KR102555592B1 - Curable resin composition, cured film, laminate, method for producing cured film, semiconductor device, and thermal base generator - Google Patents

Abstract

A curable resin composition containing a heterocycle-containing polymer precursor and a compound represented by the following formula (1-1), a cured film formed by curing the curable resin composition, a laminate comprising the cured film, a method for producing the cured film, And to provide a semiconductor device including the cured film or the laminate. Moreover, it relates to a novel heat base generator.
In formula (1-1), R ¹ and R ² each independently represent a monovalent organic group, L ¹ represents a divalent linking group, R ³ represents a hydrogen atom or a monovalent organic group, and R ¹ and R ² may combine to form a ring structure.

Description

Curable resin composition, cured film, laminate, method for producing cured film, semiconductor device, and thermal base generator

The present invention relates to a curable resin composition containing a heterocycle-containing polymer precursor, a cured film, a laminate, a method for producing a cured film, a semiconductor device, and a thermal base generator.

Resins cured by cyclization of heterocycle-containing polymer precursors such as polyimide resins and polybenzoxazole resins (also referred to as “heterocycle-containing polymer precursors”) are excellent in heat resistance and insulating properties, so they can be used in a variety of applications. is being applied Although it does not specifically limit as said use, If the semiconductor device for mounting is given as an example, the material of an insulating film or sealing material, or use as a protective film is mentioned. Moreover, it is also used as a base film or cover lay of a flexible substrate.

For example, in the use described above, the heterocycle-containing polymer precursor is used as a curable resin composition containing the heterocycle-containing polymer precursor. The cured resin can be formed on the substrate by applying such a curable resin composition to a substrate by, for example, coating and then cyclizing the heterocycle-containing polymer precursor by heating or the like. Since the curable resin composition can be applied by a known coating method or the like, it can be said to have excellent manufacturing adaptability, such as a high degree of freedom in designing, for example, the shape, size, and application position of the curable resin composition to be applied. In addition to the high performance possessed by polyimide resins and the like, industrial application development of curable resin compositions containing heterocycle-containing polymer precursors is expected gradually from the viewpoint of such excellent adaptability in manufacturing.

For example, in Patent Document 1, an acidic compound that generates a base when heated to 40 ° C. or higher, and an ammonium salt having an anion and an ammonium cation with a pKa 1 of 0 to 4. Thermal base generation containing at least one selected from A thermosetting resin composition comprising a thermosetting resin and a thermosetting resin are disclosed.

Further, Patent Literature 2 describes a curable resin composition containing a polyimide precursor having a specific structural unit and a compound that generates radicals when irradiated with actinic light.

Patent Document 1: International Publication No. 2015/199219 Patent Document 2: Japanese Unexamined Patent Publication No. 2014-201695

In a curable resin composition containing a heterocycle-containing polymer precursor such as a polyimide precursor, during storage of the curable resin composition (for example, storage at room temperature (25° C., the same applies hereinafter), etc.), it is difficult for cyclization to proceed. It is difficult, and provision of a curable resin composition excellent in breaking elongation of the obtained cured product has been desired.

In this specification, what cyclization does not progress easily at the time of storage of curable resin composition is also called "excellent storage stability of curable resin composition."

One aspect of the present invention is a curable resin composition having excellent storage stability and excellent elongation at break of a cured film obtained, a cured film obtained by curing the curable resin composition, a laminate containing the cured film, and production of the cured film It is an object to provide a method and a semiconductor device including the cured film or the laminate.

Another aspect of the present invention aims to provide a novel heat base generator.

<1> Heterocycle-containing polymer precursor, and

Containing a compound represented by the following formula (1-1),

A curable resin composition.

[Formula 1]

In formula (1-1), R ¹ and R ² each independently represent a monovalent organic group, L ¹ represents a divalent linking group, R ³ represents a hydrogen atom or a monovalent organic group, and R ¹ and R ² may combine to form a ring structure.

<2> The curable resin composition according to <1>, wherein L ¹ is a divalent linking group having a link chain length of 1 to 5.

<3> The curable resin composition according to <1> or <2>, wherein R ¹ and R ² are each independently a hydrocarbon group.

<4> L ¹ is 1,2-ethylene group, 1,3-propanediyl group, 1,2-cyclohexanediyl group, cisvinylene group, 1,2-phenylene group, 1,2-phenyl group The curable resin composition according to any one of <1> to <3>, which is a lenmethylene group or a 1,2-ethyleneoxy-1,2-ethylene group.

<5> The curable resin composition according to any one of <1> to <4>, wherein R ³ is a hydrogen atom, an alkyl group, or an aryl group.

<6> The curable resin composition according to any one of <1> to <5>, wherein the compound represented by the formula (1-1) has a molecular weight of 100 or more and 2,000 or less.

<7> The curable resin composition according to any one of <1> to <6>, further comprising a photoradical polymerization initiator and a radically polymerizable compound.

<8> The curable resin composition according to any one of <1> to <7>, containing at least one precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor as the heterocycle-containing polymer precursor.

<9> The curable resin composition according to any one of <1> to <8>, comprising a polyimide precursor as the heterocycle-containing polymer precursor.

<10> Curable resin composition as described in <9> in which the said polyimide precursor has a repeating unit represented by following formula (1);

[Formula 2]

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

<11> The curable resin composition according to <10>, wherein at least one of R ¹¹³ and R ¹¹⁴ in the formula (1) contains a radical polymerizable group.

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

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

<14> A laminate comprising two or more layers of the cured film according to <13> and including a metal layer between any of the cured films.

<15> A method for producing a cured film including a film formation step of applying the curable resin composition according to any one of <1> to <12> to a substrate to form a film.

<16> The method for producing a cured film according to <15>, which further includes a heating step of heating the film to decompose the compound represented by the formula (1-1).

<17> A semiconductor device comprising the cured film according to <13> or the laminate according to <14>.

<18> A thermobase generator represented by the following formula (1-2).

[Formula 3]

In Formula (1), R ²¹ and R ²² each independently represent a monovalent organic group, L ²¹ represents a divalent linking group, all atoms at bonding positions at both ends of L ²¹ are carbon atoms, and R ²³ represents a hydrogen atom or a monovalent organic group.

According to one aspect of the present invention, a curable resin composition having excellent storage stability and excellent elongation at break of a cured film obtained, a cured film obtained by curing the curable resin composition, a laminate containing the cured film, and the cured film A manufacturing method, and a semiconductor device including the cured film or the laminate are provided.

Moreover, according to another aspect of this invention, a novel heat base generator is provided.

EMBODIMENT OF THE INVENTION Hereinafter, the main embodiment of this invention is described. However, the present invention is not limited to the specific embodiments.

In this specification, the numerical range represented by the symbol "-" means the range which includes the numerical value described before and after "-" as a lower limit value and an upper limit value, respectively.

In this specification, the word "process" is meant to include not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended action of the process can be achieved.

In the notation of a group (atomic group) in this specification, the notation that does not describe substitution and unsubstitution includes a group (atomic group) having a substituent as well as a group (atomic group) having no substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In this specification, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Further, examples of light used for exposure include bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), active rays such as X-rays and electron beams, or radiation.

In the present specification, "(meth)acrylate" means either or both of "acrylate" and "methacrylate", and "(meth)acryl" means "acryl" and "methacryl". , and "(meth)acryloyl" means both or either of "acryloyl" and "methacryloyl".

In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

In this specification, the total solid content refers to the total mass of the components excluding the solvent from all components of the composition. Moreover, in this specification, solid content concentration is the mass percentage of other components except a solvent with respect to the total mass of a composition.

In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as values in terms of polystyrene according to gel permeation chromatography (GPC measurement) unless otherwise specified. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, using HLC-8220GPC (manufactured by Tosoh Co., Ltd.), and as a column, guard column HZ-L, TSKgel Super HZM-M , TSKgel Super HZ4000, TSKgel Super HZ3000, TSKgel Super HZ2000 (manufactured by Tosoh Corporation) can be obtained by using. These molecular weights shall be measured using THF (tetrahydrofuran) as an eluent unless otherwise specified. In addition, detection in the GPC measurement assumes that a detector with a wavelength of 254 nm of UV rays (ultraviolet rays) is used unless otherwise specified.

In this specification, when the positional relationship of each layer constituting the laminate is described as "upper" or "lower", another layer is located above or below the reference layer among a plurality of layers of interest. should have this That is, a third layer or element may be further interposed between the layer serving as the standard and the other layer, and the layer serving as the standard and the other layer need not be in contact with each other. In addition, unless otherwise specified, the direction in which layers are laminated with respect to the substrate is referred to as "upper", or in the case of a photosensitive layer, the direction from the substrate to the photosensitive layer is referred to as "upper", and the opposite direction is called "Ha". Note that the setting of such a vertical direction is for convenience in this specification, and in an actual aspect, there may be cases where the “up” direction in this specification is different from vertically upward.

In this specification, as long as there is no special description, a composition may also contain two or more types of compounds corresponding to the component as each component contained in a composition. In addition, unless otherwise specified, the content of each component in the composition means the total content of all the compounds corresponding to the component.

In this specification, the physical property values are values under conditions of a temperature of 23°C and an atmospheric pressure of 101,325 Pa (1 atm) unless otherwise specified.

In this specification, a combination of preferable aspects is a more preferable aspect.

(curable resin composition)

The curable resin composition of the present invention (hereinafter, simply referred to as "the composition of the present invention") contains a heterocycle-containing polymer precursor and a compound represented by formula (1-1).

Moreover, it is preferable that the curable resin composition of this invention further contains the radical photopolymerization initiator mentioned later and the radical polymerizable compound mentioned later.

Curable resin composition of this invention is excellent in storage stability, and also excellent in the breaking elongation rate of the cured film obtained.

Although the mechanism by which the said effect is obtained is unknown, it is guessed as follows.

Since the compound represented by formula (1-1) contained in the curable resin composition of the present invention is difficult to decompose at storage temperatures such as room temperature, it is excellent in storage stability and, for example, when cured by heating or the like It is considered that since the generation efficiency of the base is excellent in , the cyclization of the heterocycle-containing polymer precursor tends to proceed, and the elongation at break of the obtained cured film is excellent.

In addition, since the curable resin composition contains the compound represented by formula (1-1), cyclization of the heterocycle-containing polymer precursor tends to proceed by heating or the like as described above, so that it is easy to have excellent adhesion to substrates such as copper. I think. That is, it is thought that the use of the curable resin composition of the present invention makes it easy to obtain a laminate excellent in adhesion between layers.

Here, in Patent Documents 1 and 2, there is neither description nor suggestion about the curable resin composition containing the compound represented by Formula (1-1).

Hereinafter, components included in the curable resin composition of the present invention will be described in detail.

<Heterocycle-containing polymer precursor>

The curable resin composition of the present invention contains a heterocycle-containing polymer precursor.

The curable resin composition of the present invention preferably contains, as the heterocycle-containing polymer precursor, at least one precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, and more preferably contains a polyimide precursor. desirable.

[Polyimide precursor]

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

[Formula 4]

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

-A ¹ and A ² -

A ¹ and A ² in Formula (1) each independently represent an oxygen atom or -NH-, and an oxygen atom is preferable.

-R ¹¹¹ -

R ¹¹¹ in Formula (1) represents a divalent organic group. Examples of the divalent organic group include a straight-chain or branched-chain aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group combining two or more of these, and a straight-chain aliphatic group having 2 to 20 carbon atoms and 3 carbon atoms. A branched aliphatic group of ~20, a cyclic aliphatic group of 3 to 20 carbon atoms, an aromatic group of 6 to 20 carbon atoms, or a group consisting of a combination thereof is preferable, and an aromatic group of 6 to 20 carbon atoms is more preferable.

R ¹¹¹ in Formula (1) is preferably derived from diamine. As diamine used for manufacture of a polyimide precursor, linear or branched aliphatic, cyclic aliphatic, or aromatic diamine, etc. are mentioned. As for diamine, only 1 type may be used and 2 or more types may be used.

Specifically, the diamine is a diamine containing a group consisting of a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof. It is preferable, and it is more preferable that it is diamine containing an aromatic group of 6-20 carbon atoms. As an example of an aromatic group, the following is mentioned.

[Formula 5]

In formula, A is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) ₂ - , -NHC(=O)- and a group selected from combinations thereof, preferably a single bond or an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)- , -S- and S(=O) ₂ -, more preferably a group selected from -CH ₂ -, -O-, -S-, -S(=O) ₂ -, -C(CF ₃ ) ₂ It is more preferably a divalent group selected from the group consisting of -, and -C(CH ₃ ) ₂ -.

As diamine, specifically, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexyl three; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (Aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane phosphorus or isophoronediamine; Meta or paraphenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether , 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenylsulfone, 4,4'- or 3,3'-diaminodiphenylmethane Phenylsulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'- Diaminobiphenyl (4,4'-diamino-2,2'-dimethylbiphenyl), 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis (4 -Aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3 -Hydroxy-4-aminophenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) Hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoparaterphenyl, 4,4'- Bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy) cy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenyl Sulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl -4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2- Bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl) -10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5 -Diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3 '-diaminodiphenylsulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2-(3',5'-diaminobenzoyloxy)ethylmethacryl rate, 2,4- or 2,5-diaminocumene, 2,5-dimethyl-paraphenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-paraphenylenediamine, 2 ,4,6-trimethyl-metaphenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis( 4-aminophenyl)ethane, diaminobenzanilide, diaminobenzoic acid ester, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane , 1,4-bis (4-aminophenyl) octafluorobutane, 1,5-bis (4-aminophenyl) decafluoropentane, 1,7-bis (4-aminophenyl) tetradecafluoro Heptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2 ,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis( Trifluoromethyl) phenyl] hexafluoropropane, parabis (4-amino-2-trifluoromethylphenoxy) benzene, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) ) Biphenyl, 4,4'-bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone , 4,4'-bis (3-amino-5-trifluoromethylphenoxy) diphenylsulfone, 2,2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl] hexa Fluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl , 2,2', 5,5', 6,6'-hexafluorotolidine and at least one diamine selected from 4,4'-diaminoquaterphenyl.

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

[Formula 6]

[Formula 7]

Further, a diamine having at least two alkylene glycol units in its main chain is also mentioned as a preferable example. Preferably, it is a diamine containing two or more of ethylene glycol chains or propylene glycol chains in combination in one molecule, and more preferably diamines that do not contain an aromatic ring. As specific examples, 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 (above trade names, manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy) )ethoxy)propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, etc., but are limited to these It doesn't work.

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, The structure of Jeffamine (registered trademark) EDR-176 is shown below.

[Formula 8]

In the above, x, y, and z are arithmetic mean values.

R ¹¹¹ in Formula (1) is preferably represented by -Ar ⁰ -L ⁰ -Ar ⁰ - from the viewpoint of flexibility of the resulting cured film. Ar ⁰ is each independently an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and particularly preferably 6 to 10), preferably a phenylene group. L ⁰ is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) ₂ -, -NHCO -, and a group selected from the group consisting of two or more combinations thereof. The preferable range of L ⁰ has the same meaning as A mentioned above.

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

[Formula 9]

In Formula (51), R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group, a fluoromethyl group, or a difluoromethyl group. , or a trifluoromethyl group.

Examples of the monovalent organic group among R ⁵⁰ to R ⁵⁷ include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and the like. can

[Formula 10]

In Formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group.

As the diamine compound giving the structure of Formula (51) or (61), dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-di Amino biphenyl, 2,2'-bis(fluoro)-4,4'-diamino biphenyl, 4,4'-diamino octafluoro biphenyl, etc. are mentioned. These 1 type may be used, or you may use in combination of 2 or more types.

-R ¹¹⁵ -

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

[Formula 11]

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

As for the tetravalent organic group represented by ^R115 in Formula (1), the tetracarboxylic acid residue etc. which remain|survive after removing the acid dianhydride group from tetracarboxylic acid dianhydride are mentioned specifically,. As for tetracarboxylic dianhydride, only 1 type may be used, and 2 or more types may be used. As for tetracarboxylic dianhydride, the compound represented by following formula (7) is preferable.

[Formula 12]

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

Specific examples of tetracarboxylic dianhydride include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-di Phenylsulfidetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfotetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4 '-diphenylmethanetetracarboxylic acid dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, 2,3 ,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic acid 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 acid dianhydride, 1,4,5,6-naphthalenetetracarboxylic acid dianhydride Water, 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-benzene tetracarboxylic acid dianhydride, and at least one selected from alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms thereof One paper is exemplified.

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

[Formula 13]

-R ¹¹³ and R ¹¹⁴ -

R ¹¹³ and R ¹¹⁴ in Formula (1) each independently represent a hydrogen atom or a monovalent organic group. It is preferable that at least one of R ¹¹³ and R ¹¹⁴ contains a radical polymerizable group, and it is more preferable that both contain a radical polymerizable group. The radical polymerizable group is a group capable of undergoing a crosslinking reaction by the action of a radical, and examples thereof include a group having an ethylenically unsaturated bond.

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

[Formula 14]

In Formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and a methyl group is preferable.

In formula (III), R ²⁰¹ is an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH(OH)CH ₂ - or a (poly)oxyalkylene group having 4 to 30 carbon atoms (the alkylene group preferably has 1 to 12 carbon atoms) 1 to 6 are more preferred, and 1 to 3 are particularly preferred; the number of repetitions is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3). In addition, an oxyalkylene group (poly) means an oxyalkylene group or a polyoxyalkylene group.

Examples of suitable R ²⁰¹ include ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butanediyl group, 1,3-butanediyl group, pentamethylene group, hexamethylene group, octamethylene group , a dodecamethylene group, -CH ₂ CH(OH)CH ₂ -, and an ethylene group, a propylene group, a trimethylene group, and -CH ₂ CH(OH)CH ₂ - are more preferable.

Especially preferably, R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethylene group.

As a preferable embodiment of the polyimide precursor in the present invention, an aliphatic group, an aromatic group and an arylalkyl group having 1, 2 or 3, preferably 1 acid group as the monovalent organic group of R ¹¹³ or R ¹¹⁴ etc. can be mentioned. Specifically, an aromatic group having 6 to 20 carbon atoms having an acid group and an arylalkyl group having 7 to 25 carbon atoms having an acid group are exemplified. More specifically, a phenyl group having an acid group and a benzyl group having an acid group are exemplified. The acid group is preferably a hydroxy group. That is, R ¹¹³ or R ¹¹⁴ is preferably a group having a hydroxyl group.

As the monovalent organic group represented by R ¹¹³ or R ¹¹⁴ , a substituent that improves solubility in a developing solution is preferably used.

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

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

As for carbon number of an alkyl group, 1-30 are preferable (3 or more in the case of cyclic|annular). Alkyl groups may be straight-chain, branched, or cyclic. Examples of the straight-chain or branched alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, and iso. A propyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, and 2-ethylhexyl group are mentioned. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. As a monocyclic cyclic alkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group are mentioned, for example. Examples of the polycyclic cyclic alkyl group include adamantyl group, norbornyl group, bornyl group, campenyl group, decahydronaphthyl group, tricyclodecanyl group, tetracyclodecanyl group, camphoroyl group, dicyclohexyl group and pinenyl group. can be heard As the alkyl group substituted with an aromatic group, a straight-chain alkyl group substituted with an aromatic group described below is preferable.

As an aromatic group, specifically, a substituted or unsubstituted aromatic hydrocarbon group (as a cyclic structure constituting the group, a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring , indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene ring, triphenylene ring, etc.), or a substituted or unsubstituted aromatic heterocyclic group (cyclic ring constituting the group) As the structure, fluorene ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzo Furan ring, benzothiophene ring, isobenzofuran ring, quinolizine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acri Dean ring, phenanthroline ring, cyanthrene ring, chromen ring, xanthene ring, phenoxacyin ring, phenothiazine ring or phenazine ring).

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

Moreover, you may copolymerize the aliphatic group which has a siloxane structure in the repeating unit represented by Formula (1) for the purpose of improving adhesiveness with a base material. Specifically, as the diamine component, bis(3-aminopropyl)tetramethyldisiloxane, bis(paraaminophenyl)octamethylpentasiloxane, and the like are exemplified.

It is preferable that the repeating unit represented by Formula (1) is a repeating unit represented by Formula (1-A) or (1-B).

[Formula 15]

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

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

The preferred range of R ¹¹² has the same meaning as R ¹¹² in Formula (5), and among these, an oxygen atom is more preferred.

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

The polyimide precursor WHEREIN: Although 1 type may be sufficient as the repeating unit represented by Formula (1), 2 or more types may be sufficient as it. Moreover, structural isomers of the repeating unit represented by Formula (1) may be included. Moreover, a polyimide precursor may also contain other types of repeating units other than the repeating unit of said Formula (1).

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

The weight average molecular weight (Mw) of the polyimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, still more 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, still more preferably 4,000 to 25,000.

1.5-3.5 are preferable and, as for the degree of dispersion of the molecular weight of a polyimide precursor, 2-3 are more preferable.

In the present specification, the degree of dispersion of molecular weight refers to a value obtained by removing the weight average molecular weight by the number average molecular weight (weight average molecular weight/number average molecular weight).

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

In the manufacturing method of a polyimide precursor, it is preferable to use an organic solvent in the case of reaction. 1 type may be sufficient as an organic solvent, and 2 or more types may be sufficient as it.

Although it can determine suitably according to a raw material as an organic solvent, pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone are illustrated.

It is preferable to include the process of depositing solid at the time of manufacture of a polyimide precursor. 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.

[Polybenzoxazole precursor]

It is preferable that a polybenzoxazole precursor contains the repeating unit represented by following formula (2).

[Formula 16]

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

-R ¹²¹ -

In Formula (2), R ¹²¹ represents a divalent organic group. As the divalent organic group, an aliphatic group (preferably 1 to 24 carbon atoms, more preferably 1 to 12, and particularly preferably 1 to 6 carbon atoms) and an aromatic group (preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms) preferably, and 6 to 12 are particularly preferable), a group containing at least one of them is preferable. Examples of the aromatic group constituting R ¹²¹ include R ¹¹¹ in the formula (1). As said aliphatic group, a straight-chain aliphatic group is preferable. R ¹²¹ is preferably derived from 4,4'-oxydibenzoyl chloride.

-R ¹²² -

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

-R ¹²³ and R ¹²⁴ -

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

A polybenzoxazole precursor may also contain other types of repeating units other than the repeating unit of said Formula (2).

It is preferable that the polybenzoxazole precursor further contains a diamine residue represented by the following formula (SL) as another type of repeating unit, from the viewpoint of being able to suppress the occurrence of curvature of the cured film due to ring closure.

[Formula 17]

Z has structure a and structure b, R ^1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and R ^2s is 1 carbon atom -10 hydrocarbon group (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and at least one of R ^3s , R ^4s , R ^5s , and R ^6s is an aromatic group (preferably 6 to 6 carbon atoms). 22, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), the remainder being hydrogen atoms or 1 to 30 carbon atoms (preferably 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, particularly It is preferably an organic group having 1 to 6 carbon atoms, which may be the same or different. The polymerization of structure a and structure b may be block polymerization or random polymerization. In the Z portion, preferably, the a structure is 5 to 95 mol%, the b structure is 95 to 5 mol%, and a+b is 100 mol%.

In formula (SL), examples of preferred Z include those in which R ^5s and R ^6s in b structure are phenyl groups. Moreover, it is preferable that it is 400-4,000, and, as for the molecular weight of the structure represented by Formula (SL), 500-3,000 are more preferable. Molecular weight can be determined by gel permeation chromatography, which is generally used. By making the said molecular weight into the said range, the effect of reducing the elastic modulus after dehydration ring closure of a polybenzoxazole precursor, and suppressing warpage, and the effect of improving solubility can be made compatible.

When the polybenzoxazole precursor contains a diamine residue represented by formula (SL) as another type of repeating unit, from the point of improving the alkali solubility of the curable resin composition, after removal of the acid dianhydride group from the tetracarboxylic acid dianhydride It is preferable to further include the remaining tetracarboxylic acid residue as a repeating unit. As an example of such a tetracarboxylic acid residue, the example of ^R115 in Formula (1) is mentioned.

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

1.5-3.5 are preferable and, as for the degree of dispersion of the molecular weight of a polybenzoxazole precursor, 2-3 are more preferable.

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

Curable resin composition of this invention may contain only 1 type of heterocyclic containing polymer precursor, and may contain 2 or more types. When including 2 or more types, it is preferable that a total amount becomes the said range.

<Compound represented by formula (1-1)>

Curable resin composition of this invention contains the compound represented by Formula (1-1).

[Formula 18]

In formula (1-1), R ¹ and R ² each independently represent a monovalent organic group, L ¹ represents a divalent linking group, R ³ represents a hydrogen atom or a monovalent organic group, and R ¹ and R ² may combine to form a ring structure.

It is preferable that the compound represented by Formula (1-1) is a compound which decomposes and generates a base. Moreover, when hardening a curable resin composition with heat, it is more preferable that the compound represented by Formula (1-1) is a compound which decomposes with heat and generates a base. That is, it is preferable that it is a base generator, and, as for the compound represented by Formula(1-1), it is more preferable that it is a heat base generator.

For example, the compound represented by the following formula (B-1) is decomposed by heating, for example, as described in the following reaction formula, and the generated diisopropylamine acts as a base to form a heterocyclic ring in the curable resin composition. It is thought to accelerate the cyclization of the containing polymer precursor.

[Formula 19]

-R ¹ and R ² -

In Formula (1-1), each of R ¹ and R ² independently is preferably a hydrocarbon group, more preferably a hydrocarbon group of 1 to 20 carbon atoms, and more preferably a hydrocarbon group of 1 to 10 carbon atoms. . As said hydrocarbon group, an alkyl group or an aryl group is preferable, a C1-C10 alkyl group or a phenyl group is more preferable, and a C1-C10 alkyl group is still more preferable. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, A 1-ethylpentyl group, a 2-ethylhexyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, or a phenyl group is preferable, and a methyl group, an ethyl group, a propyl group, a view ethyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, 2-ethylhexyl group, A cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, or a cyclooctyl group is more preferred, and a methyl group, ethyl group, isopropyl group, or cyclohexyl group is most preferred.

Further, R ¹ and R ² may be bonded to form a ring structure, and the ring structure formed is preferably an aliphatic ring structure having 5 or 6 reduced numbers, and is a pyrrolidine ring, piperidine ring, piperazine ring, or morpholine ring. structure is more desirable.

The formula of R ¹ and R ² (total sum of atomic weights of atoms in R ¹ or R ² ) is preferably 29 to 300, more preferably 57 to 282, still more preferably 57 to 200, respectively. do.

In addition, R ¹ and R ² of the generated base increase the basicity of the generated base, and the interaction of the generated base with substrates such as copper substrates is small, and from the viewpoint of improving the adhesion between the obtained cured film and the substrate , R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms, or R ¹ and R ² are preferably combined to form an aliphatic ring structure having 5 or 6 reducing numbers, and R ¹ and R ² are each independently More preferably, it is an ethyl group or an isopropyl group, or R ¹ and R ² combine to form a piperidine ring structure.

In addition, the structure of R ¹ and R ² , for example, the strength of the basicity of the generated base, the strength of the interaction between the generated base and the substrate, the motility of the generated base, and the interaction of the generated base with other materials in the film It can be selected in consideration of interactions, etc.

-L ¹ -

In formula (1-1), L ¹ is preferably a divalent linking group having a linked chain length of 1 to 5, and more preferably a divalent linking group having a linked chain length of 2 or 3.

In this specification, the link chain length of L ¹ is an atom contained in L ¹ , and between two carbon atoms C ¹ and C ² in the compound represented by the following formula (1-1') The smallest number of atoms present.

In the following formula (1-1'), carbon atoms in the above-mentioned formula (1-1) are each represented by the symbols C ¹ and C ² , and R ¹ and R ² in the formula (1-1') , R ³ and L ¹ respectively have the same meaning as R ¹ , R ² , R ³ and L ¹ in formula (1-1).

For example, L ¹ in the compound represented by the formula (B-1) described above is a 1,2-phenylene group, and the length of the linked chain is 2.

[Formula 20]

It is preferable that all atoms at the bonding positions of both ends of L ¹ are carbon atoms. The bonding positions of both ends of L ¹ refer to the two positions of the bonding site between L ¹ and carbon atom C ¹ and the bonding site between L ¹ and carbon atom C ² in the formula (1-1′) described above.

From the viewpoint of base generation efficiency, the structure present between carbon atom C ¹ and carbon atom C ² in L ¹ is preferably a part of an aromatic ring structure or an unsaturated aliphatic hydrocarbon structure, and phenyl A rene group (especially preferably a 1,2-phenylene group) or a cisvinylene group is more preferable. The said phenylene group or cisvinylene group may further have a well-known substituent.

In addition, L ¹ may further include a base generating site in a structure other than the structure existing between the carbon atom C ¹ and the carbon atom C ² . As a base generating site|part, the structure except L ^<1> in the above-mentioned formula (1-1) (combination of two structures described in following formula (1-1A)) is mentioned, for example. Examples of compounds in which L ¹ further includes a base generating site in a structure other than the structure existing between carbon atom C ¹ and carbon atom C ² are represented by the formulas (B-16, B-17, and B-18) described later. The compound etc. which appear are mentioned.

In addition, the structure of L ¹ can be selected in consideration of, for example, the generation efficiency of a base.

[Formula 21]

In formula (1-1A), * each independently represents a binding site with another structure, and R ^1A , R ^2A , and R ^3A are respectively R ¹ , R ² , and R ³ in formula (1-1) It has the same meaning and the preferred aspect is also the same. Moreover, it is preferable that the two structures in Formula (1-1A) are bonded by a linking group having a linked chain length of 1 to 5, and preferably bonded by a linking group having a linked chain length of 2 or 3. Moreover, it is preferable that the structure which exists between the two structures in Formula (1-1A) is a part of aromatic ring structure, or is an unsaturated aliphatic hydrocarbon structure.

It is also preferable that L ¹ is a hydrocarbon group. As the hydrocarbon group, an alkylene group having 1 to 5 carbon atoms, an alkenylene group having 2 to 5 carbon atoms, or an arylene group is preferable, and an alkylene group having 2 to 3 carbon atoms, an alkenylene group having 2 to 3 carbon atoms, or It is more preferably a phenylene group, more preferably an alkenylene group having 2 to 3 carbon atoms or a phenylene group, and more preferably a vinylene group or a phenylene group.

In addition, L ¹ is a 1,2-ethylene group, a 1,3-propanediyl group (trimethylene group), a 1,2-cyclohexanediyl group, a cisvinylene group, a 1,2-phenylene group, 1, A 2-phenylenemethylene group or a 1,2-ethyleneoxy-1,2-ethylene group is preferable, and a cisvinylene group or a 1,2-phenylene group is more preferable.

-R ³ -

R ³ is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably an alkyl group of 1 to 20 carbon atoms or an aryl group of 6 to 20 carbon atoms, and It is more preferably an alkyl group of 2 to 8 carbon atoms or a phenyl group, and the interaction of the generated base with substrates such as copper substrates is small, and from the viewpoint of improving the adhesion between the obtained cured film and the substrate, an alkyl group of 2 to 4 carbon atoms Or, a phenyl group is more preferable.

When R ³ is an alkyl group, the alkyl group may have either a linear or branched structure, or may have a cyclic structure, but from the viewpoint of the efficiency of base generation, the alkyl group is preferably linear.

In addition, the structure of R ³ can be selected in consideration of, for example, the efficiency of base generation, the strength of interaction of the decomposed compound with substrates such as copper substrates, and the strength of electron donating ability.

-Molecular Weight-

The molecular weight of the compound represented by formula (1-1) may be determined in consideration of, for example, decomposition temperature, volatility, etc., but is preferably 100 or more, more preferably 150 or more, more preferably 200 or more, and 250 or more it is more preferable Although it does not specifically limit as an upper limit, It is preferable that it is 1,000 or less.

-Decomposition temperature-

When the compound represented by formula (1-1) is a thermobase generator, the decomposition temperature is preferably 50°C or higher, more preferably 80°C or higher, still more preferably 120°C or higher, and still more preferably 140°C or higher. . As an upper limit, it is more preferable that it is 450 degrees C or less, it is more preferable that it is 350 degrees C or less, and it is more preferable that it is 250 degrees C or less.

By using a compound that decomposes at a lower temperature, the energy required for curing the curable resin composition can be reduced.

On the other hand, by making the decomposition temperature equal to or higher than the above lower limit, inadvertently generating a base during storage at room temperature or the like to promote the effect is suppressed, and the storage stability of the curable resin composition is improved.

The decomposition temperature is obtained as the peak temperature of the exothermic peak having the lowest temperature when the compound represented by Formula (1-1) is heated to 500°C at 5°C/min in a pressure-resistant capsule.

Although the following compounds are mentioned as a specific example of a compound represented by Formula(1-1), It is not limited to these compounds.

[Formula 22]

[Formula 23]

These compounds can be synthesized, for example, by reacting an acid anhydride compound and an amine compound to synthesize an amide acid compound, and then further subjecting the amide acid compound to a condensation reaction of the amine compound. What is necessary is just to select suitably the said acid anhydride compound and the said amine compound considering the structure of the compound to be finally obtained. Specifically, it can be synthesized using the method described in Organic Chemistry International (2014), 576715/1-576715/10, 10pp and the like.

The compound represented by Formula (1-1) preferably has a pKa of 8 or more, more preferably 9 or more, and still more preferably 10 or more, of the conjugate acid of the generated base. Although there is no particular upper limit, it is practical that it is 14 or less. By setting the pKa of the specific thermal base generator within the above range, the base generated can efficiently promote the cyclization reaction of the heterocycle-containing polymer precursor, and the elongation at break of the cured film can be increased at low temperatures. Here, pKa is set to a specific value by the following method.

The pKa as used herein refers to a dissociation reaction in which hydrogen ions are released from an acid, and the equilibrium constant Ka is expressed by the negative common logarithm pKa. It shows that it is a strong acid, so that pKa is small. Unless otherwise specified, pKa is a calculated value by ACD/ChemSketch (registered trademark). Alternatively, you may refer to the values published in the "Basic Edition of the 5th Edition Chemistry Handbook" edited by the Chemical Society of Japan.

It is preferable that content of the compound represented by Formula (1-1) is 0.005-50 mass % with respect to the total solid content of curable resin composition from a viewpoint of improving the storage stability of a composition and the elongation at break of the cured film obtained. The lower limit is more preferably 0.05% by mass or more, more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more. The upper limit is more preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less, from the viewpoint of corrosion resistance of metal (for example, copper used for wiring, etc.).

The content of the compound represented by formula (1-1) with respect to 100 parts by mass of the heterocycle-containing polymer precursor is preferably 0.005 parts by mass or more, from the viewpoint of improving the storage stability of the composition and the elongation at break of the resulting cured film, and the like. It is more preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and still more preferably 1 part by mass or more. The upper limit is, for example, preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less, from the viewpoint of corrosion resistance of metal (for example, copper used for wiring, etc.), etc. and 7.5 parts by mass or less is particularly preferred.

1 type or 2 or more types can be used for the compound represented by Formula(1-1). When using 2 or more types, it is preferable that the total amount is the said range.

<Other base generators>

The curable resin composition of the present invention may contain other base generators.

It is assumed that the compound represented by the formula (1-1) described above is not contained in the other base generator.

Examples of other base generators include thermal base generators and photobase generators.

When another heat base generator is included, what was described in international publication 2015/199219 and international publication 2015/199220 is illustrated, These content is integrated in this specification. Moreover, in this invention, it can also be set as the structure which does not contain other heat base generating agents substantially. Substantially not included means that in the curable resin composition of the present invention, the content of other heat base generators is 5% by mass or less of the content of the compound represented by formula (1-1), preferably 3% by mass Hereinafter, it is more preferably 1% by mass.

<Photoinitiator>

It is preferable that curable resin composition of this invention contains a photoinitiator.

The photopolymerization initiator is preferably a radical photopolymerization initiator. The photo-radical polymerization initiator is not particularly limited, and can be appropriately selected from known photo-radical polymerization initiators. For example, photoradical polymerization initiators having photosensitivity to light rays in the visible range from the ultraviolet range are preferred. Moreover, it may be an activator that generates an active radical by generating some kind of action with a photoexcited sensitizer.

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

As an optical radical polymerization initiator, a known compound can be used arbitrarily. For example, acylphosphine compounds such as halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.) and acylphosphine oxides. , hexaarylbiimidazole, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds , metallocene compounds, organoboron compounds, iron arene complexes, and the like. About these details, Paragraph 0165 of Unexamined-Japanese-Patent No. 2016-027357 - 0182 and Paragraph 0138 of International Publication No. 2015/199219 - description of 0151 can be considered into consideration, and this content is integrated in this specification.

As a ketone compound, the compound of Paragraph 0087 of Unexamined-Japanese-Patent No. 2015-087611 is illustrated, for example, This content is integrated in this specification. In a commercial product, Kayacure DETX (Nippon Kayaku Co., Ltd. product) is also used suitably.

As an optical radical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be used suitably. More specifically, for example, the aminoacetophenone-based initiator described in Japanese Unexamined Patent Publication No. 10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent Publication No. 4225898 can also be used.

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

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

As an aminoacetophenone system initiator, the compound of Unexamined-Japanese-Patent No. 2009-191179 in which absorption maximum wavelength was matched with wavelength light sources, such as 365 nm or 405 nm, can also be used.

Examples of the acylphosphine initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. In addition, commercially available IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) can be used.

As a metallocene compound, IRGACURE-784 (made by BASF) etc. are illustrated.

As an optical radical polymerization initiator, an oxime compound is mentioned more preferably. By using an oxime compound, it becomes possible to improve exposure latitude more effectively. An oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a photocuring accelerator.

As a specific example of an oxime compound, the compound of Unexamined-Japanese-Patent No. 2001-233842, the compound of Unexamined-Japanese-Patent No. 2000-080068, and the compound of Unexamined-Japanese-Patent No. 2006-342166 can be used.

As a preferable oxime compound, for example, a compound having the following structures, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2 -Acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy) Iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, etc. are mentioned. In the curable resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as the radical photopolymerization initiator. An oxime-based photopolymerization initiator has a linking group of >C=N-O-C(=O)- in its molecule.

[Formula 24]

Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKA Co., Ltd., an optical radical described in Japanese Laid-Open Patent Publication No. 2012-014052 The polymerization initiator 2) is also suitably used. In addition, TR-PBG-304 (manufactured by Changzhou Trolly New Electronic Materials Co., Ltd.), Adeka Arcles NCI-831 and Adeka Arcles NCI-930 (Co., Ltd.) ADEKA) can also be used. Also, DFI-091 (manufactured by Daito Chemicals Co., Ltd.) can be used.

Moreover, it is also possible to use the oxime compound which has a fluorine atom. As a specific example of such an oxime compound, the compound described in Unexamined-Japanese-Patent No. 2010-262028, the compound 24, 36-40 described in Paragraph 0345 of Unexamined-Japanese-Patent No. 2014-500852, and Unexamined-Japanese-Patent No. 2013- and the compound (C-3) described in paragraph 0101 of No. 164471.

As the most preferable oxime compound, the oxime compound which has a specific substituent shown in Unexamined-Japanese-Patent No. 2007-269779, the oxime compound which has a thioaryl group shown in Unexamined-Japanese-Patent No. 2009-191061, etc. are mentioned.

Radical photopolymerization initiators are, from the viewpoint of exposure sensitivity, trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metal Rosene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complexes and their salts, halomethyloxa Compounds selected from the group consisting of diazole compounds and 3-aryl-substituted coumarin compounds are preferred.

More preferable photoradical polymerization initiators are trihalomethyltriazine compounds, α-amino ketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and onium salt compounds. , A benzophenone compound, an acetophenone compound, at least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-amino ketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound It is preferable, and it is more preferable to use a metallocene compound or an oxime compound, and an oxime compound is still more preferable.

In addition, the radical photopolymerization initiator is N,N'-tetraalkyl-4,4'-diamino, such as benzophenone and N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone). Benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholyl Aromatic ketones such as no-propanone-1, quinones condensed with aromatic rings such as alkylanthraquinone, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, and benzyldi Benzyl derivatives, such as methyl ketal, etc. can also be used. Moreover, the compound represented by following formula (I) can also be used.

[Formula 25]

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

[Formula 26]

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

Moreover, as an optical radical polymerization initiator, Paragraph 0048 of International Publication No. 2015/125469 - the compound of 0055 can also be used.

When a photopolymerization initiator is included, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.5 to 15% by mass with respect to the total solid content of the curable resin composition of the present invention. It is mass %, More preferably, it is 1.0-10 mass %. The photoinitiator may contain only 1 type, and may contain 2 or more types. When 2 or more types of photoinitiators are contained, it is preferable that the sum total is the said range.

<Thermal polymerization initiator>

Curable resin composition of this invention may contain a thermal polymerization initiator as a polymerization initiator, and may also contain a thermal radical polymerization initiator especially. A thermal radical polymerization initiator is a compound that generates radicals by thermal energy to initiate or accelerate a polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the polymerization reaction of the heterocycle-containing polymer precursor can be promoted along with cyclization of the heterocycle-containing polymer precursor, so that a higher degree of heat resistance can be achieved.

As a thermal radical polymerization initiator, specifically, the compound described in Paragraph 0074 of Unexamined-Japanese-Patent No. 2008-063554 - 0118 is mentioned.

When a thermal radical polymerization initiator is included, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 5% by mass with respect to the total solid content of the curable resin composition of the present invention. ~ 15% by mass. The thermal radical polymerization initiator may contain only 1 type, and may contain 2 or more types. When 2 or more types of thermal radical polymerization initiators are contained, it is preferable that the sum total is the said range.

<Polymerizable compound>

[Radically polymerizable compound]

It is preferable that curable resin composition of this invention contains a polymeric compound. As the polymerizable compound, a radical polymerizable compound can be used. A radically polymerizable compound is a compound having a radically polymerizable group. Examples of the radical polymerizable group include groups having ethylenically unsaturated bonds such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth)acryloyl group. The radical polymerizable group has a preferable (meth)acryloyl group.

The radical polymerizable compound may have one or two or more radical polymerizable groups, but the radical polymerizable compound preferably has two or more radical polymerizable groups, more preferably three or more. The upper limit is preferably 15 or less, more preferably 10 or less, and still 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. As for the lower limit of the molecular weight of a radically polymerizable compound, 100 or more are preferable.

From the standpoint of developability, the curable resin composition of the present invention preferably contains at least one difunctional or higher radical polymerizable compound containing two or more radical polymerizable groups, and at least one trifunctional or higher radical polymerizable compound. It is more preferable to include Moreover, a mixture of a bifunctional radical polymerizable compound and a trifunctional or higher functional radical polymerizable compound may be used. For example, the number of functional groups of a bifunctional or higher functional polymerizable monomer means that the number of radical polymerizable groups in one molecule is two or more.

Specific examples of the radically polymerizable compound include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably , esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyhydric amine compounds. In addition, an addition reaction product between an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group, or a sulfanyl group, and monofunctional or polyfunctional isocyanates or epoxies, or a monofunctional or polyfunctional carboxylic acid A dehydration condensation reaction product of is also suitably used. In addition, an addition reaction product between an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group, and a monofunctional or polyfunctional alcohol, amine, or thiol group, furthermore, a halo xeno group, a tosyloxy group, etc. Also suitable are substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent with monofunctional or polyfunctional alcohols, amines, or thiols. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers and the like instead of the above unsaturated carboxylic acids. As a specific example, Paragraph 0113 of Unexamined-Japanese-Patent No. 2016-027357 - description of 0122 can be considered into consideration, and these content is integrated in this specification.

Moreover, the compound which has a boiling point of 100 degreeC or more under normal pressure of a radically polymerizable compound is also preferable. Examples thereof include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol. Tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol(meth)acrylate, trimethylolpropane tri(acryloyloxy Compound obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohol such as propyl) ether, tri(acryloyloxyethyl) isocyanurate, glycerin or trimethylolethane, and then (meth)acrylated compound, Japanese Public Notice Urethane (meth)acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Unexamined Patent Publication No. 51-037193, Japanese Unexamined Patent Publication No. Polyester acrylates described in Japanese Publication No. 48-064183, Japanese Publication No. 49-043191, Japanese Publication No. 52-030490, and epoxy acrylate, which is a reaction product of epoxy resin and (meth)acrylic acid. Polyfunctional acrylates and methacrylates, such as molasses, and mixtures thereof are exemplified. Moreover, Paragraph 0254 of Unexamined-Japanese-Patent No. 2008-292970 - the compound of 0257 are also suitable. Moreover, the polyfunctional (meth)acrylate obtained by making the compound which has a cyclic ether group, such as glycidyl (meth)acrylate, and an ethylenically unsaturated bond react with polyfunctional carboxylic acid, etc. are mentioned.

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

In addition, as other examples, the specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. Hei 01-040337, and Japanese Patent Publication Hei 01-040336, and Japanese Unexamined Patent Publication Hei 02-025493 and the vinylphosphonic acid-based compounds described in No. Moreover, the compound containing the perfluoroalkyl group of Unexamined-Japanese-Patent No. 61-022048 can also be used. Also, Journal of the Japan Adhesion Association vol. 20, no. Those introduced as photopolymerizable monomers and oligomers on pages 7, 300 to 308 (1984) can also be used.

In addition to the above, the compound of Paragraph 0048 of Unexamined-Japanese-Patent No. 2015-034964 - 0051, and the compound of Paragraph 0087 of International Publication No. 2015/199219 - 0131 can also be used preferably, These content is integrated in this specification.

In addition, after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described with specific examples as formula (1) and formula (2) in Japanese Unexamined Patent Publication No. 10-062986, (meth)acrylated A compound can also be used as a radically polymerizable compound.

In addition, Paragraph 0104 of Unexamined-Japanese-Patent No. 2015-187211 - the compound of 0131 can also be used as another radically polymerizable compound, and these content is integrated in this specification.

As a radically polymerizable compound, dipentaerythritol triacrylate (as a commercial item, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial item, KAYARAD D-320; Nippon Kayaku Co., Ltd.) ) agent, A-TMMT: manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd.), dipentaerythritol penta(meth)acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth) Acrylates (commercially available, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and their (meth)acryloyl groups are ethylene glycol residues or propylene glycol residues A structure that is coupled through is preferable. These oligomeric types can also be used.

As a commercial item of a radically polymerizable compound, for example, SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, and SR-494, manufactured by Sartomer, a bifunctional methacrylate having four ethyleneoxy chains, manufactured by Sartomer, 209, 231, 239, DPCA-60 which is a hexafunctional acrylate having 6 pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd., TPA-330 which is a trifunctional acrylate having 3 isobutyleneoxy chains, oil Retainer oligomer UAS-10, UAB-140 (manufactured by Nippon Seishi Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd.), DPHA-40H (Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (Ni Healing Co., Ltd.) etc. are mentioned.

As a radical polymerizable compound, as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. 02-032293, Japanese Patent Publication No. 02-016765 The same urethane acrylates or ethylene described in Japanese Publication No. 58-049860, Japanese Publication No. 56-017654, Japanese Publication No. 62-039417, Japanese Publication No. 62-039418 Urethane compounds having an oxide-based backbone are also suitable. In addition, as a radical polymerizable compound, as described in Japanese Unexamined Patent Publication No. 63-277653, Japanese Unexamined Patent Publication No. 63-260909, and Japanese Unexamined Patent Publication No. Hei 01-105238, having an amino structure or sulfide structure in the molecule compounds can also be used.

The radically polymerizable compound may be a radically polymerizable compound having an acid group such as a carboxy group or a phosphoric acid group. The radically polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a radical polymerizable compound obtained by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give an acid group. compounds are more preferred. Particularly preferably, in a radically polymerizable compound obtained by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound to have an acid group, the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol It is a phosphorus compound. As a commercial item, M-510, M-520 etc. are mentioned, for example as a polybasic acid denatured acrylic oligomer by Toagosei Co., Ltd. product.

The acid value of the radically polymerizable compound having an acid group is preferably 0.1 to 40 mgKOH/g, particularly preferably 5 to 30 mgKOH/g. When the acid value of the radically polymerizable compound is within the above range, the handleability in production is excellent, and furthermore, the developability is excellent. Moreover, polymerizability is good. The said acid value is measured based on description of JISK0070:1992.

Curable resin composition of this invention can preferably use a monofunctional radically polymerizable compound as a radically polymerizable compound from a viewpoint of curvature suppression accompanying control of the elastic modulus of a cured film. Examples of monofunctional radically polymerizable compounds include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol ( meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol (meth)acrylic acid derivatives such as lycol mono(meth)acrylate and polypropylene glycol mono(meth)acrylate, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allyl glycol Allyl compounds, such as cydyl ether, diallyl phthalate, and triallyl trimellitate, etc. are used preferably. As the 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 preferable.

[Polymerizable compounds other than the above-mentioned radically polymerizable compounds]

Curable resin composition of this invention can further contain polymeric compounds other than the above-mentioned radically polymerizable compound. Examples of polymerizable compounds other than the radical polymerizable compounds described above include compounds having a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl group; epoxy compounds; oxetane compounds; and benzoxazine compounds.

-Compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group-

As a compound which has a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl group, the compound represented by the following formula (AM1), (AM4), or (AM5) is preferable.

[Formula 27]

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

[Formula 28]

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

[Formula 29]

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

Specific examples of the compound represented by formula (AM4) include 46DMOC, 46DMOEP (above, trade names, manufactured by Asahi Yukizai Kogyo Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, and DML. -PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (above, brand name, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 ( Trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, and the like.

In addition, as specific examples of the compound represented by formula (AM5), TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP , HMOM-TPPHBA, HMOM-TPHAP (above, product name, Honshu Chemical Industry Co., Ltd.), TM-BIP-A (product name, Asahi Yukizai Kogyo Co., Ltd. product), NIKALAC MX-280, NIKALAC MX-270 , NIKALAC MW-100LM (above, trade name, manufactured by Sanwa Chemical Co., Ltd.).

-Epoxy compound (compound having an epoxy group)-

As an epoxy compound, it is preferable that it is a compound which has 2 or more epoxy groups in 1 molecule. Since the epoxy group undergoes a crosslinking reaction at 200°C or less and no dehydration reaction resulting from the crosslinking occurs, film shrinkage is unlikely to occur. For this reason, containing an epoxy compound is effective in low-temperature hardening of a composition and suppression of warpage.

It is preferable that the epoxy compound contains a polyethylene oxide group. Thereby, the modulus of elasticity is lowered and the warpage can be suppressed. A polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and it is preferable that the number of repeating units is 2-15.

As an example of an epoxy compound, it is bisphenol-A epoxy resin; bisphenol F-type epoxy resin; Alkylene glycol type epoxy resins, such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; Epoxy group-containing silicones, such as polymethyl (glycidyloxypropyl) siloxane, etc. are mentioned, 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) EXA-4850-150, Epiclon (registered trademark) EXA-4850-1000, Epiclon (registered trademark) EXA-4816, Epiclon (registered trademark) EXA-4822 (above product names) . . Among these, an epoxy resin containing a polyethylene oxide group is preferred in terms of suppression of curvature and 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 compound (compound having an oxetanyl group)-

As the oxetane compound, a compound having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy ]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl] ester, and the like. . As a specific example, the Aronoxetane series (eg, OXT-121, OXT-221, OXT-191, OXT-223) manufactured by Toagosei Co., Ltd. can be suitably used, and these can be used alone or in combination of two or more. do.

-Benzoxazine compound (compound having a benzoxazolyl group)-

The benzoxazine compound is preferable in that it does not generate degassing during curing due to a crosslinking reaction derived from a ring-opening addition reaction, and suppresses occurrence of warpage by reducing heat shrinkage.

Preferred examples of the benzoxazine compound include B-a-type benzoxazine, B-m-type benzoxazine (above, trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resins, and phenol novolac-type dihydrobenzene. An oxazine compound is mentioned. These may be used independently or may mix 2 or more types.

When containing a polymeric compound, it is preferable that the content is more than 0 mass % and 60 mass % or less with respect to the total solids of curable resin composition of this invention. As for a lower limit, 5 mass % or more is more preferable. As for an upper limit, it is more preferable that it is 50 mass % or less, and it is still more preferable that it is 30 mass % or less.

A polymeric compound may be used individually by 1 type, but may mix and use 2 or more types. When using 2 or more types together, it is preferable that the total amount becomes said range.

<Solvent>

Curable resin composition of this invention preferably contains a solvent. A well-known solvent can be used arbitrarily as a solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.

As esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkylalkyloxyacetate (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionate alkyl esters (eg, 3-alkyloxymethylpropionate, 3-alkyloxyethylpropionate, etc.) (e.g., 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-ethoxymethylpropionate, 3-ethoxyethylpropionate, etc.), 2-alkyloxypropionic acid alkyl esters (e.g., 2 -Alkyloxymethylpropionate, 2-alkyloxyethylpropionate, 2-alkyloxypropylpropionate, etc. (e.g., 2-methoxymethylpropionate, 2-methoxyethylpropionate, 2-methoxypropylpropionate, 2-ethoxy methyl propionate, 2-ethoxyethylpropionate)), 2-alkyloxy-2-methylmethylpropionate and 2-alkyloxy-2-methylethylpropionate (e.g. 2-methoxy-2-methylmethylpropionate, 2 -ethoxy-2-methylethylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like are mentioned as suitable ones.

As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve Acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate , propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. are mentioned as suitable ones.

As the ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like can be cited as suitable ones.

As aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc. are mentioned as suitable ones.

As sulfoxides, for example, dimethyl sulfoxide is mentioned as a suitable one.

As the amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide and the like are mentioned as suitable ones.

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

In the present invention, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptane one, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and A single solvent selected from propylene glycol methyl ether acetate or a mixed solvent composed of two or more solvents is preferred. Combination use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

The content of the solvent is preferably an amount such that the total solid concentration of the curable resin composition of the present invention is 5 to 80% by mass, and more preferably 5 to 75% by mass, from the viewpoint of applicability, It is more preferable to set it as 10-70 mass %, and it is still more preferable to set it as 40-70 mass %. What is necessary is just to adjust solvent content according to the desired thickness and coating method.

The solvent may contain only 1 type, and may contain 2 or more types. When containing 2 or more types of solvents, it is preferable that the sum total is the said range.

<Migration inhibitor>

It is preferable that curable resin composition of this invention further contains a migration inhibitor. By including a migration inhibitor, it becomes possible to effectively suppress the migration of metal ions derived from the metal layer (metal wiring) into the curable resin composition layer.

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

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

As other migration inhibitors, the rust inhibitor described in paragraph 0094 of JP-A-2013-015701, the compound described in paragraphs 0073 to 0076 of JP-A-2009-283711, the compound described in paragraph 0052 of JP-A-2011-059656, The compound described in Paragraph 0114 of Unexamined-Japanese-Patent No. 2012-194520, 0116, and 0118, the compound of Paragraph 0166 of International Publication No. 2015/199219, etc. can be used.

Specific examples of the migration inhibitor include the following compounds.

[Formula 30]

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

One type of migration inhibitor may be sufficient as it, and 2 or more types may be sufficient as it. When there are 2 or more types of migration inhibitors, it is preferable that the sum total is the said range.

<Polymerization inhibitor>

It is preferable that curable resin composition of this invention contains a polymerization inhibitor.

As a polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogalol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p -Benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitroso- N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol Terdiamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1- Naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxyamine ammonium salt, bis(4-hydroxy-3 ,5-tert-butyl)phenylmethane and the like are suitably used. Moreover, the polymerization inhibitor of Paragraph 0060 of Unexamined-Japanese-Patent No. 2015-127817, and Paragraph 0031 of International Publication No. 2015/125469 - the compound of 0046 can also be used.

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

[Formula 31]

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

1 type of polymerization inhibitor may be sufficient as it, and 2 or more types may be sufficient as it. When there are 2 or more types of polymerization inhibitors, it is preferable that the sum total is the said range.

<Metal Adhesion Improver>

The curable resin composition of the present invention preferably contains a metal adhesion improving agent for improving adhesion to metal materials used for electrodes, wiring, and the like. As a metal adhesion improver, a silane coupling agent etc. are mentioned.

As an example of a silane coupling agent, the compound described in Paragraph 0167 of International Publication No. 2015/199219, the compound of Paragraph 0062 of Unexamined-Japanese-Patent No. 2014-191002 - 0073, Paragraph 0063 - 0071 of International Publication No. 2011/080992 The compound described, the compound described in paragraphs 0060 to 0061 of Japanese Laid-Open Patent Publication No. 2014-191252, the compound described in paragraphs 0045 to 0052 of Unexamined-Japanese-Patent No. 2014-041264, and the compound described in paragraph 0055 of International Publication No. 2014/097594. can Moreover, it is also preferable to use another 2 or more types of silane coupling agents as Paragraph 0050 of Unexamined-Japanese-Patent No. 2011-128358 - 0058 describe. Moreover, it is also preferable to use the following compound as a silane coupling agent. In the formulas below, Et represents an ethyl group.

[Formula 32]

Moreover, as a metal adhesion improver, the compound of Paragraph 0046 of Unexamined-Japanese-Patent No. 2014-186186 - 0049, and the sulfide type compound of Paragraph 0032 of Unexamined-Japanese-Patent No. 2013-072935 - 0043 can also be used.

The content of the metal adhesion improving agent is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, still more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the heterocycle-containing polymer precursor. am. When the value is equal to or greater than the lower limit, the adhesion between the cured film and the metal layer after the curing step is improved, and when the value is equal to or less than the upper limit, the heat resistance and mechanical properties of the cured film after the curing step are improved. The metal adhesion improver may be one type or two or more types. When using 2 or more types, it is preferable that the sum total is the said range.

<Other additives>

The curable resin composition of the present invention, as necessary, various additives such as a thermal acid generator, a sensitizer such as N-phenyldiethanolamine, a chain transfer agent, a surfactant, Higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, anti-aggregation agents and the like can be blended. When blending these additives, the total compounding amount is preferably 3% by mass or less of the solid content of the composition.

[sensitizer]

Curable resin composition of this invention may contain the sensitizer. A sensitizer absorbs specific actinic radiation and becomes an electronic excited state. The sensitizer in an electronically excited state comes into contact with a thermal base generator, a thermal radical polymerization initiator, an optical radical polymerization initiator, and the like, and actions such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal base generator, thermal radical polymerization initiator, and photoradical polymerization initiator undergo chemical change and are decomposed to generate radicals, acids, or bases. About the detail of a sensitizer, Paragraph 0161 of Unexamined-Japanese-Patent No. 2016-027357 - description of the sensitizing dye of 0163 can be considered into consideration, and this content is integrated in this specification.

When the curable resin composition of the present invention contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, and more preferably 0.1 to 15% by mass with respect to the total solid content of the curable resin composition of the present invention. It is preferable, and it is more preferable that it is 0.5-10 mass %. A sensitizer may be used individually by 1 type, and may use 2 or more types together.

[Chain transfer agent]

Curable resin composition of this invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in Polymer Dictionary 3rd Edition (The Polymer Society, 2005), pages 683-684. As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule are used. These can generate radicals by donating hydrogen to radicals with low activity to generate radicals, or by deprotonating after being oxidized. In particular, a thiol compound can be preferably used.

Moreover, as a chain transfer agent, Paragraph 0152 of International Publication No. 2015/199219 - the compound of 0153 can also be used.

When the curable resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the total solids of the curable resin composition of the present invention. , 1 to 5 parts by mass is more preferable. 1 type of chain transfer agent may be sufficient as it, and 2 or more types may be sufficient as it. When there are 2 or more types of chain transfer agents, it is preferable that the sum total is the said range.

〔Surfactants〕

You may add each kind of surfactant to the curable resin composition of this invention from a viewpoint of further improving applicability. As surfactant, each kind of surfactant, such as a fluorochemical surfactant, a nonionic surfactant, a cationic surfactant, anionic surfactant, and a silicone type surfactant, can be used. Moreover, the following surfactants are also preferable. In the following formula, parentheses indicating the repeating unit of the main chain indicate the content (mol%) of each repeating unit, and parentheses indicating the repeating unit of the side chain indicate the repeating number of each repeating unit.

[Formula 33]

Moreover, Paragraph 0159 of International Publication No. 2015/199219 - the compound of 0165 can also be used for surfactant.

When the curable resin composition of the present invention has a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass with respect to the total solid content of the curable resin composition of the present invention. am. 1 type of surfactant may be sufficient as it, and 2 or more types may be sufficient as it. When there are 2 or more types of surfactants, it is preferable that the sum total is the said range.

[Higher Fatty Acid Derivatives]

In order to prevent inhibition of polymerization due to oxygen, the curable resin composition of the present invention may add a higher fatty acid derivative such as behenic acid or behenic acid amide, and may be unevenly distributed on the surface of the composition during drying after application.

Moreover, the compound of Paragraph 0155 of International Publication No. 2015/199219 can also be used for a higher fatty acid derivative.

When the curable resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass with respect to the total solid content of the curable resin composition of the present invention. 1 type of higher fatty acid derivative may be sufficient as it, and 2 or more types may be sufficient as it. When two or more types of higher fatty acid derivatives are used, it is preferable that the total is within the above range.

<Restrictions on other substances contained>

The water content of the curable resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass, from the viewpoint of coated surface properties.

From an insulating viewpoint, the metal content of the curable resin composition of the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and still more preferably less than 0.5 ppm by mass. As a metal, sodium, potassium, magnesium, calcium, iron, chromium, nickel, etc. are mentioned. When a plurality of metals are included, it is preferable that the sum of these metals is within the above range.

In addition, as a method for reducing metal impurities unintentionally contained in the curable resin composition of the present invention, a raw material having a low metal content is selected as a raw material constituting the curable resin composition of the present invention, or the curable resin composition of the present invention is constituted A method of filtering the raw material to be treated, lining the inside of the apparatus with polytetrafluoroethylene or the like, and distilling under conditions in which contamination is suppressed as much as possible can be cited.

In the curable resin composition of the present invention, considering the use as a semiconductor material, the content of halogen atoms is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and less than 200 ppm by mass, from the viewpoint of wiring corrosiveness. this is more preferable Especially, as for what exists in the state of a halogen ion, less than 5 mass ppm is preferable, less than 1 mass ppm is more preferable, and less than 0.5 mass ppm is still more preferable. As a halogen atom, a chlorine atom and a bromine atom are mentioned. It is preferable that the sum of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, respectively is within the above range.

A conventionally well-known container can be used as a container for the curable resin composition of the present invention. In addition, as the container, for the purpose of suppressing the mixing of impurities into the raw material or composition, a multi-layered bottle whose inner wall is composed of 6 types of 6-layer resin or a bottle in which 6 types of resin are used in a 7-layer structure is also used. desirable. As such a container, the container of Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

<Preparation of composition>

Curable resin composition of this invention can be prepared by mixing each said component. The mixing method is not particularly limited, and a conventionally known method can be used.

Moreover, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the composition. The filter hole diameter is preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. As the filter, one previously washed with an organic solvent may be used. In the filter filtration process, you may connect and use multiple types of filters in series or parallel. In the case of using a plurality of types of filters, filters having different pore diameters or materials may be used in combination. Moreover, you may filter various materials multiple times. When filtering multiple times, circulation filtration may be sufficient. Moreover, you may perform filtration by pressurizing. When filtration is performed by pressurization, the pressurized pressure is preferably 0.05 MPa or more and 0.3 MPa or less.

In addition to filtration using a filter, an impurity removal treatment using an adsorbent may be performed. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

<Use of the composition>

The curable resin composition of the present invention is preferably used for forming an interlayer insulating film for a redistribution layer.

In addition, it can also be used for forming an insulating film of a semiconductor device or forming a stress buffer film.

(Cured film, laminate, semiconductor device, and manufacturing method thereof)

Next, a cured film, a laminate, a semiconductor device, and their manufacturing method are described.

The cured film of the present invention is obtained by curing the curable 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.

It is good also as a laminated body by laminating the cured film of this invention in 2 or more layers, and also 3-7 layers. It is preferable that the layered product of the present invention includes two or more layers of cured films and includes a metal layer between any one of the cured films. Such a metal layer is preferably used as metal wiring such as a redistribution layer.

Examples of applicable fields of the cured film of the present invention include insulating films for semiconductor devices, interlayer insulating films for redistribution layers, and stress buffer films. In addition, pattern formation of a sealing film, a substrate material (a base film or cover lay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting use as described above by etching may be used. Regarding these applications, for example, Science & Technology Co., Ltd. "Highly functional polyimide and application technology" April 2008, Masaaki Kakimoto/Supervisor, CMC Technical Library "Fundamentals and Development of Polyimide Materials" November 2011, Japanese Polyimide/Aromatic Polymer Research Society/edition "Latest Polyimide Basics and Applications", N.T.S., August 2010, etc. can be referenced.

In addition, the cured film in the present invention can also be used for the production of a plate surface such as an offset plate surface or a screen plate surface, use for etching of molded parts, production of protective lacquer and dielectric layer in electronics, particularly microelectronics.

The method for producing a cured film of the present invention (hereinafter also simply referred to as "the production method of the present invention") preferably includes a film forming step of applying the curable resin composition of the present invention to a substrate to form a film. Further, the method for producing a cured film of the present invention preferably includes the film formation step and further includes a heating step of heating the film to decompose the compound represented by the formula (1-1).

Specifically, it is also preferable to include the following steps (a) to (d).

(a) Film formation step of forming a film (curable resin composition layer) by applying a curable resin composition to a substrate

(b) an exposure step of exposing the film to light after the film forming process

(c) a developing step of subjecting the exposed film to development

(d) a heating step of decomposing the compound represented by Formula (1-1) by heating the developed film

By heating in the said heating process, the resin layer hardened by exposure can be further hardened. In this heating step, for example, the compound represented by the formula (1-1) is decomposed, and sufficient curability is obtained.

The method for producing a laminate according to a preferred embodiment of the present invention includes the method for producing a cured film of the present invention. The manufacturing method of the laminated body of this embodiment, according to the manufacturing method of the said cured film, after forming a cured film, the process of (a) again, or the process of (a) - (c), or (a) - ( The process of d) is further performed. In particular, it is preferable to perform each of the above steps sequentially in a plurality of times, for example, 2 to 5 times (ie, 3 to 6 times in total). By laminating the cured film in this way, it can be set as a laminated body. In this invention, it is preferable to provide a metal layer especially on the part where the cured film was provided, or between cured films, or both. In addition, in the manufacture of the laminate, it is not necessary to repeat all of the steps (a) to (d), and as described above, at least (a), preferably (a) to (c) or (a) to A layered product of a cured film can be obtained by performing the process of (d) a plurality of times.

<Film formation process (layer formation process)>

A manufacturing method according to a preferred embodiment of the present invention includes a film formation step (layer formation step) in which the curable resin composition is applied to a base material to form a film (layer form).

The type of base material can be appropriately determined depending on the application, but semiconductor manufacturing base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film, reflective film, Ni , metal substrates such as Cu, Cr, and Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, electrode plates of plasma display panels (PDP), and the like are not particularly limited. In the present invention, a semiconductor fabrication substrate is particularly preferred, and a silicon substrate is more preferred.

Moreover, as a base material, a plate-shaped base material (substrate) is used, for example.

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

As a means of applying the curable resin composition to the substrate, application is preferable.

Specifically, as the means to be applied, a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, a slit coating method, and An inkjet method etc. are illustrated. From the viewpoint of the uniformity of the thickness of the curable resin composition layer, spin coating method, slit coating method, spray coating method, and inkjet method are more preferable. A resin layer having a desired thickness can be obtained by appropriately adjusting the solid content concentration and application conditions according to the method. In addition, the coating method can be appropriately selected depending on the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, or ink jetting are preferable, and for rectangular substrates, slit coating, spray coating, or inkjet methods are preferred. etc. are preferred. In the case of spin coating, it can be applied for about 10 seconds to 1 minute at a rotational speed of 500 to 2,000 rpm, for example.

In addition, a method of transferring onto a base material a coating film formed by applying on a temporary support body in advance according to the above application method may be applied.

Regarding the transfer method, the production methods described in paragraphs 0023 and 0036 to 0051 of JP2006-023696 and paragraphs 0096 to 0108 of JP2006-047592 can be suitably used in the present invention.

<Drying process>

The production method of the present invention may include a step of drying to remove the solvent after the film (curable resin composition layer) is formed and after the film formation step (layer formation step). A preferable drying temperature is 50 to 150°C, more preferably 70°C to 130°C, still more preferably 90°C to 110°C. As drying time, 30 seconds - 20 minutes are illustrated, 1 minute - 10 minutes are preferable, and 3 minutes - 7 minutes are more preferable.

<Exposure process>

The production method of the present invention may also include an exposure step of exposing the film (curable resin composition layer). The exposure amount is not particularly determined as long as the curable resin composition can be cured, but is preferably irradiated at 100 to 10,000 mJ/cm ² , and irradiated at 200 to 8,000 mJ/cm ² in terms of exposure energy at a wavelength of 365 nm, for example. it is more preferable

The exposure wavelength can be appropriately determined in the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.

Regarding the exposure wavelength, 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), broad (three wavelengths of g, h, i-ray), (4) excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F ₂ excimer laser (wavelength 157 nm), (5) extreme ultraviolet; EUV (wavelength 13.6 nm), (6) electron beam, etc. are mentioned. Regarding the curable resin composition of the present invention, exposure by a high-pressure mercury lamp is particularly preferred, and exposure by i-line is particularly preferred. In this way, a particularly high exposure sensitivity can be obtained.

<Development process>

The manufacturing method of the present invention may also include a developing treatment step of performing developing treatment on the exposed film (curable resin composition layer). By developing, the unexposed part (unexposed part) is removed. The developing method is not particularly limited as long as a desired pattern can be formed, and for example, developing methods such as puddle, spray, immersion, and ultrasonic waves can be employed.

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

The organic solvent is esters, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate , ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyloxyacetic acid (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g. methoxyacetic acid) methyl, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionate alkyl esters (eg: 3-alkyloxymethylpropionate, 3-alkyloxyethylpropionate, etc.) (e.g., 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-ethoxymethylpropionate, 3-ethoxyethylpropionate, etc.), 2-alkyloxypropionate alkyl esters (e.g., 2-alkyl Methyl oxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate , 2-ethoxyethylpropionate)), 2-alkyloxy-2-methylmethylpropionate and 2-alkyloxy-2-methylethylpropionate (e.g., 2-methoxy-2-methylmethylpropionate, ethyl oxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., and as ethers, for example For example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol Col monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol mono Ethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl- Examples of 2-pyrrolidone and the like and aromatic hydrocarbons include, for example, toluene, xylene, anisole and limonene, and dimethyl sulfoxide as sulfoxides.

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

It is preferable that 50 mass % or more of a developing solution is an organic solvent, it is more preferable that it is 70 mass % or more of an organic solvent, and it is still more preferable that 90 mass % or more is an organic solvent. Moreover, 100 mass % of a developing solution may be an organic solvent.

As developing time, 10 second - 5 minutes are preferable. The temperature of the developing solution at the time of development is not particularly determined, but it can be usually performed at 20 to 40°C.

You may further rinse after the process using a developing solution. It is preferable to rinse with a solvent different from the developing solution. For example, it can rinse using the solvent contained in curable resin composition. The rinse time is preferably 5 seconds to 1 minute.

<Heating process>

The production method of the present invention preferably includes a step of heating the film to decompose the compound represented by the formula (1-1) (heating step).

The heating step is preferably included after the film forming step (layer forming step), the drying step, and the developing step. In the heating step, a base is generated by decomposition of the compound represented by the formula (1-1), and the cyclization reaction of the heterocycle-containing polymer precursor proceeds. Further, the composition of the present invention may contain a radically polymerizable compound other than the heterocycle-containing polymer precursor, but curing of the unreacted radically polymerizable compound other than the heterocycle-containing polymer precursor can also proceed in this step. The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50°C or higher, more preferably 80°C or higher, still more preferably 140°C or higher, still more preferably 150°C or higher, and 160°C or higher It is more preferable, and it is still more preferable that it is 170 degreeC or more. The upper limit is preferably 500°C or less, more preferably 450°C or less, still more preferably 350°C or less, still more preferably 250°C or less, and even more preferably 220°C or less.

Heating is preferably carried out at a heating rate of 1 to 12°C/minute from the temperature at the start of heating to the highest heating temperature, more preferably 2 to 10°C/minute, and still more preferably 3 to 10°C/minute. By setting the temperature increase rate to 1°C/min or more, excessive volatilization of amine can be prevented while securing productivity, and by setting the temperature increase rate to 12°C/min or less, the residual stress of the cured film can be relieved.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, still more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the time of starting the process of heating to the highest heating temperature. For example, when drying after applying curable resin composition on a substrate, it is the temperature of the film (layer) after this drying, for example, from a temperature 30 to 200°C lower than the boiling point of the solvent contained in curable resin composition. It is preferable to raise the temperature gradually.

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

In particular, in the case of forming a multi-layered laminate, the heating temperature is preferably from 180°C to 320°C, more preferably from 180°C to 260°C, from the viewpoint of the interlayer adhesion of the cured film. Although the reason for this is not certain, it is considered that the crosslinking reaction between the ethynyl groups of the interlayer heterocycle-containing polymer precursor is proceeding at this temperature.

Heating may be performed stepwise. For example, a pretreatment step such as raising the temperature from 25 ° C to 180 ° C at 3 ° C / min, holding at 180 ° C for 60 minutes, raising the temperature from 180 ° C to 200 ° C at 2 ° C / min, and holding at 200 ° C for 120 minutes You can do it. The heating temperature as a pretreatment step is preferably 100 to 200°C, more preferably 110 to 190°C, and still more preferably 120 to 185°C. In this pretreatment process, it is also preferable to process while irradiating ultraviolet rays as described in US Patent Publication No. 9159547. It is possible to improve the properties of the film by such a pretreatment process. What is necessary is just to perform a pretreatment process in a short time of about 10 second - about 2 hours, and 15 second - 30 minutes are more preferable. The pretreatment may be carried out in two or more steps, for example, the pretreatment step 1 may be performed in the range of 100 to 150°C, and then the pretreatment step 2 may be performed in the range of 150 to 200°C.

Moreover, you may cool after heating, and as a cooling rate in this case, it is preferable that it is 1-5 degrees C/min.

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

<Metal layer formation process>

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

As the metal layer, without particular limitation, known metal species can be used, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are exemplified, copper and aluminum are more preferable, and copper is still more preferable. .

As the method of forming the metal layer, a known method can be applied without particular limitation. For example, the method described in Unexamined-Japanese-Patent No. 2007-157879, Unexamined-Japanese-Patent No. 2001-521288, Unexamined-Japanese-Patent No. 2004-214501, and Unexamined-Japanese-Patent No. 2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and methods combining these may be considered. More specifically, a patterning method in which sputtering, photolithography and etching are combined, and a patterning method in which photolithography and electrolytic plating are combined are exemplified.

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

<Laminating process>

It is preferable that the manufacturing method of this invention further includes a lamination process.

The lamination step is, on the surface of the cured film (resin layer) or metal layer, (a) film formation step (layer formation step), (b) exposure step, (c) development treatment step, (d) heating step, It is a series of steps including performing in this order. However, an aspect in which only the film formation step of (a) is repeated may be used. Further, (d) the heating step may be performed collectively at the end or in the middle of the lamination. That is, it is good also as an aspect in which the laminated curable resin composition layer is cured collectively by repeating the steps (a) to (c) a predetermined number of times and then heating in (d). Further, after the developing step (c), the metal layer forming step (e) may be included, and even at this time, the heating in (d) may be performed each time, or the heating in (d) may be performed collectively after laminating a predetermined number of times. . Needless to say, the above-described drying step, heating step, and the like may be appropriately further included in the lamination step.

When the lamination process is further performed after the lamination process, a surface activation treatment process may be further performed after the heating process, the exposure process, or the metal layer forming process. As the surface activation treatment, plasma treatment is exemplified.

It is preferable to perform the said lamination process 2 to 5 times, and it is more preferable to perform it 3 to 5 times.

For example, a resin layer/metal layer/resin layer/metal layer/resin layer/metal layer is preferably composed of 3 or more layers and 7 or less layers, more preferably 3 or more and 5 layers or less.

In this invention, after providing a metal layer especially, the aspect which further forms the cured film (resin layer) of the said curable resin composition so that the said metal layer may be covered is preferable. Specifically, (a) film formation process, (b) exposure process, (c) development process, (e) metal layer formation process, (d) heating process, or (a) film formation process, (b) Exposure process, (c) Development process, (e) Metal layer formation process are repeated in order, and the aspect which provides (d) heating process collectively at the end or in the middle is mentioned. By alternately performing the lamination step of laminating the curable resin composition layer (resin layer) and the metal layer forming step, the curable resin composition layer (resin layer) and the metal layer can be alternately laminated.

The present invention also discloses a semiconductor device having the cured film or laminate of the present invention. As a specific example of a semiconductor device in which the curable resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer, the description in paragraphs 0213 to 0218 of Japanese Patent Laid-Open No. 2016-027357 and the description in FIG. 1 can be referred to. incorporated herein by reference.

(thermal base generator)

The thermal base generator of the present invention is a thermal base generator represented by the following formula (1-2).

[Formula 34]

In Formula (1-2), R ²¹ and R ²² each independently represent a monovalent organic group, L ²¹ represents a divalent linking group, and atoms at bonding positions at both ends of L ²¹ are all carbon atoms; , R ²³ represents a hydrogen atom or a monovalent organic group.

R ²¹ , R ²² , and R ²³ in formula (1-2) each independently have the same meaning as R ¹ , R ² , and R ³ in formula (1-1), and preferred embodiments are also same.

L ²¹ in the formula (1-2) has the same meaning as L ¹ in the formula (1-1), except that the atoms at the bonding positions at both ends are all limited to carbon atoms. Preferred Embodiments is also the same

<Use>

Although it does not specifically limit as a use of the heat base generator of this invention, Curable resin composition can be comprised, for example by using together with the above-mentioned heterocycle containing polymer precursor.

In addition, it is considered that the thermal base generator of the present invention is difficult to decompose, for example, at room temperature, and is excellent in base generation efficiency during heating. Therefore, in various applications where known thermal base generators are used, it is useful to use the thermal base generator of the present invention instead of the conventional thermal base generator or in combination with the conventional thermal base generator. I think.

Example

The present invention will be described in more detail by way of examples below. The materials, usage amount, ratio, treatment content, treatment procedure, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. "Part" and "%" are based on mass unless otherwise specified.

<Synthesis Example 1>

[Synthesis of polyimide precursor (A-1: polyimide precursor having no radical polymerizable group) from pyromellitic dianhydride, 4,4'-diaminodiphenyl ether and benzyl alcohol]

14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140° C. for 12 hours) and 14.22 g (131.58 mmol) of benzyl alcohol were suspended in 50 mL of N-methylpyrrolidone, and sieved with a molecular sieve. dried. The suspension was heated at 100°C for 3 hours. The reaction mixture was cooled to room temperature, and 21.43 g (270.9 mmol) of pyridine and 90 mL of N-methylpyrrolidone were added. The reaction mixture was then cooled to -10 °C and 16.12 g (135.5 mmol) SOCl ₂ was added over 10 minutes maintaining the temperature at -10 ± 4 °C. While adding SOCl ₂ , the viscosity increased. After diluting with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, a solution in which 11.08 g (58.7 mmol) of 4,4'-diaminodiphenyl ether was dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at -5 to 0°C for 20 minutes. Next, after making the reaction mixture react at 0 degreeC for 1 hour, 70g of ethanol was added, and it stirred at room temperature overnight. Then, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimide precursor mixture was stirred at a speed of 5,000 rpm for 15 minutes. The polyimide precursor was removed by filtration, stirred again for 30 minutes in 4 liters of water, and filtered again. Next, the obtained polyimide precursor was dried at 45°C for 3 days under reduced pressure. The weight average molecular weight of this polyimide precursor was 18,000.

[Formula 35]

<Synthesis Example 2>

[Synthesis of polyimide precursor (A-2: polyimide precursor having radical polymerizable group) from pyromellitic dianhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate]

14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, and 20.4 g of (258 mmol) of pyridine and 100 g of diglyme (diethylene glycol dimethyl ether) were mixed, stirred at a temperature of 60 ° C. for 18 hours, pyromellitic acid and 2-hydroxyethyl methacrylate of diesters were prepared. Subsequently, the obtained diester was chlorinated with SOCl ₂ , and then converted into a polyimide precursor with 4,4′-diaminodiphenyl ether in the same manner as in Synthesis Example 1, to obtain a polyimide precursor in the same manner as in Synthesis Example 1. got The weight average molecular weight of this polyimide precursor was 19,000.

[Formula 36]

<Synthesis Example 3>

[Polyimide precursor from 4,4'-oxydiphthalic anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate (A-3: polyimide precursor having a radical polymerizable group) Synthesis of ]

20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, , 20.4 g (258 mmol) of pyridine and 100 g of diglyme were mixed, stirred at a temperature of 60 ° C. for 18 hours, diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate has manufactured Subsequently, the obtained diester was chlorinated with SOCl ₂ , and then converted into a polyimide precursor with 4,4′-diaminodiphenyl ether in the same manner as in Synthesis Example 1, to obtain a polyimide precursor in the same manner as in Synthesis Example 1. got The weight average molecular weight of this polyimide precursor was 18,000.

[Formula 37]

<Synthesis Example 4>

[Polyimide precursor from 4,4'-oxydiphthalic anhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (orthotolidine) and 2-hydroxyethyl methacrylate (A- 4: Synthesis of polyimide precursor having a radical polymerizable group)]

20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, , 20.4 g (258 mmol) of pyridine and 100 g of diglyme were mixed, stirred at a temperature of 60 ° C. for 18 hours, diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate has manufactured Subsequently, the resulting diester was chlorinated with SOCl ₂ , and then converted into a polyimide precursor with 4,4'-diamino-2,2'-dimethylbiphenyl in the same manner as in Synthesis Example 1, A polyimide precursor was obtained in the same manner. The weight average molecular weight of this polyimide precursor was 19,000.

[Formula 38]

<Synthesis Example 5>

[Synthesis of polybenzoxazole precursor (A-5) from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 4,4'-oxydibenzoyl chloride]

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

[Formula 39]

<Synthesis Example 6>

[Synthesis of Compounds B-1 to B-18]

Compounds B-1 to B-18 were synthesized with reference to the method described in Organic Chemistry International (2014), 576715/1-576715/10, 10pp.

<Synthesis Example 7>

[Polyimide precursor from 4,4'-oxydiphthalic anhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate (A-6: polyimide precursor having a radical polymerizable group ) Synthesis of]

155.1 g of 4,4'-oxydiphthalic anhydride (ODPA) was placed in a separable flask with a capacity of 2 liters, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added. A reaction mixture was obtained by adding 79.1 g of pyridine while stirring at room temperature. After completion of heat generation due to the reaction, it was allowed to cool to room temperature and was further left still for 16 hours.

Next, a solution in which 206.3 g of dicyclohexylcarbodiimide (DCC) was dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture under ice-cooling over 40 minutes while stirring. Subsequently, a suspension obtained by suspending 93.0 g of 4,4'-diaminodiphenyl ether in 350 ml of γ-butyrolactone was added over 60 minutes while stirring. Furthermore, after stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and stirred for 1 hour. After that, 400 ml of γ-butyrolactone was added. A precipitate generated in the reaction mixture was removed by filtration to obtain a reaction liquid.

The obtained reaction liquid was added to 3 liters of ethyl alcohol to produce a precipitate composed of a crude polymer. The resulting crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 liters of water to precipitate the polymer, and the obtained precipitate was collected by filtration and vacuum dried to obtain a powdery polymer A-6. It was 20,000 as a result of measuring the weight average molecular weight (Mw) of this polymer A-6.

<Synthesis Example 8>

[Polyimide precursor from 3,3'4,4'-biphenyltetracarboxylic dianhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate (A-7: radical polymerization Synthesis of Polyimide Precursor with Sexual Groups]

In Synthesis Example 7, the method described in Synthesis Example 7 is the same except that 147.1 g of 3,3'4,4'-biphenyltetracarboxylic dianhydride was used instead of 155.1 g of 4,4'-oxydiphthalic anhydride. Polymer A-7 was obtained by allowing the reaction to occur. It was 22,000 as a result of measuring the weight average molecular weight (Mw) of this polymer A-7.

<Examples 1 to 40 and Comparative Examples C1 and C2>

In each Example and Comparative Example, each curable resin composition was obtained by mixing the components described in Table 1 or Table 2 below, respectively. The obtained curable resin composition was filtered under pressure through a polytetrafluoroethylene filter having a fine pore width of 0.45 µm.

In Table 1 or Table 2, the numerical value in the "parts by mass" column shows the content (parts by mass) of each component.

In Table 1 or Table 2, "-" indicates that the corresponding component is not contained.

[Table 1]

[Table 2]

The detail of each component described in Table 1 or Table 2 is as follows.

[Heterocycle-Containing Polymer Precursor]

A-1 to A-5: A-1 to A-5 synthesized above

[Compound represented by Formula (1-1)]

B-1 to B-18: Exemplary compounds B-1 to B-18 above

Compound RB-1 for Comparative Example: a compound represented by the following formula (RB-1)

[Formula 40]

[Radical Photopolymerization Initiator]

・C-1: IRGACURE OXE 01 (manufactured by BASF)

・C-2: IRGACURE OXE 02 (manufactured by BASF)

C-3: IRGACURE 369 (manufactured by BASF)

[Radically polymerizable compound]

D-1: A-DPH (manufactured by Shin Nakamura Chemical Industry Co., Ltd., dipentaerythritol hexaacrylate)

D-2: SR-209 (manufactured by Sartomer, the following compound))

[Formula 41]

D-3: A-TMMT (Shin Nakamura Chemical Industry Co., Ltd., pentaerythritol tetraacrylate))

[Polymerization inhibitor]

E-1: 2,6-di-tert-butyl-4-methylphenol (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

E-2: Parabenzoquinone (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

E-3: Paramethoxyphenol (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

E-4: 2-nitroso-1-naphthol (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

[migration inhibitor]

F-1 to F-4: Compounds represented by the following formulas (F-1) to (F-4)

[Formula 42]

[Metal Adhesion Improver]

G-1 to G-3: Compounds represented by the following formulas (G-1) to (G-4)

[Formula 43]

〔solvent〕

I-1: γ-butyrolactone (manufactured by Sanwa Yuka Co., Ltd.)

I-2: Dimethyl sulfoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

I-3: N-methyl-2-pyrrolidone (manufactured by Ashland)

I-4: Ethyl lactate (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

〔additive〕

H-1: N-phenyldiethanolamine (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

<evaluation>

In each Example and Comparative Example, storage stability, elongation at break, and adhesion were evaluated using the curable resin composition described in Table 3, respectively.

The details of the evaluation method in each evaluation are described below.

[Storage stability]

In each Example and Comparative Example, the viscosity (0 day) of each curable resin composition was measured using an E-type viscometer, respectively. After leaving the curable resin composition still at 25°C for 14 days in a light-shielded airtight container, the viscosity (14 days) of each curable resin composition after the stationary was measured again using an E-type viscometer. In each Example and each Comparative Example, the viscosity fluctuation rate was calculated from the following equation using the values of the viscosity (0th day) and the viscosity (14th day), respectively. The lower the viscosity fluctuation rate, the higher the storage stability. Evaluation was performed according to the following evaluation criteria. The evaluation results were described in the "storage stability" column of Table 3.

Viscosity change rate (%)=|100×{1-(viscosity (14 days)/viscosity (0 days))}|

Viscosity was measured at 25°C, and the rest was in accordance with JIS Z 8803:2011.

-Evaluation standard-

A: The viscosity fluctuation rate was 5% or less.

B: The viscosity fluctuation rate was more than 5% and 20% or less.

C: The viscosity fluctuation rate exceeded 20%.

[Elongation at break]

In each Example and Comparative Example, each curable resin composition was applied (coated) layer by layer on a silicon wafer by a spin coating method to form a curable resin composition layer. The silicon wafer to which the obtained curable resin composition layer was applied was dried on a hot plate at 100°C for 5 minutes to form a curable resin composition layer having a uniform thickness of 20 µm on the silicon wafer. The curable resin composition layer on the silicon wafer was exposed with an exposure energy of 500 mJ/cm ² using a stepper (Nikon NSR 2005 i9C). The exposed curable resin composition layer (resin layer) was heated at a temperature increase rate of 10°C/min under a nitrogen atmosphere, and after reaching 180°C, this temperature was maintained for 3 hours. The cured resin layer was immersed in a 4.9% hydrofluoric acid solution, and the resin layer was peeled from the silicon wafer to obtain a resin film 1.

The elongation at break of the resin film 1 was measured using a tensile tester (Tensilon) at a cross head speed of 300 mm/min, a sample width of 10 mm, and a sample length of 50 mm in the longitudinal and width directions of the film at 25° C. and 65% relative humidity ( RH), the elongation at break was measured based on JIS-K6251:2017. Elongation at break is, E _b (%) = (L _b -L ₀ ) / L _{0 ×} 100 (E _b : tensile at break, L ₀ : length of the test piece before testing, L _b : length of the test piece when the test piece is cut length) was calculated. For evaluation, the elongation at break in the longitudinal direction was measured 5 times, and the average value was used. Evaluation was performed according to the following evaluation criteria. The evaluation results are shown in the "elongation at break" column of Table 3.

-Evaluation standard-

A: The elongation at break exceeded 60%.

B: The elongation at break was more than 55% and 60% or less.

C: The elongation at break was more than 40% and 55% or less.

D: The elongation at break was 40% or less.

[adhesion (copper adhesion)]

In each Example and Comparative Example, each curable resin composition was applied in layers on a copper substrate by a spin coating method, and dried at 100 ° C. for 5 minutes to form a curable resin composition layer having a film thickness of 20 μm. . The copper substrate to which the obtained curable resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes, and a curable resin composition layer having a uniform thickness of 20 μm was formed on the copper substrate. The curable resin composition layer on the copper substrate was exposed to light using a stepper (Nikon NSR 2005 i9C) at an exposure energy of 500 mJ/cm ² using a photomask having a 100 square μm square non-mask portion, and then cyclopentane. It was developed at on for 60 seconds to obtain a 100 µm square resin layer. Further, in a nitrogen atmosphere, the temperature was raised at a heating rate of 10°C/min, and after reaching 180°C, this temperature was maintained for 3 hours.

The shear force was measured for a 100 μm square resin layer on a copper substrate in an environment of 25° C. and 65% relative humidity (RH) using a bond tester (manufactured by XYZTEC, CondorSigma). The greater the shear force, the greater the adhesion, resulting in a desirable result. Evaluation was performed according to the following evaluation criteria. The evaluation results are described in the "Adhesiveness" column of Table 3.

-Evaluation standard-

A: The shear force exceeded 40 gf.

B: The shear force was more than 25 gf and 40 gf or less.

C: The shear force was 25 gf or less.

However, 1 gf is 9.80665 × 10 ^-3 N (Newton).

[Table 3]

From the above results, it was found that the curable resin composition containing the heterocycle-containing polymer precursor and the compound represented by formula (1-1) according to the present invention has excellent storage stability and excellent elongation at break of the resulting cured film. can

The curable resin composition according to Comparative Example 1 does not contain the compound represented by formula (1-1), but contains the compound represented by formula (RB-1) as a heat base generator. It is understood that the curable resin composition according to Comparative Example 1 is inferior in storage stability.

The curable resin composition according to Comparative Example 2 does not contain a compound represented by Formula (1-1). It is understood that the curable resin composition according to Comparative Example 2 is inferior in elongation at break.

<Example 101>

The curable resin composition described in Example 1 was applied in layers to the surface of the resin substrate on which the copper foil layer was formed by spin coating, and dried at 100 ° C. for 5 minutes to form a curable resin composition layer having a film thickness of 20 μm, Exposure was performed using a stepper (manufactured by Nikon, NSR1505 i6). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-and-space pattern and a line width of 10 μm). After exposure, it was developed for 30 seconds with cyclopentanone and rinsed with PGMEA for 20 seconds to obtain a pattern.

Subsequently, it was heated at 230°C for 3 hours to form an interlayer insulating film for a redistribution layer. This interlayer insulating film for the redistribution layer was excellent in insulating properties.

In addition, as a result of manufacturing semiconductor devices using these interlayer insulating films for redistribution layers, it was confirmed that they operated without problems.

Claims (18)

a heterocycle-containing polymer precursor, and
Curable resin composition containing the compound represented by following formula (1-1).
[Formula 1]

In formula (1-1), R ¹ and R ² each independently represent a monovalent organic group, L ¹ represents an alkylene group having 1 to 5 carbon atoms or an alkenylene group having 2 to 5 carbon atoms, and R ³ is a hydrogen atom. Alternatively, it represents a monovalent organic group, and R ¹ and R ² may combine to form a ring structure. The method of claim 1,
Curable resin composition, wherein said L ¹ is a divalent linking group having a link chain length of 1 to 5. According to claim 1 or claim 2,
Wherein R ¹ and R ² are each independently a hydrocarbon group, curable resin composition. According to claim 1 or claim 2,
L ¹ is a 1,2-ethylene group, a 1,3-propanediyl group, a 1,2-cyclohexanediyl group, a cisvinylene group, or a 1,2-ethyleneoxy-1,2-ethylene group. , curable resin composition. According to claim 1 or claim 2,
The curable resin composition in which said ^R3 is a hydrogen atom, an alkyl group, or an aryl group. According to claim 1 or claim 2,
Curable resin composition whose molecular weight of the compound represented by said Formula (1-1) is 100 or more and 2,000 or less. According to claim 1 or claim 2,
A curable resin composition further comprising an optical radical polymerization initiator and a radically polymerizable compound. According to claim 1 or claim 2,
A curable resin composition comprising at least one precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor as the heterocycle-containing polymer precursor. According to claim 1 or claim 2,
Curable resin composition containing a polyimide precursor as said heterocycle containing polymer precursor. The method of claim 9,
Curable resin composition in which the said polyimide precursor has a repeating unit represented by following formula (1);
[Formula 2]

In Formula (1), A ¹ and A ² each independently represent an oxygen atom or -NH-, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ represents a hydrogen atom or a monovalent organic group each independently. The method of claim 10,
Curable resin composition in which at least one of ^R113 and ^R114 in said Formula (1) contains a radical polymerizable group. According to claim 1 or claim 2,
A curable resin composition used for forming an interlayer insulating film for a redistribution layer. A cured film obtained by curing the curable resin composition according to claim 1 or 2. A laminate comprising two or more layers of the cured film according to claim 13 and including a metal layer between any of the cured films. A method for producing a cured film comprising a film formation step of applying the curable resin composition according to claim 1 or 2 to a substrate to form a film. The method of claim 15
A method for producing a cured film, further comprising a heating step of heating the film to decompose the compound represented by the formula (1-1). A semiconductor device comprising the cured film according to claim 13. A thermobase generator represented by the following formula (1-2).
[Formula 3]

In Formula (1-2), R ²¹ and R ²² each independently represent a monovalent organic group, L ²¹ represents an alkylene group having 1 to 5 carbon atoms or an alkenylene group having 2 to 5 carbon atoms, and both ends of L ²¹ All atoms at the bonding position of are carbon atoms, and R ²³ represents a hydrogen atom or a monovalent organic group.