JP6901596B2 - Manufacturing method of laminate and manufacturing method of semiconductor device - Google Patents

Description

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

Thermosetting resins such as polyimide resins and polybenzoxazole resins are used as insulating layers of semiconductor devices because they have excellent heat resistance and insulating properties.
In addition, since the polyimide resin and polybenzoxazole resin have low solubility in a solvent, they are used in the state of a precursor (polyimide precursor or polybenzoxazole precursor) before the cyclization reaction, and after being applied to a substrate or the like. , The polyimide precursor is cyclized by heating to form a cured film.

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

International Publication WO2004 / 050352 Gazette

Here, assuming that the thermoplastic polyimide resin described in Patent Document 1 is used as the interlayer insulating film for the rewiring layer of the semiconductor device, it is on the laminate composed of the thermoplastic polyimide layer and the metal layer on the surface of the thermoplastic polyimide layer. Further, it is necessary to provide a thermoplastic polyimide layer. However, when it was examined to further provide a thermoplastic polyimide layer on the above-mentioned laminate in Patent Document 1, the adhesion between the thermoplastic polyimide layer and the metal layer or the thermoplastic polyimide layers is insufficient. It turned out.
An object of the present invention is to solve such a problem, and a method for producing a laminate having excellent adhesion between a resin layer containing a resin such as polyimide and a resin layer, or a resin layer and a metal layer. , And, an object of the present invention is to provide a method for manufacturing a semiconductor device including the above-mentioned manufacturing method.

As a result of studies by the present inventor based on the above problems, it has been found that the above problems can be solved by negatively developing the photosensitive resin composition to form a resin layer. Specifically, the above problems were solved by the following means <1>, preferably by <2> to <8>.
<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 step of exposing the photosensitive resin composition layer, a development treatment step of performing a negative type development treatment on the exposed photosensitive resin composition layer, and a photosensitive resin composition after the development treatment. A metal layer forming step of forming a metal layer on the surface of the layer and a surface activating treatment step of surface activating at least a part of the metal layer and the photosensitive resin composition layer are included, and further, again. The photosensitive resin composition layer forming step, the exposure step, and the development treatment step are performed in the above order, and the photosensitive resin composition is a polyimide precursor, a polyimide, a polybenzoxazole precursor, and a poly. A method for producing a laminate, which comprises a resin selected from benzoxazole, further satisfies at least one of the above-mentioned resin containing a polymerizable group and the above-mentioned photosensitive resin composition containing a polymerizable compound.
<2> The method for producing a laminate according to <1>, wherein the photosensitive resin composition layer forming step, the exposure step, and the developing treatment step are performed 3 to 7 times in the above order.
<3> The method for producing a laminate according to <1> or <2>, wherein the metal layer contains copper.
<4> The method for producing a laminate according to any one of <1> to <3>, wherein the resin is a polyimide precursor or a polybenzoxazole precursor.
<5> The method for producing a laminate according to any one of <1> to <4>, wherein the resin contains a partial structure represented by -Ar-L-Ar-; however, Ar is independent of each other. , an aromatic group, L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O -, - CO -, - S -, - SO 2 - or -NHCO -Or, it is a group consisting of a combination of two or more of the above.
<6> The method for producing a laminate according to any one of <1> to <5>, wherein the surface activation treatment is selected from plasma treatment and corona discharge treatment.
<7> The method for producing a laminate according to any one of <1> to <6>, wherein the photosensitive resin composition contains a photopolymerization initiator.
<8> A method for manufacturing a semiconductor device, which comprises the method for manufacturing a laminate according to any one of <1> to <7>.

INDUSTRIAL APPLICABILITY The present invention provides a method for producing a laminate having excellent adhesion between a resin layer and a resin layer, or a resin layer and a metal layer, and a method for producing a semiconductor device including the above-mentioned production method.

It is a schematic diagram which shows the structure of one Embodiment of a semiconductor device. It is the schematic which shows the structure of one Embodiment of the laminated body obtained by the manufacturing method 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 a group having a substituent as well as a group having no substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
Unless otherwise specified, the term "exposure" as used herein includes not only exposure using light but also drawing using particle beams such as an electron beam and an ion beam. 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" represents both "acrylate" and "methacrylate", or either, and "(meth) allyl" means both "allyl" and "metharyl", or. "(Meta) 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" not only refers to an independent process, but also refers to the term as long as the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. include.
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 measured by gel permeation chromatography (GPC) 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.

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 step of exposing the photosensitive resin composition layer, and the above. A development treatment step of performing a negative type development treatment on the exposed photosensitive resin composition layer, a metal layer formation step of forming a metal layer on the surface of the photosensitive resin composition layer after the development treatment, and the above. The surface activation treatment step of surface-activating at least a part of the metal layer and the photosensitive resin composition layer is included, and further, the photosensitive resin composition layer forming step, the exposure step, and the development treatment are performed again. The steps include performing the steps in the above order, wherein the photosensitive resin composition comprises a resin selected from a polyimide precursor, a polyimide, a polybenzoxazole precursor and a polybenzoxazole.
Further, the resin is characterized by containing a polymerizable group, and the photosensitive resin composition is characterized by containing at least one of a polymerizable compound.
As described above, when the insulating films are laminated, the adhesion between the layers can be improved by performing negative type development and further surface activating treatment. On the other hand, in Patent Document 1, there is no example in which such a resin layer is laminated. Further, in Patent Document 1, since positive development is performed and the exposed portion is alkaline-developed, the adhesion tends to be insufficient. Further, when positive development is performed, it is presumed that the unexposed portion of the resin layer is subjected to surface activation treatment, the photosensitive resin composition (resin layer) is easily damaged, and the adhesion is deteriorated. .. On the other hand, in the negative type, a three-dimensional crosslinked structure can be formed, the strength of the film can be increased, and the surface activation treatment can be less likely to be damaged.
Based on the above, in the present invention, by adopting the above means, high adhesion between the resin layer and the resin layer and between the resin layer and the metal layer can be achieved even in a multilayer structure.
The details of the present invention will be described below.

<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 spin coating method, a slit scan method, and an inkjet method. Is exemplified. From the viewpoint of the uniformity of the thickness of the photosensitive resin composition layer, the spin coating method is more preferable. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 2000 rpm for about 10 seconds to 1 minute.
The thickness of the photosensitive resin composition layer (resin layer) is preferably 0.1 to 100 μm after exposure, and more preferably 1 to 50 μm. Further, as shown in FIG. 2 described later, 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, the resin layers will have different thicknesses as shown in FIG. In particular, when a plurality of layers are laminated, a recess having a large depth can be formed as the recess, but the present invention has high technical value in that peeling between layers can be more effectively suppressed with respect to such a configuration. When the laminate of the present invention has resin layers having different thicknesses, it is preferable that the thickness of the resin layer in the thinnest portion is the above thickness.
The type of substrate can be appropriately determined depending on the application, but semiconductor fabrication substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, thin film, and magnetic film. , Reflective film, metal substrate such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, electrode plate of plasma display panel (PDP), 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 resin layer or the surface of the metal layer, the resin layer or the metal layer serves as a substrate.
Details of the photosensitive resin composition will be described later.

<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, various materials may be filtered a plurality of times, and the step of filtering the various materials a plurality of times may be a circulation filtration step. Further, pressurization may be performed for filtration, and the pressurization pressure is preferably 0.05 MPa or more and 0.3 MPa or less.
In addition to filtration using a filter, impurities may be removed using an adsorbent, or filter filtration and an adsorbent may be used in combination. 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.

<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 ° C to 130 ° C, still more preferably 90 ° C to 110 ° C. The drying time is preferably 30 seconds to 20 minutes, more preferably 1 minute to 10 minutes, still more preferably 3 minutes to 7 minutes.

<Exposure process>
The method for producing a laminate of the present invention includes an exposure step of exposing the photosensitive resin composition layer. Exposure is not particularly limited so long as it can cure the photosensitive resin composition, for example, it is preferable that 100~10,000mJ / cm ² is irradiated at exposure energy conversion at a wavelength 365nm, 200~8000mJ / cm ² irradiation It is more preferable to do so.
The exposure wavelength can be appropriately determined in the range of 190 to 1000 nm, preferably 240 to 550 nm.

<Development process>
The method for producing a laminate of the present invention includes a development treatment step in which a negative type development treatment is performed on the exposed photosensitive resin composition layer. By performing negative type development, the unexposed portion (non-exposed portion) is removed. Development is carried out using a developing solution. The developing solution can be used without particular limitation as long as it can remove an unexposed portion (non-exposed portion). Solvents are preferred and the esters include, 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, γ-butyrolactone. , Ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (eg, methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.) )), 3-alkoxypropionate alkyl esters (eg, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionate) Methyl, ethyl 3-ethoxypropionate, etc.)), 2-alkoxypropionate alkyl esters (eg, methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (eg, 2-methoxy) Methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and 2-alkoxy-2 -Ethyl methyl propionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, acetoacetate Ethyl, 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 acetate, etc., and as ketones, for example, methylethyl Luctone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc., and sulfoxides. Preferable examples thereof include dimethyl sulfoxide, ethyl carbitol acetate, and butyl carbitol acetate. Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone. , Dimethylsulfoxide, ethylcarbitol acetate, butylcarbitol acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate are preferable, and cyclopentanone and γ-butyrolactone are more preferable.
The developing 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.

<Heating process>
The method for producing a laminate of the present invention preferably includes a heating step. In the heating step, the cyclization reaction of the polyimide precursor and the polybenzoxazole precursor proceeds. Polyimide and polybenzoxazole form a three-dimensional network structure when heated with a cross-linking agent. In addition, curing of unreacted radically polymerizable compounds also proceeds. The maximum heating temperature is preferably 100 to 500 ° C, more preferably 140 to 400 ° C, and even more preferably 160 to 350 ° C.
The heating is preferably performed at a heating rate of 1 to 12 ° C./min from a temperature of 20 to 150 ° C. to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min. 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 means the temperature at which the process of heating to the maximum heating temperature is started. 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 a temperature 30 to 200 ° C. lower than the boiling point of the solvent contained in the photosensitive resin composition. It is preferable to raise the temperature to.
After reaching the maximum heating temperature, heating is preferably performed for 10 to 360 minutes, more preferably 20 to 300 minutes, and particularly preferably 30 to 240 minutes.

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

It is preferable that the heating step is 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 polyimide precursor and the like. The oxygen concentration is preferably 50 ppm (v / v) or less, and more preferably 20 ppm (v / v) or less.

<< 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 the development treatment.
The metal layer is not particularly limited, and existing metal species can be used, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are exemplified, copper and aluminum are more preferable, and copper Is even more preferable.
The method for forming the metal layer is not particularly limited, and an existing method can be applied. For example, the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used. For example, photolithography, lift-off, electroplating, electroless plating, etching, printing, and a combination method thereof can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electroplating can be mentioned.
The thickness of the metal layer is preferably 0.1 to 50 μm at the thickest portion, and more preferably 1 to 10 μm.

<Surface activation treatment process>
The method for producing a laminate of the present invention includes 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 performed after the metal layer formation step, but after the exposure development step, the photosensitive resin composition layer may be subjected to the surface activation treatment step and then the metal layer formation step. Good.
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 exposure, or on the metal layer and the photosensitive resin after exposure. For both of the composition layers, each may be at least partially. The surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable to perform the surface activation treatment on a part or all of the region of the metal layer in which the photosensitive resin composition layer is formed on the surface. .. By performing the surface activation treatment on the surface of the metal layer in this way, the adhesion to the resin layer 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 (resin layer) after exposure. By performing the surface activating treatment on the surface of the photosensitive resin composition layer in this way, it is possible to improve the adhesion to the metal layer or the resin layer provided on the surface of the surface activating treatment. In particular, when positive development is performed, the unexposed portion is subjected to a surface activation treatment, the photosensitive resin composition (resin layer) is easily damaged, and the adhesion is deteriorated. In the present invention, since the negative type development is performed, 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 (resin layer) is not damaged. There is no such problem.
Specifically, the surface activation treatment includes plasma treatment of various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixed gas, argon / oxygen mixed gas, etc.), corona discharge treatment, CF ₄ / O ₂ , NF ₃ / O ₂ , SF ₆ , NF ₃ , NF ₃ / O ₂ , surface treatment by ultraviolet (UV) ozone method, immersion in hydrochloric acid aqueous solution to remove oxide film, then amino group and thiol group It is selected from a dipping treatment in an organic surface treatment agent containing at least one compound and a mechanical roughening treatment using a brush, and a plasma treatment is preferable, and an oxygen plasma treatment using oxygen as a raw material gas is particularly preferable. For corona discharge treatment, the energy is preferably 500~200,000J / ^{m 2,} more preferably ^{1000~100,000J / m 2, 10,000~50,000J / m} 2 is most preferred.

<Laminating process>
The production method of the present invention further includes the following laminating step.
The laminating step is a series of steps including performing the photosensitive resin composition layer forming step, the exposure step, and the developing treatment step again in the above order. That is, it goes without saying that the laminating step may further include the drying step, the heating step, and the like.
When the laminating step is further performed after the laminating step, it is preferable to further perform the surface activation treatment step 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 resin layer / metal layer / resin layer / metal layer / resin layer / metal layer is preferable, and the resin layer is preferably 3 layers or more and 7 layers or less, and more preferably 3 layers or more and 5 layers or less. If the number of layers is two or less, they may be sufficiently adhered without oxygen plasma treatment, but the more multi-layered the structure is, the more it is exposed to repeated developing solutions, metal etching treatments, and high-temperature treatments by curing. Peeling is likely to occur at the layer interface and the resin layer / resin layer interface.
With such a configuration, the photosensitive resin composition layer (resin layer) and the metal layer can be alternately laminated, and can be used as a multi-layer wiring structure of a semiconductor.

<Photosensitive resin composition>
The photosensitive resin composition used in the present invention (hereinafter, may be referred to as “composition used in the present invention”) is a resin selected from a polyimide precursor, a polyimide, a polybenzoxazole precursor, and a polybenzoxazole (hereinafter, referred to as “composition”). It may be referred to as "polyimide precursor or the like"), and preferably contains a polyimide precursor or a polybenzoxazole precursor, and more preferably contains a polyimide precursor.
Further, it satisfies at least one of the fact that the resin such as the polyimide precursor contains a polymerizable group and that the photosensitive resin composition contains a polymerizable compound. In particular, it is preferable that the resin such as the polyimide precursor contains a polymerizable group and 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, the photosensitive resin composition (resin layer) is not damaged by the surface activation treatment, and the surface activation treatment is performed. , Adhesion is improved more effectively.
Furthermore, it is preferable that the resin such as the polyimide precursor 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 (preferably an alkylene group), −O−, which may be substituted with a fluorine atom. -CO-, _{-S-, -SO 2-} or -NHCO-, or a group consisting of a combination of two or more of the above. With such a configuration, the resin layer has a flexible structure, and the effect of suppressing the occurrence of peeling is more effectively exhibited. Ar is a phenylene group is preferably, L is an aliphatic hydrocarbon group which optionally or 1 carbon atoms which may disubstituted by fluorine atoms, -O -, - CO -, - S- or -SO ₂ - is preferred ..
Hereinafter, the details of the photosensitive resin composition used in the present invention will be described.

式（２）中、Ａ^１およびＡ^２は、それぞれ独立に、酸素原子またはＮＨを表し、Ｒ^１１１は、２価の有機基を表し、Ｒ^１１５は、４価の有機基を表し、Ｒ^１１３およびＲ^１１４は、それぞれ独立に、水素原子または１価の有機基を表す。 << Polyimide precursor >>
The type of the polyimide precursor used in the present invention is not particularly specified, but 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 represent a hydrogen atom or a monovalent organic group.

^{A 1} and A ² in the formula (2) independently represent an oxygen atom or NH, and an oxygen atom is preferable.
^{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 60 carbon atoms is more preferable. As a particularly preferable embodiment of the present invention, a group represented by -Ar-L-Ar- is exemplified. 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-, or a group consisting of a combination of two or more of the above. These preferred ranges are as described above.

R ¹¹¹ is preferably derived from diamine. Examples of the diamine used for producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one kind of diamine may be used, or two or more kinds of diamines may be used.
Specifically, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group 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 60 carbon atoms. Examples of aromatic groups include:

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

In the formula, 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 are preferable, and 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 -, - C More preferably, it is a divalent group selected from the group consisting of (CF ₃ ) _2- and −C (CH ₃ ) _2-.

Specific examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1 , 3-Diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4-) Aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- Or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'-and 3,3'-diaminodiphenylmethane, 4,4'-and 3,3'-diamino Diphenylsulfone, 4,4'-and 3,3'-diaminodiphenylsulfide, 4,4'-or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2 '-Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) ) Hexafluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2-bis (3-amino) -4-Hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) ) Sulfur, 4,4'-diaminoparaterphenyl, 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'-diaminodiphenylsulfone, 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-p-phenylenediamine, acetoguanamine, 2,3,5,6- Tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, 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-Dimethylphenyl] Hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-bis (trifluoromethyl) phenyl] Hexafluoropropane, p-bis (4-amino-2-) Trifluoromethylphenoxy) benzene, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-4'-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'-hexafluorotrizine and 4,4'''-diaminoquaterphenyl At least one diamine selected from.

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 Co., Ltd.), 1- (2- (2- (2-) Examples thereof include (2-aminopropoxy) ethoxy) propoxy) propoxy) propoxy) and 1- (1- (1- (2-aminopropoxy) propoxy-2-yl) oxy) propan-2-amine. Not limited to.
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 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 (preferably an alkylene group), −O−, which may be substituted with a fluorine atom. -CO-, _{-S-, -SO 2-} or -NHCO-, or 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.

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

式（６１）中、Ｒ^１８およびＲ^１９は、それぞれ独立に、フッ素原子またはトリフルオロメチル基である。
式（５１）または（６１）の構造を有す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種でまたは２種以上を組み合わせて用いてもよい。 Further, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61) from the viewpoint of i-ray transmittance. In particular, from the viewpoint of i-ray transmittance and availability, a divalent organic group represented by the formula (61) is more preferable.
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, methyl group or trifluoro. It is a methyl group.
The ^{monovalent organic groups of R 10 to} R ¹⁷ include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples thereof include an alkyl fluoride group.
Equation (61)

In formula (61), R ¹⁸ and R ¹⁹ are independently fluorine atoms or trifluoromethyl groups, respectively.
Examples of the diamine compound having the structure of the formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2'-. Examples thereof include bis (fluoro) -4,4'-diaminobiphenyl and 4,4'-diaminooctafluorobiphenyl. These may be used alone or in combination of two or more.

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

Equation (6)

式（０）中、Ｒ^１１５は、４価の有機基を表す。Ｒ^１１５の好ましい範囲は式（２）におけるＲ^１１５と同義であり、好ましい範囲も同様である。 Specific examples of R ¹¹⁵ 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 (0).
Equation (O)

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

Specific examples of the tetracarboxylic dianhydride include pyromellitic dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-. Diphenylsulfide tetracarboxylic 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-naphthalenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2 , 2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,5-tetracarboxylic dianhydride, 1,4,5, 6-naphthalenetetracarboxylic dianhydride, 2,2', 3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4 5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthenetetracarboxylic dianhydride, 1,1-bis (2, 3-dicarboxyphenyl) ethanedianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethanedianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and these Examples thereof include alkyl having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

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 has an OH group.} More specifically, ^{as R 111} , a residue of a bisaminophenol derivative can be mentioned.

R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, ^{and it is preferable that at least one of R 113} and R ¹¹⁴ contains a polymerizable group, and both contain a polymerizable group. preferable. The polymerizable group is a group capable of a cross-linking reaction by the action of heat, radicals, etc., and 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. The group is mentioned. As the radically polymerizable group contained in the polyimide precursor or the like, 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), ^R200 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 and R ¹¹⁴ independently represent a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include an aromatic group and an aralkyl group having one, two or three, preferably one acidic group bonded to the carbon constituting the aryl group. 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 an OH group.
R ¹¹³ or R ¹¹⁴ is preferably a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl.

From the viewpoint of solubility in an organic solvent, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. The alkyl group preferably has 1 to 30 carbon atoms. The alkyl group may be linear, branched or cyclic. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group and an octadecyl group. , Isobutyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, 2-ethylhexyl group, 2- (2- (2-methoxyethoxy) ethoxy) ethoxy group, 2- (2-( 2-ethoxyethoxy) ethoxy) ethoxy) ethoxy group, 2- (2- (2- (2-methoxyethoxy) ethoxy) ethoxy) ethoxy group, and 2- (2- (2- (2-ethoxyethoxy) ethoxy) Ethoxy) ethoxy group is mentioned. The cyclic alkyl group 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 include substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, inden ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, and anthracene. Ring, naphthalene ring, chrysene ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indridin ring. , Indol ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthylidine ring, quinoxalin ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthrene ring, acrydin ring, phenanthrene ring, It is a thianthrene ring, a chromene ring, a xanthene ring, a phenoxatiin ring, a phenothiazine ring or a phenazine ring. The benzene ring is most preferable.

In formula (2), when R ¹¹³ is a hydrogen atom or R ¹¹⁴ is a hydrogen atom, the polyimide precursor forms a salt with a tertiary amine compound having an ethylenically unsaturated bond. May be good. 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, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specific examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylpentasiloxane.

式（２−Ａ）中、Ａ^１およびＡ^２は、酸素原子を表し、Ｒ^１１１およびＲ^１１２は、それぞれ独立に、２価の有機基を表し、Ｒ^１１３およびＲ^１１４は、それぞれ独立に、水素原子または１価の有機基を表し、Ｒ^１１３およびＲ^１１４の少なくとも一方は、重合性基を含む基であり、両方が重合性基であることが好ましい。 The repeating unit represented by the formula (2) is preferably the repeating unit represented by the formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention 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 it is preferable that both are polymerizable groups.

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

The polyimide precursor may contain one kind of repeating structural unit represented by the formula (2), but may also contain two or more kinds. Further, it may contain a structural isomer of a repeating unit represented by the formula (2). Needless to say, the polyimide precursor may contain other types of repeating structural units in addition to the repeating unit of the above formula (2).

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

The weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and even more preferably 22,000 to 25,000. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.
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、Ｒ^１３１は、２価の有機基を表し、Ｒ^１３２は、４価の有機基を表す。
重合性基を有する場合、重合性基は、Ｒ^１３１およびＲ^１３２の少なくとも一方に位置していてもよいし、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位置していてもよい。
式（４−１）

式（４−２）中、Ｒ^１３３は重合性基であり、他の基は式（４）と同義である。
式（４−２）

Ｒ^１３４およびＲ^１３５の少なくとも一方は重合性基であり、重合性基でない場合は有機基であり、他の基は式（４）と同義である。 << Polyimide >>
The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide ring, but is preferably a compound represented by the following formula (4), and a compound represented by the formula (4). It is more preferable that the compound has 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, the polymerizable group ^{may be located at at least one of R 131} and R ¹³² , or may be located at the end of the polyimide as shown in the following formula (4-1) or formula (4-2). It may be located in.
Equation (4-1)

In formula (4-2), ^R133 is a polymerizable group, and the other groups are synonymous with formula (4).
Equation (4-2)

At ^{least one of R 134} and R ¹³⁵ is a polymerizable group, when it is not a polymerizable group, it is an organic group, and the other group is synonymous with the formula (4).

The polymerizable group has the same meaning as the polymerizable group described in the above-mentioned polymerizable group possessed by the polyimide precursor and the like.
R ¹³¹ represents a divalent organic group. ^{Examples of the divalent organic group include those similar to R 111} in the formula (2), and the preferred 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 an example of R ^{111 in} the polyimide precursor formula (2).

It is preferable that R ¹³¹ 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 diamines containing two or more of an ethylene glycol chain and / or a propylene glycol chain in one molecule include Jeffamine (registered trademark) KH-511, Jeffamine (registered trademark) ED-600, and Jeffamine ( Registered Trademarks) ED-900, Jeffamine® ED-2003, Jeffamine® EDR-148, Jeffamine® EDR-176, D-200, D-400, D-2000, D -4000 (trade name, manufactured by HUNTSMAN Co., Ltd.), 1- (2- (2- (2-aminopropoxy) ethoxy) propoxy) propoxy-2-amine, 1- (1- (1- (2-amino)) Examples thereof include, but are not limited to, propoxy) propoxy) propoxy-2-yl) oxy) propan-2-amine and 1- (2- (2- (2-aminopropoxy) ethoxy) propoxy) propoxy) propoxy-2-amine.

R ¹³² represents a tetravalent organic group. ^{Examples of the tetravalent organic group include those similar to R 115} in the formula (2), and the preferred range is also the same.
For example, ^{four conjugates of a tetravalent organic group exemplified as R 115} combine with four −C (= O) − moieties in the above formula (4) to form a fused ring.

In addition, R ¹³² includes a tetracarboxylic acid residue remaining after removal of an anhydride group from the tetracarboxylic dianhydride. Specific examples include an 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 has an OH group.} More specifically, ^{as R 131} , 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2- Bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and (DA-1) to (DA-18) above are preferred examples. As R ¹³² , the above-mentioned (DAA-1) to (DAA-5) are preferable examples.

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

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

Further, in order to improve the storage stability of the composition, the main chain end of polyimide may be sealed with an end-capping agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound or monoactive ester compound. preferable. 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 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 due to ring closure that occurs when imidized by heating is reduced, and the occurrence of warpage can be suppressed.

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

Polyimide 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 an acid) at a low temperature. A method of reacting a diamine compound with an anhydride or a monoacid chloride compound or a terminal capping agent which is a monoactive ester compound), a diester is obtained by tetracarboxylic dianhydride and an alcohol, and then diamine (partly monoamine) is obtained. A method of reacting in the presence of a condensing agent with (replaced with an end-capping agent), a diester is obtained by tetracarboxylic acid dianhydride and alcohol, and then the remaining dicarboxylic acid is acid-chlorided to diamine (partly monoamine). A polyimide precursor is obtained by using a method such as a method of reacting with an end-capping agent (replaced with an end-capping agent), which is completely imidized by a known imidization reaction method, or an imide in the middle. Synthesis using a method of stopping the conversion reaction and introducing a partially imidized structure, and further, a method of introducing a partially imidized structure by blending a completely imidized polymer with its polyimide precursor. Can be done.
Examples of commercially available polyimide products include Durimide (registered trademark) 284 (manufactured by FUJIFILM Corporation) and Matrimide 5218 (manufactured by HUNTSMAN Co., Ltd.).

The weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, still more 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 particularly preferably 20,000 or more. When two or more kinds of polyimides are contained, it is preferable that the weight average molecular weight of at least one kind of polyimide is in the above range.

式（３）中、Ｒ^１２１は、２価の有機基を表し、Ｒ^１２２は、４価の有機基を表し、Ｒ^１２３およびＲ^１２４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 polybenzoxazole precursor used in the present invention is not particularly defined for its structure and the like, but is preferably 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.

In the formula (3), R ¹²³ and R ^{124 are synonymous with R 113} in the formula (2), respectively, and the preferable range is also the same. That is, at least one is preferably a polymerizable group.
In formula (3), R ¹²¹ represents a divalent organic group. As the divalent organic group, 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.
As the dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a linear or branched (preferably straight chain) aliphatic group is preferable, and a linear or branched (preferably straight chain) aliphatic group and two COOH are used. 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 more preferably 15, and particularly 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, hentoria-contanedioic acid, dotria-contandioic 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.

式中、Ａは−ＣＨ_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ_３）_２−、および、−Ｃ（ＣＨ_３）_２−からなる群から選択される２価の基を表す。

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

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

In formula (3), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same ^{meaning as R 115} in the above formula (2), and the preferable range is also the same.
R ¹²² is also preferably a group derived from a bisaminophenol derivative, and examples of the group derived from a bisaminophenol derivative include, for example, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'. -Diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis- (3-amino-) 4-Hydroxyphenyl) methane, 2,2-bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis -(4-Amino-3-hydroxyphenyl) hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, 2,2-bis- (4-amino-3-hydroxyphenyl) propane, 4,4 '-Diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-dihydroxy-4 , 4'-Dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene and the like. These bis-aminophenols may be used alone or in combination.

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

式中、Ｘ_１は、−Ｏ−、−Ｓ−、−Ｃ（ＣＦ_３）_２−、−ＣＨ_２−、−ＳＯ_２−、−ＮＨＣＯ−を表す。

In the formula, X ₁ represents -O-, -S-, -C (CF ₃ ) _2- , -CH _2- , -SO _2- , -NHCO-.

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). R ₂ is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different. R ₃ is 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。）

(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).)

The formula (A-s) in ortho position of the phenolic hydroxyl groups, i.e., to have also substituent R ₃ is believed to closer the distance of the carbonyl carbon and the hydroxyl group of the amide bond was cured at a low temperature It is particularly preferable in that the effect of increasing the cyclization rate 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. The effect can be maintained, which is preferable.

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 according to 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 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 bis-aminophenol derivative represented by the above formula (As), for example, paragraph numbers 0085-0094 and Example 1 (paragraph numbers 0189 to 0190) of JP2013-256506A are referred to. These contents can be incorporated herein by reference.

Specific examples of the structure of the bis-aminophenol 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. Incorporated in. Of course, it goes without saying that it is not limited to these.

The polybenzoxazole precursor may contain other types of repeating structural units in addition to the repeating units of the above formula (3).
It is preferable to include a diamine residue represented by the following formula (SL) as another type of repeating structural unit in that the occurrence of warpage due to ring closure 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＋ｂは１００モル％である。

In the 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. At ^{least one of R 3s} , R ^4s , R ^5s , and R ^6s 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 100 mol% for a + b.

In the formula (SL), preferred Z includes those in which R ^5s and R ^6s in the b structure are phenyl groups. The molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the molecular weight in the above range, it is possible to more effectively reduce the elastic modulus of the polybenzoxazole precursor after dehydration ring closure, suppress warpage, and improve solvent solubility.

When a diamine residue represented by the formula (SL) is included as another type of repeating structural unit, the tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic dianhydride is included as the repeating structural unit. Is also preferable. 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 20,000 to 29,000, and further, when used in the compositions described below. It is preferably 22,000 to 28,000. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.
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、Ｒ^１３３は、２価の有機基を表し、Ｒ^１３４は、４価の有機基を表す。
重合性基を有する場合、重合性基は、Ｒ^１３３およびＲ^１３４の少なくとも一方に位置していても良いし、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位置していてもよい。
式（Ｘ−１）

式（Ｘ−１）中、Ｒ^１３５およびＲ^１３６の少なくとも一方は、重合性基であり、重合性基でない場合は有機基であり、他の基は式（Ｘ）と同義である。
式（Ｘ−２）

式（Ｘ−２）中、Ｒ^１３５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。 << Polybenzoxazole >>
The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but is preferably a compound represented by the following formula (X), and a compound represented by the following formula (X). It is more preferable that the compound has a polymerizable group.

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

In formula (X-1), ^{at least one of R 135} and R ¹³⁶ is a polymerizable group, and if it is not a polymerizable group, it is an organic group, and the other group is synonymous with formula (X).
Equation (X-2)

In formula (X-2), R ¹³⁵ is a polymerizable group, the other is a substituent, and the other group is synonymous with formula (X).

The polymerizable group has the same meaning as the polymerizable group described in the above-mentioned polymerizable group possessed by the polyimide precursor and the like.

R ¹³³ represents a divalent organic group. Examples of the divalent organic group include an aliphatic or 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.}

R ¹³⁴ 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 membrane shrinkage due to ring closure that occurs when oxazoled by heating is reduced, and the occurrence of warpage can be suppressed more effectively.

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

The resulting polybenzoxazole, for example, a bis-aminophenol derivative, a dicarboxylic acid or the dicarboxylic acid containing R ^133, is reacted with a compound selected from dicarboxylic acid dichloride and dicarboxylic acid derivatives, the polybenzoxazole precursor , This is obtained by oxazole using a known oxazole 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, still more 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 particularly preferably 20,000 or more. When two or more kinds of polybenzoxazole are contained, it is preferable that the weight average molecular weight of at least one kind of polybenzoxazole is in the above range.

<< Manufacturing method of polyimide precursor, etc. >>
A polyimide precursor or the like is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, the dicarboxylic acid or the dicarboxylic acid derivative is obtained by halogenating it with a halogenating agent and then reacting it with a diamine.
In the method for producing a polyimide precursor or the like, 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.
The polyimide may be produced by synthesizing a polyimide precursor and then heating and cyclizing it, or may directly synthesize a polyimide.

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

<<< Solid Precipitation >>>
A step of precipitating a solid may be included in the production of the polyimide precursor or the like. Specifically, the polyimide precursor or the like in the reaction solution can be precipitated in water, and the polyimide precursor or the like such as tetrahydrofuran can be dissolved in a soluble solvent to precipitate a solid.
Then, the polyimide precursor or the like can be dried to obtain a powdery polyimide precursor or the like.

The 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 content of the polyimide precursor and the like in the composition used in the present invention is preferably 10 to 99% by mass, more preferably 50 to 98% by mass, and even more preferably 70 to 96% by mass.
Hereinafter, the components that can be contained in the composition used in the present invention will be described. Needless to say, the present invention may contain components other than these, and these components are not essential.

<< Polymerizable compound >>
In the present invention, as described above, it is preferable that the resin such as the polyimide precursor 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 and the like. 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, monomers, prepolymers, oligomers and mixtures thereof and multimers 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 2,000 or less, more preferably a low molecular weight compound having a molecular weight of 1,500 or less, and having a molecular weight of 900 or less. It is more preferably a low molecular weight compound. The molecular weight of the polymerizable monomer is usually 100 or more.
The oligomer-type polymerizable compound is typically a polymer having a relatively low molecular weight, and is preferably a polymer in which 10 to 100 polymerizable monomers are bonded. The weight average molecular weight of the oligomer-type polymerizable compound is preferably 2,000 to 20,000, more preferably 2,000 to 15,000, and most preferably 2,000 to 10,000.

The number of functional groups of the polymerizable compound in the present invention means the number of polymerizable groups in one molecule.
From the viewpoint of resolution, the polymerizable compound preferably contains at least one bifunctional or higher polymerizable compound containing two or more polymerizable groups, and preferably contains at least one trifunctional or higher functional polymerizable compound. More preferred.
Further, the polymerizable compound in the present invention preferably contains at least one 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 a bifunctionality or less and a polymerizable compound having a trifunctionality or higher.

<<< Compound with 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 having an ethylenically unsaturated bond include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, and the like. Examples thereof include esters of unsaturated carboxylic acids and polyhydric alcohol compounds, amides of unsaturated carboxylic acids and 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 reactions 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 methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylpropantrimethacrylate, trimethylol ethanetrimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol dimethacrylate. Hexylenediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacrylicyloxy-). Examples thereof include 2-hydroxypropoxy) phenyl] dimethylmethane and bis- [p- (methacrylicyloxyethoxy) phenyl] dimethylmethane.

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. , Sorbitolte tritaconate and the like.

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 hydroxyl 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 a vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule in which a vinyl monomer containing a hydroxyl group represented by the following formula is added 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 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 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, Toku-Kosho Polyfunctional acrylates and methacrylates such as polyester acrylates described in JP-A-49-43191 and JP-A-52-30490, and epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid, And mixtures thereof. 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 cyclic ether group such as glycidyl (meth) acrylate and a compound having an ethylenically unsaturated group can also be mentioned.
Further, as other compounds having a preferable ethylenically unsaturated bond, which are described in JP-A-2010-160418, JP-A-2010-129825, Patent No. 4364216 and the like, they have a fluorene ring and are ethylenically property. A compound having two or more groups having an unsaturated bond, a cardo resin, can also be used.
Further, as other examples, the specific unsaturated compounds described in Japanese Patent Publication No. 46-43946, Japanese Patent Publication No. 1-4537, and Japanese Patent Application Laid-Open No. 1-4536, and JP-A-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 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 the above formula, n is an integer of 0 to 14, and m is an integer of 0 to 8. A plurality of R and T existing in one 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 compounds 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 can also be preferably used in the present invention.

Further, in JP-A-10-62986, the compound described as the formulas (1) and (2) together with specific examples thereof, which is obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated, is also used. It can be used as a polymerizable 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.

Examples of the compound 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 those having 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, and SR-209, which is a bifunctional methacrylate having four ethyleneoxy chains (these are Sartmer Japan Co., Ltd.). ), DPCA-60, which is a hexafunctional acrylate having 6 pentyleneoxy chains, TPA-330, which is a trifunctional acrylate having 3 isobutyleneoxy chains (all manufactured by Nippon Kayaku Co., Ltd.), urethane oligomer. UAS-10, UAB-140 (above, manufactured by Sanyo Kokusaku Pulp Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (above, Shin-Nakamura Kagaku) Industrial Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (above, Kyoeisha Chemical Co., Ltd.) ), Blemmer PME400 (manufactured by Nichiyu Co., Ltd.) and the like.

Examples of the compound having an ethylenically unsaturated bond include those described in Japanese Patent Application Laid-Open No. 48-41708, Japanese Patent Application Laid-Open No. 51-37193, Japanese Patent Application Laid-Open No. 2-32293, and Japanese Patent Application Laid-Open No. 2-16765. 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 are also suitable. Is. Further, as a polymerizable compound, an addition-polymerizable compound having an amino structure or a sulfide structure in the molecule, which is described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. Monomers can also be used.

The compound having an ethylenically unsaturated bond may be a polyfunctional monomer having an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. The polyfunctional monomer having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid group is obtained by reacting an unreacted hydroxy group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. More preferably, and particularly preferably, the aliphatic polyhydroxy compound in this ester is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include M-510 and M-520, which are polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
As the polyfunctional monomer having an acid group, one 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 polymerizable property is good.

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

In the composition, the content of the compound having an ethylenically unsaturated bond is preferably 1 to 50% by mass with respect to the total solid content of the composition from the viewpoint of good 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. As the compound having an ethylenically unsaturated bond, one kind may be used alone, or two or more kinds may be mixed and used.
The mass ratio of the polyimide precursor or the like to the compound having an ethylenically unsaturated bond (polyimide precursor or the like / polymerizable compound) is preferably 98/2 to 10/90, more preferably 95/5 to 30/70. It is preferably 90/10 to 50/50, most preferably 90/10 to 50/50. When the mass ratio of the polyimide precursor or the like and the compound having an ethylenically unsaturated bond is within 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、Ｒ^４は、炭素数１〜２００のｔ価の有機基を示し、Ｒ^５は、下記式（ＡＭ２）または下記式（ＡＭ３）で示される基を示す。） (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 represented by the following formula (AM2) or the following formula (AM3). Indicates a group to be used.)

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

(In the formula, R ⁶ 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 polyimide precursor or the like. 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、Ｒ^４は、炭素数１〜２００の２価の有機基を示し、Ｒ^５は、下記式（ＡＭ２）または下記式（ＡＭ３）で示される基を示す。） (AM4)

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

（式中、ｕは３〜８の整数を示し、Ｒ^４は、炭素数１〜２００のｕ価の有機基を示し、Ｒ^５は、下記式（ＡＭ２）または下記式（ＡＭ３）で示される基を示す。） (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 is represented by the following formula (AM2) or the following formula (AM3). Indicates a group.)

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

(In the formula, R ⁶ 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 composition is cured on an 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, dimethylBisOC-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- Examples include p-cresol.

Specific examples of the compound represented by the formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, 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.).

<<< Epoxy compound (compound having an epoxy group) >>>
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group undergoes a cross-linking reaction at 200 ° C. or lower, and the dehydration reaction due to cross-linking does not occur, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective for low-temperature curing and low warpage of the composition.

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

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

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

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

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

<<< Benzoxazine compound (compound having a benzoxazolyl group) >>>
Since the benzoxazine compound undergoes a cross-linking reaction by a cycloaddition reaction, degassing due to curing does not occur, and shrinkage due to heat is small, so that warpage is suppressed, which is preferable.

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

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

<< Photopolymerization Initiator >>
The composition used in the present invention may contain a photopolymerization initiator. In particular, since the composition contains a photoradical polymerization initiator, the composition is applied to a semiconductor wafer or the like to form a composition layer, and then irradiation with light causes curing by radicals, which causes a light irradiation portion. Solubility can be reduced. Therefore, for example, by exposing the 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 produced according to the electrode pattern.

The photopolymerization initiator is not particularly limited as long as it has the ability to initiate a polymerization reaction (crosslinking reaction) of the polymerizable compound with light, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to light rays in the ultraviolet region to the visible region are preferable. Further, it may be an active agent 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 a 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 halogenated hydrocarbon derivatives 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. J. by Schaefer et al. 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.

Further, as photopolymerization initiators other than the above, the compounds described in paragraph No. 0083 of JP-A-2015-087611, JP-A-53-133428, JP-A-57-1819, and JP-A-57-6096. , And the compounds described in US Pat. No. 3,615,455, and the like are incorporated herein by reference.

Examples of the ketone compound include the compounds described in paragraph No. 0087 of Japanese Patent Application Laid-Open No. 2015-087611, and the contents thereof 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 in a long wave region 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. 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-on, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, 1-phenyl-1,2-butandion-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-butandion-2- (O) -Ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, 1- Phenyl-1,2-propanedione-2- (O-benzoyl) oxime, 1,3-diphenylpropanthrion-2- (O-ethoxycarbonyl) oxime, and 1-phenyl-3-ethoxypropanthrion-2- ( O-benzoyl) oxime and the like can be mentioned.

Examples of oxime compounds include JCSPerkin II (1979) pp.1653-1660, JCSPerkin II (1979) pp.156-162, Journal of Photopolymer Science and Technology (1995) pp.202-232, and JP-A-2000. Examples thereof include the compounds described in JP-A-66385, JP-A-2000-80068, JP-A-2004-534977, and JP-A-2006-342166.
As commercially available products, IRGACURE OXE-01 (manufactured by BASF), IRGACURE OXE-02 (manufactured by BASF), and N-1919 (manufactured by ADEKA Corporation) are also preferably used. Further, TR-PBG-304 (manufactured by Changshu Powerful Electronics New Materials Co., Ltd.), ADEKA ARCLUDS NCI-831 and ADEKA ARCULDS NCI-930 (manufactured by ADEKA Corporation) can also be used. Further, TR-PBG-304 (manufactured by Joshu Powerful Electronics New Materials Co., Ltd.), ADEKA ARCLUDS NCI-831 and ADEKA ARCULDS NCI-930 (manufactured by ADEKA Corporation) 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としては、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 carbazole, the compound described in US Pat. No. 6,626,957 in which a hetero Substituent is introduced at the benzophenone moiety, and a nitro group at the dye moiety. The introduced compound described in JP-A-2010-15025 and US Patent Publication No. 2009-292039, the keto-oxime compound described in International Publication WO2009-131189, and the United States containing a triazine skeleton and an oxime skeleton in the same molecule. The compound described in Patent No. 7556910, 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 No. 0345 of JP-A-2014-500852, and JP-A-2014. Examples thereof include the compound (C-3) described in paragraph No. 0101 of the publication No. 2013-164471. 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、Ｒ^５０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２〜１２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、Ｒ^５１は、式（ＩＩ）で表される基であるか、Ｒ^５０と同じ基であり、Ｒ^５２〜Ｒ^５４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、Ｒ^５５〜Ｒ^５７は、上記式（Ｉ）のＲ^５２〜Ｒ^５４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 preferably, it is a trihalomethyltriazine compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium salt compound, a benzophenone compound, an acetophenone compound, and a trihalomethyltriazine compound. , Α-Aminoketone compound, metallocene compound, oxime compound, triarylimidazole dimer, benzophenone compound, at least one compound selected from the group is more preferable, metallocene compound or oxime compound is more preferable, and oxime compound is particularly preferable. preferable.
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.

Wherein ^{(I), R 50} is an alkyl group having 1 to 20 carbon atoms; a phenyl group; an alkoxy group having 1 to 12 carbon atoms, alkyl group of the 2 to 20 carbon atoms interrupted by one or more oxygen atoms; Alkyl group with 1 to 20 carbon atoms, alkoxy group with 1 to 12 carbon atoms, halogen atom, cyclopentyl group, cyclohexyl group, alkenyl group with 2 to 12 carbon atoms, carbon number 2 to interrupted by one or more oxygen atoms It is a substituted phenyl group; or biphenylyl with at least one of the 18 alkyl groups and the alkyl groups having 1 to 4 carbon atoms, and R ⁵¹ is the group represented by the formula (II) or R ⁵⁰ . They are the same group, and 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 composition contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the composition. , More preferably 0.1 to 10% by mass.
The photopolymerization initiator may be only one kind or two or more kinds. When there are two or more photopolymerization initiators, the total is preferably in the above range.

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

It is also possible to use an ion trap agent that captures anions such as halogen ions. The ion trapping agent is not particularly limited, and conventionally known ones can be used. In particular, hydrotalcite represented by the following composition formula or bismuth hydrous oxide represented by the following composition formula is preferable.
Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X / 2}・ mH ₂ O
(In the above composition formula, 0 <X≤0.5, m is a positive number)
BiO _x (OH) _y (NO ₃ ) _z
(In the above composition formula, 0.9 ≦ x ≦ 1.1, 0.6 ≦ y ≦ 0.8, 0.2 ≦ z ≦ 0.4)
The hydrotalcite is commercially available from Kyowa Chemical Industry Co., Ltd. under the trade name: DHT-4A. The bismuth is commercially available from Toagosei Co., Ltd. under the trade name: IXE500. Further, other ion trapping agents may be used if necessary. For example, hydrous oxides of elements selected from magnesium, aluminum, titanium, zirconium, antimony and the like can be mentioned. These ion trapping agents can be used alone or in combination of two or more.

Other migration inhibitors include rust preventives described in paragraph No. 0094 of JP2013-15701, compounds described in paragraphs 0073 to 0076 of JP2009-283711, and JP2011-59656A. The compound described in paragraph No. 0052 of the above, the compound described in paragraph numbers 0114, 0116 and 0118 of JP2012-194520A can be used.

When the composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, preferably 0.05 to 2.0% by mass, based on the total solid content of the composition. More preferably, 0.1 to 1.0% by mass is further preferable.
The migration inhibitor may be only one kind or two or more kinds. 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 production method of the present invention preferably contains a polymerization inhibitor.
Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,3,5-tris (4-t-butyl-3-3). Hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, p-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis (3-Methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N -Phenylnaphthylamine, 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 No. 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 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 production method of 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 contain a thermobase generator containing at least one of these. _{Here, pKa1 indicates a logarithmic representation (-Log 10} Ka) of the dissociation constant (Ka) of the first proton of a polyvalent acid.
By blending such a compound, the cyclization reaction of the polyimide 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 the polyimide precursor, the cyclization of the polyimide precursor during storage can be suppressed, and the storage stability is excellent.

The thermobase generator in the present invention is at least one selected from an acidic compound (A1) that generates a base when heated to 40 ° C. or higher, and an ammonium salt (A2) having an anion having a pKa1 of 0 to 4 and an ammonium cation. including.
Since the acidic compound (A1) and the ammonium salt (A2) generate bases when heated, the bases generated from these compounds can promote the cyclization reaction of the polyimide precursor and cyclize the polyimide precursor. It can be done at low temperature. Further, even if these compounds coexist with a polyimide precursor that is cyclized and cured by a base, the cyclization of the polyimide precursor hardly proceeds unless it is heated. Therefore, a polyimide precursor composition having excellent stability can be obtained. 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. Stir. It means a compound having a value of less than 7 measured at 20 ° C. using a pH meter for the solution.

In the present invention, the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40 ° C. or higher, more preferably 120 to 200 ° C. The upper limit of the base generation temperature is more preferably 190 ° C. or lower, further preferably 180 ° C. or lower, and even more preferably 165 ° C. or lower. The lower limit of the base generation temperature is more preferably 130 ° C. or higher, and even more preferably 135 ° C. or higher.
If the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 40 ° C. or higher, and further, 120 ° C. or higher, bases are less likely to be generated during storage, so that the polyimide precursor composition has excellent stability. Can be prepared. When the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 200 ° C. or lower, the cyclization temperature of the polyimide precursor can be reduced. 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 can be further lowered. The boiling point of the base generated by the thermal base generator is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and most preferably 140 ° C. or higher. The molecular weight of the generated base is preferably 80 to 2,000. The lower limit is more preferably 100 or more. The upper limit is more preferably 500 or less. The 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 other than an acidic compound that generates a base when heated.

式中、Ｒ^１〜Ｒ^６は、それぞれ独立に、水素原子または炭化水素基を表し、Ｒ^７は炭化水素基を表す。Ｒ^１とＲ^２、Ｒ^３とＲ^４、Ｒ^５とＲ^６、Ｒ^５とＲ^７はそれぞれ結合して環を形成してもよい。 <<< Ammonium salt >>>
In the present invention, the ammonium salt means a salt of an ammonium cation represented by the following formula (101) or formula (102) and an anion. The anion may be bonded to any part of the ammonium cation via a covalent bond, 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 is also referred to as a counter anion.
Equation (101) Equation (102)

In the formula, 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 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 the above formula, R ¹⁰¹ represents an n-valent organic group, and R ¹ and R ⁷ are synonymous with the formula (101) or the formula (102).
Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group.
n represents an integer of 1 or more
m represents an integer from 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 more preferably 0.5 or more, and even more preferably 1.0 or more. When the pKa1 of the anion is in the above range, the polyimide precursor can be cyclized at a low temperature, and the stability of the polyimide precursor composition 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 polyimide precursor composition is good. When pKa1 is 0 or more, the generated base is not easily neutralized, and the cyclization efficiency of the polyimide precursor is good.
The type of anion is preferably one selected from a carboxylic acid anion, a phenol anion, a phosphate anion and a sulfate anion, and a 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 the polyimide precursor composition. In particular, by using a divalent carboxylic acid anion, the stability, curability and developability of the polyimide precursor composition 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 polyimide precursor composition can be further improved.
Here, pKa1 represents the logarithm of the reciprocal of the first dissociation constant of the acid, and the Determination of Organic Structures by Physical Methods (author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; compilation: Braude, You can refer to the values described in EA, Nachod, FC; Academic Press, New York, 1955) and Data for Biochemical Research (author: Dawson, RMCet al; Oxford, Clarendon Press, 1959). 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。 In the present invention, 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 Hammett's substituent constant σm 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 groups (σm = 0.43), CF ₃ CO groups (σm = 0.63), HC≡C groups (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。 In the present invention, EWG preferably represents a group represented by the following formulas (EWG-1) to (EWG-6).

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

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

In formula ^{(X), L 10} represents a single bond or an alkylene group, an alkenylene group, an aromatic group, -NR ^X - represents, and a divalent linking group selected from combinations thereof, ^{R X} is hydrogen Represents an 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.
Hereinafter, the thermobase generator preferably used in the present invention will be illustrated. Needless to say, the thermobase generator used in the present invention is not limited to these.

When a thermobase generator is used, the content of the thermobase generator in the composition is preferably 0.1 to 50% by mass with respect to the total solid content of the composition. The lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, 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 kinds are used, the total amount is preferably in the above range.

<< Photobase generator >>
The photosensitive resin composition used in the production method of 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 exposed as an external stimulus, that is, irradiation with electromagnetic waves and heating are performed, the base is generated. It is not particularly limited as long as it generates (basic substance). Since the base generated by exposure acts as a catalyst when the polyimide precursor is cured 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 30 parts by mass or less, 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.

In the present invention, known photobase generators can be used. For example, M. Shirai, and M. Tsunooka, Prog. Polym. Sci. , 21, 1 (1996); Masahiro Kakuoka, 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.
In the present invention, as the photobase generator, carbamate derivatives, amide derivatives, imide derivatives, α-cobalt complexes, imidazole derivatives, cinnamic acid amide derivatives, oxime derivatives and the like are more preferable examples.

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

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

Further, for the above reasons, as the photobase generator, it is preferable that the base generated as described above is latent using a covalent bond, and the generated base has an amide bond, a carbamate bond, and an oxime bond. It is preferably latent using.
Examples of the photobase generator according to the present invention include a photobase generator having a katsura acid amide structure as disclosed in JP-A-2009-80452 and JP-A-2009 / 123122, JP-A-2006-189591. A photobase generator having a carbamate structure as disclosed in JP-A and JP-A-2008-247747, an oxime structure as disclosed in JP-A-2007-249013 and JP-A-2008-003581, Carbamoyl. Examples thereof include a photobase generator having an oxime structure, but the present invention is not limited to these, and other known photobase generator structures can be used.

In addition, as the photobase generator, the compounds described in paragraph Nos. 0185 to 0188, 0199 to 0200 and 0202 of JP2012-93746A, and the compounds described in paragraphs 0022 to 0069 of JP2013-194205A. Examples thereof include the compounds described in paragraphs 0026 to 0074 of JP2013-204319A, and the compounds described in paragraph number 0052 of International Publication WO2010 / 064631.

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

<< Thermal Acid Generator >>
The composition used in the production method of the present invention may contain a thermoacid generator. The thermoacid generator generates an acid by heating, promotes cyclization of a polyimide precursor, etc., and further improves the mechanical properties of the cured film. In addition, a compound having a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl group, an epoxy. It has the effect of promoting the cross-linking reaction of at least one compound selected from the compound, the oxetane compound and the benzoxazine compound.

The thermal decomposition start temperature of the thermal acid generator is preferably 50 ° C. to 270 ° C., more preferably 250 ° C. or lower. Further, no acid is generated during drying (pre-baking: about 70 to 140 ° C.) after the composition is applied to the substrate, and during final heating (cure: about 100 to 400 ° C.) after patterning by subsequent exposure and development. It is preferable to select a substance that generates an acid because it can suppress a decrease in sensitivity during development.

The acid generated from the thermoacid generator is preferably a strong acid, for example, aryl sulfonic acid such as p-toluene sulfonic acid and benzene sulfonic acid, alkyl sulfonic acid such as methane sulfonic acid, ethane sulfonic acid and butane sulfonic acid and trifluoromethane sulfonic acid. Haloalkyl sulfonic acids such as acids are preferred. Examples of such a thermoacid generator include those described in paragraph No. 0055 of JP2013-072935A.

Among them, a thermoacid generator that generates alkylsulfonic acid having 1 to 4 carbon atoms or haloalkylsulfonic acid having 1 to 4 carbon atoms is more preferable, and methane, from the viewpoint that the residue in the cured film is small and the physical properties of the cured film are not deteriorated. Sulphonic acid (4-hydroxyphenyl) dimethylsulfonium, methanesulfonic acid (4-((methoxycarbonyl) oxy) phenyl) dimethylsulfonium, benzyl methanesulphonate (4-hydroxyphenyl) methylsulfonium, benzyl methanesulphonate (4-( (Methoxycarbonyl) oxy) phenyl) methylsulfonium, methanesulfonic acid (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium, trifluoromethanesulfonic acid (4-hydroxyphenyl) dimethylsulfonium, trifluoromethanesulfonic acid ( 4-((methoxycarbonyl) oxy) phenyl) dimethylsulfonium, benzyl (4-hydroxyphenyl) methylsulfonium trifluoromethanesulfonate, benzyl trifluoromethanesulfonate (4-((methoxycarbonyl) oxy) phenyl) methylsulfonium, trifluoromethane Methyl sulfonic acid (4-hydroxyphenyl) ((2-methylphenyl) methyl) sulfonium, 3-(5-(((propylsulfonyl) oxy) imino) thiophene-2 (5H) -iriden) -2- (o- Trill) propanenitrile and 2,2-bis (3- (methanesulfonylamino) -4-hydroxyphenyl) hexafluoropropane are preferred.

Further, the compound described in paragraph No. 0059 of JP2013-167742A is also preferable as the 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 or the like. By containing 0.01 part by mass or more, the cross-linking reaction and the cyclization of the polyimide precursor and the like 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 further 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.

<< Thermal Polymerization Initiator >>
The composition used in the present invention may contain a thermal polymerization initiator (preferably a thermal radical polymerization initiator). As the thermal radical polymerization initiator, a known thermal radical polymerization initiator can be used.
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 a thermal radical polymerization initiator, the polymerization reaction of the polymerizable compound can be allowed to proceed when the cyclization reaction of the polyimide precursor or the like is allowed to proceed. Further, when the polyimide precursor or the like contains an ethylenically unsaturated bond, the polymerization reaction of the polyimide precursor or the like can be allowed to proceed together with the cyclization of the polyimide precursor or the like, so that higher heat resistance can be achieved. ..
Examples of the thermal radical polymerization initiator include aromatic ketones, onium salt compounds, peroxides, thio compounds, hexaarylbiimidazole compounds, ketooxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, and carbon halogens. Examples thereof include compounds having a bond and azo compounds. Among them, peroxides or azo compounds are more preferable, and peroxides are particularly preferable.
The thermal radical polymerization initiator used in the present invention preferably has a 10-hour half-life temperature of 90 to 130 ° C, more preferably 100 to 120 ° C.
Specific examples thereof include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-63554.
As commercially available products, Perbutyl Z and Park Mill D (manufactured by NOF CORPORATION) can be preferably used.

When the composition has a thermal radical polymerization initiator, the content of the thermal radical polymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.1 to 30% by mass, based on the total solid content of the composition. , 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.

金属接着性改良剤の含有量は、ポリイミド前駆体等１００質量部に対して、好ましくは０．１〜３０質量部であり、より好ましくは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熱硬化後の膜と金属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後の膜の耐熱性、機械特性が良好となる。
金属接着性改良剤は１種のみでもよいし、２種以上であってもよい。２種以上用いる場合は、その合計が上記範囲であることが好ましい。 << Metal Adhesive Improvement Agent >>
The composition used in the production method of 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 JP2013-072935. Further, as the metal adhesion improver, the following compound (N- [3- (triethoxysilyl) propyl] maleic acid monoamide) is also exemplified.

The content of the metal adhesive improving agent is preferably 0.1 to 30 parts by mass, and more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the polyimide precursor or the like. When the amount is 0.1 parts by mass or more, the adhesiveness between the thermosetting film and the metal is good, and when the amount is 30 parts by mass or less, the heat resistance and mechanical properties of the cured film are good.
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.

<< Silane Coupling Agent >>
The composition used in the production method of the present invention preferably contains a silane coupling agent in that the adhesiveness to the substrate can be improved. Examples of the silane coupling agent include the compounds described in paragraphs 0062 to 0073 of JP2014-191002, the compounds described in paragraphs 0063 to 0071 of International Publication WO2011 / 080992A1, JP2014-191252. Examples thereof include the compounds described in paragraphs 0060 to 0061 of Japanese Patent Application Laid-Open No. 2014, the compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Laid-Open No. 2014-41264, and the compounds described in paragraph 0055 of International Publication WO2014 / 0975994. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A.
The content of the silane coupling agent is preferably 0.1 to 20 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the polyimide precursor or the like. 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.

<< Sensitive Dye >>
The composition used in the production method of 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 a maximum absorption wavelength in the region of 300 nm to 450 nm. For example, polynuclear aromatics (eg, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9.10-dialkoxyanthracene), xanthenes (eg, fluoressein, eosin, erythrosin, rhodamine B, rosebenzene), thioxanthones. (For example, 2,4-diethylthioxanthone), cyanins (eg, thiacarbocyanine, oxacarbocyanin), merocyanines (eg, merocyanine, carbomerocyanine), thiadins (eg, thionin, methylene blue, toluidine blue), acrydins (For example, acrydin orange, chloroflavin, acryflabin), anthraquinones (eg, anthraquinone), squaryliums (eg, squarylium), coumarins (eg, 7-diethylamino-4-methylcoumarin), 3,3'-carbonyl -Bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylamino Examples thereof include coumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyldiethanolamine, styrylbenzenes, distyrylbenzenes, carbazoles and the like.

Among them, in the present invention, it is preferable to combine with polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene), thioxanthones, distyrylbenzenes, and styrylbenzenes from the viewpoint of starting efficiency, and has an anthracene skeleton. It is more preferable to use a compound. Particularly preferred specific compounds include 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene and the like.

When the composition contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, based on the total solid content of the composition. 5 to 10% by mass is more preferable. The sensitizing dye may be used alone or in combination of two or more.

<< Chain Transfer Agent >>
The composition used in the production method of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in 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 hydrogenate low-activity radical species to generate radicals, or they can be oxidized and then deprotonated to produce radicals. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazol, etc.) can be preferably used.

When the composition has a chain transfer agent, the preferred content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the total solid content of the composition. Particularly preferably, it is 1 to 5 parts by mass.
The chain transfer agent may be only one kind or two or more kinds. When there are two or more types of chain transfer agents, the total is preferably in the above range.

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

上記の化合物の重量平均分子量は、例えば、１４，０００である。 The fluorine content of the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid saving property, and has good solvent solubility.
Examples of the fluorine-based surfactant include Megafuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, and F479. F482, F554, F780, F781 (above, manufactured by DIC Co., Ltd.), Florard FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Ltd.), Surfron S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (all manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320 , PF6520, PF7002 (all manufactured by OMNOVA) and the like.
A block polymer can also be used as the fluorine-based surfactant, and specific examples thereof include compounds described in JP-A-2011-89090.
The following compounds are also exemplified as the fluorine-based surfactant used in the present invention.

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

Specifically, as nonionic surfactants, glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (BASF's Pluronic L10, L31, L61, L62, Examples thereof include 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1) and Solsparse 20000 (Nippon Lubrizol Co., Ltd.). Further, Pionin D-6112-W manufactured by Takemoto Oil & Fat Co., Ltd. and NCW-101, NCW-1001 and NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. can also be used.

Specifically, as cationic surfactants, phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shinetsu Chemical Industry Co., Ltd.), (meth) acrylic acid-based (meth) acrylic acid-based (meth) Co) Polymer Polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like can be mentioned.

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

Examples of the silicone-based surfactant include "Torre Silicone DC3PA", "Torre Silicone SH7PA", "Torre Silicone DC11PA", "Torre Silicone SH21PA", "Torre Silicone SH28PA" and "Torre Silicone SH28PA" manufactured by Toray Dow Corning Co., Ltd. Silicone SH29PA ”,“ Torre Silicone SH30PA ”,“ Torre Silicone SH8400 ”,“ TSF-4440 ”,“ TSF-4300 ”,“ TSF-4445 ”,“ TSF-4460 ”,“ TSF -4452 ”,“ KP341 ”,“ KF6001 ”,“ KF6002 ”manufactured by Shin-Etsu Chemical Co., Ltd.,“ BYK307 ”,“ BYK323 ”,“ BYK330 ”manufactured by Big Chemie Japan Co., Ltd., and the like.

When the composition has a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0, based on the total solid content of the composition. It is mass%.
The surfactant may be only one kind or two or more kinds. When there are two or more types of surfactant, the total is preferably in the above range.

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

<< Solvent >>
When the composition used in the production method of the present invention is layered by coating, it is preferable to add a solvent. As the solvent, known ones can be used without limitation as long as the composition can be formed in layers.
Examples of esters include ethyl acetate, -n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, and ε-caprolactone. , Δ-Valerolactone, alkyl alkoxyacetate (eg, methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3. -Alkyl alkoxypropionate esters (eg, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Ethyl propionate ethoxypropionate, etc.)), Alkyl esters 2-alkoxypropionate (eg, methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (eg, methyl 2-methoxypropionate, etc.) Ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and 2-alkoxy-2-methylpropionate Ethyl (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2- Methyl 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 acetate, etc., and as ketones, for example, methyl ethyl ketone, cyclo Hexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and aromatic hydrocarbons such as toluene, xylene, anisole, limonene and the like, and dimethyl sulfoxide as sulfoxides. Is preferably mentioned.

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. , Dimethylsulfoxide, ethylcarbitol acetate, butylcarbitol 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 composition has a solvent, the content of the solvent is preferably an amount such that the total solid content concentration of the composition is 5 to 80% by mass, more preferably 5 to 70% by mass, from the viewpoint of coatability. , 10-60% by mass is particularly preferable.
The solvent may be only one type or two or more types. When there are two or more 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 content of N, N-dimethylformamide with respect to the total mass of the composition from the viewpoint of film strength. Less than 5% by mass is preferable, less than 1% by mass is more preferable, less than 0.5% by mass is further preferable, and less than 0.1% by mass is particularly preferable.

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

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

From the viewpoint of insulating properties, the metal content of the composition used in the production method of the present invention is 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 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 of reducing metal impurities unintentionally contained in the composition, a raw material having a low metal content is selected as a raw material constituting the composition, and filter filtration is performed on the raw material constituting the composition. Examples of the method include 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 composition used in the production method of 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.

Manufacturing Method of Semiconductor Device The present invention also discloses a manufacturing method of a semiconductor device including the manufacturing method of the above-mentioned laminate. Hereinafter, an embodiment of a semiconductor device using the laminate obtained by the method for producing a laminate of the present invention will be described.
The semiconductor device 100 shown in FIG. 1 is a so-called three-dimensional mounting device, and a semiconductor element 101 in which a plurality of semiconductor elements (semiconductor chips) 101a to 101d are laminated is arranged on a wiring board 120.
In this embodiment, the case where the number of layers of the semiconductor element (semiconductor chip) is four is mainly described, but the number of layers of the semiconductor element (semiconductor chip) is not particularly limited, and for example, 2 It may be a layer, an 8-layer, a 16-layer, a 32-layer, or the like. Moreover, it may be one layer.

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

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

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

The semiconductor element 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 element 101, and the wiring board 120 and the semiconductor element 101 are electrically connected to each other via the rewiring layer 105. It is connected. The insulating layer 115 is the exposed photosensitive resin composition layer (resin layer) in the present invention. The details of the insulating layer will be described later.
That is, one end of the rewiring layer 105 is connected to an electrode pad formed on the surface of the semiconductor element 101d on the rewiring layer 105 side 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 element 101. Further, an underfill layer 110b is formed between the insulating layer 115 and the wiring board 120.

FIG. 2 shows an example of a laminate (rewiring layer) obtained by the production method of the present invention, in which 200 is a laminate obtained by the method of the present invention and 201 is a photosensitive resin composition. A layer (resin layer) is shown, and 203 is 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 with 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 (resin layer) 201 is further laminated on the surface of the metal layer 203. Then, the photosensitive resin composition layer (resin layer) acts as an insulating film, the metal layer acts as a wiring 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.

<Synthesis example 1>
[Synthesis of Polyimide Precursor (A-1: Polyimide Precursor without Radical Polymerizable Group) from Pyromeric Acid Dianhydride, 4,4'-Oxydianiline and benzyl Alcohol]
14.06 g (64.5 mmol) of pyromeritic acid dianhydride (pyromeric acid dried at 140 ° C. for 12 hours) and 14.22 g (131.58 mmol) of benzyl alcohol in 50 mL of N-methylpyrrolidone. Suspended in and dried with a molecular sieve. The suspension was heated at 100 ° C. for 3 hours. A clear solution was obtained a few minutes after heating. The reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) of pyridine and 90 mL of N-methylpyrrolidone were added. The reaction mixture was then cooled to −10 ° C. and 16.12 g (135.5 mmol) of SOCL ₂ was added over 10 minutes while keeping the temperature at −10 ± 4 ° C. Viscosity increased while SOCL _{2 was added.} After diluting with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. A solution of 11.08 g (58.7 mmol) of 4,4'-oxydianiline in 100 mL of N-methylpyrrolidone was then added dropwise to the reaction mixture at 20-23 ° C. over 20 minutes. The reaction mixture was then stirred at room temperature overnight. The polyimide precursor was then precipitated by adding to 5 liters of water and the water-polyimide precursor mixture was stirred at a rate of 5000 rpm for 15 minutes. The polyimide precursor was collected by filtration, added to 4 liters of water, stirred again for 30 minutes, and collected again by filtration. Then, the obtained polyimide precursor (A-1) was dried under reduced pressure at 45 ° C. for 3 days.
(A-1)

<Synthesis example 2>
[Synthesis of Polyimide Precursor (A-2: Polyimide Precursor with Radical Polymerizable Group) from Pyromeric Acid Dianhydride, 4,4'-Oxydianiline and 2-Hydroxyethyl methacrylate]
14.06 g (64.5 mmol) of pyromeritic acid dianhydride (pyromellitic acid dried at 140 ° C. for 12 hours), 18.6 g (129 mmol) of 2-hydroxyethyl methacrylate, and 0.05 g of hydroquinone. , 10.7 g of pyridine and 140 g of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at a temperature of 60 ° C. for 18 hours to prepare a diester of pyromeritic acid and 2-hydroxyethyl methacrylate. Next, the obtained diester was _{chlorinated with SOCL 2} , converted to a polyimide precursor with 4,4'-oxydianiline in the same manner as in Synthesis Example 1, and then converted into a polyimide precursor in the same manner as in Synthesis Example 1. (A-2) was obtained.
(A-2)

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

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

<Synthesis example 5>
[Synthesis of Polyimide Precursor (A-5: Polyimide Precursor with Radical Polymerizable Group) from Pyromeric Acid Dianhydride, m-Trizine and 2-Hydroxyethyl Methacrylate]
14.06 g (64.5 mmol) pyromeritic acid dianhydride (pyrromeric acid dried at 140 ° C. for 12 hours), 18.6 g (129 mmol) 2-hydroxyethyl methacrylate, and 0.05 g hydroquinone. , 10.7 g of pyridine and 140 g of NMP (N-methyl-2-pyrrolidone) were mixed and stirred at a temperature of 60 ° C. for 18 hours to prepare a diester of pyromeritic 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. After diluting with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. A solution of 12.46 g (58.7 mmol) of m-trizine in 100 mL of N-methylpyrrolidone was then added dropwise to the reaction mixture at 20-23 ° C. over 20 minutes. The reaction mixture was then stirred at room temperature overnight. The polyimide precursor was then precipitated by adding to 5 liters of water and the water-polyimide precursor mixture was stirred at a rate of 5000 rpm for 15 minutes. The polyimide precursor was collected by filtration, added to 4 liters of water, stirred again for 30 minutes, and filtered again. Next, the obtained polyimide precursor was dried at 45 ° C. for 3 days under reduced pressure to obtain a polyimide precursor (A-5).
(A-5)

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

<Examples and Comparative Examples>
The following components were mixed to prepare a coating solution of the photosensitive resin composition as a uniform solution.
<< Composition of photosensitive resin composition >>
(A) Resin: Parts by mass (B) shown in Table 1 Polymerizable compound: Parts by mass shown in Table 1 (C) Photopolymerization initiator: Parts by mass shown in Table 1 (D) Polymerization inhibitor: Table 1 Γ-Butyrolactone by mass: 60.00 parts by mass

The abbreviations listed in Table 1 are as follows.
(A) Resin synthesized in Resin Synthesis Examples 1 to 5 A-6: Matrix5218 (manufactured by HUNTSMAN, polyimide)
Polymer for comparative example (RA-2): Polymethyl methacrylate (Mw: 15,000, manufactured by Sigma-Aldrich Japan Co., Ltd.)

Ｂ−２： ＮＫエステル Ａ−９３００ （新中村化学工業社製、３官能アクリレート、下記構造）

(B) Polymerizable compound B-1: SR209 (manufactured by Sartmer Japan Co., Ltd., bifunctional methacrylate, structure below)

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

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

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

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

<Evaluation>
<< Evaluation of peeling defects >>
(No heat treatment)
Each of the above-mentioned laminates 2 and 3 has a width of 5 mm in the direction perpendicular to the resin layer surface, and the portion where the resin layer and the resin layer are in contact is in contact with the metal layer and the resin layer. Each of these parts was cut out, and the cross section thereof was observed, and the presence or absence of peeling between the resin layer / resin layer and the metal layer / resin layer in one cut piece was confirmed with an optical microscope. If there is no peeling, it means that the product has excellent adhesiveness, which is a preferable result.
A: No peeling occurs B: 1 to 2 peels occur C: 3 to 5 peels occur D: 6 or more peels occur (with heat treatment)
The laminates 2 and 3 obtained above were heated in nitrogen at 300 ° C. for 3 hours. After that, each laminated body has a width of 5 mm in the direction perpendicular to the resin layer surface, and a portion where the resin layer and the resin layer are in contact and a portion where the metal layer and the resin layer are in contact, respectively. After cutting out and observing the cross section thereof, the presence or absence of peeling between the resin layer / resin layer and the metal layer / resin layer in one cut piece was confirmed by an optical microscope. If there is no peeling, it means that the product has excellent adhesiveness, which is a preferable result.
A: No peeling occurs B: 1 to 2 peels occur C: 3 to 5 peels occur D: 6 or more peels occur

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

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

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

100: Semiconductor device 101a-101d: Semiconductor element 101: Laminated body 102b-10d: Through electrodes 103a-103e: Metal bump 105: Rewiring layer 110, 110a, 110b: Underfill layer 115: Insulation layer 120: Wiring board 120a: Surface electrode 200: Laminated body 201: Photosensitive resin composition layer (resin layer)
203: Metal layer

Claims (26)

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 and
A development treatment step of performing a negative type development treatment on the exposed photosensitive resin composition layer, and
A metal layer forming step of forming a metal layer on a part of the surface of the photosensitive resin composition layer after the development treatment, and
A surface activation treatment step of surface activating at least a part of the metal layer and at least a part of the photosensitive resin composition layer is included.
Further, the step of forming the photosensitive resin composition layer, the exposure step, and the development treatment step are performed again in the above order.
The photosensitive resin composition comprises a resin selected from a polyimide precursor, a polyimide, a polybenzoxazole precursor and a polybenzoxazole.
Further, the resin may contain a polymerizable group, and, to meet at least one of said photosensitive resin composition comprises a polymerizable compound,
The resin is represented by a repeating unit represented by the following formula (2), a repeating unit represented by the following formula (4), a repeating unit represented by the following formula (3), and a following formula (X). Containing at least one repeating unit selected from the group consisting of repeating units,
Method for manufacturing a laminate.
Equation (2):

In formula (2), A ¹ and A ² represent an oxygen atom, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ are independent of each other. Represents a monovalent organic group;
Equation (4):

In formula (4), R ¹³¹ represents a divalent organic group and R ¹³² represents a tetravalent organic group;
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;
Equation (X):

In formula (X), R ¹³³ represents a divalent organic group and R ¹³⁴ represents a tetravalent organic group. The laminate according to claim 1, wherein the resin contains at least one repeating unit selected from the group consisting of the repeating unit represented by the formula (2) and the repeating unit represented by the formula (3). Production method. The method for producing a laminate according to claim 1 or 2 , wherein the photosensitive resin composition layer forming step, the exposure step, and the developing treatment step are performed 3 to 7 times in the above order. The method for producing a laminate according to any one of claims 1 to 3, wherein the metal layer contains copper. The method for producing a laminate according to any one of claims 1 to 4 , wherein the resin is a polyimide precursor or a polybenzoxazole precursor. The method for producing a laminate according to any one of claims 1 to 5, wherein the resin is polyimide or a polyimide precursor. The method for producing a laminate according to any one of claims 1 to 6 , wherein the resin contains a partial structure represented by -Ar-L-Ar-; however, Ar is independently aromatic. A group, where 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 the above two or more. The method for producing a laminate according to any one of claims 1 to 7 , wherein the surface activation treatment is selected from plasma treatment and corona discharge treatment. The method for producing a laminate according to any one of claims 1 to 8 , wherein the photosensitive resin composition contains a photopolymerization initiator. The method for producing a laminate according to claim 9, wherein the photopolymerization initiator contains an oxime compound. The method for producing a laminate according to any one of claims 1 to 10 , wherein the content of the resin is 50% by mass or more of the solid content in the photosensitive resin composition. The method for producing a laminate according to any one of claims 1 to 11 , wherein the photosensitive resin composition contains a bifunctional or higher functional polymerizable compound. The method for producing a laminate according to any one of claims 1 to 12 , wherein the resin contains a polymerizable group. The polymerizable group is selected from the group consisting of 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 and a methylol group. The method for producing a laminate according to claim 13 , which is at least one group to be used. The method for producing a laminate according to any one of claims 1 to 14, wherein the photosensitive resin composition further contains a polymerization inhibitor. The method for producing a laminate according to any one of claims 1 to 15 , wherein the surface activation treatment is a plasma treatment. The method for producing a laminate according to claim 16 , wherein the raw material gas in the plasma treatment is a mixed gas of oxygen, hydrogen, argon, nitrogen, nitrogen and hydrogen, or a mixed gas of argon and oxygen. The photosensitive resin composition layer formed by the photosensitive resin composition layer forming step, the exposure step, and the developing treatment step, which is performed again, is the metal to which the surface activation treatment has been performed. The method for producing a laminate according to any one of claims 1 to 17 , which is a layer and a layer in contact with the photosensitive resin composition layer subjected to the surface activation treatment. Any of claims 1 to 18 , wherein the photosensitive composition layer forming step, the exposure step, the developing treatment step, the metal layer forming step, and the surface activation treatment step are performed 3 to 7 times in the above order. The method for producing a laminate according to item 1. A method for manufacturing a semiconductor device, which comprises the method for manufacturing a laminate according to any one of claims 1 to 19. A step of forming a desired pattern consisting of a photosensitive resin composition layer by negative development,
A metal layer forming step of forming a metal layer on a part of the surface of a pattern made of the photosensitive resin composition layer obtained by the step of forming the pattern.
A surface activation treatment step of surface activating at least a part of the metal layer and at least a part of the pattern composed of the photosensitive resin composition layer, and a step of laminating the photosensitive resin composition layer on the surface of the metal layer. Including
The photosensitive resin composition layer in the step of forming the pattern and the photosensitive resin composition layer in the step of laminating are selected from a polyimide precursor, a polyimide, a polybenzoxazole precursor, and a polybenzoxazole, respectively. A layer formed from a photosensitive resin composition containing a resin.
Further, the resin may contain a polymerizable group, and, to meet at least one of said photosensitive resin composition comprises a polymerizable compound,
The resin is represented by a repeating unit represented by the following formula (2), a repeating unit represented by the following formula (4), a repeating unit represented by the following formula (3), and a following formula (X). Containing at least one repeating unit selected from the group consisting of repeating units,
Manufacturing method of rewiring layer.
Equation (2):

In formula (2), A ¹ and A ² represent an oxygen atom, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ are independent of each other. Represents a monovalent organic group;
Equation (4):

In formula (4), R ¹³¹ represents a divalent organic group and R ¹³² represents a tetravalent organic group;
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;
Equation (X):

In formula (X), R ¹³³ represents a divalent organic group and R ¹³⁴ represents a tetravalent organic group. The production of the rewiring layer according to claim 21, wherein the resin contains at least one repeating unit selected from the group consisting of the repeating unit represented by the formula (2) and the repeating unit represented by the formula (3). Method. The method for producing a rewiring layer according to claim 21 or 22, wherein the photosensitive resin composition contains an oxime compound as a polymerization initiator. The method for producing a rewiring layer according to any one of claims 21 to 23, wherein the resin is polyimide or a polyimide precursor. The method for producing a rewiring layer according to any one of claims 21 to 24, wherein the photosensitive resin composition further contains a polymerization inhibitor. Any one of claims 21 to 25 , wherein the laminating step is a step of laminating the photosensitive resin composition layer on the surface of the metal layer and the surface of the pattern composed of the photosensitive resin composition layer. The method for manufacturing a rewiring layer according to.

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