TWI709817B - Pattern manufacturing method, semiconductor device manufacturing method, and laminate - Google Patents

Abstract

The present invention provides a pattern manufacturing method capable of directly peeling a transparent substrate from a laminate, a semiconductor device manufacturing method, and a laminate, the laminate having a transparent substrate and a resin pattern (for example, an insulating layer) on the surface of the transparent substrate. The pattern manufacturing method of the present invention includes a peeling process in which the layered body is irradiated with radiation from the transparent substrate side of the layered body to peel the transparent substrate from the layered body, and the layered body has a transparent substrate and a resin pattern on the surface of the transparent substrate , And the resin pattern includes at least one selected from polyimide and polybenzoxazole, and the absorbance of the resin pattern in the wavelength of the irradiated radiation is 0.5 or more.

Description

Pattern manufacturing method, semiconductor device manufacturing method, and laminate

The present invention relates to a pattern manufacturing method, a semiconductor device manufacturing method, and a laminate.

In recent years, due to the requirements for high integration and miniaturization of semiconductor devices, fan-out wafer level packaging (FOWLP) has attracted attention. FOWLP generally has a structure in which an insulating layer and a redistribution layer (RDL: Redistribution layer) are alternately laminated on a semiconductor wafer. Photosensitive polyimide is often used in the insulating layer material, and copper is often used in the rewiring layer material. In recent years, the number of redistribution layers has been increasing, and there are cases in which multiple layers of four polyimide and three redistribution layers form the semiconductor wafer and bumps.

Here, as FOWLP, prepare to arrange semiconductor wafers on a wafer-like support (simulation wafer), form a rewiring layer by compression molding, and cut the virtual wafer (chip first) and in A rewiring layer is formed on a wafer-like support for the first time, semiconductor chips are arranged on it, and cut after compression molding (first RDL). Generally, the more the number of rewiring layers increases, the more the manufacturing yield decreases. However, if defects in the rewiring layers occur in the wafer priority method, the semiconductor wafer becomes redundant. In contrast, the RDL priority method can be used before the wafer connection Check the wiring layer and connect to the chip only at the good parts, so the semiconductor chip will not become redundant. Therefore, as a method of reducing manufacturing costs, expectations for the RDL priority method have increased.

Under this situation, Patent Document 1 states that "a release layer mainly composed of a thermoplastic polyimide resin is provided on a glass plate. A first insulating layer is formed on the release layer. The first insulating layer is formed by sputtering. A conductor layer including TiN, Ti, and Cu is formed on the layer 50. The 308nm laser light penetrates the glass plate and irradiates the peeling layer, so that the peeling layer is softened. The glass plate is peeled.". In addition, Patent Document 2 discloses "a method of forming an electrical structure. The method has the following steps: a first device wafer including a first electrical element is prepared, and the first device wafer is placed on the first device wafer. The surface has a first electrode, and the first surface of the first device wafer is bonded to a carrier wafer using a first bonding material. When the carrier wafer is bonded to the first device wafer, it directly faces the first device wafer. The second surface of the device wafer is processed so that the light from the laser is transmitted through the carrier wafer and abuts against the first bonding material. The first bonding material absorbs energy from the light beam and the first bonding material makes The carrier wafer is substantially released from the first device wafer, the carrier wafer is substantially transparent to the light from the laser, the carrier wafer is removed from the first device wafer, and the carrier wafer is removed from the first device wafer. The first device wafer removes the remaining first bonding material.". [Prior Art Document] [Patent Document]

Patent Document 1: Japanese Patent Application Publication No. 2014-011289 Patent Document 2: International Publication No. WO2014/037829

As a result of studying the above-mentioned Patent Documents 1 and 2, both are methods in which radiant light is irradiated from the side of the transparent substrate, and peeling is performed at the interface between the peeling layer and the transparent substrate. Therefore, in addition to the insulating layer, a peeling layer is also required. The object of the present invention is to solve the above-mentioned problems, and the object is to provide a pattern manufacturing method capable of directly peeling a transparent substrate from a laminate, a method of manufacturing a semiconductor device, and a laminate, the laminate having a transparent substrate and a surface on the transparent substrate Resin pattern (for example, insulating layer).

Based on the situation, the inventors of the present invention have conducted research and found that the above-mentioned problem can be solved by irradiating radiation to peel off the transparent substrate from the laminate having the transparent substrate and the resin pattern on the surface. The absorbance of the resin pattern in the wavelength of light is adjusted to 0.5 or more, and the above-mentioned problem can be solved by using a resin selected from polyimide and polybenzoxazole as the resin constituting the resin pattern. Specifically, the above-mentioned problem is solved by the following method <1>, preferably by <2> to <13>. <1> A pattern manufacturing method, including a peeling process, irradiating the layered body A with radiation from the transparent substrate side of the layered body A to peel the transparent substrate from the layered body A. The layered body A has a transparent substrate and a transparent substrate located on the transparent substrate. The resin pattern on the surface of the substrate, the resin pattern includes at least one selected from polyimide and polybenzoxazole, and the absorbance of the resin pattern in the wavelength of the radiated light is 0.5 or more. <2> The pattern manufacturing method as described in <1>, which is obtained by exposing the photosensitive resin film of the laminate B having a transparent substrate and a photosensitive resin film, and then performing a development process to remove a part of the photosensitive resin film. Layered body A. <3> The pattern manufacturing method described in <2>, in which the surface area of the removed portion of the resin pattern formed by removing a part of the photosensitive resin film is 20% of the surface area of the total exposed area of the photosensitive resin film the following. <4> The pattern manufacturing method as described in <2> or <3>, wherein the exposure is performed from the photosensitive resin film side of the laminate B. <5> The pattern manufacturing method as described in any one of <1> to <4>, which has a process in which the gap between the resin pattern on the transparent substrate of the laminate A or the transparent substrate on the transparent substrate and Metal is applied between the resin patterns. <6> The pattern manufacturing method according to <5>, wherein the metal includes at least one selected from copper, aluminum, nickel, vanadium, titanium, tantalum, chromium, cobalt, gold, silver, and tungsten. <7> The pattern manufacturing method according to any one of <2> to <6>, wherein the photosensitive resin film includes a precursor selected from the group consisting of polyimide, polyimide, polybenzoxazole, and At least one of polybenzoxazole. <8> The pattern manufacturing method according to any one of <2> to <6>, wherein the photosensitive resin film contains at least one selected from a polyimide precursor and a polybenzoxazole precursor. <9> The pattern manufacturing method according to any one of <1> to <8>, after the exposure and development process and before the peeling process, includes a curing process for curing the resin pattern. <10> The pattern manufacturing method according to any one of <2> to <9>, wherein the development is negative-type development. <11> A method of manufacturing a semiconductor device, including the pattern manufacturing method described in any one of <1> to <10>. <12> A laminate having a transparent substrate, a resin pattern located on the surface of the transparent substrate, and a metal in the gaps between the resin pattern on the surface of the transparent substrate, the resin pattern including a polyimide and At least one of polybenzoxazole. <13> A laminate having a transparent substrate, a resin pattern on the surface of the transparent substrate, a metal in the gaps of the resin pattern on the surface of the transparent substrate, a semiconductor element in contact with the metal, and the semiconductor The element is in contact with the metal on the side opposite to the transparent substrate side, and the resin pattern includes at least one selected from polyimide and polybenzoxazole. [Invention Effect]

According to the present invention, it is possible to provide a pattern manufacturing method capable of directly peeling a transparent substrate from a laminate, a method of manufacturing a semiconductor device, and a laminate having a transparent substrate and a resin pattern on the surface of the transparent substrate. [Illustration brief description]

Fig. 1 is a schematic diagram showing the first embodiment. Fig. 2 is a schematic diagram showing the second embodiment. Fig. 3 is a schematic diagram showing a third embodiment.

The description of the constituent elements in the present invention described below may be performed based on a representative embodiment of the present invention, but the present invention is not limited to this embodiment. Regarding the label of the group (atomic group) in this specification, it is not recorded that substituted and unsubstituted labels have both unsubstituted and substituted labels. For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). As long as "exposure" in this specification is not particularly limited, in addition to exposure with light, drawing with particle beams such as electron beams and ion beams is also included in exposure. In addition, as the light used for exposure, active rays or radiation such as extreme ultraviolet, extreme ultraviolet (EUV light), X-rays, electron beams, etc. represented by the bright-ray spectrum of mercury lamps and excimer lasers are usually cited. In this specification, the numerical range indicated by "-" refers to the range that includes the numerical values described before and after "-" as the lower limit and the upper limit. In this specification, "(meth)acrylate" means either or both of "acrylate" and "methacrylate", and "(meth)allyl" means "allyl" and "methyl Both or either "allyl", "(meth)acrylic" means both or either of "acrylic" and "methacrylic", and "(meth)acryloyl" means "acryloyl" And "methacryloyl" either or both. In this specification, the term "process" is not only an independent process, but even if it can be clearly distinguished from other processes, if it can achieve the expected effect of the process, it is also included in this term. In this specification, the solid content concentration is the mass percentage of components other than the solvent in the total mass of the composition. In addition, unless otherwise stated, the solid content concentration means the concentration at 25°C. In this specification, unless otherwise stated, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as styrene conversion values in accordance with gel permeation chromatography (GPC measurement). In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) can be, for example, HLC-8220 (manufactured by TOSOH CORPORATION), and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION). As long as there is no special description, the eluent is measured with THF (tetrahydrofuran). In addition, as long as there is no special description, the detection is to use a UV ray (ultraviolet) wavelength 254 nm detector.

The pattern manufacturing method of the present invention is characterized by including a peeling process in which the layered body is irradiated with radiation light from the transparent substrate side of the layered body A (hereinafter, sometimes simply referred to as "layered body with transparent substrate and resin pattern") And peeling the transparent substrate from the laminate A, the laminate A has a transparent substrate and a resin pattern on the surface of the transparent substrate, and the resin pattern includes at least one selected from polyimide and polybenzoxazole, The absorbance of the resin pattern in the wavelength of the irradiated radiation light is 0.5 or more. The reason for this is that at least one resin selected from the group consisting of polyimide and polybenzoxazole is used as the resin pattern to improve the durability against radiated light. Furthermore, it is irradiated so that the absorbance of the resin pattern in the wavelength of the irradiated radiation becomes 0.5 or more, and by the absorption of the radiated light, the vicinity of the transparent substrate of the resin pattern generates heat locally, so that the entire resin pattern can be prevented from heating up. The resulting film quality can be ablated at the interface between the substrate and the substrate. The transparent substrate can be peeled off directly from the laminate with the transparent substrate and the resin pattern, and there is no need for a peeling layer between the resin pattern and the transparent substrate. In particular, in the pattern manufacturing method of the present invention, with respect to the laminated body B having the transparent substrate and the photosensitive resin film, the laminated body A having the transparent substrate and the resin pattern is exposed by light having a wavelength of 500 nm or less, and more preferably Used in a way that can be developed. That is, the laminate B having a transparent substrate and a photosensitive resin film (preferably a laminate having a transparent substrate and a photosensitive resin film on the surface of the transparent substrate) is exposed and developed, so that the photosensitive resin film loses its sensitivity By this, even when the resin pattern is formed, the radiant light is irradiated in a manner that satisfies the prescribed conditions, and thereby the transparent substrate can be properly peeled from the laminate A having the transparent substrate and the resin pattern without damage to the resin pattern.

Hereinafter, the embodiments of the present invention will be described based on the drawings. There is no doubt that the structure of the present invention is not limited to the structure described in the drawings.

FIG. 1 is a schematic diagram showing the first embodiment. A photosensitive resin film 2 is provided on a transparent substrate 1 (photosensitive resin film manufacturing process), and exposure and development are performed to manufacture a resin pattern 3 (exposure and development process). Then, the radiant light is irradiated in a manner that satisfies prescribed conditions, whereby the transparent substrate 1 can be peeled off (transparent substrate peeling process). Furthermore, after the above-mentioned exposure and development process, in the gap between the resin pattern 3 on the transparent substrate 1 (preferably the surface) or between the transparent substrate 1 and the resin pattern 3 on the transparent substrate 1, the metal 4 can be applied (metal application process ). In addition, the semiconductor element 5 can be applied in a manner of being in contact with the metal 4 (semiconductor element application process). In this embodiment, it is particularly preferable to proceed in the order of the photosensitive resin film manufacturing process, the exposure and development process, the metal application process, the semiconductor element application process, and the transparent substrate peeling process. In the first embodiment, a metal (for example, metal wiring or electrode) is located in a gap between a resin pattern (for example, an insulating layer), and a semiconductor device having a semiconductor element (for example, a semiconductor wafer) in contact with the metal can be obtained. Hereinafter, the first embodiment will be described in more detail.

<Photosensitive resin film manufacturing process> The photosensitive resin film 2 is obtained by applying a photosensitive resin composition in a layer form on the transparent substrate 1, preferably on the surface. Furthermore, when the photosensitive resin composition contains a solvent, it is preferable to dry after applying the photosensitive resin composition in a layered form. In addition, the thickness of the photosensitive resin film is preferably 0.1 to 100 μm, more preferably 1 to 50 μm, and more preferably 3 to 20 μm.

<<Transparent substrate>> As long as the transparent substrate is a substrate that transmits radiant light, the type and the like are not particularly limited, and glass, quartz, liquid crystal polymer, etc. can be exemplified, and glass is preferred. Furthermore, it is preferable that the heat resistance of the transparent substrate is higher, and the Tg is preferably 150°C or higher, and more preferably 250°C or higher. The thickness of the transparent substrate is not particularly limited, but it is usually 10 to 1000 μm.

<<Application of the photosensitive resin composition>> As a method of applying the photosensitive resin composition to a transparent substrate in a layered form, coating is preferred. Specifically, as the application method, dipping method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spray coating method, spin coating method, Slit coating method and inkjet method, etc. From the viewpoint of the uniformity of the thickness of the layered photosensitive resin composition (hereinafter, sometimes referred to as "photosensitive resin composition layer"), the spin coating method, slit coating method, spray method, and inkjet method are Better. By adjusting the appropriate solid content concentration or coating conditions according to the application method, the desired photosensitive resin composition layer can be obtained. In addition, the coating method can be appropriately selected according to the shape of the substrate. As long as it is a circular substrate such as a wafer, spin coating, spray coating, inkjet, etc. are preferred, and as long as it is a rectangular substrate, the slit coating method Or spray method, inkjet method, etc. are preferable. In the case of spin coating, for example, it can be applied at 500 to 2000 rpm (revolutions per minute) for about 10 seconds to 1 minute. In addition, the photosensitive resin composition can be filtered before application. Filtering is used. As the filter aperture, 1 μm or less is preferable, 0.5 μm or less is more preferable, and 0.1 μm or less is more preferable.

<<Photosensitive resin composition>> The photosensitive resin composition constituting the photosensitive resin film in the present embodiment preferably contains a compound that forms a crosslinked structure by exposure, and the composition is more preferably used for negative development A negative photosensitive resin developed with an organic solvent is more preferred. First, the components which can be contained in the photosensitive resin composition used in this embodiment are demonstrated. The photosensitive resin composition may contain components other than these, and is not essential.

<<<Resin>>> The photosensitive resin composition used in this embodiment contains a resin. In the photosensitive resin composition used in this embodiment, resin is not specifically limited, A well-known resin can be used. The resin is preferably a resin with high heat resistance.

The photosensitive resin composition used in this embodiment preferably contains at least one resin selected from the group consisting of polyimide precursor, polyimide, polybenzoxazole precursor, and polybenzoxazole. In the pattern manufacturing method of this embodiment, it is more preferable that the photosensitive resin composition contains a polyimide precursor or a polybenzoxazole precursor, and it is more preferable to contain a polyimide precursor.

The photosensitive resin composition used in this embodiment may contain only one of polyimide precursor, polyimide, polybenzoxazole precursor, and polybenzoxazole, or two or more kinds. . In addition, two types of polyimide precursors, etc., may be included, and two or more types of resins of the same type but different structures may be included. The content of the resin in the photosensitive resin composition used in this embodiment is preferably 10 to 99% by mass of the total solid content of the photosensitive resin composition, more preferably 50 to 98% by mass, and 70 to 96% by mass % Is more preferable.

Furthermore, it is preferable that the resin contains a polymerizable group. Moreover, it is preferable that the photosensitive resin composition contains a polymerizable compound. With this structure, a three-dimensional network is formed in the exposed area to become a strong crosslinked film. The photosensitive resin composition layer (cured film) is not damaged by the surface activation treatment described later, and is cured by the surface activation treatment The adhesion between the film and the metal layer or the adhesion between the cured films is more effectively improved. In addition, the resin preferably contains a partial structure represented by -Ar-L-Ar-. Wherein, Ar is each independently an aromatic group, and L is an aliphatic hydrocarbon group with 1 to 10 carbons which may be substituted by fluorine atoms, -O-, -CO-, -S-, -SO ₂ -or -NHCO- and Including a combination of two or more of the above groups. With this structure, the photosensitive resin composition layer (cured film) becomes a flexible structure, and the effect of suppressing delamination between layers is more effectively exerted. Ar-based phenylene groups are preferred, and L-based aliphatic hydrocarbon groups with 1 or 2 carbon atoms, -O-, -CO-, -S- or -SO ₂ -which may be substituted by fluorine atoms are more preferred. Among them, aliphatic hydrocarbon-based alkylene groups are preferred.

式（2）中，A¹ 及A² 分別獨立地表示氧原子或NH，R¹¹¹ 表示2價有機基，R¹¹⁵ 表示4價有機基，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價有機基。(Polyimine precursor) The type of polyimine precursor is not particularly limited, but it is preferable to include a repeating unit represented by the following formula (2). Formula (2) [Chemical Formula 1]

In formula (2), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or monovalent Organic base.

In the formula (2), A ¹ and A ² are preferably oxygen atoms or NH, and more preferably oxygen atoms. R ¹¹¹ in the formula (2) represents a divalent organic group. Examples of divalent organic groups include groups containing linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups, linear or branched aliphatic groups with 2 to 20 carbons, and rings with 6 to 20 carbons. A fatty group, an aromatic group having 6 to 20 carbons, or a combination thereof is preferable, and a group including an aromatic group having 6 to 20 carbons is more preferable. As a particularly preferred embodiment, R ¹¹¹ in formula (2) is a group represented by -Ar-L-Ar-. However, Ar is each independently an aromatic group, and L is an aliphatic hydrocarbon group with 1 to 10 carbons that can be substituted with fluorine atoms, -O-, -CO-, -S-, -SO ₂ -or -NHCO- and Including a combination of two or more of the above groups. These preferable ranges are the same as described above.

Preferably, R ¹¹¹ in formula (2) is derived from diamine. Examples of diamines used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used. Specifically, it is one of a group containing a linear or branched aliphatic group having 2 to 20 carbons, a cyclic aliphatic group having 6 to 20 carbons, an aromatic group having 6 to 20 carbons, or a combination thereof Diamines are preferred, and diamines containing a group composed of an aromatic group having 2 to 60 carbon atoms are more preferred. As an example of an aromatic group, the following aromatic group can be mentioned.

上述芳香族基中，A係選自單鍵或可以由氟原子取代之碳數1～10的脂肪族烴基、-O-、-C（=O）-、-S-、-S（=O）₂ -、-NHCO-及它們的組合之基團為較佳，係選自單鍵、可以由氟原子取代之碳數1～3的伸烷基、-O-、-C（=O）-、-S-、-SO₂ -之基團為更佳，選自包括-CH₂ -、-O-、-S-、-SO₂ -、-C（CF₃ ）₂ -及-C（CH₃ ）₂ -之組中之2價基團為進一步較佳。[Chemical formula 2]

Among the above-mentioned aromatic groups, A is selected from single bonds or aliphatic hydrocarbon groups with 1 to 10 carbons which can be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -S(=O ) ₂ -, -NHCO- and their combination groups are preferred, which are selected from single bonds, alkylene groups with 1 to 3 carbons that can be substituted by fluorine atoms, -O-, -C (=O) -, -S-, -SO ₂ -are more preferably selected from groups including -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -and -C( The divalent group in the group of CH ₃ ) ₂ -is further preferred.

As the diamine, specifically selected from 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1 ,6-Diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclopentane Hexane or 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis( Aminomethyl) cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethyl Cyclohexylmethane and isophorone diamine; m-phenylenediamine and p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl and 3,3'-diaminobiphenyl, 4, 4'-diaminodiphenyl ether and 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4, 4'-diaminodiphenyl sulfide and 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide and 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone and 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2' -Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl) Propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4- Aminophenyl) hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, double (3-amino-4-hydroxyphenyl) ash, bis(4-amino-3-hydroxyphenyl) ash, 4,4'-diamino-p-terphenyl, 4,4'-bis(4- Aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfuric acid, bis[4-(3-aminophenoxy)phenyl]sulfuric acid, bis[4-( 2-aminophenoxy) phenyl] chrysene, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-bis Methyl-4,4'-diaminodiphenyl benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1, 3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-di Aminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4- (4-Aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl , 3,3',4,4'-tetraamino diphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'- Diaminobiphenyl, 9,9'-bis(4-amine Phenyl) pyrene, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfonium, 3,3',5,5'-tetramethyl-4,4'-diamino Diphenylmethane, 2,4-diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetguanamine, 2,3,5,6 -Tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminopyridine , 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzaniline, ester of diaminobenzoic acid, 1,5-diaminonaphthalene , Diaminobenzotrifluoride, diaminoanthraquinone, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1 ,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminobenzene) Oxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy) )-3,5-Dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoro Propane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4 '-Bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfide, 4 ,4'-bis(3-amino-5-trifluoromethylphenoxy) diphenyl sulfide, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy) Phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoro (Methyl) biphenyl, at least one diamine of 2,2',5,5',6,6'-hexafluorotolidine and 4,4"'-diaminotetraphenyl.

In addition, the diamines (DA-1) to (DA-18) shown below are also preferable.

[Chemical formula 3]

[Chemical formula 4]

Moreover, as a preferable example, the diamine which has at least two or more alkylene glycol units in the main chain can also be mentioned. Preferably, it is a diamine that combines either or both of an ethylene glycol chain and a propylene glycol chain in one molecule, and more preferably does not contain an aromatic ring. As specific examples, JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148 , JEFFAMINE (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (the above are product names, manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy) Ethoxy)propoxy)propane-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propane-2-amine, etc., but It is not limited to these. The following shows JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE ( Registered trademark) The structure of EDR-176.

[Chemical formula 5]

In the above, x, y, and z are average values.

From the viewpoint of the flexibility of the obtained cured film, R ¹¹¹ in the formula (2) is preferably represented by -Ar-L-Ar-. Wherein, Ar is each independently an aromatic group, and L includes an aliphatic hydrocarbon group with 1 to 10 carbons which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ -or -NHCO- and A group of a combination of two or more of the above. Ar-based phenylene groups are preferred, and L-based aliphatic hydrocarbon groups with 1 or 2 carbon atoms, -O-, -CO-, -S- or -SO ₂ -which may be substituted by fluorine atoms are more preferred. Among them, aliphatic hydrocarbon-based alkylene groups are preferred.

式（51）中，R¹⁰ ～R¹⁷ 分別獨立地為氫原子、氟原子或1價有機基，R¹⁰ ～R¹⁷ 中的至少一個係氟原子、甲基或三氟甲基。 作為R¹⁰ ～R¹⁷ 的1價有機基，可列舉碳數1～10（較佳為碳數1～6）的未經取代的烷基、碳數1～10（較佳為碳數1～6）的氟化烷基等。 式（61） [化學式7]

式（61）中，R¹⁸ 及R¹⁹ 分別獨立地為氟原子或三氟甲基。 作為賦予式（51）或（61）的結構之二胺化合物，可列舉2,2’-二甲基聯苯胺、2,2’-双（三氟甲基）-4,4’-二胺基聯苯、2,2’-雙（氟）-4,4’-二胺基聯苯、4,4’-二胺基八氟聯苯等。該些可以使用一種或組合使用兩種以上。From the viewpoint of i-ray transmittance, R ¹¹¹ in the formula (2) is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and easy availability, the divalent organic group represented by the formula (61) is more preferable. Formula (51) [Chemical Formula 6]

In formula (51), R ¹⁰ to R ¹⁷ are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and at least one of R ¹⁰ to R ¹⁷ is a fluorine atom, a methyl group, or a trifluoromethyl group. Examples of the monovalent organic groups of R ¹⁰ to R ¹⁷ include unsubstituted alkyl groups having 1 to 10 carbons (preferably 1 to 6 carbons), and 1 to 10 carbons (preferably 1 to 6 carbons). 6) Fluorinated alkyl groups, etc. Formula (61) [Chemical Formula 7]

In formula (61), R ¹⁸ and R ¹⁹ are each independently a fluorine atom or a trifluoromethyl group. Examples of the diamine compound imparting the structure of formula (51) or (61) include 2,2'-dimethylbenzidine and 2,2'-bis(trifluoromethyl)-4,4'-diamine Biphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. These can be used 1 type or in combination of 2 or more types.

式（5）中，R¹¹² 係選自單鍵或可以由氟原子取代之碳數1～10的脂肪族烴基、-O-、-CO-、-S-、-SO₂ -、-NHCO-以及包括它們的組合之基團為較佳，係選自單鍵、可以由氟原子取代之碳數1～3的伸烷基、-O-、-CO-、-S-及-SO₂ -之基團為更佳，選自包括-CH₂ -、-C（CF₃ ）₂ -、-C（CH₃ ）₂ -、-O-、-CO-、-S-及-SO₂ -之組中之2價基團為進一步較佳。R ¹¹⁵ in formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable. Formula (5) [Chemical Formula 8]

In formula (5), R ¹¹² is selected from a single bond or an aliphatic hydrocarbon group with 1 to 10 carbons which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ -, -NHCO- And groups including their combinations are preferred, and are selected from single bonds, alkylene groups with 1 to 3 carbons which may be substituted by fluorine atoms, -O-, -CO-, -S- and -SO _2- The group is more preferably selected from among -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S- and -SO _2- The divalent group in the group is more preferable.

Formula (6) [Chemical Formula 9]

式（O）中，R¹¹⁵ 表示4價有機基。R¹¹⁵ 的較佳範圍與式（2）中的R¹¹⁵ 的定義相同，較佳範圍亦相同。Regarding R ¹¹⁵ in the formula (2), specifically, a tetracarboxylic acid residue remaining after removing an anhydride group from tetracarboxylic dianhydride, etc. can be mentioned. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. Tetracarboxylic dianhydride is preferably represented by the following formula (O). Formula (O) [Chemical Formula 10]

In formula (O), R ¹¹⁵ represents a tetravalent organic group. The preferred range of formula R ¹¹⁵ and R ¹¹⁵ is the same as defined in (2), and preferred ranges are also the same.

As a specific example of tetracarboxylic dianhydride, can be exemplified selected from pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-Diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetra Carboxylic dianhydride, 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3 ',4'-Biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'oxydiphthalic dianhydride, 2, 3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2 -Bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3, 3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4, 9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrene Tetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2, At least one of 3,4-benzenetetracarboxylic dianhydride and their C1-C6 alkyl derivatives and C1-C6 alkoxy derivatives.

In addition, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below can also be cited as preferred examples. [Chemical formula 11]

It is also preferable that at least one of R ¹¹¹ and R ¹¹⁵ in the formula (2) has a hydroxyl group. More specifically, as R ¹¹¹ , a residue of a diaminophenol derivative can be mentioned.

R ¹¹³ and R ¹¹⁴ in formula (2) each independently represent a hydrogen atom or a monovalent organic group. At least one of R ¹¹³ and R ¹¹⁴ in the formula (2) preferably contains a polymerizable group, and it is more preferred that both of them contain a polymerizable group. The polymerizable group is a group that can undergo a crosslinking reaction by the action of heat, free radicals, and the like. As the polymerizable group, a photoradical polymerizable group is preferred. Specific examples of polymerizable groups include groups having ethylenically unsaturated bonds, alkoxymethyl, hydroxymethyl, oxomethyl, epoxy, oxetanyl, benzoxazolyl, Blocked isocyanate group, methylol group, amine group. As the radical polymerizable group having a polyimide precursor, a group having an ethylenically unsaturated bond is preferred. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, a group represented by the following formula (III), and the like.

[Chemical formula 12]

In the formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and a methyl group is more preferred. In the formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH(OH)CH ₂ -or a polyoxyalkylene group having 4 to 30 carbon atoms. Preferred examples of R ²⁰¹ include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene Methylene, octamethylene, dodecamethylene, -CH ₂ CH(OH)CH ₂ -, ethylene, propylene, trimethylene, -CH ₂ CH(OH)CH _2- good. Particularly preferably, R ²⁰⁰ is a methyl group, and R ²⁰¹ is an ethylene group.

R ¹¹³ or R ¹¹⁴ in formula (2) may be a monovalent organic group other than a polymerizable group. From the viewpoint of solubility to an organic solvent, R ¹¹³ or R ¹¹⁴ in formula (2) is preferably a monovalent organic group. As the monovalent organic group, it is preferable to include a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group. As a monovalent organic group, an aromatic group having 1, 2, or 3 (preferably 1) acidic groups bonded to the carbon atoms constituting the aryl group, and 1, 2, or having carbon atoms constituting the aryl group Three (preferably one) aralkyl groups of acidic groups are particularly preferred. Specifically, an aromatic group having 6 to 20 carbon atoms having an acidic group, and an aralkyl group having 7 to 25 carbon atoms having an acidic group can be mentioned. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group can be cited. The acidic group is preferably a hydroxyl group. R ¹¹³ or R ¹¹⁴ is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl, and 4-hydroxybenzyl are more particularly preferred.

Preferably, the alkyl group represented by R ¹¹³ or R ¹¹⁴ in the formula (2) has 1 to 30 carbon atoms. Examples of straight-chain or branched alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and tetradecyl. , Octadecyl, isopropyl, isobutyl, second butyl, tertiary butyl, 1-ethylpentyl and 2-ethylhexyl. The cyclic alkyl group represented by R ¹¹³ or R ¹¹⁴ in the formula (2) may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic cyclic alkyl groups include adamantyl, norbornyl, bornyl, camphenyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, and camphenyl. Dicyclohexyl and pinenyl (pinenyl). Among them, the cyclohexyl group is the most preferable from the viewpoint of achieving high sensitivity. In addition, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described later is preferred. As the aromatic group represented by R ¹¹³ or R ¹¹⁴ in the formula (2), specifically, substituted or unsubstituted benzene ring, naphthalene ring, pentene ring, indene ring, azulene ring, heptene ring Ring, dicyclopentacene ring, perylene ring, fused pentacene ring, acenaphthylene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring, tri-ring, terphenylene ring, pyrene ring, biphenyl ring, pyrrole Ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indoleazine ring, indole ring, benzofuran ring, benzothiophene ring , Isobenzofuran ring, quinazine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring , Phenanthroline ring, thianthracene ring, chromene ring, dibenzopyran ring, phenoxathi ring, phenanthrazine ring or phenanthrazine ring. The benzene ring is the best.

When R ¹¹³ in formula (2) is a hydrogen atom, or when R ¹¹⁴ in formula (2) is a hydrogen atom, the polyimide precursor can form a co-polymer with a tertiary amine compound having ethylenically unsaturated bonds. Conjugate base. Examples of tertiary amine compounds having such ethylenically unsaturated bonds include N,N-dimethylamino propyl methacrylate.

In addition, it is also preferable to have a fluorine atom in the structural unit of the polyimide precursor. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

In addition, for the purpose of improving the adhesion to the substrate, an aliphatic group having a siloxane structure can be copolymerized with the polyimide precursor. Specifically, as the diamine component used to introduce the aliphatic group of the silicone structure, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethyl Pentasiloxane etc.

式（2-A）中，A¹ 及A² 表示氧原子，R¹¹¹ 及R¹¹² 分別獨立地表示2價有機基，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價有機基，R¹¹³ 及R¹¹⁴ 中的至少一個係包含聚合性基之基團，係聚合性基為較佳。The repeating unit represented by the formula (2) is preferably a repeating unit represented by the following formula (2-A). That is, at least one of the polyimide precursors is preferably a precursor having a repeating unit represented by formula (2-A). With this structure, the width of exposure latitude can be further increased. Formula (2-A) [Chemical Formula 13]

In formula (2-A), A ¹ and A ² represent an oxygen atom, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, and R ¹¹³ At least one of R ¹¹⁴ and R ¹¹⁴ is a group containing a polymerizable group, preferably a polymerizable group.

Of formula (2-A) in ^{A 1, A 2, R 111} , R 113 and R ¹¹⁴ each independently have the formula ^{A 1, A 2, R 111} , the same as R ¹¹³ and R ¹¹⁴ defined in (2), more The optimal range is also the same. ¹¹² same as defined in formula R ¹¹² and R (5) in the formula (2-A), the preferred range is also the same.

In the polyimide precursor, the repeating unit represented by formula (2) may be one type or two or more types. In addition, the polyimide precursor may include structural isomers of the repeating unit represented by formula (2). Moreover, in addition to the repeating unit represented by the above formula (2), the polyimide precursor may further include another repeating unit.

As an embodiment of the polyimide precursor in the present invention, 50 mol% or more of the total repeating unit can be exemplified, further 70 mol% or more, especially 90 mol% or more, represented by formula (2) Polyimide precursor of repeating unit.

The polyimide precursor is preferably obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. The polyimide precursor is preferably obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then reacting it with a diamine. The polyimide precursor can be obtained by the following methods, for example, a method of reacting a tetracarboxylic dianhydride with a diamine compound (partially replaced by a blocking agent as a monoamine) at a low temperature, and a tetracarboxylic acid at a low temperature. The method of reacting acid dianhydride (partially replaced by blocking agent as acid anhydride or monoacid chloride or monoactive ester compound) with diamine compound, after obtaining diester from tetracarboxylic dianhydride and alcohol, in the presence of condensation agent Under the method of reacting it with diamine (partially substituted by the blocking agent as monoamine), after obtaining the diester from tetracarboxylic dianhydride and alcohol, the remaining carboxylic acid is chlorinated to make it react with diamine ( Substituting part of the blocking agent as a monoamine) reaction method and other methods. In the production method of the polyimide precursor, it is preferable to use an organic solvent when the reaction is carried out. The organic solvent may be one type or two or more types. The organic solvent can be appropriately set according to the raw material, and pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone can be exemplified.

When producing the polyimide precursor, in order to further improve the storage stability, it is preferable to seal the main chain end of the precursor with a blocking agent such as acid anhydride, monocarboxylic acid, monoacid chloride, and monoactive ester compound. Among these, it is more preferable to use monoamines. Preferred compounds for monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyl Quinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-amine Naphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-amine Naphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-amine Benzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid Acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-amine Thiophenol and so on. Two or more of these may be used, or a plurality of different terminal groups may be introduced by reacting a plurality of capping agents.

When the polyimide precursor is manufactured, a process for precipitation of solids may be included. Specifically, the polyimide precursor in the reaction solution is precipitated in water, and the polyimide precursor such as tetrahydrofuran is dissolved in a soluble solvent, thereby enabling solid precipitation. Then, the polyimide precursor can be dried to obtain a powdery polyimide precursor.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and still more preferably 22,000 to 25,000. In addition, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and still more preferably 9200 to 11200. The dispersion degree of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and even more preferably 2.8 or more. The upper limit of the degree of dispersion of the polyimide precursor is not particularly limited. For example, 4.5 or less is preferred, 4.0 or less is more preferred, 3.8 or less is more preferred, 3.2 or less is more preferred, and 3.1 or less is more preferred. More preferably, 3.0 or less is even more preferable, and 2.95 or less is especially more preferable.

式（4）中，R¹³¹ 表示2價有機基，R¹³² 表示4價有機基。 當聚醯亞胺係聚合性基時，R¹³¹ 及R¹³² 中的至少一方可以具有聚合性基，如下述式（4-1）或式（4-2）所示那樣可以於聚醯亞胺的末端具有聚合性基。(Polyimine) The polyimine is not particularly limited as long as it is a polymer compound having an imine ring. Polyimine is preferably a compound represented by the following formula (4), is a compound represented by the formula (4), and more preferably has a polymerizable group. Formula (4) [Chemical Formula 14]

In formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group. In the case of a polyimide-based polymerizable group, at least one of R ¹³¹ and R ¹³² may have a polymerizable group, as shown in the following formula (4-1) or formula (4-2). The end has a polymerizable group.

式（4-1）中，R¹³³ 係聚合性基，其他基團與式（4）的定義相同。Formula (4-1) [Chemical Formula 15]

In the formula (4-1), R ¹³³ is a polymerizable group, and other groups have the same definitions as in the formula (4).

式（4-2）中，R¹³⁴ 及R¹³⁵ 中的至少一個係聚合性基，另一個係有機基，其他基團與式（4）的定義相同。Formula (4-2) [Chemical formula 16]

In formula (4-2), at least one of R ¹³⁴ and R ¹³⁵ is a polymerizable group, the other is an organic group, and the other groups have the same definitions as in formula (4).

Regarding the preferred polymerizable group of polyimine, in the above-mentioned polyimine precursor, the difference between the polymerizable group described by the polymerizable group that R ¹¹³ and R ¹¹⁴ in formula (2) may contain The definition is the same.

R ¹³¹ in the formula (4) represents a divalent organic group. As the divalent organic group, the same divalent organic group as R ¹¹¹ in formula (2) is exemplified, and the preferred range is also the same. Moreover, as R ¹³¹ , the diamine residue remaining after removing the amine group of the diamine can be mentioned. Examples of diamines include aliphatic, cycloaliphatic, or aromatic diamines. As a specific example, an example of R ¹¹¹ in the formula (2) of the polyimide precursor can be cited.

Generating warpage considered aspect more effectively suppress the firing formula R ¹³¹ line (4) has at least two diamine residue of alkylene glycol units of the main chain is preferred. It is more preferable to combine any one or two of an ethylene glycol chain and a propylene glycol chain in one molecule to include two or more diamine residues, and still more preferably a diamine residue that does not include an aromatic ring.

As a diamine that combines any one or two of an ethylene glycol chain and a propylene glycol chain in one molecule to include two or more diamines, the same specific examples as the diamine capable of derivatizing R ¹¹¹ in formula (2) can be cited. , But not limited to this.

R ¹³² in formula (4) represents a tetravalent organic group. As the tetravalent organic group represented by R ¹³² , the same as R ¹¹⁵ in formula (2) is exemplified, and the preferred range is also the same. For example, the four bonds of the tetravalent organic group of the following structure exemplified as R ¹¹⁵ in the formula (2) are bonded to a part of the four -C(=O)- in the above formula (4) to form Condensed ring. [Chemical formula 17]

Examples of R ¹³² in formula (4) include tetracarboxylic acid residues remaining after removing anhydride groups from tetracarboxylic dianhydride. As a specific example, an example of R ¹¹⁵ in formula (2) of the polyimide precursor can be cited. From the viewpoint of the strength of the cured film, R ¹³² is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

It is also preferable that at least one of R ¹³¹ and R ¹³² in the formula (4) has a hydroxyl group. More specifically, as R ¹³¹ in the formula (4), 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl) Base) hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, the above (DA- 1) ~ (DA-18) are cited as preferred examples. As R ¹³² in the formula (4), the above-mentioned (DAA-1) to (DAA-5) are exemplified as preferable examples.

Furthermore, it is also preferable that the polyimide has a fluorine atom in the structural unit. The fluorine atom content in the polyimide is preferably 10% by mass or more, and more preferably 20% by mass or less.

In addition, for the purpose of improving the adhesion to the substrate, an aliphatic group having a siloxane structure can be copolymerized with polyimide. Specifically, as the diamine component used to introduce an aliphatic group having a silicone structure, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl) Methylpentasiloxane etc.

Moreover, in order to improve the storage stability of the photosensitive resin composition, it is preferable to seal the main chain end of the polyimide with a blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride, and a monoactive ester compound. Among these, it is more preferable to use monoamine. Preferred compounds of monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-amino Naphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene Naphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene Naphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid , 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6- Dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used, or a plurality of different terminal groups may be introduced by reacting a plurality of capping agents.

The imidization rate of polyimide is preferably 85% or more, and more preferably 90% or more. The imidization rate is 85% or more, whereby the film shrinkage caused by the closed loop generated when the imidization is heated by heating is reduced, and the occurrence of substrate warping can be suppressed.

Polyimide based only one kind comprising all R or R ^{131 is} the repeating unit represented by the above formula (4) of ^132, may also comprise two or more R ¹³² or R ^{131 is} different from the repeating units. Furthermore, in addition to the repeating unit represented by the above formula (4), the polybenzoxazole may contain another repeating unit.

Regarding the polyimide, it can be produced by synthesizing the polyimide precursor and then heating and cyclizing it, or it can be synthesized directly. Polyimine can be synthesized by the following method, that is, the polyimine precursor is obtained, and the known method of the imine reaction method is used to complete the imidization method or the imidization reaction is stopped on the way, and A method of introducing a part of the imine structure, and then a method of pulverizing the completely imidized polymer and the polyimide precursor, thereby introducing a part of the imine structure.

As a commercially available product of polyimide, Durimide (registered trademark) 284 (manufactured by Fujifilm Corporation) and Matrimide 5218 (manufactured by HUNTSMAN) are exemplified.

The weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and particularly preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the cured film can be improved. In order to obtain a cured film with excellent mechanical properties, the weight average molecular weight is more preferably 20,000 or more. Moreover, when two or more types of polyimines are contained, it is preferable that the weight average molecular weight of at least one type of polyimines is within the above-mentioned range.

式（3）中，R¹²¹ 表示2價有機基，R¹²² 表示4價有機基，R¹²³ 及R¹²⁴ 分別獨立地表示氫原子或1價有機基。(Polybenzoxazole Precursor) The polybenzoxazole precursor is not particularly limited in its kind and the like, but preferably contains a repeating unit represented by the following formula (3). Formula (3) [Chemical Formula 18]

In the formula (3), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group.

R ¹²³ and R ¹²⁴ in formula (3) have the same definitions as R ¹¹³ in formula (2), and their preferred ranges are also the same. That is, at least one of R ¹²³ and R ¹²⁴ in formula (3) is preferably a polymerizable group.

R ¹²¹ in the formula (3) represents a divalent organic group. The divalent organic group represented by R ¹²¹ preferably contains at least one of an aliphatic group and an aromatic group. As the aliphatic group, a straight-chain aliphatic group is preferred. R ¹²¹ is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.

As the dicarboxylic acid, a dicarboxylic acid containing an aliphatic group and a dicarboxylic acid containing an aromatic group are preferable, and a dicarboxylic acid containing an aromatic group is more preferable. As dicarboxylic acids containing aliphatic groups, dicarboxylic acids containing linear or branched (preferably linear) aliphatic groups are preferred, including linear or branched (preferably linear) aliphatic groups and two A COOH dicarboxylic acid is more preferable. The carbon number system of the linear or branched (preferably linear) aliphatic group is preferably 2-30, more preferably 2-25, more preferably 3-20, particularly preferably 4-15, and 5-10 For further better. The straight-chain aliphatic group is preferably an alkylene group. Examples of dicarboxylic acids containing linear aliphatic groups include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, and succinic acid , Tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoro Glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methyl Glutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorooctane Diacid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, Hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, behenicanedioic acid, behenedioic acid, tricosanedioic acid , Tetracosanedioic acid, pentadecanedioic acid, hexadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, nonacosanedioic acid, triaconanedioic acid, three Undecanedioic acid, tridodecanedioic acid, diglycolic acid, dicarboxylic acid represented by the following formula, etc.

（式中，Z係碳數1～6的烴基，n係1～6的整數。）[Chemical formula 19]

(In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.)

As the dicarboxylic acid containing the aromatic group, the dicarboxylic acid having the following aromatic group is preferable, and the dicarboxylic acid containing only the following aromatic group and two COOH is more preferable.

上述芳香族基中，A表示選自包括-CH₂ -、-O-、-S-、-SO₂ -、-CO-、-NHCO-、-C（CF₃ ）₂ -及-C（CH₃ ）₂ -之組中之2價基團。[Chemical formula 20]

In the above aromatic group, A represents selected from the group consisting of -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, -C(CF ₃ ) ₂ -and -C(CH ₃ ) A divalent group in the group ₂ -.

As specific examples of dicarboxylic acids containing aromatic groups, 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid are preferred.

R ¹²² in the formula (3) represents a tetravalent organic group. As the tetravalent organic group represented by R ¹²² , the same as R ¹¹⁵ in the above formula (2) is exemplified, and the preferred range is also the same. R ¹²² in formula (3) is further preferably a group derived from a diaminophenol derivative. As the group derived from diaminophenol derivatives, for example, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'- Dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfide, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfide, bis-( 3-amino-4-hydroxyphenyl)methane, 2,2-bis-(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl) ) Hexafluoropropane, 2,2-bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-( 4-amino-3-hydroxyphenyl) propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxy Benzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-di Amino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, etc. These diaminophenols can be used alone or in combination.

Among diaminophenol derivatives, diaminophenol derivatives having the following aromatic groups are preferred.

上述式中，X₁ 表示-O-、-S-、-C（CF₃ ）₂ -、-CH₂ -、-SO₂ -或-NHCO-。[Chemical formula 21]

In the above formula, X ₁ represents -O-, -S-, -C(CF ₃ ) ₂ -, -CH ₂ -, -SO ₂ -or -NHCO-.

The diaminophenol derivative is represented by formula (As), for example. [Chemical formula 22]

In formula (As), R ₁ is selected from hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, single bond or the following The organic group in the group of formula (A-sc). In the formula (As), R ₂ is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, which may be the same or different. In the formula (As), R ₃ is any one of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different.

（式（A-sc）中，*表示與由上述式（A-s）表示之二胺基酚衍生物的胺基苯酚的芳香環鍵結之情況。）Formula (A-sc) [Chemical formula 23]

(In the formula (A-sc), * indicates the condition of bonding to the aromatic ring of the aminophenol of the diaminophenol derivative represented by the above formula (As).)

In the above formula (As), the ortho position of the phenolic hydroxyl group, that is, R ₃ is considered to also have a substituent, which can make the distance between the carbonyl carbon of the amide bond and the hydroxyl group closer, and it will become a high ring when hardened at low temperature. Considering the effect of reduction rate, it is particularly good.

In addition, in the above formula (As), when R ₂ is an alkyl group and R ₃ is an alkyl group, it can maintain high transparency to i-rays and has the effect of achieving a high cyclization rate when cured at low temperature, so it is preferable .

Furthermore, in the above formula (As), R ₁ is an alkylene group or a substituted alkylene group is more preferred. Specific examples of the alkylene and substituted alkylene represented by R ₁ include -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -CH(CH ₂ CH ₃ ) -, -C (CH ₃ ) (CH ₂ CH ₃ ) -, -C (CH ₂ CH ₃ ) (CH ₂ CH ₃ )-, -CH (CH ₂ CH ₂ CH ₃ ) -, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ ) -, -CH (CH (CH ₃ ) ₂ ) -, -C (CH ₃ ) (CH (CH ₃ ) ₂ ) -, -CH (CH ₂ CH ₂ CH ₂ CH ₃ ) -, -C (CH ₃ ) (CH ₂ CH ₂ CH ₂ CH ₃ ) -, -CH (CH ₂ CH (CH ₃ ) ₂ ) -, -C (CH ₃ ) (CH ₂ CH (CH ₃ ) ₂ ) -, -CH (CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ ) -, -C (CH ₃ ) (CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ ) -, -CH (CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ ) -, -C (CH ₃ ) (CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-etc., where -CH ₂ -, -CH (CH ₃ ) -, -C (CH ₃ ) ₂ -It can also maintain high transparency to i-rays and the effect of high cyclization rate when cured at low temperature, while obtaining a polybenzoxazole precursor with sufficient solubility in solvents and excellent balance, Therefore it is better.

As a method of producing the diaminophenol derivative represented by the above formula (As), for example, refer to paragraphs 0085 to 0094 of JP 2013-256506 A and Example 1 (paragraphs 0189 to 0190), and compare the These contents are incorporated into this manual.

Specific examples of the structure of the diaminophenol derivative represented by the above formula (As) include those described in paragraphs 0070 to 0080 of JP 2013-256506 A, and these contents are incorporated into this specification . Of course, it is not limited to these.

In addition to the repeating unit represented by the above formula (3), the polybenzoxazole precursor may also include another repeating unit. From the viewpoint of suppressing the warpage of the substrate accompanying the ring closure of the polybenzoxazole precursor, the polybenzoxazole precursor contains a diamine residue represented by the following formula (SL) as another repeating unit: Better.

式（SL）中，Z具有a結構和b結構，R^1s 係氫原子或碳數1～10的烴基，R^2s 係碳數1～10的烴基，R^3s 、R^4s 、R^5s 、R^6s 中的至少一個係芳香族基，剩餘係氫原子或碳數1～30的有機基，該些可以分別相同或不同。a結構及b結構的聚合可以係嵌段聚合或隨機聚合。關於Z部分的莫耳%，a結構係5～95莫耳%，b結構係95～5莫耳%，a結構及b結構之和係100莫耳%。[Chemical formula 24]

In the formula (SL), Z has a structure and a structure b, R ^1s is a hydrogen atom or a hydrocarbon group with 1 to 10 carbons, R ^2s is a hydrocarbon group with 1 to 10 carbons, R ^3s , R ^4s , R ^5s , R ^6s At least one of them is an aromatic group, and the remainder is a hydrogen atom or an organic group having 1 to 30 carbon atoms, and these may be the same or different. The polymerization of the a structure and the b structure can be block polymerization or random polymerization. Regarding the mole% of the Z part, the a structure is 5 to 95 mole%, the b structure is 95 to 5 mole%, and the sum of the a structure and the b structure is 100 mole%.

In the formula (SL), as a preferable Z, R ^5s and R ^6s in the structure b are phenyl groups. Moreover, the molecular weight of the diamine residue represented by the formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. Setting the molecular weight of the diamine residue represented by the formula (SL) within the above range can more effectively reduce the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure, and can also suppress the warpage of the substrate. Effect and improve solvent solubility.

When the diamine residue represented by the formula (SL) is included as another type of repeating unit, it is also preferable to include the tetracarboxylic acid residue remaining after removing the anhydride group from the tetracarboxylic dianhydride as the repeating unit. As an example of such a tetracarboxylic acid residue, an example of R ¹¹⁵ in formula (2) can be given.

In the weight average molecular weight (Mw) of the polybenzoxazole precursor, for example, when the composition described later is used, it is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and still more preferably 22,000 to 28,000. In addition, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and still more preferably 9200 to 11200. The dispersion degree of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. The upper limit of the degree of dispersion of the polybenzoxazole precursor is not particularly limited. For example, 2.6 or less is preferable, 2.5 or less is more preferable, 2.4 or less is more preferable, 2.3 or less is more preferable, and 2.2 or less is Even more preferable.

式（X）中，R¹³³ 表示2價有機基，R¹³⁴ 表示4價有機基。 當具有聚合性基時，R¹³³ 及R¹³⁴ 中的至少一個可以具有聚合性基，如由下述式（X-1）或式（X-2）表示那樣可以於聚苯并噁唑的末端具有聚合性基。(Polybenzoxazole) The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring. The polybenzoxazole is preferably a compound represented by the following formula (X), and a compound represented by the following formula (X), and a compound having a polymerizable group is more preferred. [Chemical formula 25]

In formula (X), R ¹³³ represents a divalent organic group, and R ¹³⁴ represents a tetravalent organic group. When it has a polymerizable group, at least one of R ¹³³ and R ¹³⁴ may have a polymerizable group, and may be at the end of the polybenzoxazole as represented by the following formula (X-1) or formula (X-2) Has a polymerizable group.

式（X-1）中，R¹³⁵ 及R¹³⁶ 中的至少一個係聚合性基，另一個係有機基，另一基團與式（X）的定義相同。Formula (X-1) [Chemical formula 26]

In the formula (X-1), at least one of R ¹³⁵ and R ¹³⁶ is a polymerizable group, the other is an organic group, and the other group has the same definition as the formula (X).

式（X-2）中，R¹³⁷ 係聚合性基，其他為取代基，其他基團與式（X）的定義相同。Formula (X-2) [Chemical Formula 27]

In the formula (X-2), ^R137 is a polymerizable group, the others are substituents, and the other groups have the same definitions as in the formula (X).

The polymerizable group preferably possessed by polybenzoxazole has the same definition as the polymerizable group described by the polymerizable group possessed by the polyimide precursor described above.

R ¹³³ represents a divalent organic group. As a divalent organic group, an aliphatic group or an aromatic group can be mentioned. As a specific example, an example of R ¹²¹ in the formula (3) of the polybenzoxazole precursor can be cited. In addition, this preferred example has the same definition as R ¹²¹ .

R ¹³⁴ represents a tetravalent organic group. Examples of the tetravalent organic group include R ¹²² in the formula (3) of the polybenzoxazole precursor. In addition, this preferred example has the same definition as R ¹²² . For example, four bonds of the tetravalent organic group exemplified as R ¹²² are bonded to the nitrogen atom and oxygen atom in the above formula (X) to form a condensed ring. For example, when R ¹³⁴ is the following organic group, the following structure is formed. [Chemical formula 28]

The oxazolation rate of polybenzoxazole is preferably 85% or more, and more preferably 90% or more. With the oxazolidization rate being 85% or more, the film shrinkage caused by the closed loop generated during oxazolidization due to heating is reduced, and the warpage can be effectively suppressed.

Polybenzoxazole not only contains all of the repeating units represented by the above formula (X) based on one kind of R ¹³¹ or R ¹³² , but can also include two or more different R ¹³¹ or R ¹³² groups that are represented by the above formula (X ) Represents the repeating unit. Furthermore, in addition to the repeating unit represented by the above formula (X), the polybenzoxazole may also include another repeating unit.

Polybenzoxazole is obtained, for example, by reacting a diaminophenol derivative with a compound selected from the group consisting of dicarboxylic acids containing R ¹³³ and dicarboxylic acid dichlorides and dicarboxylic acid derivatives of the above-mentioned dicarboxylic acids. The polybenzoxazole precursor is obtained by oxazolation using a known oxazolation reaction method. In addition, when it is a dicarboxylic acid, in order to increase the reaction yield, etc., an active ester-type dicarboxylic acid derivative that has been reacted in advance with 1-hydroxy-1,2,3-benzotriazole and the like can be used.

The weight average molecular weight (Mw) of polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and particularly preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the cured film can be improved. In order to obtain a cured film with excellent mechanical properties, the weight average molecular weight is more preferably 20,000 or more. Moreover, when two or more polybenzoxazoles are contained, the weight average molecular weight of at least one polybenzoxazole is preferably within the above-mentioned range.

(Other photosensitive resin) Even if it is a photosensitive resin other than the above, this embodiment can also be applied. As other resins, epoxy resins, phenol resins, and benzocyclobutane-based resins can be used.

<<<Polymerizable compound>>> It is preferable that the resin has a polymerizable group, or the photosensitive resin composition contains a polymerizable compound. With this structure, a cured film with more excellent heat resistance can be formed. The polymerizable compound is a compound having a polymerizable group, and it is possible to use a known compound capable of crosslinking reaction by a radical, an acid, a basic group, or the like. As a polymerizable group, the polymerizable group etc. demonstrated using the said polyimide precursor are illustrated. The polymerizable compound may contain only one type or two or more types. Regarding the polymerizable compound, for example, it is any one of chemical forms such as monomers, prepolymers, oligomers, their mixtures, and their multimers.

In this embodiment, the monomer type polymerizable compound (hereinafter referred to as polymerizable monomer) is a compound different from the polymer compound. The polymerizable monomer is typically a low-molecular compound, and a low-molecular compound with a molecular weight of 2000 or less is preferred, a low-molecular compound with a molecular weight of 1500 or less is more preferred, and a low-molecular compound with a molecular weight of 900 or less is more preferred. In addition, the molecular weight of the polymerizable monomer is usually 100 or more. In addition, the oligomer-type polymerizable compound is typically a polymer with a relatively low molecular weight, and preferably a polymer with 10 to 100 polymerizable monomers bonded thereto. The weight average molecular weight of the oligomer type polymerizable compound is preferably 2,000 to 20,000, more preferably 2,000 to 15,000, and most preferably 2,000 to 10,000.

The number of functional groups of a polymerizable compound refers to the number of polymerizable groups in one molecule. From the viewpoint of developability, the photosensitive resin composition preferably contains at least one bifunctional or more polymerizable compound including two or more polymerizable groups, and more preferably contains at least one trifunctional or more polymerizable compound. From the viewpoint of forming a three-dimensional crosslinked structure and improving heat resistance, the photosensitive resin composition preferably contains at least one trifunctional or higher polymerizable compound. In addition, it may be a mixture of a bifunctional or lower polymerizable compound and a trifunctional or higher polymerizable compound.

As a polymerizable compound, a compound containing a group having an ethylenically unsaturated bond; a compound having a methylol group, an alkoxymethyl group or an oxymethyl group; an epoxy compound; an oxetane compound; a benzoxazine Compounds are preferred.

(Compounds containing a group having an ethylenically unsaturated bond) As the group having an ethylenically unsaturated bond, styryl, vinyl, (meth)acrylic and (meth)allyl groups are preferred , (Meth)acrylic acid group is more preferable.

Specific examples of the compound containing a group having an ethylenically unsaturated bond include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or The esters, amides, and their multimers are preferably esters of unsaturated carboxylic acids and polyhydric alcohols, and amides of unsaturated carboxylic acids and polyamine compounds, and their multimers. In addition, addition reactants of unsaturated carboxylic acid esters or amides with monofunctional or polyfunctional isocyanates or epoxies and monofunctional or polyfunctional isocyanates or epoxy groups with affinity substituents such as hydroxyl groups, amine groups, and mercapto groups can also be preferably used. Dehydration condensation reaction product of functional or polyfunctional carboxylic acid, etc. In addition, addition reactants of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols, and halogen groups or Substitution reactants of unsaturated carboxylic acid esters or amides having detachable substituents such as toluene sulfonyloxy group and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. In addition, as another example, instead of the above-mentioned unsaturated carboxylic acid, a group of compounds substituted with unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, allyl ether, and the like can be used.

As specific examples of monomers of esters of polyhydric alcohols and unsaturated carboxylic acids, as acrylates, there are ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetraethylene glycol diacrylate. Methyl glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris (propylene oxypropyl) ether, trimethylol Ethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, two Pentaerythritol hexaacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tris(acryloxyethyl) heterotrimerization Cyanate ester, isocyanuric acid ethylene oxide modified triacrylate, polyester acrylate oligomer, etc.

As the methacrylate, there are tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, Trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, Pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, double 〔 P(3-methacryloxy-2-hydroxypropoxy)phenyl]dimethylmethane, bis-[p(methacryloxyethoxy)phenyl]dimethylmethane, etc.

As itaconates, there are ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, four Methylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetraitaconate, etc.

As crotonates, there are ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetra-dicrotonate, and the like.

As isocrotonic acid esters, there are ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, and the like.

Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

As examples of other esters, for example, the aliphatic alcohol esters described in Japanese Patent Publication No. 46-27926, Japanese Patent Publication No. 51-47334, Japanese Patent Application Publication No. 57-196231, or Those having an aromatic skeleton as described in Japanese Patent Application Publication No. 59-5240, Japanese Patent Application Publication No. 59-5241, Japanese Patent Application Publication No. 2-226149, and Japanese Patent Application Publication No. 1-165613 Those containing amine groups, etc.

In addition, as specific examples of monomers of polyamine compounds and amides of unsaturated carboxylic acids, there are methylene bis-acrylamide, methylene bis-methacrylamide, and 1,6-hexamethylene Bis-acrylamide, 1,6-hexamethylene bis-methacrylamide, diethylenetriamine triacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide, etc.

As examples of other preferable amide-based monomers, those having a cyclohexylene structure described in Japanese Patent Publication No. 54-21726 are cited.

In addition, a urethane-based addition polymerizable monomer produced by the addition reaction of an isocyanate and a hydroxyl group is also suitable. As such a specific example, for example, the one described in Japanese Patent Publication No. 48-41708 Ethylene containing two or more polymerizable vinyl groups in one molecule, which is obtained by adding a hydroxyl-containing vinyl monomer represented by the following formula to a polyisocyanate compound having two or more isocyanate groups in one molecule Carbamate compounds and the like. CH ₂ =C(R ⁴ )COOCH ₂ CH(R ⁵ )OH (where R ⁴ and R ⁵ represent H or CH ₃ .) Also, such as Japanese Patent Publication No. 51-37193 and Japanese Patent Publication No. 2-32293 The urethane acrylates described in Japanese Patent Publication No. 2-16765, or Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 62-39418 are also preferred.

In addition, in this embodiment, as the compound containing a group having an ethylenically unsaturated bond, the compound described in paragraphs 0095 to 0108 of JP 2009-288705 A can also be preferably used.

In addition, as a compound containing a group having an ethylenically unsaturated bond, a compound having a boiling point of 100°C or higher under normal pressure is also preferable. Examples thereof include monofunctional acrylates or methacrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate ; Polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol four (Meth) acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol (meth)acrylate, trimethylolpropane tris(acryloxypropyl) ) Ether, tris(acryloyloxyethyl) isocyanurate, glycerin or trimethylol ethane, etc. are added with ethylene oxide or propylene oxide to polyfunctional alcohols for (meth)acrylic acid Esterified, such as (meth)acrylate urethanes described in Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034, Japanese Patent Application Publication No. 51-37193, Japan The polyester acrylates described in JP-A-48-64183, JP-A-49-43191, and JP-A-52-30490 are used as reaction products of epoxy resin and (meth)acrylic acid. Polyfunctional acrylates or methacrylates, such as epoxy acrylates, and mixtures of these. In addition, the compounds described in paragraphs 0254 to 0257 of JP 2008-292970 A are also suitable. Moreover, the polyfunctional (meth)acrylate etc. which are obtained by making the compound which has a cyclic ether group and ethylenically unsaturated group, such as a polyfunctional carboxylic acid and glycidyl (meth)acrylate react, are mentioned. In addition, as other preferable polymerizable compounds containing a group having an ethylenically unsaturated bond, Japanese Patent Application Publication No. 2010-160418, Japanese Patent Application Publication No. 2010-129825, Japanese Patent No. 4364216 and the like can also be used. The compound or cardo resin described has a sulphur ring and two or more ethylenically unsaturated bond-containing groups. Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication No. 46-43946, Japanese Patent Publication No. 1-40337, Japanese Patent Publication No. 1-40336, or Japanese Patent Application Publication No. 2-25493 The vinyl phosphonic acid-based compounds described in the Gazette. In addition, in certain cases, the perfluoroalkyl group-containing structure described in JP 61-22048 A is suitably used. Furthermore, it is also possible to use those introduced as photocurable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pages 300 to 308 (1984).

In addition to the above, polymerizable compounds represented by the following (MO-1) to (MO-5) can be preferably used. In addition, in the formula, when T is an oxyalkylene group, the end on the carbon atom side is bonded to R.

[Chemical formula 29]

[Chemical formula 30]

In each of the above formulas, n is an integer of 0-14, and m is an integer of 1-8. A plurality of R and T may be the same or different in the molecule. In each of the polymerizable compounds represented by the above formulas (MO-1) to (MO-5), at least one of the plural Rs is represented by -OC (=O) CH=CH ₂ or, -OC (=O ) C(CH ₃ )=CH ₂ represents a group. In this embodiment, as a specific example of the compound containing a group having an ethylenically unsaturated bond represented by the above formulas (MO-1) to (MO-5), JP 2007-269779 can be preferably used The compound described in paragraphs 0248 to 0251 of the publication.

In addition, the following compounds described as formulas (1) and (2) in Japanese Patent Application Laid-Open No. 10-62986 and their specific examples can also be used as polymerizable compounds, which are ring-added to polyfunctional alcohols A compound formed by (meth)acrylic acid esterification after ethylene oxide or propylene oxide.

Furthermore, the compounds described in paragraphs 0104 to 0131 of JP 2015-187211 A can also be used, and these contents can be incorporated in this specification. In particular, as a preferable aspect, the compounds described in paragraphs 0128 to 0130 of the publication are exemplified.

As a compound containing a group having an ethylenic unsaturated bond, dipentaerythritol triacrylate (as a commercial product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product) KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (as a commercially available product is KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa ( Meth) acrylate (as a commercially available product is KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) and these (meth)acrylic acid groups are bonded via ethylene glycol residues and propylene glycol residues. good. It is also possible to use their oligomer types. Moreover, as a preferable example, the pentaerythritol derivatives and/or dipentaerythritol derivatives of the above-mentioned formula (MO-1) and (MO-2) can also be cited.

Commercial products of polymerizable compounds include, for example, SR-494 manufactured by Sartomer Company, Inc as a 4-functional acrylate having 4 ethoxy chains, and SR-494 as a difunctional acrylic having 4 ethoxy chains. SR-209 manufactured by Sartomer Company, Inc. of methyl ester, DPCA-60 manufactured by Nippon Kayaku Co., Ltd. as a 6-functional acrylate with 6 pentoxy chains, as a DPCA-60 with 3 isobutylene groups TPA-330 of trifunctional acrylate, urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd), NK ester M-40G, NK ester 4G, NK ester M- 9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH -600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), etc.

As a compound containing a group having an ethylenically unsaturated bond, such as Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. 2-32293, Japanese Patent Publication No. 2-16765 Urethane acrylates as described in the gazette, Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, Japanese Patent Publication No. 62-39418 The urethane compounds having an ethylene oxide-based skeleton described in the gazette are also preferable. Furthermore, as the polymerizable compound, those having an amino group structure in the molecule or those described in JP-A 63-277653, JP-A 63-260909, and JP-A 1-105238 can also be used. Addition polymerizable monomers of sulfide structure.

The compound containing a group having an ethylenically unsaturated bond may be a multifunctional monomer having an acid group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among the polyfunctional monomers with acid groups, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred. The unreacted hydroxyl groups of the aliphatic polyhydroxy compounds react with non-aromatic carboxylic anhydrides to have many acid groups Functional monomers are more preferable. Particularly preferably, among the polyfunctional monomers having an acid group by reacting unreacted hydroxyl groups of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride, the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol. As a commercially available product, for example, as a polyacid-modified acrylic oligomer manufactured by TOAGOSEI CO., LTD., M-510, M-520, and the like can be cited. The polyfunctional monomer having an acid group may be used alone or in combination of two or more. In addition, if necessary, a multifunctional monomer having no acid group and a multifunctional monomer having an acid group can be used in combination. The preferred acid value of the polyfunctional monomer having an acid group is 0.1-40 mgKOH/g, particularly preferably 5-30 mgKOH/g. As long as the acid value of the polyfunctional monomer is within the above-mentioned range, the production and handling properties are excellent, and furthermore, the developability is excellent. Moreover, the polymerizability is also good.

From the viewpoint of good polymerizability and heat resistance, the content of the compound containing the group having an ethylenically unsaturated bond is preferably 1 to 50% by mass relative to the total solid content of the photosensitive resin composition. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 30% by mass or less. The compound containing a group having an ethylenically unsaturated bond may be used singly or in combination of two or more. In addition, the mass ratio of the resin to the compound containing the ethylenically unsaturated bond (resin/polymerizable compound) is preferably 98/2 to 10/90, more preferably 95/5 to 30/70, and 90 /10～50/50 is the best. As long as the mass ratio of the resin and the compound containing the ethylenically unsaturated bond is within the above range, a cured film with more excellent polymerizability and heat resistance can be formed.

(The compound having a hydroxymethyl group, an alkoxymethyl group, or an oxymethyl group) As a compound having a hydroxymethyl group, an alkoxymethyl group, or an oxymethyl group, a compound represented by the following formula (AM1) is preferred.

（式中，t表示1～20的整數，R⁴ 表示碳數1～200的t價有機基團，R⁵ 表示由下述式（AM2）或下述式（AM3）表示之基團。）Formula (AM1) [Chemical Formula 31]

(In the formula, t represents an integer of 1 to 20, R ⁴ represents a t-valent organic group having 1 to 200 carbon atoms, and R ⁵ represents a group represented by the following formula (AM2) or the following formula (AM3).)

（式中，R⁶ 表示羥基或碳數1～10的有機基團。）Formula (AM2) Formula (AM3) [Chemical formula 32]

(In the formula, R ⁶ represents a hydroxyl group or an organic group with 1 to 10 carbon atoms.)

The compound represented by the formula (AM1) is preferably 5 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the polyimide precursor or the like. More preferably, it is 10 mass parts or more and 35 mass parts or less. In addition, all polymerizable compounds contain 10% by mass or more and 90% by mass or less of the compound represented by the following formula (AM4), and all thermal crosslinking agents contain 10% by mass or more and 90% by mass or less by the following formula The compound represented by (AM5) is also preferred.

（式中，R⁴ 表示碳數1～200的2價有機基團，R⁵ 表示由下述式（AM2）或下述式（AM3）表示之基團。）Formula (AM4) [Chemical Formula 33]

(In the formula, R ⁴ represents a divalent organic group having 1 to 200 carbon atoms, and R ⁵ represents a group represented by the following formula (AM2) or the following formula (AM3).)

（式中，u表示3～8的整數，R⁴ 表示碳數1～200的u價有機基團，R⁵ 表示由下述式（AM2）或下述式（AM3）表示之基團。）Formula (AM5) [Chemical Formula 34]

(In the formula, u represents an integer of 3 to 8, R ⁴ represents a u-valent organic group having 1 to 200 carbon atoms, and R ⁵ represents a group represented by the following formula (AM2) or the following formula (AM3).)

（式中，R⁶ 表示羥基或碳數1～10的有機基團。）Formula (AM2) Formula (AM3) [Chemical formula 35]

(In the formula, R ⁶ represents a hydroxyl group or an organic group with 1 to 10 carbon atoms.)

By using a compound having these methylol groups, when a photosensitive composition is formed on an uneven substrate, the occurrence of cracks is further reduced. In addition, it is possible to have excellent pattern processability, and the 5% mass reduction temperature is 350°C or higher, more preferably 380°C or higher, and high heat resistance. Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (the above are product names, manufactured by ASAHI YUKIZAI CORPORATION), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (the above are product names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX -290 (product name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-buthylphenol (2,6-dimethoxymethyl-4-t-buthylphenol), 2, 6-dimethoxymethyl-p-cresol (2,6-dimethoxymethyl-p-cresol), 2,6 acetoxymethyl-p-cresol (2,6-diacethoxymethyl-p-cresol), etc.

Moreover, as specific examples of the compound represented by the formula (AM5), TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA , HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (the above are product names, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by ASAHI YUKIZAI CORPORATION), NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW-100LM (the above are product names, manufactured by Sanwa Chemical Co., Ltd.).

(Epoxy compound (compound having epoxy group)) As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. Epoxy is based on the cross-linking reaction at 200°C or less, and the dehydration reaction from cross-linking does not occur, so film shrinkage does not occur. Therefore, if the epoxy compound is contained, the low-temperature hardening and warpage of the composition can be effectively suppressed.

The epoxy compound preferably contains a polyethylene oxide group. Thereby, it is possible to suppress a further decrease in the modulus of elasticity and to suppress warpage. In addition, the flexibility of the film can be improved to obtain a cured film that is also excellent in elongation. The polyethylene oxide group means the number of repeating units of ethylene oxide of 2 or more, and the number of repeating units is preferably 2-15.

Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether; and polypropylene glycol diglycidyl ether. Alkyl glycol type epoxy resin; epoxy resin containing epoxy groups such as polymethyl (glycidoxypropyl) silicone, etc., but not limited to this. Specifically, Epiclon (registered trademark) 850-S, Epiclon (registered trademark) HP-4032, Epiclon (registered trademark) HP-7200, Epiclon (registered trademark) HP-820, Epiclon (registered trademark) HP-4700 , Epiclon (registered trademark) EXA-4710, Epiclon (registered trademark) HP-4770, Epiclon (registered trademark) EXA-859CRP, Epiclon (registered trademark) EXA-1514, Epiclon (registered trademark) EXA-4880, Epiclon (registered trademark) ) EXA-4850-150, Epiclon EXA-4850-1000, Epiclon (registered trademark) EXA-4816, Epiclon (registered trademark) EXA-4822 (the above are product names, manufactured by DIC Corporation), Rikaresin (registered trademark) BE0-60E (Product name, Japan Chemical Co., Ltd.), EP-4003S, EP-4000S (ADEKA CORPORATION), etc. Among them, from the viewpoints of suppressing warpage and excellent heat resistance, epoxy resins containing polyoxyethylene groups are preferred. For example, Epiclon (registered trademark) EXA-4880, Epiclon (registered trademark) EXA-4822, and Rikaresin (registered trademark) BE0-60E contain polyoxyethylene groups and are therefore preferred.

The epoxy compound is preferably 5 to 50 parts by mass relative to 100 parts by mass of the resin, more preferably 10 to 50 parts by mass, and even more preferably 10 to 40 parts by mass. The compounding amount is 5 parts by mass or more to further suppress the warpage of the cured film, and 50 parts by mass or less can further suppress pattern embedding due to reflow during curing.

(Oxetane compound (compound with oxetanyl group)) Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl -3-hydroxymethoxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2 -Ethylhexyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. As a specific example, Aron Oxetane series manufactured by TOAGOSEI CO., LTD. (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, and these can be used alone or in combination. More than species.

The oxetane compound system is preferably 5-50 parts by mass, more preferably 10-50 parts by mass, and still more preferably 10-40 parts by mass relative to 100 parts by mass of polyimide precursors and the like.

(Benzoxazine compounds (compounds with benzoxazole groups)) Regarding benzoxazine compounds, due to the cross-linking reaction derived from the ring-opening addition reaction, no outgassing occurs during curing, thereby reducing heat shrinkage and inhibiting Warpage occurs, so it is preferable.

As preferred examples of the benzoxazine compound, Ba-type benzoxazine, Bm-type benzoxazine (the product name above, manufactured by Shikoku Chemicals Corporation), and benzoxazine addition of polyhydroxystyrene resin can be cited. Product, phenol novolac type dihydrobenzoxazine compound. These can be used alone, or two or more of them can be mixed and used.

With respect to 100 parts by mass of the resin, the benzoxazine compound is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and more preferably 10 to 40 parts by mass.

<<<Photopolymerization initiator>>> The photosensitive resin composition may contain a photopolymerization initiator. In particular, since the photosensitive resin composition contains a photoradical polymerization initiator, the photosensitive resin composition is applied to a substrate such as a semiconductor wafer to form a photosensitive resin composition layer, and then light is irradiated to generate radicals. It causes hardening and can reduce the solubility in the light-irradiated part. Therefore, for example, there is an advantage that by exposing the photosensitive resin composition layer through a light mask having a pattern for shielding only the electrode portion, it is possible to easily create regions with different solubility in accordance with the electrode pattern.

The photopolymerization initiator is not particularly limited as long as it has the ability to start the polymerization reaction (crosslinking reaction) of the polymerizable compound, and it can be appropriately selected from known photopolymerization initiators. For example, it is preferable that the light from the ultraviolet region has sensitivity to the visible region. In addition, it can be an active agent that has some effects with light-excited sensitizers and generates active free radicals. The photopolymerization initiator preferably contains at least one compound having at least about 50 molar absorption coefficient in the range of about 300 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of the compound can be measured by a known method. Specifically, for example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L.

As the photopolymerization initiator, a known compound can be used arbitrarily, for example, halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, those having a trihalomethyl group, etc.), phosphine oxides Oxime compounds such as phosphine compounds, hexaarylbiimidazole, oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone , Azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron arene complexes, etc.

Examples of halogenated hydrocarbon compounds having a triazine skeleton include compounds described in Wakabayashi et al., "Bull. Chem. Soc. Japan", 42, 2924 (1969), British Patent No. 1388492 The compound described in the specification, the compound described in Japanese Patent Laid-Open No. 53-133428, the compound described in the specification of German Patent No. 3337024, FC Schaefer et al. "Journal of Organic Chemistry (J. Org) Chem.)", 29, 1527 (1964), the compound described in JP 62-58241, the compound described in JP 5-281728, JP H The compound described in 5-34920 gazette, the compound described in the specification of US Patent No. 4,212,976, etc.

As the compound described in the specification of U.S. Patent No. 4212976, for example, a compound having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2- Trichloromethyl-5-(4-chlorophenyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(1-naphthyl)-1,3,4-oxadiazole , 2-Trichloromethyl-5-(2-naphthyl)-1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2 -Tribromomethyl-5-(2-naphthyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2- Trichloromethyl-5-(4-chlorostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-methoxystyryl)-1,3, 4-oxadiazole, 2-trichloromethyl-5-(4-n-butoxystyryl)-1,3,4-oxadiazole, 2-tribromomethyl-5-styryl- 1,3,4-oxadiazole etc.) etc.

In addition, examples of photopolymerization initiators other than those described above include compounds described in paragraph 0086 of Japanese Patent Application Publication No. 2015-087611, Japanese Patent Application Publication No. 53-133428, Japanese Patent Application Publication No. 57-1819, and Japan The compounds described in Japanese Patent Publication No. 57-6096 and US Patent No. 3615455 are incorporated into this specification.

As the ketone compound, for example, the compound described in paragraph 0087 of JP 2015-087611 A is exemplified, and the content is incorporated in this specification. KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used among commercially available products.

As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and phosphine compounds can also be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in JP-A No. 10-291969 and the phosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used. As the hydroxyacetophenone-based initiator, IRGACURE-184 (IRGACURE is a registered trademark), DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (product names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, IRGACURE-907, IRGACURE-369, and IRGACURE-379 (product names: all manufactured by BASF Corporation) that are commercially available products can be used. As the aminoacetophenone-based initiator, it is also possible to use compounds described in Japanese Patent Application Laid-Open No. 2009-191179 whose maximum absorption wavelength matches the wavelength of 365 nm or 405 nm. Examples of the phosphine-based initiator include 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide. In addition, IRGACURE-819 or IRGACURE-TPO (product name: both manufactured by BASF Corporation), which are commercially available products, can be used. As a metallocene compound, IRGACURE-784 (made by BASF Corporation) etc. are illustrated.

As the photopolymerization initiator, an oxime compound is more preferred. By using oxime compounds, exposure latitude can be further effectively improved. Among the oxime ester-based compounds, the exposure latitude (exposure margin) is relatively wide, and it also functions as a thermal base generator, so it is particularly preferred. As specific examples of the oxime compound, the compounds described in JP 2001-233842, the compounds described in JP 2000-80068, and the compounds described in JP 2006-342166 can be used. . As a preferable oxime compound, for example, a compound having the following structure, 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3 -Propionyloxyiminobutan-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one , 2-benzyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyl Oxyimino-1-phenylpropan-1-one, etc. [Chemical formula 36]

Examples of oxime compounds include JCS Perkin II (1979) p p.1653-1660, JCS Perkin II (1979) pp.156-162, Journal of Photopolymer Science and Technology (1995) pp.202-232. Compounds described in the literature, compounds described in JP 2000-66385, JP 2000-80068, JP 2004-534797, JP 2006-342166, International Publication Compounds and the like described in each publication of WO2015/036910. Among the commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are made by BASF), ADEKA OPTOMER N-1919 (made by ADEKA CORPORATION, JP 2012-14052) The photopolymerization initiator described in the No. 2). In addition, TR-PBG-304 (manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.), ADEKA ARKLS NCI-831 and ADEKA ARKLS NCI-930 (manufactured by ADEKA Corporation) can be used. In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can also be used.

In addition, it is possible to use the compound described in Japanese Patent Publication No. 2009-519904 in which an oxime is linked to the N position of the carbazole ring, and the compound described in U.S. Patent No. 7626957 in which a heterosubstituent is introduced at the benzophenone site The compound, the compound described in JP 2010-15025 A and U.S. Patent Publication No. 2009-292039, the ketoxime compound described in International Publication WO2009-131189, in which the nitro group is introduced into the pigment site, in the molecule The compound described in U.S. Patent No. 7556910 containing a triazine skeleton and an oxime skeleton, the compound described in Japanese Patent Application Laid-Open No. 2009-221114, etc. having a maximum absorption at 405 nm and having good sensitivity to a g-ray light source. In addition, the cyclic oxime compounds described in JP 2007-231000 A and JP 2007-322744 A can be preferably used. From the viewpoint of high light absorption and high sensitivity, among the cyclic oxime compounds, in particular, the condensed carbazole dyes described in JP 2010-32985 A and 2010-185072 The cyclic oxime compound is also preferred. In addition, the compound described in JP 2009-242469 A, which is a compound having an unsaturated bond at a specific site of the oxime compound, can also be preferably used. Furthermore, an oxime compound having a fluorine atom can also be used. Specific examples of such oxime compounds include the compounds described in JP 2010-262028 A, the compounds 24, 36-40, and the compounds described in paragraph 0345 of JP 2014-500852 A. The compound (C-3) and the like described in paragraph 0101 of the 2013-164471 Bulletin. As the best oxime compound, oxime compounds having specific substituents shown in JP 2007-269779 A, and oxime compounds having a sulfur aryl group shown in JP 2009-191061 Wait.

式（I）中，R⁵⁰ 係碳數1～20的烷基；因1個以上的氧原子而中斷之碳數2～20的烷基；碳數1～12的烷氧基；苯基；由碳數1～20的烷基、碳數1～12的烷氧基、鹵素原子、環戊基、環己基、碳數1～12的烯基、因1個以上的氧原子而中斷之碳數2～18的烷基及碳數1～4的烷基中的至少一個取代之苯基或聯苯基，R⁵¹ 係由式（II）表示之基團，或者係與R⁵⁰ 相同的基團，R⁵² ～R⁵⁴ 各自獨立地係碳數1～12的烷基、碳數1～12的烷氧基或鹵素。 [化學式38]

式中，R⁵⁵ ～R⁵⁷ 與上述式（I）的R⁵² ～R⁵⁴ 相同。From the viewpoint of exposure sensitivity, the photopolymerization initiator is selected from the group consisting of trihalomethyl triazine compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, and phosphines. Compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene -Benzene-iron complexes and their salts, halomethyl oxadiazole compounds, and 3-aryl substituted coumarin compounds. More preferred photopolymerization initiators are selected from the group consisting of trihalomethyl triazine compounds, α-amino ketone compounds, phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, Onium salt compounds, benzophenone compounds, acetophenone compounds, particularly preferably selected from trihalomethyl triazine compounds, α-amino ketone compounds, oxime compounds, triaryl imidazole dimers, and benzophenone compounds At least one compound in the group is further preferred, metallocene compounds or oxime compounds are further preferred, and oxime compounds are particularly preferred. In addition, the photopolymerization initiator can also use N,N'-tetraalkyl groups such as benzophenone and N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler’s ketone). -4,4'-Diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-methyl-1 -[4-(Methylthio)phenyl]-2-morpholinyl-acetone-1 and other aromatic ketones, alkylanthraquinones and other quinones condensed with aromatic rings, benzoin such as benzoin alkyl ether Benzoin compounds such as ether compounds, benzoin and alkylbenzoin, benzyl derivatives such as benzyl dimethyl ketal, etc. In addition, a compound represented by the following formula (I) can also be used. [Chemical formula 37]

In formula (I), R ⁵⁰ is an alkyl group having 1 to 20 carbon atoms; an alkyl group having 2 to 20 carbon atoms interrupted by more than one oxygen atom; an alkoxy group having 1 to 12 carbon atoms; a phenyl group; Alkyl with 1 to 20 carbons, alkoxy with 1 to 12 carbons, halogen atom, cyclopentyl, cyclohexyl, alkenyl with 1 to 12 carbons, carbon interrupted by more than one oxygen atom A phenyl group or biphenyl group substituted with at least one of an alkyl group having 2 to 18 and an alkyl group having 1 to 4 carbons, R ⁵¹ is a group represented by formula (II), or the same group as R ⁵⁰ Groups, R ⁵² to R ⁵⁴ are each independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or halogen. [Chemical formula 38]

In the formula, R ⁵⁵ to R ⁵⁷ are the same as R ⁵² to R ^{54 in the} above formula (I).

In addition, the photopolymerization initiator can also use the compound described in paragraphs 0048 to 0055 of International Publication WO2015/125469.

When the photosensitive resin composition contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1-30% by mass relative to the total solid content of the photosensitive resin composition, and more preferably 0.1-20% by mass , More preferably, it is 0.1-10 mass %. Only one type of photopolymerization initiator may be used, or two or more types may be used. When two or more types of photopolymerization initiators are used, the total amount is preferably in the above range.

<<<Migration inhibitor>>> It is preferable that the photosensitive resin composition further contains a migration inhibitor. By including the migration inhibitor, it is possible to effectively suppress the transfer of metal ions originating from the metal layer (metal wiring) into the photosensitive resin composition layer. The migration inhibitor is not particularly limited, and examples include heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring). Ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazine ring, etc.). Thioureas and mercapto compounds, hindered phenol compounds, salicylic acid derivative compounds, and hydrazino derivative compounds. In particular, triazole-based compounds such as triazole and benzotriazole, and tetrazole-based compounds such as tetrazole and benzotetrazole can be preferably used.

In addition, ion scavengers that trap anions such as halogen ions can also be used.

As other migration inhibitors, the antiseptic agents described in paragraph 0094 of JP 2013-15701 A, the compounds described in paragraphs 0073 to 0076 of JP 2009-283711, and JP 2011 can be used. The compound described in paragraph 0052 of -59656, the compound described in paragraph 0114, paragraph 0116, and paragraph 0118 of JP 2012-194520, etc.

Specific examples of migration inhibitors include 1H-1,2,3-triazole and 1H-tetrazole.

When the photosensitive resin composition has a migration inhibitor, the content of the migration inhibitor relative to the total solid content of the photosensitive resin composition is preferably 0.01 to 5.0 mass%, more preferably 0.05 to 2.0 mass%, and 0.1 to 1.0% by mass is more preferable. There may be only one type of migration inhibitor, or two or more types. When there are two or more migration inhibitors, it is preferable that the total of them is in the above range.

<<<Polymerization inhibitor>>> The photosensitive resin composition used in this embodiment preferably contains a polymerization inhibitor. As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-tertiary butyl-p-cresol, pyrogallol, p-tert-butylcatechol, p- Benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tertiary butylphenol), 2,2'-methylenebis(4-methyl-6 -Tertiary butyl phenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, N-phenylenediphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-Cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1 -Nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamine)phenol, N-nitroso -N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tertiarybutyl)phenylmethane, etc. In addition, the polymerization inhibitor described in paragraph 0060 of JP 2015-127817 A and the compound described in paragraphs 0031 to 0046 of International Publication WO2015/125469 can also be used. When the composition has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass relative to the total solid content of the photosensitive resin composition. The polymerization inhibitor may be only one type or two or more types. When there are two or more kinds of polymerization inhibitors, it is preferable that the sum total is the above range.

<<<Thermal alkali generator>>> The photosensitive resin composition used in this embodiment may contain a thermal alkali generator. The type of the thermal base generator is not particularly limited, and it is preferable to include a thermal base generator. The thermal base generator includes an acidic compound selected from the group that generates a base heated to 40°C or higher and those having a pKa1 of 0-4 At least one of ammonium salt of anion and ammonium cation. Here, pKa1 represents the logarithm (-Log ₁₀ Ka) of the dissociation constant (Ka) of the first proton of the acid, and the details will be described later. By blending these compounds, the cyclization reaction of the polyimide precursor and the polybenzoxazole precursor can be performed at low temperature, and a composition with more excellent stability can be obtained. In addition, the thermal alkali generator does not generate alkali as long as it is not heated. Therefore, even if it coexists with polyimide precursors and polybenzoxazole precursors, it can suppress the polyimide precursors and polyimide precursors during storage. The cyclization of polybenzoxazole precursors, etc., makes storage stability more excellent.

The thermal base generator preferably contains at least one selected from the group consisting of acidic compounds (A1) that generate bases when heated to 40°C or higher, and ammonium salts (A2) of anions with pKa1 of 0-4 and ammonium cations (A2). Regarding the acidic compound (A1) and the ammonium salt (A2), when heated, an alkali is generated. Therefore, the alkali generated by these compounds can promote the improvement of polyimide precursors and polybenzoxazole precursors. Cyclization reaction, and can perform cyclization of polyimide precursors and polybenzoxazole precursors at low temperature. In addition, with regard to these compounds, even if they coexist with polyimide precursors and polybenzoxazole precursors that are cyclized and hardened by an alkali, the polyimide precursors and polybenzoxazole precursors are hardly performed as long as they are not heated. Cyclization of polybenzoxazole precursors, etc., makes it possible to prepare photosensitive resin compositions containing polyimide precursors and polybenzoxazole precursors with excellent stability. In addition, in this specification, an acidic compound refers to a compound whose value is less than 7 by measuring the following solution at 20°C with a pH (power of hydrogen) meter. The solution is to extract 1g of the compound into a container and add 50ml of ions The mixed solution of exchange water and tetrahydrofuran (mass ratio of water/tetrahydrofuran=1/4) is obtained by stirring at room temperature for 1 hour.

In this embodiment, the alkali generation temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40°C or higher, and more preferably 120 to 200°C. The upper limit of the alkali generation temperature is preferably 190°C or lower, more preferably 180°C or lower, and even more preferably 165°C or lower. The lower limit of the alkali generation temperature is preferably 130°C or higher, and more preferably 135°C or higher. As long as the alkali generation temperature of the acidic compound (A1) and ammonium salt (A2) is 120°C or higher, it is not easy to generate alkali during storage. Therefore, it is possible to prepare polyimide precursors and polybenzoxazole precursors with excellent stability Photosensitive resin composition such as objects. As long as the alkali generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 200° C. or lower, the cyclization temperature of the polyimide precursor and the polybenzoxazole precursor can be lowered. Regarding the alkali generation temperature, for example, differential scanning calorimetry can be used to heat the compound in a pressure-resistant capsule at 5°C/min to 250°C, read the peak temperature of the lowest heat generation peak, and use the peak temperature as the alkali Generate temperature for measurement.

In this embodiment, alkali-based secondary amines or tertiary amines produced by thermal alkali generators are preferred, and tertiary amines are more preferred. The tertiary amine has high basicity, so it can further reduce the cyclization temperature of the polyimine precursor and the polybenzoxazole precursor. In addition, the boiling point of the alkali produced by the thermal alkali generator is preferably 80°C or higher, more preferably 100°C or higher, and more preferably 140°C or higher. In addition, the molecular weight of the base generating base is preferably 80 to 2,000. More preferably, the lower limit is 100 or more. The upper limit is more preferably 500 or less. In addition, the value of the molecular weight is the theoretical value obtained from the structural formula.

In this embodiment, the acidic compound (A1) preferably contains one or more selected from the group consisting of ammonium salts and compounds represented by formula (101) or (102) described later.

In this embodiment, the above-mentioned ammonium salt (A2)-based acidic compound is preferable. In addition, the above-mentioned ammonium salt (A2) may be a compound containing an acidic compound that generates a base when heated to 40°C or higher (preferably 120-200°C), or may be a compound other than heating to 40°C or higher (preferably 120-200°C). ℃) when it produces alkali compounds other than acidic compounds.

式（101）及式（102）中，R¹ ～R⁶ 分別獨立地表示氫原子或烴基，R⁷ 表示烴基。式（101）及式（102）中的R¹ 與R² 、R³ 與R⁴ 、R⁵ 與R⁶ 、R⁵ 與R⁷ 可以分別鍵結而形成環。In this embodiment, the ammonium salt means a salt of an ammonium cation and an anion represented by the following formula (101) or (102). The anion may be bonded to any part of the ammonium cation by a covalent bond, or it may be present outside the molecule of the ammonium cation, but it is preferred to have it outside the molecule of the ammonium cation. In addition, the presence of the anion outside the molecule of the ammonium cation means that the ammonium cation and the anion are not bonded by a covalent bond. Hereinafter, the anion outside the molecule of the cation part is also referred to as an anion. Formula (101) Formula (102) [Chemical formula 39]

In formula (101) and formula (102), R ¹ to R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, and R ⁷ represents a hydrocarbon group. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , and R ⁵ and R ^{7 in} formula (101) and formula (102) may be respectively bonded to form a ring.

The ammonium cation is preferably represented by any one of the following formulas (Y1-1) to (Y1-5). [Chemical formula 40]

In formulas (Y1-1) to (Y1-5), R ¹⁰¹ represents an n-valent organic group, and R ¹ and R ^{7 have the} same definitions as in formula (101) or formula (102). In formulas (Y1-1) to (Y1-5), Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group, n represents an integer of 1 or more, and m represents an integer of 0-5.

In this embodiment, it is preferable that the ammonium salt has an anion having a pKa1 of 0-4 and an ammonium cation. The upper limit of the pKa1 of the anion is more preferably 3.5 or less, and more preferably 3.2 or less. The lower limit is preferably 0.5 or more, and more preferably 1.0 or more. As long as the pKa1 of the anion is in the above range, it is possible to cyclize polyimide precursors and polybenzoxazole precursors at low temperatures, and furthermore, it is possible to increase the inclusion of polyimide precursors and polybenzoxazole precursors. Stability of photosensitive resin compositions such as materials. As long as pKa1 is 4 or less, the stability of the thermal alkali generator is good, and the generation of alkali is suppressed without heating, and a photosensitive resin composition containing polyimide precursors and polybenzoxazole precursors, etc. The stability of the material is good. As long as pKa1 is 0 or more, the generated alkali is not easily neutralized, and the cyclization efficiency of the polyimide precursor and the polybenzoxazole precursor is good. The type of anion is preferably one selected from the group consisting of carboxylic acid anion, phenol anion, phosphoric acid anion, and sulfuric acid anion, and carboxylic acid anion is more preferable from the viewpoint of compatibility of salt stability and thermal decomposition. That is, a salt of an ammonium cation and a carboxylic anion is more preferable. The carboxylic acid anion is preferably an anion of a divalent or more carboxylic acid having two or more carboxyl groups, and more preferably an anion of a divalent carboxylic acid. According to this aspect, it can be used as a thermal alkali generator that can further improve the stability, curability, and developability of a photosensitive resin composition including a polyimide precursor and a polybenzoxazole precursor. In particular, by using an anion of a divalent carboxylic acid, it is possible to further improve the stability, curability, and developability of a photosensitive resin composition including a polyimide precursor and a polybenzoxazole precursor. In this embodiment, the anion of the carboxylic acid whose pKa1 of the carboxylic acid anion system is 4 or less is preferable. The pKa1 is more preferably 3.5 or less, and more preferably 3.2 or less. According to this aspect, the stability of the photosensitive resin composition including the polyimide precursor, the polybenzoxazole precursor, and the like can be further improved. Thereto, and pKa1 of the solution represents a first proton acid dissociation constant of the reciprocal, and can see the Determination of Organic Structures by Physical Methods (OF: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; codification: Braude, EA, Nachod, FC; Academic Press, New York, 1955), Data for Biochemical Research (OF: Dawson, RMCet al; Oxford, Clarendon Press, 1959 values) described in the. For compounds not described in these documents, the value calculated by the structural formula using software using ACD/pKa (manufactured by ACD/Labs) was used.

式（X1）中，EWG表示吸電子基。The carboxylic acid anion is preferably represented by the following formula (X1). [Chemical formula 41]

In formula (X1), EWG represents an electron withdrawing group.

In the present embodiment, the electron withdrawing group refers to a Hammett substituent constant σm showing a positive value. Among them, σm is described in detail in Tono Ooto, Journal of Synthetic Organic Chemistry, Japan Volume 23, No. 8 (1965) p.631-642. In addition, the electron withdrawing group in this embodiment is not limited to the substituent described in the above-mentioned document. Examples of substituents whose σm represents a positive value include CF ₃ groups (σm=0.43), CF ₃ CO groups (σm=0.63), HC≡C groups (σm=0.21), CH ₂ =CH groups ( σm=0.06), Ac group (σm=0.38), MeOCO group (σm=0.37), MeCOCH=CH group (σm=0.21), PhCO group (σm=0.34), H ₂ NCOCH ₂ group (σm=0.06), etc. . In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group.

式（EWG-1）～（EWG-6）中，R^x1 ～R^x3 分別獨立地表示氫原子、烷基、烯基、芳基、羥基或羧基，Ar表示芳香族基團。EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6). [Chemical formula 42]

In the formulas (EWG-1) to (EWG-6), R ^x1 to R ^x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group, or a carboxyl group, and Ar represents an aromatic group.

式（XA）中，L¹⁰ 表示選自單鍵或伸烷基、伸烯基、芳香族基團、-NR^X -及它們的組合中之2價連接基，R^X 表示氫原子、烷基、烯基或芳基。In this embodiment, the carboxylic acid anion is preferably represented by the following formula (XA). Formula (XA) [Chemical formula 43]

In the formula (XA), L ¹⁰ represents a divalent linking group selected from a single bond or an alkylene group, an alkenylene group, an aromatic group, -NR ^X -and a combination thereof, and R ^X represents a hydrogen atom, an alkyl group , Alkenyl or aryl.

Specific examples of the carboxylic acid anion include maleic acid anion, phthalic acid anion, N-phenyliminodiacetic acid anion, and oxalic acid anion. These can be used preferably.

[化學式45]

As specific examples of the thermal base generator, the following compounds can be cited. [Chemical formula 44]

[Chemical formula 45]

[Chemical formula 46]

When a thermal alkali generator is used, the content of the thermal alkali generator in the photosensitive resin composition is preferably 0.1 to 50% by mass relative to the total solid content of the photosensitive resin composition. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and more preferably 20% by mass or less. One kind or two or more kinds of thermal base generators can be used. When two or more are used, the total amount is preferably in the above-mentioned range.

金屬黏附性改良劑相對於樹脂100質量份較佳為0.1～30質量份，更佳為0.5～15質量份的範圍。藉由設為0.1質量份以上，硬化製程後的硬化膜與金屬層的黏附性變良好，藉由設為30質量份以下，硬化製程後的硬化膜的耐熱性、機械特性變良好。 <<<Metal adhesion improver>>> The photosensitive resin composition used in the present embodiment preferably contains a metal adhesion improver for improving the adhesion to metal materials used in electrodes, wiring, and the like. Examples of the metal adhesion improver include the sulfides described in paragraphs 0046 to 0049 of JP 2014-186186 and paragraphs 0032 to 0043 of JP 2013-072935. As the metal adhesion improver, the following compounds (N-[3-(triethoxysilyl)propyl] maleic acid monoamide etc.) are also exemplified. [Chemical formula 47]

The metal adhesion modifier is preferably in the range of 0.1 to 30 parts by mass, and more preferably in the range of 0.5 to 15 parts by mass with respect to 100 parts by mass of the resin. By setting it as 0.1 parts by mass or more, the adhesion between the cured film and the metal layer after the curing process becomes good, and by setting it as 30 parts by mass or less, the heat resistance and mechanical properties of the cured film after the curing process become better.

The metal adhesion modifier may be only one type or two or more types. When two or more are used, it is preferable that the sum total is the above-mentioned range.

<<<Solvent>>>

When the photosensitive resin composition used in this embodiment is formed into a layer by coating, it is preferable to blend a solvent. Regarding the solvent, any known ones can be used as long as the photosensitive resin composition can be formed into a layered form. Examples of solvents include compounds such as esters, ethers, ketones, aromatic hydrocarbons, and sulfites.

As esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl Butyl acid, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxy acetate (example: methyl alkoxy acetate, alkoxy Ethyl acetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, methoxybutyl, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-Alkoxy propionic acid alkyl esters (e.g. 3-alkoxy methyl propionate, 3-alkoxy ethyl propionate, etc. (e.g., 3-methoxy propionate methyl, 3-methyl Ethyl oxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionate (e.g. 2-alkoxypropionate) Methyl ester, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methyl Propyl oxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and 2-oxo-2 -Ethyl methyl propionate (for example, methyl 2-methoxy-2-methyl propionate, ethyl 2-ethoxy-2-methyl propionate, etc.), methyl pyruvate, ethyl pyruvate Ester, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc. As the ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl siloxol acetate, ethyl siloxol Acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetic acid Ester, propylene glycol monopropyl ether acetate, etc. As the ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc. are preferably mentioned. As aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc. are preferably mentioned.

Regarding the solvent, from the viewpoint of improving the properties of the coating surface, etc., a form in which two or more types are mixed is also preferable. Among them, it is selected from the group consisting of 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, ethyl cyrus acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, Methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol ethyl A mixed solution composed of two or more of acid ester, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable. It is particularly preferred to use both dimethyl sulfoxide and γ-butyrolactone.

When the photosensitive resin composition has a solvent, regarding the content of the solvent, from the viewpoint of coatability, the total solid content concentration of the photosensitive resin composition is preferably 5 to 80% by mass, 5 to 70% by mass is more preferable, and 10 to 60% by mass is particularly preferable. The solvent content can be adjusted by the coating method according to the desired thickness. For example, as long as the coating method is a spin coating method or a slit coating method, the content of the solvent having the solid content concentration in the above-mentioned range is preferable. As long as it is a spray method, it is preferable to set it as 0.1 mass%-50 mass %, and it is preferable to set it as 1.0 mass%-25 mass %. By adjusting the amount of the solvent by the coating method, a photosensitive resin composition layer with a desired thickness can be uniformly formed. The solvent may be only one type or two or more types. When two or more types of solvents are used, it is preferable that the sum total is the above range. Also, from the viewpoint of film strength, the content of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide and N,N-dimethylformamide It is preferably less than 5% by mass relative to the total mass of the photosensitive resin composition, more preferably less than 1% by mass, more preferably less than 0.5% by mass, and still more preferably less than 0.1% by mass.

＜＜＜Other additives＞＞＞ The photosensitive resin composition used in this embodiment can be used for various additives, such as photobase generators, thermal polymerization initiators, as required, within the range that does not impair the effects of the present invention. Agents, thermal acid generators, silane coupling agents, sensitizing dyes, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic particles, hardeners, hardening catalysts, fillers, antioxidants, ultraviolet absorbers, aggregation inhibitors Agent, etc. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the composition.

(Photobase generator) The photosensitive resin composition used in this embodiment may contain a photobase generator. Photobase generators are those that generate alkali by exposure and do not show activity under normal temperature and pressure conditions. However, if they are irradiated and heated by electromagnetic waves as an external stimulus, there is nothing special as long as they generate alkali (alkaline substances). limited. The base generated by exposure functions as a catalyst when the polyimide precursor and the benzoxazole precursor are hardened by heating, and therefore can be preferably used in the negative type.

The content of the photobase generator is not particularly limited as long as it can form a desired pattern, and can be set to a normal content. The photobase generator is preferably within the range of 0.01 parts by mass or more and less than 30 parts by mass relative to 100 parts by mass of the resin, more preferably within the range of 0.05 parts by mass to 25 parts by mass, and is preferably 0.1 parts by mass to 20 parts by mass Within the range of is further preferred. The photobase generator may be one type or two or more types. When there are two or more photobase generators, the total range is preferably the above range. In this embodiment, what is known as a photobase generator can be used. For example, such as M. Shirai, and M. Tsunooka, Prog. Polym. Sci., 21, 1 (1996); Kadooka Masahiro, Polymer Processing, 46, 2 (1997); C. Kutal, Coord. Chem. Rev .,211,353(2001); Y.Kaneko,A.Sarker, and D.Neckers,Chem.Mater.,11,170(1999); H.Tachi,M.Shirai, and M.Tsunooka,J.Photopolym.Sci.Technol .,13,153(2000); M.Winkle, and K.Graziano,J.Photopolym.Sci.Technol.,3,419(1990); M.Tsunooka,H.Tachi, and S.Yoshitaka,J.Photopolym.Sci.Technol ., 9, 13 (1996); K. Suyama, H. Araki, M. Shirai, J. Photopolym. Sci. Technol., 19, 81 (2006), as described in the migration metal compound complex, having Structures such as ammonium salts, such as those where the amidino moiety is latentized by forming carboxylic acids and salts, ionic compounds, urethane derivatives, and oxime esters in which alkali components are neutralized by forming salts Nonionic compounds such as urethane bonds or oxime bonds, such as compounds, acyl compounds, etc., with alkali components latentized. The photobase generator that can be used in the present embodiment is not particularly limited, and known ones can be used. For example, carbamate derivatives, amide derivatives, imine derivatives, α-cobalt complexes, and imidazoles can be used. Derivatives, cinnamic acid amide derivatives, oxime derivatives, etc. Examples of photobase generators include photobase generators having a cinnamic acid amide structure as disclosed in Japanese Patent Application Publication No. 2009-80452 and International Publication No. WO2009/123122, such as those disclosed in Japanese Patent Application Publication No. 2006-189591 A photobase generator having a urethane structure as disclosed in Japanese Patent Application Publication No. 2008-247747 and Japanese Patent Application Publication No. 2008-247747 has an oxime as disclosed in Japanese Patent Application Publication No. 2007-249013 and Japanese Patent Application Publication No. 2008-003581 Although it is not limited to the photobase generator of a structure, a carbamate structure, etc., well-known photobase generators other than these can also be used. In addition, examples of photobase generators include the compounds described in paragraphs 0185 to 0188, 0199 to 0200, and paragraph 0202 of JP 2012-93746 A, and 0022 to JP 2013-194205 of JP 2013-194205. The compound described in paragraph 0069, the compound described in paragraphs 0026 to 0074 of JP 2013-204019 A, and the compound described in paragraph 0052 of International Publication WO2010/064631.

(Thermal polymerization initiator) The photosensitive resin composition used in this embodiment may contain a thermal polymerization initiator (preferably a thermal radical polymerization initiator). As the thermal radical polymerization initiator, a known thermal radical polymerization initiator can be used. The thermal radical polymerization initiator is a compound that generates free radicals by thermal energy and initiates or promotes the polymerization reaction of the polymerizable compound. By adding a thermal radical polymerization initiator, the polymerization reaction of the polymerizable compound can proceed when the cyclization reaction of the polyimide precursor and the polybenzoxazole precursor is performed. In addition, when the polyimide precursor and the polybenzoxazole precursor contain ethylenically unsaturated bonds, the cyclization and polyimide of the polyimide precursor and the polybenzoxazole precursor can be performed simultaneously The polymerization reaction of the precursor and the polybenzoxazole precursor can achieve a higher degree of heat resistance. As the thermal radical polymerization initiator, specifically, the compounds described in paragraphs 0074 to 0118 of JP 2008-63554 A can be cited.

When the photosensitive resin composition has a thermal radical polymerization initiator, the content of the thermal radical polymerization initiator relative to the total solid content of the photosensitive resin composition is preferably 0.1-50% by mass, 0.1-30% by mass % Is more preferable, and 0.1-20% by mass is particularly preferable. Moreover, it is preferable to contain 0.1-50 mass parts of thermal radical polymerization initiators with respect to 100 mass parts of polymerizable compounds, and it is more preferable to contain 0.5-30 mass parts. According to this aspect, a cured film with more excellent heat resistance can be easily formed. The thermal radical polymerization initiator may be one type or two or more types. When there are two or more thermal radical polymerization initiators, the total range is preferably the above range.

(Thermal acid generator) The photosensitive resin composition used in this embodiment may contain a thermal acid generator. The thermal acid generator generates acid by heating, promotes the cyclization of the polyimide precursor and the polybenzoxazole precursor, and improves the mechanical properties of the cured film. Furthermore, the thermal acid generator has the function of promoting crosslinking of at least one compound selected from the group consisting of a compound having a methylol group, an alkoxymethyl group or an oxymethyl group, an epoxy compound, an oxetane compound, and a benzoxazine compound The effect of the reaction.

Moreover, as the thermal acid generator, the compound described in paragraph 0059 of JP 2013-167742 A is also preferable.

The content of the thermal acid generator is preferably 0.01 parts by mass or more relative to 100 parts by mass of the polyimide precursor and polybenzoxazole precursor, and more preferably 0.1 parts by mass or more. Since the content is 0.01 parts by mass or more, the crosslinking reaction and the cyclization of the polyimide precursor and the polybenzoxazole precursor are promoted, and therefore, the mechanical properties and chemical resistance of the cured film can be further improved. Also, from the viewpoint of the electrical insulation of the cured film, the content is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and particularly preferably 10 parts by mass or less. Only one type of thermal acid generator may be used, or two or more types may be used. When two or more are used, the total amount is preferably in the above range.

(Silane Coupling Agent) The photosensitive resin composition used in the present embodiment may contain a silane coupling agent in order to improve the adhesion to the substrate. Examples of silane coupling agents include the compounds described in paragraphs 0062 to 0073 of JP 2014-191002, the compounds described in paragraphs 0063 to 0071 of International Publication WO2011/080992A1, and JP 2014 The compound described in paragraphs 0060 to 0061 of -191252, the compound described in paragraphs 0045 to 0052 of JP 2014-41264, and the compound described in paragraph 0055 of International Publication WO2014/097594. Furthermore, it is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP 2011-128358 A. The silane coupling agent is preferably in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass of the resin, and more preferably in the range of 1 to 10 parts by mass. If it is 0.1 parts by mass or more, sufficient adhesion to the substrate can be imparted, and if it is 20 parts by mass or less, problems such as increase in viscosity can be suppressed during storage at room temperature. Only one type of silane coupling agent may be used, or two or more types may be used. When two or more are used, the total amount is preferably in the above range.

(Sensitizing dye) The photosensitive resin composition used in this embodiment may contain a sensitizing dye. The sensitizing dye absorbs specific active radiation and becomes an electron excited state. The sensitizing dye in an electron-excited state comes into contact with an amine generator, a thermal radical polymerization initiator, a photopolymerization initiator, etc., to generate electron transfer, energy transfer, heat generation, and the like. Thereby, the amine generator, thermal radical polymerization initiator, and photopolymerization initiator cause chemical changes to decompose, and generate radicals, acids, or bases.

As an example of a preferable sensitizing dye, those belonging to the following compound classes and having an absorption wavelength in the region of 300 nm to 450 nm can be cited. For example, polynuclear aromatics (e.g., phenanthrene, anthracene, pyrene, perylene, terylene, 9.10-dialkoxy anthracene), xanthenes (e.g., fluorescein, eosin, erythrosine, rose red B, Rose Bengal), thioxanthones (for example, 2,4-diethylthioxanthone), cyanines (for example, thiocarbocyanine, oxacarbocyanine), merocyanines ( For example, merocyanine, carbocyanine), thiazides (such as thiazol, methylene blue, toluidine blue), acridines (such as acridine orange, chloroflavin, acriflavin), anthraquinones (Such as anthraquinone), squaraine ylides (such as squaraine ylide), coumarins (such as 7-diethylamino-4-methylcoumarin), styryl Benzene, stilbene benzene, carbazole, etc.

When the photosensitive resin composition contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01-20% by mass relative to the total solid content of the photosensitive resin composition, more preferably 0.1-15% by mass, 0.5-10 The mass% is more preferable. The sensitizing dye may be used alone, or two or more kinds may be used.

(Chain transfer agent) The photosensitive resin composition used in this embodiment may contain a chain transfer agent. The chain transfer agent is defined in, for example, pages 683-684 of the third edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005). As the chain transfer agent, for example, a compound group having SH, PH, SiH, and GeH in the molecule is used. These low-activity free radicals are supplied with hydrogen to generate free radicals, or after oxidation, free radicals can be generated by deprotonation. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazole Class etc.).

When the photosensitive resin composition has a chain transfer agent, the preferred content of the chain transfer agent is preferably 0.01-20 parts by mass, more preferably 1-10 parts by mass relative to 100 parts by mass of the total solid content of the photosensitive resin composition Parts by mass, particularly preferably 1 to 5 parts by mass. The chain transfer agent may be only one type or two or more types. When there are two or more chain transfer agents, the total range is preferably the above-mentioned range.

(Surfactant) From the viewpoint of improving coatability, various surfactants can be added to the photosensitive resin composition used in this embodiment. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicon-based surfactants can be used. In addition, the following surfactants are also preferable. [Chemical formula 48]

When the photosensitive resin composition has a surfactant, the content of the surfactant relative to the total solid content of the photosensitive resin composition is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass. The surfactant may be only one type or two or more types. When there are two or more surfactants, the total range is preferably the above-mentioned range.

(Higher fatty acid derivatives) In order to prevent polymerization inhibition due to oxygen, the photosensitive resin composition used in this embodiment may be coated with a higher fatty acid derivative such as behenic acid or behenic acid amide. It is locally present on the surface of the composition during the subsequent drying process. When the photosensitive resin composition has a higher fatty acid derivative, the content of the higher fatty acid derivative relative to the total solid content of the photosensitive resin composition is preferably 0.1 to 10% by mass. The higher fatty acid derivative may be only one type or two or more types. When there are two or more higher fatty acid derivatives, the total range is preferably the above-mentioned range.

＜＜＜Restrictions on other substances contained＞＞＞ From the viewpoint of coating surface properties, the photosensitive resin composition used in this embodiment preferably has a moisture content of less than 5% by mass, and more preferably less than 1% by mass Preferably, less than 0.6% by mass is particularly preferred.

From the viewpoint of insulation, the photosensitive resin composition used in this embodiment preferably has a metal content of less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and particularly preferably less than 0.5 mass ppm. . Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel, and the like. When a plurality of metals are contained, the total of these metals is preferably in the above range. In addition, as a method of reducing the metal impurities accidentally included in the photosensitive resin composition, it can be cited as a raw material constituting the photosensitive resin composition, selecting a raw material with a low metal content, and filtering the raw material constituting the photosensitive resin composition Filtration, lining the device with polytetrafluoroethylene, and distilling under the condition of suppressing pollution as much as possible.

From the viewpoint of wiring corrosivity, in the photosensitive resin composition used in this embodiment, the content of halogen atoms is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and particularly preferably less than 200 ppm by mass. Among them, less than 5 mass ppm is preferred in the state of halogen ions, less than 1 mass ppm is more preferred, and less than 0.5 mass ppm is particularly preferred. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of the chlorine atom and the bromine atom or the chloride ion and the bromide ion be in the above-mentioned ranges.

<<Drying process>> It can include a process of drying the solvent after applying the photosensitive resin composition in a layered form. The drying temperature is preferably 50 to 150°C, more preferably 70°C to 130°C, and even more preferably 90°C to 110°C. The drying time is preferably 30 seconds to 20 minutes, more preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.

<Exposure and Development Process> In this embodiment, the photosensitive resin film is exposed and developed to produce the resin pattern 3. The thickness of the resin pattern is the same as the thickness of the photosensitive resin film, and is preferably 0.1 to 100 μm, more preferably 1 to 50 μm, and more preferably 3 to 20 μm.

<<Exposure process>> The conditions of exposure are not particularly limited, but it is better to change the solubility of the developer with respect to the exposed portion of the photosensitive resin film, and it is more preferable that the exposed portion of the photosensitive resin film can be cured. For example, as for exposure, it is preferable to irradiate the photosensitive resin film with light having a wavelength of 500 nm or less. By irradiating light with a wavelength of 500 nm or less, it is possible to make it difficult to peel the photosensitive resin from the transparent substrate. The lower limit of the exposure wavelength is preferably 100 nm or more, more preferably 190 nm or more, and more preferably 240 nm or more. The upper limit of the exposure wavelength is preferably 500 nm or less, and more preferably 400 nm or less. Regarding the amount of exposure, the exposure energy at a wavelength of 365 nm is preferably 100 to 10000 mJ/cm ² , and more preferably 200 to 8000 mJ/cm ² .

At the time of exposure, in order to form a desired resin pattern, a mask 7 is preferably used. The aperture ratio of the mask can be appropriately set according to the desired pattern. In the case of negative development, the surface area of the removed part of the resin pattern formed by removing a part of the photosensitive resin film is preferably 30% or less of the surface area of all areas of the photosensitive resin film, and more preferably 25% or less. 20% or less is more preferable, 15% or less is more preferable, 10% or less is even more preferable, 5% or less is still more preferable, and 3% or less is particularly more preferable. By setting it in this range, the yield of the obtained molded product tends to be further improved. The lower limit of the ratio of the surface area of the removed portion of the resin pattern formed by removing a part of the photosensitive resin film to the surface area of all regions of the photosensitive resin film is not particularly limited, and can be set to 0.5% or more, for example. The size of the opening of the mask can be appropriately set depending on the use and the like, and an example of a mask such as an opening having a maximum length of 30 μm or less (preferably, a maximum length of 3 μm or more) is exemplified.

The gaps (openings) of the resin pattern formed in this embodiment are contact holes, locations where wiring is provided, locations where electrodes are provided, and the like. The wiring or electrode is formed by applying the metal mentioned later.

＜＜Development treatment process＞＞ The development treatment process can be a positive type development treatment or a negative type development treatment, but a negative type development treatment is preferable. By performing negative-tone development, the unexposed part (non-exposed part) is removed. The development method is not particularly limited, and it is preferable that a desired pattern can be formed. For example, a development method such as stirring, spraying, dipping, and ultrasonic can be used. The development is preferably performed using a developer. The developer can be used without particular limitation as long as the unexposed part (non-exposed part) is removed. Development using organic solvents is preferred. Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, butyl propionate, and isopropyl butyrate. , Ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxy acetate (example: alkoxy Methyl acetate, ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxy Ethyl acetate, etc.)), 3-alkoxypropionic acid alkyl esters (e.g. 3-alkoxy methyl propionate, 3-alkoxy ethyl propionate, etc. (e.g. 3-methoxy Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionate ( Examples: Methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, 2-methoxypropionate Ethyl propionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate Ester and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.) , Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ether Class, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone. Examples of aromatic hydrocarbons include toluene, xylene, anisole, limonene and the like. As the sulfenite, preferably dimethyl sulfenite can be cited. Among them, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methyl Methyl oxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, Propylene glycol methyl ether and propylene glycol methyl ether acetate are preferred, and cyclopentanone and γ-butyrolactone are more preferred. The development time is preferably 10 seconds to 5 minutes. The temperature during development is not particularly limited, and it can usually be performed at 20 to 40°C. After treatment with developer, it can be rinsed. Rinsing is preferably performed with a solvent different from the developer. For example, the solvent contained in the photosensitive resin composition can be used for rinsing. Preferably, the rinsing time is 5 seconds to 1 minute.

<Curing process> In this embodiment, after the exposure and development process, it is preferable to include a curing process before the transparent substrate peeling process. In addition, when the metal application process is included, it is preferable to include a curing process of curing the above-mentioned resin pattern before the metal application process. When the photosensitive resin film contains at least one selected from the group consisting of polyimide precursors and polybenzoxazole precursors, through the curing process, the polyimide precursor and polybenzoxazole precursor can be cured Cyclization reaction. In addition, even when the photosensitive resin film is made of polyimide or polybenzoxazole, it can be heated together with a crosslinking agent to form a three-dimensional network structure. Furthermore, when the photosensitive resin composition contains a radical polymerizable compound etc., hardening etc. of an unreacted radical polymerizable compound can also be performed. The curing process is generally performed by raising the temperature of the photosensitive resin film to a temperature higher than the glass transition temperature of the resin constituting the photosensitive resin film. In addition, it is preferable that the final temperature reached when the temperature is increased is as follows. That is, when the photosensitive resin film contains at least one selected from the group consisting of polyimide precursors and polybenzoxazole precursors, the photosensitive resin film Above the cyclization temperature of the resin contained in it. It is preferable that the final reached temperature when the temperature is increased is the highest heating temperature. As the maximum heating temperature, 100 to 500°C is preferred, 150 to 450°C is more preferred, and 160 to 350°C is even more preferred.

Regarding the temperature increase, it is preferable to proceed from a temperature of 20 to 150°C to the maximum heating temperature at a temperature increase rate of 1 to 12°C/min, more preferably 2 to 11°C/min, and still more preferably 3 to 10°C/min. By setting the heating rate to 1°C/min or more, it is possible to prevent excessive volatilization of amine while ensuring productivity, and by setting the heating rate to 12°C/min or less, the residual stress of the cured film can be relaxed. The temperature at the start of heating is preferably 20 to 150°C, more preferably 20 to 130°C, and more preferably 25 to 120°C. The temperature at the beginning of heating refers to the heating temperature at the beginning of the heating process up to the maximum heating temperature. For example, when the photosensitive resin composition is applied to the substrate and dried, the temperature after drying is, for example, the temperature is gradually increased from the boiling point of the solvent contained in the photosensitive resin composition-(30 to 200)°C For better.

Heating can be carried out in stages. As an example, the following pre-treatment process can be performed, that is, the temperature is raised at 3°C/min until 25°C to 180°C, the temperature is raised at 180°C for 60 minutes, and the temperature is raised at 2°C/min until 180°C to 200°C. Place at ℃ for 120 minutes. The heating system used as the pre-treatment process is preferably 100-200°C, more preferably 110-190°C, and most preferably 120-185°C. In the pretreatment process, it is also preferable to perform treatment while irradiating UV as described in US Patent No. 9159547. Through this pretreatment process, the characteristics of the cured film can be improved. The pretreatment process is preferably carried out in a relatively short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment process can be a two-stage or more step, for example, the pretreatment process 1 is performed at a range of 100-150°C, and then the pretreatment process 2 is performed at a range of 150-200°C.

The heating time is preferably 20 to 200 minutes, and more preferably 20 to 100 minutes.

In this embodiment, after the temperature is increased to the final temperature, it is preferable to perform heating at the final temperature for 30 to 360 minutes, and it is more preferable to be able to perform heating for 30 to 300 minutes, and to perform heating for 30 to 240 minutes. It is especially good.

In this embodiment, it is preferable to cool the photosensitive resin film after the heating process. The cooling rate is preferably 2°C/min or less, and more preferably 1°C/min or less. The cooling rate of the cooling process is preferably 0.1°C/min or more. The cooling time is preferably 30 to 600 minutes, more preferably 60 to 600 minutes, and particularly preferably 120 to 600 minutes.

The temperature after cooling is preferably lower than the glass transition temperature (Tg) of the photosensitive resin film after the curing process by 30° C. or more. If the temperature after cooling is lowered to a temperature that is 30°C or more lower than the Tg of the photosensitive resin film, the polyimide is sufficiently cured, and the occurrence of delamination is easily suppressed.

<Metal Application Process> In this embodiment, a process in which metal 4 is applied to a laminate having a transparent substrate 1 and a resin pattern 3 located on the surface of the transparent substrate is preferable. The metal 4 in this embodiment is preferably provided in the gap of the resin pattern 3 on the surface of the transparent substrate 1. The application method of the metal is not particularly limited, and an electroless plating method can be mentioned. Moreover, it can also be provided between the transparent substrate 1 and the resin pattern 3 on a transparent substrate. As an aspect of disposing a metal between the transparent substrate 1 and the resin pattern 3, the resin pattern 3 in a direction substantially perpendicular to the transparent substrate 1 between the surface of the transparent substrate 1 and the resin pattern 3 and on the transparent substrate 1 It is set between the resin pattern 3. When it is an electroless plating method, it is better to apply metal according to the following methods (1) and (2). (1) Immerse the laminate with the transparent substrate 1 and the resin pattern 3 in a plating tank containing an electroless plating solution, and form a metal layer (plating film) on the surface of the transparent substrate 1 and the surface of the resin pattern 3, respectively. The thickness of the metal layer at this time is preferably 0.1 to 100 μm, more preferably 1 to 20 μm, and particularly preferably 1 to 10 μm. The metal layer may be one layer, or two or more layers. (2) Next, unnecessary metal layers such as the metal layer provided on the surface of the resin pattern 3 among the metal layers are scraped off by polishing or the like to expose the resin pattern. For details of electroless plating, please refer to Nikkan Kogyo Shimbun: Electroplating Research Association "Basics of Electroplating" June 28, 2006, Nikkan Kogyo Shimbun: Electroplating Research Association "Next Generation Plating Technology" November 30, 2004 And incorporate these records into this manual. In addition, as another metal application method, vapor deposition or the like is exemplified. The thickness of the metal layer in this case is also preferably in the same range as in the case of the above-mentioned electroless plating method.

As the metal used in this embodiment, it is preferable to include at least one of copper, aluminum, nickel, vanadium, titanium, tantalum, chromium, cobalt, gold, silver, and tungsten. When electroless plating is performed, copper is special good. The metal can be one type or two types.

<Laminating Process> In this embodiment, the resin pattern 3 and the metal layer may be further laminated in plural layers. Specifically, after the metal application process, the process of manufacturing the resin pattern can be repeated again and again.

<Semiconductor element application process> In this embodiment, the process of applying the semiconductor element 5 may further be included. Specifically, it has a transparent substrate 1, a resin pattern 3 located on the surface of the transparent substrate, a metal 4 located on the surface of the transparent substrate with a gap between the resin pattern, and a semiconductor element 5 in contact with the metal, the semiconductor element 5 It is preferable to arrange it in such a way that it is in contact with the above-mentioned metal on the side opposite to the transparent substrate side. Here, the gap of the resin pattern refers to the area between the resin and the resin on the side where the resin pattern is provided on the transparent substrate, and refers to, for example, an opening obtained by exposing and developing a photosensitive resin. Moreover, when the resin pattern is laminated, it becomes an area between the resin and the resin on the surface of the resin pattern and/or metal of the lower layer. As a semiconductor element among these, a semiconductor wafer etc. are illustrated.

<Transparent substrate peeling process>

In this embodiment, the layered body 6 having the transparent substrate 1 and the resin pattern on the surface of the transparent substrate is irradiated from the transparent substrate side of the layered body with radiation, and the transparent substrate is peeled from the layered body. When the above-mentioned radiation light is irradiated, the absorbance of the resin pattern in the wavelength of the irradiated radiation light is set to 0.5 or more. With this structure, the surface vicinity of the transparent substrate side of the resin pattern is irradiated, so that the transparent substrate and the resin pattern can be peeled off. In addition, in the present embodiment, metal and the like are also present on the surface of the substrate, but the transparent substrate and the metal are generally weak in adhesion, so the metal also remains on the laminate side together with the resin pattern.

In this embodiment, the above-mentioned absorbance is 0.5 or more, preferably 0.8 or more, more preferably 1.0 or more, and even more preferably 1.2 or more. The upper limit of the above-mentioned absorbance is not particularly limited, and the higher the value, the better. For example, it is 9 or less, and furthermore, 6 or less, especially when it is 4 or less, the effect of the present invention can be sufficiently achieved.

The wavelength of the radiated light passes through the transparent substrate and is preferably absorbed by the resin pattern, so it can be appropriately set according to the material used. For example, it is necessary to ensure the transparency of quartz with a wide transmission wavelength. The lower limit is preferably 170 nm or more, more preferably 220 nm or more, and even more preferably 260 nm or more. Furthermore, the upper limit of the aforementioned wavelength is preferably 4000 nm or less, and more preferably 3000 nm or less.

The type of laser is not particularly limited. THG (Third Harmonic Generation) (355nm) of YAG laser (yttrium-aluminum-garnet laser) or KrF (248nm), XeCl (308nm), XeF in excimer lasers (351nm) is preferred.

When irradiating the radiant light, it is preferable to set the focus to a distance of ±10 μm from the interface between the transparent substrate 1 and the resin pattern 3. In addition, the laser light source is preferably in an area of 100 to 1,000,000 μm ² , the repetition frequency is 10 to 5000 Hz, and the scanning speed is preferably 0.1 to 1000 mm/s. The scanning pitch is preferably 1-100 μm. As the exposure amount, 0.5-50 J/cm ² is preferable.

Second Embodiment FIG. 2 is a schematic diagram showing the second embodiment. A seed layer 21 is provided on the surface of a transparent substrate 1, and a photoresist layer 22 is further provided on the surface of the seed layer. After exposure and development are performed to form a photoresist pattern 23, After the photoresist pattern 23 is removed by applying metal, the seed layer 21 is cut off to produce the metal pattern 24 (metal pattern forming process). Next, the resin pattern 3 is placed between the metal patterns 24 (resin pattern forming process). In addition, after applying the semiconductor element 5 (semiconductor element application process) from the side of the metal pattern 24 opposite to the transparent substrate 1 and irradiating radiation to meet prescribed conditions, the transparent substrate 1 can be peeled off from the laminate 6 (Transparent substrate peeling process). In this embodiment, in particular, the metal pattern forming process, the resin pattern forming process, the semiconductor device application process, and the transparent substrate peeling process are preferred. In addition, in FIG. 2, the same symbols are used for components common to those in FIG. 1 (the same symbols are used for FIG. 3 ). In the second embodiment, a semiconductor device having a metal (for example, metal wiring or electrode) in a gap between a resin pattern (for example, an insulating layer) and a semiconductor element (for example, a semiconductor wafer) in contact with the metal can be obtained. Hereinafter, the second embodiment will be described in more detail.

<Metal Pattern Forming Process> In this embodiment, a process of forming the metal pattern 24 is included. In the process of forming the metal pattern, for example, a seed layer forming process, a photoresist pattern forming process, a metal application process, a photoresist pattern, and a seed layer removal process are preferable.

<<Seed Layer Formation Process>> In the second embodiment, a seed layer 21 is provided on the surface of the transparent substrate 1. The details of the transparent substrate are the same as in the first embodiment, and the preferred range is also the same. The seed layer is preferably formed by sputtering, CVD (chemical vapor deposition), electroless plating, or the like. As the material of the seed layer, tin, silver, and copper are exemplified. The thickness of the seed layer is preferably 0.02 to 2 μm.

<<Photoresist pattern forming process>> In the second embodiment, on the seed layer 21, it is preferable to provide a photoresist layer 22 on the surface. Next, the photoresist layer 22 is exposed and developed to form a photoresist pattern 23. As for the detailed content of the photoresist pattern, please refer to the description of Electric Theory E, Volume 131 No. 1, 2011, and these contents are incorporated into this manual. The thickness of the photoresist layer is preferably 0.5-50 μm.

<<Metal Application Process>> In this embodiment, a process of applying metal to the laminate having the transparent substrate 1 and the photoresist pattern 23 is preferable. The metal in this embodiment is applied to the pattern gaps of the photoresist pattern on the transparent substrate 1 having a laminate of the transparent substrate 1 and the photoresist pattern 23. The application method of the metal is not particularly limited, and an electroless plating method can be mentioned. The details of the electroless plating method and the metal are the same as the metal application process in the first embodiment, and the preferred range is also the same. The metal pattern 24 corresponding to the photoresist pattern 23 is thus arranged.

<<The photoresist pattern and seed layer removal process>> After the metal pattern 24 is formed, the photoresist pattern 23 is removed. The removal of the photoresist pattern can be performed by removal using a solvent or removal using a hydroxylamine-based release agent. After the photoresist pattern is removed, the seed layer 21 is removed. The seed layer 21 is preferably removed by etching according to the material of the metal pattern 24.

<Resin Pattern Formation Process> Next, the resin pattern 23 is provided on the surface of the laminate having the transparent substrate 1 and the metal pattern 24. The manufacturing method of the resin pattern is not specifically limited, It is preferable to apply|coat a resin composition and manufacture. As a preferred embodiment, it is preferable to apply a photosensitive resin composition and perform development exposure to expose the metal pattern 24. For details of the development exposure process, reference can be made to the description of the first embodiment. Furthermore, after coating the resin composition as a cured film, the surface can be ground to expose the metal pattern 24.

<Laminating Process> In this embodiment, the metal pattern 24 and the resin pattern 3 may be alternately laminated.

<Semiconductor element application process> In this embodiment, the process of applying semiconductor elements is further included. These details are the same as the semiconductor device application process in the first embodiment.

<Transparent substrate peeling process> In this embodiment, the laminated body 6 having the transparent substrate 1 and the resin pattern 3 located on the surface of the transparent substrate is irradiated with radiation light from the transparent substrate side of the laminated body, and the transparent substrate is peeled off from the laminated body. Substrate peeling process. These details are the same as the transparent substrate peeling process in the first embodiment.

Third Embodiment Fig. 3 is a schematic view showing a third embodiment. A photosensitive resin film 2 is provided on the surface of a transparent substrate 1 (photosensitive resin film manufacturing process), and exposure and development are performed to manufacture a resin pattern 3 (exposure and development process). Then, the semiconductor element 5 is applied to the side of the resin pattern 3 that is not in contact with the transparent substrate 1 (semiconductor element application process). Then, the transparent substrate 1 can be peeled off by irradiating radiation light from the transparent substrate side in a manner that satisfies the prescribed conditions (transparent substrate peeling process). After the transparent substrate 1 is peeled off, the metal 4 can be applied from one side of the peeled transparent substrate 1 (metal application process). In this embodiment, it is particularly preferable to sequentially implement the photosensitive resin film manufacturing process, the exposure and development process, the semiconductor element application process, the transparent substrate peeling process, and the metal application process in sequence. In the third embodiment, a semiconductor device in which the semiconductor element 5 on the surface of the resin pattern (for example, an insulating film) and the metal (for example, metal wiring or electrode) in the gap between the resin pattern 3 are bonded can be obtained. Hereinafter, the third embodiment will be described in detail.

<Photosensitive resin film manufacturing process> The definition is the same as in the first embodiment, and the preferred range is also the same.

<Development exposure process> The definition is the same as in the first embodiment, and the preferred range is also the same.

<Hardening process> In this embodiment, it is preferable to have a hardening process after the development and exposure process. The definition is the same as in the first embodiment, and the preferred range is also the same.

<Semiconductor element application process> In this embodiment, it is preferable to further include a process of applying the semiconductor element 5. Specifically, the surface provided on the surface of the resin pattern 3 opposite to the side in contact with the transparent substrate 1 is preferable. Among them, semiconductor wafers and the like are exemplified as semiconductor elements.

<Transparent substrate peeling process> In this embodiment, the laminated body 6 having the transparent substrate 1 and the resin pattern on the surface of the transparent substrate is irradiated with radiation from the transparent substrate side of the laminated body, and the transparent substrate is peeled from the laminated body The peeling process. These details are the same as the transparent substrate peeling process in the first embodiment.

<Metal Application Process> In this embodiment, it is further preferable to apply metal to the gaps between the resin patterns 3. Specifically, it is preferable to apply metal from the side where the transparent substrate 1 is peeled off. As an application method of metal in this embodiment, printing of metal paste is preferable. When the metal is layered, the thickness of the metal layer is preferably equivalent to the thickness of the resin pattern. With this structure, the metal layer functions as an electrode. As the metal used in this embodiment, it is preferable to include at least one selected from copper, aluminum, nickel, vanadium, titanium, tantalum, chromium, cobalt, gold, silver, and tungsten. When printing a metal paste , Silver is better. The metal can be one type or two or more types.

Method of Manufacturing Semiconductor Device Next, a method of manufacturing a semiconductor device will be described. The manufacturing method of the semiconductor device of the present invention includes the pattern manufacturing method of the present invention. Especially, it is preferable to manufacture through the following laminated body. <Laminate 1> A laminate having a transparent substrate, a resin pattern on the surface of the transparent substrate, and a metal in gaps between the resin patterns on the surface of the transparent substrate, and the resin pattern includes a polyimide selected from And at least one of polybenzoxazole. <Laminate 2> A laminate having a transparent substrate, a resin pattern on the surface of the transparent substrate, a metal in the gaps between the resin patterns on the surface of the transparent substrate, and a semiconductor element in contact with the metal, The semiconductor element is in contact with the metal on the side opposite to the transparent substrate side, and the resin pattern includes at least one selected from polyimide and polybenzoxazole.

For details of the semiconductor device, refer to paragraphs 0213 to 0218 of JP 2016-027357 A and the description in FIG. 1, and these contents are incorporated in this specification. [Example]

The following examples are given to illustrate the present invention more specifically. The materials, usage amount, ratio, processing content, and processing flow shown in the following embodiments are within the scope of the spirit of the present invention, and can be appropriately changed. Therefore, the scope of the present invention is not limited to the specific examples shown below. "Parts" and "%" within the range without special instructions are quality standards.

[Example 1] ＜Synthesis of polyimide precursor＞ ＜＜From 4,4'-oxodiphthalic dianhydride, 4,4'-diaminodiphenyl ether and 2-methacrylic acid Synthesis of the polyimide precursor Aa-1 (polyimine precursor with radical polymerizable group) of hydroxyethyl>> 20.0g (64.5 millimoles) of 4,4'-oxodi Phthalic dianhydride (obtained by drying 4,4'-oxodiphthalic acid at 140°C for 12 hours), 18.6 g (129 millimoles) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 10.7 g of pyridine, and 140 g of diglyme (diglyme) were mixed. The mixture was stirred at a temperature of 60°C for 18 hours to produce a diester of 4,4'-oxodiphthalic acid and 2-hydroxyethyl methacrylate. Next, the reaction mixture was cooled to -10°C, and 16.12 g (135.5 millimoles) of SOCl _{2 was} added over 10 minutes while maintaining the temperature at -10±4°C. After the reaction mixture was diluted with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution of 11.08 g (58.7 millimoles) of 4,4'-oxodiphenylamine dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at 20-23° C. for 20 minutes. Then, the reaction mixture was stirred at room temperature for one night. Next, the reaction mixture was added to 5 liters of water to precipitate the polyimide precursor. The mixture of water and polyimide precursor was stirred at a speed of 5000 rpm for 15 minutes. The mixture of water and the polyimide precursor was filtered to remove the filtrate, and the residue containing the polyimide precursor was added to 4 liters of water. The mixture of water and the polyimide precursor was stirred again for 30 minutes and filtered again to obtain the polyimide precursor as a residue. Next, the obtained polyimide precursor was dried under reduced pressure at 45° C. for 3 days to obtain polyimide precursor Aa-1. The structure of the polyimide precursor Aa-1 is shown below. [Chemical formula 49]

<Preparation of photosensitive resin composition> The following components were mixed, and the photosensitive resin composition was prepared as a uniform solution.

<<Composition of photosensitive resin composition A-1>> Photosensitive resin: polyimide precursor (Aa-1) 32 parts by mass polymerizable compound B-1 6.9 parts by mass photopolymerization initiator C-1 1.0 Parts by mass polymerization inhibitor: p-benzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.08 parts by mass migration inhibitor: 1H-tetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.12 parts by mass metal adhesion modifier ：N-[3-(Triethoxysilyl)propyl]maleic acid monoamide 0.70 parts by mass Solvent: γ-butyrolactone 48.00 parts by mass Solvent: dimethyl sulfide 12.00 parts by mass

The details of each additive are as follows. B-1: NK ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd., trifunctional acrylate, the following structure) [Chemical formula 50]

C-1: Compound 24 described in paragraph 0345 of JP 2014-500852 No. [Chemical formula 51]

<Pattern Manufacturing Method> The above-mentioned photosensitive resin composition was passed through a filter having a pore width of 0.8 μm, and was subjected to pressure filtration under a pressure of (0.3 MPa). After filtration, the photosensitive resin composition was applied to the surface of the transparent substrate (glass substrate with a thickness of 0.6 mm) by spin coating to form a layer, and dried on a hot plate at 100°C for 5 minutes to obtain a thickness of 10 μm Uniform photosensitive resin film. Cover the photosensitive resin film side of the laminated body including the obtained transparent substrate and photosensitive resin film with a mask (a mask with 10μm diameter holes uniformly in the mask surface, 98% aperture), and use the step The machine (Nikon NSR 2005 i9C) was exposed at an exposure wavelength of 365nm (i set line) and an exposure energy of 500mJ/cm ² . After the exposure, the resin film having the exposed part and the unexposed part was rotated and cleaned with cyclopentanone for 60 seconds to remove the unexposed part (negative development). Furthermore, it rinsed with propylene glycol-1-monoethyl ether-2-acetate (PGMEA) to remove the residue, and the resin pattern was obtained. Then, the temperature was increased from room temperature, and the maximum heating temperature reached 350° C. After heating for 1 hour to harden the resin pattern, it was cooled to room temperature. The resin pattern obtained on the surface of the transparent substrate is a resin pattern having holes with a thickness of 6 μm and a diameter of about 10 μm. In addition, the ratio of the surface area of the portion from which the photosensitive resin film has been removed to the surface area of all regions of the photosensitive resin film in the present invention is calculated by dividing 100% by the aperture ratio of the mask.

Next, an electroless copper plating film was formed by the following method. As a water-soluble organic solvent, the preparation includes 39 parts by mass of diethylene glycol diethyl ether (manufactured by Wako Pure Chemical Industries, Ltd.), 40.75 parts by mass of water, 20 parts by mass nitric acid (manufactured by Wako Pure Chemical Industries, Ltd.), and palladium acetate (Manufactured by Wako Pure Chemical Industries, Ltd.) 0.25 parts by mass of the palladium catalyst solution, the laminate including the transparent substrate and the resin pattern obtained above was immersed in the palladium catalyst solution for 5 minutes, and then washed with water. Then, using an electroless plating solution containing the following composition of THRU-CUP PGT (PGT-A, PGT-B, PGT-C) manufactured by Uyemura & Co., Ltd, the electroless plating temperature was 26°C. 60 minutes of electroless plating. The thickness of the obtained electroless copper plating film on the surface of the resin pattern and the surface of the transparent substrate exposed by exposure and development (the bottom of the hole) are both 3.0 μm.

＜＜Raw material for electroless plating bath＞＞ ・Distilled water 79.2% by mass ・PGT-A 9.0% by mass ・PGT-B 6.0% by mass ・PGT-C 3.5% by mass ・Formalin (Wako Pure Chemical Industries, Ltd.: formaldehyde Liquid) 2.3% by mass

In order to remove the electroless copper plating film formed on the part other than the surface (bottom of the hole) of the transparent substrate exposed by the above exposure and development, the electroless copper plating film on the surface was polished. The electroless copper plating film was removed with a polishing cleaning solution (acid). The excess electroless copper plating film was removed by polishing, and a laminate in which the through electrode of the electroless copper plating film was formed in the gaps (holes) of the resin pattern on the surface of the transparent substrate was obtained.

In order to verify the performance of the electroless copper plating film existing in the gaps (holes) of the resin pattern as the copper through-electrodes for the above-mentioned laminate, a conduction test was performed, and only qualified ones were selected and connected to the semiconductor wafer. Specifically, the solder bumps of the semiconductor chip and the formed copper through electrodes are aligned, and the semiconductor chip is connected to the copper through electrodes by reflow.

From the transparent substrate side of the laminated body connected to the semiconductor wafer obtained in the above, the laminated body was peeled from the transparent substrate by irradiating radiation light by the following method. ＜＜Illumination conditions＞＞ Irradiated radiation: 355nm pulse (YAG-THG) laser (pulse width: 5ns) ・Set the 60μm square laser beam (repetition frequency 50Hz) focusing on the interface between glass and resin film It is 1.5mm/s, and the scanning interval is 30μm. An exposure with a flux of 1.9 J/cm ² was performed.

<Measurement of the absorbance of the resin film> The absorbance of the resin pattern in the wavelength of the irradiated radiation was measured by the following method. Five parts were selected before metal application (before electroless plating) without the removal of the resin pattern on the transparent substrate, and the absorbance in the wavelength (wavelength 355nm) of the irradiated radiation was measured, and the average value was calculated. U-3900 manufactured by Hitachi High-Tech Science Corporation was used for the measurement of absorbance.

<Releasability> The releasability of the transparent substrate of the self-laminated body was evaluated as follows. A: Peelable B: Partially peelable, but partly remaining on the transparent substrate C: Not peelable

<Yield rate> The electrode connection of all the semiconductor wafers on the laminated body after peeling was confirmed, and the ratio of no defects was evaluated. The unit is expressed in %.

[Example 2] In Example 1, the mask was changed to a mask with an aperture ratio of 95%, and it was performed in the same manner as in Example 1, except that it was changed.

[Example 3] In Example 1, the mask was changed to a mask with an aperture ratio of 90%, and it was performed in the same manner as in Example 1, except that it was changed.

[Example 4] In Example 1, the mask was changed to a mask with an aperture ratio of 80%, and it was performed in the same manner as in Example 1, except that it was changed.

[Example 5] In Example 1, the mask was changed to a mask with an aperture ratio of 70%, and it was performed in the same manner as in Example 1, except that the mask was changed to a mask with an aperture ratio of 70%.

[Example 6] In Example 1, the photosensitive resin composition was changed to the following photosensitive resin composition A-2, and it was performed in the same manner as in Example 1, except that the photosensitive resin composition was changed to the following photosensitive resin composition A-2. <<Composition of photosensitive resin composition A-2>> Photosensitive resin: polyimide precursor (Aa-1) 32 parts by mass polymerizable compound B-1 6.9 parts by mass photopolymerization initiator C-1 1.0 Parts by mass polymerization inhibitor: 2,6-di-tert-butyl-4-methylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.1 parts by mass migration inhibitor: 1,2,4-triazole (Tokyo Chemical Industry Co., Ltd.) 0.1 parts by mass solvent: 48.00 parts by mass γ-butyrolactone solvent: 12.00 parts by mass dimethylsulfoxide

[Example 7] In Example 1, the thickness of the resin pattern that can be obtained on the surface of the transparent substrate was adjusted to adjust the absorbance to 0.55, except for this, it was performed in the same manner.

[Comparative Example 1] The same procedure as in Example 1 was performed to obtain a laminate connected to a semiconductor wafer. For the obtained laminate, an attempt was made to peel off the transparent substrate without irradiating the radiation light, but the peeling failed.

[Comparative Example 2] In Example 1, the thickness of the resin pattern that can be obtained on the surface of the transparent substrate was adjusted to 10 μm to 3 μm, and other than that, it was performed in the same manner. However, it could not be peeled off.

[Comparative Example 3] In Example 1, the thickness of the resin pattern that can be obtained on the surface of the transparent substrate was adjusted to adjust the absorbance to 0.45, except for this, it was performed in the same manner.

The results of the above-mentioned Examples and Comparative Examples are shown below. [Table 1]

From the above results, it is clear that when the absorbance of the resin pattern is 0.5 or more, the transparent substrate can be peeled from the laminate. On the other hand, when the absorbance is less than 0.5, the transparent substrate can be peeled from the laminate.

1‧‧‧Transparent substrate 2‧‧‧Photosensitive resin film 3‧‧‧Resin pattern 4‧‧‧Metal 5‧‧‧Semiconductor element 6‧‧‧Laminate 7‧‧‧Mask 21‧‧‧Seed layer 22 ‧‧‧Photoresist layer 23‧‧‧Photoresist pattern 24‧‧‧Metal pattern

1‧‧‧Transparent substrate

2‧‧‧Photosensitive resin film

3‧‧‧Resin pattern

4‧‧‧Metal

5‧‧‧Semiconductor components

6‧‧‧Layered body

7‧‧‧Mask

Claims (10)

A pattern manufacturing method, which includes a peeling process, irradiating the layered body A with radiation from the transparent substrate side of the layered body A, and peeling off the transparent substrate from the layered body A, the layered body A having the transparent substrate and the transparent substrate located on the transparent substrate. The resin pattern on the surface, the resin pattern contains at least one selected from polyimide and polybenzoxazole, the absorbance of the resin pattern in the wavelength of the radiated light is 0.5 or more, and has the following manufacturing process: Metal is applied between the gaps of the resin pattern on the transparent substrate of the laminate A or between the transparent substrate and the resin pattern on the transparent substrate. The pattern manufacturing method described in the first item of the patent application, wherein the photosensitive resin film of the laminated body B having a transparent substrate and a photosensitive resin film is exposed, and then a development process is performed to remove a part of the photosensitive resin film Thus, the aforementioned laminate A is obtained. The pattern manufacturing method described in the second claim, wherein the surface area of the removed portion of the resin pattern formed by removing a part of the photosensitive resin film is 20% of the surface area of the total area where the photosensitive resin film is exposed %the following. The pattern manufacturing method described in the 2nd or 3rd item of the scope of patent application, wherein said exposure is performed from the photosensitive resin film side of said laminated body B. The pattern manufacturing method according to the first item of the patent application, wherein the aforementioned metal includes at least one selected from copper, aluminum, nickel, vanadium, titanium, tantalum, chromium, cobalt, gold, silver, and tungsten. Such as the pattern manufacturing method described in item 2 or item 3 of the scope of patent application, wherein The aforementioned photosensitive resin film includes at least one selected from a polyimide precursor, a polyimide, a polybenzoxazole precursor, and a polybenzoxazole. The pattern manufacturing method described in item 2 or item 3 of the scope of patent application, wherein the photosensitive resin film contains at least one selected from the group consisting of polyimide precursors and polybenzoxazole precursors. The pattern manufacturing method according to any one of items 1 to 3 of the scope of the patent application includes a curing process for curing the resin pattern after the exposure and development process and before the peeling process. The pattern manufacturing method described in item 2 or item 3 of the scope of patent application, wherein the aforementioned development is negative development. A manufacturing method of a semiconductor device, which includes the pattern manufacturing method described in any one of items 1 to 3 of the scope of the patent application.

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