WO2021020344A1 - Photosensitive resin composition, photosensitive sheet, cured film, method for producing cured film, interlayer insulating film and electronic component - Google Patents

Abstract

The purpose of the present invention is to provide a photosensitive resin composition which has good pattern formability, and which enables the achievement of a cured film having a low dielectric constant, a low dielectric loss tangent and high elongatability, said cured film being obtained by curing this photosensitive resin composition. The present invention is a photosensitive resin composition which contains (A) a polyimide precursor and (B) a photopolymerization initiator, wherein: the polyimide precursor (A) contains a polyvalent carboxylic acid residue and/or a polyvalent amine residue having a structure of an alicyclic hydrocarbon having 4 to 8 carbon atoms, said hydrocarbon optionally having an unsaturated bond; and at least four hydrogen atoms in the structure of an alicyclic hydrocarbon are substituted by a hydrocarbon group having 4 to 12 carbon atoms, said hydrocarbon group optionally having an unsaturated bond.

Description

Photosensitive resin composition, photosensitive sheet, cured film, method for manufacturing cured film, interlayer insulating film and electronic components

The present invention relates to a photosensitive resin composition, a photosensitive sheet, a cured film, a method for producing a cured film, an interlayer insulating film, and an electronic component. More specifically, the present invention relates to a photosensitive resin composition preferably used for a surface protective film of an electronic component such as a semiconductor element, an interlayer insulating film, an insulating layer of an organic electroluminescent element, and the like.

Typical materials for surface protective films and interlayer insulating films of semiconductor elements, insulating layers of organic electrolytic elements, and flattening films of TFT substrates include polyimide resins having excellent heat resistance and electrical insulation. Further, in order to improve the productivity, a photosensitivity polyimide imparted with negative-type photosensitivity and a precursor thereof are also being studied.

In recent years, along with the expansion of semiconductor applications and performance improvements, efforts have been made to reduce costs and increase integration by improving the efficiency of manufacturing processes. Therefore, attention has been focused on semiconductor devices that form multi-layered metal rewiring. Such an insulating film for multi-layer metal rewiring is required to have crack resistance against stress due to multi-layering and low dielectric constant due to high integration. Further, in high-frequency communication device applications for high-speed wireless communication, a low dielectric loss tangent is required for the insulating film in order to reduce transmission loss.

As a means for improving crack resistance, a method of introducing a flexible alkylene oxide skeleton into the main chain of polyimide has been proposed (Patent Document 1). As a means for lowering the dielectric constant, a method using an alicyclic polyimide has been proposed (Patent Document 2). As a means for making a low dielectric loss tangent, a soluble polyimide using a dimer diamine has been proposed as an adhesive layer (Patent Document 3).

Japanese Unexamined Patent Publication No. 2012-208360 Japanese Unexamined Patent Publication No. 2009-186861 JP-A-2018-2030959

When the conventional technique is applied as a multilayer wiring insulating film for a high-frequency communication device for high-speed wireless communication, for example, in Patent Document 1, the dielectric constant is poor because the alkylene oxide group improves water absorption, and in Patent Document 2, the elongation There is a problem that sufficient exposure sensitivity cannot be obtained in Patent Document 3 due to insufficient crack resistance due to the low frequency.

In order to solve the above problems, the present invention relates to the following.
A photosensitive resin composition containing (A) a polyimide precursor and (B) a photopolymerization initiator, wherein the (A) polyimide precursor contains a resin having a structural unit represented by the general formula (11). ..

In the general formula (11), X ⁴ represents a 4- to hexavalent organic group, and Y ⁴ represents a 2- to 6-valent organic group. Provided that at least one of X ⁴ and Y ⁴ represents an organic group containing one or more cycloaliphatic ring structures and a plurality of carbon atoms of 4 or more hydrocarbon structure. A plurality of R ⁸ is independently a monovalent organic group or a hydrogen atom with an ethylenically unsaturated bond. Provided that at least one of the plurality of R ⁸ is a monovalent organic group having an ethylenically unsaturated bond. x indicates an integer of 2 to 4. A plurality of R ⁹ each independently represents a monovalent organic group having a carboxyl group, a hydroxyl group or an ethylenically unsaturated bond. y represents an integer from 0 to 4. * Indicates the connection point.

Another aspect of the present invention is as follows.

A photosensitive resin composition containing (A) a polyimide precursor and (B) a photopolymerization initiator, wherein the (A) polyimide precursor contains a resin having a structural unit represented by the general formula (1). ..

In the general formula (1), X ¹ represents a 4- to hexavalent organic group, and Y ¹ represents a 2- to 6-valent organic group. However, at least ^one of X ¹ and Y ¹ has an alicyclic hydrocarbon structure having 4 to 8 carbon atoms which may have an unsaturated bond. In the structure of the alicyclic hydrocarbon, at least four or more hydrogen atoms are substituted with hydrocarbon groups having 4 to 12 carbon atoms which may have unsaturated bonds. The plurality of R ^1s may be the same or different and represent a monovalent organic group or a hydrogen atom having an ethylenically unsaturated bond. However, not all R ^1s are hydrogen atoms. p represents an integer of 2 to 4. The plurality of R ^2s may be the same or different and represent a monovalent organic group having a carboxyl group, a hydroxyl group or an ethylenically unsaturated bond. q indicates an integer from 0 to 4. * Indicates the connection point.

The photosensitive resin composition of the present invention has excellent exposure sensitivity. Further, the cured film obtained by curing it is excellent in elongation, low dielectric constant, and low dielectric loss tangent.

It is a figure which showed the enlarged cross section of the pad part of the semiconductor device which has a bump. It is a figure which showed the detailed manufacturing method of the semiconductor device which has a bump. It is the schematic of the coplanar feed type microstrip antenna. It is the schematic about the cross section of the semiconductor package including an IC chip (semiconductor element), a rewiring layer, a sealing resin and an antenna element.

The present invention provides a photosensitive resin composition containing (A) a polyimide precursor and (B) a photopolymerization initiator. Each component will be described below.

The photosensitive resin composition of the present invention contains (A) a polyimide precursor (hereinafter, may be abbreviated as "component (A)"). By containing the component (A), the cured film obtained by curing the photosensitive composition has a low dielectric constant and a low dielectric loss tangent. The polyimide precursor (A) contains the structural unit of the following general formula (11).

In the general formula (11), X ⁴ represents a 4- to hexavalent organic group, and Y ⁴ represents a 2- to 6-valent organic group. Provided that at least one of X ⁴ and Y ⁴ represents an organic group containing one or more cycloaliphatic ring structures and a plurality of carbon atoms of 4 or more hydrocarbon structure. A plurality of R ⁸ is independently a monovalent organic group or a hydrogen atom with an ethylenically unsaturated bond. Provided that at least one of the plurality of R ⁸ is a monovalent organic group having an ethylenically unsaturated bond. x indicates an integer of 2 to 4. A plurality of R ⁹ each independently represents a monovalent organic group having a carboxyl group, a hydroxyl group or an ethylenically unsaturated bond. y represents an integer from 0 to 4. * Indicates the connection point.

In another aspect of the present invention, the (A) polyimide precursor contains the structure of the following general formula (1).

In the general formula (1), X ¹ represents a 4- to hexavalent organic group, and Y ¹ represents a 2- to 6-valent organic group. However, at least ^one of X ¹ and Y ¹ has an alicyclic hydrocarbon structure having 4 to 8 carbon atoms which may have an unsaturated bond. In the structure of the alicyclic hydrocarbon, at least four or more hydrogen atoms are substituted with hydrocarbon groups having 4 to 12 carbon atoms which may have unsaturated bonds. The plurality of R ^1s may be the same or different and represent a monovalent organic group or a hydrogen atom having an ethylenically unsaturated bond. However, not all R ^1s are hydrogen atoms. p represents an integer of 2 to 4. The plurality of R ^2s may be the same or different and represent a monovalent organic group having a carboxyl group, a hydroxyl group or an ethylenically unsaturated bond. q indicates an integer from 0 to 4. * Indicates the connection point.

In the general formula (1), X ¹ represents a 4- to hexavalent organic group and represents a residue of a polyvalent carboxylic acid. Examples of the polycarboxylic acid include tetracarboxylic acid, tetracarboxylic dianhydride, tetracarboxylic acid diester dichloride and the like. Here, when "-" is expressed in the present specification, it means that the upper and lower limit numbers are included unless otherwise specified. Y ¹ represents a 2- to hexavalent organic group and represents a residue of a polyvalent amine. At least ^one of X ¹ and Y ¹ may have a structure of an alicyclic hydrocarbon having 4 to 8 carbon atoms which may have an unsaturated bond (hereinafter, may be abbreviated as “structure (a)”). ). However, in the structure of the alicyclic hydrocarbon, at least four or more hydrogen atoms are substituted with hydrocarbon groups having 4 to 12 carbon atoms which may have unsaturated bonds.

That is, when X ¹ indicates a polyvalent carboxylic acid residue having a structure (a) and Y ¹ indicates a polyvalent amine residue having a structure (a), X ¹ and Y ¹ are structures (a), respectively. It may show a polyvalent carboxylic acid residue having a structure (a) and a polyvalent amine residue having a structure (a). By containing such a structure, the cured film obtained by curing the resin composition has high elongation, low dielectric constant, and low dielectric loss tangent.

A specific example of the structure (a) will be described. Examples of the alicyclic hydrocarbon having 4 to 8 carbon atoms which may have an unsaturated bond include a cyclobutyl group, a cyclocyclobutenyl group, a cyclopentyl group, a cyclopentenyl group, a cyclohexyl group, a cyclohexenyl group and a cycloheptyl. Examples include a group, a cycloheptenyl group, a cyclooctyl group, a cyclooctenyl group and the like. Of these, a cyclohexyl group, a cyclohexenyl group, a cycloheptyl group, and a cycloheptenyl group are preferable from the viewpoint of thermal stability.

Examples of the hydrocarbon group having 4 to 12 carbon atoms which may have an unsaturated bond include an n-butyl group, an i-butyl group, a t-butyl group, a 1-butenyl group, a 2-butenyl group and an n-pentyl group. , I-pentyl group, 1-pentenyl group, 2-pentenyl group, n-hexyl group, i-hexyl group, 1-hexenyl group, 2-hexenyl group, n-heptyl group, i-heptyl group, 1- Heptenyl group, 2-heptenyl group, n-octyl group, i-octyl group, 1-octenyl group, 2-octenyl group, nonyl group, 1-nonenyl group, decanyl group, 1-decenyl group, undecanyl group, 1-undecenyl group Examples include a group, a dodecanyl group, a 1-dodecenyl group and the like.

The structure Y ¹ having (a) is a polyamine residue, a diamine having the structure (a), derived from a triamine or a residue of a derivative thereof. Further, by using the amino compound corresponding to the polyvalent amine residue at the time of polymerization, these polyvalent amine residues can be included in the structural unit. Examples of the polyvalent amine having the structure (a) include the polyvalent amine represented by the following general formula (2) or the following general formula (3). Of these, the polyvalent amine listed in the general formula (2), which does not contain a double bond, is preferable from the viewpoint of reliability of the obtained cured film. Further, the polyvalent amine represented by the following formula (4) is more preferable from the viewpoint of economy and the elongation of the obtained cured film.

In the general formula (2), m indicates an integer of 4 to 8. W independently represents any of the structural units represented by the general formulas (2a), (2b) or (2c). Of the m Ws, two or more structural units of (2c) are contained, and the sum of the numbers of (2b) and (2c) is 4 or more and 8 or less. n or o independently represent an integer of 3 to 11.

In the general formula (3), e, f, g, and h are natural numbers, and e + f = 6 to 17, g + h = 8 to 19. The wavy line part means a carbon-carbon single bond or a carbon-carbon double bond. However, at least one in one molecule shows a double bond.

Specific examples of the polyvalent amine having the structure (a) include "versamine 551", "versamine 552" (above, trade name (manufactured by BASF Ltd.)) and "priamine" as commercially available products of dimerdiamine and trimertriamine. Examples thereof include "1071", "Priamine 1073", "Priamine 1074", and "Priamine 1075" (above, trade name (manufactured by Crowder Japan Co., Ltd.)). Here, "versamine 551" and "priamine 1074" are all dimer diamine compounds containing a compound represented by the following formula (5), and "versamine 552", "priamine 1073" and "priamine 1075" are all. , A diamine diamine compound containing the compound represented by the above formula (4). "Priamine 1071" is a mixture of dimer diamine and trimer triamine.

X ¹ having the structure (a) is a polyvalent carboxylic acid residue, and is derived from a polyvalent carboxylic acid residue having the structure (a) or a residue thereof. Examples of the polyvalent carboxylic acid compound serving as a polyvalent carboxylic acid residue include tetracarboxylic acid and octacarboxylic acid hexacarboxylic acid. Further, by using the polyvalent carboxylic acid component corresponding to the polyvalent carboxylic acid residue at the time of polymerization, these polyvalent carboxylic acid residues can be included in the structural unit. The polyvalent carboxylic acids having the structure (a), include reaction products of polyamines and trimellitic anhydride acid chloride as exemplified by Y ¹ having the above structure (a). More specifically, the following general formula (6) can be mentioned.

In the general formula (6), i, j, k, l are natural numbers, and i + j = 6 to 17, k + l = 8 to 19. The wavy line part means a carbon-carbon single bond or a carbon-carbon double bond.

In the general formula (11), X ⁴ represents a 4-6 valent organic group, a residue of a polycarboxylic acid component. Examples of the polyvalent carboxylic acid component include tetracarboxylic acid, tetracarboxylic dianhydride, tetracarboxylic acid diester dichloride and the like. Y ⁴ represents a divalent to hexavalent organic group, a polyamine residue. At least one of X ⁴ and Y ^4, one or more alicyclic structures and a plurality of organic groups comprising C 4+ hydrocarbon structure carbon (hereinafter sometimes abbreviated as "structure (b)") Is shown. That is, when X ⁴ indicates a polyvalent carboxylic acid residue having a structure (b), and Y ⁴ indicates a polyvalent amine residue having a structure (b), X ⁴ and Y ⁴ have a structure (b), respectively. It may indicate a polyvalent carboxylic acid residue having and a polyvalent amine residue having structure (b). By containing such a structure, the cured film obtained by curing the resin composition has high elongation, low dielectric constant, and low dielectric loss tangent.

A specific example of the structure (b) will be described. Any structure can be used as the alicyclic structure, but a bicyclo ring and a tricyclo ring having a plurality of cyclic structures are preferable from the viewpoint of heat resistance. Specific examples of the alicyclic structure include an organic group exemplified as a specific example of the alicyclic hydrocarbon of the structure (a), a norbornyl group, a norbonel group, a tricyclodecanyl group and the like, and have heat resistance. From the viewpoint, a norbornyl group, a norbonel group and a tricyclodecanyl group are preferable.

As the hydrocarbon structure having 4 or more carbon atoms, in addition to the organic group exemplified as a specific example of the hydrocarbon group having 4 to 12 carbon atoms which may have an unsaturated bond of the structure (a), a tetradecanyl group and a hexadecanyl group are used. Examples include a group, an octadecanol group, and an icosanyl group.

Is Y ⁴ is a polyvalent amine residue having the structure (b), the polyhydric amine compound, in addition to the polyvalent amine exemplified in the construction (a), the multi represented by the following general formula (12) Valuable amines can be mentioned.

In the general formula (12), u and t represent integers of 4 to 16, respectively.

X ⁴ having the structure (b) is a polyvalent carboxylic acid residue, as the polycarboxylic acid, in addition to the polycarboxylic acid exemplified in the construction (a), is represented by the following general formula (13) Polyvalent carboxylic acid.

In the general formula (13), o and p represent integers of 4 to 16, respectively.

The component (A) is preferably a resin having a structural unit represented by the general formula (1) and the following general formula (7). Further, it is preferable that the resin has a structural unit represented by the general formula (11) and the following general formula (7). By having these structural units, it is possible to impart heat resistance and organic solvent solubility while maintaining a low dielectric constant and a low dielectric loss tangent.

In the general formula (7), X ² represents a 4- to hexavalent organic group, and Y ² represents a 2- to 6-valent organic group. However, at least X ² is X ³ or Y ² is Y ³ . X ³ is a divalent to hexavalent organic group containing any one or more of a bisphenol A skeleton, a biphenyl skeleton or a hexafluoroisopropylidene skeleton, or a residue of an acid anhydride represented by the following general formula (8). Indicates any one or more of. Y ³ is any one of a diamine residue represented by the following formula (9) or a divalent to hexavalent organic group containing any one or more of a bisphenol A skeleton, a biphenyl skeleton or a hexafluoroisopropylidene skeleton. The above is shown. The plurality of R ³ may be the same or different, represents a monovalent organic group or a hydrogen atom with an ethylenically unsaturated bond. However, not all R ^3s are hydrogen atoms. r indicates an integer of 2 to 4. The plurality of R ⁴ may be the same or different, showing a carboxyl group, a monovalent organic group having a hydroxyl group or an ethylenically unsaturated bond. s represents an integer from 0 to 4. * Indicates the connection point.

In the general formula (8), a represents an integer of 6 to 20. * Indicates the connection point.

In general formula (9), * indicates a connection point.

In general formula (7), X ² and X ³ are derived from carboxylic acid residues or residues of derivatives thereof. When X ² is X ³ , examples of the carboxylic acid compound having X ³ as an acid residue include 3,3', 4,4'-biphenyltetracarboxylic acid and 2,3,3', 4'-biphenyl. Tetracarboxylic acid, 2,2', 3,3'-biphenyltetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 2,2-bis (2,3-dicarboxyphenyl) ) Hexafluoropropane, 4,4'-(4,4'-isopropyridene diphenoxy) bis (phthalic acid), 4,4'-(4,4'-isopropyridene diphenoxycarbonyl) bis (phthalic acid) and , Carboxylic acid anhydrides listed in the general formula (7), and derivatives thereof. Among these, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane and 2,2-bis (2,3-bis) from the viewpoint of solubility in organic solvents, transparency, and low dielectric constant. Dicarboxyphenyl) hexafluoropropane, 4,4'-(4,4'-isopropyridene diphenoxy) bis (phthalic acid) are preferred.

In general formula (7), Y ² and Y ³ are derived from amine residues or residues of derivatives thereof. When Y ² is Y ³ , examples of the amino compound having Y ³ as an amine residue include 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'. -Diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2', 3,3'-Tetramethyl-4,4'-diaminobiphenyl,3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl,2,2'-bis (trifluoromethyl) -4,4'- Diaminobiphenyl, bis (3-amino-4-hydroxy) biphenyl, 4,4'-diamino-6,6'-bis (trifluoromethyl)-[1,1'-biphenyl] -3,3'-diol, Bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2'-bis [N- (3-Aminobenzoyl) -3-amino-4-hydroxyphenyl] hexafluoropropane, 2,2'-bis [N- (4-aminobenzoyl) -3-amino-4-hydroxyphenyl] hexafluoro Examples thereof include propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, a diamine compound represented by the general formula (8), or a derivative thereof. Among these, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, bis (3-amino-4-) from the viewpoint of solubility in organic solvents, transparency, and low dielectric constant. Aromatic diamines such as hydroxyphenyl) hexafluoropropane and 2,2-bis [4- (4-aminophenoxy) phenyl] propane, and 1,4-cyclohexanediamine and 1,2-bis in the general formula (9). (Aminomethyl) cyclohexane and 1,3-bis (aminomethyl) cyclohexane are preferred.

X ¹ may be an acid residue other than the polyvalent carboxylic acid residue having the structure (a) as long as the requirements of the general formula (1) are satisfied. Further, X ² may be an acid residue other than X ³ as long as it satisfies the requirement of the general formula (7).

Further, X ⁴ may be an acid residue other than the polyvalent carboxylic acid residue having the structure (b) as long as the requirements of the general formula (11) are satisfied.

Examples of the carboxylic acid compound as another acid residue include pyromellitic acid, 3,3', 4,4'-benzophenone tetracarboxylic acid, 2,2', 3,3'-benzophenone tetracarboxylic acid, 1, 1-bis (3,4-dicarboxyphenyl) ethane, 1,1-bis (2,3-dicarboxyphenyl) ethane, bis (3,4-dicarboxyphenyl) methane, bis (2,3-dicarboxyphenyl) Phenyl) methane, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) thioether, bis (3,4-dicarboxyphenyl) ether, 1,3-bis (3,4-) Dicarboxyphenoxy) benzene, trimellitic acid (3,4-dicarboxyphenyl), 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5 , 6-pyridinetetracarboxylic acid or aromatic tetracarboxylic acid such as 3,4,9,10-perylenetetracarboxylic acid or bicyclo [3.1.1. ] Hept-2-enetetracarboxylic acid, bicyclo [2.2.2. ] Aliphatic tetracarboxylic acids such as octane tetracarboxylic acid and adamatane tetracarboxylic acid can be mentioned.

These acids can be used as they are or as acid anhydrides, acid chlorides or active esters. Examples of the activated ester group include, but are not limited to, the following structures.

In the formula, A and D represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, a trifluoromethyl group, a halogen group, a phenoxy group and a nitro group. * Indicates the connection point.

Further, by using a silicon atom-containing tetracarboxylic acid such as dimethylsilanediphthalic acid or 1,3-bis (phthalic acid) tetramethyldisiloxane, adhesion to a substrate, oxygen plasma used for cleaning, etc., UV ozone The resistance to treatment can be increased. It is preferable to use 1 to 30 mol% of the total acid component of these silicon atom-containing tetracarboxylic acids.

Y ¹ may be an amine residue other than the polyvalent amine residue having the structure (a) as long as the requirements of the general formula (1) are satisfied. Further, Y ² may be an amine residue other than Y ³ as long as it satisfies the requirement of the general formula (7).

Further, Y ⁴ is as long as it meets the requirements of the general formula (11) may be a polyvalent amine other amine residues other than residue having the structure (a).

Examples of polyvalent amine compounds that serve as other amine residues include m-phenylenediamine, p-phenylenediamine, 3,5-diaminobenzoic acid, 1,5-naphthalenediamine, and 2,6 as aromatic diamines. -Naphthalenediamine, 9,10-anthracenediamine, 4,4'-diaminobenzanilide, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3-carboxy-4,4'-diaminodiphenyl ether, 3- Sulphonic acid-4,4'-diaminodiphenyl ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene , 1,3-bis (4-aminophenoxy) benzene, bis (3-amino-4-hydroxyphenyl) ether, 3,4'-diaminodiphenylmethane, bis (3-amino-4-hydroxyphenyl) methylene, 4, 4'-diaminodiphenylmethane, 3,3'-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, bis [N- (3-aminobenzoyl) -3-amino-4- Hydroxyphenyl] sulfone, bis [N- (4-aminobenzoyl) -3-amino-4-hydroxyphenyl] sulfone, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-aminophenoxyphenyl) sulfone, Bis (3-aminophenoxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) propane, 2,2'-bis [N- (3-aminobenzoyl) -3-amino-4-hydroxyphenyl] propane, 2,2'-bis [N- (4-aminobenzoyl) -3-amino-4-hydroxyphenyl] propane, 9,9-bis (3-amino-4-hydroxyphenyl) fluorene, 2,7-diaminofluorene , 9,9-bis (4-aminophenyl) fluorene, 9,9-bis [N- (3-aminobenzoyl) -3-amino-4-hydroxyphenyl] fluorene, 9,9-bis [N- (4) -Aminobenzoyl) -3-amino-4-hydroxyphenyl] fluorene, 2- (4-aminophenyl) -5-aminobenzoxazole, 2- (3-aminophenyl) -5-aminobenzoxazole, 2- (4) -Aminophenyl) -6-aminobenzoxazole, 2- (3-amino Phenyl) -6-aminobenzoxazole, 1,4-bis (5-amino-2-benzoxazolyl) benzene, 1,4-bis (6-amino-2-benzoxazolyl) benzene, 1,3 -Bis (5-amino-2-benzoxazolyl) benzene, 1,3-bis (6-amino-2-benzoxazolyl) benzene, 2,6-bis (4-aminophenyl) benzobisoxazole, 2,6-bis (3-aminophenyl) benzobisoxazole, bis [(3-aminophenyl) -5-benzoxazolyl], bis [(4-aminophenyl) -5-benzoxazolyl], bis [(3-Aminophenyl) -6-benzoxazolyl], bis [(4-aminophenyl) -6-benzoxazolyl], N, N'-bis (3-aminobenzoyl) -2,5- Diamino-1,4-dihydroxybenzene, N, N'-bis (4-aminobenzoyl) -2,5-diamino-1,4-dihydroxybenzene, N, N'-bis (4-aminobenzoyl) -4, 4'-diamino-3,3-dihydroxybiphenyl, N, N'-bis (3-aminobenzoyl) -3,3'-diamino-4,4-dihydroxybiphenyl, N, N'-bis (4-aminobenzoyl) ) -3,3'-Diamino-4,4-dihydroxybiphenyl, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 4-aminobenzoic acid 4-aminophenyl ester, 1,3-bis Aromatic diamines such as (4-anilino) tetramethyldisiloxane, and compounds in which a part of the hydrogen atom of these aromatic rings is replaced with an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, a halogen atom, or the like. However, it is not limited to these.

The above-mentioned multivalent amine compound can be used as it is or as a compound in which the amine moiety is isocyanated or trimethylsilylated. Further, these two or more kinds of polyvalent amine compounds may be used in combination.

Examples of the aliphatic diamine include ethylenediamine, 1,3-diaminopropane, 2-methyl-1,3-propanediamine, 1,4-diaminobutane, 1,5-diaminopentane, and 2-methyl-1,5-. Diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane Examples of the diamine having a siloxane structure include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylpentasiloxane, which are preferable because they can improve the adhesiveness to the substrate. ..

A plurality of R ¹ in the general formula (1) in the ^general formula (7) each of the plurality of the plurality of R ⁸ R ³ and Formula (11) in the in, at least one ethylenically unsaturated bond It is a monovalent organic group having. As a method for introducing an organic group having an ethylenically unsaturated bond, for example, a tetracarboxylic acid dianhydride is reacted with an alcohol having an ethylenically unsaturated bond to form a tetracarboxylic acid diester, which is then combined with a polyvalent amine compound. It is obtained by an amide polycondensation reaction with. Other methods include, for example, a method in which a polyamic acid is obtained from an acid dianhydride and a diamine, and then an alcohol having a trifluoroacetic acid and an ethylenically unsaturated bond is reacted with the amic acid.

As the method for producing the above-mentioned tetracarboxylic dianhydride, the above-mentioned acid dianhydride and alcohol can be reacted as they are in a solvent, but it is preferable to use a reaction activator from the viewpoint of reactivity. Examples of the reaction activator include tertiary amines such as pyridine, dimethylaminopyridine, triethylamine, N-methylmorpholine, and 1,8-diazabicycloundecene. The amount of the reaction activator added is preferably 3 mol% or more and 300 mol% or less, more preferably 20 mol% or more and 150 mol% or less, based on the acid anhydride group to be reacted. In addition, a small amount of a polymerization inhibitor may be used for the purpose of preventing the ethylenically unsaturated bond site from being crosslinked during the reaction. As a result, in the reaction between alcohols having an ethylenically unsaturated bond having low reactivity and tetracarboxylic dianhydride, the reaction can be promoted by heating in a range of 120 ° C. or lower. Examples of the polymerization inhibitor include phenol compounds such as hydroquinone, 4-methoxyphenol, t-butylpyrocatechol, and bis-t-butylhydroxytoluene. The amount of the polymerization inhibitor added is preferably 0.1 mol% or more and 5 mol% or less of the phenolic hydroxyl group of the polymerization inhibitor with respect to the ethylenically unsaturated bond of alcohols.

Various methods can be mentioned as the above-mentioned amide polycondensation reaction. Examples thereof include a method of acid chloride-forming a tetracarboxylic acid diester and then reacting it with a diamine, a method using a carbodiimide-based dehydration condensing agent, and a method of activating esterification and then reacting it with a diamine. Of these, the method using an activated ester as an intermediate is preferable because the reactivity is good regardless of whether aromatic diamine or aliphatic diamine is selected as the monomer.

Examples of the alcohols having an ethylenically unsaturated bond include (meth) acrylates having a hydroxyl group and unsaturated fatty acid-modified alcohols. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 1- (meth) acryloyloxy-2-propyl alcohol, and the like. 2- (Meta) acrylamide ethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl (meth) acrylate, 2-hydroxy-3-butoxypropyl (meth) acrylate, 2-hydroxy- 3-Phenoxypropyl (meth) acrylate, 2-hydroxy-3-t-butoxypropyl (meth) acrylate, 2-hydroxy-3-cyclohexylalkoxypropyl (meth) acrylate, 2-hydroxy-3-cyclohexyloxypropyl (meth) Alcohols such as acrylate, 2- (meth) acryloxyethyl-2-hydroxypropylphthalate, which have an ethylenically unsaturated bond and one hydroxyl group, glycerin-1,3-di (meth) acrylate, glycerin-1,2- Di (meth) acrylate, trimethylpropandi (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerin-1-allyloxy-3-methacrylate, glycerin-1-allyloxy-2- Two or more ethylenically unsaturated bonds such as methacrylate, 2-ethyl-2- (hydroxymethyl) propane-1,3-diylbis (2-methacrylate), 2- (acryloyloxy) -2- (hydroxymethyl) butyl methacrylate, etc. And alcohol having 1 hydroxyl group. Here, "(meth) acrylate" means methacrylate or acrylate. The same applies to similar notations.

Examples of unsaturated fatty acid-modified alcohols include unsaturated fatty acid-modified alcohols having 6 or more carbon atoms. From the viewpoint of exposure sensitivity, an alcohol having an unsaturated group at the terminal or having a double bond having a cis structure is preferable, and from the viewpoint of dielectric constant and dielectric loss tangent, 12 or more carbon atoms are preferable. Specific examples of unsaturated fatty acid-modified alcohols include 5-hexen-1-ol, 3-hexen-1-ol, 6-heptene-1-ol, cis-5-octene-1-ol, and cis-3-octen-1. -All, cis-3-nonen-1-ol, cis-6-nonen-1-ol, 9-decane-1-ol, cis-4-decane-1-ol, 10-undecene-1-ol, 11 -Dodecane-1-ol, eride linoleil alcohol, oleyl alcohol, linoleil alcohol, linolenyl alcohol, elsyl alcohol and the like. Of these, oleyl alcohol, linoleyl alcohol, and linoleyl alcohol are preferable from the viewpoint of the dielectric properties of the obtained cured film and the exposure sensitivity.

Other alcohols may be used at the same time when the acid anhydride and alcohols having an ethylenically unsaturated bond are reacted. Other alcohols can be appropriately selected according to various purposes such as adjustment of exposure sensitivity and adjustment of solubility in an organic solvent. Specifically, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, i-butanol, t-butanol, 1-pentanol, 2-pentanol, 3-pentanol, i-pen Aliper alcohols such as tanol or ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, Triethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol Examples thereof include monoalcohol derived from alkylene oxide such as monoethyl ether and tripropylene glycol monobutyl ether.

As a method for introducing an organic group R ¹ in the general formula ^(1), the general formula (7) in R ^3, and in formula (11) a plurality of R ⁸ in having an ethylenically unsaturated bond, an ionic bond May be via. As a method for introducing an organic group having an ethylenically unsaturated bond by an ionic bond, for example, a method of reacting a polyamic acid obtained by a reaction between an acid dianhydride and a diamine with a tertiary amine having an ethylenically unsaturated bond. Can be mentioned. Examples of the tertiary amine having an ethylenically unsaturated bond include a compound represented by the following general formula (10).

In the general formula (10), R ⁵ represents a hydrogen atom or a methyl group. R ⁶ and R ⁷ each independently represent either a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s-butyl group, a t-butyl group or a phenyl group. b represents an integer from 1 to 10.

Among these, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and diethylaminopropyl (merylate are preferable because they can easily increase the exposure sensitivity.

Further, in order to improve the storage stability of the photosensitive resin composition of the present invention and to exhibit various functions, the component (A) may be sealed at the end of the main chain with an end-capping agent. Examples of the terminal encapsulant include monoamines, acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds. In addition, monoalcohol can also be used as an end-capping agent in the latter stage of the above-mentioned amide polycondensation reaction. Further, by sealing the end of the resin with a terminal sealant having a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, a vinyl group, an ethynyl group or an allyl group, exposure sensitivity, mechanical properties of the obtained cured film, etc. Can be easily adjusted to a preferable range.

The introduction ratio of the end sealant is preferably 0.1 mol% or more and 60 mol% or less, and particularly preferably 5 mol% or more and 50 mol% or less, from the viewpoint of solubility in a developing solution and mechanical properties of the obtained cured film. A plurality of end sealants may be reacted to introduce a plurality of different end groups.

Known compounds can be used as the monoamine used for the terminal sealant, but aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 1-hydroxy-7-aminonaphthalene, 1-carboxy-7 -Aminonaphthalene, 3-aminobenzoic acid, 3-aminophenol, 3-aminothiophenol, etc. are preferable. Two or more of these may be used.

Known compounds can be used as the acid anhydride, monocarboxylic acid, monoacid chloride compound, and monoactive ester compound, but phthalic anhydride, maleic anhydride, nadic acid anhydride, cyclohexanedicarboxylic acid anhydride, 3 -Acid anhydrides such as hydroxyphthalic anhydride and itaconic anhydride are preferable. Two or more of these may be used.

Examples of the monoalcohol used as the terminal sealant include those exemplified as alcohols that react with the acid anhydride described above.

Further, the monomer and the end-capping agent containing the structure (a) introduced into the component (A) used in the present invention can be easily detected by the following method. For example, a resin into which an end-capping agent has been introduced is dissolved in an acidic solution, decomposed into an amine component and an acid anhydride component, which are structural units, and this is measured by gas chromatography (GC) or NMR. The end-capping agent used in the present invention can be easily detected. In addition, the GC measurement is performed at the same time as the external standard substance whose peaks do not overlap with each component, and the integral value of each peak of the chromatogram is compared with the external standard substance. The ratio can be estimated. Separately, the resin component into which the terminal encapsulant has been introduced shall be directly measured by a pyrolysis gas chromatograph (PGC), an infrared spectrum, a ¹ H-NMR spectrum, a ¹³ C-NMR spectrum and a two-dimensional NMR spectrum. It can also be easily detected by. In this case, the molar ratio of each monomer can be analyzed from the integrated value of the infrared spectrum, ¹ H-NMR spectrum or two-dimensional NMR.

The component (A) in the present invention preferably has a weight average molecular weight of 5,000 or more and 100,000 or less. By setting the weight average molecular weight to 5,000 or more in terms of polystyrene by GPC (gel permeation chromatography), mechanical properties such as elongation after curing, strength at break point, and elastic modulus can be improved. On the other hand, by setting the weight average molecular weight to 100,000 or less, the developability can be improved. More than 20,000 is more preferable in order to obtain mechanical properties. When the component (A) contains two or more kinds of resins, the weight average molecular weight of at least one kind may be in the above range.

Further, the component (A) used in the present invention is preferably polymerized using a solvent. The type of the polymerization solvent is not particularly limited as long as it can dissolve the acid component, the amine component, the alcohols, and the catalyst which are the raw material monomers. For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N, N'-dimethylpropylene urea, N, N-dimethyliso. Cyclic esters such as butyric acid amide, methoxy-N, N-dimethylpropionamide amides, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone , Ester carbonates, carbonates such as propylene carbonate, glycols such as triethylene glycol, phenols such as m-cresol and p-cresol, acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethylsulfoxide, etc. Can be mentioned.

The photosensitive resin composition of the present invention contains (B) a photopolymerization initiator. (B) By containing the photopolymerization initiator, pattern processing becomes possible through the exposure and development steps. The photopolymerization initiator (B) is not particularly limited as long as it is a compound that generates radicals upon exposure, but is an alkylphenone compound, an aminobenzophenone compound, a diketone compound, a ketoester compound, a phosphine oxide compound, an oxime ester compound and a benzoic acid ester. The compound is preferable because it has excellent sensitivity, stability, and ease of synthesis. Among them, an alkylphenone compound and an oxime ester compound are preferable from the viewpoint of sensitivity, and an oxime ester compound is particularly preferable. Further, in the case of a thick film having a processed film thickness of 5 μm or more, a phosphine oxide compound is preferable from the viewpoint of resolution.

Examples of the alkylphenone compound include 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-dimethylamino-2- (4-methylbenzyl) -1- (4-). Α-Aminoalkylphenone compounds such as morpholin-4-yl-phenyl) -butane-1-one or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-hydroxy -2-Methyl-1-phenylpropane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy) -2-propyl) ketone, 2-hirodoxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1-one, 1-hydroxycyclohexyl -Α-Hydroxyalkylphenone compounds such as phenylketone and benzoin, 4-benzoyl-4-methylphenylacetophenone, 2,3-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy Α-alkoxy such as -2-methylpropiophenone, pt-butyldichloroacetophenone, benzylmethoxyethylacetophenone, 2,3-diethoxyacetophenone, benzyldimethylketal, benzoinethyl ether, benzoinisopropyl ether, benzoinisobutyl ether, etc. Examples thereof include acetophenone compounds such as alkylphenone compounds, acetophenone, and pt-butyldichloroacetophenone. Among these, 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4) Α-Aminoalkylphenone compounds such as -yl-phenyl) -butane-1-one or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 are preferred because of their high sensitivity.

Examples of the phosphine oxide compound include 6-trimethylbenzoylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxybenzoyl)-(2,4,4-trimethyl). Penthyl) -phosphine oxide.

Examples of the oxime ester compound include 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-methoxycarbonyl) oxime, and the like. 1-Phenyl-2- (benzoyloxime imino) -1-propanone, 2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)], 1-phenyl-1,2-butadione- 2- (o-methoxycarbonyl) oxime, 1,3-diphenylpropanthrion-2- (o-ethoxycarbonyl) oxime, etanone, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, 1-Phenyl-3-ethoxypropanetrione-2- (o-benzoyl) oxime, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (0-) Acetyloxime), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (0-acetyloxime), NCI-831, NCI-930 (above, ADEKA) XXE-03, OXE-04 (above, manufactured by BASF) and the like. Among these, from the viewpoint of sensitivity, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (0-acetyloxime), 2-octanedione, 1 -[4- (Phenylthio) -2- (O-benzoyloxime)], NCI-831, NCI-930, OXE-03, OXE-04 are preferable.

Examples of the aminobenzophenone compound include 4,4-bis (dimethylamino) benzophenone and 4,4-bis (diethylamino) benzophenone.
Examples of the diketone compound include benzyl.
Examples of the ketoester compound include methyl benzoyl formate and ethyl benzoyl formate.

Examples of the benzoic acid ester compound include methyl o-benzoyl benzoate, ethyl p-dimethylaminobenzoate, 2-ethylhexyl 4- (dimethylamino) benzoate, and ethyl p-diethylaminobenzoate.

Other specific examples of the (B) photopolymerization initiator include benzophenone, 4-benzoyl-4'-methyldiphenylketone, dibenzylketone, fluorenone, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, hydroxybenzophenone, and the like. 4-Benzoyl-4'-methyl-diphenylsulfide, alkylated benzophenone, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 4-benzoyl-N, N-dimethyl-N- [ 2- (1-oxo-2-propenyloxy) ethyl] benzenemethanamineium bromide, (4-benzoylbenzyl) trimethylammonium chloride, 2-hydroxy-3- (4-benzoylphenoxy) -N, N, N-trimethyl -1-Propenaminium chloride monohydrate, thioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2 -Hydroxy-3- (3,4-dimethyl-9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propanaminium chloride, anthraquinone, 2-t-butylanthraquinone, 2-Aminoanthraquinone, β-chloroanthraquinone, antron, benzanthron, dibenzsberon, methyleneanthrone, 4-azidobenzalacetophenone, 2,6-bis (p-azidobenzylene) cyclohexane, 2,6-bis (p-azidobenzylene) ) -4-Methylcyclohexanone, naphthalensulfonyl chloride, quinoline sulfonyl chloride, N-phenylthioacridone, benzthiazole disulfide, triphenylphosphine, carbon tetrabromide, tribromophenyl sulfone and the like.

The content of the photopolymerization initiator (B) is 100 parts by mass when the sum of the component (A) and the compound having 2 or more ethylenically unsaturated bonds described later (D) contained as needed is 100 parts by mass. 0.5 parts by mass or more and 20 parts by mass or less are preferable because sufficient sensitivity can be obtained and the amount of degassing during thermosetting can be suppressed. Above all, 1.0 part by mass or more and 10 parts by mass or less are more preferable.

The photosensitive resin composition of the present invention may contain a sensitizer for the purpose of enhancing the function of (B) the photopolymerization initiator. By containing a sensitizer, it is possible to improve the sensitivity and adjust the photosensitive wavelength. Examples of the sensitizer include bis (dimethylamino) benzophenone, bis (diethylamino) benzophenone, diethylthioxanthone, N-phenyldiethanolamine, N-phenylglycine, 7-diethylamino-3-benzoylcoumarin, 7-diethylamino-4-methylcoumarin, Examples include, but are not limited to, N-phenylmorpholine and derivatives thereof.

The photosensitive resin composition of the present invention preferably further contains (C) a compound having two or more ethylenically unsaturated bonds (hereinafter, may be abbreviated as "component (C)"). However, the component (C) has a molecular weight of 100 or more and 2000 or less. By containing the component (C), the crosslink density at the time of exposure is improved, so that the exposure sensitivity is further improved, which contributes to the reduction of the exposure amount and the reduction of the developing film.

As the component (C), a known (meth) acrylate compound can be contained, and in particular, a polyfunctional (meth) acrylate containing an alicyclic structure can achieve both a low dielectric constant, a low dielectric loss tangent and an exposure sensitivity at a high level. Therefore, it is preferable.

Examples of the polyfunctional (meth) acrylate containing an alicyclic structure include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and polyethylene glycol di (meth) acrylate. Trimethylol propandi (meth) acrylate, trimethylpropan di (meth) acrylate, 1,3-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate , 1,4-Butanediol dimethacrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, dimethylol-tricyclo Decandy (meth) acrylate, 1,3-adamantandiol di (meth) acrylate, 1,3,5-adamantantrioldi (meth) acrylate, 1,3,5-adamantantrioltri (meth) acrylate, 1,4 -Cyclohexanedimethanol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) ) Acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, pentapentaerythritol undeca (meth) acrylate, pentapentaerythritol dodeca (meth) acrylate, ethoxy Bisphenol A di (meth) acrylate, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, (2- (meth) acryloyloxypropoxy) -3-methylphenyl] fluorene or 9 , 9-Bis [4- (2- (meth) acryloyloxyethoxy) -3,5-dimethylphenyl] fluorene. Among them, dimethylol-tricyclodecanedi (meth) acrylate, 1,3-adamantandiol di (meth) acrylate, 1,3,5-adamantantrioldi (meth) acrylate, 1,3,5-adamantantrioltri (meth) acrylate. ) Acrylate, 1,4-cyclohexanedimethanol di (meth) acrylate and the like.

Examples of the compound of the other component (C) include epoxy (meth) acrylate obtained by reacting a polyfunctional epoxy compound with (meth) acrylic acid. Since epoxy (meth) acrylate adds hydrophilicity, it can be used for the purpose of improving alkali developability. Examples of the polyfunctional epoxy compound include the following compounds. These polyfunctional epoxy compounds are preferable because they have excellent heat resistance and chemical resistance.

The content of the component (C) is preferably 5 parts by mass or more and 100 parts by mass or less, and more preferably 10 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the component (A). Within such a range, the effect of improving the exposure sensitivity, the low dielectric constant, and the low dielectric loss tangent can be easily obtained.

The photosensitive resin composition of the present invention may contain an antioxidant. By containing the antioxidant, it is possible to suppress deterioration of mechanical properties such as yellowing and elongation of the cured film in the heat treatment in the subsequent process. Further, it is preferable because the rust preventive action on the metal material can suppress the oxidation of the metal material.

As the antioxidant, a hindered phenol-based antioxidant or a hindered amine-based antioxidant is preferable.
Examples of the hindered phenolic antioxidant include Irganox245, Irganox3114, Irganox1010, Irganox1098, Irganox1135, Irganox259, Irganox1035, (trade name, manufactured by BASF Corporation), or 2,6-di. ) -P-Cresol, but is not limited to these.

Examples of hindered amine-based antioxidants include TINUVIN144, TINUVIN292, TINUVIN765, TINUVIN123 (trade name, manufactured by BASF Corporation), 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2. , 6,6-Tetramethyl-4-piperidyl methacrylate, or tetrakis (1,2,2,6,6-pentamethyl-4-pyridyl) butane-1,2,3,4-tetracarboxylate.

Examples of other antioxidants include phenol, catechol, resorcinol, hydroquinone, 4-t-butylcatechol, 2,6-di (t-butyl) -p-cresol, phenothiazine, and 4-methoxyphenol. The amount of the antioxidant added is preferably 0.1 part by mass or more and 10.0 parts by mass or less, and more preferably 0.3 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the component (A). preferable. Within such a range, the developability and the discoloration suppressing effect due to the heat treatment can be appropriately maintained.

The photosensitive resin composition of the present invention may have a heterocyclic compound containing a nitrogen atom. By having a heterocyclic compound containing a nitrogen atom, high adhesion can be obtained on a substrate of a metal that is easily oxidized such as copper, aluminum, and silver. The mechanism is not clear, but it is presumed that the metal coordination ability of the nitrogen atom interacts with the metal surface, and the bulkiness of the heterocycle stabilizes the interaction.

Examples of the heterocyclic compound containing a nitrogen atom include imidazole, pyrazole, indazole, carbazole, pyrazoline, pyrazoline, triazole, tetrazole, pyridine, piperidine, pyrimidine, pyrazine, triazine, cyanuric acid, isocyanuric acid and derivatives thereof.

Examples of the heterocyclic compound containing a nitrogen atom include 1H-benzotriazole, 4-methyl-1H-methylbenzotriazole, 5-methyl-1H-methylbenzotriazole, and 4-carboxy-1H from the viewpoint of reactivity with metals. -Benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole and the like are preferable.

The amount of the heterocyclic compound containing a nitrogen atom is preferably 0.01 part by mass or more and 5.0 part by mass or less, and 0.05 part by mass or more and 3.0 part by mass with respect to 100 parts by mass of the component (A). Less than a part is more preferable. Within such a range, the developability and the stabilizing effect of the base metal can be appropriately maintained.

The photosensitive resin composition of the present invention may contain a solvent. As the solvent, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, 1,3-dimethyl-2 -Polar aprotonic solvents such as imidazolidinone, N, N'-dimethylpropylene urea, N, N-dimethylisobutyric acid amide, methoxy-N, N-dimethylpropionamide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene Ethers such as glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone and diisobutyl ketone, esters such as ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate and 3-methyl-3-methoxybutyl acetate. Examples include alcohols such as ethyl lactate, methyl lactate, diacetone alcohol, 3-methyl-3-methoxybutanol, and aromatic hydrocarbons such as toluene and xylene. Two or more of these may be contained.

The content of the solvent is preferably 100 parts by mass or more in order to dissolve the composition with respect to 100 parts by mass of the component (A), and 1,500 mass by mass in order to form a coating film having a film thickness of 1 μm or more. It is preferable to contain less than a portion.

The photosensitive resin composition of the present invention contains a surfactant, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, cyclohexanone, and methyl for the purpose of improving wettability with a substrate, if necessary. It may contain ketones such as isobutyl ketone and ethers such as tetrahydrofuran and dioxane.

Further, in order to enhance the adhesiveness to the substrate, a silane coupling agent may be contained as a silicon component in the photosensitive resin composition of the present invention as long as the storage stability is not impaired. Examples of the silane coupling agent include trimethoxyaminopropylsilane, trimethoxycyclohexylepoxyethylsilane, trimethoxyvinylsilane, trimethoxythiolpropylsilane, trimethoxyglycidyloxypropylsilane, tris (trimethoxysilylpropyl) isocyanurate, and triethoxyamino. With propylsilane, triethoxycyclohexylepoxyethylsilane, triethoxyvinylsilane, triethoxythiolpropylsilane, triethoxyglycidyloxypropylsilane, tris (triethoxysilylpropyl) isocyanurate, and trimethoxyaminopropylsilane or triethoxyaminopropylsilane. Examples thereof include a reaction product with acid anhydride. The reactants can be used in the state of amic acid or in the imidized state. Examples of the acid anhydride to be reacted include succinic anhydride, maleic anhydride, nadic acid anhydride, cyclohexanedicarboxylic acid anhydride, 3-hydroxyphthalic anhydride, pyromellitic dianhydride, 3,3', 4,4. '-Biphenyltetracarboxylic dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) sulfonate dianhydride, 4,4'-oxydiphthalic acid Dianhydride is mentioned. The preferable content of the silane coupling agent is 0.01 to 10 parts by mass with respect to 100 parts by mass of the component (A).

Next, the shape of the photosensitive resin composition of the present invention will be described.

The shape of the photosensitive resin composition of the present invention is not limited as long as it contains the component (A) and the photopolymerization initiator (B), and may be in the form of a paste or a sheet, for example. ..

The photosensitive sheet of the present invention is completely obtained by applying the photosensitive resin composition of the present invention on a support and drying at a temperature and time within a range in which the solvent can be volatilized. An uncured sheet-like material that is soluble in an organic solvent or an alkaline aqueous solution.

The support is not particularly limited, but various commercially available films such as polyethylene terephthalate (PET) film, polyphenylene sulfide film, and polyimide film can be used. The bonding surface between the support and the photosensitive resin composition may be subjected to surface treatment such as silicone, silane coupling agent, aluminum chelating agent, polyurea, etc. in order to improve adhesion and peelability. The thickness of the support is not particularly limited, but is preferably in the range of 10 to 100 μm from the viewpoint of workability. Further, in order to protect the film surface of the photosensitive composition obtained by coating, a protective film may be provided on the film surface. Thereby, the surface of the photosensitive resin composition can be protected from pollutants such as dust and dust in the atmosphere.

As a method of applying the photosensitive resin composition to the support, rotary coating using a spinner, spray coating, roll coating, screen printing, blade coater, die coater, calendar coater, meniscus coater, bar coater, roll coater, comma roll Examples include coaters, gravure coaters, screen coaters, and slit die coaters. The coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, etc., but usually, the film thickness after drying is 0.5 μm or more and 100 μm or less from the viewpoint of coating film uniformity and the like. preferable.

An oven, hot plate, infrared rays, etc. can be used for drying. The drying temperature and drying time may be within a range in which the solvent can be volatilized, and it is preferable to appropriately set the drying range so that the photosensitive resin composition is in an uncured or semi-cured state. Specifically, it is preferably carried out in the range of 40 ° C. to 150 ° C. for 1 minute to several tens of minutes. Further, these temperatures may be combined to raise the temperature stepwise, and for example, heat treatment may be performed at 80 ° C. and 90 ° C. for 2 minutes each.

Next, a method of forming a relief pattern of a cured film using the photosensitive resin composition or the photosensitive sheet of the present invention will be described.

The photosensitive resin composition of the present invention is applied onto a substrate, or the photosensitive sheet is laminated on a substrate. Metallic copper-plated substrates and silicon wafers are used as the substrates, and ceramics, gallium arsenide, and the like are used as the materials, but the substrate is not limited thereto. As a coating method, there are methods such as rotary coating using a spinner, spray coating, and roll coating. The coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, but is usually applied so that the film thickness after drying is 0.1 to 150 μm.

The substrate can also be pretreated with the above-mentioned silane coupling agent in order to enhance the adhesiveness between the substrate and the photosensitive resin composition. For example, a solution prepared by dissolving 0.5 to 20% by mass of a silane coupling agent in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diethyl adipate. To make. Next, the prepared solution is surface-treated on the substrate by spin coating, dipping, spray coating, steam treatment, or the like. In some cases, heat treatment is then performed at 50 ° C. to 300 ° C. to allow the reaction between the substrate and the silane coupling agent to proceed.

Next, the photosensitive resin composition is applied, or the substrate on which the photosensitive sheet of the present invention is laminated is dried to obtain a photosensitive resin composition film. Drying is preferably carried out in the range of 50 ° C. to 150 ° C. for 1 minute to several hours using an oven, a hot plate, infrared rays or the like. In the case of a photosensitive sheet, it is not always necessary to go through the drying step.

Next, the photosensitive resin composition film is exposed to chemical rays through a mask having a desired pattern. The chemical rays used for exposure include ultraviolet rays, visible rays, electron beams, X-rays, etc., but in the present invention, it is preferable to use i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) of mercury lamps. ..

Next, the exposed photosensitive resin composition film may be subjected to a post-exposure baking (PEB) step, if necessary. The PEB step is preferably carried out in the range of 50 ° C. to 150 ° C. for 1 minute to several hours using an oven, a hot plate, infrared rays or the like.

Next, the photosensitive resin film after exposure is developed. To form a resin pattern, after exposure, a developer is used to remove unexposed areas. As the developing solution used for development, a good solvent for the photosensitive resin composition or a combination of the good solvent and a poor solvent is preferable. For example, as a good solvent, N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone and the like are preferable. As the poor solvent, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, water and the like are preferable. When a good solvent and a poor solvent are mixed and used, it is preferable to adjust the ratio of the poor solvent to the good solvent by the solubility of the polymer in the photosensitive resin composition. In addition, two or more kinds of each solvent, for example, several kinds can be used in combination.

Further, when the photosensitive resin composition is dissolved in an alkaline aqueous solution, the alkaline aqueous solution may be developed. The developer used for development dissolves and removes an alkaline aqueous solution-soluble polymer, and is typically an alkaline aqueous solution in which an alkaline compound is dissolved. Examples of alkaline compounds include tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, and dimethyl. Examples thereof include aminoethyl methacrylate, cyclohexylamine, ethylenediamine and hexamethylenediamine. In some cases, these alkaline aqueous solutions are mixed with polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone and dimethylacrylamide, methanol, ethanol, etc. Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone may be contained alone or in combination of several kinds. Good.

After development, it is preferable to rinse with an organic solvent or water. When an organic solvent is used, in addition to the above developer, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate and the like can be mentioned. When water is used, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to the water for rinsing.

Next, the developed photosensitive resin film is heat-treated. After development, a temperature of 150 ° C. to 400 ° C. is applied to allow the thermal cross-linking reaction to proceed and cure. This heat treatment is carried out for 5 minutes to 5 hours while selecting a certain temperature and gradually raising the temperature, or selecting a certain temperature range and continuously raising the temperature. As an example, heat treatment is performed at 130 ° C. and 200 ° C. for 30 minutes each. The lower limit of the cure condition in the present invention is preferably 170 ° C. or higher, but more preferably 180 ° C. or higher in order to sufficiently proceed with curing. The upper limit of the cure condition is not particularly limited, but is preferably 280 ° C. or lower, more preferably 250 ° C. or lower, and even more preferably 230 ° C. or lower, from the viewpoint of suppressing film shrinkage and stress. Further, for the purpose of raising the glass transition point or the thermal decomposition temperature, the lower limit is preferably 250 ° C. or higher, and the upper limit is preferably 350 ° C. or lower.

The cured film formed by the photosensitive resin composition of the present invention can be used as an insulating film or a protective film constituting an electronic component.

Here, examples of electronic components include active components having semiconductors such as transistors, diodes, integrated circuits (ICs), and memories, and passive components such as resistors, capacitors, inductors, and antenna elements. In addition, electronic components using semiconductors are also referred to as semiconductor devices.

Specific examples of the cured film in electronic components include a semiconductor passivation film, a semiconductor element, a surface protective film such as a TFT (Thin Film Transistor), and interlayer insulation between rewiring in a multilayer wiring for high-density mounting of 2 to 10 layers. It is suitably used for applications such as an interlayer insulating film such as a film, an insulating film for a touch panel display, a protective film, and an insulating layer for an organic electric field light emitting element, but the present invention is not limited to this, and various structures can be adopted.

The surface of the substrate on which the cured film is formed can be appropriately selected depending on the application and process, but examples thereof include silicon, ceramics, glass, metal, and epoxy resin, and a plurality of these may be arranged on the same surface.

Next, an example of application to a semiconductor device having bumps using a cured film obtained by curing the photosensitive resin composition of the present invention will be described with reference to the drawings. FIG. 1 is an enlarged cross-sectional view of a pad portion of a semiconductor device having a bump of the present invention. As shown in FIG. 1, in the silicon wafer 1, a passivation film 3 is formed on an aluminum (hereinafter abbreviated as Al) pad 2 for input / output, and a via hole is formed in the passivation film 3. An insulating film 4 is formed on this as a pattern of a cured film obtained by curing the photosensitive resin composition of the present invention, and a metal (Cr, Ti, etc.) film 5 is further formed so as to be connected to the Al pad 2. Metal wiring (Al, Cu, etc.) 6 is formed by electrolytic plating or the like. The metal film 5 etches the periphery of the solder bump 10 to insulate between the pads. A barrier metal 8 and a solder bump 10 are formed on the insulated pad. The cured film obtained by curing the photosensitive resin composition of the insulating film 7 can be subjected to thick film processing on the scribe line 9.

Next, FIG. 2 shows a detailed manufacturing method of the semiconductor device. As shown in 2a of FIG. 2, an Al pad 2 for input / output and a passivation film 3 are formed on the silicon wafer 1, and an insulating film 4 is formed as a pattern by the cured film of the photosensitive resin composition of the present invention. .. Subsequently, as shown in 2b of FIG. 2, a metal (Cr, Ti, etc.) film 5 is formed so as to be connected to the Al pad 2, and as shown in 2c of FIG. 2, the metal wiring 6 is plated. Form a film. Next, as shown in 2d'of FIG. 2, the photosensitive resin composition before curing of the present invention is applied, and the insulating film 7 is formed as a pattern as shown in 2d of FIG. 2 through a photolithography step. At this time, the photosensitive resin composition before curing of the insulating film 7 is subjected to thick film processing on the scribe line 9. When forming a multi-layer wiring structure having three or more layers, each layer can be formed by repeating the above steps.

Next, as shown in 2e and 2f of FIG. 2, the barrier metal 8 and the solder bump 10 are formed. Then, dicing along the last scribe line 9 and cutting into chips. If the insulating film 7 does not have a pattern formed on the scribe line 9 or if a residue remains, cracks or the like occur during dicing, which affects the reliability evaluation of the chip. Therefore, it is very preferable to be able to provide pattern processing excellent in thick film processing as in the present invention in order to obtain high reliability of the semiconductor device.

Next, an antenna element using a cured film obtained by curing the photosensitive resin composition of the present invention will be described. FIG. 3 is a schematic view of a coplanarity-fed microstrip antenna, which is a type of planar antenna. 3a is a cross-sectional view and 3b is a top view. First, the forming method will be described. The photosensitive resin composition of the present invention is applied onto the copper foil, prebaked, and after exposure, the copper foil is laminated and heat-cured to form a cured film having the copper foil on both sides. Then, through patterning by the construct method, an antenna element having the antenna pattern of the copper wiring of the microstrip line (MSL) shown in FIG. 3 is obtained.

Next, the antenna pattern of FIG. 3 will be described. In 3a, 35 represents the ground (entire surface), and 36 represents the insulating film used as the substrate of the antenna. The upper layers 31 to 33 show the cross section of the antenna wiring obtained by the patterning. The ground wiring thickness J and the antenna wiring thickness K can have arbitrary thicknesses depending on the impedance design, but are generally 2 to 20 μm. In 3b, 31 is an antenna unit, 32 is a matching circuit, 33 is an MSL feeding line, and 34 is a feeding point. In order to match the impedances of the antenna portion 31 and the feeding line 33, the length M of the matching circuit 32 has a length of 1/4 λr (λr = (wavelength of transmission radio wave) / (insulating material permittivity) ^{1 /. 2} ). Further, the width W and the length L of the antenna portion 31 are designed to have a length of 1 / 2λr. The antenna portion length L may be 1 / 2λr or less depending on the impedance design. Since the cured film of the present invention has a low dielectric constant and a low dielectric loss tangent, it is possible to provide an antenna element having high efficiency and high gain. Further, from these characteristics, the antenna element using the insulating film of the present invention is suitable as an antenna for high frequency, and by making the area (= L × W) of the antenna part 1000 mm ² or less, a small antenna element Can be formed. In this way, a high-frequency antenna element having high efficiency, high gain, and small size can be obtained.

Next, a semiconductor package including an IC chip (semiconductor element), a rewiring layer, a sealing resin, and an antenna wiring will be described. FIG. 4 is a schematic view of a cross section of a semiconductor package including an IC chip (semiconductor element), rewiring, a sealing resin, and an antenna element. A rewiring layer (copper 2 layer, insulating film 3 layer) is formed on the electrode pad 402 of the IC chip 401 by the copper wiring 409 and the insulating film 410 formed by the cured film of the present invention. Barrier metal 411 and solder bump 412 are formed on the pads of the rewiring layer (copper wiring 409 and insulating film 410). In order to seal the IC chip, a first sealing resin 408 made of the cured film of the present invention is formed, and a copper wiring 409 serving as a ground for an antenna is further formed on the first sealing resin 408. A first via wiring 407 that connects the ground 406 and the rewiring layer (copper wiring 409 and insulating film 410) is formed through the via hole formed in the first sealing resin 408. A second sealing resin 405 made of the cured film of the present invention is formed on the first sealing resin 408 and the ground wiring 406, and a flat antenna wiring 404 is formed on the second sealing resin 405. A second via wiring that connects the flat antenna wiring 404 and the rewiring layer (copper wiring 409 and insulating film 410) via the via holes formed in the first sealing resin 408 and the second sealing resin 405. 403 is formed. The thickness of the insulating film 410 per layer is preferably 10 to 20 μm, and the first sealing resin and the second sealing resin are preferably 50 to 200 μm and 100 to 400 μm, respectively. Since the cured film of the present invention has a low dielectric constant and a low dielectric loss tangent, the semiconductor package provided with the obtained antenna element has high efficiency and high gain, and the transmission loss in the package is small.

That is, the electronic component of the present invention is an electronic component including at least one antenna wiring and an antenna element provided with the cured film of the present invention, and the antenna wiring is a meander-shaped loop antenna, a coil-shaped loop antenna, or a meander. One or more types selected from the group consisting of a monopole antenna, a meander dipole antenna, or a planar antenna are included, and the occupied area per antenna portion in the antenna wiring is 1000 mm ² or less, and the cured film is ground. It is preferable that the insulating film insulates between the antenna and the antenna wiring.

Further, the electronic component of the present invention is an electronic component including at least a semiconductor element, a rewiring layer, a sealing resin, and a semiconductor package including antenna wiring, and the insulating layer and / or the sealing of the rewiring layer. It is preferable that the resin contains the cured film of the present invention, and the sealing resin also has a function as an insulating film that insulates between the ground and the antenna wiring.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. First, the evaluation method in each Example and Comparative Example will be described. For the evaluation, a photosensitive resin composition (hereinafter referred to as varnish) before curing, which had been filtered in advance with a filter made of polytetrafluoroethylene having an average pore size of 1 μm (manufactured by Sumitomo Electric Industries, Ltd.), was used.

(1) Molecular Weight Measurement The weight average molecular weight (Mw) of the component (A) was confirmed using a GPC (gel permeation chromatography) apparatus Waters2690-996 (manufactured by Japan Waters Corp.). The developing solvent was measured as N-methyl-2-pyrrolidone (hereinafter referred to as NMP), and the weight average molecular weight (Mw) and the dispersity (PDI = Mw / Mn) were calculated in terms of polystyrene.

(2) Pattern processability (2) -1 Developability and sensitivity After spin-coating a silicon wafer with a spin coater (1H-360S manufactured by Mikasa Co., Ltd.), a hot plate (Dainippon Screen Mfg. Co., Ltd.) SCW-636) was prebaked at 120 ° C. for 3 minutes to prepare a prebaked film having a film thickness of 11 μm. A parallel light mask aligner (hereinafter referred to as PLA) (PLA-501F manufactured by Canon Inc.) is used on the obtained prebake film using an ultrahigh pressure mercury lamp as a light source (g, h, i-line mixing), and gray for sensitivity measurement. Scale masks (2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 8 μm, 10 μm, 12.5 μm, 15 μm, 20 μm, 25 μm, 30 μm, 40 μm and 50 μm, with 1: 1 line and space patterns, 1% each. Has areas with transmission rates of 5, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 25%, 30%, 35%, 40%, 50% and 60%. .) Was exposed to 1000 mJ / cm ² by contact. Then, it was exposed at 120 ° C. for 3 minutes, baked, and developed using a coating and developing apparatus MARK-7. Shower development was performed with cyclopentanone (CP) for 2 minutes, followed by rinsing with propylene glycol monomethyl ether acetate (PGMEA) for 30 seconds. When the development was excessive or insufficient, the development time and the rinse time were adjusted as appropriate.

The film thickness was measured after development, and the minimum exposure amount exceeding 95 when the film thickness of the 1000 mJ exposed portion was set to 100 was set as the optimum exposure amount. In addition, the residual film ratio was measured by dividing the film thickness at the optimum exposure amount by the prebake film thickness. The sensitivity was evaluated with 90% or more as sensitivity A, 80% or more and less than 90% as B, 70 or more and less than 80% as C, 50% or more and less than 70% as D, and less than 50% as E. The exposure amount was measured with an I-line illuminometer. The film thickness was measured with a refractive index of 1.629 using Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd. The same applies to the film thickness described below.

(2) -2 resolution The minimum pattern size after development at the optimum exposure amount defined in (2) -1 was measured.

(3) Measurement of Permittivity and Dielectric Direct Contact A spin coating method using a coating developer ACT-8 on a 6-inch silicon wafer with a coating varnish so that the film thickness after prebaking at 120 ° C. for 3 minutes is 11 μm. After coating and prebaking with PLA, 300 mJ / cm ² was exposed on the entire surface using PLA, and using an inert oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.), the oxygen concentration was 20 ppm or less and 3.5 ° C. The temperature was raised to 320 ° C. at / min, and heat treatment was performed at each temperature for 1 hour. When the temperature became 50 ° C. or lower, the silicon wafer was taken out and immersed in 45% by mass of hydrofluoric acid for 5 minutes to peel off the cured film of the resin composition from the wafer. This film is cut into strips with a width of 1.5 cm and a length of 3 cm, and the permittivity and dielectric constant at a frequency of 1 GHz by the perturbation cavity resonator method compliant with ASTMD2520 at room temperature of 23.0 ° C. and humidity of 45.0% RH. The positive connection was measured. The dielectric properties were determined in 5 steps as shown in Table 1 below.

(4) Measurement of breaking point elongation of the cured film after curing A self-supporting film of the cured film was prepared in the same manner as in "(3) Measurement of permittivity and dielectric tangent" described above, and this film was 1.5 cm wide. , Cut into strips with a length of 9 cm, and pull with Tencilon RTM-100 (manufactured by Orientec Co., Ltd.) at room temperature of 23.0 ° C. and humidity of 45.0% RH at a tensile speed of 50 mm / min (chuck). Interval = 2 cm) and breaking point elongation (%) were measured. The measurement was performed on 10 strips per sample, and the average value of the top 5 points with high numerical values was obtained from the results (significant figures = 2 digits).

(5) Evaluation of break point elongation of the cured film after high temperature storage (HTS) Place the varnish on a 6-inch silicon wafer so that the film thickness after prebaking at 120 ° C. for 3 minutes is 11 μm. After coating and prebaking by the spin coating method using the coating and developing device MARK-7, 300 mJ / cm ² is exposed on the entire surface using PLA, and the inert oven CLH-21CD-S (Koyo Thermo System Co., Ltd.) is used using PLA. ) Was used, the temperature was raised to 320 ° C. at 3.5 ° C./min at an oxygen concentration of 20 ppm or less, and heat treatment was performed at 320 ° C. for 1 hour. When the temperature became 50 ° C. or lower, the wafer was taken out, and then treated at 150 ° C. for 250 hours using a high temperature storage tester. The wafer is taken out, and a self-supporting film of a cured film is prepared according to the procedure after the hydrofluoric acid treatment described in "(3) Measurement of dielectric constant and dielectric tangent" described above.) "(4) Cured film after curing" The breaking point elongation (%) was evaluated in the same manner as in "Measurement of breaking point elongation". The measurement was performed on 10 strips per sample, and the average value of the top 5 points with high numerical values was obtained from the results (significant figures = 2 digits).

Hereinafter, abbreviations of compounds used in Synthesis Examples and Examples will be described.
BPDA: 3,3', 4,4'-biphenyltetracarboxylic dianhydride ODPA: 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride 6FDA: 2,2-bis (2,3-bis) Dicarboxyphenyl) Hexafluoropropane dianhydride BSAA: 4,4'-(4,4'-isopropyridenediphenoxy) bis (phthalic acid) dianhydride HPMDA: 1,2,4,5-cyclohexanetetracarboxylic acid Dianoxide DAE: 4,4'-diaminodiphenyl ether TFMB: 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl,
Priamine 1075: Dimer diamine compound containing the compound represented by the above formula (4) (trade name, manufactured by Croda Japan Co., Ltd.) (average amine value: 205)
Versamine 551: A dimer diamine compound containing the compound represented by the above formula (5) (trade name, manufactured by BASF Limited) (average amine value: 205).
6FAP: Bis (3-amino-4-hydroxyphenyl) Hexafluoropropane DACH: Diaminocyclohexane MAP: m-aminophenol NCI-831: Oxime ester-based photopolymerization initiator (trade name, manufactured by ADEKA Corporation)
IRGANOX3114: Hindered phenolic antioxidant (trade name, manufactured by BASF Limited)
4G: Tetraethylene glycol dimethacrylate (trade name, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
DCP-A: Dicyclopentadiene dimethacrylate (trade name, manufactured by Kyoeisha Chemical Co., Ltd.)
HEMA: 2-Hydroxyethyl methacrylate OA: Oleyl alcohol DMM: Dimethylaminoethyl methacrylate NMP: N-methyl-2-pyrrolidone EL: Ethyl lactate CP: Cyclopentanone PGMEA: Propylene glycol methyl ether acetate Polyflow 77: Acrylic surfactant Agent (trade name, manufactured by Kyoeisha Chemical Co., Ltd.)
Diamine A: A compound having the following structure

[Synthesis Example 1 Synthesis of Polyimide Precursor (P-1)]
Put 31.02 g (0.10 mol) of ODPA in a separable flask with a capacity of 500 ml, add 26.03 g (0.20 mol) of HEMA and 123 ml of NMP, and add 22.26 g (0.22 mol) of triethylamine while stirring at room temperature. In addition, a reaction mixture was obtained. After the exothermic reaction was completed, the mixture was allowed to cool to room temperature and left for 16 hours.

Next, the temperature was raised to 40 ° C., 76.7 g (0.2 mol) of diphenyl phosphonate (2,3-dihydro-2-thioxo-3-benzoxazolyl) was added to the reaction mixture, and the mixture was stirred for 30 minutes. did. Subsequently, a solution prepared by dissolving 52.51 g of Priamine 1075 (0.192 mol as an amino group) in 130 mL of NMP was added dropwise over 10 minutes with stirring. After further stirring at room temperature for 2 hours, 0.87 g (0.008 mol) of MAP was added and the mixture was stirred for 1 hour to obtain a reaction solution.

The obtained reaction solution was allowed to cool to room temperature, and 3 L was added to form a precipitate composed of a crude polymer. This precipitate was collected by filtration, washed with water three times, washed twice with 500 mL of isopropyl alcohol, and vacuum dried to obtain a powdery polyimide precursor (P-1). When the molecular weight of the polyimide precursor (P-1) was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 18,000 and the PDI was 2.4.

[Synthesis Examples 2-14, 16]
The polyimide precursors (P-2) to (P-14) and (P-16) were synthesized in the same manner as in Synthesis Example 1 at the molar ratios shown in Table 2 below.

[Synthesis Example 15 Synthesis of Polyimide Precursor (P-15)]
52.05 g (0.10 mol) of BSAA was dissolved in 250 g of NMP under a dry nitrogen stream. To this, 16.41 g of preamine 1075 (0.06 mol as an amino group) and TFMB 21.14 (0.066 mol) were added together with 100 g of NMP, and the mixture was reacted at 20 ° C. for 1 hour and then at 50 ° C. for 2 hours. Next, 0.87 g (0.08 mol) of 3-aminophenol was added as an end-capping agent together with 30 g of NMP, and the mixture was reacted at 50 ° C. for 2 hours. Then, the temperature was returned to room temperature, 31.44 g of DMM was added, and the mixture was stirred for 30 minutes to obtain a reaction solution. Further, it was diluted with NMP until the solid content concentration became 25% to obtain a solution of the polyimide precursor (P-15). Since the molecular weight of the polyimide precursor (P-15) cannot be measured accurately, the molecular weight of the polymer before the DMM reaction was measured by gel permeation chromatography (standard polystyrene conversion), and Mw was 34000 and PDI was 2.8. there were.

[Example 1]
Under a yellow light, 10.00 g of polyimide precursor (P-1), 0.5 g of NCI-831, 0.10 g of IRGANOX3114, 0.30 g of 3-trimethoxysilylphthalamic acid, NMP 15.15 g and EL 3 It was dissolved in .81 g, 0.10 g of a 1% by mass EL solution of Polyflow 77 was added, and the mixture was stirred to obtain a varnish. The characteristics of the obtained varnish were measured for pattern workability, dielectric constant, dielectric loss tangent, and breaking point elongation by the above evaluation method.

[Example 2]
It was carried out in the same manner as in Example 1 except that P-1 was replaced with P-2.

[Example 3]
It was carried out in the same manner as in Example 1 except that P-1 was replaced with P-3.

[Example 4]
It was carried out in the same manner as in Example 1 except that P-1 was replaced with P-4.

[Example 5]
It was carried out in the same manner as in Example 1 except that P-1 was replaced with P-5.

[Example 6]
It was carried out in the same manner as in Example 1 except that P-1 was replaced with P-6.

[Example 7]
It was carried out in the same manner as in Example 1 except that P-1 was replaced with P-7.

[Example 8]
It was carried out in the same manner as in Example 1 except that P-1 was replaced with P-8.

[Example 9]
It was carried out in the same manner as in Example 1 except that P-1 was replaced with P-9.

[Example 10]
It was carried out in the same manner as in Example 1 except that P-1 was replaced with P-10.

[Example 11]
It was carried out in the same manner as in Example 1 except that P-1 was replaced with P-11.

[Example 12]
It was carried out in the same manner as in Example 1 except that P-1 was replaced with P-12.

[Example 13]
Under yellow light, in 40.00 g of the solution of the polyimide precursor (P-13) synthesized in Synthesis Example 13, NCI-831 0.5 g, IRGANOX3114 0.10 g, 3-trimethoxysilylphthalamic acid 0. 30 g was dissolved. Next, 0.10 g of a 1% by mass EL solution of Polyflow 77 was added and stirred to obtain a varnish. The characteristics of the obtained varnish were measured for pattern workability, dielectric constant, dielectric loss tangent, and breaking point elongation by the above evaluation method. However, a mixed solution of NMP / PGMEA / water = 8/1/1 (weight ratio) was used as the developing solution, and isopropyl alcohol was used as the rinsing solution after development.

[Example 14]
The procedure was carried out in the same manner as in Example 1 except that P-1 was replaced with P-9 and 0.2 g of 4G was further added.

[Example 15]
The procedure was carried out in the same manner as in Example 1 except that P-1 was replaced with P-9 and 0.2 g of DCP-A was further added.

[Comparative Example 1]
It was carried out in the same manner as in Example 1 except that P-1 was replaced with P-13.

The compositions and evaluation results of Examples and Comparative Examples are shown in Tables 3 and 4 below.

1 Silicon wafer 2 Al pad 3 Passivation film 4 Insulation film 5 Metal (Cr, Ti, etc.) film 6 Metal wiring (Al, Cu, etc.)
7 Insulation film 8 Barrier metal 9 Scribline 10 Handa bump 31 Antenna part 32 Matching circuit 33 MSL power supply line 34 Feeding point 35 Ground 36 Insulation film J Ground thickness K Antenna wiring thickness M Matching circuit length L Antenna part length W Antenna part width 401 IC chip 402 Electrode pad 403 Second via wiring 404 Flat antenna wiring 405 Second sealing resin 406 Ground 407 First via wiring 408 First sealing resin 409 Copper wiring 410 Insulation film 411 Barrier metal 412 Handa bump

Claims (15)

1. A photosensitive resin composition containing (A) a polyimide precursor and (B) a photopolymerization initiator, wherein the (A) polyimide precursor contains a resin having a structural unit represented by the general formula (11). ..
   

   

   (In the general formula (11), X ⁴ represents a 4- to hexavalent organic group, and Y ⁴ represents a 2- to 6-valent organic group. However, at least one of X ⁴ and Y ⁴ is one. an organic group containing an alicyclic structure and a plurality of carbon number of 4 or more hydrocarbon structure or more. a plurality of R ⁸ each independently represent a monovalent organic group or a hydrogen atom with an ethylenically unsaturated bond. However, it monovalent organic groups .x represents an integer of 2 to 4. a plurality of R ⁹ are each independently a carboxyl group having at least one ethylenically unsaturated bond among the plurality of R ^8, a hydroxyl group Alternatively, it indicates a monovalent organic group having an ethylenically unsaturated bond. Y indicates an integer of 0 to 4. * Indicates a bond point.)
2. A photosensitive resin composition containing (A) a polyimide precursor and (B) a photopolymerization initiator, wherein the (A) polyimide precursor contains a resin having a structural unit represented by the general formula (1). ..
   

   

   (In the general formula (1), X ¹ represents a 4- to hexavalent organic group and Y ¹ represents a 2- to 6-valent organic group. However, at least ^one of X ¹ and Y ¹ is not. It has a structure of an alicyclic hydrocarbon having 4 to 8 carbon atoms which may have a saturated bond. In the structure of the alicyclic hydrocarbon, at least four or more hydrogen atoms have an unsaturated bond. It may be substituted with a hydrocarbon group having 4 to 12 carbon atoms. Multiple R ^1s may be the same or different and represent a monovalent organic group or a hydrogen atom having an ethylenically unsaturated bond, but all. of R ¹ is not hydrogen atom .p is. more R ² represents an integer of 2 to 4 may be the same or different, a carboxyl group, a monovalent organic group having a hydroxyl group or an ethylenically unsaturated bond Indicates. Q indicates an integer from 0 to 4. * Indicates a coupling point.)
3. In the general formula (1), Y ¹ is a residue of the polyvalent amine represented by the general formula (2), or in the general formula (11), Y ³ is represented by the general formula (2). The photosensitive resin composition according to claim 1 or 2, which is a residue of a polyvalent amine.
   

   

   (In the general formula (2), m represents an integer of any of 4 to 8. W is any of the structural units represented by the general formula (2a), (2b) or (2c) independently. Of the m Ws, 2 or more structural units of (2c) are contained, and the sum of the numbers of (2b) and (2c) is 4 or more and 8 or less. N and o are independently. Indicates an integer of 3 to 11.)
4. In the general formula (1), Y ¹ is a diamine residue represented by the formula (4), or in the general formula (11), Y ³ is a diamine residue represented by the formula (4). The photosensitive resin composition according to any one of claims 1 to 3.
   

   
5. Either of claims 1 to 4 in which R ¹ is a residue of an unsaturated fatty acid-modified alcohol in the general formula (1), or R ⁸ is a residue of an unsaturated fatty acid-modified alcohol in the general formula (11). The photosensitive resin composition described in C.
6. The (A) polyimide precursor contains a resin having a structural unit represented by the general formulas (1) and (7), or is represented by the general formulas (11) and (7). The photosensitive resin composition according to any one of claims 1 to 5, which comprises a resin having a structural unit.
   

   

   (In the general formula (7), X ² indicates a 4- to hexavalent organic group, and Y ² indicates a 2- to 6-valent organic group. However, at least X ² is X ³ or Y ² is Y. a ³ .X ³ are bisphenol a skeleton, a biphenyl skeleton or hexafluoroisopropylidene one acid anhydride represented by the divalent to hexavalent organic group or a group represented by the general formula containing one or more (8) of the framework the .Y ³ selected from the residues of a diamine represented by the bisphenol a skeleton, containing one or more of biphenyl skeleton or hexafluoroisopropylidene skeleton divalent to hexavalent organic group or the following formula (9) selected from residues. a plurality of R ³ may be the same or different, represents a monovalent organic group or a hydrogen atom with an ethylenically unsaturated bond. However, all of R ³ is not a hydrogen atom .r Indicates an integer of 2 to 4. Multiple R ^4s may be the same or different and indicate a monovalent organic group having a carboxyl group, a hydroxyl group or an ethylenically unsaturated bond. S represents an integer of 0 to 4. Indicates. * Indicates the connection point.)
   

   

   (In the general formula (8), a indicates an integer of 6 to 20. * Indicates a connection point.)
   

   

   (In general formula (9), * indicates a connection point.)
7. The photosensitive resin composition according to any one of claims 1 to 6, further comprising (C) a compound having 2 or more ethylenically unsaturated bonds, and the component (C) having a molecular weight of 100 or more and 2000 or less. ..
8. The photosensitive resin composition according to any one of claims 1 to 7, wherein the component (C) is a compound having an alicyclic structure.
9. A photosensitive sheet formed from the photosensitive resin composition according to any one of claims 1 to 8.
10. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 8 or the photosensitive sheet according to claim 9.
11. A method for producing a cured film using the photosensitive resin composition according to any one of claims 1 to 8 or the photosensitive sheet according to claim 9.
    A step of applying the photosensitive resin composition on a substrate or laminating the photosensitive sheet on a substrate and drying to form a photosensitive resin film, a step of exposing the photosensitive resin film, and exposure. A method for producing a cured film, which comprises a step of developing a subsequent photosensitive resin film and a step of heat-treating the developed photosensitive resin film.
12. An interlayer insulating film in which the cured film according to claim 10 is arranged.
13. An electronic component having the cured film according to claim 10.
14. An electronic component including at least one antenna wiring and an antenna element provided with the cured film according to claim 10, wherein the antenna wiring is a meander-shaped loop antenna, a coil-shaped loop antenna, a meander-shaped monopole antenna, or a meander-shaped antenna. It contains one or more of the group selected from the group consisting of a dipole antenna or a flat antenna, the occupied area per antenna portion in the antenna wiring is 1000 mm ² or less, and the cured film insulates between the ground and the antenna wiring. The electronic component according to claim 13, which is an insulating film.
15. The cured film according to claim 10, wherein the electronic component includes at least a semiconductor element, a rewiring layer, a sealing resin, and a semiconductor package including antenna wiring, and the insulating layer and / or the sealing resin of the rewiring layer is the cured film according to claim 10. The electronic component according to claim 13 or 14, wherein the sealing resin also has a function as an insulating film that insulates between the ground and the antenna wiring.

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