen stream, 13.745 g of m-TB (0.0648 mol) and 170.0 g of DMAc were added to a 300 ml separable flask so that the solid concentration was 15% by weight, and stirred at room temperature. And dissolved. Next, 6.920 g of PMDA (0.0317 mol) and 9.335 g of s-BPDA (0.0317 mol) were added, and then the polymerization reaction was continued for 3 hours at room temperature to obtain a polyamic acid solution i. And the viscosity was 9800 cP.

(Synthesis Example 10)
Under a nitrogen stream, 1.466 g of p-PDA (0.0136 mol), 11.514 g of m-TB (0.0542 mol) in a 300 ml separable flask so that the solid concentration is 15% by weight. ) And 170.0 g of DMAc were added and dissolved by stirring at room temperature. Next, after adding 7.246 g of PMDA (0.0332 mol) and 9.774 g of s-BPDA (0.0332 mol), the polymerization reaction was continued by stirring at room temperature for 3 hours to obtain a polyamic acid solution j. And the viscosity was 11500 cP.

[Example 1-1]
About the polyamic-acid solution a, the thickness of the polyimide layer after hardening is about about 1 mm on a glass substrate (Corning Corp. make, brand name; E-XG, size; 150 mm x 150 mm, thickness; 0.7 mm). Coating was carried out to 7.5 μm. Subsequently, heating was performed at 120 ° C. for 2 minutes in an air atmosphere.

  And it heated up from room temperature to 360 degreeC with the fixed temperature increase rate (5 degreeC / min) in the air atmosphere, the polyimide layer (polyimide a) was formed on the glass substrate, and the polyimide laminated body a was obtained.

  About the obtained sample, the polyimide film A was obtained by peeling a polyimide film from a glass substrate by laser lift-off (LLO). At this time, the CTE in the MD direction was 12.3 ppm / K, the CTE in the TD direction was 11.7 ppm / K, the glass transition temperature (Tg) was 388 ° C., and the elastic modulus was 6.5 GPa.

[Example 1-2]
The obtained polyimide laminate a was immersed in a 0.5N aqueous potassium hydroxide solution (50 ° C.) for 5 minutes. Thereafter, the immersed polyimide laminate a was washed with water, and an alkali modified layer was formed on the surface of the polyimide laminate a.

  Next, the palladium ion impregnation layer was formed by immersing in an aqueous solution (25 ° C.) mixed with 10 mM palladium acetate and 60 mM ammonia for 60 minutes, and impregnating the alkali-modified layer with palladium ions.

  The polyimide laminate a on which the impregnation layer is formed is immersed in a 50 mM aqueous dimethylamine borane solution (30 ° C.) for 5 minutes to reduce the palladium ions in the impregnation layer, thereby forming a palladium deposition layer. Nickel plating was performed by dipping in a nickel plating (nickel-phosphorus alloy-based) aqueous solution (90 ° C.) for 20 seconds.

  For the polyimide laminate a after electroless plating, a dry film resist is laminated on the plating surface at 90 ° C., exposed to ultraviolet rays through a photomask, and developed with a 0.5 wt% sodium carbonate aqueous solution, A surface-modified polyimide film laminate A on which a mask pattern was formed was obtained.

Next, it was immersed in a nickel plating bath and electroplated to obtain a nickel pattern-formed polyimide laminate A in which a nickel layer (thickness: 10 μm) was formed by electroplating on a portion not covered with a resist mask. .
The obtained nickel pattern-formed polyimide laminate A was immersed in a 2% by weight sodium hydroxide aqueous solution (25 ° C.) for 3 minutes and then washed with water to remove the resist pattern.

  Then, reimidation of the alkali-modified layer was completed by heating at 360 ° C. for 10 minutes in a nitrogen atmosphere, and the electroless nickel plating layer was removed using a flash etching solution. About the polyimide exposed part of the obtained laminate, through holes are formed in the polyimide at regular intervals using a YAG laser of 355 nm, and then peeled off from the glass substrate by laser lift-off, and the nickel layer and the polyimide layer have a through-opening pattern A polyimide film A was formed. This polyimide film A was not warped.

[Examples 2-1 to 8-1 and Comparative Example 1-1, Comparative Example 2-1]
Polyimide films B to J were produced in the same manner as in Example 1-1 except that the polyamic acid solutions b to j were used in place of the polyamic acid solution a. The physical properties of the produced film are shown in Table 1.

[Examples 2-2 to 8-1 and Comparative Example 1-2, Comparative Example 2-2]
Based on Examples 2-1 to 8-1, Comparative Example 1-1, and Comparative Example 2-1, polyimide films B to J having patterns formed on nickel and polyimide were prepared in the same manner as in Example 1-2. . Under the present circumstances, about nickel pattern formation polyimide film BH, the curvature of a film was not confirmed. Moreover, curvature was confirmed about the nickel pattern formation polyimide films IJ.

  As described above, by using the polyamic acid of the present embodiment, a laminate in which a polyimide layer and a metal layer are laminated and warpage is suppressed can be manufactured. This laminated body is useful as, for example, a vapor deposition mask, and can improve the production efficiency of a display device such as an organic EL display device, and can cope with higher definition.

As mentioned above, although embodiment of this invention was described in detail for the purpose of illustration, this invention is not restrict | limited to the said embodiment. For example, the polyamic acid of the present invention can also be applied in the case of producing a vapor deposition mask by a method other than the semi-additive method. That is, when a metal-clad laminate having a metal layer and a resin layer in which no opening is formed is prepared, and the evaporation mask is manufactured by forming an opening by etching or the like, the polyamic acid of the present invention is used. Can be used.

Claims (17)

A vapor deposition mask for vapor-depositing a thin film pattern of a certain shape on a deposition target,
A metal layer having a plurality of openings;
A single-layer or multiple-layer polyimide layered on the metal layer, having a through hole located within the opening range of the opening, and the through hole forming an opening pattern corresponding to the thin film pattern Layers,
With
The coefficient of thermal expansion (CTE) of the metal layer is in the range of 5 ppm / K to 15 ppm / K,
The thermal expansion coefficient (CTE) of the polyimide layer is within a range of ± 5 ppm / K with respect to the thermal expansion coefficient (CTE) of the metal layer, and the tensile elastic modulus of the polyimide layer is 4.5 GPa or more and 8 GPa. An evaporation mask characterized by being within a range of less than.   The difference between the thermal expansion coefficient (CTE-MD) in the longitudinal (MD) direction and the thermal expansion coefficient (CTE-TD) in the width (TD) direction of the polyimide layer is ± 2.5 ppm / K or less. The vapor deposition mask of description. While the polyimide constituting the polyimide layer contains an acid anhydride residue derived from an acid anhydride component and a diamine residue derived from a diamine component,
Containing 50 mol parts or more of an acid anhydride residue derived from pyromellitic dianhydride with respect to 100 mol parts in total of the acid anhydride residues;
The diamine residue derived from the diamine compound represented by the following general formula (1) with respect to a total of 100 mol parts of the diamine residues is within the range of 50 to 90 mol parts, and the following general formula ( The vapor deposition mask of Claim 1 or 2 which contains the diamine residue induced | guided | derived from the at least 1 sort (s) of diamine compound represented by a)-(d) within the range of 10 mol part or more and 50 mol part or less.

[In the general formula (1), the substituent Y represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group or an alkenyl group having 2 to 3 carbon atoms which may be independently substituted with a halogen atom, and p and q are Independently represents an integer of 0-4. ]

[In the general formulas (a) to (d), the substituent R ₁ independently represents a monovalent hydrocarbon group or alkoxy group having 1 to 4 carbon atoms, and the linking group A is independently —O— or —S—. _{, -CO -, - SO -,} - SO 2 -, - COO -, - CH 2 -, - C (CH 3) 2 -, - NH- or -CONH- indicates the linking group B is a single bond or a - C (CH ₃ ) ₂ —, and n1 independently represents an integer of 0-4. ]   The vapor deposition mask according to claim 1, wherein the polyimide layer is a single layer.   The vapor deposition mask according to claim 1, wherein the metal layer contains nickel element as a main component. A metal layer having a plurality of openings and a through hole that is stacked on the metal layer and is located within the opening range of the opening, and the through hole forms an opening pattern corresponding to the thin film pattern. A polyamic acid for forming a vapor deposition mask used in the formation of the polyimide layer in a vapor deposition mask for vapor deposition formation of a thin film pattern having a fixed shape on the vapor-deposited body. There,
The coefficient of thermal expansion (CTE) of the metal layer is in the range of 5 ppm / K to 15 ppm / K,
The thermal expansion coefficient (CTE) of the polyimide layer is within a range of ± 5 ppm / K with respect to the thermal expansion coefficient (CTE) of the metal layer, and the tensile elastic modulus of the polyimide layer is 4.5 GPa or more and 8 GPa. A polyamic acid for forming a vapor deposition mask, which is within a range of less than   The difference between the thermal expansion coefficient (CTE-MD) in the longitudinal (MD) direction of the polyimide layer and the thermal expansion coefficient (CTE-TD) in the width (TD) direction is ± 2.5 ppm / K or less. The polyamic acid for vapor deposition mask formation as described in 2. Containing an acid anhydride residue derived from an acid anhydride component and a diamine residue derived from a diamine component;
Containing 50 mol parts or more of an acid anhydride residue derived from pyromellitic dianhydride with respect to 100 mol parts in total of the acid anhydride residues;
The diamine residue derived from the diamine compound represented by the following general formula (1) with respect to a total of 100 mol parts of the diamine residues is within the range of 50 to 90 mol parts, and the following general formula ( The vapor deposition mask formation of Claim 6 or 7 which contains the diamine residue induced | guided | derived from the at least 1 sort (s) of diamine compound represented by a)-(d) in 10 mol part or more and 50 mol part or less. Polyamic acid.

[In the general formula (1), the substituent Y represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group or an alkenyl group having 2 to 3 carbon atoms which may be independently substituted with a halogen atom, and p and q are Independently represents an integer of 0-4. ]

[In the general formulas (a) to (d), the substituent R ₁ independently represents a monovalent hydrocarbon group or alkoxy group having 1 to 4 carbon atoms, and the linking group A is independently —O— or —S—. _{, -CO -, - SO -,} - SO 2 -, - COO -, - CH 2 -, - C (CH 3) 2 -, - NH- or -CONH- indicates the linking group B is a single bond or a - C (CH ₃ ) ₂ —, and n1 independently represents an integer of 0-4. ] A laminated body for forming a vapor deposition mask used for forming a vapor deposition mask for vapor-depositing a thin film pattern having a predetermined shape on the vapor-deposited body,
A metal layer,
A single layer or multiple layers of polyimide layer laminated on the metal layer;
With
The coefficient of thermal expansion (CTE) of the metal layer is in the range of 5 ppm / K to 15 ppm / K,
The thermal expansion coefficient (CTE) of the polyimide layer is within a range of ± 5 ppm / K with respect to the thermal expansion coefficient (CTE) of the metal layer, and the tensile elastic modulus of the polyimide layer is 4.5 GPa or more and 8 GPa. A laminate for forming a vapor deposition mask, characterized by being within the range of less than.   The difference between the thermal expansion coefficient (CTE-MD) in the longitudinal (MD) direction of the polyimide layer and the thermal expansion coefficient (CTE-TD) in the width (TD) direction is ± 2.5 ppm / K or less. The laminated body for vapor deposition mask formation of description. While the polyimide constituting the polyimide layer contains an acid anhydride residue derived from an acid anhydride component and a diamine residue derived from a diamine component,
Containing 50 mol parts or more of an acid anhydride residue derived from pyromellitic dianhydride with respect to 100 mol parts in total of the acid anhydride residues;
The diamine residue derived from the diamine compound represented by the following general formula (1) with respect to a total of 100 mol parts of the diamine residues is within the range of 50 to 90 mol parts, and the following general formula ( The vapor deposition mask formation of Claim 9 or 10 which contains the diamine residue induced | guided | derived from the at least 1 sort (s) of diamine compound represented by a)-(d) in 10 mol part or more and 50 mol part or less. Laminated body.

[In the general formula (1), the substituent Y represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group or an alkenyl group having 2 to 3 carbon atoms which may be independently substituted with a halogen atom, and p and q are Independently represents an integer of 0-4. ]

[In the general formulas (a) to (d), the substituent R ₁ independently represents a monovalent hydrocarbon group or alkoxy group having 1 to 4 carbon atoms, and the linking group A is independently —O— or —S—. _{, -CO -, - SO -,} - SO 2 -, - COO -, - CH 2 -, - C (CH 3) 2 -, - NH- or -CONH- indicates the linking group B is a single bond or a - C (CH ₃ ) ₂ —, and n1 independently represents an integer of 0-4. ]   The laminated body for vapor deposition mask formation of Claim 9 whose said polyimide layer consists of a single layer.   The laminated body for vapor deposition mask formation of Claim 9 whose said metal layer contains a nickel element as a main component. A method of manufacturing a vapor deposition mask for vapor-depositing a thin film pattern having a fixed shape on a deposition target,
The following steps I to III;
I) A step of forming a single layer or a plurality of polyimide layers by applying a polyamic acid solution on a supporting substrate and then heat-treating to obtain a first laminate,
II) forming a metal layer having a plurality of openings on the first laminated body to obtain a second laminated body;
III) forming a plurality of through holes in the polyimide layer in a range overlapping the opening of the metal layer, and forming an opening pattern corresponding to the thin film pattern;
Including
The coefficient of thermal expansion (CTE) of the metal layer is in the range of 5 ppm / K to 15 ppm / K,
The thermal expansion coefficient (CTE) of the polyimide layer is within a range of ± 5 ppm / K with respect to the thermal expansion coefficient (CTE) of the metal layer, and the tensile elastic modulus of the polyimide layer is 4.5 GPa or more and 8 GPa. A method for producing a vapor deposition mask, characterized by being within a range of less than.   The difference between the thermal expansion coefficient (CTE-MD) in the longitudinal (MD) direction and the thermal expansion coefficient (CTE-TD) in the width (TD) direction of the polyimide layer is ± 2.5 ppm / K or less. The manufacturing method of the vapor deposition mask of description. The polyamic acid used in the step I contains an acid anhydride residue derived from an acid anhydride component and a diamine residue derived from a diamine component,
Containing 50 mol parts or more of an acid anhydride residue derived from pyromellitic dianhydride with respect to 100 mol parts in total of the acid anhydride residues;
The diamine residue derived from the diamine compound represented by the following general formula (1) with respect to a total of 100 mol parts of the diamine residues is within the range of 50 to 90 mol parts, and the following general formula ( The manufacturing of the vapor deposition mask of Claim 14 or 15 which contains the diamine residue induced | guided | derived from the at least 1 sort (s) of diamine compound represented by a)-(d) in the range of 10 mol part or more and 50 mol part or less. Method.

[In the general formula (1), the substituent Y represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group or an alkenyl group having 2 to 3 carbon atoms which may be independently substituted with a halogen atom, and p and q are Independently represents an integer of 0-4. ]

[In the general formulas (a) to (d), the substituent R ₁ independently represents a monovalent hydrocarbon group or alkoxy group having 1 to 4 carbon atoms, and the linking group A is independently —O— or —S—. _{, -CO -, - SO -,} - SO 2 -, - COO -, - CH 2 -, - C (CH 3) 2 -, - NH- or -CONH- indicates the linking group B is a single bond or a - C (CH ₃ ) ₂ —, and n1 independently represents an integer of 0-4. ] The said process II is a manufacturing method of the vapor deposition mask of Claim 14 which forms the said metal layer by a semi-additive construction method.