TWI704418B - Negative photosensitive resin composition, cured film, cured film manufacturing method, and semiconductor element - Google Patents

Abstract

The present invention provides a negative photosensitive resin composition with a wide exposure latitude, a cured film, a method for manufacturing a cured film, and a semiconductor element. A negative photosensitive resin composition comprising: a polyimide precursor having a repeating unit represented by the following general formula (1), and a photoradical polymerization initiator; in the general formula (1), A ¹ and A ² each independently represent an oxygen atom or -NH-, R ¹¹ is a divalent linking group having a group represented by -(LO-) _n1 -in the main chain, and L is an alkylene group or -Si (R) ₂ -, R is a monovalent organic group, n1 is an integer of 2 or more, R ¹² is a tetravalent organic group, and R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a monovalent organic group. General formula (1)

Description

Negative photosensitive resin composition, cured film, cured film manufacturing method, and semiconductor element

The present invention relates to a negative photosensitive resin composition, a cured film, a method for manufacturing a cured film, and a semiconductor element. In particular, it relates to a negative photosensitive resin composition suitable for an interlayer insulating film for a rewiring layer.

The thermosetting resin that undergoes cyclization of polyimide and the like and is cured is excellent in heat resistance and insulating properties, so it is used for insulating layers of semiconductor elements and the like.

In addition, polyimine has low solubility in solvents, so it is used as a precursor (heterocyclic-containing polymer precursor) before the cyclization reaction. After being applied to a substrate, etc., it is heated and contains impurities. The polymer precursor of the ring is cyclized to form a cured film.

As a photosensitive resin composition using such a polyimide precursor, Patent Document 1 discloses the following negative photosensitive resin composition, which includes: (A) having the following general formula (1): [化1]

(In formula (1), X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n is an integer from 2 to 150, R ₁ and R ₂ are each independently a hydrogen atom, and are represented by the following general formula (2):

(In the formula, R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or an organic group with 1 to 3 carbons, and m is an integer of 2 to 10) represented by a monovalent organic group, or a carbon number of 1 ~4 saturated aliphatic group; among them, there is no case where both of R ₁ and R ₂ are hydrogen atoms at the same time) Polyimide precursor of the structure represented by: 100 parts by mass; (B) photopolymerization start Agent: 1 part by mass to 20 parts by mass; and (C) a monocarboxylic acid compound with 2 to 30 carbons having one or more functional groups selected from the group consisting of hydroxyl, ether and ester groups: 0.01 mass Parts ~ 10 parts by mass.

Patent Document 2 discloses the following positive photosensitive resin composition comprising: (a) having a structural unit represented by the following general formula (1) and having the following general formula (1) The polyimide resin of the structural unit represented by the formula (2), and (b) the quinonediazide compound; the positive photosensitive resin composition is characterized in that: the (a) has the following general formula (1) The polyimide resin of the structural unit represented by the structural unit and the structural unit represented by the following general formula (2) has an imidization rate of 85% or more, and is represented by the following general formula (1) The ratio of the structural unit to the structural unit represented by the following general formula (2) is in the range of 30:70 to 90:10.

(In the general formula (1), X ₁ represents a tetracarboxylic acid residue having 1 to 4 aromatic rings, and Y ₁ represents an aromatic diamine residue having 1 to 4 aromatic rings)

(In the general formula (2), X ₂ represents a tetracarboxylic acid residue having 1 to 4 aromatic rings, and Y ₂ represents a diamine residue having at least two alkanediol units in the main chain)

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2011-191749

[Patent Document 2] International Publication WO2014/050558 Publication

Here, when it is used for an interlayer insulating film for a rewiring layer of a semiconductor, etc., a negative photosensitive resin composition with a wide analytical suitable exposure range, that is, a negative photosensitive resin composition with a wide exposure latitude, is required. However, all the photosensitive resin compositions described in Patent Document 1 and Patent Document 2 have a narrow exposure latitude.

The present invention has been made for the purpose of solving the above-mentioned problems, and the object is to provide a negative photosensitive resin composition, a cured film, a cured film manufacturing method, and a semiconductor element with a wide exposure latitude.

Based on the above-mentioned problems, the inventors conducted studies and found that by using a polyimide precursor having a predetermined structure in the negative photosensitive resin composition, the exposure tolerance of the negative photosensitive resin composition can be improved. Broadened, thus solving the problem. Specifically, the problem is solved by the following <1>, preferably by <2> to <15>.

<1> A negative photosensitive resin composition comprising: a polyimide precursor having a repeating unit represented by the following general formula (1), and a photoradical polymerization initiator; general formula (1) )

In the general formula (1), A ¹ and A ² each independently represent an oxygen atom or -NH-, R ¹¹ is a divalent linking group having a group represented by -(LO-) _n1 -in the main chain, and L It is an alkylene group or -Si(R) ₂ -, R is a hydrogen atom or a monovalent organic group, n1 is an integer of 2 or more, R ¹² represents a tetravalent organic group, R ¹³ and R ¹⁴ each independently represent hydrogen Atom or monovalent organic group.

<2> The negative photosensitive resin composition according to <1>, wherein in the general formula (1), R ^{11 is} selected from the structure represented by the following general formula (2), and is represented by the following general formula ( 3) In the structure represented and the structure represented by the following general formula (4);

In the general formula (2), R ²¹ and R ²² each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbons. A plurality of R ²¹ may be the same or different; n2 is an integer of 2 or more; * represents the same as the general formula (1) The -NH- link site;

In the general formula (3), R ³¹ and R ³² each independently represent a hydrogen atom or a monovalent organic group, L ³¹ represents a single bond or a divalent organic group, and L ³² and L ³³ each independently represent a divalent organic group. Base, n3 is an integer greater than or equal to 2; * represents the site connected to -NH- of the general formula (1);

In the general formula (4), R ⁴¹ and R ⁴² each independently represent a hydrogen atom or a monovalent organic group, L ⁴¹ represents a single bond or a divalent organic group, and L ⁴² and L ⁴³ each independently represent a divalent organic group. The group, n4 is an integer of 2 or more; * represents a site connected to -NH- of the general formula (1).

<3> The negative photosensitive resin composition according to <1> or <2>, wherein at least one of R ¹³ and R ¹⁴ in the general formula (1) includes a radical polymerizable group.

<4> The negative photosensitive resin composition according to any one of <1> to <3>, which further contains a radically polymerizable compound.

<5> The negative photosensitive resin composition according to <4>, wherein the radically polymerizable compound is a compound that is bifunctional or more.

<6> The negative photosensitive resin composition according to <4>, wherein the radically polymerizable compound is a bifunctional compound.

<7> The negative photosensitive resin composition according to any one of <1> to <6>, wherein R ¹² in the general formula (1) is a tetravalent organic group containing an aromatic ring.

<8> The negative photosensitive resin composition according to any one of <1> to <7>, wherein n1 in the general formula (1) is an integer of 2 to 200.

<9> The negative photosensitive resin composition according to any one of <1> to <8>, which is used for an interlayer insulating film for a rewiring layer.

<10> A cured film obtained by curing the negative photosensitive resin composition according to any one of <1> to <9>.

<11> The cured film according to <10>, which is an interlayer insulating film for a rewiring layer.

<12> A method of manufacturing a cured film, comprising: using the negative photosensitive resin composition as described in any one of <1> to <9>.

<13> The method of manufacturing a cured film as described in <12>, including: applying the negative photosensitive resin composition to a substrate; corresponding to the negative photosensitive resin composition used on the substrate The step of irradiating actinic rays or radiation to expose the object; and the step of developing the exposed negative photosensitive resin composition Sudden.

<14> The method for producing a cured film as described in <13>, which further includes performing the developed negative photosensitive resin composition at a temperature of 50°C to 500°C after the step of performing the development treatment. Heating step.

<15> A semiconductor element having the cured film as described in <10> or <11>, or the cured film produced by the method as described in any one of <12> to <14>.

According to the present invention, it is possible to provide a negative photosensitive resin composition with a wide exposure latitude, a cured film, a method for manufacturing a cured film, and a semiconductor element.

100: Semiconductor components

101: layered body

101a~101d: Semiconductor devices (semiconductor wafers)

102b~102d: Through electrode

103a~103e: Metal bump

105: redistribution layer

110, 110a, 110b: underfill layer

115: insulating layer

120: Wiring board

120a: Surface electrode

FIG. 1 is a schematic diagram showing the structure of an embodiment of a semiconductor element.

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

In the expression of the group (atomic group) in this specification, the expression that does not describe substituted and unsubstituted includes a group (atomic group) not having a substituent, and also includes a group (atomic group) having a substituent. For example, the term "alkyl" includes not only an unsubstituted alkyl group (unsubstituted alkyl group) but also a substituted alkyl group (substituted alkyl group).

In this specification, "actinic rays" refer to, for example, the bright-ray spectrum of a mercury lamp, extreme ultraviolet rays represented by excimer lasers, extreme ultraviolet light (Extreme Ultraviolet (EUV) light), X-rays, electron beams, etc. . In addition, in the present invention, light means actinic rays or radiation. Unless otherwise specified, the "exposure" in this manual includes not only exposure using mercury lamps, extreme ultraviolet light such as excimer lasers, X-rays, EUV light, etc., but also particle beams such as electron beams and ion beams. The depiction of is also included in the exposure.

In this manual, the numerical range indicated by "~" refers to the range that includes the numerical values described before and after "~" as the lower limit and the upper limit.

In this specification, "(meth)acrylate" means either or both of "acrylate" and "methacrylate", and "(meth)allyl" means "allyl" and Both or either of "methallyl", "(meth)acrylic" means both or either of "acrylic" and "methacrylic", "(meth)acrylic "Means both or either of "acryloyl" and "methacryloyl".

In this specification, the term "step" not only refers to an independent step, even when it cannot be clearly distinguished from other steps, as long as the step achieves the expected effect, it is also included in this term.

In this specification, the solid content concentration refers to the mass percentage of the mass of other components other than the solvent relative to the total mass of the composition. In addition, unless otherwise stated, the solid content concentration means the concentration at 25°C.

In this specification, as long as there is no special description, the weight average molecular weight (Mw) and number average molecular weight (Mn) are used as the method by gel permeation chromatography (Gel Permeation Chromatography, GPC) measured by polystyrene conversion value. In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) can be used, for example, by using HLC-8220 (manufactured by Tosoh (Co., Ltd.)) and protecting the column HZ-L, TSKgel Super HZM -M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Co., Ltd.) were used as a column to determine. As long as there is no special description, the eluent shall be one that has been measured using tetrahydrofuran (THF). In addition, as long as there is no special description, the detection result shall be obtained by using an ultraviolet (UV (ultraviolet)) 254 nm detector.

Negative photosensitive resin composition

The negative photosensitive resin composition of the present invention includes a polyimide precursor having a repeating unit represented by the following general formula (1), and a photoradical polymerization initiator.

In the general formula (1), A ¹ and A ² each independently represent an oxygen atom or -NH-, R ¹¹ is a divalent linking group having a group represented by -(LO-) _n1 -in the main chain, and L It is an alkylene group or -Si(R) ₂ -, R is a hydrogen atom or a monovalent organic group, n1 is an integer of 2 or more, R ¹² represents a tetravalent organic group, R ¹³ and R ¹⁴ each independently represent hydrogen Atom or monovalent organic group.

In the present invention, by incorporating a soft structure into the R ¹¹ portion, the exposure latitude can be enlarged. The mechanism is not certain, but it is speculated that by incorporating a soft structure, the solubility can be improved.

In addition, in the present invention, the exposure latitude can be expanded while suppressing warpage. In addition, in the present invention, the exposure latitude can be enlarged, and the adhesion to the substrate can be improved. Furthermore, not only these effects can be achieved, but heat resistance can also be maintained.

Hereinafter, the details of the present invention will be described.

<Polyimide precursor>

The negative photosensitive resin composition of the present invention includes a polyimide precursor having a repeating unit represented by the general formula (1) (hereinafter, it may be referred to as a "specific polyimine precursor"). The specific polyimide precursor may have only one type of repeating unit represented by the general formula (1), or may have two or more types. In addition, the negative photosensitive resin composition of the present invention may include only one type of specific polyimide precursor, or may include two or more types. Furthermore, the negative photosensitive resin composition of this invention may contain the other repeating unit which is an imine precursor other than the repeating unit represented by general formula (1).

<<Repeating unit represented by general formula (1)>>

In the general formula (1), A ¹ and A ² each independently represent an oxygen atom or -NH-, and preferably an oxygen atom.

R ¹¹ is a divalent linking group having a group represented by -(LO-) _n1 -in the main chain, L is an alkylene group or -Si(R) ₂ -, and R is a hydrogen atom or a monovalent organic group , N1 is an integer of 2 or more.

When L is an alkylene group, the alkylene group may be any of linear, branched, and cyclic alkylene groups, and is preferably a linear alkylene group or a branched alkylene group. The carbon number of the alkylene group is preferably 1-22, more preferably 2-16, still more preferably 2-8, particularly preferably 2-4.

When L is -Si(R) ₂ -, R is a hydrogen atom or a monovalent organic group, preferably a monovalent organic group, as a monovalent organic group, preferably an alkyl group, an aryl group, or an alkoxy group Alkyl and alkenyl are more preferably alkyl and aryl. As the alkyl group, a linear alkyl group is preferred. The carbon number of the alkyl group is preferably from 1 to 20, more preferably from 1 to 10, even more preferably from 1 to 5, and particularly preferably from 1 to 3. The aryl group is preferably a phenyl group.

n1 is an integer of 2 or more, preferably an integer of 2 to 200, more preferably an integer of 4 to 200, and even more preferably an integer of 4 to 60.

L may include only one type in one R ¹¹ or two or more types.

R ¹¹ preferably includes only a group represented by -(LO-) _n1 -, or a group represented by -(LO-) _n1 -and an alkylene group. As the alkylene group here, a linear or branched alkylene group having 1 to 10 carbon atoms can be cited.

In the general formula (1), R ^{11 is} preferably selected from the structure represented by the general formula (2), the structure represented by the general formula (3), and the structure represented by the general formula (4), and more preferably It is the structure represented by the general formula (2).

General formula (2) [化 10]

In the general formula (2), R ²¹ and R ²² each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbons. A plurality of R ²¹ may be the same or different; n2 is an integer of 2 or more; * represents the same as the general formula (1) The -NH- linking site.

In the general formula (3), R ³¹ and R ³² each independently represent a hydrogen atom or a monovalent organic group, L ³¹ represents a single bond or a divalent organic group, and L ³² and L ³³ each independently represent a divalent organic group. The group, n3 is an integer of 2 or more; * represents a site connected to -NH- of the general formula (1).

In the general formula (4), R ⁴¹ and R ⁴² each independently represent a hydrogen atom or a monovalent organic group, L ⁴¹ represents a single bond or a divalent organic group, and L ⁴² and L ⁴³ each independently represent a divalent organic group. The group, n4 is an integer of 2 or more; * represents a site connected to -NH- of the general formula (1).

In the general formula (2), R ²¹ and R ²² each independently represent a hydrogen atom or a C 1-20 alkyl group, preferably a hydrogen atom or a C 1-10 linear alkyl group, more preferably a hydrogen atom Or a linear alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a linear alkyl group having 1 to 3 carbon atoms.

n2 is an integer of 2 or more, preferably an integer of 2 to 200, more preferably an integer of 4 to 200, and even more preferably an integer of 4 to 60.

In the general formula (3), R ³¹ and R ³² each independently represent a hydrogen atom or a monovalent organic group, preferably a monovalent organic group, more preferably an alkyl group, an aryl group, an alkoxy group, or an alkenyl group, Particularly preferred are alkyl and aryl groups. As the alkyl group, a linear alkyl group is preferred. The carbon number of the alkyl group is preferably from 1 to 20, more preferably from 1 to 10, even more preferably from 1 to 5, and particularly preferably from 1 to 3. The aryl group is preferably a phenyl group.

L ³¹ represents a single bond or a divalent organic group, preferably a single bond or an alkylene group, more preferably a single bond. Examples of the alkylene group include linear or branched alkylene groups having 1 to 10 carbon atoms.

L ³² and L ³³ each independently represent a divalent organic group, preferably an alkylene group, more preferably a linear or branched alkylene group having 1 to 10 carbon atoms.

n3 is an integer of 2 or more, preferably an integer of 2 to 200, more preferably an integer of 4 to 200, and even more preferably an integer of 4 to 60.

In the general formula (4), R ⁴¹ and R ⁴² each independently represent a hydrogen atom or a monovalent organic group, preferably a monovalent organic group, more preferably an alkyl group, an aryl group, an alkoxy group, or an alkenyl group, Particularly preferred are alkyl and aryl groups. As the alkyl group, a linear alkyl group is preferred. The carbon number of the alkyl group is preferably from 1 to 20, more preferably from 1 to 10, even more preferably from 1 to 5, and particularly preferably from 1 to 3. The aryl group is preferably a phenyl group. The plurality of R ⁴¹ and R ⁴² contained in one molecule may be the same or different.

L ⁴¹ represents a single bond or a divalent organic group, preferably a single bond or an alkylene group, more preferably a single bond. Examples of the alkylene group include linear or branched alkylene groups having 1 to 10 carbon atoms.

L ⁴² and L ⁴³ each independently represent a divalent organic group, preferably an alkylene group, and more preferably a linear or branched alkylene group having 1 to 10 carbon atoms.

n4 is an integer of 2 or more, preferably an integer of 2 to 200, more preferably an integer of 4 to 200, and even more preferably an integer of 4 to 60.

Preferred examples of the structure represented by the general formula (2), the structure represented by the general formula (3), and the structure represented by the general formula (4) are shown below, but the present invention is of course not limited to these Preferred example.

[化13]

In the above, x, y, z, n, and m are arbitrary numbers and represent the molar ratio of each repeating unit. Preferably, x is an integer from 2 to 200, y is an integer from 2 to 200, z is an integer from 2 to 200, n is an integer from 2 to 200, and m is an integer from 2 to 200.

In addition, R ^{11 is} also preferably a diamine residue remaining after removal of the amine group of a diamine containing two or more of ethylene glycol chains and propylene glycol chains or both in total in one molecule, More preferably, diamine residues that do not contain an aromatic ring may also be cited. Examples include: Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D- 2000, D-4000 (the above are trade names, manufactured by Huntsman (Stock)); 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propane- 2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propane-2-amine, etc., but not limited to these. The following shows the structure of Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, and a total of two or more propylene glycol contained in the molecule Specific examples of chain diamines.

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

In addition, R ^{11 is} also preferably a diamine residue containing three or more divalent linking chains having silicon atoms. As a diamine residue containing three or more divalent linking chains which have a silicon atom, the diamine residue of the diamine represented by the following general formula (5) can be illustrated.

In the general formula (5), R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent organic group, L ⁵¹ represents a single bond or a divalent organic group, and L ⁵² and L ⁵³ each independently represent a divalent organic group. The group, n4 is an integer of 2 or more; * represents a site connected to -NH- of the general formula (1).

R ⁵¹ and R ⁵² each independently include methyl, ethyl, propyl, butyl, phenyl and the like. From the viewpoint of raw material availability, L ^{51 is} preferably a single bond. Examples of L ⁵² and L ⁵³ include optionally substituted methylene, ethylene, butyl, and phenyl groups.

n4 is preferably an integer of 2 to 200, more preferably an integer of 4 to 100, and even more preferably an integer of 4 to 60.

As an example, one can cite: two-terminal amine modified methyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.: KF-8010, X-22-161A, X-22-161B, KF-8012, KF-8008; Chisso) Manufacturing: Silaplane FM-3311, Silaplane FM-3321, Silaplane FM-3325), and both-terminal amine modified phenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.: X22-1660B-3, X-22-9409).

In the general formula (1), R ¹² represents a tetravalent organic group, preferably a tetravalent group containing an aromatic ring, and more preferably represented by the following general formula (1-1) or general formula (1-2) Represents the base.

In the general formula (1-1), R ^{112 is} preferably a single bond, or is selected from a hydrocarbon group having 1 to 10 carbons which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO _2- , And -NHCO-, and the group in the combination of these, more preferably a single bond, or selected from alkylene groups with 1 to 3 carbons, -O-, -CO-, -S which may be substituted by fluorine atoms The divalent groups in-and -SO ₂ -are more preferably selected from -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, A divalent group in the group consisting of -S- and -SO ₂ -.

Examples of R ¹² include a tetracarboxylic acid residue remaining after removing an anhydride group from tetracarboxylic dianhydride.

Specifically, the tetracarboxylic acid residue etc. which remain after removing an anhydride group from the following tetracarboxylic dianhydride are mentioned.

Selected from Pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic acid Dianhydride, 3,3',4,4'-diphenyl tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4, 4'-Diphenylmethanetetracarboxylic dianhydride, 2,2',3,3'-Diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-Biphenyltetracarboxylic dianhydride , 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride , 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2- Bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexa Fluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2', 3,3'-Diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5, 8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrene tetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis( 3,4-Dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and these alkyl groups with 1 to 6 carbons and alkoxy with 1 to 6 carbons At least one tetracarboxylic dianhydride in the group derivative.

In addition, the tetracarboxylic acid residue remaining after removing the anhydride group from the tetracarboxylic dianhydride (DAA-1) to the tetracarboxylic dianhydride (DAA-5) shown below can also be cited as an example of R ¹² .

From the viewpoint of solubility with respect to an alkaline developer, R ¹² preferably has an OH group. More specifically, as R ¹² , the tetracarboxylic acid residue remaining after removing the anhydride group from the above-mentioned (DAA-1) to (DAA-5) can be cited as a preferable example.

In the general formula (1), R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a monovalent organic group.

As the monovalent organic group represented by R ¹³ and R ¹⁴ , it is preferable to use a substituent that improves the solubility to the developer.

From the viewpoint of solubility with respect to the aqueous developer, R ¹³ and R ^{14 are} preferably hydrogen atoms or monovalent organic groups. Examples of the monovalent organic group include an aryl group, an aralkyl group, and the like having one, two, or three carbon atoms bonded to the aryl group, preferably one acidic group. Specifically, an aryl group having 6 to 20 carbon atoms and an aralkyl group having 7 to 25 carbon atoms having an acidic group can be mentioned. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group can be mentioned. The acidic group is preferably an OH group.

In terms of solubility to an aqueous developer, R ¹³ and R ¹⁴ are preferably hydrogen atoms, 2-hydroxybenzyl, 3-hydroxybenzyl, and 4-hydroxybenzyl.

From the viewpoint of solubility in an organic solvent, R ¹³ and R ^{14 are} preferably monovalent organic groups. The monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, and an aryl group, and more preferably an aryl group substituted alkyl group.

The carbon number of the alkyl group is preferably 1-30. The alkyl group may be any of linear, branched, and cyclic. Examples of linear or branched alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, Octadecyl, isopropyl, isobutyl, second butyl, tertiary butyl, 1-ethylpentyl, and 2-ethylhexyl. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic cyclic alkyl groups include adamantyl, norbornyl, bornyl, camphenyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, and camphenyl , Dicyclohexyl and pinenyl. Among them, from the viewpoint of coexistence with high sensitivity, cyclohexyl is most preferable. In addition, as the alkyl group substituted with an aryl group, a linear alkyl group substituted with an aryl group described later is preferred.

環、三伸苯環、茀環、聯苯環、吡咯環、呋喃環、噻吩環、咪唑環、噁唑環、噻唑環、吡啶環、吡嗪環、嘧啶環、噠嗪環、吲哚嗪環、吲哚環、苯并呋喃環、苯并噻吩環、異苯并呋喃環、喹嗪環、喹啉環、酞嗪環、萘啶環、喹噁啉環、喹噁唑啉環、異喹啉環、咔唑環、啡啶環、吖啶環、啡啉環、噻蒽環、苯并吡喃環、呫噸環、啡噁噻環、啡噻嗪環或啡嗪環。最佳為苯環。 As the aryl group, specifically: substituted or unsubstituted benzene ring, naphthalene ring, pentene ring, indene ring, azulene ring, heptene ring, indenene ring, perylene ring, fused pentabenzene ring, Ethane and naphthalene (acenaphthene) ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring,

Ring, terphenylene ring, pyridine ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indoleazine Ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinazine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, iso Quinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thiaxanthene ring, benzopyran ring, xanthene ring, phenoxathi ring, phenanthrazine ring or phenanthrazine ring. The best is a benzene ring.

Examples of the polymerizable group possessed by R ¹³ and R ¹⁴ include epoxy groups, oxetanyl groups, groups having ethylenically unsaturated bonds, blocked isocyanate groups, alkoxymethyl groups, methylol groups, Amine group and so on.

As a preferable embodiment of R ¹³ and R ¹⁴ in the present invention, a form including a radical polymerizable group can be exemplified, and a group having an ethylenically unsaturated bond is more preferable. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, a group represented by the following formula (III), and the like.

In formula (III), R ²⁰⁰ represents hydrogen or methyl, more preferably methyl.

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

Examples of suitable R ²⁰¹ include: ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene Group, octamethylene, dodecamethylene, -CH ₂ CH(OH)CH ₂ -, more preferably ethylene, propylene, trimethylene, -CH ₂ CH(OH)CH ₂ -.

Particularly preferably, R ²⁰⁰ is methyl and R ²⁰¹ is ethylene.

When R ¹³ and R ¹⁴ in the general formula (1) contain a polymerizable group (preferably a radical polymerizable group), the molar ratio of the polymerizable group: the non-polymerizable group is preferably 100:0 to 5:95 , More preferably 100:0~20:80, and even more preferably 100:0~50:50.

In the general formula (1), when A ² is an oxygen atom and R ¹³ is a hydrogen atom, or/and A ¹ is an oxygen atom and R ¹⁴ is a hydrogen atom, it may also be combined with a tertiary ethylenically unsaturated bond. Amine compounds form counter salts. As an example of such a tertiary amine compound having an ethylenically unsaturated bond, N,N-dimethylaminopropyl methacrylate can be cited.

In addition, in the case of alkali development, it is preferable that the specific polyimide precursor has a fluorine atom in the structural unit in terms of improving the resolution. The fluorine atoms can impart water repellency to the surface of the film during alkali development, thereby suppressing permeation from the surface. The content of fluorine atoms in the specific polyimide precursor is preferably 10% by mass or more, and in terms of solubility in an alkaline aqueous solution, it is preferably 20% by mass or less.

In addition, for the purpose of improving the adhesion to the substrate, the specific polyimide precursor may also copolymerize an aliphatic group having a siloxane structure. Specifically, examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

In addition, in order to improve the storage stability of the negative photosensitive resin composition, the specific polyimide precursor preferably uses a blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monochlorine compound, and a monoactive ester compound. The main chain ends are closed. Among these, it is more preferable to use monoamine. Preferred compounds of monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-amine Naphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-amine Naphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-amine Naphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid Acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6 - Dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these can be used, and multiple different end groups can also be introduced by reacting multiple end-capping agents.

<<Other repeating units>>

The specific polyimide precursor may include repeating units other than the repeating unit represented by the general formula (1) (hereinafter, sometimes referred to as "other repeating unit"). As other repeating units, it is preferable that in the general formula (1), R ¹¹ is a divalent organic group other than a divalent linking group having a group represented by -(LO-) _n1 -in the main chain (Hereinafter, it may be referred to as R ¹¹¹ ) repeating unit. That is, it is preferable that in the general formula (1), R ¹¹ is a group substituted with R ¹¹¹ described later.

As the divalent organic group of R ¹¹¹ , a group including a linear or branched aliphatic group, a cyclic aliphatic group, and an aryl group can be exemplified, and it is preferably a linear or branched aliphatic group having 2 to 20 carbon atoms. A group, a cyclic aliphatic group with 6 to 20 carbons, an aryl group with 6 to 20 carbons, or a group containing these combinations, more preferably an aryl group with 6 to 20 carbons. As an example of an aryl group, the following can be mentioned.

In the formula, A is preferably a single bond, or is selected from a hydrocarbon group with 1 to 10 carbons which can be substituted by a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) ₂ The group in -, -NHCO-, and combinations of these is more preferably a single bond, or is selected from alkylene groups having 1 to 3 carbons which may be substituted with fluorine atoms, -O-, -C(=O )-, -S-, -SO ₂ -, and more preferably selected from -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -, and- The divalent group in C(CH ₃ ) ₂ -.

In addition, the specific polyimide precursor may include a structure in which R ^{11 of the} general formula (1) is set to another repeating unit as listed below.

Using a part of the divalent organic group as R ¹¹ can also be in a position, after removal of the amine include diamine diamine residue remaining. As the diamine, an aliphatic diamine, a cycloaliphatic diamine, an aromatic diamine, etc. are mentioned.

Specifically, the following diamine residues and the like remaining after the removal of the amine group of the diamine are mentioned.

Selected from 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane or 1,4-diamine Cyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane, Bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophorone Amine; m-phenylenediamine and p-phenylenediamine, diaminotoluene, 4,4'-diaminodiphenyl and 3,3'-diaminodiphenyl, 4,4'-diaminodiphenyl Ether and 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane Phenyl chloride and 3,3'-diaminodi Phenyl sulfide, 4,4'-diaminodiphenyl sulfide and 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone and 3,3'-diamine Benzophenone, 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)sulfonate, bis(4-amino) -3-Hydroxyphenyl) sulfide, 4,4'-diamino-p-terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy) Yl) phenyl] ash, bis[4-(3-aminophenoxy)phenyl] ash, bis[4-(2-aminophenoxy)phenyl] ash, 1,4-bis(4 -Aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenyl sulfide, 1,3- Bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4 -Aminophenoxy)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenyl Methane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-amine) (Phenoxy)phenyl)hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3 ',4,4'-tetraamino diphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diamino Biphenyl, 9,9'-bis(4-aminophenyl) sulfide, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfide, 3,3',5,5' -Tetramethyl-4,4'-diaminodiphenylmethane, 2,4-diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine , Acetguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyl Disiloxane, 2,7-diaminopyridine, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzaniline, diaminopyridine Esters of benzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane , 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-amine Benzylphenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminobenzene) Oxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl] Hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4 ,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfide , 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfide, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy) Phenyl) hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis( At least one diamine among trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolidine, and 4,4'-diaminotetrabiphenyl.

In addition, the diamine residue remaining after the amine group of the diamine (DA-1) to the diamine (DA-18) shown below is removed can also be cited as an example of R ¹¹¹ .

[化21]

[化22]

R ^{111 is} preferably a diamine residue remaining after the amine group of the following diamine is removed.

Selected from 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane or 1,4-diamine Cyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane, Bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane; m-phenylenediamine and p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl and 3,3'-diaminodiphenyl, 4,4'-diaminodiphenyl ether and 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane Ketones and 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-di Amino biphenyl, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxyl -4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoro Propane, bis(3-amino-4-hydroxyphenyl) sulfide, bis(4-amino-3-hydroxyphenyl) sulfide, bis(3-aminopropyl) tetramethyldisiloxane, 4 ,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl; said (DA-7), (DA-8), (DA-12), (DA-13); At least one diamine among diamines having at least two alkanediol units in the main chain.

R ^{111 is more} preferably a diamine residue remaining after the amine group of the following diamine is removed.

Selected from p-phenylenediamine, 4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfonate, bis(3-aminopropyl)tetramethyldisil Oxane, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl; said (DA-7), (DA-8), (DA-12), (DA-13); Jeffamine (registered trademark) KH-511, ED-600, ED-900, EDR-148, EDR-176, D-200, D-400, D-2000 (the above are trade names, Huntsman (Stock) Manufacturing); 1-(2-(2-(2-Aminopropoxy)ethoxy)propoxy)propane-2-amine, 1-(1-(1-(2-amino) Propoxy)propane-2-yl)oxy)propane-2-amine, 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propane-2-amine Of at least one diamine.

Regarding the repeating units other than the repeating unit represented by the general formula (1), in the general formula (1), the part excluding R ¹¹ being R ¹¹¹ is the same as A ¹ , A ² in the general formula (1) , R ¹² , R ¹³ and R ^{14 have} the same meaning, and the preferred ranges are also the same. Furthermore, the particular polyimide precursor ^{in, A 1, A 2, R} 12, R 13 and R repeating unit represented by the general formula (1) is represented by ¹⁴ with other repeating units A ^1, A ^2. R ¹² , R ¹³ and R ¹⁴ may be the same or different.

When the specific polyimide precursor contains other repeating units, the content of the other repeating units is preferably 1 mol% to 60 mol%, more preferably 5 mol% to 50 mol%.

The weight average molecular weight (Mw) of the specific polyimide precursor is preferably 20,000-28,000, more preferably 22,000-27,000, and even more preferably 23,000-25,000.

The degree of dispersion (Mw/Mn) of the specific polyimide precursor is not particularly limited, but is preferably 1.0 or more, more preferably 2.5 or more, and still more preferably 2.8 or more. The upper limit of the degree of dispersion of the specific polyimide precursor is not particularly limited. For example, it is preferably 4.5 or less, and may be 3.4 or less.

The content of the specific polyimide precursor in the negative photosensitive resin composition of the present invention is preferably 20% by mass to 100% by mass, and more preferably 50% by mass, relative to the total solid content of the negative photosensitive resin composition. Mass% to 99% by mass, more preferably 70% to 99% by mass, and particularly preferably 80% to 99% by mass.

<<Other polyimide precursors>>

The negative photosensitive resin composition of the present invention may include other polyimide precursors other than the specific polyimide precursor. As other polyimide precursors, polyimide precursors that do not contain the repeating unit represented by the general formula (1), such as a polyimide precursor that only includes the other repeating unit, can be exemplified.

In addition, in the present invention, it may also be a configuration that does not substantially contain other polyimide precursors. The term "substantially free" means, for example, that the content of the other polyimide precursor contained in the negative photosensitive resin composition of the present invention is 3% by mass or less of the content of the specific polyimide precursor.

<Other resin components>

The negative photosensitive resin composition of the present invention may contain other resin components within a range that does not deviate from the gist of the present invention. Examples of other resin components include polybenzoxazole precursors and polyimide resins. In addition, in the present invention, it is also possible to have a configuration that does not substantially contain resins other than the polyimide precursor. The term "substantially free" means, for example, that the content of resins other than the polyimide precursor contained in the negative photosensitive resin composition of the present invention is 3% by mass or less of the content of the polyimide precursor.

<Photo radical polymerization initiator>

The negative photosensitive resin composition of the present invention contains a radical photopolymerization initiator. The photoradical polymerization initiator can perform negative-type development by initiating polymerization of the radical polymerizable group that the repeating unit represented by the general formula (1) may have, or the radical polymerizable compound described later. More specifically, after the negative photosensitive resin composition is applied to a semiconductor wafer or the like to form a layered composition layer, light is irradiated to produce curing caused by free radicals, and the light irradiated part The solubility decreases. Therefore, for example, by exposing the composition layer through a photomask having a pattern covering only the electrode portion, there is an advantage that regions with different solubility can be easily produced according to the electrode pattern.

The radical photopolymerization initiator is not particularly limited as long as it has the ability to initiate the polymerization reaction (crosslinking reaction) of radical polymerizable compounds and the like, and it can be appropriately selected from known photoradical polymerization initiators. . For example, those having sensitivity to light from the ultraviolet region to the visible region are preferable. In addition, it may be an active agent that produces a certain effect with a sensitizer excited by light to generate active free radicals.

The photo-radical polymerization initiator preferably contains at least one compound having a molecular absorption coefficient of at least about 50 in the range of about 300 nm to 800 nm (preferably 330 nm to 500 nm). The molecular absorption coefficient of the compound can be measured using a known method. For example, it is preferable to use an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian), and use an ethyl acetate solvent to measure at a concentration of 0.01 g/L.

As the photoradical polymerization initiator, known compounds can be used without limitation, and examples include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, those having a trihalomethyl group, etc.), Phosphine compounds such as phosphine oxide, Oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, Azide compounds, metallocene compounds, organoboron compounds, iron arene complexes, etc.

Examples of halogenated hydrocarbon derivatives having a triazine skeleton include compounds described in Wakabayashi et al., "Bull. Chem. Soc. Japan", 42, 2924 (1969), British Patent No. 1388492 The compound described in the specification, the compound described in Japanese Patent Laid-Open No. 53-133428, the compound described in the specification of German Patent No. 3337024, FC Schaefer et al. "J.Org.Chem .)", the compound described in 29,1527 (1964), the compound described in Japanese Patent Laid-Open No. 62-58241, the compound described in Japanese Patent Laid-Open No. 5-281728, the compound described in Japanese Patent Laid-Open No. 5-281728 The compound described in 34920 gazette, the compound described in the specification of U.S. Patent No. 4,212,976, and the like.

As the compound described in the specification of U.S. Patent No. 4212976, for example, compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2-tris Chloromethyl-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-tris Chloromethyl-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 Azole, 2-tribromomethyl-5-styryl-1,3,4-oxadiazole, etc.).

In addition, examples of photoradical polymerization initiators other than those described above include the compounds described in paragraph 0086 of Japanese Patent Laid-Open No. 2015-087611, and Japanese Patent Laid-Open No. 53-133428 and Japanese Patent The compounds described in the publication No. 57-1819, Japanese Patent Publication No. 57-6096, and the specification of U.S. Patent No. 3615455 are incorporated into this specification.

As the ketone compound, for example, the compound described in paragraph 0087 of JP-A-2015-087611 can be exemplified, and these contents are incorporated in this specification.

Among commercially available products, Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be suitably used.

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

As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-184 IRGACURE-127 (trade name: all manufactured by BASF).

As the aminoacetophenone-based initiator, commercially available products such as IRGACURE-907, IRGACURE-369, and IRGACURE-369 can be used. (IRGACURE)-784, and IRGACURE-379 (trade name: all manufactured by BASF). IRGACURE is a registered trademark.

As the aminoacetophenone-based initiator, the compound described in Japanese Patent Laid-Open No. 2009-191179 whose absorption wavelength matches a light source such as 365 nm or 405 nm can also be used.

As the phosphine-based initiator, commercially available products such as IRGACURE-819 or DAROCUR-TPO (brand name: both manufactured by BASF) can be used.

As the photoradical polymerization initiator, an oxime compound is more preferable. As specific examples of the oxime compound, the compound described in Japanese Patent Laid-Open No. 2001-233842, the compound described in Japanese Patent Laid-Open No. 2000-80068, and the compound described in Japanese Patent Laid-Open No. 2006-342166 can be used.

As a preferable oxime compound, for example, 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxy Iminobutan-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzyl Acetoxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino -1-Phenylpropan-1-one and so on.

Examples of oxime compounds include: "Journal of the British Chemical Society, JCSPerkin II" (1979) pp.1653-1660, "Journal of the British Chemical Society, Perkin II" (1979) Pp.156-162, and the compounds described in "Journal of Photopolymer Science and Technology" (1995) pp.202-232, and Japanese Patent Laid-Open No. 2000-66385, The compounds described in Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open No. 2004-534797, and Japanese Patent Laid-Open No. 2006-342166.

Among the commercially available products, IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), and N-1919 (manufactured by ADEKA) can also be suitably used. ).

In addition, the compound described in Japanese Patent Publication No. 2009-519904 in which an oxime is linked to the N position of the carbazole ring, and the compound described in U.S. Patent No. 7626957 in which a heterosubstituent is introduced at the benzophenone site can also be used. The compound and the compound described in Japanese Patent Laid-Open No. 2010-15025 and U.S. Patent Publication No. 2009-292039, the ketoxime-based compound described in International Publication WO2009/131189, in which a nitro group is introduced into the pigment site, are in the same The compound described in U.S. Patent No. 7556910 containing a triazine skeleton and an oxime skeleton in the molecule, the compound described in Japanese Patent Laid-Open No. 2009-221114 and the like having a maximum absorption at 405 nm and good sensitivity to g-ray light sources.

In addition, the cyclic oxime compounds described in Japanese Patent Application Publication No. 2007-231000 and Japanese Patent Application Publication No. 2007-322744 can also be suitably used. Among the cyclic oxime compounds, the cyclic oxime compounds condensed in the carbazole dye described in Japanese Patent Laid-Open No. 2010-32985 and Japanese Patent Laid-Open No. 2010-185072 in particular have high light absorption. It is preferable from the viewpoint of high sensitivity.

In addition, the compound described in JP 2009-242469 A, which is a compound having an unsaturated bond at a specific site of the oxime compound, can also be suitably used.

In addition, oxime compounds having fluorine atoms can also be used. Specific examples of such an initiator include: the compound described in JP 2010-262028 A, and the compound 24 and compound 36 described in paragraph 0345 of JP 2014-500852 A ~ Compound 40, the compound (C-3) described in paragraph 0101 of JP 2013-164471 A, etc. As specific examples, the following compounds can be cited.

As the optimal oxime compound, the oxime compound having a specific substituent shown in Japanese Patent Laid-Open No. 2007-269779 or the thioaryl group shown in Japanese Patent Laid-Open No. 2009-191061 can be cited The oxime compound and so on.

From the viewpoint of exposure sensitivity, a photoradical polymerization initiator is preferably selected Free trihalomethyl triazine compound, benzyl dimethyl ketal compound, α-hydroxy ketone compound, α-amino ketone compound, phosphine compound, phosphine oxide compound, metallocene compound, oxime compound, triaryl imidazole Dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complexes and their salts, halomethyl oxadiazole compounds, The 3-aryl group is substituted for a compound in the group of coumarin compounds.

More preferably, trihalomethyl triazine compound, α-amino ketone compound, phosphine compound, phosphine oxide compound, oxime compound, triaryl imidazole dimer, onium compound, benzophenone compound, acetophenone compound , More preferably trihalomethyl triazine compound, α-amino ketone compound, oxime compound, triaryl imidazole dimer, benzophenone compound, most preferably oxime compound.

Relative to the total solid content of the negative photosensitive resin composition, the content of the radical photopolymerization initiator is preferably 0.1% by mass to 30% by mass, more preferably 0.1% by mass to 20% by mass, and still more preferably 0.1 Mass%~10% by mass. In addition, with respect to 100 parts by mass of the radically polymerizable compound, the photo radical polymerization initiator is preferably contained from 1 part by mass to 20 parts by mass, and more preferably from 3 parts by mass to 10 parts by mass.

The photo radical polymerization initiator may be only one type or two or more types. When there are two or more kinds of photoradical polymerization initiators, it is preferable that the total amount is the above range.

<radical polymerizable compound>

The negative photosensitive resin composition of the present invention may contain a radical polymerizable compound other than the polyimide precursor. By containing a radically polymerizable compound, a cured film with more excellent heat resistance can be formed. Furthermore, it can also be used for photolithography The case is formed.

The radically polymerizable compound is preferably a compound having an ethylenically unsaturated bond, and more preferably a compound containing two or more ethylenically unsaturated groups.

The radically polymerizable compound may be any of chemical forms such as monomers, prepolymers, oligomers, mixtures of these, and polymers of these, for example.

In the present invention, a monomeric radical polymerizable compound (hereinafter, also referred to as a radical polymerizable monomer) is a compound different from a polymer compound. The radically polymerizable monomer is typically a low-molecular compound, preferably a low-molecular compound having a molecular weight of 2000 or less, more preferably a low-molecular compound having a molecular weight of 1500 or less, and still more preferably a low-molecular compound having a molecular weight of 900 or less. In addition, the molecular weight of the radical polymerizable monomer is usually 100 or more.

In addition, the oligomer-type radical polymerizable compound is typically a polymer having a relatively low molecular weight, and preferably a polymer formed by bonding 10 to 100 radical polymerizable monomers. As the molecular weight, the weight average molecular weight in terms of polystyrene obtained by Gel Permeation Chromatography (GPC) is preferably 2000 to 20000, more preferably 2000 to 15000, and even more preferably 2000 to 10000.

The number of functional groups of the radical polymerizable compound in the present invention refers to the number of radical polymerizable groups in one molecule.

From an analytical viewpoint, the radically polymerizable compound preferably contains at least one bifunctional or more radically polymerizable compound containing two or more radically polymerizable groups, and more preferably contains at least one bifunctional free radically polymerizable compound. Base polymerizable compound.

<<Compounds with ethylenically unsaturated bonds>>

The group having an ethylenically unsaturated bond is preferably a styryl group, a vinyl group, a (meth)acryloyl group, and a (meth)allyl group, and more preferably a (meth)acryloyl group.

Specific examples of compounds having ethylenically unsaturated bonds include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters, The amides and these multimers are preferably esters of unsaturated carboxylic acids and polyol compounds, amides of unsaturated carboxylic acids and polyamine compounds, and these multimers. In addition, addition reactants of esters or amides of unsaturated carboxylic acids having nucleophilic substituents such as hydroxyl groups, amino groups, and mercapto groups, and monofunctional or polyfunctional isocyanates or epoxy groups can also be suitably used. Or dehydration condensation reaction product with monofunctional or polyfunctional carboxylic acid, etc. In addition, addition reactants of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols, and furthermore, have Substitution reactants of unsaturated carboxylic acid esters or amides with a detachable substituent such as a halogen group or a toluenesulfonyloxy group and monofunctional or polyfunctional alcohols, amines, and thiols are also suitable. In addition, as another example, a group of compounds substituted with vinylbenzene derivatives such as unsaturated phosphonic acid and styrene, vinyl ether, and allyl ether may be used instead of the unsaturated carboxylic acid.

As specific examples of the monomer of the ester of the polyol compound and the unsaturated carboxylic acid, as the acrylate, there are ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, Methylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylol Propyl propane tris (propylene oxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, Pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbose Alcohol hexaacrylate, tris(acryloxyethyl) isocyanurate, isocyanuric ethylene oxide modified triacrylate, polyester acrylate oligomer, etc.

As the methacrylate, there are tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, Trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, Pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, double 〔 P(3-Methylpropenoxy-2-hydroxypropoxy)phenyl]dimethylmethane, bis-[p-(methacryloxyethoxy)phenyl]dimethylmethane, etc. .

As itaconates, there are ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, four Methylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetraitaconate, etc.

As crotonates, there are ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetra-dicrotonate, and the like.

As isocrotonic acid esters, there are ethylene glycol diisocrotonate, pentaerythritol di Isocrotonate, sorbitol tetraisocrotonate, etc.

As the maleate, there are ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleic acid. Ester etc.

As examples of other esters, for example, aliphatic alcohol-based esters described in Japanese Patent Publication No. 46-27926, Japanese Patent Publication No. 51-47334, and Japanese Patent Application Publication No. 57-196231 can also be suitably used. Or compounds having an aromatic skeleton described in Japanese Patent Laid-Open No. 59-5240, Japanese Patent Laid-Open No. 59-5241, and Japanese Patent Laid-Open No. 2-226149, Japanese Patent Laid-Open No. 1 -165613 A compound containing an amine group, etc.

In addition, as specific examples of monomers of polyamine compounds and amides of unsaturated carboxylic acids, there are methylene bis-acrylamide, methylene bis-methacrylamide, and 1,6-hexamethylene Bis-acrylamide, 1,6-hexamethylene bis-methacrylamide, diethylenetriamine triacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide, etc.

As examples of other preferable amide-based monomers, the monomers having a cyclohexylene structure described in Japanese Patent Publication No. 54-21726 can be cited.

In addition, a urethane-based addition polymerizable monomer produced by the addition reaction of an isocyanate and a hydroxyl group is also suitable. As such a specific example, for example, the description in Japanese Patent Publication No. 48-41708 may be mentioned. A vinyl amine containing two or more polymerizable vinyl groups in one molecule by adding a vinyl monomer containing a hydroxyl group to a polyisocyanate compound having two or more isocyanate groups in one molecule Carboxylate compounds, etc.

In addition, for example, the urethane acrylates described in Japanese Patent Publication No. Sho 51-37193, Japanese Patent Publication No. 2-32293, Japanese Patent Publication No. 2-16765, or Japanese Patent Publication No. 58 -49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, Japanese Patent Publication No. 62-39418, urethane carboxylic acid having an ethylene oxide skeleton Ester compounds are also suitable.

In addition, in the present invention, as the compound having an ethylenically unsaturated bond, the compound described in paragraph number 0095 to paragraph number 0108 of JP 2009-288705 A can also be suitably used.

In addition, as the compound having an ethylenically unsaturated bond, a compound having a boiling point of 100°C or higher under normal pressure is also preferable. Examples thereof include monofunctional acrylates and methacrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate ; Polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol four (Meth) acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol (meth)acrylate, trimethylolpropane tris(acryloxypropyl) ) Ether, tris(acryloxyethyl) isocyanurate, glycerin or trimethylol ethane, etc. are added with ethylene oxide or propylene oxide to polyfunctional alcohols for (meth)acrylic acid Esterification, such as (meth)propylene described in Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034, and Japanese Patent Publication No. 51-37193 Urethanes, such as the polyester acrylates described in Japanese Patent Publication No. 48-64183, Japanese Patent Publication No. 49-43191, and Japanese Patent Publication No. 52-30490, as the ring Polyfunctional acrylates and methacrylates, such as epoxy acrylates, which are the reaction product of an oxygen resin and (meth)acrylic acid, and mixtures of these. In addition, the compounds described in paragraphs 0254 to 0257 of JP 2008-292970 A are also suitable. In addition, a polyfunctional (meth)acrylate obtained by reacting a compound having a cyclic ether group and an ethylenically unsaturated group, such as glycidyl (meth)acrylate, with a polyfunctional carboxylic acid, and the like can also be cited.

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

Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication No. 46-43946, Japanese Patent Publication No. 1-40337, Japanese Patent Publication No. 1-40336, or Japanese Patent Vinylphosphonic acid compounds and the like described in JP-A-2-25493. In addition, in certain cases, the perfluoroalkyl group-containing structure described in JP 61-22048 A is suitably used. Furthermore, it is also possible to use those introduced as radical polymerizable monomers and oligomers in "Journal of Japan Adhesive Association" vol.20, No.7, pages 300 to 308 (1984).

In addition to the above, the following general formula (MO-1)~ A compound having an ethylenically unsaturated bond represented by general formula (MO-5). Furthermore, in the formula, when T is an oxyalkylene group, the end on the carbon atom side is bonded to R.

[化25]

In the general formula, n is an integer from 0 to 14, and m is an integer from 1 to 8. Multiple R and T in one molecule may be the same or different.

In each of the compounds having an ethylenically unsaturated bond represented by the general formula (MO-1) to the general formula (MO-5), at least one of the multiple R is represented by -OC(=O)CH =CH ₂ , or -OC(=O)C(CH ₃ )=CH ₂ represents the group.

In the present invention, as a specific example of the compound having an ethylenically unsaturated bond represented by the general formula (MO-1) to the general formula (MO-5), Japanese Patent Laid-Open No. 2007- The compound described in paragraph 0248 to paragraph 0251 of 269779 publication.

In addition, the following compounds described as general formula (1) and general formula (2) in Japanese Patent Laid-Open No. 10-62986 and their specific examples can also be used as compounds having ethylenically unsaturated bonds. The compound is A compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol followed by (meth)acrylate esterification.

As the compound having an ethylenically unsaturated bond, dipentaerythritol triacrylate (the commercially available product is KAYARAD D-330; Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (the commercially available product is Kayarad (KAYARAD) D-320; Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercial product is KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available product is Kayalad (KAYARAD) DPHA; manufactured by Nippon Kayaku Co., Ltd.) ), and the structure in which these (meth)acrylic groups are bonded via ethylene glycol residues and propylene glycol residues. These oligomer types can also be used.

The compound having an ethylenically unsaturated bond may also be a polyfunctional monomer having an acid group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. The polyfunctional monomer having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably an unreacted hydroxyl group of the aliphatic polyhydroxy compound reacts with a non-aromatic carboxylic anhydride to have an acid group The polyfunctional monomer of is particularly preferred in the ester, and the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol. Examples of commercially available products include M-510 and M-520 which are polyacid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

The polyfunctional monomer having an acid group may be used alone or in combination of two or more kinds. In addition, if necessary, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination.

The preferred acid value of the polyfunctional monomer having an acid group is 0.1 mgKOH/g-40 mgKOH/g, particularly preferably 5 mgKOH/g-30 mgKOH/g. When the acid value of the polyfunctional monomer is in the above range, the manufacturing or handling properties are excellent, and furthermore, the developability is excellent. In addition, the radical polymerizability is good.

Compounds with ethylenically unsaturated bonds can also be used with caprolactone bonds Constitutional compound.

The compound having a caprolactone structure and an ethylenically unsaturated bond is not particularly limited as long as it has a caprolactone structure in the molecule. For example, it can be exemplified by adding trimethylolethane, di-trimethylolethane Polyols such as alkane, trimethylolpropane, di-trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, and (meth)acrylic acid and ε-caprolactone are added The ε-caprolactone obtained by esterification is modified to a polyfunctional (meth)acrylate. Among them, a compound having an ethylenically unsaturated bond having a caprolactone structure represented by the following general formula (C) is preferred.

(In the formula, all 6 Rs are groups represented by the following general formula (D), or 1 to 5 of the 6 Rs are groups represented by the following general formula (D), and the remainder are (The group represented by the following general formula (E))

General formula (D) [化27]

(In the formula, R ¹ represents a hydrogen atom or a methyl group, m represents an integer of 1 or 2, and "*" represents a bond)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and "*" represents a bond)

Such a compound having a caprolactone structure and having an ethylenically unsaturated bond is commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, for example, and includes: DPCA-20 (the general formula ( C) - in general formula (E), m = 1, the number of groups represented by the formula (D) represented by = 2, R ¹ are both hydrogen atoms), DPCA-30 (by the general formula (C) ~In the general formula (E), m=1, the number of groups represented by the general formula (D)=3, and R ¹ is a compound in which all hydrogen atoms are used), DPCA-60 (the general formula (C) ~ general In the formula (E), m=1, the number of groups represented by the general formula (D)=6, and R ¹ is a compound in which all hydrogen atoms are used), DPCA-120 (the general formula (C) ~ general formula ( E) in, m = 2, the number of groups represented by the formula (D) represented by = 6, R ¹ compound are hydrogen atoms) and the like.

In the present invention, the compound having a caprolactone structure and an ethylenically unsaturated bond can be used alone or in combination of two or more.

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

In general formula (i) and general formula (ii), E independently represents -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)-, y respectively Each independently represents an integer of 0-10, and X each independently represents a (meth)acryloyl group, a hydrogen atom, or a carboxyl group.

In the general formula (i), the total of (meth)acrylic groups is 3 or 4, m each independently represents an integer of 0-10, and the total of each m is an integer of 0-40. However, when the total of each m is 0, any one of X is a carboxyl group.

In general formula (ii), the total of (meth)acrylic groups is 5 or 6, n each independently represents an integer of 0-10, and the total of each n is an integer of 0-60. However, when the total of each n is 0, any one of X is a carboxyl group.

In general formula (i), m is preferably an integer of 0-6, and more preferably an integer of 0-4.

In addition, the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.

In general formula (ii), n is preferably an integer of 0-6, and more preferably an integer of 0-4.

In addition, the total of each n is preferably an integer of 3-60, more preferably an integer of 3-24, and particularly preferably an integer of 6-12.

-((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)- in general formula (i) or general formula (ii) is preferably a terminal bond on the side of the oxygen atom The form knotted on X. In particular, it is preferable that in the general formula (ii), all six Xs are in the form of acryloyl groups.

The compound represented by the general formula (i) or the general formula (ii) can be synthesized by the following step, which is a previously known step: by subjecting ethylene oxide or propylene oxide to a ring-opening addition reaction with pentaerythritol or dipentaerythritol For the step of bonding the ring-opening skeleton, and the step of reacting the terminal hydroxyl group of the ring-opening skeleton with, for example, (meth)acrylic chloride to introduce a (meth)acrylic group. Each step is a well-known step, and a person with ordinary knowledge in the relevant technical field can easily synthesize the compound represented by the general formula (i) or the general formula (ii).

Among the compounds represented by general formula (i) and general formula (ii), more preferred are pentaerythritol derivatives and dipentaerythritol derivatives.

Specifically, the compounds represented by the following formula (a) to formula (f) (hereinafter, also referred to as "exemplary compound (a) to exemplified compound (f)") are exemplified, and among them, exemplified compounds are preferred (a), exemplified compound (b), exemplified compound (e), example Show compound (f).

[化31]

As a commercially available product of the compound having an ethylenically unsaturated bond represented by the general formula (i) and the general formula (ii), for example, a product made by Sartomer Co., Ltd. has four ethoxy groups. SR-494 as a tetrafunctional acrylate with six pentoxy chains, DPCA-60 as a hexafunctional acrylate with 6 pentoxyl chains manufactured by Nippon Kayaku Co., Ltd., and as a trifunctional acrylate with 3 isobutoxy chains. Functional acrylate TPA-330 etc.

As a compound having an ethylenically unsaturated bond, for example, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. 2-32293, Japanese Patent Publication No. 2-16765 Acrylic urethanes described in, or Japanese Patent Publication No. 58-49860, Japanese Patent The urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 are also suitable. Furthermore, as a compound having an ethylenically unsaturated bond, the compounds described in Japanese Patent Laid-Open No. 63-277653, Japanese Patent Laid-Open No. 63-260909, and Japanese Patent Laid-Open No. 1-105238 can also be used. Addition polymerizable monomers having an amine group structure or a thioether group structure in the molecule.

Commercial products of compounds having ethylenically unsaturated bonds include: urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp), NK ester (NK ESTER) ) M-40G, NK ESTER 4G, NK ESTER M-9300, NK ESTER A-9300, UA-7200 (manufactured by Shinnakamura Chemical Industry Co., Ltd.), DPHA-40H (Manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (manufactured by NOF Corporation), etc.

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

As a compound having an ethylenically unsaturated bond with the partial structure Specific examples of the material include, for example, trimethylolpropane tri(meth)acrylate, isocyanuric acid ethylene oxide modified di(meth)acrylate, isocyanuric ethylene oxide modified Quality tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, Dipentaerythritol hexa(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, etc., in the present invention, these compounds having ethylenically unsaturated bonds can be particularly preferably used.

In the negative photosensitive resin composition, from the viewpoint of good radical polymerizability and heat resistance, the content of the radical polymerizable compound is preferably 1 relative to the total solid content of the negative photosensitive resin composition. Mass%~50% by mass. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 30% by mass or less, and still more preferably 25% by mass or less. A radical polymerizable compound may be used individually by 1 type, and may mix and use 2 or more types.

In addition, the mass ratio of the polyimide precursor to the radical polymerizable compound (polyimine precursor/radical polymerizable compound) is preferably 98/2 to 10/90, more preferably 95/5 to 30 /70, more preferably 90/10~50/50, still more preferably 90/10~70/30. If the mass ratio of the polyimide precursor and the radical polymerizable compound is within the above range, a cured film with more excellent curability and heat resistance can be formed.

<Photobase Generator>

The negative photosensitive resin composition of this invention may contain a photobase generator. The so-called photoalkali generators are those that generate alkalis by exposure and do not show activity under normal conditions of normal temperature and pressure, as long as they are used as external stimuli when exposed to electromagnetic waves and heating There is no particular limitation on the one that generates alkali (alkaline substance). Since the alkali generated by the exposure functions as a catalyst when the polyimide precursor is cured by heating, it can be suitably used in the negative type.

The content of the photobase generator is not particularly limited as long as a desired pattern can be formed, and it can be set to a normal content. Relative to 100 parts by mass of the negative photosensitive resin composition, the content of the photobase generator is preferably in the range of 0.05 parts by mass or more and less than 30 parts by mass, more preferably in the range of 0.1 to 25 parts by mass, Furthermore, it is more preferable to exist in the range of 0.2 mass part-20 mass parts.

In the present invention, those known as photobase generators can be used. Examples include: M. Shirai and M. Tsunooka (M. Shirai, and M. Tsunooka), "Progress in Polymer Science (Progress in Polymer Science, Prog. Polym. Sci.)", 21, 1 (1996) ; Kadooka Masahiro, "Polymer Processing", 46, 2 (1997); C. Kutal, "Coordination Chemistry Reviews (Coordination Chemistry Reviews, Coord. Chem. Rev.)", 211, 353 (2001); Y. Gold and A. Kaneko, A. Sarker, and D. Neckers, "Chemistry of Materials (Chemistry of Materials, Chem. Mater.)", 11, 170 (1999); H. Duo Zhi and M. Shirai and M. Kakuoka (H. Tachi, M. Shirai, and M. Tsunooka), "Journal of Photopolymer Science and Technology (J. Photopolymer Science and Technology, J. Photopolym. Sci. Technol.)", 13,153 (2000); M. Winkle and Graziano (M. Winkle, and Graziano), "J. Photopolym. Sci. Technol.", 3,419 (1990); M Kadooka and H. Tachi and S. Yoshitaka (M.Tsunooka, H.Tachi, and S.Yoshitaka), "Journal of Photopolymer Science and Technology (J. Photopolym.Sci.Technol.)", 9, 13 (1996); K. Suyama, H. Araki and M. Shirai (K. Suyama, H. Araki, M. Shirai), "Journal of Photopolymer Science and Technology ( J. Photopolym. Sci. Technol.)", 19, 81 (2006), transition metal compound complexes, or those having a structure such as an ammonium salt, or those having a structure such as a diamine moiety and a carboxylic acid. Potentializers are generally ionic compounds that are neutralized by forming a salt with a base component, or urethane derivatives, oxime ester derivatives, acyl compounds, etc., are alkalised by urethane bonds or oxime bonds, etc. A nonionic compound whose ingredients are latent.

The photobase generators that can be used in the present invention can be used without particular limitation. Known ones can be used, for example, carbamate derivatives, amide derivatives, imine derivatives, α-cobalt complexes, and imidazole derivatives. Compounds, cinnamic acid amide derivatives, oxime derivatives, etc.

The basic substance generated from the photobase generator is not particularly limited, and examples thereof include compounds having an amine group, especially polyamines such as monoamines or diamines, or amidines.

The generated basic substance is preferably a compound having an amine group with higher basicity. The reason is that it has a strong catalytic effect on the dehydration condensation reaction in the imidization of the polyimide precursor, and it is added in a smaller amount and can exhibit dehydration condensation reaction at a lower temperature. In the catalytic effect. That is, since the generated alkaline substance has a large catalytic effect, the apparent sensitivity as a negative photosensitive resin composition is improved.

From the viewpoint of the catalytic effect, amidines and aliphatic amines are preferred.

The photobase generator is preferably a photobase generator that does not contain a salt in the structure. In addition, in the photobase generator, it is preferable that there is no nitrogen atom in the base part generated In charge. The photobase generator is preferably latentized by using a covalent bond for the generated base, and more preferably the base generating mechanism is that the covalent bond between the nitrogen atom of the generated base portion and the adjacent atom is cut. Compounds that produce bases. If it is an alkali generator without salt in the structure, the alkali generator can be made neutral, so the solvent solubility is good, and the pot life is improved. For this reason, the amine generated from the photobase generator used in the present invention is preferably a primary amine or a secondary amine.

In addition, for the above-mentioned reasons, it is preferable that the photobase generator is latentized by using a covalent bond for the base produced in this way, and it is more preferable that the base produced by using an amide bond or urethane Ester bond and oxime bond are latent.

As the alkali generator in the present invention, for example, the alkali generator having a cinnamic acid amide structure as disclosed in Japanese Patent Laid-Open No. 2009-80452 and International Publication No. WO2009/123122, such as Japanese Patent The base generators having a carbamate structure as disclosed in JP 2006-189591 and JP 2008-247747, such as Japanese Patent Publication 2007-249013 and JP 2008-247747 Although the base generator etc. which have an oxime structure and a carbamate oxime structure as disclosed in 003581, it is not limited to these, The structure of a well-known base generator can also be used other than these.

Hereinafter, specific examples will be given to describe the photobase generator that can be used in the present invention.

As an ionic compound, the following structural formula is mentioned, for example.

[化33]

As an acyl compound, the compound shown by the following formula is mentioned, for example.

[化34]

Moreover, as a photobase generator, the compound represented by the following general formula (PB-1) is mentioned, for example.

[化35]

(In the general formula (PB-1), R ⁴¹ and R ⁴² are each independently a hydrogen atom or an organic group, and may be the same or different; wherein, at least one of R ⁴¹ and R ⁴² is an organic group; or, regarding R ⁴¹ and R4 ² , these can be bonded to form a ring structure, and may also include a heteroatom bond; R ⁴³ and R ⁴⁴ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a silyl group, or a silane Alcohol group, nitro group, nitroso group, sulfinic group, sulfo group, sulfonate group, phosphine group, phosphinyl group, phosphinyl group, phosphonate group, or organic group, which may be the same or different; R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfinic acid group, a sulfonic group, and a sulfonic acid Radical, phosphino, phosphinyl, phosphinyl, phosphonate, amine, ammonium or organic group, which may be the same or different; or, with regard to R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ , these Two or more can be bonded to form a ring structure, and may also include a heteroatom bond; R ⁴⁹ is a hydrogen atom, or a protecting group that can be deprotected by heating and/or electromagnetic wave irradiation)

Although the specific example of general formula (PB-1) is given below, it is not limited to this.

[化36]

[化37]

[化38]

In addition, examples of photobase generators include the compounds described in paragraphs 0185 to 0188, 0199 to 0200, and 0202 of Japanese Patent Laid-Open No. 2012-93746. Japanese Patent Special The compound described in paragraph number 0022 to paragraph number 0069 of the Japanese Patent Application Publication No. 2013-194205, the compound described in paragraph number 0026 to paragraph number 0074 of JP 2013-204019 A, and the paragraph number of WO2010/064631 The compound described in 0052 is taken as an example.

<Hot alkali generator>

The negative photosensitive resin composition of the present invention may contain a thermal base generator.

The type of the thermal base generator is not particularly limited, and preferably includes at least one selected from the group consisting of acidic compounds that generate bases when heated to 40°C or higher, and ammonium salts with anions and ammonium cations having a pKa1 of 0 to 4 The hot alkali generator. Here, pKa1 represents the logarithmic notation (-Log ₁₀ Ka) of the dissociation constant (Ka) of the first proton of the polybasic acid.

By blending such a compound, the cyclization reaction of the polyimide precursor can be performed at a low temperature, and a negative photosensitive resin composition with more excellent stability can be formed. In addition, the thermal alkali generator does not generate alkali as long as it is not heated. Therefore, even if it coexists with the polyimide precursor, the cyclization of the polyimide precursor during storage can be suppressed, and the storage stability is excellent.

The thermal base generator in the present invention contains at least one selected from the group consisting of acidic compounds (A1) that generate bases when heated to 40°C or higher, and ammonium salts (A2) of anions and ammonium cations having pKa1 of 0 to 4.

The acidic compound (A1) and the ammonium salt (A2) generate a base when heated. Therefore, the base generated from these compounds can promote the cyclization reaction of the polyimide precursor and can The cyclization of the polyimide precursor is performed at low temperature. In addition, even if these compounds are coexisted with a polyimide precursor that is cyclized and hardened by a base, the cyclization of the polyimide precursor will hardly proceed unless heating is performed. A negative photosensitive resin composition with excellent stability is prepared.

Furthermore, in this specification, the so-called acidic compound refers to the following compound: 1 g of the compound is extracted into a container, and 50 ml of a mixture of ion-exchanged water and tetrahydrofuran (mass ratio of water/tetrahydrofuran=1/4) is added, and Stir at room temperature for 1 hour, and use a potential hydrogen (pH) meter to measure the resulting solution at 20°C. The value is less than 7.

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

If the alkali generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 120°C or higher, it is difficult to generate alkali during storage, and therefore, a negative photosensitive resin composition having excellent stability can be prepared. If the alkali 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 lowered. The alkali generation temperature can be measured by, for example, differential scanning calorimetry. Heat the compound in a pressure capsule at 5°C/min to 250°C, read the peak temperature of the lowest heat generation peak, and use the peak temperature as the alkali generation temperature. Determination.

In the present invention, the base produced by the thermal base generator is preferably a secondary amine or a tertiary amine, and more preferably a tertiary amine. Because tertiary amines are highly alkaline, they can further reduce the cyclization temperature of the polyimide precursor. In addition, the boiling point of the alkali generated by the thermal alkali generator is preferably 80°C or higher, more preferably 100°C or higher, and most preferably 140°C or higher. In addition, the molecular weight of the base produced is preferably 80 to 2,000. The lower limit is more preferably 100 or more. The upper limit is more preferably 500 or less. In addition, the value of the molecular weight is a theoretical value obtained from the structural formula.

In the present invention, the acidic compound (A1) preferably contains one or more selected from the group consisting of ammonium salts and compounds represented by the general formula (1) described later.

In the present invention, the ammonium salt (A2) is preferably an acidic compound.

Furthermore, the ammonium salt (A2) may contain if heated to above 40°C (preferably 120°C to 200°C), a compound that generates an acidic compound that generates a base may be a compound other than an acidic compound that generates a base when heated to 40°C or higher (preferably 120°C to 200°C).

<<Ammonium salt>>

In the present invention, the ammonium salt refers to a salt of an ammonium cation and an anion represented by the following general formula (1) or (2). The anion may be bonded to any part of the ammonium cation via a covalent bond, and may also exist outside the molecule of the ammonium cation, preferably outside the molecule of the ammonium cation. Furthermore, the fact that the anion exists outside the molecule of the ammonium cation means that the ammonium cation and the anion are not bonded by a covalent bond. Hereinafter, the anion outside the molecule of the cation part is also referred to as a counter anion.

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

In the present invention, the ammonium salt is preferably an anion and an ammonium cation having a pKa1 of 0-4. The upper limit of the pKa1 of the anion is more preferably 3.5 or less, and still more preferably 3.2 the following. The lower limit is more preferably 0.5 or more, and even more preferably 1.0 or more. If the pKa1 of the anion is in the above range, the polyimide precursor can be cyclized at a low temperature, and furthermore, the stability of the negative photosensitive resin composition can be improved. If pKa1 is 4 or less, the stability of the thermal alkali generator is good, the generation of alkali without heating can be suppressed, and the stability of the negative photosensitive resin composition is good. If pKa1 is 0 or more, the generated alkali is difficult to be neutralized, and the cyclization efficiency of the polyimide precursor is good.

The type of anion is preferably one selected from the group consisting of carboxylate anion, phenol anion, phosphate anion, and sulfate anion. In terms of the stability and thermal decomposition of the salt, the carboxylate anion is more preferred. . That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion.

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

In the present invention, the carboxylate anion is preferably an anion of a carboxylic acid having a pKa1 of 4 or less. pKa1 is more preferably 3.5 or less, and still more preferably 3.2 or less. According to this aspect, the stability of the negative photosensitive resin composition can be further improved.

Here, the so-called pKa1 represents the logarithm of the reciprocal of the first dissociation constant of the acid. Refer to "Determination of Organic Structures by Physical Methods" (Author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; Editor: Braude, EA, Nachod, FC; American Academic Press (Academic Press, New York, 1955), or "Data for Biochemical Research" (Author: Dawson, RMC, etc.; Oxford, Clarendon Press, 1959 ). For compounds not described in these documents, the value calculated from the structural formula using software using ACD/pKa (manufactured by ACD/Labs) was used.

In the present invention, the carboxylate anion is preferably represented by the following general formula (X1).

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

In the present invention, the so-called electron withdrawing group refers to the substituent constant σm of Hammett showing a positive value. Here, σm is described in detail in Tono Yufu's general theory, "Journal of the Society of Synthetic Organic Chemistry" Vol. 23, No. 8 (1965) P.631-642. In addition, the electron withdrawing group of the present invention is not limited to the substituents described in the literature.

As an example of a substituent whose σm shows a positive value, for example, CF ₃ group (σm=0.43), CF ₃ CO group (σm=0.63), HC≡C group (σm=0.21), 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. . 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 general formulas (EWG-1) to (EWG-6).

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

In the present invention, the carboxylate anion is also preferably represented by the following general formula (X).

In the general formula (X), L ¹⁰ represents a single bond, or a divalent linking group selected from the group consisting of alkylene, alkenylene, arylene, -NR ^X -and combinations of these, and R ^X represents hydrogen Atom, alkyl, alkenyl, or aryl.

As a specific example of the carboxylate anion, there may be mentioned: maleate anion Ion, phthalate anion, N-phenyliminodiacetate anion and oxalate anion. These carboxylate anions can be preferably used.

The ammonium cation is preferably represented by any one of the following general formula (Y1-1) to (Y1-6).

In the general formula, R ¹⁰¹ represents an n-valent organic group, R ¹⁰² to R ¹¹¹ each independently represent a hydrogen atom or a hydrocarbon group, R ¹⁵⁰ and R ¹⁵¹ each independently represent a hydrocarbon group, R ¹⁰⁴ and R ¹⁰⁵ , R ¹⁰⁴ It can bond with R ¹⁵⁰ , R ¹⁰⁷ and R ¹⁰⁸ , and R ¹⁰⁹ and R ¹¹⁰ to form a ring. Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group, n represents an integer of 1 or more, and m represents an integer of 0 to 5 .

<Compound represented by general formula (A1)>

In the present invention, the acidic compound is preferably a compound represented by the following general formula (A1). This compound is acidic at room temperature, but by heating, the carboxyl group is decarboxylated or dehydrated and cyclized and disappears, whereby the previously neutralized and deactivated amine site becomes active, thereby becoming basic. Hereinafter, the general formula (A1) will be described.

In the general formula (A1), A ¹ represents a p-valent organic group, R ¹ represents a monovalent organic group, L ¹ represents a (m+1) valent organic group, m represents an integer of 1 or more, and p represents 1 or more The integer.

In the general formula (A1), A ¹ represents a p-valent organic group. As the organic group, an aliphatic group, an aryl group, etc. can be cited, and an aryl group is preferred.

In the present invention, the compound represented by the general formula (A1) is preferably a compound represented by the following general formula (1a).

General formula (1a) [化45]

In the general formula (1a), A ¹ represents a p-valent organic group, L ¹ represents a (m+1)-valent linking group, L ² represents a (n+1)-valent linking group, m represents an integer of 1 or more, and n Represents an integer of 1 or more, and p represents an integer of 1 or more.

The meanings of A ¹ , L ¹ , L ² , m, n, and p in the general formula (1a) are the same as those described in the general formula (1), and the preferred ranges are also the same.

In the present invention, the compound represented by the general formula (A1) is preferably N-aryliminodiacetic acid. N-aryliminodiacetic acid is a compound in which A ¹ is an aryl group, L ¹ and L ² are methylene groups, m is 1, n is 1, and p is 1 in the general formula (A1). N-Aryliminodiacetic acid is prone to produce tertiary amines with high boiling points at 120℃~200℃.

Hereinafter, specific examples of the thermal base generator in the present invention are described, but the present invention is not limited to these specific examples. These can be used alone or in combination of two or more. Me in the following formula represents a methyl group.

[Table 1]

[Table 2]

As the thermal base generator used in the present invention, the compounds described in paragraph number 0015 to paragraph number 0055 of the Japanese Patent Application No. 2015-034388 specification can also be preferably used, and these contents are incorporated in this specification.

When a thermal alkali generator is used, the content of the thermal alkali generator in the negative photosensitive resin composition is preferably 0.1% by mass to 50% by mass relative to the total solid content of the negative photosensitive resin composition. The lower limit is more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less.

One kind or two or more kinds of thermal base generators can be used. When two or more are used, it is preferable that the total amount falls within the above-mentioned range.

<Thermal radical polymerization initiator>

The negative photosensitive resin composition of the present invention may contain a thermal radical polymerization initiator. As the thermal radical polymerization initiator, a known thermal radical polymerization initiator can be used.

The thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or accelerates the polymerization reaction of the polymerizable compound. By adding a thermal radical polymerization initiator, when the cyclization reaction of the polyimide precursor proceeds, the The polymerization reaction of the polymerizable compound proceeds. In addition, when the polyimide precursor contains ethylenically unsaturated bonds, the cyclization of the polyimide precursor can also be carried out together with the polymerization reaction of the polyimide precursor, so higher heat resistance can be achieved. .

Examples of thermal radical polymerization initiators include aromatic ketones, onium salt compounds, peroxides, sulfur compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, Metal compounds, active ester compounds, compounds having carbon halogen bonds, azo compounds, etc. Among them, peroxides or azo compounds are more preferred, and peroxides are particularly preferred.

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

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

Among the commercially available products, Perbutyl Z and Percumyl D (manufactured by NOF Corporation) can be suitably used.

When the negative photosensitive resin composition contains a thermal radical polymerization initiator, the content of the thermal radical polymerization initiator is preferably 0.1% by mass to 50% by mass relative to the total solid content of the negative photosensitive resin composition %, more preferably 0.1% by mass to 30% by mass, particularly preferably 0.1% by mass to 20% by mass. In addition, with respect to 100 parts by mass of the polymerizable compound, the thermal radical polymerization initiator preferably contains 0.1 to 50 parts by mass, and more preferably contains 0.5 to 30 parts by mass. According to this aspect, it is easy to form a cured film with more excellent heat resistance.

The thermal radical polymerization initiator may be only one type or two or more types. When hot When there are two or more types of radical polymerization initiators, it is preferable that the total of them is in the above range.

<Anti-corrosion agent>

In the negative photosensitive resin composition of the present invention, it is preferable to add an anticorrosive agent. The anti-corrosion agent is added for the purpose of preventing ions from flowing out of the metal wiring. As a compound, for example, the anti-corrosion agent described in paragraph number 0094 of JP 2013-15701 A, JP 2009-283711 can be used. The compound described in paragraph number 0073 to paragraph number 0076 of the publication, the compound described in paragraph number 0052 of Japanese Patent Laid-Open No. 2011-59656, paragraph number 0114 and paragraph number 0116 of Japanese Patent Application Publication No. 2012-194520 And the compound described in paragraph number 0118. Among them, compounds having a triazole ring or compounds having a tetrazole ring can be preferably used, more preferably 1,2,4-triazole, 1,2,3-benzotriazole, 5-methyl-1H -Benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, the most preferred is 1H-tetrazole.

When the anti-corrosion agent is added, relative to 100 parts by mass of the polyimide precursor, the blending amount of the anti-corrosion agent is preferably in the range of 0.1 parts by mass to 10 parts by mass, more preferably in the range of 0.2 parts by mass to 5 parts by mass.

The anti-corrosion agent may be only one type or two or more types. When there are two or more kinds of anticorrosive agents, it is preferable that the total amount is the above range.

<Metal Adhesion Improver>

The negative photosensitive resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion with metal materials used in electrodes, wiring, and the like. As an example of the metal adhesion improver, Paragraph No. 0046 to Paragraph No. 0049 of Japanese Patent Laid-Open No. 2014-186186 or Japanese Patent Laid-Open No. 2013-072935 The thioether compound described in paragraph number 0032 to paragraph number 0043 of the publication. When a metal adhesive modifier is used, relative to 100 parts by mass of the polyimide precursor, the blending amount of the metal adhesive modifier is preferably in the range of 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass The range of parts by mass. By setting it as 0.1 parts by mass or more, the adhesiveness of the film after thermal curing to the metal becomes good, and by setting it as 30 parts by mass or less, the heat resistance and mechanical properties of the film after curing become better.

There may be only one type of metal adhesion improver, or two or more types. When two or more types of metal adhesion improvers are used, it is preferable that the total of them is the above range.

<Silane Coupling Agent>

In terms of improving the adhesion to the substrate, the negative photosensitive resin composition of the present invention preferably contains a silane coupling agent. Examples of the silane coupling agent include: the compounds described in paragraphs 0062 to 0073 of JP 2014-191002, the compounds described in paragraphs 0063 to 0071 of WO2011/080992A1, The compound described in paragraph number 0060 to paragraph number 0061 of JP 2014-191252 A, the compound described in paragraph number 0045 to paragraph number 0052 of JP 2014-41264 A, the compound described in paragraph number 0052 of WO2014/097594 The compound described in Paragraph No. 0055. In addition, it is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP 2011-128358 A.

When using a silane coupling agent, relative to 100 parts by mass of the polyimide precursor, the blending amount of the silane coupling agent is preferably in the range of 0.1 parts by mass to 20 parts by mass, more preferably in the range of 1 parts by mass to 10 parts by mass . If it is 0.1 parts by mass or more, it can give If the sufficient adhesiveness with the substrate is 20 parts by mass or less, problems such as increase in viscosity during storage at room temperature can be further suppressed.

The silane coupling agent may be only one type or two or more types. When two or more types of silane coupling agents are used, it is preferable that the total of them is in the above-mentioned range.

<Sensitizing Pigment>

The negative photosensitive resin composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs specific active radiation and becomes an electronically excited state. The sensitizing dye in an electronically excited state comes into contact with a thermal base generator, a thermal radical polymerization initiator, a photo radical polymerization initiator, etc., to cause electron movement, energy movement, heat generation, and the like. Thereby, the thermal base generator, the thermal radical polymerization initiator, and the photo radical polymerization initiator undergo chemical changes to decompose and generate free radicals, acids or bases.

Examples of preferable sensitizing dyes include those belonging to the following compounds and having an absorption wavelength in the region of 300 nm to 450 nm. Examples include: polynuclear aromatics (such as phenanthrene, anthracene, pyrene, perylene, terphenylene, 9,10-dialkoxy anthracene), xanthenes (such as luciferin, eosin, fluorescein, if Danmin B, Rose Bengal), thioxanthones (e.g. 2,4-diethyl thioxanthone), cyanines (e.g. thiocarbocyanine, oxacarbocyanine), merocyanine Class (e.g. merocyanine, carbocyanine), thiazides (e.g. thiazole, methylene blue, toluidine blue), acridines (e.g. acridine orange, chloroflavin, acriflavin), anthracene Quinones (such as anthraquinone), squaraine ylides (such as squaraine ylide), coumarins (such as 7-diethylamino-4-methylcoumarin), benzene Vinylbenzenes, stilbene benzenes, carbazoles, etc.

Among them, in the present invention, from the viewpoint of initial efficiency, it is preferable to use Polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, terylene), thioxanthones, stilbene benzenes, and styryl benzenes are used, and compounds having an anthracene skeleton are more preferably used. As particularly preferable specific compounds, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, and the like can be cited.

When the negative photosensitive resin composition contains a sensitizing dye, relative to the total solid content of the negative photosensitive resin composition, the content of the sensitizing dye is preferably 0.01% by mass to 20% by mass, more preferably 0.1% by mass ~15% by mass, more preferably 0.5% by mass to 10% by mass. A sensitizing dye may be used individually by 1 type, and may use 2 or more types together.

<Chain transfer agent>

The negative photosensitive resin composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined in, for example, the third edition of the Polymer Dictionary (Edited by the Society of Polymer Science, 2005), pages 683-684. As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule can be used. These chain transfer agents donate hydrogen to low-activity free radical species to generate free radicals, or deprotonate after being oxidized, thereby generating free radicals. In particular, thiol compounds (such as 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.) can be preferably used. Wait).

When the negative photosensitive resin composition contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the total solid content of the negative photosensitive resin composition, and more preferably 1 part by mass to 10 parts by mass, and more preferably 1 part by mass to 5 parts by mass.

The chain transfer agent may be only one type or two or more types. When the chain transfer agent is two kinds In the above, it is preferable that the total is the above-mentioned range.

<Polymerization inhibitor>

In order to prevent unnecessary thermal polymerization of the polyimide precursor and the radical polymerizable compound during the manufacturing process or the storage process, the negative photosensitive resin composition of the present invention preferably contains a small amount of polymerization inhibitor.

As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, gallic phenol, p-tert-butylcatechol, benzoquinone, 4, 4'-thiobis(3-methyl-6-tertiary butylphenol), 2,2'-methylene bis(4-methyl-6-tertiary butylphenol), N-nitroso -N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid , Glycol ether diamine tetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2- Nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxyamine ammonium Salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane.

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

The polymerization inhibitor may be only one type or two or more types. When two or more kinds of polymerization inhibitors are used, it is preferable that the sum of them is in the above-mentioned range.

<Surfactant>

In the negative photosensitive resin composition of the present invention, from the viewpoint of further improving coating properties, various surfactants can be added. As a surfactant, can make Various surfactants such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants are used.

In particular, 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 or the liquid-saving property can be further improved.

When a coating liquid containing a fluorine-based surfactant is used to form a film, the interfacial tension between the coated surface and the coating liquid is reduced, thereby improving the wettability of the coated surface and improving the Improved surface coating. Therefore, even in the case of forming a thin film of about several μm with a small amount of liquid, it is effective from the viewpoint that a film with a small thickness unevenness and a uniform thickness can be formed more appropriately.

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

Examples of the fluorine-based surfactant include: Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac ) F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, Megafac F479, Megafac F482, Megafac F554, Megafac F780, Megafac F781 (above, manufactured by DIC (Stock)), Flo Fluorad FC430, Fluorad FC431, Fluorad FC171 (above, manufactured by Sumitomo 3M (Stock)), Surflon S-382, Saffron Surflon) SC-101, Surflon (Surflon) SC-103, Surflon (Surflon) SC-104, Surflon (Surflon) SC-105, Surflon (Surflon) SC1068, Surflon (Surflon) SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (above, manufactured by Asahi Glass), PF636, PF656, PF6320, PF6520, PF7002 (Manufactured by OMNOVA) etc.

As a fluorine-based surfactant, a block polymer can also be used. As a specific example, for example, the compound described in JP 2011-89090 A can be cited.

In addition, the following compounds can also be exemplified as the fluorine-based surfactant used in the present invention.

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

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

Specific examples of cationic surfactants include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.) (Stock) Manufacturing), (meth)acrylic (co)polymer Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 ( Kyoeisha Chemical (manufactured by shares), W001 (manufactured by Yushang (shares)), etc.

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

As silicone-based surfactants, for example, Toray. Dow Corning (shares Parts) manufactured by "Toray Silicone DC3PA", "Toray Silicone SH7PA", "Toray Silicone DC11PA", and "Toray Silicone SH21PA" ", "Toray Silicone SH28PA", "Toray Silicone SH29PA", "Toray Silicone SH30PA", "Toray Silicone SH8400", "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460", "TSF-4452" manufactured by Momentive Performance Materials, shares of Shinetsu silicone "KP341", "KF6001", "KF6002" manufactured by Co., Ltd., "BYK307", "BYK323", "BYK330" manufactured by BYK Chemie, etc.

When the negative photosensitive resin composition contains a surfactant, relative to the total solid content of the negative photosensitive resin composition, the content of the surfactant is preferably 0.001% to 2.0% by mass, more preferably 0.005% by mass ~1.0% by mass.

The surfactant may be only one type or two or more types. When two or more kinds of surfactants are contained, it is preferable that the total amount is the above range.

<Higher fatty acid derivatives, etc.>

In the negative photosensitive resin composition of the present invention, in order to prevent polymerization inhibition caused by oxygen, higher fatty acid derivatives such as behenic acid or behenamide may be added and applied to the coating. During the drying process after the cloth, it is present on the surface of the negative photosensitive resin composition.

When the negative photosensitive resin composition contains higher fatty acid derivatives etc., relative to the total solid content of the negative photosensitive resin composition, the higher fatty acid derivatives etc. The content is preferably 0.1% by mass to 10% by mass.

There may be only one type of higher fatty acid derivatives, or two or more types. When two or more kinds of higher fatty acid derivatives and the like are contained, it is preferable that the total amount is the above range.

<Solvent>

When the negative photosensitive resin composition of the present invention is formed into a layered form by coating, it is preferable to prepare a solvent. As long as the negative photosensitive resin composition can be formed into a layered form, a known solvent can be used without limitation.

As the solvent used in the negative photosensitive resin composition of the present invention, as esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, oxyacetic acid Alkyl esters (e.g. methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g. methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate Ester, ethyl ethoxy acetate, etc.)), alkyl 3-oxypropionate (e.g. methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (e.g. 3-methoxypropyl Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-oxypropionate (e.g. 2 -Methyl oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (e.g. methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2- Propyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and 2-oxy-2 -Ethyl methyl propionate (e.g. 2-methoxy-2-methyl propionate, 2-ethoxy-2-methyl propionate, etc.), methyl pyruvate, ethyl pyruvate , Propylpyruvate, Methyl Acetate, Ethyl Acetate, 2-oxobutane Methyl ester, ethyl 2-oxobutyrate, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl ether Base cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether ethyl Ester, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and, as aromatic hydrocarbons, for example, toluene, xylene, anisole, and limonene, etc. can be suitably cited, as well as sulfites, Dimethyl sulfenite can be suitably cited.

From the viewpoint of improvement of the coating surface state, etc., a form in which two or more solvents are mixed is also preferable. Among them, the following mixed solution is preferably selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, and diethylene diacetate. Dimethyl ethoxylate, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol Two or more of acid ester, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate. Particularly preferred is the combined use of dimethyl sulfoxide and γ-butyrolactone.

When the negative photosensitive resin composition contains a solvent, from the viewpoint of coatability, the content of the solvent is preferably such that the total solid content concentration of the negative photosensitive resin composition becomes 5 mass% to 80 mass% The amount is more preferably 5 mass% to 70 mass%, and still more preferably 10 mass% to 60 mass%.

The solvent may be only one type or two or more types. When two or more kinds of solvents are contained, it is preferable that the total of them is the above-mentioned range.

In addition, from the viewpoint of film strength, relative to the total mass of the negative photosensitive resin composition, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-di The content of methylacetamide and N,N-dimethylformamide is preferably less than 5% by mass, more preferably less than 1% by mass, still more preferably less than 0.5% by mass, and particularly preferably less than 0.1% by mass.

<Other additives>

Within a range that does not impair the effects of the present invention, the negative photosensitive resin composition of the present invention may be blended with various additives as necessary, such as inorganic particles, hardeners, hardening catalysts, fillers, antioxidants, ultraviolet absorbers, and antioxidants. Coagulant etc. When blending these additives, it is preferable to set the total blending amount to 3% by mass or less of the solid content of the negative photosensitive resin composition.

From the viewpoint of the coating surface state, the moisture content of the negative photosensitive resin 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 negative photosensitive resin composition of the present invention is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and particularly preferably less than 0.5 ppm by mass. Examples of metals include sodium, potassium, magnesium, calcium, iron, chromium, nickel, and the like. When multiple metals are included, it is preferable that the total of these metals is in the above-mentioned range.

In addition, as a method of reducing the metal impurities unintentionally contained in the negative photosensitive resin composition, the following methods can be cited: selecting a raw material with a low metal content as a raw material constituting the negative photosensitive resin composition, Photosensitive resin composition The raw material of the substance is filtered by a filter, and the device is lined with polytetrafluoroethylene, etc., and the distillation is carried out under the condition of suppressing pollution as much as possible.

From the viewpoint of wiring corrosion, the content of halogen atoms in the negative photosensitive resin composition of the present invention is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and still more preferably less than 200 mass ppm ppm. Among them, those present in the state of halogen ions are 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 total of chlorine atoms and bromine atoms, or chloride ions and bromide ions are in the above-mentioned ranges.

<Preparation of negative photosensitive resin composition>

The negative photosensitive resin composition of the present invention can be prepared by mixing the components described above. The mixing method is not particularly limited, and it can be performed by a previously known method.

In addition, it is preferable to perform filtration using a filter for the purpose of removing foreign matter such as dust and fine particles in the negative photosensitive resin composition. The pore diameter of the filter is preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.1 μm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. The filter can also be washed with an organic solvent in advance. In the filter filtration step, multiple filters can be connected in series or parallel for use. When multiple filters are used, filters with different pore sizes and/or materials can also be used in combination. In addition, various materials can be filtered multiple times, and the step of multiple filtering can also be a cyclic filtering step. In addition, it is also possible to perform filtration under pressure, and the pressure of the pressure is preferably 0.05 MPa or more and 0.3 MPa or less.

In addition to filtration using filters, adsorption materials can also be used to remove impurities. In addition, regarding the removal of impurities, a filter can be combined with an adsorbent. As the adsorbent, a known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.

<Uses of negative photosensitive resin composition>

The negative photosensitive resin composition of the present invention can be cured and used as a cured film. The negative photosensitive resin composition of the present invention can form a cured film excellent in heat resistance and insulation, and therefore can be suitably used for insulating films of semiconductor elements, interlayer insulating films for rewiring layers, and the like. In particular, it can be preferably used as an interlayer insulating film for a rewiring layer in a three-dimensional mounting device.

In addition, it can also be used for electronic photoresists (galvanic resist, etching resist, solder top resist), etc.

In addition, it can also be used for the manufacture of lithographic or screen layouts, the etching of molded parts, and the manufacture of protective paint and dielectric layers in electronics, especially microelectronics.

<Method of manufacturing cured film>

Next, the manufacturing method of the cured film of this invention is demonstrated. There are no particular limitations on the production method of the cured film as long as it is formed using the negative photosensitive resin composition of the present invention. The method of manufacturing the cured film of the present invention preferably includes a step of applying the negative photosensitive resin composition of the present invention to a substrate, and a step of curing the negative photosensitive resin composition used on the substrate.

<<The step of applying the negative photosensitive resin composition to the substrate> >

Examples of the application method of the negative photosensitive resin composition on the substrate include spinning, dipping, knife coating, suspended casting, coating, spraying, electrostatic spraying, reverse roll coating, etc. For the reason that it can be uniformly applied to a substrate, spin coating, electrostatic spray, and reverse roll coating are preferred.

Examples of the substrate include inorganic substrates, resins, and resin composite materials.

Examples of inorganic substrates include glass substrates, quartz substrates, silicon substrates, silicon nitride substrates, and composite substrates in which molybdenum, titanium, aluminum, copper, etc. are vapor-deposited on such substrates.

Examples of resin substrates include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, poly Chlorine, polyether ether, polyarylate, allyl diethylene glycol carbonate, polyamide, polyimide, polyimide, polyetherimide, polybenzoxazole, polyphenylene sulfide , Polycyclic olefins, norbornene resins, polychlorotrifluoroethylene and other fluororesins, liquid crystal polymers, acrylic resins, epoxy resins, silicone resins, ionomer resins, cyanate ester resins, cross-linked transbutene Synthetic resin substrates such as acid diesters, cyclic polyolefins, aromatic ethers, maleimides, olefins, cellulose, and episulfide compounds. These substrates are rarely used directly in the above-mentioned form. Generally, depending on the form of the final product, for example, a multilayer structure such as a thin film transistor (TFT) device can be formed.

The amount of the negative photosensitive resin composition applied (the thickness of the layer) and the type of the substrate (the carrier of the layer) depend on the field of the intended use. Especially advantageous is negative The type photosensitive resin composition can be used with a widely variable layer thickness. The thickness of the layer is preferably in the range of 0.5 μm to 100 μm.

Preferably, after the negative photosensitive resin composition is applied to the substrate, it is dried. Drying is preferably performed at 60°C to 150°C for 10 seconds to 2 minutes.

<<Heating Step>>

By heating the negative photosensitive resin composition applied to the substrate, the polyimide precursor undergoes a cyclization reaction to form a cured film with excellent heat resistance.

The heating temperature is preferably 50°C to 300°C, more preferably 100°C to 250°C.

According to the present invention, since a large amount of isomers with a faster cyclization rate are contained, the cyclization reaction of the polyimide precursor can also be performed at a lower temperature.

From the viewpoint of reducing the internal stress of the cured film or suppressing warpage, it is preferable to adjust at least one selected from the group consisting of heating rate, heating time, and cooling rate.

Using 20°C to 150°C as the heating start temperature, the heating rate is preferably 3°C/min to 5°C/min.

When the heating temperature is 200°C to 240°C, the heating time is preferably 180 minutes or more. The upper limit is preferably 240 minutes or less, for example. When the heating temperature is 240°C to 300°C, the heating time is preferably 90 minutes or more. The upper limit is preferably 180 minutes or less, for example. When the heating temperature is 300°C to 380°C, the heating time is preferably 60 minutes or more. The upper limit is preferably 120 minutes or less, for example.

The cooling rate is preferably 1°C/min~5°C/min.

Heating can be carried out in stages. As an example, the following steps can be cited: increase the temperature from 20°C to 150°C at 5°C/min, and leave it at 150°C for 30 minutes, then Then, the temperature was increased from 150°C to 230°C at 5°C/min, and it was left at 230°C for 180 minutes.

In terms of preventing the decomposition of the polyimide precursor, the heating step is preferably performed in an environment with a low oxygen concentration by flowing inert gas such as nitrogen, helium, and argon. The oxygen concentration is preferably 50 volume ppm or less, more preferably 20 volume ppm or less.

In the present invention, a pattern forming step may be performed between the step of applying the negative photosensitive resin composition on the substrate and the heating step. The pattern formation step can be performed by, for example, photolithography. For example, a method of performing an exposure step and a step of performing a development process can be cited.

The pattern formation by the photolithography method is preferably performed using a photosensitive resin composition containing a polyimide precursor and a photoradical polymerization initiator.

Hereinafter, the case of pattern formation by the photolithography method will be described.

<<Exposure Step>>

In the exposure step, actinic rays or radiation rays in a predetermined pattern corresponding to the negative photosensitive resin composition used on the substrate are irradiated.

The wavelength of actinic rays or radiation varies depending on the composition of the negative photosensitive resin composition, but is preferably 200 nm to 600 nm, and more preferably 300 nm to 450 nm.

As the light source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a chemical lamp, a light emitting diode (Light Emitting Diode, LED) light source, an excimer laser generator, etc. can be used, and i-rays (365nm), Actinic rays having a wavelength of 300 nm or more and 450 nm or less, such as h-ray (405 nm) and g-ray (436 nm). In addition, the irradiated light may be adjusted by a spectroscopic filter such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter as necessary. The exposure amount is preferably 1mJ/cm ² ~1000mJ/cm ² , more preferably 200mJ/cm ² ~800mJ/cm ² . The value of the present invention is high in terms of enabling development in a wide range and high developability in this manner.

As the exposure device, various methods such as mirror projection aligner, stepper, scanner, proximity type, contact type, microlens array type, lens scanner type, and laser exposure type can be used. Exposure machine.

Furthermore, when (meth)acrylates and similar olefinic unsaturated compounds are used, the photopolymerization of these is as well known, especially in the thin layer due to oxygen in the air and prevented. This effect can be alleviated by well-known conventional methods such as introduction of a temporary coating layer of polyvinyl alcohol, or pre-exposure or pre-adjustment in an inert gas.

<<Procedure for developing process>>

In the step of performing the development process, the unexposed portion of the negative photosensitive resin composition is developed using a developing solution. As the developer, an aqueous alkaline developer, an organic solvent, etc. can be used.

As the alkaline compound used in the aqueous alkaline developer, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, metasilica Sodium, potassium metasilicate, ammonia or amine, etc. Examples of amines include ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, and quaternary ammonium hydroxide. , Tetramethyl Ammonium Hydroxide (TMAH) or hydrogen Tetraethylammonium oxide and so on. Among them, a basic compound containing no metal is preferred. A suitable aqueous alkaline developer is usually alkaline up to 0.5N, but it may be appropriately diluted before use. For example, an aqueous alkaline developer of about 0.15N to 0.4N, preferably 0.20N to 0.35N is also suitable. The basic compound may be only one type or two or more types. When two or more kinds of basic compounds are used, it is preferable that the total amount is the above range.

As the organic solvent, the same solvents that can be used for the negative photosensitive resin composition can be used. For example, n-butyl acetate, γ-butyrolactone, cyclopentanone, and those obtained by mixing these are suitably mentioned.

Furthermore, it is also preferable to include a step of heating the developed negative photosensitive resin composition at a temperature of 50° C. to 500° C. after the step of developing treatment. By going through this step, it has the advantage of improved heat resistance or adhesion to the substrate.

As a field to which the method for producing a cured film of the present invention can be applied, it can be preferably used for an insulating film of a semiconductor element, an interlayer insulating film for a rewiring layer, and the like. In particular, since the resolution is good, it can be suitably used as an interlayer insulating film for a rewiring layer in a three-dimensional mounted device.

In addition, it can also be used for electronic photoresists (galvanic resist, etching resist, solder top resist), etc.

In addition, it can also be used for the manufacture of lithographic or screen layouts, the etching of molded parts, and the manufacture of protective paint and dielectric layers in electronics, especially microelectronics.

<Semiconductor Components>

Next, an embodiment of a semiconductor element using a negative photosensitive resin composition for an interlayer insulating film for a rewiring layer will be described.

The semiconductor element 100 shown in FIG. 1 is a so-called three-dimensional mounted element, and a laminated body 101 in which a plurality of semiconductor devices (semiconductor wafers) 101 a to 101 d are laminated is arranged on a wiring board 120.

In addition, in this embodiment, the description is centered on the case where the number of layers of the semiconductor device (semiconductor wafer) is 4 layers. However, the number of layers of the semiconductor device (semiconductor wafer) is not particularly limited. For example, it may be 2 layers, 8 floors, 16 floors, 32 floors, etc. In addition, it may be one layer.

Each of the plurality of semiconductor devices 101a to 101d includes a semiconductor wafer such as a silicon substrate.

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

The semiconductor device 101b to the semiconductor device 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 device.

The laminated body 101 has a structure in which a semiconductor device 101a without a through electrode and a semiconductor device 101b to a semiconductor device 101d having a through electrode 102b to a through electrode 102d are connected by flip chip.

That is, the electrode pad of the semiconductor device 101a without the through electrode and the connection pad on the side of the semiconductor device 101a of the semiconductor device 101b with the through electrode 102b adjacent to it are connected by metal bumps 103a such as solder bumps. electrode The connection pad on the other side of the semiconductor device 101b of 102b and the connection pad on the side of the semiconductor device 101b of the semiconductor device 101c having the through electrode 102c adjacent thereto are connected by metal bumps 103b such as solder bumps. Similarly, the connection pad on the other side of the semiconductor device 101c having the through electrode 102c and the connection pad on the side of the semiconductor device 101c of the semiconductor device 101d having the through electrode 102d adjacent to it are made of metal bumps 103c such as solder bumps. To connect.

An underfill layer 110 is formed in the gap between each of the semiconductor devices 101a to 101d, and each of the semiconductor devices 101a to 101d is laminated via the underfill layer 110.

The laminated body 101 is laminated on the wiring board 120.

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

A surface electrode 120 a is provided on one surface of the wiring substrate 120.

The insulating layer 115 in which the rewiring layer 105 is formed is arranged between the wiring substrate 120 and the laminated body 101, and the wiring substrate 120 and the laminated body 101 are electrically connected via the rewiring layer 105. The insulating layer 115 is formed using the negative photosensitive resin composition of the present invention.

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

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

[Example]

Hereinafter, the present invention will be explained more specifically with examples, but as long as the present invention does not exceed the gist, it is not limited to the following examples. Furthermore, as long as there is no special explanation in advance, "%" and "parts" are the quality standards. NMR is an abbreviation for nuclear magnetic resonance.

<Synthesis Example 1: Polyimide precursor (A-1) containing pyromellitic dianhydride, poly(propylene glycol) bis(2-aminopropyl ether), and 2-hydroxyethyl methacrylate>

14.06g (64.5 millimoles) of pyromellitic dianhydride (dried at 140°C for 12 hours), 18.6g (129 millimoles) of 2-hydroxyethyl methacrylate, and 0.05g of hydroquinone , 10.7g of pyridine, and 140g of diglyme were mixed, and stirred at 60°C for 18 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate . Then, the reaction mixture was cooled to -10°C, while maintaining the temperature at -10°C±4°C, 16.12 g (135.5 millimoles) of SOCl _{2 was} added over 10 minutes. During the addition of SOCl ₂ , the viscosity increased. After diluting with 50 ml of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, 23.5g (58.7 millimoles) of poly(propylene glycol) bis(2-aminopropyl ether) (Mn=400) will be dissolved in 100ml of N-methyl at 20℃~23℃ for 20 minutes. The solution in pyrrolidone was added dropwise to the reaction mixture. Then, the reaction mixture was stirred at room temperature for 1 night. Then, it was poured into 5 liters of water to precipitate the polyimide precursor, and the water-polyimine precursor mixture was stirred for 15 minutes at a speed of 5000 rpm. The polyimide precursor was filtered out, poured into 4 liters of water again, and stirred for 30 minutes, and filtered again. Then, the obtained polyimide precursor was dried at 45°C under reduced pressure for 3 days to obtain a polyimide precursor (A-1) having a repeating unit represented by the following formula.

In the above, n (average value) is 6.

<Synthesis Example 2: Polyimide precursor (A-2) containing pyromellitic dianhydride, poly(propylene glycol) bis(2-aminopropyl ether), and benzyl alcohol>

14.06g (64.5 millimoles) of pyromellitic dianhydride (dried at 140°C for 12 hours), 13.95g (129 millimoles) of benzyl alcohol, 0.05g of hydroquinone, 10.7g of pyridine, and 140 g of diethylene glycol dimethyl ether was mixed and stirred at a temperature of 60° C. for 18 hours to produce a diester of pyromellitic acid and benzyl alcohol. Then, the reaction mixture was cooled to -10°C, while maintaining the temperature at -10°C±4°C, 16.12 g (135.5 millimoles) of SOCl _{2 was} added over 10 minutes. During the addition of SOCl ₂ , the viscosity increased. After diluting with 50 ml of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, 23.5g (58.7 millimoles) of poly(propylene glycol) bis(2-aminopropyl ether) (Mn=400) will be dissolved in 100ml of N-methyl at 20℃~23℃ for 20 minutes. The solution in pyrrolidone was added dropwise to the reaction mixture. Then, the reaction mixture was stirred at room temperature for 1 night. Then, it was poured into 5 liters of water to precipitate the polyimide precursor, and the water-polyimine precursor mixture was stirred for 15 minutes at a speed of 5000 rpm. The polyimide precursor was filtered out, poured into 4 liters of water again, and stirred for 30 minutes, and filtered again. Then, the obtained polyimide precursor was dried at 45°C under reduced pressure for 3 days to obtain a polyimide precursor (A-2) having a repeating unit represented by the following formula.

In the above, n (average value) is 6.

<Synthesis Example 3: Polyimide precursor (A-3) containing pyromellitic dianhydride, modified silicone with amine groups at both ends, and 2-hydroxyethyl methacrylate (A-3)>

14.06g (64.5 millimoles) of pyromellitic dianhydride (dried at 140°C for 12 hours), 18.6g (129 millimoles) of 2-hydroxyethyl methacrylate, and 0.05g of hydroquinone , 10.7 g of pyridine, and 140 g of diethylene glycol dimethyl ether were mixed, and stirred at a temperature of 60° C. for 18 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Then, the reaction mixture was cooled to -10°C, while maintaining the temperature at -10°C±4°C, 16.12 g (135.5 millimoles) of SOCl _{2 was} added over 10 minutes. During the addition of SOCl ₂ , the viscosity increased. After diluting with 50 ml of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, 23.48g (58.7 millimoles) of X-22-161A (manufactured by Shin-Etsu Chemical Co., Ltd., modified silicone with both terminal amine groups, functional group equivalent is 800g/) at 20°C~23°C for 20 minutes. mol) is dissolved in 100 ml of N-methylpyrrolidone and added dropwise to the reaction mixture. Then, the reaction mixture was stirred at room temperature for 1 night. Then, it was poured into 5 liters of water to precipitate the polyimide precursor, and the water-polyimine precursor mixture was stirred for 15 minutes at a speed of 5000 rpm. The polyimide precursor was filtered out, poured into 4 liters of water again, and stirred for 30 minutes, and filtered again. Then, under reduced pressure, the obtained polyimide precursor was dried at 45° C. for 3 days to obtain a polyimide precursor (A-3).

<Synthesis Example 4: Polypropylene containing pyromellitic dianhydride, poly(propylene glycol) bis(2-aminopropyl ether), 4,4'-oxydiphenylamine, and 2-hydroxyethyl methacrylate Amine precursor (A-4)>

14.06g (64.5 millimoles) of pyromellitic dianhydride (dried at 140°C for 12 hours), 18.6g (129 millimoles) of 2-hydroxyethyl methacrylate, and 0.05g of hydroquinone , 10.7 g of pyridine, and 140 g of diethylene glycol dimethyl ether were mixed, and stirred at a temperature of 60° C. for 18 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Then, the reaction mixture was cooled to -10°C, while maintaining the temperature at -10°C±4°C, 16.12 g (135.5 millimoles) of SOCl _{2 was} added over 10 minutes. During the addition of SOCl ₂ , the viscosity increased. After diluting with 50 ml of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, at 20℃~23℃, it will make 12.3g (29.4 millimoles) of poly(propylene glycol) bis(2-aminopropyl ether) (Mn=400) and 5.9g (29.3 millimoles) in 20 minutes. Ear) 4,4'-oxydiphenylamine dissolved in 100ml of N-methylpyrrolidone was added dropwise to the reaction mixture. Then, the reaction mixture was stirred at room temperature for 1 night. Then, it was poured into 5 liters of water to precipitate the polyimide precursor, and the water-polyimine precursor mixture was stirred for 15 minutes at a speed of 5000 rpm. The polyimide precursor was filtered out, poured into 4 liters of water again, and stirred for 30 minutes, and filtered again. Then, the obtained polyimide precursor was dried at 45°C under reduced pressure for 3 days to obtain a polyimide precursor (A-4) having a repeating unit represented by the following formula.

In the above, n (average value) is 6. In addition, the molar ratio of the repeating unit on the left to the repeating unit on the right is 50:50.

<Synthesis Example 5: Containing 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, poly(propylene glycol) bis(2-aminopropyl ether), and 2-hydroxyethyl methacrylate Polyimide precursor (A-5)>

Except that 14.06g (64.5 millimoles) of pyromellitic dianhydride in Synthesis Example 1 was changed to 20.00g (64.5 millimoles) of 3,3',4,4'-diphenyl ether tetracarboxylic acid two Except for the anhydride, it was synthesized by the same method as Synthesis Example 1, and a polyimide precursor (A-5) having a repeating unit represented by the following formula was obtained.

In the above, n (average value) is 6.

<Synthesis Example 6: Polyimide precursor containing pyromellitic dianhydride, 4,4'-oxydiphenylamine, and 2-hydroxyethyl methacrylate (RA-1 for comparative examples)>

14.06g (64.5 millimoles) of pyromellitic dianhydride (dried at 140°C for 12 hours), 18.6g (129 millimoles) of 2-hydroxyethyl methacrylate, and 0.05g of hydroquinone , 10.7 g of pyridine, and 140 g of diethylene glycol dimethyl ether were mixed, and stirred at a temperature of 60° C. for 18 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Then, the reaction mixture was cooled to -10°C, while maintaining the temperature at -10°C±4°C, 16.12 g (135.5 millimoles) of SOCl _{2 was} added over 10 minutes. During the addition of SOCl ₂ , the viscosity increased. After diluting with 50 ml of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, 11.8g (58.7 millimoles) of 4,4'-oxydiphenylamine was dissolved in 100ml of N-methylpyrrolidone in 20 minutes at 20°C to 23°C for 20 minutes. Add to the reaction mixture. Then, the reaction mixture was stirred at room temperature for 1 night. Then, it was poured into 5 liters of water to precipitate the polyimide precursor, and the water-polyimine precursor mixture was stirred for 15 minutes at a speed of 5000 rpm. The polyimide precursor was filtered out, 4 liters of water was added again, and the mixture was stirred for 30 minutes and filtered again. Then, the obtained polyimide precursor was dried at 45°C under reduced pressure for 3 days to obtain a polyimide precursor (RA-1) having a repeating unit represented by the following formula.

<Synthesis Example 7: Polyimide precursor containing pyromellitic dianhydride, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 2-hydroxyethyl methacrylate (RA-2 for comparative example)>

Except that 11.8 g (58.7 millimoles) of 4,4'-oxydiphenylamine in Synthesis Example 6 was changed to 14.6 g (58.7 millimoles) of 1,3-bis(3-aminopropyl)tetramethyl Except for the base disiloxane, it was synthesized by the same method as in Synthesis Example 6, and a polyimide precursor (RA-2) having a repeating unit represented by the following formula was obtained.

[化52]

<Synthesis Example 8: Polyimide precursor containing pyromellitic dianhydride and poly(propylene glycol) bis(2-aminopropyl ether) (RA-3 for comparative examples)>

14.06g (64.5 millimoles) of pyromellitic dianhydride (dried at 140°C for 12 hours), 13.95g (129 millimoles) of benzyl alcohol, 0.05g of hydroquinone, 10.7g of pyridine, and 140 g of N-methylpyrrolidone was mixed, and the mixture was stirred at a temperature of 60°C for 18 hours to produce a diester of pyromellitic acid and benzyl alcohol. Then, the reaction mixture was cooled to -10°C, while maintaining the temperature at -10°C±4°C, 16.12 g (135.5 millimoles) of SOCl _{2 was} added over 10 minutes. During the addition of SOCl ₂ , the viscosity increased. After diluting with 50 ml of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, 23.5g (58.7 millimoles) of poly(propylene glycol) bis(2-aminopropyl ether) (Mn=400) will be dissolved in 100ml of N-methyl at 20℃~23℃ for 20 minutes. The solution in pyrrolidone was added dropwise to the reaction mixture. Then, the reaction mixture was stirred at room temperature for 1 night. Then, it heated up to 200 degreeC, and made it react for 12 hours. After the reaction, it was cooled to room temperature, poured into 5 liters of water to precipitate the polyimide precursor, and the water-polyimide precursor mixture was stirred for 15 minutes at a speed of 5000 rpm. The polyimide precursor was filtered out, 4 liters of water was added again, and the mixture was stirred for 30 minutes and filtered again. Then, the obtained polyimide precursor was dried at 45°C under reduced pressure for 3 days to obtain a polyimide precursor (RA-3) having a structure represented by the following formula.

In the above, n (average value) is 6.

<Examples and Comparative Examples>

The components described below are mixed to form a uniform solution, and a coating liquid of the negative photosensitive resin composition is prepared.

<<Composition of negative photosensitive resin composition>>

(A) Polyimide precursor: mass% listed in Table 5

(B) Light radical polymerization initiator: mass% listed in Table 5

(C) Radical polymerizable compound: mass% listed in Table 5

Solvent (γ-butyrolactone): 60.00% by mass

After passing each negative photosensitive resin composition through a filter with a pore width of 0.8 μm to perform pressure filtration, it was applied by spin coating on a silicon wafer (3500 rpm, 30 seconds). On the hot plate, the silicon wafer to which the negative photosensitive resin composition was applied was dried at 100°C for 5 minutes to form a uniform photosensitive resin composition layer with a thickness of 16 μm on the silicon wafer.

<evaluation>

[Exposure Tolerance]

A stepper (Nikon NSR2005i9C) was used to expose the photosensitive resin composition layer on the silicon wafer. The exposure is carried out using i-rays at a wavelength of 365nm at 200mJ/cm ² , 300mJ/cm ² , 400mJ/cm ² , 500mJ/cm ² , 600mJ/cm ² , 700mJ/cm ² , 800mJ/cm ² each The exposure energy is exposed using a line and space mask with a unit of 1 μm from 5 μm to 25 μm.

The exposed photosensitive resin composition layer was developed with cyclopentanone for 60 seconds. The following criteria are used to evaluate the line width with good edge sharpness. The smaller the line width of the photosensitive resin composition layer is, the larger the difference in solubility between the light-irradiated portion and the non-light-irradiated portion in the developer solution becomes, and it is a better result. In addition, the smaller the change in line width with respect to the change in exposure energy, the wider the exposure latitude, which becomes a better result. The measurement limit is 5 μm. The results are shown in Table 5.

A: 5μm or more, 8μm or less

B: More than 8μm, 10μm or less

C: Over 10μm, 15μm or less

D: Over 15μm, 20μm or less

E: more than 20μm

[Warpage]

After passing each negative photosensitive resin composition through a filter with a pore width of 0.8 μm to perform pressure filtration, it was applied by spin coating on a silicon wafer (3500 rpm, 30 seconds). On a hot plate, the silicon wafer applied with the negative photosensitive resin composition was dried at 100°C for 5 minutes, and a uniform photosensitive resin composition layer with a thickness of 16 μm was formed on the silicon wafer, and then i-rays were used at 500 mJ The entire surface was exposed with an exposure energy of /cm ² and further heated at 300° C. for 3 hours to prepare a sample for warpage measurement. The Bow value of the sample for warpage measurement was measured using FLX-2320 manufactured by KLA-Tencor. Furthermore, 1 inch is 2.54 cm.

A: Bow value is below 40μm

B: Bow value exceeds 40μm but less than 80μm

C: Bow value above 80μm

[Continuity]

After passing each negative photosensitive resin composition through a filter with a pore width of 0.8 μm to perform pressure filtration, it was applied by spin coating on a copper substrate (3500 rpm, 30 seconds). On a hot plate, the copper substrate applied with the negative photosensitive resin composition was dried at 100°C for 5 minutes, and a uniform photosensitive resin composition layer with a thickness of 16 μm was formed on the copper substrate, and then i-ray was used at 500 mJ/cm Exposure energy of ² exposed the entire surface, and further heated at 300°C for 3 hours. Furthermore, in accordance with the cross-cut method of Japanese Industrial Standards (JIS) K5600-5-6, the adhesion characteristics to the copper substrate were evaluated based on the following criteria.

A: The photosensitive resin composition layer adhering to the substrate is 100

B: The photosensitive resin composition layer adhering to the substrate is 80 to 99

C: The photosensitive resin composition layer adhering to the substrate is 50 to 79

D: The photosensitive resin composition layer adhering to the substrate is less than 50

[table 5]

The numerical value of the exposure latitude in Table 5 represents the exposure energy (unit: mJ/cm ² ).

The abbreviations described in Table 5 are as follows.

(A) Polyimide precursor

Polyimide precursor used in the synthesis example

(B) Light radical polymerization initiator

B-1: Irgacure-OXE01 (manufactured by BASF)

B-2: Irgacure 369 (made by BASF)

B-3: Irgacure 784 (made by BASF)

(C) Radical polymerizable compound

C-1: NK ESTER M-40G (manufactured by Shinnakamura Chemical Industry Co., Ltd.; monofunctional methacrylate; the following structure)

C-2: NK ESTER 4G (manufactured by Shinnakamura Chemical Industry Co., Ltd.; difunctional methacrylate; the following structure)

C-3: NK ESTER A-9300 (manufactured by Shinnakamura Chemical Industry Co., Ltd.; trifunctional acrylate; the following structure)

C-4: NK ESTER A-BPE-4 (manufactured by Shinnakamura Chemical Industry Co., Ltd.; difunctional acrylate; the following structure)

C-5: NK ESTER A-HD-N (manufactured by Shinnakamura Chemical Industry Co., Ltd.; difunctional acrylate; the following structure)

<Example 100>

The negative photosensitive resin composition of Example 1 was filtered under pressure through a filter with a pore width of 0.8 μm, and then applied by spin coating (3500 rpm, 30 seconds) on a resin substrate with a thin copper layer . After drying the negative photosensitive resin composition applied to the resin substrate at 100°C for 5 minutes, exposure was performed using an aligner (Karl-Suss MA150). Exposure was performed with a high-pressure mercury lamp, and the exposure energy at a wavelength of 365nm was measured. After exposure, the image was developed with cyclopentanone for 75 seconds.

Then, heating was performed at 180°C for 20 minutes. In this way, an interlayer insulating film for the rewiring layer is formed.

The interlayer insulating film for the rewiring layer has excellent insulating properties.

In addition, a semiconductor element was manufactured using the interlayer insulating film for the rewiring layer, and as a result, it was confirmed that the operation was performed without any problems.

100‧‧‧Semiconductor components

101‧‧‧Layered body

101a~101d‧‧‧Semiconductor device (semiconductor wafer)

102b~102d‧‧‧through electrode

103a~103e‧‧‧Metal bump

105‧‧‧Rewiring layer

110, 110a, 110b‧‧‧underfill

115‧‧‧Insulation layer

120‧‧‧Wiring board

120a‧‧‧surface electrode

Claims (14)

A negative photosensitive resin composition comprising: a polyimide precursor having a repeating unit represented by the following general formula (1), and a photo-radical polymerization initiator;

In the general formula (1), A ¹ and A ² each independently represent an oxygen atom or -NH-, R ¹¹ is a structure represented by the following general formula (2), R ¹² represents a tetravalent organic group, R ¹³ and R ¹⁴ each independently represents a hydrogen atom or a monovalent organic group;

In the general formula (2), R ²¹ and R ²² each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbons. A plurality of R ²¹ may be the same or different; n2 is an integer of 2 or more; * represents the same as the general formula (1) The -NH- linking site. The negative photosensitive resin composition as described in claim 1, wherein at least one of R ¹³ and R ¹⁴ in the general formula (1) contains a radical polymerizable group. The negative photosensitive resin composition as described in item 1 or item 2 of the scope of patent application further contains a radical polymerizable compound. The negative photosensitive resin composition as described in claim 3, wherein the radically polymerizable compound is a compound that is bifunctional or higher. The negative photosensitive resin composition as described in claim 3, wherein the radically polymerizable compound is a bifunctional compound. The negative photosensitive resin composition as described in claim 1 or 2, wherein R ¹² in the general formula (1) is a tetravalent organic group containing an aromatic ring. The negative photosensitive resin composition according to the first or second item of the scope of patent application, wherein n2 in the general formula (2) is an integer of 2 to 200. The negative photosensitive resin composition as described in item 1 or item 2 of the scope of the patent application is used for an interlayer insulating film for a rewiring layer. A cured film obtained by curing the negative photosensitive resin composition described in any one of items 1 to 8 in the scope of the patent application. The cured film described in claim 9 is an interlayer insulating film for a rewiring layer. A method for manufacturing a cured film, comprising: using the negative photosensitive resin composition as described in any one of items 1 to 8 of the scope of patent application. The method for manufacturing a cured film as described in the eleventh scope of the patent application includes the step of applying the negative photosensitive resin composition to a substrate; A step of irradiating the negative photosensitive resin composition applied on the substrate with actinic rays or radiation to perform exposure; and a step of performing development processing on the exposed negative photosensitive resin composition. The method for manufacturing a cured film as described in item 12 of the scope of the patent application, after the step of the development process, further includes the composition of the developed negative photosensitive resin at a temperature of 50°C to 500°C The step of heating the material. A semiconductor element having a cured film as described in item 9 of the scope of patent application.

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