WO2017146153A1

WO2017146153A1 - Method for manufacturing laminate and method for manufacturing semiconductor device

Info

Publication number: WO2017146153A1
Application number: PCT/JP2017/006846
Authority: WO
Inventors: 悠岩井; 勝志伊藤; ステファンヴァンクロースター
Original assignee: 富士フイルム株式会社
Priority date: 2016-02-26
Filing date: 2017-02-23
Publication date: 2017-08-31
Also published as: CN108700836A; KR102187512B1; CN108700836B; TW202115498A; TW201741772A; JPWO2017146153A1; KR20180104069A; JP6901596B2; JP2020091490A; TWI767436B

Abstract

Provided are the following: a method for manufacturing a laminate having excellent adhesion between a resin layer and another resin layer, or between a resin layer and a metal layer; and a method for manufacturing a semiconductor device including said manufacturing method. The method for manufacturing a laminate includes: a photosensitive resin composition layer forming step of forming a photosensitive resin composition in a layer shape adapted to a substrate; a step of exposing the photosensitive resin composition layer to light; a step of performing negative development processing of the photosensitive resin composition layer that has been exposed to light; a step of forming a metal layer on the surface of the photosensitive resin composition layer after development processing; and a surface activation processing step of performing surface activation processing on the metal layer and at least a portion of the photosensitive resin composition layer. The method further includes again performing, in the order set forth above, the photosensitive resin composition layer forming step, the light exposing step, and the development processing step. The photosensitive resin composition includes a resin selected from polyimide precursors and the like. Further, at least one of the following conditions is satisfied: the resin including a polymerizable group; and the photosensitive resin composition including a polymerizable compound.

Description

LAMINATE MANUFACTURING METHOD AND SEMICONDUCTOR DEVICE MANUFACTURING METHOD

The present invention relates to a laminate manufacturing method and a semiconductor device manufacturing method. In particular, the present invention relates to a method for manufacturing a laminate used for manufacturing an interlayer insulating film for a rewiring layer of a semiconductor device.

Thermosetting resins such as polyimide resins and polybenzoxazole resins are excellent in heat resistance and insulation, and thus are used for insulating layers of semiconductor devices.
In addition, since polyimide resins and polybenzoxazole resins have low solubility in solvents, they are used in the state of a precursor (polyimide precursor or polybenzoxazole precursor) before cyclization reaction and applied to a substrate or the like. Heating to cyclize the polyimide precursor to form a cured film is also performed.

Here, Patent Document 1 discloses a laminate comprising a thermoplastic polyimide layer and a metal layer on the surface of the thermoplastic polyimide layer. Patent Document 1 also describes that a thermoplastic polyimide layer functions as an insulating layer.

International Publication WO2004 / 050352

Here, when the thermoplastic polyimide resin described in Patent Document 1 is used as the interlayer insulating film for the rewiring layer of the semiconductor device, the top of the laminate composed of the thermoplastic polyimide layer and the metal layer on the surface of the thermoplastic polyimide layer is used. Furthermore, it is necessary to provide a thermoplastic polyimide layer. However, when it was considered to further provide a thermoplastic polyimide layer on the laminate in Patent Document 1, the adhesion between the thermoplastic polyimide layer and the metal layer, or between the thermoplastic polyimide layers is insufficient. I understood that.
The present invention is intended to solve such problems, and a method for producing a laminate having excellent adhesion between a resin layer containing a resin such as polyimide and a resin layer, or a resin layer and a metal layer And it aims at providing the manufacturing method of the semiconductor device containing the said manufacturing method.

As a result of investigation by the present inventors based on the above problems, it has been found that the above problems can be solved by forming a resin layer by negative development of the photosensitive resin composition. Specifically, the above problem has been solved by the following means <1>, preferably <2> to <8>.
<1> a photosensitive resin composition layer forming step of applying a photosensitive resin composition to a substrate to form a layer;
An exposure process for exposing the photosensitive resin composition layer, a development process for performing a negative development process on the exposed photosensitive resin composition layer, and a photosensitive resin composition after the development process A metal layer forming step of forming a metal layer on the surface of the layer, and a surface activation treatment step of subjecting at least a part of the metal layer and the photosensitive resin composition layer to a surface activation treatment. Including performing the photosensitive resin composition layer forming step, the exposure step, and the development processing step in the order described above, wherein the photosensitive resin composition comprises a polyimide precursor, a polyimide, a polybenzoxazole precursor, and a poly A resin selected from benzoxazole, and further satisfying at least one of the resin containing a polymerizable group and the photosensitive resin composition containing a polymerizable compound. Method of manufacturing a layer body.
<2> The method for producing a laminate according to <1>, wherein the photosensitive resin composition layer forming step, the exposing step, and the developing step are performed 3 to 7 times in the order described above.
<3> The method for producing a laminate according to <1> or <2>, wherein the metal layer contains copper.
<4> The method for producing a laminate according to any one of <1> to <3>, wherein the resin is a polyimide precursor or a polybenzoxazole precursor.
<5> The method for producing a laminate according to any one of <1> to <4>, wherein the resin includes a partial structure represented by -Ar-L-Ar-; , An aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—, —SO ₂ — or —NHCO -Or a group consisting of a combination of two or more of the above.
<6> The method for producing a laminate according to any one of <1> to <5>, wherein the surface activation treatment is selected from plasma treatment and corona discharge treatment.
<7> The method for producing a laminate according to any one of <1> to <6>, wherein the photosensitive resin composition contains a photopolymerization initiator.
<8> A method for producing a semiconductor device, comprising the method for producing a laminate according to any one of <1> to <7>.

According to the present invention, there are provided a method for producing a laminate having excellent adhesion between a resin layer and a resin layer, or a resin layer and a metal layer, and a method for producing a semiconductor device including the production method.

It is the schematic which shows the structure of one Embodiment of a semiconductor device. It is the schematic which shows the structure of one Embodiment of the laminated body obtained with the manufacturing method of this invention.

The description of the components in the present invention described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the notation of a group (atomic group) in this specification, the notation which does not describe substitution and unsubstituted includes the group which has a substituent with the group which does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, “exposure” includes not only exposure using light, but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. The light used for exposure generally includes active rays or radiation such as an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present specification, “(meth) acrylate” represents both and / or “acrylate” and “methacrylate”, and “(meth) allyl” means both “allyl” and “methallyl”, or “(Meth) acryl” represents either “acryl” and “methacryl” or any one, and “(meth) acryloyl” represents both “acryloyl” and “methacryloyl”, or Represents either.
In this specification, the term “process” not only indicates an independent process, but also if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes, include.
In this specification, solid content concentration is the mass percentage of the other component except a solvent with respect to the gross mass of a composition. Moreover, solid content concentration says the density | concentration in 25 degreeC unless there is particular mention.
In this specification, a weight average molecular weight (Mw) and a number average molecular weight (Mn) are defined as polystyrene conversion values measured by gel permeation chromatography (GPC) unless otherwise specified. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and guard columns HZ-L, TSKgel Super HZM-M, TSKgel. It can be determined by using Super HZ4000, TSKgel Super HZ3000, TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise stated, the eluent was measured using THF (tetrahydrofuran). Unless otherwise specified, detection is performed using a UV ray (ultraviolet) wavelength 254 nm detector.

The method for producing a laminate of the present invention includes a photosensitive resin composition layer forming step of applying a photosensitive resin composition to a substrate to form a layer, an exposure step of exposing the photosensitive resin composition layer, and the above A development process for performing a negative development process on the exposed photosensitive resin composition layer, a metal layer formation process for forming a metal layer on the surface of the photosensitive resin composition layer after the development process, and the above A surface activation treatment step of performing surface activation treatment on at least a part of the metal layer and the photosensitive resin composition layer, and again, the photosensitive resin composition layer formation step, the exposure step, and the development treatment. Including performing steps in the above order, wherein the photosensitive resin composition includes a resin selected from a polyimide precursor, a polyimide, a polybenzoxazole precursor, and a polybenzoxazole,
Furthermore, the resin satisfies at least one of containing a polymerizable group and the photosensitive resin composition containing a polymerizable compound.
As described above, when laminating the insulating films, it is possible to improve the adhesion between the layers by performing the negative development and further performing the surface activation treatment. On the other hand, Patent Document 1 does not have an example in which such a resin layer is laminated. In Patent Document 1, since positive development is performed and the exposed portion is alkali-developed, the adhesion tends to be insufficient. Furthermore, when performing positive development, it is estimated that the unexposed portion of the resin layer is subjected to surface activation treatment, and the photosensitive resin composition (resin layer) is easily damaged, resulting in a decrease in adhesion. . On the other hand, the negative type can form a three-dimensional crosslinked structure, can increase the strength of the film, and can be hardly damaged even by the surface activation treatment.
Based on the above, in the present invention, by adopting the above means, high adhesion between the resin layer and the resin layer and between the resin layer and the metal layer can be achieved even in a multilayer configuration.
Details of the present invention will be described below.

<Photosensitive resin composition layer forming step>
The manufacturing method of the laminated body of this invention includes the photosensitive resin composition layer formation process which applies the photosensitive resin composition to a board | substrate, and makes it layered.
As a means for applying the photosensitive resin composition to the substrate, coating is preferable.
Specifically, examples of applicable means include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spin coating, slit scanning, and inkjet. Is exemplified. From the viewpoint of the uniformity of the thickness of the photosensitive resin composition layer, the spin coating method is more preferable. In the case of the spin coating method, for example, it can be applied at a rotational speed of 500 to 2000 rpm for about 10 seconds to 1 minute.
The thickness of the photosensitive resin composition layer (resin layer) is preferably applied to be 0.1 to 100 μm after exposure, and more preferably 1 to 50 μm. Moreover, as shown in FIG. 2 described later, the thickness of the formed photosensitive resin composition layer is not necessarily uniform. In particular, when a photosensitive resin composition layer is provided on an uneven surface, the resin layers will have different thicknesses as shown in FIG. In particular, when a plurality of layers are laminated, a concave portion having a large depth can be formed as the concave portion. However, the present invention has a high technical value in that the delamination between layers can be more effectively suppressed with respect to such a configuration. In addition, when the laminated body of this invention has a resin layer from which thickness differs, it is preferable that the thickness of the resin layer of the thinnest part is the said thickness.
The type of the substrate can be appropriately determined according to the application, but a semiconductor production substrate such as silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film , Reflective films, metal substrates such as Ni, Cu, Cr, and Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, plasma display panel (PDP) electrode plates, and the like are not particularly limited. In the present invention, a semiconductor manufacturing substrate is particularly preferable, and silicon is more preferable.
Moreover, when forming the photosensitive resin composition layer on the surface of a resin layer or the surface of a metal layer, a resin layer or a metal layer becomes a board | substrate.

Details of the photosensitive resin composition will be described later.

<Filtration process>
The manufacturing method of the laminated body of this invention may include the process of filtering the photosensitive resin composition, before applying the photosensitive resin composition to a board | substrate. Filtration is preferably performed using a filter. The filter pore diameter is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. As a material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. A filter that has been washed in advance with an organic solvent may be used. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different pore diameters and / or materials may be used in combination. Moreover, various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step. Moreover, you may pressurize and filter and the pressure to pressurize is 0.05 MPa or more and 0.3 MPa or less. In addition to filtration using a filter, impurities may be removed using an adsorbent, or a combination of filter filtration and adsorbent may be used. As the adsorbent, known adsorbents can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.

<Drying process>
The manufacturing method of the laminated body of this invention may include the process of drying a solvent, after forming the photosensitive resin composition layer. A preferable drying temperature is 50 to 150 ° C, more preferably 70 to 130 ° C, and further preferably 90 to 110 ° C. The drying time is preferably 30 seconds to 20 minutes, more preferably 1 minute to 10 minutes, and further preferably 3 minutes to 7 minutes.

<Exposure process>
The manufacturing method of the laminated body of this invention includes the exposure process which exposes the said photosensitive resin composition layer. The exposure is not particularly defined as long as the photosensitive resin composition can be cured, but for example, it is preferable to irradiate 100 to 10,000 mJ / cm ^{2 in} terms of exposure energy at a wavelength of 365 nm, and 200 to 8000 mJ / cm ² irradiation. More preferably.
The exposure wavelength can be appropriately determined in the range of 190 to 1000 nm, and is preferably 240 to 550 nm.

<Development process>
The manufacturing method of the laminated body of this invention includes the image development process process which performs negative development processing with respect to the exposed photosensitive resin composition layer. By performing negative development, the unexposed part (non-exposed part) is removed. Development is performed using a developer. The developer can be used without particular limitation as long as it can remove the unexposed part (non-exposed part). Solvents are preferred, and examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and γ-butyrolactone. , Ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (eg, methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc. )), 3-alkoxypropionic acid alkyl esters (for example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate) Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkoxypropionic acid alkyl esters (for example, methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc.) For example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate 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, aceto vinegar Methyl, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like, and ethers such as 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., and ketones such as methyl ethyl Ketones, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and aromatic hydrocarbons such as toluene, xylene, anisole, limonene and the like, and sulfoxides Preferable examples include dimethyl sulfoxide, ethyl carbitol acetate, and butyl carbitol acetate. Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve 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 acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate are preferred, and cyclopentanone and γ-butyrolactone are more preferred.
The development time is preferably 10 seconds to 5 minutes. The temperature at the time of development is not particularly defined, but it can usually be carried out at 20 to 40 ° C.
After treatment with a developer, rinsing may be further performed. The rinsing is preferably performed with a solvent different from the developer. For example, it can rinse using the solvent contained in the photosensitive resin composition. The rinse time is preferably 5 seconds to 1 minute.

<Heating process>
It is preferable that the manufacturing method of the laminated body of this invention includes a heating process. In the heating step, the cyclization reaction of the polyimide precursor and the polybenzoxazole precursor proceeds. In polyimide and polybenzoxazole, when heated with a crosslinking agent, a three-dimensional network structure is formed. In addition, curing of the unreacted radical polymerizable compound also proceeds. The maximum heating temperature is preferably 100 to 500 ° C, more preferably 140 to 400 ° C, and further preferably 160 to 350 ° C.
Heating is preferably performed at a temperature rising rate of 1 to 12 ° C./min from a temperature of 20 to 150 ° C. to a maximum heating temperature, more preferably 2 to 10 ° C./min, and further 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 the amine while ensuring productivity, and by setting the heating rate to 12 ° C./min or less, the cured film Residual stress can be relaxed.
The temperature at the start of heating is preferably 20 to 150 ° C., more preferably 20 to 130 ° C., and further preferably 25 to 120 ° C. The temperature at the start of heating refers to the temperature at the start of the step of heating to the maximum heating temperature. For example, when the photosensitive resin composition is applied onto a substrate and then dried, the temperature is the temperature after the drying, for example, gradually from a temperature lower by 30 to 200 ° C. than the boiling point of the solvent contained in the photosensitive resin composition. It is preferable to raise the temperature to
Heating is preferably performed for 10 to 360 minutes after reaching the maximum heating temperature, more preferably for 20 to 300 minutes, and particularly preferably for 30 to 240 minutes.

Heating may be performed in stages. As an example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min, placed at 180 ° C. for 60 minutes, heated from 180 to 200 ° C. at 2 ° C./minute, and placed at 200 ° C. for 120 minutes. Is mentioned.
Further, it may be cooled after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.

The heating step is preferably performed in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon in order to prevent decomposition of the polyimide precursor or the like. The oxygen concentration is preferably 50 ppm (v / v) or less, and more preferably 20 ppm (v / v) or less.

<< Metal layer formation process >>
The manufacturing method of the laminated body of this invention includes the metal layer formation process which forms a metal layer on the surface of the photosensitive resin composition layer after image development processing.
The metal layer is not particularly limited, and an existing metal species can be used. Examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten, and copper and aluminum are more preferable. Is more preferable.
The method for forming the metal layer is not particularly limited, and an existing method can be applied. For example, the methods described in JP 2007-157879 A, JP 2001-521288 A, JP 2004-214501 A, and JP 2004-101850 A can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a combination of these can be considered. More specifically, a patterning method that combines sputtering, photolithography, and etching, and a patterning method that combines photolithography and electrolytic plating may be mentioned.
The thickness of the metal layer is preferably 0.1 to 50 μm, more preferably 1 to 10 μm at the thickest portion.

<Surface activation treatment process>
The manufacturing method of the laminated body of this invention includes the surface activation process process of carrying out the surface activation process of at least one part of the said metal layer and the photosensitive resin composition layer.
The surface activation treatment step is usually performed after the metal layer formation step, but after the exposure and development step, the surface activation treatment step is performed on the photosensitive resin composition layer, and then the metal layer formation step is performed. Good.
The surface activation treatment may be performed only on at least a part of the metal layer, or may be performed only on at least a part of the photosensitive resin composition layer after exposure, or the metal layer and the photosensitive resin after exposure. You may go to at least one part about both of a composition layer, respectively. The surface activation treatment is preferably performed on at least a part of the metal layer, and the surface activation treatment is preferably performed on a part or all of the region of the metal layer where the photosensitive resin composition layer is formed on the surface. . Thus, by performing the surface activation treatment on the surface of the metal layer, the adhesion with the resin layer provided on the surface can be improved.
The surface activation treatment is also preferably performed on part or all of the photosensitive resin composition layer (resin layer) after exposure. Thus, by performing the surface activation treatment on the surface of the photosensitive resin composition layer, it is possible to improve the adhesion with a metal layer or a resin layer provided on the surface subjected to the surface activation treatment. In particular, when positive development is performed, the unexposed portion is subjected to a surface activation treatment, and the photosensitive resin composition (resin layer) is easily damaged, resulting in a decrease in adhesion. In the present invention, since the negative development is performed, the exposed portion is subjected to a surface treatment, and the strength of the film is improved by curing or the like, so that the photosensitive resin composition (resin layer) is not damaged, There is no such problem.
Specifically, the surface activation treatment includes plasma treatment of various source gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixed gas, argon / oxygen mixed gas, etc.), corona discharge treatment, CF ₄ / O _2. Etching treatment with NF ₃ / O ₂ , SF ₆ , NF ₃ , NF ₃ / O ₂ , surface treatment by ultraviolet (UV) ozone method, immersion in hydrochloric acid aqueous solution to remove oxide film, amino group and thiol group It is selected from an immersion treatment in an organic surface treatment agent containing at least one compound and a mechanical surface roughening treatment using a brush, and a plasma treatment is preferred, and an oxygen plasma treatment using oxygen as a raw material gas is particularly preferred. For corona discharge treatment, the energy is preferably 500 ~ 200,000J / ^{m 2,} more preferably 1000 ~ 100,000J / ^{m 2,} and most preferably 10,000 ~ 50,000J / ^{m 2.}

<Lamination process>
The manufacturing method of the present invention further includes the following lamination steps.
A lamination process is a series of processes including performing the said photosensitive resin composition layer formation process, the said exposure process, and the said image development process again in the said order again. That is, it goes without saying that the laminating step may further include the drying step and the heating step.
When the lamination process is further performed after the lamination process, it is preferable that the surface activation treatment process is further performed after the exposure process or after the metal layer formation process.
The lamination step is preferably performed 3 to 7 times, more preferably 3 to 5 times.
For example, the resin layer / metal layer / resin layer / metal layer / resin layer / metal layer has a resin layer structure of 3 to 7 layers, more preferably 3 to 5 layers. If there are two layers or less, there may be sufficient adhesion without oxygen plasma treatment or the like, but the more the multi-layer structure, the more repeatedly exposed to a high temperature treatment by a developing solution, metal etching treatment, and curing. Peeling tends to occur at the layer interface or at the resin layer / resin layer interface.
By setting it as such a structure, the photosensitive resin composition layer (resin layer) and a metal layer can be laminated | stacked alternately, and it can use as a multilayer wiring structure of a semiconductor.

<Photosensitive resin composition>
The photosensitive resin composition used in the present invention (hereinafter sometimes referred to as “the composition used in the present invention”) is a resin selected from a polyimide precursor, a polyimide, a polybenzoxazole precursor, and a polybenzoxazole (hereinafter referred to as “polybenzoxazole”). It is preferable that a polyimide precursor or a polybenzoxazole precursor is included, and a polyimide precursor is more preferable.
Furthermore, it satisfies at least one of a resin such as a polyimide precursor containing a polymerizable group and a case where the photosensitive resin composition contains a polymerizable compound. In particular, it is preferable that a resin such as a polyimide precursor contains a polymerizable group, and the photosensitive resin composition contains a polymerizable compound. By adopting such a configuration, a three-dimensional network is formed in the exposed area, and a strong cross-linked film is formed. The photosensitive resin composition (resin layer) is not damaged by the surface activation treatment, and the surface activation treatment , Adhesion is more effectively improved.
Furthermore, it is preferable that the resin such as a polyimide precursor includes a partial structure represented by —Ar—L—Ar—. However, Ar is each independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms (preferably an alkylene group) which may be substituted with a fluorine atom, —O—, —CO—, —S—, —SO ₂ — or —NHCO—, or a group consisting of a combination of two or more of the above. By setting it as such a structure, a resin layer becomes a flexible structure and the effect which suppresses generation | occurrence | production of peeling is exhibited more effectively. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S— or —SO ₂ —. .
Hereinafter, the detail of the photosensitive resin composition used by this invention is demonstrated.

<< Polyimide precursor >>
The polyimide precursor used in the present invention is not particularly defined in terms of its type and the like, but preferably contains a repeating unit represented by the following formula (2).
Formula (2)

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, R ¹¹³ And R ¹¹⁴ each independently represents a hydrogen atom or a monovalent organic group.

A ¹ and A ² in Formula (2) each independently represent an oxygen atom or NH, and preferably an oxygen atom.
R ¹¹¹ in Formula (2) represents a divalent organic group. Examples of the divalent organic group include a straight chain or branched aliphatic group, a group containing a cyclic aliphatic group and an aromatic group, a straight chain or branched aliphatic group having 2 to 20 carbon atoms, a carbon number A group consisting of a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms or a combination thereof is preferable, and a group containing an aromatic group having 6 to 60 carbon atoms is more preferable. As a particularly preferred embodiment of the present invention, a group represented by —Ar—L—Ar— is exemplified. However, Ar is each independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—. , —SO ₂ — or —NHCO—, or a group comprising a combination of two or more of the above. These preferable ranges are as described above.

R ¹¹¹ is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamine. One type of diamine may be used, or two or more types may be used.
Specifically, a group consisting of a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof. A diamine containing is preferable, and a diamine containing a group consisting of an aromatic group having 6 to 60 carbon atoms is more preferable. The following are mentioned as an example of an aromatic group.

In the formula, A is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —C (═O) —, —S—, —S (═O) ₂ — and —NHCO—, and a group selected from these combinations are preferable, a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, —O It is more preferably a group selected from —, —C (═O) —, —S—, —SO ₂ —, —CH ₂ —, —O—, —S—, —SO ₂ —, —C More preferably, it is a divalent group selected from the group consisting of (CF ₃ ) ₂ — and —C (CH ₃ ) ₂ —.

Specific examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1 , 3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4- Aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4′-diamino-3,3′-dimethylcyclohexylmethane and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4′- Or 3,3′-diaminobiphenyl, 4,4′-diaminodiphenyl ether, 3,3-diaminodiphenyl ether 4,4'- and 3,3'-diaminodiphenylmethane, 4,4'- and 3,3'-diaminodiphenyl sulfone, 4,4'- and 3,3'-diaminodiphenyl sulfide, 4,4 ' -Or 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-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 4,4'-diamino Paraterphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (2-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 9,10-bis (4-aminophenyl) anthracene, 3,3′-dimethyl-4,4′-diaminodiphenyl Sulfone, 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′-diaminodiphenylmethane, 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'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diamino Anthraquinone, 3,3-dihydroxy-4,4′-diaminobiphenyl, 9,9′-bis (4-aminophenyl) fluorene, 4 4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5 -Dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis (3-aminopropyl) tetramethyldi Siloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-aminophenyl) ethane, diaminobenzanilide, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride 1,3-bis (4-aminophenyl) hexafluoropropane, 1,4-bis (4-amino) Phenyl) octafluorobutane, 1,5-bis (4-aminophenyl) decafluoropentane, 1,7-bis (4-aminophenyl) tetradecafluoroheptane, 2,2-bis [4- (3-aminophenoxy) ) Phenyl] hexafluoropropane, 2,2-bis [4- (2-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] hexa Fluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-bis (trifluoromethyl) phenyl] hexafluoropropane, 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 sulfone, 4,4'-bis (3-amino-5-trifluoromethylphenoxy) ) Diphenylsulfone, 2,2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl] hexafluoropropane, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminobiphenyl 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 2,2 ′, 5,5 ′, 6,6′-hexafluorotolidine and 4,4 ′ ″-diaminoquater The at least 1 sort (s) of diamine chosen from phenyl is mentioned.

Further, diamines (DA-1) to (DA-18) shown below are also preferable.

A diamine having at least two alkylene glycol units in the main chain is also a preferred example. Preferred is a diamine containing at least two ethylene glycol chains or propylene glycol chains in one molecule, more preferably a diamine containing no aromatic ring. Specific examples include Jeffermin (registered trademark) KH-511, Jeffermin (registered trademark) ED-600, Jeffermin (registered trademark) ED-900, Jeffermin (registered trademark) ED-2003, Jeffermin (registered trademark). ) EDR-148, Jeffamine (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (trade name, manufactured by HUNTSMAN Co., Ltd.), 1- (2- (2- (2-aminopropoxy) ethoxy) propoxy) propan-2-amine, 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propan-2-amine, and the like. It is not limited to.
Jeffermin (registered trademark) KH-511, Jeffermin (registered trademark) ED-600, Jeffermin (registered trademark) ED-900, Jeffermin (registered trademark) ED-2003, Jeffermin (registered trademark) EDR-148, The structure of Jeffamine (registered trademark) EDR-176 is shown below.

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

R ¹¹¹ is preferably represented by —Ar—L—Ar— from the viewpoint of the flexibility of the resulting cured film. However, Ar is each independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms (preferably an alkylene group) which may be substituted with a fluorine atom, —O—, —CO—, —S—, —SO ₂ — or —NHCO—, or a group consisting of a combination of two or more of the above. Ar is preferably a phenylene group, and L is an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S— or —SO ₂ —. preferable.

R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61) from the viewpoint of i-line transmittance. In particular, from the viewpoints of i-line transmittance and availability, a divalent organic group represented by the formula (61) is more preferable.
Formula (51)

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 trifluoro It is a methyl group.
Examples of the monovalent organic group represented by R ¹⁰ to R ¹⁷ include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and an alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples include a fluorinated alkyl group.
Formula (61)

In formula (61), R ¹⁸ and R ¹⁹ are each independently a fluorine atom or a trifluoromethyl group.
Examples of the diamine compound having the structure of the formula (51) or (61) include 2,2′-dimethylbenzidine, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 2,2′- Bis (fluoro) -4,4′-diaminobiphenyl, 4,4′-diaminooctafluorobiphenyl and the like can be mentioned. These may be used alone or in combination of two or more.

R ¹¹⁵ in the 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)

In the formula (5), R ¹¹² represents a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—, —SO. ₂ -, and -NHCO-, and is preferably a group selected from these combinations, a single bond, an alkylene group which ~ 1 carbon atoms which may be 3-substituted by fluorine atoms, -O -, - More preferably, it is a group selected from CO—, —S— and —SO ₂ —, and —CH ₂ —, —C (CF ₃ ) ₂ —, —C (CH ₃ ) ₂ —, —O—, More preferably, it is a divalent group selected from the group consisting of —CO—, —S— and —SO ₂ —.

Formula (6)

Specific examples of R ¹¹⁵ include a tetracarboxylic acid residue remaining after removal of the anhydride group from tetracarboxylic dianhydride. Only one tetracarboxylic dianhydride may be used, or two or more tetracarboxylic dianhydrides may be used.
The tetracarboxylic dianhydride is preferably represented by the following formula (0).
Formula (O)

In formula (0), R ¹¹⁵ represents a tetravalent organic group. A preferred range of R ¹¹⁵ has the same meaning as ^{R 115} in formula (2), and preferred ranges are also the same.

Specific examples of tetracarboxylic dianhydride include pyromellitic dianhydride (PMDA), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′- Diphenyl sulfide tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic 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 , 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-phenanthrenetetracarboxylic dianhydride, 1,1-bis (2,3 Dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and their carbon number Examples thereof include alkyl having 1 to 6 and alkoxy derivatives having 1 to 6 carbon atoms.

Further, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below are also preferable examples.

It is also preferred that at least one of R ¹¹¹ and R ¹¹⁵ has an OH group. More specifically, examples of R ¹¹¹ include a residue of a bisaminophenol derivative.

R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, and at least one of R ¹¹³ and R ¹¹⁴ preferably contains a polymerizable group, and more preferably both contain a polymerizable group. preferable. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, radicals, etc., and is preferably a photoradical polymerizable group. Specific examples of the polymerizable group include an ethylenically unsaturated bond group, alkoxymethyl group, hydroxymethyl group, acyloxymethyl group, epoxy group, oxetanyl group, benzoxazolyl group, blocked isocyanate group, methylol group, amino group. Groups. The radical polymerizable group possessed by the polyimide precursor or the like is preferably a group having an ethylenically unsaturated bond.
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.

In the formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and a methyl group is more preferable.
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.
Examples of suitable R ²⁰¹ are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butanediyl group, 1,3-butanediyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group. , —CH ₂ CH (OH) CH ₂ —, and ethylene group, propylene group, trimethylene group, and —CH ₂ CH (OH) CH ₂ — are more preferable.
Particularly preferably, R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethylene group.

R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include an aromatic group and an aralkyl group having one, two, or three, preferably one acidic group bonded to carbon constituting the aryl group. Specific examples include 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. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group can be mentioned. The acidic group is preferably an OH group.
R ¹¹³ or R ¹¹⁴ is preferably a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl.

From the viewpoint of solubility in an organic solvent, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. The alkyl group preferably has 1 to 30 carbon atoms. The alkyl group may be linear, branched or cyclic. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, and an octadecyl group. , Isopropyl, isobutyl, sec-butyl, t-butyl, 1-ethylpentyl, 2-ethylhexyl, 2- (2- (2-methoxyethoxy) ethoxy) ethoxy, 2- (2- ( 2-ethoxyethoxy) ethoxy) ethoxy) ethoxy group, 2- (2- (2- (2-methoxyethoxy) ethoxy) ethoxy) ethoxy group, and 2- (2- (2- (2-ethoxyethoxy) ethoxy) Ethoxy) ethoxy group. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a camphenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group, and a pinenyl group. Is mentioned. Among these, a cyclohexyl group is most preferable from the viewpoint of achieving high sensitivity. Moreover, as an alkyl group substituted by the aromatic group, the linear alkyl group substituted by the aromatic group mentioned later is preferable.
Specific examples of the aromatic group include substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene. Ring, naphthacene ring, chrysene ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring , Indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, fluorine Nantororin ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxathiin ring, a phenothiazine ring or a phenazine ring. A benzene ring is most preferred.

In the formula (2), when R ¹¹³ is a hydrogen atom, or when R ¹¹⁴ is a hydrogen atom, the polyimide precursor forms a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. Also good. Examples of such tertiary amine compounds having an ethylenically unsaturated bond include N, N-dimethylaminopropyl methacrylate.

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

Further, for the purpose of improving the adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylpentasiloxane.

The repeating unit represented by the formula (2) is preferably a repeating unit represented by the formula (2-A). That is, at least one of the polyimide precursors and the like used in the present invention is preferably a precursor having a repeating unit represented by the formula (2-A). By adopting such a structure, it becomes possible to further widen the width of the exposure latitude.
Formula (2-A)

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

^{^{^{A 1, A 2, R 111}}} , R 113 and ^{R 114} are each independently the same meaning as ^{^{^{A 1, A 2, R 111}}} , R 113 and ^{R 114} in formula (2), and preferred ranges are also the same .
R ¹¹² has the same meaning as R ¹¹² in formula (5), and the preferred range is also the same.

The polyimide precursor may contain one type of repeating structural unit represented by the formula (2), but may contain two or more types. Moreover, the structural isomer of the repeating unit represented by Formula (2) may be included. Needless to say, the polyimide precursor may contain other types of repeating structural units in addition to the repeating unit of the above formula (2).

As one embodiment of the polyimide precursor in the present invention, there is a polyimide precursor in which 50 mol% or more, further 70 mol% or more, particularly 90 mol% or more of all repeating units are repeating units represented by the formula (2). Illustrated.

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 further preferably 22,000 to 25,000. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and still more preferably 9,200 to 11,200.
The dispersion degree of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and further preferably 2.8 or more. The upper limit of the degree of dispersion of the polyimide precursor is not particularly defined, but is, for example, preferably 4.5 or less, more preferably 4.0 or less, still more preferably 3.8 or less, still more preferably 3.2 or less, 3.1 or less is even more preferable, 3.0 or less is even more preferable, and 2.95 or less is particularly preferable.

<< Polyimide >>
The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide ring, but is preferably a compound represented by the following formula (4), and a compound represented by the formula (4) And it is more preferable that it is a compound which has a polymeric group.
Formula (4)

In formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group.
In the case of having a polymerizable group, the polymerizable group may be located in at least one of R ¹³¹ and R ¹³² , or as shown in the following formula (4-1) or formula (4-2), May be located.
Formula (4-1)

In the formula (4-2), R ¹³³ is a polymerizable group, and other groups are as defined in the formula (4).
Formula (4-2)

At least one of R ¹³⁴ and R ¹³⁵ is a polymerizable group. When it is not a polymerizable group, it is an organic group, and the other groups have the same meanings as in formula (4).

A polymerizable group is synonymous with the polymerizable group described in the polymerizable group which said polyimide precursor etc. have.
R ¹³¹ represents a divalent organic group. Examples of the divalent organic group include those similar to R ¹¹¹ in formula (2), and the preferred range is also the same.
As the R ^131, include diamine residues remaining after removal of the amino groups of the diamine. Examples of the diamine 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 given.

R ¹³¹ is preferably a diamine residue having at least two alkylene glycol units in the main chain from the viewpoint of more effectively suppressing the occurrence of warpage during firing. More preferred is a diamine residue containing at least two ethylene glycol chains or propylene glycol chains in one molecule, and more preferred is a diamine residue containing no aromatic ring.

Examples of diamines containing two or more ethylene glycol chains and / or propylene glycol chains in one molecule include Jeffamine (registered trademark) KH-511, Jeffamine (registered trademark) ED-600, Jeffamine ( (Registered trademark) ED-900, Jeffermin (registered trademark) ED-2003, Jeffermin (registered trademark) EDR-148, Jeffermin (registered trademark) EDR-176, D-200, D-400, D-2000, D -4000 (trade name, manufactured by HUNTSMAN Co., Ltd.), 1- (2- (2- (2-aminopropoxy) ethoxy) propoxy) propan-2-amine, 1- (1- (1- (2-amino) Propoxy) propan-2-yl) oxy) propan-2-amine, 1- (2- (2- (2-aminopropoxy) Ethoxy) propoxy) the like-2-amine include, but are not limited to.

R ¹³² represents a tetravalent organic group. Examples of the tetravalent organic group include those similar to R ¹¹⁵ in formula (2), and the preferred range is also the same.
For example, four bonds of a tetravalent organic group exemplified as R ¹¹⁵ are bonded to four —C (═O) — moieties in the above formula (4) to form a condensed ring.

Examples of R ¹³² include a tetracarboxylic acid residue remaining after removal of the anhydride group from tetracarboxylic dianhydride. Specific examples include those exemplified R ¹¹⁵ in formula (2) of the polyimide precursor. 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 has an OH group. More specifically, as R ¹³¹ , 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2- Preferred examples include bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and (DA-1) to (DA-18) above. As R ¹³² , the above-mentioned (DAA-1) to (DAA-5) are mentioned as preferred examples.

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

Also, for the purpose of improving the adhesion to the substrate, the polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylpentasiloxane.

In order to improve the storage stability of the composition, the end of the main chain of the polyimide may be sealed with a terminal blocking agent such as a monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound. preferable. Of these, it is more preferable to use a monoamine. Preferred examples of the monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, and 1-hydroxy-7. -Aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2, -Hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6- Aminonaphthalene, 2-carbo Ci-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-amino Benzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4 -Aminothiophenol and the like. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.

The polyimide preferably has an imidization ratio of 85% or more, more preferably 90% or more. When the imidization ratio is 85% or more, film shrinkage due to ring closure that occurs when imidization is performed by heating is reduced, and generation of warpage can be suppressed.

The polyimide may contain repeating units based on two or more different types of these groups in addition to the repeating structural unit of the above formula (4) all based on one kind of R ¹³¹ or R ¹³² . The polyimide may also contain other types of repeating structural units in addition to the repeating unit of the above formula (4).

For example, polyimide can be prepared by reacting tetracarboxylic dianhydride with a diamine compound (partially replaced with a monoamine end-capping agent) at low temperature, or tetracarboxylic dianhydride (partially acid at low temperature). A method of reacting an anhydride, a monoacid chloride compound or a mono-active ester compound with an end-capping agent) and a diamine compound, a tetracarboxylic dianhydride and an alcohol to obtain a diester, and then a diamine (partly a monoamine) A method of reacting in the presence of a condensing agent and a tetracarboxylic dianhydride and an alcohol to obtain a diester, and then converting the remaining dicarboxylic acid to an acid chloride to obtain a diamine (partially a monoamine) The polyimide precursor is obtained using a method such as a method of reacting with an end-capping agent that is a known method. A method of complete imidization using the imidation reaction method, a method of stopping the imidization reaction in the middle and introducing a part of an imide structure, and further blending a completely imidized polymer and its polyimide precursor By some things, it can synthesize | combine using the method of introduce | transducing a partial imide structure.
Examples of commercially available polyimide products include Durimide (registered trademark) 284 (manufactured by FUJIFILM Corporation) and Matrimid 5218 (manufactured by HUNTSMAN Co., Ltd.).

The weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and still more 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 having excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. Moreover, when it contains 2 or more types of polyimides, it is preferable that the weight average molecular weight of at least 1 type of polyimide is the said range.

<< Polybenzoxazole precursor >>
The polybenzoxazole precursor used in the present invention is not particularly defined with respect to its structure and the like, but is preferably represented by the following formula (3).
Formula (3)

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

In the formula (3), R ¹²³ and R ¹²⁴ have the same meaning as R ¹¹³ in the formula (2), respectively, and the preferred range is also the same. That is, at least one is preferably a polymerizable group.
In the formula (3), R ¹²¹ represents a divalent organic group. The divalent organic group is preferably a group containing at least one of an aliphatic group and an aromatic group. As the aliphatic group, a linear aliphatic group is preferable. 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 preferred, and a dicarboxylic acid containing an aromatic group is more preferred.
As the dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group is preferable, and a linear or branched (preferably linear) aliphatic group and two COOHs are used. More preferred is a dicarboxylic acid. The linear or branched (preferably linear) aliphatic group preferably has 2 to 30 carbon atoms, more preferably 2 to 25 carbon atoms, still more preferably 3 to 20 carbon atoms. 15 is more preferable, and 5 to 10 is particularly preferable. The linear aliphatic group is preferably an alkylene group.
Examples of the dicarboxylic acid containing a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2, 2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberin Acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid Dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosandioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosane diacid Acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosandioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, and the following formula And dicarboxylic acid.

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

The dicarboxylic acid containing an aromatic group is preferably a dicarboxylic acid having the following aromatic group, more preferably a dicarboxylic acid comprising only the following aromatic group and two COOH.

In the formula, A represents —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, and —C (CH ₃ ) ₂ —. Represents a divalent group selected from the group consisting of

Specific examples of the dicarboxylic acid containing an aromatic group include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.

In the formula (3), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same meaning as R ¹¹⁵ in the formula (2), and preferred ranges are also the same.
R ¹²² is preferably a group derived from a bisaminophenol derivative. Examples of the group derived from a bisaminophenol derivative include 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4 ′ -Diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, 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'-dihydroxybenzophenone, 4,4'- Diamino-3,3′-dihydroxydiphenyl ether, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene 1,3-diamino-4,6-dihydroxybenzene and the like. These bisaminophenols may be used alone or in combination.

Of the bisaminophenol derivatives, bisaminophenol derivatives having the following aromatic groups are preferred.

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

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

(In the formula (A-sc), * indicates binding to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by the above formula (As).)

In the above formula (As), it is considered that the ortho position of the phenolic hydroxyl group, that is, that R ₃ also has a substituent is considered to make the distance between the carbonyl carbon of the amide bond and the hydroxyl group closer, and cured at a low temperature. In particular, it is particularly preferable in that the effect of increasing the cyclization rate is further increased.

Further, in the above formula (As), R ₂ is an alkyl group and R ₃ is an alkyl group, which means that it has high transparency to i-line and a high cyclization rate when cured at low temperature. The effect can be maintained and is preferable.

In the above formula (As), it is more preferable that R ₁ is alkylene or substituted alkylene. Specific examples of alkylene and substituted alkylene according to 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 C _{_{_{_{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) - but the like Among them, —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ — maintain the effect of high transparency to i-line and high cyclization rate when cured at low temperature. However, it is more preferable in that a polybenzoxazole precursor having sufficient solubility in a solvent and excellent in balance can be obtained.

As a method for producing the bisaminophenol derivative represented by the above formula (As), for example, refer to paragraph numbers 0085 to 0094 and Example 1 (paragraph numbers 0189 to 0190) of JP2013-256506A. The contents of which are incorporated herein.

Specific examples of the structure of the bisaminophenol derivative represented by the formula (As) include those described in JP-A-2013-256506, paragraphs 0070 to 0080, and the contents thereof are described in the present specification. Incorporated into. Of course, it is needless to say that the present invention is not limited to these.

The polybenzoxazole precursor may contain other types of repeating structural units in addition to the repeating unit of the above formula (3).
It is preferable that the diamine residue represented by the following formula (SL) is included as another type of repeating structural unit in that the occurrence of warpage accompanying ring closure can be suppressed.

In formula (SL), Z has an a structure and a b structure, R ^1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ^2s is a hydrocarbon group having 1 to 10 carbon atoms. And at least one of R ^3s , R ^4s , R ^5s and R ^6s is an aromatic group, and the remainder is a hydrogen atom or an organic group having 1 to 30 carbon atoms, which may be the same or different. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. The mol% of the Z moiety is 5 to 95 mol% for the a structure, 95 to 5 mol% for the b structure, and a + b is 100 mol%.

In the formula (SL), preferred Z includes those in which R ^5s and R ^6s in the b structure are phenyl groups. The molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. By making the said molecular weight into the said range, the effect which can lower the elasticity modulus after spin-drying | dehydration cyclization of a polybenzoxazole precursor, and can suppress curvature, and the effect which improves solvent solubility can be made more effective.

When a diamine residue represented by the formula (SL) is included as another type of repeating structural unit, a tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic dianhydride is included as a repeating structural unit. Is also preferable. Examples of such tetracarboxylic acid residue, and examples of R ¹¹⁵ in formula (2).

The weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, preferably 18,000 to 30,000, more preferably 20,000 to 29,000 when used in the composition described below. It is preferably 22,000 to 28,000. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and still more preferably 9,200 to 11,200.
The degree of dispersion of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and further preferably 1.6 or more. The upper limit value of the degree of dispersion of the polybenzoxazole precursor is not particularly defined, but is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, and more preferably 2.3 or less. Preferably, 2.2 or less is even more preferable.

<< Polybenzoxazole >>
The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but is preferably a compound represented by the following formula (X), and a compound represented by the following formula (X) And it is more preferable that it is a compound which has a polymeric group.

In formula (X), R ¹³³ represents a divalent organic group, and R ¹³⁴ represents a tetravalent organic group.
In the case of having a polymerizable group, the polymerizable group may be located in at least one of R ¹³³ and R ¹³⁴ , or polybenzoxazole as shown in the following formula (X-1) or formula (X-2) It may be located at the end of.
Formula (X-1)

In formula (X-1), at least one of R ¹³⁵ and R ¹³⁶ is a polymerizable group, and when not a polymerizable group, it is an organic group, and the other groups are as defined in formula (X).
Formula (X-2)

In the formula (X-2), R ¹³⁵ is a polymerizable group, the other is a substituent, and the other groups are as defined in the formula (X).

The polymerizable group has the same meaning as the polymerizable group described in the polymerizable group possessed by the polyimide precursor or the like.

R ¹³³ represents a divalent organic group. Examples of the divalent organic group include an aliphatic or aromatic group. Specific examples include R ^{121 in} the polybenzoxazole precursor (3). Moreover, the preferable example is the same as that of ^R121 .

R ¹³⁴ represents a tetravalent organic group. As a tetravalent organic group, the example of ^R122 in Formula (3) of a polybenzoxazole precursor is mentioned. Moreover, the preferable example is the same as that of ^R122 .
For example, four bonds of a tetravalent organic group exemplified as R ¹²² are bonded to a nitrogen atom or an 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.

Polybenzoxazole preferably has an oxazolation rate of 85% or more, more preferably 90% or more. When the oxazolation rate is 85% or more, film shrinkage due to ring closure that occurs when oxazolation is performed by heating is reduced, and the occurrence of warpage can be more effectively suppressed.

Polybenzoxazoles, In addition to all the repeating structural units of the formula based on one ^{R 131} or ^{R 132} (X), the table in the above formula (X) comprising two or more different types of ^{R 131} or ^{R 132} May be included. The polybenzoxazole may also contain other types of repeating structural units in addition to the repeating unit of the above formula (X).

Polybenzoxazole is obtained, for example, by reacting a bisaminophenol derivative with a dicarboxylic acid containing R ¹³³ or a compound selected from dicarboxylic acid dichloride and dicarboxylic acid derivative of the above dicarboxylic acid to obtain a polybenzoxazole precursor. This can be obtained by oxazolation using a known oxazolation reaction method.
In the case of dicarboxylic acid, an active ester type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1,2,3-benzotriazole or the like in advance may be used in order to increase the reaction yield or the like.

The weight average molecular weight (Mw) of polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and still more 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 having excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. Moreover, when it contains 2 or more types of polybenzoxazole, it is preferable that the weight average molecular weight of at least 1 type of polybenzoxazole is the said range.

<< Method for producing polyimide precursor, etc. >>
A polyimide precursor or the like is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, it is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then reacting with a diamine.
In the method for producing a polyimide precursor or the like, an organic solvent is preferably used for the reaction. One or more organic solvents may be used.
The organic solvent can be appropriately determined according to the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.
Polyimide may be produced by synthesizing a polyimide precursor and then cyclized by heating, or may be synthesized directly.

<<< End sealant >>>
In order to further improve the storage stability in the production method of the polyimide precursor, etc., the end of the polyimide precursor etc. is terminated with an end-capping agent such as an acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound, etc. It is preferable to seal. As the end-capping agent, it is more preferable to use monoamine, and preferable monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1- Hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-amino Naphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy -6-aminonaphthalene, 2- Ruboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-amino Benzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4 -Aminothiophenol and the like. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.

<<< Solid precipitation >>>
When manufacturing a polyimide precursor etc., the process of depositing a solid may be included. Specifically, solid precipitation can be achieved by precipitating a polyimide precursor or the like in the reaction solution in water and dissolving the polyimide precursor or the like such as tetrahydrofuran in a soluble solvent.
Then, a polyimide precursor etc. can be dried and a powdery polyimide precursor etc. can be obtained.

The composition used in the present invention may contain only one of polyimide precursor, polyimide, polybenzoxazole precursor and polybenzoxazole, or may contain two or more. Also, two or more types of polyimide precursors may be included, which are the same type of resin and have different structures.
The content of the polyimide precursor or the like in the composition used in the present invention is preferably 10 to 99% by mass, more preferably 50 to 98% by mass, and further preferably 70 to 96% by mass.
Hereinafter, components that can be contained in the composition used in the present invention will be described. It goes without saying that the present invention may contain components other than these, and these components are not essential.

<< polymerizable compound >>
In this invention, as above-mentioned, it is preferable that resin, such as a polyimide precursor, has a polymeric group or the photosensitive resin composition contains a polymeric compound. By setting it as such a structure, the cured film excellent in heat resistance can be formed.
The polymerizable compound is a compound having a polymerizable group, and a known compound that can be crosslinked by a radical, an acid, a base, or the like can be used. Examples of the polymerizable group include the polymerizable groups described in the above-mentioned polyimide precursor and the like. The polymerizable compound may contain only 1 type, and may contain 2 or more types.
The polymerizable compound may be in any chemical form such as, for example, a monomer, a prepolymer, an oligomer and a mixture thereof, and a multimer thereof.

In the present invention, a monomer type polymerizable compound (hereinafter also referred to as a polymerizable monomer) is a compound different from a polymer compound. The polymerizable monomer is typically a low molecular compound, preferably a low molecular compound having a molecular weight of 2,000 or less, more preferably a low molecular compound having a molecular weight of 1,500 or less, and a molecular weight of 900 or less. More preferably, it is a low molecular weight compound. The molecular weight of the polymerizable monomer is usually 100 or more.
The oligomer type polymerizable compound is typically a polymer having a relatively low molecular weight, and is preferably a polymer in which 10 to 100 polymerizable monomers are bonded. 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 the polymerizable compound in the present invention means the number of polymerizable groups in one molecule.
From the viewpoint of resolution, the polymerizable compound preferably contains at least one bifunctional or higher functional polymerizable compound containing two or more polymerizable groups, and preferably contains at least one trifunctional or higher functional polymerizable compound. More preferred.
Moreover, it is preferable that the polymeric compound in this invention contains at least 1 sort (s) of polymeric compounds more than trifunctional from the point that a three-dimensional crosslinked structure can be formed and heat resistance can be improved. Also, a mixture of a bifunctional or lower polymerizable compound and a trifunctional or higher functional polymerizable compound may be used.

<<< Compound having an ethylenically unsaturated bond >>>
As the group having an ethylenically unsaturated bond, a styryl group, a vinyl group, a (meth) acryloyl group and a (meth) allyl group are preferable, and a (meth) acryloyl group is more preferable.

Specific examples of the compound having an ethylenically unsaturated bond include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, and the like. Preferred are an ester of an unsaturated carboxylic acid and a polyhydric alcohol compound, an amide of an unsaturated carboxylic acid and a polyvalent amine compound, and a multimer thereof. Further, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxy group, amino group, mercapto group, etc., monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, and further a halogen group A substituted reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as thiol or tosyloxy group with a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a compound group in which an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like is used instead of the unsaturated carboxylic acid.

Specific examples of esters of polyhydric alcohol compounds and unsaturated carboxylic acids include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol diacrylate. , Propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetra Ethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Pentaerythritol diacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, isocyanuric acid ethylene oxide modified triacrylate, polyester acrylate An oligomer etc. are mentioned.

Methacrylic acid esters include 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, bis [p- (3-methacryloxy- 2-hydroxyp Epoxy) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane, and the like.

Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate Sorbitol tetritaconate and the like.

Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.

Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

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

Examples of other esters include aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, and JP-A-59-5240. No. 1, JP-A-59-5241, JP-A-2-226149, those having an aromatic skeleton, those having an amino group described in JP-A-1-165613, etc. are preferably used. It is done.

Specific examples of amide monomers of polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis-methacrylic. Examples include amide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, and xylylene bismethacrylamide.

Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.

In addition, urethane-based addition-polymerizable monomers produced using an addition reaction of isocyanate and hydroxyl group are also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708. Examples thereof include a vinylurethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following formula to a polyisocyanate compound having two or more isocyanate groups.
_{^{_{CH 2 = C (R 4)}}} COOCH 2 CH (R 5) OH
(However, R ⁴ and R ⁵ represent H or CH _3. )
Further, urethane acrylates as described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56- Urethane compounds having an ethylene oxide skeleton described in JP 17654, JP-B 62-39417, and JP-B 62-39418 are also suitable.

As the compound having an ethylenically unsaturated bond, the compounds described in paragraph numbers 0095 to 0108 of JP-A-2009-288705 can also be suitably used in the present invention.

Moreover, as a compound which has an ethylenically unsaturated bond, the compound which has a boiling point of 100 degreeC or more under a normal pressure is also preferable. Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri (meta ) Acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) ) Acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as nurate, glycerin and trimethylolethane, JP-B-48-41708, JP-B-50-6034, JP-A-51- Urethane (meth) acrylates as described in JP-B-37193, polyester acrylates described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490 And polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, and mixtures thereof. Further, the compounds described in paragraph numbers 0254 to 0257 of JP-A-2008-292970 are also suitable. Moreover, the polyfunctional (meth) acrylate obtained by making cyclic ether groups, such as glycidyl (meth) acrylate, and the compound which has an ethylenically unsaturated group, react with polyfunctional carboxylic acid etc. can be mentioned.
Further, as other preferable compounds having an ethylenically unsaturated bond, those having a fluorene ring described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, etc. A compound having two or more groups having an unsaturated bond, a cardo resin can also be used.
Other examples include specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and JP-A-2-25493. The vinyl phosphonic acid-type compound of these can also be mentioned. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photopolymerizable monomers and oligomers, can also be used.

In addition to the above, compounds having an ethylenically unsaturated bond represented by the following formulas (MO-1) to (MO-5) can also be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

In the above formula, n is an integer from 0 to 14, and m is an integer from 0 to 8. A plurality of R and T present in one molecule may be the same or different.
In each of the polymerizable compounds represented by the above formulas (MO-1) to (MO-5), at least one of a plurality of R is —OC (═O) CH═CH ₂ or —OC (= O) represents a group represented by C (CH ₃ ) ═CH ₂ .
Specific examples of the compound having an ethylenically unsaturated bond represented by the above formulas (MO-1) to (MO-5) are described in paragraph numbers 0248 to 0251 of JP-A-2007-267979. The compound can also be suitably used in the present invention.

In addition, in JP-A-10-62986, compounds (meth) acrylates obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol described in the formulas (1) and (2) together with specific examples thereof are also provided. It can be used as a polymerizable compound.

Furthermore, the compounds described in paragraph numbers 0104 to 0131 of JP-A No. 2015-187211 can also be employed, the contents of which are incorporated herein. In particular, the compounds described in paragraph numbers 0128 to 0130 of the publication are exemplified as preferred forms.

Examples of the compound having an ethylenically unsaturated bond include dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D- 320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available products are KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available product) As such, KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and those having a structure in which these (meth) acryloyl groups are bonded via ethylene glycol and propylene glycol residues are preferred. These oligomer types can also be used.
Further, preferred examples include pentaerythritol derivatives and / or dipentaerythritol derivatives of the above formulas (MO-1) and (MO-2).

Examples of commercially available polymerizable compounds include SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains, and SR-209, which is a bifunctional methacrylate having four ethyleneoxy chains (above, Sartomer Japan, Inc. )), DPCA-60 which is a 6-functional acrylate having 6 pentyleneoxy chains, TPA-330 which is a 3-functional acrylate having 3 isobutyleneoxy chains (above, Nippon Kayaku Co., Ltd.), urethane oligomer UAS-10, UAB-140 (Sanyo Kokusaku Pulp Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (above, Shin-Nakamura Chemical Industrial Co., Ltd.), DPHA-40H (Nippon Kayaku Co., Ltd.), UA-306H, UA-306 , UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co.), BLEMMER PME400 (NOF Corporation) and the like.

Examples of the compound having an ethylenically unsaturated bond include those described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. Urethane acrylates and urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. It is. Furthermore, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are described as polymerizable compounds. Monomers can also be used.

The compound having an ethylenically unsaturated bond may be a polyfunctional monomer having an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. The polyfunctional monomer having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an unreacted hydroxy group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid group. More preferably, the ester is a polyfunctional monomer in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include M-510 and M-520, which are polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
As the polyfunctional monomer having an acid group, one kind may be used alone, or two or more kinds may be mixed and used. Moreover, you may use together the polyfunctional monomer which does not have an acid group, and the polyfunctional monomer which has an acid group as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When the acid value of the polyfunctional monomer is in the above range, the production and handling properties are excellent, and further, the developability is excellent. Also, the polymerizability is good.

Such a polymerizable compound having a caprolactone structure is commercially available, for example, from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and DPCA-20 (m = 1 in the above formulas (C) to (E), The number of groups represented by D) = 2, a compound in which R ¹ is all hydrogen atoms), DPCA-30 (formula, m = 1, the number of groups represented by formula (D) = 3, R ¹ In which all are hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (D) = 6, R ¹ is all hydrogen atoms), DPCA-120 (same as above) In the formula, m = 2, the number of groups represented by formula (D) = 6, and compounds in which R ¹ is all a hydrogen atom).
In the present invention, the compounds having a caprolactone structure and an ethylenically unsaturated bond can be used alone or in admixture of two or more.

In the composition, the content of the compound having an ethylenically unsaturated bond is preferably 1 to 50% by mass with respect to the total solid content of the composition from the viewpoint of good polymerizability and heat resistance. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 30% by mass or less. As the compound having an ethylenically unsaturated bond, one kind may be used alone, or two or more kinds may be mixed and used.
The mass ratio of the polyimide precursor or the like and the compound having an ethylenically unsaturated bond (polyimide precursor or the like / polymerizable compound) is preferably 98/2 to 10/90, more preferably 95/5 to 30/70. 90/10 to 50/50 is most preferable. If the mass ratio of a polyimide precursor etc. and the compound which has an ethylenically unsaturated bond is the said range, the cured film excellent in polymerizability and heat resistance can be formed.

<<< Compound having hydroxymethyl group, alkoxymethyl group or acyloxymethyl group >>>
As the compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, a compound represented by the following formula (AM1) is preferable.

(AM1)

(Wherein 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 the following formula (AM2) or the following formula (AM3): Represents a group to be selected.)

Formula (AM2) Formula (AM3)

(Wherein R ⁶ represents a hydroxyl group or an organic group having 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 to 35 mass parts. Moreover, 10 mass% or more and 90 mass% or less of the compound represented by a following formula (AM4) are contained in all the polymeric compounds, and the compound represented by a following formula (AM5) is 10 mass% or more in a total thermal crosslinking agent. It is also preferable to contain 90 mass% or less.

(AM4)

(Wherein 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)).

(AM5)

(Wherein 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 is represented by the following formula (AM2) or the following formula (AM3) Group.)

Formula (AM2) Formula (AM3)

By setting it within this range, cracks are less likely to occur when the composition is cured on an uneven substrate. It has excellent pattern processability and can have high heat resistance such that the 5% mass reduction temperature is 350 ° C. or higher, more preferably 380 ° C. or higher. Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (trade name, manufactured by Asahi Organic Materials Co., Ltd.), 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 (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), NIKACALAC MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl- Examples thereof include p-cresol.

Specific examples of the compound represented by the formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.), NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW-100LM (trade name, manufactured by Sanwa Chemical Co., Ltd.).

<<< Epoxy Compound (Compound Having Epoxy Group) >>>
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group undergoes a cross-linking reaction at 200 ° C. or less and does not cause a dehydration reaction due to cross-linking, so that film shrinkage hardly occurs. For this reason, containing an epoxy compound is effective for low-temperature curing and low warpage of the composition.

The epoxy compound preferably contains a polyethylene oxide group. As a result, the elastic modulus can be further reduced and the warpage can be further reduced. Moreover, since the flexibility is high, a cured film having excellent elongation and the like can be obtained. The polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.

Examples of the epoxy compound include bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resin such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resin such as polypropylene glycol diglycidyl ether; polymethyl (glycidyl Examples include, but are not limited to, epoxy group-containing silicones such as (roxypropyl) siloxane. Specifically, Epicron (registered trademark) 850-S, Epicron (registered trademark) HP-4032, Epicron (registered trademark) HP-7200, Epicron (registered trademark) HP-820, Epicron (registered trademark) HP-4700, Epicron (registered trademark) EXA-4710, Epicron (registered trademark) HP-4770, Epicron (registered trademark) EXA-859CRP, Epicron (registered trademark) EXA-1514, Epicron (registered trademark) EXA-4880, Epicron (registered trademark) EXA-4850-150, Epicron EXA-4850-1000, Epicron (registered trademark) EXA-4816, Epicron (registered trademark) EXA-4822 (trade name, manufactured by DIC Corporation), Rica Resin (registered trademark) BEO-60E (Product name, Shin Nippon Rika Co., Ltd.), EP 4003S, EP-4000S (trade names, Ltd. Adeka), and the like. Among these, an epoxy resin containing a polyethylene oxide group is preferable in terms of excellent low warpage and heat resistance. For example, Epicron (registered trademark) EXA-4880, Epicron (registered trademark) EXA-4822, and Licaredin (registered trademark) BEO-60E are preferable because they contain a polyethylene oxide group.

The compounding amount of the epoxy compound is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and further preferably 10 to 40 parts by mass with respect to 100 parts by mass of the polyimide precursor or the like. When the blending amount is 5 parts by mass or more, warpage of the cured film can be further suppressed, and when it is 50 parts by mass or less, pattern filling due to reflow during curing can be further suppressed.

<<< Oxetane compound (compound having oxetanyl group) >>>
Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, Examples include 3-ethyl-3- (2-ethylhexylmethyl) oxetane and 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester. As a specific example, Aron Oxetane series (for example, OXT-121, OXT-221, OXT-191, OXT-223) manufactured by Toagosei Co., Ltd. can be preferably used. Or you may mix 2 or more types.

The blending amount of the oxetane compound is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and further preferably 10 to 40 parts by mass with respect to 100 parts by mass of the polyimide precursor or the like.

<<< benzoxazine compound (compound having a benzoxazolyl group) >>>
A benzoxazine compound is preferable because it undergoes a crosslinking reaction by a ring-opening addition reaction, so that degassing due to curing does not occur, and further, since shrinkage due to heat is small, generation of warpage is suppressed.

Preferred examples of the benzoxazine compound include Ba type benzoxazine, Bm type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, phenol novolac type dihydro A benzoxazine compound is mentioned. These may be used alone or in combination of two or more.

The blending amount of the benzoxazine compound is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and further preferably 10 to 40 parts by mass with respect to 100 parts by mass of the polyimide precursor or the like.

<< photopolymerization initiator >>
The composition used in the present invention may contain a photopolymerization initiator. In particular, when the composition contains a photo radical polymerization initiator, the composition is applied to a semiconductor wafer or the like to form a composition layer, and then irradiation with light causes curing by radicals. Solubility can be reduced. For this reason, there exists an advantage that the area | region from which solubility differs can be easily produced according to the pattern of an electrode by exposing the said composition layer through the photomask with the pattern which masked only the electrode part, for example.

The photopolymerization initiator is not particularly limited as long as it has the ability to initiate a polymerization reaction (crosslinking reaction) of the polymerizable compound with light, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to light in the ultraviolet region to the visible region are preferable. Further, it may be an activator that generates some active radicals by generating some action with the photoexcited sensitizer.
The photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 to 800 nm (preferably 330 to 500 nm). The molar extinction coefficient of the compound can be measured using a known method. Specifically, for example, it is preferable to measure with a UV-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) at a concentration of 0.01 g / L using an ethyl acetate solvent.

As the photopolymerization initiator, known compounds can be used without limitation. For example, halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, those having a trihalomethyl group), Acylphosphine compounds such as acylphosphine oxide, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo series Examples thereof include compounds, azide compounds, metallocene compounds, organoboron compounds, iron arene complexes, and the like.

Examples of halogenated hydrocarbon derivatives having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3333724, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US patents And the compounds described in the specification of No. 42122976.

Examples of the compounds described in US Pat. No. 4,221,976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2-trichloro Methyl-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.).

Further, as photopolymerization initiators other than those described above, compounds described in paragraph No. 0086 of JP-A-2015-087611, JP-A-53-133428, JP-B-57-1819, JP-A-57-6096 And the compounds described in US Pat. No. 3,615,455, and the like, the contents of which are incorporated herein.

Examples of the ketone compound include compounds described in paragraph No. 0087 of JP-A-2015-087611, the contents of which are incorporated herein.
As a commercial product, Kaya Cure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators 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 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, compounds described in JP-A-2009-191179 having a maximum absorption wavelength matched in a long wave region such as 365 nm or 405 nm can also be used.
Examples of the acylphosphine initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) which are commercially available products can be used.
Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF).

More preferred examples of the photopolymerization initiator include oxime compounds. By using the oxime compound, the exposure latitude can be improved more effectively. Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
Preferred oxime compounds include, for example, the following compounds, 3-benzooxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentane- 3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, 1-phenyl-1,2-butanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-butanedione-2- (O -Ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-me Xycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-benzoyl) oxime, 1,3- Examples thereof include diphenylpropanetrione-2- (O-ethoxycarbonyl) oxime and 1-phenyl-3-ethoxypropanetrione-2- (O-benzoyl) oxime.

Examples of oxime compounds include JCSPerkin II (1979) pp.1653-1660, JCSPerkin II (1979) pp.156-162, Journal of Photopolymer Science and Technology (1995) pp.202-232, and -66385, JP-A 2000-80068, JP-T 2004-534797, JP-A 2006-342166, and the like.
IRGACURE OX-01 (manufactured by BASF), IRGACURE OXE-02 (manufactured by BASF), and N-1919 (manufactured by ADEKA) are also preferably used as commercial products. In addition, TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), Adeka Arcles NCI-831 and Adeka Arcles NCI-930 (manufactured by ADEKA Corporation) can also be used. Also, TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), Adeka Arkles NCI-831 and Adeka Arkles NCI-930 (manufactured by ADEKA Corporation) can be used. Further, DFI-091 (manufactured by Daitokemix Co., Ltd.) can also be used.

Further, compounds described in JP-A-2009-519904 in which an oxime is linked to the N-position of carbazole, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into a benzophenone moiety, and a nitro group in a dye moiety The compound described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039, the ketoxime compound described in International Publication No. WO2009-131189, the United States containing a triazine skeleton and an oxime skeleton in the same molecule A compound described in Japanese Patent No. 7556910, a compound described in JP2009-221114A having an absorption maximum at 405 nm and good sensitivity to a g-ray light source may be used.
In addition, the cyclic oxime compounds described in JP-A-2007-231000 and JP-A-2007-322744 can also be suitably used. Among cyclic oxime compounds, in particular, cyclic oxime compounds fused to carbazole dyes described in JP2010-32985A and JP2010-185072A have high light absorptivity and high sensitivity. preferable.
In addition, a compound described in JP-A-2009-242469, which is a compound having an unsaturated bond at a specific site of the oxime compound, can also be suitably used.
Furthermore, it is also possible to use an oxime compound having a fluorine atom. Specific examples of such oxime compounds include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in paragraph No. 0345 of JP-T-2014-500852, JP Examples thereof include compound (C-3) described in paragraph No. 0101 of 2013-164471. Specific examples include the following compounds.

As the most preferred oxime compounds, there are oxime compounds having a specific substituent as disclosed in JP-A-2007-267979, oxime compounds having a thioaryl group as disclosed in JP-A-2009-191061, and the like.

Photopolymerization initiators are trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryls from the viewpoint of exposure sensitivity. Selected from the group consisting of imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds. Are preferred.
More preferably, they are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, acetophenone compounds, and trihalomethyltriazine compounds. , Α-aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and at least one compound selected from the group consisting of benzophenone compounds is more preferable, metallocene compounds or oxime compounds are more preferable, and oxime compounds are particularly preferable. preferable.
Photopolymerization initiators include N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-, such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone), etc. Aromatic ketones such as 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, alkyl anthraquinones, etc. It is also possible to use quinones fused with an aromatic ring, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, and benzyl derivatives such as benzyldimethyl ketal. A compound represented by the following formula (I) can also be used.

In the formula (I), R ⁵⁰ represents an alkyl group having 1 to 20 carbon atoms; an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms; an alkoxy group having 1 to 12 carbon atoms; a phenyl group; An alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, and 2 to 2 carbon atoms interrupted by one or more oxygen atoms A phenyl group substituted with at least one of 18 alkyl groups and an alkyl group having 1 to 4 carbon atoms; or biphenylyl, and R ⁵¹ is a group represented by the formula (II), or R ⁵⁰ and R ⁵² to R ⁵⁴ are each independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or halogen.

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

As the photopolymerization initiator, compounds described in paragraph numbers 0048 to 0055 of International Publication No. WO2015 / 125469 can be used.

When the composition contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass with respect to the total solid content of the composition. More preferably, the content is 0.1 to 10% by mass.
Only one type of photopolymerization initiator may be used, or two or more types may be used. When there are two or more photopolymerization initiators, the total is preferably in the above range.

<Migration inhibitor>
The photosensitive resin composition used in the production method of the present invention preferably further contains a migration inhibitor. By including a migration inhibitor, it becomes possible to effectively suppress the migration of metal ions derived from the metal layer (metal wiring) into the photosensitive resin composition.
The migration inhibitor is not particularly limited, but a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, A compound having a pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), a compound having a thiourea and a mercapto group, a hindered phenol compound, Examples include salicylic acid derivative compounds and hydrazide derivative compounds. In particular, triazole compounds such as triazole and benzotriazole, and tetrazole compounds such as tetrazole and benzotetrazole can be preferably used.

In addition, an ion trapping agent that captures anions such as halogen ions can also be used. There is no restriction | limiting in particular as an ion trap agent, A conventionally well-known thing can be used. In particular, hydrotalcite represented by the following composition formula or hydrated oxide of bismuth represented by the following composition formula is preferable.
Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X / 2} · mH ₂ O
(In the above composition formula, 0 <X ≦ 0.5, m is a positive number)
BiO _x (OH) _y (NO ₃ ) _z
(In the above composition formula, 0.9 ≦ x ≦ 1.1, 0.6 ≦ y ≦ 0.8, 0.2 ≦ z ≦ 0.4)
The hydrotalcite is a commercial product available from Kyowa Chemical Industry Co., Ltd. under the trade name: DHT-4A. Moreover, the said bismuth is available as a brand name: IXE500 by Toagosei Co., Ltd. with a commercial item. Moreover, you may use another ion trap agent as needed. Examples thereof include hydrated oxides of elements selected from magnesium, aluminum, titanium, zirconium, antimony, and the like. These ion trapping agents can be used alone or in combination of two or more.

Examples of other migration inhibitors include a rust inhibitor described in paragraph No. 0094 of JP2013-15701A, a compound described in paragraph Nos. 0073 to 0076 of JP2009-283711A, and JP2011-59656A. And the compounds described in paragraph Nos. 0114, 0116 and 0118 of JP 2012-194520 A, and the like.

When the composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, and 0.05 to 2.0% by mass with respect to the total solid content of the composition. More preferred is 0.1 to 1.0% by mass.
Only one type of migration inhibitor may be used, or two or more types may be used. When there are two or more migration inhibitors, the total is preferably within the above range.

<< Polymerization inhibitor >>
The photosensitive resin composition used in the production method of the present invention preferably contains a polymerization inhibitor.
Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,3,5-tris (4-t-butyl-3- Hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, p-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N -Phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediamy Tetraacetic acid, glycol ether diamine tetraacetic 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-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, bis (4-hydroxy-3,5-tert-butyl) phenyl Methane or the like is preferably used. In addition, a polymerization inhibitor described in paragraph No. 0060 of JP-A-2015-127817 and compounds described in paragraph Nos. 0031 to 0046 of International Publication No. 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 with respect to the total solid content of the composition.
Only one polymerization inhibitor may be used, or two or more polymerization inhibitors may be used. When two or more polymerization inhibitors are used, the total is preferably within the above range.

<< thermal base generator >>
The photosensitive resin composition used in the production method of the present invention may contain a thermal base generator.
The type of the thermal base generator is not particularly defined, but it is selected from an acidic compound that generates a base when heated to 40 ° C. or higher, and an ammonium salt having an anion having an pKa1 of 0 to 4 and an ammonium cation. It is preferable to include a thermal base generator containing at least one of the above. Here, pKa1 represents a logarithmic representation (−Log ₁₀ Ka) of the dissociation constant (Ka) of the first proton of the polyvalent acid.
By mix | blending such a compound, the cyclization reaction of a polyimide precursor can be performed at low temperature, and it can be set as the composition excellent in stability. Moreover, since the base is not generated unless heated, the thermal base generator can suppress cyclization of the polyimide precursor during storage even if it coexists with the polyimide precursor, and is excellent in storage stability.

The thermal base generator in the present invention is at least one selected from an acidic compound (A1) that generates a base when heated to 40 ° C. or higher, and an ammonium salt (A2) having an anion having a pKa1 of 0 to 4 and an ammonium cation. including.
Since the acidic compound (A1) and the ammonium salt (A2) generate a base when heated, the base generated from these compounds can accelerate the cyclization reaction of the polyimide precursor, thereby cyclizing the polyimide precursor. Can be performed at low temperatures. In addition, even if these compounds coexist with a polyimide precursor that is cured by cyclization with a base, since the cyclization of the polyimide precursor hardly proceeds unless heated, a polyimide precursor composition having excellent stability can be obtained. Can be prepared.
In the present specification, an acidic compound means that 1 g of a compound is collected in a container, and 50 mL of a mixed solution of ion-exchanged water and tetrahydrofuran (mass ratio is water / tetrahydrofuran = 1/4) is added to the mixture at room temperature for 1 hour. Stir. The value of the solution measured at 20 ° C. using a pH meter is less than 7.

In the present invention, the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40 ° C. or higher, more preferably 120 to 200 ° C. The upper limit of the base generation temperature is more preferably 190 ° C or lower, further preferably 180 ° C or lower, and further preferably 165 ° C or lower. The lower limit of the base generation temperature is more preferably 130 ° C or higher, and still more preferably 135 ° C or higher.
If the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 40 ° C. or higher, and further 120 ° C. or higher, the base is unlikely to be generated during storage, so the polyimide precursor composition has excellent stability. Can be prepared. When the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 200 ° C. or less, the cyclization temperature of the polyimide precursor can be reduced. The base generation temperature is measured, for example, by using differential scanning calorimetry, heating the compound to 250 ° C. at 5 ° C./min in a pressure capsule, reading the peak temperature of the lowest exothermic peak, and measuring the peak temperature as the base generation temperature. can do.

In the present invention, the base generated by the thermal base generator is preferably a secondary amine or a tertiary amine, more preferably a tertiary amine. Since tertiary amine has high basicity, the cyclization temperature of a polyimide precursor can be lowered more. Further, the boiling point of the base generated by the thermal base generator is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and most preferably 140 ° C. or higher. The molecular weight of the generated base is preferably 80 to 2,000. The lower limit is more preferably 100 or more. The upper limit is more preferably 500 or less. The molecular weight value is a theoretical value obtained from the structural formula.

In the present invention, the acidic compound (A1) preferably contains one or more selected from an ammonium salt and a compound represented by the formula (101) or (102) described later.

In the present invention, the ammonium salt (A2) is preferably an acidic compound. The ammonium salt (A2) may be a compound containing an acidic compound that generates a base when heated to 40 ° C. or higher (preferably 120 to 200 ° C.), or 40 ° C. or higher (preferably 120 to 200 ° C.). ) May be a compound other than an acidic compound that generates a base when heated.

<<< Ammonium salt >>>
In the present invention, the ammonium salt means a salt of an ammonium cation represented by the following formula (101) or formula (102) and an anion. The anion may be bonded to any part of the ammonium cation via a covalent bond, and may be outside the molecule of the ammonium cation, but may be outside the molecule of the ammonium cation. preferable. In addition, that an anion has outside the molecule | numerator of an ammonium cation means the case where an ammonium cation and an anion are not couple | bonded through a covalent bond. Hereinafter, the anion outside the cation molecule is also referred to as a counter anion.
Formula (101) Formula (102)

In the formula, R ¹ to R ⁶ each independently represents 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 , R ⁵ and R ⁷ may be bonded to form a ring.

The ammonium cation is preferably represented by any of the following formulas (Y1-1) to (Y1-5).

In the above formula, R ¹⁰¹ represents an n-valent organic group, and R ¹ and R ⁷ are synonymous with the formula (101) or the formula (102).
Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group,
n represents an integer of 1 or more,
m represents an integer of 0 to 5.

In the present invention, the ammonium salt preferably has an anion having an pKa1 of 0 to 4 and an ammonium cation. The upper limit of the anion pKa1 is more preferably 3.5 or less, and even more preferably 3.2 or less. The lower limit is more preferably 0.5 or more, and further preferably 1.0 or more. If the pKa1 of the anion is in the above range, the polyimide precursor can be cyclized at a low temperature, and further, the stability of the polyimide precursor composition can be improved. If pKa1 is 4 or less, the stability of the thermal base generator is good, the generation of a base without heating can be suppressed, and the stability of the polyimide precursor composition is good. If pKa1 is 0 or more, the generated base is hardly neutralized, and the cyclization efficiency of the polyimide precursor is good.
The kind of anion is preferably one selected from a carboxylate anion, a phenol anion, a phosphate anion, and a sulfate anion, and a carboxylate anion is more preferable because both the stability of the salt and the thermal decomposability can be achieved. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion.
The carboxylic acid anion is preferably a divalent or higher carboxylic acid anion having two or more carboxyl groups, and more preferably a divalent carboxylic acid anion. According to this aspect, it can be set as the thermal base generator which can improve more stability, sclerosis | hardenability, and developability of a polyimide precursor composition. In particular, the stability, curability and developability of the polyimide precursor composition can be further improved by using an anion of a divalent carboxylic acid.
In the present invention, the carboxylic acid anion is preferably a carboxylic acid anion having a pKa1 of 4 or less. pKa1 is more preferably 3.5 or less, and even more preferably 3.2 or less. According to this aspect, the stability of the polyimide precursor composition can be further improved.
Here, pKa1 represents the logarithm of the reciprocal of the first dissociation constant of the acid, and is determined by Organic Structures by Physical Methods (author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; Compilation: Braude, EA, Nachod, FC; Academic Press, New York, 1955) and Data for Biochemical Research (author: Dawson, RMC et al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, values calculated from the structural formula using software of ACD / pKa (manufactured by ACD / Labs) are used.

In the present invention, the carboxylate anion is preferably represented by the following formula (X1).

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

In the present invention, the electron withdrawing group means a group having a positive Hammett's substituent constant σm. Here, σm is a review by Yugo Tono, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965) P.I. 631-642. In addition, the electron withdrawing group in this invention is not limited to the substituent described in the said literature.
Examples of substituents in which σm has a positive value include, for example, CF ₃ group (σm = 0.43), CF ₃ CO group (σm = 0.63), HC≡C group (σm = 0.21), CH ₂ ═CH group (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), and the like. Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group.

In the present invention, EWG preferably represents a group represented by the following formulas (EWG-1) to (EWG-6).

In the formula, R ^x1 to R ^x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxy group, or a carboxyl group, and Ar represents an aromatic group.

In the present invention, the carboxylate anion is also preferably represented by the following formula (X).

In the formula (X), L ¹⁰ represents a single bond or a divalent linking group selected from an alkylene group, an alkenylene group, an aromatic group, —NR ^X —, and combinations thereof, and R ^X represents hydrogen An atom, an alkyl group, an alkenyl group or an aryl group is represented.

Specific examples of the carboxylate anion include a maleate anion, a phthalate anion, an N-phenyliminodiacetic acid anion, and an oxalate anion.
Below, the thermal base generator preferably used by this invention is illustrated. It goes without saying that the thermal base generator used in the present invention is not limited to these.

When a thermal base generator is used, the content of the thermal base generator in the composition is preferably 0.1 to 50% by mass relative to the total solid content of the composition. The lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and further preferably 20% by mass or less.
1 type (s) or 2 or more types can be used for a thermal base generator. When using 2 or more types, it is preferable that a total amount is the said range.

<< Photobase generator >>
The photosensitive resin composition used in the production method of the present invention may contain a photobase generator. A photobase generator generates a base by exposure and does not exhibit activity under normal conditions of normal temperature and pressure, but when exposed to an external stimulus, that is, irradiated with an electromagnetic wave and heated, the base There is no particular limitation as long as it generates (basic substance). Since the base generated by the exposure works as a catalyst for curing the polyimide precursor by heating, it can be suitably 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 a general content. The photobase generator is preferably in the range of 0.01 to 30 parts by mass, more preferably in the range of 0.05 to 25 parts by mass with respect to 100 parts by mass of the resin. Preferably, it is in the range of 0.1 to 20 parts by mass.

In the present invention, known photobase generators can be used. For example, M.M. Shirai, and M.M. Tsunooka, Prog. Polym. Sci. , 21, 1 (1996); Masahiro Kadooka, polymer processing, 46, 2 (1997); Kutal, Coord. Chem. Rev. , 211, 353 (2001); Kaneko, A .; Sarker, and D.C. Neckers, Chem. Mater. 11, 170 (1999); Tachi, M .; Shirai, and M.M. Tsunooka, J. et al. Photopolym. Sci. Technol. , 13, 153 (2000); Winkle, and K.K. Graziano, J. et al. Photopolym. Sci. Technol. 3,419 (1990); Tsunooka, H .; Tachi, and S.M. Yoshitaka, J. et al. Photopolym. Sci. Technol. , 9, 13 (1996); Suyama, H .; Araki, M .; Shirai, J. et al. Photopolym. Sci. Technol. , 19, 81 (2006), as described in transition metal compound complexes, those having a structure such as an ammonium salt, and those formed by salt formation of an amidine moiety with a carboxylic acid, An ionic compound neutralized by forming a salt with a base component, or a nonionic compound in which the base component is made latent by a urethane bond or oxime bond such as a carbamate derivative, an oxime ester derivative, or an acyl compound. Can be mentioned.
In the present invention, carbamate derivatives, amide derivatives, imide derivatives, α-cobalt complexes, imidazole derivatives, cinnamic acid amide derivatives, oxime derivatives and the like are more preferred examples of photobase generators.

The basic substance generated from the photobase generator is not particularly limited, and examples thereof include compounds having amino groups, particularly monoamines, polyamines such as diamines, and amidines.
The generated basic substance is preferably a compound having an amino group having a higher basicity. This is because the catalytic action for the dehydration condensation reaction or the like in the imidization of the polyimide precursor is strong, and the catalytic effect in the dehydration condensation reaction or the like at a lower temperature can be expressed with a smaller amount of addition. That is, since the catalytic effect of the generated basic substance is great, the apparent sensitivity as a negative photosensitive resin composition is improved.
From the viewpoint of the catalytic effect, an amidine and an aliphatic amine are preferable.

The photobase generator is preferably a photobase generator that does not contain salt in the structure, and preferably has no charge on the nitrogen atom of the base moiety generated in the photobase generator. As the photobase generator, it is preferable that the generated base is latentized using a covalent bond, and the base generation mechanism is such that the covalent bond between the nitrogen atom of the generated base portion and the adjacent atom is broken. It is preferable that a base is generated. When the photobase generator contains no salt in the structure, the photobase generator can be neutralized, so that the solvent solubility is better and the pot life is improved. For these reasons, the amine generated from the photobase generator used in the present invention is preferably a primary amine or a secondary amine.

For the above reasons, as the photobase generator, it is preferable that the generated base is latentized using a covalent bond as described above, and the generated base has an amide bond, carbamate bond, or oxime bond. It is preferably latentized by using.
Examples of the photobase generator according to the present invention include a photobase generator having a cinnamic acid amide structure as disclosed in Japanese Patent Application Laid-Open No. 2009-80452 and International Publication WO2009 / 123122, and Japanese Patent Application Laid-Open No. 2006-189591. Photobase generator having a carbamate structure as disclosed in JP-A No. 2008-247747 and oxime structure as disclosed in JP-A No. 2007-249013 and JP-A-2008-003581, carbamoyl Although the photobase generator etc. which have an oxime structure are mentioned, It is not limited to these, In addition, the structure of a well-known photobase generator can be used.

In addition, examples of the photobase generator include compounds described in paragraph numbers 0185 to 0188, 0199 to 0200 and 0202 of JP2012-93746A, compounds described in paragraph numbers 0022 to 0069 of JP2013-194205A. Examples thereof include compounds described in JP-A-2013-204019, paragraphs 0026 to 0074, and compounds described in paragraph No. 0052 of international publication WO2010 / 064631.

Commercially available photobase generators include WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-027, PBG-018, WPGB-015, WPBG-041, WPGB-172, WPGB-174, WPBG-166, WPGB-158, WPGB-025, WPGB-168, WPGB-167, and WPBG-082 (manufactured by Wako Pure Chemical Industries, Ltd.) can also be used.

<< thermal acid generator >>
The composition used in the production method of the present invention may contain a thermal acid generator. Thermal acid generator generates acid by heating, promotes cyclization of polyimide precursor, etc., and further improves the mechanical properties of the cured film, as well as compounds having a hydroxymethyl group, alkoxymethyl group or acyloxymethyl group, epoxy There is an effect of promoting a crosslinking reaction of at least one compound selected from a compound, an oxetane compound and a benzoxazine compound.

The thermal decomposition starting temperature of the thermal acid generator is preferably 50 ° C. to 270 ° C., more preferably 250 ° C. or less. In addition, no acid is generated during drying (pre-baking: about 70 to 140 ° C.) after the composition is applied to the substrate, and during final heating (curing: about 100 to 400 ° C.) after patterning by subsequent exposure and development. It is preferable to select one that generates an acid, since a decrease in sensitivity during development can be suppressed.

The acid generated from the thermal acid generator is preferably a strong acid. For example, arylsulfonic acid such as p-toluenesulfonic acid and benzenesulfonic acid, alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid and butanesulfonic acid, and trifluoromethanesulfone. Haloalkyl sulfonic acids such as acids are preferred. Examples of such a thermal acid generator include those described in paragraph No. 0055 of JP2013-072935A.

Of these, thermal acid generators that generate alkyl sulfonic acids having 1 to 4 carbon atoms or haloalkyl sulfonic acids having 1 to 4 carbon atoms are more preferred from the viewpoint of little remaining in the cured film and no deterioration in the properties of the cured film. Sulfonic acid (4-hydroxyphenyl) dimethylsulfonium, methanesulfonic acid (4-((methoxycarbonyl) oxy) phenyl) dimethylsulfonium, benzyl methanesulfonate (4-hydroxyphenyl) methylsulfonium, benzyl methanesulfonate (4- ( (Methoxycarbonyl) oxy) phenyl) methylsulfonium, methanesulfonic acid (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium, trifluoromethanesulfonic acid (4-hydroxyphenyl) dimethylsulfonium, trif Oromethanesulfonic acid (4-((methoxycarbonyl) oxy) phenyl) dimethylsulfonium, trifluoromethanesulfonic acid benzyl (4-hydroxyphenyl) methylsulfonium, trifluoromethanesulfonic acid benzyl (4-((methoxycarbonyl) oxy) phenyl) Methylsulfonium, trifluoromethanesulfonic acid (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium, 3- (5-(((propylsulfonyl) oxy) imino) thiophene-2 (5H) -ylidene)- 2- (o-Tolyl) propanenitrile and 2,2-bis (3- (methanesulfonylamino) -4-hydroxyphenyl) hexafluoropropane are preferred.

Further, the compound described in paragraph No. 0059 of JP2013-167742A is also preferable as the thermal acid generator.

The content of the thermal acid generator is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the polyimide precursor or the like. By containing 0.01 part by mass or more, the cyclization of the crosslinking reaction and the polyimide precursor is promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved. Moreover, from a viewpoint of the electrical insulation of a cured film, 20 mass parts or less are preferable, 15 mass parts or less are more preferable, and 10 mass parts or less are more preferable.
One type of thermal acid generator may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.

<< Thermal polymerization initiator >>
The composition used in the present invention 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 radicals by heat energy and initiates or accelerates the polymerization reaction of the polymerizable compound. By adding a thermal radical polymerization initiator, the polymerization reaction of the polymerizable compound can be advanced when the cyclization reaction of the polyimide precursor or the like is advanced. Moreover, when a polyimide precursor etc. contain an ethylenically unsaturated bond, since polymerization reaction, such as a polyimide precursor, can also be advanced with cyclization of a polyimide precursor etc., higher heat resistance will be achieved. .
Thermal radical polymerization initiators include aromatic ketones, onium salt compounds, peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, carbon halogens. Examples thereof include a compound having a bond and an azo compound. Among these, a peroxide or an azo compound is more preferable, and a peroxide is particularly preferable.
The thermal radical polymerization initiator used in the present invention preferably has a 10-hour half-life temperature of 90 to 130 ° C, more preferably 100 to 120 ° C.
Specific examples include compounds described in paragraph numbers 0074 to 0118 of JP-A-2008-63554.
In a commercial item, perbutyl Z and park mill D (made by NOF Corporation) can be used conveniently.

When the composition has a thermal radical polymerization initiator, the content of the thermal radical polymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.1 to 30% by mass with respect to the total solid content of the composition. 0.1 to 20% by mass is particularly preferable. Further, the thermal radical polymerization initiator is preferably contained in an amount of 0.1 to 50 parts by mass, and more preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the polymerizable compound. According to this aspect, it is easy to form a cured film having more excellent heat resistance.
Only one type of thermal radical polymerization initiator may be used, or two or more types may be used. When there are two or more thermal radical polymerization initiators, the total is preferably in the above range.

<< Metal adhesion improver >>
The composition used in the production method of the present invention preferably contains a metal adhesion improver for improving adhesion to a metal material used for electrodes, wirings and the like. Examples of the metal adhesion improver include sulfide compounds described in paragraph numbers 0046 to 0049 of JP-A-2014-186186 and paragraph numbers 0032 to 0043 of JP-A-2013-072935. Examples of the metal adhesion improver include the following compound (N- [3- (triethoxysilyl) propyl] maleic acid monoamide).

The content of the metal adhesion improving agent is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the polyimide precursor and the like. By setting it as 0.1 mass part or more, the adhesiveness of the film | membrane and metal after thermosetting becomes favorable, and the heat resistance of the film | membrane after hardening and mechanical characteristics become favorable by setting it as 30 mass parts or less.
Only one type of metal adhesion improver may be used, or two or more types may be used. When using 2 or more types, it is preferable that the sum total is the said range.

<< Silane coupling agent >>
The composition used in the production method of the present invention preferably contains a silane coupling agent in terms of improving the adhesion to the substrate. Examples of the silane coupling agent include compounds described in paragraph numbers 0062 to 0073 of JP2014-191002, compounds described in paragraph numbers 0063 to 0071 of international publication WO2011 / 080992A1, and JP2014-191252. And compounds described in paragraph Nos. 0060 to 0061 of JP, No. 2014-41264, compounds described in paragraph Nos. 0045 to 0052 of JP-A-2014-41264, and compounds described in paragraph No. 0055 of WO 2014/097594. It is also preferred to use two or more different silane coupling agents as described in paragraph numbers 0050 to 0058 of JP2011-128358A.
The content of the silane coupling agent is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the polyimide precursor and the like. When it is 0.1 part by mass or more, sufficient adhesion to the substrate can be imparted, and when it is 20 parts by mass or less, problems such as an increase in viscosity during storage at room temperature can be further suppressed.
Only one type of silane coupling agent may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.

<< Sensitizing dye >>
The composition used in the production method of the present invention may contain a sensitizing dye. A sensitizing dye absorbs specific actinic radiation and enters an electronically excited state. The sensitizing dye in an electronically excited state comes into contact with an amine generator, a thermal radical polymerization initiator, a photopolymerization initiator, and the like, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, an amine generator, a thermal radical polymerization initiator, and a photopolymerization initiator cause a chemical change and are decomposed to generate radicals, acids, or bases.

Examples of preferable sensitizing dyes include those belonging to the following compounds and having a maximum absorption wavelength in the region of 300 nm to 450 nm. For example, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9.10-dialkoxyanthracene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), thioxanthones (For example, 2,4-diethylthioxanthone), cyanines (for example, thiacarbocyanine, oxacarbocyanine), merocyanines (for example, merocyanine, carbomerocyanine), thiazines (for example, thionine, methylene blue, toluidine blue), acridines (Eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squaryliums (eg, squarylium), coumarins (eg, 7-die) Tilamino-4-methylcoumarin), 3,3′-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl- Examples include 7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyldiethanolamine, styrylbenzenes, distyrylbenzenes, and carbazoles.

Among them, in the present invention, combination with polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene), thioxanthones, distyrylbenzenes, and styrylbenzenes is preferable from the viewpoint of starting efficiency, and has an anthracene skeleton. More preferably, the compound is used. Particularly preferred specific compounds include 9,10-diethoxyanthracene and 9,10-dibutoxyanthracene.

When the composition contains a sensitizing dye, the content of the sensitizing dye is preferably from 0.01 to 20% by mass, more preferably from 0.1 to 15% by mass, based on the total solid content of the composition. More preferably, it is 5 to 10% by mass. A sensitizing dye may be used individually by 1 type, and may use 2 or more types together.

<< Chain transfer agent >>
The composition used in the production method of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in Polymer Dictionary 3rd Edition (edited by the Society of Polymer Science, 2005) pages 683-684. As the chain transfer agent, for example, a compound group having SH, PH, SiH, GeH in the molecule is used. These can donate hydrogen to low-activity radical species to generate radicals, or can be oxidized and then deprotonated to generate radicals. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.) can be preferably used.

When the composition has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, with respect to 100 parts by mass of the total solid content of the composition. Particularly preferred is 1 to 5 parts by mass.
Only one type of chain transfer agent may be used, or two or more types may be used. When there are two or more chain transfer agents, the total is preferably in the above range.

<< Surfactant >>
Various surfactants may be added to the composition used in the production method of the present invention from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
In particular, by including a fluorosurfactant, liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, so that the uniformity of coating thickness and liquid-saving properties can be further improved. .
In the case of forming a film using a coating liquid containing a fluorosurfactant, the wettability to the coated surface is improved by reducing the interfacial tension between the coated surface and the coating liquid, and the coated surface The coating property of is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that a film having a uniform thickness with small thickness unevenness can be more suitably formed.

The fluorine content of the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content in this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and also has good solvent solubility.
Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320 PF6520, PF7002 (manufactured by OMNOVA) and the like.
A block polymer can also be used as the fluorosurfactant, and specific examples thereof include compounds described in JP-A-2011-89090.
The following compounds are also exemplified as the fluorosurfactant used in the present invention.

The weight average molecular weight of the above compound is, for example, 14,000.

Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R ), Solsperse 20000 (Lubrizol Japan Co., Ltd.), and the like. In addition, Pionein D-6112-W manufactured by Takemoto Yushi Co., Ltd., NCW-101, NCW-1001, NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. can also be used.

Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.

Specific examples of anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.

Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Tore Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400, Momentive Performance Materials TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF -4552 ”,“ KP341 ”,“ KF6001 ”,“ KF6002 ”manufactured by Shin-Etsu Chemical Co., Ltd.,“ BYK307 ”,“ BYK323 ”,“ BYK330 ”manufactured by Big Chemie Japan Co., Ltd., and the like.

When the composition has a surfactant, the surfactant content is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0%, based on the total solid content of the composition. % By mass.
Only one surfactant may be used, or two or more surfactants may be used. When there are two or more surfactants, the total is preferably in the above range.

<< Higher fatty acid derivatives, etc. >>
In order to prevent polymerization inhibition due to oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide or the like is added to the composition used in the production method of the present invention, and the composition is dried during coating. The surface may be unevenly distributed.
When the composition has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass with respect to the total solid content of the composition.
Only one type of higher fatty acid derivative or the like may be used. When there are two or more higher fatty acid derivatives, the total is preferably in the above range.

<< Solvent >>
When the composition used in the production method of the present invention is layered by coating, it is preferable to blend a solvent. Any known solvent can be used without limitation as long as the composition can be formed into a layer.
Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, and ε-caprolactone , Δ-valerolactone, alkyl alkoxyacetate (eg, methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3 -Alkoxypropionic acid alkyl esters (for example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionate) Methyl 2-onoxypropionate), 2-alkoxypropionic acid alkyl esters (for example, methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc.) -Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and 2-alkoxy -Ethyl 2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, Acetoacetic acid Ethyl, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like, and ethers such as 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., and ketones such as methyl ethyl ketone, cyclohexyl Non, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and aromatic hydrocarbons such as toluene, xylene, anisole, limonene and the like, and dimethyl sulfoxide as sulfoxides Are preferable.

The solvent is preferably in the form of a mixture of two or more types from the viewpoint of improving the coated surface. Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone A mixed solution composed of two or more selected from dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable. The combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

When the composition has a solvent, the content of the solvent is preferably such that the total solid concentration of the composition is 5 to 80% by mass, more preferably 5 to 70% by mass, from the viewpoint of applicability. 10 to 60% by mass is particularly preferable.
One type of solvent may be sufficient and 2 or more types may be sufficient as it. When there are two or more solvents, the total is preferably in the above range.
The contents of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide and N, N-dimethylformamide are based on the total mass of the composition from the viewpoint of film strength. It is preferably less than 5% by weight, more preferably less than 1% by weight, even more preferably less than 0.5% by weight, and particularly preferably less than 0.1% by weight.

<< Other additives >>
The composition used in the production method of the present invention is various additives such as inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet rays as necessary, as long as the effects of the present invention are not impaired. Absorbers, anti-aggregation agents and the like can be blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the composition.

The water content of the composition used in the production method of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and particularly preferably less than 0.6% by mass from the viewpoint of the coated surface.

The metal content of the composition used in the production method of the present invention is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and particularly preferably less than 0.5 ppm by mass from the viewpoint of insulation. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are included, the total of these metals is preferably in the above range.
In addition, as a method for reducing metal impurities unintentionally contained in the composition, a raw material having a low metal content is selected as a raw material constituting the composition, and filter filtration is performed on the raw material constituting the composition. Examples thereof include a method of performing distillation under a condition in which the inside of the apparatus is lined with polytetrafluoroethylene or the like and contamination is suppressed as much as possible.

In the composition used in the production method of the present invention, the halogen atom content 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 from the viewpoint of wiring corrosiveness. Especially, what exists in the state of a halogen ion is less than 5 mass ppm, more preferably less than 1 mass ppm, and especially less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. The total of chlorine atoms and bromine atoms, or chloride ions and bromide ions is preferably in the above range.

The manufacturing method of a semiconductor device This invention also discloses the manufacturing method of a semiconductor device containing the manufacturing method of the said laminated body. Below, one Embodiment of the semiconductor device using the laminated body obtained with the manufacturing method of the laminated body of this invention is described.
A semiconductor device 100 shown in FIG. 1 is a so-called three-dimensional mounting device, and a semiconductor element 101 in which a plurality of semiconductor elements (semiconductor chips) 101 a to 101 d are stacked is arranged on a wiring board 120.
In this embodiment, the case where the number of stacked semiconductor elements (semiconductor chips) is four will be mainly described. However, the number of stacked semiconductor elements (semiconductor chips) is not particularly limited. It may be a layer, 8 layers, 16 layers, 32 layers or the like. Moreover, one layer may be sufficient.

Each of the plurality of semiconductor elements 101a to 101d is made of a semiconductor wafer such as a silicon substrate.
The uppermost semiconductor element 101a does not have a through electrode, and an electrode pad (not shown) is formed on one surface thereof.
The semiconductor elements 101b to 101d have through electrodes 102b to 102d, and connection pads (not shown) provided integrally with the through electrodes are provided on both surfaces of each semiconductor element.

The semiconductor element 101 has a structure in which a semiconductor element 101a having no through electrode and semiconductor elements 101b to 101d having through electrodes 102b to 102d are flip-chip connected.
That is, the electrode pad of the semiconductor element 101a having no through electrode and the connection pad on the semiconductor element 101a side of the semiconductor element 101b having the adjacent through electrode 102b are connected by the metal bump 103a such as a solder bump, The connection pad on the other side of the semiconductor element 101b having the electrode 102b is connected to the connection pad on the semiconductor element 101b side of the semiconductor element 101c having the penetrating electrode 102c adjacent thereto by a metal bump 103b such as a solder bump. Similarly, the connection pad on the other side of the semiconductor element 101c having the through electrode 102c is connected to the connection pad on the semiconductor element 101c side of the semiconductor element 101d having the adjacent through electrode 102d by the metal bump 103c such as a solder bump. ing.

An underfill layer 110 is formed in the gaps between the semiconductor elements 101a to 101d, and the semiconductor elements 101a to 101d are stacked via the underfill layer 110.

The semiconductor element 101 is stacked on the wiring board 120.
As the wiring substrate 120, for example, a multilayer wiring substrate using an insulating substrate such as a resin substrate, a ceramic substrate, or a glass substrate as a base material is used. Examples of the wiring board 120 to which the resin board is applied include a multilayer copper-clad laminate (multilayer printed wiring board).

A surface electrode 120 a is provided on one surface of the wiring board 120.
An insulating layer 115 in which a rewiring layer 105 is formed is disposed between the wiring board 120 and the semiconductor element 101, and the wiring board 120 and the semiconductor element 101 are electrically connected via the rewiring layer 105. It is connected. The insulating layer 115 is the exposed photosensitive resin composition layer (resin layer) in the present invention. Details of the insulating layer will be described later.
That is, one end of the rewiring layer 105 is connected to an electrode pad formed on the surface of the semiconductor element 101d on the rewiring layer 105 side through a metal bump 103d such as a solder bump. The other end of the rewiring layer 105 is connected to the surface electrode 120a of the wiring board via a metal bump 103e such as a solder bump.
An underfill layer 110 a is formed between the insulating layer 115 and the semiconductor element 101. In addition, an underfill layer 110 b is formed between the insulating layer 115 and the wiring substrate 120.

FIG. 2 shows an example of a laminate (rewiring layer) obtained by the production method of the present invention, wherein 200 is a laminate obtained by the method of the present invention, 201 is a photosensitive resin composition. Reference numeral 203 denotes a layer (resin layer), and reference numeral 203 denotes a metal layer. In FIG. 2, the metal layer 203 is a layer indicated by oblique lines. The photosensitive resin composition layer 201 has a desired pattern formed by negative development. The metal layer 203 is formed so as to cover a part of the surface of the pattern, and a photosensitive resin composition layer (resin layer) 201 is further laminated on the surface of the metal layer 203. The photosensitive resin composition layer (resin layer) functions as an insulating film, and the metal layer functions as a wiring layer, and is incorporated as a rewiring layer in the semiconductor element as described above.

The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. “Parts” and “%” are based on mass unless otherwise specified.

<Synthesis Example 1>
[Synthesis of polyimide precursor (A-1: polyimide precursor having no radically polymerizable group) from pyromellitic dianhydride, 4,4′-oxydianiline and benzyl alcohol]
14.06 g (64.5 mmol) of pyromellitic dianhydride (pyromellitic acid dried at 140 ° C. for 12 hours) and 14.22 g (131.58 mmol) of benzyl alcohol were mixed with 50 mL of N-methylpyrrolidone. And dried with molecular sieves. The suspension was heated at 100 ° C. for 3 hours. A few minutes after heating, a clear solution was obtained. The reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) pyridine and 90 mL N-methylpyrrolidone were added. The reaction mixture was then cooled to −10 ° C. and 16.12 g (135.5 mmol) of SOCl ₂ was added over 10 minutes while maintaining the temperature at −10 ± 4 ° C. During the addition of SOCl ₂ the viscosity increased. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. A solution of 11.08 g (58.7 mmol) of 4,4′-oxydianiline dissolved in 100 mL of N-methylpyrrolidone was then added dropwise to the reaction mixture over 20 minutes at 20-23 ° C. The reaction mixture was then stirred overnight at room temperature. The polyimide precursor was then precipitated in 5 liters of water and the water-polyimide precursor mixture was stirred for 15 minutes at a speed of 5000 rpm. The polyimide precursor was collected by filtration, added to 4 liters of water, stirred again for 30 minutes, and collected again by filtration. Next, the obtained polyimide precursor (A-1) was dried at 45 ° C. under reduced pressure for 3 days.
(A-1)

<Synthesis Example 2>
[Synthesis of polyimide precursor (A-2: polyimide precursor having a radical polymerizable group) from pyromellitic dianhydride, 4,4′-oxydianiline and 2-hydroxyethyl methacrylate]
14.06 g (64.5 mmol) pyromellitic dianhydride (pyromellitic acid dried at 140 ° C. for 12 hours), 18.6 g (129 mmol) 2-hydroxyethyl methacrylate, 0.05 g hydroquinone And 10.7 g of pyridine and 140 g of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at a temperature of 60 ° C. for 18 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Next, the obtained diester was chlorinated with SOCl ₂ and then converted into a polyimide precursor with 4,4′-oxydianiline in the same manner as in Synthesis Example 1, and the polyimide precursor in the same manner as in Synthesis Example 1. (A-2) was obtained.
(A-2)

<Synthesis Example 3>
[Synthesis of polyimide precursor (A-3: polyimide precursor having radical polymerizable group) from 4,4′-oxydiphthalic anhydride, 4,4′-oxydianiline and 2-hydroxyethyl methacrylate]
20.0 g (64.5 mmol) of 4,4′-oxydiphthalic anhydride (4,4′-oxydiphthalic acid dried at 140 ° C. for 12 hours) and 18.6 g (129 mmol) of 2-hydroxy Ethyl methacrylate, 0.05 g of hydroquinone, 10.7 g of pyridine, and 140 g of diglyme are mixed and stirred at a temperature of 60 ° C. for 18 hours to give 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The diester was prepared. Next, the obtained diester was chlorinated with SOCl ₂ and then converted into a polyimide precursor with 4,4′-oxydianiline in the same manner as in Synthesis Example 1, and the polyimide precursor in the same manner as in Synthesis Example 1. (A-3) was obtained.
(A-3)

<Synthesis Example 4>
[Synthesis of polyimide precursor (A-4: polyimide precursor having carboxyl group) from 4,4′-oxydiphthalic anhydride and 4,4′-oxydianiline]
20.0 g (64.5 mmol) of 4,4′-oxydiphthalic anhydride (4,4′-oxydiphthalic acid dried at 140 ° C. for 12 hours) in 180 mL of NMP (N-methyl-2-pyrrolidone) In addition, 21.43 g (270.9 mmol) of pyridine was added, and the reaction solution was cooled to −10 ° C., while maintaining the temperature at −10 ± 4 ° C., 11.08 g (58.7 mmol). 4) '4,4'-oxydianiline dissolved in 100 mL of NMP was added dropwise over 30 minutes, and then the reaction mixture was stirred at room temperature overnight. The polyimide precursor was then precipitated in 5 liters of water and the water-polyimide precursor mixture was stirred for 15 minutes at a speed of 5000 rpm. The polyimide precursor was collected by filtration, added to 4 liters of water, stirred again for 30 minutes, and collected again by filtration. Next, the obtained polyimide precursor (A-4) was dried at 45 ° C. under reduced pressure for 3 days.
(A-4)

<Synthesis Example 5>
[Synthesis of polyimide precursor (A-5: polyimide precursor having radical polymerizable group) from pyromellitic dianhydride, m-tolidine and 2-hydroxyethyl methacrylate]
14.06 g (64.5 mmol) pyromellitic dianhydride (pyromellitic acid dried at 140 ° C. for 12 hours), 18.6 g (129 mmol) 2-hydroxyethyl methacrylate, 0.05 g hydroquinone 10.7 g of pyridine and 140 g of NMP (N-methyl-2-pyrrolidone) were mixed and stirred at a temperature of 60 ° C. for 18 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to −10 ° C. and 16.12 g (135.5 mmol) of SOCl ₂ was added over 10 minutes while maintaining the temperature at −10 ± 4 ° C. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. A solution of 12.46 g (58.7 mmol) of m-tolidine in 100 mL of N-methylpyrrolidone was then added dropwise to the reaction mixture at 20-23 ° C. over 20 minutes. The reaction mixture was then stirred overnight at room temperature. The polyimide precursor was then precipitated in 5 liters of water and the water-polyimide precursor mixture was stirred for 15 minutes at a speed of 5000 rpm. The polyimide precursor was collected by filtration, added to 4 liters of water, stirred again for 30 minutes, and collected again by filtration. Next, the obtained polyimide precursor was dried at 45 ° C. under reduced pressure for 3 days to obtain a polyimide precursor (A-5).
(A-5)

<Synthesis Example 6>
[Synthesis of Comparative Polymer (RA-1)]
27.0 g (153.2 mmol) benzyl methacrylate, 20 g (157.3 mmol) N-isopropylmethacrylamide, 39 g (309.2 mmol) allyl methacrylate, 13 g (151.0 mmol) methacrylic acid, A polymerization initiator (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) (3.55 g, 15.4 mmol) and 3-methoxy-2-propanol (300 g) were mixed. The mixture was added dropwise over 2 hours into 300 g of 3-methoxy-2-propanol heated to 75 ° C. under a nitrogen atmosphere. After completion of the dropwise addition, the mixture was further stirred at 75 ° C. for 2 hours under a nitrogen atmosphere. After completion of the reaction, the polymer was precipitated in addition to 5 liters of water and stirred for 15 minutes at a speed of 5000 rpm. The acrylic resin was collected by filtration, added to 4 liters of water, stirred again for 30 minutes, and collected again by filtration. Next, the obtained acrylic resin (RA-1) was dried at 45 ° C. under reduced pressure for 3 days. The numerical value in the following chemical formula (RA-1) is the mass ratio of the raw material monomers.
(RA-1)

<Examples and Comparative Examples>
The following components were mixed to prepare a photosensitive resin composition coating solution as a uniform solution.
<< Composition of photosensitive resin composition >>
(A) Resin: part by mass described in Table 1 (B) polymerizable compound: part by mass described in Table 1 (C) photopolymerization initiator: part by mass described in Table 1 (D) polymerization inhibitor: Table 1 Parts by weight γ-butyrolactone: 60.00 parts by weight

Abbreviations described in Table 1 are as follows.
(A) Resin A-6 synthesized in Resin Synthesis Examples 1 to 5: Matrimide 5218 (manufactured by HUNTSMAN Co., Ltd., polyimide)
Polymer for Comparative Example (RA-2): Polymethyl methacrylate (Mw: 15,000, manufactured by Sigma-Aldrich Japan)

(B) Polymerizable compound B-1: SR209 (bifunctional methacrylate, manufactured by Sartomer Japan, Inc., the following structure)

B-2: NK ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd., trifunctional acrylate, the following structure)

(C) Photopolymerization initiator C-1: IRGACURE OXE-01 (manufactured by BASF)
C-2: IRGACURE-784 (BASF)

(D) Polymerization inhibitor D-1: 2,6-di-tert-butyl-4-methylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)
D-2: p-benzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.)

Each photosensitive resin composition was filtered under pressure through a filter having a pore width of 0.8 μm, and then a photosensitive resin composition layer was formed on a silicon wafer by spin coating. The silicon wafer to which the obtained photosensitive resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes, and the photosensitive resin composition layer having a uniform thickness described in the table below was formed on the silicon wafer. did. The photosensitive resin composition layer on the silicon wafer was exposed using a stepper (Nikon NSR 2005 i9C) with an exposure energy of 500 mJ / cm ² at a wavelength of 365 nm, and the exposed photosensitive resin composition layer (resin layer). Was developed with cyclopentanone for 60 seconds to form a 10 μm diameter hole. Next, the temperature was raised from room temperature at a rate of 10 ° C./min in a nitrogen atmosphere, and after reaching 250 ° C. (maximum heating temperature), heating was performed for 3 hours. After cooling to room temperature, a metal layer (copper layer) having a thickness of 5 μm was formed on a part of the surface of the photosensitive resin composition layer (resin layer) by vapor deposition to form a laminate 1.
After irradiating the surface of the metal layer (copper layer) and the resin layer of the laminate 1 with the plasma of the gas species described in the table below, the photosensitive resin composition is again used to form a photosensitive resin. Formation of the composition layer, exposure, development and heating were repeated to obtain a laminate 2.
Further, a metal layer (copper layer) is formed on the surface of the laminate 2 by vapor deposition in the same manner as described above, and again irradiated with plasma of the gas species shown in the table below, and then the same photosensitivity as described above. The laminate 3 was obtained by repeating the formation, exposure, development and heating of the photosensitive resin composition layer using the photosensitive resin composition.
In Examples 27 to 30, instead of the above-described plasma, a laminate 2 was produced by performing corona discharge treatment.

<Evaluation>
<< Evaluation of peeling defects >>
(No heat treatment)
Each of the laminates 2 and 3 obtained as described above has a width of 5 mm in the vertical direction with respect to the resin layer surface, and a portion where the resin layer and the resin layer are in contact with each other; Each portion was cut out and the cross section thereof was observed, and the presence or absence of peeling between the resin layer / resin layer and the metal layer / resin layer in one cut piece was confirmed with an optical microscope. If peeling does not occur, it means that the film has excellent adhesiveness, which is a preferable result.
A: No occurrence of peeling B: 1-2 occurrences of peeling C: 3-5 occurrences of peeling D: 6 or more occurrences of peeling (with heat treatment)
Laminates 2 and 3 obtained above were heated in nitrogen at 300 ° C. for 3 hours. Thereafter, each laminated body has a width of 5 mm in the vertical direction with respect to the resin layer surface, and a portion where the resin layer and the resin layer are in contact with each other, and a portion where the metal layer and the resin layer are in contact with each other, It cut out and the cross section was observed and the presence or absence of peeling between the resin layer / resin layer and the metal layer / resin layer in one cut piece was confirmed with an optical microscope. If peeling does not occur, it means that the film has excellent adhesiveness, which is a preferable result.
A: No peeling occurred B: 1 to 2 peeling occurrences C: 3 to 5 peeling occurrences D: 6 or more peeling occurrences

As is clear from the above results, the laminate obtained by the production method of the present invention was excellent in both the adhesion between the resin layer and the resin layer and the adhesion between the metal layer and the resin layer. On the other hand, when a resin other than a polyimide precursor or the like is used as the resin (Comparative Examples 1, 2, 7, and 8), the adhesion between the resin layer and the resin layer and the adhesion between the metal layer and the resin layer are inferior. It was. Further, when the surface activation treatment was not performed, both or one of the adhesion between the resin layer and the resin layer and between the metal layer and the resin layer was inferior (Comparative Examples 3 to 6, 9 to 12).

As a result of forming and evaluating a laminate in the same manner except that the thicknesses of the resin layers of Example 2 and Example 9 were changed to 10 μm, 20 μm, and 30 μm, respectively, good results were obtained as in Examples 2 and 9. It was confirmed that.

In Example 18, when the second resin layer was formed using the photosensitive resin composition 2 and the others were performed in the same manner, the same excellent effect as in Example 18 was obtained.
In Example 18, the metal layer (copper thin film) was changed to an aluminum thin film and the others were performed in the same manner. As a result, the results were as good as in Example 18.

100: Semiconductor devices 101a to 101d: Semiconductor element 101: Stacked bodies 102b to 10d: Through electrodes 103a to 103e: Metal bump 105: Rewiring layers 110, 110a, 110b: Underfill layer 115: Insulating layer 120: Wiring substrate 120a: Surface electrode 200: Laminate 201: Photosensitive resin composition layer (resin layer)
203: Metal layer

Claims

Applying a photosensitive resin composition to a substrate to form a layer, and forming a photosensitive resin composition layer; and
An exposure step of exposing the photosensitive resin composition layer;
A development processing step of performing a negative development processing on the exposed photosensitive resin composition layer;
A metal layer forming step of forming a metal layer on the surface of the photosensitive resin composition layer after the development treatment;
A surface activation treatment step of performing a surface activation treatment on at least a part of the metal layer and the photosensitive resin composition layer,
Furthermore, the photosensitive resin composition layer forming step, the exposure step, and the development processing step are performed again in the order described above.
The photosensitive resin composition includes a resin selected from a polyimide precursor, a polyimide, a polybenzoxazole precursor, and a polybenzoxazole,
Furthermore, the manufacturing method of a laminated body which satisfy | fills at least one of the said resin containing a polymeric group and the said photosensitive resin composition containing a polymeric compound.
The method for producing a laminate according to claim 1, wherein the photosensitive resin composition layer forming step, the exposure step, and the development processing step are performed 3 to 7 times in the order.
The manufacturing method of the laminated body of Claim 1 or 2 with which the said metal layer contains copper.
The method for producing a laminate according to any one of claims 1 to 3, wherein the resin is a polyimide precursor or a polybenzoxazole precursor.
The method for producing a laminate according to any one of claims 1 to 4, wherein the resin contains a partial structure represented by -Ar-L-Ar-; wherein Ar is independently aromatic And L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—, —SO 2 — or —NHCO—, and , A group consisting of a combination of two or more of the above.
The method for producing a laminate according to any one of claims 1 to 5, wherein the surface activation treatment is selected from plasma treatment and corona discharge treatment.
The method for producing a laminate according to any one of claims 1 to 6, wherein the photosensitive resin composition contains a photopolymerization initiator.
A method for manufacturing a semiconductor device, comprising the method for manufacturing a laminate according to any one of claims 1 to 7.