TWI824035B - Resin composition, cured film, laminate, cured film manufacturing method, and semiconductor element - Google Patents

Abstract

The present invention provides a resin composition, which contains: at least one resin selected from the group consisting of polyimide precursors, polyimide, polybenzoethazole precursors and polybenzoethazole; and respectively Compound B containing a group that generates a base by heating and a group represented by formula (b1) and having a pKa of 5 or more. Formula (b1); -M(R ¹ )(R ² )(R ³ ). M represents Si or the like, R ¹ to R ³ each independently represent Rb ¹ or ORb ¹ , and Rb ¹ represents a hydrocarbon group having 1 to 10 carbon atoms. Also provided are a cured film using a resin composition, a laminate, a method for manufacturing the cured film, and a semiconductor element.

Description

Resin composition, cured film, laminate, cured film manufacturing method, and semiconductor element

唑前驅物之群組中之至少一種聚合物前驅物之樹脂組成物。又，本發明有關一種使用包含前述聚合物前驅物之樹脂組成物之硬化膜、積層體、硬化膜的製造方法及半導體元件。 The present invention relates to a product comprising a polyimide precursor and a polybenzo

A resin composition of at least one polymer precursor from the group of azole precursors. Furthermore, the present invention relates to a cured film, a laminate, a cured film manufacturing method and a semiconductor element using a resin composition containing the aforementioned polymer precursor.

唑等樹脂由於耐熱性及絕緣性優異，因此用於電子元件的絕緣層等。又，聚醯亞胺或聚苯并

唑對溶劑的溶解性低，因此亦以環化反應前的前驅物(聚醯亞胺前驅物或聚苯并

唑前驅物)的狀態適用於支撐體等之後加熱環化聚醯亞胺前驅物或聚苯并

唑前驅物而形成硬化膜。 Polyimide or polybenzo

Resins such as azole are used for insulating layers of electronic components and the like because they have excellent heat resistance and insulation properties. Also, polyimide or polybenzo

Azoles have low solubility in solvents, so they are also used as precursors before the cyclization reaction (polyimide precursor or polybenzo

The state of the azole precursor) is suitable for heating the support, etc. to cyclize the polyimide precursor or polybenzo

The azole precursor forms a hardened film.

唑前驅物等聚合物前驅物和熱鹼產生劑之樹脂組成物之發明。 Patent Document 1 describes a material containing a polyimide precursor or polybenzo

The invention of a resin composition of polymer precursors such as azole precursors and thermal base generators.

[Prior technical literature]

[Patent Document]

[Patent Document 1] International Publication No. 2015/199219

唑前驅物等聚合物前驅物之樹脂組成物的保存穩定性。 Through the technology of the above-mentioned Patent Document 1, it is possible to improve the quality of products containing polyimide precursors or polybenzoyl

Storage stability of resin compositions of polymer precursors such as azole precursors.

On the other hand, in order to respond to the diversified required properties required for resin compositions containing such polymer precursors and the like in recent years, further research and development is required. For example, there is a demand for further improvement in the storage stability of the resin composition or the adhesion or reliability to the metal or the like of the obtained cured film.

Therefore, an object of the present invention is to provide a resin composition, a cured film, a laminate, a cured film manufacturing method, and a semiconductor element that have good storage stability and can form a cured film excellent in adhesion and reliability.

唑前驅物及聚苯并

唑之群組中之至少一種樹脂之樹脂組成物進行深入研究的結果，發現藉由進一步添加後述之規定化合物，能夠實現上述目的，以至完成本發明。本發明提供以下內容。 The inventors of the present invention are interested in polyimide precursors, polyimide, polybenzo

Azole precursors and polybenzo

As a result of intensive studies on the resin composition of at least one resin in the azole group, it was found that the above object can be achieved by further adding a specified compound described below, and the present invention was completed. The present invention provides the following.

唑前驅物及聚苯并

唑之群組中之至少一種樹脂；以及分別包含藉由加熱生成鹼基之基團和由下述式(b1)表示之基團之pKa為5以上的化合物B；-M¹(R¹)(R²)(R³)‧‧‧‧‧‧(b1) <1> A resin composition containing: selected from polyimide precursors, polyimide, polybenzoyl

Azole precursors and polybenzo

At least one resin in the group of azoles; and compound B having a pKa of 5 or more including a group that generates a base by heating and a group represented by the following formula (b1); -M ¹ (R ¹ ) (R ² )(R ³ )‧‧‧‧‧‧(b1)

In formula (b1), M ¹ represents Si, Ti or Zr, R ¹ to R ³ each independently represent Rb ¹ or ORb ¹ , and Rb ¹ represents a hydrocarbon group having 1 to 10 carbon atoms.

<2> The resin composition according to <1>, wherein R ¹ to R ³ in the formula (b1) each independently represent ORb ¹ , and Rb ¹ represents a hydrocarbon group having 1 to 10 carbon atoms.

<3> The resin composition according to <1> or <2>, wherein M ¹ in formula (b1) represents Si.

<4> The resin composition according to any one of <1> to <3>, wherein the base generation temperature of compound B is 160°C or higher.

<5> The resin composition according to any one of <1> to <4>, wherein the group that generates a base by heating includes a heterocyclic group containing a nitrogen atom, a amide group, and a urea group. , at least one group selected from an isocyanate group, a urethane group, an allophanate group, a biuret group and an amide group.

<6> The resin composition according to any one of <1> to <4>, wherein the group generating a base by heating includes a heterocyclic group each containing a nitrogen atom and a group selected from -OCO- and - At least one group in COO-, or at least one selected from the group consisting of amide group, urea group, isocyanate group, urethane group, allophanate group, biuret group and amide imide group group.

<7> The resin composition according to any one of <1> to <6>, wherein compound B is a compound represented by the following formula (I),

In the formula (I), A ¹ represents a group that generates a base by heating, L ¹ represents a single bond or a divalent linking group, M ¹ represents Si, Ti or Zr, and R ¹ to R ³ each independently represent Rb. ¹ or ORb ¹ , Rb ¹ represents a hydrocarbon group with 1 to 10 carbon atoms.

<8> The resin composition according to any one of <1> to <7>, which contains 0.01 to 5 mass % of Compound B in the total solid content of the resin composition.

唑前驅物中的至少一種。 <9> The resin composition according to any one of <1> to <8>, wherein the resin includes a polyimide precursor and a polybenzoyl resin.

At least one of the azole precursors.

<10> The resin composition according to any one of <1> to <9>, which further contains a photoradical polymerization initiator.

<11> The resin composition according to <10>, wherein the photoradical polymerization initiator contains an oxime compound.

<12> The resin composition according to any one of <1> to <11>, which is used to form an interlayer insulating film for a rewiring layer.

<13> A cured film formed by curing the resin composition according to any one of <1> to <12>.

<14> A laminated body having two or more layers of the cured film described in <13> and having a metal layer between the two cured films.

<15> A method for manufacturing a cured film, which includes a film forming step of applying the resin composition according to any one of <1> to <12> to a substrate to form a film.

<16> The manufacturing method of the cured film according to <15>, which includes: an exposure step of exposing the film; and a development step of developing the film.

<17> The manufacturing method of the cured film according to <15> or <16>, which includes the step of heating the film at 80 to 450°C.

<18> A semiconductor element having the cured film according to <13> or the laminated body according to <14>.

According to the present invention, it is possible to provide a resin composition, a cured film, a laminate, a cured film manufacturing method, and a semiconductor element that have good storage stability and can form a cured film that is excellent in adhesion and reliability.

The contents of the present invention will be described in detail below. In addition, in this specification, "~" is used to mean a range including the numerical values described before and after it as the lower limit and the upper limit.

The description of the constituent elements in the present invention described below may be based on representative embodiments of the present invention, but the present invention is not limited to these embodiments.

Regarding the labels for groups (atomic groups) in this specification, labels that do not describe substituted or unsubstituted include both those without a substituent and those with a substituent. For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

As long as "exposure" in this specification is not particularly limited, in addition to exposure using light, drawing using particle beams such as electron beams and ion beams is also included in the exposure. In addition, the light used for exposure generally includes active light or radiation such as far ultraviolet light, extreme ultraviolet light (EUV light), X-rays, and electron beams, represented by the bright line spectrum of a mercury lamp and excimer laser.

In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", and "(meth)acrylic acid" means both "acrylic acid" and "methacrylic acid". Both or either of them, "(meth)acrylyl" means "acrylyl" "Alkenyl" and "methacryl" or either one of them.

In this specification, the term "step" is not only an independent step, but also includes it in this term if it can achieve the expected effect of the step even if it cannot be clearly distinguished from other steps.

Unless otherwise specified, the physical property values in the present invention are values at a temperature of 23°C and an air pressure of 101325 Pa or less.

In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured by gel permeation chromatography (GPC measurement), and are defined as styrene-converted values. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be, for example, HLC-8220 (manufactured by TOSOH CORPORATION), and as the column, a guard column HZ-L, TSKgel Super HZM-M, or TSKgel Super can be used. HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION). In this measurement, unless otherwise specified, THF (tetrahydrofuran) was used as the eluent. In addition, unless otherwise specified, a detector with a wavelength of 254 nm for UV rays (ultraviolet rays) will be used for detection.

[Resin composition]

唑前驅物及聚苯并

唑之群組中之至少一種樹脂；以及分別包含藉由加熱生成鹼基之基團和由後述式(b1)表示之基團之pKa為5以上的化合物B。 The resin composition of the present invention is characterized by containing: selected from the group consisting of polyimide precursor, polyimide, polybenzo

Azole precursors and polybenzo

At least one resin in the group of azoles; and Compound B having a pKa of 5 or more each including a group that generates a base by heating and a group represented by the formula (b1) described below.

唑前驅物時，藉由從化合物B產生之鹼基，亦能夠促進該等前驅物的環化反應。因此，能夠顯著提高與基板的密接性，並且即使進行將形成於基板上之硬化膜長期暴露於高溫高濕環境等可靠性試驗之後亦能夠維持優異之密接性，亦能夠顯著提高硬化膜的可靠性。進而，亦能夠提高硬化膜的延性等機械特性。 By containing the above-mentioned compound B, the resin composition of the present invention can form a cured film with good storage stability and excellent adhesion and reliability. Since the pKa of the compound B is 5 or more, it is possible to suppress the progression of resin reactions and the like during storage of the resin composition. As a result, a resin composition having excellent storage stability can be obtained. In addition, this compound contains a group that generates a base by heating (hereinafter, also referred to as a specific functional group) and a group represented by the formula (b1) described below, thereby forming adhesion and reliability with the substrate and the like. Excellent hardened film. That is, it is presumed that the group represented by the formula (b1) contained in the compound B interacts with the substrate and the like by heating during the formation of the cured film to cause a coupling reaction, and is generated from the above-mentioned specific functional group contained in the compound B. The bases interact with the resin to form bonds, etc., and it is estimated that as a result, a cured film with excellent adhesion can be formed. Furthermore, it is speculated that a polyimide precursor or polybenzoyl resin is used as the resin.

When using azole precursors, the cyclization reaction of these precursors can also be promoted by the base generated from compound B. Therefore, the adhesiveness with the substrate can be significantly improved, and even after a reliability test such as exposing the cured film formed on the substrate to a high temperature and high humidity environment for a long time, excellent adhesiveness can be maintained, and the reliability of the cured film can also be significantly improved. sex. Furthermore, mechanical properties such as ductility of the cured film can also be improved.

Furthermore, since the resin composition of the present invention can form a cured film excellent in adhesion and reliability, it can be suitably used as a resin composition for forming an interlayer insulating film for a rewiring layer.

Each component of the resin composition of the present invention will be described in detail below.

<Resin>

唑前驅物及聚苯并

唑之群組中之至少一種樹脂。本 發明的樹脂組成物中使用的樹脂包含選自聚醯亞胺前驅物及聚苯并

唑前驅物中的至少一種為較佳，包含聚醯亞胺前驅物為更佳。以下，將聚醯亞胺前驅物和聚苯并

唑前驅物統稱為聚合物前驅物。 The resin composition of the present invention contains polyimide precursors, polyimide, polybenzoyl

Azole precursors and polybenzo

At least one resin from the group of azoles. The resin used in the resin composition of the present invention includes polyimide precursors and polybenzoides.

Preferably, it contains at least one azole precursor, and more preferably it contains a polyimide precursor. In the following, the polyimide precursor and polybenzo

Azole precursors are collectively referred to as polymer precursors.

唑前驅物時，容易顯著獲得本發明的效果。其中，作為樹脂使用聚醯亞胺前驅物時，容易更顯著獲得本發明的效果。 When a resin composition containing a polymer precursor undergoes reactions such as cyclization of the polymer precursor during storage, the viscosity of the resin composition tends to change easily. According to the present invention, by using the above-mentioned specified compound B, even if it is used as a resin Those containing polymer precursors can also achieve excellent storage stability. Therefore, polyimide precursors or polybenzoyl resins are used as resins.

When using an azole precursor, it is easy to significantly obtain the effects of the present invention. Among them, when a polyimide precursor is used as the resin, the effects of the present invention can be more easily obtained.

<<Polyimide precursor>>

As the polyimide precursor, a polyimide precursor containing a structural unit represented by the following formula (1) is preferred. By using this polyimide precursor, a resin composition with better film strength can be obtained.

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

A ¹ and A ² are each independently an oxygen atom or NH, with an oxygen atom being preferred.

<<<R ¹¹¹ >>>

R ¹¹¹ represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group containing a combination thereof, and a linear aliphatic group having 2 to 20 carbon atoms. Preferably, a group including a family group, a branched chain aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof, and carbon Aromatic groups with a number of 6 to 20 are more preferred.

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

Specifically, the diamine includes a linear aliphatic group with 2 to 20 carbon atoms, a branched or cyclic aliphatic group with 3 to 20 carbon atoms, an aromatic group with 6 to 20 carbon atoms, or a group containing these combinations. Groups are preferred, and diamines containing aromatic groups with 6 to 20 carbon atoms are more preferred. Examples of the aromatic group include the following aromatic groups.

In the formula, A is a single bond or an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be substituted by a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) ₂ - , -NHCO- and the groups in these combinations are preferably single bonds or selected from alkylene groups with 1 to 3 carbon atoms that can be substituted by fluorine atoms, -O-, -C(=O)-, The groups in -S- and -SO ₂ - are more preferably selected from the group consisting of -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ - and -C(CH ₃ ) A divalent group in the group of _2- is further preferred.

Specific examples of the diamine include those selected from the group consisting of 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclopentane Cyclohexane or 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis (Aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethyl cyclohexylmethane and isophoronediamine; m-phenylenediamine and p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl and 3,3'-diaminobiphenyl, 4 ,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4 ,4'-diaminodiphenylsulfide and 3,3-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide and 3,3'-diaminodiphenylsulfide, 4,4'-Diaminobenzophenone and 3,3'-Diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2' -Dimethyl-4,4'-diaminobiphenyl (4,4'-diamino-2,2'-dimethylbiphenyl), 3,3'-dimethoxy-4,4 '-Diaminobiphenyl, 2,2-bis(4-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)terine, bis(4-amino-3-hydroxyphenyl)terine, 4,4'-Diamino-p-terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]triphenyl, bis[ 4-(3-Aminophenoxy)benzene base] terine, bis[4-(2-aminophenoxy)phenyl]terine, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl) ) anthracene, 3,3'-dimethyl-4,4'-diaminodiphenyl terine, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-amine phenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-di Methyl-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-hydranthracene, 3,3',4 ,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3 -Dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluoride, 4,4'-dimethyl-3,3'-diaminobiphenyl Base, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2-(3',5'-diaminobenzyloxy)methyl Ethyl acrylate, 2,4-diaminocumene 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-diaminofluoride, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzoaniline, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, Diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4- Aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropentane Fluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis Methylphenyl]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-amine methyl-3-trifluoromethylphenoxy) Benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylsine, 4,4'-bis(3-amino-5-trifluoromethylphenoxy) )diphenylsine, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl -4,4'-Diaminobiphenyl, 4,4'-Diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6' -At least one diamine among hexafluorobenzidine and 4,4'-diaminotetraphenyl.

In addition, the diamines (DA-1) to (DA-18) shown below are also preferred.

Preferable examples include diamines having at least two alkylene glycol units in the main chain. Preferably, two or more B are combined in one molecule. The diamine of any one or both of the glycol chain and the propylene glycol chain is more preferably a diamine that does not contain an aromatic ring. Specific examples include JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR- 148. JEFFAMINE (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy)ethyl) Oxy)propoxy)propane-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propane-2-amine, etc., but are not limited to to such.

The following shows JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE (registered trademark) Registered Trademark) Structure of EDR-176.

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

From the viewpoint of flexibility of the obtained cured film, R ¹¹¹ is preferably represented by -Ar ⁰ -L ⁰ -Ar ⁰ -. Among them, Ar ⁰ is each independently an aromatic hydrocarbon group (carbon number 6 to 22 is preferred, 6 to 18 is more preferred, 6 to 10 is particularly preferred), and phenylene group is preferred. L ⁰ represents a single bond, selected from aliphatic hydrocarbon groups with 1 to 10 carbon atoms that may be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -S(=O) ₂ -, - NHCO- and groups in combinations thereof. The definition of the preferred range is the same as A above.

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

R ⁵⁰ ~ R ⁵⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ⁵⁰ ~ R ⁵⁷ is a fluorine atom, methyl, fluoromethyl, difluoromethyl or trifluoromethyl .

Examples of the monovalent organic group of R ⁵⁰ to R ⁵⁷ include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). 1~6) fluorinated alkyl group, etc.

R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, fluoromethyl, difluoromethyl or trifluoromethyl.

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

<<<R ¹¹⁵ >>>

R ¹¹⁵ in formula (1) represents a tetravalent organic group. As the tetravalent organic group, a group containing an aromatic ring is preferred, and a group represented by the following formula (5) or formula (6) is more preferred.

The meaning of R ¹¹² is the same as A, and the preferred range is also the same.

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

R ¹¹⁵ represents a tetravalent organic group. The meaning of R ¹¹⁵ is the same as that of R ¹¹⁵ in formula (1).

Specific examples of tetracarboxylic dianhydride include those selected from the group consisting of pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 3,3 ',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethyl Ketone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3 ,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxodiphthalic dianhydride, 2,3,6,7-Naphthalenetetracarboxylic dianhydride, 1,4,5,7-Naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane Dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1 ,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1, 2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2 ,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride and the like At least one of alkyl derivatives with 1 to 6 carbon atoms and alkoxy derivatives with 1 to 6 carbon atoms.

Moreover, tetracarboxylic dianhydride (DAA-1) - (DAA-5) shown below are also mentioned as a preferable example.

<<<R ¹¹³ and R ¹¹⁴ >>>

In formula (1), R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group. It is preferred that at least one of R ¹¹³ and R ¹¹⁴ is a repeating unit containing a radical polymerizable group, and it is more preferred that both of R 113 and R 114 contain a radical polymerizable group. The radically polymerizable group is a group that can undergo a cross-linking reaction by the action of radicals, and a preferred example thereof includes a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a (meth)acrylyl group, a group represented by the following formula (III), and the like.

In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and a methyl group is 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 (poly)oxyalkylene group having 4 to 30 carbon atoms (as an alkylene group, carbon Numbers 1 to 12 are better, 1 to 6 are better, and 1 to 3 are particularly good; repeat numbers of 1 to 12 are better, 1 to 6 are better, and 1 to 3 are particularly good). Furthermore, the (poly)oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group.

Preferable examples of R ²⁰¹ include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, and hexamethylene. Methylene, octamethylene, dodecylmethylene, -CH ₂ CH(OH)CH ₂ -, ethylidene, propylene, trimethylene, -CH ₂ CH(OH)CH ₂ - are more good.

Particularly preferably, R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethyl group.

As a preferred embodiment of the polyimide precursor in the present invention, examples of the monovalent organic group of R ¹¹³ or R ¹¹⁴ include 1, 2 or 3 acid groups, preferably one acid group. Aliphatic groups, aromatic groups and aralkyl groups, etc. Specific examples include an aromatic group having 6 to 20 carbon atoms and an aralkyl group having 7 to 25 carbon atoms. More specific examples include a phenyl group having an acidic group and a benzyl group having an acidic group. The acid group is preferably a hydroxyl group. That is, it is preferable that R ¹¹³ or R ¹¹⁴ is a group having a hydroxyl group.

As the monovalent organic group represented by R ¹¹³ or R ¹¹⁴ , a substituent that improves the solubility of the developer can preferably be used.

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

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

The carbon number of the alkyl group is preferably 1 to 30 (when it is cyclic, it is 3 or more). The alkyl group may be linear, branched, or cyclic. Examples of linear or branched alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, Alkyl, octadecyl, isopropyl, isobutyl, second butyl, third butyl, 1-ethylpentyl and 2-ethylhexyl. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Examples of the polycyclic cyclic alkyl group include adamantyl, norbornyl, camphenyl, camphenyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, and camphenyl. Dihydryl, dicyclohexyl and pinenyl. Also, as an alkyl group substituted by an aromatic group, A linear alkyl group substituted by an aromatic group as described below is preferred.

環、三伸苯環等)或經取代或未經取代的芳香族雜環基(作為構成基團之環狀結構，茀環、聯苯環、吡咯環、呋喃環、噻吩環、咪唑環、

唑環、噻唑環、吡啶環、吡

環、嘧啶環、嗒

環、吲

環、吲哚環、苯并呋喃環、苯并噻吩環、異苯并呋喃環、喹

環、喹啉環、呔

環、萘啶環、喹

啉環、喹唑啉環、異喹啉環、咔唑環、啡啶環、吖啶環、啡啉環、噻蒽環、色烯環、

環、啡

噻環、啡噻

環或啡

環)。 The aromatic group is specifically a substituted or unsubstituted aromatic hydrocarbon group (the cyclic structure constituting the group includes benzene ring, naphthalene ring, biphenyl ring, fluorine ring, pentene ring, Indene ring, azulene ring, heptacene ring, indene ring, perylene ring, fused pentaphenyl ring, acenaphthylene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring,

ring, triphenyl ring, etc.) or substituted or unsubstituted aromatic heterocyclic group (as the cyclic structure of the constituent group, fluorine ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring,

Azole ring, thiazole ring, pyridine ring, pyridine ring

ring, pyrimidine ring, da

ring, indigo

ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinine

Ring, quinoline ring, nidine

ring, naphthyridine ring, quinine

Phenoline ring, quinazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring,

ring, coffee

thiocycline, thiophene

ring or brown

ring).

Moreover, it is also preferable that the polyimide precursor has a fluorine atom in the structural unit. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less. The upper limit is not particularly limited, but is actually 50% by mass or less.

In addition, for the purpose of improving the adhesiveness with the substrate, an aliphatic group having a siloxane structure and a structural unit represented by formula (1) may be copolymerized. Specific examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

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

[Chemical 12]

A ¹¹ and A ¹² represent an oxygen atom or NH, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, among R ¹¹³ and R ¹¹⁴ It is preferred that at least one of the groups contains a radically polymerizable group, and a radically polymerizable group is more preferred.

The preferred ranges of A ¹¹ , A ¹² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ respectively have the same meanings as the preferred ranges of A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (1).

The preferred range of R ¹¹² has the same meaning as R ¹¹² in formula (5), among which oxygen atom is more preferred.

In the formula, the bonding position of the carbonyl group on the benzene ring is preferably 4, 5, 3’, or 4’ in the formula (1-A). In formula (1-B), 1, 2, 4, and 5 are preferred.

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

As an embodiment of the polyimide precursor of the present invention, it can be exemplified by 50 mol% or more of the total structural units, further 70 mol% or more, especially 90 mol%. % or more is a polyimide precursor having a structural unit represented by formula (1). As an upper limit, it is actually 100 mol% or less.

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

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

Polyimide precursors can be obtained by reacting dicarboxylic acids or dicarboxylic acid derivatives with diamines. It is preferably obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative using a halogenating agent and then reacting it with a diamine.

In the method for producing the polyimide precursor, it is preferable to use an organic solvent when carrying out the reaction. The number of organic solvents may be one type, or two or more types.

The organic solvent can be appropriately set depending on the raw material, and examples thereof include pyridine, diglyme, N-methylpyrrolidone, and N-ethylpyrrolidone.

When producing the polyimide precursor, it is preferred to include a step of precipitating a solid. Specifically, solid precipitation can be performed by precipitating the polyimide precursor in the reaction solution in water and dissolving the polyimide precursor such as tetrahydrofuran in a soluble solvent.

唑前驅物>> <<polybenzo

Azole precursor>>

唑前驅物係包含由下述式(2)表示之構成單元之聚苯并

唑前驅物為較佳。 polybenzo

The azole precursor is a polybenzo containing a structural unit represented by the following formula (2)

Azole precursors are preferred.

[Chemical 13]

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.

R ¹²¹ represents a divalent organic group. The divalent organic group includes an aliphatic group (carbon number 1 to 24 is preferred, 1 to 12 is more preferred, 1 to 6 is particularly preferred) and aromatic group (carbon number 6 to 22 is preferred, 6 is preferred) ~14 is more preferred, 6~12 is particularly preferred) at least one group is preferred. Examples of the aromatic group constituting R ¹²¹ include R ¹¹¹ of the above formula (1). As the above-mentioned aliphatic group, a linear aliphatic group is preferred. R ¹²¹ is preferably derived from 4,4'-oxobenzoyl chloride.

In formula (2), R ¹²² represents a tetravalent organic group. As a tetravalent organic group, the meaning is the same as R115 in the above formula (1), and the preferable range is also the same. R ¹²² is preferably derived from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane.

R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group, and have the same meaning as R ¹¹³ and R ¹¹⁴ in the above formula (1), and the preferred ranges are also the same.

唑前驅物還可以包含其他種類的構成單元。 In addition to the structural units of the above-mentioned formula (2), polybenzo

Azole precursors may also contain other types of building blocks.

唑前驅物包含由下述式(SL)表示之二胺殘基來作為其他種類的構成單元為較佳。 From the viewpoint of being able to suppress the occurrence of warpage of the cured film accompanying loop closure, polybenzo

The azole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of structural unit.

[Chemical 14]

Z has a structure and b structure, R ^1s is a hydrogen atom or a hydrocarbon group with a carbon number of 1 to 10 (preferably a carbon number of 1 to 6, more preferably a carbon number of 1 to 3), R ^2s is a carbon number of 1 to 10 Hydrocarbon group (preferably having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and at least one of R ^3s , R ^4s , R ^5s , and R ^6s is an aromatic group (preferably having 6 to 22 carbon atoms, More preferably, it has a carbon number of 6 to 18, particularly preferably a carbon number of 6 to 10), and the remaining part is a hydrogen atom or a carbon number of 1 to 30 (more preferably, a carbon number of 1 to 18, more preferably a carbon number of 1 to 12, especially Preferably, they are organic groups having 1 to 6 carbon atoms, and they may be the same or different. The polymerization of structure a and structure b may be block polymerization or random polymerization. In the Z part, it is preferable that the a structure is 5 to 95 mol%, the b structure is 95 to 5 mol%, and a+b is 100 mol%.

唑前驅物的脫水閉環後的彈性率，且抑制翹曲之效果和提高溶解性之效果。 In the formula (SL), preferred examples of Z include those in which R ^5s and R ^6s in the b structure are phenyl groups. In addition, the molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. The molecular weight can be determined by commonly used gel permeation chromatography. By setting the above molecular weight to the above range, it is possible to simultaneously reduce the polybenzo

The elastic modulus of the azole precursor after dehydration and ring closure, and the effect of inhibiting warpage and improving the solubility.

When the diamine residue represented by the formula (SL) is included as another type of structural unit, the precursor further includes the tetracarboxylic acid remaining after removing the acid dianhydride group from the tetracarboxylic dianhydride in order to improve the alkali solubility. Residues are preferred as structural units. Examples of these tetracarboxylic acid residues include R ¹¹⁵ in formula (1).

唑前驅物的重量平均分子量(Mw)較佳為2000~500000，更佳為5000~100000，進一步較佳為10000~50000。又，數平均分子量(Mn)較佳為800~250000，更佳為2000~50000，進一步較佳為4000~25000。 polybenzo

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

唑前驅物的分子量的分散度為1.5~3.5為較佳，2~3為更佳。 polybenzo

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

<<Polyimide>>

The polyimide is not particularly limited as long as it is a polymer compound having an imine ring. Preferably, it is a compound represented by the following formula (4). It is a compound represented by the following formula (4). In addition, compounds having radically polymerizable groups are more preferred. Examples of the radically polymerizable group include the radically polymerizable groups described above for the polyimide precursor, and the preferred ranges are also the same.

In formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group.

When the polyimide has a radically polymerizable group, a radically polymerizable group may be introduced into at least one of R ¹³¹ and R ¹³² , or a radically polymerizable group may be introduced into the terminal of the polyimide. group.

Examples of the divalent organic group represented by R ¹³¹ include the same group as R ¹¹¹ in the formula (1) of the polyimide precursor, and the preferred ranges are also the same. Examples of the tetravalent organic group represented by R ¹³² include the same group as R ¹¹⁵ in the formula (1) of the polyimide precursor, and the preferred ranges are also the same.

The imidization rate of the polyimide is preferably 85% or more, and more preferably 90% or more. When the imidization rate is 85% or more, the film shrinkage associated with the closed loop that occurs when imidized by heating is reduced, and the occurrence of warpage can be suppressed.

唑>> <<polybenzo

Azole>>

唑，係具有苯并

唑環之化合物即可，並無特別限定，係下述式(X)表示之具有重複單元之化合物為較佳，係由下述式(X)表示之化合物且具有自由基聚合性基團之化合物為更佳。作為自由基聚合性基團，可舉出在上述聚醯亞胺前驅物中說明的自由基聚合性基團，較佳範圍亦相同。 as polybenzo

Azole, which has benzo

It is not particularly limited as long as it is a compound with an azole ring. It is preferably a compound represented by the following formula (X) and having a repeating unit. It is a compound represented by the following formula (X) and having a radically polymerizable group. Compounds are better. Examples of the radically polymerizable group include the radically polymerizable groups described for the above-mentioned polyimide precursor, and the preferred ranges are also the same.

In formula (X), R ¹³³ represents a divalent organic group, and R ¹³⁴ represents a tetravalent organic group.

唑具有自由基聚合性基團時，可以在R¹³³及R¹³⁴中的至少一個導入有自由基聚合性基團，亦可以在聚苯并

唑的末端導入有自由基聚合性基團。 polybenzo

When the azole has a radically polymerizable group, a radically polymerizable group may be introduced into at least one of R ¹³³ and R ¹³⁴ , or a radically polymerizable group may be introduced into the polybenzo

A radically polymerizable group is introduced into the end of the azole.

唑前驅物的式(2)的R¹²¹中說明之基團，較佳範圍亦相同。R¹³⁴所表示之4價有機基團，可舉出聚苯并

唑前驅物的式(2)的R¹²²中說明之基團，較佳範圍亦相同。 Examples of the divalent organic group represented by R ¹³³ include an aliphatic group or an aromatic group. Specific examples include polybenzo

The preferable ranges of the groups described for R ¹²¹ in the formula (2) of the azole precursor are also the same. Examples of the tetravalent organic group represented by R ¹³⁴ include polybenzo

The preferable ranges of the groups described for R ¹²² in formula (2) of the azole precursor are also the same.

The resin content in the resin composition of the present invention is preferably 20 mass% or more, more preferably 30 mass% or more, more preferably 40 mass% or more, and 50 mass% or more relative to the total solid content of the resin composition. In order to be more preferable, it is more preferable that it is 60 mass % or more, and it is still more preferable that it is 70 mass % or more. Furthermore, the content of the polymer precursor in the resin composition of the present invention is preferably 99.5 mass% or less, more preferably 99 mass% or less, and further preferably 98 mass% or less relative to the total solid content of the resin composition. , 95% by mass or less is further preferred.

In addition, the content of the polymer precursor (preferably the polyimide precursor) in the resin composition of the present invention is preferably 20 mass% or more, and 30 mass% or more relative to the total solid content of the resin composition. More preferably, 40% by mass or more is still more preferably, 50% by mass or more is still more preferably, 60% by mass or more is still more preferably, and 70% by mass or more is still more preferably. Furthermore, the content of the polymer precursor in the resin composition of the present invention is preferably 99.5 mass% or less, more preferably 99 mass% or less, and further preferably 98 mass% or less relative to the total solid content of the resin composition. , 95% by mass or less is still more preferred, and 95% by mass or less is still more preferred.

The resin composition of the present invention may contain only one type of resin, or may contain two or more types of resin. When two or more types are included, the total amount is preferably within the above range.

<Compound B>

The resin composition of the present invention includes Compound B having a pKa of 5 or more including a group that generates a base by heating and a group represented by Formula (b1). Hereinafter, a group that generates a base by heating is also referred to as a specific functional group. In addition, the group represented by formula (b1) is also called group (b1).

-M ¹ (R ¹ )(R ² )(R ³ )‧‧‧‧‧‧(b1)

In the formula (b1), M ¹ represents Si, Ti or Zr, R ¹ to R ³ each independently represent Rb ¹ or ORb ¹ , and Rb ¹ each independently represents a hydrocarbon group having 1 to 10 carbon atoms.

The pKa of compound B is 5 or more, preferably 8 or more, more preferably 10 or more, more preferably 12 or more, still more preferably 12.5 or more, and still more preferably 13 or more. The upper limit is preferably 20 or less, more preferably 18 or less, and still more preferably 15 or less. In addition, the pKa of compound B is the value in water at 23°C.

The molecular weight of compound B is preferably 100~2000. The upper limit is preferably 1,900 or less, more preferably 1,500 or less, and still more preferably 500 or less. The lower limit is preferably 150 or more, more preferably 200 or more, and still more preferably 250 or more.

The amine value of compound B is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and still more preferably 300 mgKOH/g or less.

The base generation temperature of compound B is preferably 160°C or higher, more preferably 170°C, and further preferably 180°C or higher. The upper limit of the base generation temperature is preferably 300°C or lower, more preferably 280°C or lower, and further preferably 250°C or lower. According to this aspect, it is possible to effectively generate bases when forming a cured film. Therefore, it is possible to form a cured film excellent in adhesion and reliability while maintaining the storage stability of the resin composition. That is, transform The above-mentioned specific functional group of compound B is preferably a group that decomposes at a temperature of 160°C or above to generate a base, and more preferably a group that decomposes at a temperature of 170°C or above to generate a base. At 180°C A group that decomposes at the above temperature to generate a base is further preferred. The upper limit of the temperature is preferably 300°C or lower, more preferably 280°C or lower, and still more preferably 250°C or lower.

環基、苯并二

環基等。 The specific functional group of compound B (a group that generates a base by heating) includes a heterocyclic group containing a nitrogen atom, an amide group, a urea group, an isocyanate group, a urethane group, and an ureidomethyl group. At least one group selected from the group consisting of an acid ester group, a biuret group and an acyl imine group is preferred. Examples of the heterocyclic group containing a nitrogen atom include an azole ring group, a pyrrole ring group, an indole ring group, a pyridine ring group, a pyrazole ring group, and a dioxazole ring group.

Ring group, benzodi

Ring base etc.

Preferred aspects of the specific functional group include the following (1) and (2). Among them, the aspect (2) below is preferred from the viewpoint of storage stability in liquid, and the aspect containing at least an isocyanate group is even more preferred.

(1) An aspect including a heterocyclic group containing a nitrogen atom and at least one group selected from -OCO- and -COO-.

(2) An aspect containing at least one group selected from a amide group, a urea group, an isocyanate group, a urethane group, an allophanate group, a biuret group, and a amide group.

Next, the group (b1) possessed by compound B will be described.

In the formula (b1), M ¹ represents Si, Ti or Zr, preferably Si. When M ¹ is Si, the storage stability of the resin composition can be further improved, or the adhesiveness or reliability of the obtained cured film can be further improved. In addition, M ¹ is also preferably Ti or Zr. It is preferable to further improve the mechanical properties such as ductility of the obtained cured film.

In formula (b1), R ¹ to R ³ each independently represent Rb ¹ or ORb ¹ , and Rb ¹ represents a hydrocarbon group having 1 to 10 carbon atoms. Examples of the hydrocarbon group represented by Rb ¹ include an aliphatic saturated hydrocarbon group, an aliphatic unsaturated hydrocarbon group, and an aromatic hydrocarbon group. The aliphatic saturated hydrocarbon group and the aliphatic unsaturated hydrocarbon group may be linear, branched, or cyclic. As the hydrocarbon group represented by Rb ¹ , an aliphatic saturated hydrocarbon group and an aliphatic unsaturated hydrocarbon group are preferred, and an aliphatic saturated hydrocarbon group is more preferred. In addition, the carbon number of the aliphatic saturated hydrocarbon group is preferably 1 to 6, and more preferably 1 to 3.

In formula (b1), it is preferred that at least one of R ¹ to R ³ is ORb ¹ . Among them, it is more preferable that R ¹ to R ³ each independently be ORb ¹ , in order to easily obtain a cured film having better adhesion or reliability.

In addition, in the formula (b1), the types of bonds between M ¹ and R ¹ to R ³ are not particularly limited, and may be any of covalent bonds, ionic bonds, and coordination bonds. Among them, covalent bonds are preferred because it is easier to obtain a cured film having better adhesion or reliability.

Compound B used in the present invention is preferably a compound represented by the following formula (I).

In the formula (I), A ¹ represents a group that generates a base by heating, L ¹ represents a single bond or a divalent linking group, M ¹ represents Si, Ti or Zr, and R ¹ to R ³ each independently represent Rb. ¹ or ORb ¹ , Rb ¹ represents a hydrocarbon group with 1 to 10 carbon atoms.

The preferred ranges of M ¹ , R ¹ to R ³ and Rb ¹ in formula (I) have the same meanings as the above ranges.

A ¹ in formula (I) represents a group that generates a base by heating. The preferred range of A ¹ has the same meaning as the above-mentioned specific functional group. L ¹ in formula (I) represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, an alkenylene group, an aryl group, -O-, and groups including these combinations.

Specific examples of compound B include compounds having the following structures.

The content of compound B is preferably 0.01 to 5% by mass in the total solid content of the resin composition. The upper limit is preferably 4 mass% or less, more preferably 3 mass% or less, further preferably 2 mass% or less, and particularly preferably 1.5 mass% or less. The lower limit is 0.05% by mass or more is preferred.

In addition, the content of compound B is preferably 0.02 to 15 parts by mass relative to 100 parts by mass of the resin. The upper limit is preferably 11 parts by mass or less, more preferably 8 parts by mass or less, and still more preferably 6 parts by mass or less. The lower limit is preferably 0.05 parts by mass or more, more preferably 0.5 parts by mass or more, and still more preferably 1 part by mass or more. There may be only one type of compound B, or two or more types of compounds B may be used. When two or more types are used, the total amount is preferably within the above range.

<Thermal base generator>

The resin composition of the present invention may further contain a thermal base generator as a component other than the above-mentioned compound B. The thermal base generator is not particularly limited in type, etc., but it contains at least one selected from the group consisting of an acidic compound that generates a base when heated to 40° C. or above, and an ammonium salt having a pKa of 0 to 4, and an ammonium cation. Base generators are preferred.

By blending these compounds, a cyclization reaction of a polymer precursor or the like can be performed at low temperature. In addition, the thermal base generator does not generate a base without heating. Therefore, even if it coexists with the polymer precursor, it can suppress cyclization of the polymer precursor during storage and has excellent storage stability.

The thermal base generator preferably contains at least one selected from the group consisting of an acidic compound (A1) that generates a base when heated to 40° C. or above, and an ammonium salt (A2) having an anion with a pKa of 0 to 4 and an ammonium cation. The above-mentioned acidic compound (A1) and the above-mentioned ammonium salt (A2) generate a base when heated. Therefore, the cyclization reaction of the polymer precursor can be promoted by the base generated from these compounds, and the polymer precursor can be processed at low temperature. of cyclization. In addition, in this specification, the acidic compound refers to the following compound: Collect 1 g of the compound into a container, add 50 mL of a mixture of ion-exchange water and tetrahydrofuran (mass ratio: water/tetrahydrofuran = 1/4), and stir at room temperature for 1 hour. , a compound whose value is less than 7 when the value of the solution thus obtained is measured with a pH (power of hydrogen: pH) meter at 20°C.

The alkali generation temperature of the thermal base generator used in the present invention is preferably 40°C or higher, and more preferably 120 to 200°C. The upper limit of the alkali generation temperature is preferably 190°C or lower, more preferably 180°C or lower, and still more preferably 165°C or lower. The lower limit of the alkali generation temperature is preferably 130°C or higher, more preferably 135°C or higher. The base generation temperature can be measured as follows: for example, using differential scanning calorimetry, the compound is heated to 250°C in a pressure-resistant capsule at 5°C/min, and the peak temperature of the heat peak with the lowest temperature is read, and the peak temperature is regarded as the base generation temperature. temperature.

The base generated by a hot base generator is a secondary amine or a tertiary amine, and a tertiary amine is more preferred. Tertiary amines are highly basic and therefore enable lower cyclization temperatures of the polymer precursor. In addition, the boiling point of the base generated by the thermal base generator is preferably 80°C or higher, more preferably 100°C or higher, and further preferably 140°C or higher. In addition, the molecular weight of the produced base is preferably 80 to 2000. It is better if the lower limit is 100 or more. It is better if the upper limit is less than 500. In addition, the value of molecular weight is a theoretical value calculated from the structural formula.

In this embodiment, the acidic compound (A1) preferably contains one or more compounds selected from ammonium salts and compounds represented by formula (101) or (102) described below.

In this embodiment, the ammonium salt (A2) is preferably an acidic compound. In addition, the above-mentioned ammonium salt (A2) may be heated to 40°C or above (preferably 120~200 °C), the compound may be an acidic compound that generates a base when heated to 40°C or higher (preferably 120 to 200°C).

In this embodiment, the ammonium salt represents a salt of an ammonium cation and anion represented by the following formula (101) or formula (102). The anion may be bonded to any part of the ammonium cation via a covalent bond, or may exist outside the molecule of the ammonium cation, but it is preferably present outside the molecule of the ammonium cation. In addition, the presence of an anion outside the molecule of the ammonium cation means that the ammonium cation and the anion are not bonded through a covalent bond. Hereinafter, the extramolecular anion in the cation part is also called a counter anion.

In formula (101) and formula (102), R ¹ to R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, and R ⁷ represents a hydrocarbon group. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , and R ⁵ and R ⁷ in the formula (101) and the formula (102) may each be bonded to form a ring.

The ammonium cation is preferably represented by any one of the following formulas (Y1-1) to (Y1-5).

[Chemistry 20]

In the formulas (Y1-1) to (Y1-5), R ¹⁰¹ represents an n-valent organic group, and the meanings of R ¹ and R ⁷ are the same as those of the formula (101) or the formula (102).

In the formulas (Y1-1) to (Y1-5), Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group, n represents an integer of 1 or more, and m represents an integer of 0 to 5.

In this embodiment, the ammonium salt preferably has an anion and an ammonium cation with a pKa of 0 to 4. The upper limit of the pKa of the anion is more preferably 3.5 or less, and still more preferably 3.2 or less. It is preferable that the lower limit is 0.5 or more, and it is more preferable that it is 1.0 or more. If the pKa of the anion is within the above range, the polymer precursor can be cyclized at a lower temperature, thereby improving the stability of the resin composition. When the pKa is 4 or less, the stability of the thermal base generator is good, the generation of alkali without heating can be suppressed, and the stability of the resin composition is good. If the pKa is 0 or more, the generated base will not be easily neutralized, and the cyclization efficiency of the polymer precursor will be good.

The type of anion is preferably one selected from carboxylate anions, phenol anions, phosphate anions and sulfate anions, so as to take into account the stability and thermal decomposition of the salt. For sex reasons, the carboxylate anion is better. That is, the ammonium salt is more preferably a salt of ammonium cation and carboxylate anion.

The carboxylate anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxyl groups, and more preferably an anion of a divalent carboxylic acid. According to this aspect, it can be a thermal base generator that can further improve the stability, curability and developability of the resin composition. In particular, by using a divalent carboxylic acid anion, the stability, curability, and developability of the resin composition can be further improved.

In this embodiment, a carboxylate anion is preferably a carboxylic acid anion having a pKa of 4 or less. A pKa of 3.5 or less is more preferred, and a pKa of 3.2 or less is still more preferred. According to this aspect, the stability of the resin composition can be further improved.

Among them, pKa represents the logarithm of the inverse of the dissociation constant of the proton of the acid. You can refer to Determination of Organic Structures by Physical Methods (Authors: Brown, H.C., McDaniel, D.H., Hafliger, O., Nachod, F.C.; Editor: Braude, E.A. , Nachod, F.C.; Academic Press, New York, 1955) or Data for Biochemical Research (author: Dawson, R.M.C. et al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, values calculated from structural formulas using the software ACD/pKa (manufactured by ACD/Labs) were used.

The carboxylate anion is preferably represented by the following formula (X1).

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

In this embodiment, the electron-withdrawing group is one in which the Hammett substituent constant σm represents a positive value. Among them, σm is described in detail in Mr. Yuhio Tsuno, Journal of Synthetic Organic Chemistry, Japan, Vol. 23, No. 8 (1965) p. 631-642. In addition, the electron-withdrawing group in this embodiment is not limited to the substituent described in the above-mentioned document.

Examples of substituents in which σm represents a positive value include CF ₃ group (σm=0.43), CF ₃ CO group (σm=0.63), HC≡C group (σm=0.21), and CH ₂ =CH group (σm=0.06), Ac group (σm=0.38), MeOCO group (σm=0.37), MeCOCH=CH group (σm=0.21), phCO group (σm=0.34), H ₂ NCOCH ₂ group (σm=0.06) wait. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group.

EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).

In the formulas (EWG-1) to (EWG-6), R ^x1 to R ^x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group or a carboxyl group, and Ar represents an aromatic group.

In this embodiment, the carboxylate anion is preferably represented by the following formula (XA).

Formula (XA)

In the formula (XA), L ¹⁰ represents a divalent connecting group selected from a single bond or ^an alkylene group, an alkenylene group, an aromatic group, ^-NR base, alkenyl or aryl group.

Specific examples of carboxylate anions include maleate anions, phthalate anions, N-phenyliminodiacetate anions, and oxalate anions. Can better use these.

Specific examples of the thermal base generator include the following compounds.

The content of the thermal base generator is preferably 0.1 to 50% by mass relative to the total solid content of the resin composition of the present invention. It is more preferable that the lower limit is 0.5 mass % or more, and it is further more preferable that it is 1 mass % or more. It is more preferable that the upper limit is 30 mass % or less, and it is further more preferable that it is 20 mass % or less. One type or two or more types of thermal base generators can be used. When two or more types are used, the total amount is preferably within the above range.

<Photosensitizer>

The resin composition of the present invention preferably contains a photosensitizer. Examples of the photosensitizer include a photopolymerization initiator, and in addition, for example, a photocuring accelerator may be included.

<<Photopolymerization initiator>>

The photopolymerization initiator used for the photosensitizer is preferably a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited, and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light from an ultraviolet region to a visible region is preferred. In addition, it can be an active agent that interacts with the sensitizer excited by light and generates active free radicals. It is preferred that the photoradical polymerization initiator contains at least one compound with 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 absorption coefficient of a compound can be measured using a known method. For example, by using a UV-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Corporation) and using It is better to measure at a concentration of 0.01g/L using ethyl acid ester solvent.

骨架之化合物、具有

二唑骨架之化合物、具有三鹵甲基之化合物等)、醯基氧化膦等醯基膦化合物、六芳基雙咪唑、肟衍生物等肟化合物、有機過氧化物、硫化合物、酮化合物、芳香族鎓鹽、酮肟醚、胺基苯乙酮化合物、羥基苯乙酮化合物、偶氮系化合物、疊氮化合物、茂金屬化合物、有機硼化合物、鐵芳烴錯合物等。關於該等的詳細內容，能夠參閱日本特開2016-027357號公報的0165~0182、國際公開第2015/199219號的0138~0151段的記載，該內容編入本說明書中。 As the photoradical polymerization initiator, any known compound can be used. For example, halogenated hydrocarbon derivatives (for example, having three

A compound with a skeleton

Compounds with an oxadiazole skeleton, compounds with trihalomethyl groups, etc.), acylphosphine compounds such as acylphosphine oxide, oxime compounds such as hexaarylbisimidazole, oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, Aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone compounds, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron aromatic hydrocarbon complexes, etc. For details, please refer to paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219, and these contents are incorporated into this specification.

Examples of the ketone compound include the compounds described in paragraph 0087 of Japanese Patent Application Laid-Open No. 2015-087611, and this content is incorporated into this specification. Among commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can be preferably used.

As the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in Japanese Patent Application Laid-Open No. 10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used. As the hydroxyacetophenone-based starter, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (product names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, commercially available IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, compounds described in Japanese Patent Application Laid-Open No. 2009-191179 whose absorption maximum wavelength matches a light source with a wavelength of 365 nm or 405 nm can also be used. Examples of the acylphosphine-based initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and the like. In addition, commercially available IRGACURE-819 or IRGACURE-TPO (trade name: both manufactured by BASF Corporation) can be used. Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF Corporation) and the like.

As a photoradical polymerization initiator, an oxime compound is more preferable. By using oxime compounds, the exposure latitude can be further effectively increased. Among oxime compounds, they are particularly preferred because they have a wide exposure latitude (exposure margin) and also function as a photohardening accelerator. As specific examples of the oxime compound, compounds described in Japanese Patent Application Laid-Open No. 2001-233842, compounds described in Japanese Patent Application Laid-Open No. 2000-080068, and compounds described in Japanese Patent Application Laid-Open No. 2006-342166 can be used. Preferred oxime compounds include, for example, compounds with the following structures, 3-benzoyloxyiminobutan-2-one, 3-acetyloxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetyloxyiminopentan-3-one, 2-acetyloxyiminobutan-1-phenylpropane-1- ketone, 2-benzyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyl Oxyimino-1-phenylpropan-1-one, etc. In the resin composition of the present invention, it is particularly preferred to use an oxime compound (oxime-based photopolymerization initiator) as a photoradical polymerization initiator. The oxime-based photopolymerization initiator is a compound having a linking group >C=N-O-C(=O)- in the molecule.

[Chemical 27]

Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are manufactured by BASF Corporation), ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, Japanese Patent Application Publication No. 2012-014052 Photoradical polymerization initiator 2) described in the Gazette No. Moreover, TR-PBG-304 (manufactured by Changzhou Trolly New Electronic Materials CO., LTD.), ADEKAARKLS NCI-831, and ADEKAARKLS NCI-930 (manufactured by ADEKA CORPORATION) can be used. In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can be used.

Furthermore, an oxime compound having a fluorine atom can also be used. Specific examples of these oxime compounds include compounds described in Japanese Patent Application Laid-Open No. 2010-262028, compounds 24, 36 to 40 described in paragraph 0345 of Japanese Patent Application Publication No. 2014-500852, and Japanese Patent Application Laid-Open No. 2013. - Compound (C-3) described in paragraph 0101 of Publication No. 164471, etc.

Preferred oxime compounds include oxime compounds having specific substituents shown in Japanese Patent Application Laid-Open No. 2007-269779 or Japanese Patent Application Laid-Open No. 2009-191061. Oxime compounds having a sulfur aryl group shown in Publication No. 1, etc.

化合物、苄基二甲基縮酮化合物、α-羥基酮化合物、α-胺基酮化合物、醯基膦化合物、氧化膦化合物、茂金屬化合物、肟化合物、三芳基咪唑二聚體、鎓鹽化合物、苯并噻唑化合物、二苯甲酮化合物、苯乙酮化合物及其衍生物、環戊二烯基-苯-鐵錯合物及其鹽、鹵甲基

二唑化合物、3-芳基取代香豆素化合物之群組中之化合物。更佳的光自由基聚合起始劑係三鹵甲基三

化合物、α-胺基酮化合物、醯基膦化合物、氧化膦化合物、茂金屬化合物、肟化合物、三芳基咪唑二聚體、鎓鹽化合物、二苯甲酮化合物、苯乙酮化合物，選自包括三鹵甲基三

化合物、α-胺基酮化合物、肟化合物、三芳基咪唑二聚體、二苯甲酮化合物之群組中之至少一種化合物為進一步較佳，使用茂金屬化合物或肟化合物為更進一步較佳，肟化合物為更進一步較佳。 From the perspective of exposure sensitivity, the photoradical polymerization initiator is selected from the group consisting of trihalomethyltri

Compounds, benzyldimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds , benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl-benzene-iron complexes and their salts, halomethyl

Compounds in the group of oxadiazole compounds and 3-aryl substituted coumarin compounds. A better photoradical polymerization initiator is trihalomethyltri

Compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, acetophenone compounds, selected from the group consisting of Trihalomethyltri

It is further preferred to use at least one compound from the group consisting of a compound, an α-aminoketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound, and it is further preferred to use a metallocene compound or an oxime compound, Oxime compounds are further preferred.

啉基苯基)-丁酮-1,2-甲基-1-[4-(甲硫基)苯基]-2-

啉基-丙酮-1等芳香族酮、烷基蒽醌等與芳香環進行縮環而成之醌類、安息香烷基醚等安息香醚化合物、安息香、烷基安息香等安息香化合物、苄基二甲基縮酮等苄基衍生物等。又，還能夠使用由下述式(I)表示之化合物。 In addition, as the photoradical polymerization initiator, N benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), etc. can also be used. ,N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-

Phyllinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-

Aromatic ketones such as pholinyl-acetone-1, alkyl anthraquinones and other quinones formed by ring condensation with aromatic rings, benzoin ether compounds such as benzoin alkyl ether, benzoin, alkyl benzoin and other benzoin compounds, benzyl dimethyl Benzyl derivatives such as ketals, etc. Moreover, the compound represented by the following formula (I) can also be used.

In formula (I), R ^I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, or a phenyl group. It consists of an alkyl group with 1 to 20 carbon atoms, an alkoxy group with 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, and an alkenyl group with 2 to 12 carbon atoms interrupted by one or more oxygen atoms. At least one of the alkyl groups with 2 to 18 carbon atoms and the alkyl groups with 1 to 4 carbon atoms is a substituted phenyl group or biphenyl group, R ^I01 is a group represented by formula (II), or is the same group as R ^I00 group, R ^I02 to R ^I04 are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen.

In the formula, R ^I05 to R ^I07 are the same as R ^I02 to R ^I04 of the above formula (I).

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

When a photopolymerization initiator is included, its content is preferably 0.1 to 30 mass%, more preferably 0.1 to 20 mass%, and further preferably 0.5 to 15 mass% relative to the total solid content of the resin composition of the present invention. , further preferably 1.0~10% by mass. The photopolymerization initiator may contain only one type, or two or more types. Contains two kinds of When the photopolymerization initiator is used, the total amount is preferably within the above range.

<Thermal radical polymerization initiator>

The resin composition of the present invention may contain a thermal radical polymerization initiator. Thermal radical polymerization initiator is a compound that generates free radicals by heat energy and starts or promotes the polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the polymer precursor can be cyclized and the polymerization reaction of the polymer precursor can proceed. Therefore, a higher degree of heat resistance can be achieved. Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Laid-Open No. 2008-063554.

When the thermal radical polymerization initiator is contained, its content is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, and further preferably 5 to 15 mass % relative to the total solid content of the resin composition of the present invention. Mass %. Thermal radical polymerization initiator may contain only one type or two or more types. When two or more thermal polymerization initiators are contained, the total amount is preferably within the above range.

<Polymerizable compound>

<<Radically polymerizable compound>>

The resin composition of the present invention preferably contains a polymerizable compound. As the polymerizable compound, a radical polymerizable compound can be used. The radically polymerizable compound is a compound having a radically polymerizable group. Examples of the radically polymerizable group include groups having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth)acrylyl group. The radically polymerizable group is preferably a (meth)acrylyl group.

The number of radically polymerizable groups the radically polymerizable compound has It may be one, or it may be two or more. It is preferable that the radically polymerizable compound has two or more radically polymerizable groups, and it is more preferable that it has three or more radically polymerizable groups. The upper limit is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.

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

From the viewpoint of developability, the resin composition of the present invention preferably contains at least one bifunctional or higher radically polymerizable compound containing two or more polymerizable groups, and at least one trifunctional or higher radically polymerizable compound. Compounds are better. Moreover, it may be a mixture of a bifunctional radically polymerizable compound and a trifunctional or higher radically polymerizable compound. In addition, the number of functional groups of a radically polymerizable compound means the number of radically polymerizable groups in one molecule.

Specific examples of radically polymerizable compounds include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides. , preferably esters of unsaturated carboxylic acids and polyol compounds and amides of unsaturated carboxylic acids and polyamine compounds. Furthermore, addition reaction products of unsaturated carboxylic esters or amides having affinity substituents such as hydroxyl groups, amine groups, and mercapto groups, and monofunctional or polyfunctional isocyanates or epoxy groups can also be preferably used. Dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, etc. In addition, the addition reaction product of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, thiols, and halogen groups or toluene Unsaturated carboxylic acid esters or amides with detachable substituents such as sulfonyloxy groups and monofunctional or polyfunctional alcohols and amines Substitution reactants such as thiols and thiols are also preferred. As another example, instead of the unsaturated carboxylic acid, a group of compounds substituted by unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, allyl ether, etc. can be used. As a specific example, reference can be made to the descriptions in paragraphs 0113 to 0122 of Japanese Patent Application Laid-Open No. 2016-027357, and these contents are incorporated into this specification.

In addition, the radically polymerizable compound is also preferably a compound having a boiling point of 100° C. or higher under normal pressure. Examples thereof include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, and neopenterythritol triacrylate. (Meth)acrylate, neopenterythritol tetra(meth)acrylate, dineopenterythritol penta(meth)acrylate, dineopenterythritol hexa(meth)acrylate, hexanediol (meth)acrylate acrylate, trimethylolpropane tris(acrylyloxypropyl) ether, tris(acrylyloxyethyl)isocyanurate, glycerin or trimethylolethane, etc. in multifunctional alcohols Compounds that are (meth)acrylated after adding ethylene oxide or propylene oxide, Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, Japanese Patent Publication No. 51-037193 (Meth)acrylic urethanes described in Japanese Patent Publication No. 48-064183, Japanese Patent Publication No. 49-043191, and polyester acrylates described in Japanese Patent Publication No. 52-030490 polyfunctional acrylates or methacrylates such as epoxy acrylates, which are the reaction products of epoxy resin and (meth)acrylic acid; and mixtures thereof. Furthermore, compounds described in paragraphs 0254 to 0257 of Japanese Patent Application Laid-Open No. 2008-292970 are also preferred. Furthermore, polyfunctional (meth)acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group and an ethylenically unsaturated bond such as glycidyl (meth)acrylate and the like can also be cited.

In addition, as preferred radically polymerizable compounds other than the above, those having fusidium described in Japanese Patent Application Laid-Open No. 2010-160418, Japanese Patent Application Laid-Open No. 2010-129825, Japanese Patent No. 4364216, etc. can also be used. A compound or cardo resin having a ring and two or more groups containing ethylenically unsaturated bonds.

Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, Japanese Patent Publication No. 01-040336, and Japanese Patent Publication No. 02 - Vinylphosphonic acid-based compounds described in Publication No. 025493, etc. In addition, compounds containing a perfluoroalkyl group described in Japanese Patent Application Publication No. Sho 61-022048 can also be used. Furthermore, those introduced as photocurable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pages 300 to 308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese Patent Application Laid-Open No. 2015-034964 and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used, and these contents are incorporated into this document. in the manual.

In addition, the following compounds described as formula (1) and formula (2) together with specific examples in Japanese Patent Application Laid-Open No. 10-062986 can also be used as radical polymerizable compounds. These compounds are added to a polyfunctional alcohol. A compound formed by (meth)acrylation into ethylene oxide or propylene oxide.

Furthermore, the compounds described in paragraphs 0104 to 0131 of Japanese Patent Application Laid-Open No. 2015-187211 can also be used as other radical polymerizable compounds, and these contents are incorporated in this specification.

As the radical polymerizable compound, dipenterythritol triacrylate (commercially available product: KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipenterythritol tetraacrylate (commercially available product: KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dipenterythritol penta(meth)acrylate (commercially available as KAYARAD D -310; manufactured by Nippon Kayaku Co., Ltd.), dipenterythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; Shin-Nakamura Chemical Co., Ltd.) and the structure in which the (meth)acrylyl group is bonded via an ethylene glycol residue or a propylene glycol residue is preferred. These oligomer types can also be used.

Examples of commercially available radical polymerizable compounds include SR-494, a tetrafunctional acrylate having four ethoxyl chains, and SR-494, a tetrafunctional acrylate having four vinyloxy chains, manufactured by Sartomer Company, Inc. Functional methyl acrylate SR-209, 231, 239 manufactured by Sartomer Company, Inc., Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having 6 pentyleneoxy chains, and DPCA-60, which is a hexafunctional acrylate having 3 pentyleneoxy chains TPA-330, trifunctional acrylate of isobutoxy chain, urethane oligomer UAS-10, UAB-140 (manufactured by NIPPON PAPER INDUSTRIES 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.), BLEMMER PME400 (manufactured by NOF CORPORATION.), etc.

Examples of radically polymerizable compounds include those described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765. Urethane acrylates, environmentally friendly products described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 Urethane compounds having an oxyethane-based skeleton are also preferred. Furthermore, as the radically polymerizable compound, compounds having an amine group in the molecule described in Japanese Patent Application Laid-Open Nos. 63-277653, 63-260909, and 01-105238 can also be used. Structure or sulfide structure of compounds.

The radical polymerizable compound may be a radical polymerizable compound having an acid group such as a carboxyl group or a phosphate group. Among the radically polymerizable compounds having acidic groups, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred, and those having acidic groups are obtained by reacting unreacted hydroxyl groups of the aliphatic polyhydroxy compounds with non-aromatic carboxylic acid anhydrides. Radically polymerizable compounds are more preferred. Particularly preferred are radically polymerizable compounds having acidic groups by reacting unreacted hydroxyl groups of aliphatic polyhydroxy compounds with non-aromatic carboxylic acid anhydrides. The aliphatic polyhydroxy compounds are neopentyl erythritol and/or dineopenterythritol. of compounds. As commercially available products, for example, polybasic acid-modified acrylic oligomers manufactured by TOAGOSEI CO., Ltd. include M-510, M-520, and the like.

The preferred acid value of the radically polymerizable compound having an acid group is 0.1 to 40 mgKOH/g, particularly preferably 5 to 30 mgKOH/g. As long as the acid value of the radically polymerizable compound is within the above range, the production and workability will be excellent, and the developability will be excellent. again, Polymerization is also good.

From the viewpoint of suppressing warpage associated with elastic modulus control of the cured film, the resin composition of the present invention can preferably use a monofunctional radical polymerizable compound as the radical polymerizable compound. As the monofunctional radical polymerizable compound, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxy acrylate can be preferably used. Ethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-hydroxymethyl (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate and other (meth)acrylates Derivatives, N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, allyl glycidyl ether, diallyl phthalate, triallyl trimellitate Allyl compounds such as esters, etc. As a monofunctional radically polymerizable compound, in order to suppress volatilization before exposure, a compound having a boiling point of 100° C. or higher under normal pressure is also preferred.

<<Polymerizable compounds other than the above-mentioned radically polymerizable compounds>>

化合物。 The resin composition of the present invention may also contain polymerizable compounds other than the above-mentioned radically polymerizable compounds. Examples of polymerizable compounds other than the above-mentioned radically polymerizable compounds include compounds having a hydroxymethyl group, an alkoxymethyl group, or a hydroxymethyl group; epoxy compounds; oxetane compounds; and benzo compounds.

compound.

<<Compounds with hydroxymethyl, alkoxymethyl or acyloxymethyl>>

As the compound having a hydroxymethyl group, an alkoxymethyl group or a carboxyloxymethyl group, a compound represented by the following formula (AM1), (AM4) or (AM5) is preferred.

(In the formula, t represents an integer from 1 to 20, R ¹⁰⁴ represents a t-valent organic group with a carbon number of 1 to 200, R ¹⁰⁵ represents a group represented by -OR ¹⁰⁶ or -OCO-R ¹⁰⁷ , and R ¹⁰⁶ represents a hydrogen atom Or an organic group with 1 to 10 carbon atoms, R ¹⁰⁷ represents an organic group with 1 to 10 carbon atoms.)

(In the formula, R ⁴⁰⁴ represents a divalent organic group with 1 to 200 carbon atoms, R ⁴⁰⁵ represents a group represented by -OR ⁴⁰⁶ or -OCO-R ⁴⁰⁷ , and R ⁴⁰⁶ represents a hydrogen atom or an organic group with 1 to 10 carbon atoms. Group, R ⁴⁰⁷ represents an organic group with 1 to 10 carbon atoms.)

(In the formula, u represents an integer of 3 to 8, R ⁵⁰⁴ represents a u-valent organic group with a carbon number of 1 to 200, R ⁵⁰⁵ represents a group represented by -OR ⁵⁰⁶ or -OCO-R ⁵⁰⁷ , and R ⁵⁰⁶ represents hydrogen Atom or organic group with 1 to 10 carbon atoms, R ⁵⁰⁷ represents an organic group with 1 to 10 carbon atoms.)

Specific examples of the compound represented by formula (AM4) include 46DMOC, 46DMOEP (manufactured by ASAHI YUKIZAI CORPORATION), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML- PFP, DML-PSBP, DML-MTrisPC (manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 (manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol (2, 6-dimethoxymethyl-4-tert-butylphenol), 2,6-dimethoxymethyl-p-cresol (2,6-dimethoxymethyl-p-cresol), 2,6-diacetoxymethyl- p-cresol (2,6-diethyloxymethyl-p-cresol), etc.

Specific examples of the compound represented by formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML- TPPHBA, HML-TPPHAP, HMOM-TPPHBA, HMOM-TPPHAP (manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (manufactured by ASAHI YUKIZAI CORPORATION), NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW- 100LM (manufactured by Sanwa Chemical Co., Ltd.).

<<<Epoxy compounds (compounds with epoxy groups)>>>

As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. The epoxy group undergoes a cross-linking reaction at 200° C. or lower, and does not cause dehydration reaction due to cross-linking, making it difficult to cause film shrinkage. Therefore, by containing an epoxy compound, low-temperature hardening and warpage of the composition can be effectively suppressed.

The epoxy compound preferably contains a polyethylene oxide group. Thereby, the elastic modulus is further reduced, and warpage can be suppressed. The polyethylene oxide group refers to one whose number of structural units of ethylene oxide is 2 or more, and the number of structural units is preferably 2 to 15.

Examples of the epoxy compound include bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resin such as propylene glycol diglycidyl ether; Polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; epoxy-containing silicone such as polymethyl (glycidyloxypropyl) siloxane, etc., but are not limited to these. Specifically, EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP- 4700, EPICLON (registered trademark) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) Trademark) EXA-4850-150, EPICLON (Registered Trademark) EXA-4850-1000, EPICLON (Registered Trademark) EXA-4816, EPICLON (Registered Trademark) EXA-4822 (manufactured by DIC Corporation), RIKARESIN (Registered Trademark) BEO-60E (manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S (manufactured by ADEKA CORPORATION), etc. Among them, an epoxy resin containing a polyethylene oxide group is preferable from the viewpoint of suppressing warpage and having excellent heat resistance. For example, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, and RIKARESIN (registered trademark) BEO-60E are preferred because they contain a polyethylene oxide group.

<<<Oxetane compounds (compounds having an oxetanyl group)>>>

Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethoxetane, 1,4-bis{ [(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4- Benzene dicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl] ester, etc. As a specific example, ARON OXETANE series (for example, OXT-121, OXT-221, OXT-191, OXT-223) manufactured by TOAGOSEI CO., LTD. can be preferably used, and these can be used alone, or both of them can be mixed. More than one species.

化合物(具有聚苯并

唑基之化合物)>>> <<<Benzo

Compounds (with polybenzo

Azolyl compounds)>>>

化合物因源自開環加成反應之交聯反應而在硬化時不產生脫氣，進而減少熱收縮而抑制產生翹曲，因此為較佳。 Benzo

The compound is preferable because it does not produce outgassing during hardening due to a cross-linking reaction derived from a ring-opening addition reaction, thereby reducing heat shrinkage and suppressing warpage.

化合物的較佳的例子，可舉出B-a型苯并

、B-m型苯并

(Shikoku Chemicals Corporation製)、聚羥基苯乙烯樹脂的苯并

加成物、酚醛清漆型二氫苯并

化合物。該等可以單獨使用，或者可以混合兩種以上。 as benzo

Preferable examples of the compound include Ba-type benzo

, Bm type benzo

(manufactured by Shikoku Chemicals Corporation), polyhydroxystyrene resin benzo

Adduct, novolak type dihydrobenzo

compound. These may be used alone, or two or more types may be mixed.

When a polymerizable compound is contained, its content is preferably greater than 0% by mass and not more than 60% by mass relative to the total solid content of the resin composition of the present invention. It is more preferable that the lower limit is 5 mass % or more. It is more preferable that the upper limit is 50 mass % or less, and it is further more preferable that it is 30 mass % or less.

Moreover, when a radical polymerizable compound is contained, its content is preferably more than 0 mass % and 60 mass % or less based on the total solid content of the resin composition of the present invention. It is more preferable that the lower limit is 5 mass % or more. The upper limit is more preferably 50 mass% or less, and further preferably 30 mass% or less.

One type of other polymerizable compounds may be used alone, or two or more types may be mixed and used. When two or more types are used at the same time, the total amount is preferably within the above range.

<Solvent>

The resin composition of the present invention preferably contains a solvent. Any known solvent can be used as the solvent. The solvent is preferably an organic solvent. Examples of organic solvents include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sericene, and amide compounds.

Examples of preferred esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, and ethyl butyrate. ester, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (for example, methyl alkoxyacetate, Alkoxyethyl acetate, alkoxybutyl acetate (e.g., methyl methoxyacetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, ethoxyethyl acetate etc.)), 3-alkoxypropionic acid alkyl esters (for example, 3-alkoxypropionic acid methyl ester, 3-alkoxypropionic acid ethyl ester, etc. (for example, 3-methoxypropionic acid methyl ester , ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxypropionic acid alkyl esters (for example, 2- Methyl alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate , 2-methoxypropionic acid propyl ester, 2-ethoxypropionic acid methyl ester, 2-ethoxypropionic acid ethyl ester)), 2-alkoxy-2-methylpropionic acid methyl ester and 2- Alkoxy-2-methylpropionic acid ethyl ester (for example, 2-methoxy-2-methylpropionic acid methyl ester, 2-ethoxy-2-methylpropionic acid ethyl ester, etc.), methyl pyruvate Ester, ethyl pyruvate, propyl pyruvate, methyl acetyl acetate, ethyl acetyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc.

Examples of preferred ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, and ethyl cellosolve. Acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc.

Examples of preferred ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and the like.

Preferable aromatic hydrocarbons include toluene, xylene, anisole, limonene, and the like.

Preferable examples of the sericene include dimethyl serotonin.

Preferred examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N- Dimethylformamide, etc.

Regarding the solvent, it is also preferable to mix two or more forms from the viewpoint of improving the properties of the coating surface.

In the present invention, it is selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, and butyl acetate. , methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethylsulfoxide, ethyl carbitol acetate, butyl carbitol One solvent among acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate or a mixed solvent composed of two or more is preferred. It is particularly good to use dimethylsulfoxide and γ-butyrolactone at the same time.

Regarding the content of the solvent, from the viewpoint of coatability, the total solid content concentration of the resin composition of the present invention is preferably 5 to 80 mass %, and is more preferably 5 to 75 mass %. Preferably, the amount is 10 to 70 mass %, which is still more preferable, and the amount of 40 to 70 mass % is still more preferable. The content of the solvent can be adjusted according to the desired thickness and coating method.

The solvent may contain only one type or two or more types. When two or more solvents are contained, the total amount is preferably within the above range.

<Migration inhibitor>

The resin composition of the present invention preferably further contains a migration inhibitor. By including a migration inhibitor, it is possible to effectively suppress metal ions originating from the metal layer (metal wiring) from being transferred into the resin composition layer.

唑環、噻唑環、吡唑環、異

唑環、異噻唑環、四唑環、吡啶環、嗒

環、嘧啶環、吡

環、哌啶環、哌

環、

啉環、2H-吡喃環及6H-吡喃環、三

環)之化合物、具有硫脲類及氫硫基之化合物、受阻酚系化合物、水楊酸衍生物系化合物、醯肼衍生物系化合物。尤其，能夠較佳地使用1,2,4-三唑、苯并三唑等三唑系化合物、1H-四唑、5-苯基四唑等四唑系化合物。 The migration inhibitor is not particularly limited, and examples thereof include heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring,

Azole ring, thiazole ring, pyrazole ring, iso

Azole ring, isothiazole ring, tetrazole ring, pyridine ring,

ring, pyrimidine ring, pyridine

ring, piperidine ring, piperazine

ring,

Phenyl ring, 2H-pyran ring and 6H-pyran ring, three

ring), compounds with thiourea and hydrogen sulfide groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazine derivative compounds. In particular, triazole compounds such as 1,2,4-triazole and benzotriazole, and tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole can be suitably used.

In addition, an ion scavenger that captures anions such as halogen ions can also be used.

As other migration inhibitors, the rust inhibitors described in paragraph 0094 of Japanese Patent Application Laid-Open No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Laid-Open No. 2009-283711, and the compounds described in Japanese Patent Application Laid-Open No. 2011-059656 can be used. Compounds described in Paragraph 0052 of Japanese Patent Application Publication No. 2012-194520, compounds described in Paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, compounds described in Paragraph 0166 of International Publication No. 2015/199219, etc.

Specific examples of the migration inhibitor include the following compounds.

[Chemical 33]

When the resin composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass%, more preferably 0.05 to 2.0 mass%, and further preferably 0.1 to 1.0 mass% relative to the total solid content of the resin composition. good. There may be only one type of migration inhibitor, or two or more types of migration inhibitors may be used. When there are two or more migration inhibitors, the total amount is preferably within the above range.

<Polymerization inhibitor>

、N-亞硝基二苯胺、N-苯基萘胺、伸乙基二胺四乙酸、1,2-環己二胺四乙酸、乙二醇醚二胺四乙酸、2,6-二-第三丁基-4-甲基苯酚、5-亞硝基-8-羥基喹啉、1-亞硝基-2-萘酚、2-亞硝基-1-萘酚、2-亞硝基-5-(N-乙基-N-磺基丙基胺)苯酚、N-亞硝基-N-(1-萘基)羥胺銨鹽、雙(4-羥基-3,5-第三丁基)苯基甲烷等。又，亦能夠使用日本特開2015-127817號公報的0060段中記載之聚合抑制劑及國際公開第 2015/125469號的0031~0046段中記載之化合物。又，還能夠使用下述化合物(Me為甲基)。 The resin composition of the present invention preferably contains a polymerization inhibitor. As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1 ,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl (6-tert-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, thiophene

, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, ethylene glycol ether diaminetetraacetic acid, 2,6-diaminetetraacetic acid 3-Butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso -5-(N-ethyl-N-sulfopropylamine)phenol, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tertiary butylamine) base) phenylmethane, etc. In addition, the polymerization inhibitor described in paragraph 0060 of Japanese Patent Application Laid-Open No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used. Furthermore, the following compounds (Me is methyl) can also be used.

When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5 mass %, more preferably 0.02 to 3 mass %, and 0.05 to 0.05 mass % relative to the total solid content of the resin composition of the present invention. 2.5% by mass is further more preferable. There may be only one type of polymerization inhibitor, or two or more types of polymerization inhibitors may be used. When there are two or more polymerization inhibitors, the total amount is preferably within the above range.

<Other additives>

The resin composition of the present invention can contain various additives as necessary, such as thermal acid generators, sensitizing dyes, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic Particles, hardener, hardening catalyst, filler, antioxidant, ultraviolet absorber, aggregation inhibitor, etc. are blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the composition.

<<Thermal acid generator>>

The resin composition of the present invention may contain a thermal acid generator. The content of the thermal acid generator is preferably 0.01 parts by mass or more based on 100 parts by mass of the resin, and more preferably 0.1 parts by mass or more. Contains 0.01 parts by mass or more of a thermal acid generator to promote cross-linking reaction and cyclization of polymer precursors, etc., so the mechanical properties and chemical resistance of the cured film can be further improved. Moreover, from the viewpoint of the electrical insulation of the cured film, the content of the thermal acid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 10 parts by mass or less. Only one type of thermal acid generator may be used, or two or more types may be used. When two or more types are used, the total amount is preferably within the above range.

<<sensitizing pigment>>

The resin composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs specific active radiation and enters an electronically excited state. The sensitizing dye in the electronically excited state comes into contact with the thermal hardening accelerator, thermal radical polymerization initiator, photo radical polymerization initiator, etc., resulting in electron transfer, energy transfer, heat generation and other effects. Thereby, the thermal hardening accelerator, thermal radical polymerization initiator, and photo radical polymerization initiator undergo chemical changes and decompose, and generate free radicals, acids, or bases. For details of the sensitizing dye, please refer to the description in paragraphs 0161 to 0163 of Japanese Patent Application Laid-Open No. 2016-027357, and this content is incorporated into this specification.

When the resin composition of the present invention contains a sensitizing dye, the content of the sensitizing dye relative to the total solid content of the resin composition of the present invention is preferably 0.01 to 20 mass %, more preferably 0.1 to 15 mass %, and 0.5 to 0.5 mass %. 10% by mass is further more preferable. One type of sensitizing dye may be used alone, or two or more types of sensitizing dyes may be used simultaneously.

<<Chain transfer agent>>

The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined in, for example, pages 683-684 of the Polymer Dictionary, third edition (edited by The Society of Polymer Science, Japan, 2005). As a chain transfer agent, for example, it is used in The group of compounds containing SH, PH, SiH and GeH. These can generate free radicals by donating hydrogen to low-activity free radicals, or by deprotonating them after oxidation. In particular, thiol compounds can be preferably used.

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

When the resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, and more preferably 1 to 10 parts by mass relative to 100 parts by mass of the total solid content of the resin composition of the present invention. , 1 to 5 parts by mass is further preferred. There may be only one type of chain transfer agent, or two or more types of chain transfer agents may be used. When there are two or more chain transfer agents, the total range is preferably within the above range.

<<Surfactant>>

From the viewpoint of further improving coatability, various surfactants may be added to the resin composition of the present invention. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used. In addition, the following surfactants are also preferred.

In addition, as the surfactant, the compounds described in paragraphs 0159 to 0165 of International Publication No. 2015/199219 can also be used.

When the resin composition of the present invention contains a surfactant, the content of the surfactant relative to the total solid content of the resin composition of the present invention is preferably 0.001 to 2.0 mass %, and more preferably 0.005 to 1.0 mass %. There may be only one type of surfactant, or two or more types of surfactants may be used. When there are two or more surfactants, the total range is preferably within the above range.

<<Higher fatty acid derivatives>>

In order to prevent polymerization inhibition due to oxygen, higher fatty acid derivatives such as behenic acid or behenic acid amide can be added to the resin composition of the present invention to bias the composition during the drying process after coating. surface.

In addition, compounds described in paragraph 0155 of International Publication No. 2015/199219 can also be used as the higher fatty acid derivatives.

When the resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the resin composition of the present invention. The number of higher fatty acid derivatives may be only one type or two or more types. When there are two or more types of higher fatty acid derivatives, the total range is preferably within the above range.

<Restrictions on other contained substances>

From the viewpoint of the properties of the coated surface, the moisture content of the resin composition of 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.

Considering its use as a semiconductor material and from the viewpoint of wiring corrosion, the content of halogen atoms in the resin composition of the present invention is less than 500 mass ppm. It is more preferable, less than 300 mass ppm is more preferable, and less than 200 mass ppm is still more preferable. Among them, the amount of halogen ions present in the state is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and still more preferably less than 0.5 ppm by mass. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total number of chlorine atoms and bromine atoms or chlorine ions and bromide ions is within the above range.

As a container for storing the resin composition of the present invention, a conventionally known container can be used. In addition, as a storage container, in order to prevent impurities from being mixed into raw materials or compositions, it is also preferable to use a multi-layer bottle with an inner wall of six types of six-layer resins or a bottle with six types of resins formed into a seven-layer structure. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.

[Preparation of resin composition]

The resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited and can be performed by conventionally known methods.

In addition, for the purpose of removing foreign matter such as garbage and particles in the composition, it is preferable to perform filtration using a filter. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene or nylon. Filters can be pre-cleaned with organic solvents. In the filtration step of the filter, multiple types of filters can be used in parallel or in series. When using multiple types of filters, filters with different pore sizes or materials can be used in combination. Also, various materials can be filtered multiple times. When filtering multiple times, cyclic filtering can be used. In addition, filtration may be performed after pressurization. When performing filtration after pressurization, the pressurization pressure is preferably 0.05 MPa or more and 0.3 MPa or less.

In addition to filtration using filters, impurity removal using adsorbent materials can also be performed. It is also possible to combine filter filtration with impurity removal using adsorbent materials. As the adsorbent material, known adsorbent materials can be used. Examples include inorganic adsorbent materials such as silica gel and zeolite, and organic adsorbent materials such as activated carbon.

[Cure film, laminated body, semiconductor device, and manufacturing method thereof]

Next, the cured film, the laminated body, the semiconductor device, and the manufacturing method of these are demonstrated.

The cured film of the present invention is formed by curing the resin composition of the present invention. The film thickness of the cured film of the present invention can be, for example, 0.5 μm or more, and can be 1 μm or more. Moreover, as an upper limit, it can be 100 micrometers or less, and can also be 30 micrometers or less. The film thickness of the cured film of the present invention is preferably 1 to 30 μm.

The cured film of the present invention can be laminated in two or more layers and further in 3 to 7 layers to form a laminated body. The laminate system having two or more layers of the cured film of the present invention is preferably one in which a metal layer is provided between the cured films. This kind of metal layer can be preferably used as a metal wiring layer such as a rewiring layer.

Examples of fields to which the cured film of the present invention can be applied include insulating films for semiconductor elements, interlayer insulating films for rewiring layers, stress buffer films, and the like. In addition, examples include the case where a sealing film, a substrate material (a base film or a cover layer of a flexible printed circuit board, an interlayer insulating film), or an insulating film for actual mounting purposes such as those described above are patterned by etching. Regarding such uses, for example, you can refer to Science & Technology Co., Ltd. "High Functionalization and Application Technology of Polyimide" April 2008, Masaaki Kakimoto/Supervisor, CMC Technical Library "Polyimide Materials" the basis and opening Issued in November 2011, Japan Polyimide and Aromatic Polymer Research Society/edited "Latest Polyimide Fundamentals and Applications" NTS, August 2010, etc.

Furthermore, the cured film in the present invention can also be used in the production of offset printing plates or screen plates, use of molded parts, production of protective paints and dielectric layers in electronics, especially microelectronics, and the like.

The manufacturing method of the cured film of this invention includes using the resin composition of this invention. Specifically, it is preferable to include the following steps (a) to (d).

(a) Film formation step of applying a resin composition to a substrate to form a film

(b) After the film forming step, the exposure step of exposing the film

(c) The development step of developing the exposed resin composition layer

(d) Heating step of heating the developed resin composition at 80~450°C

As in this embodiment, the exposed resin layer can be further hardened by heating after development.

The manufacturing method of the laminated body in the preferred embodiment of this invention includes the manufacturing method of the cured film of this invention. The manufacturing method of the laminated body of this embodiment is based on the manufacturing method of the cured film mentioned above, and after forming a cured film, further performs the step (a) or the steps (a) to (c), or (a) to (d) again. ) steps. In particular, it is preferable to perform each of the above steps in sequence a plurality of times, for example, 2 to 5 times (that is, 3 to 6 times in total). By laminating the cured films in this way, a laminated body can be formed. In the present invention, it is particularly preferred to provide a metal layer on the portion where the cured film is provided, between the cured films, or both. In addition, in the production of the laminated body, it is not necessary to repeat all the steps (a) to (d). As mentioned above, it is possible to perform at least (a), preferably (a) to (d) a plurality of times. (c) or the steps (a) to (d) to obtain a laminated body of the cured film.

<Film formation step (layer formation step)>

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

The type of substrate can be appropriately set according to the application, but is not particularly limited. Examples include semiconductor manufacturing substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, and evaporated films. , magnetic film, reflective film, Ni, Cu, Cr, Fe and other metal substrates, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, electrode plate of plasma display panel (PDP), etc. In the present invention, a semiconductor manufacturing substrate is particularly preferred, and a silicon substrate is even more preferred. In addition, it is also preferable that the substrate is a substrate capable of forming a covalent bond with the compound B through a chemical reaction.

In addition, when the resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer becomes the substrate.

As a method of applying the resin composition to the substrate, coating is preferred.

Specifically, examples of applicable methods include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, and spin coating. Slit coating method and inkjet method, etc. From the viewpoint of the uniformity of the thickness of the resin composition layer, spin coating, slit coating, spray coating, and inkjet are more preferred. By adjusting the appropriate solid content concentration or coating conditions according to the method, a resin layer with a desired thickness can be obtained. In addition, the coating method can be appropriately selected according to the shape of the substrate. As long as it is a circular substrate such as a wafer, spin coating, spray coating, inkjet, etc. are preferable. If it is a rectangular substrate, slit coating is preferable. Or spraying method, inkjet method, etc. are better. In the case of spin coating, For example, it can be used at a speed of 500~2000rpm for about 10 seconds to 1 minute.

<Drying step>

The manufacturing method of the present invention may further include a step of drying to remove the solvent after forming the resin composition layer and after the film forming step (layer forming step). The preferred drying temperature is 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. The drying time is, for example, 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.

<Exposure steps>

The manufacturing method of the present invention may include an exposure step of exposing the resin composition layer. The amount of exposure is not particularly limited as long as it can harden the resin composition. For example, it is preferably 100 to 10000 mJ/cm ² in terms of exposure energy at a wavelength of 365 nm, and more preferably 200 to 8000 mJ/cm ² .

The exposure wavelength can be appropriately set within the range of 190~1000nm, with 240~550nm being preferred.

Regarding the exposure wavelength, if described in relation to the light source, (1) semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm, etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g Ray (wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), wide (3 wavelengths of g, h, i-ray), (4) excimer laser, KrF excimer laser (wavelength 248nm) , ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beam, etc. Regarding the resin composition in the present invention, exposure based on a high-pressure mercury lamp is particularly preferred. Among them, exposure based on i-rays is preferred. Light is better. As a result, particularly high exposure sensitivity can be achieved.

<Development Processing Steps>

The manufacturing method of the present invention may include a development treatment step of developing the exposed resin composition layer. By performing development, the unexposed portion (non-exposed portion) is removed. The development method is not particularly limited as long as a desired pattern can be formed. For example, development methods such as spin immersion, spray, immersion, and ultrasonic waves can be used.

Development is performed using a developer. The developer can be used without particular limitation as long as it can remove the unexposed portion (non-exposed portion). It is preferred that the developer contains an organic solvent, and it is even more preferred that the developer contains more than 90% organic solvent. In the present invention, it is preferred that the developer contains an organic solvent with a ClogP value of -1 to 5, and it is even more preferred that the developer contains an organic solvent with a ClogP value of 0 to 3. The ClogP value can be calculated as a calculated value by inputting the structural formula into ChemBioDraw.

Regarding the organic solvent, suitable examples of esters include ethyl acetate, n-butyl acetate, amyl formate, isopentyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, and butyric acid. Ethyl ester, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (example: methyl alkoxyacetate , ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxyethyl acetate esters, etc.)), 3-alkoxypropionic acid alkyl esters (for example: 3-alkoxypropionic acid methyl ester, 3-alkoxypropionic acid ethyl ester, etc. (for example, 3-methoxypropionic acid methyl ester) Ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxypropionic acid alkyl esters (example: 2 -Methyl alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g. For example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate ester)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate , ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxobutanate acid methyl ester, ethyl 2-oxobutyrate, etc., and as ethers, suitable examples include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and methyl ether. 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 acetic acid ester, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as ketones, suitable examples include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3- Heptanone, N-methyl-2-pyrrolidone, etc., and as aromatic hydrocarbons, toluene, xylene, anisole, limonene, etc. can be suitably mentioned, and as teresine, preferably Give dimethyl sulfoxide.

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

It is more preferred that 50% by mass or more of the developer is an organic solvent, more preferably 70% by mass or more is an organic solvent, and it is still more preferred that 90% by mass or more is an organic solvent. In addition, 100% by mass of the developer may be an organic solvent.

The development time is preferably 10 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, but it can usually be performed at 20 to 40°C.

After using the developer, it can then be rinsed. It is better to use a different solvent from the developer for rinsing. For example, a solvent contained in the resin composition can be used for flushing. The optimal flushing time is 5 seconds to 1 minute.

<Heating step>

The manufacturing method of the present invention preferably includes a heating step after the film formation step (layer formation step), drying step or development step. In particular, when using a resin containing a polymer precursor, it is preferable to include a heating step. In the heating step, the cyclization reaction of the polymer precursor can be carried out. The heating temperature (maximum heating temperature) of the middle layer in the heating step is preferably 50°C or higher, more preferably 80°C or higher, further preferably 140°C or higher, further preferably 150°C or higher, and still further preferably 160°C or higher. Preferable, and above 170°C is even more preferable. The upper limit is preferably 500°C or lower, more preferably 450°C or lower, further preferably 350°C or lower, further preferably 250°C or lower, and still further preferably 220°C or lower.

Regarding heating, it is preferable to conduct the heating at a temperature rising rate of 1 to 12°C/min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min. By setting the temperature rise rate to 1°C/min or more, excessive volatilization of amine can be prevented while ensuring productivity, and by setting the temperature rise rate to 12°C/min or less, the residual stress of the cured film can be relaxed.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and still more preferably 25°C to 120°C. The temperature at the beginning of heating refers to the temperature at which the step of heating to the maximum heating temperature begins. For example, when the resin composition is applied to the substrate and then dried, the temperature of the dried film (layer) is, for example, from a temperature that is 30 to 200°C lower than the boiling point of the solvent contained in the resin composition. Warming up is better.

The heating time (heating time at the highest heating temperature) is 10 to 360 minutes. Preferably, 20 to 300 minutes is more preferably, and 30 to 240 minutes is still more preferably.

In particular, when forming a multilayer laminated body, from the viewpoint of interlayer adhesion of the cured film, heating is preferably performed at a heating temperature of 180°C to 320°C, and more preferably 180°C to 260°C. The reason for this is not certain, but it is considered that the reason is that by setting this temperature, the ethynyl groups of the polymer precursor between the layers undergo a cross-linking reaction.

Heating can be done in stages. As an example, the temperature can be increased from 25°C to 180°C at 3°C/min and held at 180°C for 60 minutes, and the temperature can be raised from 180°C to 200°C at 2°C/min and held at 200°C for 120 minutes. steps. The heating temperature as the pretreatment step is preferably 100~200°C, more preferably 110~190°C, and further preferably 120~185°C. In this pretreatment step, it is also preferable to perform the treatment while irradiating ultraviolet rays as described in U.S. Patent No. 9159547. The characteristics of the membrane can be improved through these pre-treatment steps. The pre-processing step can be carried out in a short time of about 10 seconds to 2 hours, and preferably 15 seconds to 30 minutes. The pretreatment can be more than two stages. For example, pretreatment step 1 can be performed in the range of 100 to 150°C, and then pretreatment step 2 can be performed in the range of 150 to 200°C.

Furthermore, cooling may be performed after heating. In this case, the cooling rate is preferably 1 to 5° C./minute.

Regarding the heating step, from the viewpoint of preventing decomposition of the resin, it is preferably performed in an environment with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

<Metal layer formation step>

The manufacturing method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the resin composition layer after development.

The metal layer is not particularly limited, and existing metal types can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper and aluminum are more preferred, and copper is even more preferred.

The method of forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in Japanese Patent Application Laid-Open Nos. 2007-157879, 2001-521288, 2004-214501, and 2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and methods combining these can be considered. More specifically, a patterning method that combines sputtering, photolithography, and etching, and a patterning method that combines photolithography and electrolytic plating can be cited.

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

<Layering step>

The manufacturing method of the present invention preferably further includes a lamination step.

The lamination step includes sequentially performing (a) film formation step (layer formation step), (b) exposure step, (c) development treatment step, and (d) heating step on the surface of the cured film (resin layer) or metal layer a series of steps. However, only the film forming step of (a) may be repeated. Alternatively, the heating step (d) may be performed collectively at the end or in the middle of lamination. That is, the following aspect may be adopted: repeating the steps (a) to (c) a predetermined number of times, and then performing the heating of (d) to thereby The laminated resin composition layer is collectively hardened. Furthermore, the (c) development step may be followed by the (e) metal layer forming step. In this case, the heating of (d) may be performed each time, or the heating of (d) may be performed collectively after laminating a predetermined number of times. It goes without saying that the above-described drying step, heating step, etc. may be appropriately included in the lamination step.

When the lamination step is performed after the lamination step, the surface activation treatment step may be performed after the above-mentioned heating step, after the above-mentioned exposure step, or after the above-mentioned metal layer forming step. As a surface activation treatment, plasma treatment is exemplified.

It is better to perform the above lamination step 2 to 5 times, and even more preferably 3 to 5 times.

For example, a structure in which the resin layer has three to seven layers is preferable, such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, and more preferably three to five layers.

In the present invention, it is particularly preferred to form a cured film (resin layer) of the resin composition to cover the metal layer after the metal layer is provided. Specifically, the method of sequentially repeating (a) the film formation step, (b) the exposure step, (c) the development step, (e) the metal layer formation step, (d) the heating step, or sequentially repeating (a ) film formation step, (b) exposure step, (c) development step, (e) metal layer formation step, and (d) heating step is provided at the end or in the middle. By alternately performing the lamination step of laminating the resin composition layer (resin) and the metal layer formation step, the resin composition layer (resin layer) and the metal layer can be alternately laminated.

The present invention also discloses a semiconductor element having the cured film or laminate of the present invention. As a specific example of a semiconductor element using the resin composition of the present invention in the formation of an interlayer insulating film for a rewiring layer, refer to Japanese Patent Application Laid-Open No. 2016-027357 The descriptions in paragraphs 0213 to 0218 of the Public Notice and the descriptions in Figure 1 are incorporated into this manual.

[Example]

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

<Preparation of resin composition>

The components described in the following table were mixed to obtain a resin composition.

The raw materials listed in the above table are as follows.

(resin)

A-1: Polyimide precursor with the following structure (Mw=25000)

唑前驅物(Mw=25000) A-2: Benzo with the following structure

Azole precursor (Mw=25000)

(coupling agent)

B-1: Compound with the following structure (pKa=14.45)

B-2: Compound with the following structure (pKa=12.33)

B-3: Compound with the following structure (pKa=13.06)

B-4: Compound with the following structure (pKa=12.96)

B-5: Compound with the following structure (pKa=14.27)

B-6: Compound with the following structure (pKa=12.68)

B-7: Compound with the following structure (pKa=5.99)

B-101: Compound with the following structure (pKa=12.47)

B-102: Compound with the following structure (pKa=14.75)

B-103: Compound with the following structure (pKa=13.22)

B-1 to B-7 are compounds containing groups that generate bases by heating. The base generation temperature of B-1 to B-7 is above 160°C.

B-101~B-103 are compounds that do not contain a group that generates a base by heating.

(starter)

C-1: IRGACURE OXE 01 (made by BASF)

C-2: IRGACURE OXE 02 (made by BASF)

C-3: IRGACURE 784 (made by BASF)

C-4: NCI-831 (made by ADEKA CORPORATION)

(migration inhibitor)

D-1: 1,2,4-triazole

D-2: 1H-tetrazole

(solvent)

E-1: N-methylpyrrolidone

E-2: Ethyl lactate

E-3: γ-butyrolactone

E-4: dimethyl sulfoxide

(polymerizable monomer)

F-1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)

F-2: SR-209 (made by Arkema Corporation)

(Other additives)

G-1: 4-methoxyphenol (polymerization inhibitor)

G-2: 1,4-p-benzoquinone (polymerization inhibitor)

G-3: Compound with the following structure (thermal base generator)

<evaluation>

<<Storage stability>>

Seal 10 g of the newly produced resin composition in a container (container material: light-shielding glass, capacity: 100 mL), and let it stand for 2 hours in an environment of 25°C and 65% relative humidity. week. The viscosity of the resin composition before and after standing was measured using an E-type viscometer (TV-25, Toki Sangyo Co., Ltd.), and the viscosity change rate was calculated based on the following equation. The lower the viscosity change rate, the higher the storage stability.

Viscosity change rate (%) = | 100 × {1 - (viscosity of the resin composition after standing for 2 weeks / viscosity of the resin composition before standing)} |

The viscosity measurement was performed at 25°C. Otherwise, it was performed in accordance with JIS Z 8803:2011.

A: The viscosity change rate is less than 1%

B: Viscosity change rate is more than 1% and less than 3%

C: Viscosity change rate is more than 3% and less than 5%

D: Viscosity change rate is more than 5%

<<Tightness>>

By a spin coating method, the resin composition is applied in a layered form on the copper substrate to form a resin composition layer. The obtained copper substrate to which the resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes, thereby forming a resin composition layer with a thickness of 20 μm on the copper substrate. Using a stepper (Nikon NSR 2005 i9C) and a 100 μm square photomask, the resin composition layer was exposed with an exposure energy of 500 mJ/cm ² and then developed with cyclopentanone for 60 seconds to obtain 100μm square resin layer. Furthermore, in a nitrogen atmosphere, the temperature was raised at a heating rate of 10° C./min. After reaching 250° C., the temperature was maintained for 3 hours to obtain a cured film.

In an environment of 25°C and 65% relative humidity (RH), the peeling force between the copper substrate and the cured film was measured on a 100 μm square cured film on the copper substrate using an adhesive strength testing machine (CondorSigma manufactured by XYZTEC Corporation). Regarding measurement conditions, use 200 μm needle, the peeling speed was set to 10 μm/S, and the distance between the copper substrate and the needle was set to 2 μm.

A: Peeling force is above 60gf

B: Peeling force is 50gf or more and less than 60gf

C: Peeling force is 40gf or more and less than 50gf

D: Peeling force is 40gf or less

<<Reliability>>

A cured film was formed by the same method as the evaluation of adhesiveness. A reliability test was conducted using a highly accelerated life test device (PC-422R8D, Hirayama Manufacturing Co., Ltd.) in an environment of 121°C and 100% relative humidity (RH), and the obtained cured film was left to stand for 1,000 hours. The peeling force between the copper substrate and the cured film was measured using an adhesive strength testing machine (CondorSigma manufactured by XYZTEC Corporation) on a 100 μm square cured film on the copper substrate before and after the reliability test. Regarding the measurement conditions, a 200 μm needle was used, the peeling speed was set to 10 μm/S, and the distance between the copper substrate and the needle was set to 2 μm.

The adhesion force reduction rate was calculated based on the following equation.

Adhesion force reduction rate (%) = 100 × {1-(peeling force of the cured film after the reliability test/peeling force of the cured film before the reliability test)}

A: The reduction rate of close contact force is less than 1%

B: The reduction rate of close contact force is more than 1% and less than 3%

C: The reduction rate of close contact force is more than 3% and less than 10%

D: The reduction rate of close contact force is more than 10%

<<Evaluation of mechanical properties (ductility)>>

On the silicon wafer, the resin composition is spin-coated until the cured film thickness becomes approximately 10 μm, and after drying, a cured film was obtained by heating at 180° C. for 2 hours in a nitrogen atmosphere using a programmed temperature curing furnace (VF-2000 model, manufactured by KOYO THERMO SYSTEMS CO., LTD.). The obtained cured film was cut into short strips with a width of 3 mm using a cutting machine (DAD3350 model, manufactured by DISCO Corporation), and then peeled from the silicon wafer using 46% hydrofluoric acid. The ductility of the cured film was measured in accordance with ASTM D882-09 using a tensile testing machine (UTM-II-20 model, manufactured by ORIENTEC Co., Ltd.). The ductility is judged as follows.

A: Ductility is over 60%

B: Ductility is more than 50% and less than 60%

C: Ductility is more than 40% and less than 50%

D: Ductility is less than 40%

As shown in the above table, the storage stability, adhesion, and reliability of the examples were evaluated as good.

Claims (16)

A resin composition, which contains: selected from polyimide precursors, polyimide, polybenzo

Azole precursors and polybenzo

At least one resin in the group of azoles; and a compound B having a pKa of 5 or more, each including a group that generates a base by heating and a group represented by the following formula (b1), which generates a base by heating The groups respectively include a heterocyclic group containing a nitrogen atom and at least one group selected from -OCO- and -COO-, -M ¹ (R ¹ ) (R ² ) (R ³ )‧‧ ‧‧‧‧(b1) In formula (b1), M ¹ represents Si, Ti or Zr, R ¹ to R ³ independently represent Rb ¹ or ORb ¹ , and Rb ¹ represents a hydrocarbon group having 1 to 10 carbon atoms. The resin composition according to claim 1, wherein R ¹ to R ³ of the formula (b1) each independently represent ORb ¹ , and Rb ¹ represents a hydrocarbon group having 1 to 10 carbon atoms. The resin composition according to claim 1 or 2, wherein M ¹ in the formula (b1) represents Si. The resin composition according to claim 1 or 2, wherein the base generation temperature of compound B is 160°C or above. The resin composition as claimed in claim 1 or 2, wherein the compound B is a compound represented by the following formula (I),

In the formula (I), A ¹ represents a group that generates a base by heating, L ¹ represents a single bond or a divalent linking group, M ¹ represents Si, Ti or Zr, and R ¹ to R ³ each independently represent Rb. ¹ or ORb ¹ , Rb ¹ represents a hydrocarbon group with 1 to 10 carbon atoms. The resin composition according to claim 1 or 2, which contains 0.01 to 5 mass % of the compound B in the total solid content of the resin composition. The resin composition as claimed in claim 1 or 2, wherein the resin includes polyimide precursors and polybenzoyl

At least one of the azole precursors. The resin composition according to claim 1 or 2, further comprising a photoradical polymerization initiator. The resin composition of claim 8, wherein the photoradical polymerization initiator includes an oxime compound. The resin composition according to claim 1 or 2, which is used to form an interlayer insulating film for a rewiring layer. A cured film formed by curing the resin composition according to any one of claims 1 to 10. A laminated body having two or more layers of the cured film according to Claim 11 and having a metal layer between the two layers of cured films. A method for manufacturing a hardened film, which includes: In the film forming step, the resin composition according to any one of claims 1 to 10 is applied to a substrate to form a film. The method for manufacturing a cured film according to claim 13, which includes: an exposure step for exposing the film; and a development step for developing the film. The method for manufacturing a cured film according to claim 13 or 14, which includes the step of heating the film at 80 to 450°C. A semiconductor element having the cured film according to claim 11.