JP7403268B2 - Photosensitive resin compositions, dry films, cured products, and electronic components - Google Patents

Description

The present invention relates to a photosensitive resin composition containing a polyimide precursor having a specific structure, a dry film having a resin layer formed from the photosensitive resin composition, a cured product formed from the photosensitive resin composition, and The present invention relates to electronic components such as printed wiring boards and semiconductor devices that have the cured product as a forming material.

Photosensitive resin compositions containing polyimide precursors exhibit excellent properties such as insulation, heat resistance, and mechanical strength, and are therefore widely used in various fields. For example, it is being applied to flexible printed wiring boards, buffer coat films for semiconductor devices, and insulating films for redistribution layers in wafer level packages (WLP).

Specifically, an alkali-developable photosensitive resin composition is applied onto a substrate, dried to form a coating film, exposed through a pattern mask, and then exposed and unexposed areas are treated with an alkaline developer. By performing alkaline development utilizing the difference in solubility of , a film having a desired pattern is formed, and by heating this pattern film, the polyimide precursor contained in the photosensitive resin composition is subjected to a ring-closing reaction, A cured film can be obtained.

In recent semiconductor devices, with the demand for higher functionality and miniaturization, it is required to form cured films with finer patterns on buffer coat films and insulating films for rewiring layers of wafer level packages. Photosensitive resin compositions are required to have excellent resolution. In response to such demands, Patent Document 1 discloses a photosensitive polyimide resin composition containing a polyimide precursor, and Patent Document 2 discloses a photosensitive polyimide resin composition that has properties equivalent to those of polyimide resin but with high resolution. A composition using a polybenzoxazole precursor as a photosensitive resin having imageability is disclosed.

In order to achieve such excellent resolution, in a coating film made of a photosensitive resin composition, the dissolution rate of the exposed area in an alkaline developer (hereinafter simply referred to as the dissolution rate of the exposed area) must be high, and It is important that the unexposed area has excellent dissolution resistance to an alkaline developer. That is, there is a need for a photosensitive resin composition that has a large difference in dissolution rate in an alkaline developer between exposed areas and unexposed areas, that is, a large so-called dissolution contrast.

On the other hand, in a cured film formed from a photosensitive resin composition containing a polyimide precursor, attempts have been made to lower the heating temperature of the patterned film in order to suppress the occurrence of warpage accompanying the ring-closing reaction (Patent Document 3 reference).

Japanese Patent Application Publication No. 2006-267800 Japanese Patent Application Publication No. 2003-241377 Japanese Patent Application Publication No. 2018-146964

However, the compositions described in Patent Documents 1 and 2 cannot be said to sufficiently satisfy the dissolution contrast required to achieve the resolution required for recent semiconductor devices, and the compositions described in Patent Document 3 In addition to the resolution problem, the described composition requires the use of a high boiling point solvent such as N-methyl-2-pyrrolidone (NMP) or γ-butyrolactone (GBL), so it is difficult to use a low heating temperature. Even if curing was achieved, there was a problem in that high boiling point solvents remained in the cured product.

The present invention has been made in view of the above problems, and its main purpose is to provide a polyimide precursor that has solubility in various solvents (hereinafter simply referred to as solvent solubility) and that has a large dissolution contrast (resolution). It is an object of the present invention to provide a photosensitive resin composition having imageability).

Another object of the present invention is to provide dry films and electronic components such as printed wiring boards and semiconductor devices using the photosensitive resin composition.

The present inventors focused on obtaining excellent dissolution contrast by increasing the dissolution rate of the exposed area, and as a result of intensive study, the present inventors discovered a specific method that can significantly improve the resolution of photosensitive resin compositions. We have newly discovered a polyimide precursor having the structure and completed the present invention. In addition, the polyimide precursor has been shown to have high solubility in various solvents including low boiling point solvents such as 2-methoxy-1-methylethyl acetate (PGMEA) and 4-methyl-2-pentanone. I found it.

（式中、
Ｘは、４価の有機基であり、
Ａは、単結合、Ｏおよび２価の有機基から選択され、
Ｂは、フルオロアルコール基であり、
Ｒは、置換または無置換のアルキル基であり、
ｎ１は、それぞれ独立して、１以上の整数であり、
ｎ２およびｎ３は、それぞれ独立して、０～４の整数であり、かつｎ２＋ｎ３は１以上であり、
ｎ４は、それぞれ独立して、０～３の整数であり、
ｎ５は、１～４の整数であり、
ｎ６は、０～３の整数である。） That is, the photosensitive resin composition of the present invention is characterized by containing (A) a polyimide precursor having at least one of the structures represented by the following general formulas (1) and (2), and (B) a photosensitizer. shall be.

(In the formula,
X is a tetravalent organic group,
A is selected from a single bond, O and a divalent organic group,
B is a fluoroalcohol group,
R is a substituted or unsubstituted alkyl group,
n1 is each independently an integer of 1 or more,
n2 and n3 are each independently an integer of 0 to 4, and n2+n3 is 1 or more,
n4 is each independently an integer from 0 to 3,
n5 is an integer from 1 to 4,
n6 is an integer from 0 to 3. )

（上記式中、ａは、それぞれ独立して０～２の整数であり、ｂは、それぞれ独立して１～３の整数である。） In the present invention, X in general formulas (1) and (2) is preferably selected from a tetravalent organic group having the following structure.

(In the above formula, a is each independently an integer of 0 to 2, and b is each independently an integer of 1 to 3.)

In the present invention, the number of carbon atoms of the fluoroalcohol represented by B in general formulas (1) and (2) is each independently from 1 to 10, and the number of fluorine is each independently from 1 to 10. is preferred.

In the present invention, the carboxyl group concentration in the polyimide precursor is preferably 300 to 800 mol/g.

In the present invention, the fluorine concentration in the polyimide precursor is preferably 20 to 200 mol/g.

In the present invention, it is preferable that the photosensitive resin composition further contains an adhesive.

In the present invention, the photosensitizer is preferably a naphthoquinone diazide compound.

The dry film of the present invention is characterized in that it includes a resin layer formed from the above photosensitive resin composition on the film.

The cured product of the present invention is characterized in that it is formed from the resin layer of the photosensitive resin composition or the dry film.

The electronic components of the present invention, such as printed wiring boards and semiconductor devices, are characterized by having the above-mentioned cured product as a forming material.

According to the present invention, it is possible to provide a photosensitive resin composition that has a high dissolution rate in exposed areas and can realize excellent dissolution contrast (resolution). Furthermore, since the polyimide precursor contained in the photosensitive resin composition has excellent solubility in various solvents including low boiling point solvents, the above-mentioned problem of residual solvent can be solved.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention includes (A) a polyimide precursor having at least one structure represented by the following general formulas (1) and (2), and (B) a photosensitizer. Features.

The dissolution rate of the exposed area formed from the photosensitive resin composition of the present invention in a 2.38% TMAH aqueous solution at 25°C is preferably 200 to 1000 nm/min, more preferably 500 to 900 nm/min. More preferred.
This makes it easy to control the conditions of the developing process, making it extremely easy to form fine patterns.
Note that the dissolution rate is measured as follows.
A photosensitive resin composition is applied and dried on a silicon substrate to form a dried coating film with a thickness of 2 μm, and this dried coating film is irradiated with broad light through a patterned photomask. The exposure amount is 200 mJ/cm ² .
The dried coating film after exposure was developed using a 2.38% TMAH aqueous solution at 25°C, and the dry coating film in the exposed area was measured using a development rate measuring device (RDA-790 manufactured by Lithotech Japan Co., Ltd.). Measure the dissolution rate of the membrane.

Hereinafter, the components contained in the photosensitive resin composition of the present invention will be explained in detail.

[(A) Polyimide precursor]
The photosensitive resin composition of the present invention has (A) at least one structure represented by the following general formulas (1) and (2).

In the above general formulas (1) and (2), X is a tetravalent organic group.
Examples of the tetravalent organic group include, but are not limited to, groups having the following structures.
Note that a in the structure is an integer of 0 to 2, each independently selected, and from the viewpoint of solvent solubility, is preferably 0 to 1, and particularly preferably 0. Further, b in the structure is an integer of 1 to 3, preferably 2 to 3, and particularly preferably 3 from the viewpoint of solvent solubility and transparency of the cured product.

Among the above-mentioned tetravalent organic groups, groups having the following structures are preferred from the viewpoint of solvent solubility.

Specific examples of the tetravalent organic group having the above-mentioned preferred structure include, but are not limited to, groups having the following structure.

Among the above-mentioned tetravalent organic groups, groups having the following structures are particularly preferred from the viewpoint of dissolution rate of exposed areas and dissolution contrast.

A is selected from a single bond, O and a divalent organic group.
The divalent organic group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms.
Examples of divalent organic groups include alkylene groups, cycloalkylene groups, arylene groups, alkyl ether groups, ketone groups, and ester groups.

In the above general formulas (1) and (2), B is a fluoroalcohol group.
The number of carbon atoms in each fluoroalcohol group is preferably 1 to 10, more preferably 3 to 6.
The number of fluorine atoms in each fluoroalcohol group is preferably 1 to 10, more preferably 4 to 8. Thereby, solvent solubility and transparency of the cured product can be improved.
Specific examples of the fluoroalcohol group include, but are not limited to, groups having the following structures.

In the above general formulas (1) and (2), R is a substituted or unsubstituted alkyl group or aryl group.
The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.
Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, n-pentyl group, sec-pentyl group, n-hexyl group, and cyclohexyl group. group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group group, chloroethyl group, dichloroethyl group, trichloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, hydroxymethyl group, hydroxyethyl group, hydroxylpropyl group, methoxy group, ethoxy group, n-propoxy group, n- Butoxy group, n-pentyloxy group, sec-pentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, trifluoro Examples include methoxy group, methylamino group, dimethylamino group, trimethylamino group, ethylamino group, and propylamino group.
Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a phenanthrenyl group, and a biphenyl group.
Examples of the substituent include an alkyl group, an alkyl group having a halogen such as a fluoro group and a chloro group, a halogen group, an amino group, a nitro group, a hydroxyl group, a cyano group, a carboxyl group, and a sulfonic acid group.

In the above general formulas (1) and (2), n1 is each independently an integer of 1 or more, preferably an integer of 1 to 20.
In the above general formula (1), n2 and n3 are each independently an integer of 0 to 4, preferably an integer of 1 to 2. Note that n2+n3 is 1 or more.
In the above general formula (1), n4 is each independently an integer of 0 to 3, preferably an integer of 0 to 1.
In the above general formula (2), n5 is an integer of 1 to 4, preferably an integer of 1 to 2.
In the above general formula (2), n6 is an integer of 0 to 3, preferably an integer of 0 to 1.

Structures satisfying the above general formula (1) or (2) include, but are not limited to, the following structures.

The number average molecular weight (Mn) of the polyimide precursor is preferably 2,000 to 30,000, more preferably 5,000 to 10,000. This provides a good balance between the solubility of the exposed areas of the photosensitive resin composition in the alkaline developer and the solubility of the unexposed areas in the alkaline developer.
Further, the weight average molecular weight (Mw) of the polyimide precursor is preferably 4,000 to 80,000, more preferably 10,000 to 30,000. This can further reduce the occurrence of cracks in the cured product.
Furthermore, Mw/Mn is preferably 2.0 to 4.0, more preferably 2.3 to 3.0. This reduces residue and swelling generated during development.
In the present invention, the number average molecular weight and the weight average molecular weight are values measured by gel permeation chromatography (GPC) and converted using standard polystyrene.

The glass transition temperature (Tg) of the polyimide prepared by subjecting a polyimide precursor to a ring-closing reaction is preferably 180°C or higher, more preferably 200°C or higher. As a result, excellent heat resistance can be obtained as a cured product.
In the present invention, Tg is a value determined by differential scanning calorimetry (DSC) in accordance with JIS K 7121.

The carboxyl group concentration in the polyimide precursor of the present invention is preferably 300 to 800 mol/g, more preferably 300 to 600 mol/g. Thereby, the dissolution rate and dissolution contrast of the exposed area can be further improved.

The fluorine concentration in the polyimide precursor of the present invention is preferably 20 to 200 mol/g, more preferably 50 to 100 mol/g. Thereby, solvent solubility and transparency can be further improved.

As long as the characteristics of the present invention are not impaired, the photosensitive resin composition of the present invention may have a structure in which the structures represented by the above general formulas (1) and (2) are ring-closed. For example, the following structures may be mentioned.

The content of the structure in which the structures represented by general formulas (1) and (2) are ring-closed in the polyimide precursor (A), that is, the imidization rate is preferably 50% or less, and 40% or less. More preferably, it is 20% or less. This improves the dissolution resistance of the unexposed area to an alkaline developer.

[(B) Photosensitizer]
The photosensitive resin composition of the present invention contains a photosensitizer, and thereby the solubility of the photosensitive resin composition in an alkaline developer can be adjusted. Examples of the photosensitizer include photoacid generators and photobase generators. Among these, photoacid generators are preferred from the viewpoint of dissolution contrast.
This photosensitizer can be blended in a known and commonly used ratio; for example, for a photoacid generator, 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight, per 100 parts by weight of the polyimide precursor. It is preferable to mix in the ratio of .
In addition, the photosensitive resin composition may contain two or more types of photosensitizers.

A photoacid generator is a compound that generates an acid when irradiated with light such as ultraviolet rays or visible light, and includes, for example, naphthoquinone diazide compounds, diarylsulfonium salts, triarylsulfonium salts, dialkylphenacylsulfonium salts, diaryliodonium salts, and aryldiazonium salts. Examples include salts, aromatic tetracarboxylic acid esters, aromatic sulfonic acid esters, nitrobenzyl esters, aromatic N-oximide sulfonates, aromatic sulfamides, and benzoquinonediazosulfonic acid esters.
Among the above, naphthoquinone diazide compounds are preferred from the viewpoint of dissolution contrast.
Specifically, the naphthoquinone diazide compound includes, for example, a naphthoquinone diazide adduct of tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene (for example, TS533, TS567, TS583 manufactured by Sanpo Chemical Research Institute, TS593), naphthoquinone diazide adducts of tetrahydroxybenzophenone (for example, BS550, BS570, BS599 manufactured by Sanpo Chemical Research Institute), and 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]-α , α-dimethylbenzyl}phenol and naphthoquinonediazide adducts (for example, TKF-428 and TKF-528 manufactured by Sanpo Chemical Research Institute).

A photobase generator generates one or more basic substances (secondary amines, tertiary amines, etc.) by changing the molecular structure or by cleavage of the molecules due to light irradiation such as ultraviolet rays or visible light. It is a compound that
The photobase generator may be an ionic photobase generator or a nonionic photobase generator, but from the viewpoint of the sensitivity of the photosensitive resin composition, an ionic photobase generator is preferable.
Examples of ionic photobase generators include salts of aromatic component-containing carboxylic acids and tertiary amines, and commercially available products include ionic PBGs WPBG-082 and WPBG- manufactured by Wako Pure Chemical Industries, Ltd. 167, WPBG-168, WPBG-266 and WPBG-300.
Examples of nonionic photobase generators include α-aminoacetophenone compounds, oxime ester compounds, N-formylated aromatic amino groups, N-acylated aromatic amino groups, nitrobenzyl carbamate groups, and alkoxybenzyl Examples include compounds having substituents such as carbamate groups.
Other photobase generators include WPBG-018 (product name: 9-anthrylmethyl N,N'-diethylcarbamate) and WPBG-027 (product name: (E)-1-[3-(2) manufactured by Wako Pure Chemical Industries, Ltd. -hydroxyphenyl)-2-propenoyl]piperidine), WPBG-140 (trade name: 1-(anthraquinon-2-yl)ethyl imidazolecarboxylate), and WPBG-165.

[Crosslinking agent]
The photosensitive resin composition of the present invention can contain a crosslinking agent. By adding a crosslinking agent, the curing temperature of the photosensitive resin composition can be lowered. The crosslinking agent is not particularly limited, and examples thereof include known and commonly used crosslinking agents.
In this specification, the crosslinking agent is preferably a compound capable of reacting with carboxyl groups in the polyimide precursor to form a crosslinked structure.
Compounds that react with the hydroxyl group in the polyimide precursor or polyimide include crosslinking agents having a cyclic ether group such as an epoxy group, a cyclic thioether group such as an episulfide group, and a hydroxyl group on an alkylene group having 1 to 12 carbon atoms such as a methylol group. Examples include a crosslinking agent having an alcoholic hydroxyl group bonded to , a compound having an ether bond such as an alkoxymethyl group, a crosslinking agent having a triazine ring structure, and a urea-based crosslinking agent.
Among these, crosslinking agents having a cyclic ether group, particularly an epoxy group, and alcoholic hydroxyl groups, particularly crosslinking agents having a methylol group to which a hydroxyl group is bonded, are preferred.
One type of crosslinking agent may be used alone, or two or more types may be used in combination.
The amount of the crosslinking agent in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by weight based on 100 parts by weight of the nonvolatile components of the polyimide precursor. Further, 0.1 to 20 parts by mass is more preferable.

(Crosslinking agent with epoxy group)
The photosensitive resin composition of the present invention preferably contains a crosslinking agent having an epoxy group as a crosslinking agent. A crosslinking agent having an epoxy group thermally reacts with a polyimide precursor or a hydroxyl group of polyimide to form a crosslinked structure. The number of functional groups of the crosslinking agent having an epoxy group is preferably 2 to 4. When the photosensitive resin composition contains a crosslinking agent having an epoxy group, low-temperature curability can be obtained, and the dissolution contrast of the dried coating film formed can be further improved.
Among the crosslinking agents having an epoxy group, a difunctional or higher functional epoxy compound having a naphthalene skeleton is preferred. Not only can an insulating film with excellent flexibility and chemical resistance be obtained, but also a low CTE, which is in a trade-off relationship with flexibility, can be achieved, and warping and cracking of the insulating film can be suppressed. Furthermore, bisphenol A type epoxy compounds can also be suitably used from the viewpoint of flexibility.

（一般式（５）中、Ｒ^Ａ１は２～１０価の有機基を示す。Ｒ^Ａ２は、それぞれ独立に、水素原子または炭素数１～４のアルキル基を示す。ｒは２～１０の整数を示す。） (Crosslinking agent with methylol group)
The photosensitive resin composition of the present invention preferably contains a crosslinking agent having a methylol group as a crosslinking agent. The crosslinking agent having a methylol group preferably has two or more methylol groups, and is more preferably a compound represented by the following general formula (5).

(In general formula (5), R ^A1 represents a divalent to 10-valent organic group. R ^A2 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. r is an integer of 2 to 10. )

In the general formula (5), R ^A1 is preferably an alkylene group having 1 to 3 carbon atoms which may have a substituent.

In the general formula (5), R ^A2 is preferably a hydrogen atom.

In the general formula (5), r is preferably an integer of 2 to 4, and more preferably 2.

Further, the crosslinking agent having a methylol group preferably has a fluorine atom, and more preferably has a trifluoromethyl group. The fluorine atom or the trifluoromethyl group is preferably a divalent to 10-valent organic group represented by R ^A1 in the general formula (5), and R ^A1 is a di(trifluoromethyl)methylene group. is preferred. Moreover, it is preferable that the crosslinking agent which has a methylol group has a bisphenol structure, and it is more preferable that it has a bisphenol AF structure.

[Plasticizer]
The photosensitive resin composition of the present invention preferably contains a plasticizer. In the present invention, the plasticizing effect of the plasticizer, that is, the aggregation effect between polymer molecular chains is reduced, and the mobility and flexibility between molecular chains are improved, thereby improving the thermal molecular motion of the polyimide precursor. It is thought that low temperature curability is imparted by promoting the cyclization reaction. The plasticizer is not particularly limited as long as it is a compound that improves plasticity, and includes bifunctional (meth)acrylic compounds, sulfonamide compounds, phthalate ester compounds, maleate ester compounds, aliphatic dibasic acid esters, and phosphate esters. and ether compounds such as crown ether. Among these, bifunctional (meth)acrylic compounds are preferred. The bifunctional (meth)acrylic compound is preferably a compound that does not form a crosslinked structure with other components in the composition. Further, the bifunctional (meth)acrylic compound is preferably a compound that forms a linear structure through self-polymerization from the viewpoint of further relaxing the internal stress of the cured product. The amount of plasticizer blended in the photosensitive resin composition of the present invention is preferably 3 to 40 parts by weight based on 100 parts by weight of the nonvolatile components of the polyimide precursor.

Among difunctional (meth)acrylic compounds, di(meth)acrylates of alkylene oxide adducts (such as ethylene oxide and propylene oxide) of diols and difunctional polyester (meth)acrylates are preferred; ) Acrylate is more preferred.

As the di(meth)acrylate of an alkylene oxide adduct of a diol, specifically, one in which a diol is modified with an alkylene oxide and then a (meth)acrylate is added to the terminal is preferable, and one in which the diol has an aromatic ring is more preferable. . Examples include bisphenol A EO (ethylene oxide) adduct diacrylate, bisphenol A PO (propylene oxide) adduct diacrylate, and the like. A specific structure of di(meth)acrylate, which is an alkylene oxide adduct of diol, is shown in the following general formula (6), but the structure is not limited thereto.

In general formula (6), p+q is 2 or more, preferably from 2 to 40, more preferably from 3.5 to 25.

[Adhesive]
The photosensitive resin composition of the present invention preferably contains an adhesive, thereby improving adhesion to a base material and the like. As the adhesive, a silane coupling agent, a titanate coupling agent, and an aluminum coupling agent can be used.
Examples of the silane coupling agent include N-phenyl-3-aminopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ- Examples include acryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3-ureidopropyltrialkoxysilane, and phenyltrimethoxysilane.
Examples of the titanate coupling agent include isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, tetraisopropyl bis(dioctyl phosphite) titanate, and tetraoctyl bis(ditridecyl phosphite). Titanate, tetra(2,2-diallyloxymethyl)bis(di-tridecyl)phosphite titanate, bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate)ethylene titanate, and the like.
Examples of the aluminum coupling agent include acetalkoxyaluminum diisopropylate, etc. Among the above, N-phenyl-3-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane is preferable because it improves adhesion to the substrate and does not adversely affect the development speed.

The blending amount of the adhesive in the photosensitive resin composition of the present invention is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the nonvolatile components of the polyimide precursor.

[Thermal acid generator, sensitizer, and other ingredients]
The photosensitive resin composition of the present invention further contains a known thermal acid generator to promote the cyclization reaction of the polyimide precursor, and a known thermal acid generator to improve photosensitivity, within a range that does not impair the effects of the present invention. A sensitizer or the like may also be added. Furthermore, in order to impart processing characteristics and various functionalities to the photosensitive resin composition of the present invention, various other organic or inorganic low-molecular or high-molecular compounds may be blended. For example, surfactants, leveling agents, fine particles, etc. can be used. The fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, and inorganic fine particles such as silica, carbon, and layered silicates. Furthermore, various coloring agents, fibers, etc. may be added to the photosensitive resin composition of the present invention.

[solvent]
The photosensitive resin composition of the present invention may contain a solvent. In the present invention, the solvent is not particularly limited, but a solvent having a boiling point of 200° C. or lower is preferable in consideration of residual property when the heating temperature of the patterned film is lowered.
Solvents with such melting points include 2-methoxy-1-methylethyl acetate (PGMEA), 4-methyl-2-pentanone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, and hexane. Methyl sulfoxide, ethyl acetate, butyl acetate, ethyl lactate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, 2-ethoxy Ethyl propionate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene Glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, carbitol acetate, ethyl cellosolve acetate, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, and 2- Examples include heptanone.

The content of the solvent in the photosensitive resin composition is not particularly limited, and it is preferable to change it as appropriate depending on the use. , 200 to 2000 parts by mass or less.
In addition, the photosensitive resin composition may contain two or more types of solvents.

[Dry film]
The dry film of the present invention includes a film (for example, a support (carrier) film) and a resin layer formed on the film using the photosensitive resin composition. Further, the dry film may further include a protective (covering) film (so-called protective film) on the resin layer formed on the film.

(film)
The film is not particularly limited, and for example, films made of thermoplastic resins such as polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyimide films, polyamideimide films, polypropylene films, and polystyrene films can be used. can.
Among these, polyethylene terephthalate is preferred from the viewpoints of heat resistance, mechanical strength, handleability, and the like. Moreover, a laminate of these films can also be used as a film.

Furthermore, from the viewpoint of improving mechanical strength, the thermoplastic resin film as described above is preferably a film stretched in a uniaxial direction or a biaxial direction.

The thickness of the film is not particularly limited, but may be, for example, 10 to 150 μm.

(resin layer)
The resin layer is formed using the above-mentioned photosensitive resin composition, and its thickness is not particularly limited and is preferably changed as appropriate depending on the application, but for example, 1 μm or more, 150 μm. It can be as follows.

The resin layer is formed by applying a photosensitive resin composition onto the film to a uniform thickness using a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater, spray coater, etc. It can be formed by coating and drying.
Moreover, in other embodiments, the resin layer can be formed by applying a photosensitive resin composition on the protective film and drying it.

(Protective film)
In the present invention, it is preferable to laminate a removable protective film on the surface of the resin layer for the purpose of preventing dust from adhering to the surface of the resin layer.

The removable protective film is not particularly limited as long as the adhesive force between the resin layer and the protective film is smaller than the adhesive force between the resin layer and the film when the protective film is peeled off. For example, polyethylene film, polytetrafluoroethylene film, polypropylene film, surface-treated paper, etc. can be used.

The thickness of the protective film is not particularly limited, but may be, for example, 10 μm or more and 150 μm or less.

[Cured product]
The cured product of the present invention is characterized by being formed using the above photosensitive resin composition. Further, the cured product may have a pattern formed thereon.
Hereinafter, the method for producing a cured product of the present invention will be explained.

[First step]
The method for producing a cured product of the present invention includes coating a photosensitive resin composition on a substrate to form a coating film and drying this, or transferring a resin layer from the dry film onto the substrate. The method includes a step of forming a dry coating film.

The method of applying the photosensitive resin composition onto the substrate is not particularly limited, and examples include methods of applying using a spin coater, bar coater, blade coater, curtain coater, screen printer, etc., and spraying using a spray coater. and an inkjet method.

As a method for drying the coating film, methods such as air drying, heating drying using an oven or hot plate, and vacuum drying are used.
Further, it is desirable that the coating film be dried under conditions that do not cause ring closure of the polyimide precursor in the photosensitive resin composition.
Specifically, it is preferable to perform natural drying, blow drying, or heat drying at 70 to 140° C. for 1 to 30 minutes. Further, since the operating method is simple, it is preferable to use a hot plate for drying for 1 to 20 minutes.
Vacuum drying is also possible, and in this case it can be carried out at room temperature for 20 minutes to 1 hour.

Transfer of the dry film onto the base material is preferably performed under pressure and heat using a vacuum laminator or the like. By using such a vacuum laminator, when using a circuit board with a circuit formed thereon, even if the circuit board surface has irregularities, the resin layer of the dry film will fill the irregularities of the circuit board under vacuum conditions. , there is no air bubbles mixed in, and the ability to fill in the recesses on the substrate surface is also improved.

In addition to printed wiring boards and flexible printed wiring boards on which circuits are pre-formed using copper, the base materials include paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/nonwoven epoxy, glass cloth/paper epoxy, Copper-clad laminates of all grades (FR-4, etc.) using materials such as synthetic fiber epoxy, fluororesin/polyethylene/polyphenylene ether, polyphenylene oxide/cyanate, etc. for high-frequency circuits. Other examples include metal substrates, polyimide films, polyethylene terephthalate films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer plates, and the like.

[Second step]
Next, the coating film is exposed to active energy rays selectively through a patterned photomask or non-selectively without passing through the photomask.

The active energy ray used has a wavelength capable of activating, for example, the photoacid generator (B) as the photosensitizer. Specifically, the active energy ray preferably has a maximum wavelength in the range of 350 to 410 nm.
The exposure amount varies depending on the film thickness, etc., but can generally be in the range of 10 to 1000 mJ/cm ² , preferably 20 to 800 mJ/cm ² .
The exposure machine used for the active energy ray irradiation may be any device that is equipped with a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, etc., and irradiates ultraviolet rays in the range of 350 to 450 nm. Furthermore, a direct drawing device (for example, a laser direct imaging device that draws an image directly with a laser using CAD data from a computer) can also be used.

[Third step]
This step is performed as necessary, and by heating the coating film for a short time, a part of the polyimide precursor in the unexposed area may be ring-closed. Here, the ring closure rate is about 30%. The heating time and heating temperature are appropriately changed depending on the type of polyimide precursor, the coating film thickness, and the type of (B) photosensitizer.

[Fourth step]
Next, the exposed coating film is treated with a developer to remove exposed portions of the coating film, thereby obtaining a patterned film.
In this step, any method can be selected from conventionally known photoresist development methods, such as a rotary spray method, a paddle method, and an immersion method accompanied by ultrasonic treatment.

Examples of developing solutions include inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, and aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine, and tetramethylammonium hydroxide and tetrabutylammonium hydroxide. Examples include aqueous solutions of quaternary ammonium salts such as .
Further, if necessary, a suitable amount of a water-soluble organic solvent such as methanol, ethanol, isopropyl alcohol, or a surfactant may be added to these.

Thereafter, if necessary, the coating film is washed with a rinsing liquid to obtain a patterned film.
As the rinsing liquid, distilled water, methanol, ethanol, isopropyl alcohol, etc. can be used alone or in combination. Further, the above-mentioned solvents may be used as the developer.

[Fifth step]
Next, the pattern film is heated to obtain a cured coating film (cured product).
Through the heating step, the polyimide precursor contained in the photosensitive resin composition undergoes a cyclization reaction and becomes polyimide.

The heating temperature is preferably 120 to 250°C, more preferably 150 to 200°C, from the viewpoint of preventing warping of the cured product.
For heating, for example, a hot plate, an oven, and a heating oven in which a temperature program can be set can be used.
It may be under a heating atmosphere (gas), air, or under an inert gas such as nitrogen or argon.

[Application]
The use of the photosensitive resin composition of the present invention is not particularly limited, and for example, it is suitably used as a forming material for paints, printing inks, adhesives, display devices, semiconductor elements, electronic parts, optical parts, building materials, and the like.

Specifically, materials for forming display devices include layer-forming materials and image-forming materials for color filters, films for flexible displays, resist materials, alignment films, and the like.
Examples of materials for forming semiconductor elements include layer forming materials for resist materials, buffer coat films, insulating films for rewiring layers of wafer level packages (WLP), and the like.
Examples of materials for forming electronic components include sealing materials and layer-forming materials for printed wiring boards, interlayer insulating films, wiring coating films, and the like.
Furthermore, examples of forming materials for optical components include optical materials and layer-forming materials for holograms, optical waveguides, optical circuits, optical circuit components, antireflection films, and the like.
Further, as a building material, it can be used as a paint, a coating agent, etc.

The photosensitive resin composition of the present invention is mainly used as a pattern forming material, particularly as a surface protective film, a buffer coat film, an interlayer insulating film, an insulating film for rewiring, and a flip chip for semiconductor devices, display devices, and light emitting devices. Suitable as a protective film for devices, a protective film for devices with a bump structure, an interlayer insulating film for multilayer circuits, an insulating material for passive components, a protective film for printed wiring boards such as solder resist and coverlay film, and a liquid crystal alignment film. Available.

Hereinafter, the present invention will be explained in more detail using examples, but the present invention is not limited to the examples. In addition, all "parts" and "%" below are based on mass unless otherwise specified.

(Reference Example 1: Synthesis of polyimide precursor A-1)
53 g of N-methylpyrrolidone was charged into a 0.5 liter flask equipped with a stirrer and a thermometer.
13.95 g (26.30 mmol) of 3,3'-bis(1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl)-4,4'-methylene dianiline was dissolved with stirring.
After confirming that the monomer was completely dissolved, 5,5'-[1-methyl-1,1-ethanediylbis(1,4-phenylene)bisoxy]bis(isobenzofuran-1,3-diol) (BPADA) 13.95 g (26.30 mmol) was added as a solid over 5 minutes, and stirring was continued for 1 hour at room temperature.
Thereafter, 0.85 g (5.19 mmol) of 5-norbornene-2,3-dicarboxylic anhydride was added as a solid to the stirred solution, and the mixture was stirred at room temperature for 16 hours. The stirred solution was poured into 1 L of ion-exchanged water (specific resistance value: 18.2 MΩ·cm), and the precipitate was collected.
After recovery, it was dried under reduced pressure to obtain a polyimide precursor A-1 having norbornene terminals and having the following repeating structure. The number average molecular weight (Mn) of polyimide precursor A-1 was 6,800, the weight average molecular weight (Mw) was 16,790, and the Mw/Mn was 2.47. Further, the carboxyl group concentration of the obtained polyimide precursor A-1 was 525 g/mol, and the fluorine concentration was 88 g/mol.

(Reference Example 2: Synthesis of polyimide precursor A-2)
In a 0.5 liter flask equipped with a stirrer and a thermometer, 53 g of N-methylpyrrolidone was charged, and 3,3'-bis(1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) was added. 14.40 g (26.45 mmol) of -2,2'-dimethylbenzidine was dissolved with stirring.
After confirming that the monomer was completely dissolved, 10.46 g (23.55 mmol) of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) was added as a solid over 10 minutes, and the mixture was stirred at room temperature. Stirring was continued for 1 hour.
Thereafter, 0.96 g (5.82 mmol) of 5-norbornene-2,3-dicarboxylic anhydride was added as a solid to the stirred solution, and the mixture was stirred at room temperature for 16 hours.
The stirred solution was poured into 1 L of ion-exchanged water (specific resistance value: 18.2 MΩ·cm), and the precipitate was collected.
After recovery, it was dried under reduced pressure to obtain a polyimide precursor A-2 having norbornene terminals and having the following repeating structure. The number average molecular weight (Mn) of polyimide precursor A-2 was 8,700, the weight average molecular weight (Mw) was 22,100, and the Mw/Mn was 2.54. Further, the carboxyl group concentration of the obtained polyimide precursor A-2 was 494 g/mol, and the fluorine concentration was 55 g/mol.

(Reference Example 3: Synthesis of polyimide precursor A-3)
Pour 150 g of N-methylpyrrolidone into a 0.5 liter flask equipped with a stirrer and a thermometer, and prepare 3,3'-bis(1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl). 8.43 g (15.91 mmol) of -4,4'-methylene dianiline was dissolved with stirring.
After confirming that the monomers were completely dissolved, 1.88 g (4.23 mmol) of 6FDA and 5.14 g (9.87 mmol) of BPADA were added as solids over 10 minutes, and stirring was continued for 1 hour at room temperature.
Thereafter, 0.59 g (3.62 mmol) of 5-norbornene-2,3-dicarboxylic anhydride was added as a solid to the stirred solution, and the mixture was stirred at room temperature for 16 hours.
The stirred solution was poured into 1 L of ion-exchanged water (specific resistance value: 18.2 MΩ·cm), and the precipitate was collected.
After recovery, it was dried under reduced pressure to obtain a polyimide precursor A-3 having a norbornene group terminal and having the following repeating structure. The number average molecular weight (Mn) of polyimide precursor A-3 was 9,500, the weight average molecular weight (Mw) was 24,800, and the Mw/Mn was 2.61. Furthermore, the carboxyl group concentration of the obtained polyimide precursor A-3 was 514 g/mol, and the fluorine concentration was 73 g/mol.

(Reference Example 4: Synthesis of polyimide precursor A-4)
150 g of N-methylpyrrolidone was charged into a 0.5 liter flask equipped with a stirrer and a thermometer.
8.33 g (15.71 mmol) of 3,3'-bis(1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl)-4,4'-methylene dianiline was dissolved with stirring.
After confirming that the monomers were completely dissolved, 1.33 g (4.29 mmol) of 4,4'-oxydiphthalic anhydride (ODPA) and 5.21 g (10.01 mmol) of BPADA were added as solids over 10 minutes. , stirring was continued for 1 hour at room temperature.
Thereafter, 0.46 g (2.82 mmol) of 5-norbornene-2,3-dicarboxylic anhydride was added as a solid to the stirred solution, and the mixture was stirred at room temperature for 16 hours. The stirred solution was poured into 1 L of ion-exchanged water (specific resistance value: 18.2 MΩ·cm), and the precipitate was collected.
After recovery, it was dried under reduced pressure to obtain a polyimide precursor A-4 having norbornene terminals and having the following repeating structure. The number average molecular weight (Mn) of polyimide precursor A-4 was 10,200, the weight average molecular weight (Mw) was 24,680, and the Mw/Mn was 2.42. Further, the carboxyl group concentration of the obtained polyimide precursor A-1 was 494 g/mol, and the fluorine concentration was 82 g/mol.

(Reference Example 5: Synthesis of polyimide precursor A-5)
100 g of N-methylpyrrolidone was charged into a 0.5 liter flask equipped with a stirrer and a thermometer, and 5.16 g (25.75 mmol) of diaminodiphenyl ether was dissolved with stirring.
After confirming that the monomer was completely dissolved, 5.29 g (24.25 mmol) of pyromellitic anhydride (PMDA) was added as a solid over 5 minutes, and stirring was continued for 1 hour at room temperature.
Thereafter, 0.49 g (2.98 mmol) of 5-norbornene-2,3-dicarboxylic anhydride was added as a solid to the stirred solution, and the mixture was stirred at room temperature for 16 hours.
The stirred solution was poured into 600 mL of ion-exchanged water (specific resistance value: 18.2 MΩ·cm), and the precipitate was collected. After recovery, it was dried under reduced pressure to obtain a polyimide precursor A-5 having norbornene terminals and having the following repeating structure. The number average molecular weight (Mn) of polyimide precursor A-5 was 6,800, the weight average molecular weight (Mw) was 17,000, and the Mw/Mn was 2.51. Further, the carboxyl group concentration of the obtained polyimide precursor A-1 was 210 g/mol.

(Reference Example 6: Synthesis of polybenzoxazole precursor)
In a 0.5 liter flask equipped with a stirrer and a thermometer, 10.0 g (27.3 mmol) of bis(3-amino-4-hydroxyphenyl)hexafluoropropane was dissolved in 1500 g of N-methylpyrrolidone with stirring. .
Thereafter, the flask was immersed in an ice bath, and while keeping the inside of the flask at 0 to 5°C, 8.78 g (29.8 mmol) of 4,4'-diphenyl ether dicarboxylic acid chloride was added as a solid over 10 minutes. The mixture was stirred for 30 minutes.
Stirring was then continued at room temperature for 18 hours. The stirred solution was poured into 700 mL of ion-exchanged water (specific resistance value: 18.2 MΩ·cm), and the precipitate was collected.
Thereafter, the obtained solid was dissolved in 420 mL of acetone and poured into 1 L of ion-exchanged water.
After collecting the precipitated solid, it was dried under reduced pressure to obtain a carboxyl group-terminated polybenzoxazole precursor. Mw was 29,500, Mn was 11,600, and Mw/Mn was 2.54.

<Example 1>
100 parts by mass of the polyimide precursor A-1 obtained in Reference Example 1, 20 parts by mass of a naphthoquinonediazide compound (TKF-528, manufactured by Sanpo Chemical Research Institute), and an adhesive (manufactured by Shin-Etsu Chemical Co., Ltd., KBM- 573) and 400 parts by mass of PGMEA were placed in a light-shielding container and stirred to obtain a varnish containing a photosensitive resin composition.

<Examples 2-4 and Comparative Examples 1-2>
Varnishes were obtained in the same manner as in Example 1, except that polyimide precursor A-1 was changed to polyimide precursors A-2 to A-5 or polybenzoxazole precursors as shown in Table 1.

<<Solubility evaluation>>
The varnishes obtained in the above Examples and Comparative Examples were visually observed, and the solubility was evaluated based on the following evaluation criteria. The evaluation results are summarized in Table 1.
In addition, the solvent was changed to 4-methyl-2-pentanone, and the solubility was evaluated in the same manner as above, and the results are summarized in Table 1.
(Evaluation criteria)
○: There was no undissolved material (precipitate), and no turbidity of the varnish was observed.
△: There was no undissolved residue, but turbidity of the varnish was observed.
x: There was some undissolved material.

<<Dissolution rate evaluation>>
The varnishes obtained in the above examples and the varnishes obtained in Comparative Examples 1 and 2 in which PGMEA was changed to γ-butyrolactone were prepared.
This varnish was applied to a silicon substrate to a thickness of about 2 μm using a spin coater.
Next, it was dried for 3 minutes at 110°C using a hot plate to obtain a dry coating film. Using a high-pressure mercury lamp, half of the dried coating film was irradiated with i-line at 200 mJ/cm ² . After exposure, the sample was immersed in a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution, the time for dissolution was measured, and the dissolution rate was calculated using the following formula, and the dissolution rate of the exposed and unexposed areas was evaluated using the following evaluation criteria. The evaluation was based on the following. The evaluation results are summarized in Table 1.
Further, the dissolution contrast (dissolution rate of the unexposed area/dissolution rate of the exposed area) was determined from the determined dissolution rate of the exposed area and the dissolution rate of the unexposed area, and evaluated based on the following evaluation criteria. The evaluation results are summarized in Table 1.
Dissolution rate = initial film thickness (nm)/dissolution time (s)
(Exposed area dissolution rate evaluation criteria)
◎: Dissolution rate of 500 nm/s or more and 1000 nm/s or less ○: Dissolution rate of 200 nm/s or more and less than 500 nm/s ×: Dissolution rate of less than 200 nm/s or more than 1000 nm/s
(Unexposed area dissolution rate evaluation criteria)
◎: Dissolution rate less than 5 nm/s,
○: Dissolution rate 5 nm/s or more, less than 20 nm/s ×: Dissolution rate 20 nm/s or more (dissolution contrast evaluation criteria)
◎: Dissolution contrast is 200 or more ○: Dissolution contrast is 100 or more but less than 200 ×: Dissolution contrast is less than 100

<<Resolution evaluation>>
Similar to the above dissolution rate evaluation, the varnish obtained in the above example and the varnish obtained in Comparative Examples 1 and 2 in which PGMEA was changed to γ-butyrolactone were prepared.
This varnish was applied to a silicon substrate to a thickness of about 2 μm using a spin coater.
Next, it was dried for 3 minutes at 110°C using a hot plate to obtain a dry coating film. A high-pressure mercury lamp was used to irradiate the coating film with broad light of 200 mJ/cm ² through a patterned mask. After exposure, the film was developed with a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds and rinsed with water to obtain a positive pattern film.
The L/S (line/space) of the pattern engraved on the mask was changed from 1 μm/1 μm to 30 μm/30 μm (L=S, and L and S are integers), and JSM-6010'') at which a poly-type pattern film can be formed in the exposed area without scum (development residue) was determined and evaluated based on the following evaluation criteria. The evaluation results are summarized in Table 1.
(Evaluation criteria)
◎: Even when the L/S of the pattern was 2 μm/2 μm, it was possible to form a poly-type pattern film that could be patterned without leaving any scum (development residue) in the exposed area.
○: When the L/S of the pattern was 2 μm/2 μm, it was not possible to form a poly-type pattern film that could be patterned without scum (development residue) in the exposed area, but when the L/S of the pattern was 3 μm/3 μm. In the case of , it was possible.
△: When the L/S of the pattern was 3 μm/3 μm, it was not possible to form a poly-type pattern film that could be patterned without scum (development residue) in the exposed area, but when the L/S of the pattern was 5 μm/5 μm. In the case of , it was possible.
×: When the L/S of the pattern was 5 μm/5 μm, it was not possible to form a poly-type pattern film that could be patterned without leaving any scum (development residue) in the exposed area.

<<Glass transition temperature (Tg) measurement>>
Similar to the above dissolution rate evaluation, the varnish obtained in the above example and the varnish obtained in Comparative Examples 1 and 2 in which PGMEA was changed to γ-butyrolactone were prepared.
This varnish was applied to a silicon substrate using a spin coater. Next, it was dried on a hot plate at 110°C for 3 minutes, then heated at 110°C for 10 minutes in an inert gas oven (CLH-21CD-S manufactured by Koyo Thermo Systems Co., Ltd.) under a nitrogen atmosphere, and then at 150°C for 30 minutes. The mixture was maintained and heated at 320° C. for 60 minutes to obtain a cured film with a thickness of about 10 μm. The obtained cured film was peeled off from the substrate, and its Tg was measured using a DSC manufactured by TA Instruments. The measurement results are summarized in Table 1.

As is clear from the evaluation results shown in Table 1 above, the photosensitive resin composition containing the polyimide precursor having at least one of the structures represented by general formulas (1) and (2) has a high dissolution rate and dissolution contrast. It can be seen that excellent and high resolution can be achieved. It is also found that the polyimide precursor has high solubility in low boiling point solvents such as PGMEA and 4-methyl-2-pentanone. Furthermore, it can be seen that the cured product formed from the photosensitive resin composition has a high Tg and is excellent in heat resistance.

Claims (10)

(A) a polyimide precursor having at least one structure represented by the following general formulas (1) and (2);
(B) a photosensitizer;
A photosensitive resin composition comprising:
A dry coating film with a thickness of 2 μm formed by forming the photosensitive resin composition on a silicon substrate is irradiated with i-line at an exposure dose of 200 mJ/cm ² and the exposed area is exposed to a 2.38% TMAH aqueous solution at 25°C. A photosensitive resin composition having a dissolution rate (formula: initial film thickness (nm)/dissolution time (s)) of 200 to 1000 nm/min .
(In the formula,
X is a tetravalent organic group,
A is selected from a single bond, O and a divalent organic group,
B is a fluoroalcohol group,
R is a substituted or unsubstituted alkyl group,
n1 is each independently an integer of 1 or more,
n2 and n3 are each independently an integer of 0 to 4, and n2+n3 is 1 or more,
n4 is each independently an integer from 0 to 3,
n5 is an integer from 1 to 4,
n6 is an integer from 0 to 3. ) The photosensitive resin composition according to claim 1, wherein X in the general formulas (1) and (2) is selected from a tetravalent organic group having the following structure.
(In the above formula, a is each independently an integer of 0 to 2, and b is each independently an integer of 1 to 3.) 1 or 2, wherein the fluoroalcohol represented by B in the general formulas (1) and (2) each independently has a carbon number of 1 to 10, and a fluorine number each independently of 1 to 10. 2. The photosensitive resin composition according to 2. The photosensitive resin composition according to any one of claims 1 to 3, wherein the polyimide precursor has a carboxyl group concentration of 300 to 800 g/mol . The photosensitive resin composition according to any one of claims 1 to 4, wherein the polyimide precursor has a fluorine concentration of 20 to 200 g/mol . The photosensitive resin composition according to any one of claims 1 to 5, further comprising an adhesive. The photosensitive resin composition according to any one of claims 1 to 6, wherein the photosensitizer is a naphthoquinone diazide compound. A dry film comprising a resin layer formed from the photosensitive resin composition according to any one of claims 1 to 7 on the film. A cured product, characterized in that it is formed from the photosensitive resin composition according to any one of claims 1 to 7 or the resin layer of the dry film according to claim 8. An electronic component comprising the cured product according to claim 9 as a forming material.