JP6511146B2 - Method of manufacturing cured film, method of manufacturing interlayer insulating film for rewiring layer, and method of manufacturing semiconductor device - Google Patents

Description

  The present invention relates to a method of manufacturing a cured film, a method of manufacturing an interlayer insulating film for redistribution layers, and a method of manufacturing a semiconductor device. In particular, the present invention relates to a method for producing a cured film using a heterocycle-containing polymer precursor selected from a polyimide precursor and a polyben oxazole precursor.

  Thermosetting resins such as polyimide and polybenzoxazole that cure and cure are excellent in heat resistance and insulation, and thus are used in the insulating layer of semiconductor devices and the like.

  In addition, since polyimide and the like have low solubility in a solvent, they are used in the state of a precursor (heterocycle-containing polymer precursor) before the cyclization reaction, and after application to a substrate and the like, the heterocycle-containing polymer is heated. It has been practiced to cyclize the precursor to form a cured film.

Here, Patent Document 1 is a polyimide precursor composition containing a polyimide precursor, a thermal base generator that generates a base by heat, and a solvent, and the polyimide precursor has the following formula (1): Disclosed is a polyimide precursor composition, which is a polyamide acid having a repeating unit of the following: a thermal base generator is a neutral compound which is thermally decomposed by heating at a temperature of 200 ° C. or less to generate a secondary amine. It is done.
(Wherein, X represents a tetravalent organic group, Y represents a divalent organic group, and each —COOH group is in an ortho position relative to the —CONH group)

  Patent Document 2 discloses a polyamic acid composition comprising a polyamic acid, polyaniline, a dopant for making the polyaniline conductive, a solvent, and a basic additive. There is.

Japanese Patent Application Publication No. 2007-056196 Unexamined-Japanese-Patent No. 2007-056182

When a cured film obtained by cyclizing a heterocycle-containing polymer precursor is used as an interlayer insulating film for a rewiring layer or the like, the corrosion resistance and chemical resistance of the cured film become problems. However, when the inventors examined, the cured films described in the examples of Patent Document 1 and Patent Document 2 were found to be inferior in corrosion resistance and chemical resistance.
This invention aims at solving the said subject, and provides the method of manufacturing the cured film excellent in corrosion resistance and chemical resistance. The present invention also relates to a method of manufacturing an interlayer insulating film for a redistribution layer and a method of manufacturing a semiconductor device, the method including the method of manufacturing the cured film.

Under these circumstances, as a result of investigation conducted by the present inventor, it is possible to provide a cured film excellent in corrosion resistance and chemical resistance by manufacturing so that the amount of amine in the cured film is within a predetermined range. It has been found that the present invention has been completed. Specifically, the above problems are solved by the following means.
The amine content is 50 including heating the layer which consists of a composition containing at least 1 sort (s) of a polyimide precursor and a polybenzoxazole precursor, and an amine generator at the temperature of 250 degrees C or less of maximum heating temperature Method of producing a cured film of ~ 5,000 ppm.
<2> The method for producing a cured film according to <1>, wherein the amine generator is at least one of a photoamine generator and a thermal amine generator.
The manufacturing method of the cured film as described in <1> or <2> whose <3> above-mentioned amine generator is a thermal amine generator.
The manufacturing method of the cured film in any one of <1>-<3> in which the <4> above-mentioned composition does not contain the amine more than pKa8 of a conjugate acid.
The manufacturing method of the cured film in any one of <1>-<4> which performs <5> said heating at the temperature increase rate of 1 to 10 degree C / min from the temperature of 20-150 degreeC to the said maximum heating temperature .
The manufacturing method of the cured film as described in <5> which heats for 60 to 240 minutes after performing <6> the said heating at the said temperature increase rate and reaching maximum heating temperature.
Any one of <1>-<6> in which <7> said composition contains the said amine generator in a ratio of 0.01-45 mass% with respect to the total amount of a polyimide precursor and a polybenzoxazole precursor. Method for producing a cured film according to
<8> The curing according to any one of <1> to <7>, wherein the polyimide precursor is represented by the following general formula (2), and the polybenzoxazole precursor is represented by the following general formula (3) A method of producing a membrane;
General formula (2)
In general formula (2), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group;
General formula (3)
In formula (3), 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 Represents
<9> In the general formula (2), at least one of A ¹ and A ² is an oxygen atom, and among R ¹¹³ and R ¹¹⁴ , adjacent A ¹ and A ² are oxygen atoms R ¹¹³ and R ¹¹⁴ Or represents a monovalent organic group, or
The manufacturing method of the cured film as described in <8> whose R < ¹²¹ > is a linear aliphatic group in General formula (3).
The manufacturing method of the cured film in any one of <1>-<9> whose <10> above-mentioned maximum heating temperature is 160-250 degreeC.
The manufacturing method of the cured film in any one of <1>-<10> whose amine content of the <11> above-mentioned cured film is 500-2,000 ppm.
The manufacturing method of the cured film in any one of <1>-<11> in which the <12> above-mentioned composition further contains a crosslinking agent.
The manufacturing method of the cured film as described in <12> whose molecular weight of the <13> above-mentioned crosslinking agent is 100-800.
<14> The amine generator is at least one selected from an acidic compound which generates an amine when heated to 40 to 250 ° C., and an ammonium salt having an anion of pKa 1 of 0 to 4 and an ammonium cation. The manufacturing method of the cured film in any one of 1>-<13>.
The manufacturing method of the cured film as described in <14> which is a compound which generate | occur | produces an amine when the <15> above-mentioned acidic compound heats at 40-250 degreeC.
The manufacturing method of the cured film as described in <14> or <15> whose <16> above-mentioned acidic compound is a salt of ammonium cation and a carboxylate anion.
The manufacturing method of the interlayer insulation film for rewiring layers including the manufacturing method of the cured film in any one of <17><1>-<16>.
The manufacturing method of the semiconductor device containing the manufacturing method of the cured film in any one of <18><1>-<16>.
The cured film obtained by the manufacturing method of the cured film in any one of <19><1>-<16>.
The semiconductor device obtained by the manufacturing method of the cured film in any one of <20><1>-<16>.

  According to the present invention, it has become possible to provide a method for producing a cured film excellent in corrosion resistance and chemical resistance. In addition, it has become possible to provide a method of manufacturing an interlayer insulating film for a redistribution layer and a method of manufacturing a semiconductor device, including the method of manufacturing the above-described cured film.

FIG. 1 is a schematic view showing the configuration of an embodiment of a semiconductor device.

The description of components in the present invention described below may be made based on the representative embodiments of the present invention, but the present invention is not limited to such embodiments.
In the notation of groups (atomic groups) in the present specification, the notations not describing substitution and non-substitution include those having no substituent and those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, "active light" means, for example, a bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet (EUV light), X-rays, electron beams and the like. In the present invention, light means actinic rays or radiation. Unless otherwise specified, the "exposure" in the present specification means not only exposure using far ultraviolet rays represented by a mercury lamp or excimer laser, X-rays, EUV light, etc., but also particle beams such as electron beams and ion beams. Include drawing in using in the exposure.
In the present specification, a numerical range represented using “to” means a range including numerical values described before and after “to” as the lower limit value and the upper limit value.
In the present specification, “(meth) acrylate” represents both “acrylate” and “methacrylate” or any of “acrylate” and “(meth) allyl” represents both “allyl” and “methallyl” or "(Meth) acrylic" represents either or both of "acrylic" and "methacrylic", and "(meth) acryloyl" represents both "acryloyl" and "methacryloyl" or Represents one.
As used herein, the term "step" does not only mean an independent step, but if the intended function of that step is achieved even if it can not be clearly distinguished from other steps, this term include.
In the present specification, the solid content concentration is a mass percentage of the mass of the other components excluding the solvent with respect to the total mass of the composition. Moreover, solid content concentration means the density | concentration in 25 degreeC unless it mentions specially.
In the present specification, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group.

The production method of the present invention comprises a layer comprising a composition comprising at least one of a polyimide precursor and a polybenzoxazole precursor (hereinafter sometimes referred to as “heterocycle-containing polymer precursor”), and an amine generator. The method is characterized by producing a cured film having an amine content of 50 to 5,000 ppm including heating at a maximum heating temperature of 250 ° C. or less. Thus, by adjusting the amine content, it is possible to provide a cured film excellent in corrosion resistance and chemical resistance. Although it is described in Patent Document 1 that the generated amine may remain in the cured film depending on the purpose in the cured film, no specific amount is specified. Further, Patent Document 2 states that the range of 1 to 5% by mass of the tertiary amine remaining in the cured film is preferable. However, the relationship between the amount of amine in the cured film and the corrosion resistance and chemical resistance has not been studied at all. It is surprising that the amount of amine in the cured film contributes to the corrosion resistance and chemical resistance of the cured film.
In the production method of the present invention, the amine content of the obtained cured film is preferably 100 ppm or more, more preferably 400 ppm or more, and still more preferably 500 ppm or more. The upper limit thereof is preferably 2,000 ppm or less, more preferably 1,000 ppm. By setting it as such a range, it is excellent in corrosion resistance and chemical resistance. Furthermore, it tends to be excellent in outgassing properties, which is preferable.

The method for producing a cured film of the present invention includes heating a layer comprising the above composition at a maximum heating temperature of 250 ° C. or less.
The layer consisting of the above composition is usually formed by applying, preferably applying, the composition on a substrate. Methods of applying the composition to a substrate include spinning, dipping, doctor blade coating, suspended casting, coating, spraying, electrostatic spraying, reverse roll coating, etc., spinning, electrostatic spraying and reverse Roll coating is preferred because it can be applied uniformly on the substrate. It is also possible to introduce a layer consisting of the above composition onto a temporary, flexible carrier and then to apply the final substrate, for example a copper-clad printed circuit board by layer transfer by lamination. .

As the substrate, an inorganic substrate, a resin, a resin composite material and the like can be mentioned.
Examples of the inorganic substrate include a glass substrate, a quartz substrate, a silicon substrate, a silicon nitride substrate, and a composite substrate in which molybdenum, titanium, aluminum, copper or the like is vapor-deposited on a substrate such as them.
As the resin substrate, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyether sulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamide imide, polyether imide, Polybenzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, fluorine resin such as polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin Groups consisting of synthetic resins such as aromatic ethers, maleimide-olefins, celluloses and episulfide compounds And the like. These substrates are rarely used as they are in the above-mentioned form, and usually, a multilayer laminate structure such as a thin film transistor (TFT) element is formed by the form of the final product.

The amount of application of the composition (layer thickness) and the type of substrate (layer carrier) depend on the field of application desired. The range of the layer thickness is preferably 0.5 to 100 μm.
After applying the composition to the substrate, it is preferred to dry. Drying is preferably performed, for example, at 60 to 150 ° C. for 10 seconds to 2 minutes.

Heating is performed such that the maximum heating temperature is 250 ° C. or less. 240 degrees C or less is preferable, 230 degrees C or less is more preferable, 220 degrees C or less is further more preferable, 210 degrees C or less is further more preferable, and 200 degrees C or less is still more preferable. 140 degreeC or more is preferable, as for the lower limit of maximum heating temperature, 160 degreeC or more is more preferable, 170 degreeC or more is further more preferable, and 180 degreeC or more is especially preferable. Here, with the maximum heating temperature, the temperature range in which the sample experiences the accumulated temperature for 30 seconds or more among the temperatures experienced by the sample due to the heating performed for the cyclization reaction of the heterocycle-containing polymer precursor is confirmed And the highest temperature among them.
The maximum heating temperature is preferably 0 to 100 ° C. higher than the temperature at which the amine generator generates amine, and more preferably 30 to 60 ° C. higher.

The heating is preferably performed at a temperature rising rate of 1 to 10 ° C./min from a temperature of 20 to 150 ° C. to the maximum heating temperature, and the temperature rising rate is more preferably 2 to 10 ° C./min, 3 to 8 ° C./min Is more preferred, and 3 to 6 ° C./min is particularly preferred. By setting the temperature rise rate to 1 ° C./min or more, excessive volatilization of the amine can be prevented while securing productivity, and by setting the temperature rise rate to 10 ° C./min or less, the cured film Excess residual of amine can be prevented while relieving residual stress.
When heating at a low temperature of the maximum heating temperature of 250 ° C. or less to cyclize and cure the heterocycle-containing polymer precursor, it is difficult to adjust the amount of amine in the cured film, but from the temperature of 150 ° C. or less By heating slowly at a temperature rising rate, volatilization of the amine by initial heating can be suppressed, and the amount of amine in the cured film can be easily adjusted.
20-150 degreeC is preferable, as for the temperature at the time of a heating start, 20 degreeC-130 degreeC are more preferable, and 25 degreeC-120 degreeC are more preferable. The temperature at the start of heating refers to the temperature of the layer comprising the composition when the heating step to the maximum heating temperature is started. For example, when the composition is applied on a substrate and then dried, the temperature after drying is the temperature, for example, the temperature may be gradually raised from the boiling point-(30 to 200) ° C of the solvent contained in the composition. preferable.
The heating is preferably performed for 60 to 240 minutes after reaching the maximum heating temperature, more preferably 100 to 230 minutes, and particularly preferably 150 to 220 minutes. With such a range, the amount of amine in the cured film can be more easily adjusted.

The heating may be performed stepwise. As an example, the temperature is raised at 25 ° C. to 180 ° C. at 3 ° C./min, kept at 180 ° C. for 60 minutes, raised to 180-200 ° C. at 2 ° C./min, put at 200 ° C. for 120 min. Can be mentioned. In this case, it is preferable to set the heating conditions so that all of the stepwise heatings satisfy the above heating conditions.
Furthermore, cooling after heating may be performed, and the cooling rate in this case is preferably 1 to 5 ° C./minute.

  The heating step is preferably performed in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, from the viewpoint of preventing the decomposition of the heterocycle-containing polymer precursor such as polyimide. The oxygen concentration is preferably 50 ppm by volume or less, and more preferably 20 ppm by volume or less.

In the method for producing a cured film of the present invention, as described above, preferably, the step of applying (preferably applying) the composition to a substrate, and a layer comprising a composition applied to the substrate (layered composition) And curing the resin. In the present invention, a pattern forming step may be further performed between the step of applying the composition to the substrate and the step of curing. The pattern formation step can be performed, for example, by photolithography. For example, the method of performing through the process of performing the process to expose and the development process is mentioned.
In the case of negative-working pattern formation by photolithography, a photosensitive resin composition comprising a heterocycle-containing polymer precursor, a compound having an ethylenically unsaturated bond as a crosslinking agent, and a radical photopolymerization initiator is used. Is preferred. In the case of the positive type, it is preferable to use a photosensitive resin composition containing a heterocycle-containing polymer precursor and a photoacid generator. In the case of the negative type, the heterocycle-containing polymer precursor preferably has an ethylenically unsaturated bond. Details of these will be described later.
Hereinafter, the case of forming a pattern by photolithography will be described. The step of applying (preferably applying) the composition to the substrate and the step of curing the layered composition applied to the substrate are the same as described above, and the preferred ranges are also the same.

<Step of exposure>
In the step of exposing, the photosensitive resin composition applied to the substrate is irradiated with actinic rays or radiation of a predetermined pattern.
Although the wavelength of an actinic ray or a radiation changes with compositions of the photosensitive resin composition, 200-600 nm is preferable and 300-450 nm is more preferable.
As a light source, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, a light emitting diode (LED) light source, an excimer laser generator or the like can be used. An actinic ray having a wavelength of 300 nm or more and 450 nm or less, such as 436 nm) can be preferably used. In addition, it is also possible to adjust the irradiation light through a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter as needed. Exposure is preferably 1~1,000mJ / cm ^2, more preferably 200~800mJ / cm ^2.
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, a lens scanner, a laser exposure, and the like can be used.
In addition, when (meth) acrylates and similar olefinically unsaturated compounds are used, their photopolymerization is prevented by oxygen in the air, in particular in thin layers, as is known. This effect can be mitigated by known conventional methods such as, for example, temporary film layer introduction of polyvinyl alcohol, or pre-exposure or preconditioning in an inert gas.

<Step of developing processing>
At the process of developing, the unexposed part of the photosensitive resin composition is developed using a developing solution. As the developer, an aqueous alkaline developer, an organic solvent or the like can be used.
Examples of the alkali compound used in the aqueous alkali developer include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, sodium hydrogencarbonate, sodium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate and metasilicate And potassium, ammonia or an amine. Examples of the amine include ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyl diethylamine, alkanolamine, dimethylethanolamine, triethanolamine, quaternary ammonium hydroxide, tetramethylammonium hydroxide (TMAH) or tetraethylammonium hydroxide. Among them, alkali compounds containing no metal are preferable. Suitable aqueous alkaline developers are generally up to 0.5 normal with respect to alkali, but may be suitably diluted prior to use. For example, an aqueous alkaline developing solution of about 0.15 to 0.4N, preferably 0.20 to 0.35N is also suitable. The alkali compound may be used alone or in combination of two or more. When two or more alkali compounds are used, the total is preferably in the above range.
As an organic solvent, the thing similar to the solvent which can be used for the composition mentioned later can be used. For example, preferred are n-butyl acetate, γ-butyrolactone, cyclopentanone, and mixtures thereof.

<Polyimide Precursor and Polybenzoxazole Precursor>
The composition used in the present invention contains at least one of a polyimide precursor and a polybenzoxazole precursor (hereinafter sometimes referred to as “heterocycle-containing polymer precursor”).

<< Polyimide Precursor >>
The polyimide precursor used in the present invention does not particularly define its structure etc. as long as it can be polyimidated, and it is intended to include also a polyamideimide precursor. It is preferable that the polyimide precursor used by this invention contains the repeating unit represented by following General formula (2).

General formula (2)
In general formula (2), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R Each of ¹¹³ and R ¹¹⁴ independently represents a hydrogen atom or a monovalent organic group.
A ¹ and A ² in the general formula (2) each independently represent an oxygen atom or NH, preferably an oxygen atom. In particular, at least one of A ¹ and A ² is an oxygen atom, and R ¹¹³ and / or adjacent to A ¹ and A ² which are oxygen atoms, to promote cyclization at a low temperature more effectively. It is preferable that R ¹¹⁴ is a monovalent organic group.

R ¹¹¹ represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a group containing a cyclic aliphatic group and an aryl group, and a linear or branched aliphatic group having 2 to 20 carbon atoms The group which consists of a C6-C20 cyclic aliphatic group, a C6-C20 aryl group, or these combination is preferable, and the group which consists of a C2-C60 aryl group is more preferable. The following is mentioned as an example of an aryl group.

In the formula, A represents a single bond or a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C (= O)-, -S-, -S (= O) _2- and -NHCO- and a combination thereof are preferable, and a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C It is more preferable that it is a group selected from (= O)-, -S- and -SO _2- , and -CH _2- , -O-, -S-, -SO ₂ -and -C (CF ₃ ) _{2 -, - C (CH 3} ) 2 - and more preferably a divalent group selected from.

More specifically, R ¹¹¹ includes a diamine residue remaining after removal of the amino group of the diamine. As the diamine, linear or branched aliphatic, cyclic aliphatic or aromatic diamines and the like can be mentioned.
Specifically, the diamine residue etc. which remain after removal of the amino group of the following diamine are mentioned.
1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2 2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis (4-aminocyclohexyl) methane, bis (3-amino) Cyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophorone diamine; m- and p-phenylene diamine, diaminotoluene, 4,4'- and 3,3'-diaminobiphenyl, 4,4, 4'- and 3,3'-diaminodiphenyl ether, 4,4'- and 3,3'-diaminodiphenylmethane, 4,4'- And 3,3'-diaminodiphenyl sulfone, 4,4'- and 3,3'-diaminodiphenyl sulfide, 4,4'- and 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4 ' -Diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis (4-aminophenyl) propane, 2,2 -Bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2, 2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3- Amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) 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′-diaminodiphenyl sulfone, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3 -Aminophenoxy) benzene, 1,3-bis (4-aminophenyl) benzene, 3,3'-diethyl-4,4'-diaminodiphenyl Nylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-Aminophenoxy) phenyl] hexafluoropropane, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 3,3 ', 4,4'-tetraaminobiphenyl, 3,3' , 4,4'-Tetraaminodiphenylether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis (4-aminophenyl) Fluorene, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfone, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodi Phenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6 -Trimethyl-m-phenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-aminophenyl) ethane, diaminobenzanilide , 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-amino) Nophenyl) tetradecafluoroheptane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (2-aminophenoxy) phenyl] hexafluoropropane, 2,2 -Bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-bis (trifluoromethyl) phenyl] Hexafluoropropane, p-bis (4-amino-2-trifluoromethylphenoxy) benzene, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4- Amino-3-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-2-trifluoromethylpheno) C) Diphenylsulfone, 4,4'-bis (3-amino-5-trifluoromethylphenoxy) diphenylsulfone, 2,2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl] hexafluoro Propane, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 4,4′-diamino-2,2′- At least one diamine selected from bis (trifluoromethyl) biphenyl, 2,2 ′, 5,5 ′, 6,6′-hexafluorotrizine and 4,4 ′ ′ ′-diaminoquaterphenyl.

Further, the diamine residues remaining after removal of the amino groups of the diamine shown below (DA-1) ~ (DA -18) may also be mentioned as examples of ^{R 111.}

Further, the diamine residues remaining two or more alkylene glycol units after the removal of the amino groups of the diamine having the main chain may also be mentioned as examples of R ^111. Preferably, it is a diamine residue containing two or more of ethylene glycol chain and / or propylene glycol chain together in one molecule, and more preferably a diamine residue not containing an aromatic ring. As an example, Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 ( The trade names above, HUNTSMAN Co., Ltd. product, 1- (2- (2- (2-aminopropoxy) ethoxy) propoxy) propan-2-amine, 1- (1- (1- (2-aminopropoxy) propane) -2-yl) oxy) propan-2-amine and the like, but it is not limited thereto. The structures of Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, and EDR-176 are shown below.

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

R ¹¹⁵ represents a tetravalent organic group. As a tetravalent organic group, the tetravalent organic group containing an aromatic ring is preferable, and the group represented by following General formula (5) or General formula (6) is more preferable.
General formula (5)
In formula (5), R ¹¹² represents a single bond or a divalent group. And the divalent group is selected from a hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ -and -NHCO- and combinations thereof It is preferable that it is a selected group. R ¹¹² is a single bond or a divalent selected from an alkylene group of 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- and -SO _2- It is more preferable that the group be a single bond, or a single bond, or -CH _2- , -C (CF ₃ ) _2- , -C (CH ₃ ) _2- , -O-, -CO-, -S- and -SO ₂ - divalent radical selected from the group consisting of is more preferable.

General formula (6)

Specific examples of R ¹¹⁵ include tetracarboxylic acid residues remaining after removal of the anhydride group from tetracarboxylic acid dianhydride.
Specifically, the tetracarboxylic acid residue etc. which remain after removal of an anhydride group from the following tetracarboxylic acid dianhydride are mentioned.
Pyromellitic dianhydride (PMDA), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl sulfide tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenyl sulfone tetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3 ', 4,4'-diphenylmethane tetracarboxylic acid dianhydride , 2,2 ', 3,3'-Diphenylmethanetetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenonetetra Carboxylic acid dianhydride, 4,4′-oxydiphthalic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,4,5,7-naphthalenetetracarboxylic acid dianhydride, 2 , 2-bis (3,4-dika Voxyphenyl) 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 acid dianhydride, 1,4,5,6-naphthalenetetracarboxylic acid dianhydride, 2,2 ', 3,3'-diphenyltetracarboxylic acid Acid dianhydride, 3,4,9,10-perylene tetracarboxylic acid dianhydride, 1,2,4,5-naphthalene tetracarboxylic acid dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid Anhydride, 1,8,9,10-phenanthrene tetracarboxylic acid dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxylic acid) Ciphenyl) ethane dianhydride, 1,2,3,4-benzene tetracarboxylic acid dianhydride, and at least one selected from these C 1 to C 6 alkyl and / or C 1 to C 6 alkoxy derivatives Seed of tetracarboxylic acid dianhydride.

Also, tetracarboxylic acid residue remaining tetracarboxylic dianhydride represented by the following from (DAA-1) ~ (DAA -5) after removal of the anhydride groups mentioned as examples of R ^115.

From the viewpoint of solubility in an alkaline developer, at least one of R ¹¹¹ and R ¹¹⁵ preferably has an OH group. More specifically, as R ¹¹¹ , 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2- Bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino) -3-hydroxyphenyl) sulfone, the above (DA-1) to (DA-18) is mentioned as a preferred example, and as R ¹¹⁵ , the above (DAA-1) to (DAA-5) is mentioned as a preferred example Be

R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group.
As the monovalent organic group represented by R ¹¹³ and R ^114, a substituent that improves the solubility in a developer is preferably used.

From the viewpoint of solubility in an aqueous developer, R ¹¹³ and R ¹¹⁴ are preferably a hydrogen atom or a monovalent organic group. The monovalent organic group includes, for example, aryl groups and aralkyl groups having one, two or three, preferably one acidic group bonded to a carbon atom of the aryl group. Specifically, a C6-C20 aryl group which has an acidic group, and a C7-C25 aralkyl group which has an acidic group are mentioned. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group can be mentioned. The acidic group is preferably an OH group.
It is preferable that R ¹¹³ and R ¹¹⁴ be a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl from the viewpoint of solubility in an aqueous developer.

From the viewpoint of solubility in organic solvents, R ¹¹³ and R ¹¹⁴ are preferably monovalent organic groups. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, or an aryl group, and more preferably an alkyl group substituted with an aryl group.
The carbon number of the alkyl group is preferably 1 to 30. The alkyl group may be linear, branched or cyclic. As a linear or branched alkyl group, 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, Examples include octadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, and 2-ethylhexyl group. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. As a polycyclic cyclic alkyl group, for example, an adamantyl group, a norbornyl group, a bornyl group, a camphenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group, and a pinenyl group Groups are mentioned. Among them, a cyclohexyl group is most preferable in terms of coexistence with high sensitivity. Moreover, as an alkyl group substituted by the aryl group, the linear alkyl group substituted by the aryl group mentioned later is preferable.
Specific examples of the aryl group include substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring Naphthacene ring, chrysene ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, Indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolizine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, Enantororin ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring, and a phenazine ring. The benzene ring is most preferred.

In the general formula (2), at least one of R ¹¹³ and R ¹¹⁴ preferably has a polymerizable unsaturated group. According to this, a negative photosensitive resin having better sensitivity and resolution can be obtained. By thus having a polymerizable unsaturated group (in particular, a radically polymerizable group), it is more effective in the case of negative development of a cured film obtained by the production method of the present invention. However, even in the case of negative development, the polymerizable unsaturated group is not essential when a crosslinking agent (particularly, a radically polymerizable compound) is blended.
Examples of the polymerizable unsaturated group include an epoxy group, an oxetanyl group, a group having an ethylenically unsaturated bond, a blocked isocyanate group, an alkoxymethyl group, a methylol group and an amino group. Among them, a group having an ethylenically unsaturated bond is preferable because the sensitivity is good. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a group represented by the following formula (III).

In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, with a methyl group being more preferred.
In Formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, —CH ₂ CH (OH) CH ₂ — or a polyoxyalkylene group having 4 to 30 carbon atoms.
Examples of suitable R ²⁰¹ include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene, octamethylene, dodecamethylene, -CH ₂ CH (OH) CH ₂ - and the like, ethylene, propylene, _{trimethylene, -CH 2 CH (OH) CH} 2 - is preferred.
Particularly preferably, R ²⁰⁰ is methyl and R ²⁰¹ is ethylene.

When the repeating unit of the general formula (2) contains a polymerizable group, the ratio of R ¹¹³ and R ^{114 to} be a polymerizable unsaturated group is preferably 100: It is 0-5: 95, More preferably, it is 100: 0-20: 80, More preferably, it is 100: 0-50: 50.

In the general formula (2), when R ¹¹³ is a hydrogen atom and / or when R ¹¹⁴ is a hydrogen atom, the polyimide precursor forms a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. It may be Examples of such tertiary amine compounds having an ethylenically unsaturated bond include N, N-dimethylaminopropyl methacrylate.

  Moreover, in the case of alkaline development, it is preferable that a polyimide precursor has a fluorine atom in a structural unit from the point which improves resolution. The fluorine atom imparts water repellency to the surface of the film during alkali development, and it is possible to suppress the penetration from the surface. 10 mass% or more is preferable, and, as for the fluorine atom content in a polyimide precursor, 20 mass% or less is preferable from the soluble point with respect to aqueous alkali solution.

  In addition, in order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized. Specifically, as the diamine component, bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane and the like can be mentioned.

  Moreover, in order to improve the storage stability of the composition, the polyimide precursor is sealed at the main chain terminal with an end capping agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound, etc. Is preferred. Among these, it is more preferable to use a monoamine. Examples of monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, and 1-hydroxy-6-aminonaphthalene. Hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-amino Naphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-amino Benzoic acid, 3-aminobenzoic acid, -Aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxy Pyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like can be mentioned. Two or more of these may be used, and a plurality of different end groups may be introduced by reacting a plurality of end capping agents.

The repeating unit represented by the general formula (2) is preferably a repeating unit represented by the general formula (1-1). That is, it is preferable that at least 1 sort (s) of the heterocyclic containing polymer precursor used by this invention is a precursor which has a repeating unit represented by General formula (1-1). Such a structure makes it possible to further widen the exposure latitude.
In general formula (1-1), A ¹ and A ² represent an oxygen atom, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, and R ¹¹³ and R ¹¹⁴ each independently. , A hydrogen atom or a monovalent organic group.

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

  In the polyimide precursor, the repeating structural unit represented by the general formula (2) may be of one type, or of two or more types. Moreover, the structural isomer of the repeating unit represented by General formula (2) may be included. Further, it goes without saying that the polyimide precursor may contain other types of repeating structural units in addition to the repeating unit of the above general formula (2).

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

The weight average molecular weight (Mw) of the polyimide precursor is preferably 10,000 to 50,000, and more preferably 14,000 to 30,000. Further, the number average molecular weight (Mn) is preferably 5,000 to 14,000.
The degree of dispersion of the polyimide precursor is preferably 2.0 or more, and more preferably 2.1 or more. The upper limit of the degree of dispersion of the polyimide precursor is not particularly limited, but is preferably 4.5 or less, more preferably 4.0 or less, still more preferably 3.8 or less, and still more preferably 3.2 or less 3.1 or less is still more preferable, 3.0 or less is still more preferable, 2.95 or less is particularly preferable, and 2.6 or less is most preferable

<< Polybenzoxazole Precursor >>
The polybenzoxazole precursor used in the present invention is not particularly limited as long as it is a compound capable of forming polybenzoxazole, and its structure etc. is not particularly limited, but is preferably a compound represented by the following general formula (3).

General formula (3)
In formula (3), 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 Represents

R ¹²¹ represents a divalent organic group. An aliphatic group or an aryl group is mentioned as a bivalent organic group.
Examples of the divalent aryl group include the following.

In the formula, A represents —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, or —C (CH ₃ ) ₂ — And b represents a divalent group selected from the group consisting of

  As the divalent aliphatic group, a linear aliphatic group is preferable in terms of promoting cyclization at a low temperature. The carbon number of the linear aliphatic group is preferably 2 to 30, more preferably 2 to 25, still more preferably 3 to 20, and still more preferably 4 to 15. , And 5 to 10 are particularly preferable. The linear aliphatic group is preferably an alkylene group. Examples of dicarboxylic acids containing a linear aliphatic group include malonic acid, dimethyl malonic acid, ethyl malonic acid, isopropyl malonic acid, di-n-butyl malonic acid, succinic acid, tetrafluorosuccinic acid, methyl succinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutarate Acid, 3,3-dimethyl glutaric acid, 3-ethyl-3-methyl glutaric acid, adipic acid, octafluoro adipic acid, 3-methyl adipic acid, pimelic acid, 2,2,6,6-tetramethyl pimelic acid , Suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9- Nandioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosane diacid, henicosane diacid, docosandioic acid, trichosandiic acid Acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosane diacid, octacosanedioic acid, nonacosane diacid, triacontandioic acid, hendriacontan diacid, dotriacontanedioic acid, diglycolic acid, etc. The dicarboxylic acid etc. which are represented by a formula are mentioned.

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

R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same meaning as R ¹¹⁵ in the general formula (2), and preferred ranges are also the same.
Further, R ¹²² is preferably a residue of a bisaminophenol derivative represented by the following general formula (A).
Ar (NH ₂ ) ₂ (OH) ₂ (A)
In the formula, Ar is an aryl group.

  Examples of bisaminophenol derivatives of the above general formula (A) include 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, 3,3 ′ -Diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfone, bis (3-amino-4-hydroxyphenyl) methane, 2,2-bis (3-amino) -4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane, bis (4- Amino-3-hydroxyphenyl) methane, 2,2-bis (4-amino-3-hydroxyphenyl) propane, 4,4, '-Diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4 4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene and the like. These bisaminophenols may be used alone or in combination of two or more.

  Among the bisaminophenol derivatives represented by formula (A), bisaminophenol derivatives having the following aryl group are preferred.

_{Wherein, X} 1 _{is, -O -, - S -,} - C (CF 3) 2 -, - CH 2 -, - SO 2 -, - representing the NHCO-. Further, in the above structure, -OH and -NH ₂ contained in the structure of the general formula (A) are mutually bonded in the ortho position (adjacent position).
The bisaminophenol derivative of the above general formula (A) is represented by the following general formula (A-s) from the viewpoint of being able to obtain a polybenzoxazole precursor which is highly transparent to i-ray and which can be cured at low temperature. It is preferable that it is a bisphenol.

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

(In the formula, * represents bonding to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by the above formula (As).)

In the above formula (As), having a substituent at the ortho position of the phenolic hydroxyl group, that is, R ₃ is considered to make the distance between the carbonyl carbon of the amide bond and the hydroxyl group closer and cure at low temperature It is particularly preferable in that the effect of achieving a high degree of cyclization is further enhanced.

Further, in the above formula (A-s), that R ₂ is an alkyl group and R ₃ is an alkyl group is said to have a high degree of transparency to i-line and a high degree of cyclization when cured at low temperature It is particularly preferable in that a polybenzoxazole precursor having sufficient solubility and excellent balance can be obtained when using an aqueous alkaline solution as a developer while maintaining the effect.

Moreover, it is preferable that R < ₁ > is alkylene or substituted alkylene in said Formula (A-s). Specific examples of the alkylene and substituted alkylene for R ₁ include -CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , -CH (CH ₂ CH ₃ )-, -C _{(CH 3) (CH 2 CH} 3) -, - C (CH 2 CH 3) (CH 2 CH 3) -, - CH (CH 2 CH 2 CH 3) -, - C (CH 3) (CH 2 CH ₂ CH ₃ ) —, —CH (CH (CH ₃ ) ₂ ) —, —C (CH ₃ ) (CH (CH ₃ ) ₂ ) —, —CH (CH ₂ CH ₂ CH ₂ CH ₃ ) —, —C _{(CH 3) (CH 2 CH} 2 CH 2 CH 3) -, - CH (CH 2 CH (CH 3) 2) -, - C (CH 3) (CH 2 CH (CH 3) 2) -, - CH _{(CH 2 CH 2 CH 2 CH} 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 2 C _{2 CH 3) -, - CH} (CH 2 CH 2 CH 2 CH 2 CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 2 CH 2 CH 2 CH 3) - but the like Among them, -CH _2- , -CH (CH ₃ )-and -C (CH ₃ ) _2- maintain high transparency to i-line and high cyclization ratio when cured at low temperature. However, it is more preferable at the point which can obtain the polybenzoxazole precursor which has sufficient solubility with respect to not only aqueous alkali solution but solvent, and is excellent in balance.

  As a manufacturing method of the bisamino phenol derivative shown by said Formula (As), paragraph number 0085-0094 of Unexamined-Japanese-Patent No. 2013-256506 and Example 1 (Paragraph number 0189-0190) are referred to, for example The contents of which are incorporated herein.

  Specific examples of the structure of the bisaminophenol derivative represented by the above formula (A-s) include those described in paragraphs [0070] to [0080] of JP-A-2013-256506, the contents of which are incorporated herein by reference. Incorporated into Of course, it is needless to say that it is not limited to these.

  Among them, those shown below are preferable as the bisaminophenol derivative represented by the above formula (A-s).

R ¹²³ and R ¹²⁴ each represent a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a polymerizable unsaturated group. It is preferable that at least one of R ¹²³ and R ¹²⁴ represents a polymerizable unsaturated group in that a negative photosensitive resin having better sensitivity and resolution can be obtained. The polymerizable unsaturated group is the same as described aspects R ¹¹³ and R ¹¹⁴ in formula (2), and preferred ranges are also the same.

The polybenzoxazole precursor may also contain other types of repeating structural units in addition to the repeating unit of the general formula (3) above.
It is preferable that the diamine residue represented by the following general formula (SL) is included as another kind of repeating structural unit from the point which can suppress generation | occurrence | production of the curvature accompanying ring closing.

In the general formula (SL), Z has an a structure and a b structure, R ^1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ^2s is a hydrocarbon group having 1 to 10 carbon atoms And at least one of R ^3s , R ^4s , R ^5s , and R ^6s is an aryl group, and the remainder is a hydrogen atom or an organic group having 1 to 30 carbon atoms, which may be the same or different. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. The mole percentage of the Z moiety is 5 to 95 mole% for the a structure, 95 to 5 mole% for the b structure, and a + b is 100 mole%.

In the general formula (SL), preferable Z includes those in which R ^5s and R ^6s in the b structure are a phenyl group. Moreover, it is preferable that it is 400-4,000, and, as for the molecular weight of the structure shown by general formula (SL), 500-3,000 are more preferable. Molecular weight can be determined by commonly used gel permeation chromatography. By making the said molecular weight into the said range, the elastic modulus after dehydration ring-closing of a polybenzoxazole precursor can be reduced, and the effect which can control curvature, and the effect of improving solubility can be compatible.

When the diamine residue represented by General Formula (SL) is included as another type of repeating structural unit, tetramer remaining after removal of the anhydride group from the tetracarboxylic acid dianhydride is further added in that the alkali solubility is improved. It is preferable to include a carboxylic acid residue as a repeating structural unit. Examples of such tetracarboxylic acid residues include the examples of R ^{115 in} the general formula (2).

  Also, in order to improve the storage stability of the composition, an acid anhydride containing an aliphatic group or a cyclic group having at least one alkenyl group or at least one alkynyl group is used for the terminal amino group of the polybenzoxazole precursor. It is preferable to make it into an amide and cap.

  As such a group derived from an acid anhydride containing an aliphatic group or a cyclic group having at least one alkenyl group or alkynyl group after reaction with an amino group, that is, the end capping group is, for example, The groups shown below can be mentioned. These may be used alone or in combination of two or more.

  In particular, the groups shown below are preferable in that they can improve the storage stability.

The polybenzoxazole precursor includes, for example, a bisaminophenol derivative represented by the general formula (A), a dicarboxylic acid containing R ¹²¹ , and a compound selected from the dicarboxylic acid dichloride and the dicarboxylic acid derivative of the dicarboxylic acid, etc. It can be obtained by reaction.
In addition, when using dicarboxylic acid, in order to raise reaction yield etc., you may use the dicarboxylic acid derivative of the active ester type which made 1-hydroxy 1,2,3- benzotriazole etc. react beforehand.

The weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, preferably 8,000 to 30,000, more preferably 9,000 to 29,000, when used in the composition described later. Preferably it is 10,000-28,000. Further, the number average molecular weight (Mn) is preferably 5,000 to 14,000, more preferably 6,000 to 12,000, and still more preferably 6,500 to 11,200.
The degree of dispersion of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and still more preferably 1.6 or more. The upper limit value of the degree of dispersion of the polybenzoxazole precursor is not particularly limited, but is preferably 2.6 or less, more preferably 2.5 or less, still more preferably 2.4 or less, and still more preferably 2.3 or less. Preferably, 2.2 or less is more preferable.

20-50 mass% of a composition is preferable, and, as for content of the heterocyclic containing polymer precursor in the composition used by this invention, 25-40 mass% is more preferable. The content of the heterocycle-containing polymer precursor in the composition used in the present invention is preferably 70% by mass or more, and more preferably 75% by mass or more, based on the solid content of the composition. The upper limit value is not particularly limited, but the total amount of the heterocycle-containing polymer precursor and the amine generator may be 100% by mass of the solid content of the composition.
The composition used in the present invention may contain only one type of heterocycle-containing polymer precursor, or may contain two or more types. When it contains 2 or more types, it is preferable that a total amount becomes said range. In addition, although both a polyimide precursor and a polybenzoxazole precursor may be included, an embodiment consisting of only one or more types of polyimide precursors and an embodiment consisting only of two or more types of polybenzoxazole precursors are more preferable. preferable.

<Amine generator>
In the present invention, the amine generator is preferably a thermal amine generator and a photoamine generator, and more preferably a thermal amine generator.

Examples of such an amine generator generally include amines which are inactivated by a protecting group such as an alkoxycarbonyl group, nifedipines, salts formed with an amine and an acid, quaternary ammonium salts and the like.
By blending such a compound, the cyclization reaction of the heterocycle-containing polymer can be carried out at a low temperature, and a composition with more excellent stability can be obtained. In addition, since the amine generator used in the present invention does not generate an amine without giving a stimulus, coexistence with the heterocycle-containing polymer precursor can suppress the cyclization of the heterocycle-containing polymer precursor during storage, Excellent storage stability.

<< Thermal amine generator >>
The type and the like of the thermal amine generator is not particularly limited, but it has an acidic compound (A1) which generates an amine when heated to 40 to 250 ° C., and an anion having a pKa 1 of 0 to 4 and an ammonium cation. It is preferable to include at least one selected from ammonium salts (A2). By employing such a compound, the outgassing property can be further improved. Here, pKa1 is a logarithmic expression (−Log ₁₀ Ka) of the dissociation constant (Ka) of the first proton of a polyvalent acid.
By blending such a compound, the cyclization reaction of the heterocycle-containing polymer precursor can be carried out at a low temperature, and a composition with more excellent stability can be obtained. In addition, since the thermal amine generator does not generate an amine unless it is heated, cyclization of the heterocycle-containing polymer precursor during storage can be suppressed even in the presence of the heterocycle-containing polymer precursor, which leads to storage stability. Are better.

Since the thermal amine generator generates amines when heated, the amines generated from these compounds can accelerate the cyclization reaction of the heterocycle-containing polymer precursor, and the heterocycle-containing polymer precursor is cyclized at a low temperature be able to. In addition, these compounds are excellent in stability because the cyclization of the heterocycle-containing polymer precursor hardly progresses without heating even when coexisting with the heterocycle-containing polymer precursor which is cyclized and cured by an amine. The composition can be prepared.
In this specification, 1 g of the compound is collected in a container as an acidic compound, and 50 mL of a mixed solution of ion exchanged water and tetrahydrofuran (mass ratio is water / tetrahydrofuran = 1/4) is added, and it is performed for 1 hour at room temperature. Stir. The solution is a compound having a value of less than 7 when measured at 20 ° C. using a pH (potential hydrogen) meter.

40-250 degreeC is preferable and, as for the amine generation | occurrence | production temperature of the thermal amine generator in this invention, 120-250 degreeC is more preferable. The upper limit of the temperature at which the amine is generated is preferably 240 ° C. or less, more preferably 230 ° C. or less, still more preferably 220 ° C. or less, still more preferably 200 ° C. or less, still more preferably 190 ° C. or less, 180 ° C. or less Particularly preferred. The lower limit of the temperature at which the amine is generated is more preferably 130 ° C. or more, and still more preferably 135 ° C. or more. Amine generation temperature is obtained by heating the thermal amine generator to 250 ° C. at 5 ° C./min in a pressure-resistant capsule using differential scanning calorimetry, reading the peak temperature of the exothermic peak with the lowest temperature, peak temperature as amine generation temperature It can be measured as
If the temperature at which the amine of the thermal amine generator is generated is 40 ° C. or more, the amine is less likely to be generated during storage, so that a composition with more excellent stability can be prepared. If the temperature for generating the amine of the thermal amine generator is 250 ° C. or less, the cyclization temperature of the heterocycle-containing polymer precursor can be lowered.

In the present invention, the amine from which the thermal amine generator is generated is preferably a secondary amine or a tertiary amine, more preferably a tertiary amine. Since the tertiary amine is highly basic, the cyclization temperature of the heterocycle-containing polymer precursor can be further lowered. The boiling point of the amine generated by the amine generator is preferably 80 ° C. or more, more preferably 100 ° C. or more, and still more preferably 140 ° C. or more.
Moreover, as for the molecular weight of the amine to generate | occur | produce, 60-300 are preferable. The lower limit is more preferably 100 or more, and still more preferably 120 or more. The upper limit is more preferably 250 or less, still more preferably 200 or less. In addition, the value of molecular weight is a theoretical value calculated | required from structural formula.

  In the present invention, the acidic compound (A1) preferably contains one or more selected from an ammonium salt and a compound represented by the general formula (1A) described later.

  In the present invention, the ammonium salt (A2) is preferably an acidic compound. The ammonium salt (A2) may be a compound containing an acidic compound which generates an amine when heated to 40 ° C. to 250 ° C. (preferably 120 to 200 ° C.), or 40 ° C. to 250 ° C. (preferably) It may be a compound which does not contain an acidic compound which generates an amine when heated to 120 to 200 ° C.

<<< Ammonia salt >>>
In the present invention, the ammonium salt means a salt of an ammonium cation represented by the general formula (11) or the general formula (12) and an anion. The anion may be covalently bonded to any part of the ammonium cation, or may be outside the molecule of the ammonium cation, but is preferably outside the molecule of the ammonium cation. In addition, that the anion is outside the molecule of the ammonium cation means that the ammonium cation and the anion are not bonded via a covalent bond. Hereinafter, the anion outside the molecule of the cation part is also referred to as a counter anion.
In formulas (11) and (12), R ^{1N to} R ^6N each independently represent a hydrogen atom or a hydrocarbon group, and R ^7N represents a hydrocarbon group. R ^1N and R ^2N , R ^3N and R ^4N , R ^5N and R ^6N , and R ^5N and R ^7N may be combined to form a ring.

In the present invention, the ammonium salt preferably has an anion having a pKa of 0 to 4 and an ammonium cation. As for the upper limit of pKa1 of the anion, 3.5 or less is more preferable, and 3.2 or less is more preferable. The lower limit is more preferably 0.5 or more, and still more preferably 1.0 or more. When the pKa1 of the anion is in the above range, the heterocycle-containing polymer precursor can be cyclized at a low temperature, and the stability of the composition can be further improved. If pKa1 is 4 or less, the stability of the thermal amine generator is good, generation of amine without heating can be suppressed, and the stability of the composition is good. If pKa1 is 0 or more, the generated amine is hardly neutralized, and the cyclization efficiency of the heterocycle-containing polymer precursor is good.
The type of the anion is preferably one selected from a carboxylate anion, a phenol anion, a phosphate anion and a sulfate anion, and a carboxylate anion is more preferred because both the stability of the salt and the thermal decomposition are compatible. That is, the ammonium salt is more preferably a salt of ammonium cation and carboxylic acid anion.
The carboxylate anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxy groups, and more preferably an anion of a divalent carboxylic acid. According to this aspect, it is possible to provide a thermal amine generator capable of further improving the stability, the curability and the developability of the composition. In particular, the stability, the curability and the developability of the composition can be further improved by using the anion of a divalent carboxylic acid.
In the present invention, the carboxylate anion is preferably an anion of a carboxylic acid having a pKa 1 of 4 or less. As for pKa1, 3.5 or less is more preferable, and 3.2 or less is further more preferable. According to this aspect, the stability of the composition can be further improved.
Here, pKa1 represents the logarithm of the reciprocal of the first dissociation constant of the acid, and is determined by Determination of Organic Structures by Physical Methods (author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; Editing: Braude, The values described in EA, Nachod, FC; Academic Press, New York, 1955) and Data for Biochemical Research (Author: Dawson, RMC et al .; Oxford, Clarendon Press, 1959) can be referred to. For compounds not described in these documents, values calculated from the structural formula using software of ACD / pKa (manufactured by ACD / Labs) are used.

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

In the present invention, the electron withdrawing group means that the Hammett's substituent constant σm exhibits a positive value. Here, σ m is a review by Tono Yuya, Journal of Organic Synthetic Chemistry, Vol. 23, No. 8 (1965), P.I. 631-642. In addition, the electron withdrawing group of this invention is not limited to the substituent described in the said literature.
Examples of the substituent having a positive value of σ m include, for example, CF ₃ group (σ m = 0.43), CF ₃ CO group (σ m = 0.63), HC≡C group (σ m = 0.21) , CH ₂ CHCH group (σ m 0.06 0.06), Ac group (σ m = 0. 0.38), MeOCO group (σ m = 0. 0.37), MeCOCH CH CH group (σ m = 0. 0.21), PhCO group (σ m And H ₂ NCOCH ₂ (σ m = 0.06). Here, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group.

In the present invention, EWG preferably represents a group represented by the following general formulas (EWG-1) to (EWG-6).
In the formula, 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 represents an aryl group.
1-30 are preferable, as for carbon number of an alkyl group, 1-20 are more preferable, and 1-10 are more preferable. The alkyl group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear. The alkyl group may have a substituent or may be unsubstituted. Examples of the substituent include those described for the substituent which the organic group represented by A ¹ described later may have. As a substituent, a carboxy group is preferable.
2-30 are preferable, as for carbon number of an alkenyl group, 2-20 are more preferable, and 2-10 are more preferable. The alkenyl group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear. The alkenyl group may have a substituent or may be unsubstituted. Examples of the substituent include those described for the substituent which the organic group represented by A ¹ described later may have. As a substituent, a carboxy group is preferable.
6-30 are preferable, as for carbon number of an aryl group, 6-20 are more preferable, and 6-12 are more preferable. The aryl group may have a substituent or may be unsubstituted. Examples of the substituent include those described for the substituent which the organic group represented by A ¹ described later may have. As a substituent, a carboxy group is preferable.

In the present invention, the carboxylate anion is also preferably one represented by the following general formula (X).
In the general formula (X), L ¹⁰ represents a single bond or a divalent linking group selected from an alkylene group, an alkenylene group, an arylene group, -NR ^X -and a combination thereof, and R ^X represents a hydrogen atom , An alkyl group, an alkenyl group or an aryl group.

The alkylene groups L ¹⁰ represents preferably 1 to 30, more preferably from 1 to 20, 1 to 10 is more preferred. The alkylene group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear. The alkylene group may have a substituent or may be unsubstituted. Examples of the substituent include those described for the substituent which the organic group represented by A ¹ described later may have.
The number of carbon atoms of the alkenylene group L ¹⁰ represents preferably 2 to 30, more preferably from 2 to 20, more preferably 2 to 10. The alkenylene group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear. The alkenylene group may have a substituent or may be unsubstituted. Examples of the substituent include those described for the substituent which the organic group represented by A ¹ described later may have.
L ¹⁰ carbon atoms of the arylene group represented by is preferably 6 to 30, more preferably 6 to 20, 6 to 12 is more preferable. The arylene group may have a substituent or may be unsubstituted. Examples of the substituent include those described for the substituent which the organic group represented by A ¹ described later may have.

Number of carbon atoms of the alkyl group R ^X represents preferably 1 to 30, more preferably from 1 to 20, 1 to 10 is more preferred. The alkyl group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear. The alkyl group may have a substituent or may be unsubstituted. Examples of the substituent include those described for the substituent which the organic group represented by A ¹ described later may have.
The number of carbon atoms of the alkenyl group R ^X represents preferably 2 to 30, more preferably from 2 to 20, more preferably 2 to 10. The alkenyl group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear. The alkenyl group may have a substituent or may be unsubstituted. Examples of the substituent include those described for the substituent which the organic group represented by A ¹ described later may have.
R ^X number of carbon atoms of the aryl group represented by is preferably 6 to 30, more preferably 6 to 20, 6 to 12 is more preferable. The aryl group may have a substituent or may be unsubstituted. Examples of the substituent include those described for the substituent which the organic group represented by A ¹ described later may have.

  Specific examples of carboxylic acid anions include maleic acid anion, phthalic acid anion, N-phenyliminodiacetic acid anion and oxalic acid anion. These can be preferably used.

The ammonium cation is preferably represented by any one of formulas (Y1-1) to (Y1-6).

In the above formula, R ¹⁰¹ represents an n-valent organic group,
R ^{102 to} R ¹¹¹ each independently represent a hydrogen atom or a hydrocarbon group,
R ¹⁵⁰ and R ¹⁵¹ each independently represent a hydrocarbon group,
R ¹⁰⁴ and R ¹⁰⁵ , R ¹⁰⁴ and R ¹⁵⁰ , R ¹⁰⁷ and R ¹⁰⁸ , and R ¹⁰⁹ and R ¹¹⁰ may be combined with each other to form a ring,
Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group,
n represents an integer of 1 or more,
m represents an integer of 0 to 5;

R ¹⁰¹ represents an n-valent organic group. Examples of monovalent organic groups include alkyl groups, alkylene groups, and aryl groups. Examples of the divalent or higher organic group include ones in which one or more hydrogen atoms are removed from a monovalent organic group to form an n-valent group.
R ¹⁰¹ is preferably an aryl group. Specific examples of the aryl group include those described for Ar ¹⁰ described later.

R ^{102 to} R ¹¹¹ each independently represent a hydrogen atom or a hydrocarbon group, and R ¹⁵⁰ and R ¹⁵¹ each independently represent a hydrocarbon group.
The hydrocarbon group represented by R ^{102 to} R ¹¹¹ , R ¹⁵⁰ and R ¹⁵¹ is preferably an alkyl group, an alkenyl group or an aryl group. The alkyl group, the alkenyl group and the aryl group may further have a substituent. Examples of the substituent include those described for the substituent which the organic group represented by A ¹ described later may have.

1-30 are preferable, as for carbon number of an alkyl group, 1-20 are more preferable, and 1-10 are more preferable. The alkyl group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear. The alkyl group may have a substituent or may be unsubstituted.
2-30 are preferable, as for carbon number of an alkenyl group, 2-20 are more preferable, and 2-10 are more preferable. The alkenyl group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear. The alkenyl group may have a substituent or may be unsubstituted.
6-30 are preferable, as for carbon number of an aryl group, 6-20 are more preferable, and 6-12 are more preferable. The aryl group may have a substituent or may be unsubstituted.

Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group.
6-30 are preferable, as for carbon number of an aryl group, 6-20 are more preferable, and 6-12 are more preferable. The aryl group may have a substituent or may be unsubstituted.

R ¹⁰⁴ and R ¹⁰⁵ , R ¹⁰⁴ and R ¹⁵⁰ , R ¹⁰⁷ and R ¹⁰⁸ , and R ¹⁰⁹ and R ¹¹⁰ may bond to each other to form a ring. Examples of the ring include cyclic aliphatic (non-aromatic hydrocarbon ring), aromatic ring, heterocyclic ring and the like. The ring may be monocyclic or polycyclic. As the linking group in the case where the above groups are combined to form a ring, -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aryl group and a combination thereof are preferable. The bivalent coupling group chosen is mentioned. Specific examples of the ring formed include pyrrolidine ring, pyrrole ring, piperidine ring, pyridine ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, pyrazine ring, morpholine ring, thiazine ring, indole ring, isoindole Rings, benzimidazole rings, purine rings, quinoline rings, isoquinoline rings, quinoxaline rings, cinnoline rings, carbazole rings and the like.

In the present invention, the ammonium cation preferably has a structure represented by formula (Y1-1) or (Y1-2), is represented by formula (Y1-1) or (Y1-2), and R ¹⁰¹ is an aryl group. A certain structure is more preferable, and a structure which is represented by a formula (Y1-1) and in which R ¹⁰¹ is an aryl group is particularly preferable. That is, in the present invention, the ammonium cation is more preferably represented by the following general formula (Y).
In general formula (Y), Ar ¹⁰ represents an aryl group, R ^{11 to} R ¹⁵ each independently represent a hydrogen atom or a hydrocarbon group, and R ¹⁴ and R ¹⁵ are combined with each other to form a ring N may represent an integer of 1 or more.

Ar ¹⁰ represents an aryl group. Specific examples of the aryl group include substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring Naphthacene ring, chrysene ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, Indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolizine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, Enantororin ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring, and a phenazine ring. Among them, from the viewpoint of storage stability and high sensitivity, a benzene ring, a naphthalene ring, an anthracene ring, a phenothiazine ring, or a carbazole ring is preferable, and a benzene ring or a naphthalene ring is most preferable.
As an example of the substituent which the aryl group may have, those described for the substituent which the organic group represented by A ¹ described later may have can be mentioned.

Each of R ¹¹ and R ¹² independently represents a hydrogen atom or a hydrocarbon group. The hydrocarbon group is not particularly limited, but an alkyl group, an alkenyl group or an aryl group is preferable.
R ¹¹ and R ¹² are preferably hydrogen atoms.

1-30 are preferable, as for carbon number of an alkyl group, 1-20 are more preferable, and 1-10 are more preferable. The alkyl group may be linear, branched or cyclic.
As a linear or branched alkyl group, 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, Examples include ocdadecyl, 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 the monocyclic alkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group. Examples of polycyclic cyclic alkyl groups include an adamantyl group, norbornyl group, bornyl group, camphenyl group, decahydronaphthyl group, tricyclodecanyl group, tetracyclodecanyl group, camphoroyl group, dicyclohexyl group and pinenyl group Can be mentioned. Among them, a cyclohexyl group is most preferable in terms of coexistence with high sensitivity.
2-30 are preferable, as for carbon number of an alkenyl group, 2-20 are more preferable, and 2-10 are more preferable. The alkenyl group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear.
6-30 are preferable, as for carbon number of an aryl group, 6-20 are more preferable, and 6-12 are more preferable.

R ¹³ to R ¹⁵ represents a hydrogen atom or a hydrocarbon group.
Examples of the hydrocarbon group include a hydrocarbon group described for R ^11, R ¹² described above. In particular, R ^{13 to} R ¹⁵ are preferably an alkyl group, and preferred embodiments are also the same as described for R ¹¹ and R ¹² .

R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring. Examples of the ring include cyclic aliphatic (non-aromatic hydrocarbon ring), aromatic ring, heterocyclic ring and the like. The ring may be monocyclic or polycyclic. The linking group when R ⁴ and R ⁵ combine to form a ring is composed of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aryl group and a combination thereof The bivalent coupling group chosen from a group is mentioned. Specific examples of the ring formed include pyrrolidine ring, pyrrole ring, piperidine ring, pyridine ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, pyrazine ring, morpholine ring, thiazine ring, indole ring, isoindole Rings, benzimidazole rings, purine rings, quinoline rings, isoquinoline rings, quinoxaline rings, cinnoline rings, carbazole rings and the like.

In R ^{13 to} R ¹⁵ , R ¹⁴ and R ¹⁵ are bonded to each other to form a ring, or alternatively, R ¹³ is a linear alkyl group having 5 to 30 carbon atoms (more preferably 6 to 18 carbon atoms) It is preferable that R ¹⁴ and R ¹⁵ be each independently an alkyl group having 1 to 3 carbon atoms (more preferably 1 or 2 carbon atoms). According to this aspect, it is possible to easily generate an amine species having a high boiling point.
^Further, R 13 ^{to R 15,} from the viewpoint of the basic and the boiling point of the amine species ^generated, it is preferable that the total number of carbon atoms of ^{R 13} and ^{R 14} and ^{R 15} is 7-30, and 10-20 Is more preferred.
Moreover, the reason that the high amine species boiling-prone chemical formula weight of ^"-NR 13 ^R 14 ^{R 15} 'in formula (Y) is preferably 80～2,000, 100-500 are more preferred.

On the other hand, as an embodiment for further improving the adhesion to a copper wiring, in the general formula (Y), R ¹³ and R ¹⁴ are a methyl group or an ethyl group, and R ¹⁵ is a linear chain having 5 or more carbon atoms And a branched or cyclic alkyl group or an aryl group. In the embodiment, R ¹³ and R ¹⁴ are methyl groups, R ¹⁵ is a linear alkyl group having 5 to 20 carbon atoms, a branched alkyl group having 6 to 17 carbon atoms, and a cyclic alkyl group having 6 to 10 carbon atoms. Or a phenyl group is preferable, R ¹³ and R ¹⁴ are a methyl group, R ¹⁵ is a linear alkyl group having 5 to 10 carbon atoms, a branched alkyl group having 6 to 10 carbon atoms, and 6 to 8 carbon atoms More preferably, it is a cyclic alkyl group or a phenyl group. By reducing the hydrophobicity of the amine species in this manner, it is possible to more effectively suppress the reduction in the affinity between the copper surface and the polyimide even when the amine is attached onto the copper wiring. In the present embodiment, preferred ranges of Ar ¹⁰ , R ¹¹ , R ¹² and n are the same as described above.

<<< Compound Represented by General Formula (1A) >>
In the present invention, the acidic compound is also preferably a compound represented by the following general formula (1A). This compound is acidic at room temperature but is denatured by decarboxylation or dehydrative cyclization of the carboxy group upon heating, whereby the amine site that has been neutralized and inactivated becomes basic. It becomes. The general formula (1A) will be described below.

General formula (1A)
In General Formula (1A), A ¹ represents a p-valent organic group, R ¹ represents a monovalent organic group, L ¹ represents a (m + 1) -valent organic group, and m represents an integer of 1 or more. , P represents an integer of 1 or more.

In general formula (1A), A ¹ represents a p-valent organic group. As an organic group, an aliphatic group, an aryl group, etc. are mentioned, An aryl group is preferable. By making A ^{1 an} aryl group, it is possible to easily generate an amine having a high boiling point at a lower temperature. By raising the boiling point of the generated amine, volatilization or decomposition by heating during curing of the heterocycle-containing polymer precursor can be suppressed, and cyclization of the heterocycle-containing polymer precursor can proceed more effectively.
As a monovalent | monohydric aliphatic group, an alkyl group, an alkenyl group etc. are mentioned, for example.
1-30 are preferable, as for carbon number of an alkyl group, 1-20 are more preferable, and 1-10 are more preferable. The alkyl group may be linear, branched or cyclic. The alkyl group may have a substituent or may be unsubstituted. Specific examples of the alkyl group include methyl group, ethyl group, tert-butyl group, dodecyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, adamantyl group and the like.
2-30 are preferable, as for carbon number of an alkenyl group, 2-20 are more preferable, and 2-10 are more preferable. The alkenyl group may be linear, branched or cyclic. The alkenyl group may have a substituent or may be unsubstituted. As an alkenyl group, a vinyl group, a (meth) allyl group, etc. are mentioned.
Examples of the divalent or higher aliphatic group include groups in which one or more hydrogen atoms have been removed from the above-mentioned monovalent aliphatic group.
The aryl group may be monocyclic or polycyclic. The aryl group may be a heteroaryl group containing a heteroatom. The aryl group may have a substituent or may be unsubstituted. No substitution is preferred. Specific examples of the aryl group include benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthylene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene ring, Triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzo Thiophene ring, isobenzofuran ring, quinolizine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, Antoren ring, chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring, and include phenazine ring, a benzene ring is most preferred.
In the aryl group, a plurality of aromatic rings may be linked via a single bond or a linking group described later. As the linking group, for example, an alkylene group is preferable. The alkylene group is preferably linear or branched. Specific examples of the aryl group in which a plurality of aromatic rings are linked via a single bond or a linking group include biphenyl, diphenylmethane, diphenylpropane, diphenylisopropane, triphenylmethane, tetraphenylmethane and the like.

Examples of the substituent which the organic group represented by A ¹ may have include, for example, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; methoxy group, ethoxy group and tert-butoxy group Alkoxy group; aryloxy group such as phenoxy group and p-tolyloxy group; alkoxycarbonyl group such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; acyloxy group such as acetoxy group, propionyloxy group and benzoyloxy group; acetyl group Acyl groups such as benzoyl, isobutyryl, acryloyl, methacryloyl and methoxalyl; alkylsulfanyl such as methylsulfanyl and tert-butylsulfanyl; phenylsulfanyl and p-tolylsulfani Arylsulfanyl groups such as alkyl group; linear or branched alkyl groups such as methyl group, ethyl group, tert-butyl group and dodecyl group; halogenated alkyl groups such as fluorinated alkyl group; cyclopentyl group, cyclohexyl group, Cyclic alkyl groups such as cycloheptyl group and adamantyl group; aryl groups such as phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group and phenanthryl group; hydroxy group; carboxy group; formyl group Group; cyano group; alkylaminocarbonyl group; arylaminocarbonyl group; sulfonamide group; silyl group; amino group; monoalkylamino group; dialkylamino group; arylamino group; diarylamino group; It can be mentioned.

L ¹ represents a (m + 1) -valent linking group. The linking group is not particularly limited, and -COO-, -OCO-, -CO-, -O-, -S-, -SO-, -SO _2- , an alkylene group (preferably having 1 to 10 carbon atoms) Chain or branched alkylene group), a cycloalkylene group (preferably a cycloalkylene group having 3 to 10 carbon atoms), an alkenylene group (preferably a linear or branched alkenylene group having 2 to 10 carbon atoms), and a plurality of these are linked A linking group etc. can be mentioned. The total carbon number of the linking group is preferably 3 or less. The linking group is preferably an alkylene group, a cycloalkylene group or an alkenylene group, more preferably a linear or branched alkylene group, still more preferably a linear alkylene group, particularly preferably an ethylene group or a methylene group, and most preferably a methylene group.

R ¹ represents a monovalent organic group. Examples of monovalent organic groups include aliphatic groups and aryl groups. As the aliphatic group and the aryl group, those described in the above A ¹ can be mentioned. The monovalent organic group represented by R ¹ may have a substituent.
R ¹ is preferably a group having a carboxy group. That is, R ¹ is preferably a group represented by the formula.
-L ^2- (COOH) _n
In the formula, L ² represents a (n + 1) -valent linking group, and n represents an integer of 1 or more.
Examples of the linking group represented by L ² include the groups described for L ¹ described above, and the preferred range is also the same, with an ethylene group or a methylene group being particularly preferred, and a methylene group being most preferred.
n represents an integer of 1 or more, preferably 1 or 2, and more preferably 1. The upper limit of n is the maximum number of substituents that the linking group represented by L ² can take. If n is 1, heating at a temperature lower than the maximum heating temperature tends to generate a tertiary amine having a high boiling point. Furthermore, the stability of the composition can be improved.

m represents an integer of 1 or more, preferably 1 or 2, and more preferably 1. The upper limit of m is the maximum number of substituents that the linking group represented by L ¹ can take. When m is 1, heating at a temperature lower than the maximum heating temperature tends to generate a tertiary amine having a high boiling point. Furthermore, the stability of the composition can be improved.
p represents an integer of 1 or more, preferably 1 or 2, and more preferably 1. The upper limit of p is the maximum number of substituents that the organic group represented by A ¹ can take. If p is 1, heating at a temperature lower than the maximum heating temperature tends to generate a tertiary amine having a high boiling point.

In the present invention, the compound represented by General Formula (1A) is preferably a compound represented by the following General Formula (1a).
General formula (1a)
In Formula (1a), A ¹ represents a p-valent organic group, L ¹ represents a (m + 1) -valent linking group, L ² represents a (n + 1) -valent linking group, and m is an integer of 1 or more N represents an integer of 1 or more, and p represents an integer of 1 or more.
A ¹ , L ¹ , L ² , m, n and p in the general formula (1a) are as defined in the general formula (1A), and preferred ranges are also the same.

In the present invention, the compound represented by the general formula (1A) is preferably N-aryliminodiacetic acid. In the N-aryliminodiacetic acid, A ¹ in the general formula (1A) is an aryl group, L ¹ and L ² are methylene groups, m is 1, n is 1 and p is 1 It is a compound. N-aryliminodiacetic acid tends to generate a tertiary amine having a high boiling point at 120 to 200 ° C.

Although the specific example of the thermal amine generator in this invention is described below, this invention is not limited to these. These can be used alone or in combination of two or more. Me in the following formulas represents a methyl group. Among the compounds shown below, (A-1) to (A-11), (A-18) and (A-19) are compounds represented by the above formula (1). Among the compounds shown below, (A-1) to (A-11) and (A-18) to (A-26) are more preferable, and (A-1) to (A-9) and (A-18) are preferable. ) To (A-21), (A-23) and (A-24) are more preferable.
In addition, from the viewpoint of improving adhesion to copper, (A-18) to (A-26) and (A-38) to (A-43) are preferable, and (A-26) and (A-38) are preferable. ) To (A-43) are more preferable.

<< Photo amine generator >>
The photoamine generator can be suitably used in the negative type since the base generated by exposure to light serves as a catalyst for curing the heterocycle-containing polymer precursor by heating.

  In the present invention, known photoamine generators can be used. For example, M. Shirai, and M. Tsunooka, Prog. Polym. Sci. , 21, 1 (1996); Masahiro Tsukaoka, polymer processing, 46, 2 (1997); Kutal, Coord. Chem. Rev. , 211, 353 (2001); Kaneko, A. Sarker, and D. Neckers, Chem. Mater. , 11, 170 (1999); Tachi, M. Shirai, and M. Tsunooka, J. et al. Photopolym. Sci. Technol. , 13, 153 (2000); Winkle, and K. Graziano, J. et al. Photopolym. Sci. Technol. , 3, 419 (1990); Tsunooka, H. Tachi, and S. Yoshitaka, J. et al. Photopolym. Sci. Technol. , 9, 13 (1996); Suyama, H. et al. Araki, M. Shirai, J. et al. Photopolym. Sci. Technol. , 19, 81 (2006), such as those having a structure such as an ammonium salt, or those in which the amidine moiety is latent by forming a salt with a carboxylic acid, the amine forms a salt And ionic compounds neutralized by the reaction, and non-ionic compounds such as carbamate derivatives, oxime ester derivatives, acyl compounds and the like in which the base component is made latent by urethane bonds or oxime bonds.

Examples of the amine generated from the photoamine generator include monoamines, polyamines such as diamines, and amidines.
The generated amine is preferably a diamine or an aliphatic amine. Such an amine has a strong catalytic action on the imidization of a heterocycle-containing polymer precursor or the dehydration condensation reaction in oxazolization, and the addition of a smaller amount of the amine exerts a catalytic effect on the dehydration condensation reaction at a lower temperature, etc. Because it is possible. That is, since the catalytic effect of the generated amine is large, the appearance sensitivity of the composition is improved.
As the amine according to the present invention, for example, a base generator having a cinnamic acid amide structure as disclosed in JP-A-2009-80452 and WO2009 / 123122, JP-A-2006-189591 and A base generator having a carbamate structure as disclosed in JP-A-2008-247747, and an oxime structure and a carbamoyl oxime structure as disclosed in JP-A-2007-249013 and JP-A-2008-003581 Although an amine etc. are mentioned, it is not limited to these, In addition, the structure of a well-known amine can be used.

Hereinafter, the photoamine generator which can be used in the present invention will be described with reference to specific examples.
Examples of the ionic compound include those of the following structural formula.

  Examples of the acyl compound include compounds as shown in the following formula.

  Moreover, as a photoamine generator, the compound shown to the following general formula (PB-1) is mentioned, for example.

(In formula (PB-1), R ⁴¹ and R ⁴² each independently represent a hydrogen atom or an organic group, and may be the same or different, provided that at least one of R ⁴¹ and R ⁴² Is an organic group, or R ⁴¹ and R ⁴² may combine to form a ring structure, and may contain a hetero atom bond, R ⁴³ and R ⁴⁴ are each independently Hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato group, or an organic group, may be different even in the same ^{.R 45, R 46,} R ⁴⁷ and ^{R 48} are each independently a hydrogen atom, a halogen atom, a hydroxyl Mercapto group, sulfide group, silyl group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, ammonio group, or organic group Or two or more of R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ may be combined to form a ring structure, and the hetero atoms of A bond may be included, and R ⁴⁹ is a hydrogen atom or a protective group which can be deprotected by heating and / or irradiation of electromagnetic waves.)

  Although the specific example of Formula (PB-1) is given to the following, it is not limited to this.

  In addition, as the photoamine generator, compounds described in paragraph Nos. 0185 to 0188, 0199 to 0200 and 0202 of JP 2012-93746A, and compounds described in paragraph No. 0022 to 0069 of JP 2013-194205A. The compounds described in paragraphs 0026 to 0074 of JP 2013-204019, and the compounds described in paragraph 0052 of International Publication WO 2010/064631 are cited as examples, the contents of which are incorporated herein. Be

When using an amine generator, as for content of the amine generator in a composition, 0.1-50 mass% is preferable with respect to the total solid of a composition. As for a minimum, 0.5 mass% or more is more preferable, and 1 mass% or more is further more preferable. The upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less.
Moreover, it is preferable that an amine generator is included in the ratio of 0.01-45 mass% with respect to the total amount of a polyimide precursor and a polybenzoxazole precursor. The lower limit value of the amine generator to the total amount of the polyimide precursor and the polybenzoxazole precursor is more preferably 0.2% by mass or more, still more preferably 0.5% by mass or more, and 1.0% by mass or more. preferable. 35.0 mass% or less is more preferable, 28.0 mass% or less is further more preferable, 12 mass% or less is further more preferable, and the ratio of 6.0 mass% or less is still more preferable. By setting it as the said range, the effect of this invention is exhibited more effectively. In particular, by setting the amount of the amine generator to 6.0% by mass or less, the amine generator hardly remains in the cured film, and the outgas component can be further reduced. Further, by setting the amount of the amine generator to 0.2% by mass or more, curing can be further promoted and the outgas component can be reduced.
The amine generator can be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount is the said range.

  The composition used in the present invention may or may not use another thermal base generator in addition to the amine generator. The composition in the present invention may be configured to be substantially free of other thermal base generators. Substantially free means that it is 0.1 mass% or less of the quantity of the amine generator contained in a composition, for example.

The composition used in the present invention preferably contains no amine having a conjugated acid pKa of 8 or more. Here, the composition does not contain an amine having a conjugated acid pKa of 8 or more in addition to the case where it contains no amine having a conjugated acid pKa of 8 or more in the composition, it also includes the case containing substantially no amine. . Substantially means including in the range which does not deviate from the meaning of the present invention, for example, when it is 0.001 mass% or less of the amine generating agent contained in a composition, or when it is below a detection limit It can be said that it does not contain substantially.
Thus, the amine content of a cured film can be adjusted more easily by not including an amine having a pKa of 8 or more of the conjugate acid in the composition before initiating the cyclization reaction of the heterocycle-containing polymer precursor.
Furthermore, the composition in the present invention is preferably substantially free of an amine before heating. Substantially includes the case of including within the scope of the present invention without departing from the scope of the present invention, for example, substantially not including when it is 0.001% by mass or less of the amine generator contained in the composition It can be said that.

<Other ingredients contained in the composition>
If the composition used in the present invention contains a heterocycle-containing polymer precursor and an amine generator, the other components are not particularly defined, but other components are appropriately blended depending on the application etc. be able to. In particular, the composition used in the present invention is preferably a photosensitive resin composition, but is not necessarily limited to the use having photosensitivity.
The first embodiment of the photosensitive resin composition in the present invention comprises a heterocycle-containing polymer precursor and a radical photopolymerization initiator. Such a photosensitive resin composition is preferably used as a negative photosensitive resin composition. When used as a negative photosensitive resin composition, it is preferable that the heterocycle-containing polymer precursor has a polymerizable unsaturated group or contains a crosslinking agent. When the photosensitive resin composition is a negative photosensitive resin composition, it is preferable that the crosslinking agent contains a compound having an ethylenically unsaturated bond.
The second embodiment of the photosensitive resin composition in the present invention comprises a heterocycle-containing polymer precursor and a photoacid generator. Such a photosensitive resin composition is preferably used as a positive photosensitive resin composition. When used as a positive photosensitive resin composition, it is preferable to include a curable composition. When the photosensitive resin composition is a positive photosensitive resin composition, the crosslinking agent is selected from compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxetane compound and a benzoxazine compound At least one compound is preferred.
Furthermore, the negative photosensitive resin composition may contain a sensitizer, a polymerization inhibitor and the like. It goes without saying that other components may also be included.
On the other hand, the positive photosensitive resin composition may contain a resin containing a phenolic OH group. It goes without saying that other components may also be included.
Details of these components will be described later.
In particular, in the case of a positive photosensitive resin composition, the heterocycle-containing polymer precursor preferably contains a polybenzoxazole precursor.
The composition used in the present invention may also contain a closed ring polyimide, polybenzoxazole and the like.

The content of the heterocycle-containing polymer precursor in the composition used in the present invention is preferably 20 to 100% by mass, more preferably 50 to 99% by mass, and 70 to 98% by mass with respect to the total solids of the composition. Further preferred is 80 to 95% by mass.
Hereinafter, the component which the composition used by this invention may contain is demonstrated. It goes without saying that the present invention may contain other components than these, and these components are not essential.

<Crosslinking agent>
The composition used in the present invention is exemplified as a preferred embodiment that contains a crosslinking agent. By including a crosslinking agent, the cyclization reaction at a low temperature of the heterocycle-containing polymer precursor can proceed more effectively. Furthermore, the cured film which was more excellent in heat resistance can be formed by containing a crosslinking agent. In addition, pattern formation by photolithography can also be performed.
When it mix | blends, 1-40 mass% is preferable with respect to the total amount of a heterocyclic polymer precursor in a composition, and, as for content of a crosslinking agent, 10-30 mass% is more preferable. The crosslinking agent may be used alone or in combination of two or more. When using 2 or more types of crosslinking agents, it is preferable that a total amount becomes said range.

The crosslinking agent is a compound having a crosslinking group, and a known compound which can be crosslinked by a radical, an acid, a base or the like can be used. The crosslinkable group is a group capable of undergoing a crosslinking reaction by the action of an actinic ray, radiation, radical, acid or base, and a preferred example is a group having an ethylenically unsaturated bond, a hydroxymethyl group Acyloxymethyl group, alkoxymethyl group, epoxy group, oxetanyl group, benzoxazolyl group can be mentioned. The compound having an ethylenically unsaturated bond to be used in the present invention is more preferably a compound having two or more ethylenic unsaturated groups, and further preferably a compound having two to six ethylenic unsaturated groups. Particularly preferred is a compound containing 2 to 4 ethylenically unsaturated groups.
The crosslinking agent may be in any chemical form, such as, for example, monomers, prepolymers, oligomers and mixtures thereof and multimers thereof. The compound having an ethylenically unsaturated bond is preferably a monomer.

In the present invention, a monomer type crosslinking agent (hereinafter, also referred to as a crosslinking monomer) is a compound different from the polymer compound. The crosslinkable monomer is typically a low molecular weight compound, preferably a low molecular weight compound having a molecular weight of 2,000 or less, more preferably a low molecular weight compound having a molecular weight of 1,500 or less, and a molecular weight of 900 or less It is more preferable that it is a low molecular weight compound of The molecular weight of the crosslinkable monomer is usually 100 or more.
The oligomer type crosslinking agent is typically a polymer of relatively low molecular weight, preferably a polymer in which 10 to 100 crosslinking monomers are bonded. As a molecular weight, a weight average molecular weight is preferably 2,000 to 20,000, more preferably 2,000 to 15,000, and most preferably 2,000 to 10,000.

In the present invention, the functional group number of the crosslinking agent means the number of crosslinkable groups in one molecule.
The crosslinking agent preferably contains at least one bifunctional or more crosslinking agent containing two or more crosslinking groups, and more preferably includes at least one trifunctional or more crosslinking agent, from the viewpoint of resolution. The upper limit of the crosslinkable group is not particularly limited, but is, for example, 8 or less, preferably 6 or less. The crosslinkable group is preferably a radically polymerizable group. That is, as a crosslinking agent in this invention, the compound which has a 2 or more radically polymerizable group is illustrated. In the present invention, in particular, it is preferable that the heterocycle-containing polymer precursor has one of a radically polymerizable group and a crosslinking agent having a radically polymerizable group.
In addition, the crosslinking agent in the present invention preferably contains at least one trifunctional or higher crosslinking agent from the viewpoint that the heat resistance can be improved by forming a three-dimensional crosslinked structure. In addition, a mixture of a bifunctional or less crosslinking agent and a trifunctional or more crosslinking agent may be used.

<< Compounds Having an Ethylenically Unsaturated Bond >>
As a group which has an ethylenically unsaturated bond, a styryl group, a vinyl group, a (meth) acryloyl group, and a (meth) allyl group are preferable, and a (meth) acryloyl group is more preferable.

  Specific examples of the compound having an ethylenically unsaturated bond include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid etc.) and esters thereof, amides, and these And the esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and the amides of unsaturated carboxylic acids and polyhydric amine compounds, and multimers thereof. Also, an addition reaction product of an ester or amide of unsaturated carboxylic acid having a nucleophilic substituent such as a hydroxy group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, a monofunctional or Dehydration condensation products with polyfunctional carboxylic acids and the like are also suitably used. Also, addition reaction products of esters or amides of unsaturated carboxylic acids having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, thiols, and halogens Substitution products of esters or amides of unsaturated carboxylic acids having leaving substituents such as groups and tosyloxy groups with monofunctional or polyfunctional alcohols, amines and thiols are also suitable. As another example, instead of the above unsaturated carboxylic acid, it is also possible to use unsaturated phosphonic acid, a vinyl benzene derivative such as styrene, a vinyl ether, an allyl ether or the like, and a group of compounds replaced.

  Specific examples of monomers of esters of polyhydric alcohol compounds and unsaturated carboxylic acids include, as acrylic acid esters, ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate and tetramethylene glycol diacrylate Propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetramer Ethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, di Interaerythritol diacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, isocyanuric acid ethylene oxide modified triacrylate, polyester acrylate There are oligomers and the like.

  As methacrylic acid esters, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy-) 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

  As itaconic acid esters, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetraitaconate.

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

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

  Examples of maleic esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  As examples of other esters, for example, aliphatic alcohol-based esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, and JP-A-59-5240. Compounds having an aromatic skeleton described in JP-A-59-5241 and JP-A-2-226149, compounds containing an amino group described in JP-A-1-165613, and the like are also suitably used. Be

  Moreover, as a specific example of the monomer of the amide of a polyvalent amine compound and unsaturated carboxylic acid, methylene bis- acrylamide, methylene bis- methacrylamide, 1, 6- hexamethylene bis- acrylamide, 1, 6- hexamethylene bis- methacryl Amide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bis methacrylamide and the like.

  As an example of another preferable amide-type monomer, the monomer which has the cyclohexylene structure of Japanese Patent Publication No.54-21726 can be mentioned.

In addition, a urethane addition polymerization monomer produced by using an addition reaction of an isocyanate and a hydroxyl group is also preferable, and as such a specific example, for example, one molecule described in JP-B-48-41708 is used. Examples include vinyl urethane compounds containing two or more polymerizable vinyl groups in one molecule, in which a vinyl monomer containing a hydroxyl group represented by the following general formula is added to a polyisocyanate compound having two or more isocyanate groups. .
CH ₂ = C (R ⁴ ) COOCH ₂ CH (R ⁵ ) OH
(However, R ⁴ and R ⁵ represent H or CH _3. )
Also, urethane acrylates as described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56- Urethane compounds having an ethylene oxide-based skeleton described in JP-A-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable.

  Moreover, as a compound which has an ethylenically unsaturated bond, the compound described in Paragraph No. 0095-0108 of Unexamined-Japanese-Patent No. 2009-288705 can be used suitably also in this invention.

Moreover, as a compound which has an ethylenically unsaturated bond, the compound which has a boiling point of 100 degreeC or more under normal pressure is also preferable. Examples thereof include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, 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 ( Meta) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) Those obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as socyanurate, glycerin or trimethylolethane and then converting it to (meth) acrylate, JP-B-48-41708, JP-B-50-6034, JP-A-51- Urethane (meth) acrylates as described in each publication of JP-A-37193, and polyester acrylates described in JP-A-48-64183, JP-B-49-43191, and JP-B-52-30490 And polyfunctional acrylates and methacrylates such as epoxy acrylates, which are reaction products of epoxy resins and (meth) acrylic acid, and mixtures thereof. Moreover, the compound as described in Paragraph No. 0254-0257 of Unexamined-Japanese-Patent No. 2008-292970 is also suitable. In addition, polyfunctional (meth) acrylates obtained by reacting a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group with a polyfunctional carboxylic acid can also be mentioned.
Moreover, as a compound having another preferable ethylenically unsaturated bond, it has a fluorene ring described in JP-A-2010-160418, JP-A-2010-129825, JP-A-4364216, etc. Compounds having two or more groups having unsaturated bonds, cardo resins can also be used.
Further, as other examples, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and JP-A-2-25493 are disclosed. And the like. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Japan Adhesiveness Association magazine vol. 20, no. Also those introduced as photocrosslinkable monomers and oligomers on pages 7, 300-308 (1984) can be used.

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

In the general formula, n is an integer of 0 to 14, and m is an integer of 1 to 8. A plurality of R and T present in one molecule may be identical to or different from each other.
In each of the polymerizable compounds represented by the above general formulas (MO-1) to (MO-5), at least one of the plurality of R is —OC (OCO) CH = CH ₂ or — Represents a group represented by OC (= O) C (CH ₃ ) = CH ₂ .
As a specific example of the compound which has an ethylenically unsaturated bond represented by said general formula (MO-1)-(MO-5), it is described in stage number 0248-0251 of Unexamined-Japanese-Patent No. 2007-269779 The following compounds can also be suitably used in the present invention.

  Further, in JP-A-10-62986, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then converting it into (meth) acrylate are also described as general formulas (1) and (2) together with specific examples thereof. And can be used as a polymerizable compound.

  Examples of compounds having an ethylenically unsaturated bond include dipentaerythritol triacrylate (commercially available as KAYARAD D-330; Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320). Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and a structure in which these (meth) acryloyl groups are linked via ethylene glycol and propylene glycol residues are preferable. These oligomer types can also be used.

The compound having an ethylenically unsaturated bond may be a polyfunctional monomer having an acid group such as a carboxy group, a sulfonic acid group or a phosphoric acid group. The polyfunctional monomer having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and the unreacted hydroxy group of the aliphatic polyhydroxy compound is reacted with a nonaromatic carboxylic acid anhydride to obtain an acid group. More preferred are polyfunctional monomers having an alkyl group, particularly preferably in this ester, where the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include M-510 and M-520, which are polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
The polyfunctional monomer having an acid group may be used singly or in combination of two or more. Moreover, you may use together the polyfunctional monomer which does not have an acidic radical, and the polyfunctional monomer which has an acidic radical as needed.
As a preferable acid value of the polyfunctional monomer which has an acidic radical, it is 0.1-40 mgKOH / g, Especially preferably, it is 5-30 mgKOH / g. When the acid value of the polyfunctional monomer is in the above-mentioned range, it is excellent in production and handling, and further, excellent in developability. Also, the crosslinkability is good.

As the compound having an ethylenically unsaturated bond, a compound having a caprolactone structure can also be used.
The compound having a caprolactone structure and an ethylenically unsaturated bond is not particularly limited as long as it has a caprolactone structure in the molecule, and examples thereof include trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, and the like. An ε-caprolactone modified multifunctional obtained by esterifying (meth) acrylic acid and ε-caprolactone with a polyhydric alcohol such as pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine etc. Mention may be made of (meth) acrylates. Among them, a polymerizable compound having a caprolactone structure represented by the following general formula (C) is preferable.

General formula (C)

(Wherein, all six Rs are groups represented by the following general formula (D), or one to five of the six Rs are groups represented by the following general formula (D) And the remainder is a group represented by the following general formula (E).)

General formula (D)

(Wherein, R ¹ represents a hydrogen atom or a methyl group, m represents 1 or 2 and “*” represents a bond.)

General formula (E)

(Wherein, R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond.)

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

  The compound having an ethylenically unsaturated bond is also preferably at least one selected from the group of compounds represented by the following general formulas (i) or (ii).

In general formulas (i) and (ii), E each independently represents-((CH ₂ ) _y CH ₂ O)-or-((CH ₂ ) _y CH (CH ₃ ) O)-, Each y independently represents an integer of 0 to 10, and each X independently represents a (meth) acryloyl group, a hydrogen atom or a carboxy group.
In general formula (i), the total of (meth) acryloyl groups is three or four, m independently represents an integer of 0 to 10, and the sum of each m is an integer of 0 to 40 It is. However, when the sum of each m is 0, any one of X is a carboxy group.
In general formula (ii), the total of (meth) acryloyl groups is five or six, n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60 It is. However, when the sum of each n is 0, any one of X is a carboxy group.

In general formula (i), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Moreover, the integer of 2-40 is preferable, the integer of 2-16 is more preferable, and, as for the sum of each m, the integer of 4-8 is especially preferable.
In general formula (ii), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Moreover, the integer of 3-60 is preferable, the integer of 3-24 is more preferable, and, as for the sum of each n, the integer of 6-12 is especially preferable.
Formula (i) or formula (ii) in the _{- ((CH 2) y CH} 2 O) - or _{- ((CH 2) y CH} (CH 3) O) - , the terminal oxygen atom side X Preferred is a form of binding to In particular, in the general formula (ii), a form in which all six X's are an acryloyl group is preferable.

  In the compound represented by the general formula (i) or (ii), a ring-opened skeleton is connected by ring-opening addition reaction of ethylene oxide or propylene oxide with pentaerythritol or dipentaerythritol, which is a conventionally known step. And the terminal hydroxyl group of the ring-opened skeleton, for example, by reacting (meth) acryloyl chloride to introduce a (meth) acryloyl group. Each step is a well-known step, and those skilled in the art can easily synthesize a compound represented by general formula (i) or (ii).

Among the compounds represented by the general formulas (i) and (ii), pentaerythritol derivatives and dipentaerythritol derivatives are more preferable.
Specific examples thereof include compounds represented by the following formulas (a) to (f) (hereinafter, also referred to as “exemplified compounds (a) to (f)”), and among them, exemplified compounds (a) and (f) b), (e) and (f) are preferred.

  As commercially available products of the polymerizable compounds represented by the general formulas (i) and (ii), for example, SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmar, manufactured by Nippon Kayaku Co., Ltd. Examples include DPCA-60, which is a hexafunctional acrylate having six pentylene oxy chains, and TPA-330, which is a trifunctional acrylate having three isobutylene oxy chains.

Examples of compounds having an ethylenically unsaturated bond include those described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293 and JP-B-2-16765. Urethane acrylates and urethane compounds having an ethylene oxide skeleton as described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417 and JP-B-62-39418 are also suitable. It is. Furthermore, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, JP-A-1-105238 as a polymerizable compound Monomers can also be used.
As a commercial item of the compound which has an ethylenically unsaturated bond, Urethane oligomer UAS-10, UAB-140 (made by Sanyo Kokusaku Pulp Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A -9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (Manufactured by Kyoeisha Chemical Co., Ltd.), Blenmer PME 400 (manufactured by NOF Corporation), and the like.

  From the viewpoint of heat resistance, the compound having an ethylenically unsaturated bond preferably has a partial structure represented by the following formula. However, * in the formula is a linkage.

Specific examples of the compound having an ethylenically unsaturated bond having the above partial structure include, for example, trimethylolpropane tri (meth) acrylate, ethylene oxide modified with isocyanuric acid ethylene oxide, di (meth) acrylate, ethylene oxide oxide modified tri (meth) isocyanuric acid. Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tetramethylolmethane tetra ( Examples thereof include meta) acrylates, and in the present invention, these polymerizable compounds can be particularly preferably used.
Moreover, in the following compounds, compounds in which n is 3 to 25 are also mentioned as preferable examples.

In the composition, the content of the compound having an ethylenically unsaturated bond is preferably 1 to 50% by mass with respect to the total solid content of the composition, from the viewpoint of good crosslinkability and heat resistance. The lower limit is more preferably 5% by mass or more. 30 mass% or less is more preferable, and, as for the upper limit, 25 mass% or less is more preferable. Although the compound which has an ethylenically unsaturated bond may be used individually by 1 type, you may mix and use 2 or more types.
Further, the mass ratio of the heterocycle-containing polymer precursor to the compound having an ethylenically unsaturated bond (heterocycle-containing polymer precursor / polymerizable compound) is preferably 98/2 to 10/90, and 95/5 to 30 / 70 is more preferable, 90/10 to 50/50 is more preferable, and 90/10 to 70/30 is more preferable. If the mass ratio of the heterocycle-containing polymer precursor and the compound having an ethylenically unsaturated bond is in the above-mentioned range, a cured film excellent in crosslinkability and heat resistance can be formed.
The compound having an ethylenically unsaturated bond may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes said range.

<Compound Having Hydroxymethyl Group, Alkoxymethyl Group or Acyloxymethyl Group >>
As the compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, a compound represented by the following general formula (AM1) is preferable.

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

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

The content of the compound represented by General Formula (AM1) is preferably 5 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the heterocycle-containing polymer precursor. More preferably, it is 10 parts by mass or more and 35 parts by mass or less. Further, the total crosslinking agent contains 10% by mass to 90% by mass of the compound represented by the following general formula (AM4), and 10% by mass or more of the compound represented by the following general formula (AM5) in all the crosslinking agent It is also preferable to contain 90 mass% or less.
These compounds may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes said range.

(Wherein, R ⁴ represents a divalent organic group having 1 to 200 carbon atoms, and R ⁵ represents a group represented by the following general formula (AM 2) or the following general formula (AM 3).)

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

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

Among the above, the following compounds are exemplified as a compound having two or more hydroxymethyl groups.
(In the chemical formula (1), R ^a is an organic group having 2 to 20 carbon atoms, and P ¹ is a hydrogen atom or an alkyl group.)
R ^a is preferably a hydrocarbon group. P ¹ is preferably a hydrogen atom.
These details can be referred to the description of paragraphs 0010 to 0024 of International Publication WO 2010/038742, the contents of which are incorporated herein.

  By using the above-mentioned compound, when a composition layer is formed on a substrate with unevenness, cracks are less likely to occur. Furthermore, it is excellent in pattern processability, and 5% mass loss temperature can have high heat resistance which becomes 350 degreeC or more preferably more preferably 380 degreeC or more. Specific examples of the compound represented by the general formula (AM4) include 46DMOC, 46DMOEP (all trade names, manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethyol BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 (all trade names, Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl -P-cresol etc. are mentioned.

  In addition, specific examples of the compound represented by the general formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, and 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 Materials Co., Ltd.), NIKALAC MX-280, NIKALAC Examples include MX-270 and NIKALAC MW-100 LM (all trade names, manufactured by Sanwa Chemical Co., Ltd.).

Moreover, the following compounds are also preferable as a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group. As a commercial item, T2058 and B1525 (above, brand name, Tokyo Chemical Industry Co., Ltd. make) are illustrated.

<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 compound crosslinks at a temperature of 200 ° C. or less, and a dehydration reaction does not occur in the crosslinking reaction, so that film contraction hardly occurs. Therefore, containing an epoxy compound is effective for low temperature curing and low warpage of the composition.

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

  Examples of epoxy compounds are: bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resin such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resin such as polypropylene glycol diglycidyl ether; Examples include epoxy group-containing silicones such as (oxypropyl) siloxane and the like, but are not limited thereto. 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 (R) EXA-4710, Epiclon (R) HP-4770, Epiclon (R) EXA-859 CRP, Epiclon (R) EXA-1514, Epiclon (R) EXA-4880, Epiclon (R) EXA-4850-150, Epiclon (registered trademark) EXA-4850-1000, Epiclon (registered trademark) EXA-4816, Epiclon (registered trademark) EXA-4822 (trade names, manufactured by Dainippon Ink and Chemicals, Inc.), Rika Resin (registered trademark) BEO-60E (Products above , New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S (trade name, (Ltd.) and the like Adeka). Among these, the epoxy resin containing a polyethylene oxide group is preferable at the point which is excellent in low curvature and heat resistance. For example, Epiclon (registered trademark) EXA-4880, Epiclon (registered trademark) EXA-4822, and Rikaresin (registered trademark) BEO-60E are preferable because they contain polyethylene oxide groups.

The content of the epoxy compound is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and still more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the heterocycle-containing polymer precursor. If the compounding amount is 5 parts by mass or more, warpage of the cured film can be further suppressed, and if 50 parts by mass or less, pattern filling accompanying reflow at the time of final heating (cure) can be further suppressed.
The epoxy compound may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes said range.

<Oxetane Compound (Compound Having an Oxetanyl Group)>
Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyl oxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, Examples include 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester, and the like. As a specific example, Aon oxetane series (for example, OXT-121, OXT-221, OXT-191, OXT-223) manufactured by Toagosei Co., Ltd. can be suitably used, and these can be used alone or in combination. You may mix species or more.

The content of the oxetane compound is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and still more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the heterocycle-containing polymer precursor.
The oxetane compounds may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes said range.

<Benzoxazine compound (compound having a benzoxazolyl group)>
Since a benzoxazine compound causes a crosslinking reaction by a ring opening addition reaction, no degassing due to curing occurs, and furthermore, the shrinkage due to heat is small. Therefore, the occurrence of warpage can be suppressed.

  Preferred examples of the benzoxazine compound include B-a type benzoxazine, B-m type benzoxazine (all trade names, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, phenol novolac type dihydrobenzoxazine Compounds are mentioned. These may be used alone or in combination of two or more.

The content of the benzoxazine compound is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and still more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the heterocycle-containing polymer precursor.
The benzoxazine compounds may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes said range.

  The molecular weight of the crosslinking agent used in the present invention is preferably 100 to 1,500, more preferably 100 to 800, and still more preferably 100 to 600. By setting the molecular weight to 800 or less, or even 600 or less, it is possible to more effectively improve the outgassing property.

<Resin containing phenolic OH group>
When the composition in the present invention is an alkali-developable positive photosensitive resin composition, the inclusion of a resin containing a phenolic OH group adjusts the solubility in an alkaline developer, and good sensitivity is obtained. Preferred in that
As resins containing phenolic OH groups, novolak resins and polyhydroxystyrene resins are mentioned as preferred examples.

<< Novolak resin >>
The novolak resin is obtained by polycondensation of phenols and aldehydes by a known method. The novolak resin may be used in combination of two or more.
Preferred examples of the above-mentioned phenols include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3 There can be mentioned 5-trimethylphenol, 3,4,5-trimethylphenol and the like. In particular, phenol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol and 2,3,5-trimethylphenol are preferred. Two or more of these phenols may be used in combination. From the viewpoint of solubility in an alkaline developer, m-cresol is preferable, and a combination of m-cresol and p-cresol is also preferable. That is, it is preferable to include, as a novolac resin, a cresol novolac resin containing m-cresol residue or m-cresol residue and p-cresol residue. At this time, the molar ratio (m-cresol residue / p-cresol residue, m / p) of m-cresol residue to p-cresol residue in cresol novolac resin is preferably 1.8 or more. If it is in this range, it exhibits appropriate solubility in an alkali developer and good sensitivity can be obtained. More preferably, it is 4 or more.
Further, as preferable examples of the above-mentioned aldehydes, formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde and the like can be mentioned. Two or more of these aldehydes may be used.

  Also, a wholly aromatic novolak resin obtained by polycondensation with an acidic catalyst using a compound represented by the following general formula (Phe) as a phenol and a compound represented by the following general formula (Ald) as an aldehyde Is preferable at the point which can provide high heat resistance to the cured film of the composition in this invention.

General formula (Phe)
In the general formula (Phe), R ₁ represents an organic group selected from an alkyl group having 1 to 20 carbon atoms and an alkoxy group, and p is an integer of 1 to 3 and preferably 2 to 3 It is an integer.

General formula (Ald)
In general formula (Ald), R ₂ represents a group selected from hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group and a hydroxy group, and q is an integer of 0 to 3.

As a phenol compound represented by the above general formula (Phe), a phenol compound having 1 to 3 and preferably 2 to 3 substituents is used, and the above-mentioned substituent has one or more carbon atoms. It is an organic group selected from an alkyl group and an alkoxy group of 20 or less. Specific examples of the alkyl group and alkoxy group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a methoxy group and an ethoxy group. Preferred examples of such a phenol compound include o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol and 3,4-dimethylphenol 3,5-Dimethylphenol, 2-methyl-3-ethyl-phenol, 2-methyl-3-methoxyphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol 2,3, 6 -Trimethylphenol etc. can be used. Among these, although not particularly limited, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,6-dimethylphenol Those selected from among those are preferred. Furthermore, these phenols can be used 1 type or in mixture of 2 or more types.
By using a phenol compound having a number of substituents of 1 or more and 3 or less, preferably 2 or more and 3 or less as the above-mentioned phenol compound, the intramolecular rotation is suppressed, and a phenol resin having sufficient heat resistance necessary for the composition You can get

As the aromatic aldehyde compound represented by the above general formula (Ald), an aromatic aldehyde compound which is unsubstituted or has 3 or less substituents is used, and the above-mentioned substituent has 1 to 20 carbon atoms. It is an organic group selected from the following alkyl group, alkoxy group and hydroxy group. Specific examples of the alkyl group and alkoxy group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a methoxy group and an ethoxy group. As such aromatic aldehyde compounds, for example, benzaldehyde, 2-methyl benzaldehyde, 3-methyl benzaldehyde, 4-methyl benzaldehyde, 2,3-dimethyl benzaldehyde, 2,4-dimethyl benzaldehyde, 2,5-dimethyl benzaldehyde, 2,6-dimethyl benzaldehyde, 3,4-dimethyl benzaldehyde, 3,5-dimethyl benzaldehyde, 2,3,4-trimethyl benzaldehyde, 2,3,5-trimethyl benzaldehyde, 2,3,6-trimethyl benzaldehyde, 2, 4,5-trimethyl benzaldehyde, 2,4,6-trimethyl benzaldehyde, 3,4,5-trimethyl benzaldehyde, 4-ethyl benzaldehyde, 4-tert-butyl benzaldehyde, 4-i Butyl benzaldehyde, 4-methoxy benzaldehyde, salicylaldehyde, 3-hydroxy benzaldehyde, 4-hydroxy benzaldehyde, 3-methyl salicylaldehyde, 4-methyl salicyl aldehyde, 2-hydroxy-5-methoxy benzaldehyde, 2,4-dihydroxy benzaldehyde, 2 It is possible to use 5-dihydroxy benzaldehyde, 2,3,4- trihydroxy benzaldehyde and the like, without being limited thereto, among these, R ₂ in the general formula (2) is hydrogen, methyl group, hydroxy group The aromatic aldehyde compound is preferably a compound selected from among the aromatic aldehyde compounds shown below. Furthermore, these aldehydes can be used 1 type or in mixture of 2 or more types.

  In a synthesis reaction for obtaining a novolak resin from phenols and aldehydes, it is preferable to react the aldehyde compound at 0.5 mol or more and 2 mol or less, preferably 0.6 mol or more and 1.2 mol or less, with 1 mol of the phenol compound. It is more preferable to make it react by these, and it is especially preferable to make it react by 0.7 mol or more and 1.0 mol or less. By setting it as the said molar ratio, the molecular weight which can exhibit a characteristic sufficient as a composition can be obtained.

An acidic catalyst is usually used for the polycondensation reaction of phenols and aldehydes. Examples of the acidic catalyst include hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, p-toluenesulfonic acid and the like. The amount of these acidic catalysts to be used is usually 1 × 10 ^{−5 to} 5 × 10 ⁻¹ mol per 1 mol of phenols. In the polycondensation reaction, water is usually used as the reaction medium, but when it becomes heterogeneous from the initial stage of the reaction, a hydrophilic solvent or a lipophilic solvent is used as the reaction medium. Examples of the hydrophilic solvent include alcohols such as methanol, ethanol, propanol, butanol and propylene glycol monomethyl ether; cyclic ethers such as tetrahydrofuran and dioxane. Examples of lipophilic solvents include ketones such as methyl ethyl ketone, methyl isobutyl ketone and 2-heptanone. The amount of the reaction medium used is usually 20 to 1,000 parts by mass per 100 parts by mass of the reaction raw material.

  The reaction temperature of the polycondensation can be appropriately adjusted depending on the reactivity of the raw material, but is usually 10 to 200 ° C. As a reaction method for polycondensation, a method in which phenols, aldehydes, acidic catalysts, etc. are charged at one time and reacted, or a method in which phenols, aldehydes, etc. are added with the progress of reaction in the presence of acidic catalysts, etc. Can be adopted as appropriate. After completion of the polycondensation reaction, the reaction temperature is generally raised to 130 to 230 ° C. in order to remove unreacted raw materials, acidic catalysts, reaction media, etc. present in the system, and volatile components are removed under reduced pressure. Remove and recover the novolak resin.

  1,000 or more are preferable and, as for polystyrene conversion weight average molecular weight (henceforth "Mw") of novolak resin, 2,000 or more are more preferable. Moreover, 5,000 or less is preferable. Within this range, good sensitivity can be obtained.

  The content of the novolac resin is preferably 1 part by mass to 70 parts by mass and more preferably 10 parts by mass to 70 parts by mass with respect to 100 parts by mass of the heterocycle-containing polymer precursor. Within this range, a pattern with high sensitivity and which does not flow after heat treatment at high temperature can be obtained. The novolak resin may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes said range.

<< Polyhydroxystyrene resin >>
The hydroxystyrene resin is a polymer containing hydroxystyrene and / or a derivative thereof, and may be a copolymer including, but not limited to, hydroxystyrene and / or a derivative thereof and a monomer other than these. Examples of the monomer used herein include ethylene, propylene, 1-butene, 2-methylpropene, styrene and derivatives thereof. Among them, a copolymer composed of hydroxystyrene and / or a derivative thereof and styrene and / or a derivative thereof is preferable from the viewpoint of easily adjusting the solubility in an aqueous alkali solution. The above derivatives are those in which an alkyl group, an alkoxyl group, a hydroxy group and the like are substituted at the ortho, meta and para positions of the aromatic rings of hydroxystyrene and styrene. The hydroxystyrene of the hydroxystyrene resin may be any of orthohydroxystyrene, metahydroxystyrene and parahydroxystyrene. Further, a plurality of the above-mentioned hydroxystyrenes may be mixed.

  The proportion of the hydroxystyrene and the derivative thereof in the hydroxystyrene resin is preferably 50% or more, more preferably 60% or more. The upper limit is preferably 90% or less, more preferably 80% or less. By setting it as the said range, it has an effect which is excellent in coexistence of reduction of the after-exposure residue of an exposure part, and high sensitivity.

  Among them, a hydroxystyrene resin having a repeating structural unit represented by the following general formula (PHS-1) is preferable.

General formula (PHS-1)
In the general formula (PHS-1), R ₁ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, a represents 1 to 4, b represents 1 to 3, and a + b is in the range of 1 to 5 is there. R ₂ represents an atom or one group selected from a hydrogen atom, a methyl group, an ethyl group or a propyl group.

The structural unit represented by the above general formula (PHS-1) is, for example, p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenyl phenol, m-isopropenyl phenol, o-isopropenyl phenol And aromatic vinyl compounds having a phenolic hydroxyl group such as, and aromatic vinyl compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene and the like, singly or in combination of two or more thereof by a known method A portion of the polymer or copolymer thus obtained is obtained by addition reaction of an alkoxy group by a known method.
As the aromatic vinyl compound having a phenolic hydroxyl group, p-hydroxystyrene and / or m-hydroxystyrene are preferably used, and as the aromatic vinyl compound, styrene is preferably used.

  Among hydroxystyrene resins having a repeating structural unit represented by the above general formula (PHS-1), from the viewpoint of convenience that sensitivity can be further improved and solubility in an alkali developer can be adjusted, general formula (PHS- 2), the copolymer containing the structural unit represented by general formula (PHS-3), and general formula (PHS-4) is preferable. Furthermore, as for the structural unit of general formula (PHS-4), it is preferable that it is 50 mol% or less from the soluble point to alkaline developing solution.

General formula (PHS-2)
In general formula (PHS-2), R ₄ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, c represents 1 to 4 and d represents 1 to 3 and c + d is in the range of 2 to 5 is there. R ₃ represents an atom or one group selected from a hydrogen atom, a methyl group, an ethyl group or a propyl group.

General formula (PHS-3)
In the general formula (PHS-3), _{R 5} represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, e is representative of 1-5.

General formula (PHS-4)
In general formula (PHS-4), R ₆ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

The weight average molecular weight (Mw) of the hydroxystyrene resin is preferably 1,000 or more, more preferably 2,000 or more, particularly preferably 2,500 or more, preferably 10,000 or less, more preferably 8, or more. It is at most 000, particularly preferably at most 7,000. By setting it as the said range, it has an effect which is excellent in coexistence of high sensitivity-ization and the normal temperature storage property of a varnish.
The content of the hydroxystyrene resin is preferably 1 part by mass to 70 parts by mass and more preferably 10 parts by mass to 70 parts by mass with respect to 100 parts by mass of the heterocycle-containing polymer precursor. Within this range, a pattern with high sensitivity and which does not flow after heat treatment at high temperature can be obtained. The hydroxystyrene resin may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes said range.

<Photo radical polymerization initiator>
The composition in the present invention may contain a photo radical polymerization initiator. When the composition contains a photo radical polymerization initiator, the composition is applied to a semiconductor wafer or the like to form a composition layer, and then irradiation with light causes curing by radicals, resulting in solubility in a light irradiated portion. Can be lowered. Therefore, for example, by exposing the composition layer through a photomask having a pattern in which only the electrode portion is masked, there is an advantage that regions having different solubility can be easily manufactured according to the pattern of the electrode.

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

  As the photo radical polymerization initiator, known compounds can be used without any limitation, and for example, halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, those having a trihalomethyl group, etc.) Acyl phosphine compounds such as acyl phosphine oxide, oxime compounds such as hexaaryl biimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ether, aminoacetophenone compounds, hydroxyacetophenone, azo The compounds include azide compounds, metallocene compounds, organic boron compounds, iron arene complexes and the like.

  As a halogenated hydrocarbon derivative having a triazine skeleton, for example, Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3337024, F . C. Schaefer et al. Org. Chem. Compounds described in JP-A-62-58241; compounds described in JP-A-5-281728; compounds described in JP-A-5-34920; Examples thereof include the compounds described in Japanese Patent No. 4212976.

  Examples of the compounds described in US Pat. No. 4,129,976 include compounds having an oxadiazole skeleton (eg, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2-trichloro) Methyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl)- 1,3,4-oxadiazole, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl)- , 3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) -1 , 3,4-oxadiazole, 2-tribromomethyl-5-styryl-1,3,4-oxadiazole and the like) and the like.

  Moreover, as a radical radical polymerization initiator other than the above, the compound described in Paragraph No. 0086 of JP-A-2015-087611, JP-A-53-133428, JP-B-57-1819, JP-A-57-6096 And compounds described in US Pat. No. 3,615,455, the contents of which are incorporated herein.

As a ketone compound, the compound as described in Paragraph No. 0087 of Unexamined-Japanese-Patent No. 2015-087611 is illustrated, for example, These content is integrated in this specification.
Among commercial products, Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.

As a radical photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acyl phosphine compound can also be used suitably. More specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 and an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used.
As a hydroxy acetophenone type initiator, IRGACURE-184 (IRGACURE is a registered trademark), DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (brand name: all are BASF Corporation make) can be used.
As aminoacetophenone initiators, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF Corporation) can be used.
As the aminoacetophenone initiator, a compound described in JP 2009-191179 A, in which the absorption maximum wavelength is matched to a light source such as 365 nm or 405 nm, can also be used.
As an acyl phosphine type initiator, IRGACURE-819 and DAROCUR-TPO (brand name: all made by BASF Corporation) which are commercial items can be used.
As a metallocene compound, IRGACURE-784 (made by BASF Corporation) etc. are illustrated.

As a photo radical polymerization initiator, More preferably, an oxime compound is mentioned. As specific examples of the oxime compound, compounds described in JP-A-2001-233842, compounds described in JP-A-2000-80068 and compounds described in JP-A-2006-342166 can be used.
As preferable oxime compounds, for example, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-Acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxycarbonyloxy Examples include imino-1-phenylpropan-1-one and the like.

As oxime compounds, JCS Perkin II (1979) pp. 1653-1660, JCS Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995, pp. 202-232), JP-A-2000 The compound etc. which are described in each gazette of -66385, Unexamined-Japanese-Patent No. 2000-80068, Japanese Patent Publication No. 2004-534797, and Unexamined-Japanese-Patent No. 2006-342166 are mentioned.
Among commercially available products, IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), and N-1919 (manufactured by ADEKA) are also suitably used. In addition, TR-PBG-304 (made by Changzhou Strong Electronic New Material Co., Ltd.), Adeka Akuls NCI-831 and Adeka Ark's NCI-930 (made by ADEKA) can also be used.

Further, compounds described in JP-T-2009-519904, in which an oxime is linked to the N-position of a carbazole ring, compounds described in US Pat. No. 7,626,957, in which a hetero substituent is introduced in the benzophenone site, Compounds described in introduced JP-A-2010-15025 and US-A-2009-29203, ketoxime compounds described in WO-A-2009 / 131189, US patents containing triazine skeleton and oxime skeleton in the same molecule The compound described in 7556910, the compound described in JP-A 2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source may be used.
Moreover, the cyclic oxime compound described in Unexamined-Japanese-Patent No. 2007-231000 and Unexamined-Japanese-Patent No. 2007-322744 can also be used suitably. Among cyclic oxime compounds, cyclic oxime compounds fused to a carbazole dye described in, for example, JP-A-2010-32985 and JP-A-2010-185072 have high light absorption and high sensitivity. It is preferable from the viewpoint.
Moreover, the compound of Unexamined-Japanese-Patent No. 2009-242469 which is a compound which has an unsaturated bond in the specific site | part of an oxime compound can also be used suitably.
Moreover, it is also possible to use an oxime compound having a fluorine atom. As a specific example of such an oxime compound, a compound described in JP-A-2010-262028, a compound 24 described in JP-A-2014-500852, paragraph No. 0345, 36 to 40, JP-A The compound (C-3) etc. which are described in stage number 0101 of the 2013-164471 gazette etc. are mentioned. Specific examples include the following compounds.
As a most preferable oxime compound, the oxime compound which has a specific substituent shown by Unexamined-Japanese-Patent No. 2007-269779, the oxime compound which has a thioaryl group shown by Unexamined-Japanese-Patent No. 2009-191061, etc. are mentioned.

The photo radical polymerization initiator is a trihalomethyl triazine compound, a benzyl dimethyl ketal compound, an α-hydroxy ketone compound, an α-amino ketone compound, an acyl phosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, tria from the viewpoint of exposure sensitivity. It is selected from the group consisting of reelyl imidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, halomethyl oxadiazole compound, 3-aryl substituted coumarin compound Compounds are preferred.
More preferable are trihalomethyl triazine compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, and more preferably trihalomethyl triazine compounds Α-amino ketone compounds, oxime compounds, triarylimidazole dimers, benzophenone compounds, and the use of oxime compounds is most preferred.

When the composition contains a radical photopolymerization initiator, the content of the radical photopolymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the composition. More preferably, it is 0.1-10 mass%.
The photo radical polymerization initiator may be only one type or two or more types. When 2 or more types of radical photopolymerization initiators are used, it is preferable that the sum total is the said range.

<Photo acid generator>
The composition in the present invention may contain a photoacid generator. By containing a photo-acid generator, an acid is generated in the exposed area, and the solubility of the exposed area in an alkaline aqueous solution is increased, so that it can be used as a positive composition.

  Examples of the photoacid generator include quinone diazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts. Above all, a quinonediazide compound is preferably used from the viewpoint of exhibiting an excellent dissolution inhibiting effect and obtaining a composition with high sensitivity and small film loss. Moreover, you may contain 2 or more types of photo-acid generators. Thereby, the ratio of the dissolution rates of the exposed area and the unexposed area can be further increased, and a highly sensitive positive composition can be obtained.

As a quinone diazide compound, a polyhydroxy compound obtained by ester bond of sulfonic acid of quinone diazide, a polyamino compound obtained by sulfonamide bond of sulfonic acid of quinone diazide, a polyhydroxy polyamino compound obtained by sulfonic acid of quinone diazide And the like. By using such a quinone diazide compound, it is possible to obtain a positive type composition sensitive to i-line (wavelength 365 nm), h-line (wavelength 405 nm) and g-line (wavelength 436 nm) of a general ultraviolet ray of a mercury lamp. . Further, all functional groups of these polyhydroxy compounds, polyamino compounds and polyhydroxy polyamino compounds may not be substituted with quinonediazide, but it is preferable that two or more functional groups per molecule be substituted with quinonediazide. .
The following compounds are illustrated as an example.
In the above compounds, 1 to 10% of the entire Q may be a hydrogen atom, and 4 to 6% may be a hydrogen atom.

  Examples of polyhydroxy compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylene Tris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC , DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35 XL, TML-BP, TML HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP , BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (all trade names, manufactured by Asahi Organic Materials Industry), 2, 6 -Dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A, bisphenol E, Methylene bisphenol, BisP-AP (brand name, Honshu Chemical Industries, Ltd. Ltd.), but such a novolak resin include, but are not limited to.

  As polyamino compounds, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfone, 4,4′-diamino Although diphenyl sulfide etc. are mentioned, it is not limited to these.

  Moreover, as a polyhydroxy polyamino compound, although 2, 2-bis (3-amino 4-hydroxyphenyl) hexafluoro propane, 3,3'- dihydroxy benzidine etc. are mentioned, it is not limited to these.

  As the quinone diazide compound, any of a compound having a 5-naphthoquinone diazide sulfonyl group and a compound having a 4-naphthoquinone diazide sulfonyl group is preferably used. A compound having both of these groups in the same molecule may be used, or compounds using different groups may be used in combination.

  Examples of the method for producing the quinone diazide compound include a method in which 5-naphthoquinone diazide sulfonyl chloride is reacted with a phenol compound in the presence of triethylamine. The synthesis method of a phenol compound includes a method of reacting an α- (hydroxyphenyl) styrene derivative with a polyhydric phenol compound under an acidic catalyst.

The content of the photoacid generator is preferably 3 to 40 parts by mass with respect to 100 parts by mass of the heterocycle-containing polymer precursor. By setting the content of the photoacid generator in this range, higher sensitivity can be achieved. Furthermore, a sensitizer may be contained as required.
The photoacid generator may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes said range.

Thermal acid generator
The composition in the present invention may contain a thermal acid generator. The thermal acid generator generates an acid upon heating, promotes cyclization of the heterocycle-containing polymer precursor and further improves the mechanical properties of the cured film, and a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group. It has the effect of promoting the crosslinking reaction of at least one compound selected from epoxy compounds, oxetane compounds and benzoxazine compounds.

  50 degreeC-270 degreeC are preferable, and, as for the thermal decomposition start temperature of a thermal acid generator, 250 degrees C or less is more preferable. In addition, no acid is generated during drying (pre-baking: about 70 to 140 ° C.) after the composition is applied to the substrate, and at the time of final heating (curing: about 100 to 400 ° C.) after patterning by exposure and development thereafter. It is preferable to select one that generates an acid, because a decrease in sensitivity during development can be suppressed.

  The acid generated from the thermal acid generator is preferably a strong acid, for example, p-toluenesulfonic acid, arylsulfonic acid such as benzenesulfonic acid, methanesulfonic acid, alkylsulfonic acid such as ethanesulfonic acid, butanesulfonic acid, and trifluoromethane. Preferred are haloalkyl sulfonic acids such as sulfonic acids. As an example of such a thermal acid generator, the thing as described in Paragraph No. 0055 of Unexamined-Japanese-Patent No. 2013-072935 is mentioned.

  Among them, from the viewpoint of having less residual in the cured film and not reducing the physical properties of the cured film, those which generate alkylsulfonic acid having 1 to 4 carbon atoms and haloalkylsulfonic acid having 1 to 4 carbon atoms are more preferable, and methanesulfonic acid (4-hydroxyphenyl) dimethylsulfonium, methanesulfonic acid (4-((methoxycarbonyl) oxy) phenyl) dimethylsulfonium, benzyl methanesulfonate (4-hydroxyphenyl) methylsulfonium, benzyl methanesulfonate (4-((methoxy (Carbonyl) oxy) phenyl) methyl sulfonium, methanesulfonic acid (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium, trifluoromethane sulfonic acid (4-hydroxyphenyl) dimethyl sulfonium, trifluoro Lomethanesulfonic acid (4-((methoxycarbonyl) oxy) phenyl) dimethylsulfonium, benzyl trifluoromethanesulfonate (4-hydroxyphenyl) methylsulfonium, benzyl trifluoromethanesulfonate (4- ((methoxycarbonyl) oxy) phenyl) methyl Sulfonium, trifluoromethanesulfonic acid (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium, 3- (5- (((propylsulfonyl) oxy) imino) thiophene-2 (5H)-ylidene)-2 -(O-tolyl) propanenitrile and 2,2-bis (3- (methanesulfonylamino) -4-hydroxyphenyl) hexafluoropropane are preferred.

  Moreover, the compound of Paragraph No. 0059 of Unexamined-Japanese-Patent No. 2013-167742 is also preferable as a thermal acid generator.

When a thermal acid generator is used, the content of the thermal acid generator is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the heterocycle-containing polymer precursor. By containing 0.01 parts by mass or more, the crosslinking reaction and the cyclization of the heterocycle-containing polymer precursor are promoted, so that the mechanical properties and the chemical resistance of the cured film can be further improved. Moreover, from a viewpoint of the electrical insulation of a cured film, 20 mass parts or less are preferable, 15 mass parts or less are more preferable, and 10 mass parts or less are more preferable.
The thermal acid generator may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes said range.

<Thermal radical polymerization initiator>
The composition in the present invention may contain a thermal radical polymerization initiator. A well-known thermal radical polymerization initiator can be used as a thermal radical polymerization initiator.
The thermal radical polymerization initiator is a compound which generates a radical by the energy of heat to initiate or accelerate the polymerization reaction of the polymerizable compound. By adding the thermal radical polymerization initiator, when advancing the cyclization reaction of the heterocycle-containing polymer precursor, the polymerization reaction of the polymerizable compound can be advanced. In addition, when the heterocycle-containing polymer precursor contains an ethylenically unsaturated bond, the polymerization reaction of the heterocycle-containing polymer precursor can be progressed together with the cyclization of the heterocycle-containing polymer precursor, so the heat resistance is further improved. Can be achieved.
As a thermal radical polymerization initiator, aromatic ketones, onium salt compounds, peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, carbon halogen Compounds having a bond, azo compounds and the like can be mentioned. Among them, peroxides or azo compounds are more preferable, and peroxides are particularly preferable.
The thermal radical polymerization initiator used in the present invention preferably has a 10-hour half-life temperature of 90 to 130 ° C., and more preferably 100 to 120 ° C.
Specifically, compounds described in Paragraph Nos. 0074 to 0118 of JP-A-2008-63554 can be mentioned.
As a commercial item, Perbutyl Z and Percumil D (manufactured by NOF Corporation) can be suitably used.

When the composition contains a thermal radical polymerization initiator, the content of the thermal radical polymerization initiator is preferably 0.1 to 50% by mass, and more preferably 0.1 to 30% by mass with respect to the total solid content of the composition Preferably, 0.1 to 20% by mass is particularly preferable. Moreover, it is preferable to contain 0.1-50 mass parts of thermal radical polymerization initiators with respect to 100 mass parts of polymeric compounds, and it is more preferable to contain 0.5-30 mass parts. According to this aspect, it is easy to form a cured film more excellent in heat resistance.
The thermal radical polymerization initiator may be used alone or in combination of two or more. When two or more thermal radical polymerization initiators are used, the total is preferably in the above range.

<Corrosion inhibitor>
It is preferable to add a corrosion inhibitor to the composition in the present invention. The corrosion inhibitor is added for the purpose of preventing the outflow of ions from the metal wiring, and as a compound, for example, a rust inhibitor described in paragraph No. 0094 of JP 2013-15701 A, JP 2009-283711 A Using the compounds described in paragraphs 0073 to 0076, the compounds described in paragraph 0052 of JP2011-59656A, the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520A, etc. be able to. Among them, compounds having a triazole ring or compounds having a tetrazole ring can be preferably used, and 1,2,4-triazole, 1,2,3-benzotriazole, 5-methyl-1H-benzotriazole, 1H-tetrazole More preferred is 5-methyl-1H-tetrazole, and most preferred is 1H-tetrazole.
When a corrosion inhibitor is used, the content of the corrosion inhibitor is preferably in the range of 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the heterocycle-containing polymer precursor. The scope of the department.
The corrosion inhibitor may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes said range.

Metal adhesion improver
The composition in the present invention preferably contains a metal adhesion improver for improving the adhesion to a metal material used for electrodes, wiring and the like. Examples of metal adhesion improvers include sulfide compounds described in paragraphs 0046 to 0049 of JP-A 2014-186186 and paragraphs 0032 to 0043 of JP-A 2013-072935. The following compounds may also be exemplified as metal adhesion improvers.
When a metal adhesion improver is used, the content of the metal adhesion improver is preferably in the range of 0.1 to 30 parts by mass, and more preferably 0.5 to 15 with respect to 100 parts by mass of the polyimide precursor. It is the range of the mass part. When the amount is 0.1 parts by mass or more, the adhesion between the film after heat curing and the metal becomes good, and when the amount is 30 parts by mass or less, the heat resistance and mechanical properties of the film after curing become good.
The metal adhesion improver may be used alone or in combination of two or more. When using 2 or more types, it is preferable that the sum is the said range.

<Silane coupling agent>
The composition in the present invention preferably contains a silane coupling agent in that it can improve the adhesion to the substrate. As examples of silane coupling agents, compounds described in paragraphs 0062 to 0073 of JP-A 2014-191002, compounds described in paragraphs 0063 to 0071 of International Publication WO 2011/09092 A1, and JP-A 2014-191252 The compounds described in paragraphs 0060 to 0061 of the gazette, the compounds described in paragraphs 0045 to 0052 in JP-A 2014-41264, and the compounds described in paragraph 0055 of International Publication WO 2014/097594. Moreover, as described in Paragraph No. 0050-0058 of Unexamined-Japanese-Patent No. 2011-128358, it is also preferable to use 2 or more types of different silane coupling agents.
When a silane coupling agent is used, the content of the silane coupling agent is preferably in the range of 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the heterocycle-containing polymer precursor. The scope of the department. When the amount is 0.1 parts by mass or more, sufficient adhesion to the substrate can be imparted, and when the amount is 20 parts by mass or less, problems such as viscosity increase can be further suppressed during storage at room temperature.
The silane coupling agent may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes said range.

<Dissolution accelerator>
When the composition in the present invention is a positive type using an alkali developing solution, it is preferable to add a dissolution accelerator (a compound which promotes solubility) from the viewpoint of sensitivity improvement. As the dissolution accelerator, low molecular weight phenols (for example, Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIR- PC, BIR-PTBP, BIR-BIPC-F (above, trade name, manufactured by Asahi Organic Materials Industry Co., Ltd., phenols described in paragraphs 0056 to 0062 of JP-A-2013-152381) and aryl sulfonamide derivatives (for example, And compounds described in Paragraph No. 0058 of JP-A-2011-164454).
When a dissolution accelerator is used, the content of the dissolution accelerator is preferably in the range of 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the heterocycle-containing polymer precursor. It is a range.
The dissolution accelerator may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes said range.

<Dissolution inhibitor>
When the composition of the present invention is a positive type using an alkaline developer, it can contain a dissolution inhibitor (a compound that inhibits the solubility) in order to adjust the solubility in the alkaline developer. As such compounds, onium salts, diaryl compounds and tetraalkylammonium salts are preferred.
Examples of the onium salt include iodonium salts such as diaryliodonium salts, sulfonium salts such as triarylsulfonium salts, and diazonium salts such as phosphonium salts and aryldiazonium salts.
Examples of the diaryl compound include compounds in which two aryl groups such as diaryl urea, diaryl sulfone, diaryl ketone, diaryl ether, diaryl propane, and diaryl hexafluoropropane are linked via a linking group, and examples of the aryl group include phenyl Groups are preferred.
Examples of the tetraalkylammonium salt include tetraalkylammonium halides in which the alkyl group is a methyl group or an ethyl group.

  Among them, those showing a good dissolution inhibiting effect include diaryliodonium salts, diarylureas, diarylsulfones, tetramethyl ammonium halides, etc., and diarylureas include diphenylurea, dimethyldiphenylurea etc. Examples of methyl ammonium halides include tetramethyl ammonium chloride, tetramethyl ammonium bromide, tetramethyl ammonium iodide and the like.

Among them, diaryl iodonium salts represented by the general formula (Inh) are preferable.
(Wherein, X ⁻ represents a counter anion, R ⁷ and R ⁸ each independently represent a monovalent organic group, and a and b are each independently an integer of 0 to 5)

Examples of the counter anion X ^- include nitrate ion, boron tetrafluoride ion, perchlorate ion, trifluoromethanesulfonate ion, p-toluenesulfonate ion, thiocyanate ion, chloride ion, bromide ion, iodide ion and the like. Be

Examples of diaryl iodonium salts include diphenyl iodonium nitrate, bis (p-tert-butylphenyl) iodonium nitrate, diphenyl iodonium trifluoromethane sulfonate, bis (p-tert-butyl phenyl) iodonium trifluoromethane sulfonate, diphenyl iodonium Bromide, diphenyliodonium chloride, diphenyliodonium iodide, diphenyliodonium-8-anilinonaphthalene-1-sulfonate and the like can be used.
Among these, diphenyliodonium nitrate, diphenyliodonium trifluoromethanesulfonate and diphenyliodonium-8-anilinonaphthalene-1-sulfonate are mentioned as highly effective and preferable.

When the dissolution inhibitor is contained, the content of the dissolution inhibitor is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the heterocycle-containing polymer precursor from the viewpoint of sensitivity and an allowable range of development time, 0.1-15 mass parts is more preferable, and 0.5-10 mass parts is further more preferable.
The dissolution inhibitor may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes said range.

<Sensitizing dye>
The composition in the present invention may contain a sensitizing dye. The sensitizing dye absorbs specific actinic radiation to be in an electronically excited state. The sensitizing dye in the electronically excited state comes into contact with an amine generator, a thermal radical polymerization initiator, a photo radical polymerization initiator and the like to cause actions such as electron transfer, energy transfer and heat generation. As a result, the amine generator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo a chemical change and decompose to form a radical, an acid or a base.

  Examples of preferable sensitizing dyes include those belonging to the following compounds and having a maximum absorption wavelength in the range of 300 nm to 450 nm. For example, polynuclear aromatics (eg, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9, 10-dialkoxyanthracene), xanthenes (eg, fluorescein, eosin, erythrosin, rhodamine B, rose bengal), thioxanthones (eg, 2,4-diethylthioxanthone), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, For example, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squaliliums (eg, squalilium), coumarins (eg, 7-di) Chiruamino 4-methylcoumarin), styryl benzenes, distyryl benzenes, carbazoles, and the like.

  Among them, in the present invention, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene), thioxanthones, distyrylbenzenes and styrylbenzenes are preferably used in view of initiation efficiency, and anthracene skeleton It is more preferable to use the compound which it has. Particularly preferable specific compounds include 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene and the like.

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

<Chain transfer agent>
The composition in the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in Polymer Dictionary Third Edition (edited by the Polymer Society of Japan, 2005) pages 683 to 684. As the chain transfer agent, for example, a compound group having SH, PH, SiH, GeH in the molecule is used. They can donate hydrogen to a low active radical species to form a radical or be oxidized and then deprotonated to form a radical. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazole, etc.) can be preferably used.

When the composition contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, with respect to 100 parts by mass of the total solid content of the composition. More preferably, it is 1 to 5 parts by mass.
The chain transfer agent may be used alone or in combination of two or more. When two or more chain transfer agents are used, the total is preferably in the above range.

<Polymerization inhibitor>
The composition in the present invention preferably contains a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the heterocycle-containing polymer precursor and the radically polymerizable compound during production or storage.
Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butyl catechol, 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 ether diamine tetraacetic acid, 2,6-di-tert-butyl-p-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-) Preferred is butyl) phenylmethane.
As for content of a polymerization inhibitor, when a composition contains a polymerization inhibitor, 0.01-5 mass% is preferable with respect to the total solid of a composition.
The polymerization inhibitor may be used alone or in combination of two or more. When two or more polymerization inhibitors are used, the total is preferably in the above range.

<Surfactant>
Various surfactants may be added to the composition of the present invention from the viewpoint of further improving the coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, a silicone surfactant and the like can be used.
In particular, by containing a fluorine-based surfactant, the liquid properties (in particular, the flowability) when prepared as a coating liquid are further improved, so that the uniformity of coating thickness and the liquid saving property can be further improved. .
In the case of film formation using a coating liquid containing a fluorine-based surfactant, the wettability to the surface to be coated is improved by lowering the interfacial tension between the surface to be coated and the coating liquid, and the coating surface is to be coated. Coating properties are improved. For this reason, even in the case where a thin film of about several μm is formed with a small amount of liquid, it is effective in that film formation with a uniform thickness with small thickness unevenness can be more suitably performed.

3-40 mass% is suitable for the fluorine content rate of a fluorine-type surfactant, More preferably, it is 5-30 mass%, Most preferably, it is 7-25 mass%. The fluorine-based surfactant having a fluorine content in this range is effective in terms of the uniformity of the thickness of the coating film and the liquid saving property, and the solubility is also good.
Examples of fluorine-based surfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F44, R30, F437, F475, F479, and the like. The F482, the F554, the F780, the F781 (above, made by DIC Corporation), the Florard FC430, the same FC431, the same FC171 (above, Sumitomo 3M Co., Ltd.), Surfron S-382, the same SC-101, The same SC-103, the same SC-104, the same SC-105, the same SC 1068, the same SC-383, the same S393, the same KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320 , PF6520, PF7002 (manufactured by OMNOVA), and the like.
A block polymer can also be used as a fluorine-type surfactant, and the compound described in Unexamined-Japanese-Patent No. 2011-89090 is mentioned as a specific example, for example.
Further, the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.
The weight average molecular weight of the above compound is, for example, 14,000.

  Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and ethoxylates and propoxylates thereof (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronics 304, 701, 704, 901, 904, 150R1) Solsperse 20000 (Lubrizol Japan Co., Ltd.), and the like. In addition, Pionin D-6112-W manufactured by Takemoto Oil & Fat Co., Ltd., NCW-101, NCW-1001 and NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. can also be used.

  Specific examples of cationic surfactants include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid Co) polymer poly flow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like.

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

  As silicone type surfactant, for example, Toray Dow Corning Co., Ltd. product "Tore silicone DC3PA", "Tore silicone SH7PA", "Tore silicone DC11PA", "Tore silicone SH21PA", "Tore silicone SH28PA", "Tore silicone SH21PA" Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400, Momentive Performance Materials, Inc. "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460", "TSF “4452”, “KP341”, “KF6001”, “KF6002” manufactured by Shin-Etsu Silicone Co., Ltd., “BYK307”, “BYK323”, “BYK330” manufactured by BIC Chemie, and the like.

When the composition contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.% by mass with respect to the total solid content of the composition. It is 0 mass%.
The surfactant may be used alone or in combination of two or more. When two or more surfactants are used, the total is preferably in the above range.

<Higher fatty acid derivatives etc>
In the composition of the present invention, in order to prevent polymerization inhibition by oxygen, behenic acid, higher fatty acid derivatives such as behenic acid amide, etc. are added, and uneven distribution is made on the surface of the composition in the process of drying after coating. May be
When the composition contains a higher fatty acid derivative or the like, the content of the higher fatty acid derivative or the like is preferably 0.1 to 10% by mass with respect to the total solid content of the composition.
The higher fatty acid derivatives may be used alone or in combination of two or more. When two or more kinds of higher fatty acid derivatives and the like are used, the total is preferably in the above range.

<Solvent>
When making the composition in this invention into a layer by application, it is preferable to mix | blend a solvent. As the solvent, known ones can be used without limitation as long as the composition can be formed into a layer.
As a solvent used for the composition of the present invention, as esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, lactic acid Methyl, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyl oxyacetate (for example, methyl alkyl oxyacetate, ethyl alkyl oxy acetate, butyl alkyl oxy acetate (for example, methyl methoxy acetate, methoxy ethyl acetate, Butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate etc.), 3-alkyloxypropionic acid alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, 3-methoxy) Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate etc.), 2-alkyloxypropionic acid alkyl esters (eg methyl 2-alkyloxypropionate, 2- Ethyl alkyl oxypropionate, propyl 2-alkyl oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionic acid Ethyl)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionic acid) Methyl etc., methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate etc. and as ethers, eg, 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 , And propylene glycol Chole monopropyl ether acetate and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and N-methyl-2-pyrrolidone and the like, and as aromatic hydrocarbons, For example, toluene, xylene, anisole, limonene etc., dimethyl sulfoxide is suitably mentioned as sulfoxides.

  The solvent is also preferably in the form of a mixture of two or more, from the viewpoint of improvement of the coated surface condition. Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone A mixed solution composed of two or more selected from dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable. In particular, the combined use of dimethyl sulfoxide and γ-butyrolactone is preferred.

When the composition contains a solvent, the content of the solvent is preferably from 5% to 80% by mass from the viewpoint of coatability, and the total solid content concentration of the composition is 5% to 70% by mass. Preferably, 10 to 60% by mass is more preferable.
The solvent may be used alone or in combination of two or more. When two or more solvents are used, the total is preferably in the above range.
In addition, the contents of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide and N, N-dimethylformamide are relative to the total mass of the composition from the viewpoint of film strength. Less than 5% by mass is preferable, less than 1% by mass is more preferable, less than 0.5% by mass is more preferable, and less than 0.1% by mass is more preferable.

<Other additives>
The composition according to the present invention may contain various additives, for example, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet light absorbers, aggregation prevention, as needed, as long as the effects of the present invention are not impaired. Agents and the like can be blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the composition.

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

From the viewpoint of insulation, the metal content of the composition in the present invention is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and still more preferably less than 0.5 mass ppm. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are included, the total of these metals is preferably in the above range.
In addition, as a method of reducing metal impurities which are unintentionally contained in the composition, the raw material constituting the composition is selected by using a raw material having a small metal content as a raw material constituting the composition. There may be mentioned a method in which the inside of the apparatus is lined with polytetrafluoroethylene or the like, and distillation is performed under the condition where contamination is suppressed as much as possible.

  The content of halogen atoms in the composition of the present invention is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and still more preferably less than 200 mass ppm, from the viewpoint of wiring corrosion. Among them, those less than 5 mass ppm are preferable, those less than 1 mass ppm are more preferable, and less than 0.5 mass ppm is more preferable. The halogen atom includes a chlorine atom and a bromine atom. It is preferable that the total of a chlorine atom and a bromine atom, or a chloride ion and a bromide ion is respectively in the above range.

<Preparation of composition>
The composition in the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and can be carried out by a conventionally known method.
Moreover, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and particles in the composition. The pore diameter of the filter is preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.1 μm or less. As a material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. The filter may be one previously washed with an organic solvent. In the filter filtration step, a plurality of filters may be connected in series or in parallel. When multiple types of filters are used, filters with different pore sizes and / or different materials may be used in combination. Also, the various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulation filtration step. Moreover, you may pressurize and you may filter, and the pressure to pressurize has preferable 0.05-0.3 MPa.
Besides filtration using a filter, removal of impurities may be performed using an adsorbent. In addition, filtration using a filter and removal of impurities using an adsorbent may be performed in combination. As the adsorbent, known adsorbents can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.

<Use>
The method for producing a cured film of the present invention can be preferably used in the fields of insulating films for semiconductor devices, interlayer insulating films for rewiring layers, and the like. That is, the present invention also discloses a method of manufacturing a semiconductor device including the method of manufacturing a cured film of the present invention. In particular, since the resolution is good, it can be preferably used for the production of an interlayer insulating film for rewiring layers in a three-dimensional mounting device. That is, the present invention also discloses a method for producing an interlayer insulating film for rewiring layer, including the method for producing a cured film of the present invention. Furthermore, a cured film obtained by the method for producing a cured film of the present invention, and a semiconductor device obtained by the method for producing a cured film of the present invention are disclosed.
Moreover, the cured film manufactured by this invention can also be used for the photoresist (galvanic (electrolytic) resist (galvanic resist), an etching resist, a solder top resist (solder top resist)) etc. for electronics.
The cured films produced according to the invention can also be used for the production of printing plates, such as offset printing plates or screen printing plates, for use in the etching of molded parts, for the production of protective lacquers and dielectric layers in electronics, especially in microelectronics .

Next, an embodiment of a semiconductor device using the above composition for an interlayer insulating film for redistribution layers will be described.
A semiconductor device 100 illustrated in FIG. 1 is a so-called three-dimensional mounting device, and a stacked body 101 in which a plurality of semiconductor elements (semiconductor chips) 101 a to 101 d are stacked is disposed on a wiring substrate 120.
Although this embodiment will be described focusing on the case where the number of stacked semiconductor elements (semiconductor chips) is four, the number of stacked semiconductor elements (semiconductor chips) is not particularly limited. It may be a layer, eight layers, sixteen layers, thirty two layers or the like. Also, it may be a single layer.

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

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

  Underfill layers 110 are formed in the gaps between the semiconductor elements 101a to 101d, and the semiconductor elements 101a to 101d are stacked via the underfill layer 110.

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

A surface electrode 120 a is provided on one surface of the wiring substrate 120.
The insulating layer 115 on which the rewiring layer 105 is formed is disposed between the wiring substrate 120 and the stacked body 101, and the wiring substrate 120 and the stacked body 101 are electrically connected to each other through the rewiring layer 105. It is connected. The insulating layer 115 is formed by using the photosensitive resin composition of the present invention.
That is, one end of the redistribution layer 105 is connected to an electrode pad formed on the surface of the semiconductor element 101d on the redistribution layer 105 side via the metal bump 103d such as a solder bump. Further, the other end of the rewiring layer 105 is connected to the surface electrode 120a of the wiring board via the metal bump 103e such as a solder bump.
An underfill layer 110 a is formed between the insulating layer 115 and the stack 101. Also, an underfill layer 110 b is formed between the insulating layer 115 and the wiring substrate 120.

In addition to the above, the cured film produced by the present invention can be widely adopted in various applications using polyimide and polybenzoxazole.
In addition, since polyimide and polybenzoxazole are resistant to heat, the cured film produced according to the present invention is used for transparent plastic substrates for display devices such as liquid crystal displays and electronic papers, automobile parts, heat resistant paints, coating agents and films Can also be suitably used.

  Hereinafter, the present invention will be more specifically described by way of examples. The materials, amounts used, proportions, treatment contents, treatment procedures and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below.

<Method of measuring weight average molecular weight (Mw) / number average molecular weight (Mn)>
Mw and Mn are the polystyrene conversion value by gel permeation chromatography (GPC) measurement, and were measured by the following method.
Using HLC-8220 (manufactured by Tosoh Corp.) as a measuring apparatus, guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ 3000, TSKgel Super HZ 2000 (manufactured by Tosoh Corp.) Using. The eluent was THF (tetrahydrofuran), and the measurement was performed at 40 ° C. and at a flow rate of 0.35 mL / min. The detection used the ultraviolet-ray (UV) 254 nm detector. Further, as a measurement sample, a sample in which the heterocycle-containing polymer precursor was diluted to 0.1% by mass with THF was used.

Synthesis Example 1 Synthesis of PIp-A
21.2 g of 4,4'-oxydiphthalic dianhydride (dried at 140 ° C for 12 hours), 18.1 g of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 23.9 g of pyridine, 150 mL The mixture was mixed with diglyme (diethylene glycol dimethyl ether) and stirred at a temperature of 60.degree. C. for 2 hours to produce a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to −10 ° C. and 17.1 g of SOCl ₂ was added over 60 minutes, keeping the temperature at −10 ± 4 ° C. After dilution with 50 mL of N-methylpyrrolidone, a solution of 11.7 g of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture over 60 minutes at -10 ± 4 ° C The mixture was stirred for 2 hours. Then, it was poured into 6 liters of water to precipitate the polyimide precursor, and the water-polyimide precursor mixture was stirred at a speed of 5,000 rpm for 15 minutes. The polyimide precursor was filtered off, again poured into 4 liters of water, stirred for a further 30 minutes and filtered again. Next, the obtained polyimide precursor was dried at 45 ° C. for 3 days under reduced pressure.
The polyimide precursor had a weight average molecular weight of 16,000, a number average molecular weight of 7,620, and a degree of dispersion of 2.1.

Synthesis Example 2 Synthesis of PIp-B
Mix 10.5 g of pyromellitic dianhydride, 10.0 g of 4,4'-diaminodiphenyl ether, 4.0 g of pyridine and 150 mL of N-methyl-2-pyrrolidone at a temperature of 60 ° C. The mixture was stirred for 3 hours. Then, it was poured into 6 liters of water to precipitate the polyimide precursor, and the water-polyimide precursor mixture was stirred at a speed of 5,000 rpm for 15 minutes. The polyimide precursor was filtered off, poured again into 6 liters of water, stirred for a further 30 minutes and filtered again. Next, the obtained polyimide precursor was dried at 45 ° C. for 3 days under reduced pressure.
The polyimide precursor had a weight average molecular weight of 20,000, a number average molecular weight of 8,000, and a degree of dispersion of 2.5.

Synthesis Example 3 Synthesis of PBp-D
To 100 mL of N-methyl-2-pyrrolidone, 13.92 g of 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added and dissolved by stirring. Subsequently, 8.00 g of suberic acid dichloride was added dropwise over 10 minutes while maintaining the temperature at 0 to 5 ° C., and stirring was continued for 60 minutes. Then, it was poured into 6 liters of water to precipitate the polybenzoxazole precursor, and the water-polybenzoxazole precursor mixture was stirred at a speed of 5,000 rpm for 15 minutes. The polybenzoxazole precursor was filtered off, poured again into 6 liters of water, stirred for a further 30 minutes and filtered again. Then, the obtained polybenzoxazole precursor was dried under reduced pressure at 45 ° C. for 3 days.
The polybenzoxazole precursor had a weight average molecular weight of 11,500, a number average molecular weight of 6,800, and a dispersity of 1.7.

Synthesis Example 4 Synthesis of PBp-E
A polybenzoxazole precursor was obtained in the same manner as in Synthesis Example 3, except that suberic acid dichloride was changed to 11.21 g of 4,4′-oxydibenzoyl chloride.
The polybenzoxazole precursor had a weight average molecular weight of 15,000, a number average molecular weight of 7,100, and a degree of dispersion of 2.1.

Synthesis Example 5 Synthesis of PB-F
A polybenzoxazole precursor was obtained in the same manner as in Synthesis Example 3, except that suberic acid dichloride was changed to 8.55 g of azelaic acid chloride. The obtained precursor was dissolved in 100 mL of N-methyl-2-pyrrolidone, 100 mg of p-toluenesulfonic acid was added, and stirred at 200 ° C. for 48 hours to complete oxazolization. Then, it was poured into 6 liters of water to precipitate polybenzoxazole, and the water-polybenzoxazole mixture was stirred at a speed of 5,000 rpm for 15 minutes. The polybenzoxazole was filtered off, poured again into 6 liters of water, stirred for a further 30 minutes and filtered again. The resulting polybenzoxazole was then dried at 45 ° C. for 3 days under reduced pressure.
The polybenzoxazole had a weight average molecular weight of 17,500, a number average molecular weight of 10,000, and a dispersion degree of 1.8.

Synthesis Example 6 PIp-C
The same procedure as in Synthesis Example 1 was repeated except that 21.2 g of 4,4'-oxydiphthalic acid dianhydride was changed to 20.1 g of diphenyl-3,3 ', 4,4'-tetracarboxylic acid dianhydride. The polyimide precursor was obtained.
20.1 g of diphenyl-3,3 ′, 4,4′-tetracarboxylic acid dianhydride (dried at 140 ° C. for 12 hours), 18.1 g of 2-hydroxyethyl methacrylate and 0.05 g of hydroquinone 23.9 g of pyridine and 150 mL of N-methylpyrrolidone were mixed and stirred at a temperature of 60 ° C. for 2 hours to produce a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to −10 ° C. and 17.1 g of SOCl ₂ was added over 60 minutes, keeping the temperature at −10 ± 4 ° C. After dilution with 50 mL of N-methylpyrrolidone, a solution of 11.7 g of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture over 60 minutes at -10 ± 4 ° C The mixture was stirred for 2 hours. Then, 6 liters of water was added to precipitate the polyimide precursor, and the water-polyimide precursor mixture was stirred at a speed of 5,000 rpm for 15 minutes. The polyimide precursor was filtered off, again poured into 4 liters of water, stirred for a further 30 minutes and filtered again. Next, the obtained polyimide precursor was dried at 45 ° C. for 3 days under reduced pressure.
The polyimide precursor had a weight average molecular weight of 15,000, a number average molecular weight of 6,820, and a degree of dispersion of 2.2.

<Example and Comparative Example>
The following components were mixed to prepare a composition (coating solution) as a homogeneous solution.
<< Composition Composition >>
Heterocycle-containing polymer precursor: mass% according to Table 6 or 7
Amine generator: mass% described in Table 6 or 7
Polymerization initiator: mass% described in Table 6 or 7
Crosslinking agent: mass% described in Table 6 or 7
Solvent:% by mass listed in Table 6 or 7
In Example 1, “PIp-A” of the heterocycle-containing polymer precursor indicates the type of precursor, and the numerical value “33” indicates the compounding amount (unit: mass%) in the composition. The same applies to the other components. The same applies to other examples and comparative examples.

TBG1 has an amine generation temperature of 150 ° C. and pKa1 = 1.9.
TBG2 has an amine generation temperature of 150 ° C. and pKa1 = 1.9.
TBG3 has an amine generation temperature of 150 ° C. and pKa1 = 1.9.
TBG 4 has an amine generation temperature of 145 ° C.
TBG 5 has an amine generation temperature of 150 ° C.
TBG 6 has an amine generation temperature of 180 ° C.

INI1 is a product of BASF, IRGACURE-OXE01.
INI2 is IRGACURE-OXE02 manufactured by BASF.
INI 3 was synthesized by the method described in Synthesis Example 4 of International Publication WO 05/069075 Pamphlet.
INI 4 is IRGACURE 784 manufactured by BASF.

SLV1: Γ-butyrolactone SLV2: dimethyl sulfoxide SLV3: N-methyl-2-pyrrolidone

link 1 has a molecular weight of 330 and is 4G manufactured by Shin-Nakamura Chemical Co., Ltd.
link2 has a molecular weight of 536 and is 9G manufactured by Shin-Nakamura Chemical Co., Ltd.
link 3 has a molecular weight of 1136 and is 23 G manufactured by Shin-Nakamura Chemical Co., Ltd.
link4 has a molecular weight of 318 and is T2058 manufactured by Tokyo Chemical Industry Co., Ltd.
link5 has a molecular weight of 168 and is B1525 manufactured by Tokyo Chemical Industry Co., Ltd.
link 6 has a molecular weight of 951.

<Amine amount>
The amount of amine in the cured film was quantified using gas chromatography (manufactured by Agilent) connected with a head space sampler under the following conditions.
The composition described in Table 6 or 7 was spin-coated on a 4-inch silicon wafer (1 inch: 2.54 cm) at 1,000 rpm, and film formation was performed by heating at 100 ° C. for 2 minutes on a hot plate. The obtained wafer was heated and cured on a hot plate under a stream of nitrogen under the conditions described in Table 6 or 7. Here, the heating temperature in Tables 6 and 7 means the maximum heating temperature at the time of heat curing, and the heating time means the heating time after reaching the maximum heating temperature. Further, the temperature at the start of the temperature rise is 25.degree.
The obtained wafer was divided, packed in a 20 mL vial, and the components in the cured film were volatilized by a head space sampler at 230 ° C. for 7 minutes.
The volatilized component is introduced into gas chromatography (manufactured by Agilent), heated at 150 ° C. for 5 minutes using capillary column HP-1MS (manufactured by Agilent), and then heated at a temperature rising rate of 5 ° C./min. It isolate | separated, heating at 230 degreeC for 5 minutes, and it detected with the detector (Flame Ionization Detector, FID) (made by Agilent). The amine content in the cured film was calculated from the peak area of the obtained amine and the calibration curve of the amine prepared separately. The corresponding amines were weighed in various amounts into vials, measured under the same conditions as the samples, and a calibration curve was prepared from the obtained peak areas and the weighed values.

<Corrosion resistance>
The composition described in Table 6 or 7 was spin-coated at 1,000 rpm onto a copper-deposited 4-inch silicon wafer, and was deposited on a hot plate by heating at 100 ° C. for 2 minutes. The obtained wafer was heat cured on the hot plate under a stream of nitrogen under the conditions described in Table 6 or 7.
After curing, the obtained wafer was left under the conditions of a temperature of 85 ° C. and a relative humidity of 85%, and the time until the copper surface was colored was measured. The color was checked visually. The corrosion resistance was evaluated from the following viewpoints.
A: No color was observed even after 3 hours or more B: Color was observed within 3 hours over 1 hour C: Color was observed within 1 hour

<Chemical resistance>
The composition described in Table 6 or 7 was spin-coated on a 4-inch silicon wafer at 1,000 rpm, and film formation was performed by heating at 100 ° C. for 2 minutes on a hot plate. The obtained wafer was heated and cured on a hot plate under a stream of nitrogen under the conditions described in Table 6 or 7.
After curing, the obtained wafer was immersed in N-methyl-2-pyrrolidone for 3 hours, washed with isopropyl alcohol and air dried. The presence or absence of cracks in the cured film of the obtained wafer was visually observed. The chemical resistance was evaluated from the following viewpoints.
A: No cracks were observed on the entire surface of the wafer B: Cracks were observed on part of the wafer C: Cracks were observed on the entire surface of the wafer

<Outgassing>
The composition described in Table 6 or 7 was spin-coated on a 4-inch silicon wafer at 1,000 rpm, and film formation was performed by heating at 100 ° C. for 2 minutes on a hot plate. The obtained wafer was heated and cured on a hot plate under a stream of nitrogen under the conditions described in Table 6 or 7.
After curing, the obtained wafer was heated by a thermogravimetric analyzer (Q-500, manufactured by TA Instruments) to 350 ° C. at a rate of 10 ° C./min under a nitrogen stream to measure a mass reduction rate.
The outgassing properties were evaluated in the following points.
A: The mass reduction rate is less than 1% B: The mass reduction rate is 1% or more and less than 5% C: The mass reduction rate is 5% or more

  As is clear from the above-mentioned table, in the production method of the present invention, a cured film excellent in corrosion resistance and chemical resistance was obtained. In particular, by setting the temperature rising temperature for heating to a predetermined range, a cured film having more excellent various performances was obtained.

Example 100
After pressure-filtering the photosensitive resin composition of Example 11 through a filter having a pore width of 0.8 μm, it is applied by spinning (3,500 rpm, 30 seconds) to a resin substrate on which a copper thin layer is formed. did. The photosensitive resin composition applied to the resin substrate was dried at 100 ° C. for 5 minutes and then exposed using an aligner (Karl-Suss MA150). The exposure was performed with a high pressure mercury lamp, and the exposure energy at a wavelength of 365 nm was measured. After exposure, the image was developed for 75 seconds with cyclopentanone.
It was then heated at 180 ° C. for 20 minutes. Thus, an interlayer insulating film for rewiring layer was formed.
The interlayer insulation film for the redistribution layer was excellent in insulation.
Moreover, when the semiconductor device was manufactured using this interlayer insulation film for rewiring layers, it confirmed that it operate | moveed without a problem.

100: semiconductor devices 101a to 101d: semiconductor elements 101: laminates 102b to 102d: through electrodes 103a to 103e: metal bumps 105: rewiring layers 110, 110a, 110b: underfill layer 115: insulating layer 120: wiring substrate 120a: Surface electrode

Claims (18)

The layer comprising the composition containing at least one of the polyimide precursor and the polybenzoxazole precursor and the amine generator is heated at a temperature of 250 ° C. or less at the maximum heating temperature, the amine content is 50 to 5, Method of producing a cured film of 000 ppm. The method for producing a cured film according to claim 1, wherein the amine generator is at least one of a photoamine generator and a thermal amine generator. The method for producing a cured film according to claim 1, wherein the amine generator is a thermal amine generator. The manufacturing method of the cured film of any one of Claims 1-3 in which the said composition does not contain the amine more than pKa8 of a conjugate acid. The method for producing a cured film according to any one of claims 1 to 4, wherein the heating is performed at a temperature rising rate of 1 to 10 ° C / minute from a temperature of 20 to 150 ° C to the maximum heating temperature. The method for producing a cured film according to claim 5, wherein the heating is performed at the temperature rising rate, and heating is performed for 60 to 240 minutes after reaching the maximum heating temperature. The composition according to any one of claims 1 to 6, wherein the composition comprises the amine generator in a proportion of 0.01 to 45% by mass with respect to the total amount of the polyimide precursor and the polybenzoxazole precursor. Of the cured film of The manufacturing of the cured film according to any one of claims 1 to 7, wherein the polyimide precursor is represented by the following general formula (2), and the polybenzoxazole precursor is represented by the following general formula (3). Method;
General formula (2)
In general formula (2), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group;
General formula (3)
In formula (3), 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 Represents In formula (2), at least one of ^{A 1} and ^{A 2} is an oxygen ^atom, of ^{R 113} and ^{R 114, R 113} and ^{R 114} adjacent ^{A 1} and ^{A 2} is an oxygen atom, 1 Represent a valent organic group, or
The manufacturing method of the cured film of Claim 8 whose R ^<121> is a linear aliphatic group in General formula (3). The manufacturing method of the cured film of any one of Claims 1-9 whose said maximum heating temperature is 160-250 degreeC. The manufacturing method of the cured film of any one of Claims 1-10 whose amine content of the said cured film is 500-2,000 ppm. The manufacturing method of the cured film of any one of Claims 1-11 in which the said composition contains a crosslinking agent further. The manufacturing method of the cured film of Claim 12 whose molecular weight of the said crosslinking agent is 100-800. The amine generator is at least one selected from an acidic compound which generates an amine when heated to 40 to 250 ° C., and an ammonium salt having an anion of pKa 1 of 0 to 4 and an ammonium cation. The manufacturing method of the cured film of any one of 13. The manufacturing method of the cured film of Claim 14 which is a compound which generate | occur | produces an amine when the said acidic compound is heated at 40-250 degreeC. The manufacturing method of the cured film of Claim 14 or 15 whose said acidic compound is a salt of ammonium cation and carboxylic acid anion. The manufacturing method of the interlayer insulation film for rewiring layers including the manufacturing method of the cured film of any one of Claims 1-16. The manufacturing method of a semiconductor device containing the manufacturing method of the cured film of any one of Claims 1-16.