KR102104806B1 - Photosensitive resin composition, cured film, laminate, manufacturing method of cured film, manufacturing method of laminate, and semiconductor device - Google Patents

Abstract

Provided are a photosensitive resin composition excellent in adhesiveness, a cured film, a laminate, a method for producing a cured film, a method for producing a laminate, and a semiconductor device using the same. A polyimide precursor and at least one resin among polyimides and at least one of urethane (meth) acrylates, and urethane (meth) acrylates are represented by formula (A) in one molecule. Photosensitive resin composition which has at least one of the partial structure represented by Formula (B), and 4-15 (meth) acrylate groups, and a uretain structure; However, * in the formula is a connecting hand.

Description

Photosensitive resin composition, cured film, laminate, manufacturing method of cured film, manufacturing method of laminate, and semiconductor device

The present invention relates to a photosensitive resin composition, a cured film using the same, a laminate, a method for producing a cured film, a method for producing a laminate, and a semiconductor device. In particular, it relates to a photosensitive resin composition used for an interlayer insulating film for a redistribution layer of a semiconductor device.

Thermosetting resins, such as polyimide resins, which are cured by cyclization, are excellent in heat resistance and insulating properties, and are used for insulating layers of semiconductor devices and the like.

Moreover, since the polyimide resin has low solubility in a solvent, it is also used as a precursor (polyimide precursor) before cyclization reaction, applied to a substrate, etc., and then heated to cyclize the polyimide precursor to form a cured film.

Here, in Patent Document 1, for example, (A) an alkali-soluble polyamic acid having a structure represented by a given formula, (B) a photopolymerizable compound having a ureain bond and an ethylenically unsaturated group in a molecule, ( C) A photosensitive resin composition for an interlayer insulating film of a semiconductor element comprising a photopolymerization initiator is disclosed.

Patent Document 1: Japanese Patent Application Publication No. 2008-197160

However, it was found that in the photosensitive resin composition described in Patent Document 1, the adhesiveness was poor. The present invention aims to solve these problems, and aims to provide a photosensitive resin composition excellent in adhesiveness, a cured film, a laminate, a method for producing a cured film, a method for producing a laminate, and a semiconductor device using the same. do.

As a result of the inventor's examination under the above problems, the above problems have been solved by the following means <1>, preferably <2> to <23>.

<1> a polyimide precursor, and at least one resin of polyimide and at least one of urethane (meth) acrylate,

The urethane (meth) acrylate includes at least one of a partial structure represented by formula (A) and a partial structure represented by formula (B) in one molecule, and 4 to 15 (meth) acrylate groups, A photosensitive resin composition having a phosphorus structure;

[Formula 1]

However, * in the formula is a connecting hand.

<2> In <1>, the urethane (meth) acrylate has a partial structure represented by formula (A) in one molecule, 4 to 15 (meth) acrylate groups, and a urethane structure. Photosensitive resin composition described.

<3> The photosensitive resin composition according to <1> or <2>, wherein the resin is a polyimide precursor.

<4> The photosensitive resin composition as described in <3>, in which the polyimide precursor contains the repeating unit represented by following formula (2);

Equation (2)

[Formula 2]

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

<5> The photosensitive resin composition according to <4>, wherein at least one of R ¹¹³ and R ¹¹⁴ in the formula (2) contains a radical polymerizable group.

<6> The photosensitive resin composition according to <4> or <5>, wherein R ¹¹⁵ in the formula (2) is a tetravalent organic group containing an aromatic ring.

<7> the formula (2), R ¹¹¹ is, represented by -Ar-L-Ar- <1> to <6> of the photosensitive resin composition according to any one of the; However, Ar is each independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO _2- , or -NHCO -Or a group consisting of two or more of the above.

<8> In said Formula (2), R ¹¹¹ is a photosensitive resin composition in any one of <1>-<6> which is a following formula (51) or a formula (61);

Expression (51)

[Formula 3]

In formula (51), R ¹⁰ to R ¹⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ¹⁰ to R ¹⁷ is a fluorine atom, a methyl group, a fluoromethyl group, or a difluoromethyl group Or a trifluoromethyl group;

Expression (61)

[Formula 4]

In formula (61), R ¹⁸ and R ¹⁹ are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group.

<9> The photosensitive resin composition according to any one of <1> to <8>, further comprising a migration inhibitor.

<10> The photosensitive resin composition according to any one of <1> to <9>, further comprising a polymerization inhibitor.

<11> The photosensitive resin composition according to any one of <1> to <10>, further comprising a photoradical polymerization initiator.

<12> The photosensitive resin composition according to <11>, wherein the photoradical polymerization initiator is an oxime compound.

<13> The photosensitive resin composition as described in any one of <1> to <12>, which is for an interlayer insulating film for a redistribution layer.

<14> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <13>.

<15> A laminate having two or more layers of the cured film according to <14>.

<16> The laminate according to <15>, having a metal layer between the cured films.

<17> A method for producing a cured film comprising using the photosensitive resin composition according to any one of <1> to <13>.

<18> The photosensitive resin composition layer forming step of applying the photosensitive resin composition to a substrate to form a layer,

An exposure process for exposing the photosensitive resin composition layer,

The manufacturing method of the cured film as described in <17> which has the process of developing process about the said exposed photosensitive resin composition layer.

<19> The method for producing a cured film according to <18>, wherein the developing treatment is a negative developing treatment.

<20> The method for producing a cured film according to <18> or <19>, comprising a step of heating the developed photosensitive resin composition layer at a temperature of 50 to 500 ° C after the developing treatment step.

<21> The method for producing a cured film according to any one of <17> to <20>, wherein the cured film has a film thickness of 1 to 30 μm.

<22> According to the method for producing a cured film according to any one of <18> to <21>, after the cured film is formed, the photosensitive resin composition layer forming process, the exposure process, and the developing treatment process are further repeated. The manufacturing method of a laminated body which is performed 2-5 times in sequence.

<23> The semiconductor device which has the cured film as described in <14> or the laminated body as described in <15> or <16>.

ADVANTAGE OF THE INVENTION According to this invention, it became possible to provide the photosensitive resin composition excellent in adhesiveness, the cured film using this, the manufacturing method of a cured film, the manufacturing method of a laminated body, and a semiconductor device.

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

Although the description of the components in the present invention described below may be made based on representative embodiments of the present invention, the present invention is not limited to such embodiments.

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

In the present specification, the term "active light" means, for example, a bright spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X rays, electron beams, and the like. In addition, in the present invention, light means actinic light or radiation. In the present specification, "exposure", unless specifically described, is not only exposure to ultraviolet rays, X-rays, EUV light, etc., represented by mercury lamps, excimer lasers, but also exposure to drawing by particle beams such as electron beams and ion beams. To include.

In this specification, the numerical range indicated by using "~" means a range including the numerical values described before and after "~" as the lower limit and the upper limit.

In the present specification, “(meth) acrylate” refers to both or both of “acrylate” and “methacrylate,” and “(meth) allyl” means “allyl” and “metalyl”. It represents both or both, and "(meth) acrylic" represents both or both of "acrylic" and "methacryl", and "(meth) acryloyl" means "acryloyl" and " Methacryloyl ", or either.

In the present specification, the term "process" is included in this term when the desired action of the process is achieved even if it is not clearly distinguishable from other processes as well as independent processes.

In the present specification, the solid content concentration is the mass percentage of the mass of other components excluding the solvent relative to the total mass of the composition. In addition, the solid content concentration refers to the concentration at 25 ° C unless otherwise specified.

In this specification, a weight average molecular weight (Mw) and a number average molecular weight (Mn) are defined as polystyrene conversion values by 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, HLC-8220 (manufactured by Tosoh Corporation), and are used as guard columns HZ-L and TSKgel Super HZM-M as columns. , TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). The eluent is measured using THF (tetrahydrofuran) unless otherwise specified. In addition, unless specifically described, it is assumed that a detector having a wavelength of 254 nm of UV rays (ultraviolet rays) is used.

The photosensitive resin composition of the present invention includes at least one resin of a polyimide precursor and a polyimide, and at least one of urethane (meth) acrylate, and the urethane (meth) acrylate is In one molecule, it is characterized by having at least one of a partial structure represented by formula (A) and a partial structure represented by formula (B), 4 to 15 (meth) acrylate groups, and a urethane structure.

[Formula 5]

However, * in the formula is a connecting hand.

By setting it as such a structure, the cured film excellent in adhesiveness with another layer (especially a board | substrate) is obtained. This mechanism, the intermolecular interaction between urethane (meth) acrylate and the polyimide precursor becomes stronger, thereby obtaining a uniform cured film in which polyimide is introduced into a three-dimensional crosslinked structure by urethane (meth) acrylate. It is presumed that, along with Jim, the urethane structure and the imide ring structure strongly interact with the other layer to express a synergistic effect.

Moreover, in this invention, by having at least one of the partial structure represented by Formula (A) and the partial structure represented by Formula (B), the photosensitive resin composition excellent in heat resistance is obtained. In addition, by increasing the compatibility of urethane (meth) acrylate with a polyimide precursor, etc., a photosensitive resin composition having excellent exposure latitude is obtained.

<Resin>

The photosensitive resin composition of the present invention (hereinafter sometimes referred to as “the composition of the present invention”) may be referred to as a polyimide precursor and at least one resin (hereinafter, “polyimide precursor, etc.”) of the polyimide. ), And at least a polyimide precursor.

<< polyimide precursor >>

Although the polyimide precursor used in the present invention is not particularly defined, such as its kind, it is preferable to include a repeating unit represented by the following formula (2).

Equation (2)

[Formula 6]

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

As for A ¹ and A ² in Formula (2), an oxygen atom or NH is preferable, and an oxygen atom is more preferable.

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

R ¹¹¹ is preferably derived from diamine. Examples of the diamine used in the production of the polyimide precursor include straight-chain or branched aliphatic, cyclic aliphatic or aromatic diamines, and the like. As for diamine, only 1 type may be used and 2 or more types may be used.

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

[Formula 7]

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

Specific examples of diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane ; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (Aminomethyl) cyclohexane, bis- (4-aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethe Phosphorus and isophoronediamine; m- and p-phenylenediamine, diaminotoluene, 4,4'- and 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl Ether, 4,4'- and 3,3'-diaminodiphenylmethane, 4,4'- and 3,3'-diaminodiphenylsulfone, 4,4'- and 3,3'-di Aminodiphenylsulfide, 4,4'- and 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4 '-Diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl ) Hexafluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2, 2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) ) Sulfone, bis (4-amino-3- Idroxyphenyl) sulfone, 4,4'-diaminoparaterphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [ 4- (3-aminophenoxy) phenyl] sulfone, bis [4- (2-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 9,10-bis (4- Aminophenyl) anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) Benzene, 1,3-bis (4-aminophenyl) benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diamino Diphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-amino Phenoxy) 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, 2,4- and 2,5-diaminocumene, 2, 5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, Bis (3-aminopropyl) tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-aminophenyl) ethane, diaminobenzanilide, di Ester of aminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis (4-aminophenyl) hexafluoropropane, 1,4-bis (4-aminophenyl) octafluoro Robutane, 1,5-bis (4-aminophenyl) decafluoropentane, 1,7-bis (4-aminophenyl) te Radecafluoroheptein, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (2-aminophenoxy) phenyl] hexafluoro Propane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3, 5-bis (trifluoromethyl) phenyl] hexafluoropropane, p-bis (4-amino-2-trifluoromethylphenoxy) benzene, 4,4'-bis (4-amino-2-tri Fluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy City) diphenylsulfone, 4,4'-bis (3-amino-5-trifluoromethylphenoxy) diphenylsulfone, 2,2-bis [4- (4-amino-3-trifluoromethylphenoxy) Si) phenyl] hexafluoropropane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoro Romethyl) Is selected from phenyl, 2,2 ', 5,5', 6,6'-hexafluoro to tolidine and 4,4 '' '- may be the die of at least one diamine selected from amino quarter phenyl.

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

[Formula 8]

[Formula 9]

Moreover, diamine which has at least 2 or more alkylene glycol units in a main chain is also mentioned as a preferable example. Preferably, it is a diamine containing two or more of one or both of ethylene glycol chain and propylene glycol chain in one molecule, and more preferably a diamine that does not contain an aromatic ring. Specific examples include Jeffamine (registered trademark) KH-511, Jeffamine (registered trademark) ED-600, Jeffamine (registered trademark) ED-900, Jeffamine (registered trademark) ED-2003, Jeffamine (registered trademark) EDR -148, Jeffamine (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (above trade names, manufactured by HUNTSMAN Corporation), 1- (2- (2- (2- Aminopropoxy) ethoxy) propoxy) propane-2-amine, 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propane-2-amine, and the like. However, it is not limited to this.

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 10]

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

R ¹¹¹ is preferably represented by -Ar-L-Ar- from the viewpoint of flexibility of the resulting cured film. However, Ar is each independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ₂ -or -NHCO- And a group consisting of a combination of two or more of the above. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms, which may be substituted with a fluorine atom, -O-, -CO-, -S- or -SO _2- . The aliphatic hydrocarbon group here is preferably an alkylene group.

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

Expression (51)

[Formula 11]

In formula (51), R ¹⁰ to R ¹⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ¹⁰ to R ¹⁷ is a fluorine atom, a methyl group, a fluoromethyl group, or a difluoromethyl group Or it is preferably a trifluoromethyl group, and at least one is a fluorine atom, a methyl group, or a trifluoromethyl group.

Examples of the monovalent organic group of R ¹⁰ to R ¹⁷ 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. You can.

Expression (61)

[Formula 12]

In formula (61), R ¹⁸ and R ¹⁹ are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group, and at least one is preferably a fluorine atom, a methyl group, or a trifluoromethyl group. Do. As a diamine compound which gives the structure of Formula (51) or (61), 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, And 2,2'-bis (fluoro) -4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, and the like. These may be used alone or in combination of two or more.

R ¹¹⁵ in Formula (2) represents a tetravalent organic group. As a 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.

Equation (5)

[Formula 13]

In formula (5), R ¹¹² is a single bond or a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO _2- , -NHCO-, It is preferable that it is a group selected from these combinations, and it is a group selected from a single bond, a C1-C3 alkylene group which may be substituted with a fluorine atom, -O-, -CO-, -S-, and -SO _2-. Preferred, divalent selected from the group consisting of -CH _2- , -C (CF ₃ ) _2- , -C (CH ₃ ) _2- , -O-, -CO-, -S- and -SO _2- Giga is more preferred.

Equation (6)

[Formula 14]

R ¹¹⁵ is specifically, a tetracarboxylic acid residue or the like remaining after the removal of the anhydride group from the tetracarboxylic dianhydride. As for tetracarboxylic dianhydride, only 1 type may be used and 2 or more types may be used.

It is preferable that tetracarboxylic dianhydride is represented by following formula (O).

Formula (O)

[Formula 15]

In Formula (O), R ¹¹⁵ represents a tetravalent organic group. A preferable range of the R ¹¹⁵ is R ^115, and accept in the formula (2) are also the same preferable range.

As specific examples of the tetracarboxylic dianhydride, pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfide tetracarboxylic dianhydride Water, 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylmethe Phosphate tetracarboxylic dianhydride, 2,2 ', 3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,3,3 ', 4 '-Benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2, 2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) Hexafluoropropane dianhydride, 1,3-diphenylhexafluoro Lopein-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2 ', 3,3'-diphenyltetracarboxylic dianhydride, 3,4 , 9,10-Perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrene Tetracarboxylic dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2,3,4-benzene Tetracarboxylic dianhydride, at least 1 sort (s) selected from these C1-C6 alkyl derivatives and / or C1-C6 alkoxy derivatives are illustrated.

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

[Formula 16]

Moreover, it is also preferable to have an OH group in at least one of R ¹¹¹ and R ¹¹⁵ . More specifically, R ¹¹¹ is a residue of a bisaminophenol derivative.

R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, and at least one of R ¹¹³ and R ¹¹⁴ preferably contains a radically polymerizable group, and both preferably contain a radically polymerizable group. The radical polymerizable group is a group capable of crosslinking reaction by the action of a radical, and examples of the group having an ethylenically unsaturated bond are preferred examples.

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

[Formula 17]

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

In Formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, a -CH ₂ CH (OH) CH ₂ -or a polyoxyalkylene group having 4 to 30 carbon atoms.

Examples of suitable R ²⁰¹ are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butanediyl group, 1,3-butanediyl group, pentamethylene group, hexamethylene group, octamethylene group , Dodecamethylene group, -CH ₂ CH (OH) CH _2- , and more preferably ethylene group, propylene group, trimethylene group, -CH ₂ CH (OH) CH _2- .

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

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

From the viewpoint of solubility in an aqueous developer, examples of the monovalent organic group include an aromatic group, an aralkyl group, and the like having 1, 2 or 3, preferably 1, acidic groups bound to the carbon constituting the aryl group. . Specifically, an aromatic group having 6 to 20 carbon atoms having an acidic group and an aralkyl group having 7 to 25 carbon atoms having an acidic group are exemplified. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group are exemplified. The acidic group is preferably an OH group.

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

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

The alkyl group preferably has 1 to 30 carbon atoms. The alkyl group may be linear, branched or cyclic. Examples of the straight-chain or branched alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, octadecyl group, and iso Propyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, and 2-ethylhexyl group. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group. Examples of the polycyclic cyclic alkyl group include, for example, adamantyl group, norbornyl group, carbonyl group, campenyl group, decahydronaphthyl group, tricyclodecaneyl group, tetracyclodecaneyl group, camphoroyl group, dicyclohexyl group, and pinenyl group. Can be lifted. Especially, a cyclohexyl group is most preferable from a viewpoint of compatibility with high sensitivity. Moreover, as the alkyl group substituted with an aromatic group, a straight chain alkyl group substituted with an aromatic group described later is preferable.

As an aromatic group, specifically, a substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptane ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring, naphtha ring Sen ring, chrysene ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridane ring True ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolizine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring , Carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thiarene ring, chromene ring, xanthene ring, phenoxacyin ring, phenothiazine ring or phenazine ring. Among these, the benzene ring is most preferable.

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

Moreover, it is also preferable that a polyimide precursor has a fluorine atom in a structural unit. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

Moreover, you may copolymerize the aliphatic group which has a siloxane structure for the purpose of improving adhesiveness with a board | substrate. Specifically, bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, etc. are mentioned as a diamine component.

It is preferable that the repeating unit represented by Formula (2) is a repeating unit represented by Formula (2-A). That is, it is preferable that at least 1 type, such as the polyimide precursor used by this invention, is a precursor which has a repeating unit represented by Formula (2-A). By setting it as such a structure, it becomes possible to widen the width of an exposure latitude.

Equation (2-A)

[Formula 18]

In formula (2-A), A ¹ and A ² represent an oxygen atom, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or 1 It represents a valent organic group, and at least one of R ¹¹³ and R ¹¹⁴ is a group containing a polymerizable group, and is preferably a polymerizable group.

A ^1, A ^2, R ^111, R ¹¹³ and R ¹¹⁴ each independently, is A ^1, A ^2, R ^111, R ¹¹³ and R ^114, and accept in the formula (2) are also the same preferable range.

R ¹¹² is synonymous with R ¹¹² in Formula (5), and a preferable range is also the same.

The repeating structural unit represented by formula (2) contained in the polyimide precursor may be one type, or two or more types. Moreover, the structural isomer of the repeating unit represented by Formula (2) may be included. Moreover, the polyimide precursor may also contain other types of repeating structural units in addition to the repeating units of formula (2) above.

As one embodiment of the polyimide precursor in the present invention, 50 mol% or more, and 70 mol% or more, and particularly 90 mol% or more of the total repeating units are polyimide precursors that are repeating units represented by formula (2). do.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 2000 to 500000, more preferably 5000 to 100000, and further preferably 10000 to 50000. Moreover, the number average molecular weight (Mn) is preferably 800 to 250000, more preferably 2000 to 50000, and even more preferably 4000 to 25000.

The dispersion degree of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and even more preferably 2.8 or more. Although the upper limit of the dispersion degree of a polyimide precursor is not specifically set, For example, 4.5 or less is preferable, 4.0 or less is more preferable, 3.8 or less is more preferable, 3.2 or less is more preferable, 3.1 or less is further more More preferably, 3.0 or less is particularly preferred, and 2.95 or less is most preferred.

<< polyimide >>

The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide ring, but is preferably a polymer compound having a polymerizable group. Although there is no restriction | limiting in particular, It is preferable that it is a compound represented by following formula (4), and it is more preferable that it is a compound which has a polymerizable group.

Equation (4)

[Formula 19]

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

The polymerizable group may be located on at least one of R ¹³¹ and R ¹³² , and may have a polymerizable group at the terminal of the polyimide as shown in the following formula (4-1) or formula (4-2).

Equation (4-1)

[Formula 20]

In formula (4-2), R ¹³³ is a polymerizable group, and the other groups are synonymous with formula (4).

Equation (4-2)

[Formula 21]

At least one of R ¹³⁴ and R ¹³⁵ is a polymerizable group, the other is an organic group, and the other group is synonymous with formula (4).

The polymerizable group is synonymous with the polymerizable group described in the polymerizable group of the polyimide precursor and the like.

R ¹³¹ represents a divalent organic group. As a divalent organic group, the thing similar to R ¹¹¹ in Formula (2) is illustrated, and a preferable range is also the same.

Moreover, as R ¹³¹ , the diamine residue which remains after removal of the amino group of diamine is mentioned. Examples of the diamines include aliphatic, cyclic aliphatic or aromatic diamines. As a specific example, the example of R ¹¹¹ in Formula (2) of the polyimide precursor is given.

R ¹³¹ is preferably a diamine residue having at least two or more alkylene glycol units in the main chain, from the viewpoint of more effectively suppressing the occurrence of warpage during firing. More preferably, it is a diamine residue containing two or more of one or both of ethylene glycol chain and propylene glycol chain in one molecule, and more preferably a diamine residue not containing an aromatic ring.

As a diamine containing two or more of one or both of ethylene glycol chain and propylene glycol chain in one molecule, Jeffamine (registered trademark) KH-511, Jeffamine (registered trademark) ED-600, and FAMIN (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 name, manufactured by HUNTSMAN Corporation), 1- (2- (2- (2-aminopropoxy) ethoxy) propoxy) propan-2-amine, 1- (1- (1 -(2-aminopropoxy) propan-2-yl) oxy) propan-2-amine, 1- (2- (2- (2- (2-aminopropoxy) ethoxy) propoxy) propane-2-amine And the like, but are not limited to these.

R ¹³² represents a tetravalent organic group. As a tetravalent organic group, the thing similar to R ¹¹⁵ in Formula (2) is illustrated, and a preferable range is also the same.

For example, four bonds of the tetravalent organic group exemplified as R ¹¹⁵ combine with the four -C (= O)-moieties in the formula (4) to form a condensed ring. For example, when R ¹³² is the following organic group, a structure represented by PI-C employed in the examples of the present application is formed.

[Formula 22]

R ¹³² may further include a tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic dianhydride. As a specific example, the example of R ¹¹⁵ in Formula (2) of the polyimide precursor is given. From the viewpoint of the strength of the cured film, R ¹³² is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

It is also preferable to have an OH group on at least one of R ¹³¹ and R ¹³² . More specifically, as R ¹³¹ , 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, the above (DA-1) to ( DA-18) is mentioned as a preferable example, and as R ¹³² , the above (DAA-1) to (DAA-5) are mentioned as a preferable example.

Moreover, you may copolymerize the aliphatic group which has a siloxane structure for the purpose of improving adhesiveness with a board | substrate. Specifically, bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, etc. are mentioned as a diamine component.

Moreover, in order to improve the storage stability of the composition, it is preferable that the polyimide is sealed with a terminal sealant such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a mono-active ester compound. Among these, it is more preferable to use a monoamine, and preferred compounds of the monoamine include aniline, 2-ethanylaniline, 3-ethanylaniline, 4-ethanylaniline, and 5-amino-8-hydroxy. Quinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-amino Naphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2 -Carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid , 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-a Mino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, and the like. You can. Two or more of these may be used, or a plurality of different terminal groups may be introduced by reacting a plurality of terminal sealants.

The polyimide preferably has an imidation ratio of 85% or more, more preferably 90% or more. When the imidation ratio is 85% or more, the film shrinkage due to ring closure occurring when imidization by heating becomes small, and the occurrence of warpage can be suppressed.

Polyester represented by the formula (4) containing the formula (4) R ¹³¹ or R ¹³² in addition to the repeating structural units, other types of two or more of polyimide, are both based on one kind of R ¹³¹ or R ¹³² You may include a repeating unit. Moreover, the polyimide may also include other types of repeating structural units in addition to the repeating units of the formula (4).

The polyimide is, for example, a method of reacting a tetracarboxylic dianhydride with a diamine compound (partly substituted with a monoamine terminal sealant) at low temperature, a tetracarboxylic dianhydride (partly acid anhydride or mono acid chloride compound or A method of reacting a diamine compound with a monoactive ester compound (substituting with a terminal sealant), obtaining a diester with tetracarboxylic dianhydride and alcohol, and then diamine (partly substituting with a monoamine terminal sealant) and condensing agent A method of reacting in the presence of, a method of obtaining a diester by tetracarboxylic dianhydride and alcohol, and then reacting the remaining dicarboxylic acid with acid to react with diamine (a part of which is replaced with a terminal sealant which is a monoamine). Using the method, a polyimide precursor is obtained, which is A method of completely imidizing using a dehydration method, or a method of stopping the imidation reaction in the middle and introducing some imide structure, and further, by blending a fully imidized polymer and its polyimide precursor, some imides It can be synthesized using a method of introducing a structure.

As a commercial item of polyimide, Durimide (trademark) 284, Fujifilm Corporation make, Matrimide5218, HUNTSMAN agent are illustrated.

The weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and particularly preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the film after curing can be improved. In order to obtain a cured film excellent in mechanical properties, the weight average molecular weight is more preferably 20,000 or more. Moreover, when it contains 2 or more types of polyimides, it is preferable that the weight average molecular weight of at least 1 type of polyimide is the said range.

The composition of the present invention may contain only one type of the polyimide precursor and the polyimide, or may include two or more types. Moreover, you may contain 2 or more types of resins with different structures as resins of the same type, such as 2 types of polyimide precursors.

In the composition of the present invention, the content of the polyimide precursor or the like is preferably 20 to 90% by mass, more preferably 30 to 80% by mass, still more preferably 40 to 75% by mass, and 50 to It is particularly preferable that it is 70% by mass.

Hereinafter, the components that may be included in the composition of the present invention will be described. It is needless to say that the present invention may contain components other than these, and that these components are not essential.

<< Method for producing polyimide precursors >>

The polyimide precursor or the like is obtained by reacting a 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, etc., it is preferable to use an organic solvent at the time of reaction. The organic solvent may be used alone or in combination of two or more.

As an organic solvent, although it can be suitably determined according to the raw material, pyridine, diethylene glycol dimethyl ether (Digrim), N-methylpyrrolidone and N-ethylpyrrolidone are exemplified.

The polyimide may be prepared by synthesizing a polyimide precursor, then heating to cyclize, or directly synthesize a polyimide.

<<< terminal sealant >>>

In the production method of a polyimide precursor or the like, in order to further improve storage stability, it is preferable to seal with a terminal sealant such as an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a mono-active ester compound. Among these, it is more preferable to use a monoamine, and preferred compounds of the monoamine include aniline, 2-ethanylaniline, 3-ethanylaniline, 4-ethanylaniline, and 5-amino-8-hydroxy. Quinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-amino Naphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2 -Carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid , 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-a Mino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, and the like. You can. Two or more of these may be used, or a plurality of different terminal groups may be introduced by reacting a plurality of terminal sealants.

<<< solid precipitation >>>

In the production of a polyimide precursor or the like, a step of depositing a solid may be included. Specifically, solid precipitation can be performed by precipitating a polyimide precursor or the like in the reaction solution in water and dissolving a polyimide precursor such as tetrahydrofuran in a soluble solvent.

Thereafter, the polyimide precursor or the like is dried to obtain a powdery polyimide precursor or the like.

<Uretain (meth) acrylate>

The photosensitive resin composition of this invention contains at least 1 sort (s) of urethane (meth) acrylate. The urethane (meth) acrylate used in the present invention includes at least one of a partial structure represented by formula (A) and a partial structure represented by formula (B) in one molecule, and 4 to 15 (meth) acrylate groups , Has a urethane structure.

[Formula 23]

However, * in the formula is a connecting hand.

It is preferable that the urethane (meth) acrylate contains at least a partial structure represented by formula (A). The urethane (meth) acrylate in the present invention is a partial structure selected from a partial structure represented by formula (A) and a partial structure represented by formula (B) in one molecule (hereinafter simply referred to as "partial structure"). It may be desirable to have one).

As for the number of (meth) acrylate groups contained in the said urethane (meth) acrylate, 5-15 pieces are more preferable in 1 molecule, and 6-15 pieces are more preferable. By setting it as such a range, adhesiveness tends to improve more effectively.

The (meth) acrylate group included in the urethane (meth) acrylate is preferably an acrylate group. By setting it as such a structure, exposure latitude tends to improve more effectively. Moreover, it is preferable that the (meth) acrylate group contained in the said urethane (meth) acrylate is a (meth) acryloyloxy group.

In the present invention, in particular, in one molecule, a partial structure represented by one formula (A), 4 to 15 (meth) acrylate groups, and one or more urethane structures, urethane (meth) acrylate Is preferred.

The urethane (meth) acrylate used in the present invention preferably has 2 to 8 urethane bonds in one molecule, and more preferably 3 to 6 urethane bonds. By setting it as such a range, adhesiveness tends to be exhibited more effectively.

Moreover, it is preferable that the number of atoms which connects the said partial structure and the (meth) acrylate group closest to the said partial structure is 4-15, and it is more preferable that it is 9-13. Here, the number of atoms connecting the partial structure and the (meth) acrylate group closest to the partial structure refers to the shortest number of atoms connecting between the partial structure and the (meth) acrylate group, for example For the following compounds, there will be 12.

[Formula 24]

Further, the group connecting the partial structure and the (meth) acrylate group is preferably a combination of groups selected from -CH _2- , -N (H)-, -O- and -C (= O)-. More preferably, the group connecting the partial structure and the (meth) acryloxy group is an embodiment composed of a combination of -CH ₂ -and a urethane bond. By setting it as such a structure, the obtained cured film is more excellent in flexibility, and it becomes possible to make it into a cured film excellent in film strength.

The molecular weight of the urethane (meth) acrylate in the present invention is preferably 500 to 5000, more preferably 800 to 3000. By setting it as such a range, the number of functional groups per mass becomes large, and the effect of this invention is exhibited more effectively.

Below, the specific example of the urea (meth) acrylate used by this invention is shown. It goes without saying that the present invention is not limited to these.

[Formula 25-1]

[Formula 25-2]

[Formula 25-3]

[Formula 25-4]

It is preferable that the composition of the present invention contains 5 to 50 parts by mass of the urethane (meth) acrylate with respect to the polyimide precursor (resin), and more preferably 10 to 30 parts by mass. . By setting it as such a range, the cured film excellent in heat resistance and adhesiveness is obtained.

The said urethane (meth) acrylate may contain only 1 type, and may contain 2 or more types. When 2 or more types are included, it is preferable that a total amount becomes the said range.

The composition of the present invention includes the polyimide precursor and the like and urethane (meth) acrylate. However, other components may be appropriately blended according to the application. Specifically, it is preferable that the composition of the present invention contains at least one of a migration inhibitor, a polymerization inhibitor, and a photoradical polymerization initiator.

The photosensitive resin composition of this invention is used suitably as a negative photosensitive resin composition.

<Migration inhibitor>

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

The migration inhibitor is not particularly limited, but is heterocyclic (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isooxazole 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), thiourea and mercapto groups The compound to have, a hindered phenol type compound, a salicylic acid derivative type compound, and a hydrazide derivative type compound are mentioned. In particular, triazole-based compounds such as triazole and benzotriazole, and tetrazole-based compounds such as tetrazole and benzotetrazole can be preferably used.

In addition, an ion trapping agent that supplements anions such as halogen ions can also be used. There is no restriction | limiting in particular as an ion trap agent, A conventionally well-known thing can be used. In particular, hydrotalcite represented by the following composition formula or bismuth hydrous oxide represented by the following composition formula is preferable.

Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X /} 2mH ₂ O

(In the formula, 0 <X≤0.5, m is a positive number)

BiO _x (OH) _y (NO ₃ ) _z

(In the formula, 0.9≤x≤1.1, 0.6≤y≤0.8, 0.2≤z≤0.4)

In addition, the said hydrotalcite is available as a commercial item, manufactured by Kyowa Kagaku Kogyo Co., Ltd., brand name: DHT-4A. Moreover, the said bismuth is commercially available, and it is available as Toa Kosei Co., Ltd., brand name: IXE500. Moreover, you may use other ion trap agents as needed. For example, hydrous oxides of elements selected from magnesium, aluminum, titanium, zirconium, antimony, and the like can be given. These ion trap agents can be used alone or in combination of two or more.

When the 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 even more preferably 0.1 to 1.0% by mass relative to the total solid content of the composition.

The migration inhibitor may be used alone or in combination of two or more. When two or more types of migration inhibitors are present, it is preferable that the total is within the above range.

<Polymerization inhibitor>

It is preferable that the photosensitive resin composition of this invention contains a polymerization inhibitor. The storage stability of the photosensitive resin composition coating liquid and the photosensitive resin composition is effectively achieved by including a polymerization inhibitor.

Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, p-benzoquinone, diphenyl-p-benzo Quinone, 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 ether diamine 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. Further, the polymerization inhibitors described in paragraph 0060 of JP 2015-127817 A and the compounds described in paragraphs 0031-0046 of JP 2015/125469 A may be used.

When the composition has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass relative to the total solid content of the composition.

One type of polymerization inhibitor may be used, or two or more types may be used. When the polymerization inhibitor is two or more, it is preferable that the total is within the above range.

<Photo-radical polymerization initiator>

It is preferable that the photosensitive resin composition of this invention contains a photoradical polymerization initiator (it may be hereafter simply referred to as a "photopolymerization initiator"). By including a photo-radical polymerization initiator, the composition is applied to a semiconductor wafer or the like to form a composition layer, and then, by irradiating light, curing by the generated radicals occurs, solubility in the light-irradiated portion can be reduced. For this reason, for example, by exposing the composition layer through a photomask having a pattern in which only the electrode portion is masked, there is an advantage that a region having different solubility can be easily produced according to the pattern of the electrode.

The photopolymerization initiator is not particularly limited as long as it has the ability to initiate the polymerization reaction (crosslinking reaction) of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, it is preferable to have photosensitivity to light rays from the ultraviolet region to the visible region. In addition, it may be an active agent that generates an active radical by generating any action with a photoexcited sensitizer.

It is preferable that the photopolymerization initiator contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 to 800 nm (preferably 330 to 500 nm). The molar extinction coefficient of the compound can be measured using a known method, but specifically, for example, with an ultraviolet visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian, Inc.), using an ethyl acetate solvent, 0.01 g / L It is preferable to measure the concentration.

As the photopolymerization initiator, a known compound can be used without limitation, for example, a halogenated hydrocarbon derivative (for example, having a triazine skeleton, having an oxadiazole skeleton, or having a trihalomethyl group) Etc.), acylphosphine compounds such as acylphosphine oxide, oxime compounds such as hexaaryl biimidazole, and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds , Hydroxyacetophenone, azo-based compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, and the like.

Examples of the halogenated hydrocarbon compound having a triazine skeleton include Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), the compound described in British Patent Publication No. 1388492, the compound described in Japanese Patent Publication No. 53-133428, the compound described in German Patent No. 3337024, F. C. Schaefer et al. J. Org. Chem. ; Compounds described in 29, 1527 (1964), compounds described in Japanese Patent Application Laid-open No. 62-58241, compounds described in Japanese Patent Application Laid-open No. Hei 5-281728, compounds described in Japanese Patent Application Laid-open No. Hei 5-34920, USA And compounds described in Patent Publication No. 4212976.

As a compound described in U.S. Patent Publication No. 4212976, for example, a compound having an oxadiazole skeleton (e.g., 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2- Trichloromethyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2- Trichloromethyl-5- (2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5 -(2-naphthyl) -1,3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4- Chlorostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) -1,3,4-oxadiazole, 2-tribromomethyl-5-styryl-1,3,4-oxadiazole, and the like).

Moreover, as a photoinitiator other than the above, the compound described in paragraph 0086 of JP 2015-087611 A, JP-A 53-133428, JP-A-57-1819, 57-6096, and The compounds and the like described in U.S. Patent Publication No. 3615455 are exemplified, and these contents are incorporated herein.

As a ketone compound, the compound described in paragraph 0087 of Unexamined-Japanese-Patent No. 2015-087611 is illustrated, for example, and these content is used in this specification.

Kayacure DETX (made by Nippon Kayaku) is also suitably used in commercial products.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be suitably used. More specifically, for example, the aminoacetophenone-based initiator described in Japanese Patent Application Laid-open No. Hei 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 aminoacetophenone-based initiators, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used.

As an aminoacetophenone-based initiator, a compound described in Japanese Patent Application Publication No. 2009-191179 in which an absorption maximum wavelength is matched to a wavelength light source such as 365 nm or 405 nm can also be used.

As an acylphosphine type initiator, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide etc. are mentioned. In addition, commercially available products IRGACURE-819 and IRGACURE-TPO (trade names: all manufactured by BASF) can be used.

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

As a photopolymerization initiator, an oxime compound is more preferably mentioned. By using an oxime compound, it becomes possible to improve exposure latitude more effectively. As a specific example of an oxime compound, the compound of Unexamined-Japanese-Patent No. 2001-233842, the compound of Unexamined-Japanese-Patent No. 2000-80068, and the compound of Unexamined-Japanese-Patent No. 2006-342166 can be used.

Preferred oxime compounds include, for example, the following compounds, but 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxy Minopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane -2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, and the like.

[Formula 26]

As the oxime compound, J. C. S. Perkin II (1979) p p. 1653-1660, J. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. Compounds described in each document of 202-232, compounds described in Japanese Unexamined Patent Publication No. 2000-66385, Japanese Unexamined Patent Publication No. 2000-80068, Japanese Unexamined Patent Publication No. 2004-534797, Japanese Unexamined Patent Publication No. 2006-342166 And compounds described in the foregoing.

In commercial products, IRGACURE OXE-01 (manufactured by BASF), IRGACURE OXE-02 (manufactured by BASF), and N-1919 (manufactured by ADEKA) are also suitably used. In addition, TR-PBG-304 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD), Adeka Arkles NCI-831 and Adeka Arkles NCI-930 (manufactured by ADEKA) You can. In addition, TR-PBG-304 (manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), Adeka Arkles NCI-831, and Adeka Arkles NCI-930 (manufactured by ADEKA) can also be used. Moreover, DFI-091 (made by Daito Chemicals) can also be used.

In addition, the compound disclosed in Japanese Patent Publication No. 2009-519904 in which an oxime is connected to the N position of the carbazole ring, the compound described in U.S. Patent Publication No. 7626957 in which a hetero substituent is introduced at the benzophenone site, and a Nitro group introduced at the pigment site The compound described in Patent Publication Nos. 2010-15025 and U.S. Patent Publication No. 2009-292039, the ketoxime compound described in International Publication No.WO2009-131189, the U.S. Patent Publication No. 7556910 containing the triazine skeleton and the oxime skeleton in the same molecule. You may use the compound described, the compound described in Unexamined-Japanese-Patent No. 2009-221114 which has a maximum absorption at 405 nm, and has good sensitivity to a g-ray light source.

Moreover, the cyclic oxime compound described in Unexamined-Japanese-Patent No. 2007-231000 and Unexamined-Japanese-Patent No. 2007-322744 can also be used conveniently. Among the cyclic oxime compounds, cyclic oxime compounds condensed with carbazole dyes described in JP 2010-32985 and JP 2010-185072 are particularly preferred from the viewpoint of high light absorption and high sensitivity. .

Moreover, the compound of Unexamined-Japanese-Patent No. 2009-242469 which is a compound which has an unsaturated bond in the specific site of an oxime compound can also be used conveniently.

It is also possible to use an oxime compound having a fluorine atom. As a specific example of such an oxime compound, the compound described in Unexamined-Japanese-Patent No. 2010-262028 and the compound 24, 36-40, Unexamined-Japanese-Patent No. 2013- of the 0345 paragraph of Unexamined-Japanese-Patent No. 2014-500852 And compound (C-3) described in paragraph 0101 of 164471. Moreover, the following compounds are mentioned as a specific example.

[Formula 27]

The most preferable oxime compound includes an oxime compound having a specific substituent shown in JP 2007-269779, an oxime compound having a thioaryl group shown in JP 2009-191061, and the like.

From the viewpoint of exposure sensitivity, the photopolymerization initiator is a trihalomethyltriazine compound, a benzyldimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, and metallocene. Compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazoles Compounds, compounds selected from the group consisting of 3-aryl substituted coumarin compounds are preferred.

More preferably, trihalomethyltriazine compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, oxime compound, triarylimidazole dimer, onium salt compound, benzophenone compound, acetophenone compound Is, a trihalomethyltriazine compound, an α-aminoketone compound, an oxime compound, a triarylimidazole dimer, at least one compound selected from the group consisting of benzophenone compounds is most preferred, and an oxime compound is used. Most preferred.

Moreover, the photopolymerization initiator is N, N'-tetraalkyl-4,4'-diaminobenzophenone, such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Mihiler ketone). , 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- Aromatic ketones such as propanone-1, aromatic rings such as alkylanthraquinones and condensed quinones, benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkylbenzoin, and benzyl dimethyl ketal Benzyl derivatives, such as, can also be used. Moreover, the compound represented by following formula (I) can also be used.

[Formula 28]

In formula (I), R ⁵⁰ is a C1-C20 alkyl group; 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; Phenyl group; Alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 12 carbon atoms, halogen atom, cyclopentyl group, cyclohexyl group, alkenyl group having 2 to 12 carbon atoms, alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms And a phenyl group substituted with at least one of an alkyl group having 1 to 4 carbon atoms; Or biphenylyl, R ⁵¹ is a group represented by formula (II), or a group such as R ^50, and R ⁵² to R ⁵⁴ are each independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or ha It is Rosen.

[Formula 29]

In the formula, R ⁵⁵ to R ⁵⁷ are the same as R ⁵² to R ^{54 in} the formula (I).

Moreover, the compound described in paragraph 0048-0055 of international publication 2015/125469 can also be used for a photoinitiator.

When the composition includes a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total solid content of the composition. to be.

One type of photopolymerization initiator may be sufficient, and two or more types may be sufficient as it. When 2 or more types of photoinitiators, it is preferable that the total is the said range.

<Other polymerizable compounds>

The composition of the present invention may contain a polymerizable compound other than the urethane (meth) acrylate. Other polymerizable compounds are compounds having a polymerizable group, and known compounds capable of crosslinking reaction with radicals, acids, bases, and the like can be used. As a polymerizable group, the polymerizable group etc. which were demonstrated at the location of the said polyimide precursor etc. are illustrated.

The compound having an ethylenically unsaturated bond used in the present invention is more preferably a compound containing two or more ethylenically unsaturated groups.

The polymerizable compound may be any of chemical forms such as monomers, prepolymers, oligomers or mixtures thereof and multimers thereof.

In the present invention, the monomer type polymerizable compound (hereinafter also referred to as polymerizable monomer) is a compound different from the polymer compound. The polymerizable monomer is typically a low-molecular compound, preferably a low-molecular compound with a molecular weight of 2000 or less, more preferably a low-molecular compound with a molecular weight of 1500 or less, and more preferably a low-molecular compound with a molecular weight of 900 or less. Moreover, the molecular weight of a polymerizable monomer is 100 or more normally.

Moreover, the oligomer type polymerizable compound is typically a polymer having a relatively low molecular weight, and is preferably a polymer in which 10 to 100 polymerizable monomers are bonded. The weight average molecular weight of the oligomer type polymerizable compound is preferably 2000 to 20,000, more preferably 2000 to 15000, and most preferably 2000 to 10,000.

The number of functional groups in the polymerizable compound in the present invention means the number of polymerizable groups in one molecule.

From the viewpoint of resolution, the polymerizable compound preferably contains at least one polymerizable compound having two or more functional groups containing two or more polymerizable groups, and more preferably contains at least one polymerizable compound having three or more functionalities. .

Moreover, since the polymerizable compound in this invention can improve heat resistance by forming a three-dimensional bridge | crosslinked structure, it is preferable to contain at least 1 sort (s) of polymerizable compounds more than trifunctional. Moreover, the mixture of a bifunctional or less polymerizable compound and a trifunctional or more functional polymerizable compound may be sufficient.

As another polymerizable compound, a compound having an ethylenically unsaturated bond, a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound (a compound having an epoxy group), an oxetane compound (a compound having an oxetanyl group), and benz And oxazine compounds (compounds having a benzoxazolyl group).

When blending another polymerizable compound, 1 to 30 mass% of the solid content of the composition of the present invention is preferred. As for these other polymerizable compounds, only 1 type may be used and 2 or more types may be used. When using 2 or more types, it is preferable that a total amount falls into the said range.

Moreover, the composition of this invention can also be set as the structure which does not contain substantially another polymerizable compound. The term "substantially free" refers to 5 mass% or less, preferably 1 mass% or less, of the amount of a predetermined urethane (meth) acrylate contained in the composition of the present invention.

<Heat base generator>

The composition of the present invention may contain a heat base generator.

As the heat base generator, the type and the like are not particularly defined, but include an acidic compound that generates a base when heated to 40 ° C or higher, and at least one selected from ammonium salts having an anion and an ammonium cation of 0-4 pKa1. It is preferable to include the said heat base generator. Here, pKa1 represents the logarithmic display (-Log ₁₀ Ka) of the dissociation constant (Ka) of the first proton of the polyvalent acid.

By blending such a compound, a cyclization reaction of the polyimide precursor can be carried out at a low temperature, and a more excellent composition can be obtained. Moreover, since the base is not generated without heating, the heat base generator can suppress cyclization of the polyimide precursor during storage even if it coexists with the polyimide precursor, and is excellent in storage stability.

The heat base generator in the present invention is at least one selected from an acidic compound (A1) that generates a base when heated to 40 ° C or higher, and an ammonium salt (A2) having an anion and an ammonium cation with pKa1 of 0-4. It includes.

Since the acidic compound (A1) and the ammonium salt (A2) generate a base upon heating, the cyclization reaction of the polyimide precursor can be accelerated by the base generated from these compounds, and cyclization of the polyimide precursor is performed at a low temperature. You can. Further, even if these compounds coexist with a polyimide precursor that is cyclized and cured by a base, cyclization of the polyimide precursor hardly proceeds without heating, so that a polyimide precursor composition having excellent stability can be prepared.

In addition, in the present specification, with the acidic compound, 1 g of the compound is collected in a container, 50 ml of a mixed solution of ion-exchanged water and tetrahydrofuran (mass ratio of water / tetrahydrofuran = 1/4) is added, and at room temperature for 1 hour. Stir. The solution means a compound having a value measured at 20 ° C of less than 7 using a pH meter.

In the present invention, the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40 ° C or higher, and more preferably 120 to 200 ° C. The upper limit of the base generation temperature is preferably 190 ° C or less, more preferably 180 ° C or less, and even more preferably 165 ° C or less. The lower limit of the base generation temperature is preferably 130 ° C or higher, and more preferably 135 ° C or higher.

When the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 120 ° C or higher, it is difficult to generate a base during storage, so that a polyimide precursor composition having excellent stability can be prepared. When the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 200 ° C or less, the cyclization temperature of the polyimide precursor can be reduced. The base generation temperature is, for example, by using differential scanning calorimetry, heating the compound to 250 ° C. at 5 ° C./min in an internal pressure capsule, and reading the peak temperature of the lowest exothermic peak to read the peak. The temperature can be measured as the base generation temperature.

In the present invention, the base generated by the heat base generator is preferably a secondary amine or a tertiary amine, and more preferably a tertiary amine. Since the tertiary amine has high basicity, it is possible to further lower the cyclization temperature of the polyimide precursor. Moreover, the boiling point of the base generated by the heat base generator is preferably 80 ° C or higher, preferably 100 ° C or higher, and most preferably 140 ° C or higher. Moreover, 80-2000 is preferable as the molecular weight of the generated base. The lower limit is more preferably 100 or more. The upper limit is more preferably 500 or less. In addition, the value of molecular weight is a theoretical value calculated from a structural formula.

In the present invention, it is preferable that the acidic compound (A1) contains at least one selected from ammonium salts.

In the present invention, it is preferable that the ammonium salt (A2) is an acidic compound. Further, the ammonium salt (A2) may be a compound containing an acidic compound that generates a base when heated to 40 ° C or higher (preferably 120 to 200 ° C), or 40 ° C or higher (preferably 120 to 200 ° C). A compound other than an acidic compound that generates a base upon heating may be used.

<< ammonium salt >>

In the present invention, the ammonium salt means a salt of an ammonium cation and an anion represented by the following formula (101) or formula (102). The anion may be bonded to a part of any of the ammonium cations through a covalent bond, or may be outside the molecule of the ammonium cation, but preferably outside the molecule of the ammonium cation. In addition, having an anion outside the molecule of an ammonium cation means a case where the ammonium cation and the anion are not bound through a covalent bond. Hereinafter, an anion outside the molecule of the cation portion is also referred to as a counter anion.

Expression (101) Expression (102)

[Formula 30]

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

It is preferable that the ammonium cation is represented by any one of the following formulas (Y1-1) to (Y1-5).

[Formula 31]

In the formula, R ¹⁰¹ is, represents an n-valent organic, R ¹ and R ⁷ is a R ¹ and R ⁷ and the consent of the formula (101) or (102).

Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group,

n represents an integer of 1 or more,

m represents the integer of 0-5.

In the present invention, it is preferable that the ammonium salt has an anion and an ammonium cation whose pKa1 is 0-4. The upper limit of the pKa1 of the anion is more preferably 3.5 or less, and even more preferably 3.2 or less. The lower limit is preferably 0.5 or more, and more preferably 1.0 or more. When the pKa1 of the anion is within the above range, the polyimide precursor can be cyclized at a low temperature, and further, the stability of the polyimide precursor composition can be improved. When pKa1 is 4 or less, the stability of the heat base generator is good, it is possible to suppress generation of a base without heating, and the stability of the polyimide precursor composition is good. When pKa1 is 0 or more, the generated base is difficult to neutralize, and the cyclization efficiency of the polyimide precursor is good.

The kind of anion is preferably one selected from carboxylic acid anions, phenol anions, phosphate anions, and sulfate anions, and a carboxylic acid anion is more preferable because it is compatible with salt stability and thermal decomposition. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylic acid anion.

The carboxylic acid anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxy groups, and more preferably an anion of the divalent carboxylic acid. According to this aspect, it can be set as a heat base generator which can further improve the stability, curability and developability of the polyimide precursor composition. In particular, by using an anion of a divalent carboxylic acid, stability, curability and developability of the polyimide precursor composition can be further improved.

In the present invention, it is preferable that the carboxylic acid anion is an anion of a carboxylic acid having pKa1 of 4 or less. pKa1 is more preferably 3.5 or less, and even more preferably 3.2 or less. According to this aspect, the stability of the polyimide precursor composition can be further improved.

Here, pKa1 denotes the logarithm of the reciprocal of the first dissociation constant of the acid, and Determination of Organic Structures by Physical Methods (author: Brown, HC McDaniel, DH Hafliger, O. Nachod, FC; edited: Braude, EA Nachod, FC ; Academic Press, New York, 1955) or Data for Biochemical Research (author: Dawson, RMC et al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, it is assumed that a value calculated from the structural formula is used using software of ACD / pKa (manufactured by ACD / Labs).

In the present invention, it is preferable that the carboxylic acid anion is represented by the following formula (X1).

[Formula 32]

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

In the present invention, the electron withdrawing group means that the substituent constant σm of Hammett represents a positive value. Here, σm is described in detail in Tsuno-Yu's general guide, Journal of Organic Synthetic Chemistry, Vol. 23, No. 8 (1965) P. 631-642. Moreover, the electron withdrawing group of the present invention is not limited to the substituents described in the above documents.

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

In the present invention, EWG preferably represents a group represented by the following formulas (EWG-1) to (EWG-6).

[Formula 33]

In the formula, R ^x1 to R ^x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group or a carboxy group, and Ar represents an aromatic group.

In the present invention, it is preferable that the carboxylic acid anion is represented by the following formula (X).

[Formula 34]

In the formula (X), L ¹⁰ represents a single bond or a divalent linking group selected from an alkylene group, an alkenylene group, an arylene group, -NR ^X- , and combinations thereof, and R ^X is a hydrogen atom, an alkyl group, An alkenyl group or an aryl group.

Examples of the carboxylic acid anion include maleic acid anion, phthalic acid anion, N-phenylimino diacetic acid anion and oxalic acid anion. These can be preferably used.

[Formula 35]

[Formula 36]

[Formula 37]

When a heat base generator is used, the content of the heat base generator in the composition is preferably 0.1 to 50% by mass relative to the total solid content of the composition. The lower limit is more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and even more preferably 20% by mass or less.

As the heat base generator, one type or two or more types can be used. When using 2 or more types, it is preferable that a total amount is the said range.

<Photobase generator>

The negative photosensitive resin composition of the present invention may contain a photobase generator. The photobase generator is a base that is generated by exposure, and does not exhibit activity under normal conditions at room temperature and normal pressure, but is particularly limited as long as it generates base (basic substance) when electromagnetic waves are irradiated and heated as external stimuli. It does not work. Since the base generated by exposure acts as a catalyst for curing the polyimide precursor by heating, it can be suitably used in a negative form.

The content of the photobase generator is not particularly limited as long as it can form a desired pattern, and can be a general content. The photobase generator is preferably in the range of 0.01 parts by mass or more and less than 30 parts by mass with respect to 100 parts by mass of the resin, more preferably in the range of 0.05 parts by mass to 25 parts by mass, and in the range of 0.1 parts by mass to 20 parts by mass It is more preferable.

In this invention, a well-known thing can be used as a photobase generator. For example, M. Shirai, and M. Tsunooka, Prog. Polym. Sci. 21, 1 (1996); Tsunooka Masahiro, Polymer Processing, 46, 2 (1997); C. Kutal, Coord. Chem. Rev. 211, 353 (2001); Y. Kaneko, A. Sarker, and D. Neckers, Chem. Mater. 11, 170 (1999); H. Tachi, M. Shirai, and M. Tsunooka, J. Photopolym. Sci. Technol. 13, 153 (2000); M. Winkle, and K. Graziano, J. Photopolym. Sci. Technol. 3, 419 (1990); M. Tsunooka, H. Tachi, and S. Yoshitaka, J. Photopolym. Sci. Technol. 9, 13 (1996); K. Suyama, H. Araki, M. Shirai, J. Photopolym. Sci. Technol. As described in 19, 81 (2006), the base component is neutralized by forming a salt, such as having a transition metal compound complex, a structure such as an ammonium salt, or the amidine moiety is potential by salting with a carboxylic acid And ionic compounds such as carbamate derivatives, oxime ester derivatives, and acyl compounds, and nonionic compounds in which the base component is latent by urein bonds or oxime bonds.

The photobase generator that can be used in the present invention is not particularly limited, and a known one can be used. For example, carbamate derivatives, amide derivatives, imide derivatives, α-cobalt complexes, imidazole derivatives, cinnamic acid amide derivatives And oxime derivatives.

Although it does not specifically limit as a basic substance generated from a photobase generator, The compound which has an amino group, especially polyamines, such as monoamine and diamine, and amidine etc. are mentioned.

The basic substance generated is preferably a compound having an amino group with a higher basicity. This is because the catalytic action for the dehydration-condensation reaction in imidization of the polyimide precursor is strong, and the addition of a smaller amount enables expression of the catalytic effect in the dehydration-condensation reaction at a lower temperature. As a result, since the catalytic effect of the generated basic substance is large, the sensitivity of the appearance as a negative photosensitive resin composition is improved.

It is preferable that it is amidine and an aliphatic amine from a viewpoint of the said catalyst effect.

As a photobase generator, it is preferable that it is a photobase generator which does not contain a salt in a structure, and it is preferable that there is no charge on the nitrogen atom of the base part generated in a photobase generator. As the photobase generator, it is preferable that the base to be generated is latent using a covalent bond, and the mechanism for generating the base is to cut the covalent bond between the nitrogen atom and the adjacent atom in the base portion to be generated, thereby reducing the base. It is desirable to occur. If it is a photobase generator which does not contain a salt in a structure, since a photobase generator can be made neutral, solvent solubility is more favorable and pot life improves. For this reason, the amine generated from the photobase generator used in the present invention is preferably a primary amine or a secondary amine.

Further, from the above reason, as the photobase generator, it is preferable that the base generated as described above is latent using a covalent bond, and the base generated using an amide bond, a carbamate bond, or an oxime bond It is desirable to be latent.

As a photobase generator according to the present invention, for example, a photobase generator having a cinnamic acid amide structure as disclosed in Japanese Patent Application Laid-Open No. 2009-80452 and International Publication No. 2009/123122, Japanese Patent Application Laid-Open No. 2006 Photobase generator having a carbamate structure as disclosed in -189591 and JP 2008-247747, oxime structure as disclosed in JP 2007-249013 and JP 2008-003581, And photobase generators having a carbamoyl oxime structure, and the like, but are not limited to these, and other structures of known photobase generators can be used.

In addition, as the photobase generator, the compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 in Japanese Patent Application Publication No. 2012-93746, the compounds described in paragraphs 0022 to 0069 in Japanese Patent Application Publication No. 2013-194205, Japanese Patent Application The compounds described in paragraphs 0026 to 0074 of publication 2013-204019 and the compounds described in paragraph 0052 of international publication WO2010 / 064631 are exemplified.

<Thermal acid generator>

The composition of the present invention may contain a thermal acid generator. The thermal acid generator generates an acid by heating, promotes cyclization of polyimide precursors, etc., further improves the mechanical properties of the cured film, and has a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, It has an effect of accelerating the crosslinking reaction of at least one compound selected from oxetane compounds and benzoxazine compounds.

The thermal decomposition initiation temperature of the thermal acid generator is preferably 50 ° C to 270 ° C, and more preferably 250 ° C or less. In addition, no acid is generated upon drying (pre-baking: about 70 to 140 ° C) after the composition is applied to the substrate, and then subjected to final heating (curing: about 100 to 400 ° C) after patterning by exposure and development. It is preferable to select one that generates, because it is possible to suppress a decrease in sensitivity during development.

The acid generated from the thermal acid generator is preferably a strong acid, for example, arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid or trifluor Haloalkylsulfonic acids, such as romethane sulfonic acid, are preferable. Examples of such thermal acid generators include those described in paragraph 0055 of JP 2013-072935 A.

Especially, it is more preferable to generate alkyl sulfonic acid having 1 to 4 carbon atoms or haloalkylsulfonic acid having 1 to 4 carbon atoms from the viewpoint of little residual in the cured film and not deteriorating the properties of the cured film, and methanesulfonic acid (4 -Hydroxyphenyl) dimethylsulfonium, methanesulfonic acid (4-((methoxycarbonyl) oxy) phenyl) dimethylsulfonium, methanesulfonic acid benzyl (4-hydroxyphenyl) methylsulfonium, methanesulfonic acid Benzyl (4-((methoxycarbonyl) oxy) phenyl) methylsulfonium, methanesulfonic acid (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium, trifluoromethanesulfonic acid (4- Hydroxyphenyl) dimethylsulfonium, trifluoromethanesulfonic acid (4-((methoxycarbonyl) oxy) phenyl) dimethylsulfonium, trifluoromethanesulfonic acid benzyl (4-hydroxyphenyl) methylsulfone Phonium, benzyl trifluoromethanesulfonic acid (4-((methoxycarbonyl) oxy) phenyl) methylsulfonium, tri Fluoromethanesulfonic acid (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium, 3- (5-(((propylsulfonyl) oxy) imino) thiophen-2 (5H) -Ily Den) -2- (o-tolyl) propanenitrile, 2,2-bis (3- (methanesulfonylamino) -4-hydroxyphenyl) hexafluoropropane is preferred.

Moreover, the compound described in paragraph 0059 of JP 2013-167742 A is also preferred as a thermal acid generator.

The content of the thermal acid generator is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more, relative to 100 parts by mass, such as a polyimide precursor. By containing 0.01 part by mass or more, since crosslinking reaction and cyclization of the polyimide precursor are promoted, mechanical properties and chemical resistance of the cured film can be further improved. Moreover, from the viewpoint of electrical insulation of a cured film, 20 parts by mass or less is preferable, 15 parts by mass or less is more preferable, and 10 parts by mass or less is more preferable.

The thermal acid generator may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount falls into the said range.

<Thermal polymerization initiator>

The composition of the present invention may contain a thermal polymerization initiator (preferably a thermal radical polymerization initiator). As the thermal radical polymerization initiator, a known thermal radical polymerization initiator can be used.

A thermal radical polymerization initiator is a compound that generates radicals by heat energy and initiates or accelerates a polymerization reaction of a polymerizable compound. When a cyclization reaction, such as a polyimide precursor, is advanced by adding a thermal radical polymerization initiator, the polymerization reaction of a polymerizable compound can be advanced. In addition, when the polyimide precursor or the like contains an ethylenically unsaturated bond, the polymerization reaction of the polyimide precursor or the like can be carried out along with cyclization of the polyimide precursor or the like, so that higher heat resistance can be achieved.

Examples of the thermal radical polymerization initiator include aromatic ketones, onium salt compounds, peroxides, thio compounds, hexaaryl biimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, and carbon halogens And a compound having an bond, an azo-based compound, and the like. Especially, a peroxide or an azo-type compound is more preferable, and a peroxide is especially preferable.

The thermal radical polymerization initiator used in the present invention preferably has a 10-hour half-life temperature of 90 to 130 ° C, more preferably 100 to 120 ° C.

Specifically, the compounds described in paragraphs 0074 to 0118 of JP 2008-63554 A can be cited.

As commercial products, Perbutyl Z and Percumyl D (manufactured by Nichiyu Co., Ltd.) can be suitably used.

When the composition has a thermal radical polymerization initiator, the content of the thermal radical polymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.1 to 30% by mass, and particularly 0.1 to 20% by mass relative to the total solid content of the composition. desirable. Moreover, it is preferable to contain 0.1-50 mass parts of thermal radical polymerization initiators with respect to 100 mass parts of polymerizable compounds, and it is preferable to contain 0.5-30 mass parts. According to this aspect, it is easy to form a cured film excellent in heat resistance.

The thermal radical polymerization initiator may be used alone or in combination of two or more. When a thermal radical polymerization initiator is 2 or more types, it is preferable that the total is the said range.

<Anti-corrosion agent>

It is preferable to add a corrosion inhibitor to the composition of this invention. Corrosion inhibitors are added for the purpose of preventing the leakage of ions from the metal wiring, and as compounds, for example, the rust inhibitor described in paragraph 0094 of JP 2013-15701 A, paragraphs 0073 to 0076 of JP 2009-283711 A The compound described in Japanese Patent Application Laid-Open No. 2011-59656, the compound described in Paragraph 0052, Japanese Patent Application Laid-Open No. 2012-194520, the compounds described in Paragraphs 0114, 0116, and 0118 can be used. Among them, a compound having a triazole ring or a compound having a tetrazole ring can be preferably used, and 1,2,4-triazole, 1,2,3-benzotriazole, 5-methyl-1H-benzotriazole , 1H-tetrazole, 5-methyl-1H-tetrazole are more preferred, and 1H-tetrazole is most preferred.

The blending amount of the corrosion inhibitor is preferably 0.1 to 10 parts by mass, and more preferably 0.2 to 5 parts by mass with respect to 100 parts by mass, such as a polyimide precursor.

Corrosion inhibitors may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount falls into the said range.

<Metal adhesive improving agent>

It is preferable that the composition of this invention contains the metal adhesive improving agent for improving the adhesiveness with the metal material used for electrodes, wiring, etc. Examples of the metal adhesive improving agent include sulfide-based compounds described in paragraphs 0046 to 0049 of JP 2014-186186 and paragraphs 0032 to 0043 of JP 2013-072935 A. The following compound is also illustrated as a metal adhesive improving agent.

[Formula 38]

The blending amount of the metal adhesive improving agent is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, based on 100 parts by mass, such as a polyimide precursor. By setting it as 0.1 mass part or more, the adhesiveness of the film | membrane after heat hardening and metal becomes favorable, and when it is 30 mass parts or less, the heat resistance and mechanical property of a film after hardening become favorable.

Only one type may be sufficient as the metal adhesive improving agent, or two or more types may be used. When using 2 or more types, it is preferable that the total is the said range.

<Silane coupling agent>

It is preferable that the composition of this invention contains a silane coupling agent from the point which can improve adhesiveness with a board | substrate. Examples of the silane coupling agent include compounds described in paragraphs 0062 to 0073 of Japanese Unexamined Patent Publication No. 2014-191002, compounds described in paragraphs 0063 to 007 of WO2011 / 080992A1, and paragraphs 0060 to 0061 of Japanese Unexamined Patent Publication No. 2014-191252 The compound described in, the compound described in paragraphs 0045 to 0052 of Japanese Unexamined Patent Publication No. 2014-41264, and the compound described in paragraph 0055 of WO2014 / 097594 are exemplified. It is also preferable to use two or more other silane coupling agents as described in Japanese Patent Laid-Open No. 2011-128358, paragraphs 0050 to 0058.

The blending amount of the silane coupling agent is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass, such as a polyimide precursor. When it is 0.1 mass part or more, more sufficient adhesiveness with a board | substrate can be provided, and if it is 20 mass parts or less, problems, such as a viscosity increase in storage at room temperature, can be suppressed more.

The silane coupling agent may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount falls into the said range.

<Sensitive coloring>

The composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs specific active radiation and becomes an electron excited state. The sensitizing dye in the electron excited state is brought into contact with an amine generator, a thermal radical polymerization initiator, a photopolymerization initiator, and the like, and thus effects such as electron transfer, energy transfer, and heat generation occur. As a result, the amine generator, thermal radical polymerization initiator, and photopolymerization initiator undergo chemical changes and decompose to generate radicals, acids or bases.

Examples of preferable sensitizing dyes include those belonging to the following compounds and having absorption wavelengths in the 300 to 450 nm range. For example, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (for example, fluorescein, eosin, erythrosine) , Rhodamine B, Rose Bengal), thioxanthones (e.g., 2,4-diethylthioxanthone), cyanines (e.g. thiocarbocyanine, oxacarbocyanine), merocyanine Type (for example, merocyanine, carbomerocyanine), thiazines (for example, thionine, methylene blue, toluidine blue), acridines (for example, acridine orange, chloroflavin) , Acriflavin), anthraquinones (eg anthraquinone), squaryliums (eg squarylium), coumarins (eg 7-diethylamino-4-methylcoumarin), And styrylbenzenes, distyrylbenzenes, and carbazoles.

Among them, in the present invention, the combination of polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene), thioxanthones, distyrylbenzenes, and styrylbenzenes is the starting efficiency. It is preferable from the viewpoint of, and it is more preferable to use a compound having an anthracene skeleton. 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, etc. are mentioned as a particularly preferable specific compound.

When the composition contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass relative to the total solid content of the composition. . The sensitizing dye may be used alone or in combination of two or more.

<Chain transfer agent>

The composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, on pages 683-684 of the 3rd edition of the Polymer Dictionary (Polymer Society, 2005). As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. These can generate hydrogen by donating hydrogen to a low-active radical species, or generate a radical by oxidizing and then deprotonating. In particular, thiol compounds (eg, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles) Etc.) can be preferably used.

When the composition has a chain transfer agent, the preferred content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, particularly preferably 1 to 100 parts by mass of the total solids of the composition. 5 parts by mass.

Only one type of chain transfer agent may be used, or two or more types may be used. When chain transfer agent is 2 or more types, it is preferable that the total is the said range.

<Surfactant>

Various surfactants may be added to the composition of the present invention from the viewpoint of further improving the coatability. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used.

Particularly, by including a fluorine-based surfactant, the liquid properties (especially, fluidity) when prepared as a coating liquid are further improved, so that the uniformity of the coating thickness and the liquid-liquidity can be further improved.

In the case of film formation using a coating liquid containing a fluorine-based surfactant, by reducing the interfacial tension between the coated surface and the coating liquid, the wettability to the coated surface is improved, and the coatability to the coated surface is improved. For this reason, even when a thin film having a small amount of liquid is formed on the order of several μm, it is effective in that film formation of a uniform thickness with a small thickness variation can be more suitably performed.

The fluorine-containing surfactant has a fluorine content of 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. The fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and liquid-repellency, and also has good solvent solubility.

Examples of the fluorine-based surfactant include Megapac F171, Copper F172, Copper F173, Copper F176, Copper F177, Copper F141, Copper F142, Copper F143, Copper F144, Copper R30, Copper F437, Copper F475, Copper F479, Copper F482 , Copper F554, Copper F780, Copper F781 (above, manufactured by DIC Corporation), Fluorad FC430, Copper FC431, Copper FC171 (above, Sumitomo 3M Co., Ltd.), Surfon S-382, Copper SC-101, Copper SC-103, Copper SC-104, Copper SC-105, Copper SC1068, Copper SC-381, Copper SC-383, Copper S393, Copper KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, And PF6320, PF6520, and PF7002 (manufactured by OMNOVA).

A block polymer may also be used as the fluorine-based surfactant, and specific examples thereof include compounds described in JP 2011-89090 A.

In addition, the following compounds are also exemplified as fluorine-based surfactants used in the present invention.

[Formula 39]

The weight average molecular weight of the above-mentioned compound is 14,000, for example.

As a nonionic surfactant, specifically, glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxy Ethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol Distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1 from BASF), Solspers 20000 (Nihon Lu And Brisol Co., Ltd.). In addition, Pionein D-6112-W manufactured by Takemoto Yushi Co., Ltd., manufactured by Wako Junyaku High School, NCW-101, NCW-1001, NCW-1002 can also be used.

As a cationic surfactant, specifically, a phthalocyanine derivative (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), an organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (Met ) Acrylic acid (co) polymer, polyflo No. 75, No. 90, No. 95 (made by Kyoeisha Chemical Co., Ltd.), W001 (made by Yusho Corporation), and the like.

As an anionic surfactant, W004, W005, W017 (made by Yusho Co., Ltd.) etc. are mentioned specifically ,.

Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Toray Silicone SH21PA”, “Toray Silicone SH28PA”, and “Toray Silicone SH29PA” manufactured by Toray Dow Corning Co., Ltd. "," Toray silicon SH30PA "," Toray silicon SH8400 "," TSF-4440 "," TSF-4300 "," TSF-4445 "," TSF-4460 "," TSF-4460 "," TSF-4460 "made by Momentive Performance Materials &Quot;, " KP341 ", " KF6001 ", " KF6002 " manufactured by Shin-Etsu Silicone Co., Ltd., " BYK307 ", " BYK323 ", " BYK330 "

When the composition has a surfactant, the surfactant content is preferably 0.001 to 2.0 mass%, more preferably 0.005 to 1.0 mass%, based on the total solid content of the composition.

As for surfactant, only 1 type may be sufficient and 2 or more types may be sufficient as it. When surfactant is 2 or more types, it is preferable that the total is the said range.

<High-grade fatty acid derivatives, etc.>

In order to prevent polymerization inhibition by oxygen, to the composition of the present invention, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added, and may be localized on the surface of the composition in the course of drying after application.

When the composition has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the composition.

Higher fatty acid derivatives, etc. may be used alone or in combination of two or more. When a higher fatty acid derivative or the like is two or more, it is preferable that the total is within the above range.

<Adhesion promoter>

The composition of the present invention may contain an adhesion promoter. By including an adhesion promoter, adhesion can be improved more.

As a preferable example of an adhesion promoter, the compound represented by the following formula (42) is mentioned.

Equation (42)

[Formula 40]

(In formula (42), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or a monovalent organic group.)

As another preferable example of the adhesion promoter, a compound represented by the following formula (43) can be given.

[Formula 41]

(In formula (43), R ⁹ and R ¹⁰ are each independently an alkyl group having 1 to 5 carbon atoms, and when plural R ⁹ is present, they may be the same or different, and when plural R ¹⁰ are present, they may be the same. It may be different, q is an integer of 1-10, and r is an integer of 0-3.)

As a specific example of an adhesion promoter, aluminum chelate A (w) (brand name) (Kawaken Fine Chemicals, aluminum trisacetylacetonate), aluminum chelate D (brand name) (Kawaken Fine Chemicals, aluminum bisethylacetate acetate monoacetyl Acetonate), TC-401 (trade name) (manufactured by Matsumoto Fine Chemical, titanium tetraacetylacetonate), ZC-150 (trade name) (made by Matsumoto fine chemical, zirconium tetraacetylacetonate), KBM1003, KBM403, KBM503 and KBM803 ( As mentioned above, a brand name and Shin-Etsu Silicone make) are illustrated.

When blending, the blending amount of the adhesion promoter is preferably 0.01 to 50% by mass, more preferably 0.5 to 20% by mass, and even more preferably 0.5 to 10% by mass, of the total solid content of the composition. The adhesion promoter may contain only 1 type, or may contain 2 or more types. When 2 or more types are included, it is preferable that a total amount falls into the said range.

<Solvent>

When the composition of the present invention is layered by application, it is preferable to blend a solvent. As long as the composition is capable of forming the composition in a layered form, a known one can be used without limitation.

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, alkyl alkyloxyacetate (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g. methyl methoxyacetate, methoxyacetic acid) Ethyl, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl esters of 3-alkyloxypropionic acid (e.g. methyl 3-alkyloxypropionic acid, ethyl 3-alkyloxypropionic acid, etc.) 3-methoxypropionic acid methyl, 3-methoxypropionic acid ethyl, 3-ethoxypropionic acid methyl, 3-ethoxypropionic acid ethyl, etc.), 2-alkyloxypropionic acid alkyl esters (eg : 2-alkyloxypropionic acid methyl, 2-alkyloxypropionic acid ethyl, 2-alkyloxypropionic acid propyl, etc. (e.g., 2-methoxypropionic acid methyl, 2-methoxypropionic acid ethyl, 2-methoxypropionic acid propyl, 2- Methyl ethoxypropionate, ethyl 2-ethoxypropionate), methyl 2-alkyloxy-2-methylpropionic acid and ethyl 2-alkyloxy-2-methylpropionic acid (for example methyl 2-methoxy-2-methylpropionic acid) , 2-ethoxy-2-methylpropionate ethyl, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., 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 Lycol Mono To ethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Teracetate, propylene glycol monopropyl ether acetate, etc., as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolid Dimethyl sulfoxide is suitably mentioned as sulfoxides, such as toluene, xylene, anisole, limonene, etc. as aromatic hydrocarbons, such as money.

The solvent is also preferably in a form of mixing two or more types from the viewpoint of improving the shape of the coated surface. Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone , Cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate A mixed solution composed of two or more types is preferred. The combination of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

When the composition has a solvent, the content of the solvent is preferably an amount such that the total solid content concentration of the composition is 5 to 80% by mass, more preferably 5 to 70% by mass, and more preferably 10 to 60 Mass% is particularly preferred.

Only 1 type may be sufficient as a solvent, and 2 or more types may be sufficient as it. When two or more solvents are used, it is preferable that the total is within the above range.

In addition, the content of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide and N, N-dimethylformamide is a composition from the viewpoint of film strength. It is preferably less than 5% by mass, more preferably less than 1% by mass, even more preferably less than 0.5% by mass, and particularly preferably less than 0.1% by mass relative to the total mass of.

<Other additives>

The composition of the present invention can be blended with various additives, for example, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, aggregation inhibitors, and the like, as long as the effects of the present invention are not impaired. . When blending these additives, the total blending amount is preferably 3% by mass or less of the solid content of the composition.

From the viewpoint of the shape of the coated surface, the moisture content of the composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and particularly preferably less than 0.6% by mass.

From the viewpoint of insulation, the metal content of the composition of the present invention is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and particularly preferably less than 0.5 mass ppm. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, and nickel. When containing a plurality of metals, it is preferable that the sum of these metals is within the above range.

Moreover, as a method for reducing the metal impurities contained in the composition unintentionally, as a raw material constituting the composition, a raw material with a low metal content is selected, or filter filtration is performed on the raw material constituting the composition, or polytetrafluoroethylene is used in the apparatus. And lining with fluoroethylene or the like to perform distillation under conditions where the suppression of the contamination is as much as possible.

In the composition of the present invention, the content of the halogen atom is preferably less than 500 ppm by mass, preferably less than 300 ppm by mass, and particularly preferably less than 200 ppm by mass from the viewpoint of wiring corrosion. Especially, what exists in a halogen ion state is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and particularly preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the sum of chlorine atom and bromine atom, or chloride ion and bromide ion is within the above range, respectively.

<Preparation of composition>

The composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited, and can be performed by a conventionally known method.

Moreover, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the composition. As a filter hole diameter, 1 micrometer or less is preferable, 0.5 micrometer or less is more preferable, 0.1 micrometer or less is more preferable. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. The filter may be one previously washed with an organic solvent. In the filter filtration step, a plurality of types of filters may be used in series or in parallel. When a plurality of types of filters are used, filters having different pore diameters and / or materials may be used in combination. Further, various materials may be filtered a plurality of times, or a step of filtering a plurality of times may be a circulating filtration step. Moreover, you may pressurize and filter, and the pressure to pressurize is preferably 0.05 MPa or more and 0.3 MPa or less.

In addition to filtration using a filter, impurities may be removed by the adsorbent, or a filter filtration and an adsorbent may be used in combination. As the adsorbent, a known adsorbent can be used, and for example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.

As the storage container of the composition used in the present invention, a conventionally known storage container can be used. Moreover, as a storage container, for the purpose of suppressing the mixing of impurities into raw materials and compositions, it is also preferable to use a bottle in which the inner wall of the container is composed of six types of six-layer resins or a bottle in which six types of resins have a seven-layer structure. Do. As such a container, the container of Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

Next, the cured film of the present invention, a method for manufacturing the cured film, and a semiconductor device will be described.

The cured film of the present invention is made by curing the composition of the present invention. The thickness of the cured film of the present invention can be, for example, 1 μm or more, and 5 μm or more. Moreover, as an upper limit, it can be 100 micrometers or less, and also 30 micrometers or less. Moreover, the laminated body of this invention has two or more layers of the cured films of this invention. It is preferable that such a laminate has a metal layer between cured films. Such a metal layer is preferably used as a metal wiring which will be described later in detail.

Examples of the applicable field of the cured film or laminate of the present invention include an insulating film of a semiconductor device, an interlayer insulating film for a redistribution layer, and the like. In particular, since the resolution is good, it can be suitably used for an interlayer insulating film for a redistribution layer in a three-dimensional mounting device.

Moreover, the cured film in this invention can also be used for electronic photoresists (galvanic resist, etching resist, solder top resist), etc.

Moreover, the cured film in this invention can also be used for manufacture of a plate surface, such as an offset plate surface or a screen plate surface, use by etching of a molded part, manufacture of a protective lacquer and a dielectric layer in electronics, especially microelectronics, etc.

The manufacturing method of the cured film of this invention includes using the composition of this invention, Preferably the photosensitive resin composition layer formation process of applying a photosensitive resin composition to a board | substrate, and exposing the photosensitive resin composition layer It has an exposure process and a process of developing the exposed photosensitive resin composition layer. The production method of the present invention is particularly excellent in the case of performing a negative development process. Moreover, in the manufacturing method of this invention, after the developing process process, it can also be set as the aspect including the process of heating the developed photosensitive resin composition layer to a temperature of 50-500 degreeC. Since the cured film of the present invention has excellent heat resistance, good performance can be maintained even when heated at 150 to 500 ° C.

According to the method for producing a cured film of the present invention, the method for producing a layered product of the present invention, after forming the cured film, further performs a photosensitive resin composition layer formation process, an exposure process, and a development treatment process again in the above order. Includes. In particular, it is preferable to perform the photosensitive resin composition layer forming step, exposure step, and developing treatment step 2 to 5 times (i.e., 3 to 6 times in total) in the above order. By laminating a cured film in this way, a laminate can be obtained. In the present invention, it is particularly preferable to prepare a cured film, and then develop and then provide a metal layer on the developed portion.

The present invention also discloses a semiconductor device comprising at least one of a cured film and a laminate of the present invention.

Next, an embodiment of a semiconductor device using the composition as an interlayer insulating film for a redistribution layer will be described.

The semiconductor device 100 shown in FIG. 1 is a so-called three-dimensional mounting device, and a stacked body 101 in which a plurality of semiconductor elements (semiconductor chips) 101a to 101d are stacked is disposed on the wiring board 120. .

In addition, in this embodiment, although the stacking number of semiconductor elements (semiconductor chips) will be mainly described, the number of stacking layers of semiconductor elements (semiconductor chips) is not particularly limited, for example, 2 layers, 8 layers, 16 A layer, a 32 layer, etc. may be sufficient. Also, the first floor may be sufficient.

The plurality of semiconductor elements 101a to 101d are all made of a semiconductor wafer such as a silicon substrate.

The uppermost semiconductor element 101a does not have a through electrode, and an electrode pad (not shown) is formed on one surface thereof.

The semiconductor elements 101b to 101d have through electrodes 102b to 102d, and connection pads (not shown) integrally provided on the through electrodes are provided on both surfaces of each semiconductor element.

The laminate 101 has a structure in which a semiconductor element 101a having no through electrode and a semiconductor element 101b to 101d having through electrodes 102b to 102d are flip-chip connected.

That is, the electrode pad of the semiconductor element 101a not having a through electrode and the connection pad on the semiconductor element 101a side of the semiconductor element 101b having a through electrode 102b adjacent thereto are metals such as solder bumps. The connection pad on the other side of the semiconductor element 101b connected by the bump 103a and having the through electrode 102b is on the semiconductor element 101b side of the semiconductor element 101c having the through electrode 102c adjacent thereto. It is connected to the connection pad of the metal bump 103b, such as a solder bump. Similarly, the connection pad on the other side of the semiconductor element 101c having the through electrode 102c, the connection pad on the semiconductor element 101c side of the semiconductor element 101d having the through electrode 102d adjacent thereto, and solder It is connected by metal bumps 103c such as bumps.

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

The laminate 101 is laminated on the wiring board 120.

As the wiring substrate 120, for example, a multilayer wiring board using an insulating substrate such as a resin substrate, a ceramic substrate, or a glass substrate as a substrate is used. A multilayer copper-clad laminate (multilayer printed wiring board) or the like is exemplified as the wiring board 120 to which the resin substrate is applied.

The surface electrode 120a is provided on one surface of the wiring board 120.

Between the wiring board 120 and the stacked body 101, an insulating layer 115 on which the redistribution layer 105 is formed is disposed, and the redistribution layer 105 is provided between the wiring board 120 and the stacked body 101. It is electrically connected through. The insulating layer 115 is formed by using the composition in the present invention.

That is, one end of the redistribution layer 105 is connected to an electrode pad formed on the side of the redistribution layer 105 side of the semiconductor element 101d through a metal bump 103d such as a solder bump. In addition, the other end of the redistribution layer 105 is connected to the surface electrode 120a of the wiring board through a metal bump 103e such as a solder bump.

In addition, an underfill layer 110a is formed between the insulating layer 115 and the laminate 101. In addition, an underfill layer 110b is formed between the insulating layer 115 and the wiring substrate 120.

In addition to the above, the cured film in the present invention can be widely used for various uses using polyimide.

Moreover, since polyimide is strong against heat, the cured film or the like in the present invention can be suitably used as a transparent plastic substrate for display devices such as liquid crystal displays and electronic paper, automotive parts, heat-resistant paints, coating agents, and film applications.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. Materials, amounts, proportions, treatment contents, treatment procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. "Part" and "%" are on a mass basis 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 to form a molecular sieve. It was dried. The suspension was heated at 100 ° C for 3 hours. A few minutes after heating a clear solution was obtained. 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 min while maintaining the temperature at -10 ± 4 ° C. While SOCl ₂ was added, the viscosity increased. After diluted with 50 ml of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Subsequently, 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 20 to 23 ° C for 20 minutes. Subsequently, the reaction mixture was stirred overnight at room temperature. Subsequently, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimide precursor mixture was stirred for 15 minutes at a rate of 5000 rpm. The polyimide precursor was removed by filtration, stirred for 30 minutes in 4 liters of water again, and filtered again. Subsequently, the obtained polyimide precursor was dried under reduced pressure at 45 ° C for 3 days.

[Formula 42]

<Synthesis Example 2>

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

14.06 g (64.5 mmol) pyromellitic dianhydride (dried at 140 ° C. for 12 hours), 18.6 g (129 mmol) 2-hydroxyethyl methacrylate, 0.05 g hydroquinone, 10.7 g The pyridine of the mixture and diglyme (diethylene glycol dimethyl ether) of 140g were mixed and stirred at a temperature of 60 ° C for 18 hours to obtain a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Manufactured. Subsequently, the obtained diester was chlorinated by SOCl ₂ and then converted into a polyimide precursor by 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example 1, and polyimide in the same manner as in Synthesis Example 1. The precursor was obtained.

[Formula 43]

<Synthesis Example 3>

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

20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140 ° C for 12 hours), 18.6 g (129 mmol) of 2-hydroxyethyl methacrylate, and 0.05 g of hydroquinone , 10.7 g of pyridine, 140 g of diglyme were mixed and stirred at a temperature of 60 ° C. for 18 hours to prepare a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Subsequently, after chlorinating the obtained diester with SOCl ₂ , the polyimide precursor was converted to 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example 1, and the polyimide precursor was synthesized in the same manner as in Synthesis Example 1. Got.

[Formula 44]

<Synthesis Example 4>

[Synthesis of polyimide precursor (A-4: polyimide precursor having a carboxy group) from 4,4'-oxydiphthalic anhydride and 4,4'-diaminodiphenyl ether]

20.0 g (64.5 mmol) of 4,4′-oxydiphthalic anhydride (dried at 140 ° C. for 12 hours) was dissolved in 180 ml of NMP (N-methyl-2-pyrrolidone), and 21.43 g (270.9 mmol) ), The reaction solution was cooled to -10 ° C, and while maintaining the temperature at -10 ± 4 ° C, 11.08g (58.7mmol) of 4,4'-diaminodiphenyl ether was dissolved in NMP100ml. The resulting solution was added dropwise for 30 minutes, and then the reaction mixture was stirred overnight at room temperature. Subsequently, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimide precursor mixture was stirred for 15 minutes at a rate of 5000 rpm. The polyimide precursor was removed by filtration, stirred for 30 minutes in 4 liters of water again, and filtered again. Subsequently, the obtained polyimide precursor was dried under reduced pressure at 45 ° C for 3 days.

[Formula 45]

<Synthesis Example 5>

[Synthesis of polyimide precursor (A-5: polyimide precursor having a radically polymerizable group) from 4,4'-oxydiphthalic anhydride, orthoolidine and 2-hydroxyethyl methacrylate]

20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140 ° C for 12 hours), 18.6 g (129 mmol) of 2-hydroxyethyl methacrylate, and 0.05 g of hydroquinone , 10.7 g of pyridine, 140 g of diglyme were mixed and stirred at a temperature of 60 ° C. for 18 hours to prepare a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Subsequently, the obtained diester was chlorinated by SOCl ₂ , and then converted into a polyimide precursor by 4,4'-diamino-2,2'-dimethylbiphenyl in the same manner as in Synthesis Example 1, and Synthesis Example 1 Polyimide precursor was obtained in the same manner as.

[Formula 46]

<Synthesis Example 6>

[4,4'-Oxydiphthalic dianhydride, polyimide precursor from 2,2'-bis (trifluoromethyl) benzidine and 2-hydroxyethylmethacrylate (A-7: polyyi having radically polymerizable groups) Synthesis of mid precursor)]

20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140 ° C for 12 hours), 18.6 g (129 mmol) of 2-hydroxyethyl methacrylate, and 0.05 g of hydroquinone , 10.7 g of pyridine, 140 g of diglyme were mixed and stirred at a temperature of 60 ° C. for 18 hours to prepare a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Subsequently, the obtained diester was chlorinated by SOCl ₂ and then converted into a polyimide precursor by 2,2′-bis (trifluoromethyl) benzidine in the same manner as in Synthesis Example 1, and in the same manner as in Synthesis Example 1. A polyimide precursor was obtained.

[Formula 47]

<Synthesis Example 7>

[Synthesis of Comparative Example Polymer (RA-1)]

27.0 g (153.2 mmol) benzyl methacrylate, 20 g (157.3 mmol) N-isopropylmethacrylamide, 39 g (309.2 mmol) allyl methacrylate, 13 g (151.0 mmol) methacrylic acid, polymerization initiator ( V-601, 3.55 g (15.4 mmol) of Wako Pure Chemical Industries, Ltd., and 300 g of 3-methoxy-2-propanol were mixed. The mixed solution was added dropwise in 300 g of 3-methoxy-2-propanol heated to 75 ° C. under a nitrogen atmosphere for 2 hours. After completion of the dropwise addition, the mixture was further stirred under a nitrogen atmosphere at 75 ° C for 2 hours. After completion of the reaction, in 5 liters of water, the polymer precipitated and stirred at a rate of 5000 rpm for 15 minutes. The acrylic resin was removed by filtration, stirred for 30 minutes again in 4 liters of water, and filtered again. Next, the obtained acrylic resin was dried under reduced pressure at 45 ° C for 3 days.

[Formula 48]

<Examples and Comparative Examples>

The components of the following substrate were mixed, and a uniform solution was used to prepare a coating solution for the photosensitive resin composition. The photosensitive resin composition obtained above was pressure-filtered through a filter having a width of 0.8 μm in the fine pores.

<< Composition of the photosensitive resin composition >>

(A) Resin: parts by mass shown in Table 1

(B) Uretain (meth) acrylate or a comparative compound thereof: parts by mass shown in Table 1

(C) Photo radical polymerization initiator: parts by mass shown in Table 1

(D) polymerization inhibitor: parts by mass shown in Table 1

(Other components): The following amounts were added in all Examples and Comparative Examples.

Tetrazol (migration inhibitor): 0.100 parts by mass

N-methyl-2-pyrrolidone (solvent): 60.0 parts by mass

[Table 1]

The abbreviations described in the table are as follows.

(A) Resin

The A-1 to A-5 and RA-1 are polyimide precursors or comparative resins synthesized in the above Synthesis Examples.

The A-6 is Matrimide5218 (manufactured by HUNTSMAN, polyimide).

The RA-2 is methyl polymethacrylate (Mw: 15,000, manufactured by Aldrich).

(B) Uretain (meth) acrylate or a comparative compound thereof

[Formula 49-1]

[Formula 49-2]

[Formula 49-3]

[Formula 50]

(C) Photo radical polymerization initiator

C-1: oxime-based photo radical polymerization initiator, IRGACURE OXE-01 (manufactured by BASF)

C-2: aminoacetophenone type photo radical polymerization initiator, IRGACURE-369 (manufactured by BASF)

C-3: Metallocene compound-based photo radical polymerization initiator, IRGACURE-784 (manufactured by BASF)

Polymerization inhibitor

D-1: 2,6-di-tert-butyl-4-methylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)

D-2: p-benzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Evaluation>

[Exposure Latitude]

Each photosensitive resin composition was applied by spinning on a silicon wafer. The silicon wafer to which the photosensitive resin composition was applied was dried on a hot plate at 100 ° C. for 5 minutes, and a polymer layer having a uniform thickness in Table 1 was formed on the silicon wafer. The photosensitive resin composition layer on the silicon wafer was exposed using a stepper (Nikon NSR 2005 i9C). The exposure is performed with i-rays, and at a wavelength of 365 nm, using photomasks with line and space intervals of 1 μm from 5 μm to 25 μm at exposure energy of 200, 300, 400, 500, 600, 700, and 800 mJ / cm ² , Exposure was performed.

The exposed photosensitive resin composition layer was negatively developed for 60 seconds with cyclopentanone. The smaller the line width of the obtained photosensitive resin composition layer (pattern), the larger the difference in solubility in the developing solution of the light-irradiating portion and the light-irradiating portion, indicating a favorable result. Moreover, with respect to the change in exposure energy, when the change in line width is small, it indicates that the exposure latitude is wide, which is a preferable result. The measurement limit is 5 μm.

A: 5 μm or more and 8 μm or less

B: 8 μm or more but 10 μm or less

C: 10 μm or more and 15 μm or less

D: 15 μm or more and 20 μm or less

E: It exceeded 20 micrometers.

F: A pattern having a line width with a sharpness of the edge was not obtained.

[Heat resistance]

The photosensitive resin composition was applied to the surface of the silicon wafer by spinning on the silicon wafer. The silicon wafer to which the photosensitive resin composition was applied was dried on a hot plate at 100 ° C. for 5 minutes, and a polymer layer having a uniform thickness in Table 1 was formed on the silicon wafer. The photosensitive resin composition layer on the silicon wafer was exposed using a stepper (Nikon NSR 2005 i9C). The exposure was performed by i-line, and at a wavelength of 365 nm, exposure was performed with an exposure energy of 400 mJ / cm ² .

After heating the exposed photosensitive resin composition layer in a nitrogen atmosphere at 250 ° C. for 3 hours, the exposed photosensitive resin composition layer was scraped off, and thermal mass spectrometry was measured in nitrogen under conditions of a heating rate of 10 ° C./min. The pyrolysis temperature was measured and evaluated based on the following criteria.

A: 5% mass reduction temperature is 300 ° C or higher

B: 5% mass reduction temperature is less than 300 ° C

[Adhesiveness]

(Silicon wafer)

After filtering through a filter having a width of 0.8 µm, the micropores were filtered under pressure, and then applied by spinning on a silicon wafer. The silicon wafer to which the photosensitive resin composition was applied was dried on a hot plate at 100 ° C. for 5 minutes, and a polymer layer having a uniform thickness in Table 1 was formed on the silicon wafer. The photosensitive resin composition layer on the silicon wafer was exposed using a stepper (Nikon NSR 2005 i9C). The exposure was performed by i-line, and at a wavelength of 365 nm, exposure was performed with an exposure energy of 400 mJ / cm ² .

After the exposed photosensitive resin composition was heated at 250 ° C. for 3 hours in a nitrogen atmosphere, the adhesive force between the 100 μm × 100 μm photosensitive resin composition layer and the silicon wafer was measured. For the adhesive force measurement, a bond tester (manufactured by XYZTEC) was applied to the silicon wafer in a horizontal direction to measure the maximum load at the time of peeling. The higher the value, the better the adhesiveness, and the preferable result.

A: 30N or more

B: 10N or more and less than 30N

C: less than 10N

(Cu-plated silicon wafer)

The above-described silicon wafer was changed to a silicon wafer on which the entire surface of the silicon wafer was copper-plated, and the adhesive force was measured in the same manner.

The higher the value, the better the adhesiveness, and the preferable result.

A: 30N or more

B: 10N or more and less than 30N

C: less than 10N

(Glass substrate)

The above-described silicon wafer was changed to a glass substrate, and adhesive force was measured in the same manner.

The higher the value, the better the adhesiveness, and the preferable result.

A: 30N or more

B: 10N or more and less than 30N

C: less than 10N

[Peeling defect]

Each photosensitive resin composition was applied by spinning on a silicon wafer. The silicon wafer to which the photosensitive resin composition was applied was dried on a hot plate at 100 ° C. for 5 minutes, and a photosensitive resin composition layer having a uniform thickness in Table 1 was formed on the silicon wafer. The photosensitive resin composition layer on the silicon wafer was exposed with an exposure energy of 400 mJ / cm ² using a stepper (Nikon NSR 2005 i9C), and the exposed photosensitive resin composition layer was developed with cyclopentane for 60 seconds, and the diameter was 10 μm. Formed a hole. Subsequently, the mixture was heated at 250 ° C for 3 hours under a nitrogen atmosphere. After cooling to room temperature, a copper plating treatment was performed, and a metal layer (copper thin film) having a thickness of 5 μm was formed on the surface of the photosensitive resin composition layer by vapor deposition, thereby forming laminate 1. To the copper thin film of the laminate 1, again using the same type of photosensitive resin composition, application of the photosensitive resin composition, exposure, development, and heating at 250 ° C. were repeated to obtain a laminate 2.

<Evaluation>

[Peeling defect evaluation]

(No heating treatment)

For each laminate 2, after heating at 80 ° C and cooling at -40 ° C 100 times every 30 minutes, each laminate 2 was 5 mm wide in the vertical direction with respect to the exposed photosensitive resin composition layer surface. Moreover, the part which the photosensitive resin composition layer and the photosensitive resin composition layer are contacting, and the part which the metal layer and the photosensitive resin composition layer are contacting are respectively cut out and the cross section is observed, and between the photosensitive resin composition layer / photosensitive resin composition layer and The presence or absence of peeling between the metal layers / photosensitive resin composition layers was confirmed. Specifically, it refers to the number of peels confirmed by confirming a sample having a width of 5 mm with an optical microscope. When there is no occurrence of peeling, it shows that it has excellent adhesiveness, and it becomes a preferable result.

A: No peeling occurred

B: 1 to 2 occurrences of peeling

C: 3 to 5 occurrences of peeling

D: 6 or more occurrences of peeling

[Table 2]

In the above table, the numerical value of the exposure latitude indicates exposure energy (unit: mJ / cm ² ).

<Other Examples>

The experiments were conducted in the same manner as in Examples 1 to 18, except that the film thickness of the photosensitive resin composition layer was 5 μm, and evaluation was conducted in the same way.

The photosensitive resin composition layer using the photosensitive resin composition which made solid content concentration into 10 mass% and 60 mass%, respectively, without changing the ratio of each component other than the solvent of each composition of Examples 2, 3, 12, 14 and 18 Formed. Although the film thickness of the photosensitive resin composition layer after exposure changed, it confirmed that the favorable photosensitive resin composition layer was obtained like Example 2, 3, 12, 16, and 18, respectively.

The photosensitive resin which increased the solvent so that the compounding quantity of (B) urethane (meth) acrylate of Example 1 was 3.2 mass% with respect to (A) resin, and (B) urethane (meth) acrylate was reduced. The composition was prepared to form a photosensitive resin composition layer. Similarly, it was confirmed that a good photosensitive resin composition layer was obtained.

The photosensitive resin which reduced the solvent so that the compounding quantity of (B) urethane (meth) acrylate of Example 1 was 9.6 mass% with respect to (A) resin, and (B) urethane (meth) acrylate increased. The composition was prepared to form a photosensitive resin composition layer. Similarly, it was confirmed that a good photosensitive resin composition layer was obtained.

<Example 100>

The photosensitive resin composition of Example 1 was subjected to pressure filtration through a filter having a micropore width of 1.0 μm, followed by spin coating (3500 rpm, 30 seconds) on the surface of the resin substrate on which a thin copper layer was formed. The photosensitive resin composition applied to the resin substrate was dried at 100 ° C for 2 minutes, and then exposed using a stepper (manufactured by Nikon, NSR1505i6). The exposure was exposed through a mask at a wavelength of 365 nm and an exposure amount of 200 mJ / cm ² . After exposure, baking was performed, and development was performed with cyclopentanone for 30 seconds, followed by rinsing with PGMEA (propylene glycol 1 -monomethyl ether 2-acetate) for 20 seconds to obtain a pattern.

Next, heating was performed at 230 ° C for 3 hours to form an interlayer insulating film for the redistribution layer. This interlayer insulating film for redistribution layer was excellent in insulating properties.

100: semiconductor device
101a ~ 101d: semiconductor device
101: laminate
102b ~ 102d: through electrode
103a ~ 103e: Metal bump
105: redistribution layer
110, 110a, 110b: under layer
115: insulating layer
120: wiring board
120a: surface electrode

Claims (23)

A polyimide precursor and at least one resin among polyimides,
Contains at least one of urea (meth) acrylate,
The urethane (meth) acrylate includes at least one of a partial structure represented by formula (A) and a partial structure represented by formula (B) in one molecule, and 4 to 15 (meth) acrylate groups, Has a phosphorus structure,
A photosensitive resin composition in which the polyimide precursor contains a repeating unit represented by the following formula (2);

However, * in the formula is a connecting hand.
Equation (2)

In Formula (2), A ¹ and A ² each independently represent an oxygen atom or NH, and R ¹¹¹ is represented by -Ar-L-Ar- or the following Formula (51) or Formula (61) , Ar are each independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO _2- , or -NHCO- Or a combination of two or more of the above, R ¹¹⁵ represents a tetravalent organic group containing an aromatic ring, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group. However, at least one of R ¹¹³ and R ¹¹⁴ represents a group represented by the following formula (III).
Expression (51)

In formula (51), R ¹⁰ to R ¹⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ¹⁰ to R ¹⁷ is a fluorine atom, a methyl group, a fluoromethyl group, or a difluoromethyl group Or a trifluoromethyl group;
Expression (61)

In formula (61), R ¹⁸ and R ¹⁹ are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group.

In formula (III), R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethylene group. The method according to claim 1,
The urethane (meth) acrylate has a partial structure represented by formula (A) in one molecule, 4 to 15 (meth) acrylate groups, and a photosensitive resin composition having a urethane structure. The method according to claim 1 or claim 2,
A photosensitive resin composition in which the resin is a polyimide precursor. delete delete delete The method according to claim 1 or claim 2,
In the formula (2), R ¹¹¹ is represented by -Ar-L-Ar-, a photosensitive resin composition. The method according to claim 1 or claim 2,
In said Formula (2), R ¹¹¹ is said Formula (51) or Formula (61), The photosensitive resin composition. The method according to claim 1 or claim 2,
A photosensitive resin composition further comprising a migration inhibitor. The method according to claim 1 or claim 2,
A photosensitive resin composition further comprising a polymerization inhibitor. The method according to claim 1 or claim 2,
A photosensitive resin composition further comprising a photoradical polymerization initiator. The method according to claim 11,
The photosensitive resin composition whose photoradical polymerization initiator is an oxime compound. The method according to claim 1 or claim 2,
A photosensitive resin composition for an interlayer insulating film for a redistribution layer. A cured film obtained by curing the photosensitive resin composition according to claim 1 or 2. A laminate having two or more layers of the cured film according to claim 14. The method according to claim 15,
A laminate having a metal layer between the cured films. The manufacturing method of the cured film containing using the photosensitive resin composition of Claim 1 or Claim 2. The method according to claim 17,
A step of forming a photosensitive resin composition layer by applying the photosensitive resin composition to a substrate to form a layer;
An exposure process for exposing the photosensitive resin composition layer,
The manufacturing method of the cured film which has the process of developing process about the said exposed photosensitive resin composition layer. The method according to claim 18,
A method for producing a cured film, wherein the developing treatment is a negative developing treatment. The method according to claim 18,
After the developing treatment step, a method of manufacturing a cured film comprising the step of heating the developed photosensitive resin composition layer at a temperature of 50 to 500 ° C. The method according to claim 17,
The manufacturing method of the cured film whose film thickness of the said cured film is 1-30 micrometers. According to the method for producing a cured film according to claim 18, after the cured film is formed, the photosensitive resin composition layer forming step, the exposure step, and the developing treatment step are repeated 2 to 5 times in the above order. Manufacturing method. A semiconductor device having the cured film according to claim 14.

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