JP6721689B2 - Chip manufacturing method and laminated body - Google Patents

Description

The present invention relates to a chip manufacturing method and a laminated body.

In recent years, there have been increasing demands for thinner, lighter, and flexible (flexible) devices, and it has become necessary to form the devices on a flexible base material instead of a hard base material. For example, an organic electroluminescence (organic EL) display device has conventionally been formed on a glass base material or a metal base material, but recently, a device using a polyimide film or a polyethylene naphthalate (PEN) film as a flexible base material. The number of cases that form Not only displays (organic EL, liquid crystal, electrophoresis, magnetophoresis, etc.), but also sensors (image, light, heat, acceleration, geomagnetism, etc.), light emitting devices (LED (light emitting diode), organic EL, etc.), Practical applications of transmitting and receiving devices (electromagnetic waves, microwaves, etc.), memory devices, logic devices, and devices that combine these devices (such as wireless tags and position detection devices such as GPS (Global Positioning System)) are also being considered. There is.

As a method of manufacturing such a flexible device, the following measures have been taken in order to use the existing hard substrate manufacturing apparatus. First, a flexible base material (polyimide film, etc.) is placed on a hard carrier substrate, various devices are formed on it using a hard base material manufacturing device, and then the carrier substrate is made flexible at the final stage of the manufacturing process. It is a method of obtaining a flexible device by peeling it from the base material.
The problem with this method is that when the carrier substrate is peeled from the flexible substrate, it is difficult to peel the flexible device without damaging it. The following measures have been taken as a method for solving this.
A method of adhering a carrier base material and a flexible base material with a temporary adhesive has been proposed, but the flatness and process resistance of the temporary adhesive are insufficient, and there are problems of yield reduction and poor characteristics.
As a method for solving this, the following method has become the mainstream recently. By coating, drying, and curing a solution polyimide resin on a transparent carrier substrate, and forming a device using this resin layer as a substrate, by irradiating an ultraviolet pulse laser from the transparent carrier substrate side, This is a method of obtaining a flexible device formed on a resin layer base material from a carrier substrate by ablating the interface of the resin layer on the carrier base material side (for example, Patent Document 1).
In many cases, a plurality of chips are arranged in this flexible device, and finally, it is divided into a plurality of chips to obtain a final flexible device chip.

Further, as another method, in Patent Document 2, providing a first substrate in which a plurality of depressions are formed, forming a first plastic film in each depression, and each first plastic. Forming a thin film transistor on the film, forming a display element electrically connected to the thin film transistor on each thin film transistor, sealing an upper portion of the display element, and cutting the first substrate. And separating the first substrate from the first plastic film, a method of manufacturing a flexible display device is disclosed.

Japanese Patent Publication No. 2016-506061 JP, 2011-187446, A

Here, in the case of manufacturing a flexible device chip on which a device is mounted, the method described in FIG. 3 was considered. That is, the resin film 32 is formed on the base material 31, and the plurality of devices 33 are mounted on the resin film 32 at equal intervals. Then, it was conceived that light is irradiated from the base material 31 side to separate the base material 31 from the resin film 32, and then the resin film 32 is divided for each device 33 to obtain the chip 34. It has been considered that the division of each device here is performed using, for example, a laser cutter or a dicing device (mechanical cutter).
However, it has been found that trouble is likely to occur when the device 33 is divided into each device. For example, when dividing using a laser cutter, debris derived from ablation may adhere to the device and become a defect. Further, when the dicing device is used for division, a problem is likely to occur in the cutting accuracy due to the deformation of the resin film. Further, it has been found that even in handling the chip after cutting the film-shaped resin film, if the resin film is deformed, chip handling errors (displacement, omission, etc.) are likely to occur.
Further, as described in Patent Document 2, a method of obtaining a resin film divided for each device from a substrate divided into pieces has been proposed. However, since the resin film and the base material are cut at the same time by using the dicing device, problems such as peeling of the resin film and adhesion of cutting waste are likely to occur in addition to poor cutting accuracy.
Therefore, there is a demand for a method capable of dividing into chips without using a laser cutter or a dicing device.
An object of the present invention is to solve such a problem, and an object of the present invention is to provide a novel chip manufacturing method capable of manufacturing a chip without using a laser cutter or a dicing device. Furthermore, a novel laminate is also provided.

Under the above problems, as a result of the present inventor's study, it is possible to solve the above problems by exposing and developing a resin film to separate the resin film itself into pieces and then separating the base material. Found. Specifically, it was solved by the following means <1>, preferably <2> to <21>.
<1> An exposure and development step of exposing and developing a photosensitive resin layer located on the base material to form two or more resin regions, and a step of exposing the photosensitive resin layer or the surface of the resin region. , A device material applying step of applying a device material on a surface opposite to the surface on the base material side,
A method for manufacturing a chip, wherein after the device material application step, the base material is separated from the resin region and the resin region is singulated.
<2> The method for manufacturing a chip according to <1>, wherein a device material application step is performed after the exposure and development step.
<3> The method for manufacturing a chip according to <2>, including a step of applying at least one of heat and light to the resin region before the device material applying step.
<4> The method for manufacturing a chip according to any one of <1> to <3>, wherein the device material is one or more selected from a conductor material, a semiconductor material, an insulator material, and an electronic device.
<5> The method for producing a chip according to any one of <1> to <4>, wherein the development is negative development.
<6> The method for manufacturing a chip according to any one of <1> to <5>, in which the resin region is located on the surface of the base material.
<7> The base material is a transparent base material, and it is possible to separate the base material from the resin area by irradiating light from a surface opposite to the surface of the base material on the resin area side. A method of manufacturing a chip according to <6>, including:
<8> The method for producing a chip according to any one of <1> to <5>, including separating the base material from a resin region by applying thermal energy to the base material.
<9> A temporary adhesive layer is provided between the base material and the photosensitive resin layer, and the interface between the temporary adhesive layer and the base material or the interface between the temporary adhesive layer and the resin region is peeled off. The method for producing a chip according to any one of <1> to <5>, wherein the base material is separated from the resin region by dissolving or removing the temporary adhesive layer.
<10> The method for manufacturing a chip according to any one of <1> to <9>, in which the resin region contains a polyimide resin or a polybenzoxazole resin.
<11> The method for manufacturing a chip according to any one of <1> to <10>, further including applying a second device material so as to be in contact with the device material after the device material application step.
<12> The method for manufacturing a chip according to any one of <1> to <11>, in which the longest part of the surface of the base material is 50 to 4000 mm.
<13> The method for producing a chip according to any one of <1> to <12>, which includes forming an opening in the resin region by the exposure and development.
<14> The method for manufacturing a chip according to <13>, wherein the device material is applied so as to be in contact with the surface of the base material through the opening.
<15> The chip according to any one of <1> to <14>, wherein application of the device material is selected from a printing method, a photolithography method, an inkjet method, an imprint method, a mask vapor deposition method, and a laser transfer method. Manufacturing method.
<16> a base material, two or more resin regions located on the base material, and a device material located on a surface opposite to the base material side surface of each of the resin areas, Laminate.
<17> The laminate according to <16>, in which the resin region contains a polyimide resin or a polybenzoxazole resin.
<18> The laminate according to <16> or <17>, wherein the device material is selected from a conductor material, a semiconductor material, an insulator material, and an electronic device.
<19> The laminate according to any one of <16> to <18>, in which the resin region is located on the surface of the base material.
<20> The laminated body according to any one of <16> to <19>, including a second device material in contact with the device material.
<21> The laminated body according to any one of <16> to <20>, in which the longest portion of the substrate surface has a length of 50 to 4000 mm.

According to the present invention, it is possible to provide a novel chip manufacturing method capable of manufacturing a chip without using a laser cutter or a dicing device. Furthermore, a new laminated body can be provided.

It is a schematic diagram showing an example of a manufacturing method of a chip of the present invention. It is a schematic diagram showing another example of a manufacturing method of a chip of the present invention. It is a schematic diagram showing a conventional manufacturing method of a chip.

The components of the present invention described below may be described based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the description of the group (atom group) in the present specification, the notation in which substitution and non-substitution are not included includes not only those having no substituent but also those having 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).
Unless otherwise specified, the term “exposure” as used herein includes not only exposure using light but also drawing using a particle beam such as an electron beam or an ion beam. In addition, the light used for the exposure generally includes a bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), active rays such as X-rays and electron rays, or radiation.
In the present specification, a numerical range represented by "to" means a range including the numerical values before and after "to" as a lower limit value and an upper limit value.
In the present specification, “(meth)acrylate” means both “acrylate” and “methacrylate” or either, and “(meth)acrylic” means both “acrylic” and “methacrylic”, or "(Meth)acryloyl" means both "acryloyl" and "methacryloyl", or either.
In the present specification, the term “step” is included in this term as long as the intended action of the step is achieved not only as an independent step but also when it cannot be clearly distinguished from other steps. ..
In the present specification, the solid content concentration is a mass percentage of the other components excluding the solvent with respect to the total mass of the composition. The solid content concentration refers to the concentration at 25°C unless otherwise specified.
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene-converted values according to gel permeation chromatography (GPC measurement), unless otherwise specified. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220GPC (manufactured by Tosoh Corp.), and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. It can be determined by using Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). The eluent is measured with THF (tetrahydrofuran) unless otherwise specified. In addition, detection is performed using a UV ray (ultraviolet) wavelength 254 nm detector unless otherwise specified.

The chip manufacturing method of the present invention comprises an exposure and development step of exposing and developing a photosensitive resin layer located on a substrate to form two or more resin regions, and the photosensitive resin layer or the resin region. A device material application step of applying a device material on the surface (preferably on the surface) of the substrate and on the surface (preferably on the surface) opposite to the surface on the side of the base material, and the application of the device material. After the step, the base material is separated from the resin region to divide the resin region into individual pieces. With such a configuration, chips can be manufactured without using a laser cutter or a dicing device.
Embodiments of the present invention will be described below with reference to the drawings. It goes without saying that the configuration of the present invention is not limited to the configuration shown in the drawings.

FIG. 1 is a diagram showing an example of a schematic view of a method for manufacturing a chip of the present invention, in which 1 is a base material, 2 is a photosensitive resin layer, 3 is a mask, 4 is a chip, and 22 is a resin. Each area is shown.

<Photosensitive resin layer forming step>
As shown in FIG. 1, the photosensitive resin layer 2 is formed on the base material 1. The photosensitive resin layer 2 may be formed by applying a photosensitive resin composition onto a substrate, or a commercially available product in which the photosensitive resin layer 2 is already formed on the substrate 1 is used. You may.

The resin constituting the photosensitive resin layer preferably contains at least one selected from a polyimide resin, a polybenzoxazole resin, an epoxy resin and an acrylate resin, and more preferably contains a polyimide resin or a polybenzoxazole resin, It is more preferable to include a polyimide resin. These resins are preferably photosensitive resins, that is, photosensitive resins that can be exposed and developed by light irradiation. Further, the photosensitive resin layer may contain resin components other than the photosensitive resin and other components. However, it is preferable that the photosensitive resin accounts for 60% by mass or more of the photosensitive resin layer, and more preferably 70% by mass or more.
Examples of other components include polymerizable compounds, polymerization initiators (photopolymerization initiators, thermal polymerization initiators), polymerization inhibitors, migration inhibitors, metal adhesion improvers, and the like. Specific examples of these will be described later.

In the present invention, the photosensitive resin layer is preferably formed by applying the photosensitive resin composition described below on a substrate and drying. In particular, the photosensitive resin layer containing a polyimide resin or a polybenzoxazole resin is a photosensitive resin composition containing a polyimide precursor or a polybenzoxazole precursor, applied in a layer form on a substrate, dried, and then cyclized. It is preferable to form it.
The drying temperature of the photosensitive resin composition is preferably 50 to 150°C, more preferably 70°C to 130°C, and further preferably 90°C to 110°C. The drying time is preferably 30 seconds to 20 minutes, more preferably 1 minute to 10 minutes, still more preferably 3 minutes to 7 minutes.
As means for applying the photosensitive resin composition to the substrate in layers, coating is preferred.
Specifically, as means for applying, dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spray coating method, spin coating method, slit coating method, And the inkjet method and the like. From the viewpoint of the thickness uniformity of the layered photosensitive resin composition (hereinafter sometimes referred to as “photosensitive resin composition layer”), the spin coating method, the slit coating method, the spray coating method, and the inkjet method are more preferable. .. A desired photosensitive resin composition layer can be obtained by adjusting appropriate solid content concentration and coating conditions according to the means to which it is applied. Further, the coating method can be appropriately selected depending on the shape of the base material, and spin coating method, spray coating method, ink jet method or the like is preferable for circular base materials such as wafers, and slit coating method or spray coating for rectangular base materials. Method, ink jet method and the like are preferable. In the case of the spin coating method, for example, it can be applied at a rotation speed of 300 to 4000 rpm (revolutions per minute) for about 2 seconds to 5 minutes.
The photosensitive resin composition may be filtered before its application. The filtration is preferably performed using a filter. The pore size of the filter is preferably 1 μm or less, more preferably 0.5 μm or less, still more preferably 0.1 μm or less.

The photosensitive resin layer 2 may be located on the surface of the base material 1, or may be located on the base material 1 via another layer or film. In the present invention, the photosensitive resin layer 2 is preferably located on the surface of the substrate 1.
The thickness of the photosensitive resin layer is preferably 0.1 to 100 μm, more preferably 1 to 50 μm, and further preferably 3 to 20 μm.

The type of the base material is not particularly limited as long as it can support the photosensitive resin layer 2 and the device material mounted in the subsequent steps.
In the present invention, when the base material is separated from the resin region by light irradiation, the base material is a base material that transmits light. Examples of the substrate that transmits light include a glass substrate, a quartz substrate, and a liquid crystal polymer substrate, and a glass substrate is preferable.
On the other hand, when the base material is separated from the resin region by a method other than light irradiation, a silicon substrate or the like is exemplified.
Further, the base material preferably has high heat resistance. For example, when the base material is a resin base material, the glass transition temperature (Tg) is preferably 150° C. or higher, and more preferably 250° C. or higher. The upper limit of Tg is preferably 350°C or lower.
The thickness of the base material is not particularly limited, but is usually 10 to 1000 μm.
The length of the longest part of the substrate surface of the substrate is preferably 50 to 4000 mm. By setting the length of the longest part of the base material surface to 50 mm or more, the production efficiency can be improved, and by setting it to 4000 mm or less, it is possible to suppress the cost increase due to the enlargement of the device size. The length of the longest portion of the base material surface refers to the distance between the two points having the longest distance in the combination of the two end portions of the base material surface of the base material.

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

<<<<resin>>>>
The photosensitive resin composition used in this embodiment contains a resin. The resin is preferably a photosensitive resin, but the resin itself may not have photosensitivity when another photosensitive component such as a polymerizable compound is added.
The resin is preferably a high heat resistant resin.

The photosensitive resin composition used in this embodiment preferably contains at least one resin selected from a polyimide precursor, a polyimide, a polybenzoxazole precursor, and a polybenzoxazole. In the chip manufacturing method of the present invention, the photosensitive resin composition more preferably contains a polyimide precursor or a polybenzoxazole precursor, and further preferably contains a polyimide precursor.

The photosensitive resin composition used in the present embodiment may contain only one kind of polyimide precursor, polyimide, polybenzoxazole precursor and polybenzoxazole, or may contain two or more kinds thereof. Further, the same kind of resin, such as containing two kinds of polyimide precursors, but may include two or more kinds of resins having different structures.
The content of the resin in the photosensitive resin composition used in the present embodiment is preferably 10 to 99% by mass of the total solid content of the photosensitive resin composition, more preferably 50 to 98% by mass, and 70 to 96% by mass. Is more preferable.

Further, the resin preferably contains a polymerizable group.
Moreover, it is preferable that the photosensitive resin composition contains a polymerizable compound. With such a structure, a three-dimensional network is formed in the exposed area and a strong crosslinked film is formed, and the photosensitive resin composition layer (cured film) is not damaged by the surface activation treatment described later, and the surface activation is performed. By the chemical treatment, the adhesion between the cured film and the metal layer or the adhesion between the cured films is more effectively improved.
Furthermore, it is preferable that the resin contains a partial structure represented by -Ar-L-Ar-. However, Ar is independently an aromatic group, L is a C1-C10 aliphatic hydrocarbon group which may be substituted by the fluorine atom, -O-, -CO-, -S-. , —SO ₂ — or —NHCO—, and a group consisting of a combination of two or more of the above. With such a structure, the photosensitive resin composition layer (cured film) has a flexible structure, and the effect of suppressing the occurrence of delamination is more effectively exhibited. 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. The aliphatic hydrocarbon group here is preferably an alkylene group.

式（２）中、Ａ^１およびＡ^２は、それぞれ独立に酸素原子またはＮＨを表し、Ｒ^１１１は、２価の有機基を表し、Ｒ^１１５は、４価の有機基を表し、Ｒ^１１３およびＲ^１１４は、それぞれ独立に、水素原子または１価の有機基を表す。(Polyimide precursor)
The polyimide precursor is not particularly limited as to 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, and R ¹¹³ and R ^114's each independently represent a hydrogen atom or a monovalent organic group.

A ¹ and A ² in the formula (2) are preferably an oxygen atom or NH, more preferably an oxygen atom.
R ¹¹¹ in the formula (2) represents a divalent organic group. Examples of the divalent organic group include groups containing a linear or branched aliphatic group, a cyclic aliphatic group and an aromatic group, and a linear or branched aliphatic group having 2 to 20 carbon atoms, or a carbon number. A cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group composed of a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable. As a particularly preferred embodiment, it is exemplified that R ¹¹¹ in formula (2) is a group represented by —Ar—L—Ar—. However, Ar is independently an aromatic group, L is a C1-C10 aliphatic hydrocarbon group which may be substituted by the fluorine atom, -O-, -CO-, -S-. , —SO ₂ — or —NHCO—, and a group consisting of a combination of two or more of the above. The preferable ranges of these are as described above.

R ¹¹¹ in formula (2) is preferably derived from a diamine. Examples of the diamine used for producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamine. Only one diamine may be used, or two or more diamines may be used.
Specifically, 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 group formed of a combination thereof. Is preferable, and more preferable is a diamine containing a group consisting of an aromatic group having 6 to 20 carbon atoms. Examples of the aromatic group include the following aromatic groups.

上記芳香族基中、Ａは、単結合、または、フッ素原子で置換されていてもよい炭素数１〜１０の脂肪族炭化水素基、−Ｏ−、−Ｃ（＝Ｏ）−、−Ｓ−、−Ｓ（＝Ｏ）_２−、−ＮＨＣＯ−ならびに、これらの組み合わせから選択される基であることが好ましく、単結合、フッ素原子で置換されていてもよい炭素数１〜３のアルキレン基、−Ｏ−、−Ｃ（＝Ｏ）−、−Ｓ−、−ＳＯ_２−から選択される基であることがより好ましく、−ＣＨ_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（ＣＦ_３）_２−、および、−Ｃ（ＣＨ_３）_２−からなる群から選択される２価の基であることがさらに好ましい。

In the aromatic group, 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 —, —NHCO—, and a group selected from a combination thereof, preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O -, - C (= O ) -, - S -, - SO 2 - , more preferably a group selected _{from, -CH 2 -, - O -} , - S -, - SO 2 -, More preferably, it is a divalent group selected from the group consisting of —C(CF ₃ ) ₂ — and —C(CH ₃ ) ₂ —.

As the diamine, specifically, the description in paragraph 0083 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated in the present specification.

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

In addition, diamines having at least two or more alkylene glycol units in the main chain are also mentioned as preferable examples. Diamine containing one or both of ethylene glycol chain and propylene glycol chain in one molecule, preferably two or more, more preferably diamine having no aromatic ring. As a specific example, Jeffamine (registered trademark) KH-511, Jeffarmin (registered trademark) ED-600, Jeffermin (registered trademark) ED-900, Jeffermin (registered trademark) ED-2003, Jeffermin (registered trademark) ) EDR-148, Jeffermin (registered trademark) EDR-176, Jeffermin (registered trademark) D-200, Jeffermin (registered trademark) D-400, Jeffermin (registered trademark) D-2000, Jeffermin (registered trademark) ) D-4000 (trade name, manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, 1-(1-(1-(2-amino) Examples include, but are not limited to, propoxy)propan-2-yl)oxy)propan-2-amine.
Jeffarmin (registered trademark) KH-511, Jeffarmin (registered trademark) ED-600, Jeffermin (registered trademark) ED-900, Jeffermin (registered trademark) ED-2003, Jeffermin (registered trademark) EDR-148, The structure of Jeffamine® EDR-176 is shown below.

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

R ¹¹¹ in Formula (2) is preferably represented by —Ar—L—Ar— from the viewpoint of flexibility of the obtained cured film. However, Ar is independently an aromatic group, L is a C1-C10 aliphatic hydrocarbon group which may be substituted by the fluorine atom, -O-, -CO-, -S-. , —SO ₂ — or —NHCO—, and 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. The aliphatic hydrocarbon group here is preferably an alkylene group.

式（５１）中、Ｒ^１０〜Ｒ^１７は、それぞれ独立に水素原子、フッ素原子または１価の有機基であり、Ｒ^１０〜Ｒ^１７の少なくとも１つはフッ素原子、メチル基またはトリフルオロメチル基である。
Ｒ^１０〜Ｒ^１７の１価の有機基として、炭素数１〜１０（好ましくは炭素数１〜６）の無置換のアルキル基、炭素数１〜１０（好ましくは炭素数１〜６）のフッ化アルキル基等が挙げられる。
式（６１）

式（６１）中、Ｒ^１８およびＲ^１９は、それぞれ独立にフッ素原子またはトリフルオロメチル基である。
式（５１）または（６１）の構造を与えるジアミン化合物としては、２，２’−ジメチルベンジジン、２，２’−ビス（トリフルオロメチル）−４，４’−ジアミノビフェニル、２，２’−ビス（フルオロ）−４，４’−ジアミノビフェニル、４，４’−ジアミノオクタフルオロビフェニル等が挙げられる。これらは１種を用いるか、または２種以上を組み合わせて用いてもよい。R ¹¹¹ in the formula (2) is preferably a divalent organic group represented by the following formula (51) or formula (61) from the viewpoint of i-ray transmittance. In particular, the divalent organic group represented by the formula (61) is more preferable from the viewpoints of i-ray transmittance and availability.
Expression (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 a trifluoromethyl group. Is.
As the monovalent organic group of R ^{10 to} R ¹⁷ , an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a fluorine atom having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) is used. Alkyl groups and the like.
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 giving the structure of formula (51) or (61) include 2,2′-dimethylbenzidine, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 2,2′- Examples thereof include bis(fluoro)-4,4′-diaminobiphenyl and 4,4′-diaminooctafluorobiphenyl. These may be used alone or in combination of two or more.

式（５）中、Ｒ^１１２は、単結合、または、フッ素原子で置換されていてもよい炭素数１〜１０の脂肪族炭化水素基、−Ｏ−、−ＣＯ−、−Ｓ−、−ＳＯ_２−、−ＮＨＣＯ−ならびに、これらの組み合わせから選択される基であることが好ましく、単結合、フッ素原子で置換されていてもよい炭素数１〜３のアルキレン基、−Ｏ−、−ＣＯ−、−Ｓ−および−ＳＯ_２−から選択される基であることがより好ましく、−ＣＨ_２−、−Ｃ（ＣＦ_３）_２−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−ＣＯ−、−Ｓ−および−ＳＯ_２−からなる群から選択される２価の基がさらに好ましい。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 formula (5), R ¹¹² is 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- , -NHCO-, and a group selected from a combination thereof are preferable, and a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-. , -S- and -SO ₂ -, more preferably a group selected _{from, -CH 2 -, - C (} CF 3) 2 -, - C (CH 3) 2 -, - O -, - CO -, - S- and -SO ₂ - 2 divalent radical selected from the group consisting of is more preferable.

Formula (6)

式（Ｏ）中、Ｒ^１１５は、４価の有機基を表す。Ｒ^１１５の好ましい範囲は式（２）におけるＲ^１１５と同義であり、好ましい範囲も同様である。Specific examples of R ¹¹⁵ in the formula (2) include a tetracarboxylic acid residue remaining after the removal of the anhydride group from the tetracarboxylic dianhydride. The tetracarboxylic dianhydride may be used alone or in combination of two or more.
The tetracarboxylic dianhydride is preferably represented by the following formula (O).
Formula (O)

In formula (O), 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 the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfide tetracarboxylic acid. Acid dianhydride, 3,3′,4,4′-diphenylsulfone tetracarboxylic acid dianhydride, 3,3′,4,4′-benzophenone tetracarboxylic acid dianhydride, 3,3′,4,4 '-Diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyl tetracarboxylic dianhydride, 2,3,3 3',4'-benzophenone tetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 1,4,5,7-naphthalene Tetracarboxylic acid 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-naphthalenetetra Carboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetra Carboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyl Phenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, and carbon numbers 1 to 1 of these. Examples thereof include at least one selected from an alkyl derivative having 6 and an alkoxy derivative having 1 to 6 carbon atoms.

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

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

R ¹¹³ and R ¹¹⁴ in formula (2) each independently represent a hydrogen atom or a monovalent organic group.
At least one of R ¹¹³ and R ¹¹⁴ in formula (2) preferably contains a polymerizable group, and more preferably both contain a polymerizable group. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, radicals or the like. As the polymerizable group, a photoradical polymerizable group is preferable. Specific examples of the polymerizable group, a group having an ethylenically unsaturated bond, alkoxymethyl group, hydroxymethyl group, acyloxymethyl group, epoxy group, oxetanyl group, benzoxazolyl group, blocked isocyanate group, methylol group, amino group Is mentioned. The radically polymerizable group contained in the polyimide precursor 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, and a group represented by the following formula (III).

In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and a methyl group is more preferable.
In 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 include 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 an ethylene group, a propylene group, a trimethylene group, and —CH ₂ CH(OH)CH ₂ — are more preferable.
Particularly preferably, R ²⁰⁰ is a methyl group and R ²⁰¹ is a combination of ethylene groups.

R ¹¹³ or R ¹¹⁴ in the formula (2) may be a monovalent organic group other than the polymerizable group.
From the viewpoint of solubility in an organic solvent, R ¹¹³ or R ¹¹⁴ in formula (2) is preferably a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group. As the monovalent organic group, an aromatic group having one, two or three (preferably one) acidic group bonded to the carbon constituting the aryl group, and a carbon bonded to the carbon constituting the aryl group Particularly preferred are aralkyl groups having 1, 2 or 3 (preferably 1) acidic groups as defined above. Specifically, examples thereof 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, examples thereof include a phenyl group having an acidic group and a benzyl group having an acidic group. The acidic group is preferably a hydroxyl group.
It is particularly preferable that R ¹¹³ or R ¹¹⁴ is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl.

The alkyl group represented by R ¹¹³ or R ¹¹⁴ in the formula (2) preferably has 1 to 30 carbon atoms. 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 group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, and 2-ethylhexyl group.
The cyclic alkyl group represented by R ¹¹³ or R ¹¹⁴ in the formula (2) may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. Examples of the polycyclic cyclic 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. Are listed. Of these, a cyclohexyl group is most preferable from the viewpoint of compatibility with high sensitivity. The alkyl group substituted with an aromatic group is preferably a linear alkyl group substituted with an aromatic group described later.
Specific examples of the aromatic group represented by R ¹¹³ or R ¹¹⁴ in the formula (2) include a substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalen ring, indacene ring, and 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, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiine ring, phenothiazine ring or phenazine ring. Most preferred is a benzene ring.

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

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

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

式（２−Ａ）中、Ａ^１およびＡ^２は、酸素原子を表し、Ｒ^１１１およびＲ^１１２は、それぞれ独立に、２価の有機基を表し、Ｒ^１１３およびＲ^１１４は、それぞれ独立に、水素原子または１価の有機基を表し、Ｒ^１１３およびＲ^１１４の少なくとも一方は、重合性基を含む基であり、重合性基であることが好ましい。The repeating unit represented by the formula (2) is preferably a repeating unit represented by the following formula (2-A). That is, it is preferable that at least one of the polyimide precursors is a precursor having a repeating unit represented by the formula (2-A). With such a structure, the width of the exposure latitude can be further widened.
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 is preferably a polymerizable group.

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

In the polyimide precursor, the repeating unit represented by the formula (2) may be one type or two or more types. Further, the polyimide precursor may contain a structural isomer of the repeating unit represented by the formula (2). Further, the polyimide precursor may include other types of repeating units in addition to the repeating unit represented by the above formula (2).

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

The polyimide precursor is preferably obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. More preferably, the polyimide precursor is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then reacting it with a diamine. The polyimide precursor is, for example, a method of reacting a tetracarboxylic dianhydride and a diamine compound (a part of which is replaced with a terminal blocking agent which is a monoamine) at a low temperature, a tetracarboxylic dianhydride (a part of which is replaced at a low temperature). Is substituted with an endcapping agent which is an acid anhydride or a monoacid chloride compound or a monoactive ester compound) and a diamine compound, a diester is obtained by tetracarboxylic dianhydride and an alcohol, and then a diamine (partly) Is replaced with a monoamine end capping agent) in the presence of a condensing agent, a diester is obtained with tetracarboxylic dianhydride and an alcohol, and then the remaining dicarboxylic acid is converted to an acid chloride to form a diamine (partially). Is substituted with a terminal blocking agent that is a monoamine).
In the method for producing a polyimide precursor, it is preferable to use an organic solvent during the reaction. The organic solvent may be one kind or two or more kinds.
The organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.

During the production of the polyimide precursor, in order to further improve the storage stability, the main chain end of the precursor is capped with an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, an end capping agent such as a monoactive ester compound. It is preferable. Among these, it is more preferable to use monoamine, and preferable compounds of 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-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfone Acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3- Aminothiophenol, 4-aminothiophenol, etc. are mentioned. Two or more of these may be used, and a plurality of different end groups may be introduced by reacting a plurality of end capping agents.

A step of depositing a solid may be included in the production of the polyimide precursor. Specifically, solid precipitation can be performed by precipitating the polyimide precursor in the reaction liquid in water and dissolving it in a solvent in which the polyimide precursor is soluble, such as tetrahydrofuran.
Then, the polyimide precursor can be dried to obtain a powdery polyimide precursor.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and further preferably 22,000 to 25,000. The number average molecular weight (Mn) is preferably 7200 to 14000, more preferably 8000 to 12000, and further preferably 9200 to 11200.
The degree of dispersion 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 polydispersity of the polyimide precursor is not particularly limited, but is, for example, preferably 4.5 or less, more preferably 4.0 or less, further preferably 3.8 or less, and further preferably 3.2 or less, 3.1 or less is more preferable, 3.0 or less is still more preferable, and 2.95 or less is particularly preferable.

式（４）中、Ｒ^１３１は、２価の有機基を表し、Ｒ^１３２は、４価の有機基を表す。
ポリイミドが重合性基を有する場合、Ｒ^１３１およびＲ^１３２の少なくとも一方に重合性基を有していてもよいし、下記式（４−１）または式（４−２）に示すようにポリイミドの末端に重合性基を有していてもよい。(Polyimide)
The polyimide is not particularly limited as long as it is a polymer compound having an imide ring. The polyimide is preferably a compound represented by the following formula (4), more preferably a compound represented by the formula (4) and having a polymerizable group.
Formula (4)

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

式（４−１）中、Ｒ^１３３は重合性基であり、他の基は式（４）と同義である。Formula (4-1)

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

式（４−２）中、Ｒ^１３４およびＲ^１３５の少なくとも一方は重合性基であり、他方は有機基であり、他の基は式（４）と同義である。Formula (4-2)

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

The polymerizable group that the polyimide preferably has has the same meaning as the polymerizable group described in the polymerizable group which may be contained in R ¹¹³ and R ¹¹⁴ in the formula (2) in the polyimide precursor.

R ¹³¹ in the formula (4) represents a divalent organic group. Examples of the divalent organic group include the same divalent organic groups as R ¹¹¹ in Formula (2), and the preferred ranges are also the same.
Examples of R ¹³¹ include a diamine residue remaining after removal of the amino group of diamine. Examples of diamines include aliphatic, cycloaliphatic or aromatic diamines. A specific example is the example of R ¹¹¹ in the formula (2) of the polyimide precursor.

R ¹³¹ in formula (4) is preferably a diamine residue having at least two or more alkylene glycol units in the main chain, from the viewpoint of more effectively suppressing the occurrence of warpage during firing. More preferably, it is a diamine residue containing one or both of an ethylene glycol chain and a propylene glycol chain in one molecule, and more preferably a diamine residue containing no aromatic ring.

Examples of the diamine containing one or both of an ethylene glycol chain and a propylene glycol chain in one molecule in combination of two or more include the same specific examples as the diamine capable of deriving R ¹¹¹ in the formula (2). It is not limited to these.

R ¹³² in the formula (4) represents a tetravalent organic group. Examples of the tetravalent organic group represented by R ¹³² are the same as those of R ¹¹⁵ in the formula (2), and the preferable ranges are also the same.
For example, four bonds of a tetravalent organic group having the structure shown below, which is exemplified as R ¹¹⁵ in formula (2), are bonded to four —C(═O)— moieties in formula (4) above. Form a fused ring.

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

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

It is also 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 20% by mass or less.

Further, an aliphatic group having a siloxane structure may be introduced into the polyimide for the purpose of improving the adhesion to the substrate. Specifically, examples of the diamine component for introducing an aliphatic group having a siloxane structure include bis(3-aminopropyl)tetramethyldisiloxane and bis(paraaminophenyl)octamethylpentasiloxane.

Further, in order to improve the storage stability of the photosensitive resin composition, the main chain end of the polyimide is sealed with a terminal blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, and a monoactive ester compound. Preferably. Of these, it is more preferable to use monoamine. Preferred compounds of monoamine are 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-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-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-amino Benzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like can be mentioned. To be Two or more of these may be used, and a plurality of different end groups may be introduced by reacting a plurality of end capping agents.

The imidization ratio of the polyimide is preferably 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 imidized by heating is reduced, and occurrence of warpage of the substrate can be suppressed.

The polyimide may include a repeating unit represented by the above formula (4) in which all are one kind of R ¹³¹ or R ¹³² , and may also include a repeating unit in which two or more of R ¹³¹ or R ¹³² are different kinds. Further, the polyimide may include other types of repeating units in addition to the repeating unit represented by the above formula (4).

The polyimide may be produced by synthesizing a polyimide precursor and then cyclizing it by heating, or the polyimide may be directly synthesized.
Polyimide, to obtain a polyimide precursor, it is a method of completely imidizing using a known imidization reaction method, or a method of stopping the imidization reaction in the middle, a method of introducing a partial imide structure, further, By blending the completely imidized polymer and its polyimide precursor, it can be synthesized by utilizing a method of introducing a partial imide structure.

Examples of commercially available polyimides include Durimide (registered trademark) 284 (manufactured by FUJIFILM) and Matrimid 5218 (manufactured by HUNTSMAN).

The weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and particularly preferably 10,000 to 30,000. By setting the weight average molecular weight to be 5,000 or more, the crease 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 more preferably 20,000 or more. When two or more kinds of polyimide are contained, it is preferable that the weight average molecular weight of at least one kind of polyimide is within the above range.

(Polybenzoxazole precursor)
The polybenzoxazole precursor is not particularly limited in terms of its type and the like, and for example, the description in paragraphs 0097 to 0107 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated in the present specification. ..

Even photosensitive resins other than those described above can be applied to this embodiment. As the other resin, an epoxy resin, a phenol resin, or a benzocyclobutene resin can be used.

<<<<Polymerizable compound>>>>
It is preferable that the resin has a polymerizable group or the photosensitive resin composition contains a polymerizable compound. With such a structure, a cured film having more excellent heat resistance can be formed.
The polymerizable compound is a compound having a polymerizable group, and a known compound capable of undergoing a crosslinking reaction with a radical, an acid, a base or the like can be used. Examples of the polymerizable group include the polymerizable group described in the above polyimide precursor. Only one kind of the polymerizable compound may be contained, or two or more kinds thereof may be contained.
The polymerizable compound may be in any chemical form such as, for example, a monomer, a prepolymer, an oligomer or a mixture thereof and a multimer thereof.

In the present embodiment, the monomer type polymerizable compound (hereinafter, also referred to as a polymerizable monomer) is a compound different from the polymer compound. The polymerizable monomer is typically a low molecular weight compound, preferably a low molecular weight compound having a molecular weight of 2000 or less, more preferably a low molecular weight compound having a molecular weight of 1500 or less, and a low molecular weight compound having a molecular weight of 900 or less. It is more preferable that there is. The molecular weight of the polymerizable monomer is usually 100 or more.
Further, 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 means the number of polymerizable groups in one molecule.
From the viewpoint of developability, the photosensitive resin composition preferably contains at least one bifunctional or more polymerizable compound containing two or more polymerizable groups, and at least one trifunctional or more polymerizable compound. Is more preferable.
The photosensitive resin composition preferably contains at least one trifunctional or higher functional polymerizable compound from the viewpoint that a three-dimensional crosslinked structure can be formed and heat resistance can be improved. Further, it may be a mixture of a bifunctional or lower polymerizable compound and a trifunctional or higher functional polymerizable compound.

The polymerizable compound is preferably a compound containing a group having an ethylenically unsaturated bond; a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group; an epoxy compound; an oxetane compound; a benzoxazine compound.

(Compound containing a group 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.

As the compound having a group having an ethylenically unsaturated bond, the radically polymerizable compounds described in paragraphs 0112 to 0157 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated herein. ..

Examples of commercially available polymerizable compounds include SR-494, which is a tetrafunctional acrylate manufactured by Sartomer having four ethyleneoxy chains, and SR-209, which is a bifunctional methacrylate having four ethyleneoxy chains manufactured by Sartomer. DPCA-60, which is a hexafunctional acrylate having 6 pentyleneoxy chains, manufactured by Nippon Kayaku Co., Ltd., NK ester M-40G, NK ester 4G, NK ester M, which is a trifunctional acrylate having 3 isobutyleneoxy chains. -9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), TPA-330, DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-. 306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Bremmer PME400 (manufactured by NOF CORPORATION) and the like can be mentioned.

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

(Compounds having a hydroxymethyl group, an alkoxymethyl group or an 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.

（式中、ｔは、１〜２０の整数を示し、Ｒ^４は炭素数１〜２００のｔ価の有機基を示し、Ｒ^５は下記式（ＡＭ２）または下記式（ＡＭ３）で示される基を示す。）Expression (AM1)

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

（式中Ｒ^６は、水酸基または炭素数１〜１０の有機基を示す。）

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

The amount of the compound represented by the formula (AM1) is preferably 5 parts by mass or more and 40 parts by mass or less based on 100 parts by mass of the polyimide precursor and the like. More preferably, it is 10 parts by mass or more and 35 parts by mass or less. Further, in all the polymerizable compounds, the compound represented by the following formula (AM4) is contained in an amount of 10% by mass or more and 90% by mass or less, and the compound represented by the following formula (AM5) is contained in the total thermal crosslinking agent in an amount of 10% by mass or more. It is also preferable to contain 90% by mass or less.

（式中、Ｒ^４は炭素数１〜２００の２価の有機基を示し、Ｒ^５は下記式（ＡＭ２）または下記式（ＡＭ３）で示される基を示す。）Expression (AM4)

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

（式中ｕは３〜８の整数を示し、Ｒ^４は炭素数１〜２００のｕ価の有機基を示し、Ｒ^５は下記式（ＡＭ２）または下記式（ＡＭ３）で示される基を示す。）Expression (AM5)

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

（式中Ｒ^６は、水酸基または炭素数１〜１０の有機基を示す。）Formula (AM2) (AM3)

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

By using these compounds having a hydroxymethyl group or the like, cracks are less likely to occur when the photosensitive composition is formed on a substrate having irregularities. Further, it can have high heat resistance with a 5% mass reduction temperature of 350° C. or higher, more preferably 380° C. or higher. Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (trade names, 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, dimethyolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC. MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethyloxymethyl-4-t-butylphenol, 2,6-dimethyloxymethyl-p-cresol, and 2,6-diacetyloxymethyl-p-cresol. To be

In addition, 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-TPHAP (above, 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 and NIKALAC MW-100LM (above, brand name, Sanwa Chemical Co., Ltd. make) are mentioned.

(Epoxy compound (compound having an 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 lower, and a dehydration reaction resulting from the cross-linking does not occur, so that the film shrinkage hardly occurs. Therefore, the inclusion of the epoxy compound is effective for low-temperature curing of the composition and suppression of warpage.

The epoxy compound preferably contains a polyethylene oxide group. As a result, the elastic modulus is further reduced and the warp can be suppressed. Further, the flexibility of the film can be increased, and a cured film excellent in 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 (glycidic Examples include, but are not limited to, epoxy group-containing silicones such as loxypropyl)siloxane. Specifically, Epiclon (registered trademark) 850-S, Epiclon (registered trademark) HP-4032, Epiclon (registered trademark) HP-7200, Epiclon (registered trademark) HP-820, Epicron (registered trademark) HP-4700, Epicron (registered trademark) EXA-4710, epiclon (registered trademark) HP-4770, epiclon (registered trademark) EXA-859CRP, epiclon (registered trademark) EXA-1514, epiclon (registered trademark) EXA-4880, epicuron (registered trademark) EXA-4850-150, Epiclon (registered trademark) EXA-4850-1000, Epiclon (registered trademark) EXA-4816, Epiclon (registered trademark) EXA-4822 (the above trade name, manufactured by Dainippon Ink and Chemicals, Inc.), Examples thereof include Licarezin (registered trademark) BEO-60E (trade name, Shin Nippon Rika Co., Ltd.), EP-4003S, EP-4000S (the above trade names, manufactured by ADEKA). Among these, an epoxy resin containing a polyethylene oxide group is preferable in terms of suppression of warpage and excellent heat resistance. For example, Epiclon (registered trademark) EXA-4880, Epiclon (registered trademark) EXA-4822, and lycaredin (registered trademark) BEO-60E are preferable because they contain a polyethylene oxide group.

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 resin. When the blending amount is 5 parts by mass or more, the warp of the cured film can be further suppressed.

(Oxetane compound (compound having oxetanyl group))
As the oxetane compound, a compound having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, Examples thereof include 3-ethyl-3-(2-ethylhexylmethyl)oxetane and 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester. As a specific example, Toagosei Co., Ltd.'s Aron oxetane series (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be used suitably, and these can be used alone or You may mix 2 or more types.

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

(Benzoxazine compound (compound having benzoxazolyl group))
The benzoxazine compound is preferable because it promotes the crosslinking reaction derived from the ring-opening addition reaction, so that degassing does not occur during curing, and further the heat shrinkage is reduced to suppress the occurrence of warpage.

Preferred examples of the benzoxazine compound include Ba type benzoxazine, Bm type benzoxazine (these are trade names, manufactured by Shikoku Chemicals Co., Ltd.), a benzoxazine adduct of polyhydroxystyrene resin, and a phenol novolac type. Examples include dihydrobenzoxazine compounds. These may be used alone or in combination of two or more.

The content 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 resin.

<<<photopolymerization initiator>>
The photosensitive resin composition may contain a photopolymerization initiator.
As the photopolymerization initiator, the description in paragraphs 0165 to 0182 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated in the present specification.
An oxime compound is more preferable as the photopolymerization initiator. By using the oxime compound, the exposure latitude can be more effectively improved. Oxime ester compounds are particularly preferable because they have a wide exposure latitude (exposure margin) and also act as a thermal base generator.
As specific examples of the oxime compound, the compounds described in JP 2001-233842 A, the compounds described in JP 2000-80068 A, and the compounds described in JP 2006-342166 A can be used.
Examples of preferable oxime compounds include compounds having the following structures, 3-benzooxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, and 2-acetoxy. Iminopentan-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.

Examples of the oxime compound include J. C. S. Perkin II (1979) pp. 1653-1660, J. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. Compounds described in each document of 202-232, JP-A-2000-66385, JP-A-2000-80068, JP-A-2004-534797, JP-A-2006-342166, and International Publication WO2015/036910. The compounds and the like described in the respective publications are listed.
As commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKA, Inc., JP 2012-14052 A). The polymerization initiator 2) is also preferably used. In addition, TR-PBG-304 (manufactured by Changzhou Power Electronics Co., Ltd.), ADEKA ARKUL'S NCI-831 and ADEKA ARKRUZ NCI-930 (manufactured by ADEKA Corporation) can also be used. In addition, DFI-091 (manufactured by Daito Chemix Corporation) can also be used.
Further, the 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 preferably used.
Furthermore, it is also possible to use an oxime compound having a fluorine atom. Specific examples of such an oxime compound include compounds described in JP 2010-262028 A, compounds 24, 36-40 described in paragraphs 0345 to 0348 of JP-A-2014-500852, and The compound (C-3) etc. which are described in paragraph 0101 of Kai 2013-164471 gazette are mentioned.
Further, as the photopolymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication WO2015/125469 can also be used.

When the photosensitive resin composition contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1 to 30% by mass, and more preferably 0.1 to 30% by mass based on the total solid content of the photosensitive resin composition. It is -20 mass%, More preferably, it is 0.1-10 mass%.
The photopolymerization initiator may be used alone or in combination of two or more. When two or more photopolymerization initiators are used, the total is preferably within the above range.

<<<migration inhibitor>>>
The photosensitive resin composition preferably further contains a migration inhibitor. By including the migration inhibitor, it is possible to effectively suppress the migration of metal ions derived from the metal layer (metal wiring) into the photosensitive resin composition layer.
The migration inhibitor is not particularly limited, but a heterocycle (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, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring, a morpholine ring, a 2H-pyran ring and a 6H-pyran ring, a triazine ring), a compound having a thiourea and a mercapto group, a hinderphenol compound, Examples thereof include salicylic acid derivative-based compounds and hydrazide derivative-based compounds. In particular, triazole compounds such as triazole and benzotriazole, and tetrazole compounds such as tetrazole and benzotetrazole can be preferably used.

Also, an ion trap agent that traps anions such as halogen ions can be used.

Other migration inhibitors include rust preventives described in paragraph 0094 of JP2013-15701A, compounds described in paragraphs 0073 to 0076 of JP2009-283711, and JP2011-59656A. The compounds described in Paragraph 0052, the compounds described in Paragraphs 0114, 0116 and 0118 of JP2012-194520A, and the like can be used.

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

When the photosensitive resin composition contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass% with respect to the total solid content of the photosensitive resin composition, and 0.05 ˜2.0 mass% is more preferred, and 0.1 to 1.0 mass% is even more preferred.
Only one type of migration inhibitor may be used, or two or more types may be used. When two or more migration inhibitors are used, it is preferable that the total amount thereof is within the above range.

<<<Polymerization inhibitor>>>
The photosensitive resin composition used in this embodiment preferably contains a polymerization inhibitor.
Examples of the polymerization inhibitor include hydroquinone, paramethoxyphenol, di-tert-butyl-paracresol, pyrogallol, para-tert-butylcatechol, parabenzoquinone, diphenyl-parabenzoquinone, 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-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol , 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxyamine ammonium salt, bis(4-hydroxy) -3,5-tert-Butyl)phenylmethane and the like are preferably used. Further, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Publication WO2015/125469 can also be used.
When the composition contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5 mass% with respect to the total solid content of the photosensitive resin composition.
Only one type of polymerization inhibitor may be used, or two or more types may be used. When two or more polymerization inhibitors are used, it is preferable that the total amount is within the above range.

<<< Thermal base generator >>>
The photosensitive resin composition used in this embodiment may contain a thermal base generator.
The type and the like of the thermal base generator are not particularly specified, but are selected from acidic compounds that generate a base when heated to 40° C. or higher, and ammonium salts having an anion having a pKa1 of 0 to 4 and an ammonium cation. It is preferable to include a thermal base generator containing at least one of the following. Here, pKa1 represents the logarithm (−Log ₁₀ Ka) of the dissociation constant (Ka) of the first proton of the acid, which will be described in detail later.
By compounding such a compound, the cyclization reaction of the polyimide precursor and the polybenzoxazole precursor can be carried out at a low temperature, and a composition having more excellent stability can be obtained. Further, since the thermal base generator does not generate a base unless heated, even if it coexists with a polyimide precursor and a polybenzoxazole precursor, cyclization of the polyimide precursor and the polybenzoxazole precursor during storage. Can be suppressed and has excellent storage stability.

The thermal base generator contains 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. It is preferable.
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 and the polybenzoxazole precursor, Cyclization of polyimide precursors and polybenzoxazole precursors can be performed at low temperatures. Further, even if these compounds are made to coexist with a polyimide precursor and a polybenzoxazole precursor which are cyclized and cured by a base, the cyclization of the polyimide precursor and the polybenzoxazole precursor progresses almost without heating. Therefore, it is possible to prepare a photosensitive resin composition containing a polyimide precursor and a polybenzoxazole precursor having excellent stability.
In the present specification, the acidic compound means that 1 g of the compound is collected in a container, 50 mL of a mixed liquid of ion-exchanged water and tetrahydrofuran (mass ratio water/tetrahydrofuran=1/4) is added, and the mixture is allowed to stand at room temperature for 1 hour. The solution obtained by stirring means a compound having a value of less than 7 measured at 20° C. using a pH (power of hydrogen) meter.

In the present embodiment, 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 preferably 190°C or lower, more preferably 180°C or lower, and even more preferably 165°C or lower. The lower limit of the base generation temperature is preferably 130°C or higher, more preferably 135°C or higher.
If the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 120° C. or higher, a base is less likely to be generated during storage, and thus a polyimide precursor and a polybenzoxazole precursor having excellent stability are included. A photosensitive resin composition can be prepared. When the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 200° C. or lower, the cyclization temperature of the polyimide precursor and the polybenzoxazole precursor can be lowered. For the base generation temperature, for example, by using differential scanning calorimetry, the compound is heated to 250° C. in a pressure-resistant capsule at 5° C./minute, the peak temperature of the lowest exothermic peak is read, and the peak temperature is measured as the base generation temperature. can do.

In the present embodiment, the base generated by the thermal base generator is preferably a secondary amine or a tertiary amine, more preferably a tertiary amine. Since the tertiary amine has high basicity, the cyclization temperature of the polyimide precursor and the polybenzoxazole precursor can be further lowered. 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 further preferably 140°C or higher. The molecular weight of the generated base is preferably 80 to 2000. 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 embodiment, the acidic compound (A1) preferably contains one or more selected from ammonium salts and compounds represented by the formula (101) or (102) described below.

In the present embodiment, 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). ) It is also possible to use compounds other than acidic compounds that generate a base when heated.

式（１０１）および式（１０２）中、Ｒ^１〜Ｒ^６は、それぞれ独立に、水素原子または炭化水素基を表し、Ｒ^７は炭化水素基を表す。式（１０１）および式（１０２）におけるＲ^１とＲ^２、Ｒ^３とＲ^４、Ｒ^５とＲ^６、Ｒ^５とＲ^７はそれぞれ結合して環を形成してもよい。In the present embodiment, 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 bound to any part of the ammonium cation via a covalent bond, and may be present outside the ammonium cation molecule, but may be present outside the ammonium cation molecule. preferable. In addition, that the anion has outside the molecule of the ammonium cation means that the ammonium cation and the anion are not bound to each other through a covalent bond. Hereinafter, the anion outside the molecule of the cation portion is also referred to as a counter anion.
Expression (101) Expression (102)

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

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

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

In the present embodiment, the ammonium salt preferably has an anion having a pKa1 of 0 to 4 and an ammonium cation. The upper limit of pKa1 of the anion is more preferably 3.5 or less and even more preferably 3.2 or less. The lower limit is preferably 0.5 or more, more preferably 1.0 or more. When the pKa1 of the anion is within the above range, the polyimide precursor and the polybenzoxazole precursor can be cyclized at a low temperature, and the stability of the photosensitive resin composition containing the polyimide precursor and the polybenzoxazole precursor can be further improved. Can be improved. In particular, when pKa1 is 4 or less, the stability of the thermal base generator is good, generation of a base can be suppressed without heating, and a photosensitive resin composition containing a polyimide precursor, a polybenzoxazole precursor, and the like. The stability of is good. When pKa1 is 0 or more, the generated base is hardly neutralized, and the cyclization efficiency of the polyimide precursor and the polybenzoxazole precursor is good.
The type of anion is preferably one selected from a carboxylate anion, a phenol anion, a phosphate anion, and a sulfate anion, and the carboxylate anion is more preferable because the stability of the salt and the thermal decomposability can be compatible. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion.
The carboxylic acid anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxyl groups, and more preferably a divalent carboxylic acid anion. According to this aspect, it is possible to provide a thermal base generator capable of further improving the stability, curability and developability of the photosensitive resin composition containing a polyimide precursor, a polybenzoxazole precursor and the like. In particular, by using the anion of divalent carboxylic acid, the stability, curability and developability of the photosensitive resin composition containing the polyimide precursor and the polybenzoxazole precursor can be further improved.
In the present embodiment, the carboxylic acid anion is preferably an anion of a carboxylic acid having a pKa1 of 4 or less. The pKa1 is more preferably 3.5 or less, still more preferably 3.2 or less. According to this aspect, the stability of the photosensitive resin composition containing the polyimide precursor and the polybenzoxazole precursor can be further improved.
Here, pKa1 represents the logarithm of the reciprocal of the dissociation constant of the first proton of the acid, and is known as Determination of Organic Structures by Physical Methods (author: Brown, H. C., McDaniel, D. H., Haflig. , Nachod, F. C.; Compilation: Braude, E. A., Nachod, F. C.; Academic Press, New York, 1955), and Data for Biochemical Research. Author: D. Reach. al; Oxford, Clarendon Press, 1959) can be referred to. For compounds not described in these documents, the value calculated from the structural formula using ACD/pKa (manufactured by ACD/Labs) is used.

式（Ｘ１）において、ＥＷＧは、電子求引性基を表す。The carboxylate anion is preferably represented by the following formula (X1).

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

In the present embodiment, the electron-withdrawing group means that the Hammett's substituent constant σm shows a positive value. Here, σm is as described in Yuho Tono, Review of Organic Synthetic Chemistry, Vol. 23, No. 8 (1965) p. 631-642. The electron-withdrawing group in this embodiment is not limited to the substituents described in the above documents.
Examples of the substituent having a positive σm 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. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group.

式（ＥＷＧ−１）〜（ＥＷＧ−６）中、Ｒ^ｘ１〜Ｒ^ｘ３は、それぞれ独立に、水素原子、アルキル基、アルケニル基、アリール基、ヒドロキシル基またはカルボキシル基を表し、Ａｒは芳香族基を表す。EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).

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

式（ＸＡ）において、Ｌ^１０は、単結合、または、アルキレン基、アルケニレン基、芳香族基、−ＮＲ^Ｘ−およびこれらの組み合わせから選ばれる２価の連結基を表し、Ｒ^Ｘは、水素原子、アルキル基、アルケニル基またはアリール基を表す。In the present embodiment, the carboxylate anion is preferably represented by the following formula (XA).
Formula (XA)

In formula (XA), 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 a combination thereof, and R ^X represents a hydrogen atom. Represents an alkyl group, an alkenyl group or an aryl group.

Specific examples of the carboxylate anion include maleate anion, phthalate anion, N-phenyliminodiacetic acid anion and oxalate anion. These can be preferably used.

The following compounds may be mentioned as specific examples of the thermal base generator.

When the thermal base generator is used, the content of the thermal base generator in the photosensitive resin composition is preferably 0.1 to 50 mass% with respect to the total solid content of the photosensitive resin composition. The lower limit is more preferably 0.5% by mass or more, still more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less.
The thermal base generator can use 1 type(s) or 2 or more types. When two or more kinds are used, the total amount is preferably within the above range.

金属接着性改良剤は樹脂１００質量部に対して好ましくは０．１〜３０質量部であり、さらに好ましくは０．５〜１５質量部の範囲である。０．１質量部以上とすることで硬化工程後の硬化膜と金属層との接着性が良好となり、３０質量部以下とすることで硬化工程後の硬化膜の耐熱性、機械特性が良好となる。
金属接着性改良剤は１種のみでもよいし、２種以上であってもよい。２種以上用いる場合は、その合計が上記範囲であることが好ましい。<<<Metal adhesion improver>>>>
The photosensitive resin composition used in this embodiment preferably contains a metal adhesion improver for improving the adhesion to a metal material used for electrodes, wirings and the like. Examples of the metal adhesion improver include the sulfide compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and paragraphs 0032 to 0043 of JP-A-2013-072935. Examples of the metal adhesion improver include the following compounds (N-[3-(triethoxysilyl)propyl]maleic acid monoamide and the like).

The metal adhesion improver is preferably 0.1 to 30 parts by mass, and more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the resin. When the amount is 0.1 part by mass or more, the adhesiveness between the cured film and the metal layer after the curing step is good, and when the amount is 30 parts by mass or less, the heat resistance and mechanical properties of the cured film after the curing step are good. Become.
The metal adhesion improver may be only one kind or two or more kinds. When two or more kinds are used, the total is preferably within the above range.

<<<<solvent>>>>
When the photosensitive resin composition used in this embodiment is formed into a layer by coating, it is preferable to add a solvent. As the solvent, any known solvent can be used as long as it can form the photosensitive resin composition into a layer. Examples of the solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons and sulfoxides.
As the esters, for example, ethyl acetate, -n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl oxyacetate (eg, methyl oxyacetate, ethyl oxyacetate, butyl acetoacetate), 3-oxypropionic acid alkyl esters (eg: methyl 3-oxypropionate, 3-oxypropione) Ethyl acid salts (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-oxypropionic acid alkyl esters (eg, 2- Methyl oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate and the like (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-Ethoxypropionate ethyl)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (eg methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2- (Methyl propionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like are preferable.
Examples of ethers include 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. Preference is given to monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like.
Preferable examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and N-methyl-2-pyrrolidone.
Preferable examples of the aromatic hydrocarbons include toluene, xylene, anisole, limonene and the like.

From the viewpoint of improving the properties of the coated surface, the solvent is preferably a mixture of two or more kinds. 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 photosensitive resin composition contains a solvent, the content of the solvent is preferably 5 to 80% by mass of the total solid content concentration of the photosensitive resin composition from the viewpoint of coatability. ˜70 mass% is more preferred, and 10˜60 mass% is particularly preferred. The solvent content may be adjusted according to the desired thickness and coating method. For example, when the coating method is spin coating or slit coating, the content of the solvent having the solid content concentration in the above range is preferable. In the case of spray coating, the amount is preferably 0.1% by mass to 50% by mass, and more preferably 1.0% by mass to 25% by mass. By adjusting the amount of solvent according to the coating method, a photosensitive resin composition layer having a desired thickness can be uniformly formed.
Only one type of solvent may be used, or two or more types may be used. When two or more kinds of solvents are used, it is preferable that the total thereof is within the above range.
The content of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide and N,N-dimethylformamide is the total mass of the photosensitive resin composition from the viewpoint of film strength. Is less than 5% by mass, more preferably less than 1% by mass, even more preferably less than 0.5% by mass, still more preferably less than 0.1% by mass.

<<<< other additives >>>
The photosensitive resin composition used in the present embodiment, as long as the effects of the present invention are not impaired, if necessary, various additives, for example, a photobase generator, a thermal polymerization initiator, a thermal acid generator, an increase agent. A dye, a chain transfer agent, a surfactant, a higher fatty acid derivative, inorganic particles, a curing agent, a curing catalyst, a filler, an antioxidant, an ultraviolet absorber, an anticoagulant and the like can be added. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the composition.

(Photobase generator)
The photosensitive resin composition used in this embodiment may contain a photobase generator. The photobase generator is a substance that generates a base upon exposure to light, and does not show activity under normal conditions of normal temperature and pressure. ) Is not particularly limited as long as it is generated. Since the base generated by exposure acts as a catalyst when the polyimide precursor and the benzoxazole precursor are cured by heating, they can be preferably used in a negative type.

The content of the photobase generator is not particularly limited and can be a general content. The photobase generator is preferably in the range of 0.01 parts by mass or more and less than 30 parts by mass, more preferably in the range of 0.05 parts by mass to 25 parts by mass with respect to 100 parts by mass of the resin. It is more preferably in the range of 0.1 parts by mass to 20 parts by mass.
The photobase generator may be used alone or in combination of two or more. When two or more photobase generators are used, it is preferable that the total amount thereof be within the above range.
In the present embodiment, known photobase generators can be used. For example, 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.M. Neckers, Chem. Mater. H., 11, 170 (1999); Tachi, M.; Shirai, and M.M. Tsunooka, J.; Photopolym. Sci. Technol. 13, 153 (2000); Winkle, and K.K. Graziano, J.; Photopolym. Sci. Technol. , 3, 419 (1990); Tsunooka, H.; Tachi, and S.M. Yoshitaka, J.; Photopolym. Sci. Technol. K., 9, 13 (1996); Suyama, H.; Araki, M.; Shirai, J.; Photopolym. Sci. Technol. , 19, 81 (2006), a compound having a structure such as a transition metal compound complex or an ammonium salt, or a compound hidden by forming a salt with a carboxylic acid at an amidine moiety. , An ionic compound neutralized by the base component forming a salt, or a nonionic compound such as a carbamate derivative, an oxime ester derivative, or an acyl compound in which the base component is hidden by a urethane bond or an oxime bond. Can be mentioned.
The photobase generator that can be used in the present embodiment is not particularly limited, and known ones can be used. For example, carbamate derivatives, amide derivatives, imide derivatives, α-cobalt complexes, imidazole derivatives, cinnamic acid amide derivatives. , Oxime derivatives and the like.
Examples of the photobase generator include photobase generators having a cinnamic acid amide structure as disclosed in JP2009-80452A and WO2009/123122, and JP2006-189591A and JP2006-189591A. Photobase generator having a carbamate structure as disclosed in JP-A 2008-247747, light having an oxime structure and a carbamoyl oxime structure as disclosed in JP2007-249013A and JP2008-003581A. Examples thereof include base generators, but the present invention is not limited to these, and other known photobase generators can be used.
In addition, as the photobase generator, compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 of JP 2012-93746 A, compounds described in paragraphs 0022 to 0069 of JP 2013-194205 A, Examples include the compounds described in paragraphs 0026 to 0074 of JP2013-201419A, and the compounds described in paragraph 0052 of International Publication WO2010/064631.

(Thermal polymerization initiator)
The photosensitive resin composition used in this embodiment may contain a thermal polymerization initiator (preferably a thermal radical polymerization initiator). As the thermal radical polymerization initiator, a known thermal radical polymerization initiator can be used.
The thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of the polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the polymerizable compound can be promoted when the cyclization reaction of the polyimide precursor and the polybenzoxazole precursor is promoted. When the polyimide precursor and the polybenzoxazole precursor contain an ethylenically unsaturated bond, the polymerization reaction of the polyimide precursor and the polybenzoxazole precursor proceeds together with the cyclization of the polyimide precursor and the polybenzoxazole precursor. It is also possible to achieve higher heat resistance.
Specific examples of the thermal radical polymerization initiator include the compounds described in paragraphs 0074 to 0118 of JP 2008-63554 A.

When the photosensitive resin composition contains a thermal radical polymerization initiator, the content of the thermal radical polymerization initiator is preferably 0.1 to 50 mass% with respect to the total solid content of the photosensitive resin composition, -30 mass% is more preferable, and 0.1-20 mass% is especially 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, relative 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 two or more thermal radical polymerization initiators are used, it is preferable that the total amount thereof be within the above range.

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

Further, the compounds described in JP-A-2013-167742, paragraph 0059 are also preferable as the thermal acid generator.

The content of the thermal acid generator is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the polyimide precursor and the polybenzoxazole precursor. Since the crosslinking reaction and the cyclization of the polyimide precursor and the polybenzoxazole precursor are promoted by containing 0.01 part by mass or more, the mechanical properties and chemical resistance of the cured film can be further improved. Further, the content thereof is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and particularly preferably 10 parts by mass or less, from the viewpoint of electric insulation of the cured film.
The thermal acid generator may be used alone or in combination of two or more. When two or more kinds are used, the total amount is preferably within the above range.

(Silane coupling agent)
The photosensitive resin composition used in the present embodiment may contain a silane coupling agent in order to improve the adhesion to the substrate.
Examples of the silane coupling agent include compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, compounds described in paragraphs 0063 to 0071 of WO2011/080992A1, and JP-A-2014-191252. The compounds described in Paragraphs 0060 to 0061, the compounds described in Paragraphs 0045 to 0052 of JP-A-2014-41264, and the compounds described in Paragraph 0055 of International Publication WO2014/097594. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A.
The content of the silane coupling agent is preferably 0.1 to 20 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the resin. When the amount is 0.1 parts by mass or more, sufficient adhesion to the substrate can be imparted, and when the amount is 20 parts by mass or less, problems such as viscosity increase during storage at room temperature can be suppressed.
The silane coupling agent may be used alone or in combination of two or more. When two or more kinds are used, the total amount is preferably within the above range.

(Sensitizing dye)
The photosensitive resin composition used in this embodiment may contain a sensitizing dye. The sensitizing dye absorbs specific actinic radiation to be in an electronically excited state. The sensitizing dye in the electronically excited state comes into contact with an amine generator, a thermal radical polymerization initiator, a photopolymerization initiator, etc., and effects such as electron transfer, energy transfer, and heat generation. As a result, the amine generator, the thermal radical polymerization initiator, and the photopolymerization initiator undergo a chemical change to decompose and generate a radical, an acid, or a base.

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 (eg phenanthrene, anthracene, pyrene, perylene, triphenylene, 9.10-dialkoxyanthracene), xanthenes (eg fluorescein, eosin, erythrosine, rhodamine B, rose bengal), thioxanthones (eg. , 2,4-diethylthioxanthone), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), thiazines (eg thionine, methylene blue, toluidine blue), acridines (eg , Acridine orange, chloroflavin, acriflavine), anthraquinones (eg anthraquinone), squaryliums (eg squarylium), coumarins (eg 7-diethylamino-4-methylcoumarin), styrylbenzenes, distyrylbenzenes , Carbazoles and the like.

When the photosensitive resin composition contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01 to 20% by mass, and 0.1 to 15% by mass based on the total solid content of the photosensitive resin composition. Is more preferable, and 0.5-10 mass% is still more preferable. The sensitizing dyes may be used alone or in combination of two or more.

(Chain transfer agent)
The photosensitive resin composition used in this embodiment may contain a chain transfer agent. The chain transfer agent is defined, for example, in Polymer Dictionary, Third Edition (edited by The Polymer Society of Japan, 2005), pages 683-684. As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. These can donate hydrogen to a low-activity radical to generate a radical, or can generate a radical by being deprotonated after being oxidized. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazole, etc.) can be preferably used.

When the photosensitive resin composition contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 100 parts by mass of the total solid content of the photosensitive resin composition. Is 1 to 10 parts by mass, particularly preferably 1 to 5 parts by mass.
The chain transfer agent may be only one type or two or more types. When two or more chain transfer agents are used, the total is preferably within the above range.

(Surfactant)
From the viewpoint of further improving coatability, each type of surfactant may be added to the photosensitive resin composition used in this embodiment. As the surfactant, various kinds of surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. The following surfactants are also preferable.

When the photosensitive resin composition contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0 mass% with respect to the total solid content of the photosensitive resin composition, and more preferably It is 0.005 to 1.0 mass %.
The surfactant may be used alone or in combination of two or more. When two or more kinds of surfactants are used, it is preferable that the total amount is within the above range.

(Higher fatty acid derivative)
In order to prevent polymerization inhibition due to oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide is added to the photosensitive resin composition used in the present embodiment, and the composition is dried in the process of coating. It may be unevenly distributed on the surface of the object.
When the photosensitive resin composition contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass based on the total solid content of the photosensitive resin composition.
Only one type of higher fatty acid derivative may be used, or two or more types may be used. When two or more higher fatty acid derivatives are used, the total is preferably within the above range.

<<<Restrictions on other contained substances>>>
The water content of the photosensitive resin composition used in this embodiment 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 properties of the coated surface.

From the viewpoint of insulation, the metal content of the photosensitive resin composition used in the present embodiment is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and particularly preferably less than 0.5 mass ppm. preferable. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium and nickel. When a plurality of metals are contained, the total of these metals is preferably within the above range.
Further, as a method for reducing the metal impurities unintentionally included in the photosensitive resin composition, a raw material having a low metal content is selected as a raw material forming the photosensitive resin composition, and the photosensitive resin composition is formed. Examples of such a method include filtering the raw material with a filter, and lining the inside of the apparatus with polytetrafluoroethylene or the like to carry out distillation under conditions in which contamination is suppressed as much as possible.

The content of halogen atoms in the photosensitive resin composition used in the present embodiment is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and particularly preferably less than 200 mass ppm, from the viewpoint of wiring corrosivity. Among them, those present in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, particularly preferably less than 0.5 mass ppm. Examples of the halogen atom include chlorine atom and bromine atom. It is preferable that the total of chlorine atom and bromine atom, or the total of chlorine ion and bromine ion be within the above ranges.

<Exposure and development process>
In the present invention, the photosensitive resin layer located on the substrate is exposed and developed to form two or more resin regions. In the present invention, by forming two or more resin regions, the chips can be singulated without using a laser cutter or the like. The resin region after exposure and development is usually not photosensitive.
The resin region in the present invention is formed by exposing and developing the photosensitive resin layer. Therefore, it may contain a component other than the resin described above.
In the present invention, preferably 2 to 100,000 resin regions are formed on one substrate, and more preferably 4 to 10,000 resin regions are formed. The interval between the resin regions can be, for example, 1 μm to 5 mm.

In this embodiment, the photosensitive resin layer 2 is exposed and developed to manufacture the resin region 22. The thickness of the resin region 22 is similar to the thickness of the photosensitive resin layer 2, and is preferably 0.1 to 100 μm, more preferably 1 to 50 μm, and further preferably 3 to 20 μm.

The exposure conditions are not particularly limited, and it is preferable that the solubility of the exposed portion of the photosensitive resin layer 2 in the developing solution can be changed, and it is more preferable that the exposed portion of the photosensitive resin layer 2 can be cured.
The lower limit of the exposure wavelength is preferably 100 nm or more, more preferably 190 nm or more, even more preferably 240 nm or more. The upper limit of the exposure wavelength is preferably 500 nm or less, more preferably 400 nm or less.
Exposure is preferably 100~10000mJ / cm ² at an exposure energy conversion at a wavelength 365 nm, and more preferably 200~8000mJ / cm ^2.

It is preferable to use the mask 3 in order to form a desired resin region 22 upon exposure. The mask is designed so that a plurality of resin regions 22 can be formed. When the negative development process is performed, the region covered with the mask and not exposed remains as the resin region 22. In the present invention, the resin region 22 is formed along the line dividing the chip by exposure and development. Further, as shown in FIG. 2 described later, the non-exposed portion (mask) also has openings such as contact holes, portions where wiring is provided, and portions where electrodes are provided, which are through holes for providing electrodes and wiring. , May be designed to be formed together.
The development processing may be positive development processing or negative development processing, but negative development processing is preferred. By performing the negative development process, the unexposed portion (non-exposed portion) is removed. The developing method is not particularly limited, and for example, a developing method such as paddle, spraying, dipping or ultrasonic wave can be adopted.
Development is preferably performed using a developer. The developer can be used without particular limitation as long as it can remove the unexposed portion (non-exposed portion). Development using an organic solvent is preferable, and examples of the esters include ethyl acetate, -n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, and lactic acid. Methyl, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, 3-methoxypropionic acid Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate , Methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, aceto Methyl acetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like, and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve. Examples thereof include 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, and propylene glycol monopropyl ether acetate.
Examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like.
Examples of aromatic hydrocarbons include toluene, xylene, anisole, limonene and the like.
Preferable examples of sulfoxides include dimethyl sulfoxide.
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 methyl ether, and propylene glycol methyl ether acetate are preferable, and cyclopentanone and γ-butyrolactone are more preferable.
The development time is preferably 10 seconds to 5 minutes.
The temperature at the time of development is not particularly limited, but can usually be 20 to 40°C.
A rinse may be further performed after the treatment with the developing solution. The rinsing is preferably performed in a solvent different from the developing solution. For example, rinsing can be performed using the solvent contained in the photosensitive resin composition. The rinse time is preferably 5 seconds to 1 minute.

<Step of applying at least one of heat and light>
In this embodiment, it is preferable to include a step of applying at least one of heat and light to the resin region after the exposure and development step.
When the photosensitive resin layer (or the photosensitive resin composition layer) contains at least one selected from a polyimide precursor and a polybenzoxazole precursor, heat is applied to the polyimide precursor and the polybenzoxazole precursor. The cyclization reaction of the body can proceed. Even when the photosensitive resin layer is polyimide or polybenzoxazole, it can be heated together with the crosslinking agent to form a three-dimensional network structure. Further, when the photosensitive resin composition contains a radically polymerizable compound or the like, the unreacted radically polymerizable compound can be cured by applying at least one of heat and light.

When heat is applied, the photosensitive resin layer is usually heated to a temperature equal to or higher than the glass transition temperature of the resin forming the photosensitive resin layer. When the photosensitive resin layer contains at least one selected from a polyimide precursor and a polybenzoxazole precursor, the final temperature when the temperature is raised is equal to or higher than the cyclization temperature of the resin contained in the photosensitive resin layer. Is preferred.
The final temperature reached when the temperature is raised is preferably the maximum heating temperature. The maximum heating temperature is preferably 100 to 500°C, more preferably 150 to 450°C, and further preferably 160 to 350°C.

The temperature is preferably raised from a temperature of 20 to 150° C. to the maximum heating temperature at a temperature rising rate of 1 to 12° C./min, more preferably 2 to 11° 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 the excessive volatilization of the amine while ensuring the productivity, and by setting the heating rate to 12° C./min or less, the The residual stress of the film can be relaxed.
The temperature at the start of heating is preferably 20 to 150°C, more preferably 20°C to 130°C, further preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at which the step of heating to the maximum heating temperature is started. 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, from the boiling point of the solvent contained in the photosensitive resin composition-(30 to 200)°C. It is preferable to raise the temperature gradually.

The heating may be performed in stages. As an example, before raising the temperature from 25° C. to 180° C. at 3° C./min, leaving at 180° C. for 60 minutes, raising the temperature from 180° to 200° C. at 2° C./min, and placing at 200° C. for 120 minutes A treatment step may be performed. The heating in the pretreatment step is preferably 100 to 200°C, more preferably 110 to 190°C, and most preferably 120 to 185°C. In this pretreatment step, it is also preferable to perform the treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547. By such a pretreatment step, it is possible to improve the characteristics of the film after heating. The pretreatment step is preferably performed for a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment process may be performed in two or more steps. For example, the pretreatment process 1 may be performed in the range of 100 to 150°C, and the pretreatment process 2 may be performed in the range of 150 to 200°C thereafter.

The temperature rising time is preferably 20 to 200 minutes, more preferably 20 to 100 minutes.

In the present embodiment, after reaching the final reached temperature by heating, it is preferable to perform heating at the final reached temperature for 30 to 360 minutes, more preferably 30 to 300 minutes, and further 30 to 240 minutes. It is particularly preferable to carry out.

In this embodiment, it is preferable to cool the photosensitive resin layer after the temperature raising step. The cooling rate is preferably 2° C./min or less, more preferably 1° C./min or less. The cooling rate in the cooling step is preferably 0.1° C./minute or more. The cooling time is preferably 30 to 600 minutes, more preferably 60 to 600 minutes, and particularly preferably 120 to 600 minutes.

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

<Device material application process>
The manufacturing method of the present invention includes a device material application step of applying a device material on the surface of the photosensitive resin layer 2 or the resin region 22 on the surface opposite to the surface on the base material 1 side.
The device material may be applied before the photosensitive resin layer 2, that is, the exposure and development step, or may be applied after the resin region 22, that is, after the exposure and development step. In the present invention, the device material application step is preferably performed after the exposure and development step.
Further, when the step of applying at least one of heat and light to the resin region is performed, it is preferable to perform the device material applying step after the above step.
The method of applying the device material is preferably selected from a printing method, a photolithography method, an inkjet method, an imprint method, a mask vapor deposition method and a laser ablation method, and a printing method is more preferable.

Examples of the printing method include screen printing, gravure printing, offset printing, letterpress printing, and tampo printing.
Examples of the photolithography method include an etching method, a lift-off method, and a direct lithography method.
Examples of the inkjet method include a piezo method, a thermal method, and an electrolytic acceleration method.
Examples of the imprint method include a resist imprint method, a resin imprint method, and a conductive paste imprint method.
Examples of the mask vapor deposition method include a sputtering method, a CVD (chemical vapor deposition) method, a PVD (Physical Vapor Deposition) method, and a metal mask method.
Examples of the laser ablation method include a resist ablation method and a direct ablation method.

The device material is preferably one or more selected from a conductor material, a semiconductor material, an insulator material and an electronic device.
Examples of the conductor material include metals such as Cu, Al, Au, Ag and Ni, and organic pastes such as Ag paste, Cu paste, Au paste and Ni paste.
Examples of the semiconductor material include inorganic semiconductor materials such as Si, SiC, GaAs, InGaAs, InSb, and GaN, and pentacene, anthracene, rubrene, tetracyanoquinodimethane, polyacetylene, poly-3-hexylthiophene, polyparaphenylene vinylene, Examples are organic semiconductor materials such as polypyrrole, polyaniline, and phthalocyanine.
As the insulating material, inorganic insulating materials such as alumina, aluminum nitride, boron nitride, and glass, and organic materials such as epoxy resin, polyimide resin, polyethylene resin, polypropylene resin, polystyrene resin, polycarbonate resin, fluororesin, and phenol resin An insulating material is exemplified.
Examples of the electronic device include a display device, a light emitting device, a sensor device, a MEMS (Micro Electro Mechanical Systems) device, a communication device, a logic device, a memory device, a power supply device, and a power generation device.
Examples of the display device include organic EL, liquid crystal, electrochromic, and LED (light emitting diode) array.
Examples of the light emitting device include an LED and a semiconductor laser. Examples of the sensor device include a photodiode, a CMOS (semos) image sensor, a silicon microphone, a touch sensor, a vibration sensor, a geomagnetic sensor, an acceleration sensor, a gas sensor, a liquid sensor, an electromagnetic wave sensor, and a GPS (Global Positioning System).
Examples of the MEMS device include an optical scanner, an optical switch, an acceleration sensor, a pressure sensor, a gyroscope, a micro flow path, and an inkjet head.
Examples of communication devices include an antenna, a microwave transmitter/receiver, BlueTooth (registered trademark), and WiFi.
Examples of the logic device include a CPU (Central Processing Unit), MPU (Microprocessor), FPGA (field-programmable gate array), Gate Array, and image processing chip.
Examples of the memory device include DRAM (Dynamic Random Access Memory), SRAM (Static Random Access Memory), flash memory, and MRAM (Magnetoresistive Random Access Memory).
Examples of the power supply device include a Li-ion battery and a capacitor.
Examples of the power generation device include vibration power generation, thermal power generation, and electromagnetic wave power generation.

<Resin area separation process>
The present invention includes a step of separating the base material 1 from the resin region 22. By separating the base material 1, the resin regions are singulated, and the chips 4 are obtained.

In the first embodiment of the method for separating the base material from the resin region, as shown in FIG. 1, a transparent base material is used as the base material 1, and the surface opposite to the surface of the base material 1 on the resin region 22 side is used. From this surface, the base material 1 is separated from the resin region 22 by irradiating light.
Examples of the type of light include ultraviolet rays, infrared rays, and visible rays, which can be appropriately determined according to the type of resin forming the resin region 22 and the like.
When ultraviolet rays are used, examples of solid-state lasers include ultraviolet rays having a wavelength of 355 nm, gas lasers (excimer lasers) include ultraviolet rays of wavelengths 351 nm, 308 nm, and 248 nm, and examples of semiconductor lasers include ultraviolet rays of wavelengths 405 nm and 365 nm. ..
When infrared rays are used, examples of solid-state lasers include infrared rays having a wavelength of 1064 nm, and examples of semiconductor lasers include infrared rays having wavelengths of 980 nm, 905 nm, 850 nm, 830 nm, and 780 nm.
In the case of using visible light, examples of the solid laser include visible light having a wavelength of 532 nm, and examples of the semiconductor laser include visible light having a wavelength of 690 nm, 635 nm, 532 nm, and 450 nm.
In the present invention, the light irradiation is preferably pulsed laser irradiation. The pulse width is preferably 5 ns or less, more preferably 3 ps or less. With such a configuration, thermal deterioration of the material of the resin region layer to be peeled off can be further reduced, and residue, discoloration, surface roughness, etc. can be suppressed.

In the present invention, it is also preferable that the resin region has an absorbance of 0.5 or more at the wavelength of the irradiation light. With such a configuration, when the resin region uses at least one resin selected from polyimide and polybenzoxazole, the durability against light can be increased. Furthermore, by irradiating the resin region so that the absorbance of the resin region at the wavelength of the irradiation light is 0.5 or more, the absorption of light locally generates heat in the vicinity of the transparent base material of the resin region. It is possible to perform ablation at the interface of the transparent base material while avoiding deterioration of the film quality due to heat generation, and it is possible to easily peel the transparent base material from the resin region.
The absorbance is preferably 0.8 or higher, more preferably 1.0 or higher, and even more preferably 1.2 or higher. The upper limit of the absorbance is not particularly limited and is preferably as high as possible, but for example, the effect of the present invention can be sufficiently achieved even if it is 9 or less, further 6 or less, and particularly 5 or less.
At the time of irradiation with light, it is preferable that the focal point is located at a position of a distance of ±10 μm at the interface between the base material and the resin region. The light source preferably has an area of 100 to 1,000,000 μm ² , a repetition frequency of 10 to 5000 Hz, and a scanning speed of 0.1 to 1000 mm/s. The scanning pitch is preferably 1 to 100 μm. The exposure dose is preferably 0.5 to 50 J/cm ² .
Further, as described later, a transparent base material may be easily peeled from the resin region by providing a peeling layer or the like that can reduce the releasing force by light irradiation or the like.
Further, in the first embodiment, it is preferable that the base material is not separated from the resin region by heating in the manufacturing process such as drying or post baking. With such a configuration, it is possible to effectively prevent the base material from being separated from the photosensitive resin layer or the resin region due to heating during the manufacturing process.

A second embodiment of the method of separating the base material from the resin region is to separate the base material from the resin region by applying thermal energy to the base material. Preferably, it is conceivable that a layer or the like whose physical properties change due to heat is provided on the surface of the base material, and the physical properties of the above-mentioned layers are changed by heat to separate the layers. Specific examples include thermal foaming (for example, Riva Alpha manufactured by Nitto Denko Corporation), thermal melting (for example, wax), and thermal slide (Brewer Science).
In the second embodiment, when there is a heating step such as drying or post-baking in the step prior to the step of separating the base material from the resin region, the heating in the previous step is performed by applying the thermal energy. It is better to carry out at a temperature lower than the above temperature.

In the third embodiment of the method for separating the base material from the resin region, by applying light energy to the base material, the physical properties of the surface of the base material are changed, and the base material is separated from the resin region. is there. Preferably, it is conceivable that a layer or the like whose physical properties are changed by light irradiation is provided on the surface of the base material, and the physical properties of the above-mentioned layer are changed by light to separate the layers. Specific examples include UV foaming (for example, UV peeling tape SELFA-SE manufactured by Sekisui Chemical Co., Ltd.), an adhesive layer whose adhesive strength is reduced by ultraviolet rays, and the like.

The fourth embodiment of the method for separating the base material from the resin region is an aspect using a temporary adhesive layer. A temporary adhesive layer is provided between the base material and the photosensitive resin layer, the base material and the photosensitive resin layer are temporarily fixed, and the temporary adhesive layer is peeled off to separate the base material and the resin region. It is a method of separating. Specifically, a temporary adhesive layer is provided between the base material and the photosensitive resin layer, and the interface between the temporary adhesive layer and the base material, or the temporary adhesive layer and the resin region is separated. Or by dissolving and removing the temporary adhesive layer, the base material and the resin region are separated.
As a method of providing a temporary adhesive layer between the base material and the photosensitive resin layer, a temporary adhesive layer is formed on the surface of the base material, and the photosensitive resin composition is applied to the surface of the temporary adhesive layer. The photosensitive resin layer may be provided by using the above method, or the base material and the photosensitive resin layer formed in advance in a film shape may be attached to each other with a temporary adhesive.

As an example of the temporary adhesive forming the temporary adhesive layer, the temporary adhesive described in JP-A-2014-189731 and the temporary adhesive described in JP-A-2014-189696 can be used. The content is incorporated herein. Examples of the peeling method include a method of physically peeling by hand or using a machine, and a method of dissolving the temporary adhesive layer in a solvent and peeling it. When peeling using a hand or a machine, it is preferable to peel the interface between the temporary adhesive layer and the substrate or the interface between the temporary adhesive layer and the resin region.
Examples of the solvent include organic solvents. Further, an acid, an alkali, a surfactant or the like may be added to the solvent used for peeling.
In addition, by forming a base material/release layer/temporary adhesive layer/resin area or a base material/temporary adhesive layer/release layer/resin area, and removing/removing the release layer, A method of peeling is also exemplified.

When the release layer and the temporary adhesive layer are used, the adhesive layer precursor and the protective layer described in JP-A-2005-50269 can be used, and the contents thereof are incorporated in the present specification.

FIG. 2 is a schematic view showing another example of the chip manufacturing method of the present invention, and reference numerals 1 to 3 are common to FIG. Further, 5 is a chip, 6 is an opening, and 222 is a resin region.
FIG. 2 includes forming an opening in the resin region 222 by the exposure and development. That is, at the time of exposure and development, in addition to forming two or more resin regions, the opening 6 is formed in each resin region. Such an opening 6 is preferably provided so as to penetrate from the surface of the resin region 222 on the base material side to the surface on the opposite side. The opening 6 is preferably used as a region for forming wirings and electrodes.
That is, in the manufacturing method shown in FIG. 2, the device material is applied so as to contact the surface of the base material 1 through the opening 6. Then, after the device material applying step, by further including a step of applying the second device material so as to contact the device material, for example, after applying a conductor material as the device material to form an electrode, An electronic device can be provided to connect to the electrodes. Then, as shown in FIG. 2, the electrode is embedded in the opening 6 in the resin region 222, and the chip 5 on which the electronic device is mounted is obtained.
Further, even if the device material is applied to the opening 6 in the resin region 222 so as to contact the surface of the base material 1, the base material 1 and the resin region 222 are in close contact with each other. You can go through the process without doing. Further, when the base material 1 and the resin region 222 are peeled off by laser irradiation, the device material is also peeled from the base material 1 together with the resin region 222, so that the device material having no laser peeling function has the laser peeling function. Can be used in the same way. In this case, the contact area between the device material and the base material is preferably 10% or less of the contact area between the resin region 222 and the base material 1.

<Laminate>
In the present invention, the base material, the two or more resin regions located on the base material, and the resin regions each located on a surface opposite to the base material side surface (preferably on the surface). Disclosed is a laminated body including the device material. A chip can be easily manufactured by passing through such a laminated body.
The base material, the resin region, the device material, and other preferable ranges are the same as those described in the above-mentioned chip manufacturing method. Further, a preferred embodiment of the present invention is a laminated body before the resin region separating step (step of separating the base material from the resin region) shown in FIG. 1 or 2.

Hereinafter, the present invention will be described more specifically with reference to examples. Materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed 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.

[Example 1]
<Synthesis of polyimide precursor>
<<Synthesis of Polyimide Precursor Aa-1 (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 dianhydride (4,4′-oxydiphthalic acid dried at 140° C. for 12 hours) and 18.6 g (129 mmol) of 2- Hydroxyethyl methacrylate, 0.05 g of hydroquinone, 10.7 g of pyridine and 140 g of diglyme (diethylene glycol dimethyl ether) were mixed. The mixture was stirred at a temperature of 60° C. for 18 hours to produce a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to −10° C. and 16.12 g (135.5 mmol) SOCl ₂ was added over 10 minutes keeping the temperature at −10±4° C. After diluting the reaction mixture with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, a solution of 11.08 g (58.7 mmol) of 4,4′-oxydianiline dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at 20 to 23° C. over 20 minutes. The reaction mixture was then stirred overnight at room temperature. Then, the reaction mixture was added into 5 liters of water to precipitate the polyimide precursor. The mixture of water and polyimide precursor was stirred for 15 minutes at a speed of 5000 rpm. The mixture of water and the polyimide precursor was filtered to remove the filtrate, and the residue containing the polyimide precursor was added to 4 liters of water. The mixture of water and the polyimide precursor was stirred again for 30 minutes and filtered again to obtain the polyimide precursor as a residue. Then, the obtained polyimide precursor was dried under reduced pressure at 45° C. for 3 days to obtain a polyimide precursor Aa-1.
The structure of the polyimide precursor Aa-1 is shown below.

<Preparation of photosensitive resin composition>
The following components were mixed to prepare a photosensitive resin composition as a uniform solution.
<<Composition of Photosensitive Resin Composition A-1>>
Photosensitive resin: Polyimide precursor (Aa-1) 32 parts by mass Polymerizable compound B-1 6.9 parts by mass Photopolymerization initiator C-1 1.0 part by mass Polymerization inhibitor: Parabenzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd. ) 0.08 parts by mass of migration inhibitor: 1H-tetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
0.12 parts by mass Metal adhesion improver: N-[3-(triethoxysilyl)propyl]maleic acid monoamide 0.70 parts by mass Solvent: γ-butyrolactone 48.00 parts by mass Solvent: dimethyl sulfoxide 12.00 parts by mass

Details of each additive are as follows.
B-1: NK ester A-9300 (Shin-Nakamura Chemical Co., Ltd. trifunctional acrylate, the following structure)

C-1: Compound 24 described in paragraph 0345 of JP-T-2014-500852

<Formation of resin region>
The photosensitive resin composition was filtered under a pressure of 0.4 MPa through a filter having a pore width of 0.8 μm. After filtration, the photosensitive resin composition was applied to the surface of a transparent substrate (100 mm×100 mm size, glass substrate having a thickness of 0.6 mm) by a spin coating method to form a layer, which was then heated on a hot plate at 100° C. for 5 hours. After drying for a minute, a uniform photosensitive resin layer having a thickness of 10 μm was obtained.

The photosensitive resin layer side of the obtained laminated body including the transparent base material and the photosensitive resin layer was exposed to an exposure mask (a chip dividing line was shielded from light and the inside of the chip was transparent) using a stepper (Nikon NSR 2005 i9C). It was partially covered with a mask) and exposed at an exposure wavelength of 365 nm (i-line) and an exposure energy of 500 mJ/cm ² . After the exposure, the resin film having the exposed portion and the unexposed portion was spin-washed with cyclopentanone for 60 seconds to remove the unexposed portion (negative development). Furthermore, the residue was removed by rinsing with propylene glycol-1-monomethyl ether-2-acetate (PGMEA).
Next, the temperature was raised from room temperature, and after the maximum heating temperature reached 350° C., heating was performed for 1 hour to cure the resin region, and then the temperature was cooled to room temperature. A resin region having a thickness of 6 μm and divided along the chip dividing line was obtained on the surface of the transparent substrate.

<Application of device material to resin area>
2.04 g (20.0 mmol) of N,N-dimethyl-1,3-diaminopropane (manufactured by Tokyo Kasei Co., Ltd.) and 1.94 g (15.0 mmol) of n-octylamine (manufactured by Kao, purity 98%). ) And n-dodecylamine (Kanto Chemical Co., Inc. special grade) 0.93 g (5.0 mmol) are mixed, and silver oxalate (Kanto Chemical Co., Inc. primary) and ammonium oxalate monohydrate are added to the mixed solution. Compound or oxalic acid dihydrate (manufactured by Kanto Chemical Co., Inc., special grade), 6.08 g (20.0 mmol), was added and stirred for 3 minutes to obtain oxalate ion/alkylamine/alkyldiamine/silver complex compound. Prepared. When this was heated and stirred at 95° C. for 20 to 30 minutes, the reaction involving the bubbling of carbon dioxide was completed, and the suspension turned into a blue-glossy suspension. Methanol (Kanto Chemical Co., Inc., first grade) (10 mL) was added to this, and the precipitate obtained by centrifugation was naturally dried. 4.62 g of a blue-gloss coated silver ultrafine particle solid (silver-based yield 97.0%) )was gotten. This solid substance was dispersed in 4.62 g of a mixed solvent (4/1: volume ratio) of n-butanol (Kanto Chemical Co., Inc. special grade) and n-octane (Kanto Chemical Co., special grade) to obtain a conductive paste. It was

Using the DP-320 type screen printer (manufactured by New Long Precision Co., Ltd.), the conductive paste obtained above was provided on the surface of the resin region with L/S=75/75 μm wiring and a diameter of 100 μm. The bump circuit (using a 420 mesh screen) was printed. Then, an LED (light emitting diode) device was connected on a part of the bumps so that the electrodes of the LED device corresponded to the positions of the printed bump circuits. Then, it was baked in an oven at 230° C. for 1 hour.

<Substrate separation process>
The glass substrate was then separated from the resin area where the device was mounted. Specifically, laser debonding was used to irradiate the interface between the glass substrate and the resin region with light from the side of the glass substrate where the resin region was not provided. The light irradiation is performed under the conditions of a wavelength of 355 nm and a pulse (YAG) laser (pulse width: 5 ns), and a laser beam of 60 μm square (repetition frequency 50 Hz) focused on the interface between the glass substrate and the resin region is 1.5 mm/ The entire surface was scanned with s. The glass substrate was separated from the resin region by performing irradiation with fluence of ² J/cm ² .
The absorbance (OD) of the resin region at the wavelength of irradiation light (355 nm) was 4.8. As a result, the resin region (chip) on which the LED device was mounted was placed on the glass substrate in a non-bonded state. The chip was removed by a chip handler, and a flexible device chip having an LED device mounted thereon was obtained.

<<Measurement of absorbance in resin region>>
The absorbance of the resin region at the wavelength of the irradiation light was measured by the following method.
An arbitrary value was selected at five points in the resin region on the transparent substrate, the absorbance at the wavelength of the irradiated light was measured, and the average value was obtained. U-3900 manufactured by Hitachi High-Tech Science was used for the measurement of the absorbance.

[Example 2]
In Example 1, the laser was changed to an excimer laser having an oscillation wavelength of 308 nm and a pulse width of 3 ps, and the other operations were performed in the same manner. A chip was obtained in the same manner as in Example 1.

[Example 3]
In the same manner as in Example 1, <Synthesis of polyimide precursor> and <Preparation of photosensitive resin composition> were performed.
Next, in <Formation of resin region> of Example 1, as the exposure mask, the chip dividing line is shielded from light, only the portion corresponding to the electrode portion in the chip is shielded, and the other portion is formed into a transparent mask. The same procedure as in Example 1 was carried out except that it was used. As a result, on the surface of the transparent base material, a resin region having a thickness of 6 μm and divided along the chip division line, in which an opening (through hole) for forming an electrode portion is formed. Was obtained.

<Application of device material to resin area>
A DP-320 type screen printer (manufactured by New Long Precision Co., Ltd.) was used, and a screen mask was used so that the silver paste would permeate only at the positions corresponding to the openings for forming the electrode portions in the resin region. An electrode was formed in the opening.
Then, the same procedure as in Example 1 was performed to print a wiring (L/S=75/75 μm) and a bump circuit having a diameter of 100 μm (using a 420 mesh screen).
Further, a logic IC (integrated circuit) chip was connected so that the electrodes of the IC chip corresponded to the positions of the printed bump circuits. Then, it was baked in an oven at 230° C. for 1 hour.

Then, the same procedure as in <Substrate separation step> of Example 1 was performed.
As a result, the resin region (chip) having the IC chip mounted therein and having the electrode connected to the IC chip therein was placed on the glass base material in a non-bonded state. The chip was removed with a chip handler to obtain a flexible device chip on which an IC chip was mounted.

1 Base Material 2 Photosensitive Resin Layer 3 Mask 4 Chip 5 Chip 6 Opening 22 Resin Region 222 Resin Region 31 Base Material 32 Resin Film 33 Device 34 Chip

Claims (15)

An exposure and development step of exposing and developing a photosensitive resin layer located on the substrate to form two or more resin regions,
On the surface of the photosensitive resin layer or the resin region, on the surface opposite to the surface of the base material side, a device material applying step of applying a device material,
A step of separating the base material from the resin region and dividing the resin region into individual pieces after the device material applying step. The chip manufacturing method according to claim 1, wherein a device material application step is performed after the exposure and development step. The chip manufacturing method according to claim 2, further comprising a step of applying at least one of heat and light to the resin region before the device material applying step. The method for manufacturing a chip according to claim 1, wherein the device material is at least one selected from a conductor material, a semiconductor material, an insulator material, and an electronic device. The method for manufacturing a chip according to claim 1, wherein the development is negative development. The method for manufacturing a chip according to claim 1, wherein the resin region is located on the surface of the base material. The base material is a transparent base material, and includes separating the base material from the resin region by irradiating light from a surface opposite to a surface of the base material on the resin region side, Item 7. A method for manufacturing a chip according to Item 6. The method for manufacturing a chip according to any one of claims 1 to 5, comprising separating the base material from a resin region by applying thermal energy to the base material. By providing a temporary adhesive layer between the base material and the photosensitive resin layer, and peeling the interface between the temporary adhesive layer and the base material or the interface between the temporary adhesive layer and the resin region. Alternatively, the method for producing a chip according to claim 1, wherein the base material is separated from the resin region by dissolving and removing the temporary adhesive layer. The chip manufacturing method according to claim 1, wherein the resin region contains a polyimide resin or a polybenzoxazole resin. The method for manufacturing a chip according to claim 1, further comprising applying a second device material so as to be in contact with the device material after the device material applying step. The chip manufacturing method according to any one of claims 1 to 11, wherein a length of the longest portion of the base surface of the base material is 50 to 4000 mm. The chip manufacturing method according to claim 1, further comprising forming an opening in the resin region by the exposure and development. The method for manufacturing a chip according to claim 13, wherein the device material is applied so as to be in contact with the surface of the base material through the opening. 15. The method for manufacturing a chip according to claim 1, wherein the application of the device material is selected from a printing method, a photolithography method, an inkjet method, an imprint method, a mask vapor deposition method, and a laser transfer method. ..

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