JP7320618B2 - Method for producing dry resin, method for producing composition, method for producing cured film, method for producing laminate, and method for producing semiconductor device - Google Patents

Description

The present invention relates to a method for producing a dry resin, a method for producing a composition, a method for producing a cured film, a method for producing a laminate, and a method for producing a semiconductor device.

For example, when a resin is synthesized by a method such as performing a polymerization reaction in a solvent, the resin is a solution dissolved in a solvent, a composition such as a slurry containing a solvent, or a resin containing a solvent such as a dispersion dispersed in a solvent. It is obtained in the form of a composition.
It is also possible to obtain the above resin composition by purchase or the like.
For example, when preparing a composition using these resins, the resin may be used not in the form of the resin composition described above, but as a dry resin obtained by removing at least a portion of the solvent from the resin composition. By using the resin as a dry resin, the solvent contained in the composition can be changed from a solvent in which the resin is dissolved to a solvent suitable for the composition. There are advantages such as the ability to easily adjust the resin content in the composition, such as by increasing the resin content in the composition, and the improved storage stability of the resin by storing the resin as a dry resin. exist.

For example, in Patent Document 1, it is characterized by comprising a melting step of melting a resin under high temperature and pressure, and a drying step of extruding the molten resin under reduced pressure with an enlarged surface area and removing moisture in the resin by suction. A method for drying a synthetic resin is described.

JP-A-04-278310

In the method for producing a dry resin, when a resin composition containing a thermosetting resin is dried, particulate impurities (particles) may occur in the resulting dry resin.

The present invention provides a method for producing a dry resin that suppresses the generation of particles in the resulting dry resin, a method for producing a composition using the dry resin obtained by the above method for producing a dry resin, and a method for producing the above composition. A method for producing a cured film obtained by curing the obtained composition, a method for producing a laminate by laminating the cured film obtained by the method for producing the cured film, and a device containing the cured film or the laminate The object is to provide a manufacturing method.

Examples of representative embodiments of the present invention are described below.
<1> A low-temperature and low-pressure step of reducing the pressure of the resin composition containing a resin and a solvent to 10 kPa or less at a temperature of -150 to 45 ° C., and
After the low-temperature, low-pressure step, a high-temperature, low-pressure step in which the resin composition is set to a temperature 5 ° C. or more higher than the temperature in the low-temperature, low-pressure step under reduced pressure,
The resin has thermosetting properties,
A method for producing a dry resin.
<2> The method for producing a dry resin according to <1>, wherein the time from the end of the low-temperature, low-pressure step to the start of the high-temperature, low-pressure step is within 3 minutes.
<3> The method for producing a dry resin according to <1> or <2>, wherein the resin contains a repeating unit having an amic acid ester structure.
<4> The method for producing a dry resin according to any one of <1> to <3>, wherein the resin has a (meth)acryloyl group.
<5> Any one of <1> to <4>, wherein the content of the solvent is 20% by mass or more with respect to the total mass of the resin composition before being subjected to the low temperature and low pressure step. A method for producing a dry resin.
<6> The method for producing a dry resin according to any one of <1> to <5>, wherein the difference between the temperature in the high-temperature, low-pressure step and the temperature in the low-temperature, low-pressure step is 5 to 50°C.
<7> The method for producing a dry resin according to any one of <1> to <6>, wherein the temperature in the high temperature and low pressure step is 40 to 150°C.
<8> The method for producing a dry resin according to any one of <1> to <7>, wherein the solvent contains at least one solvent selected from the group consisting of water and ether solvents.
<9> The method for producing a dry resin according to <3>, wherein the resin further has at least one crosslinkable group selected from the group consisting of a group having an ethylenically unsaturated bond and a cyclic ether group. .
<10> The method for producing a dry resin according to any one of <1> to <9>, wherein in the low temperature and low pressure step, the pressure is reduced to 5 kPa or less at a temperature of -150 to 30°C.
<11> A step of mixing the dry resin obtained by the method for producing a dry resin according to any one of <1> to <10> with at least one other component,
A method of making the composition.
<12> A method for producing a cured film, comprising a step of curing the composition obtained by the method for producing a composition according to <11>.
<13> A method for producing a laminate, comprising a step of laminating at least two layers of the cured film obtained by the method for producing a cured film according to <12>.
<14> A method for producing a device, including the method for producing a cured film according to <12> or the method for producing a laminate according to <13>.

According to the present invention, there are provided a method for producing a dry resin in which generation of particles in the resulting dry resin is suppressed, a method for producing a composition using the dry resin obtained by the above method for producing a dry resin, and production of the above composition. A method for producing a cured film obtained by curing the composition obtained by the method, a method for producing a laminate by laminating the cured film obtained by the method for producing the cured film, and the cured film or the laminate. A device manufacturing method is provided.

Principal embodiments of the present invention are described below. However, the invention is not limited to the illustrated embodiments.
In this specification, a numerical range represented by the symbol "to" means a range including the numerical values before and after "to" as lower and upper limits, respectively.
As used herein, the term "process" is meant to include not only independent processes, but also processes that are indistinguishable from other processes as long as the desired effects of the process can be achieved.
In the description of a group (atomic group) in the present specification, a description that does not describe substitution or unsubstituted includes a group (atomic group) having no substituent as well as a group (atomic group) having a substituent. For example, the term “alkyl group” includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).
As used herein, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Light used for exposure includes actinic rays or radiation such as emission line spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
As used herein, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", and "(meth)acrylic" means both "acrylic" and "methacrylic", or , and “(meth)acryloyl” means either or both of “acryloyl” and “methacryloyl”.
In this specification, Me in the structural formulas represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
As used herein, the term "total solid content" refers to the total mass of all components of the composition excluding the solvent. Moreover, in this 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, weight average molecular weight (Mw) and 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, the weight average molecular weight (Mw) and number average molecular weight (Mn) are, for example, HLC-8220GPC (manufactured by Tosoh Corporation), guard column HZ-L, TSKgel Super HZM-M, TSKgel It can be obtained by using Super HZ4000, TSKgel Super HZ3000, TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise stated, their molecular weights were determined using THF (tetrahydrofuran) as an eluent. In addition, unless otherwise specified, detection in GPC measurement uses a UV ray (ultraviolet) wavelength detector of 254 nm.
In this specification, when the positional relationship of each layer constituting the laminate is described as "above" or "below", it means that another layer is above or below the reference layer among the layers of interest. It would be nice if there was That is, a third layer or element may be 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. In addition, unless otherwise specified, the direction in which the layers are stacked with respect to the substrate is referred to as "upper", or when there is a composition layer, the direction from the substrate toward the composition layer is referred to as "upper". , the opposite direction is called "down". It should be noted that such setting of the vertical direction is for the sake of convenience in this specification, and in an actual aspect, the "upward" direction in this specification may differ from the vertical upward direction.
In this specification, unless otherwise specified, the composition may contain two or more compounds corresponding to each component contained in the composition. In addition, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component.
In this specification, the temperature is 23° C., the pressure is 101,325 Pa (1 atm), and the relative humidity is 50% RH, unless otherwise stated.
Combinations of preferred aspects are more preferred aspects herein.

(Method for producing dry resin)
The method for producing a dry resin of the present invention includes a low-temperature and low-pressure step of reducing the pressure of a resin composition containing a resin and a solvent to 10 kPa or less at a temperature of -150 to 45 ° C., and after the low-temperature and low-pressure step, the resin composition. is set to a temperature 5° C. or more higher than the temperature in the low-temperature, low-pressure step under reduced pressure, and the resin has thermosetting properties.
In the present invention, the dry resin means that the solvent content is less than 10% by mass with respect to the total mass. The content is preferably 5% by mass or less, more preferably 3% by mass or less, and more preferably 1% by mass or less. The lower limit of the content is not particularly limited as long as it is 0% by mass or more.
The content of the solvent is measured by the same method as "Measurement of solid content after drying" in Examples described later. Moreover, the "solid content after drying" in the present invention is obtained by subtracting the mass of the solvent from the total mass of the dried resin. That is, for example, if the solid content after drying is 99% by mass, the solvent content is 1% by mass.

According to the method for producing a dry resin of the present invention, generation of particles in the obtained dry resin is suppressed.
Although the mechanism by which the above effects are obtained is not clear, it is presumed as follows.

For the purpose of obtaining a dry resin, for example, a resin composition containing a solvent and a thermosetting resin (hereinafter also referred to as "thermosetting resin") is placed in a heated dryer, and then vacuum drying is started. In this case, the composition is exposed to a heated state before it is cooled by the heat of vaporization accompanying the volatilization of the solvent.
In that case, the thermosetting resin is heated while the solvent remains in the resin composition, so curing of the thermosetting resin (groups containing ethylenically unsaturated bonds, crosslinkable groups such as cyclic ether groups, etc. cross-linking, imide cyclization of polyimide precursors, etc.) proceeds. When the curing of the thermosetting resin progresses in this way, even if the thermosetting resin after drying (dried resin) is dissolved again, the thermosetting resin after curing that is difficult to dissolve in the solution will be included. , it is assumed that particles are generated in the solution.
Therefore, as a result of intensive studies, the present inventors have found that the generation of particles is suppressed by a method of producing a heated resin by performing a high temperature and low pressure process after reducing the pressure in the dryer at a low temperature by a low temperature and low pressure process. I found
The present inventors have found that when the resin is cooled by the low temperature and low pressure process and then subjected to the high temperature and low pressure process, the removal of the solvent has progressed by the time the resin reaches a high temperature, and the curing of the above-mentioned thermosetting resin It is speculated that the generation of particles is suppressed because it is difficult to progress.

Here, Patent Literature 1 does not describe or suggest a method for producing a dry resin including a low-temperature, low-pressure process and a high-temperature, low-pressure process.
Each step included in the method for producing a dry resin of the present invention will be described in detail below.

<Low temperature and low pressure process>
The method for producing a dry resin of the present invention includes a low-temperature, low-pressure step of reducing the pressure of a resin composition containing a resin and a solvent to 10 kPa or less at a temperature of -150 to 45°C.

〔temperature〕
The temperature in the low temperature and low pressure process is -150 to 45°C.
From the viewpoint of particle suppression, the upper limit of the temperature is preferably 35° C. or lower, more preferably 30° C. or lower.
The lower limit of the above temperature is preferably −100° C. or higher, more preferably −50° C. or higher, from the viewpoint of the amount of solvent in the dried resin.
The temperature in the low temperature, low pressure step may vary within the above ranges.
For example, an aspect in which the range of variation is ±2° C. or less is preferable.
As another embodiment, it is also preferable to perform the low-temperature, low-pressure step by varying the temperature between -150°C and 25°C, and perform the later-described high-temperature, low-pressure step at a temperature within the range of 30°C to 150°C.
When the temperature in the low-temperature, low-pressure process fluctuates, the temperature in the high-temperature, low-pressure process, which will be described later, is preferably at least 5° C. higher than the maximum temperature in the low-temperature, low-pressure process.
The temperature in the low-temperature, low-pressure step may be the set temperature of the device. For example, when the temperature inside the device is set to 25°C and the pressure is reduced, the temperature of the resin inside the device may be lower than 25°C due to the absorption of the heat of vaporization by the solvent that evaporates during the pressure reduction. good.

〔pressure〕
The pressure in the low-temperature, low-pressure step is 10 kPa or less, preferably 5 kPa or less, more preferably 3 kPa or less, and even more preferably 1 kPa or less.
The lower limit of the pressure is not particularly limited, and may be 0 kPa (vacuum state).
The pressure in the low temperature, low pressure step may vary within the above ranges.
The temperature in the low-temperature, low-pressure step may be the set pressure in the apparatus.
Also, the low-temperature, low-pressure process may be performed in air set to a pressure within the above range, or may be performed in _N2 gas, Ar gas, or the like.

〔time〕
The time for the low-temperature low-pressure step may be appropriately set according to the type and content of the resin contained in the resin composition, the type and content of the solvent, etc., but it is preferably 10 minutes to 24 hours. , more preferably 20 minutes to 12 hours, more preferably 30 minutes to 6 hours.
The above time is calculated as the time from when the temperature and pressure in the measuring device attached to the apparatus reach the set values to when the temperature goes out of the above range.

〔Device〕
The low-temperature, low-pressure step can be performed, for example, using an apparatus equipped with a pressure reducing means such as a known vacuum dryer.
The above apparatus may be any apparatus provided with a pressure reduction means. When the low-pressure step is carried out at a temperature higher than room temperature, an apparatus equipped with depressurizing means and heating means can be used, respectively.
In addition, the low-temperature, low-pressure process and the high-temperature, low-pressure process described later may be performed in the same apparatus or in separate apparatuses. preferably.
When the low-temperature, low-pressure process and the high-temperature, low-pressure process described later are performed in the same apparatus, an apparatus equipped with decompression means and heating means is preferable, and when the low-temperature, low-pressure process is performed at a temperature lower than room temperature, decompression means and cooling means. and heating means, and when the low-temperature, low-pressure step is performed at a temperature higher than room temperature, it is more preferable to use an apparatus equipped with decompression means and heating means, respectively.
The decompression means is not particularly limited, and known decompression means such as a vacuum pump can be used.
The cooling means is not particularly limited, and known cooling means such as cooling using a cooling plate, cooling using a cooling medium such as a cooling gas, a cooling liquid, or a cooling solid, or cooling using a semiconductor element such as a Peltier element is used. be able to.
The heating means is not particularly limited, and includes heating by a hot plate, heating by using a heat source such as a heating gas, a heating liquid, and a heating solid, heating by a heating wire, heating by irradiation with infrared radiation, etc. A known heating means such as heating using a semiconductor element can be used.

[Resin composition]
The resin composition used in the present invention contains a thermosetting resin (thermosetting resin) and a solvent. Details of preferred embodiments of the resin composition will be described later.

<High temperature and low pressure process>
The method for producing a dry resin of the present invention includes, after the low-temperature, low-pressure step, a high-temperature, low-pressure step in which the resin composition is brought to a temperature higher than the temperature in the low-temperature, low-pressure step by 5°C or more under reduced pressure.

〔temperature〕
The temperature in the high-temperature, low-pressure step may be higher than the temperature in the low-temperature, low-pressure step by 5°C or more, but the difference between the temperature in the high-temperature, low-pressure step and the temperature in the low-temperature, low-pressure step is 5 to 100°C. It is preferably 5 to 50°C, and more preferably 5 to 50°C.
Also, the temperature in the high-temperature, low-pressure step is preferably 40 to 150.degree. From the viewpoint of particle suppression, the upper limit of the temperature is preferably 120° C. or lower, more preferably 70° C. or lower, and particularly preferably 50° C. or lower.
The temperature in the high temperature, low pressure step may vary within the above ranges. Specifically, as long as the temperature is 5°C or more higher than the temperature of the low-temperature, low-pressure step, it may vary within that range, for example, within the range of 40 to 150°C.
When the temperature in the high-temperature, low-pressure process fluctuates, the temperature in the high-temperature, low-pressure process is the minimum value of the temperature in the high-temperature, low-pressure process.
The temperature in the high-temperature, low-pressure step may be the set temperature of the apparatus. For example, when the temperature inside the device is set to 45°C and the pressure is reduced, the temperature of the resin in the device is lower than 45°C due to the absorption of the heat of vaporization by the solvent that evaporates during the pressure reduction. good too. In particular, the temperature of the resin immediately after the start of the high-temperature, low-pressure process may be lower than the set temperature due to the effect of cooling due to absorption of heat of vaporization in the low-temperature, low-pressure process.

〔pressure〕
The pressure in the high-temperature, low-pressure step may be under reduced pressure, but is preferably 10 kPa or less, more preferably 5 kPa or less, even more preferably 3 kPa or less, and particularly preferably 1 kPa or less.
The lower limit of the pressure is not particularly limited, and may be 0 kPa (vacuum state).
Moreover, the pressure in the high-temperature, low-pressure step may be the same as or different from the pressure in the low-temperature, low-pressure step, but is preferably the same.
Also, for the purpose of improving the drying speed, enhancing the cooling effect by the heat of vaporization, etc., it is also preferable to set the pressure in the high-temperature, low-pressure process to be lower than the pressure in the low-temperature, low-pressure process.
The absolute value of the difference between the pressure in the high-temperature, low-pressure step and the pressure in the low-temperature, low-pressure step is preferably 5 kPa or less, more preferably 3 kPa or less, and even more preferably 1 kPa or less. The minimum absolute value of the difference may be 0 kPa.
The pressure in the high temperature, low pressure step may vary within the above ranges.
The temperature in the high-temperature, low-pressure step may be the set pressure in the apparatus.
Also, the high-temperature, low-pressure step may be performed in reduced pressure air, or may be performed in _N2 gas, Ar gas, or the like.

〔time〕
The time to be subjected to the high-temperature and low-pressure step may be appropriately set according to the type and content of the resin contained in the resin composition, the type and content of the solvent, etc., but it is preferably 1 hour to 240 hours. , more preferably 2 hours to 120 hours, and even more preferably 4 hours to 96 hours.
The above time is calculated as the time from the time when the value indicated by the thermometer provided in the apparatus is 5 ° C. higher than the temperature in the low temperature and low pressure process to the end of heating for the high temperature and low pressure process. .

〔Device〕
The high-temperature, low-pressure step can be performed using, for example, a device equipped with a pressure reduction means such as a known vacuum dryer.
The apparatus may be any apparatus provided with pressure reduction means, and when the high temperature and low pressure process is performed at a temperature lower than room temperature (e.g., 23 ° C.), an apparatus provided with pressure reduction means and cooling means may be used for the high temperature and low pressure process. is carried out at a temperature higher than room temperature, an apparatus equipped with pressure reducing means and heating means can be used.
As these devices, pressure reducing means, cooling means and heating means, the devices, pressure reducing means, cooling means and heating means described in the description of the device in the low temperature and low pressure step can be used.

[Time from the end of the low temperature and low pressure process]
The time from the end of the low-temperature, low-pressure step to the start of the high-temperature, low-pressure step is preferably within 3 minutes, more preferably within 1 minute. The lower limit of the time is not particularly limited, and the high-temperature, low-pressure process may be started immediately after the low-temperature, low-pressure process ends.
The end of the low-temperature, low-pressure process is the time at which at least one of heating and depressurization for the low-temperature process is completed, and the start of the high-temperature, low-pressure process is the start of heating for the high-temperature, low-pressure process.
According to the above aspect, generation of particles is suppressed. It is presumed that this is because the high-temperature, low-pressure process can be started in a state in which the resin is cooled by absorbing the heat of vaporization in the low-temperature, low-pressure process.

[Resin composition]
Details of the resin composition to be subjected to the low-temperature, low-pressure process are described below.
The resin composition used in the present invention contains a thermosetting resin and a solvent.

-Thermosetting resin-
As the thermosetting resin, a group having an ethylenically unsaturated bond such as a vinyl group, an allyl group, or an acryloyl group, a cyclic ether group such as an epoxy group or an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a methylol group. , Acyloxymethyl group, benzoxazolyl group, resin having a crosslinkable group such as a blocked isocyanate group in its structure, or a structure in which a ring (e.g., imide ring) is formed by heating (e.g., amic acid ester structure, etc.) ) in the structure.
According to the method for producing a dry resin of the present invention, cross-linking of the cross-linkable groups in the thermosetting resin, formation of a ring structure, and the like are suppressed, so it is thought that generation of particles is suppressed.
From the viewpoint of easily obtaining the effects of the present invention, the thermosetting resin is preferably a resin containing a repeating unit having at least one structure selected from the group consisting of an amic acid structure and an amic acid ester structure. A resin containing a repeating unit having an acid ester structure is more preferable.
In addition, from the viewpoint of easily obtaining the effects of the present invention, the thermosetting resin is a resin having at least one crosslinkable group selected from the group consisting of a group having an ethylenically unsaturated bond and a cyclic ether group. is preferred, and a resin having a (meth)acryloxy group is more preferred.
Moreover, the thermosetting resin may further have a structure that is decomposed by heating. For example, when the thermosetting resin is a resin having a structure in which an acid group is protected by a thermally decomposable protective group and a cyclic ether group, an acid group generated by decomposition of the thermally decomposable protective group by heat (e.g. , a carboxyl group or a phenolic hydroxy group) and a cyclic ether group may easily generate particles due to a reaction such as crosslinking by heat. Examples of the structure in which the acid group is protected by a thermally decomposable protective group include known structures such as an acetal structure and a t-butoxycarbonyl group.
However, according to the method for producing a dry resin of the present invention, since the generation of particles is suppressed, it is also suitable as a method for producing a dry resin using a resin composition containing a resin that easily generates particles due to such heating. It is considered to be
Among these, the thermosetting resin contains a repeating unit having an amic acid ester structure, and at least one crosslinkable group selected from the group consisting of a group having an ethylenically unsaturated bond and a cyclic ether group It preferably contains a resin having a group, more preferably a resin containing a repeating unit having an amic acid ester structure and having a (meth)acryloxy group.

<<Repeating unit represented by formula (1)>>
The thermosetting resin preferably contains a repeating unit represented by the following formula (1).
In the following formula (1), a repeating unit in which A ¹ and A ² are oxygen atoms and both R ¹¹³ and R ¹¹⁴ are hydrogen atoms is a preferred embodiment among repeating units having an amic acid structure Applicable.
Further, in the following formula (1), a repeating unit in which A ¹ and A ² are oxygen atoms and either R ¹¹³ or R ¹¹⁴ is a monovalent organic group has the above-described amic acid ester structure. It corresponds to a preferred embodiment among repeating units.
Moreover, hereinafter, a resin containing a repeating unit represented by the following formula (1) is also referred to as a "polyimide precursor".

In formula (1), A ¹ and A ² each independently represent an oxygen atom or —NH—, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group.

- A ¹ and A ² -
A ¹ and A ² in formula (1) each independently represent an oxygen atom or —NH—, preferably an oxygen atom.

-R ¹¹¹ -
R ¹¹¹ in formula (1) represents a divalent organic group. Examples of divalent organic groups include linear or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or groups in which two or more of these are combined. 2 to 20 linear aliphatic groups, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, aromatic groups having 6 to 20 carbon atoms, or two of these Groups in which the above are combined are preferred, and aromatic groups having 6 to 20 carbon atoms are more preferred.

R ¹¹¹ in formula (1) is preferably derived from a diamine. Diamines used in the production of polyimide precursors include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one type of diamine may be used, or two or more types may be used.

Specifically, 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 A diamine containing a combination of two or more groups is preferable, and a diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable. Examples of aromatic groups include: In the following formulas, each * independently represents a binding site to another structure.

In the formula, A is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms optionally substituted with a fluorine atom, -O-, -C (= O) -, -S-, -S (=O) ₂ -, -NHC(=O)-, or a group in which two or more of these are combined, preferably a single bond, an alkylene group having 1 to 3 carbon atoms optionally substituted with a fluorine atom , -O-, -C(=O)-, -S- and -S(=O) ₂ -, more preferably a group selected from -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 diamines 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 para-phenylenediamine, 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'-diaminodiphenyl sulfone , 4,4′- or 3,3′-diaminodiphenyl sulfide, 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'-diaminoparaterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy ) phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10- Bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene , 1,3-bis(4-aminophenyl)benzene, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 4,4′-diamino Octafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4- aminophenyl)-10-hydroanthracene, 3,3′,4,4′-tetraaminobiphenyl, 3,3′,4,4′-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone , 3,3-dihydroxy-4,4′-diaminobiphenyl, 9,9′-bis(4-aminophenyl)fluorene, 4,4′-dimethyl-3,3′-diaminodiphenylsulfone, 3,3′, 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2-(3',5'-diaminobenzoyloxy)ethyl methacrylate, 2,4- or 2,5-diaminocumene, 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, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis (4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl) ) tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2- Bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexa Fluoropropane, 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 at least one selected from '-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolyzine and 4,4'-diaminoquaterphenyl species of diamines.

Also preferred are the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of WO 2017/038598.

Also preferably used are diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of WO 2017/038598.

R ¹¹¹ in formula (1) is preferably represented by -Ar ⁰ -L ⁰ -Ar ⁰ - from the viewpoint of the flexibility of the resulting pattern. Each 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), preferably a phenylene group. L ⁰ is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms optionally substituted with a fluorine atom, -O-, -C(=O)-, -S-, -S(= O) ₂ —, —NHCO—, or a group in which two or more of these are combined. The preferred range of L ⁰ is synonymous with A above.

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

In formula (51), R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, 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 each * independently represents a binding site to another structure.

The monovalent organic groups represented by R ⁵⁰ to R ⁵⁷ include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), A fluorinated alkyl group and the like can be mentioned.

In formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group. Each * independently represents a binding site with another structure.

Diamine compounds that give the structure of formula (51) or (61) include dimethyl-4,4′-diaminobiphenyl, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 2,2 '-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl and the like. One of these may be used, or two or more may be used in combination.

-R ¹¹⁵ -
R ¹¹⁵ in 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 (6) is more preferable.

R ¹¹² has the same definition as A in AR-9 above, and the preferred range is also the same. Each * independently represents a binding site with another structure. Each * independently represents a binding site with another structure.

Specific examples of the tetravalent organic group represented by R ¹¹⁵ in formula (1) include a tetracarboxylic acid residue remaining after removal of the acid dianhydride group from the tetracarboxylic dianhydride. Only one kind of tetracarboxylic dianhydride may be used, or two or more kinds thereof may be used. Tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).

R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ has the same definition as R ¹¹⁵ in formula (1).

Specific examples of tetracarboxylic dianhydrides include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3′,4,4′-biphenyltetracarboxylic dianhydride (4,4′-biphthal acid anhydride), 3,3′,4,4′-diphenylsulfidetetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3′,4, 4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3 ,3′,4′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-benzophenonetetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 2,3,6, 7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4, 4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2′,3,3′-diphenyltetracarboxylic dianhydride, 3,4,9,10 -perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrene Tetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3 ,4-benzenetetracarboxylic dianhydride, and at least one selected from alkyl derivatives of 1 to 6 carbon atoms and alkoxy derivatives of 1 to 6 carbon atoms thereof.

Further, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017/038598 are also preferred examples.

It is also preferred that at least one of R ¹¹¹ and R ¹¹⁵ has an OH group. More specifically, R ¹¹¹ includes residues of bisaminophenol derivatives.

-R ¹¹³ and R ¹¹⁴ -
R ¹¹³ and R ¹¹⁴ in formula (1) each independently represent a hydrogen atom or a monovalent organic group. At least one of R ¹¹³ and R ¹¹⁴ preferably contains a crosslinkable group, more preferably both contain a crosslinkable group. The crosslinkable group is preferably a group capable of undergoing a crosslink reaction by the action of a radical, an acid, a base, or the like, such as a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group. , an epoxy group, a cyclic ether group such as an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group and a methylol group, preferably a group having an ethylenically unsaturated bond, a cyclic ether group, an alkoxymethyl group or a methylol group. The group having an ethylenically unsaturated bond is preferably a group having radical polymerizability.

The group having an ethylenically unsaturated bond includes a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, the following formula ( Groups represented by III) and the like can be mentioned.

In formula (III), R ²⁰⁰ represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, preferably a hydrogen atom or a methyl group.
In formula (III), * represents a binding site with another structure.
In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, —CH ₂ CH(OH)CH ₂ —, a cycloalkylene group or a polyalkyleneoxy group.
Examples of suitable R ²⁰¹ are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butanediyl group, 1,3-butanediyl group, pentamethylene group, hexamethylene group, octamethylene group and dodecamethylene group. , —CH ₂ CH(OH)CH ₂ — and polyalkyleneoxy groups, and more preferably ethylene, propylene, trimethylene, —CH ₂ CH(OH)CH ₂ — and polyalkyleneoxy groups, and ethylene group or a polyalkyleneoxy group is more preferred.
In the present invention, a polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
When the polyalkyleneoxy group contains multiple types of alkyleneoxy groups with different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement or a block arrangement. Alternatively, it may be arranged in a pattern such as an alternating pattern.
The number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, and 2 to 6. is more preferred, 2 to 5 is more preferred, 2 to 4 is even more preferred, 2 or 3 is particularly preferred, and 2 is most preferred.
Moreover, the said alkylene group may have a substituent. Preferred substituents include alkyl groups, aryl groups, and halogen atoms.
The number of alkyleneoxy groups contained in the polyalkyleneoxy group (repeating number of polyalkyleneoxy groups) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.
As the polyalkyleneoxy group, from the viewpoint of solvent solubility and solvent resistance, a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a plurality of ethyleneoxy groups and a plurality of propylene A group to which an oxy group is bonded is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is still more preferable. In the group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, or may be arranged to form blocks. , may be arranged in a pattern such as alternately. Preferred aspects of the number of repetitions of ethyleneoxy groups and the like in these groups are as described above.

More preferably, R ¹¹³ or R ¹¹⁴ is a hydrogen atom, a benzyl group, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group or a 4-hydroxybenzyl group from the viewpoint of solubility in an aqueous developer.

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

The number of carbon atoms in the alkyl group is preferably 1 to 30 (3 or more in the case of cyclic). Alkyl groups may be linear, branched or cyclic. Linear or branched alkyl groups include, for example, 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. , isopropyl, isobutyl, sec-butyl, t-butyl, 1-ethylpentyl, and 2-ethylhexyl groups. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of monocyclic cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups. Examples of polycyclic cyclic alkyl groups include adamantyl group, norbornyl group, bornyl group, camphenyl group, decahydronaphthyl group, tricyclodecanyl group, tetracyclodecanyl group, camphoroyl group, dicyclohexyl group and pinenyl group. is mentioned. Moreover, 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 aromatic groups include substituted or unsubstituted aromatic hydrocarbon groups (cyclic structures constituting the group include benzene ring, naphthalene ring, biphenyl ring, fluorene ring, pentalene ring, indene ring, azulene ring, ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene ring, triphenylene ring, etc.), or a substituted or unsubstituted aromatic heterocyclic group ( 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 indolizine ring, an indole ring, and a benzofuran. ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring , xanthene ring, phenoxathiin ring, phenothiazine ring or phenazine ring).

Also, the polyimide precursor preferably has a fluorine atom in the repeating unit. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, more preferably 20% by mass or more. Although there is no particular upper limit, 50% by mass or less is practical.

For the purpose of improving adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with the repeating unit represented by formula (1). Specific examples of diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(para-aminophenyl)octamethylpentasiloxane.

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

A ¹¹ and A ¹² each independently represent an oxygen atom or —NH—, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or 1 more preferably, at least one of R ¹¹³ and R ¹¹⁴ is a crosslinkable group.

The preferred ranges of A ¹¹ , A ¹² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ are the same as the preferred ranges of A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in Formula (1).

The preferred range of R ¹¹² has the same meaning as R ¹¹² in formula (5), and more preferably an oxygen atom.

The bonding positions of the carbonyl group in the formula to the benzene ring are preferably 4, 5, 3' and 4' in formula (1-A). In formula (1-B), 1, 2, 4 and 5 are preferred.

In the polyimide precursor, the number of repeating units represented by formula (1) may be one, or two or more. It may also contain structural isomers of the repeating unit represented by formula (1). The polyimide precursor may also contain other types of repeating units in addition to the repeating units of formula (1) above.

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

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

The polyimide precursor preferably has a molecular weight distribution of 1.5 to 3.5, more preferably 2 to 3.
In the present specification, the molecular weight dispersity refers to the value obtained by dividing the weight average molecular weight by the number average molecular weight (weight average molecular weight/number average molecular weight).

A polyimide precursor is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. For example, it can be obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative using a halogenating agent and then reacting it with a diamine.

It is also preferable to synthesize the polyimide precursor using a non-halogen catalyst. As the non-halogen catalyst, known amidation catalysts containing no halogen atoms can be used without particular limitation. Examples include salts, urea compounds, and carbodiimide compounds. Examples of the carbodiimide compound include N,N'-diisopropylcarbodiimide and N,N'-dicyclohexylcarbodiimide.

In the method for producing a polyimide precursor, it is preferable to use an organic solvent in the reaction. One type of organic solvent may be used, or two or more types may be used.

Examples of the organic solvent include pyridine, diethylene glycol dimethyl ether (diglyme), N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone. Ether-based solvents, which will be described later, are also preferred organic solvents.
Also, a synthesis reaction liquid containing such an organic solvent and a synthesized polyimide precursor may be used as the resin composition in the present invention.

The production of the polyimide precursor preferably includes a step of depositing a solid. Specifically, the polyimide precursor in the reaction solution is precipitated in water, and dissolved in a solvent such as tetrahydrofuran in which the polyimide precursor is soluble, whereby solid deposition can be performed.
The resin composition of the present invention may be a resin composition prepared by redissolving or dispersing the solid-deposited resin in a solvent described below.

<<Repeating unit represented by formula (2)>>
The thermosetting resin may contain a repeating unit represented by the following formula (2).
Hereinafter, the resin containing the repeating unit represented by formula (2) is also referred to as "polybenzoxazole precursor".

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

-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 is more preferred, and 6 to 12 are particularly preferred). Examples of the aromatic group constituting R ¹²¹ include the examples of R ¹¹¹ in 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 preferred 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 each independently represent a hydrogen atom or a monovalent organic group, have the same meanings as R ¹¹³ and R ¹¹⁴ in formula (1) above, and the preferred ranges are also the same.

The polybenzoxazole precursor may contain repeating units of formula (2) above, as well as other types of repeating units.

The polybenzoxazole precursor preferably further contains a diamine residue represented by the following formula (SL) as another type of repeating unit in order to suppress the occurrence of pattern warpage due to ring closure.

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), the remainder being hydrogen atoms or 1 to 30 carbon atoms (preferably 1 to 18 carbon atoms, more It is preferably an organic group having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and may be the same or different. Polymerization of a structure and b structure may be block polymerization or random polymerization. In the Z portion, preferably the a structure is 5-95 mol %, the b structure is 95-5 mol %, and a+b is 100 mol %.

In formula (SL), preferred Z include those in which R ^5s and R ^6s in the b structure are phenyl groups. Further, the molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. Molecular weights can be determined by commonly used gel permeation chromatography. By setting the molecular weight in the above range, it is possible to reduce the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure, thereby achieving both the effect of suppressing warpage and the effect of improving solubility.

When the polybenzoxazole precursor contains a diamine residue represented by the formula (SL) as another type of repeating unit, in terms of improving the alkali solubility of the composition, the tetracarboxylic dianhydride is further converted to an acid It preferably contains, as a repeating unit, a tetracarboxylic acid residue remaining after removal of the dianhydride group. Examples of such tetracarboxylic acid residues include those of R ¹¹⁵ in 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. be. Also, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, still more preferably 4,000 to 25,000.

The molecular weight dispersity of the polybenzoxazole precursor is preferably 1.5-3.5, more preferably 2-3.

<<other resins>>
The thermosetting resin may be a thermosetting resin other than the polyimide precursor and polybenzoxazole precursor described above.
Other thermosetting resins include, for example, polyimide precursors other than those mentioned above, polybenzoxazole precursors other than those mentioned above, polyimide resins, polybenzoxazole resins, polyamideimide precursors, polyamideimide resins, polysiloxane resins, Resins containing siloxane structures, epoxy resins, (meth)acrylic resins, polyethylene resins, olefin resins such as polypropylene, vinyl resins such as polyvinyl chloride and polyvinyl ester, polyurethane resins, polyurea resins, polyamide resins, polycarbonate resins, polyesters Examples thereof include resins, polystyrene resins, polyacetal resins, cellulose resins, phenolic resins, and fluorine-based resins such as polytetrafluoroethylene.
These thermosetting resins are preferably resins having the crosslinkable groups described above.

<<(Meth) acrylic resin>>
Among these, a (meth)acrylic resin can be mentioned as a thermosetting resin that is preferably used in the method for producing a dry resin of the present invention.
A (meth)acrylic resin is a polymer having a structure obtained by polymerizing at least one compound selected from the group consisting of (meth)acrylic acid and (meth)acrylate.

<<<Repeating unit having a crosslinkable group>>>
As the (meth)acrylic resin, a (meth)acrylic resin containing a repeating unit having a crosslinkable group is preferable. Examples of the crosslinkable group include the crosslinkable groups described above.
As the repeating unit having a crosslinkable group contained in the (meth)acrylic resin, a repeating unit represented by the following formula (A-1) is preferable.
In formula (A-1), L ^A1 represents a single bond or an n+1-valent linking group, R ^A1 represents a crosslinkable group, n represents an integer of 1 or more, and R represents a hydrogen atom or a methyl group.

In formula (A-1), L ^A1 is preferably an n+1 valent linking group, a hydrocarbon group, or a hydrocarbon group and -O-, -S-, -NR ^N -, -C (= O)- and -S(=O) ₂ - are more preferably a structure represented by bonding at least one selected from the group. R 3 ^N represents a hydrogen atom or a hydrocarbon group, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom.
The hydrocarbon group in L ^A1 is preferably a hydrocarbon group having 1 to 30 carbon atoms, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms, or , a hydrocarbon group having 1 to 30 carbon atoms represented by a combination thereof is more preferable.
The above hydrocarbon group may have a known substituent such as a hydroxy group, a carboxy group, an alkoxy group, an aryloxy group, and a halogen atom.

In formula (A-1), R ^A1 represents a crosslinkable group, a group having an ethylenically unsaturated bond, a cyclic ether group, an alkoxymethyl group such as a methoxymethyl group, a methylol group, an acyloxymethyl group, and benzoxazolyl. A group or a blocked isocyanate group is preferred, and a group having an ethylenically unsaturated bond or a cyclic ether group is more preferred.
The group having an ethylenically unsaturated bond is preferably a vinyl group, an allyl group, a vinylphenyl group, a (meth)acrylamide group, or a (meth)acryloxy group, more preferably a (meth)acryloxy group.
The cyclic ether group is preferably an epoxy group or an oxetanyl group, more preferably an epoxy group.

In formula (A-1), n represents an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 5, more preferably an integer of 1 to 3 1 or 2 is particularly preferred, and 1 is most preferred.

Specific examples of repeating units having a crosslinkable group include, but are not limited to, the following repeating units. In the specific examples below, each R independently represents a hydrogen atom or a methyl group, a represents an integer of 1 or more, and ^RN is as described above.

The (meth)acrylic resin may contain one repeating unit having a crosslinkable group, or may contain two or more repeating units.
The molar content of the crosslinkable group in 1 g of the (meth)acrylic resin is preferably 0.5 to 4.0 mmol/g, more preferably 1.0 to 3.5 mmol/g.

<<<Repeating unit having a structure that decomposes upon heating>>>
The (meth)acrylic resin may further contain a repeating unit having a structure that decomposes upon heating, and may further contain a repeating unit having a structure in which the acid group is protected by a thermally decomposable protective group.
Structures in which an acid group is protected by a thermally decomposable protective group include, for example, a repeating unit represented by the following formula (A-2), a repeating unit represented by the following formula (A-3), and a repeating unit represented by the following formula At least one repeating unit selected from the group consisting of repeating units represented by (A-4) is preferred.
In the repeating units represented by the following formulas (A-2), (A-3) and (A-4), the acetal protecting group is eliminated by heating to form an acid group (carboxy group or phenolic hydroxy group). including the structure in which
In formulas (A-2) to (A-4), R represents a hydrogen atom or a methyl group, R ^A21 and R ^A22 each independently represent a hydrogen atom or a monovalent organic group, R ^A23 each independently represents a monovalent organic group, L ^A2 represents a + 1 valent linking group, a represents an integer of 1 or more, Ar represents an aromatic ring structure, b is 1 or more and the maximum number of substituents in Ar -1 represents the following integers, and at least two of R ^A21 , R ^A22 and R ^A23 may combine to form a ring structure.

In formulas (A-2) to (A-4), R ^A21 and R ^A22 each independently represent a hydrogen atom or a monovalent organic group, and at least one of R ^A21 and R ^A22 is a monovalent organic group. is preferably represented. The monovalent organic group is preferably a monovalent hydrocarbon group, more preferably an alkyl group or an aromatic hydrocarbon group, and still more preferably an alkyl group. As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable. A phenyl group is preferable as the aromatic hydrocarbon group.

In formulas (A-2) to (A-4), R ^A23 represents a monovalent organic group, preferably a monovalent hydrocarbon group, more preferably an alkyl group, and an alkyl group having 1 to 10 carbon atoms. more preferred.

In formula (A-3) or formula (A-4), L ^A2 represents an a+1 valent linking group, a hydrocarbon group, or a hydrocarbon group and -O-, -S-, -NR ^N -, A structure represented by bonding at least one selected from the group consisting of -C(=O)- and -S(=O) ₂ - is preferred. ^RN is as described above.
The hydrocarbon group in L ^A2 is preferably a hydrocarbon group having 1 to 30 carbon atoms, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms, or , a hydrocarbon group having 1 to 30 carbon atoms represented by a combination thereof is more preferable.
The above hydrocarbon group may have a known substituent such as a hydroxy group, a carboxy group, an alkoxy group, an aryloxy group, and a halogen atom.

In formula (A-3) or formula (A-4), a represents an integer of 1 or more, preferably 1 to 4, more preferably 1 or 2, even more preferably 1 .

In formula (A-4), Ar is preferably an aromatic hydrocarbon group, more preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and b+1 hydrogen atoms are removed from the benzene ring structure. is more preferably a group.

In formula (A-4), b represents an integer of 1 or more and the maximum number of substituents in Ar −1 or less, preferably an integer of 1 to 4, more preferably 1 or 2, and 1 is more preferred.
The maximum number of substituents in Ar refers to the maximum number of substituents in the aromatic group represented by Ar. For example, if Ar has a benzene ring structure, the maximum number of substituents is 6, and if Ar has a thiophene ring structure, the maximum number of substituents is 4. be.

In formulas (A-2) to (A-4), at least two of R ^A21 , R ^A22 and R ^A23 may combine to form a ring structure, and R ^A23 and R ^A21 and R ^A22 It is preferable that one of them forms a ring structure. The ring structure to be formed is preferably a 5-membered ring structure, a 6-membered ring structure, or a structure obtained by condensing a 5-membered ring structure or a 6-membered ring structure with another ring structure, and more preferably a tetrahydrofuran ring or a tetrahydropyran ring.

Structures in which an acid group is protected by a thermally decomposable protective group include, for example, a repeating unit represented by the following formula (A-5), a repeating unit represented by the following formula (A-6), and At least one repeating unit selected from the group consisting of repeating units represented by the following formula (A-7) is also preferred.
In the repeating units represented by the following formulas (A-5), (A-6) and (A-7), the tertiary alkyl group is eliminated by heating to form an acid group (carboxy group or phenolic hydroxyl group). group) occurs.
In formulas (A-5) to (A-7), R represents a hydrogen atom or a methyl group, R ^A51 , R ^A52 and R ^A53 each independently represent a hydrocarbon group, and L ^A3 is a+1 valent represents a linking group, a represents an integer of 1 or more, Ar represents an aromatic ring structure, b represents an integer of 1 or more and the maximum number of substituents in Ar −1 or less, and at least R ^A51 , R ^A52 and R ^A53 The two may combine to form a ring structure.

In formulas (A-5) to (A-7), R ^A51 , R ^A52 and R ^A53 each independently represent a hydrocarbon group. The hydrocarbon group is preferably an alkyl group or an aromatic hydrocarbon group, more preferably an alkyl group. As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group is even more preferable. A phenyl group is preferable as the aromatic hydrocarbon group.

In formula (A-6) or formula (A-7), L ^A3 represents an a+1-valent linking group, a hydrocarbon group, or a hydrocarbon group and -O-, -S-, -NR ^N -, A structure represented by bonding at least one selected from the group consisting of -C(=O)- and -S(=O) ₂ - is preferred. ^RN is as described above.
The hydrocarbon group in L ^A3 is preferably a hydrocarbon group having 1 to 30 carbon atoms, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms, or , a hydrocarbon group having 1 to 30 carbon atoms represented by a combination thereof is more preferable.
The above hydrocarbon group may have a known substituent such as a hydroxy group, a carboxy group, an alkoxy group, an aryloxy group, and a halogen atom.

In formula (A-6) or formula (A-7), a represents an integer of 1 or more, preferably 1 to 4, more preferably 1 or 2, even more preferably 1 .

In formula (A-7), Ar is preferably an aromatic hydrocarbon group, more preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and b+1 hydrogen atoms are removed from the benzene ring structure. is more preferably a group.

In formula (A-7), b represents an integer of 1 or more and the maximum number of substituents in Ar −1 or less, preferably an integer of 1 to 4, more preferably 1 or 2, and 1 is more preferred.
The maximum number of substituents in Ar refers to the maximum number of substituents in the aromatic group represented by Ar. For example, if Ar has a benzene ring structure, the maximum number of substituents is 6, and if Ar has a thiophene ring structure, the maximum number of substituents is 4. be.

In formulas (A-5) to (A-7), at least two of R ^A51 , R ^A52 and R ^A53 may combine to form a ring structure. The ring structure to be formed is preferably a hydrocarbon ring structure, and includes monocyclic structures such as cyclopentane ring structure and cyclohexane ring structure, and polycyclic structures such as norbornane ring and adamantane ring.

Examples of the repeating unit having a structure that decomposes upon heating, contained in the (meth)acrylic resin, include, but are not limited to, the following structures. In the structures below, R is a hydrogen atom or a methyl group.

The (meth)acrylic resin may contain one repeating unit having a structure decomposed by heating, or may contain two or more repeating units.

<<<Other repeating units>>>
Moreover, the (meth)acrylic resin may further contain other repeating units.
Other repeating units include repeating units containing acid groups such as carboxy groups and phenolic hydroxy groups (for example, repeating units derived from (meth)acrylic acid), repeating units containing known substituents such as hydroxy groups, Examples thereof include repeating units contained in polystyrene resins described later. That is, the (meth)acrylic resin may be a resin containing a structure derived from a styrene compound such as a styrene-acrylic resin.
The (meth)acrylic resin may contain one type of other repeating unit alone, or may contain two or more types.

According to the method for producing a dry resin of the present invention, for example, when the (meth)acrylic resin contains a repeating unit containing an acid group and a repeating unit having a crosslinkable group that reacts with the acid group, or A resin that easily generates particles by heating, such as a repeating unit containing a known substituent such as a group and a repeating unit having a crosslinkable group that reacts with a known substituent such as the hydroxy group, is used. Even in this case, it is considered that a dry resin in which generation of particles is suppressed can be obtained.

<<<molecular weight>>>
Although the weight average molecular weight of the (meth)acrylic resin is not particularly limited, it is preferably from 1,000 to 1,000,000, more preferably from 2,000 to 50,000.
In addition, the larger the molecular weight of the resin, the more likely it is that particles having a large particle size will be formed when crosslinked. , 000 or more) is more likely to obtain the effect of the present invention.

<<polystyrene resin>>
Among these, a polystyrene resin can be mentioned as a thermosetting resin that is preferably used in the method for producing a dry resin of the present invention.
A polystyrene resin is a polymer having a structure obtained by polymerizing at least one styrene compound which may have a substituent.

<<<Repeating unit having a crosslinkable group>>>
As the polystyrene resin, a polystyrene resin containing a repeating unit having a crosslinkable group is preferred. Examples of the crosslinkable group include the crosslinkable groups described above.
As the repeating unit having a crosslinkable group contained in the polystyrene resin, a repeating unit represented by the following formula (B-1) is preferable.
In formula (B-1), L ^B1 represents a single bond or an n+1 valent linking group, R ^B1 represents a crosslinkable group, n represents an integer of 1 or more, m represents an integer of 1 to 5, R represents a hydrogen atom or a monovalent substituent.

In formula (B-1), L ^B1 is preferably an n+1 valent linking group, a hydrocarbon group, or a hydrocarbon group and -O-, -S-, -NR ^N -, -C (= O)- and -S(=O) ₂ - are more preferably a structure represented by bonding at least one selected from the group. The above ^RN is as described above.
Among them, as L ^B1 , the bonding site between L ^B1 in L ^B1 and the benzene ring in formula (B-1) is -O-, -C(=O)-, or -NR ^N -n+1 A valent linking group is preferred.
The hydrocarbon group in L ^B1 is preferably a hydrocarbon group having 1 to 30 carbon atoms, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or , a hydrocarbon group having 1 to 30 carbon atoms represented by a combination thereof is more preferable.
The above hydrocarbon group may have a known substituent such as a hydroxy group, a carboxy group, an alkoxy group, an aryloxy group, and a halogen atom.

In formula (B-1), R ^{1 B1} has the same definition as R ^{1 A1} in formula (A-1), and preferred embodiments are also the same.

In formula (B-1), n is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, even more preferably an integer of 1 to 3, 1 or 2 is particularly preferred, and 1 is most preferred.

In formula (B-1), m is preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1.

In formula (B-1), R is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

Polystyrene may also contain, for example, a repeating unit represented by the above formula (A-1) as a repeating unit having a crosslinkable group.

Examples of repeating units having a crosslinkable group include, but are not limited to, the following repeating units.

The polystyrene resin may contain one repeating unit having a crosslinkable group, or may contain two or more repeating units.
The molar content of crosslinkable groups in 1 g of polystyrene resin is preferably 0.5 to 4.0 mmol/g, more preferably 1.0 to 3.5 mmol/g.

<<<Repeating unit having a structure that decomposes upon heating>>>
Moreover, the polystyrene resin may further contain a repeating unit having a structure that decomposes upon heating, and may further contain a repeating unit having a structure in which the acid group is protected by a thermally decomposable protective group.
Structures in which an acid group is protected by a thermally decomposable protective group include, for example, a repeating unit represented by the following formula (B-2), a repeating unit represented by the following formula (B-3), and a repeating unit represented by the following formula At least one repeating unit selected from the group consisting of repeating units represented by (B-4) is preferred.
In the repeating units represented by the following formulas (B-2), (B-3) and (B-4) below, the acetal protective group is eliminated by heating to form an acid group (carboxy group or phenolic hydroxy group). This is the structure where
In formulas (B-2) to (B-4), R represents a hydrogen atom or a monovalent organic group, R ^B21 and R ^B22 each independently represent a hydrogen atom or a monovalent organic group, R ^B23 each independently represents a monovalent organic group, L ^B2 represents a b+1 valent linking group, a represents an integer of 1 to 5, b represents an integer of 1 or more, and Ar represents an aromatic ring structure. and c represents an integer of 1 or more and the maximum number of substituents in Ar minus 1 or less, and at least two of R ^B21 , R ^B22 and R ^B23 may combine to form a ring structure.

In formulas (B-2) to (B-4), R ^B21 and R ^B22 are respectively synonymous with R ^A21 and R ^A22 in formulas (A-2) to (A-4), and preferred embodiments The same is true for

In formulas (B-2) to (B-4), R ^{2 B23} has the same meaning as R ²³ in formulas (A-2) to (A-4), and preferred embodiments are also the same.

In formulas (B-2) to (B-4), a is preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1.

In formulas (B-2) to (B-4), R has the same definition as R in formula (B-1), and preferred embodiments are also the same.

In formula (B-3) or formula (B-4), L ^B2 is a hydrocarbon group, or a hydrocarbon group and -O-, -S-, -NR ^N -, -C(=O)-, and --S(=O) _.sub.2-- is more preferably a structure represented by bonding at least one member. The above ^RN is as described above.
Among these, as L ^B2 , the bonding site between L ^{B2 in L B2 and} the benzene ring in formula (B-3) or formula (B-4) is —O—, —C(=O)—, or A b+1 valent linking group that is -NR ^N - is preferred.
The hydrocarbon group in L ^B2 is preferably a hydrocarbon group having 1 to 30 carbon atoms, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or , a hydrocarbon group having 1 to 30 carbon atoms represented by a combination thereof is more preferable.
The above hydrocarbon group may have a known substituent such as a hydroxy group, a carboxy group, an alkoxy group, an aryloxy group, and a halogen atom.

In formula (B-3) or formula (B-4), b is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, and more preferably an integer of 1 to 3. 1 or 2 is particularly preferred, and 1 is most preferred.

In formula (B-4), Ar is preferably an aromatic hydrocarbon group, more preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and c + 1 hydrogen atoms are removed from the benzene ring structure. is more preferably a group.

In formula (B-4), c is preferably an integer of 1 to 4, more preferably 1 or 2, even more preferably 1.

In formulas (B-2) to (B-4), at least two of R ^B21 , R ^B22 and R ^B23 may combine to form a ring structure, and R ^B23 and R ^B21 and R ^B22 It is preferable that one of them forms a ring structure. The ring structure to be formed is preferably a 5-membered ring structure, a 6-membered ring structure, or a structure obtained by condensing a 5-membered ring structure or a 6-membered ring structure with another ring structure, and more preferably a tetrahydrofuran ring or a tetrahydropyran ring.

Polystyrene may contain a repeating unit in which an acid group is protected by a tertiary alkyl group as a repeating unit having a structure that decomposes upon heating.
Polystyrene may also contain, for example, a repeating unit represented by any one of the above formulas (A-2) to (A-7) as a repeating unit having a structure that decomposes upon heating.

Examples of the repeating unit having a structure that decomposes upon heating, contained in the polystyrene resin, include the following structures, but are not limited thereto. In the structures below, R is a hydrogen atom or a monovalent organic group.

The polystyrene resin may contain one repeating unit having a structure that decomposes upon heating, or may contain two or more repeating units.

<<<Other repeating units>>>
Also, the polystyrene resin may further contain other repeating units.
Other repeating units include repeating units containing acid groups such as carboxy groups and phenolic hydroxy groups (for example, repeating units derived from hydroxystyrene or carboxystyrene).
The polystyrene resin may contain one type of other repeating unit alone, or may contain two or more types.

According to the method for producing a dry resin of the present invention, for example, when the polystyrene resin contains a repeating unit containing an acid group and a repeating unit having a crosslinkable group that reacts with the acid group, particles are formed by heating. Even in the case of using a resin that easily generates , it is considered that a dry resin in which generation of particles is suppressed can be obtained.

<<<molecular weight>>>
Although the weight average molecular weight of the polystyrene resin is not particularly limited, it is preferably from 1,000 to 1,000,000, more preferably from 2,000 to 50,000.
In addition, the larger the molecular weight of the resin, the more likely it is that particles having a large particle size will be formed when crosslinked. , 000 or more) is more likely to obtain the effect of the present invention.

<< content of thermosetting resin >>
The resin composition used in the present invention preferably contains 1% by mass or more, more preferably 10% by mass or more, and 15% by mass or more of a thermosetting resin with respect to the total mass of the resin composition. is more preferable, and it is particularly preferable to contain 20% by mass or more. The upper limit of the content is not particularly limited, and can be, for example, 90% or less.
In addition, the resin composition used in the present invention preferably contains 50% by mass or more, more preferably 70% by mass or more, of a thermosetting resin based on the total solid mass of the resin composition. It is more preferable to contain more than mass %. The upper limit of the content is not particularly limited, and may be, for example, 100% by mass.
The resin composition used in the present invention may contain only one type of thermosetting resin, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

-solvent-
The resin composition used in the present invention contains a solvent.
The solvent is not particularly limited, and a known solvent can be used, but water or an organic solvent is preferably included.
Organic solvents include compounds such as ester-based solvents, ether-based solvents, ketone-based solvents, aromatic hydrocarbon-based solvents, sulfoxide-based solvents, amide-based solvents, and alcohol-based solvents.
Among these, the resin composition used in the present invention preferably contains at least one solvent selected from the group consisting of water and ether solvents, and more preferably contains water and ether solvents. and tetrahydrofuran are more preferred.
In the resin composition used in the present invention, the total content of water and ether solvent is preferably 50% by mass or more, more preferably 80% by mass or more, relative to the total mass of the solvent. More preferably, it is 90% by mass or more.

Examples of ester solvents 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, alkyl alkyloxyacetate (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g. methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate) etc.)), 3-alkyloxypropionate alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3 -methyl ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyloxypropionic acid propyl, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyloxy-2-methyl methyl propionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, Suitable examples include propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like.

Ether solvents such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene Suitable examples include glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethyl carbitol acetate, butyl carbitol acetate, and the like.

Examples of suitable ketone solvents include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, levoglucosenone, dihydrolevoglucosenone and the like.

Suitable aromatic hydrocarbon solvents include, for example, toluene, xylene, anisole, and limonene.

As a sulfoxide-based solvent, for example, dimethyl sulfoxide is suitable.

Suitable amide solvents include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide and the like.

Suitable alcoholic solvents include methanol, ethanol, 1-propanol, isopropanol, butanol, and the like.
In the present invention, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, n-butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone , γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate, levoglucosenone, dihydrolevoglucosenone or a mixed solvent composed of two or more kinds. A combination of dimethyl sulfoxide and γ-butyrolactone or a combination of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred.

The content of the solvent with respect to the total mass of the resin composition before being subjected to the low temperature and low pressure process is preferably more than 10% by mass, more preferably 20% by mass or more, and 30% by mass or more. more preferred.
The upper limit of the content is preferably 99% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less.
The resin composition may contain one solvent alone, or may contain two or more solvents. When the resin composition contains two or more solvents, the total amount is preferably within the above range.

-Other ingredients-
The resin composition used in the present invention may contain components other than the above-described thermosetting resin and solvent.
Other components include a polymerizable compound used in synthesizing the thermosetting resin, a compound used to introduce a crosslinkable group, a thermally decomposable group, etc. into the thermosetting resin, a reaction catalyst, A compound that assists the dissolution of the resin, a compound that adjusts other reactions, and the like are included.
In the resin composition used in the present invention, the content of other components is preferably 10% by mass or less, more preferably 5% by mass or less.
Moreover, in this invention, it can also be set as the aspect which does not contain other components substantially.
In this case, the total content of the thermosetting resin and the solvent with respect to the total mass of the resin composition is preferably 95% by mass or more, more preferably 98% by mass or more, and 99% by mass or more. is more preferred. The upper limit of the total content is not particularly limited, and may be 100% by mass.

<Removal process>
Moreover, the method for producing a dry resin of the present invention may further include a step of removing other components in the resin composition (removing step) before the low-temperature, low-pressure step.
The step of removing other components can be carried out by known methods such as purification using column chromatography, removal of impurities by reprecipitation, recrystallization, and the like.

<Recovery process>
The method for producing a dry resin of the present invention may further include a recovery step of recovering the dry resin after the high-temperature, low-pressure step.
The dried resin recovered in the recovery step may be stored, for example, in a conventionally known storage container, or may be used for preparation of the composition immediately after recovery.

(Method for producing composition)
The method for producing the composition of the present invention includes the step of mixing the dry resin obtained by the method for producing the dry resin of the present invention with at least one other component.
The mixing method is not particularly limited, and conventionally known methods can be used.

The at least one other component includes the solvent contained in the resin composition described above, the solvent described in paragraphs 0249 to 0251 of WO 2017/110982, and the following components (photosensitizer, thermal polymerization initiation agents, thermal acid generators, polymerizable compounds, onium salts, thermal base generators, migration inhibitors, polymerization inhibitors, metal adhesion improvers, and other additives). be done.
For example, by using a solvent, a composition that can be used in steps such as coating can be obtained.
For example, a photosensitive resin composition can be obtained by using a photosensitive agent.
For example, a negative composition can be obtained by using a photopolymerization initiator and a radically polymerizable compound.
For example, by using a photoacid generator, the cross-linking of the cross-linkable groups in the thermosetting resin or other polymerizable compound can be promoted to form a negative composition.
For example, by using a photoacid generator, decomposition of a thermally decomposable group in a thermosetting resin can be promoted with an acid, and a positive composition can be obtained.
For example, a thermosetting resin composition can be obtained by using a thermal polymerization initiator or a thermal acid generator.

<Photosensitizer>
A photosensitizer may be used in the method for producing the composition of the present invention.
The photosensitizer preferably contains a polymerization initiator capable of initiating polymerization by light and/or heat. Photopolymerization initiators are particularly preferred.

[Photopolymerization initiator]
The photopolymerization initiator is preferably a photoradical polymerization initiator. The radical photopolymerization initiator is not particularly limited and can be appropriately selected from known radical photopolymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferred. It may also be an activator that produces an active radical by producing some action with a photoexcited sensitizer.

The radical photopolymerization initiator contains at least one compound having a molar extinction coefficient of at least about 50 L·mol ⁻¹ ·cm ⁻¹ within the wavelength range of about 300 to 800 nm (preferably 330 to 500 nm). is preferred. The molar extinction coefficient of a compound can be measured using known methods. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L.

As the radical photopolymerization initiator, any known compound can be used. For example, halogenated hydrocarbon derivatives (e.g., 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, etc. oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. mentioned. For details of these, paragraphs 0165 to 0182 of JP-A-2016-027357 and paragraphs 0138 to 0151 of WO 2015/199219 can be referred to, the contents of which are incorporated herein.

Examples of ketone compounds include compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated herein. As a commercial product, Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.

In one embodiment of the present invention, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be preferably used as the radical photopolymerization initiator. More specifically, for example, aminoacetophenone-based initiators described in JP-A-10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used.

As the hydroxyacetophenone initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF) can be used.

As the aminoacetophenone-based initiator, commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.

As the aminoacetophenone-based initiator, compounds described in JP-A-2009-191179, whose maximum absorption wavelength is matched to a wavelength light source such as 365 nm or 405 nm, can also be used.

Acylphosphine oxide initiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and the like. In addition, commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) can be used.

Examples of metallocene compounds include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF) and Keycure VIS 813 (manufactured by King Brother Chem).

As the radical photopolymerization initiator, an oxime compound is more preferable. By using an oxime compound, the exposure latitude can be improved more effectively. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.

Specific examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, and compounds described in JP-A-2006-342166. Also, J. C. S. Compounds described in Perkin II (1979, pp. 1653-1660), J. Am. C. S. Perkin II (1979, pp.156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232), compounds described in JP-A-2000-066385, Compounds described in JP-A-2004-534797, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-019766, compounds described in Patent No. 6065596, International Publication No. 2015 / 152153, compounds described in WO 2017/051680, compounds described in JP 2017-198865, compounds described in paragraphs 0025 to 0038 of WO 2017/164127, Examples include compounds described in WO 2013/167515, the contents of which are incorporated herein.

Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxy iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one , and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. In the composition, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as the radical photopolymerization initiator. An oxime-based photopolymerization initiator has 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 (manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKA Co., Ltd., the light described in JP 2012-014052 A radical polymerization initiator 2) is also preferably used. In addition, TR-PBG-304 (manufactured by Changzhou Yuan Electronics New Materials Co., Ltd.), Adeka Arkles NCI-831 and Adeka Arkles NCI-930 (manufactured by ADEKA Co., Ltd.) can also be used. Also, DFI-091 (manufactured by Daito Chemix Co., Ltd.) can be used. Also, an oxime compound having the following structure can be used.

An oxime compound having a fluorene ring can also be used as the radical photopolymerization initiator. Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466 and compounds described in Japanese Patent No. 06636081, the contents of which are incorporated herein.
As the radical photopolymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in WO2013/083505, the contents of which are incorporated herein.
It is also possible to use oxime compounds having fluorine atoms. Specific examples of such oxime compounds 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. and compound (C-3) described in paragraph 0101 of JP-A-164471, the contents of which are incorporated herein.
An oxime compound having a nitro group can be used as the radical photopolymerization initiator. The oxime compound having a nitro group is also preferably a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraph numbers 0031 to 0047 of JP-A-2013-114249 and paragraph numbers 0008-0012 and 0070-0079 of JP-A-2014-137466; Included are compounds described in paragraphs 0007-0025 of Japanese Patent No. 4223071, the contents of which are incorporated herein. Further, the oxime compound having a nitro group also includes ADEKA Arkles NCI-831 (manufactured by ADEKA Co., Ltd.).
An oxime compound having a benzofuran skeleton can also be used as the radical photopolymerization initiator. Specific examples include OE-01 to OE-75 described in WO 2015/036910.
As the radical photopolymerization initiator, an oxime compound in which a substituent having a hydroxy group is bonded to a carbazole skeleton can also be used. Such photoinitiators include compounds such as those described in WO2019/088055, the contents of which are incorporated herein.
As the radical photopolymerization initiator, an oxime compound having an aromatic ring group Ar ^{2 OX1} in which an electron-withdrawing group is introduced into the aromatic ring (hereinafter also referred to as oxime compound OX) can be used. Examples of the electron-withdrawing group of the aromatic ring group Ar ^OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group. An acyl group and a nitro group are preferred, an acyl group is more preferred, and a benzoyl group is even more preferred because a film having excellent light resistance can be easily formed. A benzoyl group may have a substituent. Examples of substituents include halogen atoms, cyano groups, nitro groups, hydroxy groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic groups, heterocyclic oxy groups, alkenyl groups, alkylsulfanyl groups, arylsulfanyl groups, It is preferably an acyl group or an amino group, more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group or an amino group. A sulfanyl group or an amino group is more preferred.
The oxime compound OX is preferably at least one selected from the compounds represented by the formula (OX1) and the compounds represented by the formula (OX2), more preferably the compound represented by the formula (OX2). preferable.

In the formula, R ^X1 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl a group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group or a sulfamoyl group,
R ^X2 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, aryl represents a sulfonyl group, an acyloxy group or an amino group,
R ^X3 to R ^X14 each independently represent a hydrogen atom or a substituent;
However, at least one of R ^X10 to R ^X14 is an electron-withdrawing group.
In the above formula, R ^X12 is an electron-withdrawing group, and R ^X10 , R ^X11 , R ^X13 and R ^X14 are preferably hydrogen atoms.
Specific examples of the oxime compound OX include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein.
The most preferable oxime compounds include oxime compounds having specific substituents described in JP-A-2007-269779 and oxime compounds having a thioaryl group described in JP-A-2009-191061.

From the viewpoint of exposure sensitivity, photoradical polymerization initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl selected from the group consisting of imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds; are preferred.

More preferred radical photopolymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds. More preferably, at least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds, more preferably metallocene compounds or oxime compounds, and oxime compounds. is even more preferred.

Further, the photoradical polymerization initiator includes benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone such as N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), 2-benzyl -aromatic ketones such as 2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, alkylanthraquinones, etc. quinones condensed with the aromatic ring of , benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, and benzyl derivatives such as benzyl dimethyl ketal can also be used. A compound represented by the following formula (I) can also be used.

In formula (I), R ¹⁰⁰ 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, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, and 2 to 2 carbon atoms interrupted by one or more oxygen atoms; a phenyl group substituted with at least one of an alkyl group of 18 and an alkyl group having 1 to 4 carbon atoms, or biphenyl, and R ^I01 is a group represented by formula (II) or is the same as R ^I00 and each of R ¹⁰² to R ¹⁰⁴ is independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or halogen.

In the formula, R ¹⁰⁵ to R ¹⁰⁷ are the same as R ¹⁰² to R ¹⁰⁴ in formula (I) above.

Further, as the photoradical polymerization initiator, compounds described in paragraphs 0048 to 0055 of WO 2015/125469 can also be used, the contents of which are incorporated herein.
As the radical photopolymerization initiator, a difunctional or trifunctional or higher radical photopolymerization initiator may be used. By using such a radical photopolymerization initiator, two or more radicals are generated from one molecule of the radical photopolymerization initiator, so good sensitivity can be obtained. In addition, when a compound having an asymmetric structure is used, the crystallinity is lowered, the solubility in a solvent or the like is improved, and precipitation becomes difficult over time, and the stability over time of the resin composition can be improved. . Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No. 2015/004565, and Japanese Patent Publication No. 2016-532675. Paragraph numbers 0407 to 0412, dimers of oxime compounds described in paragraph numbers 0039 to 0055 of International Publication No. 2017/033680, compound (E) and compounds described in JP-A-2013-522445 ( G), Cmpd1 to 7 described in International Publication No. 2016/034963, oxime ester photoinitiators described in paragraph number 0007 of JP 2017-523465, JP 2017-167399 Photoinitiators described in paragraph numbers 0020 to 0033, photoinitiators (A) described in paragraph numbers 0017 to 0026 of JP-A-2017-151342, described in Japanese Patent No. 6469669 and oxime ester photoinitiators, the contents of which are incorporated herein.

When containing a photopolymerization initiator, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the composition It is 0.5 to 15% by mass, 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 photopolymerization initiators are contained, the total amount is preferably within the above range.
In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, the crosslinking by the photopolymerization initiator may be further promoted by heating with an oven, a hot plate, or the like.

[Photoacid generator]
A photoacid generator may be used as the photosensitizer.
The photoacid generator is not particularly limited as long as it generates an acid upon exposure, and includes quinonediazide compounds, diazonium salts, phosphonium salts, sulfonium salts, onium salt compounds such as iodonium salts, imidosulfonates, and oximes. Sulfonate compounds such as sulfonate, diazodisulfone, disulfone, and o-nitrobenzylsulfonate can be used.

The quinonediazide compound includes a polyhydroxy compound in which the sulfonic acid of quinonediazide is ester-bonded, a polyamino compound in which the sulfonic acid of quinonediazide is sulfonamide-bonded, and a polyhydroxypolyamino compound in which the sulfonic acid of quinonediazide is ester-bonded and sulfonamide-bonded. and those bound by at least one of In the present invention, for example, it is preferable that 50 mol % or more of all the functional groups of these polyhydroxy compounds and polyamino compounds are substituted with quinonediazide.

In the present invention, both 5-naphthoquinonediazide sulfonyl group and 4-naphthoquinonediazide sulfonyl group are preferably used as quinonediazide. A 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. A 5-naphthoquinonediazide sulfonyl ester compound has absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinonediazide sulfonyl ester compound or a 5-naphthoquinone diazidesulfonyl ester compound depending on the exposure wavelength. Further, a naphthoquinonediazide sulfonyl ester compound having a 4-naphthoquinone diazidesulfonyl group and a 5-naphthoquinone diazidesulfonyl group in the same molecule may be contained, or a 4-naphthoquinone diazidesulfonyl ester compound and a 5-naphthoquinone diazidesulfonyl ester compound may be contained. may contain.

The naphthoquinonediazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxy group and a quinonediazide sulfonic acid compound, and can be synthesized by a known method. By using these naphthoquinonediazide compounds, the resolution, sensitivity and film retention rate are further improved.
Examples of the naphthoquinonediazide compound include 1,2-naphthoquinone-2-diazide-5-sulfonic acid, 1,2-naphthoquinone-2-diazide-4-sulfonic acid, salts and ester compounds of these compounds, and the like. be done.

Examples of the onium salt compound or sulfonate compound include compounds described in paragraphs 0064 to 0122 of JP-A-2008-013646.
In addition, you may use a commercial item as a photo-acid generator. Commercially available products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-367, WPAG-370, WPAG-469, WPAG-638, WPAG-699 (all from Fujifilm manufactured by Kojunyaku Co., Ltd.) and the like.

When a photoacid generator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the composition, and 2 to It is more preferably 15% by mass. Only one type of photoacid generator may be contained, or two or more types may be contained. When two or more photoacid generators are contained, the total is preferably within the above range.

<Thermal polymerization initiator>
In the method for producing the composition of the present invention, a thermal polymerization initiator, particularly a thermal radical polymerization initiator, may be used. A thermal radical polymerization initiator is a compound that generates radicals by heat energy and initiates or promotes a polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the thermosetting resin and the polymerizable compound can be advanced in the heating step described later, so that the chemical resistance can be further improved.

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

When a thermal polymerization initiator is used, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the composition. 5 to 15% by mass. One type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more thermal polymerization initiators are contained, the total amount is preferably within the above range.

<Thermal acid generator>
A thermal acid generator may be used in the method for producing the composition of the present invention.
The thermal acid generator generates an acid by heating and is at least one compound selected from compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxetane compound and a benzoxazine compound, or a thermosetting It has the effect of promoting the cross-linking reaction of methylol groups and the like contained in the organic resin.
Moreover, when the composition contains a thermal acid generator, the thermosetting resin preferably contains a methylol group or an alkoxymethyl group as a polymerizable group.

The thermal decomposition initiation temperature of the thermal acid generator is preferably 50°C to 270°C, more preferably 50°C to 250°C. In addition, no acid is generated during drying (prebaking: about 70 to 140° C.) after the composition is applied to the substrate, and the final heating (curing: about 100 to 400° C.) after patterning by subsequent exposure and development. It is preferable to select an acid-generating agent as the thermal acid generator, because it can suppress a decrease in sensitivity during development.
The thermal decomposition initiation temperature is determined as the lowest exothermic peak temperature when the thermal acid generator is heated up to 500° C. in a pressure-resistant capsule at 5° C./min.
Equipment used for measuring the thermal decomposition initiation temperature includes Q2000 (manufactured by TA Instruments).

The acid generated from the thermal acid generator is preferably a strong acid, and examples thereof include arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid and butanesulfonic acid, and trifluoromethane. Haloalkyl sulfonic acids, such as sulfonic acids, and the like are preferred. Examples of such thermal acid generators include those described in paragraph 0055 of JP-A-2013-072935.

Among them, from the viewpoint of less residue in the cured film and less deterioration in cured film physical properties, those that generate C 1-4 alkylsulfonic acids and C 1-4 haloalkylsulfonic acids are more preferable, and methanesulfonic acid. (4-hydroxyphenyl)dimethylsulfonium, (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium methanesulfonate, benzyl(4-hydroxyphenyl)methylsulfonium methanesulfonate, benzyl methanesulfonate (4-((methoxy carbonyl)oxy)phenyl)methylsulfonium, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)sulfonium methanesulfonate, (4-hydroxyphenyl)dimethylsulfonium trifluoromethanesulfonate, (4- ((Methoxycarbonyl)oxy)phenyl)dimethylsulfonium, benzyl(4-hydroxyphenyl)methylsulfonium trifluoromethanesulfonate, benzyl(4-((methoxycarbonyl)oxy)phenyl)methylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)sulfonium, 3-(5-(((propylsulfonyl)oxy)imino)thiophene-2(5H)-ylidene)-2-(o-tolyl) Propanenitrile, 2,2-bis(3-(methanesulfonylamino)-4-hydroxyphenyl)hexafluoropropane, is preferred as the thermal acid generator.

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

The content of the thermal acid generator is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the thermosetting resin. By containing 0.01 parts by mass or more, the crosslinking reaction is promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved. From the viewpoint of the electrical insulation properties of the cured film, the amount is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less.

<Polymerizable compound>
A polymerizable compound may be used in the method for producing the composition of the present invention.
As the polymerizable compound, a polyfunctional polymerizable compound is preferred. As used herein, a polyfunctional polymerizable compound refers to a compound having two or more polymerizable groups.
Moreover, as the polymerizable compound, a radically polymerizable compound is preferable, and a compound having two or more radically polymerizable groups is more preferable.

[Radical polymerizable compound]
A radically polymerizable compound can be used as the polymerizable compound. A radically polymerizable compound is a compound having a radically polymerizable group. Radically polymerizable groups include groups having an ethylenically unsaturated bond, such as vinyl groups, allyl groups, vinylphenyl groups, and (meth)acryloyl groups. The radically polymerizable group is preferably a (meth)acryloyl group, a (meth)acrylamide group, or a vinylphenyl group, and more preferably a (meth)acryloyl group from the viewpoint of reactivity.

The number of radically polymerizable groups possessed by 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 may have three or more radically polymerizable groups. more preferred. The upper limit is preferably 15 or less, more preferably 10 or less, even more preferably 8 or less.

The molecular weight of the radical 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 composition preferably contains at least one difunctional or higher radically polymerizable compound containing two or more radically polymerizable groups, and contains at least one trifunctional or higher radically polymerizable compound. is more preferred. It may also be a mixture of a difunctional radically polymerizable compound and a trifunctional or higher radically polymerizable compound. For example, the number of functional groups of a polymerizable monomer 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 (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably They are an ester of an unsaturated carboxylic acid and a polyhydric alcohol compound, and an amide of an unsaturated carboxylic acid and a polyvalent amine compound. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxy group, an amino group, or a sulfanyl group with monofunctional or polyfunctional isocyanates or epoxies, or monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and halogeno groups Also suitable are substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as a tosyloxy group and monofunctional or polyfunctional alcohols, amines, and thiols. As another example, it is also possible to use a group of compounds in which the unsaturated carboxylic acid is replaced with unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an allyl ether, or the like. As specific examples, paragraphs 0113 to 0122 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated herein.

Moreover, the radically polymerizable compound is preferably a compound having a boiling point of 100° C. or higher under normal pressure. Examples include polyethylene glycol di(meth)acrylate, trimethylolethane tri(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, trimethylolpropane tri(acryloyloxypropyl)ether, tri(acryloyloxyethyl)isocyanurate, glycerin and trimethylolethane. Compounds obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth)acrylated are described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Patent Publication No. 51-037193. Urethane (meth)acrylates such as those described in JP-A-48-064183, JP-B-49-043191, JP-B-52-030490, polyester acrylates, epoxy resins and (meth)acryl Polyfunctional acrylates and methacrylates such as epoxy acrylates, which are reaction products with acids, and mixtures thereof can be mentioned. Compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Further, polyfunctional (meth)acrylate obtained by reacting polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth)acrylate and an ethylenically unsaturated bond can also be used.

Further, as preferred radically polymerizable compounds other than those described above, JP-A-2010-160418, JP-A-2010-129825, JP-A-4364216, etc. have a fluorene ring and an ethylenically unsaturated bond. It is also possible to use compounds having two or more groups having and cardo resins.

Furthermore, other examples include specific unsaturated compounds described in JP-B-46-043946, JP-B-01-040337, JP-B-01-040336, and JP-A-02-025493. vinyl phosphonic acid compounds and the like can also be mentioned. Compounds containing perfluoroalkyl groups described in JP-A-61-022048 can also be used. Furthermore, the journal of Japan Adhesive Association vol. 20, No. 7, pages 300-308 (1984) as photopolymerizable monomers and oligomers can also be used.

In addition to the above, compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964, compounds described in paragraphs 0087 to 0131 of WO 2015/199219 can also be preferably used, the contents of which are herein incorporated into the book.

Further, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylated, which are described together with specific examples as formulas (1) and (2) in JP-A-10-062986, It can be used as a radical polymerizable compound.

Furthermore, the compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as other radically polymerizable compounds, the contents of which are incorporated herein.

Examples of radically polymerizable compounds include dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; Nippon Kayaku ( Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa ( meth) acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.), and their (meth) acryloyl groups are ethylene glycol residues or propylene glycol residues. Structures that are linked via are preferred. These oligomeric types can also be used.

Examples of commercially available radically polymerizable compounds include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, and SR-209, a bifunctional methacrylate having four ethyleneoxy chains manufactured by Sartomer. , 231, 239, Nippon Kayaku Co., Ltd. DPCA-60, a hexafunctional acrylate having six pentyleneoxy chains, TPA-330, a trifunctional acrylate having three isobutyleneoxy chains, urethane oligomer UAS- 10, UAB-140 (manufactured by Nippon Paper Industries), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H ( Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blenmar PME400 (manufactured by NOF Corporation), etc. is mentioned.

Examples of radically polymerizable compounds include urethane acrylates such as those described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765. , JP-B-58-049860, JP-B-56-017654, JP-B-62-039417 and JP-B-62-039418 are also suitable. Furthermore, 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. 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. A radically polymerizable compound having a group is more preferred. Particularly preferably, in a radically polymerizable compound obtained by reacting an unreacted hydroxy group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give an acid group, the aliphatic polyhydroxy compound is pentaerythritol or dipenta A compound that is erythritol. Commercially available products include, for example, 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 0.1-40 mgKOH/g, particularly preferably 5-30 mgKOH/g. If the acid value of the radically polymerizable compound is within the above range, it is excellent in handleability in production and also excellent in developability. Moreover, the polymerizability is good. The acid value is measured according to JIS K 0070:1992.
From the viewpoint of pattern resolution and film stretchability, the resin composition preferably uses a bifunctional methacrylate or acrylate.
Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, and PEG600 diacrylate. methacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6 hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO adduct dimetharylate of bisphenol A, PO (propylene) of bisphenol A oxide) adduct diacrylate, EO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, other bifunctional acrylates having urethane bonds, urethane bonds can be used. These can be used in combination of two or more as needed.
For example, PEG200 diacrylate is a polyethylene glycol diacrylate having a polyethylene glycol chain formula weight of about 200.

In the composition, a monofunctional radically polymerizable compound can be preferably used as the radically polymerizable compound from the viewpoint of suppressing warpage associated with the elastic modulus control of the cured film. Monofunctional radically polymerizable compounds include n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl ( (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, etc. ) Acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allyl glycidyl ether, diallyl phthalate and triallyl trimellitate are preferably used. As the monofunctional radically 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]
In the method for producing the composition of the present invention, a polymerizable compound other than the radically polymerizable compound described above may be used. Examples of polymerizable compounds other than the radically polymerizable compounds described above include compounds having a hydroxymethyl group (methylol group), alkoxymethyl group or acyloxymethyl group; epoxy compounds; oxetane compounds; and benzoxazine compounds.

-Compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group-
Compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group are preferably compounds represented by the following formulas (AM1), (AM4) or (AM5).

(Wherein, t represents an integer of 1 to 20, R ¹⁰⁴ represents a t-valent organic group having 1 to 200 carbon atoms, and R ¹⁰⁵ represents a group represented by —OR ¹⁰⁶ or —OCO—R ¹⁰⁷ , R ¹⁰⁶ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R ¹⁰⁷ represents an organic group having 1 to 10 carbon atoms.)
(Wherein, 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 represents a hydrogen atom or carbon represents an organic group having 1 to 10 carbon atoms, and R ⁴⁰⁷ represents 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 formula (AM4) include 46DMOC, 46DMOEP (trade names, manufactured by Asahi Organic Chemicals Industry Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, and DML. -PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethyloxymethyl-4-t-butylphenol, 2,6-dimethyloxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, etc. be done.

Further, specific examples of the compound represented by formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by Asahi Organic Chemical Industry Co., Ltd.), NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW-100LM (both trade names, 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 less and does not undergo a dehydration reaction resulting from the cross-linking, so film shrinkage does not easily occur. Therefore, containing an epoxy compound is effective for low-temperature curing of the composition and for suppressing warpage.

The epoxy compound preferably contains a polyethylene oxide group. As a result, the elastic modulus is further lowered, and warping 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 2-15.

Examples of epoxy compounds include bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; Epoxy group-containing silicones such as (oxypropyl)siloxane, etc., but not limited to these. Specifically, Epiclon (registered trademark) 850-S, Epiclon (registered trademark) HP-4032, Epiclon (registered trademark) HP-7200, Epiclon (registered trademark) HP-820, Epiclon (registered trademark) HP-4700, Epiclon (registered trademark) EXA-4710, Epiclon (registered trademark) HP-4770, Epiclon (registered trademark) EXA-859CRP, Epiclon (registered trademark) EXA-1514, Epiclon (registered trademark) EXA-4880, Epiclon (registered trademark) EXA-4850-150, Epiclon EXA-4850-1000, Epiclon (registered trademark) EXA-4816, Epiclon (registered trademark) EXA-4822 (trade names, manufactured by DIC Corporation), Ricaresin (registered trademark) BEO-60E (trade name, Shin Nippon Rika Co., Ltd.), EP-4003S, EP-4000S (trade names, manufactured by ADEKA Corporation), and the like. Among these, an epoxy resin containing a polyethylene oxide group is preferable from the viewpoint of suppressing warpage and being excellent in heat resistance. For example, Epiclon (registered trademark) EXA-4880, Epiclon (registered trademark) EXA-4822, and Ricaresin (registered trademark) BEO-60E are preferable because they contain polyethylene oxide groups.

-Oxetane compound (compound having an oxetanyl group)-
The oxetane compounds 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, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester and the like can be mentioned. As a specific example, Aron oxetane series manufactured by Toagosei Co., Ltd. (e.g., OXT-121, OXT-221, OXT-191, OXT-223) can be suitably used, and these can be used alone or You may mix 2 or more types.

-Benzoxazine compound (compound having a benzoxazolyl group)-
A benzoxazine compound is preferable because it is a cross-linking reaction derived from a ring-opening addition reaction, so that degassing does not occur during curing, and thermal shrinkage is reduced to suppress the occurrence of warping.

Preferable examples of benzoxazine compounds include Ba-type benzoxazine, Bm-type benzoxazine (these are trade names, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resins, phenol novolac dihydrobenzoxazine oxazine compounds. These may be used alone or in combination of two or more.

The content of the polymerizable compound is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the composition. More preferably, the lower limit is 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

The polymerizable compounds may be used singly or in combination of two or more. When two or more are used in combination, the total amount is preferably within the above range.

<Onium salt>
An onium salt may be used in the method for producing the composition of the present invention.
Although the type of onium salt is not particularly limited, ammonium salts, iminium salts, sulfonium salts, iodonium salts and phosphonium salts are preferred.
Among these, ammonium salts or iminium salts are preferred from the viewpoint of high thermal stability, and sulfonium salts, iodonium salts or phosphonium salts are preferred from the viewpoint of compatibility with polymers.

In addition, an onium salt is a salt of a cation having an onium structure and an anion, and the cation and anion may be bonded via a covalent bond or may not be bonded via a covalent bond. .
That is, the onium salt may be an intramolecular salt having a cation part and an anion part in the same molecular structure, or a cation molecule and an anion molecule, which are different molecules, are ionically bonded. It may be an intermolecular salt, but an intermolecular salt is preferred. Moreover, in the composition of the present invention, the cationic moiety or cationic molecule and the anionic moiety or anionic molecule may be bonded or dissociated by ionic bonding.
The cations in the onium salt are preferably ammonium cations, pyridinium cations, sulfonium cations, iodonium cations or phosphonium cations, and more preferably at least one cation selected from the group consisting of tetraalkylammonium cations, sulfonium cations and iodonium cations.

The onium salt used in the present invention may be a thermal base generator.
A thermal base generator is a compound that generates a base when heated, and includes, for example, acidic compounds that generate a base when heated to 40° C. or higher.

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

-Ammonium cation-
Preferred ammonium cations are quaternary ammonium cations.
Moreover, 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 combine to form a ring.

In 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. 12 aryl groups are more preferred. R ¹ to R ⁴ may have substituents, and examples of substituents include hydroxy group, aryl group, alkoxy group, aryloxy group, arylcarbonyl group, alkylcarbonyl group, alkoxycarbonyl group, aryloxy A carbonyl group, an acyloxy group, and the like can be mentioned.
When at least two of R ¹ to R ⁴ each combine to form a ring, the ring may contain a heteroatom. A nitrogen atom is mentioned as said hetero atom.

The ammonium cation is preferably represented by either formula (Y1-1) or (Y1-2) below.

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

-Anion-
The anion in the ammonium salt is preferably one selected from carboxylate anions, phenol anions, phosphate anions and sulfate anions, and carboxylate anions are more preferable because both salt stability and thermal decomposition can be achieved. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion.
The carboxylate anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxy groups, more preferably an anion of a divalent carboxylic acid. According to this aspect, the stability, curability and developability of the composition can be further improved. In particular, the use of a divalent carboxylic acid anion can further improve the stability, curability and developability of the composition.

The carboxylate anion is preferably represented by the following formula (X1).
In Formula (X1), EWG represents an electron-withdrawing group.

In the present embodiment, the electron-withdrawing group means a group having a positive Hammett's substituent constant σm. Here, σm is described in Yuho Tsuno Review, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965) p. 631-642. In addition, the electron-withdrawing group in the present embodiment is not limited to the substituents described in the above documents.
Examples of substituents in which σm shows a positive value include a CF ₃ group (σm=0.43), a CF ₃ C(=O) group (σm=0.63), and an HC≡C group (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), etc. be done. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (hereinafter the same).

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

In the present invention, the carboxylate anion is preferably represented by the following formula (XA).
In formula (XA), L ¹⁰ represents a single bond or a divalent linking group selected from the group consisting of an alkylene group, an alkenylene group, an aromatic group, —NR ^X — and a combination thereof, and R ^X is , represents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group.

Specific examples of carboxylate anions include maleate anion, phthalate anion, N-
Phenyliminodiacetate anions and oxalate anions are included.

The onium salt in the present invention contains an ammonium cation as a cation, and the onium salt has an anion of It preferably contains an anion whose pKa (pKaH) of the conjugate acid is 2.5 or less, more preferably 1.8 or less.
The lower limit of the pKa is not particularly limited, but it is preferably -3 or more, from the viewpoint of improving the cyclization efficiency of thermosetting resins and the like, because the generated base is not easily neutralized, and -2 or more. It is more preferable to have
The above pKa is determined according to Determination of Organic Structures by Physical Methods (authors: Brown, H.C., McDaniel, D.H., Hafliger, O., Nachod, F.C.; compilation: Braude, E.A. ， Nachod, F. C.; Academic Press, New York, 1955) and Data
for Biochemical Research (authors: Dawson, RMC et al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, values calculated from structural formulas using software ACD/pKa (manufactured by ACD/Labs) are used.

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

[Iminium salt]
In the present invention, an iminium salt means a salt of an iminium cation and an anion. Examples of the anion include the same anions as those in the ammonium salt described above, and preferred embodiments are also the same.

-iminium cation-
Preferred iminium cations are pyridinium cations.
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 each combine to form a ring. may be formed.
In formula (102), R ⁵ and R ⁶ have the same definitions as R ¹ to R ⁴ in formula (101) above, and preferred embodiments are 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 heteroatoms. A nitrogen atom is mentioned as said hetero atom. Moreover, as said ring, a pyridine ring is preferable.

The iminium cation is preferably represented by any one of the following formulas (Y1-3) to (Y1-5).
In formulas (Y1-3) to (Y1-5), R ¹⁰¹ represents an n-valent organic group, R ⁵ has the same definition as R ⁵ in formula (102), and R ⁷ represents R in formula (102). ⁷ , n represents an integer of 1 or more, and m represents an integer of 0 or more.
In formula (Y1-3), R ¹⁰¹ is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from a structure in which these are bonded, and has 2 to 30 carbon atoms. is more preferably a group obtained by removing n hydrogen atoms from saturated aliphatic hydrocarbon, benzene or naphthalene.
In formula (Y1-3), n is preferably 1 to 4, more preferably 1 or 2, even more preferably 1.
In formula (Y1-5), m is preferably 0 to 4, more preferably 1 or 2, even more preferably 1.

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

[Sulfonium salt]
In the present invention, a sulfonium salt means a salt of a sulfonium cation and an anion. Examples of the anion include the same anions as those in the ammonium salt described above, and preferred embodiments are also the same.

-Sulfonium cation-
As the sulfonium cation, a tertiary sulfonium cation is preferred, and a triarylsulfonium cation is more preferred.
Moreover, 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.
R ⁸ to R ¹⁰ 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. is more preferably an aryl group, 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. A carbonyl group, an acyloxy group, and the like can be mentioned. Among these, as a substituent, it is preferable to have an alkyl group or an alkoxy group, more preferably to have a branched alkyl group or an alkoxy group, a branched alkyl group having 3 to 10 carbon atoms, or a branched alkyl group having 1 to 1 carbon atoms More preferably it has 10 alkoxy groups.
R ⁸ to R ¹⁰ may be the same group or different groups, but from the viewpoint of synthesis suitability, they are preferably the same group.

[Iodonium salt]
In the present invention, an iodonium salt means a salt of an iodonium cation and an anion. Examples of the anion include the same anions as those in the ammonium salt described above, and preferred embodiments are also the same.

-Iodonium cation-
As the iodonium cation, a diaryliodonium cation is preferred.
Moreover, 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. is more preferably an aryl group, 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, an aryloxy A carbonyl group, an acyloxy group, and the like can be mentioned. Among these, as a substituent, it is preferable to have an alkyl group or an alkoxy group, more preferably to have a branched alkyl group or an alkoxy group, 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 synthesis suitability, they are preferably the same group.

[Phosphonium salt]
In the present invention, a phosphonium salt means a salt of a phosphonium cation and an anion. Examples of the anion include the same anions as those in the ammonium salt described above, and preferred embodiments are also the same.

-Phosphonium cation-
The phosphonium cation is preferably a quaternary phosphonium cation, and examples thereof include tetraalkylphosphonium cations and triarylmonoalkylphosphonium cations.
Moreover, as the phosphonium cation, a cation represented by the following formula (105) is preferable.

In formula (105), R ¹³ to R ¹⁶ each independently represent a hydrogen atom or a hydrocarbon group.
R ¹³ to R ¹⁶ 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. is more preferably an aryl group, 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. A carbonyl group, an acyloxy group, and the like can be mentioned. Among these, as a substituent, it is preferable to have an alkyl group or an alkoxy group, more preferably to have a branched alkyl group or an alkoxy group, 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 synthesis suitability, they are preferably the same group.

When the composition contains an onium salt, the content of the onium salt is preferably 0.1 to 50% by mass based on the total solid content of the composition. The lower limit is more preferably 0.5% by mass or more, still more 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, still more preferably 20% by mass or less, even more preferably 10% by mass or less, and may be 5% by mass or less, or may be 4% by mass or less.
One or two or more onium salts can be used. When two or more kinds are used, the total amount is preferably within the above range.

<Thermal base generator>
A thermal base generator may be used in the method for producing the composition of the present invention. Here, the base generator is a compound capable of generating a base by the action of heat.
The thermal base generator may be a compound corresponding to the onium salt described above, or may be a thermal base generator other than the onium salt described above.
Other thermal base generators include nonionic thermal base generators.
Nonionic thermal base generators include compounds represented by formula (B1), formula (B2) or formula (B3).

In Formula (B1) and Formula (B2), Rb ¹ , Rb ² and Rb ³ are each independently an organic group having no tertiary amine structure, a halogen atom or a hydrogen atom. However, Rb ¹ and Rb ² are not hydrogen atoms at the same time. Also, none of Rb ¹ , Rb ² and Rb ³ has a carboxy group. In this 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, when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when forming an amide group together with the nitrogen atom, this is not the case.

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

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

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

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

In the formula, Rb ¹¹ and Rb ¹² and Rb ³¹ and Rb ³² are respectively the same as Rb ¹ and Rb ² in formula (B1).
Rb ¹³ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 is more preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19, 7 to 12 are more preferable), and may have a substituent within the range in which the effects of the present invention are exhibited. Among them, Rb ¹³ is preferably an arylalkyl group.

Rb ³³ and Rb ³⁴ each independently represents a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms , more preferably 2 to 8, more preferably 2 to 3), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 10), an arylalkyl group (7 to 23 is preferred, 7 to 19 are more preferred, and 7 to 11 are even more preferred), and a hydrogen atom is preferred.

Rb ³⁵ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 is more preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, even more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 , 7 to 12 are more preferred), and aryl groups are preferred.
The compound represented by formula (B1-1) is also preferably the compound represented by formula (B1-1a).

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

In formula (B3), L is a divalent hydrocarbon group having a saturated hydrocarbon group on a linking chain path connecting adjacent oxygen atoms and carbon atoms, wherein the number of atoms on the linking chain path is represents a hydrocarbon group of 3 or more. RN1 and RN2 each independently represent a monovalent organic group.
As used herein, the term "saturated hydrocarbon group" refers to a hydrocarbon group having at least one carbon atom bonded to each of the four atoms via a single bond. A simple example of such a hydrocarbon group is --CH ₂ -- (methylene group). The term “connected chain” refers to an atomic chain that connects two atoms or groups of atoms to be connected in the shortest distance (minimum number of atoms) among the atomic chains on the path that connects the two atoms or groups of atoms to be connected. For example, in Exemplified Compound B-1 represented by the formula below, L is composed of a phenylene ethylene group, has an ethylene group as a saturated hydrocarbon group, and has a linking chain composed of four carbon atoms. , the number of atoms on the route of the connecting chain (that is, the number of atoms constituting the connecting chain, hereinafter also referred to as "connecting chain length" or "connecting chain length") is 4.

The number of carbon atoms in L (including carbon atoms other than the carbon atoms in the connecting chain) in formula (B3) is preferably 3-24. The upper limit is more preferably 12 or less, still more preferably 10 or less, and particularly preferably 8 or less. More preferably, the lower limit is 4 or more. From the viewpoint of rapid progress of the intramolecular cyclization reaction, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and 5 The following are particularly preferred. In particular, the linking chain length of L is preferably 4 or 5, most preferably 4. Specific preferred compounds of the base generator include, for example, the compounds described in paragraphs 0102 to 0168 of WO2020/066416, and the compounds described in paragraphs 0143 to 0177 of WO2018/038002. mentioned.
The molecular weight of the nonionic thermal base generator is preferably 800 or less, more preferably 600 or less, 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, specific examples of compounds that are thermal base generators or specific examples of other thermal base generators include the following compounds.

The content of the thermal base generator is preferably 0.1 to 50% by mass based on the total solid content of the composition. The lower limit is more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and even more preferably 20% by mass or less. One or two or more thermal base generators can be used. When two or more kinds are used, the total amount is preferably within the above range.

<Migration inhibitor>
A migration inhibitor may be used in the method for producing the composition. By containing the migration inhibitor, it becomes possible to effectively suppress migration of metal ions derived from the metal layer (metal wiring) into the composition layer.

Migration inhibitors are not particularly limited, but heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thioureas and sulfanyl groups, hindered phenolic compounds , salicylic acid derivative-based compounds, and hydrazide derivative-based compounds. In particular, triazole compounds such as 1,2,4-triazole and benzotriazole, and tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole are preferably used.

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

Other migration inhibitors include rust inhibitors described in paragraph 0094 of JP-A-2013-015701, compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, and JP-A-2011-059656. The compound described in paragraph 0052, the compound described in paragraphs 0114, 0116 and 0118 of JP-A-2012-194520, the compound described in paragraph 0166 of WO 2015/199219, etc. can be used, and these The contents are incorporated herein.

Specific examples of migration inhibitors include the following compounds.

When the composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, preferably 0.05 to 2.0%, based on the total solid content of the composition. % by mass is more preferred, and 0.1 to 1.0% by mass is even more preferred.

Only one type of migration inhibitor may be used, or two or more types may be used. When two or more migration inhibitors are used, the total amount is preferably within the above range.

<Polymerization inhibitor>
A polymerization inhibitor may be used in the method for producing the composition of the present invention. Polymerization inhibitors include phenol compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, metal compounds and the like.

Polymerization inhibitors include, for example, 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, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic 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. In addition, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817, and the compounds described in paragraphs 0031 to 0046 of WO 2015/125469 can also be used, the contents of which are herein incorporated.

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

When the composition has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass, based on the total solid content of the composition of the present invention, and 0.02 to 3 mass %, more preferably 0.05 to 2.5% by mass.

One type of polymerization inhibitor may be used, or two or more types may be used. When two or more polymerization inhibitors are used, the total amount is preferably within the above range.

<Metal adhesion improver>
In the method for producing the composition of the present invention, a metal adhesion improver may be used to improve the adhesion to metal materials used for electrodes, wiring, and the like. Examples of metal adhesion improvers include silane coupling agents and aluminum-based adhesion promoters.

〔Silane coupling agent〕
Examples of silane coupling agents include compounds described in paragraph 0167 of WO 2015/199219, compounds described in paragraphs 0062 to 0073 of JP 2014-191002, and paragraphs of WO 2011/080992. Compounds described in 0063-0071, compounds described in paragraphs 0060-0061 of JP-A-2014-191252, compounds described in paragraphs 0045-0052 of JP-A-2014-041264, International Publication No. 2014/097594 Included are compounds described in paragraph 0055, the contents of which are incorporated herein. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358. Moreover, it is also preferable to use the following compound as a silane coupling agent. In the following formulas, Me represents a methyl group and Et represents an ethyl group.

Other silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, sidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltri Methoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N- 2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine , N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- Examples include isocyanatopropyltriethoxysilane and 3-trimethoxysilylpropylsuccinic anhydride. These can be used singly or in combination of two or more.
[Aluminum Adhesion Aid]
Examples of aluminum-based adhesion promoters include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), ethylacetoacetate aluminum diisopropylate, and the like.
Further, as the metal adhesion improver, compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and sulfide compounds described in paragraphs 0032-0043 of JP-A-2013-072935 can also be used. , the contents of which are incorporated herein.

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 still more preferably 100 parts by mass of the thermosetting resin. It is 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 improved, and when it is at most the above upper limit value, the heat resistance and mechanical properties of the cured film after the curing step are improved. One type of metal adhesion improver may be used, or two or more types may be used. When two or more are used, the total amount is preferably within the above range.

<Other additives>
In the method for producing the composition of the present invention, if necessary, various additives such as sensitizers such as N-phenyldiethanolamine, photobase generators, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic Particles, curing agents, curing catalysts, fillers, antioxidants, UV absorbers, anti-agglomerating agents, etc. may be used. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the composition.

[Sensitizer]
The resin composition may contain a sensitizer.
A sensitizer may be used in the method for producing the composition of the present invention. A sensitizer absorbs specific actinic radiation and enters an electronically excited state. The electronically excited sensitizer comes into contact with a thermal curing accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, and the like, and causes electron transfer, energy transfer, heat generation, and the like. As a result, the thermosetting accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo chemical changes and are decomposed to generate radicals, acids, or bases.
Examples of sensitizers include sensitizers such as N-phenyldiethanolamine.
Moreover, you may use a sensitizing dye as a sensitizer.
Sensitizers that can be used include benzophenones, Michler's ketones, coumarins, pyrazole azos, anilinoazos, triphenylmethanes, anthraquinones, anthracenes, anthrapyridones, benzylidenes, oxonols, and pyrazolotriazole azos. , pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, penzopyran, and indigo compounds.
Sensitizers include, for example, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal) Cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamyl denindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)iso naphthothiazole, 1,3-bis(4′-dimethylaminobenzal)acetone, 1,3-bis(4′-diethylaminobenzal)acetone, 3,3′-carbonyl-bis(7-diethylaminocoumarin), 3 -acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylamino coumarin (ethyl 7-(diethylamino)coumarin-3-carboxylate), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethyl) aminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4 '-dimethylacetanilide and the like.
Other sensitizing dyes may also be used.
For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP-A-2016-027357 can be referred to, the contents of which are incorporated herein.
When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, preferably 0.1 to 15% by mass, based on the total solid content of the photosensitive resin composition. %, more preferably 0.5 to 10% by mass. The sensitizers may be used singly or in combination of two or more.

When the composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, preferably 0.1 to 15% by mass, based on the total solid content of the composition. is more preferable, and 0.5 to 10% by mass is even more preferable. The sensitizers may be used singly or in combination of two or more.

[Chain transfer agent]
A chain transfer agent may be used in the method for producing the composition of the present invention. The chain transfer agent is defined, for example, in Kobunshi Dictionary, 3rd edition (edited by Kobunshi Gakkai, 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 either donate hydrogen to less active radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals. In particular, thiol compounds can be preferably used.

In addition, the chain transfer agent can also use compounds described in paragraphs 0152 to 0153 of WO 2015/199219.

When the composition contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, and 1 to 10 parts by mass based on 100 parts by mass of the total solid content of the composition of the present invention. More preferably, 1 to 5 parts by mass is even more preferable. One type of chain transfer agent may be used, or two or more types may be used. When two or more chain transfer agents are used, the total amount is preferably within the above range.

[Surfactant]
In the method for producing the composition of the present invention, various types of surfactants may be added from the viewpoint of further improving coatability. As the surfactant, various kinds of surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants and silicone surfactants can be used. The following surfactants are also preferred. In the following formula, the parenthesis indicating the repeating unit of the main chain indicates the content (mol %) of each repeating unit, and the parenthesis indicating the repeating unit of the side chain indicates the repeating number of each repeating unit.
In addition, surfactants can also be used compounds described in paragraphs 0159 to 0165 of WO 2015/199219.

When the composition has a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 2.0% by mass, based on the total solid content of the composition It is 1.0% by mass. One type of surfactant may be used, or two or more types may be used. When two or more surfactants are used, the total amount is preferably within the above range.

[Higher Fatty Acid Derivative]
In the method for producing the composition of the present invention, a higher fatty acid derivative such as behenic acid or behenic acid amide is added in order to prevent polymerization inhibition caused by oxygen, and the surface of the composition is dried during the drying process after coating. may be unevenly distributed.

Moreover, the higher fatty acid derivative can also use the compound of the paragraph 0155 of international publication 2015/199219.
When the composition contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass based on the total solid content of the composition. Only one type of higher fatty acid derivative may be used, or two or more types thereof may be used. When two or more higher fatty acid derivatives are used, the total amount is preferably within the above range.
[Thermal polymerization initiator]
The resin composition of the present invention may contain a thermal polymerization initiator, particularly a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals by heat energy and initiates or promotes a polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can be advanced, so that the solvent resistance can be further improved. Moreover, the photopolymerization initiator described above also has a function of initiating polymerization by heat, and can be added as a polymerization initiator.
Specific examples of thermal radical polymerization initiators include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated herein.
When a thermal polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition of the present invention. , more preferably 0.5 to 15% by mass. One type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more thermal polymerization initiators are contained, the total amount is preferably within the above range.
[Inorganic particles]
The resin composition of the present invention may contain inorganic fine particles. Specific examples of inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.
The average particle diameter of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, still more preferably 0.03 to 1.0 μm, and 0.04 to 0.5 μm. Especially preferred.
The average particle size of the fine particles is the primary particle size and the volume average particle size. The volume average particle size can be measured by a known measuring method. Specifically, it can be measured by a centrifugal sedimentation light transmission method, an X-ray transmission method, a laser diffraction/scattering method, or a dynamic light scattering method. The average particle diameter represents the average value of particle size distribution, and can be measured, for example, with Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.).
[Ultraviolet absorber]
The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used.
Examples of salicylate-based UV absorbers include phenyl salicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate, and the like. Examples of benzophenone-based UV absorbers include 2,2'-dihydroxy-4- Methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2- and hydroxy-4-octoxybenzophenone. Examples of benzotriazole-based UV absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3 '-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-( 2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2 -(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5' -(1,1,3,3-tetramethyl)phenyl]benzotriazole and the like.
Examples of substituted acrylonitrile UV absorbers include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Furthermore, examples of triazine-based UV absorbers include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl )-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl) -mono(hydroxyphenyl)triazine compounds such as 1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3-methyl -4-propyloxyphenyl)-6-(4-methylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2 bis(hydroxyphenyl)triazine compounds such as ,4-dimethylphenyl)-1,3,5-triazine; 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl )-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4 tris(hydroxyphenyl)triazine compounds such as -(3-butoxy-2-hydroxypropyloxy)phenyl]-1,3,5-triazine;
In the present invention, the above various ultraviolet absorbers may be used singly or in combination of two or more.
The composition of the present invention may or may not contain an ultraviolet absorber, but when it does, the content of the ultraviolet absorber is 0.001% by mass with respect to the total solid mass of the composition of the present invention. It is preferably at least 1% by mass, more preferably at least 0.01% by mass and not more than 0.1% by mass.
[Organic titanium compound]
The resin composition of this embodiment may contain an organic titanium compound. By containing the organic titanium compound in the resin composition, it is possible to form a resin layer having excellent chemical resistance even when cured at a low temperature.
Organotitanium compounds that can be used include those in which organic groups are attached to titanium atoms through covalent or ionic bonds.
Specific examples of organotitanium compounds are shown below in I) to VII):
I) Titanium chelate compound: Among them, a titanium chelate compound having two or more alkoxy groups is more preferable because the storage stability of the resin composition is good and a good curing pattern can be obtained. Specific examples are titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate) , titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), and the like.
II) Tetraalkoxytitanium compounds: for example titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide. , titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl) butoxide}] and the like.
III) Titanocene compounds: for example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2, 4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium and the like.
IV) Monoalkoxy titanium compounds: for example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide and the like.
V) Titanium oxide compounds: for example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide and the like.
VI) Titanium tetraacetylacetonate compounds: such as titanium tetraacetylacetonate.
VII) Titanate coupling agent: For example, isopropyltridodecylbenzenesulfonyl titanate and the like.
Among them, as the organotitanium compound, at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds provides better chemical resistance. It is preferable from the viewpoint of performance. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide) and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H) -pyrrol-1-yl)phenyl)titanium is preferred.
When the organic titanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin. When the amount is 0.05 parts by mass or more, the resulting cured pattern exhibits good heat resistance and chemical resistance more effectively. Excellent.
〔Antioxidant〕
The compositions of the present invention may contain antioxidants. By containing an antioxidant as an additive, it is possible to improve the elongation properties of the cured film and the adhesion to metal materials. Antioxidants include phenol compounds, phosphite ester compounds, thioether compounds and the like. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound. Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred. A substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable as the aforementioned substituent. The antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule. Phosphorus-based antioxidants can also be suitably used as antioxidants. As a phosphorus antioxidant, tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6 -yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl ) oxy]ethyl]amine, ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite, and the like. Examples of commercially available antioxidants include Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (manufactured by ADEKA Corporation) and the like. In addition, as the antioxidant, compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used, the contents of which are incorporated herein. The composition of the present invention may also contain latent antioxidants, if desired. The latent antioxidant is a compound in which the site functioning as an antioxidant is protected with a protecting group, and is heated at 100 to 250°C, or heated at 80 to 200°C in the presence of an acid/base catalyst. A compound that functions as an antioxidant by removing the protective group by the reaction is exemplified. Examples of latent antioxidants include compounds described in WO 2014/021023, WO 2017/030005, and JP 2017-008219, the contents of which are incorporated herein. Commercially available latent antioxidants include ADEKA Arkles GPA-5001 (manufactured by ADEKA Co., Ltd.).
Examples of preferred antioxidants include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and compounds of formula (3).

In formula (3), R5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), and R6 represents an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). . R7 represents a monovalent to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), an oxygen atom and a nitrogen atom. k represents an integer of 1 to 4;
The compound represented by formula (3) suppresses oxidative deterioration of the aliphatic group and phenolic hydroxyl group of the resin. In addition, metal oxidation can be suppressed by the antirust action on the metal material.
More preferably, k is an integer of 2 to 4 because it can act on the resin and the metal material at the same time. R7 includes an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, - O--, --NH--, --NHNH--, combinations thereof, and the like, which may further have a substituent. Among these, it is preferable to have an alkyl ether group, -NH-, from the viewpoint of solubility in a developer and metal adhesion. more preferred.
Examples of the compound represented by formula (3) include, but are not limited to, the following structures.

The amount of the antioxidant to be added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on the resin. By making the addition amount 0.1 parts by mass or more, the effect of improving elongation characteristics and adhesion to metal materials can be easily obtained even in a high-temperature and high-humidity environment. The interaction with the agent improves the sensitivity of the resin composition. Only one kind of antioxidant may be used, or two or more kinds thereof may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
[Anti-aggregation agent]
The resin composition of the present embodiment may contain an anti-aggregation agent as necessary. Anti-aggregating agents include sodium polyacrylate and the like.
In the present invention, the aggregation inhibitor may be used alone or in combination of two or more.
The composition of the present invention may or may not contain an anti-aggregating agent, but when it is included, the content of the anti-aggregating agent is 0.01% by mass with respect to the total solid mass of the composition of the present invention. It is preferably at least 10% by mass, more preferably at least 0.02% by mass and not more than 5% by mass.
[Phenolic compound]
The resin composition of the present embodiment may contain a phenolic compound as necessary. Examples of phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X (these are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR -BIPC-F (these are trade names, manufactured by Asahi Organic Chemicals Industry Co., Ltd.) and the like.
In the present invention, one type of phenolic compound may be used alone, or two or more types may be used in combination.
The composition of the present invention may or may not contain a phenolic compound, but if it does, the content of the phenolic compound is 0.01% by mass relative to the total solid mass of the composition of the present invention. It is preferably at least 30% by mass, more preferably at least 0.02% by mass and not more than 20% by mass.
[Other polymer compounds]
Other polymer compounds include siloxane resins, (meth)acrylic polymers obtained by copolymerizing (meth)acrylic acid, novolac resins, resol resins, polyhydroxystyrene resins, and copolymers thereof. Other polymer compounds may be modified products into which cross-linking groups such as methylol groups, alkoxymethyl groups and epoxy groups have been introduced.
In the present invention, other polymer compounds may be used singly or in combination of two or more.
The composition of the present invention may or may not contain other polymer compounds, but if it does, the content of the other polymer compound is 0 relative to the total solid mass of the composition of the present invention. It is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.02% by mass or more and 20% by mass or less.
<Method for producing resin composition>
The resin composition of the present invention can be prepared by mixing the components described above. The mixing method is not particularly limited, and conventionally known methods can be used.
Mixing can be carried out using stirring blades, ball milling, or rotating the tank itself.
Temperature control during mixing is preferably from 10 to 30°C, more preferably from 15 to 25°C.
In addition, in the method for producing the composition, it is preferable to perform filtration using a filter for the purpose of removing foreign matters such as dust and fine particles in the composition. The filter pore size is, for example, 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. A filter that has been pre-washed with an organic solvent may be used. In the filter filtration step, multiple types of filters may be connected in series or in parallel for use. When multiple types of filters are used, filters with different pore sizes or materials may be used in combination. Also, various materials may be filtered multiple times. When filtering multiple times, circulation filtration may be used. Moreover, you may filter by pressurizing. When performing filtration by pressurization, the pressure to be applied is, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, and more preferably 0.05 MPa or more and 0.7 MPa or less. , more 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. You may combine filter filtration and the impurity removal process using an adsorbent. A known adsorbent can be used as the adsorbent. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

The composition obtained by the method for producing a composition of the present invention is preferably a composition for forming an interlayer insulating film for rewiring layers.
In addition, it can also be used for an insulating film of a semiconductor device, a stress buffer film, or the like.

(Method for producing cured film)
The method for producing a cured film of the present invention preferably includes a step of curing the composition obtained by the method for producing a composition of the present invention.
The thickness of the cured film to be formed can be, for example, 0.5 μm or more, and can also be 1 μm or more. Moreover, as an upper limit, it can be set to 100 μm or less, and can also be set to 30 μm or less.

Fields to which the cured film obtained by the method for producing a cured film of the present invention can be applied include insulating films for semiconductor devices, interlayer insulating films for rewiring layers, stress buffer films, and the like. In addition, pattern formation by etching of a sealing film, a substrate material (a base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above can be used. For these applications, for example, Science & Technology Co., Ltd. "High Functionality and Application Technology of Polyimide" April 2008, Masaaki Kakimoto / supervised, CMC Technical Library "Basics and Development of Polyimide Materials" Published November 2011 , Japan Polyimide/Aromatic Polymer Study Group/Edited "Latest Polyimide Fundamentals and Applications", NTS, August 2010, etc. can be referred to.

The cured films according to the invention can also be used in the production of printing plates such as offset or screen printing plates, in the etching of molded parts, in the production of protective lacquers and dielectric layers in electronics, especially microelectronics.
Further, for example, the cured film of the present invention can be used as a resist material.

The method for producing a cured film of the present invention preferably includes a film forming step of applying the composition (the composition obtained by the method for producing a composition of the present invention) to a substrate to form a film.
Furthermore, the method for producing a cured film of the present invention includes the film forming step, and further includes an exposure step of exposing the film and a developing step of developing the film (developing the film). is more preferable.
Furthermore, the method for producing a cured film of the present invention includes the film forming step (and the developing step if necessary), and further includes a heating step of heating the film at 50 to 450 ° C. preferable.
Specifically, it is also preferable to include the following steps (a) to (d).
(a) a film forming step of applying the composition to a substrate to form a film (composition layer); (b) an exposure step of exposing the film after the film forming step; Developing step (d) of performing development processing Heating step of heating the developed film at 50 to 450° C. By heating in the heating step, the composition layer after development can be further cured. In this heating step, for example, the above-mentioned thermal base generator is decomposed, cross-linking of cross-linkable groups proceeds, etc., so that sufficient curing is achieved.

<Film forming step (layer forming step)>
A manufacturing method according to a preferred embodiment of the present invention includes a film forming step (layer forming step) of applying the composition to a substrate to form a film (layered).

The type of base material can be appropriately determined according to the application, and includes semiconductor manufacturing base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, Magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, plasma display panel (PDP) electrode plates, etc. are not particularly limited.
In the present invention, a semiconductor production substrate is particularly preferable, and a silicon substrate is more preferable.
In addition, these substrates may be provided with a layer such as an adhesion layer or an oxide layer on the surface.
As the base material, for example, a plate-like base material (substrate) is used.
The shape of the substrate is not particularly limited, and may be circular or rectangular, preferably rectangular.
As for the size of the substrate, if it is circular, the diameter is, for example, 100 to 450 mm, preferably 200 to 450 mm. In the case of a rectangular shape, the short side length is, for example, 100 to 1000 mm, preferably 200 to 700 mm.

Moreover, when forming a composition layer on the surface of a resin layer, such as a composition layer, or the surface of a metal layer, a resin layer or a metal layer becomes a base material.

Coating is preferred as a means of applying the composition to the substrate.

Specifically, applicable means include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and ink jet method. From the viewpoint of uniformity of the thickness of the composition layer, spin coating, slit coating, spray coating, and inkjet are more preferred. A resin layer having a desired thickness can be obtained by appropriately adjusting the solid content concentration and coating conditions according to the method. In addition, the coating method can be appropriately selected depending on the shape of the substrate. Spin coating, spray coating, inkjet method, etc. are preferable for circular substrates such as wafers, and slit coating and spray coating are preferable for rectangular substrates. method, inkjet method, and the like are preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 2,000 rpm (revolutions per minute) for about 10 seconds to 1 minute.
Alternatively, a method of transferring a coating film, which is formed on a temporary support in advance by the above application method, onto a base material can also be applied.
As for the transfer method, the manufacturing methods described in paragraphs 0023 and 0036 to 0051 of JP-A-2006-023696 and paragraphs 0096-0108 of JP-A-2006-047592 can also be suitably used in the present invention.
Also, a step of removing excess film at the edge of the substrate may be performed. Examples of such processes include edge bead rinse (EBR), air knife, and the like.

<Drying process>
The production method of the present invention may include a drying step for removing the solvent after the film forming step (layer forming step). The drying temperature is preferably 50 to 150°C, more preferably 70 to 130°C, even more preferably 90 to 110°C. The drying time is exemplified from 30 seconds to 20 minutes, preferably from 1 minute to 10 minutes, more preferably from 3 minutes to 7 minutes.

<Exposure process>
The manufacturing method of the present invention may include an exposure step of exposing the film (composition layer). The amount of exposure is not particularly defined as long as the composition can be cured. For example, it is preferable to irradiate 100 to 10,000 mJ/cm ² in terms of exposure energy at a wavelength of 365 nm, and 200 to 8,000 mJ/cm ² irradiation. is more preferable.

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 wavelength is (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-line (wavelength 436 nm), h (4) excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength: 157 nm), (5) extreme ultraviolet; EUV (wavelength: 13.6 nm), (6) electron beam, and the like. For the composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferred, and exposure with i-line is particularly preferred. Thereby, particularly high exposure sensitivity can be obtained.

<Development process>
The manufacturing method of the present invention may include a developing step of developing the exposed film (composition layer). By developing, the unexposed portions (non-exposed portions) are removed. The developing method is not particularly limited as long as a desired pattern can be formed. The development process includes a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept in a substantially stationary state on the substrate, a process in which the developer is vibrated by ultrasonic waves or the like, and a combination of these processes. Adoptable.

Development is performed using a developer. If the composition is a negative composition, the developer removes the unexposed portion (unexposed portion) of the composition layer, and if the composition is a positive composition, the exposed portion is removed. Those from which a portion (exposed portion) is removed can be used without particular limitation.
In the present invention, the case where an alkaline developer is used as the developer is called alkaline development, and the case where a developer containing 50% by mass or more of an organic solvent is used as the developer is called solvent development.
Moreover, the developer may contain a known surfactant.

In alkaline development, the content of the organic solvent in the developer is preferably 10% by mass or less, more preferably 5% by mass or less, and 1% by mass or less with respect to the total mass of the developer. is more preferred, and it is particularly preferred that it does not contain an organic solvent.
The developer in alkaline development is more preferably an aqueous solution having a pH of 9-14.
Alkali compounds contained in the developer in alkali development include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, metasilicate. Potassium acid, ammonia, amines, and the like. Examples of amines include ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, quaternary ammonium hydroxide, and tetramethylammonium hydroxide. (TMAH), tetraethylammonium hydroxide, tetrabutylammonium hydroxide, and the like. Among them, alkali compounds containing no metal are preferred, and ammonium compounds are more preferred.
Alkaline compounds may be used alone or in combination of two or more. When two or more alkali compounds are used, the total amount is preferably within the above range.

In solvent development, the developer more preferably contains 90% or more of an organic solvent. In the present invention, the developer preferably contains an organic solvent with a ClogP value of −1 to 5, more preferably an organic solvent with a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by inputting the structural formula in ChemBioDraw.

Organic solvents include esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone. . ethyl ethoxyacetate, etc.)), 3-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, 3-methoxypropionic acid ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionate alkyl esters (e.g. methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl propyl oxypropionate (e.g., 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 (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, pyruvate Ethyl acid, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and , ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, and aromatic hydrocarbons such as toluene, xylene, anisole, limonene etc., dimethyl sulfoxide is preferably exemplified as sulfoxides.

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

The developer preferably contains 50% by mass or more of the organic solvent, more preferably 70% by mass or more of the organic solvent, and even more preferably 90% by mass or more of the organic solvent. Further, the developer may contain 100% by mass of the organic solvent.

The development time is preferably 10 seconds to 5 minutes. The temperature of the developer during development is not particularly specified, but the development is usually carried out at 20 to 40°C.

After processing with the developer, rinsing may be carried out.
In the case of solvent development, rinsing is preferably performed using an organic solvent different from the developer. Rinsing solutions for development with a developer containing an organic solvent include PGMEA (propylene glycol monomethyl ether acetate), IPA (isopropanol), etc. PGMEA is preferred.
In the case of alkali development, rinsing is preferably performed using pure water.
Rinsing time is preferably 5 seconds to 1 minute.

<Heating process>
The production method of the present invention preferably includes a step of heating the developed film at 50 to 450° C. (heating step).
The heating step is preferably included after the film forming step (layer forming step), the drying step, and the developing step.
The curing reaction of unreacted polymerizable compounds other than the thermosetting resin contained in the composition of the present invention, the curing reaction of unreacted polymerizable groups in the thermosetting resin, etc. can proceed in this step.
Further, when the thermosetting resin is a polyimide precursor and the composition contains a thermal base generator, in the heating step, for example, a base is generated by decomposition of the thermal base generator, and the ring of the polyimide precursor conversion reaction proceeds.
The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50° C. or higher, more preferably 80° C. or higher, even more preferably 140° C. or higher, and 150° C. or higher. is particularly preferred, 160° C. or higher is more preferred, and 170° C. or higher is most preferred. The upper limit is preferably 450° C. or lower, more preferably 350° C. or lower, even more preferably 250° C. or lower, and particularly preferably 220° C. or lower.

Heating is preferably carried out from the temperature at the start of heating to the maximum heating temperature at a temperature rising rate of 1 to 12°C/min, more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min. By setting the temperature increase rate to 1° C./min or more, it is possible to prevent excessive volatilization of the amine while ensuring productivity, and by setting the temperature increase rate to 12° C./min or less, the cured film can be cured. Residual stress can be relaxed.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, 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 up to the maximum heating temperature is started. For example, when the composition is applied onto a substrate and then dried, the temperature of the film (layer) after drying, for example, a temperature 30 to 200° C. lower than the boiling point of the solvent contained in the composition. It is preferable to gradually raise the temperature from .

The heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, even more preferably 30 to 240 minutes.

Particularly when forming a multi-layer laminate, the heating temperature is preferably 180° C. to 320° C., more preferably 180° C. to 260° C., from the viewpoint of adhesion between the layers of the cured film. Although the reason for this is not clear, it is believed that this temperature allows the polymerizable groups in the resin between the layers to undergo a cross-linking reaction.

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

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

The heating step is preferably carried out in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium or argon, in order to prevent decomposition of the resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.
A heating means in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared furnace, an electric heating oven, and a hot air oven.

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

The metal layer is not particularly limited, and existing metal species can be used, and examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten and alloys containing these metals. Aluminum is more preferred, and copper is even more preferred.

The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used. For example, photolithography, lift-off, electroplating, electroless plating, etching, printing, and a combination thereof can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electroplating can be used.

The thickness of the metal layer is preferably 0.1 to 50 μm, more preferably 1 to 10 μm, at the thickest portion.

Two or more layers of the cured film of the present invention, or three to seven layers may be laminated to form a laminate. The laminate of the present invention preferably has two or more cured films and a metal layer between the cured films. Moreover, it is preferable that the laminate of the present invention includes two or more cured films and 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 preferred. At least one of the first cured film and the second cured film is a cured film obtained by the method for producing a cured film of the present invention, for example, the first cured film and the second cured film is preferably a film obtained by curing the composition of the present invention. The composition used to form the first cured film and the composition used to form the second cured film may be the same composition or different compositions. Although there may be, from the viewpoint of production suitability, it is preferable that the compositions have the same composition. Such a metal layer is preferably used as a metal wiring such as a rewiring layer.

(Laminate manufacturing method)
The method for producing a laminate of the present invention preferably includes a step of laminating at least two layers of the cured film obtained by the method for producing a cured film of the present invention.
The laminate obtained by the method for producing a laminate of the present invention is a laminate containing two or more cured films, and may be a laminate having 3 to 7 layers laminated.
Of the two or more layers of the cured film contained in the laminate, at least one is a cured film obtained by the method for producing a cured film of the present invention, and all the cured films contained in the laminate are the cured films of the present invention. It is preferably a cured film obtained by a method for producing a film.
It is preferable that the laminate includes two or more cured films and a metal layer between any of the cured films. The metal layer is preferably formed by the metal layer forming step.
As the laminate, 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 mentioned as a preferable one.
Both the first cured film and the second cured film are preferably cured films obtained by the method for producing a cured film of the present invention. The composition used to form the first cured film and the composition used to form the second cured film may be the same composition or different compositions. There may be. The metal layer in the laminate is preferably used as a metal wiring such as a rewiring layer.

<Lamination process>
It is preferable that the method for manufacturing the laminate of the present invention includes a lamination step.
In the method for producing a laminate of the present embodiment, after forming a cured film according to the above method for producing a cured film, the above step (a), or steps (a) to (c), or Steps (a) to (d) are performed. In particular, it is preferable to perform each of the above steps in order multiple times, for example, 2 to 5 times (that is, 3 to 6 times in total). By laminating the cured films in this manner, a laminate can be obtained. In the present invention, it is particularly preferred to provide a metal layer on the portion where the cured film is provided, between the cured films, or both. In the production of the laminate, it is not necessary to repeat all the steps (a) to (d), and at least (a), preferably (a) to (c) or (a) to (d) ) can be performed a plurality of times to obtain a cured film laminate.
Moreover, after the (d) heating step, the above-described metal layer forming step may be included. Needless to say, the lamination step may further include the drying step and the like as appropriate.

After the lamination step, when the lamination step is further performed, after the exposure step, after the development step, after the heating step, or after the metal layer formation step, a surface activation treatment step may be further performed. A plasma treatment is exemplified as the surface activation treatment.

The lamination step is preferably performed 2 to 5 times, more preferably 3 to 5 times.
For example, the resin layer is preferably composed of 3 to 7 layers, such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, and more preferably composed of 3 to 5 layers. .
Further, each layer in the lamination process may be a layer having the same composition, shape, film thickness, etc., or may be a different layer.

In the present invention, it is particularly preferable to form a cured film so as to cover the metal layer after providing the metal layer. Specifically, (a) a film forming step, (b) an exposure step, (c) a developing step, (d) a heating step, and (e) a metal layer forming step are repeated in this order. By alternately performing the steps (a) to (d) for forming the cured film and the metal layer forming step, the cured film and the metal layer can be alternately laminated.

(Device manufacturing method)
The present invention also discloses a device manufacturing method including the cured film manufacturing method of the present invention or the laminate manufacturing method of the present invention. Specific examples of the device using the cured film or laminate for forming the interlayer insulating film for the rewiring layer can refer to the descriptions in paragraphs 0213 to 0218 of JP-A-2016-027357 and the description in FIG. the contents of which are incorporated herein.

EXAMPLES The present invention will be described more specifically with reference to examples below. The materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. Hereinafter, "parts" and "%" are based on mass unless otherwise specified.

<Preparation of resin composition>
In each of the examples and comparative examples, a resin composition containing each component shown in Table 1 below at a content rate (%) shown in Table 1 below was prepared.
In Table 1, the numerical value described in the "Content" column indicates the content (% by mass) of each component in the composition.
In addition, in Table 1, the description of "-" indicates that the corresponding component is not contained.

Details of each component described in Table 1 are as follows.

〔resin〕
A-1 to A-6: resins comprising repeating units represented by the following formulas (A-1) to (A-6). In the following formulas (A-1) to (A-6), * represents a binding site with another repeating unit, the numerical value attached to the repeating unit represents the content ratio (molar ratio) of each repeating unit, In a resin composed of a plurality of types of repeating units, each repeating unit is randomly bonded.
Further, in formula (A-3), # represents a bonding site with an oxygen atom to which R is bonded. In formula (A-3), the two structures described as R are contained in a molar ratio of 1:1, and each is randomly attached to two R in the repeating unit represented by formula (A-3). Combined.

[Solvent 1, solvent 2 (solvent)]
・Water: pure water ・MeOH: methanol ・PGME: propylene glycol monomethyl ether ・THF: tetrahydrofuran ・Toluene: toluene ・NMP: N-methylpyrrolidone

<Evaluation>
[Low temperature and low pressure process]
150 g of the resin composition prepared in each example and comparative example was put into a vacuum dryer (manufactured by Yamato Scientific Co., Ltd.).
The temperature and pressure of the vacuum dryer were set to the values described in the columns of "temperature (°C)" and "pressure (kPa)" in the "low temperature and low pressure process" in Table 1, respectively, and drying was started. After the temperature and pressure in the measuring device attached to the apparatus reached the set values, the apparatus was allowed to stand for the time described in the "time (h)" column of the "low temperature and low pressure process" in Table 1.
In the example where "-20 to 40" is written in the "temperature (°C)" column of the "low temperature and low pressure process" in Table 1, the temperature of the vacuum dryer is set to -20 ° C., and then the temperature of the vacuum dryer is Drying was performed while the temperature was raised to 40°C at a rate of 1°C/min. Immediately after reaching 40° C., the high-temperature, low-pressure step described below was started.
In the examples in which "-" is written in the "temperature (°C)" and "pressure (kPa)" columns of the "low temperature and low pressure process" in Table 1, the resin composition is dried under reduced pressure without performing the low temperature and low pressure process. Immediately after being put into the machine, a high temperature and low pressure process was performed.

[High temperature and low pressure process]
Immediately after the standing, the temperature of the vacuum dryer was set to the value shown in Table 1, "Temperature (°C)" under "High temperature and low pressure process".
The vacuum dryer pressure was unchanged from that in the low temperature low pressure step.
After that, after the temperature and pressure in the measuring machine attached to the apparatus reached the values set above, the apparatus was allowed to stand until the time described in the "time (h)" column of the "high temperature and low pressure process" in Table 1 was reached. After the temperature and pressure reached the set values, it was allowed to stand for the time described in the "Time (h)" column of the "High temperature and low pressure process" in Table 1.

[Measurement of solid content after drying]
After the standing, the dried resin was taken out from the dryer, and the solid content after drying was measured.
The measurement method was as follows.
150 g of the resin composition prepared in each example and comparative example was vacuum-dried at 120° C. for 4 hours, and the mass of the residue was defined as ^M1 .
The mass ^M2 of the dried resin obtained after the high temperature and low pressure process was measured, and the post-drying solid content was calculated by the following formula.
Solid content after drying (% by mass) = M ¹ /M ² × 100
The measurement results are shown in the column of "solid content after drying (% by mass)" in Table 1.

[Evaluation of particle defects]
A polymer solution was prepared by dissolving the obtained dry resin in tetrahydrofuran so as to have a concentration of 5% by mass.
Micro foreign matters (particles) mixed in the polymer solution were detected as light scatterers, and the particle size distribution of the light scatterers contained was investigated. From the above particle size distribution, the most frequent particle size value (particle size mode (μm)) was determined and evaluated according to the following evaluation criteria. The evaluation results are described in the column of "particle defects" in Table 1. It can be said that the generation of particles is suppressed as the mode of the particle diameter is smaller.

-Evaluation criteria-
A: The mode value (μm) of the particle size was 0.1 μm or less.
B: The mode value (μm) of the particle size was more than 0.1 μm and 0.5 μm or less.
C: The mode value (μm) of the particle size exceeded 0.5 μm.

From the above results, it can be seen that the generation of particles is suppressed according to the method for producing a dry resin according to the present invention.
In the manufacturing method according to Comparative Example 1, only the high-temperature, low-pressure process was performed without performing the low-temperature, low-pressure process.
In the manufacturing method according to Comparative Example 2, the temperature difference between the temperature in the low-temperature, low-pressure process and the temperature in the high-temperature, low-pressure process was less than 5°C (4°C).
In the manufacturing methods according to Comparative Examples 3 and 4, the pressure in the low-temperature, low-pressure step was set to a value exceeding 10 kPa (15 kPa and 30 kPa, respectively).
It can be seen that in the manufacturing methods according to these Comparative Examples 1, 3, and 4, particles with large particle diameters are frequently generated.
In the manufacturing method according to Comparative Example 2, the solid content after drying in the resin obtained after the high temperature and high pressure process is 88%. That is, it can be seen that the content of the solvent with respect to the total mass of the resin was 12% by mass, and no dry resin was obtained.

<Example 101>
32 parts by weight of the dry resin obtained in Example 1, 6.88 parts by weight of tetraethylene glycol dimethacrylate, 1.04 parts by weight of Irgacure OXE-01 (manufactured by BASF), and N-cyclohexyl-N,N -Dimethyl-N-phenacylammonium maleate 1.0 parts by mass, p-benzoquinone 0.08 parts by mass, 1H-tetrazole 0.12 parts by mass, N-[3-(triethoxysilyl)propyl]maleic acid monoamide 0.70 parts by mass, 48.00 parts by mass of γ-butyrolactone and 12.00 parts by mass of dimethylsulfoxide were mixed to prepare a composition.
The above composition was pressure-filtered through a filter with a pore size of 0.8 μm, and then applied by spinning onto the surface of the thin copper layer of the resin substrate having the thin copper layer formed thereon so that the film thickness would be 20 μm. . The composition applied to the resin substrate was dried at 100° C. for 2 minutes, and then exposed using a stepper (Nikon, NSR1505 i6). Exposure was carried out through a mask of a square pattern (square pattern of 100 μm in length and width, number of repetitions: 10) at a wavelength of 365 nm and an exposure amount of 400 mJ/cm ² to prepare a square pattern. After the exposure, the film was developed with cyclopentanone for 30 seconds and rinsed with PGMEA for 20 seconds to obtain a pattern.
Next, in a nitrogen atmosphere, the temperature was raised at a rate of 10° C./min, reaching 180° C., and then heated at this temperature for 3 hours to form an interlayer insulating film for rewiring layers. This interlayer insulating film for rewiring layer was excellent in insulating properties. Moreover, when a semiconductor device was manufactured using these interlayer insulating films for rewiring layers, it was confirmed that the device operated without any problem.

Claims (13)

A low-temperature and low-pressure step of reducing the pressure of the resin composition containing a resin and a solvent to 10 kPa or less at a temperature of -150 to 35 ° C., and
After the low-temperature, low-pressure step, a high-temperature, low-pressure step in which the resin composition is set to a temperature 5 ° C. or more higher than the temperature in the low-temperature, low-pressure step under reduced pressure,
The solvent content is 90% by mass or less with respect to the total mass of the resin composition before being subjected to the low temperature and low pressure step,
The time to be subjected to the low temperature and low pressure step is 30 minutes or more,
The resin has thermosetting properties,
The resin has a (meth)acryloyl group,
The temperature in the high temperature and low pressure process is 40 to 150 ° C.
A method for producing a dry resin. A low-temperature and low-pressure step of reducing the pressure of the resin composition containing a resin and a solvent to 10 kPa or less at a temperature of -150 to 35 ° C., and
After the low-temperature, low-pressure step, a high-temperature, low-pressure step in which the resin composition is set to a temperature 5 ° C. or more higher than the temperature in the low-temperature, low-pressure step under reduced pressure,
The solvent content is 90% by mass or less with respect to the total mass of the resin composition before being subjected to the low temperature and low pressure step,
The time to be subjected to the low temperature and low pressure step is 30 minutes or more,
The resin has thermosetting properties,
The resin is a resin having a group having an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, an alkoxymethyl group, an acyloxymethyl group, a benzoxazolyl group, a blocked isocyanate group, or an amic acid ester structure in its structure. the law of nature,
The temperature in the high temperature and low pressure process is 40 to 150 ° C.
A method for producing a dry resin. A low-temperature and low-pressure step of reducing the pressure of the resin composition containing a resin and a solvent to 10 kPa or less at a temperature of -150 to 35 ° C., and
After the low-temperature, low-pressure step, a high-temperature, low-pressure step in which the resin composition is set to a temperature 5 ° C. or more higher than the temperature in the low-temperature, low-pressure step under reduced pressure,
The solvent content is 90% by mass or less with respect to the total mass of the resin composition before being subjected to the low temperature and low pressure step,
The time to be subjected to the low temperature and low pressure step is 30 minutes or more,
The resin has thermosetting properties,
The resin contains a repeating unit having an amic acid ester structure ,
The temperature in the high temperature and low pressure process is 40 to 150 ° C.
A method for producing a dry resin. A low-temperature and low-pressure step of reducing the pressure of the resin composition containing a resin and a solvent to 10 kPa or less at a temperature of -150 to 35 ° C., and
After the low-temperature, low-pressure step, a high-temperature, low-pressure step in which the resin composition is set to a temperature 5 ° C. or more higher than the temperature in the low-temperature, low-pressure step under reduced pressure,
The solvent content is 90% by mass or less with respect to the total mass of the resin composition before being subjected to the low temperature and low pressure step,
The time to be subjected to the low temperature and low pressure step is 30 minutes or more,
The resin has thermosetting properties,
The resin is a group having an ethylenically unsaturated bond, a cyclic ether group, or a resin having an amic acid ester structure in its structure ,
The temperature in the high temperature and low pressure process is 40 to 150 ° C.
A method for producing a dry resin. The method for producing a dry resin according to any one of claims 1 to 4, wherein the time from the end of the low-temperature, low-pressure step to the start of the high-temperature, low-pressure step is within 3 minutes. The method for producing a dry resin according to any one of claims 1 to 5, wherein the content of the solvent is 20% by mass or more with respect to the total mass of the resin composition before being subjected to the low temperature and low pressure step. . The method for producing a dry resin according to any one of claims 1 to 6, wherein the difference between the temperature in the high-temperature, low-pressure step and the temperature in the low-temperature, low-pressure step is 5 to 50°C. The method for producing a dry resin according to any one of claims 1 to 7 , wherein the solvent contains at least one solvent selected from the group consisting of water and ether solvents. The method for producing a dry resin according to any one of claims 1 to 8 , wherein in the low temperature and low pressure step, the temperature is -150 to 30°C and the pressure is reduced to 5 kPa or less. A step of mixing a dry resin obtained by the method for producing a dry resin according to any one of claims 1 to 9 with at least one other component,
A method of making the composition. A method for producing a cured film, comprising the step of curing the composition obtained by the method for producing a composition according to claim 10 . A method for producing a laminate, comprising the step of laminating at least two layers of the cured film obtained by the method for producing a cured film according to claim 11 . A method for producing a device, comprising the method for producing a cured film according to claim 11 or the method for producing a laminate according to claim 12 .