JP2020134824A - Negative photosensitive resin composition, resin film, and electronic device - Google Patents

Abstract

To provide a photosensitive resin composition that has excellent patterning and working properties without adhering to a mask used in contact exposure, and prevents cracking in a cured film after patterning.SOLUTION: A negative photosensitive resin composition has an epoxy resin, a photoacid generator, and a polycarbonate diol represented by formula (I), the polycarbonate diol having a weight average molecular weight of 1800 or less (in the formula (I), n is 1 or more and 10 or less, Rand Rindependently represent a C1-8 alkylene group).SELECTED DRAWING: None

Description

The present invention relates to negative photosensitive resin compositions, resin films, and electronic devices. More specifically, the present invention comprises a negative photosensitive resin composition used for forming a permanent resist, a resin film which is a cured product of the negative photosensitive resin composition, and this resin film as a permanent resist. Regarding electronic devices.

In recent years, with the demand for high integration and high functionality of semiconductor devices, the element structure of semiconductor devices has been miniaturized. Correspondingly, the demand for miniaturization has increased in the wiring part of the printed wiring board on which the semiconductor device is mounted, and research and development have been carried out, and a resist film material for forming a printed wiring part having such a fine pattern. As an example, a photosensitive resin composition that is photosensitive with ultraviolet rays or visible light has been proposed (for example, Patent Document 1).

As a method for forming a patterning of a resist film made of a photosensitive resin composition, for example, a glass mask in which a resist film is formed on an upper layer of a conductive layer to be processed formed on a substrate such as a plastic substrate to form an exposure pattern. A method of exposing and developing by contact exposure using the above is used.

Patent Document 1 discloses a liquid photosensitive resin composition containing (A) an epoxy resin, (B) a polyol compound, (C) a photocationic polymerization initiator, and (D) an epoxy group-containing silane compound. There is. In Patent Document 1, a permanent resist is produced by photolithographically processing a photosensitive resin composition by contact exposure using a glass mask.

However, since the photosensitive resin composition of Patent Document 1 is in a liquid state, it may adhere to the mask and peel off from the substrate when the mask used for contact exposure is peeled off.

When the liquid component of the photosensitive resin composition is reduced in order to solve the above problems, cracks may occur in the patterned cured film obtained after exposure. Further, the occurrence of cracks was particularly remarkable in a cured film having a relatively thick film thickness of 50 μm or more.

Japanese Unexamined Patent Publication No. 2014-85525

The present invention provides a photosensitive resin composition which has good pattern forming property and workability without adhering to a mask used in contact exposure and has reduced cracks in the cured film after pattern forming. To do.

As a result of diligent studies, the present inventors have found that the above problems can be solved by blending a specific polycarbonate diol with a photosensitive resin composition, and have completed the present invention.

（式（Ｉ）中、ｎは、１以上１０以下であり、Ｒ_１およびＲ_２は、独立して、炭素数１以上８以下のアルキレン基である。） According to the present invention
Epoxy resin and
Photoacid generator and
Containing a polycarbonate diol represented by the formula (I),
A negative photosensitive resin composition having a weight average molecular weight of 1800 or less of the polycarbonate diol is provided.

(In the formula (I), n is 1 or more and 10 or less, and R ₁ and R ₂ are independently alkylene groups having 1 or more and 8 or less carbon atoms.)

Further, according to the present invention, there is provided a resin film made of a cured product of the negative photosensitive resin composition.

Further, according to the present invention, an electronic device provided with the above resin film is provided.

According to the present invention, since the mask used in contact exposure is not contaminated, the handleability and workability are good, and the occurrence of cracks in the cured film after pattern formation is reduced. Things are provided.

Hereinafter, embodiments of the present invention will be described.

<Negative photosensitive resin composition>
The negative photosensitive resin composition of the present embodiment contains an epoxy resin, a photoacid generator, and a polycarbonate diol represented by the formula (I).

In formula (I),
n is 1 or more and 10 or less,
R ₁ and R ₂ are independently alkylene groups having 1 or more and 8 or less carbon atoms.
The weight average molecular weight of the polycarbonate diol represented by the formula (I) is 1800 or less.

Since the negative photosensitive resin composition of the present embodiment contains the above components, it does not adhere to the mask used in contact exposure, and the obtained cured product does not generate cracks. Therefore, the negative photosensitive resin composition of the present embodiment can be suitably used as a permanent resist film for electronic devices.

Each component used in the negative photosensitive resin composition of the present embodiment will be described below.

(Epoxy resin)
The negative photosensitive resin composition of the present embodiment contains an epoxy resin. As the epoxy resin, a known epoxy resin can be used. Specifically, phenol novolac type epoxy resin, cresol novolac type epoxy resin, cresol naphthol type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, phenoxy resin, naphthalene skeleton type epoxy resin, bisphenol A type epoxy resin, bisphenol A diglycidyl ether type epoxy resin, bisphenol F type epoxy resin, bisphenol F diglycidyl ether type epoxy resin, bisphenol S diglycidyl ether type epoxy resin, glycidyl ether type epoxy resin, cresol novolac type epoxy resin, aromatic polyfunctional epoxy resin , An aliphatic epoxy resin, an aliphatic polyfunctional epoxy resin, an alicyclic epoxy resin, a polyfunctional alicyclic epoxy resin, and the like. Above all, it is preferable to use a cresol novolac type epoxy resin and a phenol novolac type epoxy resin as the epoxy resin because a photosensitive resin composition having excellent pattern forming property can be obtained. Further, as the epoxy resin, it is preferable to use an epoxy resin solid at 25 ° C., and by using such an epoxy resin, the tackiness of the obtained photosensitive resin composition can be reduced.

The lower limit of the content of the epoxy resin is 55% by mass or more, preferably 60% by mass or more, more preferably 65% by mass or more, based on the total solid content of the obtained photosensitive resin composition. On the other hand, the upper limit of the content of the epoxy resin is 85% by mass or less, preferably 80% by mass or less, and more preferably 75% by mass or less, based on the total solid content of the obtained photosensitive resin composition. By using an epoxy resin within the above range, a photosensitive resin composition having excellent pattern forming properties can be obtained.

(Photoacid generator)
The negative photosensitive resin composition of the present embodiment contains a photoacid generator. The photoacid generator is a compound that generates light by irradiation with active light (for example, ultraviolet rays, electron beams, X-rays), preferably with a wavelength of 200 to 500 nm, particularly preferably with a wavelength of 350 to 450 nm. It is a compound that generates acid by irradiation. Examples of such a photoacid generator include a photosensitive diazoquinone compound, a photosensitive diazonaphthoquinone compound, a diaryliodonium salt, an onium salt such as a triarylsulfonium salt or a sulfonium-borate salt, a 2-nitrobenzyl ester compound, and an N-iminosulfonate. Examples thereof include compounds, imide sulfonate compounds, 2,6-bis (trichloromethyl) -1,3,5-triazine compounds, dihydropyridine compounds and the like. These may be used alone or in combination of two or more.

The photoacid generator is used in an amount of 0.5% by mass or more and 10% by mass or less, preferably 1% by mass or more and 5% by mass or less, based on the entire epoxy resin used.

(Polycarbonate diol)
The negative photosensitive resin composition of the present embodiment contains a polycarbonate diol represented by the formula (I).

In the polycarbonate diol represented by the formula (I), n is 1 or more and 10 or less, preferably 5 or more and 8 or less.
R ₁ and R ₂ are linear or branched alkylene groups having 1 to 8 carbon atoms, and are R from the viewpoint of the availability of the polycarbonate diol and the appropriate flexibility of the obtained photosensitive resin composition. The carbon number of ₁ and R ₂ is preferably 4 to 7, and more preferably 5 to 6.
Examples of the linear or branched alkylene group having 1 to 8 carbon atoms include − (CH ₂ ) ₂ −, − (CH ₂ ) ₃ −, − (CH ₂ ) ₄ −, − (CH ₂ ) ₅ −, − (CH ₂ ) ₆ −, −C (CH ₃ ) ₂ −, −CH ₂ −CH (CH ₃ ) −, −CH ₂ −CH (CH ₃ ) −CH ₂ −, −CH ₂ −C ( CH ₃ ) _2- CH _2- and the like can be mentioned.
Particularly preferably, R ¹ is − (CH ₂ ) _5- or − (CH ₂ ) ₆ −. The same applies to R ² .

In addition, R ₁ and R ₂ may have a substituent as long as the effect of the invention is not excessively impaired. Examples of the substituent include a halogen atom, a hydroxy group, an alkoxy group and the like.

The polycarbonate diol represented by the formula (I) is preferably liquid at 20 ° C. That is, it is preferable that the polycarbonate diol represented by the formula (I) itself is liquid and not solid in an environment of 20 ° C. and 1 atm. By adopting such a polycarbonate diol, the pattern forming property of the obtained photosensitive resin composition can be improved, and the flexibility to the extent that cracks do not occur in the cured product of the obtained resin composition is ensured. Further, it is possible to achieve tackability to the extent that adhesion to the contacted mask can be prevented in contact exposure.

In the present embodiment, the weight average molecular weight of the polycarbonate diol represented by the formula (I) is 1800 or less, preferably 300 or more and 1800 or less, and more preferably 350 or more and 1500 or less. By using a polycarbonate diol having such a weight average molecular weight, the obtained resin composition has crack resistance and appropriate tackiness.

As the polycarbonate diol represented by the formula (I), a commercially available product can be used. As an example, ETERNAL COLL (registered trademark) UH-50, UH-100, PH-50, PH-100 sold by Ube Industries, Ltd., product name of Asahi Kasei Chemicals, Duranol series, product name of Mitsubishi Chemical, Ltd. Examples include the BENEBiOL series and Kuraray polyol, which is a trade name manufactured by Kuraray Corporation.

The content of the polycarbonate diol represented by the formula (I) in the photosensitive resin composition is based on the total solid content of the photosensitive resin composition from the viewpoint of obtaining appropriate tackiness and crack resistance. It is preferably 1% by mass or more and 10% by mass or less, and more preferably 3% by mass or more and 8% by mass or less.

(Phenoxy resin)
The negative photosensitive resin composition of the present embodiment may contain a phenoxy resin. By containing the phenoxy resin, the flexibility of the resin film of the obtained photosensitive resin composition can be enhanced, and the pattern forming property can be improved.

The weight average molecular weight (Mw) of the phenoxy resin is not particularly limited, but is preferably, for example, 1000 to 100,000, and more preferably 2000 to 80,000. By using such a relatively high molecular weight phenoxy resin, it is possible to impart good flexibility to the resin film and impart sufficient solubility in a solvent. In this embodiment, the weight average molecular weight is measured, for example, as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

Further, the phenoxy resin may have a reactive group such as an epoxy group at both ends of the molecular chain or inside the molecular chain. The reactive group in the phenoxy resin is one capable of cross-linking with the epoxy group in the epoxy resin. By using such a phenoxy resin, the solvent resistance and heat resistance in the resin film can be enhanced.

Further, as the phenoxy resin, one which is solid at 25 ° C. is preferably used. Specifically, a phenoxy resin having a non-volatile content of 90% by mass or more is preferably used. By using such a phenoxy resin, the mechanical properties of the cured product can be improved.

Examples of the phenoxy resin include bisphenol A type phenoxy resin, bisphenol F type phenoxy resin, bisphenol A type and bisphenol F type copolymerized phenoxy resin, biphenyl type phenoxy resin, bisphenol S type phenoxy resin, and biphenyl type phenoxy resin. Examples thereof include a phenoxy resin copolymerized with a bisphenol S-type phenoxy resin, and one or a mixture of two or more of these is used. Among these, a bisphenol A type phenoxy resin or a copolymerized phenoxy resin of a bisphenol A type and a bisphenol F type is preferably used.

The lower limit of the content of the phenoxy resin is, for example, 10 parts by mass or more, preferably 15 parts by mass or more, and more preferably 20 parts by mass or more with respect to 100 parts by mass of the epoxy resin used. This makes it possible to increase flexibility. On the other hand, the upper limit of the content of the phenoxy resin is, for example, 50 parts by mass or less, preferably 45 parts by mass or less, and more preferably 40 parts by mass or less with respect to the content of the epoxy resin. Thereby, the solubility of the phenoxy resin is enhanced, and a photosensitive resin composition having excellent coatability can be realized.

(Surfactant)
The negative photosensitive resin composition of the present embodiment may contain a surfactant. Thereby, the uniformity of the thickness of the resin film obtained by applying the photosensitive resin composition to the substrate can be improved.

The surfactant is preferably a nonionic surfactant containing at least one of a fluorine atom and a silicon atom. As commercially available products, for example, F-251, F-253, F-281, F-430, F-477, F-551, F-552, F-553 of the "Mega Fuck" series manufactured by DIC Co., Ltd. , F-554, F-555, F-556, F-557, F-558, F-559, F-560, F-561, F-562, F-563, F-565, F-568, F Fluorine-containing oligomeric structures such as -569, F-570, F-572, F-574, F-575, F-576, R-40, R-40-LM, R-41, R-94, etc. Surfactants, Fluorine-containing nonionic surfactants such as Neos Co., Ltd.'s Futagent 250 and Futagent 251's Fluorine-based surfactants, Wacker Chemie's SILFOAM® series (eg SD 100 TS, SD 670, SD 850, Examples thereof include silicone-based surfactants such as SD 860 and SD 882).

When a surfactant is used, only one type may be used, or two or more types may be used in combination.
The content of the surfactant is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, when the total solid content of the photosensitive resin composition is 100 parts by mass. Within this range, it is considered that the effect of improving the uniformity of the thickness of the resin film can be sufficiently obtained while balancing with other performances.

(Adhesion aid)
The negative photosensitive resin composition of the present embodiment may contain an adhesion aid. As a result, the adhesion of the resin film or pattern formed of the photosensitive resin composition to the substrate can be improved. The adhesive aid that can be used is not particularly limited. For example, silane coupling agents such as aminosilane, epoxysilane, acrylicsilane, mercaptosilane, vinylsilane, ureidosilane, acid anhydride functional silane, and sulfidesilane can be used. One type of silane coupling agent may be used alone, or two or more types may be used in combination. Among these, epoxysilane (ie, a compound containing both an epoxy moiety and a group that generates a silanol group by hydrolysis in one molecule) or acid anhydride functional silane (ie, acid anhydride in one molecule). A compound containing both a physical group and a group that generates a silanol group by hydrolysis) is preferable.

Examples of aminosilanes include bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, and γ-amino. Propylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, Examples thereof include N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, N-phenyl-γ-amino-propyltrimethoxysilane, and the like.

Examples of the epoxy silane include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-glycidylpropyltrimethoxy. Examples include silane.

Examples of the acrylic silane include γ- (methacryloxypropyl) trimethoxysilane, γ- (methacryloxypropyl) methyldimethoxysilane, and γ- (methacryloxypropyl) methyldiethoxysilane.

Examples of the mercaptosilane include 3-mercaptopropyltrimethoxysilane.

Examples of vinylsilane include vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, and the like.

Examples of the ureidosilane include 3-ureidopropyltriethoxysilane and the like.

Examples of the acid anhydride functional silane include 3-trimethoxysilylpropyl succinic anhydride.

Examples of the sulfide silane include bis (3- (triethoxysilyl) propyl) disulfide, bis (3- (triethoxysilyl) propyl) tetrasulfide, and the like.

When the adhesion aid is used, only one type may be used, or two or more types may be used in combination.
The content of the adhesion aid is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, when the total solid content of the photosensitive resin composition is 100 parts by mass. Within this range, it is considered that the effect of the adhesion aid, "adhesion", can be sufficiently obtained while balancing with other performances.

(solvent)
The photosensitive resin composition preferably contains a solvent. The solvent that can be used is typically an organic solvent. Specifically, a ketone solvent, an ester solvent, an ether solvent, an alcohol solvent, a lactone solvent, a carbonate solvent and the like can be used.

More specifically, acetone, methyl ethyl ketone, toluene, propylene glycol methyl ethyl ether, propylene glycol dimethyl ether, propylene glycol 1-monomethyl ether 2-acetate, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, benzyl alcohol. , Propylene Glycol Diacetate, Propylene Glycol Diacetate, Propylene Glycol Monomethyl Ether Acetate, Anisol, N-Methylpyrrolidone, Cyclohexanone, Cyclopentanone, Dipropylene Glycolmethyl-n-propyl Ether and other organic solvents. it can.

When a solvent is used, only one type may be used, or two or more types may be used.
When a solvent is used, the amount used is not particularly limited, but the solvent is used in such an amount that the concentration of the non-volatile component is, for example, 10% by mass or more and 70% by mass or less, preferably 15% by mass or more and 60% by mass or less.

(Other ingredients)
The photosensitive resin composition of the present embodiment may contain various components other than the above. For example, it may contain a basic compound, a curing accelerator, an antioxidant, a filler such as silica, a sensitizer, a filming agent, a dissolution accelerator, a dissolution inhibitor, and the like.
Among the above, as the basic compound, various amine compounds (for example, primary amine, secondary amine, tertiary amine, etc.) can be specifically mentioned.
Among the above, as the curing accelerator, a nitrogen-containing heterocyclic compound containing an amidine skeleton or a salt thereof (specifically, diazabicycloundecene or a salt thereof) can be specifically mentioned.

(Method for preparing negative photosensitive resin composition)
The method for preparing the negative photosensitive resin composition is not particularly limited, but it can be obtained, for example, by uniformly mixing the above-mentioned materials in a solvent.

<Manufacturing method of resin film>
A photosensitive resin film can be formed by using the above-mentioned photosensitive resin composition. Further, the resin film obtained by exposing, developing, and thermosetting the photosensitive resin film can be used, for example, as a permanent resist film for an electronic device. Hereinafter, the formation of the photosensitive resin film, the exposure / development of the photosensitive resin film, and the like will be specifically described.

(Formation of photosensitive resin film)
The photosensitive resin film can be obtained, for example, by applying the above-mentioned photosensitive resin composition on an arbitrary substrate and drying it if necessary.

The substrate on which the composition is applied is not particularly limited, and examples thereof include a glass substrate, a silicon wafer, a ceramic substrate, an aluminum substrate, a SiC wafer, a GaN wafer, and a copper-clad laminate. When manufacturing an organic EL device, the photosensitive resin film is typically formed on a glass substrate.
The substrate may be an unprocessed substrate or a substrate on which electrodes and elements are formed on the surface. It may be surface-treated to improve the adhesiveness.

The coating method of the photosensitive resin composition is not particularly limited, and can be carried out by rotary coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, an inkjet method, or the like.

Drying of the photosensitive resin composition applied on the substrate is typically carried out by heat treatment with a hot plate, hot air, an oven or the like. The heating temperature is usually 80 to 140 ° C, preferably 90 to 120 ° C. The heating time is usually about 30 to 600 seconds, preferably about 30 to 300 seconds.

The film thickness of the photosensitive resin film is not particularly limited and can be appropriately adjusted according to the pattern to be finally obtained, and can be, for example, in the range of 50 μm or more and 300 μm or less. The resin film obtained by curing the photosensitive resin composition of the present embodiment has excellent workability without cracks during pattern formation even when the film thickness is as thick as 50 μm or more.

(exposure)
The exposure is typically carried out by a contact exposure method. In the contact exposure method, a photomask (for example, a glass mask) on which a predetermined pattern is drawn is brought into contact with the photosensitive resin film and irradiated with active light rays. The photosensitive resin composition of the present embodiment is sensitive to active light rays, and therefore a pattern can be formed by applying a photolithography method using the active light rays.
Examples of the active light beam include X-ray, electron beam, ultraviolet light, visible light and the like. In terms of wavelength, light having a wavelength of 200 to 500 nm is preferable. From the viewpoint of pattern resolution and handleability, the light source is preferably g-line, h-line or i-line of a mercury lamp, and i-line is particularly preferable. Further, two or more light rays may be mixed and used. As the exposure apparatus, a contact aligner, a mirror projection or a stepper is preferable.
The amount of light for exposure may be appropriately adjusted depending on the amount of the photosensitizer in the photosensitive resin film and the like, and is, for example, about 100 to 500 mJ / cm ² .

After the exposure, the photosensitive resin film may be heated again if necessary (heating after exposure: Post Exposure Bake). The temperature is, for example, 70 to 150 ° C, preferably 90 to 120 ° C. The time is, for example, 30 to 600 seconds, preferably 30 to 300 seconds.

(developing)
By developing the exposed photosensitive resin film with an appropriate developing solution, a pattern can be obtained and a substrate having the pattern can be manufactured.

In the developing step, development can be carried out using a suitable developing solution, for example, by a method such as a dipping method, a paddle method, or a rotary spray method. By the development, the unexposed portion of the photosensitive resin film is eluted and removed, and a pattern is obtained.

The developer that can be used is not particularly limited. For example, an alkaline aqueous solution or an organic solvent can be used.
Specific examples of the alkaline aqueous solution include (i) an inorganic alkaline aqueous solution such as sodium hydroxide, sodium carbonate, sodium silicate and ammonia, (ii) an organic amine aqueous solution such as ethylamine, diethylamine, triethylamine and triethanolamine, and (iii). Examples thereof include an aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide.
Specific examples of the organic solvent include a ketone solvent such as cyclopentanone, an ester solvent such as propylene glycol monomethyl ether acetate (PGMEA) and butyl acetate, and an ether solvent such as propylene glycol monomethyl ether.
A water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added to the developing solution.

In the present embodiment, it is preferable to use an aqueous solution of tetramethylammonium hydroxide as a developing solution. The concentration of tetramethylammonium hydroxide in this aqueous solution is preferably 0.1% by mass or more and 10% by mass or less, and more preferably 0.5% by mass or more and 5% by mass or less. Further, it is preferable to use propylene glycol monomethyl ether acetate (PGMEA) as the developing solution of the organic solvent.

By the above steps, a pattern can be obtained / a substrate having the pattern can be produced, but various processes may be performed after development. For example, a permanent resist film can be obtained by heat-curing the resin film by heat treatment.

For example, when a pattern is formed on the resin composition of the present embodiment by using the above-mentioned contact exposure, the photomask can be peeled off without adhering to the photomask after the exposure. Further, in the pattern of the resin film obtained after exposure, no cracks are observed at all or almost.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted. Further, the present invention is not limited to the above-described embodiment, and modifications, improvements, etc. within the range in which the object of the present invention can be achieved are included in the present invention.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted.

Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

The materials used in Examples and Comparative Examples are described below.
(Epoxy resin)
-Epoxy resin 1: Cresol novolac type epoxy resin (manufactured by Choharu Artificial Resin Co., Ltd., trade name CNE-195LL, weight average molecular weight 1120, epoxy equivalent 200)
-Epoxy resin 2: Phenolic novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name "EPPN201", weight average molecular weight 4000-5000, epoxy equivalent 180-200, softening point 65-78 ° C)
-Epoxy resin 3: Tris (hydroxyphenyl) methane type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name "jER 1032H60", weight average molecular weight 800 to 900, epoxy equivalent 169, softening point 56 to 62 ° C.)

(Phenoxy resin)
-Phenoxy resin 1: Phenoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name "jER1256", weight average molecular weight 50,000)

(Additive)
Additive 1: Polycarbonate diol 1 (manufactured by Ube Industries, Ltd., trade name "Eternachol PH100", weight average molecular weight 1000, in the above formula (I), n = 6 to 7, R ₁ and R ₂ have 5 to 5 carbon atoms Polycarbonate diol which is an alkylene group of 6)
Additive 2: Polycarbonate diol 2 (manufactured by Ube Industries, Ltd., trade name "Eternacol PH200", weight average molecular weight 2000, in the above formula (I), n = 13-14, R ₁ and R ₂ have 5 to 5 carbon atoms Polycarbonate diol which is an alkylene group of 6)
-Additive 3: Modified epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name "YX7105")
-Additive 4: Liquid epoxy compound (manufactured by Mitsubishi Chemical Corporation, trade name "YED216D")

(Photoacid generator)
-Photoacid generator 1: Sulfonium-borate salt Photoacid generator (manufactured by San-Apro Co., Ltd., trade name "CPI-310B")

(Surfactant)
-Surfactant 1: Fluorine-containing oligomer (manufactured by DIC Corporation, trade name "R-41")

(Adhesion aid)
Adhesion aid 1: 3-trimethoxysilylpropyl succinic anhydride (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "X-12-967C")

(solvent)
-Solvent 1: Propylene glycol monomethyl ether acetate (PGMEA) (manufactured by Merck Performance Materials Co., Ltd., trade name "AZ5200 thinner")

(Examples, comparative examples, reference examples)
In each Example, each Comparative Example and each Reference Example, each component in the blending amount shown in Table 1 and the solvent 1 were blended with respect to 100 parts by mass of the epoxy resin shown in Table 1, and the solid content concentration was 50% by mass. A varnish-like photosensitive resin composition was prepared.
The photosensitive resin compositions obtained in each Example, each Comparative Example and each Reference Example were evaluated for the following items.

<Tackiness>
The photosensitive resin composition is spin-coated on a silicon wafer in three layers and heated at 100 ° C. on a hot plate to a thickness of 115 μm (Example, Comparative Example) or 30 μm (Reference Example). The coating film of was prepared. The heating time of each layer was 2 minutes, 3 minutes, and 10 minutes, respectively. The prepared coating film was subjected to contact exposure using an i-line stepper (FPA-3000iW manufactured by Canon) with an i-line (365 nm) using a glass mask. As the mask, a mask having a via pattern with a diameter of 50 μm was used. The exposure amount is in the range of 100~1100mJ / cm ^2, was subjected to the reduction projection exposure while changing by 100 mJ / cm ^2. During this contact exposure, it was observed whether the photosensitive resin composition adhered to the glass mask.
A glass mask having no photosensitive resin composition attached was evaluated as "good", and a glass mask having even a small amount of the photosensitive resin composition attached was evaluated as "poor". The results are shown in Table 1.

<Resolution / pattern formation>
The exposed coating film obtained above was heated at 70 ° C. for 5 minutes (post-exposure heat treatment). Propylene glycol monomethyl ether acetate (PGMEA) was used as the developing solution, and the developing solution was sprayed on the obtained coating film to dissolve and remove the unexposed portion. Then, the resin pattern was cured by heat treatment at 200 ° C. for 90 minutes. The obtained 50 μm via pattern was observed at a magnification of 800 times using a scanning electron microscope (SEM) to confirm whether or not the unexposed portion was cleanly removed and an opening was formed.
Those in which all unexposed areas were removed and openings were formed were evaluated as "good", and those in which even a small amount of unexposed areas remained were evaluated as "poor". The results are shown in Table 1.

<Presence / absence of cracks>
The surface of the 50 μm via pattern obtained as described above was observed at a magnification of 1000 using an optical microscope to confirm whether or not cracks had occurred.
Those with no cracks were evaluated as "none", and those with slight cracks were evaluated as "yes". The results are shown in Table 1.

All of the resin films obtained by curing the resin compositions of Examples had good tackiness and excellent handleability. Further, the resin film obtained in Examples has good pattern forming property, and no cracks are observed even when a resin film having a film thickness of 115 μm is formed into a pattern, which are shown in Reference Examples 1 and 2. It had excellent workability comparable to that of a resin film having a film thickness of 30 μm.

Claims (9)

Epoxy resin and
Photoacid generator and
Containing a polycarbonate diol represented by the formula (I),
The weight average molecular weight of the polycarbonate diol is 1800 or less.
Negative photosensitive resin composition.

(In the formula (I), n is 1 or more and 10 or less, and R ₁ and R ₂ are independently alkylene groups having 1 or more and 8 or less carbon atoms.) The negative photosensitive resin composition according to claim 1, further comprising a phenoxy resin. The negative photosensitive resin composition according to claim 1 or 2, further comprising a surfactant. The negative photosensitive resin composition according to any one of claims 1 to 3, further comprising an adhesion aid. The negative photosensitive resin composition according to any one of claims 1 to 4, wherein the epoxy resin contains at least one selected from the group consisting of a cresol novolac type epoxy resin and a phenol novolac type epoxy resin. The negative-type photosensitive resin composition according to any one of claims 1 to 5, which is photosensitive with i-ray. A resin film comprising a cured product of the negative photosensitive resin composition according to any one of claims 1 to 6. The resin film according to claim 7, which has a thickness of 50 μm or more and 300 μm or less. An electronic device comprising the resin film according to claim 7 or 8.