JP2020064186A - Photosensitive resin composition, method for producing pattern cured film, cured product, interlayer insulation film, cover coat layer or surface protective film, and electronic component - Google Patents

Abstract

To provide a photosensitive resin composition having excellent storage stability while containing a heat crosslinker, and capable of producing a cured film that has high adhesion to a substrate, and effectively prevents the discoloration of a copper substrate.SOLUTION: A photosensitive resin composition contains the following (a) component to (e) component: (a) a polybenzoxazole precursor; (b) a crosslinker that allows crosslinkage or polymerization by heating; (c) a photosensitizer; (d) at least one compound selected from the group consisting of a compound having a triazole ring and a compound having a tetrazole ring; and (e) at least one compound selected from the group consisting of a compound having a pyridine ring and a compound having an imidazole ring.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin composition, a method for producing a patterned cured film, a cured product, an interlayer insulating film, a cover coat layer or a surface protective film, and an electronic component.

  Conventionally, polyimide or polybenzoxazole having excellent heat resistance, electrical characteristics, mechanical characteristics and the like have been used for the surface protective film and the interlayer insulating film of the semiconductor element. In recent years, a photosensitive resin composition in which a resin itself is provided with a photosensitive property has been used. By using this, a manufacturing process of a patterned cured film can be simplified and a complicated manufacturing process can be shortened.

  In the manufacturing process of the patterned cured film, an organic solvent such as N-methyl-2-pyrrolidone was used in the developing process, but in consideration of the environment, an alkaline aqueous solution of a polyimide precursor, a polyimide, a polybenzoxazole precursor, or the like. There has been proposed a resin composition which can be developed with an alkaline aqueous solution by a method of mixing a diazonaphthoquinone compound as a photosensitizer with a resin soluble in water (for example, Patent Documents 1 and 2).

  In recent years, the miniaturization of transistors, which has supported the high performance of computers, faces the limit of scaling law, and it is considered that the technology of stacking semiconductor elements three-dimensionally is indispensable for further higher performance and higher speed. Has been. Against this background, three-dimensional packages using TSV (Through Silicon Via), 2.5-dimensional packages using interposers, or 2.1-dimensional packages have been proposed. The structure is drawing attention (for example, Non-Patent Document 1).

  Among laminated device structures, a multi-die fanout wafer level packaging is a package manufactured by encapsulating a plurality of dies in one package at a time. It is attracting attention because it can be expected to achieve lower cost and higher performance than the conventional fan-out wafer-level package manufactured by encapsulating one die.

  However, in manufacturing a multi-die fan-out wafer level package, it is not preferable to perform heat treatment at more than 200 ° C. from the viewpoint of protecting a high-performance die and a sealing material having low heat resistance to improve yield. Therefore, alkali-soluble resin used as a rewiring forming layer for rewiring copper is also strongly required to have low-temperature curability (for example, Patent Document 3).

JP, 2009-265520, A International Publication No. 2014/115233 International Publication No. 2008/111470 JP, 2010-096927, A

“Semiconductor Technology Yearbook 2013 Packaging / Mounting”, Nikkei BP, December 2012, p. 41-50

  In order to improve the low temperature curability of the alkali-soluble resin, a cross-linking agent capable of being cross-linked or polymerized by heating (hereinafter sometimes referred to as “thermal cross-linking agent”) may be used. However, when such a thermal cross-linking agent is used, the polymerizing reaction in which the thermal cross-linking agents are condensed with each other or the resin and the thermal cross-linking agent may proceed even at room temperature, and the liquid photosensitive resin composition is A problem has emerged that the storage stability is reduced when stored for a long time at room temperature. This problem becomes remarkable in the case of a thermal crosslinking agent having a low reaction temperature.

  Further, a conductor such as copper is used for rewiring of the above device, but the adhesiveness (adhesiveness) of the resin to the conductor wiring tends to be insufficient. This poor adhesiveness is a problem in that it can cause disconnection or short circuit of the conductor wiring. Further, the conventional resin has a problem that it has corrosiveness against metals such as copper. Patent Document 4 discloses that by adding a compound having an anticorrosive effect, excellent adhesiveness can be exhibited without corroding copper, but even if a compound having an anticorrosive effect is added, When a patterned resin film was formed on a copper substrate and cured by heating, the problem that the opening turned red was also raised.

  INDUSTRIAL APPLICABILITY The present invention is a photosensitive resin composition that is excellent in storage stability despite containing a thermal crosslinking agent, has high adhesiveness to a substrate, and can produce a cured film having an excellent effect of suppressing discoloration of a copper substrate. Another object of the present invention is to provide a photosensitive resin composition.

As a result of intensive studies by the present inventors, it was found that the storage stability of the photosensitive resin composition can be improved by combining the photosensitive resin composition containing a thermal crosslinking agent with two specific types of nitrogen-containing compounds. Further, they have found that a cured film obtained from the photosensitive resin composition has high adhesiveness to a substrate and can suppress discoloration of an opening on a copper substrate, and completed the present invention.
According to the present invention, the following photosensitive resin composition and the like are provided.
1. A photosensitive resin composition containing the following components (a) to (e).
One or more compounds selected from the group consisting of (a) polybenzoxazole precursor (b) crosslinking agent capable of crosslinking or polymerizing by heating (c) photosensitizer (d) compound having triazole ring and compound having tetrazole ring (E) one or more compounds selected from the group consisting of compounds having a pyridine ring and compounds having an imidazole ring; 2. The component (d) comprises 1,2,3-triazole and its derivative, 1,2,4-triazole and its derivative, 1,2,3-benzotriazole and its derivative, and 1H-tetrazole and its derivative. 2. The photosensitive resin composition according to 1, which is one or more compounds selected from the group.
3. 3. The photosensitive resin composition according to 1 or 2, wherein the component (e) is one or more compounds selected from the group consisting of pyridine and its derivatives, imidazole and its derivatives, and benzimidazole and its derivatives.
4. Content of the said (d) component is a photosensitive resin composition in any one of 1-3 which is 0.3 mass part or more with respect to 100 mass parts of the said (a) component.
5. The photosensitive resin composition according to any one of 1 to 4, wherein the content of the component (e) is 0.1 part by mass or more based on 100 parts by mass of the component (a).
6. The photosensitive resin composition according to any one of 1 to 5, wherein the content of the component (b) is 5 parts by mass or more based on 100 parts by mass of the component (a).
7. 7. The photosensitive resin composition according to any one of 1 to 6, wherein the component (c) contains a diazonaphthoquinone compound.
8. A step of applying the photosensitive resin composition according to any one of 8.1 to 7 onto a substrate and drying the composition to form a photosensitive resin film,
A step of pattern-exposing the photosensitive resin film to form a resin film,
Developing the exposed resin film with an alkaline aqueous solution to form a pattern resin film;
A step of forming a patterned cured film by heat-treating the patterned resin film,
A method for producing a patterned cured film, comprising:
A cured product obtained by curing the photosensitive resin composition according to any one of 9.1 to 7.
10. 10. The cured product according to 9, which is a patterned cured film.
An interlayer insulating film, a cover coat layer or a surface protective film produced by using the cured product according to 11.9 or 10.
An electronic component having the interlayer insulating film, the cover coat layer or the surface protective film according to 12.11.

  According to the present invention, a photosensitive resin composition having excellent storage stability in spite of containing a thermal cross-linking agent, having high adhesiveness to a substrate, and further providing a cured film having an excellent effect of suppressing discoloration of a copper substrate. A manufacturable photosensitive resin composition can be provided.

It is a schematic sectional drawing explaining the manufacturing process of the fan-out package which has a multilayer wiring structure. It is a schematic sectional drawing explaining the manufacturing process of the fan-out package which has a multilayer wiring structure. It is a schematic sectional drawing explaining the manufacturing process of the fan-out package which has a multilayer wiring structure. It is a schematic sectional drawing explaining the manufacturing process of the fan-out package which has a multilayer wiring structure. It is a schematic sectional drawing explaining the manufacturing process of the fan-out package which has a multilayer wiring structure. It is a schematic sectional drawing explaining the manufacturing process of the fan-out package which has a multilayer wiring structure. It is a schematic sectional drawing explaining the manufacturing process of the fan-out package which has a multilayer wiring structure. FIG. 4 is a schematic cross-sectional view of a fan-out package having a UBM (Under Bump Metal) free structure.

  Hereinafter, embodiments of the photosensitive resin composition, the method for producing a patterned cured film, the cured product, the interlayer insulating film, the cover coat layer or the surface protective film, and the electronic component of the present invention will be described in detail. The present invention is not limited to the embodiments described below.

  In the present specification, “A or B” may include either A or B, or may include both. Further, in the present specification, the term “process” is used not only as an independent process but also in the case where the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. included. The numerical range indicated by "-" indicates a range including the numerical values before and after "-" as the minimum value and the maximum value, respectively. In addition, in the present specification, the content of each component in the photosensitive resin composition, in the case where there are a plurality of substances corresponding to each component in the photosensitive resin composition, unless otherwise specified, in the photosensitive resin composition Means the total amount of the plurality of substances present in. Further, unless otherwise specified, the exemplified materials may be used alone or in combination of two or more kinds. In the present specification, room temperature refers to 23 ° C.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention contains the following components (a) to (e).
One or more compounds selected from the group consisting of (a) polybenzoxazole precursor (b) crosslinking agent capable of crosslinking or polymerizing by heating (c) photosensitizer (d) compound having triazole ring and compound having tetrazole ring (E) One or more compounds selected from the group consisting of a compound having a pyridine ring and a compound having an imidazole ring. Hereafter, the respective components are respectively (a) component, (b) component, (c) component, (d) Component and (e) component may be described. The photosensitive resin composition of the present invention is preferably a positive photosensitive resin composition.

Since the photosensitive resin composition of the present invention contains two specific types of nitrogen-containing compounds, that is, the component (d) and the component (e), it has high storage stability despite containing the component (b), and The cured film obtained from the photosensitive resin composition has high adhesiveness to the substrate and is also excellent in the effect of suppressing discoloration of the substrate.
Hereinafter, each component will be described.

(Component (a): polybenzoxazole precursor)
The polybenzoxazole precursor preferably has a structural unit represented by the following formula (II).
(In the formula (II), U is a tetravalent organic group and V is a divalent organic group.)
At least a part of the amide unit containing a hydroxy group in the formula (II) is converted into an oxazole ring which is excellent in heat resistance, chemical resistance and electrical properties by dehydration ring closure in the heating step.

  Further, in the structural unit represented by the formula (II), the amide unit containing a hydroxy group is effective in improving the solubility of the polymer in an alkaline aqueous solution.

The polymer having the structural unit represented by the formula (II) may contain only one type of structural unit or may contain two or more types of structural units. When the copolymer has two or more types of structural units, it is preferably a polymer having a structure represented by formula (III).
(In the formula (III), U is a tetravalent organic group, V and W are each independently a divalent organic group. J and k are mole fractions, and the sum of j and k is 100 moles. %, J is 60 to 99.9 mol% and k is 0.1 to 40 mol% (preferably j is 80 to 99.9 mol% and k is 0.1 to 20 mol%).

In formulas (II) and (III), the tetravalent organic group represented by U is a residue of a diamine used in the synthesis of polyhydroxyamide. The tetravalent organic group represented by U is preferably a tetravalent aromatic group or an organic group having 6 to 40 carbon atoms, and is preferably a tetravalent aromatic group having 6 to 40 carbon atoms. More preferable. The tetravalent aromatic group is preferably one in which all four binding sites are present on the aromatic ring.
The aromatic group means a group containing an aromatic ring.

  Examples of diamines which give a tetravalent organic group represented by U include 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl and bis (3 -Amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 2 , 2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) -1,1 , 1,3,3,3-hexafluoropropane and the like, but not limited thereto.

  The divalent organic group represented by W in the formula (III) is a residue of a diamine used in the synthesis of polyhydroxyamide. The divalent organic group represented by W is preferably a divalent aromatic group, a divalent aliphatic group, or an organic group having 4 to 20 carbon atoms, and an aromatic group having 4 to 20 carbon atoms. More preferably, it is a group. The divalent organic group represented by W is a residue of a diamine other than the diamine that provides the tetravalent organic group represented by U.

  Examples of diamines that give a divalent organic group represented by W include 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfone, and 4,4′-diaminodiphenyl sulfide. , Benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4 Examples thereof include aromatic diamine compounds such as -aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether and 1,4-bis (4-aminophenoxy) benzene. Further, as diamines having a silicone group, LP-7100, X-22-161AS, X-22-161A, X-22-161B, X-22-161C and X-22-161E (all of which are Shin-Etsu Chemical Co., Ltd. stocks Company-made, product name) and the like, but not limited to these.

In formulas (II) and (III), the divalent organic group represented by V is a residue of a dicarboxylic acid or a dicarboxylic acid derivative (hereinafter referred to as dicarboxylic acid) used in the synthesis of polyhydroxyamide. The divalent organic group represented by V is preferably a divalent aromatic group or an organic group having 6 to 40 carbon atoms.
From the viewpoint of heat resistance, a divalent aromatic group having 6 to 40 carbon atoms is preferable, and as the divalent aromatic group, those having both two bonding sites on the aromatic ring are preferable. preferable.

  From the viewpoint of having a high degree of dehydration ring closure in a heating step at low temperature (for example, 200 ° C. or lower), good heat resistance, and mechanical strength, V is a divalent organic group having an aliphatic structure having 6 to 30 carbon atoms. Is preferred. By using the component (a) in which V is a divalent organic group having an aliphatic structure having 6 to 30 carbon atoms and the component (b) described later in combination, better mechanical properties, chemical resistance and heat resistance can be obtained. A patterned cured film having properties can be provided.

Examples of the dicarboxylic acid which gives a divalent organic group represented by V include isophthalic acid, terephthalic acid, 2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane , 4,4'-dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2-bis (p-carboxyphenyl) Aromatic dicarboxylic acids such as propane, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid , 1,4-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, having an aliphatic straight chain structure As, malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2, 3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3 -Ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid , Sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid , Tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanoic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosane Diacids, heptaconedioic acid, octacosanedioic acid, nonacosanedioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, and dicarboxylic acid represented by the following formula However, the present invention is not limited to these. These compounds may be used alone or in combination of two or more.
(In formula, Z is a C1-C6 hydrocarbon group each independently, and i is an integer of 1-6.)

  In the present invention, the method for producing the component (a) is not particularly limited. Generally, it can be synthesized by using dicarboxylic acids and hydroxy group-containing diamines and, if necessary, diamines other than hydroxy group-containing diamines. Specifically, it can be synthesized by converting a dicarboxylic acid derivative into a dihalide derivative and then reacting with a diamine. The dihalide derivative is preferably a dichloride derivative.

  As a method for synthesizing the dichloride derivative, the dicarboxylic acid and the halogenating agent can be reacted in a solvent, or after reacting in an excess halogenating agent, the excess can be distilled off. As the halogenating agent, thionyl chloride, phosphoryl chloride, phosphorus oxychloride, phosphorus pentachloride and the like which are commonly used in the acid chloride reaction of carboxylic acid can be used. As the reaction solvent, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N, N-dimethylacetamide, N, N-dimethylformamide, toluene, benzene and the like can be used.

  When used in a solvent, the amount of these halogenating agents used is preferably 1.5 to 3.0 mol, more preferably 1.7 to 2.5 mol, based on 1.0 mol of the dicarboxylic acid derivative. When the reaction is carried out in a halogenating agent, it is preferably 4.0 to 50 mol, more preferably 5.0 to 20 mol. The reaction temperature is preferably -10 to 70 ° C, more preferably 0 to 20 ° C.

  The reaction of the dichloride derivative and the diamine is preferably carried out in an organic solvent in the presence of a dehydrohalogenating agent. As the dehydrohalogenating agent, an organic base such as pyridine or triethylamine can be used. Further, as the organic solvent, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N, N-dimethylacetamide, N, N-dimethylformamide and the like can be used. The reaction temperature is preferably -10 to 30 ° C, more preferably 0 to 20 ° C.

  Examples of the diamine include aromatic diamine, aliphatic diamine and alicyclic diamine. Specifically, 2,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 2,5-diaminoterephthalic acid, bis (4-amino-3-carboxyphenyl) methylene, Bis (4-amino-3-carboxyphenyl) ether, 4,4'-diamino-3,3'-dicarboxybiphenyl, 4,4'-diamino-5,5'-dicarboxy-2,2'-dimethyl Biphenyl, 1,3-diamino-4-hydroxybenzene, 1,3-diamino-5-hydroxybenzene, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3 ′ -Dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino- -Hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) ether, bis (4-amino-3-hydroxyphenyl) ether, bis (3-amino -4-hydroxyphenyl) hexafluoropropane, bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 1,4-diaminocyclohexane, 1,1,3,3-tetramethyl 1,3-bis (4 -Aminophenyl) disiloxane, poly (propylene glycol) diamine and the like can be mentioned, and these can be used alone or in combination of two or more kinds.

The component (a) is usually developed with an aqueous alkaline solution. Therefore, it is preferably soluble in an alkaline aqueous solution. Examples of the alkaline aqueous solution include organic ammonium aqueous solutions such as tetramethylammonium hydroxide (TMAH) aqueous solutions, metal hydroxide aqueous solutions, and organic amine aqueous solutions.
Generally, it is preferable to use an aqueous TMAH solution having a concentration of 2.38% by mass. Therefore, the component (a) is preferably soluble in the TMAH aqueous solution.

  One criterion that the component (a) is soluble in an aqueous alkaline solution will be described below. The component (a) is dissolved in an arbitrary solvent to form a solution, which is then spin-coated on a substrate such as a silicon wafer to form a resin film having a film thickness of about 5 μm. This is immersed in any one of TMAH aqueous solution, metal hydroxide aqueous solution, and organic amine aqueous solution at 20 to 25 ° C. As a result, when dissolved to form a solution, the component (a) used is judged to be soluble in the alkaline aqueous solution.

As for the molecular weight of the resin soluble in the alkaline aqueous solution as the component (a), the weight average molecular weight in terms of polystyrene is preferably 10,000 to 100,000, and more preferably 15,000 to 100,000. More preferably, it is 20,000 to 85,000. When the weight average molecular weight of the component (a) is 10,000 or more, appropriate solubility in an alkaline developer can be secured. Further, when the weight average molecular weight of the component (a) is 100,000 or less, good solubility in a solvent tends to be obtained, and it is possible to suppress an increase in viscosity of the solution and deterioration of handleability.
The weight average molecular weight can be measured by a gel permeation chromatography method, and can be determined by conversion using a standard polystyrene calibration curve.
Further, the dispersity obtained by dividing the weight average molecular weight by the number average molecular weight is preferably 1.0 to 4.0, and more preferably 1.0 to 3.5.

(Component (b): Crosslinking agent capable of crosslinking or polymerizing by heating)
The cross-linking agent of the component (b) usually reacts with the component (a) (cross-linking reaction) or cross-links in the step of heating the patterned resin film after coating, exposing and developing the photosensitive resin composition. The agent itself polymerizes.

Examples of the component (b) include compounds represented by the following formulas (IV) to (VIII). The reaction temperature of the compounds represented by the following formulas (VI) and (VII) is lower than that of other known thermal crosslinking agents and is usually 150 to 250 ° C.
(In the formula (IV), X is a single bond or a monovalent to tetravalent organic group, R ¹¹ is a hydrogen atom or a monovalent organic group, and R ¹² is a monovalent organic group. L is 1 Is an integer of 4 to 4, p is an integer of 1 to 4, and q is an integer of 0 to 3. When l is 2 or more, the groups in parentheses may be the same or different, and p is 2 or more. In the case of, the groups in parentheses may be the same or different, and when q is 2 or more, R ¹² may be the same or different.)

(In the formula (V), Y is independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a fluoroalkyl group in which part or all of the hydrogen atoms of the alkyl group having 1 to 10 carbon atoms are substituted with fluorine atoms. Is a hydroxyalkyl group in which a part of hydrogen atoms of an alkyl group having 1 to 10 carbon atoms is substituted with a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms, and R ¹³ and R ¹⁴ are each independently a monovalent group. R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a monovalent organic group, r and t each independently represent an integer of 1 to 3, and s and u each independently represent 0 to 3; Is an integer.
When r is 2 or more, the groups in the parentheses may be the same or different, when t is 2 or more, the groups in the parentheses may be the same or different, and when s is 2 or more, R ¹³ may be the same. R ¹⁴ may be the same or different when u is 2 or more. )

In formula (V), Y is preferably each independently a fluoroalkyl group in which some or all of the hydrogen atoms of an alkyl group having 1 to 4 carbon atoms are substituted with fluorine atoms. R ¹⁵ and R ¹⁶ are preferably hydrogen atoms. r and t are preferably 2. s and u are preferably 0.
(In formula (VI), R ¹⁷ and R ¹⁸ are each independently a hydrogen atom or a monovalent organic group, and two R ¹⁸ may be bonded to each other to form a ring structure.)
(In formula (VII), R ^{19 to} R ²⁴ are each independently a hydrogen atom, a methylol group or an alkoxymethyl group (the carbon number of the alkoxy moiety is preferably 1 to 4).)

  In formulas (IV) to (VI), examples of the monovalent organic group include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, and 1 to carbon atoms. Preferred are the 10 hydroxyalkoxy groups, or those in which some or all of the hydrogen atoms of these groups have been replaced with halogen atoms. Examples of the monovalent to tetravalent organic group for X include the above-mentioned monovalent organic groups and groups obtained by removing 1 to 3 hydrogen atoms from the monovalent organic groups.

  Among these, when the compounds represented by the formulas (VI) and (VII) are used, a cured film having excellent chemical resistance can be obtained when the photosensitive resin composition is cured at a low temperature of 200 ° C. or lower, And is preferable from the viewpoint of crosslinking with the polymer.

Specific examples of the compound represented by the formula (VI) include compounds represented by the following formula.
(In the formula, R ²⁵ , R ^26, and R ²⁸ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 or 1 to 5 carbon atoms), and R ²⁷ is each independently. Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)

Specific examples of the compounds represented by formulas (IV) and (V) include, but are not limited to, the following.

Specific examples of the compounds represented by the formulas (VI) and (VII) include the following, but are not limited to these.

  The content of the component (b) in the photosensitive resin composition of the present invention is preferably 5 parts by mass or more, more preferably 5 to 40 parts by mass, and 5 to 30 parts by mass with respect to 100 parts by mass of the component (a). It is more preferable to set it as a mass part.

(Component (c): Photosensitizer)
The photosensitizer of the component (c) is a compound that generates an acid upon irradiation with actinic rays, and has a function of increasing the solubility of the light-irradiated portion in an alkaline aqueous solution.

Examples of the photosensitizer include a diazonaphthoquinone compound, an aryldiazonium salt, a diaryliodonium salt, and a triarylsulfonium salt. Among them, the diazonaphthoquinone compound is preferable because of its high sensitivity.
The diazonaphthoquinone compound is a compound having a diazonaphthoquinone structure, and a compound having a structure represented by the following formula (A) or (B) is preferable.

  The diazonaphthoquinone compound can be obtained, for example, by subjecting an o-quinonediazidesulfonyl chloride compound to a condensation reaction with a hydroxy compound, an amino compound and the like in the presence of a dehydrochlorinating agent.

  Examples of o-quinonediazide sulfonyl chlorides include 1,2-benzoquinone-2-diazide-4-sulfonyl chloride, 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride, and 1,2-naphthoquinone-2-diazide. -4-Sulfonyl chloride and the like can be used.

  Examples of the hydroxy compound include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,2', 3'-pentahydroxybenzophenone, 2,3,4,3 ', 4', 5'-Hexahydroxybenzophenone, bis (2,3,4-trihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) propane, 4b, 5,9b, 10-tetrahydro- 1,3,6,8-Tetrahydroxy-5,10-dimethylindeno [2,1- ] Indene, tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane and the like can be used.

  Examples of the amino compound include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfone and 4,4′-diaminodiphenyl sulfide. , O-aminophenol, m-aminophenol, p-aminophenol, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis (3- Amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis ( 3-Amino-4-hydroxyphenyl) hexafluor Propane, bis (4-amino-3-hydroxyphenyl) hexafluoropropane and the like can be used.

The diazonaphthoquinone compound is preferably a compound represented by the following formula (11).
(In the formula (11), Q is each independently a hydrogen atom or a group represented by the following formula (12) or (13), and at least one of a plurality of Q is represented by the following formula (12) or ( It is a group represented by 13).)

  The content of the component (c) in the photosensitive resin composition of the present invention is 0.01 to 50 parts by mass with respect to 100 parts by mass of the component (a) in order to obtain good sensitivity and resolution during exposure. Parts, preferably 0.1 to 30 parts by mass, more preferably 0.5 to 25 parts by mass, and particularly preferably 3 to 20 parts by mass.

(Component (d): one or more compounds selected from the group consisting of compounds having a triazole ring and compounds having a tetrazole ring)
As the component (d), a compound having a triazole ring and / or a compound having a tetrazole ring is used. Either one may be used alone, or both may be used in combination. By using the component (d), the adhesion (adhesiveness) between the cured film obtained from the photosensitive resin composition and the substrate (for example, a silicon substrate or a copper substrate) can be improved, and the substrate (for example, copper) Can prevent corrosion.

The “compound having a triazole ring” is a compound having a triazole ring in its molecular structure, and also includes a compound having a triazole ring as a part of the condensed ring.
The "compound having a tetrazole ring" is a compound having a tetrazole ring in the molecular structure, and also includes a compound having a tetrazole ring as a part of the condensed ring.

Examples of the compound having a triazole ring include 1,2,3-triazole and its derivative, 1,2,4-triazole and its derivative, and 1,2,3-benzotriazole (1H-benzotriazole) and its derivative. Can be mentioned.
Examples of the derivative include compounds in which each compound is substituted with a substituent.

  As the above-mentioned substituent, an alkyl group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms), an aryl group having 6 to 10 carbon atoms, an alkoxy group (the carbon number of the alkyl portion is 1 to 10), an amino group , A nitro group, a mercapto group, an alkylthio group (the carbon number of the alkyl portion is 1 to 5), a carboxy group, a carbonyl group, a hydroxy group, and the like, and one or more of these may be substituted compounds. .

  Examples of the compound having a triazole ring include 1,2,4-triazole, 1,2,3-triazole, 3-mercapto-4-methyl-4H-1,2,4-triazole, 3-mercapto-1, 2,4-triazole, 4-amino-3,5-dimethyl-4H-1,2,4-triazole, 4-amino-3,5-dipropyl-4H-1,2,4-triazole, 3-amino- 5-isopropyl-1,2,4-triazole, 4-amino-3-mercapto-5-methyl-4H-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole, 3-amino-5-methyl-4H-1,2,4-triazole, 4-amino-1,2,4-triazole, 4-amino-3,5-dimethyl-1,2,4-triazole, 4- Ami -5-methyl-4H-1,2,4-triazole-3-thiol, 3,5-diamino-1H-1,2,4-triazole, benzotriazole, 5-methyl-1H-benzotriazole, 5,6 -Dimethylbenzotriazole, 5-amino-1H-benzotriazole, benzotriazole-4-sulfonic acid and the like can be mentioned, but the invention is not limited thereto.

  Examples of the compound having a tetrazole ring include 1H-tetrazole and its derivatives. Examples of the derivative include compounds in which 1H-tetrazole is substituted with a substituent.

  As the above-mentioned substituent, an alkyl group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms), an aryl group having 6 to 10 carbon atoms, an alkoxy group (the carbon number of the alkyl portion is 1 to 10), an amino group , A nitro group, a mercapto group, an alkylthio group (the carbon number of the alkyl portion is 1 to 5), a carboxy group, a carbonyl group, a hydroxy group, and the like, and one or more of these may be substituted compounds. .

  Examples of the compound having a tetrazole ring include 1H-tetrazole, 5-methyl-1H-tetrazole, 5- (methylthio) -1H-tetrazole, 5- (ethylthio) -1H-tetrazole, 5-phenyl-1H-tetrazole, Examples include 5-amino-1H-tetrazole, 5-nitro-1H-tetrazole 1-methyl-1H-tetrazole, and 5,5′-bis-1H-tetrazole, but are not limited thereto.

  Examples of the component (d) include 1,2,3-triazole and its derivative, 1,2,4-triazole and its derivative, 1,2,3-benzotriazole and its derivative, and 1H- having a substituent at the 5-position. Benzotriazole and its derivatives, 1H-benzotriazole and its derivatives having substituents at the 6-position, 1H-benzotriazole and its derivatives having substituents at the 5th and 6th positions, 1H-tetrazole and its derivatives, and substitutions at the 5th position 1H-tetrazole having a group and a derivative thereof, and 1H-tetrazole having a substituent at the 1-position and a derivative thereof are preferable, 1H-benzotriazole, 5-methyl-1H-benzotriazole, 1H-tetrazole and 5-amino-1H. -Tetrazole, 5-methyl-1H-tetrazole, 5,5'-bis-1H-teto Orres is more preferable.

  The blending amount of the component (d) in the photosensitive resin composition of the present invention is preferably 0.3 parts by mass or more, more preferably 0.3 to 30 parts by mass, and more preferably 0. 3 to 20 parts by mass, 0.3 to 10 parts by mass or 0.3 to 5 parts by mass are more preferable. Further, it may be 0.5 to 30 parts by mass, 1.0 to 20 parts by mass, or 2 to 20 parts by mass with respect to 100 parts by mass of the component (a).

(Component (e): one or more compounds selected from the group consisting of compounds having a pyridine ring and compounds having an imidazole ring)
As the component (e), a compound having a pyridine ring and / or a compound having an imidazole ring is used. Either one may be used alone, or both may be used in combination.

  The component (e) suppresses a polymerizing reaction in which the components (b) or the components (a) and (b) are condensed when the photosensitive resin composition is stored in a liquid state at room temperature. This makes it possible to improve the storage stability of the photosensitive resin composition, and to exhibit good solubility and photosensitive characteristics when exposing and developing the photosensitive resin film even after storage for a long period of time. You can Furthermore, the component (e) improves the adhesion between the cured film obtained from the photosensitive resin composition and the substrate (for example, a silicon substrate or a copper substrate), and when patterned on the substrate (for example, a copper substrate). Discoloration of the formed opening can be prevented.

The “compound having a pyridine ring” is a compound having a pyridine ring in its molecular structure, and also includes a compound having a pyridine ring as a part of the condensed ring.
The “compound having an imidazole ring” is a compound having an imidazole ring in its molecular structure, and also includes a compound having an imidazole ring as a part of the condensed ring.

  Examples of the compound having a pyridine ring include pyridine and its derivatives. Examples of the derivative include compounds in which pyridine is substituted with a substituent.

  Examples of the compound having a pyridine ring include pyridine, 2-acetylpyridine, 3-acetylpyridine, 4-acetylpyridine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2- (aminomethyl) pyridine, 3- (Aminomethyl) pyridine, 4- (aminomethyl) pyridine, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, 2-phenylpyridine, 3 -Phenylpyridine, 4-phenylpyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,4-dimethylpyridine, 2,6-dimethylpyridine, 3,5-dimethylpyridine, 2,4,6 -Trimethylpyridine, 2-mercaptopyridine, 3-mercapto Lysine, 4-mercaptopyridine, etc. including without being limited thereto.

  Examples of the compound having an imidazole ring include imidazole and its derivatives, and benzimidazole and its derivatives. Examples of the derivative include compounds in which a substituent is substituted on imidazole or benzimidazole.

  Examples of the compound having an imidazole ring include imidazole, 1-ethylimidazole, 2-ethylimidazole, 4-ethylimidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 2-phenyl-4-methylimidazole and benz. Examples include imidazole, 1-methylbenzimidazole, 2-methylbenzimidazole, 2-mercaptobenzimidazole, 2-mercapto-1-methylimidazole, 2-mercapto-5-methylimidazole, but are not limited thereto. Absent.

  Of the component (e), pyridine and its derivatives, pyridine having a substituent at the 3-position and derivatives thereof, pyridine having a substituent at the 4-position, imidazole and its derivatives, imidazole having a substituent at the 1-position, and Derivatives thereof, imidazole having a substituent at the 2- and 4-positions and derivatives thereof, benzimidazole and derivatives thereof, preferably pyridine and derivatives thereof, 4-methylpyridine and derivatives thereof, imidazole and derivatives thereof, 1-methylimidazole and derivatives thereof Derivatives, 2-phenyl-4-methylimidazole and its derivatives, and benzimidazole and its derivatives are more preferable.

  The blending amount of the component (e) in the photosensitive resin composition of the present invention is preferably 0.1 parts by mass or more, more preferably 0.1 to 30 parts by mass, and 0.1. It is more preferably 1 to 20 parts by mass or 0.1 to 15 parts by mass.

(solvent)
The photosensitive resin composition of the present invention usually contains a solvent.
Examples of the solvent include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, N-methyl-2-pyrrolidone, N, N. -Dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, cyclohexanone, cyclopentanone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, and the like. There is no particular limitation as long as it can sufficiently dissolve the other components in the photosensitive resin composition.

  Among these, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N from the viewpoint of excellent solubility of each component and coatability during resin film formation. , N-dimethylacetamide and dimethyl sulfoxide are preferably used.

  The content of the solvent in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 50 to 400 parts by mass, more preferably 100 to 300 parts by mass, and 150 to 250 parts by mass with respect to 100 parts by mass of the component (a). Part by mass is more preferred.

  The photosensitive resin composition of the present invention may contain a known coupling agent, a dissolution accelerator, a dissolution inhibitor, a surfactant, a leveling agent and the like other than the above components, if necessary.

For example, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 99% by mass or more, 99.5% by mass or more, 99.9% by mass or more of the photosensitive resin composition of the present invention. Alternatively, 100% by mass may be the components (a) to (e) and the solvent.
The photosensitive resin composition of the present invention may consist essentially of components (a) to (e) and a solvent. In this case, unavoidable impurities may be included.
Further, the photosensitive resin composition of the present invention may be composed of only the components (a) to (e) and a solvent.

[Method for producing patterned cured film]
The method for producing a pattern-cured film of the present invention comprises a step of applying the above-mentioned photosensitive resin composition onto a substrate and drying it to form a photosensitive resin film, and pattern-exposing the photosensitive resin film to form a resin film. And a step of developing the exposed resin film with an alkaline aqueous solution to form a pattern resin film, and a step of heat-treating the pattern resin film to form a patterned cured film.
Hereinafter, each step will be described.

(Photosensitive resin film forming step)
In this step, the photosensitive resin composition is applied onto the substrate and dried to form a photosensitive resin film.
Examples of the substrate include glass, semiconductors, metal oxide insulators such as TiO ₂ and SiO ₂ , silicon nitride, copper, and copper alloys. The coating method is not particularly limited, but it can be performed using a spinner or the like.

Drying can be performed using a hot plate, oven, or the like. The heating temperature is preferably 100 to 150 ° C. The heating time is preferably 30 seconds to 5 minutes. Thereby, a photosensitive resin film can be obtained from the photosensitive resin composition.
The film thickness of the photosensitive resin film is preferably 5 to 100 μm, more preferably 8 to 50 μm, and further preferably 10 to 30 μm.

(Exposure process)
In this step, the photosensitive resin film is exposed in a pattern through the mask.
Examples of the actinic ray to be applied include ultraviolet rays including i rays, visible rays, radiation, etc., and i rays are preferable. As the exposure device, a parallel exposure machine, a projection exposure machine, a stepper, a scanner exposure machine or the like can be used.

(Development process)
A resin film having a pattern (patterned resin film) can be obtained by developing the resin film that has undergone the exposure step. Generally, when a positive photosensitive resin composition is used, the exposed area is removed with a developing solution.

An alkaline aqueous solution can be used as the developing solution, and examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide. Tetramethylammonium hydroxide is preferred.
The concentration of the alkaline aqueous solution is preferably 0.1 to 10% by mass.

  The development time varies depending on the type of polybenzoxazole precursor used, but is preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and further preferably 30 seconds to 4 minutes from the viewpoint of productivity.

  An alcohol or a surfactant may be added to the above developing solution. The addition amount is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the developer.

(Heat treatment process)
By heat-treating the patterned resin film, a crosslinked structure is formed between the functional groups of the component (a), or between the components (a) and (b), and a patterned cured film can be obtained. Further, the component (a) undergoes dehydration and ring closure by the heat treatment step to give an oxazole ring.

  The heating temperature is preferably 250 ° C. or lower, more preferably 120 to 250 ° C., further preferably 160 to 230 ° C. Within this range, damage to the substrate and the device can be suppressed to a small value, the device can be produced with a high yield, and energy saving of the process can be realized.

  The heating time is preferably 5 hours or less, more preferably 30 minutes to 3 hours. Within this range, the crosslinking reaction or the dehydration ring closure reaction can be sufficiently advanced. The atmosphere for the heat treatment may be the air or an inert atmosphere such as nitrogen, but the nitrogen atmosphere is preferable from the viewpoint of preventing the oxidation of the pattern resin film.

  Examples of the apparatus used in the heat treatment step include a quartz tube furnace, a hot plate, rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, and a microwave curing furnace.

[Semiconductor device manufacturing process]
Next, as an example of the method for manufacturing a patterned cured film of the present invention, a manufacturing process of a semiconductor device will be described with reference to the drawings. 1 to 7 are schematic cross-sectional views illustrating a manufacturing process of a fan-out package having a multilayer wiring structure, and show a series of processes from the first process to the seventh process. FIG. 8 is a schematic sectional view of a fan-out package having a UBM (Under Bump Metal) free structure.

In these figures, a semiconductor substrate 1 such as a Si substrate having a circuit element (not shown) is covered with a protective film 2 such as a silicon oxide film except a predetermined portion of the circuit element, and a first portion is formed on the exposed circuit element. The conductor layer 3 is formed.
A film of polyimide resin or the like is formed thereon as an interlayer insulating film 4 by a spin coating method or the like (first step, FIG. 1).

  Next, a photosensitive resin layer 5 of chlorinated rubber type, phenol novolac type or the like is formed on the interlayer insulating film 4 by a spin coating method, and the interlayer insulating film 4 at a predetermined portion is exposed by a known method using this as a mask. Thus, the window 6A is provided (second step, FIG. 2).

  The interlayer insulating film 4 exposed in the window 6A portion is selectively etched by a dry etching means using a gas such as oxygen or carbon tetrafluoride to form the window 6B. Then, the photosensitive resin layer 5 is removed using an etching solution that corrodes the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed from the window 6B (third step, FIG. 3). ).

  Further, the second conductor layer 7 is formed by a known method, and the second conductor layer 7 is electrically connected to the first conductor layer 3 (fourth step, FIG. 4). When forming a multi-layer wiring structure having three or more layers, the above steps are repeated to form each layer.

Next, the surface protective film 8 is formed as follows using the photosensitive resin composition of the present invention.
That is, the photosensitive resin composition of the present invention is applied by a spin coating method, dried, irradiated with light from a mask on which a pattern for forming a window 6C is drawn on a predetermined portion, and then developed by an alkaline aqueous solution to form a pattern. A resin film is formed. Then, the patterned resin film is heated to form a patterned cured film, that is, the surface protective film 8 (fifth step, FIG. 5). The surface protective film 8 has a function of protecting the conductor layer from external stress, α rays and the like.

  Further, usually, after forming a metal thin film on the surface of the surface protection film 8 by a sputtering process, a plating resist is formed in accordance with the window 6C using a known method, and the exposed metal thin film portion is plated by UBM. A metal layer 9 called (Under Bump Metal) is deposited. Then, the plating resist is peeled off, and the metal foil film other than the region where the metal layer 9 is formed is removed by etching to form the UBM (sixth step, FIG. 6). Further, external connection terminals (bumps 10) called bumps are formed on the surface of the metal layer 9 (seventh step, FIG. 7). The metal layer 9 is formed for the purpose of relaxing the stress acting on the bump 10 and improving the electrical connection reliability.

  In recent years, in order to reduce the manufacturing cost, the UBM-free structure in which the bumps 10 are directly formed after forming the window 6C in the surface protective film 8 is proposed in order to omit the step of forming the metal layer 9 (UBM). Has been done. In the UBM-free structure, it is preferable that the second conductor layer 7 connected to the bump 10 be formed thicker than usual in order to suppress an increase in electric resistance due to the formation of the intermetallic compound. Further, it is preferable that the surface protective film 8 relieves the stress acting on the bumps 10. Therefore, it is preferable that the surface protection film 8 is formed thick in order to cover the second conductor layer 7 formed thick and enhance the stress relaxation ability (FIG. 8). Therefore, in the UBM-free structure, when forming the window 6C in the surface protective film 8, it is preferable that the resin film is applied thicker, and exposed and developed.

[Cured product]
A cured product can be obtained by applying the above heat treatment step to the photosensitive resin composition of the present invention. The cured product of the present invention may be the above-mentioned patterned cured film or a cured product having no pattern.

[Electronic parts]
The electronic component of the present invention has the above-mentioned patterned cured film or cured product, for example, the patterned cured film obtained by the above-described method for producing a patterned cured film.
Specifically, the pattern cured film or cured product can be used as a surface protective film of an electronic component, a cover coat layer, an interlayer insulating film, an interlayer insulating film of a multilayer wiring board, or the like.
Examples of electronic components include semiconductor devices, multilayer wiring boards, various electronic devices, and the like. The above-described semiconductor device is one embodiment of the electronic component of the present invention, but is not limited to the above, and can have various structures.

  Hereinafter, the present invention will be described more specifically based on Examples and Comparative Examples. The present invention is not limited to the examples below.

Synthesis example 1
[Component (a): Synthesis of Polybenzoxazole Precursor]
In a 0.2 liter flask equipped with a stirrer and a thermometer, 60 g of N-methyl-2-pyrrolidone was charged, and 13.92 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane ( 38 mmol) was added and dissolved by stirring. Subsequently, while maintaining the temperature at 0 to 5 ° C., 7.48 g (28 mmol) of dodecanedioic acid dichloride and 3.56 g (12 mmol) of 4,4′-diphenyletherdicarboxylic acid dichloride were added dropwise over 10 minutes, and then the mixture in the flask was added. The solution was stirred for 60 minutes. The solution was poured into 3 liters of water, the precipitate was collected, washed with pure water three times, and then decompressed to obtain polyhydroxyamide (polybenzoxazole precursor) (hereinafter referred to as polymer I). To). Polymer I had a weight average molecular weight of 33,100 and a dispersity of 2.0.

Synthesis example 2
[Component (a): Synthesis of Polybenzoxazole Precursor]
In a 0.2 liter flask equipped with a stirrer and a thermometer, 60 g of N-methyl-2-pyrrolidone was charged, and 13.92 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane ( 38 mmol) was added and dissolved by stirring. Subsequently, while maintaining the temperature at 0 to 5 ° C., 11.86 g (40 mmol) of 4,4′-diphenyletherdicarboxylic acid dichloride was added dropwise over 10 minutes, then the temperature was returned to room temperature and the solution in the flask was stirred for 3 hours. The above solution was poured into 3 liters of water, the precipitate was collected, washed with pure water three times, and then decompressed to obtain polyhydroxyamide (hereinafter referred to as polymer II). Polymer II had a weight average molecular weight of 22,400 and a dispersity of 3.2.

The weight average molecular weights of the polymers I and II were determined by gel permeation chromatography (GPC) method standard polystyrene conversion.
The conditions for measuring the weight average molecular weight by the GPC method are as follows. The measurement was performed using a solution of 1 ml of a solvent [tetrahydrofuran (THF) / dimethylformamide (DMF) = 1/1 (volume ratio)] with respect to 0.5 mg of the polymer.
Measuring device: Detector L4000 manufactured by Hitachi, Ltd.
UV pump: L6000 manufactured by Hitachi, Ltd.
Shimadzu Corporation C-R4A Chromatopac
Measurement conditions: Column Gelpack GL-S300MDT-5 × 2
This eluent: THF / DMF = 1/1 (volume ratio)
_{LiBr (0.03mol / l), H} 3 PO 4 (0.06mol / l)
Flow rate: 1.0 ml / min Detector: UV270nm

Examples 1-12 and Comparative Examples 1-8
[Preparation of photosensitive resin composition]
The photosensitive resin composition was prepared by mixing the components in the amounts and the amounts shown in Table 1. The blending amounts shown in Table 1 are parts by mass of each component with respect to 100 parts by mass of the component (a). The components used are as follows.

(Component (a): polybenzoxazole precursor)
A-1: Polymer I obtained in Synthesis Example 1
A-2: Polymer II obtained in Synthesis Example 2

(Component (b): Crosslinking agent capable of crosslinking or polymerizing by heating)
B-1: a compound represented by the following formula (manufactured by Allnex, trade name "Cymel 300")

-B-2: a compound represented by the following formula (manufactured by Sanwa Chemical Co., Ltd., trade name "Nikalac MX-270")

(Component (c): Photosensitizer)
C-1: compound represented by the following formula (manufactured by Daito Chemix Co., Ltd., trade name "4C-PA280")

-C-2: a compound represented by the following formula (manufactured by Daito Chemix Co., Ltd., trade name "PA-28")

(Component (d): one or more compounds selected from the group consisting of compounds having a triazole ring and compounds having a tetrazole ring)
・ D-1: 1H-tetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ D-2: 5-amino-1H-tetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ D-3: 1H-benzotriazole (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)

(Component (e): one or more compounds selected from the group consisting of compounds having a pyridine ring and compounds having an imidazole ring)
・ E-1: pyridine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
E-2: 4-methylpyridine (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
E-3: imidazole (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・ E-4: 1-methylimidazole (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
-E-5: Benzimidazole (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
-E-6: 2-phenyl-4-methylimidazole (manufactured by Shikoku Chemicals Co., Ltd., trade name "2P4MZ")

((E ') component)
・ E'-1: Pyrrole (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
E'-2: N, N-diethylaniline (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
The component (e ') means a component different from the component (e) used in the present invention.

(solvent)
BLO (γ-butyrolactone)

[Production of patterned resin film]
The photosensitive resin composition immediately after being prepared in [Preparation of photosensitive resin composition] (hereinafter, may be referred to as "photosensitive resin composition before storage") is spin-coated on a silicon substrate and a copper substrate, and hot. It heated at 110 degreeC for 3 minutes on the plate, and formed the photosensitive resin film of 11.0-11.5 micrometer (initial film thickness). The obtained photosensitive resin film was subjected to reduction projection exposure with i-line (wavelength 365 nm) using an i-line stepper (manufactured by Canon Inc., trade name “FPA-3000iW”) and a mask. At this time, the exposure amount was changed for each area, and a plurality of samples having different exposure amounts were prepared. The resin film after exposure was developed using a 2.38% aqueous solution of TMAH for a developing time such that the film thickness after development was about 70 to 80% of the initial film thickness to produce a patterned resin film. The film thickness of the obtained patterned resin film was measured.

  The same as above with respect to the photosensitive resin composition prepared in [Preparation of photosensitive resin composition] and stored at room temperature for 2 weeks (hereinafter, may be referred to as “photosensitive resin composition after storage”). The operation was performed to manufacture a patterned resin film.

[Evaluation of storage stability (change in dissolution rate of unexposed area)]
With respect to the pattern resin film on the silicon substrate obtained from the photosensitive resin composition before storage, the dissolution rate of the unexposed portion, the amount of change in the film pressure due to development (initial film thickness-film thickness after development) was determined by the development time. It was calculated by dividing. Similarly for the patterned resin film obtained from the photosensitive resin composition after storage, the dissolution rate of the unexposed part was measured in the same manner, based on the following formula, the storage rate after storage with respect to the dissolution rate of the photosensitive resin composition before storage The rate of change of the dissolution rate of the photosensitive resin composition was calculated. The results are shown in Table 1.
Change rate of dissolution rate (%) = {(dissolution rate (before storage) -dissolution rate (after storage)) / dissolution rate (before storage)} × 100
The absolute value of the rate of change of the dissolution rate thus obtained was evaluated according to the following criteria.
A: Change rate (absolute value) of dissolution rate is 0% or more and less than 10% B: Change rate (absolute value) of dissolution rate is 10% or more and less than 30% C: Change rate (absolute value) of dissolution rate is 30% that's all

[Production of patterned cured film]
The vertical diffusion furnace μ-TF (manufactured by Koyo Thermo Systems Co., Ltd.) was used for the patterned resin film on the copper substrate obtained from the photosensitive resin composition before storage obtained in [Production of patterned resin film]. After heating in a nitrogen atmosphere at 100 ° C. for 30 minutes, heat treatment was further performed at 200 ° C. for 1 hour to obtain a patterned cured film.

[Evaluation of discoloration of copper substrate opening]
With respect to the patterned cured film on the copper substrate obtained in [Production of patterned cured film], the openings were observed and evaluated based on the following criteria. The results are shown in Table 1.
A: No discoloration of the opening was observed. B: Appearance of the opening was slightly reddish. C: Severe discoloration of the opening was observed. Table 1 shows the results.

[Evaluation of adhesiveness (substrate adhesion lattice number)]
The photosensitive resin composition immediately after prepared in [Preparation of photosensitive resin composition] was spin-coated on a silicon substrate and a copper substrate, respectively, and heated on a hot plate at 110 ° C. for 3 minutes to give 11.0 to 11 A photosensitive resin film having a thickness of 0.5 μm (initial film thickness) was formed. Then, a cured film was prepared by the same operation as in [Production of patterned cured film], and the obtained cured film was adhered between the substrate and the cured film according to the cross-cut method of JIS K 5600-5-6 standard. The characteristics were evaluated for each of the silicon substrate and the copper substrate based on the following criteria. The results are shown in Table 1.
A: The number of lattices of the cured film adhered to the substrate is 100 B: The number of lattices of the cured film adhered to the substrate is 50 to 99 C: The number of lattices of the cured film adhered to the substrate is Less than 50

  From Table 1, the photosensitive resin composition of the present invention is excellent in storage stability, the cured film obtained from the photosensitive resin composition has high adhesiveness to a silicon substrate and a copper substrate, and has an effect of suppressing discoloration. It turns out to be excellent.

  The photosensitive resin composition of the present invention can be used for electronic parts such as semiconductor devices, multilayer wiring boards, and various electronic devices.

1 Semiconductor Substrate 2 Protective Film 3 First Conductor Layer 4 Interlayer Insulating Film 5 Photosensitive Resin Layer 6A, 6B, 6C Window 7 Second Conductor Layer 8 Surface Protective Film 9 Metal Layer 10 Bump

Claims (12)

A photosensitive resin composition containing the following components (a) to (e).
One or more compounds selected from the group consisting of (a) polybenzoxazole precursor (b) crosslinking agent capable of crosslinking or polymerizing by heating (c) photosensitizer (d) compound having triazole ring and compound having tetrazole ring (E) One or more compounds selected from the group consisting of compounds having a pyridine ring and compounds having an imidazole ring   The component (d) comprises 1,2,3-triazole and its derivative, 1,2,4-triazole and its derivative, 1,2,3-benzotriazole and its derivative, and 1H-tetrazole and its derivative. The photosensitive resin composition according to claim 1, which is one or more compounds selected from the group.   The photosensitive resin composition according to claim 1, wherein the component (e) is one or more compounds selected from the group consisting of pyridine and its derivatives, imidazole and its derivatives, and benzimidazole and its derivatives.   Content of the said (d) component is 0.3 mass part or more with respect to 100 mass parts of the said (a) component, The photosensitive resin composition in any one of Claims 1-3.   Content of the said (e) component is 0.1 mass part or more with respect to 100 mass parts of the said (a) component, The photosensitive resin composition in any one of Claims 1-4.   Content of the said (b) component is 5 mass parts or more with respect to 100 mass parts of the said (a) component, The photosensitive resin composition in any one of Claims 1-5.   The photosensitive resin composition according to claim 1, wherein the component (c) contains a diazonaphthoquinone compound. A step of applying the photosensitive resin composition according to any one of claims 1 to 7 on a substrate and drying the composition to form a photosensitive resin film;
A step of pattern-exposing the photosensitive resin film to form a resin film,
Developing the exposed resin film with an alkaline aqueous solution to form a pattern resin film;
A step of forming a patterned cured film by heat-treating the patterned resin film,
A method for producing a patterned cured film, comprising:   Hardened | cured material which hardened the photosensitive resin composition in any one of Claims 1-7.   The cured product according to claim 9, which is a patterned cured film.   An interlayer insulating film, a cover coat layer, or a surface protective film produced using the cured product according to claim 9.   An electronic component comprising the interlayer insulating film, the cover coat layer or the surface protective film according to claim 11.