JP6845848B2 - Laminated body manufacturing method, semiconductor element manufacturing method and laminated body - Google Patents

Description

The present invention relates to a method for manufacturing a laminated body, a method for manufacturing a semiconductor element, and a laminated body.

Resins such as polyimide resins and polybenzoxazole resins are used as insulating layers of semiconductor devices because they have excellent heat resistance and insulating properties.

International Publication WO2011 / 03492

A cured film of a resin having excellent heat resistance and insulating properties such as a polyimide resin or a polybenzoxazole resin is used as an interlayer insulating film for the rewiring layer of a semiconductor element, and the cured film and the metal layer are laminated to rewire the semiconductor element. The layer is being manufactured.
When the present inventors examined laminating a metal layer with a cured film of a resin having excellent heat resistance and insulating properties such as a polyimide resin or a polybenzoxazole resin, the adhesion between the cured film and the metal layer was insufficient. It was found that delamination occurs between the cured film and the metal layer.

Here, in a film forming method generally used for manufacturing a semiconductor element, a material constituting the wiring layer is formed on the substrate by providing a barrier metal film between the substrate and a wiring layer made of copper (Cu) or the like. It is known to prevent deterioration of wiring caused by diffusion (see Patent Document 1).
In Patent Document 1, a substrate having fine holes or grooves formed on its surface is prepared, and in a state where the temperature of the substrate is set in the range of 150 ° C. or higher and 500 ° C. or lower, titanium or a titanium compound is used for the substrate. A method for forming a barrier metal film comprising a barrier metal film is described. According to Patent Document 1, by using the method for forming the barrier metal film having the above configuration, overhang at the opening (the diameter of the opening is smaller than that at the bottom) with respect to a pattern having a high aspect ratio or the like. It is stated that the occurrence can be reduced.
However, Patent Document 1 pays attention only to the case where a silicon oxide film is formed on the surface of a silicon wafer as a substrate. That is, Patent Document 1 did not pay attention to delamination when a metal layer and a cured film of a resin having excellent heat resistance and insulating properties such as a polyimide resin and a polybenzoxazole resin were laminated.

An object to be solved by the present invention is to provide a method for producing a laminated body capable of suppressing delamination when a substrate, a cured film and a metal layer are laminated. Another object to be solved by the present invention is to provide a method for manufacturing a semiconductor element, including a method for manufacturing a laminate. Further, an object to be solved by the present invention is to provide a laminate capable of suppressing delamination when a substrate, a cured film and a metal layer are laminated.

As a result of studies by the present inventor based on the above problems, vapor deposition such as a sputtering method is performed at a temperature lower than the glass transition temperature of a cured film of a resin having excellent heat resistance and insulating properties such as a polyimide resin and a polybenzoxazole resin. It was found that the above-mentioned problems can be solved by forming a metal layer using the above.
The present invention, which is a means for solving the above problems, and preferred embodiments of the present invention are as follows.
[1] A step of forming a photosensitive resin composition layer by applying the photosensitive resin composition to a substrate to form a layer, and
An exposure process for exposing the photosensitive resin composition layer applied to the substrate, and
A developing process that performs a developing process on the exposed photosensitive resin composition layer,
A curing step of curing the photosensitive resin composition layer after development,
The metal layer forming step of forming a metal layer by vapor phase film formation on the surface of the photosensitive resin composition layer after the curing step is performed in the above order.
A method for producing a laminate, wherein the temperature of the photosensitive resin composition layer after the curing step when forming the metal layer is lower than the glass transition temperature of the photosensitive resin composition layer after the curing step.
[2] Further, the laminate according to [1], further comprising performing the photosensitive resin composition layer forming step, the exposure step, the developing treatment step, the curing step, and the metal layer forming step again in the above order. Production method.
[3] The method for producing a laminate according to [1] or [2], wherein a crosslinked structure is constructed in the photosensitive resin composition by exposure and the solubility in an organic solvent is lowered.
[4] In any one of [1] to [3], the photosensitive resin composition contains at least one resin selected from a polyimide precursor, a polyimide, a polybenzoxazole precursor and polybenzoxazole. The method for producing a laminate according to the description.
[5] The method for producing a laminate according to any one of [1] to [4], further comprising a second metal layer forming step of forming a second metal layer on the surface of the metal layer.
[6] The method for producing a laminate according to [5], wherein the second metal layer contains copper.
[7] The method for producing a laminate according to any one of [1] to [6], wherein the metal layer contains at least one of titanium, tantalum and copper and a compound containing at least one of these. ..
[8] The method for producing a laminate according to any one of [1] to [7], wherein the thickness of the metal layer formed in the metal layer forming step is 50 to 2000 nm.
[9] The method for producing a laminate according to any one of [1] to [8], wherein the residual stress measured according to the laser measurement method of the photosensitive resin composition after the curing step is less than 35 MPa.
[10] The method for producing a laminate according to any one of [1] to [9], wherein the photosensitive resin composition is for negative type development.
[11] The curing step includes a heating step of raising the temperature of the photosensitive resin composition layer and a holding step of holding the photosensitive resin composition layer at a holding temperature equal to the final reached temperature of the raising step.
The method for producing a laminate according to any one of [1] to [10], wherein the holding temperature in the holding step is 250 ° C. or lower.
[12] The method according to any one of [1] to [11], wherein the temperature of the photosensitive resin composition layer when forming the metal layer is 30 ° C. or more lower than the glass transition temperature of the photosensitive resin composition layer. Method for manufacturing a laminate.
[13] A method for manufacturing a semiconductor element, which comprises the method for manufacturing a laminate according to any one of [1] to [12].
[14] It has a substrate, a pattern-cured film, and a metal layer located on the surface of the pattern-cured film.
The pattern cured film contains polyimide or polybenzoxazole and contains
A laminate in which the penetration depth of the metal constituting the metal layer located on the surface of the pattern cured film into the pattern cured film is 130 nm or less from the surface of the pattern cured film.

[15] A laminate produced by the method for producing a laminate according to any one of [1] to [12].
[16] A semiconductor device manufactured by the method for manufacturing a semiconductor device according to [13].

According to the present invention, it is possible to provide a method for producing a laminated body capable of suppressing delamination when a substrate, a cured film and a metal layer are laminated. Further, according to the present invention, it is possible to provide a method for manufacturing a semiconductor element, including the method for manufacturing the laminate of the present invention. Further, according to the present invention, it is possible to provide a laminated body capable of suppressing delamination when the substrate, the cured film and the metal layer are laminated.

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

The description of the components in the present invention described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution includes those having no substituent as well as 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).
In the present specification, "exposure" includes not only exposure using light but also drawing using particle beams such as an electron beam and an ion beam, unless otherwise specified. Further, as the light used for exposure, generally, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation can be mentioned.
In the present specification, the numerical range represented by using "~" means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.
In the present specification, "(meth) acrylate" means both "acrylate" and "methacrylate", or either, and "(meth) allyl" means both "allyl" and "metharyl", or. Representing either, "(meth) acrylic" represents both "acrylic" and "methacrylic", or either, and "(meth) acryloyl" represents both "acryloyl" and "methacrylic", or Represents either.
In the present specification, the term "process" is included in this term not only as an independent process but also as long as the desired action of the process is achieved even if it cannot be clearly distinguished from other processes. ..
As used herein, the solid content concentration is the mass percentage of 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-equivalent values by gel permeation chromatography (GPC measurement) unless otherwise specified. In the present specification, for the weight average molecular weight (Mw) and the number average molecular weight (Mn), for example, HLC-8220 (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. It can be obtained by using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise specified, the eluate shall be measured using THF (tetrahydrofuran). Unless otherwise specified, a detector having a wavelength of 254 nm for UV rays (ultraviolet rays) is used for detection.

[Manufacturing method of laminate]
The method for producing a laminate of the present invention includes a step of forming a photosensitive resin composition layer in which a photosensitive resin composition is applied to a substrate to form a layer.
An exposure process for exposing the photosensitive resin composition layer applied to the substrate, and
A developing process that performs a developing process on the exposed photosensitive resin composition layer,
A curing step of curing the photosensitive resin composition layer after development,
The metal layer forming step of forming a metal layer by vapor phase film formation on the surface of the photosensitive resin composition layer after the curing step is performed in the above order.
The temperature of the photosensitive resin composition layer after the curing step when forming the metal layer is lower than the glass transition temperature of the photosensitive resin composition layer after the curing step.
With the above configuration, delamination can be suppressed when the substrate, the cured film, and the metal layer are laminated.
When a metal layer is formed on the surface of a cured film (a cured film is a photosensitive resin composition layer after a curing step) on a substrate by vapor phase film formation such as a sputtering method, it is usually a metal layer. The substrate (and the cured film) is heated to control the quality of the film. Conventionally, it has been presumed that when a metal layer is formed by a sputtering method at a high temperature, metal atoms can be driven into the cured film, and as a result, the occurrence of delamination can be suppressed.
In fact, as a result of analyzing the cross section of the laminate in which the metal layer was formed on the surface of the cured film by the sputtering method using a transmission electron microscope (TEM) or the like, the present inventors sputtered at a high temperature. It has been found that when a metal layer is formed by the method, a phenomenon (pentration) in which the metal enters the surface of the cured film occurs. However, it has been found that when a metal layer is formed by a sputtering method at a high temperature, delamination occurs when the substrate, the cured film, and the metal layer are laminated.
On the other hand, the metal layer is cured by forming a metal layer by vapor deposition such as a sputtering method so that the temperature of the photosensitive resin composition layer after the curing step (the temperature of the surface of the cured film) can be suppressed to less than the glass transition temperature. It was found that the phenomenon of metal entering the surface of the film (penetration) disappeared, and that delamination did not occur when the substrate, the cured film, and the metal layer were laminated. The glass transition temperature is also hereinafter referred to as Tg (glass transition temperature).
Hereinafter, the details of the preferred embodiment of the present invention will be described.

<Filtration process>
The method for producing a laminate of the present invention may include a step of filtering the photosensitive resin composition before applying the photosensitive resin composition to the substrate. Filtration is preferably performed using a filter. The filter pore diameter is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. The filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When using a plurality of types of filters, filters having different pore diameters and / or materials may be used in combination. Further, each kind of material may be used for filtration a plurality of times, and the step of filtering a plurality of times may be a circulation filtration step. Further, pressure filtration may be performed, and the pressure applied in the case of pressure filtration is preferably 0.05 MPa or more and 0.3 MPa or less.
In addition to filtration using a filter, impurities may be removed by performing filtration using an adsorbent, or filtration may be performed using a combination of filter filtration and an adsorbent. As the adsorbent, a known adsorbent can be used. For example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used.

<Photosensitive resin composition layer forming process>
The method for producing a laminate of the present invention includes a step of forming a photosensitive resin composition layer in which a photosensitive resin composition is applied to a substrate to form a layer.
Coating is preferable as a means for applying the photosensitive resin composition to the substrate.
Specifically, the means to be applied include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, and a slit coating method. And the inkjet method and the like are exemplified. From the viewpoint of the uniformity of the thickness of the 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 an appropriate solid content concentration and coating conditions according to the means to be applied. Further, the coating method can be appropriately selected depending on the shape of the substrate. For a circular substrate such as a wafer, a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular substrate, a slit coating method, a spray coating method, an inkjet method, etc. The method or the like is preferable. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 2000 rpm (revolutions per minute) in about 10 seconds to 1 minute.
The thickness of the photosensitive resin composition layer (cured film after the curing step) is preferably 0.1 to 100 μm after exposure, and is preferably 1 to 50 μm. More preferable. Further, as shown in FIG. 2, the thickness of the formed photosensitive resin composition layer does not necessarily have to be uniform. In particular, when the photosensitive resin composition layer is provided on the uneven surface, cured films having different thicknesses will be obtained as shown in FIG. In particular, when a plurality of cured films are laminated, a deep recess may be formed as a recess, but the present invention has technical value in that peeling between layers can be more effectively suppressed with respect to such a configuration. high. When the laminate has cured films having different thicknesses, it is preferable that the thickness of the cured film at the thinnest portion is the above-mentioned thickness.

<< Board >>
The type of substrate can be appropriately determined according to the application, but is a semiconductor manufacturing substrate such as silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, quartz, glass, optical film, ceramic material, thin film transistor, magnetic film. , Reflective film, metal substrate such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, plasma display panel (PDP) electrode plate, and the like are not particularly limited. In the present invention, a semiconductor-made substrate is particularly preferable, and silicon is more preferable.
Further, when the photosensitive resin composition layer is formed on the surface of the cured film or the surface of the metal layer, the cured film or the metal layer may be used as the substrate.

<< Photosensitive resin composition >>
Hereinafter, the details of the photosensitive resin composition used in the present invention will be described.
In the method for producing a laminate of the present invention, the photosensitive resin composition preferably contains a compound that forms a crosslinked structure by exposure, more preferably for negative development, and the crosslinked structure is constructed by exposure to be organic. It is particularly preferable that the solubility in a solvent is lowered, and most preferably a negative photosensitive resin developed with an organic solvent.
First, the components that may be contained in the photosensitive resin composition used in the present invention 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 the present invention contains a resin.
In the photosensitive resin composition used in the present invention, the resin is not particularly limited, and a known resin can be used. The resin is preferably a highly heat resistant resin.

The photosensitive resin composition used in the present invention preferably contains at least one resin selected from a polyimide precursor, a polyimide, a polybenzoxazole precursor, and polybenzoxazole. In the method for producing a laminate 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 invention may contain only one kind of polyimide precursor, polyimide, polybenzoxazole precursor and polybenzoxazole, or may contain two or more kinds. Further, the same type of resin such as two types of polyimide precursors may be contained, and two or more types of resins having different structures may be contained.
The resin content in the photosensitive resin composition used in the present invention is preferably 10 to 99% by mass, more preferably 50 to 98% by mass, and 70 to 96% by mass of the total solid content of the photosensitive resin composition. More preferred.

Further, the resin preferably contains a polymerizable group.
Further, it is preferable that the photosensitive resin composition contains a polymerizable compound. With such a configuration, a three-dimensional network is formed in the exposed portion to form a strong crosslinked film, and the photosensitive resin composition layer (cured film) is not damaged by the surface activation treatment described later, and the surface activity is maintained. 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 an aromatic group independently, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, −O−, −CO−, −S−. , -SO _2- or -NHCO-, and a group consisting of a combination of two or more of the above. With such a configuration, 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 a phenylene group is preferably, L is an aliphatic hydrocarbon group of fluorine carbon atoms which may be substituted with atoms 1 or 2, -O -, - CO - , - S- or -SO ₂ - and more preferable. The aliphatic hydrocarbon group here is preferably an alkylene group.

式（２）中、Ａ¹およびＡ²は、それぞれ独立に酸素原子またはＮＨを表し、Ｒ¹¹¹は、２価の有機基を表し、Ｒ¹¹⁵は、４価の有機基を表し、Ｒ¹¹³およびＲ¹¹⁴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 type of the polyimide precursor is not particularly specified, and it is preferable that the polyimide precursor contains a repeating unit represented by the following formula (2).
Equation (2)

In formula (2), A ¹ and A ² 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 independently represents a hydrogen atom or a monovalent organic group.

^{A 1} and A ² in the formula (2) are preferably an oxygen atom or NH, and more preferably an oxygen atom.
^{R 111} in the formula (2) represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group and a group containing an aromatic group, and a linear or branched aliphatic group having 2 to 20 carbon atoms and a carbon number of carbon atoms. A cyclic aliphatic group of 6 to 20, 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 preferable embodiment, it is exemplified that R 111} in the formula (2) is a group represented by −Ar−L−Ar−. However, Ar is an aromatic group independently, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, −O−, −CO−, −S−. , -SO _2- or -NHCO-, and a group consisting of a combination of two or more of the above. These preferred ranges are as described above.

^{R 111} in formula (2) is preferably derived from diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one type of diamine may be used, or two or more types may be used.
Specifically, 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 consisting of a combination thereof. It is preferably a diamine containing, and more preferably a diamine containing a group consisting of an aromatic group having 6 to 20 carbon atoms. Examples of aromatic groups 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−、−ＳＯ₂−から選択される基であることがより好ましく、−ＣＨ₂−、−Ｏ−、−Ｓ−、−ＳＯ₂−、−Ｃ（ＣＦ₃）₂−、および、−Ｃ（ＣＨ₃）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。

Among the above aromatic groups, A is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be replaced with a single bond or 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 −.}

Specific examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1 , 3-Diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4-) Aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; meta and paraphenylenediamine, diaminotoluene, 4,4'-and 3 , 3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'-and 3,3'-diaminodiphenylmethane, 4,4'-and 3,3'-diaminodiphenylsulfone , 4,4'-and 3,3'-diaminodiphenyl sulfide, 4,4'-and 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'- Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexa Fluoropropane, 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, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone , 4,4'-Diaminoparatelphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl ] Sulfone, bis [4- (2-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 9,10-bis (4-aminophenyl) anthracene, 3,3'-dimethyl- 4,4'-Diaminodiphenyl sulfone, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene , 1,3-bis (4-aminophenyl) benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diamino Octafluorobiphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 9,9-bis (4-) Aminophenyl) -10-hydroanthracene, 3,3', 4,4'-tetraaminobiphenyl, 3,3', 4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone , 3,3-Dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis (4-aminophenyl) fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3', 5,5'-Tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-paraphenylenediamine, acetoguanamine, 2,3,5,6-tetra Methyl-paraphenylenediamine, 2,4,6-trimethyl-metaphenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis ( 4-Aminophenyl) ethane, diaminobenzanilide, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis (4-aminophenyl) hexafluoropropane, 1,4-bis ( 4-Aminophenyl) Octafluorobutane, 1,5-bis (4-aminophenyl) decafluoropentane, 1,7-bis (4-aminophenyl) tetradecafluoroheptane, 2,2-bis [4- (3) -Aminophenoxy) Phenyl] Hexafluoropropane, 2,2-bis [4- (2-aminophenoxy) phenyl] Hexafluoropropane, 2,2-bis [4- (4-Aminophenoxy) -3,5-dimethyl Phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-bis (trifluoromethyl) phenyl] hexafluoropropane, parabis (4-amino-2-trifluoromethylphenoxy) Benzene, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-4'-bis) Amino-3-trifluoromethylphenoxy) Biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4,4'-bis (3-amino-5-trifluoromethylphenoxy) Diphenylsulfone, 2,2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl] hexafluoropropane, 3,3', 5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-Diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,2', 5,5', 6,6'-hexafluorotridin and 4,4'''-diaminoquaterphenyl At least one type of diamine selected from is mentioned.

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

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

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

^{R 111} in the formula (2) is preferably represented by −Ar−L−Ar− from the viewpoint of the flexibility of the obtained cured film. However, Ar is an aromatic group independently, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, −O−, −CO−, −S−. , -SO _2- or -NHCO-, and a group consisting of a combination of two or more of the above. Ar is a phenylene group is preferably, L is an aliphatic hydrocarbon group of fluorine carbon atoms which may be substituted with atoms 1 or 2, -O -, - CO - , - S- or -SO ₂ - and more preferable. The aliphatic hydrocarbon group here is preferably an alkylene group.

式（５１）中、Ｒ¹⁰〜Ｒ¹⁷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、Ｒ¹⁰〜Ｒ¹⁷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。
Ｒ¹⁰〜Ｒ¹⁷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、Ｒ¹⁸およびＲ¹⁹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種類を用いるか、または２種類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 the formula (61) from the viewpoint of i-ray transmittance. In particular, a divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-ray transmittance and availability.
Equation (51)

In formula (51), R ^{10 to} R ¹⁷ are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and ^{at least one of R 10 to} R ¹⁷ is a fluorine atom, a methyl group or a trifluoromethyl group. Is.
As ^{monovalent organic groups of R 10 to} R ¹⁷ , an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a hook having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) Examples thereof include an alkylated group.
Equation (61)

In formula (61), R ¹⁸ and R ¹⁹ are independently fluorine atoms or trifluoromethyl groups, respectively.
Examples of the diamine compound giving the structure of the 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、Ｒ¹¹²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−、−ＳＯ₂−、−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−ＳＯ₂−から選択される基であることがより好ましく、−ＣＨ₂−、−Ｃ（ＣＦ₃）₂−、−Ｃ（ＣＨ₃）₂−、−Ｏ−、−ＣＯ−、−Ｓ−および−ＳＯ₂−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.
Equation (5)

In formula (5), R ¹¹² is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be replaced with a single bond or a fluorine atom, −O−, −CO−, −S−, −SO. _{It is preferably a group selected from 2} −, −NHCO− and a combination thereof, and is 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₋ are more preferred, and −CH ₂ −, −C (CF ₃ ) ₂ −, −C (CH ₃ ) ₂ −, −O−, −CO A divalent group selected from the group consisting of −, −S− and −SO _{2− is even more preferred.}

Equation (6)

式（Ｏ）中、Ｒ¹¹⁵は、４価の有機基を表す。Ｒ¹¹⁵の好ましい範囲は式（２）におけるＲ¹¹⁵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 tetracarboxylic acid residues remaining after removal of the anhydride group from the tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used.
The tetracarboxylic dianhydride is preferably represented by the following formula (O).
Equation (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 pyromelitoic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfide tetracarboxylic. Acid dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4 '-Diphenylmethanetetracarboxylic dianhydride, 2,2', 3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,3 3', 4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalene Tetetracarboxylic 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 Carcarboxylic dianhydride, 2,2', 3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetra Carcarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis (2,3-dicarboxy) Phenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and their carbon numbers 1 to 1 At least one selected from 6 alkyl and / or alkoxy derivatives having 1 to 6 carbon atoms is exemplified.

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

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

^{R 113} and R ¹¹⁴ in the formula (2) independently represent a hydrogen atom or a monovalent organic group.
^{It is preferable that at least one of R 113} and R ¹¹⁴ in the formula (2) contains a polymerizable group, and it is preferable that both contain a polymerizable group. A polymerizable group is a group capable of a cross-linking 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 include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, a methylol group and an amino group. Can be mentioned. As the radically polymerizable group contained in the polyimide precursor, a group having an ethylenically unsaturated bond is preferable.
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, with a methyl group being more preferred.
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 are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butandyl group, 1,3-butandyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group. , -CH ₂ CH (OH) CH _{2-, and} more preferably an ethylene group, a propylene group, a trimethylene group, and -CH ₂ CH (OH) CH _2-.
Particularly preferably, R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethylene group.

^{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 the 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. The monovalent organic group is an aromatic group having one, two or three (preferably one) acidic groups bonded to the carbon constituting the aryl group, and a carbon group constituting the aryl group. Aralkyl groups having one, two or three (preferably one) acidic groups are particularly preferred. Specific examples thereof include an aromatic group having an acidic group having 6 to 20 carbon atoms and an aralkyl group having an acidic group having 7 to 25 carbon atoms. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group can be mentioned. The acidic group is preferably a hydroxy group.
More preferably, 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. , 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 phenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group and a pinenyl group. Can be mentioned. Of these, the cyclohexyl group is most preferable from the viewpoint of achieving both high sensitivity. Further, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described later is preferable.
^{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, inden ring, azulene ring, heptalene ring, indacene ring, and perylene. Ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring, naphthalene ring, chrysen 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, indridin ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinoline ring, quinoline ring, phthalazine ring, naphthylidine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring. , Phenanthridine ring, aclysin ring, phenanthrene ring, thianthrene ring, chromium ring, xanthene ring, phenoxatiin ring, phenothiazine ring or phenazine ring. The benzene ring is most preferable.

^{When R 113} in the formula (2) is a hydrogen atom, or when R ¹¹⁴ in the formula (2) is a hydrogen atom, the polyimide precursor forms a salt with a tertiary amine compound having an ethylenically unsaturated bond. You may be doing it. Examples of the tertiary amine compound having such 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 fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

Further, for the purpose of improving the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with the polyimide precursor. Specific 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、Ａ¹およびＡ²は、酸素原子を表し、Ｒ¹¹¹およびＲ¹¹²は、それぞれ独立に、２価の有機基を表し、Ｒ¹¹³およびＲ¹¹⁴は、それぞれ独立に、水素原子または１価の有機基を表し、Ｒ¹¹³およびＲ¹¹⁴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.
Equation (2-A)

In formula (2-A), A ¹ and A ² represent oxygen atoms, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, and R ¹¹³ and R ¹¹⁴ each independently. Representing a hydrogen atom or a monovalent organic group ^{, 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 formula (2-A) are independently synonymous with ^{A 1} , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (2), respectively. The same applies to the preferred range.
^{R 112} in the formula (2-A) ^{is synonymous with R 112} in the formula (5), and the preferable range is also the same.

In the polyimide precursor, the repeating unit represented by the formula (2) may be one kind, but may be two or more kinds. Further, the polyimide precursor may contain a structural isomer of a repeating unit represented by the formula (2). Further, the polyimide precursor may contain 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, 50 mol% or more, more 70 mol% or more, particularly 90 mol% or more of all the repeating units is the repeating unit 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. It is more preferable that the dicarboxylic acid or the dicarboxylic acid derivative is obtained by halogenating it with a halogenating agent and then reacting it with a diamine. The polyimide precursor is, for example, a method of reacting a tetracarboxylic acid dianhydride with a diamine compound (partially replaced with a terminal capping agent which is monoamine) at a low temperature, or a tetracarboxylic acid dianhydride (partly) at a low temperature. Is replaced with an acid anhydride or a monoacid chloride compound or a terminal encapsulant which is a monoactive ester compound) and a diamine compound. Is replaced with a terminal encapsulant which is a monoamine) in the presence of a condensing agent, a diester is obtained by tetracarboxylic acid dianhydride and alcohol, and then the remaining dicarboxylic acid is acid chlorided to diamine (partially). Can be obtained by using a method such as a method of reacting with a terminal sealant which is a monoamine).
In the method for producing a polyimide precursor, it is preferable to use an organic solvent in 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.

In the production of the polyimide precursor, it is preferable to seal it with an end-capping agent such as an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound in order to further improve the storage stability. Of these, it is more preferable to use monoamine, and preferred 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 and the like can be mentioned. Two or more kinds of these may be used, and a plurality of different end groups may be introduced by reacting a plurality of end sealants.

The production of the polyimide precursor may include a step of precipitating a solid. Specifically, the polyimide precursor in the reaction solution can be precipitated in water, and the polyimide precursor such as tetrahydrofuran can be dissolved in a soluble solvent to precipitate a solid.
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 2,000 to 27,000, and even more preferably 22,000 to 25,000. The number average molecular weight (Mn) is preferably 7200 to 14000, more preferably 8000 to 12000, and even more preferably 9200 to 11200.
The dispersity of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and even more preferably 2.8 or more. The upper limit of the dispersity of the polyimide precursor is not particularly determined, but for example, 4.5 or less is preferable, 4.0 or less is more preferable, 3.8 or less is further preferable, and 3.2 or less is further preferable. 3.1 or less is even more preferable, 3.0 or less is even more preferable, and 2.95 or less is particularly preferable.

式（４）中、Ｒ¹³¹は、２価の有機基を表し、Ｒ¹³²は、４価の有機基を表す。
重合性基を有する場合、Ｒ¹³¹およびＲ¹³²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), and more preferably a compound represented by the formula (4) and having a polymerizable group.
Equation (4)

In formula (4), R ¹³¹ represents a divalent organic group and R ¹³² represents a tetravalent organic group.
When having a polymerizable group, ^{at least one of R 131} and R ¹³² may have a polymerizable group, or as shown in the following formula (4-1) or formula (4-2), at the end of the polyimide. It may have a polymerizable group.

式（４−１）中、Ｒ¹³³は重合性基であり、他の基は式（４）と同義である。Equation (4-1)

In formula (4-1), R ¹³³ is a polymerizable group, and the other groups are synonymous with formula (4).

式（４−２）中、Ｒ¹³⁴およびＲ¹³⁵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。Equation (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 group is synonymous with formula (4).

The polymerizable group that the polyimide preferably has is the same as the polymerizable group mentioned as the polymerizable group that R ¹¹³ and R ¹¹⁴ in the formula (2) may contain in the above-mentioned polyimide precursor.

^{R 131} in the formula (4) represents a divalent organic group. As the divalent organic group, a divalent organic group ^{similar to R 111} in the formula (2) is exemplified, and the preferable range is also the same.
Further, as R ¹³¹ , a diamine residue remaining after removal of the amino group of the diamine can be mentioned. Examples of the diamine include aliphatic, cyclic aliphatic or aromatic diamines. ^{Specific examples include the example of R 111} in the formula (2) of the polyimide precursor.

^{It is preferable that R 131} in the formula (4) is 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 two or more ethylene glycol chains and / or both of propylene glycol chains in one molecule, and more preferably, it is a diamine residue containing no aromatic ring.

Examples of the diamine containing two or more of one or both of the ethylene glycol chain and the propylene glycol chain in one molecule include the same specific examples as the diamine capable of inducing ^{R 111 in the formula (2).} Not limited to these.

^{R 132} in the formula (4) represents a tetravalent organic group. As the ^{tetravalent organic group represented by R 132, the same group as R 115} in the formula (2) is exemplified, and the preferable range is also the same.
^{For example, four conjugates of a tetravalent organic group having the following structure exemplified as R 115} in the formula (2) are bonded to four −C (= O) − portions in the above formula (4). Form a fused ring.

^{Examples of R 132} in the formula (4) include tetracarboxylic acid residues remaining after removal of the anhydride group from the tetracarboxylic dianhydride. Specific examples include the example of R ^{115 in} the polyimide precursor formula (2). 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 hydroxy group. ^{More specifically, as R 131} in the formula (4), 2,2-bis (3-hydroxy-4-aminophenyl) propane and 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane. , 2,2-bisu (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, above (DA-1) to (DA-18) ) Is a preferable example. As R ¹³² in the formula (4), of the (DAA-1) ~ (DAA -5) are preferred examples.

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

Further, for the purpose of improving the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with the polyimide. Specific 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 an end sealant such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound. It is preferable to do so. Of these, it is more preferable to use monoamines. Preferred examples of monoamines 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 Examples include benzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like. Be done. Two or more kinds of these may be used, and a plurality of different end groups may be introduced by reacting a plurality of end sealants.

The imidization ratio of the polyimide is preferably 85% or more, more preferably 90% or more. When the imidization rate is 85% or more, the film shrinkage caused by ring closure that occurs when imidized by heating is reduced, and the occurrence of warpage of the substrate can be suppressed.

The polyimide may contain two or more different types of repeating units, ^{R 131} or R ¹³² , in addition to the repeating units represented by the above formula (4), all of which are one type of R ¹³¹ or R ^132. 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 heating and cyclizing it, or may directly synthesize a polyimide.
For polyimide, a method of obtaining a polyimide precursor and completely imidizing it using a known imidization reaction method, a method of stopping the imidization reaction in the middle, and a method of introducing a partial imide structure, and further By blending a completely imidized polymer with its polyimide precursor, it can be synthesized by utilizing the method of introducing a partially imidized structure.

Examples of commercially available polyimide products include Durimide (registered trademark) 284 (manufactured by FUJIFILM Corporation) and Matrimide 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 5,000 or more, the breakage resistance of the film after curing 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 types of polyimide are contained, it is preferable that the weight average molecular weight of at least one type of polyimide is in the above range.

式（３）中、Ｒ¹²¹は、２価の有機基を表し、Ｒ¹²²は、４価の有機基を表し、Ｒ¹²³およびＲ¹²⁴は、それぞれ独立に、水素原子または１価の有機基を表す。(Polybenzoxazole precursor)
The type of the polybenzoxazole precursor is not particularly specified, and it is preferable that the polybenzoxazole precursor contains a repeating unit represented by the following formula (3).
Equation (3)

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

^{R 123} and R ¹²⁴ in the formula (3) are ^{synonymous with R 113} in the formula (2), respectively, and the preferable range is also the same. ^{That is, at least one of R 123} and R ¹²⁴ in the formula (3) is preferably a polymerizable group.

^{R 121} in the formula (3) represents a divalent organic group. As the ^{divalent organic group represented by R 121} , a group containing at least one of an aliphatic group and an aromatic group is preferable. As the aliphatic group, a linear aliphatic group is preferable. R ¹²¹ is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.

As the dicarboxylic acid, a dicarboxylic acid containing an aliphatic group and a dicarboxylic acid containing an aromatic group are preferable, and a dicarboxylic acid containing an aromatic group is more preferable.
The dicarboxylic acid containing an aliphatic group is preferably a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group, and is composed of a linear or branched (preferably linear) aliphatic group and two COOHs. Dicarboxylic acid is more preferred. The number of carbon atoms of the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, further preferably 3 to 20, and 4 to 20. It is particularly preferably 15, and even more preferably 5 to 10. The linear aliphatic group is preferably an alkylene group.
Examples of the dicarboxylic acid containing a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2, 2-Dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-Dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelliic acid, 2,2,6,6-tetramethylpimelic acid, suberin Acid, dodecafluorosveric acid, azelaic acid, sebacic acid, hexadecafluorosevacinic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid , Octadecandioic acid, nonadecandioic acid, eikosandioic acid, heneicosanedioic acid, docosandioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosandioic acid, heptacosanedioic acid, octacosanedioic acid, nonakosandioic acid Examples thereof include contandioic acid, hentoriacontandioic acid, dotriacontandioic acid, diglycolic acid, and dicarboxylic acid represented by the following formula.

（式中、Ｚは炭素数１〜６の炭化水素基であり、ｎは１〜６の整数である。）

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

As the dicarboxylic acid containing an aromatic group, a dicarboxylic acid having the following aromatic groups is preferable, and a dicarboxylic acid consisting of only the following aromatic groups and two COOHs is more preferable.

上記の芳香族基中、Ａは−ＣＨ₂−、−Ｏ−、−Ｓ−、−ＳＯ₂−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ₃）₂−、および、−Ｃ（ＣＨ₃）₂−からなる群から選択される２価の基を表す。

Among the above aromatic groups, A is -CH _2- , _{-O-, -S-, -SO 2-} , -CO-, -NHCO-, -C (CF ₃ ) _2- , and -C (CH). ₃ ) Represents a divalent group selected from the group consisting of _{2 −.}

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

^{R 122} in the formula (3) represents a tetravalent organic group. As the ^{tetravalent organic group represented by R 122, the same group as R 115} in the above formula (2) is exemplified, and the preferable range is also the same.
^{R 122} in the formula (3) is also preferably a group derived from a bisaminophenol derivative. Examples of the group derived from the bisaminophenol derivative include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, and 3,3'-diamino-4. , 4'-dihydroxydiphenylsulfone, 4,4′-diamino-3,3′-dihydroxydiphenylsulfone, bis- (3-amino-4-hydroxyphenyl) methane, 2,2-bis (3-amino-4-) Hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis- (4-amino-3-hydroxyphenyl) hexafluoropropane, bis- (4-) Amino-3-hydroxyphenyl) methane, 2,2-bis- (4-amino-3-hydroxyphenyl) propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4 , 4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, Examples thereof include 1,3-diamino-2,4-dihydroxybenzene and 1,3-diamino-4,6-dihydroxybenzene. These bisaminophenols may be used alone or in combination.

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

上記式中、Ｘ₁は−Ｏ−、−Ｓ−、−Ｃ（ＣＦ₃）₂−、−ＣＨ₂−、−ＳＯ₂−、−ＮＨＣＯ−を表す。

In the above formulas, X ₁ is -O -, - S -, - C (CF 3) 2 -, - CH 2 -, - SO 2 -, - representing the NHCO-.

Equation (As)

In formula (As), R ₁ is a hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO _2- , -CO-, -NHCO-, single bond, or the following formula (A-s). It is an organic group selected from the group of sc).
In the formula (As), R ₂ is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different.
In formula (As), R ₃ is any of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different.

（式（Ａ−ｓｃ）中、＊は上記式（Ａ−ｓ）で示されるビスアミノフェノール誘導体のアミノフェノール基の芳香環に結合することを示す。）Equation (A-sc)

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

In the above formula (As), having a substituent at the ortho position of the phenolic hydroxy group, that is, R ₃ , is considered to bring the distance between the carbonyl carbon of the amide bond and the hydroxy group closer, and at a low temperature. It is particularly preferable in that the effect of increasing the cyclization rate when cured is further enhanced.

Further, in the above formula (As), _{it is said that the fact that R 2} is an alkyl group and R ₃ is an alkyl group has high transparency to i-rays and a high cyclization rate when cured at a low temperature. It is preferable because the effect can be maintained.

Further, in the above formula (As), _{it is more preferable that R 1} is an alkylene or a substituted alkylene. Specific examples of the alkylene and the substituted alkylene represented by R _{1 are −CH 2} −, −CH (CH ₃ ) −, −C (CH ₃ ) ₂ −, −CH (CH ₂ CH ₃ ) −, −C. (CH ₃ ) (CH ₂ CH ₃ ) −, −C (CH ₂ CH ₃ ) (CH ₂ CH ₃ ) −, −CH (CH ₂ CH ₂ CH ₃ ) −, −C (CH ₃ ) (CH ₂ CH) ₂ CH ₃ ) −, −CH (CH (CH ₃ ) ₂ ) −, −C (CH ₃ ) (CH (CH ₃ ) ₂ ) −, −CH (CH ₂ CH ₂ CH ₂ CH ₃ ) −, −C (CH ₃ ) (CH ₂ CH ₂ CH ₂ CH ₃ ) −, −CH (CH ₂ CH (CH ₃ ) ₂ ) −, −C (CH ₃ ) (CH ₂ CH (CH ₃ ) ₂ ) −, −CH (CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ ) −, −C (CH ₃ ) (CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ ) −, −CH (CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ ) −, −C (CH ₃ ) (CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ ) −, etc., among which −CH ₂ −, _{−CH (CH 3} ) −, −C (CH ₃ ) ₂ - is, while maintaining the effect of a high cyclization rate when cured at a high transparency and a low temperature for the i-line, has sufficient solubility in solvent, the polybenzoxazole precursor excellent in balance It is more preferable in that it can be obtained.

As a method for producing the bisaminophenol derivative represented by the above formula (As), for example, paragraphs 0085-0094 and Example 1 (paragraphs 0189 to 0190) of JP2013-256506A can be referred to. Yes, these contents are incorporated herein.

Specific examples of the structure of the bisaminophenol derivative represented by the above formula (As) include those described in paragraphs 0070 to 0080 of JP2013-256506A, and these contents are described in the present specification. Be incorporated. Of course, it is not limited to these.

The polybenzoxazole precursor may contain other types of repeating units in addition to the repeating unit represented by the above formula (3).
The polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating unit in that the occurrence of substrate warpage due to ring closure of the polybenzoxazole precursor can be suppressed. ..

式（ＳＬ）中、Ｚは、ａ構造とｂ構造を有し、Ｒ^1sは水素原子または炭素数１〜１０の炭化水素基であり、Ｒ^2sは炭素数１〜１０の炭化水素基であり、Ｒ^3s、Ｒ^4s、Ｒ^5s、Ｒ^6sのうち少なくとも１つは芳香族基で、残りは水素原子または炭素数１〜３０の有機基で、それぞれ同一でも異なっていてもよい。ａ構造およびｂ構造の重合は、ブロック重合でもランダム重合でもよい。Ｚ部分のモル％は、ａ構造は５〜９５モル％、ｂ構造は９５〜５モル％であり、ａ構造およびｂ構造の和は１００モル％である。

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

In the formula (SL), preferred Z includes those in which R ^5s and R ^6s in the b structure are phenyl groups.
The molecular weight of the diamine residue represented by the formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the molecular weight of the diamine residue represented by the formula (SL) in the above range, the elastic modulus of the polybenzoxazole precursor after dehydration ring closure can be lowered, and the warpage of the substrate can be suppressed. It is possible to achieve both the effects of improving solubility.

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

The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 2,000 to 29000, and even more preferably 22,000 to 28,000 when used in the compositions described below. The number average molecular weight (Mn) is preferably 7200 to 14000, more preferably 8000 to 12000, and even more preferably 9200 to 11200.
The dispersity of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. The upper limit of the dispersity of the polybenzoxazole precursor is not particularly defined, but for example, 2.6 or less is preferable, 2.5 or less is more preferable, 2.4 or less is further preferable, and 2.3 or less is further preferable. Preferably, 2.2 or less is even more preferable.

式（Ｘ）中、Ｒ¹³³は、２価の有機基を表し、Ｒ¹³⁴は、４価の有機基を表す。
重合性基を有する場合、Ｒ¹³³およびＲ¹³⁴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（Ｘ−１）または式（Ｘ−２）に示すようにポリベンゾオキサゾールの末端に重合性基を有していてもよい。(Polybenzoxazole)
The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring. The polybenzoxazole is preferably a compound represented by the following formula (X), and more preferably a compound represented by the following formula (X) and having a polymerizable group.

In formula (X), R ¹³³ represents a divalent organic group and R ¹³⁴ represents a tetravalent organic group.
When it ^{has a polymerizable group, it may have a polymerizable group in at least one of R 133} and R ¹³⁴ , and it is a polybenzoxazole as shown in the following formula (X-1) or formula (X-2). It may have a polymerizable group at the end.

式（Ｘ−１）中、Ｒ¹³⁵およびＲ¹³⁶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（Ｘ）と同義である。Equation (X-1)

In formula (X-1), ^{at least one of R 135} and R ¹³⁶ is a polymerizable group, the other is an organic group, and the other group is synonymous with formula (X).

式（Ｘ−２）中、Ｒ¹³⁷は重合性基であり、他は置換基であり、他の基は式（Ｘ）と同義である。Equation (X-2)

In formula (X-2), R ¹³⁷ is a polymerizable group, the other is a substituent, and the other group is synonymous with formula (X).

The polymerizable group that polybenzoxazole preferably has is synonymous with the polymerizable group described in the above-mentioned polymerizable group that the polyimide precursor has.

R ¹³³ represents a divalent organic group. Examples of the divalent organic group include an aliphatic group and an aromatic group. ^{Specific examples include the example of R 121} in the formula (3) of the polybenzoxazole precursor. A preferred example thereof is the same as that ^{of R 121.}

^R134 represents a tetravalent organic group. Examples of the ^{tetravalent organic group include R 122} in the formula (3) of the polybenzoxazole precursor. A preferred example thereof is the same as that ^{of R 122.}
For example, ^{four conjugates of a tetravalent organic group exemplified as R 122} combine with a nitrogen atom and an oxygen atom in the above formula (X) to form a condensed ring. For example, when R ¹³⁴ is the following organic group, it forms the following structure.

The oxazoleization rate of polybenzoxazole is preferably 85% or more, and more preferably 90% or more. When the oxazoleization rate is 85% or more, the film shrinkage caused by ring closure that occurs when oxazoled by heating is reduced, and the occurrence of warpage can be suppressed more effectively.

^{Polybenzoxazole comprises two or more different types of R 133} or R ¹³⁴ in addition to the repeating unit represented by the above formula (X), all of which are one type of R ¹³³ or R ^134. It may include a repeating unit represented by. Further, the polybenzoxazole may contain other types of repeating units in addition to the repeating unit represented by the above formula (X).

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

The weight average molecular weight (Mw) of polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and particularly preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the breakage resistance of the film after curing 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 types of polybenzoxazole are contained, it is preferable that the weight average molecular weight of at least one type of polybenzoxazole is in the above range.

(Other photosensitive resins)
Even photosensitive resins other than the above can be applied to the present invention. As other photosensitive resins, epoxy resins, phenol resins, and benzocyclobutene resins can be used.

<<< Polymerizable compound >>>
It is preferable that the resin has a polymerizable group or the photosensitive resin composition contains a polymerizable compound. With such a configuration, a cured film having more excellent heat resistance can be formed.
As the polymerizable compound, a known compound that has a polymerizable group and is capable of a cross-linking 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-mentioned polyimide precursor. The polymerizable compound may contain only one type, or may contain two or more types.
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 invention, 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 to have. The molecular weight of the polymerizable monomer is usually 100 or more.
The oligomer-type polymerizable compound is typically a polymer having a relatively low molecular weight, and is preferably a polymer in which 10 to 100 polymerizable monomers are bonded. The weight average molecular weight of the oligomer-type polymerizable compound is preferably 2000 to 20000, more preferably 2000 to 15000, and most preferably 2000 to 10000.

The number of functional groups of a 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 type of bifunctional or higher polymerizable compound containing two or more polymerizable groups, and preferably contains at least one type of trifunctional or higher functional polymerizable compound. Is more preferable.
The photosensitive resin composition preferably contains at least one type of trifunctional or higher functional polymerizable compound from the viewpoint of forming a three-dimensional crosslinked structure and improving heat resistance. Further, it may be a mixture of a polymerizable compound having less than two functions and a polymerizable compound having three or more functions.

As the polymerizable compound, 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; and a benzoxazine compound are preferable.

(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.

Specific examples of compounds containing a group having an ethylenically unsaturated bond include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides. , And these multimers, preferably esters of unsaturated carboxylic acids with polyhydric alcohol compounds, amides of unsaturated carboxylic acids with polyvalent amine compounds, and multimers thereof. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or an epoxy, or a monofunctional or polyfunctional group. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a parentionic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, an amine or a thiol, and a halogen group. Substitution reaction products of unsaturated carboxylic acid esters or amides having a releasable substituent such as tosyloxy group and monofunctional or polyfunctional alcohols, amines and thiols are also suitable. Further, as another example, it is also possible to use a compound group in which the unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an allyl ether or the like.

Specific examples of the monomer of the ester of the polyhydric alcohol compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol diacrylate as acrylic acid esters. , Propylene glycol diacrylate, Neopentyl glycol diacrylate, Trimethylol propan triacrylate, Trimethylol propantri (acryloyloxypropyl) ether, Trimethylol ethanetriacrylate, Hexandiol diacrylate, 1,4-Cyclohexanediol diacrylate, Tetra Ethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri ( Acryloyloxyethyl) isocyanurate, isocyanuric acid ethylene oxide-modified triacrylate, polyester acrylate oligomer and the like.

Examples of the methacrylic acid ester include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylpropantrimethacrylate, trimethylol ethanetrimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol dimethacrylate. Hexadiol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [para (3-methacryloxy-2). -Hydroxypropoxy) phenyl] dimethylmethane, bis- [para (methacryloxyethoxy) phenyl] dimethylmethane, etc.

Examples of itakonic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, and pentaerythritol diitaconate. , Sorbitol Tetri Taconate, etc.

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

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

Examples of the maleic acid ester include ethylene glycol dimalate, triethylene glycol dimalate, pentaerythritol dimalate, and sorbitol tetramalate.

Examples of other esters include the aliphatic alcohol-based esters described in JP-A-46-27726, JP-A-51-47334, JP-A-57-196231, and JP-A-59-5240. Also preferably used are those having an aromatic skeleton described in JP-A, JP-A-59-5241, JP-A-2-226149, and those containing an amino group described in JP-A-1-165613. Be done.

Specific examples of the amide monomer of the polyvalent amine compound and the unsaturated carboxylic acid include methylenebis-acrylamide, methylenebis-methacrylamide, 1,6-hexamethylenebis-acrylamide, and 1,6-hexamethylenebis-methacryl. There are amides, diethylenetriaminetrisacrylamides, xylylenebisacrylamides, xylylenebismethacrylamides and the like.

Examples of other preferable amide-based monomers include those having a cyclohexylene structure described in Japanese Patent Publication No. 54-21726.

Further, a urethane-based addition-polymerizable monomer produced by using an addition reaction of isocyanate and a hydroxy group is also suitable, and as a specific example thereof, for example, one molecule described in Japanese Patent Publication No. 48-41708. Examples thereof include vinyl urethane compounds containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxy group represented by the following formula to a polyisocyanate compound having two or more isocyanate groups. ..
CH ₂ = C (R ⁴ ) COOCH ₂ CH (R ⁵ ) OH
(However, R ⁴ and R ⁵ indicate H or CH _3. )
Further, urethane acrylates as described in JP-A No. 51-37193, JP-A-2-32293, and JP-B-2-16765, and JP-A-58-49860, JP-A-56- Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 are also suitable.

Further, as the compound containing a group having an ethylenically unsaturated bond, the compound described in paragraph Nos. 0995 to 0108 of JP2009-288705A can be preferably used in the present invention.

Further, as the compound containing a group having an ethylenically unsaturated bond, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable. Examples are monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylol ethanetri (meth). ) Acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) ) Acrylate, Trimethylol Propanetri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane after addition of ethylene oxide and propylene oxide to (meth) acrylate. Urethane (meth) acrylates as described in JP-A-48-41708, JP-A-50-6034, JP-A-51-37193, JP-A-48-64183, JP-A-49 Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acids described in -43191 and 52-30490, and these. A mixture can be mentioned. Further, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Further, a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group can also be mentioned.
Further, as another compound containing a group having a preferable ethylenically unsaturated bond, it has a fluorene ring described in JP-A-2010-160418, JP-A-2010-129825, Patent No. 4364216 and the like. Compounds having two or more groups having an ethylenically unsaturated bond and cardo resins can also be used.
Further, as other examples, specific unsaturated compounds described in Japanese Patent Publication No. 46-43946, Japanese Patent Publication No. 1-4537, Japanese Patent Publication No. 1-4536, and Japanese Patent Application Laid-Open No. 2-25493. Vinyl phosphonic acid compounds and the like can also be mentioned. In some cases, the structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, the journal of the Japan Adhesion Association vol. 20, No. Those introduced as photopolymerizable monomers and oligomers on pages 7, 300-308 (1984) can also be used.

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

In each of the above equations, n is an integer from 0 to 14 and m is an integer from 0 to 8. A plurality of R and T existing in the molecule may be the same or different from each other.
In each of the polymerizable compounds represented by the above formulas (MO-1) to (MO-5), at least one of the plurality of Rs is -OC (= O) CH = CH ₂ or -OC. (= O) C (CH ₃ ) = represents a group represented by _{CH 2.}
Specific examples of the compound containing a group having an ethylenically unsaturated bond represented by the above formulas (MO-1) to (MO-5) are described in paragraphs 0248 to 0251 of JP-A-2007-269779. The compound described above can also be preferably used in the present invention.

In addition, the compound described in JP-A-10-62986 with specific examples as formulas (1) and (2) after adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated is also polymerized. It can be used as a sex compound.

Further, the compounds described in paragraphs 0104 to 0131 of JP2015-187211A can also be adopted, and the contents thereof are incorporated in the present specification. In particular, the compounds described in paragraphs 0128 to 0130 of the same publication are exemplified as preferable forms.

Compounds containing a group having an ethylenically unsaturated bond include dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available KAYARAD D). -320; Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; Nihon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available) KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and a structure in which these (meth) acryloyl groups are bonded via ethylene glycol and propylene glycol residues are preferable. These oligomer types can also be used.
In addition, pentaerythritol derivatives and / or dipentaerythritol derivatives of the above formulas (MO-1) and (MO-2) are also mentioned as preferable examples.

Commercially available products of the polymerizable compound include, for example, SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer, and SR-209, which is a bifunctional methacrylate having four ethyleneoxy chains, manufactured by Sartmer. DPCA-60, a hexafunctional acrylate having 6 pentyleneoxy chains, TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS-10, UAB-140 manufactured by Nippon Kayaku Co., Ltd. (Manufactured by Sanyo Kokusaku Pulp Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (Nippon Kayaku Co., Ltd.) ), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (manufactured by Nichiyu Co., Ltd.) and the like.

Examples of the compound containing a group having an ethylenically unsaturated bond are described in JP-A-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. Such urethane acrylates and urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418. Kind is also suitable. Further, as a polymerizable compound, an addition-polymerizable compound having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. Monomers can also be used.

The compound containing a group having an ethylenically unsaturated bond may be a polyfunctional monomer having an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. The polyfunctional monomer having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid group is obtained by reacting an unreacted hydroxy group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. The polyfunctional monomer having the above is more preferable. Particularly preferably, in a polyfunctional monomer in which an unreacted hydroxy group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to have an acid group, the aliphatic polyhydroxy compound is pentaerythritol and / or di. It is pentaerythritol. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
As the polyfunctional monomer having an acid group, one type may be used alone, or two or more types may be mixed and used. Further, if necessary, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination.
The acid value of the polyfunctional monomer having an acid group is preferably 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When the acid value of the polyfunctional monomer is within the above range, it is excellent in manufacture and handling, and further excellent in developability. Moreover, the polymerizability is good.

The content of the compound containing a group having an ethylenically unsaturated bond is preferably 1 to 50% by mass with respect to the total solid content of the photosensitive resin composition from the viewpoint of good polymerization and heat resistance. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 30% by mass or less. One type of the compound containing a group having an ethylenically unsaturated bond may be used alone, or two or more types may be mixed and used.
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. / 10 to 50/50 is most preferable. When the mass ratio of the resin and the compound containing a group having an ethylenically unsaturated bond is in the above range, a cured film having better polymerizable properties 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、Ｒ⁴は炭素数１〜２００のｔ価の有機基を示し、Ｒ⁵は下記式（ＡＭ２）または下記式（ＡＭ３）で示される基を示す。）(AM1)

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

（式中Ｒ⁶は、水酸基または炭素数１〜１０の有機基を示す。）Equation (AM2) Equation (AM3)

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

It is preferable that the amount of the compound represented by the formula (AM1) is 5 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the resin. More preferably, it is 10 parts by mass or more and 35 parts by mass or less. Further, among the total 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 an amount of 10% by mass or more in the total thermal cross-linking agent. It is also preferable to contain 90% by mass or less.

（式中、Ｒ⁴は炭素数１〜２００の２価の有機基を示し、Ｒ⁵は下記式（ＡＭ２）または下記式（ＡＭ３）で示される基を示す。）(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、Ｒ⁴は炭素数１〜２００のｕ価の有機基を示し、Ｒ⁵は下記式（ＡＭ２）または下記式（ＡＭ３）で示される基を示す。）Equation (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Ｒ⁶は、水酸基または炭素数１〜１０の有機基を示す。）Equation (AM2) Equation (AM3)

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

Within this range, cracks are less likely to occur when the photosensitive resin composition layer is formed on the uneven substrate. It is excellent in pattern processability and can have high heat resistance such that the 5% mass reduction temperature is 350 ° C. or higher, more preferably 380 ° C. or higher. Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML. -PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.), NIKARAC MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, etc. Can be mentioned.

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, and the like. HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), NIKALAC MX-280, Examples thereof include NIKALAC MX-270 and NIKALAC MW-100LM (above, trade name, manufactured by Sanwa Chemical Co., Ltd.).

<<< Photopolymerization Initiator >>>
The photosensitive resin composition may contain a photopolymerization initiator. In particular, since the photosensitive resin composition contains a photoradical polymerization initiator, the photosensitive resin composition is applied to a substrate such as a semiconductor wafer to form a photosensitive resin composition layer, and then irradiated with light. , Curing due to radicals occurs, and the solubility in the light irradiated portion can be reduced. Therefore, for example, by exposing the photosensitive resin composition layer through a photomask having a pattern in which only the electrode portion is masked, there is an advantage that regions having different solubilities can be easily prepared according to the electrode pattern. is there.

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

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

Examples of the halogenated hydrocarbon compound having a triazine skeleton include Wakabayashi et al., Bull. Chem. Soc. Japanese Patent No. 42, 2924 (1969), British Patent No. 1388492, Compound described in JP-A-53-133428, German Patent No. 3337024, F.I. C. Written by Schaefer et al., J. Mol. Org. Chem. 29, 1527 (1964), compound described in JP-A-62-58241, compound described in JP-A-5-281728, compound described in JP-A-5-341920, US Pat. Examples include the compounds described in No. 4212976.

Examples of the compound described in US Pat. No. 4,212,976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2-trichloro. Methyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl)- 1,3,4-Oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) -1,3,4-oxa Diazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystylyl) -1,3,4-oxa Diazole, 2-tribromomethyl-5-styryl-1,3,4-oxadiazole, etc.) and the like.

In addition, as photopolymerization initiators other than the above, the compounds described in paragraph 0086 of JP-A-2015-087611, JP-A-53-133428, JP-A-57-1819, JP-A-57-6096, And the compounds described in US Pat. No. 3,615,455 are exemplified, and their contents are incorporated in the present specification.

Examples of the ketone compound include the compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated in the present specification.
As a commercially available product, KayaCure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in JP-A-10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184 (IRGACURE is a registered trademark), DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, the compound described in JP-A-2009-191179, in which the maximum absorption wavelength is matched with a wavelength such as 365 nm or 405 nm, can also be used.
Examples of the acylphosphine-based initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) can be used.
Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF).

The photopolymerization initiator is more preferably an oxime compound. By using the oxime compound, the exposure latitude can be improved more effectively. 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 compound described in JP-A-2001-233842, the compound described in JP-A-2000-80068, and the compound described in JP-A-2006-342166 can be used.
Preferred oxime compounds include, for example, the following compounds, 3-benzooxyiminobutane-2-one, 3-acetoxyiminovtan-2-one, 3-propionyloxyiminovtan-2-one, 2-acetoxyiminopentane-. 3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2 −ethoxycarbonyloxyimino-1-phenylpropane-1-one and the like can be mentioned.

Examples of the oxime compound include J. C. S. Perkin II (1979) pp. 1653-1660, J. Mol. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. Compounds described in each document of 202-232, compounds described in JP-A-2000-66385, JP-A-2000-80068, JP-A-2004-534977, JP-A-2006-342166, International Publication WO2015. Examples thereof include compounds described in each of the publications of No. 036910.
Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), ADEKA OPTMER N-1919 (manufactured by ADEKA Corporation, JP2012-14052). The polymerization initiator 2) is also preferably used. Further, TR-PBG-304 (manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.), ADEKA ARCLUDS NCI-831 and ADEKA ARCULDS NCI-930 (manufactured by ADEKA) can also be used. Further, DFI-091 (manufactured by Daito Chemix Co., Ltd.) can also be used.

最も好ましいオキシム化合物は、特開２００７−２６９７７９号公報に示される特定置換基を有するオキシム化合物や、特開２００９−１９１０６１号公報に示されるチオアリール基を有するオキシム化合物などが挙げられる。Further, the compound described in JP-A-2009-5199004 in which an oxime is linked to the N-position of the carbazole ring, the compound described in US Pat. No. 7,626,957 in which a hetero-substituent is introduced at the benzophenone moiety, and a nitro group at the dye moiety. The introduced Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039, the ketooxime compound described in International Publication No. WO2009-131189, and US Pat. No. 7,556910 containing a triazine skeleton and an oxime skeleton in the molecule. The compound described in JP-A, the compound described in JP-A-2009-221114, which has an absorption maximum at 405 nm and has good sensitivity to a g-ray light source, and the like may be used.
Further, the cyclic oxime compounds described in JP-A-2007-231000 and JP-A-2007-322744 can also be preferably used. Among the cyclic oxime compounds, the cyclic oxime compound fused to the carbazole dye described in JP-A-2010-32985 and JP-A-2010-185072 has high light absorption and has high sensitivity. preferable.
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-A-2010-262028, compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013. Examples thereof include the compound (C-3) described in paragraph 0101 of JP-A-164471. Specific examples include the following compounds.

The most preferable oxime compound includes an oxime compound having a specific substituent shown in JP-A-2007-269779 and an oxime compound having a thioaryl group shown in JP-A-2009-191061.

式（Ｉ）中、Ｒ⁵⁰は、炭素数１〜２０のアルキル基；１個以上の酸素原子によって中断された炭素数２〜２０のアルキル基；炭素数１〜１２のアルコキシ基；フェニル基；炭素数１〜２０のアルキル基、炭素数１〜１２のアルコキシ基、ハロゲン原子、シクロペンチル基、シクロヘキシル基、炭素数１〜１２のアルケニル基、１個以上の酸素原子によって中断された炭素数２〜１８のアルキル基および炭素数１〜４のアルキル基の少なくとも１つで置換されたフェニル基；またはビフェニリルであり、Ｒ⁵¹は、式（ＩＩ）で表される基であるか、Ｒ⁵⁰と同じ基であり、Ｒ⁵²〜Ｒ⁵⁴は各々独立に炭素数１〜１２のアルキル、炭素数１〜１２のアルコキシまたはハロゲンである。

式中、Ｒ⁵⁵〜Ｒ⁵⁷は、上記式（Ｉ）のＲ⁵²〜Ｒ⁵⁴と同じである。From the viewpoint of exposure sensitivity, the photopolymerization initiator is a trihalomethyltriazine compound, a benzyl dimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, or a triaryl. Selected from the group consisting of imidazole dimer, onium salt compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, halomethyloxaziazole compound, 3-aryl substituted coumarin compound. Compounds are preferred.
More preferable photopolymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds and acetophenone compounds. At least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferable, and metallocene compounds or oxime compounds are even more preferable, and oxime compounds are even more preferable. Is particularly preferred.
The photopolymerization initiator is N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-, such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone). 2-Dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1 and other aromatic ketones, alkylanthraquinone and the like Kinones fused with an aromatic ring, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkyl benzoin, and benzyl derivatives such as benzyl dimethyl ketal can also be used.
Further, a compound represented by the following formula (I) can also be used.

In formula (I), R ⁵⁰ is an alkyl group having 1 to 20 carbon atoms; an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms; an alkoxy group having 1 to 12 carbon atoms; a phenyl group; Alkyl groups with 1 to 20 carbon atoms, alkoxy groups with 1 to 12 carbon atoms, halogen atoms, cyclopentyl groups, cyclohexyl groups, alkenyl groups with 1 to 12 carbon atoms, carbon atoms 2 to 2 interrupted by one or more oxygen atoms A phenyl group substituted with at least one of 18 alkyl groups and an alkyl group having 1 to 4 carbon atoms; or biphenylyl, where R ⁵¹ is the group represented by formula (II) or is the same as ^{R 50.} The groups, R ^{52 to} R ^54, are independently alkyl having 1 to 12 carbon atoms and alkoxy or halogen having 1 to 12 carbon atoms, respectively.

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

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, more preferably 0.1, based on the total solid content of the photosensitive resin composition. It is ~ 20% by mass, more preferably 0.1 to 10% by mass.
The photopolymerization initiator may be only one type or two or more types. When there are two or more types of photopolymerization initiators, the total is preferably in 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 movement of metal ions derived from the metal layer (metal wiring) into the photosensitive resin composition layer.
The migration inhibitor is not particularly limited, but heterocycles (pyrazole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, etc. Pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring, piperazine ring, morpholin ring, 2H-pyran ring and 6H-pyran ring, triazine ring), thiourea and mercapto group compounds, hindered phenolic compounds , Salicylate derivative compound, hydrazide derivative compound and the like. In particular, triazole-based compounds such as triazole and benzotriazole, and tetrazole-based compounds such as tetrazole and benzotetrazole can be preferably used.

It is also possible to use an ion trap agent that traps anions such as halogen ions.

Examples of other migration inhibitors include rust preventives described in paragraph 0094 of JP2013-15701, 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 JP2012-194520 can be used.

Specific examples of the migration inhibitor include 1H-1,2,3-triazole, 1H-1,2,4-triazole, and 1H-tetrazole.

When the photosensitive resin composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, preferably 0.05 to 5.0% by mass, based on the total solid content of the photosensitive resin composition. 2.0% by mass is more preferable, and 0.1 to 1.0% by mass is further preferable.
Only one type of migration inhibitor may be used, or two or more types may be used. When there are two or more types of migration inhibitors, the total is preferably in the above range.

<<< Polymerization inhibitor >>>
The photosensitive resin composition used in the present invention 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, Ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol ether diamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol , 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, bis (4-hydroxy) -3,5-tert-butyl) phenylmethane and the like are preferably used. Further, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compound described in paragraphs 0031 to 0046 of International Publication WO2015 / 125469 can also be used.
When the composition has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass with respect to the total solid content of the photosensitive resin composition.
The polymerization inhibitor may be only one kind or two or more kinds. When there are two or more types of polymerization inhibitors, the total is preferably in the above range.

<<< Thermal base generator >>>
The photosensitive resin composition used in the present invention may contain a thermal base generator.
The type of thermal base generator is not particularly specified, but it is selected from an acidic compound that generates a base when heated to 40 ° C. or higher, and an ammonium salt having an anion having a pKa1 of 0 to 4 and an ammonium cation. It is preferable to include a thermobase generator containing at least one of these. _{Here, pKa1 represents the logarithm (-Log 10} Ka) of the dissociation constant (Ka) of the first proton of the acid, and the details will be described later.
By blending 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 it is heated, even if it coexists with a polyimide precursor and a polybenzoxazole precursor, cyclization of the polyimide precursor and the polybenzoxazole precursor during storage is performed. It can suppress the problem and has excellent storage stability.

The thermobase 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. Is preferable.
Since the acidic compound (A1) and the ammonium salt (A2) generate bases when heated, the bases generated from these compounds can promote the cyclization reaction of the polyimide precursor, the polybenzoxazole precursor, and the like. Cyclization of polyimide precursors and polybenzoxazole precursors can be carried out at low temperatures. Further, even if these compounds coexist with a polyimide precursor and a polybenzoxazole precursor that are cyclized and cured by a base, cyclization of the polyimide precursor and the polybenzoxazole precursor almost progresses unless they are heated. Therefore, a photosensitive resin composition containing a polyimide precursor and a polybenzoxazole precursor having excellent stability can be prepared.
In the present specification, the acidic compound means that 1 g of the compound is collected in a container, 50 mL of a mixed solution of ion-exchanged water and tetrahydrofuran (mass ratio is water / tetrahydrofuran = 1/4) is added, and the compound is added at room temperature for 1 hour. It means a compound having a value of less than 7 measured at 20 ° C. using a pH (power of hydrogen) meter for the solution obtained by stirring.

In the present invention, the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40 ° C. or higher, more preferably 120 to 200 ° C. The upper limit of the base generation temperature is 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 ammonium salt (A2) is 120 ° C. or higher, bases are unlikely to be generated during storage, and thus include a polyimide precursor and a polybenzoxazole precursor having excellent stability. 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, using differential scanning calorimetry, the compound is heated to 250 ° C. in a pressure resistant capsule at 5 ° C./min, 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 invention, the base generated by the thermal base generator is preferably a secondary amine or a tertiary amine, and more preferably a tertiary amine. Since the tertiary amine is highly basic, the cyclization temperature of the polyimide precursor and the polybenzoxazole precursor can be 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 most 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 value of the molecular weight is a theoretical value obtained from the structural formula.

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

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

式（１０１）および式（１０２）中、Ｒ¹〜Ｒ⁶は、それぞれ独立に、水素原子または炭化水素基を表し、Ｒ⁷は炭化水素基を表す。式（１０１）および式（１０２）におけるＲ¹とＲ²、Ｒ³とＲ⁴、Ｒ⁵とＲ⁶、Ｒ⁵とＲ⁷はそれぞれ結合して環を形成してもよい。In the present invention, the ammonium salt means a salt of an ammonium cation represented by the following formula (101) or formula (102) and an anion. The anion may be bonded to any part of the ammonium cation via a covalent bond, or may be held outside the molecule of the ammonium cation, but may be held outside the molecule of the ammonium cation. preferable. The fact that the anion is present outside the molecule of the ammonium cation means that the ammonium cation and the anion are not bonded via a covalent bond. Hereinafter, the extramolecular anion of the cation part is also referred to as a counter anion.
Equation (101) Equation (102)

In formulas (101) and (102), R ^{1 to} R ⁶ 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 combined to form a ring, respectively.

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 are synonymous with 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 invention, 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, and 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 further, the stability of the photosensitive resin composition containing the polyimide precursor and the polybenzoxazole precursor and the like can be obtained. Can be improved. When pKa1 is 4 or less, the stability of the thermobase generator is good, the generation of bases can be suppressed without heating, and the stability of the photosensitive resin composition containing the polyimide precursor, the polybenzoxazole precursor, and the like is stable. Good sex. When pKa1 is 0 or more, the generated base is not easily neutralized, and the cyclization efficiency of the polyimide precursor, the polybenzoxazole precursor, and the like is good.
The type of anion is preferably one selected from carboxylic acid anion, phenol anion, phosphate anion and sulfate anion, and carboxylic acid anion is more preferable because both salt stability and thermal decomposability can be achieved. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylic acid anion.
The carboxylic acid anion is preferably a divalent or higher carboxylic acid anion having two or more carboxyl groups, and more preferably a divalent carboxylic acid anion. According to this aspect, it is possible to obtain a thermobase generator capable of further improving the stability, curability and developability of a photosensitive resin composition containing a polyimide precursor, a polybenzoxazole precursor and the like. In particular, by using a divalent carboxylic acid anion, the stability, curability and developability of the photosensitive resin composition containing the polyimide precursor, the polybenzoxazole precursor and the like can be further improved.
In the present invention, 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, and even more preferably 3.2 or less. According to this aspect, the stability of the photosensitive resin composition containing the polyimide precursor, the polybenzoxazole precursor, and the like 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 Determination of Organic Structures by Physical Methods (author: Brown, HC, McDaniel, D.H., Hafli). , Nachod, F.C .; Compilation: Braude, E.A., Nachod, F.C .; Academic Press, New York, 1955) and Data for Biochemical Research (Author: D. al; Oxford, Clarendon Press, 1959) can be referred to. For compounds not described in these documents, the values calculated from the structural formulas using software of ACD / pKa (manufactured by ACD / Labs) shall be used.

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

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

In the present invention, the electron-attracting group means that the substituent constant σm of Hammett shows a positive value. Here, σm is a review by Yusuke Tono, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965), p. It is described in detail in 631-642. The electron-attracting group in the present invention is not limited to the substituents described in the above documents.
Examples of substituents in which σm shows a positive value include CF ₃ group (σm = 0.43), CF ₃ CO group (σm = 0.63), HC≡C group (σm = 0.21), and the like. CH ₂ = CH group (σm = 0.06), Ac group (σm = 0.38), MeOCO group (σm = 0.37), MeCOCH = CH group (σm = 0.21), PhCO group (σm = 0.34), H ₂ NCOCH ₂ group (σm = 0.06), and the like. Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group.

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、ヒドロキシ基またはカルボキシル基を表し、Ａｒは芳香族基を表す。The 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 independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxy group or a carboxyl group, and Ar is an aromatic group. Represents.

式（ＸＡ）において、Ｌ¹⁰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 invention, the carboxylic acid anion is preferably represented by the following formula (XA).
Equation (XA)

In the formula (XA), L ¹⁰ represents a single bond or an alkylene group, an alkenylene group, an aromatic group, -NR ^X - represents and divalent linking group selected from these combinations, R ^X is a hydrogen atom , Alkyl group, alkenyl group or aryl group.

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

Specific examples of the thermobase generator include the following compounds.

When a thermobase generator is used, the content of the thermobase generator in the photosensitive resin composition is preferably 0.1 to 50% by 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, and further preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less.
As the thermobase generator, one kind or two or more kinds can be used. When two or more types are used, the total amount is preferably in 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種類のみでもよいし、２種類以上であってもよい。２種類以上用いる場合は、その合計が上記範囲であることが好ましい。<<< Metal Adhesive Improvement Agent >>>
The photosensitive resin composition used in the present invention preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like. Examples of the metal adhesive improving agent include the sulfide compounds described in paragraphs 0046 to 0049 of JP2014-186186A and paragraphs 0032 to 0043 of JP2013-072935A. Examples of the metal adhesion improver also include the following compounds (N- [3- (triethoxysilyl) propyl] maleic acid monoamide and the like).

The metal adhesiveness improving agent is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the resin. When the amount is 0.1 parts by mass or more, the adhesiveness between the cured film and the metal layer after the curing process 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 process are good. Become.
The metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more types are used, the total is preferably in the above range.

<<< Solvent >>>
When the photosensitive resin composition used in the present invention is layered by coating, it is preferable to add a solvent. As the solvent, known ones can be used without limitation as long as the photosensitive resin composition can be formed in layers. Examples of the solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, and sulfoxides.
Examples of esters include ethyl acetate, -n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone. , Δ-Valerolactone, alkylalkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.) )), 3-Alkyloxypropionate alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Methyl ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate) Etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyloxy-2-methylpropionate, etc. Methyl acid and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, pyruvin Preferable examples thereof include propyl acid acid, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate and the like.
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, and propylene glycol. Preferable examples thereof include monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.
Preferable examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like.
Preferred examples of aromatic hydrocarbons include toluene, xylene, anisole, limonene and the like.
Dimethyl sulfoxide is preferably used as the sulfoxides.

As the solvent, a form in which two or more kinds are mixed is also preferable from the viewpoint of improving the coating surface shape. 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 a mixed solution composed of two or more selected from propylene glycol methyl ether acetate are preferable. The combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

When the photosensitive resin composition has a solvent, the content of the solvent is preferably an amount such that the total solid content concentration of the photosensitive resin composition is 5 to 80% by mass from the viewpoint of coatability. 70% by mass is more preferable, and 10 to 60% by mass is particularly preferable. The solvent content may be adjusted according to the desired thickness and coating method. For example, if the coating method is spin coating or slit coating, the content of the solvent having a 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 preferably 1.0% by mass to 25% by mass. By adjusting the content of the solvent according to the coating method, the photosensitive resin composition layer having a desired thickness can be uniformly formed.
The solvent may be only one type or two or more types. When there are two or more types of solvents, the total is preferably in 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. It is preferably less than 5% by mass, more preferably less than 1% by mass, particularly preferably less than 0.5% by mass, and even more preferably less than 0.1% by mass.

<<< Other Additives >>>
The photosensitive resin composition used in the present invention is, if necessary, various kinds of additives such as a photobase generator, a thermal polymerization initiator, a thermal acid generator, and a silane, as long as the effects of the present invention are not impaired. Coupling agents, sensitizing dyes, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, antiaggregating agents and the like can be blended. .. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the composition.

(Photobase generator)
The photosensitive resin composition used in the present invention may contain a photobase generator. A photobase generator is a substance that generates a base by exposure and does not show activity under normal conditions of normal temperature and pressure, but when it is irradiated with electromagnetic waves and heated as an external stimulus, it is a base (basic substance). ) Is not particularly limited as long as it occurs. Since the base generated by exposure acts as a catalyst for curing the polyimide precursor, the benzoxazole precursor, and the like by heating, it can be suitably used in the negative type.

The content of the photobase generator is not particularly limited as long as it can form a desired pattern, and can be a general content. The photobase generator is preferably in the range of 0.01 parts by mass or more and less than 30 parts by mass, and 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 preferably in the range of 0.1 parts by mass to 20 parts by mass, more preferably.
Only one type of photobase generator may be used, or two or more types may be used. When there are two or more types of photobase generators, the total is preferably in the above range.

In the present invention, known photobase generators can be used. For example, M. Shirai, and M. Tsunooka, Prog. Polym. Sci. , 21, 1 (1996); Masahiro Kadooka, Polymer Processing, 46, 2 (1997); C.I. Kutal, Code. Chem. Rev. , 211,353 (2001); Y. Kaneko, A.M. Sarker, and D. Neckers, Chem. Mater. , 11, 170 (1999); Tachi, M. et al. Shirai, and M. Tsunooka, J. Mol. Photopolym. Sci. Technol. , 13, 153 (2000); Winkle, and K. Graziano, J. et al. Photopolym. Sci. Technol. , 3,419 (1990); Tsunooka, H. et al. Tachi, and S. Yoshitaka, J.M. Photopolym. Sci. Technol. , 9, 13 (1996); Suyama, H. et al. Araki, M. et al. Shirai, J. et al. Photopolym. Sci. Technol. , 19, 81 (2006), such as those having a structure such as a transition metal compound complex or an ammonium salt, or those in which the amidin moiety is latent by salt formation with a carboxylic acid. Ionic compounds whose base components are neutralized by forming salts, and nonionic compounds whose base components are latent by urethane bonds or oxime bonds such as carbamate derivatives, oxime ester derivatives, and acyl compounds. Can be mentioned.
The photobase generator that can be used in the present invention 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, etc. Oxime derivatives and the like can be mentioned.
Examples of the photobase generator include a photobase generator having a katsura acid amide structure as disclosed in JP-A-2009-80452 and International Publication WO2009 / 123122, JP-A-2006-189591 and JP-A. A photobase generator having a carbamate structure as disclosed in JP-A-2008-247747, a light having an oxime structure and a carbamoyl oxime structure as disclosed in JP-A-2007-249013 and JP-A-2008-003581. Examples thereof include, but are not limited to, a base generator, and other known photobase generators can be used.
Other examples of the photobase generator include the compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 of JP2012-93746A, and the compounds described in paragraphs 0022 to 0069 of JP2013-194205. Examples include the compounds described in paragraphs 0026 to 0074 of Japanese Patent Application Laid-Open No. 2013-204319, and the compounds described in paragraphs 0052 of WO2010 / 064631.

(Thermal polymerization initiator)
The photosensitive resin composition used in the present invention may contain a thermal polymerization initiator (preferably a thermal radical polymerization initiator). As the thermal radical polymerization initiator, a known thermal radical polymerization initiator can be used.
A thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the polymerizable compound can be allowed to proceed when the cyclization reaction of the polyimide precursor and the polybenzoxazole precursor is allowed to proceed. 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 along with the cyclization of the polyimide precursor and the polybenzoxazole precursor. Therefore, it is possible to achieve a higher degree of heat resistance.
Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-63554.

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

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

Examples of the thermoacid generator include those described in paragraph 0055 of JP2013-072935A.

Further, the compound described in paragraph 0059 of JP2013-167742A is also preferable as the thermoacid generator.

The content of the thermoacid generator is preferably 0.01 part by mass or more, and more preferably 0.1 part by mass or more with respect to 100 parts by mass of the polyimide precursor and the polybenzoxazole precursor. When it is contained in an amount of 0.01 part by mass or more, the cross-linking reaction and the cyclization of the polyimide precursor and the polybenzoxazole precursor are promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved. Further, from the viewpoint of electrical insulation of the cured film, 20 parts by mass or less is preferable, 15 parts by mass or less is more preferable, and 10 parts by mass or less is particularly preferable.
Only one type of thermoacid generator may be used, or two or more types may be used. When two or more types are used, the total amount is preferably in the above range.

(Silane coupling agent)
The photosensitive resin composition used in the present invention may contain a silane coupling agent in order to improve the adhesion to the substrate.
Examples of the silane coupling agent include the compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, the compounds described in paragraphs 0063-0071 of International Publication WO2011 / 080992A1, JP-A-2014-191252. Examples thereof include 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 / 0975994. It is also preferable to use two or more different types of silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A.
The silane coupling agent is preferably in the range of 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the resin. When it is 0.1 part by mass or more, more sufficient adhesion to the substrate can be imparted, and when it is 20 parts by mass or less, problems such as an increase in viscosity during storage at room temperature can be further suppressed.
Only one type of silane coupling agent may be used, or two or more types may be used. When two or more types are used, the total amount is preferably in the above range.

(Sensitizing pigment)
The photosensitive resin composition used in the present invention may contain a sensitizing dye. The sensitizing dye absorbs a specific active radiation and becomes an electron-excited state. The sensitizing dye in the electron-excited state comes into contact with an amine generator, a thermal radical polymerization initiator, a photopolymerization initiator, or the like, and causes actions 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 and decompose to generate radicals, acids, or bases.

Examples of preferable sensitizing dyes include those belonging to the following compounds and having an absorption wavelength in the range of 300 nm to 450 nm. For example, polynuclear aromatics (eg, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9.10-dialkoxyanthracene), xanthenes (eg, fluoressein, eosin, erythrosin, rhodamine B, rosebenzene), thioxanthones. (For example, 2,4-diethylthioxanthone), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiadins (eg, thionin, methylene blue, toluidine blue), acridines. (For example, acridine orange, chloroflavin, acryflabin), anthracenes (eg, anthracene), squaryliums (eg, squarylium), coumarins (eg, 7-diethylamino-4-methylcoumarin), styrylbenzenes, distyryl Benzenes, carbazoles and the like can be mentioned.

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

(Chain transfer agent)
The photosensitive resin composition used in the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, 2005), pp. 683-684. As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. They can donate hydrogen to low-activity radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazol, etc.) can be preferably used.

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

(Surfactant)
Each type of surfactant may be added to the photosensitive resin composition used in the present invention from the viewpoint of further improving the coatability. As the surfactant, various types of surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used.

When the photosensitive resin composition has a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0, based on the total solid content of the photosensitive resin composition. It is .005 to 1.0% by mass.
Only one type of surfactant may be used, or two or more types may be used. When there are two or more types of surfactants, the total is preferably in the above range.

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

<< Characteristics of photosensitive resin composition >>
Next, the characteristics of the photosensitive resin composition used in the present invention will be described.
It is preferable that the photosensitive resin composition used in the present invention has a crosslinked structure constructed by exposure and its solubility in an organic solvent is lowered. By having the crosslinked structure, when the photosensitive resin composition layers are laminated, the adhesion between the layers can be increased. Further, since the solubility of the photosensitive resin composition layer in an organic solvent is lowered by exposure, it is advantageous when a deep groove or a deep hole is provided when the number of layers is increased.
The water content of the photosensitive resin composition used in the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and particularly preferably less than 0.6% by mass from the viewpoint of the coated surface.

The metal content of the photosensitive resin composition used in the present invention 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, from the viewpoint of insulating properties. .. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are contained, the total of these metals is preferably in the above range.
Further, as a method for reducing metal impurities unintentionally contained in the photosensitive resin composition, a photosensitive resin composition is formed by selecting a raw material having a low metal content as a raw material constituting the photosensitive resin composition. Examples thereof include a method of filtering the raw material to be used, and a method of lining the inside of the apparatus with polytetrafluoroethylene or the like and performing distillation under conditions in which contamination is suppressed as much as possible.

The photosensitive resin composition used in the present invention preferably has a halogen atom content of 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 corrosiveness. Among them, those existing in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and particularly preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of chlorine atom and bromine atom, or chloride ion and bromide ion is in the above range, respectively.

<Drying process>
The method for producing a laminate of the present invention may include a step of forming a photosensitive resin composition layer and then drying the solvent. The preferred drying temperature is 50 to 150 ° C., more preferably 70 to 130 ° C., even more preferably 90 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.

<Exposure process>
The method for producing a laminate of the present invention includes an exposure step of exposing a photosensitive resin composition layer. The exposure conditions are not particularly specified, and it is preferable that the solubility of the exposed portion of the photosensitive resin composition in the developing solution can be changed, and it is more preferable that the exposed portion of the photosensitive resin composition can be cured. For example, exposure of the photosensitive resin composition layer, it is preferable to irradiate 100~10000mJ / cm ² at an exposure energy conversion at a wavelength 365 nm, it is more preferable to irradiate 200~8000mJ / cm ^2.
The exposure wavelength can be appropriately determined in the range of 190 to 1000 nm, preferably 240 to 550 nm.

The exposure may be performed by pattern exposure, or may be performed by uniform irradiation over the entire surface.

<Development process>
The method for producing a laminate of the present invention includes a development treatment step of performing a development treatment on the exposed photosensitive resin composition layer.
The development processing step is preferably a negative type development processing step. By performing the negative development process, the unexposed portion (non-exposed portion) is removed. The developing method is not particularly limited, and it is preferable that a desired pattern can be formed. For example, a developing method such as paddle, spray, immersion, ultrasonic wave or the like can be adopted.
In the present invention, it is preferable to perform the development processing step even when the exposure is performed by uniform irradiation on the entire surface.
Development is preferably carried out using a developing solution. The developer can be used without particular limitation as long as the unexposed portion (non-exposed portion) is removed. Development with an organic solvent is preferable, and as esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, etc. γ-Butyrolactone, ε-caprolactone, δ-valerolactone, alkylalkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxy) Methyl acetate, ethyl ethoxyacetate, etc.)), alkyl esters of 3-alkyloxypropionate (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.), etc. (eg, methyl 3-methoxypropionate, 3- Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, etc.) Propyl 2-alkyloxypropionate and the like (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2- Methyl alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), pyruvate Methyl, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene Glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acete And so on.
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.
Dimethyl sulfoxide is preferably used as the sulfoxides.
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 specified, but is usually 20 to 40 ° C.
After the treatment with the developing solution, further rinsing may be performed. The rinsing is preferably performed with a solvent different from that of the developing solution. For example, it can be rinsed with a solvent contained in the photosensitive resin composition. The rinsing time is preferably 5 seconds to 1 minute.

<Curing process>
The method for producing a laminate of the present invention includes a curing step of curing the photosensitive resin composition layer after the development treatment.
The curing step preferably includes a temperature raising step of raising the temperature of the photosensitive resin composition layer and a cooling step of cooling the photosensitive resin composition layer after the temperature raising step.

The curing step (particularly the temperature raising step and the holding step) is preferably performed in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon from the viewpoint of preventing decomposition of the resin. The oxygen concentration is preferably 50 volume ppm or less, and preferably 20 volume ppm or less.

<< Heating process >>
The temperature raising step is preferably a step of raising the temperature of the photosensitive resin composition layer to a temperature equal to or higher than the glass transition temperature.
In the temperature raising step, it is preferable to proceed with the cyclization reaction of the resin (preferably the polyimide precursor and the polybenzoxazole precursor) contained in the photosensitive resin composition layer. For example, in polyimide or polybenzoxazole, a three-dimensional network structure can be formed when heated together with a cross-linking agent. In addition, curing of unreacted radically polymerizable compounds can be promoted.
The final temperature reached in the temperature raising step is preferably the imidization temperature of the resin contained in the photosensitive resin composition layer.
The final temperature reached in the temperature raising step is preferably the maximum heating temperature. The maximum heating temperature is preferably 100 to 500 ° C, more preferably 150 to 450 ° C, and even more preferably 160 to 350 ° C. In the method for producing a laminate of the present invention, it is particularly preferable that the final temperature reached in the temperature raising step is 250 ° C. or lower from the viewpoint of stress relaxation.

The heating step is preferably performed from a temperature of 20 to 150 ° C. to the maximum heating temperature at a heating rate of 1 to 12 ° C./min, more preferably 2 to 11 ° C./min, and further 3 to 10 ° C./min. preferable. By setting the temperature rise rate to 1 ° C./min or more, it is possible to prevent excessive volatilization of amine while ensuring productivity, and by setting the temperature rise rate to 12 ° C./min or less, the cured film can be prevented. Residual stress can be relaxed.
The temperature at the start of heating is preferably 20 to 150 ° C, more preferably 20 ° C to 130 ° C, and even more preferably 25 ° C to 120 ° C. The temperature at the start of heating refers to the heating temperature at the start of the process of heating to the maximum heating temperature. For example, when the photosensitive resin composition is applied onto a substrate and then dried, it is the temperature after drying, for example, gradually from the boiling point of the solvent contained in the photosensitive resin composition- (30 to 200) ° C. It is preferable to raise the temperature to.

Heating may be performed in stages. As an example, before the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min, left at 180 ° C. for 60 minutes, the temperature is raised from 180 to 200 ° C. at 2 ° C./min, and left at 200 ° C. for 120 minutes. A processing step may be performed. The heating temperature as 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 carry out the treatment while irradiating with UV as described in US Pat. No. 9,159,547. It is possible to improve the characteristics of the cured film by such a pretreatment step. The pretreatment step is preferably carried out in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment step may be two or more steps, for example, the pretreatment step 1 may be performed in the range of 100 to 150 ° C., and then the pretreatment step 2 may be performed in the range of 150 to 200 ° C.

The temperature raising step is preferably 20 to 200 minutes, more preferably 20 to 100 minutes, and particularly preferably 20 to 60 minutes.

<< Holding process >>
The method for producing a laminate of the present invention preferably includes a holding step of holding at a holding temperature equal to the final reached temperature of the raising step after the raising step and before the cooling step.
After reaching the final temperature reached in the temperature raising step, heating is preferably performed for 30 to 360 minutes at a holding temperature equal to the final temperature reached in the temperature rising step, more preferably 30 to 300 minutes, and 30 to 240. It is particularly preferable to heat for 1 minute, and more preferably to heat for 60 to 240 minutes.
The time required for the holding process is called the holding time.
The holding temperature in the holding step is preferably 150 to 450 ° C, more preferably 160 to 350 ° C. In the method for producing a laminate of the present invention, it is particularly preferable that the holding temperature in the holding step is 250 ° C. or lower from the viewpoint of stress relaxation.

<< Cooling process >>
The cooling step is preferably a step of cooling the photosensitive resin composition layer at a temperature lowering rate of 2 ° C./min or less after the temperature raising step.
The temperature lowering rate in the cooling step is preferably 2 ° C./min or less, and more preferably 1 ° C./min or less. The temperature lowering rate in the cooling step is preferably 0.1 ° C./min or more from the viewpoint of stress relaxation.
From the viewpoint of stress relaxation, it is preferable that the temperature lowering rate in the cooling step is slower than the temperature rising rate in the heating step.

The cooling step is preferably 30 to 600 minutes, more preferably 60 to 600 minutes, and particularly preferably 120 to 600 minutes.
In the method for producing a laminate of the present invention, it is preferable that the time of the cooling step is longer than the time of the raising step from the viewpoint of stress relaxation.

It is preferable that the final temperature reached in the cooling step is 30 ° C. or higher lower than the glass transition temperature (Tg) of the photosensitive resin composition layer (cured film) after the curing step. When the final temperature reached in the cooling step is lowered to a temperature 30 ° C. or higher lower than the Tg of the photosensitive resin composition layer, the polyimide is sufficiently cured and the occurrence of delamination is likely to be suppressed.
The final temperature reached in the cooling step is more preferably 160 to 250 ° C. lower than the glass transition temperature of the photosensitive resin composition layer after the curing step, and particularly preferably 180 to 230 ° C. lower.

<< Process to bring to room temperature >>
After the photosensitive resin composition layer reaches the final temperature reached in the cooling step, it is preferable to include a step of cooling the photosensitive resin composition layer at an arbitrary temperature lowering rate to bring it to room temperature.
The temperature lowering rate in the step of bringing the room temperature to room temperature is not particularly limited, and is preferably faster than the temperature lowering rate in the cooling step. The temperature lowering rate in the step of bringing the room temperature to room temperature can be, for example, 5 to 10 ° C./min.

<Metal layer forming process>
The method for producing a laminate of the present invention includes a metal layer forming step of forming a metal layer on the surface of the photosensitive resin composition layer after a curing step by vapor phase film formation.
The temperature of the photosensitive resin composition layer after the curing step when forming the metal layer is lower than the glass transition temperature of the photosensitive resin composition layer after the curing step.

In the method for producing a laminate of the present invention, the temperature of the photosensitive resin composition layer when forming the metal layer is preferably 30 ° C. or more lower than the glass transition temperature of the photosensitive resin composition layer, and is 30 to 200 ° C. lower. It is more preferable, and it is particularly preferable that it is 100 to 200 ° C. lower.
When the number of metal layers formed in the metal layer forming step is two or more, at least after the curing step when forming a metal layer (preferably a barrier metal film) that comes into direct contact with the photosensitive resin composition layer after the curing step. The temperature of the photosensitive resin composition layer is preferably in the above range. When the number of metal layers formed in the metal layer forming step is two or more, the temperature of the photosensitive resin composition layer after the curing step when forming the second metal layer is not particularly limited. However, if there is a portion directly provided on the photosensitive resin composition layer even in the second metal layer, the photosensitive resin composition layer after the curing step when forming the second metal layer. The temperature of is also preferably in the above range.
In particular, when the second metal layer is formed by using vapor deposition, the temperature of the photosensitive resin composition layer after the curing step when forming the second metal layer must also be within the above range. preferable. When the second metal layer is formed by using non-gas phase film formation (plating, etc.), the temperature of the photosensitive resin composition layer after the curing step when forming the second metal layer is generally the temperature of the photosensitive resin composition layer. Is below the glass transition temperature of the photosensitive resin composition layer.

The metal layer formed in the metal layer forming step is not particularly limited, and an existing metal can be used. The metal contained in the metal layer formed in the metal layer forming step includes copper, aluminum, nickel, vanadium, titanium, tantalum, chromium, cobalt, gold and tungsten, and compounds (including alloys) containing at least one of these. Is exemplified. In the method for producing a laminate of the present invention, it is more preferable that the metal layer formed in the metal layer forming step contains at least one of titanium, tantalum and copper and a compound containing at least one of these, and titanium. And copper and at least one of compounds containing at least one of these are particularly preferably contained, and more preferably copper is contained. Specific examples of the case where the metal layer contains at least one of titanium, tantalum and copper and a compound containing at least one of these include a metal layer made of titanium, tantalum, copper, TiN, TaN or TiW. , Titanium, tantalum, copper, TiN or TiW is preferred. The metal contained in the metal layer formed in the metal layer forming step may be one kind or two or more kinds.

In the method for producing a laminate of the present invention, the thickness of the metal layer formed in the metal layer forming step is preferably 50 to 2000 nm, more preferably 50 to 1000 nm, and 100 to 300 nm. Is particularly preferable.
In the method for producing a laminate of the present invention, the metal layer formed in the metal layer forming step may be one layer or two or more layers.
When the metal layer formed in the metal layer forming step is one layer, the metal layer is preferably used as a barrier metal film.
When the number of metal layers formed in the metal layer forming step is two or more, it is preferable that the thickness of the entire metal layer formed in the metal layer forming step is in the above range. When the number of metal layers formed in the metal layer forming step is two or more, it is preferable that the metal layer formed in the metal layer forming step is a laminate of a barrier metal film and a seed layer.
The barrier metal film is preferably a layer capable of shortening the penetration depth of the metal into the cured film. The type of metal of the barrier metal film is preferably the above-mentioned metal as the metal contained in the metal layer formed in the metal layer forming step. The thickness of the barrier metal film is preferably 50 to 2000 nm, more preferably 50 to 1000 nm, and particularly preferably 100 to 300 nm.
The seed layer is preferably a layer for facilitating the formation of a pattern of the second metal layer formed in the second metal layer forming step. The type of metal of the seed layer is preferably the same type of metal as the second metal layer formed in the second metal layer forming step. The thickness of the seed layer is preferably 50 to 2000 nm, more preferably 50 to 1000 nm, and particularly preferably 100 to 300 nm.

The method for forming the metal layer is not particularly limited, and an existing method for forming a vapor phase film can be applied. For example, a sputtering method, a chemical vapor deposition (CVD), a plasma method, or a method in which these are combined can be considered. Among these, the method for forming the metal layer is preferably a sputtering method from the viewpoint of film thickness control.

<Second metal layer forming process>
The method for producing a laminate of the present invention preferably further includes a second metal layer forming step of forming a second metal layer on the surface of the metal layer.

As the second metal layer formed in the second metal layer forming step, an existing metal can be used without particular limitation. Examples of the metal contained in the second metal layer formed in the second metal layer forming step include copper, aluminum, nickel, vanadium, titanium, tantalum, chromium, cobalt, gold and tungsten. In the method for producing a laminate of the present invention, it is preferable that the second metal layer contains copper from the viewpoint of using the laminate of the present invention as the rewiring layer of the semiconductor element.

In the method for producing the laminate, the thickness of the second metal layer formed in the second metal layer forming step is, for example, 3 to 50 μm, preferably 3 to 10 μm, and 5 to 10 μm. Is more preferable, and 5 to 7 μm is particularly preferable. When producing a laminate for power semiconductor applications, the thickness of the second metal layer formed in the second metal layer forming step is preferably 35 to 50 μm.

The method for forming the second metal layer is not particularly limited, and an existing method can be applied. For example, the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used. For example, photolithography, lift-off, chemical vapor deposition (CVD), electroplating, electroless plating, etching, printing, and a combination method thereof can be considered. More specifically, a patterning method combining photolithography and etching, a patterning method combining photolithography and electroplating, and a patterning method combining photolithography, electroplating and etching can be mentioned.
As a patterning method that combines photolithography and electroplating, a seed layer of a metal layer formed in a metal layer forming step is formed by sputtering, and then a pattern of the seed layer is formed by photolithography, and the seed in which the pattern is formed is formed. A method of forming a second metal layer by electroplating on the layer is preferable. After that, further etching may be performed to remove the seed layer in the region where the second metal layer is not formed.

<Surface activation treatment process>
The method for producing the laminate may include a surface activation treatment step of surface activating at least a part of the metal layer and the photosensitive resin composition layer.
The surface activation treatment step is usually preferably performed after the metal layer forming step. After the above curing step, the photosensitive resin composition layer may be subjected to a surface activation treatment step, and then a metal layer may be formed.
The surface activation treatment may be performed on at least a part of the metal layer, on at least a part of the photosensitive resin composition layer after the curing step, or on the metal layer and the photosensitive after the curing step. For both of the sex resin composition layers, at least a part of each may be carried out. The surface activation treatment is preferably performed on at least a part of the metal layer, and the surface activation treatment is performed on a part or all of the region of the metal layer on which the photosensitive resin composition layer is further formed. Is more preferable. By performing the surface activation treatment on the surface of the metal layer in this way, the adhesion to the cured film provided on the surface can be improved.
Further, it is preferable that the surface activation treatment is performed on a part or all of the photosensitive resin composition layer (cured film) after the curing step. By performing the surface activation treatment on the surface of the photosensitive resin composition layer in this way, it is possible to improve the adhesion to the metal layer and the cured film provided on the surface activated surface. In the case of negative development, the exposed portion is subjected to surface treatment, and the strength of the film is improved by curing or the like, so that the photosensitive resin composition layer (cured film) is not damaged.
Specific examples of the surface activation treatment include plasma treatment of each type of raw material gas (oxygen, hydrogen, argon, nitrogen, nitrogen and hydrogen mixed gas, and argon and oxygen mixed gas); corona discharge treatment; CF. _{Etching treatment using 4} and O ₂ mixed gas, NF ₃ and O ₂ mixed gas, SF ₆ , NF ₃ , and NF ₃ and O ₂ mixed gas; surface treatment using ultraviolet (ultraviolet; UV) ozone method; aqueous hydrochloric acid solution Immersion treatment in an organic surface treatment agent containing a compound having at least one amino group and thiol group after removing the oxide film by immersing in the gas; preferably selected from mechanical roughening treatment using a brush. .. Plasma treatment is more preferable, and oxygen plasma treatment using oxygen as a raw material gas is particularly preferable. For corona discharge treatment, the energy is preferably 500~200000J / m ^2, more preferably 1000~100000J / m ^2, more preferably 10000~50000J / m ^2.

<Laminating process>
In the method for producing a laminate of the present invention, after the metal layer forming step, the photosensitive resin composition layer forming step, the exposure step, the developing process, the curing step, and the metal layer forming step are performed again in the above order. It is preferable to do so. In this case, since the metal layer forming step is repeated, the effect of suppressing delamination when the substrate, the cured film, and the metal layer are laminated is great.
In the present specification, a step of performing the photosensitive resin composition layer forming step, the exposure step, the developing treatment step, the curing step, and the metal layer forming step again in the above order after the metal layer forming step. , It is called a laminating process. The laminating step is more preferably a step in which the photosensitive resin composition layer forming step, the exposure step, the developing treatment step, the curing step, the metal layer forming step, and the second metal layer forming step are performed in the above order.

When the laminating step is further performed after the laminating step, the surface activation treatment step can be further performed after the exposure step or the metal layer forming step.
The laminating step is preferably performed 3 to 7 times, more preferably 3 to 5 times.
For example, a structure such as a cured film / metal layer / cured film / metal layer / cured film / metal layer is preferable, and the cured film is preferably 3 layers or more and 7 layers or less, and more preferably 3 layers or more and 5 layers or less. The more multi-layered the structure is, the more the photosensitive resin composition layer is exposed to repeated developing solutions, metal etching treatments, and high-temperature treatments in the curing step. , It has the effect of suppressing the occurrence of delamination at the cured film / cured film interface.
With such a configuration, the photosensitive resin composition layer (cured film) and the metal layer can be alternately laminated, and can be used as a multi-layer wiring structure of a semiconductor element such as a rewiring layer.
It is preferable that the photosensitive resin composition layer (cured film) becomes thicker as the lamination goes up.

[Laminate]
The laminate of the present invention has a substrate, a pattern-cured film, and a metal layer located on the surface of the pattern-cured film.
The pattern cured film contains polyimide or polybenzoxazole and contains
The invasion of the metal constituting the metal layer located on the surface of the pattern cured film into the pattern cured film is 130 nm or less from the surface of the pattern cured film.

<Pattern cured film>
The pattern cured film in the laminated body of the present invention is preferably a photosensitive resin composition layer after the curing step in the method for producing the laminated body of the present invention.

<< Tg >>
The glass transition temperature of the pattern cured film (photosensitive resin composition layer after the curing step) is preferably 150 to 300 ° C, more preferably 160 to 250 ° C, and particularly preferably 180 to 230 ° C. preferable.

<< Residual stress >>
Pattern cured film (photosensitive resin composition layer after curing step; preferably photosensitive resin composition layer after metal layer forming step. More preferably, photosensitive resin after metal layer forming step and second metal layer forming step. The residual stress measured according to the laser measurement method of the composition layer) is preferably less than 35 MPa, more preferably less than 25 MPa, and particularly preferably less than 15 MPa.

<Metal layer>
The metal layer in the laminate of the present invention is preferably a metal layer formed in the metal layer forming step in the method for producing the laminate of the present invention.
Further, the metal layer in the laminate of the present invention is composed of a metal layer formed in the metal layer forming step in the method for producing the laminate of the present invention and a second metal layer formed in the second metal layer forming step. It may be a laminated body. In this case, the metal layer formed in the metal layer forming step in the method for producing a laminated body of the present invention and the second metal layer formed in the second metal layer forming step are integrated to form the laminated body of the present invention. It may be a metal layer in.
Further, the metal layer formed in the metal layer forming step in the method for producing a laminate of the present invention is, for example, two layers of a barrier metal film and a seed layer, and a second metal layer formed in the second metal layer forming step. When the metal layer is the same type of metal as the seed layer, only the seed layer and the second metal layer may be integrated. In this case, the laminated body of the layer in which only the seed layer and the second metal layer are integrated and the barrier metal film may be the metal layer in the laminated body of the present invention.
The thickness of the metal layer in the laminate of the present invention is preferably 0.1 to 50 μm, more preferably 1 to 10 μm at the thickest portion.
The metal layer in the laminate of the present invention is preferably a flat metal layer from the viewpoint of stabilizing the film quality of the metal layer. By forming the metal layer by using the sputtering method, a flat metal layer can be formed. Further, the metal layer is formed by a sputtering method under the condition that the temperature of the photosensitive resin composition layer after the curing step when forming the metal layer is lower than the glass transition temperature of the photosensitive resin composition layer after the curing step. By doing so, a flatter metal layer can be formed.

<Invasion depth of metal pattern cured film>
The penetration depth of the metal constituting the metal layer located on the surface of the pattern cured film into the pattern cured film is 130 nm or less, preferably 50 nm or less, and more preferably 30 nm or less from the surface of the pattern cured film. preferable.

[Manufacturing method of semiconductor device]
The method for manufacturing a semiconductor device of the present invention includes the method for manufacturing a laminate of the present invention.
With the above configuration, the method for manufacturing a semiconductor device of the present invention can provide a semiconductor device in which delamination is suppressed when a substrate, a cured film, and a metal layer are laminated.

Hereinafter, an embodiment of the semiconductor device obtained by the method for manufacturing a semiconductor device of the present invention will be described.
FIG. 1 is a schematic view showing a configuration of an embodiment of a semiconductor device. The semiconductor element 100 shown in FIG. 1 is a so-called three-dimensional mounting device, and a semiconductor chip 101 in which a plurality of semiconductor chips 101a to 101d are laminated is arranged on a wiring board 120.
In this embodiment, the case where the number of laminated semiconductor chips is 4 is mainly described, but the number of laminated semiconductor chips is not particularly limited, and for example, 2 layers, 8 layers, 16 layers, etc. It may be 32 layers or the like. Moreover, it may be one layer.

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

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

An underfill layer 110 is formed in the gap between the semiconductor chips 101a to 101d, and the semiconductor chips 101a to 101d are laminated via the underfill layer 110.

The semiconductor chip 101 is laminated on the wiring board 120.
As the wiring board 120, for example, a multilayer wiring board using an insulating substrate such as a resin substrate, a ceramics substrate, or a glass substrate as a substrate is used. Examples of the wiring board 120 to which the resin substrate is applied include a multilayer copper-clad laminate (multilayer printed wiring board) and the like.

A surface electrode 120a is provided on one surface of the wiring board 120.
An insulating layer 115 on which a rewiring layer 105 is formed is arranged between the wiring board 120 and the semiconductor chip 101, and the wiring board 120 and the semiconductor chip 101 are electrically connected to each other via the rewiring layer 105. It is connected. As the insulating layer 115, the photosensitive resin composition layer (cured film) after the curing step in the present invention can be used. As the insulating layer 115 on which the rewiring layer 105 is formed, a laminate obtained by the method for producing a laminate of the present invention can be used.
One end of the rewiring layer 105 is connected to an electrode pad formed on the surface of the semiconductor chip 101d on the rewiring layer 105 side via a metal bump 103d such as a solder bump. Further, the other end of the rewiring layer 105 is connected to the surface electrode 120a of the wiring board via a metal bump 103e such as a solder bump.
An underfill layer 110a is formed between the insulating layer 115 and the semiconductor chip 101. Further, an underfill layer 110b is formed between the insulating layer 115 and the wiring board 120.

FIG. 2 is a schematic view showing the configuration of one embodiment of the laminated body obtained by the method for producing a laminated body of the present invention. Specifically, FIG. 2 shows an example in which the laminate obtained by the method for producing a laminate of the present invention is used as a rewiring layer. In FIG. 2, 200 indicates a laminate obtained by the method of the present invention, 201 indicates a photosensitive resin composition layer (cured film), and 203 indicates a metal layer. In FIG. 2, the metal layer 203 is a layer shown by diagonal lines. The photosensitive resin composition layer 201 is formed in a desired pattern by negative development. The metal layer 203 is formed so as to cover a part of the surface of the pattern, and the photosensitive resin composition layer (cured film) 201 is further laminated on the surface of the metal layer 203. Then, the photosensitive resin composition layer (cured film) acts as an insulating layer, the metal layer acts as a rewiring layer, and is incorporated as a rewiring layer in the semiconductor element as described above.

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass.

[Example 1]
<Synthesis of polyimide precursor>
<< Synthesis of polyimide precursor Aa-1 (polyimide precursor having a radically polymerizable group) from 4,4'-oxydiphthalic dianhydride, 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) of SOCL ₂ was added over 10 minutes while keeping the temperature at −10 ± 4 ° C. The reaction mixture was diluted with 50 ml N-methylpyrrolidone and then the reaction mixture was stirred at room temperature for 2 hours. Then, a solution prepared by dissolving 11.08 g (58.7 mmol) of 4,4′-oxydianiline 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 at room temperature overnight. The reaction mixture was then added to 5 liters of water to precipitate the polyimide precursor. The mixture of water and polyimide precursor was stirred at a rate of 5000 rpm for 15 minutes. The mixture of water and 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 polyimide precursor was stirred again for 30 minutes and filtered again to give 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 >>
Resin: Polyimide precursor (Aa-1) 32 parts by mass polymerizable compound B-1 6.9 parts by mass Photopolymerization initiator C-1 1.0 parts by mass Polymerization inhibitor: Parabenzoquinone (manufactured by Tokyo Chemical Industry) 0. 08 parts by mass migration inhibitor: 1H-tetrazole (manufactured by Tokyo Chemical Industry)
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: 12.00 parts by mass of dimethyl sulfoxide

<< Composition of Photosensitive Resin Composition A-2 >>
Resin: Polyimide precursor (Aa-1) 32 parts by mass polymerizable compound B-1 6.9 parts by mass Photopolymerization initiator C-1 1.0 parts by mass Polymerization inhibitor: 2,6-di-tert-butyl- 4-Methylphenol (manufactured by Tokyo Kasei Kogyo) 0.1 parts by mass Migration inhibitor: 1H-1,2,4-triazole (manufactured by Tokyo Kasei Kogyo) 0.1 parts by mass Solvent: γ-butyrolactone 48.00 parts by mass Solvent : 12.00 parts by mass of dimethyl sulfoxide

The details of each additive are as follows.
B-1: NK ester A-9300 (manufactured by Shin Nakamura Chemical Industry Co., Ltd., trifunctional acrylate, structure below)

(C) Photopolymerization Initiator C-1: Compound 24 described in paragraph 0345 of JP-A-2014-500852.

<Filtration process>
Each photosensitive resin composition was pressure-filtered through a filter having a pore width of 0.8 μm.

<Photosensitive resin composition layer forming process>
Then, each photosensitive resin composition was applied onto a silicon wafer by a spin coating method to form a layer, and a photosensitive resin composition layer was formed.

<Drying process>
The silicon wafer having the obtained photosensitive resin composition layer was dried on a hot plate at 100 ° C. for 5 minutes to obtain a uniform photosensitive resin composition layer having a thickness of 20 μm on the silicon wafer.

<Exposure process>
Next, the photosensitive resin composition layer on the silicon wafer was exposed using a stepper (Nikon NSR 2005 i9C) at an exposure wavelength of 365 nm (i-line) with ^{an exposure energy of 500 mJ / cm 2} (uniform irradiation over the entire surface). ..
In this embodiment, in order to facilitate the measurement of stress, the entire surface is exposed with uniform irradiation, immersed in a developing solution, and a cured film is formed through a curing step. However, a cured film in which a pattern is formed may be formed through a curing step by exposing the pattern and immersing it in a developing solution to remove an unexposed portion.
When the photosensitive resin composition layer is patterned, more interfaces are generated than when the photosensitive resin composition layer is not patterned, and there are places where the contact area is small between the layers when the substrate, the cured film, and the metal layer are laminated. In this case, delamination is more likely to occur, and the effect of the present invention can be obtained more remarkably.

<Development process>
The fully exposed photosensitive resin composition layer was immersed in cyclopentanone for 60 seconds for development treatment.

<Curing process>
Next, the photosensitive resin composition layer after the development treatment was cured by the following methods (1) to (4).

<< (1) Temperature rise step >>
First, in a nitrogen atmosphere having an oxygen concentration of 20% by volume or less, a substrate having a photosensitive resin composition layer after development treatment is placed on a temperature-adjustable plate, and the temperature rises from room temperature (20 ° C.) to 10 ° C./min. The temperature was raised at a temperature rate, and the temperature was raised to the final reached temperature of 230 ° C. over 21 minutes.

<< (2) Holding process >>
Then, the photosensitive resin composition layer was maintained at 230 ° C., which is the final temperature reached in the temperature raising step (holding temperature), for 3 hours.

<< (3) Cooling process >>
The photosensitive resin composition layer after heating for 3 hours in the holding step was slowly cooled from 230 ° C. to 2 ° C./min at a temperature lowering rate of 230 ° C. over 30 minutes to the final temperature reached 170 ° C. in the cooling step.

<< (4) Step to bring to room temperature >>
After the photosensitive resin composition layer reached the final temperature of 170 ° C. in the cooling step, the photosensitive resin composition layer was cooled at a cooling rate of 5 to 10 ° C./min to bring it to room temperature to obtain a cured film. ..

<Metal layer forming process>
Next, in a sputtering apparatus (manufactured by AMAT, product name Endura), the temperature of the photosensitive resin composition layer is 150 ° C. on the photosensitive resin composition layer after the curing step by using a sputtering method. A 100 nm film of Ti was formed to form a first metal layer to be used as a barrier metal film, and a 300 nm film of Cu was continuously formed to form a second metal layer to be used as a seed layer.
The thickness of the entire metal layer formed in the metal layer forming step using the sputtering method was 400 nm.
In the sputtering device, the temperature of the photosensitive resin composition layer is the temperature of the surface of the photosensitive resin composition layer, and a sticker (Thermolabel, Nichiyu Giken Kogyo Co., Ltd.) that changes color with temperature is attached to the surface. It was measured and calculated by observing the change.

<Second metal layer forming process>
Next, a dry film resist (manufactured by Hitachi Kasei Co., Ltd., trade name Photoc RY-3525) was attached onto the seed layer with a roll laminator, and the photo tool forming the pattern was brought into close contact with the EXM-1201 manufactured by ORC Manufacturing Co., Ltd. Exposure was performed with an energy amount of ^{100 mJ / cm 2} using a mold exposure machine. Then, spray development was carried out for 90 seconds with a 1% by mass sodium carbonate aqueous solution at 30 ° C. to open a dry film resist. Next, a copper plating layer having a thickness of 7 μm was formed on the dry film resist and on the seed layer in the portion where the dry film resist was opened by using the electrolytic copper plating method. Then, the dry film resist was peeled off using a stripping solution. Next, the seed layer (300 nm Cu layer) of the portion where the dry film resist was peeled off was removed using an etching solution to form a patterned metal layer on the surface of the photosensitive resin composition layer after the curing step. ..

<Characteristics of cured film>
<< Measurement of glass transition temperature >>
The glass transition temperature of the photosensitive resin composition layer (cured film) after the curing step was measured by the following method.
It was set in a dynamic viscoelasticity measuring device, and the temperature was raised from 0 ° C. to 350 ° C. at a heating rate of 10 ° C./min at a tensile method and a frequency of 1 Hz, and Tg was determined from the peak temperature of tan δ.
The results obtained are shown in Table 1 below.

<< Measurement of stress >>
The stress of the photosensitive resin composition layer (cured film) after the metal layer forming step and the second metal layer forming step was measured by the following method.
For the silicon wafer before coating the photosensitive resin composition layer, the wafer was set in a thin film stress measuring device and laser scanned at room temperature to obtain a blank value.
A wafer on which the photosensitive resin composition layer (cured film) is formed after the metal layer forming step and the second metal layer forming step is set in the thin film stress measuring device, and after laser scanning at room temperature, the photosensitive resin composition layer is formed. The stress was measured from the film thickness and the radius of curvature by comparing with the blank value before coating.
The results obtained are shown in Table 1 below.

<Laminating process>
Further, on the surface where the unevenness is formed by the metal layer and the photosensitive resin composition layer after the curing step, the same photosensitive resin composition is used again and cured from the filtering step of the photosensitive resin composition in the same manner as described above. The procedure up to the step was carried out again to form a laminate having two layers of the photosensitive resin composition after the curing step.
Further, the metal layer forming step and the second metal layer forming step were carried out again in the same manner as described above for the laminated body having two layers of the photosensitive resin composition layer after the curing step to form the laminated body.

<Evaluation of laminated body>
<< Measurement of metal penetration depth >>
For the laminate after the metal layer forming step and the second metal layer forming step, the penetration length of the metal into the cured film after the metal layer forming step using the sputtering method was measured by the following method.
Focused ion beam (FIB) and transmission electron microscope (TEM) are used to measure the length by direct observation of the cross-sectional view, and high-angle scattered dark-field scanning transmission electron microscope (high-angle annal dark-field scanning transmission electron spectroscopy). Element analysis was performed using a combination of microscope (HAADF-STEM) and electron energy loss spectroscopy (EELS).
The results obtained are shown in Table 1 below.

<< Peeling test after cycle test >>
The peeling test after the cycle test was performed on the laminated body after the laminating step by the following method.
Each laminate was cooled in nitrogen at −55 ° C. for 30 minutes and then heated at 125 ° C. for 30 minutes for 500 cycles. After that, each laminated body has a width of 5 mm in the direction perpendicular to the surface of the cured film, and the portion where the cured film and the metal layer are in contact is in contact with the metal layer and the second metal layer. Each part was cut out, and the cross section thereof was observed, and the presence or absence of peeling between the cured film and the metal layer and between the metal layer and the second metal layer in one cut piece was confirmed with an optical microscope. .. It is preferably "no peeling".
The results obtained are shown in Table 1 below.

[Examples 2 to 6 and Comparative Examples 1 to 3]
Laminates of Examples 2 to 6 and Comparative Examples 1 to 3 were produced in the same manner as in Example 1 except that the conditions shown in the table below were changed.
In the same manner as in Example 1, the characteristics of the cured film were measured and the laminate was evaluated.

From Table 1 above, when the temperature of the photosensitive resin composition layer after the curing step when forming the metal layer is lower than the glass transition temperature of the photosensitive resin composition layer after the curing step, the residual stress of the cured film It was found that a laminate having a small metal penetration length after the metal layer forming step using the sputtering method can be provided. It was found that the laminate of the present invention having a small residual stress of the cured film and a short metal penetration length can suppress delamination when the substrate, the cured film and the metal layer are laminated.
On the other hand, from Comparative Examples 1 to 3, when the temperature of the photosensitive resin composition layer after the curing step when forming the metal layer is equal to or higher than the glass transition temperature of the photosensitive resin composition layer after the curing step, the curing is performed. A laminated body having a large residual stress of the film and a long metal penetration length after the metal layer forming step using the sputtering method was obtained. It was found that in the laminated bodies of Comparative Examples 1 to 3 in which the residual stress of the cured film was large and the penetration depth of the metal was long, delamination occurred when the substrate, the cured film and the metal layer were laminated.

In Example 1, the metal layer (copper thin film) was changed to an aluminum thin film, and the others were carried out in the same manner. As a result, good results were obtained as in Example 1.
In Example 1, except that the solid content concentration of the photosensitive resin composition 1 was reduced to 1/10 without changing the composition ratio and spray-coated using a spray gun (“NanoSpray” manufactured by Austrian EV Group (EVG)). , A laminate was formed in the same manner as in Example 1. The same excellent effect as in Example 1 was obtained.
In the production of the laminate of Example 1, the laminate was produced in the same manner as in Example 1 except that the laminate was heated at 100 ° C. for 10 minutes (pretreatment) before being heated at 230 ° C. for 3 hours. The characteristics were evaluated. An excellent effect was obtained as in Example 1.
In the production of the laminate of Example 1, the laminate was produced in the same manner as in Example 1 except that the laminate was heated at 150 ° C. for 10 minutes (pretreatment) before being heated at 230 ° C. for 3 hours. The characteristics were evaluated. An excellent effect was obtained as in Example 1.
In the production of the laminate of Example 1, the same procedure as in Example 1 was carried out except that the laminate was heated at 180 ° C. for 10 minutes (pretreatment) while being irradiated with UV light before being heated at 230 ° C. for 3 hours. A laminate was manufactured and its properties were evaluated. An excellent effect was obtained as in Example 1.

The laminate produced by the method for producing a laminate of the present invention can suppress delamination when the substrate, the cured film, and the metal layer are laminated. Further, the laminate produced by the method for producing a laminate of the present invention can suppress delamination even when two or more pairs of a substrate, a cured film and a metal layer are laminated. Such a laminate can be used for manufacturing an interlayer insulating layer for a rewiring layer of a semiconductor element, and can provide an interlayer insulating layer for a rewiring layer in which delamination is suppressed. Further, such a laminate is used to manufacture an interlayer insulating layer for power semiconductors, a copper pillar middle film or a single layer insulating layer for a three-dimensional IC (Three-Dimensional Integrated Circuit), and an interlayer insulating layer for panels. Available.

100: Semiconductor elements 101, 101a-101d: Semiconductor chips 102b, 102c, 102d: Through electrodes 103a-103e: Metal bumps 105: Rewiring layers 110, 110a, 110b: Underfill layer 115: Insulation layer 120: Wiring board 120a: Surface electrode 200: Laminated body 201: Photosensitive resin composition layer (cured film)
203: Metal layer

Claims (11)

A step of forming a photosensitive resin composition layer, in which the photosensitive resin composition is applied to a substrate to form a layer,
An exposure step for exposing the photosensitive resin composition layer applied to the substrate, and
A developing process for performing a developing process on the exposed photosensitive resin composition layer, and
A curing step of curing the photosensitive resin composition layer after development, and
The metal layer forming step of forming a metal layer by vapor phase film formation on the surface of the photosensitive resin composition layer after the curing step is performed in the above order.
The metal layer temperature of the photosensitive resin composition layer at the time of forming the rather low 30 ° C. or higher than the glass transition temperature of the photosensitive resin composition layer,
Further, a method for producing a laminate, which comprises performing the photosensitive resin composition layer forming step, the exposure step, the developing treatment step, the curing step, and the metal layer forming step again in the above order. A step of forming a photosensitive resin composition layer, in which the photosensitive resin composition is applied to a substrate to form a layer,
An exposure step for exposing the photosensitive resin composition layer applied to the substrate, and
A developing process for performing a developing process on the exposed photosensitive resin composition layer, and
A curing step of curing the photosensitive resin composition layer after development, and
The metal layer forming step of forming a metal layer by vapor phase film formation on the surface of the photosensitive resin composition layer after the curing step is performed in the above order.
The temperature of the photosensitive resin composition layer when forming the metal layer is 30 ° C. or more lower than the glass transition temperature of the photosensitive resin composition layer.
A method for producing a laminate in which a crosslinked structure of the photosensitive resin composition is constructed by exposure and the solubility in an organic solvent is reduced. The method for producing a laminate according to claim 1 or 2 , wherein the photosensitive resin composition contains at least one resin selected from a polyimide precursor, a polyimide, a polybenzoxazole precursor, and polybenzoxazole. The method for producing a laminate according to any one of claims 1 to 3 , further comprising a second metal layer forming step of forming a second metal layer on the surface of the metal layer. The method for producing a laminate according to claim 4 , wherein the second metal layer contains copper. The method for producing a laminate according to any one of claims 1 to 5 , wherein the metal layer contains at least one of titanium, tantalum and copper, and a compound containing at least one of these. The method for producing a laminate according to any one of claims 1 to 6 , wherein the thickness of the metal layer formed in the metal layer forming step is 50 to 2000 nm. The method for producing a laminate according to any one of claims 1 to 7 , wherein the residual stress measured according to the laser measurement method of the photosensitive resin composition after the curing step is less than 35 MPa. The method for producing a laminate according to any one of claims 1 to 8 , wherein the photosensitive resin composition is for negative development. The curing step includes a heating step of raising the temperature of the photosensitive resin composition layer and a holding step of holding the photosensitive resin composition layer at a holding temperature equal to the final reached temperature of the raising step.
The method for producing a laminate according to any one of claims 1 to 9 , wherein the holding temperature in the holding step is 250 ° C. or lower. A method for manufacturing a semiconductor device, which comprises the method for manufacturing a laminate according to any one of claims 1 to 10.

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