JP2020154205A - Pattern formation method, curable resin composition, film, cured film, laminate, and semiconductor device - Google Patents

Abstract

To provide: a pattern formation method in which a pattern obtained has excellent breaking elongation; a curable resin composition used in the pattern formation method; a film formed from the curable resin composition; a cured film obtained by curing the curable resin composition; a laminate containing the cured film; and a semiconductor device including the cured film or the laminate.SOLUTION: The pattern formation method comprises: an application step of forming a film by applying a curable resin composition on a substrate; and a thermal curing step of curing the film by heating. The curable resin composition comprises a polymer precursor containing a heterocyclic ring, a plasticizer, and a solvent, and contents of the plasticizer and the solvent have specific values. When, among heating temperatures in the thermal curing step, a temperature which is 100°C or higher and lasts the longest is designated by X, a boiling point at 1 atmospheric pressure of a specific solvent among the solvents is designated by Y, and a lower temperature between a boiling point of the plasticizer at 1 atmospheric pressure and a thermal decomposition temperature thereof is designated by Z, X, Y, and Z satisfy a specific relationship.SELECTED DRAWING: None

Description

The present invention relates to a pattern forming method, a curable resin composition, a film, a cured film, a laminate, and a semiconductor device.

A resin obtained by cyclizing and curing a polymer precursor such as a polyimide resin or a polybenzoxazole resin (hereinafter, the polyimide resin precursor and the polybenzoxazole resin precursor are collectively referred to as a "heterocycle-containing polymer precursor"). Is applied to various applications because it has excellent heat resistance and insulation properties. The above application is not particularly limited, and examples of a semiconductor device for mounting include use as a material for an insulating film or a sealing material, or as a protective film. It is also used as a base film and coverlay for flexible substrates.

For example, in the applications described above, the heterocycle-containing polymer precursor is used in the form of a curable resin composition containing the heterocycle-containing polymer precursor. Such a curable resin composition is applied to a substrate by, for example, coating, and then the heterocyclic-containing polymer precursor is cyclized by heating or the like to form a cured resin on the substrate. Can be done. Since the curable resin composition can be applied by a known coating method or the like, for example, there is a high degree of freedom in designing the shape, size, application position, etc. of the curable resin composition to be applied. It can be said that it has excellent adaptability. In addition to the high performance of polyimide resins and the like, from the viewpoint of excellent manufacturing adaptability, industrial application development of curable resin compositions containing heterocyclic-containing polymer precursors is expected more and more.

For example, Patent Document 1 describes at least one of a resin composed of a polyimide precursor, a polyimide, a polybenzoxazole precursor, and polybenzoxazole, a cross-linking agent, and a solvent that dissolves the resin at 25 ° C. in an amount of 5% by mass or more. Therefore, the solubility parameter distance between the first solvent selected from alcohols, esters, ketones, ethers, sulfur-containing compounds, carbonates and ureas and the first solvent is 3.0 to 11. Compositions containing a second solvent of .0 are described.

International Publication No. 2017/038664

In a pattern forming method using a curable resin composition containing a heterocyclic-containing polymer precursor such as a polyimide precursor, it is desired to provide a pattern forming method excellent in breaking elongation of the pattern of the obtained cured film.

The present invention cures a pattern forming method excellent in breaking elongation of the obtained pattern, a curable resin composition used in the pattern forming method, a film formed from the curable resin composition, and the curable resin composition. It is an object of the present invention to provide a cured film, a laminate containing the cured film, and a semiconductor device containing the cured film or the laminate.

Examples of typical embodiments of the present invention are shown below.
<1> An application step of applying the curable resin composition onto a substrate to form a film, and
Including a heat curing step of heating and curing the film,
The curable resin composition contains at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, a plasticizer, and a solvent.
The content of the plasticizer with respect to the total mass of the curable resin composition is more than 0% by mass and less than 10% by mass.
The content of the solvent with respect to the total mass of the curable resin composition is 10% by mass or more.
Of the heating temperatures in the heat curing step, the temperature at which the temperature is 100 ° C. or higher and the longest time is X ° C., the boiling point of the solvent having the highest boiling point among the solvents at 1 atm is Y ° C., and the plasticizer. A pattern forming method that satisfies the following conditions A and B when the lower temperature of the boiling point and the thermal decomposition temperature at 1 atm is Z ° C.
Condition A: X-20 ≤ Z ≤ X + 60
Condition B: Y + 1 <Z
<2> The pattern forming method according to <1>, wherein the plasticizer is a compound having a pKa of less than 11 and a conjugate acid having a pKa of more than 3.
<3> The plasticizer is not decomposed by the heat curing step, or is decomposed by the heat curing step, and the pKa of the conjugate acid of the decomposition product produced by the decomposition exceeds 3, <1> or <2>. The pattern forming method described in 1.
<4> The pattern according to any one of <1> to <3>, wherein the plasticizer contains an alkylene glycol structure, an ester structure derived from a hydrocarbon compound having 3 or more hydroxy groups, or an acetal structure. Forming method.
<5> The pattern forming method according to any one of <1> to <4>, wherein the plasticizer has a molecular weight of 100 to 600.
<6> The pattern forming method according to any one of <1> to <5>, wherein the boiling point of the plasticizer is higher than the thermal decomposition temperature of the plasticizer.
<7> The pattern forming method according to <6>, wherein the thermal decomposition temperature of the plasticizer is higher than the above X ° C.
<8> The pattern forming method according to any one of <1> to <5>, wherein the boiling point of the plasticizer is a temperature equal to or lower than the thermal decomposition temperature of the plasticizer.
<9> The pattern forming method according to any one of <1> to <8>, wherein the X ° C. is 150 to 350 ° C.
<10> One of <1> to <9>, wherein the solvent contains at least one selected from the group consisting of N-methyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone and ethyl lactate. The pattern forming method described.
<11> The pattern forming method according to any one of <1> to <10>, wherein the curable resin composition further contains a photopolymerization initiator.
<12> The pattern according to any one of <1> to <11>, wherein the curable resin composition further contains at least one selected from the group consisting of an onium salt and a thermobase generator. Forming method.
<13> Any of <1> to <12>, further including an exposure step of exposing at least a part of the film obtained in the application step and a development treatment step of performing a development treatment on the exposed film. The pattern forming method according to one.
<14> The pattern forming method according to any one of <1> to <13>, further comprising a metal layer forming step of forming a metal layer on the surface of the film after the development treatment.
<15> The pattern forming method according to any one of <1> to <14>, which is a pattern forming method used for forming an interlayer insulating film.
<16> A curable resin composition used as the curable resin composition in the pattern forming method according to any one of <1> to <15>.
<17> A film formed from the curable resin composition according to <16>.
<18> A cured film obtained by curing the curable resin composition according to <16>.
<19> A laminate containing two or more layers of the cured film according to <18> and containing a metal layer between any of the cured films.
<20> A semiconductor device comprising the cured film according to <18> or the laminate according to <19>.

According to the present invention, a pattern forming method excellent in breaking elongation of the obtained pattern, a curable resin composition used in the pattern forming method, a film formed from the curable resin composition, and the curable resin composition. Provided are a cured film obtained by curing, a laminate containing the cured film, and a semiconductor device containing the cured film or the laminate.

Hereinafter, main embodiments of the present invention will be described. However, the present invention is not limited to the specified embodiments.
In the present specification, the numerical range represented by using the symbol "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.
In the present specification, the term "process" means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the desired action of the process can be achieved.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). 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 exposure using particle beams such as an electron beam and an ion beam. Examples of the light used for exposure include 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.
As used herein, "(meth) acrylate" means both "acrylate" and "methacrylate", or either, and "(meth) acrylic" means both "acrylic" and "methacrylic", or , And "(meth) acryloyl" means both "acryloyl" and "methacrylic", or either.
In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In the present specification, the total solid content means the total mass of all the components of the composition excluding the solvent. Further, in the present specification, the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene-equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified. In the present specification, for the weight average molecular weight (Mw) and the number average molecular weight (Mn), for example, HLC-8220GPC (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, their molecular weights shall be measured using THF (tetrahydrofuran) as an eluent. Further, unless otherwise specified, the detection in the GPC measurement shall be performed by using a detector having a wavelength of 254 nm of UV rays (ultraviolet rays).
In the present specification, when the positional relationship of each layer constituting the laminate is described as "upper" or "lower", the other layer is above or below the reference layer among the plurality of layers of interest. All you need is. That is, a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer and the other layer need not be in contact with each other. Unless otherwise specified, the direction in which the layers are stacked on the base material is referred to as "upper", or if there is a photosensitive layer, the direction from the base material to the photosensitive layer is referred to as "upper". The opposite direction is referred to as "down". It should be noted that such a vertical setting is for convenience in the present specification, and in an actual embodiment, the "upward" direction in the present specification may be different from the vertical upward direction.
Unless otherwise specified in the present specification, the composition may contain, as each component contained in the composition, two or more kinds of compounds corresponding to the component. Unless otherwise specified, the content of each component in the composition means the total content of all the compounds corresponding to the component.
In the present specification, the physical property values are values under the conditions of a temperature of 23 ° C. and an atmospheric pressure of 101,325 Pa (1 atm) unless otherwise specified.
In the present specification, the combination of preferred embodiments is a more preferred embodiment.

(Pattern formation method)
The pattern forming method of the present invention includes an application step of applying a curable resin composition onto a substrate to form a film, and a thermosetting step of heating and curing the film, and the curable resin composition. However, the above-mentioned curing of the above-mentioned plasticizer containing at least one polymer precursor (heterocycle-containing polymer precursor) selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, a plasticizer, and a solvent. The content of the sex resin composition with respect to the total mass is more than 0% by mass and less than 10% by mass, the content of the solvent with respect to the total mass of the curable resin composition is 10% by mass or more, and the thermosetting is performed. Of the heating temperatures in the process, the temperature that is 100 ° C. or higher and the longest time is X ° C., the boiling point of the highest boiling point solvent among the above solvents is Y ° C. When the lower temperature of the boiling point and the thermal decomposition temperature in the above is Z ° C., the following condition A and the following condition B are satisfied.
Condition A: X-20 ≤ Z ≤ X + 60
Condition B: Y + 1 <Z

In the present invention, the pattern refers to a pattern formed by a cured film obtained by curing the curable resin composition obtained after the heat curing step, and even if it is a pore-shaped pattern, it is a line-and-space pattern. However, it may be a dot-shaped pattern, a pattern having another shape, or a pattern obtained by combining these. Further, the pattern may be a one-layer pattern formed on a flat surface, or a total of two or more layers, one layer or two or more cured films, and zero layer or one or more other layers. It may be a laminated pattern. Further, the pattern forming method of the present invention may be any method as long as the above pattern is formed.
The pattern obtained by the pattern forming method of the present invention is excellent in elongation at break.
The mechanism by which the above effect is obtained is unknown, but it is presumed as follows.
The curable resin composition used in the present invention contains a plasticizer. Therefore, the film formed in the application process also contains a plasticizer. When such a film is subjected to a heat curing step, the film is plasticized by the action of a plasticizer, so that the cyclization of the heterocyclic polymer precursor is likely to proceed, and the pattern of the cured film having excellent elongation at break is achieved. Is considered to be obtained.
Further, when the above X ° C., the above Y ° C., and the above Z ° C. satisfy the above conditions A and B, the plasticizer is present in the film at the start of the heat curing step, and after the heat curing step, the plasticizer is present. Since the plasticizer does not easily remain in the film, it is considered that the elongation at break in the obtained pattern is likely to be improved.
Further, in the method of forming a pattern using a curable resin composition containing a heterocycle-containing polymer precursor, for example, when a curable resin composition is further applied on a cured film and cured to prepare a laminate. In addition, the already formed cured film may come into contact with the developer or other composition. Therefore, in the curable resin composition, it is desired to provide a pattern forming method having excellent chemical resistance of the obtained pattern, for example, from the viewpoint of resistance to a developing solution or suppression of dissolution due to contact with other compositions. ing.
In the pattern forming method of the present invention, it is considered that cyclization is likely to proceed as described above, and therefore it is considered that a pattern having excellent chemical resistance is easily obtained.

Here, in Patent Document 1, a curable resin composition containing the above plasticizer is used, and the above X ° C., the above Y ° C. and the above X ° C. are set to temperatures satisfying the above conditions A and B. There is no description or suggestion about.
Hereinafter, the details of the steps included in the pattern forming method of the present invention will be described.

<Application process>
The pattern forming method of the present invention includes an application step of applying a curable resin composition onto a substrate to form a film.

〔Base material〕
The type of base material can be appropriately determined depending on the application, but semiconductor-made base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin-film deposition film, There are no particular restrictions on magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, paper, SOG (Spin On Glass), TFT (thin film) array substrates, and electrode plates of plasma display panels (PDPs). In the present invention, a semiconductor-made base material is particularly preferable, and a silicon base material is more preferable.
Further, as the base material, for example, a plate-shaped base material (board) is used.
Further, when a film 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 base material.

[Applicable means]
Coating is preferable as a means for applying the curable resin composition to the substrate.
Specifically, the means to be applied include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, and a slit coating method. And the inkjet method and the like are exemplified. From the viewpoint of the uniformity of the thickness of the curable resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an inkjet method are more preferable. A resin layer having a desired thickness can be obtained by adjusting an appropriate solid content concentration and coating conditions according to the method. Further, the coating method can be appropriately selected depending on the shape of the substrate. For a circular substrate such as a wafer, a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular substrate, a slit coating method or a spray coating method is preferable. The method, the inkjet method and the like are preferable. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute.
It is also possible to apply a method of transferring a coating film previously formed on a temporary support by the above-mentioned application method onto a substrate.
Regarding the transfer method, the production method described in paragraphs 0023, 0036 to 0051 of JP-A-2006-023696 and paragraphs 096 to 0108 of JP-A-2006-047592 can be preferably used in the present invention.

The pattern by the pattern forming method may be formed by applying the curable resin composition to at least a part of the base material by any of the above application means, or the curable resin composition is applied to the base material. It may be formed later by performing an exposure step and a development processing step described later.

[Dry]
The application step may include a drying process that removes at least a portion of 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 exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.

[Film thickness]
The thickness (film thickness) of the film obtained by the application step is not particularly limited, but is preferably 0.5 μm or more, and more preferably 1 μm or more. The film thickness is preferably 100 μm or less, and more preferably 30 μm or less.
The film thickness may be appropriately set in consideration of the film thickness of the pattern to be finally obtained.

[Curable resin composition]
The curable resin composition used in the application process contains a heterocyclic polymer precursor, a plasticizer, and a solvent.
Hereinafter, the description of the plasticizer and the solvent will be described, and the heterocyclic polymer precursor and other compounds contained in the curable resin composition will be described later.

-Plasticizer-
The curable resin composition contains a plasticizer.

<< Content >>
The content of the plasticizer is more than 0% by mass and less than 20% by mass, preferably 2% by mass or more and less than 15% by mass, based on the total solid content mass of the curable resin composition. It is more preferably less than 10% by mass.
Further, the content of the plasticizer is preferably 0 to 20% by mass, more preferably 2 to 15% by mass, based on the total mass of the film formed in the application step.
The plasticizer may contain only one type, or may contain two or more types.
The content of the plasticizer is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, based on the total mass of the cured film (pattern) formed in the heat curing step.

<< Boiling point and pyrolysis temperature >>
The lower temperature (Z ° C.) of the boiling point at 1 atm and the thermal decomposition temperature of the plasticizer is preferably 150 to 300 ° C., more preferably 200 to 250 ° C.
The boiling point of the plasticizer is measured by using a known technique, and is not particularly limited, but is measured, for example, by measuring the temperature at the time of boiling.
The thermal decomposition temperature can be measured as the peak temperature of the lowest exothermic peak by putting a plasticizer in a pressure resistant capsule, heating the pressure resistant capsule at 5 ° C./min, and measuring the differential scanning calorimetry. it can. When the heating is carried out to a temperature which is the boiling point of the plasticizer, for example, and no exothermic peak is observed, the thermal decomposition temperature is considered to be lower than the boiling point.

From the viewpoint of sufficiently exerting the plasticizing effect, it is preferable that the boiling point of the plasticizer is higher than the thermal decomposition temperature of the plasticizer.
When the boiling point of the plasticizing agent is higher than the thermal decomposition temperature of the plasticizing agent, the thermal decomposition temperature of the plasticizing agent is preferably higher than X ° C., more than X ° C. Is more preferably 20 ° C. higher, and even more preferably 10 ° C. higher than the above X ° C.
From the viewpoint of sufficiently exerting the plasticizing effect, the boiling point of the plasticizer is preferably a temperature equal to or lower than the thermal decomposition temperature of the plasticizer.

From the viewpoint of elongation at break, storage stability of the curable resin composition, and developability, the pKa of the plasticizer is preferably 11 or more, and the pKa of the conjugate acid of the plasticizer is preferably less than 3.
The pKa of the plasticizer is preferably 13 or more, and more preferably 15 or more.
Further, the pKa of the conjugate acid of the plasticizer is preferably 2 or less, and more preferably 1 or less.
When a plurality of pKas of the plasticizer are present, it is more preferable that all the pKas are within the above range.
Further, when a plurality of pKas of the conjugate acids of the plasticizers are present, it is more preferable that the pKas of the conjugate acids of all the plasticizers are within the above range.
The pKa of the plasticizer and the pKa of the conjugate acid of the plasticizer include Determination of Organic Structures by Physical Methods (authors: Brown, HC, McDaniel, D.H., Hafliger, O.F. Na. .; Compilation: Braude, E. A., Nachod, FC; Academic Press, New York, 1955) and Data for Biochemical Research (Author: Dawson, R. M. C. , 1959) can be referred to. For compounds not described in these documents, the values calculated from the structural formulas using ACD / pKa (manufactured by ACD / Labs) software shall be used.

From the viewpoints of elongation at break, storage stability of the curable resin composition, and developability, the plasticizer is not decomposed by the heat curing step, or is decomposed by the heat curing step, and is a decomposed product produced by the decomposition. It is preferable that the compound has a pKa of the conjugate acid of less than 3.
The pKa of the decomposition product is preferably 13 or more, and more preferably 15 or more.
The pKa of the conjugate acid of the decomposition product is preferably 2 or less, and more preferably 1 or less.
The pKa of the decomposition product can be calculated by referring to the value described in the literature or from the structural formula, similarly to the pKa of the plasticizer.

<< Structure >>
The plasticizer preferably contains an alkylene glycol structure, an ester structure derived from a hydrocarbon compound having 3 or more hydroxy groups, or an acetal structure.
When the plasticizer contains an alkylene glycol structure or an ester structure derived from a hydrocarbon compound having 3 or more hydroxy groups, the plasticizer is preferably a compound having a boiling point of a temperature equal to or lower than the thermal decomposition temperature.
When the plasticizer contains an acetal structure, the plasticizer is preferably a compound having a boiling point higher than the thermal decomposition temperature.

[[Plasticizer containing alkylene glycol structure]]
The plasticizer preferably contains an alkylene glycol structure.
The alkylene glycol structure contained in the plasticizer may be a polyalkylene glycol structure in which a plurality of alkylene glycols are bonded (for example, a diethylene glycol structure, a tripropylene glycol structure, etc.).
Hereinafter, the alkylene glycol structure and the polyalkylene glycol structure are collectively referred to as a (poly) alkylene glycol structure.
The (poly) alkylene glycol preferably has a (poly) alkylene glycol structure having 2 to 10 carbon atoms in the alkylene group, more preferably a (poly) alkylene glycol structure having 2 to 6 carbon atoms, and has an ethylene glycol structure or a propylene glycol structure. , Polyethylene glycol structure, polypropylene glycol structure, butylene glycol structure, pentene glycol structure, hexene glycol structure and the like.

The plasticizer containing an alkylene glycol structure is preferably (poly) alkylene glycol, (poly) alkylene glycol diacetate, or (poly) alkylene glycol monoalkyl ether acetate, and is preferably (poly) alkylene glycol diacetate or (poly) alkylene glycol diacetate. (Poly) alkylene glycol monoalkyl ether acetate is more preferred.
The (poly) alkylene glycol represents an alkylene glycol or a polyalkylene glycol.
The (poly) alkylene glycol diacetate represents an alkylene glycol diacetate or a polyalkylene glycol diacetate.
The (poly) alkylene glycol monoalkyl ether acetate represents an alkylene glycol monoalkyl ether acetate or a polyalkylene glycol monoalkyl ether acetate.

As the plasticizer containing an alkylene glycol structure, a compound represented by the following formula (AG-1) is preferably mentioned.

Wherein ^{(AG-1), R A1} and ^{R A2} each independently represent a hydrogen atom, an alkyl group or an acyl ^{group, L A1} represents an alkylene radical, n represents an integer of 1 or more.

In the formula (AG-1), ^RA1 and ^RA2 preferably independently represent an alkyl group or an acyl group, one of ^RA1 and ^RA2 represents an alkyl group, and the other represents an acyl group. It is more preferable that both ^RA1 and ^RA2 represent an acyl group.
Unless otherwise specified, the alkyl group may be linear or branched chain and may have a ring structure in the present specification.
The acyl group in R ^A1 and ^{R A2,} alkyl carbonyl or arylcarbonyl group, more preferably an aryl group an alkyl group or a C 7-20 having 2 to 12 carbon atoms, having 2 to 12 carbon atoms The alkylcarbonyl group is more preferred, and the acetyl group is particularly preferred.
The alkyl group in R ^A1 and ^{R A2,} preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.
Wherein ^{(AG-1), L A1} is preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 6 carbon atoms.
^LA1 is preferably, for example, an alkylene group represented by the following formula.
In the following formula, * independently represents the binding site with the oxygen atom.
In the formula (AG-1), n is preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 to 3.
Further, when n is 2 or more, 2 or more L ^A1 may be different even in the same.
The total number of carbon atoms in the formula (AG-1) is preferably 1 to 20, more preferably 1 to 10.
Further, n-number of ^{-O-L A1} in (AG-1) - The total number of carbon atoms in structure represented by is preferably 4 to 1, and more preferably 3-2.

[[Plasticizer containing an ester structure derived from a hydrocarbon compound having 3 or more hydroxy groups]]
The plasticizer preferably contains an ester structure derived from a hydrocarbon compound having 3 or more hydroxy groups.
The ester structure derived from the hydrocarbon compound having 3 or more hydroxy groups refers to an ester structure formed by the hydroxy group in the hydrocarbon structure and the oxo acid, and the hydroxy group and the organic which is the oxo acid. The ester structure formed by the acid is preferable, and the ester structure formed by the hydroxy group and the organic carboxylic acid is more preferable.
The hydrocarbon compound having 3 or more hydroxy groups is preferably an aliphatic hydrocarbon compound having 3 or more hydroxy groups as a substituent.
The number of hydroxy groups in the above-mentioned hydrocarbon compound having 3 or more hydroxy groups is preferably 3 to 10, more preferably 3 to 6, and even more preferably 3.
The ester structure in the ester structure derived from the hydrocarbon compound having 3 or more hydroxy groups is preferably a carboxy ester structure.
Specifically, among the hydroxy groups in the hydrocarbon compound having 3 or more hydroxy groups, a compound in which at least one of them forms a carboxyester structure can be mentioned.
Of the above hydroxy groups, it is preferable that two or more form a carboxy ester structure, and more preferably three or more form a carboxy ester structure.
The glycerin ester structure is preferable as the ester structure derived from the hydrocarbon compound having 3 or more hydroxy groups.
Examples of the plasticizer containing a glycerin ester structure include a glycerin monoester compound, a glycerin diester compound, and a glycerin triester compound, and a glycerin triester compound is preferable.
Further, the ester structure of the plasticizer containing the glycerin ester structure is preferably a carboxy ester structure.

As the plasticizer containing a glycerin ester structure, a compound represented by the following formula (PG-1) is preferably mentioned.
Wherein ^{(PG-1), R P1} , R P2 and ^{R P3} each independently represent a hydrogen atom, a substituent or an acyl ^group, at least one acyl group of R ^{P1, R P2} and ^{R P3} ..
Of R ^{P1, R P2} and ^{R P3,} it is preferable that at least two of an acyl group, and more preferably 3 Tsutomo is an acyl group.
^The acyl group in R ^{P1, R P2} and ^{R P3,} alkylcarbonyl group, more preferably an alkylcarbonyl group having 2 to 4 carbon atoms, more preferably an acetyl group.
The substituent in R ^{P1, R P2} and ^{R P3,} alkyl groups are preferred, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.

[[Plasticizer containing acetal structure]]
The plasticizer preferably contains an acetal structure.
When the plasticizer has an acetal structure, the plasticizer is a compound having an acetal structure and a branched alkyl group, or a compound having an acetal structure and a cyclic alkyl group, from the viewpoint of keeping the temperature Z ° C. within the above range. Is preferable.
As the branched alkyl group, an alkyl group containing a quaternary carbon atom is preferable, and a t-butyl group is more preferable.
Examples of the cyclic alkyl group include a monocyclic alkyl group such as a cyclohexyl group, a condensed ring such as a decahydronaphthyl group, a dicyclopentanyl group, an isobornyl group and an adamantyl group, or a crosslinked alkyl group, and an adamantyl group is more preferable. ..

As the plasticizer containing an acetal structure, a compound represented by the following formula (AC-1) is preferably mentioned.
Wherein ^{(AC-1), R C1} , R C2, R C3 and ^{R C4} are each independently, represent a hydrogen atom or a hydrocarbon ^group, at least one of ^{R C1} and ^{R C2} represents a hydrocarbon ^{group, R C1} , ^RC2 , ^RC3 and ^RC4 may be combined to form a ring structure.
Of ^RC1 and ^RC2 , it is preferable that one is a hydrocarbon group and the other is a hydrogen atom.
The hydrocarbon group in ^RC1 and ^RC2 is preferably a branched alkyl group or a cyclic alkyl group.
As the branched alkyl group, an alkyl group containing a quaternary carbon atom is preferable, and a t-butyl group is more preferable.
Examples of the cyclic alkyl group include a monocyclic alkyl group such as a cyclohexyl group, a condensed ring such as a decahydronaphthyl group, a dicyclopentanyl group, an isobornyl group and an adamantyl group, or a crosslinked alkyl group, and an adamantyl group is more preferable. ..
It is preferable that ^RC3 and ^RC4 are each independently a hydrocarbon group.
^RC3 and ^RC4 may be different groups, but are preferably the same group.
As the hydrocarbon group for R ^C3 and ^{R C4,} preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms.

<< Molecular Weight >>
From the viewpoint of further improving the elongation at break of the pattern, the molecular weight of the plasticizer is preferably 100 to 600, more preferably 100 to 500, and even more preferably 150 to 350.

<< Specific example >>
Specific examples of the plasticizer include, but are not limited to, the compounds listed in Table 1 below. In Table 1, the name or structure of the compound is described in the “Type” column, and the lower of the boiling point and the thermal decomposition temperature of the compound at 1 atm is described in the “Z (° C.)” column.
Further, C-1 to C-12 are compounds having a boiling point equal to or lower than the thermal decomposition temperature, and C-13 to C-15 are compounds having a boiling point higher than the thermal decomposition temperature.

− Solvent −
The curable resin composition contains a solvent.

<< Content >>
The content of the solvent is 10% by mass or more, preferably 20% by mass or more and less than 90% by mass, and preferably 30% by mass or more and less than 80% by mass with respect to the total mass of the curable resin composition. More preferred.
The content of the solvent is preferably 5% by mass or less, more preferably 2% by mass or less, and further preferably 1% by mass or less, based on the total mass of the film. The lower limit of the content is not particularly limited and may be 0% by mass.
Only one type of solvent may be contained, or two or more types may be contained.

As the solvent, an organic solvent is preferable, and compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides are more preferable.

Examples of esters include ethyl acetate, -n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone. , Δ-Valerolactone, alkylalkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.) )), 3-Alkyloxypropionate alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Methyl ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate) Etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyloxy-2-methylpropionate, etc. Methyl acid and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, pyruvin Suitable examples include propyl acid acid, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate and the like.

Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol. Suitable examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.

As the ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like are preferable.

As the aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene and the like are preferable.

As the sulfoxides, for example, dimethyl sulfoxide is preferable.

As the amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like are preferable.

As the solvent, a form in which two or more kinds are mixed is also preferable from the viewpoint of improving the properties of the coated surface.

In the present invention, 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- Consists of one solvent selected from butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, or two or more. The mixed solvent to be mixed is preferable.

Among these, the solvent preferably contains at least one selected from the group consisting of N-methyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone and ethyl lactate, and preferably contains N-methyl-2-pyrrolidone and dimethyl. It more preferably contains sulfoxide, or more preferably contains γ-butyrolactone and ethyl lactate, and even more preferably contains N-methyl-2-pyrrolidone and dimethyl sulfoxide.

Further, when the boiling point of the solvent having the highest boiling point among the solvents contained in the curable resin composition at 1 atm is Y ° C., the above Z ° C. and the above Y ° C. satisfy the following condition B.
Condition B: Y + 1 <Z
In the present specification, the solvent having the highest boiling point among the solvents contained in the curable resin composition means the boiling point of the solvent having the highest boiling point among the solvents contained in the curable resin composition at 1 atm. .. The boiling point is measured by using a known technique for measuring the boiling point, and is not particularly limited, but is measured, for example, by measuring the temperature at the time of boiling.

The Y ° C. is preferably 100 to 250 ° C., more preferably 130 to 230 ° C., and even more preferably 150 to 210 ° C.
Further, the Z ° C. and the Y ° C. preferably satisfy the following condition B2, more preferably the following condition B3, and further preferably the following condition B4.
Condition B2: Y + 5 <Z
Condition B3: Y + 15 <Z
Condition B4: Y + 20 <Z

<Heat curing process>
The pattern forming method of the present invention includes a heat curing step of heating and curing the film.
The heat curing step is included after the above application step.
When the pattern forming method of the present invention includes a development treatment step described later, it is preferable that the heat curing step is included after the development treatment step.
In the heat curing step, for example, a base is generated by decomposition of a thermal base generator described later, and the cyclization reaction of the heterocyclic polymer precursor proceeds. Further, the film to which the curable resin composition used in the present invention is applied contains a compound having a radically polymerizable group such as a heterocyclic-containing polymer precursor having a radically polymerizable group and a radically polymerizable compound. However, curing of unreacted compounds among these compounds having a radically polymerizable group can also proceed in this step.

Of the heating temperatures in the heat curing step, when the temperature is 100 ° C. or higher and the longest time is X ° C., the Z ° C. and the X ° C. satisfy the following condition A.
Condition A: X-20 ≤ Z ≤ X + 60

The X ° C. is preferably 150 to 350 ° C., more preferably 180 ° C. to 250 ° C.
Further, the Z ° C. and the X ° C. preferably satisfy the following condition A2, and more preferably the following condition A3.
Claim A2: X-15 ≤ Z ≤ X + 50
Condition A3: X-10 ≤ Z ≤ X + 40

The X ° C. is measured by a surface thermometer as the temperature of the surface of the film.
The X ° C. is preferably the temperature at which the heterocyclic polymer precursor is cyclized and is the longest.
The time at X ° C. is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and even more preferably 30 to 240 minutes.
During the time of X ° C., the temperature may change in the range of, for example, X ° C.-5 ° C. to X ° C. + 5 ° C.
Further, the heating may be performed in a plurality of times, but when the heating is performed a plurality of times, the time at X ° C. is preferably the total amount of the time at X ° C. in the plurality of heatings.

The heating in the heat curing step is preferably performed at a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and 3 to 10 ° C./min. More preferred. 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, a pattern (curing) can be prevented. The residual stress of the film) can be relaxed.

The temperature at the start of heating is preferably 20 ° C. to 150 ° C., more preferably 20 ° C. to 130 ° C., and even more preferably 25 ° C. to 120 ° C. The temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature is started. For example, when the curable resin composition is applied onto a substrate and then dried, the temperature of the film (layer) after drying is higher than, for example, the boiling point of the solvent contained in the curable resin composition. It is preferable to gradually raise the temperature from a temperature as low as 30 to 200 ° C.

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

Further, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.

The heat curing step is preferably carried out in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium or argon in order to prevent decomposition of the heterocyclic polymer precursor. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

The heating means is not particularly limited, and known heating means such as a hot plate, a convection oven (hot air circulation type dryer), a high frequency heater, and an infrared heater can be used.

<Exposure process>
The pattern forming method of the present invention preferably further includes an exposure step of exposing at least a part of the film obtained in the application step.
In the exposure step, the entire film may be exposed, but it is preferable to expose a part of the film, and it is more preferable to expose the film in a pattern (pattern exposure).
The pattern exposure may be performed using a photomask or a laser light source or the like, but it is preferably performed using a photomask.
The pattern forming method of the present invention preferably includes an exposure step after the application step and before the heat curing step.
For example, when a above-mentioned compound having a radically polymerizable group and a composition containing a photopolymerization initiator described later are used as the curable resin composition, the compound having a radically polymerizable group is subjected to an exposure step. Can be further polymerized to further improve the breaking elongation of the obtained pattern.
Further, the pattern forming method of the present invention includes an exposure step and a development processing step described later, and by performing the above pattern exposure in the exposure step, it becomes possible to easily form patterns having various shapes.
Exposure dose in the exposure step, for example, it is preferable to irradiate 100~10,000mJ / cm ² at an exposure energy conversion at a wavelength 365 nm, it is more preferable to irradiate 200~8,000mJ / cm ^2.
The exposure wavelength can be appropriately determined in the range of 190 to 1,000 nm, preferably 240 to 550 nm.

In relation to the light source, the exposure wavelengths are (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength 436 nm), h. Line (wavelength 405 nm), i-line (wavelength 365 nm), broad (3 wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer Examples thereof include a laser (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), and (6) electron beam. Regarding the curable resin composition used in the present invention, exposure with a high-pressure mercury lamp is particularly preferable, and exposure with an i-line is particularly preferable. As a result, particularly high exposure sensitivity can be obtained.
The exposure wavelength is not particularly limited, and can be determined in consideration of, for example, the maximum absorption wavelength of the photopolymerization initiator described later.

<Development process>
The pattern forming method of the present invention preferably includes a developing process step of performing a developing process (developing the film) on the exposed film (curable resin composition layer). By performing the development, the unexposed portion (non-exposed portion) is removed. The developing method is not particularly limited as long as a desired pattern can be formed, and for example, a developing method such as paddle, spray, immersion, or ultrasonic wave can be adopted.

Development is performed using a developing solution. The developer can be used without particular limitation as long as the unexposed portion (non-exposed portion) is removed. The developer preferably contains an organic solvent, and more preferably the developer contains 90% or more of the organic solvent. In the present invention, the developer preferably contains an organic solvent having a ClogP value of −1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by inputting a structural formula in ChemBioDraw.

Examples of the organic solvent include ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and γ-butyrolactone. , Ε-caprolactone, δ-valerolactone, alkylalkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, Ethyl propionate ethoxyacetate, etc.)), alkyl esters of 3-alkyloxypropionate (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.) (eg, methyl 3-methoxypropionate, 3-methoxypropionate) Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl) Propyl oxypropionate and the like (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, pyruvin Ethyl phosphate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. , Keto Examples of compounds include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, and aromatic hydrocarbons include, for example, toluene, xylene, anisole, limonene, etc. , Dimethyl sulfoxide is preferably mentioned as the sulfoxides.

In the present invention, cyclopentanone and γ-butyrolactone are particularly preferable, and cyclopentanone is more preferable.

The developing solution preferably contains 50% by mass or more of an organic solvent, more preferably 70% by mass or more of an organic solvent, and further preferably 90% by mass or more of an organic solvent. Further, the developing solution may be 100% by mass of an organic solvent.

The developing time is preferably 10 seconds to 5 minutes. The temperature of the developing solution 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 similar to that contained in the curable resin composition. The rinsing time is preferably 5 seconds to 1 minute.

<Metal layer forming process>
The pattern forming method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the film (curable resin composition layer) after the development treatment.

As the metal layer, existing metal types can be used without particular limitation, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are exemplified, copper and aluminum are more preferable, and copper is preferable. More preferred.

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, electrolytic plating, electroless plating, etching, printing, and a method combining these 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, more preferably 1 to 10 μm at the thickest portion.

<Process sequence>
The pattern forming method of the present invention includes an application step and a heat curing step, and includes (a) an application step, (b) an exposure step, (c) a development treatment step, and (d) a heat curing step in this order. It is more preferable to include (a) application step, (b) exposure step, (c) development treatment step, (d) heat curing step, and (e) metal layer forming step in this order.
Further, the pattern forming method of the present invention includes a plurality of the steps (a) described above (performing the steps (a) a plurality of times), and further steps (d) and, if necessary, (e). The step may be included, or a plurality of steps (a) to (c) may be included, and the step (d) and, if necessary, the step (e) may be included.
Further, the pattern forming method of the present invention preferably includes each of the above steps a plurality of times, for example, 2 to 5 times (that is, 3 to 6 times in total) in order. By laminating the patterns in this way, a laminated body can be obtained. In the present invention, it is particularly preferable to provide a metal layer on the portion where the pattern is provided, between the patterns, or both. In the production of the laminate, it is not necessary to repeat all the steps (a) to (e), and as described above, at least the steps (a) and (d), preferably (a) to (d). A plurality of times, and if necessary, the step (e) is further included to obtain a laminate containing the pattern.

<Laminating process>
The production method of the present invention preferably further includes a laminating step.

In the laminating step, (a) application step, (b) exposure step, (c) development treatment step, and (d) heat curing step are performed again in this order on the surface of the cured film (resin layer) or metal layer. It is a series of steps including that. However, the mode may be such that only the application step (a) is repeated. Further, (d) the heat curing step may be performed collectively at the end or the middle of the lamination. That is, the steps (a) to (c) may be repeated a predetermined number of times, and then the heating of (d) may be performed to cure the laminated curable resin composition layers all at once. Further, (c) the development treatment step may include (e) a metal layer forming step, and even if the heating is performed each time (d) at this time, the layers are laminated a predetermined number of times and then collectively (d). May be heated.

When the laminating step is further performed after the laminating step, the surface activation treatment step may be further performed after the heat curing step, the exposure step, or the metal layer forming step. An example of the surface activation treatment is plasma treatment.

The laminating step is preferably performed 2 to 5 times, more preferably 3 to 5 times.

For example, it is preferable that the resin layer is 3 or more and 7 or less, such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, and more preferably 3 or more and 5 or less.

In the present invention, it is particularly preferable to form a cured film (resin layer) of the curable resin composition so as to cover the metal layer after providing the metal layer. Specifically, an embodiment in which (a) application step, (b) exposure step, (c) development treatment step, (e) metal layer forming step, and (d) heat curing step are repeated in this order, or (a) application. Examples thereof include an embodiment in which the steps, (b) exposure steps, (c) development processing steps, and (e) metal layer forming steps are repeated in this order, and (d) heat curing steps are collectively provided at the end or in the middle. By alternately performing the laminating step of laminating the curable resin composition layer (resin layer) and the metal layer forming step, the curable resin composition layer (resin layer) and the metal layer can be laminated alternately.

(Curable resin composition)
The curable resin composition of the present invention is also referred to as a curable resin composition used as the curable resin composition in the pattern forming method of the present invention (hereinafter, also referred to as "curable resin composition used in the present invention". ).
The curable resin composition used in the present invention contains a heterocyclic polymer precursor, a plasticizer, and a solvent.
The plasticizer and solvent are as described above.
Hereinafter, each component other than the plasticizer and the solvent contained in the curable resin composition used in the present invention will be described.

<Heterocycle-containing polymer precursor>
The curable resin composition used in the present invention contains a heterocyclic polymer precursor.
The curable resin composition used in the present invention contains at least one precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor as the heterocyclic-containing polymer precursor, and comprises a polyimide precursor. It is preferable to include it.

[Polyimide precursor]
From the viewpoint of the film strength of the obtained cured film, the polyimide precursor preferably has a repeating unit represented by the following formula (1).

In formula (1), 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 each independently represent a hydrogen atom or a monovalent organic group.

-A ¹ and A ^2-
A ¹ and A ² in the formula (1) independently represent an oxygen atom or −NH−, and an oxygen atom is preferable.

−R ¹¹¹ −
R ¹¹¹ in the formula (1) represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group in which two or more of these are combined, and the number of carbon atoms is exemplified. A linear aliphatic group of 2 to 20, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or 2 of these. The group combined as described above is preferable, and an aromatic group having 6 to 20 carbon atoms is more preferable.

R ¹¹¹ in formula (1) is preferably derived from diamine. Examples of the diamine used for producing the polyimide precursor include linear or branched-chain aliphatic, cyclic aliphatic or aromatic diamines. Only one type of diamine may be used, or two or more types may be used.

Specifically, the diamine is a linear aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or these. It is preferably a diamine containing two or more combined groups, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. Examples of aromatic groups include the following.

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- , -NHC (= O)-, or a group obtained by combining two or more of these is 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- and S (= O) _2- , more preferably, -CH _2- , -O-, -S-,- It is more preferably a divalent group selected from the group consisting of S (= O) _2- , -C (CF ₃ ) _2- , and -C (CH ₃ ) _2- .

Specific examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 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 or isophoronediamine; meta or paraphenylenediamine, diaminotoluene, 4,4'-or 3 , 3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'-or 3,3'-diaminodiphenylmethane, 4,4'-or 3,3'-diaminodiphenylsulfone , 4,4'-or 3,3'-diaminodiphenylsulfide, 4,4'-or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'- Dimethyl-4,4'-diaminobiphenyl (4,4'-diamino-2,2'-dimethylbiphenyl), 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis (4-amino) Phenyl) 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-hydroxy) Phenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 4,4'-diaminoparatelphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) ) Phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (2-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 9,10- Bis (4-aminophenyl) anthracene, 3,3'-dimethyl-4,4'-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'-Diaminooctafluorobiphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 9,9 -Bis (4-aminophenyl) -10-hydroanthracene, 3,3', 4,4'-tetraaminobiphenyl, 3,3', 4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1 , 5-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- (3', 5'-diaminobenzoyloxy) ethyl methacrylate, 2,4- or 2,5-diaminocumen, 2 , 5-Dimethyl-paraphenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-paraphenylenediamine, 2,4,6-trimethyl-metaphenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane , 2,7-Diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-aminophenyl) ethane, diaminobenzanilide, diaminobenzoic acid ester, 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 (trifluoro) Methyl) Phenyl] Hexafluoropropane, Parabis (4-amino-2-trifluoromethylphenoxy) benzene, 4 , 4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-) 2-Trifluoromethylphenoxy) 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, Included are at least one diamine selected from 2', 5,5', 6,6'-hexafluorotridin and 4,4'-diaminoquaterphenyl.

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

Further, a diamine having at least two alkylene glycol units in the main chain is also mentioned as a preferable example. A diamine containing two or more of one or both of an ethylene glycol chain and a propylene glycol chain 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 (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (trade name, manufactured by HUNTSMAN), 1- (2- (2- (2)) -Aminopropoxy) ethoxy) propoxy) propoxy) propan-2-amine, 1- (1- (1- (2-aminopropoxy) propoxy-2-yl) oxy) propan-2-amine, etc., but are limited to these. Not done.

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 arithmetic mean values.

R ¹¹¹ in the formula (1) is preferably represented by −Ar ⁰ −L ⁰ −Ar ⁰ − from the viewpoint of the flexibility of the obtained cured film. Ar ⁰ is independently an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), and a phenylene group is preferable. L ⁰ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be single-bonded or substituted with a fluorine atom, −O−, −C (= O) −, −S−, −S (=). _O) 2 -, - NHCO-, or represent these two or more combined groups. The preferred range of L ⁰ is synonymous with A above.

From the viewpoint of i-ray transmittance, R ¹¹¹ in the formula (1) is preferably a divalent organic group represented by the following formula (51) or the formula (61). In particular, a divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-ray transmittance and availability.

In formula (51), R ^{50 to} R ⁵⁷ are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and at least one of R ^{50 to} R ⁵⁷ is a fluorine atom, a methyl group, a fluoromethyl group, It is a difluoromethyl group or a trifluoromethyl group, and * independently represents a binding site with another structure.

Examples of the monovalent organic group of R ^{50 to} R ⁵⁷ 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.

In formula (61), R ⁵⁸ and R ⁵⁹ are independently fluorine atoms, fluoromethyl groups, difluoromethyl groups, or trifluoromethyl groups, respectively.

Examples of the diamine compound giving the structure of the formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2. Examples thereof include'-bis (fluoro) -4,4'-diaminobiphenyl and 4,4'-diaminooctafluorobiphenyl. One of these may be used, or two or more thereof may be used in combination.

−R ¹¹⁵ −
R ¹¹⁵ in the formula (1) 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.

R ¹¹² is synonymous with A and has the same preferred range. * Independently represent a binding site with another structure.

Specific examples of the tetravalent organic group represented by R ¹¹⁵ in the formula (1) include a tetracarboxylic acid residue remaining after removing the acid dianhydride 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 a compound represented by the following formula (7).

R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ has the same meaning as ^{R 115} in formula (1).

Specific examples of the tetracarboxylic dianhydride include pyromellitic acid, 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 acid Dihydride, 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) propanedian Anhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,54-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) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, In addition, at least one selected from these alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms is exemplified.

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

-R ¹¹³ and R ^114-
R ¹¹³ and R ¹¹⁴ in the formula (1) independently represent a hydrogen atom or a monovalent organic group. At least one of R ¹¹³ and R ¹¹⁴ preferably contains a radically polymerizable group, and more preferably both contain a radically polymerizable group. Examples of the radically polymerizable group include a group capable of a cross-linking reaction by the action of a radical, and a preferable example thereof is a group having an ethylenically unsaturated bond.

Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a (meth) acryloyl group, and a group represented by the following formula (III).

In formula (III), ^R200 represents a hydrogen atom or a methyl group, and a methyl group is preferable.

In formula (III), R ²⁰¹ is an alkylene group having 2 to 12 carbon atoms, −CH ₂ CH (OH) CH ₂ −, or a (poly) oxyalkylene group having 4 to 30 carbon atoms (the alkylene group has 1 carbon atom). ~ 12 is preferable, 1 to 6 is more preferable, and 1 to 3 are particularly preferable; the number of repetitions is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3). The (poly) oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group.
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.
In formula (III), * represents a binding site with another structure.
As a preferred embodiment of the polyimide precursor in the present invention, an aliphatic group, an aromatic group and an aryl having one, two or three, preferably one acid group as the monovalent organic group of R ¹¹³ or R ^114. Alkyl groups and the like can be mentioned. Specific examples thereof include an aromatic group having an acid group having 6 to 20 carbon atoms and an arylalkyl group having an acid group having 7 to 25 carbon atoms. More specifically, a phenyl group having an acid group and a benzyl group having an acid group can be mentioned. The acid group is preferably a hydroxy group. That is, R ¹¹³ or R ¹¹⁴ is preferably a group having a hydroxy group.
As the monovalent organic group represented by R ¹¹³ or R ^114, a substituent that improves the solubility of the developing solution is preferably used.

It is more preferable that R ¹¹³ or R ¹¹⁴ is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl from the viewpoint of solubility in an aqueous developer.

From the viewpoint of solubility in an organic solvent, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. As the monovalent organic group, a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group is preferable, and an alkyl group substituted with an aromatic group is more preferable.

The alkyl group preferably has 1 to 30 carbon atoms (3 or more in the case of a cyclic group). The alkyl group may be linear, branched or cyclic. Examples of the linear or branched alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group and octadecyl group. , Isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, and 2-ethylhexyl group. 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. Further, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described below is preferable.

Specific examples of the aromatic group include a substituted or unsubstituted aromatic hydrocarbon group (the cyclic structure constituting the group includes a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an inden ring, and azulene. Rings, heptalene rings, indacen rings, perylene rings, pentacene rings, acenaphten rings, phenanthrene rings, anthracene rings, naphthacene rings, chrysen rings, triphenylene rings, etc.), or substituted or unsubstituted aromatic heterocyclic groups ( The cyclic structure constituting the group includes a fluorene ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an indolin ring, an indol ring, and a benzofuran. Ring, benzothiophene ring, isobenzofuran ring, quinolysin ring, quinoline ring, phthalazine ring, naphthylidine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridin ring, acredin ring, phenanthrolin ring, thiantolen ring, chromium ring , Xanthene ring, phenoxatiin ring, phenothiazine ring or phenazine ring).

It is also preferable that the polyimide precursor has a fluorine atom in the repeating unit. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, more preferably 20% by mass or more. There is no particular upper limit, but 50% by mass or less is practical.

Further, for the purpose of improving the adhesion to the base material, an aliphatic group having a siloxane structure may be copolymerized with a repeating unit represented by the formula (1). Specific examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (paraaminophenyl) octamethylpentasiloxane.

The repeating unit represented by the formula (1) is preferably a repeating unit represented by the formula (1-A) or the formula (1-B).

A ¹¹ and A ¹² represent an oxygen atom or -NH-, R ¹¹¹ and R ¹¹² each independently represent a divalent organic radical, and R ¹¹³ and R ¹¹⁴ independently represent a hydrogen atom or 1 Representing a valent organic group, at least one of R ¹¹³ and R ¹¹⁴ is preferably a group containing a radically polymerizable group, and more preferably a radically polymerizable group.

The preferred ranges of A ¹¹ , A ¹² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ are synonymous with the preferred ranges of A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (1), respectively.

A preferred range of R ¹¹² has the same meaning as ^{R 112} in formula (5), and more preferably among others oxygen atoms.

The bonding position of the carbonyl group to the benzene ring in the formula is preferably 4, 5, 3', 4'in the formula (1-A). In formula (1-B), it is preferably 1, 2, 4, 5.

In the polyimide precursor, the repeating unit represented by the formula (1) may be one kind, or two or more kinds. Further, the structural isomer of the repeating unit represented by the formula (1) may be contained. Further, the polyimide precursor may contain other types of repeating units in addition to the repeating units of the above formula (1).

As one embodiment of the polyimide precursor in the present invention, 50 mol% or more, more 70 mol% or more, particularly 90 mol% or more of all the repeating units are the repeating units represented by the formula (1). Is exemplified. As an upper limit, 100 mol% or less is practical.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.

The degree of dispersion of the molecular weight of the polyimide precursor is preferably 1.5 to 3.5, more preferably 2 to 3.
In the present specification, the degree of dispersion of the molecular weight means a value obtained by dividing the weight average molecular weight by the number average molecular weight (weight average molecular weight / number average molecular weight).

The polyimide precursor 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, 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.

It is preferable to include a step of precipitating a solid in the production of the polyimide precursor. Specifically, the polyimide precursor in the reaction solution can be precipitated in water, and the polyimide precursor such as tetrahydrofuran can be dissolved in a soluble solvent to precipitate a solid.

[Polybenzoxazole precursor]
The polybenzoxazole precursor preferably contains a repeating unit represented by the following formula (2).

In formula (2), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ independently represent a hydrogen atom or a monovalent organic group. Represent.

−R ¹²¹ −
In formula (2), R ¹²¹ represents a divalent organic group. The divalent organic group includes an aliphatic group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms) and an aromatic group (preferably 6 to 22 carbon atoms, 6 to 14 carbon atoms). Is more preferable, and a group containing at least one of 6 to 12 is particularly preferable). Examples of the aromatic group constituting R ¹²¹ include R ¹¹¹ of the above formula (1). As the aliphatic group, a linear aliphatic group is preferable. R ¹²¹ is preferably derived from 4,4'-oxydibenzoyl chloride.

−R ¹²² −
In formula (2), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same meaning as R ¹¹⁵ in the above formula (1), and the preferable range is also the same. R ¹²² is preferably derived from 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.

-R ¹²³ and R ^124-
R ¹²³ and R ¹²⁴ independently represent a hydrogen atom or a monovalent organic group, and have the same meaning as R ¹¹³ and R ¹¹⁴ in the above formula (1), and the preferable range is also the same.

The polybenzoxazole precursor may contain other types of repeating units in addition to the repeating units of the above formula (2).

The polybenzoxazole precursor preferably further contains a diamine residue represented by the following formula (SL) as another type of repeating unit in that the occurrence of warpage of the cured film due to ring closure can be suppressed.

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 (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and R ^2s. Is a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and at least one of R ^3s , R ^4s , R ^5s , and R ^6s is aromatic. A group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), and the rest are hydrogen atoms or 1 to 30 carbon atoms (preferably 1 to 18 carbon atoms). It is preferably an organic group having 1 to 12 carbon atoms, particularly preferably 1 to 6) carbon atoms, and may be the same or different from each other. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. In the Z moiety, preferably, the a structure is 5 to 95 mol%, the b structure is 95 to 5 mol%, and a + b is 100 mol%.

In the formula (SL), preferred Z includes those in which R ^5s and R ^6s in the b structure are phenyl groups. The molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. The molecular weight can be determined by commonly used gel permeation chromatography. By setting the molecular weight in the above range, the elastic modulus of the polybenzoxazole precursor after dehydration ring closure can be lowered, and the effect of suppressing warpage and the effect of improving solubility can be achieved at the same time.

When the polybenzoxazole precursor contains a diamine residue represented by the formula (SL) as another kind of repeating unit, the tetracarboxylic dianhydride is further provided in that it improves the alkali solubility of the curable resin composition. It is preferable that the tetracarboxylic acid residue remaining after the removal of the acid dianhydride group from the product is contained as a repeating unit. Examples of such a tetracarboxylic acid residue include the example of R ¹¹⁵ in the formula (1).

The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, still more preferably 10,000 to 50,000. is there. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.

The degree of dispersion of the molecular weight of the polybenzoxazole precursor is preferably 1.5 to 3.5, more preferably 2 to 3.

The content of the heterocycle-containing polymer precursor in the curable resin composition used in the present invention is preferably 20% by mass or more, preferably 30% by mass or more, based on the total solid content of the curable resin composition. More preferably, it is more preferably 40% by mass or more, further preferably 50% by mass or more, further preferably 60% by mass or more, further preferably 70% by mass or more. .. Further, the content of the heterocycle-containing polymer precursor in the curable resin composition used in the present invention is preferably 99.5% by mass or less based on the total solid content of the curable resin composition, preferably 99. It is more preferably mass% or less, further preferably 98 mass% or less, further preferably 97 mass% or less, and even more preferably 95 mass% or less.

The curable resin composition used in the present invention may contain only one type of heterocyclic polymer precursor, or may contain two or more types. When two or more types are included, the total amount is preferably in the above range.

<Onium salt>
The curable resin composition of the present invention preferably contains an onium salt.
The type of onium salt and the like are not particularly specified, but ammonium salt, iminium salt, sulfonium salt, iodonium salt and phosphonium salt are preferably mentioned.
Among these, ammonium salt or iminium salt is preferable from the viewpoint of high thermal stability, and sulfonium salt, iodonium salt or phosphonium salt is preferable from the viewpoint of compatibility with the polymer.

The onium salt is a salt of a cation and an anion having an onium structure, and the cation and the anion may or may not be bonded via a covalent bond. ..
That is, the onium salt may be an intermolecular salt having a cation portion and an anion portion in the same molecular structure, or a cation molecule and an anion molecule, which are separate molecules, are ionically bonded. It may be an intermolecular salt, but it is preferably an intermolecular salt. Further, in the photosensitive resin composition of the present invention, the cation portion or the cation molecule and the anion portion or the anion molecule may be bonded or dissociated by an ionic bond.
As the cation in the onium salt, an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation is preferable, and at least one cation selected from the group consisting of a tetraalkylammonium cation, a sulfonium cation and an iodonium cation is more preferable.

The onium salt used in the present invention may be a thermobase generator.
The thermal base generator refers to a compound that generates a base by heating, and examples thereof include an acidic compound that generates a base when heated to 40 ° C. or higher.

[Ammonium salt]
In the present invention, the ammonium salt means a salt of an ammonium cation and an anion.

− Ammonium cation −
As the ammonium cation, a quaternary ammonium cation is preferable.
Further, as the ammonium cation, a cation represented by the following formula (101) is preferable.
In formula (101), R ^{1 to} R ⁴ each independently represent a hydrogen atom or a hydrocarbon group, and at least two of R ^{1 to} R ⁴ may be bonded to each other to form a ring.

In the formula (101), R ^{1 to} R ⁴ are each independently preferably a hydrocarbon group, more preferably an alkyl group or an aryl group, and an alkyl group having 1 to 10 carbon atoms or 6 to 6 carbon atoms. It is more preferably 12 aryl groups. R ^{1 to} R ⁴ may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group and an aryloxy group. Examples thereof include a carbonyl group and an acyloxy group.
When at least two of R ^{1 to} R ⁴ are bonded to each other to form a ring, the ring may contain a hetero atom. Examples of the hetero atom include a nitrogen atom.

The ammonium cation is preferably represented by any of the following formulas (Y1-1) and (Y1-2).

In the formula (Y1-1) and ^{(Y1-2), R 101} represents an n-valent organic group, ^{R 1} has the same meaning as ^{R 1} in the formula ^{(101), Ar 101} and ^{Ar 102} are each independently , Represents an aryl group, and n represents an integer of 1 or more.
In the formula (Y1-1), R ¹⁰¹ is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from the structure to which these are bonded, and has 2 to 30 carbon atoms. More preferably, it is a group obtained by removing n hydrogen atoms from the saturated aliphatic hydrocarbon, benzene or naphthalene.
In the formula (Y1-1), n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
In the formula (Y1-2), Ar ¹⁰¹ and Ar ¹⁰² are preferably phenyl groups or naphthyl groups, respectively, and more preferably phenyl groups.

− Anion −
As the anion in the ammonium salt, one selected from a carboxylic acid anion, a phenol anion, a phosphoric acid anion and a sulfate anion is preferable, 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 carboxy groups, and more preferably a divalent carboxylic acid anion. According to this aspect, the stability, curability and developability of the photosensitive resin composition can be further improved. In particular, by using a divalent carboxylic acid anion, the stability, curability and developability of the photosensitive resin composition can be further improved.

The carboxylic acid anion is preferably represented by the following formula (X1).
In formula (X1), EWG represents an electron-attracting group.

In the present embodiment, the electron-attracting group means that the substituent constant σm of Hammett shows a positive value. Here, σm is a review article 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 embodiment is not limited to the substituent described in the above document.
Examples of substituents in which σm shows a positive value are CF ₃ groups (σm = 0.43), CF ₃ C (= O) groups (σm = 0.63), and HC≡C groups (σm = 0. 21), CH ₂ = CH group (σm = 0.06), Ac group (σm = 0.38), MeOC (= O) group (σm = 0.37), MeC (= O) CH = CH group ( σm = 0.21), PhC (= O) group (σm = 0.34), H ₂ NC (= O) CH ₂ group (σm = 0.06) and the like. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (hereinafter, the same applies).

The EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).
In the formulas (EWG-1) to (EWG-6), R ^{x1 to} R ^x3 independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxy group or a carboxy group, and Ar is an aromatic group. Represents.

In the present invention, the carboxylic acid anion is preferably represented by the following formula (XA).
In the formula ^{(XA), L 10} represents a single bond or an alkylene group, an alkenylene group, an aromatic group, -NR ^X - represents and divalent connecting group selected from the group consisting a combination thereof, ^{R X} is , Hydrogen atom, alkyl group, alkenyl group or aryl group.

Specific examples of the carboxylic acid anion include maleic acid anion, phthalate anion, N-phenyliminodiacetic acid anion and oxalate anion.

The onium salt in the present invention contains an ammonium cation as a cation, and the onium salt is an anion from the viewpoint that the cyclization of the specific precursor is easily performed at a low temperature and the storage stability of the photosensitive resin composition is easily improved. As a result, it is preferable to contain an anion having a pKa (pKaH) of 2.5 or less, and more preferably to contain an anion having a pKa (pKaH) of 1.8 or less.
The lower limit of pKa is not particularly limited, but it is preferably -3 or more, preferably -2 or more, from the viewpoint that the generated base is not easily neutralized and the cyclization efficiency of the specific precursor or the like is improved. Is more preferable.
The above pKa includes Determination of Organic Strategies by Physical Methods (authors: Brown, HC, McDaniel, D.H., Hafliger, O., Nachod, FC See Nachod, F.C .; Academic Press, New York, 1955) and Data for Biochemical Research (Author: Dawson, RMC et al; Oxford, Clarendon Press, 19). Can be done. For compounds not described in these documents, the values calculated from the structural formulas using ACD / pKa (manufactured by ACD / Labs) software shall be used.

Specific examples of the ammonium salt include the following compounds, but the present invention is not limited thereto.

[Iminium salt]
In the present invention, the iminium salt means a salt of an iminium cation and an anion. As the anion, the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.

-Iminium cation-
As the iminium cation, a pyridinium cation is preferable.
Further, as the iminium cation, a cation represented by the following formula (102) is also preferable.

In formula (102), R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, R ⁷ represents a hydrocarbon group, and at least two of R ^{5 to} R ⁷ are bonded to each other to form a ring. It may be formed.
In the formula (102), R ⁵ and R ⁶ have the same meaning as R 1 to R ⁴ in the above formula (101), and the preferred embodiment is also the same.
In formula (102), R ⁷ preferably combines with at least one of R ⁵ and R ⁶ to form a ring. The ring may contain a heteroatom. Examples of the hetero atom include a nitrogen atom. Further, as the ring, a pyridine ring is preferable.

The iminium cation is preferably represented by any of the following formulas (Y1-3) to (Y1-5).
In Formula ^{(Y1-3) ~ (Y1-5),} R 101 represents an n-valent organic group, ^{R 5} has the same meaning as ^{R 5} in the formula (102), ^{R 7} is R in the formula (102) Synonymous with ⁷ , n and m represent integers of 1 or more.
In the formula (Y1-3), R ¹⁰¹ is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from the structure to which these are bonded, and has 2 to 30 carbon atoms. More preferably, it is a group obtained by removing n hydrogen atoms from the saturated aliphatic hydrocarbon, benzene or naphthalene.
In the formula (Y1-3), n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
In the formula (Y1-5), m is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.

Specific examples of the iminium salt include the following compounds, but the present invention is not limited thereto.

[Sulfonium salt]
In the present invention, the sulfonium salt means a salt of a sulfonium cation and an anion. As the anion, the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.

-Sulfonium cation-
As the sulfonium cation, a tertiary sulfonium cation is preferable, and a triarylsulfonium cation is more preferable.
Further, as the sulfonium cation, a cation represented by the following formula (103) is preferable.

In formula (103), R ^{8 to} R ¹⁰ each independently represent a hydrocarbon group.
Each of R ^{8 to} R ¹⁰ is preferably an alkyl group or an aryl group independently, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. It is more preferably an aryl group, and even more preferably a phenyl group.
R ^{8 to} R ¹⁰ may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group and an aryloxy group. Examples thereof include a carbonyl group and an acyloxy group. Among these, it is preferable to have an alkyl group or an alkoxy group as the substituent, more preferably to have a branched alkyl group or an alkoxy group, and a branched alkyl group having 3 to 10 carbon atoms or a branched alkyl group having 1 to 1 carbon atoms. It is more preferable to have 10 alkoxy groups.
R ^{8 to} R ¹⁰ may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.

Specific examples of the sulfonium salt include the following compounds, but the present invention is not limited thereto.

[Iodonium salt]
In the present invention, the iodonium salt means a salt of an iodonium cation and an anion. As the anion, the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.

-Iodonium cation-
As the iodonium cation, a diallyl iodonium cation is preferable.
Further, as the iodonium cation, a cation represented by the following formula (104) is preferable.

In formula (104), R ¹¹ and R ¹² each independently represent a hydrocarbon group.
R ¹¹ and R ¹² are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. It is more preferably an aryl group, and even more preferably a phenyl group.
R ¹¹ and R ¹² may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, and an aryloxy group. Examples thereof include a carbonyl group and an acyloxy group. Among these, it is preferable to have an alkyl group or an alkoxy group as the substituent, more preferably to have a branched alkyl group or an alkoxy group, and a branched alkyl group having 3 to 10 carbon atoms or a branched alkyl group having 1 to 10 carbon atoms. It is more preferable to have an alkoxy group of.
R ¹¹ and R ¹² may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.

Specific examples of the iodonium salt include the following compounds, but the present invention is not limited thereto.

[Phoenium salt]
In the present invention, the phosphonium salt means a salt of a phosphonium cation and an anion. As the anion, the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.

-Phoenium cation-
As the phosphonium cation, a quaternary phosphonium cation is preferable, and examples thereof include a tetraalkylphosphonium cation and a triarylmonoalkylphosphonium cation.
Further, as the phosphonium cation, a cation represented by the following formula (105) is preferable.

In formula (105), R ^{13 to} R ¹⁶ independently represent a hydrogen atom or a hydrocarbon group.
Each of R ^{13 to} R ¹⁶ is preferably an alkyl group or an aryl group independently, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. It is more preferably an aryl group, and even more preferably a phenyl group.
R ^{13 to} R ¹⁶ may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group and an aryloxy group. Examples thereof include a carbonyl group and an acyloxy group. Among these, it is preferable to have an alkyl group or an alkoxy group as the substituent, more preferably to have a branched alkyl group or an alkoxy group, and a branched alkyl group having 3 to 10 carbon atoms or a branched alkyl group having 1 to 10 carbon atoms. It is more preferable to have an alkoxy group of.
R ^{13 to} R ¹⁶ may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.

Specific examples of the phosphonium salt include the following compounds, but the present invention is not limited thereto.

When the photosensitive resin composition of the present invention contains an onium salt, the content of the onium salt is preferably 0.1 to 50% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, further preferably 0.85% by mass or more, and even more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less, further preferably 10% by mass or less, 5% by mass or less, or 4% by mass or less.
As the onium salt, one kind or two or more kinds can be used. When two or more types are used, the total amount is preferably in the above range.

<Thermal base generator>
The curable resin composition of the present invention may contain a base generator.
The thermobase generator may be a compound corresponding to the above-mentioned onium salt, or may be a thermobase generator other than the above-mentioned onium salt.
Examples of other thermobase generators include nonionic thermobase generators.
Examples of the nonionic thermobase generator include compounds represented by the formula (B1) or the formula (B2).

In formulas (B1) and (B2), Rb ¹ , Rb ² and Rb ³ are independently organic groups, halogen atoms or hydrogen atoms having no tertiary amine structure. However, Rb ¹ and Rb ² do not become hydrogen atoms at the same time. Further, none of Rb ¹ , Rb ² and Rb ³ has a carboxy group. In the present specification, the tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, this does not apply when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when an amide group is formed together with a nitrogen atom.

In formulas (B1) and (B2), it is preferable that at least one of Rb ¹ , Rb ² and Rb ³ contains a cyclic structure, and it is more preferable that at least two contain a cyclic structure. The cyclic structure may be either a monocyclic ring or a condensed ring, and a monocyclic ring or a condensed ring in which two monocyclic rings are condensed is preferable. The single ring is preferably a 5-membered ring or a 6-membered ring, and preferably a 6-membered ring. As the monocycle, a cyclohexane ring and a benzene ring are preferable, and a cyclohexane ring is more preferable.

More specifically, Rb ¹ and Rb ² are hydrogen atoms, alkyl groups (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), and alkenyl groups (preferably 2 to 24 carbon atoms). , 2-18 is more preferred, 3-12 is more preferred), aryl groups (6-22 carbons are preferred, 6-18 are more preferred, 6-10 are more preferred), or arylalkyl groups (7 carbons). ~ 25 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable). These groups may have substituents as long as the effects of the present invention are exhibited. Rb ¹ and Rb ² may be coupled to each other to form a ring. As the ring to be formed, a 4- to 7-membered nitrogen-containing heterocycle is preferable. Rb ¹ and Rb ² are particularly linear, branched, or cyclic alkyl groups that may have substituents (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12). It is more preferably a cycloalkyl group which may have a substituent (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms) and having a substituent. A cyclohexyl group which may be used is more preferable.

As Rb ³ , an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms) and an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 6). 10 to 10 are more preferable), alkoxy groups (2 to 24 carbon atoms are preferable, 2 to 12 are more preferable, 2 to 6 are more preferable), arylalkyl groups (7 to 23 carbon atoms are preferable, 7 to 19 are more preferable). Preferably, 7 to 12 are more preferable), an arylalkenyl group (8 to 24 carbon atoms is preferable, 8 to 20 is more preferable, 8 to 16 is more preferable), and an alkoxyl group (1 to 24 carbon atoms is preferable, 2 to 2). 18 is more preferred, 3-12 is more preferred), aryloxy groups (6-22 carbons are preferred, 6-18 are more preferred, 6-12 are more preferred), or arylalkyloxy groups (7-carbons). 23 is preferable, 7 to 19 is more preferable, and 7 to 12 is further preferable). Among them, a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferable. Rb ³ may further have a substituent as long as the effects of the present invention are exhibited.

The compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).

In the formula, Rb ¹¹ and Rb ¹² , and Rb ³¹ and Rb ³² are the same as Rb ¹ and Rb ² in the formula (B1), respectively.
Rb ¹³ has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, more preferably 3 to 12 carbon atoms) and an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and a substituent may be provided as long as the effects of the present invention are exhibited. Of these, Rb ¹³ is preferably an arylalkyl group.

Rb ³³ and Rb ³⁴ independently have a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms). , 2-8 are more preferred, 2-3 are more preferred), aryl groups (6-22 carbon atoms are preferred, 6-18 are more preferred, 6-10 are more preferred), arylalkyl groups (7 to 7 carbon atoms). 23 is preferable, 7 to 19 is more preferable, and 7 to 11 is further preferable), and a hydrogen atom is preferable.
Further, Rb ³³ and Rb ³⁴ may be combined to form a ring structure. Examples of the ring structure formed include a benzene ring structure and the like.

Rb ³⁵ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 12 carbon atoms, 3 to 12 carbon atoms). 8 is more preferable), aryl group (6 to 22 carbon atoms is preferable, 6 to 18 is more preferable, 6 to 12 is more preferable), arylalkyl group (7 to 23 carbon atoms is preferable, 7 to 19 is more preferable). , 7-12 is more preferable), and an aryl group is preferable.

As the compound represented by the formula (B1-1), the compound represented by the formula (B1-1a) is also preferable.

Rb ¹¹ and ^{Rb 12} have the same meanings as ^{Rb 11} and ^{Rb 12} in the formula (B1-1).
Rb ¹⁵ and Rb ¹⁶ are hydrogen atoms, alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 6 carbon atoms), alkenyl groups (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms). More preferably, 2-3), aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms), arylalkyl group (preferably 7 to 23 carbon atoms, 7). ~ 19 is more preferable, and 7 to 11 are more preferable), and a hydrogen atom or a methyl group is preferable.
Rb ¹⁷ has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 3 to 8 carbon atoms) and an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 12 carbon atoms, 3 to 8 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), and an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and an aryl group is particularly preferable.

The molecular weight of the nonionic thermobase generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

Among the above-mentioned onium salts, the following compounds can be mentioned as specific examples of the compound which is a thermal base generator or other specific examples of the thermal base generator.

The content of the thermobase generator is preferably 0.1 to 50% by mass with respect to the total solid content of the curable resin composition used in the present invention. The lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less. As the thermobase generator, one kind or two or more kinds can be used. When two or more types are used, the total amount is preferably in the above range.

<Photopolymerization initiator>
The curable resin composition used in the present invention preferably contains a photopolymerization initiator.
The photopolymerization initiator is preferably a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited and may be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. Further, it may be an activator that produces an active radical by causing some action with the photoexcited sensitizer.

The photoradical polymerization initiator contains at least one compound having a molar extinction coefficient of at least about 50 L · mol ^{− 1} · cm ^-1 within the range of about 300 to 800 nm (preferably 330 to 500 nm). Is preferable. The molar extinction coefficient of a compound can be measured using a known method. 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 photoradical polymerization initiator, a known compound can be arbitrarily used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives and the like. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. Can be mentioned. For details thereof, the description of paragraphs 0165 to 0182 of JP2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219 can be referred to, and the contents thereof are incorporated in the present specification.

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

As the photoradical polymerization 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 No. 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 absorption maximum wavelength is matched with a wavelength light source 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 photoradical polymerization initiator is more preferably an oxime compound. By using the oxime compound, the exposure latitude can be improved more effectively. The oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a photocuring accelerator.

As specific examples of the oxime compound, the compound described in JP-A-2001-233842, the compound described in JP-A-2000-080068, and the compound described in JP-A-2006-342166 can be used.

Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, and 2-acetoxy. Iminopentane-3-one, 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 and the like. In the curable resin composition used in the present invention, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as the photoradical polymerization initiator. Oxime-based photopolymerization initiators have a> C = N—O—C (= O) − linking group in the molecule.

Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF Corporation), ADEKA PTOMER N-1919 (manufactured by ADEKA Corporation, JP2012-014502). The radical polymerization initiator 2) is also preferably used. Further, TR-PBG-304 (manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.), Adeka Arkuru's NCI-831 and Adeka Arkuru's NCI-930 (manufactured by ADEKA Corporation) can also be used. Further, DFI-091 (manufactured by Daito Chemix Corp.) can be used.

It is also possible to use an oxime compound having a fluorine atom. Specific examples of such an oxime compound include compounds described in JP-A-2010-262028, compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013. Examples thereof include the compound (C-3) described in paragraph 0101 of JP-A-164471.

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.

From the viewpoint of exposure sensitivity, the photoradical polymerization initiator includes trihalomethyltriazine compound, benzyldimethylketal compound, α-hydroxyketone compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, metallocene compound, oxime compound, and triaryl. Selected from the group consisting of imidazole dimer, onium salt compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, halomethyloxaziazole compound, 3-aryl substituted coumarin compound. Compounds are preferred.

More preferable photoradical polymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds and acetophenone compounds. At least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferable, and metallocene compounds or oxime compounds are even more preferable, and oxime compounds are even more preferable. Is even more preferable.

The photoradical polymerization 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-aromatic ketones such as propanone-1, alkylanthraquinone, etc. It is also possible to use quinones fused to the aromatic ring of the above, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkyl benzoin, and benzyl derivatives such as benzyl dimethyl ketal. Further, a compound represented by the following formula (I) can also be used.

In the formula (I), ^RI00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, and the like. 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 18 alkyl group and at least one substituted phenyl group of the alkyl group having 1 to 4 carbon atoms, or ^{biphenyl, R I01} is a group represented by formula ^(II), the same as ^{R I00} The groups, R ^{I02 to} R ^I04, are independently alkyls having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, or halogens, respectively.

In the formula, R ^{I05 to} R ^I07 are the same as R I ^{02 to} R I ⁰⁴ of the above formula (I).

Further, as the photoradical polymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469 can also be used.

When the photopolymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the curable resin composition used in the present invention. It is by mass, more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more kinds of photopolymerization initiators are contained, the total is preferably in the above range.

<Thermal polymerization initiator>
The curable resin composition used in the present invention may contain a thermal polymerization initiator as the polymerization initiator, and may particularly contain a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the heterocyclic polymer precursor can be promoted together with the cyclization of the heterocyclic polymer precursor, so that higher heat resistance can be achieved.

Specific examples of the thermal radical polymerization initiator include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.

When the thermal radical polymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 3% by mass, based on the total solid content of the curable resin composition used in the present invention. It is 20% by mass, more preferably 5 to 15% by mass. Only one type of thermal radical polymerization initiator may be contained, or two or more types may be contained. When two or more types of thermal radical polymerization initiators are contained, the total is preferably in the above range.

<Polymerizable compound>
[Radical polymerizable compound]
The curable resin composition used in the present invention preferably contains a polymerizable compound.
As the polymerizable compound, a radically polymerizable compound can be used. The radically polymerizable compound is a compound having a radically polymerizable group. Examples of the radically polymerizable group include groups having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth) acryloyl group. The radically polymerizable group is preferably a (meth) acryloyl group, and more preferably a (meth) acryloyl group from the viewpoint of reactivity.

The number of radically polymerizable groups contained in the radically polymerizable compound may be one or two or more, but the radically polymerizable compound preferably has two or more radically polymerizable groups, and preferably has three or more radically polymerizable groups. More preferred. The upper limit is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.

The molecular weight of the radically polymerizable compound is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radically polymerizable compound is preferably 100 or more.

From the viewpoint of developability, the curable resin composition used in the present invention preferably contains at least one bifunctional or higher functional radical polymerizable compound containing two or more radically polymerizable groups, and is preferably trifunctional or higher functional radical polymerization. It is more preferable to contain at least one sex compound. Further, it may be a mixture of a bifunctional radical polymerizable compound and a trifunctional or higher functional radical polymerizable compound. For example, the number of functional groups of a radically polymerizable compound having two or more functions means that the number of radically polymerizable groups in one molecule is two or more.

Specific examples of the radically polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides, and preferred examples thereof. Esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds. 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 sulfanyl 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, amines or thiols, and a halogeno 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 a vinylbenzene derivative such as unsaturated phosphonic acid or styrene, vinyl ether, allyl ether or the like. As a specific example, the description in paragraphs 0113 to 0122 of JP-A-2016-0273557 can be referred to, and these contents are incorporated in the present specification.

Further, as the radically polymerizable compound, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable. Examples are polyethylene glycol di (meth) acrylate, trimethyl 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, trimethylpropantri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin, trimethylolethane, etc. A compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylated, is described in JP-A-48-041708, JP-A-50-006034, and JP-A-51-0371993. Urethane (meth) acrylates, such as those described in JP-A-48-064183, JP-A-49-043191, and JP-A-52-030490, the polyester acrylates, epoxy resins and (meth) acrylics. Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with acids, 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 bond can also be mentioned.

Further, as a preferable radically polymerizable compound other than the above, it has a fluorene ring and has an ethylenically unsaturated bond, which is described in JP-A-2010-160418, JP-A-2010-129825, Patent No. 4364216 and the like. It is also possible to use a compound having two or more groups having the above, or a cardo resin.

Further, as other examples, the specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, Japanese Patent Publication No. 01-040336, and Japanese Patent Application Laid-Open No. 02-025493. Vinyl phosphonic acid compounds and the like can also be mentioned. Further, a compound containing a perfluoroalkyl group described in JP-A-61-022048 can also be used. Furthermore, the journal of the Japan Adhesive 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, the compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964 and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used, and the contents thereof are described in the present specification. Incorporated into the book.

Further, the compound described in Japanese Patent Application Laid-Open No. 10-062986 together with specific examples as formulas (1) and (2) after addition of ethylene oxide or propylene oxide to a polyfunctional alcohol is also (meth) acrylated. It can be used as a radically polymerizable compound.

Further, the compounds described in paragraphs 0104 to 0131 of JP2015-187211A can also be used as other radically polymerizable compounds, and their contents are incorporated in the present specification.

Examples of the radically polymerizable compound include dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nippon Kayaku). Manufactured by A-TMMT Co., Ltd .: Shin-Nakamura Chemical Industry Co., Ltd., Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), Dipentaerythritol hexa ( Meta) acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and these (meth) acryloyl groups contain ethylene glycol residues or propylene glycol residues. A structure that is bonded via a structure is preferable. These oligomer types can also be used.

Commercially available products of the radically polymerizable compound include, for example, SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer, and SR-209, which is a bifunctional methacrylate having four ethyleneoxy chains. , 231, 239, DPCA-60, a hexafunctional acrylate having 6 pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd., TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS- 10, UAB-140 (manufactured by Nippon Paper Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), DPHA-40H ( Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (manufactured by Nichiyu Co., Ltd.), etc. Can be mentioned.

Examples of the radically polymerizable compound include urethane acrylates as described in JP-A-48-041708, JP-A-51-0371993, JP-A-02-032293, and JP-A-02-016765. , Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable. Further, as the radically polymerizable compound, compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238 are used. It can also be used.

The radically polymerizable compound may be a radically polymerizable compound having an acid group such as a carboxy group or a phosphoric acid group. The radically polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid is obtained by reacting an unreacted hydroxy group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. A radically polymerizable compound having a group is more preferable. Particularly preferably, in a radical polymerizable compound in which an unreacted hydroxy group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to give an acid group, the aliphatic polyhydroxy compound is pentaerythritol or dipenta. It is a compound that is erythritol. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

The acid value of the radically polymerizable compound 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 radically polymerizable compound is within the above range, it is excellent in manufacturing handleability and further excellent in developability. Moreover, the polymerizable property is good. The acid value is measured according to the description of JIS K 0070: 1992.

In the curable resin composition used in the present invention, a monofunctional radically polymerizable compound can be preferably used as the radically polymerizable compound from the viewpoint of suppressing warpage associated with controlling the elastic modulus of the cured film. Examples of the monofunctional radically polymerizable compound include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, and cyclohexyl (meth). (Meta) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and the like (meth) ) Acrylate derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allylglycidyl ether, diallyl phthalate, and triallyl trimellitate are preferably used. As the monofunctional radical polymerizable compound, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.

[Polymerizable compounds other than the radically polymerizable compounds described above]
The curable resin composition used in the present invention may further contain a polymerizable compound other than the radically polymerizable compound described above. Examples of the polymerizable compound other than the above-mentioned radically polymerizable compound include a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group; an epoxy compound; an oxetane compound; and a benzoxazine compound.

-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), (AM4) or (AM5) is preferable.

(In the formula, t represents an integer of 1 to 20, R ¹⁰⁴ represents an organic group having a t-value of 1 to 200 carbon atoms, and R ¹⁰⁵ is a group represented by -OR ¹⁰⁶ or -OCO-R ^107. R ¹⁰⁶ indicates a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R ¹⁰⁷ indicates an organic group having 1 to 10 carbon atoms.
(In the formula, R ⁴⁰⁴ represents a divalent organic group having 1 to 200 carbon atoms, R ⁴⁰⁵ represents a group represented by -OR ⁴⁰⁶ or -OCO-R ⁴⁰⁷ , and R ⁴⁰⁶ is a hydrogen atom or carbon. It represents an organic group having a number of 1 to 10, and R ⁴⁰⁷ indicates an organic group having 1 to 10 carbon atoms.)
(In the formula, u represents an integer of 3 to 8, R ⁵⁰⁴ represents a u-valent organic group having 1 to 200 carbon atoms, and R ⁵⁰⁵ represents a group represented by -OR ⁵⁰⁶ or -OCO-R ^507. , R ⁵⁰⁶ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R ⁵⁰⁷ represents an organic group having 1 to 10 carbon atoms.

Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML. -PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.), NIKARAC MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, etc. Be done.

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 derived from the cross-linking does not occur, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in suppressing low-temperature curing and warpage of the curable resin composition.

The epoxy compound preferably contains a polyethylene oxide group. As a result, the elastic modulus can be further reduced and warpage can be suppressed. 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 (glycidi). Examples thereof 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, Shin Nihon Rika Co., Ltd.), EP-4003S, EP-4000S (trade name, manufactured by ADEKA Co., Ltd.) and the like can be mentioned. Among these, an epoxy resin containing a polyethylene oxide group is preferable because it is excellent in suppressing warpage and heat resistance. For example, Epicron® EXA-4880, Epicron® EXA-4822, and Ricaresin® BEO-60E are preferred because they contain a polyethylene oxide group.

-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.

-Benzoxazine compound (compound having a benzoxazolyl group)-
Since the benzoxazine compound is a cross-linking reaction derived from the cycloaddition reaction, degassing does not occur during curing, and the heat shrinkage is further reduced to suppress the occurrence of warpage, 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. Examples include dihydrobenzoxazine compounds. These may be used alone or in combination of two or more.

When the polymerizable compound is contained, the content thereof is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the curable resin composition used in the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.

One type of the polymerizable compound may be used alone, or two or more types may be mixed and used. When two or more types are used in combination, the total amount is preferably in the above range.

<Migration inhibitor>
The curable resin composition used in the present invention preferably further contains a migration inhibitor. By including the migration inhibitor, it is possible to effectively suppress the movement of metal ions derived from the metal layer (metal wiring) into the curable resin composition layer.

The migration inhibitor is not particularly limited, but is a heterocycle (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, piperazine ring, piperazine ring, morpholin ring, 2H-pyran ring and 6H-pyran ring, triazine ring), thiourea and sulfanyl group compounds, hindered phenol compounds , Salicylic acid derivative compound, hydrazide derivative compound and the like. In particular, triazole-based compounds such as 1,2,4-triazole and benzotriazole, and tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

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

Examples of other migration inhibitors include rust preventives described in paragraphs 0094 of JP2013-015701, compounds described in paragraphs 0073 to 0076 of JP2009-283711, and JP2011-059656. The compounds described in paragraph 0052, the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520A, the compounds described in paragraph 0166 of International Publication No. 2015/199219, and the like can be used.

Specific examples of the migration inhibitor include the following compounds.

When the curable resin composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the curable resin composition, and is 0. .05 to 2.0% by mass is more preferable, and 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 curable resin composition used in 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, 1,4-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 etherdiamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1 -Nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, Bis (4-hydroxy-3,5-tert-butyl) phenylmethane and the like are preferably used. Further, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compound described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used.

In addition, the following compounds can be used (Me is a methyl group).

When the curable resin composition used in the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is 0.01 to 5% by mass with respect to the total solid content of the curable resin composition used in the present invention. It is preferably%, more preferably 0.02 to 3% by mass, and even more preferably 0.05 to 2.5% by mass.

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.

<Metal adhesion improver>
The curable resin composition used in the present invention preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like. Examples of the metal adhesiveness improving agent include a silane coupling agent.

Examples of the silane coupling agent include the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, paragraphs of International Publication No. 2011/080992. Compounds described in 0063 to 0071, compounds described in paragraphs 0060 to 0061 of JP-A-2014-191252, compounds described in paragraphs 0045-0052 of JP-A-2014-041264, International Publication No. 2014/0975994. Examples include the compounds described in paragraph 0055. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A. Further, it is also preferable to use the following compounds as the silane coupling agent. In the following formula, Et represents an ethyl group.

Further, as the metal adhesiveness improving agent, the compounds described in paragraphs 0046 to 0049 of JP2014-186186A and the sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935 can also be used. ..

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further, with respect to 100 parts by mass of the heterocyclic polymer precursor. It is preferably in the range of 0.5 to 5 parts by mass. When it is at least the above lower limit value, the adhesiveness between the cured film and the metal layer after the curing step is good, and when it is at least the above upper limit value, the heat resistance and mechanical properties of the cured film after the curing step 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.

<Other additives>
The curable resin composition of the present invention contains various additives such as a thermoacid generator, a sensitizer such as N-phenyldiethanolamine, and a chain transfer agent, if necessary, as long as the effects of the present invention are not impaired. , Surfactants, higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, antiaggregating agents and the like can be blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the curable resin composition.

[Sensitizer]
The curable resin composition of the present invention may contain a sensitizer. The sensitizer absorbs specific active radiation and enters an electronically excited state. The sensitizer in the electron-excited state comes into contact with the thermal curing accelerator, the thermal radical polymerization initiator, the photoradical polymerization initiator, and the like, and acts such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal curing accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo a chemical change and decompose to generate radicals, acids, or bases.
Examples of the sensitizer include sensitizers such as N-phenyldiethanolamine.
Moreover, you may use a sensitizing dye as a sensitizer.
For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP2016-027357A can be referred to, and this content is incorporated in the present specification.

When the curable resin composition of the present invention contains a sensitizer, the content of the sensitizer may be 0.01 to 20% by mass with respect to the total solid content of the curable resin composition of the present invention. It is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass. The sensitizer may be used alone or in combination of two or more.

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

Further, as the chain transfer agent, the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219 can also be used.

When the curable resin composition used in the present invention has a chain transfer agent, the content of the chain transfer agent is 0.01 to 100 parts by mass with respect to 100 parts by mass of the total solid content of the curable resin composition used in the present invention. 20 parts by mass is preferable, 1 to 10 parts by mass is more preferable, and 1 to 5 parts by mass is further preferable. 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]
Each type of surfactant may be added to the curable resin composition used in the present invention from the viewpoint of further improving the coatability. As the surfactant, various types of surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used. The following surfactants are also preferable. In the following formula, the parentheses indicating the structural units of the main chain represent the content (mol%) of each structural unit, and the parentheses indicating the structural units of the side chain represent the number of repetitions of each structural unit.
Further, as the surfactant, the compound described in paragraphs 0159 to 0165 of International Publication No. 2015/199219 can also be used.

When the curable resin composition used in the present invention has a surfactant, the content of the surfactant is 0.001 to 2. With respect to the total solid content of the curable resin composition used in the present invention. It is preferably 0% by mass, more preferably 0.005 to 1.0% by mass. Only one type of surfactant may be used, or two or more types may be used. When there are two or more types of surfactant, the total is preferably in the above range.

[Higher fatty acid derivative]
The curable resin composition used in the present invention is curable in the process of drying after application by adding a higher fatty acid derivative such as behenic acid or behenic acid amide in order to prevent polymerization inhibition due to oxygen. It may be unevenly distributed on the surface of the resin composition.

Further, as the higher fatty acid derivative, the compound described in paragraph 0155 of International Publication No. 2015/199219 can also be used.

When the curable resin composition used in the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is 0.1 to 10% by mass with respect to the total solid content of the curable resin composition used in the present invention. % Is preferable. Only one type of higher fatty acid derivative may be used, or two or more types may be used. When there are two or more higher fatty acid derivatives, the total is preferably in the above range.

<Restrictions on other contained substances>
The water content of the curable resin composition used in the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass from the viewpoint of coating surface properties.

The metal content of the curable resin composition used in the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and further less than 0.5 mass ppm from the viewpoint of insulating properties. preferable. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are contained, it is preferable that the total of these metals is in the above range.

Further, as a method for reducing metal impurities unintentionally contained in the curable resin composition used in the present invention, a raw material having a low metal content is used as a raw material constituting the curable resin composition used in the present invention. Select, filter-filter the raw material constituting the curable resin composition used in the present invention, and distill under the condition that the inside of the apparatus is lined with polytetrafluoroethylene or the like to suppress contamination as much as possible. Methods such as this can be mentioned.

Considering the use as a semiconductor material, the curable resin composition used in the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, from the viewpoint of wiring corrosiveness. More preferably less than 200 mass ppm. 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 even more 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 amount of chlorine atom and bromine atom, or chlorine ion and bromine ion is in the above range, respectively.

A conventionally known storage container can be used as the storage container for the curable resin composition used in the present invention. In addition, as the storage container, for the purpose of suppressing impurities from being mixed into the raw materials and the curable resin composition, a multi-layer bottle having the inner wall of the container composed of 6 types and 6 layers of resin and 6 types of resin are used. It is also preferable to use a bottle having a layered structure. Examples of such a container include the container described in JP-A-2015-123351.

<Preparation of curable resin composition>
The curable resin composition used in the present invention can be prepared by mixing each of the above components. The mixing method is not particularly limited, and a conventionally known method can be used.

Further, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the curable resin composition. 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. The filter material is preferably polytetrafluoroethylene, polyethylene or nylon. 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 a plurality of types of filters are used, filters having different pore diameters or materials may be used in combination. In addition, various materials may be filtered a plurality of times. When filtering a plurality of times, circulation filtration may be used. Moreover, you may pressurize and perform filtration. When pressurizing and filtering, the pressurizing 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. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

<Use of pattern formation method>
The pattern forming method of the present invention is preferably used for forming an interlayer insulating film for a rewiring layer.
In addition, it can also be used for forming an insulating film of a semiconductor device, forming a stress buffer film, and the like.

(Membrane, cured film, laminate, semiconductor device)
The film of the present invention is a film formed from the curable resin composition used in the present invention.
The film of the present invention is produced, for example, in the application step in the pattern forming method of the present invention.
The film of the present invention preferably has a composition obtained by removing at least a part of a solvent from the curable resin composition. Examples of the method for removing the solvent include the above-mentioned drying and the like.
The content of the solvent with respect to the total mass of the film of the present invention is preferably 5% by mass or less, more preferably 2% by mass or less, and further preferably 1% by mass or less. The lower limit of the content is not particularly limited and may be 0% by mass.
In addition, the preferred embodiment of the film of the present invention is the same as the preferred embodiment of the film formed in the above-mentioned application step.

The cured film of the present invention is obtained by curing the curable resin composition of the present invention.
Further, the cured film of the present invention is formed as a pattern by the pattern forming method of the present invention.
That is, the method for producing a cured film of the present invention is the pattern forming method of the present invention.
The film thickness of the cured film of the present invention can be, for example, 0.5 μm or more, and can be 1 μm or more. Further, the upper limit value can be 100 μm or less, and can be 30 μm or less.

The cured film of the present invention may be laminated in two or more layers, and further in three to seven layers to form a laminated body. It is preferable that the laminate of the present invention contains two or more cured films and includes a metal layer between any of the cured films. For example, a laminate containing at least a layer structure in which three layers of a first cured film, a metal layer, and a second cured film are laminated in this order is preferable. The first cured film and the second cured film are both cured films of the present invention. For example, both the first cured film and the second cured film are curable of the present invention. A preferred embodiment is a film formed by curing the resin composition. The curable resin composition of the present invention used for forming the first cured film and the curable resin composition of the present invention used for forming the second cured film have the same composition. The compositions may be present or have different compositions, but from the viewpoint of production suitability, the compositions having the same composition are preferable. Such a metal layer is preferably used as a metal wiring such as a rewiring layer.

Examples of applicable fields of the cured film of the present invention include an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like. In addition, a sealing film, a substrate material (base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above may be patterned by etching. For these applications, for example, Science & Technology Co., Ltd. "High-performance and applied technology of polyimide" April 2008, Masaaki Kakimoto / supervision, CMC technical library "Basics and development of polyimide materials" November 2011 You can refer to "Latest Polyimide Basics and Applications", N.T.S., August 2010, etc., published by Japan Polyimide / Aromatic Polymer Research Association / ed.

The cured film in the present invention can also be used for manufacturing plate surfaces such as offset plate surfaces or screen plate surfaces, for etching molded parts, and for manufacturing protective lacquers and dielectric layers in electronics, especially microelectronics.

The present invention also discloses a semiconductor device including the cured film or laminate of the present invention. As specific examples of the semiconductor device in which the curable resin composition of the present invention is used to form the interlayer insulating film for the rewiring layer, the description in paragraphs 0213 to 0218 and the description in FIG. 1 of JP-A-2016-0273557 are taken into consideration. Yes, these contents are incorporated herein.
Further, the semiconductor device of the present invention is manufactured by a method including the pattern forming method of the present invention.
That is, the method for manufacturing a semiconductor device of the present invention includes the method for forming a pattern of the present invention.

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 pyromellitic dianhydride, 4,4'-diaminodiphenyl ether and benzyl alcohol]
14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C. for 12 hours) and 14.22 g (131.58 mmol) of benzyl alcohol were suspended in 50 mL of N-methylpyrrolidone. , Dryed with a molecular sieve. The suspension was heated at 100 ° C. for 3 hours. 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. Then, a solution prepared by dissolving 11.08 g (58.7 mmol) of 4,4′-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at −5 to 0 ° C. over 20 minutes. Then, the reaction mixture was reacted at 0 ° C. for 1 hour, 70 g of ethanol was added, and the mixture was stirred at room temperature overnight. The polyimide precursor was then precipitated in 5 liters of water and the water-polyimide precursor mixture was stirred at a rate of 5,000 rpm for 15 minutes. The polyimide precursor was removed by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. The obtained polyimide precursor was then dried under reduced pressure at 45 ° C. for 3 days. The weight average molecular weight of this polyimide precursor was 18,000.

<Synthesis example 2>
[Synthesis of polyimide precursor (A-2: polyimide precursor having radical polymerizable group) from pyromellitic dianhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate]
14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, and 20 .4 g (258 mmol) of pyridine and 100 g of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at a temperature of 60 ° C. for 18 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Next, the obtained diester is chlorinated with SOCL ₂ , converted to a polyimide precursor with 4,4'-diaminodiphenyl ether by the same method as in Synthesis Example 1, and the polyimide precursor is converted into a polyimide precursor by the same method as in Synthesis Example 1. Obtained. The weight average molecular weight of this polyimide precursor was 19,000.

<Synthesis example 3>
[Synthesis of polyimide precursor (A-3: polyimide precursor having radical polymerizable group) from 4,4'-oxydiphthalic anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate]
20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140 ° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, and 0.05 g of hydroquinone. , 20.4 g (258 mmol) of pyridine and 100 g of diglime were mixed and stirred at a temperature of 60 ° C. for 18 hours to prepare a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. .. Next, the obtained diester is chlorinated with SOCL ₂ , converted to a polyimide precursor with 4,4'-diaminodiphenyl ether by the same method as in Synthesis Example 1, and the polyimide precursor is converted into a polyimide precursor by the same method as in Synthesis Example 1. Obtained. The weight average molecular weight of this polyimide precursor was 18,000.

<Synthesis example 4>
[4,4'-oxydiphthalic anhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (orthotridine) and polyimide precursor from 2-hydroxyethyl methacrylate (A-4: having a radically polymerizable group) Synthesis of polyimide precursor)]
20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140 ° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, and 0.05 g of hydroquinone. , 20.4 g (258 mmol) of pyridine and 100 g of diglime were mixed and stirred at a temperature of 60 ° C. for 18 hours to prepare a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. .. Next, the obtained diester was chlorinated with SOCL ₂ and then converted into a polyimide precursor with 4,4'-diamino-2,2'-dimethylbiphenyl in the same manner as in Synthesis Example 1, and the same as in Synthesis Example 1. A polyimide precursor was obtained by the above method. The weight average molecular weight of this polyimide precursor was 19,000.

<Synthesis example 5>
[Synthesis of polybenzoxazole precursor (A-5) from 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4,4'-oxydibenzoyl chloride]
To 100 mL of N-methyl-2-pyrrolidone, 13.92 g of 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added and dissolved by stirring. Subsequently, 11.21 g of 4,4'-oxydibenzoyl chloride was added dropwise over 10 minutes while maintaining the temperature at 0 to 5 ° C., and then stirring was continued for 60 minutes. The polybenzoxazole precursor was then precipitated in 6 liters of water and the water-polybenzoxazole precursor mixture was stirred at a rate of 5000 rpm for 15 minutes. The polybenzoxazole precursor was filtered off and stirred again in 6 liters of water for 30 minutes and filtered again. The resulting polybenzoxazole precursor was then dried under reduced pressure at 45 ° C. for 3 days. The weight average molecular weight of this polybenzoxazole precursor was 15,000.

<Synthesis example 6>
[Synthesis of polyimide precursor (A-6: polyimide precursor having radical polymerizable group) from 4,4'-oxydiphthalic anhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate]
155.1 g of 4,4'-oxydiphthalic anhydride (ODPA) was placed in a 2 liter volume separable flask and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added. A reaction mixture was obtained by adding 79.1 g of pyridine with stirring at room temperature. After the exothermic reaction was completed, the mixture was allowed to cool to room temperature and allowed to stand for another 16 hours.

Next, under ice-cooling, a solution prepared by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Subsequently, a suspension of 93.0 g of 4,4'-diaminodiphenyl ether suspended in 350 ml of γ-butyrolactone was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and the mixture was stirred for 1 hour. Then 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.

The resulting reaction was added to 3 liters of ethyl alcohol to form a precipitate of crude polymer. The produced crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer, and the obtained precipitate was collected by filtration and then vacuum dried to obtain a powdery polymer A-6. The weight average molecular weight (Mw) of this polymer A-6 was measured and found to be 20,000.

<Synthesis example 7>
[3,3'4,4'-biphenyltetracarboxylic dianhydride, 4,4'-diaminodiphenyl ether, and polyimide precursor from 2-hydroxyethyl methacrylate (A-7: Polyimide precursor having a radically polymerizable group) Body) synthesis]
In Synthesis Example 6, except that 147.1 g of 3,3'4,4'-biphenyltetracarboxylic dianhydride was used instead of 155.1 g of 4,4'-oxydiphthalic acid anhydride, in Synthesis Example 6. Polymer A-7 was obtained by carrying out the reaction in the same manner as described. The weight average molecular weight (Mw) of this polymer A-7 was measured and found to be 22,000.

<Synthesis Example 8>
[Synthesis of Compound C-13]
Trimethyl orthoformate (30 g) and camphorsulfonic acid (66 mg) were placed in a three-necked flask and stirred, and the flask was immersed in an ice bath. After confirming that the internal temperature had dropped to 5 ° C or lower, pivalaldehyde (24.4 g) was slowly added dropwise, the ice bath was removed, and the mixture was reacted at room temperature for 3 hours, according to the following formula (C-13). Compound C-13 represented by is obtained.

<Synthesis example 9>
[Synthesis of Compound C-14]
In the synthesis of compound C-13, the following formula (C-14) was used in the same manner as in compound C-13, except that pivalaldehyde was changed to adamantane carvaldehide and trimethyl orthoformate was changed to triethyl orthoformate. Compound C-14 represented by this was synthesized.

[Synthesis of Compound C-15]
Adamantane carvaldehide (75 g), cyclohexaneethanol (129 g), camphorsulfonic acid (5.31 g) and 1000 mL of hexane were placed in a three-necked flask and stirred at room temperature. Anhydrous magnesium sulfate (675 g) was added thereto, and the mixture was reacted for 2 hours to obtain compound C-15 represented by the following formula (C-15).

<Examples and Comparative Examples>
In each example, the components shown in Tables 2 to 4 below were mixed to obtain each curable resin composition. Further, in each comparative example, the components shown in Table 4 below were mixed to obtain each comparative composition.
Specifically, the content of the components listed in the columns other than "solvent" in Tables 2 to 4 shall be the amounts listed in "parts by mass" in Tables 2 to 4, and the "solvent" in Tables 2 to 4 shall be used. The content of the component described in the column of "" was set so that the solid content concentration (total concentration of other components excluding the solvent) of the composition was the value shown in Tables 2 to 4.
The numerical value described in the column of "solvent" indicates the content ratio (mass ratio) of each solvent.
The obtained curable resin composition and comparative composition were pressure-filtered through a filter made of polytetrafluoroethylene having a pore width of 0.8 μm.
Further, in Tables 2 to 4, the description of "-" indicates that the corresponding component is not contained.

Details of each component shown in Tables 2 to 4 are as follows.

[Heterocycle-containing polymer precursor]
A-1 to A-7: A-1 to A-7 synthesized above

[Thermal base generator]
B-1 to B-4: Compounds with the following structure

[Plasticizer]
・ C-1: CELTOL DPMA (manufactured by Daicel Corporation)
・ C-2: CELTOL 1,4-BDDA (manufactured by Daicel Corporation)
・ C-3: CELTOL 1,3-BGDA (manufactured by Daicel Corporation)
・ C-4: CELTOL 1,6-HDDA (manufactured by Daicel Corporation)
・ C-5: CELTOL EDGAC (manufactured by Daicel Corporation)
・ C-6: CELTOL BDGAC (manufactured by Daicel Corporation)
・ C-7: CELTL DRA-150 (manufactured by Daicel Corporation)
・ C-8: CELTOL 1,3-BG (manufactured by Daicel Corporation)
・ C-9: CELTOL DPNP (manufactured by Daicel Corporation)
・ C-10: CELTOL DPNB (manufactured by Daicel Corporation)
・ C-11: CELTOL TPM (manufactured by Daicel Corporation)
・ C-12: CELTOL TPNB (manufactured by Daicel Corporation)
-C-13 to C-15: the above synthetic product-RC-1: Butyl acetate (boiling point 126 ° C)
The compounds corresponding to the above C-1 to C-15 are the same compounds as the above-mentioned C-1 to C-15 shown in Table 1.

[Photopolymerization initiator]
・ OXE01: IRGACURE OXE01 (manufactured by BASF)
784: IRGACURE 784 (manufactured by BASF)
OXE01 / 784: Mixture of IRGACURE OXE01 and IRGACURE 784 (IRGACURE OXE01: IRGACURE 784 = 50: 50 (mass ratio))

[Polymerizable compound]
SR-209: Tetraethylene glycol dimethacrylate (manufactured by Sartmer)
・ A-TMMT: Pentaerythritol tetraacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
・ DPHA: Dipentaerythritol hexaacrylate, (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)

[Polymerization inhibitor]
・ F-1 to F-3: Compounds with the following structure ・ F-4: 2-nitroso-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Migration inhibitor]
M-1 to M-4: Compounds with the following structure

[Metal adhesion improver]
-SC-1 to SC-6: Compounds with the following structure
〔Additive〕
G-1: N-Phenyldiethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
〔solvent〕
NMP: N-methyl-2-pyrrolidone (manufactured by Ashland)
Ethyl lactate: Ethyl lactate (manufactured by Tokyo Chemical Industry Co., Ltd.)
GBL: γ-Butyrolactone (manufactured by Sanwa Yuka Co., Ltd.)
DMSO: Dimethyl sulfoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

<Preparation of cured film>
In each Example and Comparative Example, a curable resin composition or a comparative composition was applied onto a silicon wafer by a spin coating method to form a resin layer. The silicon wafer on which the resin layer was formed was dried on a hot plate at 100 ° C. for 4 minutes to form a uniform resin composition layer having a thickness of 20 μm on the silicon wafer (application step).
The resin composition layer on the silicon wafer was exposed to an exposure energy of 400 mJ / cm ² using a broadband exposure machine (manufactured by Ushio, Inc .: UX-1000SN-EH01), and the exposed resin composition layer was exposed. The temperature was raised at a heating rate of 5 ° C./min under a nitrogen atmosphere, and after reaching the temperature (X ° C.) shown in Table 5, heating was performed for 2 hours (heat curing step).
The heated resin composition layer was immersed in a 3 mass% hydrofluoric acid aqueous solution, and the heated resin composition layer was peeled off from the silicon wafer. The peeled and heated resin composition layer was used as a cured film.
In Table 5, in the "X (° C.)" column, the temperature (X ° C.) that is 100 ° C. or higher and the longest time among the heating temperatures in the heat curing step is entered in the "Solvent type" column. Indicates the type of solvent having the highest boiling point among the solvents contained in the composition, and in the "Y (° C.)" column, 1 of the solvents having the highest boiling point among the solvents contained in the composition. In the column of "Z (° C.)", the boiling point (Y ° C.) at atmospheric pressure is indicated by "Z-X (° C.)", which is the lower of the boiling point (Z ° C.) In the column of "Z", the value obtained by subtracting the X ° C. from the Z ° C. is described, and in the column of "Z-Y (° C.)", the value obtained by subtracting the Y ° C. from the Z ° C. is described.

<Evaluation>
In each Example and Comparative Example, the elongation at break and the chemical resistance were evaluated using the obtained cured film.
The details of the evaluation method in each evaluation are described below.

[Elongation rate at break]
The elongation at break of the obtained cured film was measured. The breaking elongation of the cured film was set to a crosshead speed of 300 mm / min, a sample width of 10 mm, and a sample length of 50 mm using a tensile tester (Tensilon), and 25 ° C. and 65% RH (relative) in the longitudinal and width directions of the film. The measurement was performed in accordance with JIS-K6251 (Japanese Industrial Standards) in a humidity environment. The elongation at break is Eb (%) = (Lb-L0) / L0 (Eb: elongation at break, L0: length of the test piece before the test, Lb: length of the test piece when the test piece is cut) Calculated in. For the evaluation, the elongation at break was measured 10 times each, and the average value (the arithmetic mean value of the elongation at break of a total of 10 by measuring 10 times in the longitudinal direction) was used.
The evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in Table 6. It can be said that the larger the value of the elongation at break, the more excellent the cured film is at elongation at break, and it can be said that this is a pattern forming method excellent at the elongation at break of the pattern of the obtained cured film.

-Evaluation criteria-
A: The average value is 60% or more B: The average value is 50% or more and less than 60% C: The average value is less than 50%

〔chemical resistance〕
The obtained cured film was immersed in the following chemical solution under the following conditions, and the dissolution rate was calculated.
Chemicals: Mixture of dimethyl sulfoxide (DMSO) and 25% by mass tetramethylammonium hydroxide (TMAH) solution at 90:10 (mass ratio) Evaluation conditions: Immerse the cured membrane in the solution at 75 ° C. for 15 minutes before and after immersion The dissolution rate (nm / min) was calculated by comparing the measurements with the film thickness of. The film thickness was measured using a film thickness meter (KT-22 manufactured by Foothill Instruments).
The evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in Table 6. It can be said that the smaller the value of the dissolution rate, the more excellent the chemical resistance of the cured film, and it can be said that the pattern forming method of the obtained cured film pattern is excellent in chemical resistance.

-Evaluation criteria-
A: The dissolution rate is less than 250 nm / min.
B: The dissolution rate is 250 nm / min or more and less than 500 nm / min.
C: The dissolution rate is 500 nm / min or more.

From the above results, it can be seen that the pattern forming method according to the present invention is excellent in breaking elongation of the obtained pattern.
The pattern forming method according to Comparative Example 1 uses butyl acetate having a Y ° C. of 126 ° C. as a plasticizer and does not satisfy the above condition B. It can be seen that in the pattern forming method according to Comparative Example 1, the breaking elongation of the obtained pattern is inferior.
The pattern forming method according to Comparative Example 2 does not contain a plasticizer. It can be seen that in the pattern forming method according to Comparative Example 2, the breaking elongation of the obtained pattern is inferior.
In the pattern forming method according to Comparative Example 3, the content of the plasticizer is 17.6% by mass with respect to the total mass of the composition. It can be seen that in the pattern forming method according to Comparative Example 3, the breaking elongation of the obtained pattern is inferior.
The pattern forming method according to Comparative Example 4 uses butyl acetate having a Y ° C. of 126 ° C. as a plasticizer, and does not satisfy the above condition B. It can be seen that in the pattern forming method according to Comparative Example 4, the breaking elongation of the obtained pattern is inferior.
In the pattern forming method according to Comparative Example 5 or Comparative Example 6, the relationship between the X ° C. and the Z ° C. does not satisfy the above condition A. It can be seen that the pattern forming method according to Comparative Example 5 or Comparative Example 6 is inferior in breaking elongation of the obtained pattern.

<Example 101>
The curable resin composition according to Example 1 is applied in layers to the surface of a resin base material on which a thin copper layer is formed by a spin coating method, dried at 100 ° C. for 5 minutes, and has a curability of a film thickness of 20 μm. After forming the resin composition layer, it was exposed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). Exposure was performed at a wavelength of 365 nm via a mask (a binary mask with a pattern of 1: 1 line and space and a line width of 10 μm). After exposure, it was developed with cyclopentanone for 30 seconds and rinsed with PGMEA for 20 seconds to obtain a pattern.
Then, it was heated at the same temperature as X ° C. in Example 1 shown in Table 5 for 3 hours to form an interlayer insulating film for the rewiring layer. The interlayer insulating film for the rewiring layer was excellent in insulating properties.
Moreover, when a semiconductor device was manufactured using these interlayer insulating films for the rewiring layer, it was confirmed that the semiconductor device operated without any problem.

Claims (20)

An application step of applying the curable resin composition onto a substrate to form a film, and
Including a heat curing step of heating and curing the film,
The curable resin composition contains at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, a plasticizer, and a solvent.
The content of the plasticizer with respect to the total mass of the curable resin composition is more than 0% by mass and less than 10% by mass.
The content of the solvent with respect to the total mass of the curable resin composition is 10% by mass or more.
Among the heating temperatures in the heat curing step, the temperature which is 100 ° C. or higher and the longest time is X ° C., the boiling point of the solvent having the highest boiling point among the solvents at 1 atm is Y ° C., and the plasticizer. A pattern forming method that satisfies the following conditions A and B when the lower temperature of the boiling point and the thermal decomposition temperature at 1 atm is Z ° C.
Condition A: X-20 ≤ Z ≤ X + 60
Condition B: Y + 1 <Z The pattern forming method according to claim 1, wherein the plasticizer is a compound having a pKa of less than 11 and a conjugate acid having a pKa of more than 3. The pattern formation according to claim 1 or 2, wherein the plasticizer is not decomposed by the heat curing step, or is decomposed by the heat curing step, and the pKa of the conjugate acid of the decomposed product produced by the decomposition exceeds 3. Method. The pattern forming method according to any one of claims 1 to 3, wherein the plasticizer contains an alkylene glycol structure, an ester structure derived from a hydrocarbon compound having 3 or more hydroxy groups, or an acetal structure. The pattern forming method according to any one of claims 1 to 4, wherein the plasticizer has a molecular weight of 100 to 600. The pattern forming method according to any one of claims 1 to 5, wherein the boiling point of the plasticizer is higher than the thermal decomposition temperature of the plasticizer. The pattern forming method according to claim 6, wherein the thermal decomposition temperature of the plasticizer is higher than the X ° C. The pattern forming method according to any one of claims 1 to 5, wherein the boiling point of the plasticizer is a temperature equal to or lower than the thermal decomposition temperature of the plasticizer. The pattern forming method according to any one of claims 1 to 8, wherein the X ° C. is 150 to 350 ° C. The pattern forming method according to any one of claims 1 to 9, wherein the solvent comprises at least one selected from the group consisting of N-methyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone and ethyl lactate. .. The pattern forming method according to any one of claims 1 to 10, wherein the curable resin composition further contains a photopolymerization initiator. The pattern forming method according to any one of claims 1 to 11, wherein the curable resin composition further comprises at least one selected from the group consisting of an onium salt and a thermobase generator. The invention according to any one of claims 1 to 12, further comprising an exposure step of exposing at least a part of the film obtained in the application step and a development treatment step of performing a development treatment on the exposed film. Pattern formation method. The pattern forming method according to any one of claims 1 to 13, further comprising a metal layer forming step of forming a metal layer on the surface of the film after the development treatment. The pattern forming method according to any one of claims 1 to 14, which is a pattern forming method used for forming an interlayer insulating film. A curable resin composition used as the curable resin composition in the pattern forming method according to any one of claims 1 to 15. A film formed from the curable resin composition according to claim 16. A cured film obtained by curing the curable resin composition according to claim 16. A laminated body containing two or more hardened films according to claim 18 and containing a metal layer between any of the hardened films. A semiconductor device comprising the cured film according to claim 18 or the laminate according to claim 19.