TW202219630A - Photosensitive resin composition, method for producing electronic device, electronic device and method for producing photosensitive resin composition - Google Patents

Abstract

To provide a photosensitive resin composition which enables formation of a permanent film having good tensile elongation characteristics. A thermosetting photosensitive resin composition for permanent film formation contains a resin and a photosensitive agent, in which the number of particles with a diameter of 0.5-20 [mu]m counted by measurement at a flow rate of 3 g/min for 1 minute by a light-scattering type particle counter using light at a wavelength of 780 nm is 100 or less.

Description

Photosensitive resin composition, manufacturing method of electronic device, electronic device, and manufacturing method of photosensitive resin composition

The present invention relates to a photosensitive resin composition, a method for producing an electronic device, an electronic device, and a method for producing the photosensitive resin composition.

In the manufacture of electronic devices, photosensitive resin compositions are used in order to form permanent films (films that remain in the final product). Specifically, various studies have been conducted on photosensitive resin compositions for forming permanent films (typically, cured films) such as interlayer films, surface protection films, and dam materials.

For example, Patent Document 1 describes a photosensitive resin composition containing (B) with respect to 100 parts by mass of (A) a polymer (alkali-soluble phenol resin, polyhydroxystyrene, or a derivative of polyhydroxystyrene) 1-100 mass parts of photosensitive diazonaphthoquinone compounds, (C) 100-1000 mass parts of organic solvents, and (D) 0.1-20 mass parts of adjuvant (alkoxysilyl group-containing organic compound). prior art literature Patent Literature

[Patent Document 1] Japanese Patent Laid-Open No. 2012-063788

[The problem to be solved by the invention]

Permanent films in electronic devices are required to have various properties. For example, permanent films are required to have good tensile elongation properties so as not to be easily ruptured by external forces. With the permanent film having such characteristics, the productivity and reliability of the electronic device can be improved.

In recent years, with the further upgrading, complication, and miniaturization of electronic devices, the performance required for the permanent film is increasing day by day, and there is also a need for further improvement in the tensile elongation properties.

Therefore, the inventors of the present invention have studied a new photosensitive resin composition for one of the purposes of providing a photosensitive resin composition capable of forming a permanent film having favorable tensile elongation properties. [Technical means to solve the problem]

The inventors of the present invention have completed the inventions provided below, thereby solving the above-mentioned problems.

According to the present invention, there is provided a photosensitive resin composition, which is a thermosetting photosensitive resin composition for forming a permanent film, and Contains resin and sensitizer, The number of particles with a diameter of 0.5 to 20 μm counted by a particle counter using a light scattering method of light having a wavelength of 780 nm in one minute of measurement at a flow rate of 3 g/min was 100 or less.

Also, according to the present invention, a method for manufacturing an electronic device is provided, comprising: In the film-forming step, the above-mentioned photosensitive resin composition is used to form a photosensitive resin film; an exposure step of exposing the photosensitive resin film; and In the developing step, the exposed photosensitive resin film is developed.

Further, according to the present invention, there is provided an electronic device including a permanent film, This permanent film is formed from the above-mentioned photosensitive resin composition.

Further, according to the present invention, there is provided a method for producing a photosensitive resin composition, which is the method for producing the above-mentioned photosensitive resin composition and includes a filtration step by a hollow fiber membrane filter having a pore size of 0.5 μm or less. [Effect of invention]

By using the photosensitive resin composition of the present invention, a permanent film having favorable tensile elongation properties can be formed.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In the drawings, the same reference numerals are assigned to the same constituent elements, and descriptions thereof are appropriately omitted. In order to avoid complication, when there are a plurality of identical constituent elements in the same drawing, sometimes only one of the constituent elements is marked with a symbol, and all constituent elements are not marked with a symbol. The drawings are for illustrative purposes only. The shapes, size ratios, and the like of each member in the drawings do not necessarily correspond to actual articles.

In this specification, unless otherwise specified, the expression "X to Y" in the description of the numerical range means X or more and Y or less. For example, "1 to 5 mass %" means "1 mass % or more and 5 mass % or less".

In the expression of the group (atomic group) in the present specification, the expression not describing substitution or non-substitution includes both those having no substituent and those having a substituent. For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). The expression "(meth)acrylic acid" in this specification means a concept including both acrylic acid and methacrylic acid. Similar expressions about "(meth)acrylate" and the like are also the same. Unless otherwise specified, the term "organic group" in this specification means an atomic group obtained by removing one or more hydrogen atoms from an organic compound. For example, "monovalent organic group" means an atomic group obtained by removing one hydrogen atom from an arbitrary organic compound. In this specification, unless otherwise specified, the term "polyamide/polyimide resin" includes (i) resins containing a polyamide structure but not containing a polyimide structure, (ii) resins containing polyamide These three resins are resins having an amine structure but not containing a polyamide structure and (iii) resins containing both a polyamide structure and a polyimide structure. In addition, in this specification, the polyimide resin may contain the polyimide structure together with the polyimide structure, or may not contain the polyimide structure, and the polyimide resin may contain the polyimide structure together with the polyimide structure. Contains a polyamide structure or may not contain a polyamide structure. The term "electronic device" in this specification includes semiconductor chips, semiconductor elements, printed wiring boards, circuit display devices, information communication terminals, light-emitting diodes, physical batteries, chemical batteries and other components, devices, used in the meaning of the final product, etc.

<Photosensitive resin composition> The photosensitive resin composition of this embodiment is used for forming a permanent film. That is, the photosensitive resin composition of the present embodiment is not a photoresist composition that is temporarily used as a mask during etching and is removed after use. The permanent film formed using the photosensitive resin composition of the present embodiment is incorporated in a final product such as an electronic device. The photosensitive resin composition of this embodiment is thermosetting. Specifically, the photosensitive resin composition of the present embodiment may be any of the following: (i) the resin itself has thermal polymerizability and crosslinking properties, (ii) by removing the resin (may be thermosetting or In addition to thermoplastic), a crosslinking agent, a polymerizable monomer, etc. are contained, the entire composition is thermosetting, and (iii) a chemical reaction such as a ring-closure reaction is caused by heating, whereby the insolubility is improved. The photosensitive resin composition of the present embodiment contains at least a resin and a photosensitizer. When the photosensitive resin composition of the present embodiment was passed through a particle counter using a light scattering method of light having a wavelength of 780 nm, the number of particles with a diameter of 0.5 to 20 μm counted in the measurement for 1 minute at a flow rate of 3 g/min was 100 or less. . The number of particles is preferably 50 or less, more preferably 20 or less. The number of particles has no lower limit and can be 0. The number of particles is, for example, 0.1 or more, specifically, 1 or more, from the practical viewpoints of production cost and the like.

The reason why the permanent film formed from the photosensitive resin composition with "less particles" of the present embodiment has favorable tensile elongation properties is only an assumption, but it can be explained as follows. It is considered that if particles exist in the permanent film, the position where the particles exist will be the "start" of rupture. Therefore, it is presumed that by reducing the particles in the photosensitive resin composition for forming a permanent film, the "start" of cracks can be reduced, and as a result, favorable tensile elongation characteristics can be obtained.

As an additional effect, the adhesiveness between a permanent film (cured film) and a metal substrate also tends to become favorable by reducing the particle|grains of the photosensitive resin composition. It is presumed that by reducing the number of particles, the "start of peeling" is reduced.

Incidentally, regarding the photoresist composition used for etching, several attempts to reduce the number of particles in the composition are known (for example, International Publication No. 2017/163922, etc.). However, in photoresists that are temporarily used as masks during etching and removed after use, "stretch elongation properties" are generally not required. The technical idea of reducing the number of particles in the composition in order to "improve the tensile elongation characteristics of the permanent film" is based on the original researchers of the present inventors.

The photosensitive resin composition "with few particles" of the present embodiment can be produced by using appropriate materials and selecting appropriate production methods and production conditions. For example, when the photosensitive resin composition is produced, the photosensitive resin composition of the present embodiment can be produced by performing filtration using a polypropylene hollow fiber membrane filter having a pore diameter of about 0.2 μm. It will be described in Examples and the like.

Hereinafter, components which can be contained in the photosensitive resin composition of the present embodiment, and properties, physical properties, and the like of the photosensitive resin composition of the present embodiment will be described.

(resin) In view of the above-mentioned estimation mechanism that "because there are few particles, there are few "starts" of cracking", it is considered that the photosensitive resin composition of the present embodiment can obtain good tensile elongation characteristics regardless of the resin type. Hereinafter, the epoxy resin and the polyimide/polyimide resin, which are particularly preferably used resins from the viewpoint of application in the manufacture of electronic devices, will be specifically described.

·Epoxy resin As the epoxy resin, for example, an epoxy resin having two or more epoxy groups in one molecule can be used. As the epoxy resin, all monomers, oligomers and polymers can be used. The molecular weight or molecular structure of the epoxy resin is not particularly limited.

Examples of epoxy resins include phenol novolac epoxy resins, cresol novolac epoxy resins, cresol naphthol epoxy resins, biphenyl epoxy resins, biphenyl aralkyl ) type epoxy 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 Base ether type epoxy resin, bisphenol S diglycidyl ether type epoxy resin, glycidyl ether type epoxy resin, aromatic polyfunctional epoxy resin, aliphatic epoxy resin, aliphatic polyfunctional ring Oxygen resin etc. Furthermore, 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexane)carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl (3,4-epoxycyclohexylmethyl) - Epoxy-6-methylcyclohexane)carboxylate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, dicyclopentadiene oxide, bis(2 , 3-epoxycyclopentyl) ether or CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE 2085, CELLOXIDE 8000, EPOLEAD GT401 and other alicyclic epoxy resins manufactured by Daicel Corporation. Furthermore, 2,2'-(((((1-(4-(2-(4-(oxiran-2-ylmethoxy)phenyl)propan-2-yl)phenyl ) ethane-1,1-diyl)bis(4,1-phenylene))bis(oxy))bis(methylene))bis(oxirane)) (for example, manufactured by Printec Corporation Aliphatic polyglycidyl ether such as Techmore VG3101L), EPOLIGHT 100MF (manufactured by Kyoeisha Chemical Co., Ltd.), EPIOL TMP (manufactured by NOF CORPORATION), 1,1,3,3,5,5-hexamethyl -1,5-bis(3-(oxiran-2-ylmethoxy)propyl)trisiloxane (for example, DMS-E09 (manufactured by GELEST, INC.)) and the like. The epoxy resin may be used alone or in combination of a plurality of types.

The epoxy resin may contain a solid epoxy resin having two or more epoxy groups in the molecule. As a solid epoxy resin, what has two or more epoxy groups and is solid at 25 degreeC (room temperature) can be used. Thereby, the mechanical properties in the resin film of the photosensitive resin composition can be improved.

It is preferable that the epoxy resin contains a polyfunctional epoxy resin having three or more functions in a molecule (that is, a polyfunctional epoxy resin having three or more epoxy groups in one molecule). Thereby, the film is sufficiently cured, and for example, the heat resistance and durability as a permanent film can be improved. In addition, high heat resistance means that the properties of the permanent film are not easily changed even when heated, which further improves the flatness.

The trifunctional or higher polyfunctional epoxy resin is, for example, selected from phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene One or more kinds of epoxy resins selected from the group consisting of vinyl-type epoxy resins, bisphenol A-type epoxy resins, and tetramethylbisphenol F-type epoxy resins are preferred. Among them, triphenylmethane type epoxy resin or novolac type epoxy resin is more preferable. Thereby, while improving the heat resistance of a resin film, an appropriate thermal expansion coefficient can be achieved.

The epoxy resin may contain a liquid epoxy resin having two or more epoxy groups in the molecule. The liquid epoxy resin functions as a film-forming agent and can improve the brittleness of the resin film of the photosensitive resin composition.

As a liquid epoxy resin, the epoxy compound which has two or more epoxy groups and is liquid at room temperature 25 degreeC can be used. The viscosity of the liquid epoxy resin at 25° C. is, for example, 1 to 8000 mPa·s, preferably 5 to 1500 mPa·s, and more preferably 10 to 1400 mPa·s.

The liquid epoxy resin may contain, for example, a group selected from the group consisting of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, alkyl diglycidyl ether, and alicyclic epoxy resins. of more than one. These may be used alone or in combination of two or more. Among them, alkyl diglycidyl ethers can be used from the viewpoint of reduction of cracks after development.

The epoxy equivalent of the liquid epoxy resin is, for example, 100 to 200 g/eq, preferably 105 to 180 g/eq, and more preferably 110 to 170 g/eq. Thereby, the brittleness of the resin film can be improved.

The lower limit of the content of the liquid epoxy resin is, for example, 5% by mass or more, preferably 10% by mass or more, and more preferably 15% by mass or more, based on all nonvolatile components in the photosensitive resin composition. Thereby, the brittleness of the cured film finally obtained can be improved. The upper limit of the liquid epoxy resin content is, for example, 40% by mass or less, preferably 35% by mass or less, and more preferably 30% by mass or less, based on the total nonvolatile content of the photosensitive resin composition. Thereby, the balance of the film characteristics of a cured film can be achieved.

The content of the epoxy resin is, for example, 40% by mass or more, preferably 45% by mass or more, and more preferably 50% by mass or more with respect to all the nonvolatile components in the photosensitive resin composition. Thereby, the heat resistance and mechanical strength of the cured film finally obtained can be improved. The epoxy resin content is, for example, 90% by mass or less, preferably 85% by mass or less, and more preferably 80% by mass or less with respect to all nonvolatile components in the photosensitive resin composition. Thereby, the pattern formability can be improved.

·Polyamide/polyimide resin The polyamide/polyimide resin preferably contains a structural unit represented by the following general formula (PA-1) and/or a structural unit represented by the following general formula (PI-1).

In general formulas (PA-1) and (PI-1), X is a divalent organic group, Y is a tetravalent organic group.

In the general formulae (PA-1) and (PI-1), at least one of X and Y is preferably a group containing a fluorine atom. In general formulas (PA-1) and (PI-1), it is preferable that both X and Y are groups containing a fluorine atom from the viewpoint of solubility in organic solvents.

In the general formulae (PA-1) and (PI-1), the divalent organic group of X and/or the tetravalent organic group of Y preferably contain an aromatic ring structure, and more preferably contain a benzene ring structure. Thereby, the heat resistance tends to be further improved. The benzene ring here may be substituted with a fluorine atom-containing group such as a fluorine atom, a fluorinated alkyl group (preferably a trifluoromethyl group), or other groups. In the general formulae (PA-1) and (PI-1), the divalent organic group of X and/or the tetravalent organic group of Y have 2 to 6 benzene rings and are bonded via a single bond or a divalent linking group The resulting structure is better. As a divalent linking group here, an alkylene group, a fluorinated alkylene group, an ether group, etc. are mentioned. The alkylene group and the fluorinated alkylene group may be linear or branched. In general formula (PA-1) and (PI-1), the carbon number of the divalent organic group of X is 6-30, for example. In general formula (PA-1) and (PI-1), the carbon number of the tetravalent organic group of Y is 6-20, for example. Preferably, the two imide rings in the general formula (PI-1) are 5-membered rings, respectively.

More preferably, the polyamide/polyimide resin contains a structural unit represented by the following general formula (PA-2) and/or a structural unit represented by the following general formula (PI-2).

In general formula (PA-2) and (PI-2), The meaning of X is the same as that of X in the general formula (PA-1) and (PI-1), Y' represents a single bond, carbonyl or alkylene.

Regarding the specific aspect of X, the meaning is the same as that described in the general formulae (PA-1) and (PI-1). The alkylene group of Y' may be linear or branched. It is preferable that some or all of the hydrogen atoms of the alkylene group of Y' are substituted with fluorine atoms. The number of carbon atoms in the alkylene group of Y' is, for example, 1-6, preferably 1-4, and more preferably 1-3.

From the viewpoint of reducing the amount of shrinkage at the time of forming the cured film, etc., the photosensitive resin composition of the present embodiment preferably contains a polyimide resin, and more preferably contains a polyimide resin having an imide ring structure . When the number of moles of imide groups contained in the polyimide resin is IM, and the number of moles of imide groups contained in the polyimide resin is AM, the formula is {IM/(IM The imidization rate represented by +AM)}×100(%) is preferably 90% or more, more preferably 95% or more, and still more preferably 98% or more. In short, it is preferable that the polyimide resin has no or a small amount of ring-opened imide structures and a large amount of ring-closed imide structures. By using such a polyimide resin, shrinkage (hardening shrinkage) due to heating can be further suppressed (this is because dehydration due to ring-closure reaction does not occur). Thereby, the further improvement of the reliability of an electronic device, the further improvement of the flatness of a cured film, etc. can be aimed at. As an example, the imidization rate can be known from the area of the peak corresponding to the imino group in the NMR spectrum, the area of the peak corresponding to the imino group, or the like. As another example, the imidization rate can be known from the area of the peak corresponding to the imino group in the infrared absorption spectrum, the area of the peak corresponding to the imino group, or the like.

Preferably, the polyimide/polyimide resin contains fluorine atoms. According to the findings of the present inventors, the polyimide/polyimide resin containing fluorine atoms tends to have better solubility in organic solvents than those containing no fluorine atoms. Therefore, by using the polyimide/polyimide resin containing a fluorine atom, the properties of the photosensitive resin composition can be easily made into a varnish-like state. The amount (mass ratio) of fluorine atoms in the fluorine atom-containing polyimide/polyimide resin is, for example, 1 to 30 mass %, preferably 3 to 28 mass %, and more preferably 5 to 25 mass %. Sufficient organic solvent solubility is easily obtained by containing a certain amount of fluorine atoms in the resin. On the other hand, from the viewpoint of balance with other properties, it is preferable that the amount of fluorine atoms is not excessive.

By variously designing the ends of the polyimide/polyimide resin, for example, the mechanical properties (tensile elongation, etc.) of the cured product can be further improved.

As an example, it is preferable that the polyimide/polyimide resin has a group capable of forming a bond by reacting with an epoxy group at the terminal thereof. As such a group, an acid anhydride group, a hydroxyl group, an amino group, a carboxyl group, etc. are mentioned.

Preferably, the polyimide/polyimide resin has an acid anhydride group at its terminal. In the photosensitive resin composition of this embodiment, an acid anhydride group and an epoxy group are easy to form a bond sufficiently. The acid anhydride group is preferably a group of an acid anhydride skeleton having a cyclic structure. The "ring structure" here is preferably a 5-membered ring or a 6-membered ring, more preferably a 5-membered ring.

As a supplementary explanation for the terminal structure, it is preferable that the polyamide/polyimide resin does not have a maleimide structure at its terminal.

Polyamide resins can typically be obtained by reacting (polycondensation) a diamine with an acid dianhydride. The polyimide resin can be obtained by imidization (ring closing reaction) of the polyimide resin. Moreover, a desired functional group can also be introduce|transduced into a polymer terminal as needed. Regarding specific reaction conditions, the descriptions of Examples described later and International Publication No. WO 2016/172092, and the like can be referred to.

In the resulting polyamide/polyimide resin, the diamine is incorporated into the polymer as a divalent organic group X in the general formula (PA-1) or (PI-1). Moreover, the acid dianhydride is incorporated into the polymer as the tetravalent organic group Y in the general formula (PA-1) or (PI-1). In the synthesis of the polyimide/polyimide resin, one or two or more diamines may be used, and one or two or more acid dianhydrides may be used.

As the raw material diamine, for example, 3,4'-diaminodiphenyl ether (3,4'-ODA), 4,4'-diamino-2,2'-bis(trifluoromethyl) ) Biphenyl (TFMB), 3,3',5,5'-tetramethylbenzidine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 3,3'-diamine bis(trifluoromethyl)benzidine, 3,3'-bis(trifluoromethyl)benzidine, 2,2'-bis(p-aminophenyl)hexafluoropropane, bis( Trifluoromethoxy)benzidine (TFMOB), 2,2'-bis(pentafluoroethoxy)benzidine (TFEOB), 2,2'-trifluoromethyl-4,4'-oxydiphenylamine (OBABTF), 2-phenyl-2-trifluoromethyl-bis(p-aminophenyl)methane, 2-phenyl-2-trifluoromethyl-bis(m-aminophenyl)methane, 2, 2'-bis(2-heptafluoroisopropoxy-tetrafluoroethoxy)benzidine (DFPOB), 2,2-bis(m-aminophenyl)hexafluoropropane (6-FmDA), 2,2 -Bis(3-amino-4-methylphenyl)hexafluoropropane, 3,6-bis(trifluoromethyl)-1,4-diaminobenzene (2TFMPDA), 1-(3,5- diaminophenyl)-2,2-bis(trifluoromethyl)-3,3,4,4,5,5,5-heptafluoropentane, 3,5-diaminotrifluorotoluene (3 ,5-DABTF), 3,5-diamino-5-(pentafluoroethyl)benzene, 3,5-diamino-5-(heptafluoropropyl)benzene, 2,2'-dimethyl Benzidine (DMBZ), 2,2',6,6'-tetramethylbenzidine (TMBZ), 3,6-diamino-9,9-bis(trifluoromethyl)dibenzopyran ( 6FCDAM), 3,6-diamino-9-trifluoromethyl-9-phenyldibenzopyran (3FCDAM), 3,6-diamino-9,9-diphenyldibenzopyran Nan and so on.

As the raw material acid dianhydride, for example, pyromic acid dianhydride (PMDA), diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride (ODPA), benzophenone-3 ,3',4,4'-tetracarboxylic dianhydride (BTDA), biphenyl-3,3',4,4'-tetracarboxylic dianhydride (BPDA), diphenyl-3,3', 4,4'-tetracarboxylic dianhydride (DSDA), diphenylmethyl-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride) propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane (6FDA), etc. Of course, the acid dianhydride that can be used is not limited to this. One or two or more kinds of acid dianhydrides can be used.

The diamine and dianhydride are used in a substantially 1:1 ratio on a molar basis. However, in order to obtain a desired terminal structure, one of them may be used in excess. Specifically, by using too much diamine, the terminal (both terminals) of the polyimide/polyimide resin is likely to become an amine group. On the other hand, when the acid dianhydride is used too much, the terminal (both terminals) of the polyimide/polyimide resin tends to become an acid anhydride group. As described above, in the present embodiment, the polyamide/polyimide resin preferably has an acid anhydride group at its terminal. Therefore, in this embodiment, when synthesizing a polyimide/polyimide resin, it is preferable to use too much acid dianhydride.

The terminal amine group and/or acid anhydride group of the polyimide/polyimide resin obtained by polycondensation can also be reacted with a certain reagent, so that the terminal of the resin has a desired functional group.

The weight average molecular weight of the polyamide/polyimide resin is, for example, 5,000 to 100,000, preferably 7,000 to 75,000, and more preferably 10,000 to 50,000. Since the weight average molecular weight of the polyimide/polyimide resin is large to some extent, for example, sufficient heat resistance of the cured film can be obtained. In addition, since the weight average molecular weight of the polyamide/polyimide resin is not too large, it is easy to dissolve the polyamide/polyimide resin in an organic solvent. The weight average molecular weight can usually be determined by a gel permeation chromatography (GPC) method using polystyrene as a standard substance.

Incidentally, in the case of using a polyimide/polyimide resin, it is preferable to use it together with an epoxy resin. Specific examples of the epoxy resin are as described above. When using a polyamide/polyimide resin and an epoxy resin together, the amount thereof is, for example, 0.5 to 30 parts by mass, preferably 1, with respect to 100 parts by mass of the polyamide resin and/or the polyimide resin. to 20 parts by mass, more preferably 3 to 15 parts by mass.

(phenoxy resin) It is preferable that the photosensitive resin composition of this embodiment contains a phenoxy resin. In particular, when the photosensitive resin composition of the present embodiment contains an epoxy resin, it is preferable to use an epoxy resin and a phenoxy resin in combination. It is considered that by using a phenoxy resin, for example, the flexibility of the formed film can be improved. "Phenoxy resin" refers to a polyhydroxy polyether synthesized from bisphenols and epichlorohydrin in a narrow sense, but in this specification, a polyaddition reaction between a polyfunctional epoxy resin and a polyfunctional phenol is used. ) and the resulting polymer (phenoxy resin in a broad sense) is also included in the phenoxy resin.

Examples of phenoxy resins include bisphenol A-type phenoxy resins, bisphenol F-type phenoxy resins, copolymerized phenoxy resins of bisphenol A-type and bisphenol F-type, and biphenyl-type phenoxy resins. Base resin, bisphenol S type phenoxy resin, biphenyl type phenoxy resin and copolymerized phenoxy resin of bisphenol S type phenoxy resin, etc. Among them, bisphenol A type phenoxy resin or bisphenol A type and bisphenol F type copolymerized phenoxy resin are preferable. The phenoxy resin may be used alone or in combination of two or more.

The weight average molecular weight (Mw) of the phenoxy resin is preferably from 10,000 to 100,000, more preferably from 20,000 to 80,000, and even more preferably from 35,000 to 80,000. Since the Mw of the phenoxy resin is relatively large, the curing shrinkage can be further suppressed, and the flatness can be further improved. Although the details of this mechanism are not clear, it is presumed that when the Mw is relatively large, the thermal motion of the molecular chain is suppressed, and as a result, the flatness is further improved. On the other hand, from the viewpoint of solvent solubility and the like, the Mw of the phenoxy resin is preferably 100,000 or less. The weight-average molecular weight is measured, for example, as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

The phenoxy resin may have reactive groups such as epoxy groups at both ends of the molecular chain or inside the molecular chain. The reactive group in the phenoxy resin is one that can undergo a crosslinking reaction with the epoxy group in the epoxy resin. By using such a phenoxy resin, the solvent resistance and heat resistance in a resin film can be improved.

As a phenoxy resin, what is solid at 25 degreeC is used preferably. Specifically, a phenoxy resin having a nonvolatile 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.

The lower limit of the phenoxy resin content is preferably 20 parts by mass or more, more preferably 25 parts by mass or more, and further preferably 30 parts by mass relative to 100 parts by mass of the epoxy resin or polyamide/polyimide resin above. Thereby, sufficient flexibility can be obtained. In addition, it is considered that the effects of suppressing excessive thermal hardening and flattening the film surface by flow, etc., which are estimated mechanisms, can be sufficiently obtained. The upper limit of the phenoxy resin content is preferably 60 parts by mass or less, more preferably 55 parts by mass or less, and further preferably 50 parts by mass relative to 100 parts by mass of the epoxy resin or polyamide/polyimide resin the following. Thereby, the phenoxy resin can be easily and fully dissolved in the solvent mentioned later, and the photosensitive resin composition excellent in coatability can be obtained.

The photosensitive resin composition of the present embodiment may contain other thermoplastic resins other than the phenoxy resin. Examples of such thermoplastic resins include polyvinyl acetal resins, (meth)acrylic resins, polyamide-based resins (for example, nylon, etc.), thermoplastic urethane-based resins, and polyolefin-based resins (for example, polyethylene resins). , polypropylene, etc.), polycarbonate, polyester resins (for example, polyethylene terephthalate, polybutylene terephthalate, etc.), polyacetal, polyphenylene sulfide, polyether ether ketone, Liquid crystal polymer, fluororesin (for example, polytetrafluoroethylene, polyvinylidene fluoride, etc.), modified polyphenylene ether, polysulfone, polyethersulfone, polyarylate, polyamide Imide, polyether imide, thermoplastic polyimide, etc. When other thermoplastic resins are used, they may be used alone or in combination of two or more.

(photosensitive agent) The photosensitive resin composition of this embodiment contains a photosensitizer. As the photosensitizer, any photosensitizer that changes the solubility of the photosensitive resin composition in the developing solution and/or hardens the photosensitive composition by the action of light can be used.

As an example, it is preferable that the photosensitive agent contains a photocationic polymerization initiator. In particular, the photocationic polymerization initiator is preferably used when the resin contains an epoxy resin. The active species generated by the photocationic polymerization initiators polymerize the epoxy groups in the epoxy resin in a chain reaction manner by the mechanism of so-called chemical amplification. In addition, a change in solubility in a developer and hardening are caused.

As a specific example of a photocationic polymerization initiator, an onium salt compound is mentioned. More specifically, diazonium salts, iodonium salts such as diaryl iodonium salts, periconium salts such as triaryl periconium salts, triaryl pyrylium salts, and benzylpyridinium thiocyanate can be mentioned. Photoacid generators or cationic photopolymerization initiators such as benzyl pyridinium thiocyanate, dialkylbenzylmethyl sulfamate, and dialkylhydroxyphenylphosphonium salts. Among them, it is preferable to use a triaryl perionium salt from the viewpoint of pattern forming properties.

Examples of counter anions of the onium salt compound include borate anions, sulfonate anions, gallate anions, phosphorus-based anions, antimony-based anions, and the like. More specifically, a sulfonate anion, a disulfoimidate anion, a hexafluorophosphate anion, a fluoroantimonate anion, a tetrafluoroborate anion, a tetrakis(pentafluorophenyl)borate anion, etc. are mentioned.

As another example, it is preferable that the photosensitizer contains a photoradical polymerization initiator. In particular, when the photosensitive resin composition contains the polyfunctional (meth)acrylate compound described later, the photoradical generator can effectively polymerize it.

啉基丙-1-酮、2-苄基-2-二甲基胺基-1-（4-

啉基苯基）-丁酮-1、2-（二甲基胺基）-2-〔（4-甲基苯基）甲基〕-1-〔4-（4-

啉基）苯基〕-1-丁酮等的烷基苯酮系化合物；二苯甲酮、4,4’-雙（二甲基胺基）二苯甲酮、2-羧基二苯甲酮等的二苯甲酮系化合物；安息香甲基醚、安息香乙基醚、安息香異丙基醚、安息香異丁基醚等的安息香系化合物；9-氧硫𠮿

、2-乙基-9-氧硫𠮿

、2-異丙基-9-氧硫𠮿

、2-氯-9-氧硫𠮿

、2,4-二甲基-9-氧硫𠮿

、2,4-二乙基-9-氧硫𠮿

等的9-氧硫𠮿

系化合物；2-（4-甲氧基苯基）-4,6-雙（三氯甲基）-對稱三

、2-（4-甲氧基萘基）-4,6-雙（三氯甲基）-對稱三

、2-（4-乙氧基萘基）-4,6-雙（三氯甲基）-對稱三

、2-（4-乙氧基羰基萘基）-4,6-雙（三氯甲基）-對稱三

等的鹵甲基化三

系化合物；2-三氯甲基-5-（2’-苯并呋喃基）-1,3,4-

二唑、2-三氯甲基-5-〔β-（2’-苯并呋喃基）乙烯基〕-1,3,4-

二唑、4-

二唑、2-三氯甲基-5-呋喃基-1,3,4-

二唑等的鹵甲基化

二唑系化合物；2,2’-雙（2-氯苯基）-4,4’,5,5’-四苯基-1,2’-聯咪唑、2,2’-雙（2,4-二氯苯基）-4,4’,5,5’-四苯基-1,2’-聯咪唑、2,2’-雙（2,4,6-三氯苯基）-4,4’,5,5’-四苯基-1,2’-聯咪唑等的聯咪唑系化合物；1,2-辛二酮,1-〔4-（苯基硫基）苯基〕-2-（鄰苯甲醯基肟）、乙酮,1-〔9-乙基-6-（2-甲基苯甲醯基）-9H-咔唑-3-基〕-,1-（鄰乙醯基肟）等的肟酯系化合物；雙（η5-2,4-環戊二烯-1-基）-雙（2,6-二氟-3-（1H-吡咯-1-基）-苯基）鈦等的環戊二烯鈦系化合物；p-二甲基胺基安息香酸、p-二乙基胺基安息香酸等的安息香酸酯系化合物；9-苯基吖啶等的吖啶系化合物；等。其中，尤其可以較佳地使用肟酯系化合物。 The photo-radical generator that can be used is not particularly limited, and known ones can be appropriately used. For example: 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenone, 2-hydroxy-2-methyl -1-Phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4-[4-(2-Hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, 2-methyl-1-(4-methylphenylthio) base) -2-

Linoprop-1-one, 2-benzyl-2-dimethylamino-1-(4-

Linophenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-

Alkyl phenone-based compounds such as olinyl)phenyl]-1-butanone; benzophenone, 4,4'-bis(dimethylamino)benzophenone, 2-carboxybenzophenone Benzoin-based compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. benzoin-based compounds; 9-oxythiocyanate

, 2-ethyl-9-oxothio

, 2-isopropyl-9-oxothio

, 2-chloro-9-oxysulfur

, 2,4-dimethyl-9-oxothio

, 2,4-diethyl-9-oxothio

etc. 9-oxosulfur 𠮿

Series compound; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-symmetric tri

, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-symmetric three

, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-symmetric three

, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-symmetric three

halomethylated tris

Series compound; 2-trichloromethyl-5-(2'-benzofuranyl)-1,3,4-

oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl)ethenyl]-1,3,4-

oxadiazole, 4-

oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-

Halomethylation of oxadiazoles etc.

oxadiazole compounds; 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2, 4-Dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4 ,4',5,5'-tetraphenyl-1,2'-biimidazole and other biimidazole-based compounds; 1,2-octanedione, 1-[4-(phenylthio)phenyl]- 2-(O-benzyl oxime), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-, 1-(o- Acetyl oxime) and other oxime ester compounds; bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl) Cyclopentadiene titanium-based compounds such as phenyl) titanium; benzoic acid ester-based compounds such as p-dimethylaminobenzoic acid, p-diethylaminobenzoic acid, etc.; 9-phenylacridine, etc. Acridine series compounds; etc. Among them, oxime ester-based compounds can be preferably used in particular.

When the photosensitive resin composition contains a sensitizer, only one sensitizer may be contained, or two or more sensitizers may be contained. The content of the photosensitizer is, for example, 0.3 to 5.0 mass %, preferably 0.5 to 4.5 mass %, and more preferably 1.0 to 4.0 mass % with respect to the total solid content of the photosensitive resin composition. By making it 0.3 mass % or more, pattern formability can be improved. Moreover, by setting it as 5.0 mass % or less, the ion component in a film can be reduced, and the insulating property and reliability of a final film can be improved.

(Multifunctional (meth)acrylate compound) The photosensitive resin composition of this embodiment may contain a polyfunctional (meth)acrylate compound. As a polyfunctional (meth)acrylate compound, what has two or more (meth)acryloyl groups in one molecule is mentioned without a restriction|limiting in particular.

According to the findings of the present inventors, it is preferable to use a polyfunctional (meth)acrylate compound together with a polyimide/polyimide resin. Although the details are not clear, it is believed that when the polyfunctional (meth)acrylate compound hardens (polymerizes) it forms a structure that is complexly "entangled" with the polyimide resin and/or polyimide resin. In particular, it is presumed that the polyfunctional (meth)acrylate compound is polymerized to form a polyimide resin having a cyclic skeleton such as an imide ring, or that at least a part of the polyimide structure is ring-closed due to heat. A network structure of a cyclic skeleton of a polyamide resin having a cyclic skeleton. It is presumed that the performance of the cured film becomes good by forming such a complex entangled structure.

The polyfunctional (meth)acrylate compound is preferably trifunctional or more from the viewpoint of realizing the above-mentioned entangled structure or obtaining a cured film having high durability and good chemical resistance. There is no upper limit on the number of functional groups of the polyfunctional (meth)acrylate compound, but the upper limit of the number of functional groups is, for example, 11 functional groups from the viewpoints of easy availability of raw materials and the like. As a rough trend, when a polyfunctional (meth)acrylate compound having a large number of functional groups ((meth)acryloyl groups) is used, the chemical resistance of the cured film tends to improve. On the other hand, when a polyfunctional (meth)acrylate compound having a small number of functional groups ((meth)acryloyl groups) is used, mechanical properties such as tensile elongation of the cured film tend to be favorable. .

As an example, it is preferable that the polyfunctional (meth)acrylate compound contains a (meth)acrylate compound having 7 or more functions. As an example, it is preferable that the polyfunctional (meth)acrylate compound contains a (meth)acrylate compound having 5 to 6 functions or more. As an example, it is preferable that the polyfunctional (meth)acrylate compound contains a (meth)acrylate compound having 3 to 4 functions or more.

As an example, the polyfunctional (meth)acrylate compound may contain a compound represented by the following general formula. In the following general formula, R' is a hydrogen atom or a methyl group, n is 0 to 3, and R is a hydrogen atom or a (meth)acryloyl group. The plurality of R's may be the same or different.

Specific examples of the polyfunctional (meth)acrylate compound include the following. Of course, the polyfunctional (meth)acrylate compound is not limited to this.

Ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, neotaerythritol tri(meth)acrylate , polyol polyacrylates such as neopentaerythritol tetra (meth)acrylate, dipeoerythritol penta (meth)acrylate, dipivalerythritol hexa (meth)acrylate, bisphenol A Epoxy acrylates such as di(meth)acrylate of diglycidyl ether, di(meth)acrylate of hexanediol diglycidyl ether, etc., by polyisocyanate and (meth)acrylic The amine ester (meth)acrylate etc. obtained by the reaction of the hydroxyl group-containing (meth)acrylate, such as hydroxyethyl ester.

ARONIX M-400, ARONIX M-460, ARONIX M-402, ARONIX M-510, ARONIX M-520 (manufactured by TOAGOSEI CO., LTD.), KAYARAD T-1420, KAYARAD DPHA, KAYARAD DPCA20, KAYARAD DPCA30, KAYARAD DPCA60 , KAYARAD DPCA120 (made by Nippon Kayaku Co., Ltd.), Viscoat#230, Viscoat#300, Viscoat#802, Viscoat#2500, Viscoat#1000, Viscoat#1080 (made by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), NK ESTETR A -Commercial products such as BPE-10, NK ESTETR A-GLY-9E, NK ESTETR A-9550, and NK ESTETR A-DPH (manufactured by SHIN-NAKAMURA CHEMICAL CO, LTD.).

When the photosensitive resin composition contains a polyfunctional (meth)acrylate compound, only one type of polyfunctional (meth)acrylate compound may be contained, or two or more types of polyfunctional (meth)acrylate compounds may be contained . In the latter case, it is preferable to use together a polyfunctional (meth)acrylate compound having a different number of functional groups. It is considered that a more complicated "entanglement structure" can be formed by using a polyfunctional (meth)acrylate compound having a different number of functional groups in combination, thereby further improving the properties of the cured film. Incidentally, in commercially available polyfunctional (meth)acrylate compounds, mixtures of (meth)acrylates having different numbers of functional groups exist.

In the case of using a polyfunctional (meth)acrylate compound, the amount of the polyfunctional (meth)acrylate compound relative to 100 parts by mass of the epoxy resin and/or polyimide/polyimide resin is preferably 50 to 200 parts by mass, more preferably 60 to 150 parts by mass. The usage-amount of a polyfunctional (meth)acrylate compound is not specifically limited, By adjusting the usage-amount suitably as mentioned above, one or two or more of each performance can be improved further. As described above, in the photosensitive resin composition of the present embodiment, it is considered that the "entanglement structure" of the polyimide/polyimide resin and the polyfunctional (meth)acrylate can be formed by curing, and it is considered that the By appropriately adjusting the amount of the polyfunctional (meth)acrylate compound to be used relative to the polyamide/polyimide resin, the polyamide/polyimide resin and the polyfunctional (meth)acrylate compound will be appropriately The tangles, again, are reduced in extra components not related to the tangles. In addition, it is considered that the performance will be further improved.

(thermal free radical initiator) The photosensitive resin composition of this embodiment may contain a thermal radical initiator. It is considered that the polymerization reaction of the above-mentioned polyfunctional (meth)acrylate compound can be further accelerated by using a thermal radical initiator, for example.

The thermal radical initiator preferably contains an organic peroxide. Examples of the organic peroxide include octyl peroxide, lauryl peroxide, stearyl peroxide, 1,1,3,3-tetramethylbutylperoxy2-ethylhexanoic acid Esters, oxalic acid peroxide, 2,5-dimethyl-2,5-bis(2-ethylhexylperoxy)hexane, 1-cyclohexyl-1-methylethylperoxy 2-ethyl 2-ethylhexanoate, tertiary hexyl peroxy 2-ethyl hexanoate, tertiary butyl peroxy 2-ethyl hexanoate, m-toluol peroxide, benzyl peroxide, methyl Ethyl ethyl ketone peroxide, acetyl peroxide, tertiary butyl hydroperoxide, di-tertiary butyl peroxide, cumyl hydroperoxide, dicumyl peroxide, Tertiary butyl perbenzoate, p-chlorobenzyl peroxide, cyclohexanone peroxide, etc.

In the case of using a thermal radical initiator, only one thermal radical initiator may be used, or two or more thermal radical initiators may be used. In the case of using a thermal radical initiator, the amount thereof is, for example, preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the polyfunctional (meth)acrylate compound.

(hardening catalyst) The photosensitive resin composition of the present embodiment may contain a curing catalyst. The hardening catalyst has the function of promoting the reaction of the epoxy resin. By using a hardening catalyst, the reaction using an epoxy resin can fully progress, for example, the tensile elongation of a cured film can be further improved.

Examples of the curing catalyst include compounds known as curing catalysts for epoxy resins (usually, also referred to as curing accelerators). For example, diazbicycloolefins such as 1,8-diazbicyclo[5,4,0]undecene-7 and derivatives thereof; amine compounds such as tributylamine and benzyldimethylamine can be mentioned. ; Imidazole compounds such as 2-methylimidazole; Organophosphines such as triphenylphosphine, methyldiphenylphosphine, etc.; Tetraphenylphosphonium tetranaphthyloxyborate, tetraphenylphosphonium tetranaphthyloxyborate, tetraphenylphosphonium tetranaphthyloxyborate, 4,4'-sulfonyldiphenol tetraphenylphosphonium, etc.; triphenylphosphine, etc. with benzoquinone added . Among them, organic phosphines are preferably mentioned.

In the case of using a curing catalyst, the amount thereof is, for example, 1 to 80 parts by mass, or preferably 5 to 50 parts by mass, with respect to 100 parts by mass of the epoxy resin. Incidentally, in the case where the photosensitive resin composition of the present embodiment is chemically amplified and cured by a chain chemical reaction caused by an active species generated by light irradiation, the photosensitive resin of the present embodiment is The composition usually does not contain a hardening catalyst.

(Adhesion Auxiliary) It is preferable that the photosensitive resin composition of this embodiment contains an adhesion adjuvant. Thereby, the adhesiveness with a board|substrate can be improved further, for example.

The adhesion adjuvant is not particularly limited. For example, an amine group-containing silane coupling agent, an epoxy group-containing silane coupling agent, a (meth)acryloyl group-containing silane coupling agent, a mercapto group-containing silane coupling agent, a vinyl group-containing silane coupling agent, a Silane coupling agents such as urea group-containing silane coupling agents and thioether group-containing silane coupling agents. In the case of using a silane coupling agent, one type may be used alone, or two or more types may be used in combination.

Examples of the amino group-containing silane coupling agent include bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, and γ-aminopropyltriethoxysilane. Propyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β(aminoethyl)γ-aminopropyl Trimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, N -β(aminoethyl)γ-aminopropylmethyldiethoxysilane, N-phenyl-γ-amino-propyltrimethoxysilane, etc. Examples of the epoxy group-containing silane coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-epoxypropyl propyl trimethoxy silane, etc. Examples of the (meth)acryloyl group-containing silane coupling agent include γ-((meth)acryloyloxypropyl)trimethoxysilane, γ-((meth)acryloyloxypropyl) ) Methyldimethoxysilane, γ-((meth)acryloyloxypropyl)methyldiethoxysilane, etc. As a mercapto group-containing silane coupling agent, 3-mercaptopropyl trimethoxysilane etc. are mentioned, for example. Examples of the vinyl group-containing silane coupling agent include vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, and the like. As a ureido group-containing silane coupling agent, 3-ureidopropyl triethoxysilane etc. are mentioned, for example. Examples of the sulfide group-containing silane coupling agent include bis(3-(triethoxysilyl)propyl)disulfide, bis(3-(triethoxysilyl)propyl)tetrasulfide things etc. Examples of the acid anhydride-containing silane coupling agent include 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, and 3-dimethylmethoxysilylpropyl succinic anhydride. acid anhydride, etc.

Moreover, as an adhesion auxiliary agent, not only a silane coupling agent, but a titanium coupling agent, a zirconium coupling agent, etc. can be mentioned.

When an adhesion adjuvant is used, it may be used alone, or two or more adhering adjuvants may be used in combination. In the case of using an adhesion adjuvant, the amount used is preferably 0.3 to 5% by mass, more preferably 0.4 to 4% by mass, and still more preferably 0.3 to 5% by mass based on the total amount of the nonvolatile components of the photosensitive resin composition. 0.5 to 3 mass %.

(surfactant) It is preferable that the photosensitive resin composition of this embodiment contains a surfactant. Thereby, the coatability of the photosensitive resin composition and the flatness of the film can be further improved. As the surfactant, a fluorine-based surfactant, a polysiloxane-based surfactant, an alkyl-based surfactant, an acrylic-based surfactant, and the like can be mentioned.

It is preferable that the surfactant contains at least one of a fluorine atom and a silicon atom. This contributes not only to obtaining a uniform resin film (improving coatability) or improving developability, but also contributing to an improvement in adhesive strength. From another viewpoint, it is preferable that the surfactant is nonionic. The use of a nonionic surfactant is preferable, for example, from the viewpoint of improving the storage stability of the composition by suppressing unintended reactions with other components in the composition.

Examples of commercially available products that can be preferably used as surfactants include F-251, F-253, F-281, F-430, F-477, and F-551 of the "Megafac" series manufactured by DIC Corporation. , F-552, F-553, 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-569, F-570, F-572, F-574, F-575, F-576, R-40, R-40-LM, R-41, R-94, etc. Fluorine-containing oligomer structure surfactant, fluorine-containing nonionic surfactants such as Ftergent250 and Ftergent251 manufactured by NEOS COMPANY LIMITED, SILFOAM (registered trademark) series (for example, SD 100 TS, SD 670, SD 850, SD 860, SD 882) and other polysiloxane-based surfactants. Moreover, as a preferable surfactant, FC4430, FC4432 by 3M company, etc. are mentioned.

When using a surfactant, the usage-amount is 0.001-1 mass % based on the total amount of the nonvolatile component of the photosensitive resin composition, for example, Preferably it is 0.005-0.5 mass %.

(water) The photosensitive resin composition of this embodiment may contain water. Due to the presence of water, for example, the hydrolysis reaction of the silane coupling agent tends to proceed, and the adhesiveness between the substrate and the cured film tends to be further improved.

When the photosensitive resin composition of the present embodiment contains water, the amount thereof is preferably 0.1 to 5 parts by mass, and more preferably 0.2 parts by mass relative to 100 parts by mass of the total solid content (non-volatile content) of the photosensitive resin composition. to 3 parts by mass, more preferably 0.5 to 2 parts by mass. The moisture content of the photosensitive resin composition can be quantified by the Karl Fischer method.

(Properties of Solvent/Composition) It is preferable that the photosensitive resin composition of this embodiment contains a solvent. Thereby, the photosensitive resin film can be easily formed on the board|substrate by the coating method. The solvent usually contains an organic solvent. The solvent is not particularly limited as long as it can dissolve or disperse the above-mentioned components and does not substantially chemically react with the components.

Specific examples of the solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylacetamide, dimethylsulfoxide, and diethylene glycol dimethylide. Ethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate , butyl lactate, methyl 1,3-butanediol acetate, 1,3-butanediol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate and methyl 3-methoxypropionate Wait. The solvent may be used alone or in combination of two or more.

When the photosensitive resin composition of this embodiment contains a solvent, the photosensitive resin composition of this embodiment is usually varnish-like. More specifically, the photosensitive resin composition of the present embodiment is preferably a varnish-like composition in which a resin and a photosensitizer are dissolved in a solvent. Since the photosensitive resin composition of the present embodiment is in the form of a varnish, a uniform film can be formed by coating. Moreover, since resin "dissolves" in a solvent, a homogeneous cured film can be obtained.

When using a solvent, it is preferable to use it so that the density|concentration of the whole solid content (nonvolatile matter) in a photosensitive resin composition may become 10-50 mass %, and it is more preferable to use it as 20-45 mass %. By setting it as this range, each component can be melt|dissolved or dispersed sufficiently. Moreover, favorable coatability can be ensured, and the flatness at the time of spin coating can also be improved. Moreover, the viscosity of the photosensitive resin composition can be appropriately controlled by adjusting the content of the nonvolatile components.

(other ingredients) In addition to the above-mentioned components, the photosensitive resin composition of the present embodiment may contain other components as necessary. As such a component, filler particles, such as an antioxidant and silica, a sensitizer, a film-forming agent, etc. are mentioned, for example. However, in consideration of tensile elongation performance, it is preferable that the photosensitive resin composition of the present embodiment does not contain filler particles.

(Supplementary Matters) The photosensitive resin composition of the present embodiment is preferably a negative type (that is, one whose solubility in a developing solution is lowered due to a curing (crosslinking) reaction or the like due to exposure). By reducing the number of particles in the negative-type photosensitive resin composition, it is considered that the presence of particles inhibits the curing (crosslinking) reaction further. That is, it is considered that the effect "good tensile elongation characteristics" by the reduction in the number of particles can be obtained especially in a negative-type photosensitive resin composition.

The photosensitive resin composition of the present embodiment is preferably of a chemically amplified type (that is, the solubility to the developer is changed by the chain reaction caused by the active chemical species generated by the photosensitive agent (in the case of the negative type, the solubility to the developer is changed) of reduced solubility)). It is considered that it becomes difficult to inhibit the chain reaction by reducing the number of particles in the chemically amplified photosensitive resin composition. As a result, it is considered that the tensile elongation characteristics of the obtained permanent film became more favorable.

<Manufacturing method of photosensitive resin composition> The photosensitive resin composition of this embodiment can be manufactured by selecting an appropriate manufacturing method and manufacturing conditions. Specifically, the photosensitive resin composition of the present embodiment can be produced by going through a filtration step or the like through a hollow fiber membrane filter having a pore diameter of 0.5 μm or less. That is, a photosensitive resin composition at a flow rate of 3 g/min can be produced by filtering and mixing a photosensitive resin composition obtained by mixing the above-mentioned components (resin, photosensitizer, solvent, etc.) with a hollow fiber membrane filter having a pore diameter of 0.5 μm or less. The photosensitive resin composition in which the number of particles with a diameter of 0.5 to 20 μm counted in the minute measurement is 100 or less. According to the findings of the present inventors, the hollow fiber membrane filter has a higher capability of capturing particles generated from the photosensitive resin composition for permanent membrane formation than other filters such as membrane filters.

The pore diameter of the hollow fiber membrane filter is preferably 0.05 μm or more and 0.5 μm or less, and more preferably 0.05 μm or more and 0.3 μm or less. Although it is also affected by the total amount and flow rate of the photosensitive resin composition to be filtered, from the viewpoint of reducing clogging, the membrane area of the hollow fiber membrane filter is, for example, 5000 cm ² or more, preferably 10000 cm ² or more, and more Preferably, it is 15000cm ² or more. There is no upper limit on the film area, but from the viewpoint of cost and the like, the upper limit is, for example, 50,000 cm ² , specifically 40,000 cm ² , and more specifically 30,000 cm ² . The material of the hollow fiber membrane filter is preferably polyolefin, more preferably polypropylene. Various information related to hollow fiber membrane filters are usually recorded in catalogs or specifications.

The filtering step may be performed only once or a plurality of times. A specific aspect when performing a plurality of filtering steps may be cyclic filtering. Also, the filtering step may be a multi-stage filtering step including a pre-filtering step using a filter with a relatively large pore size and a main filtering step using a filter with a relatively small pore size. In this case, a hollow fiber membrane filter having a pore diameter of 0.5 μm or less is used at least in the main filtration. As a filter in the pre-filtration, a filter with a pore size larger than that used in the main filtration is usually selected. The filter used for prefiltration may be a hollow fiber membrane filter or a filter other than a hollow fiber membrane filter such as a membrane filter.

The flow rate of filtration is not particularly limited. For example, the viscosity and nonvolatile content concentration of the photosensitive resin composition, the pore diameter and membrane area of the filter, the production efficiency, etc. may be appropriately set within the range of about 10 to 1000 g/min. Incidentally, in the case of the above-described multi-stage filtration step, the flow rate may be changed between the pre-filtration step and the main filtration step. In this case, the flow rate in the pre-filtration step is usually made larger than the flow rate in the main filtration step.

Hollow fiber membrane filters are available, for example, from KITZ MICRO FILTER CORPORATION.

<Manufacturing method of electronic device, electronic device> An electronic device (an electronic device including a film formed of the photosensitive resin composition) can be produced using the photosensitive resin composition of the present embodiment. For example, an electronic device can be manufactured by a manufacturing method of an electronic device including: (i) a film forming step, in which the surface of the substrate having a level difference on the surface is composed of the photosensitive resin of the present embodiment (ii) exposure step, exposing the photosensitive resin film; and (iii) developing step, developing the exposed photosensitive resin film.

Referring to FIGS. 1A to 1D , an example of a method of manufacturing an electronic device will be described in more detail. According to the manufacturing method of the electronic device demonstrated here, a permanent film can be provided so that it may contact metal members, such as copper wiring.

(Film production step: Figure 1A) In the film forming step, the photosensitive resin film 3 is formed using the photosensitive resin composition of the present embodiment on the surface side having the level difference of the substrate 1 having the level difference 10 . The substrate 1 is not particularly limited. Examples of the substrate 1 include a silicon wafer, a ceramic substrate, an aluminum substrate, a SiC wafer, a GaN wafer, and the like. The step 10 is Cu rewiring, for example. Of course, the level difference 10 may be a level difference other than the Cu rewiring. The height of the level difference 10 is, for example, 1 to 10 μm, or preferably 1 to 5 μm. The thickness of the photosensitive resin film 3 (thickness of the part without the step 10) is, for example, 1 to 15 μm, or preferably 1 to 10 μm. The thickness may be larger than the height of the step 10.

As a method of forming the photosensitive resin film 3, a method of applying a liquid photosensitive resin composition on a substrate by spin coating, spray coating, dipping, printing, roll coating, ink jetting, or the like can be mentioned. method. Typically, the method of forming the resin film is spin coating. The thickness of the photosensitive resin film 3 can be adjusted by changing the film forming conditions or adjusting the viscosity of the photosensitive resin composition.

It is preferable to heat-dry the photosensitive resin film 3 after the film forming step and before the exposure step. This heat drying is sometimes referred to as "pre-baking". The temperature of heating and drying is usually 50 to 180°C, preferably 60 to 150°C. Moreover, the heat drying time is usually 30 to 600 seconds, preferably about 30 to 300 seconds. The solvent in the photosensitive resin composition can be sufficiently removed by this heating and drying. Typically, heating is performed by means of a hot plate or an oven or the like.

(Exposure Step: FIG. 1B ) In the exposure step, the photosensitive resin film 3 is exposed through the mask 20 . As active light rays for exposure, for example, X-rays, electron beams, ultraviolet rays, visible light, and the like are used. In terms of wavelength, active light rays of 200 to 500 nm are preferable. The light source is preferably g-ray, h-ray, or i-ray of a mercury lamp from the viewpoint of pattern resolution and ease of operation of the device. In addition, two or more kinds of light rays may be mixed and used. As the exposure device, a contact aligner, a mirror projection or a stepper are preferred. The exposure amount in the exposure step is usually between 40 to 1500 mJ/cm ² (preferably 80 to 1000 mJ/cm ² ), depending on the sensitivity of the photosensitive resin composition, the film thickness of the resin film, and the desired pattern shape wait for proper adjustment.

It is preferable to heat the resin film (post-exposure heating) between the exposure step and the development step. Thereby, a substance (photosensitive agent, etc.) that is cracked, decomposed, etc. by exposure reacts, and it can be expected that the pattern shape becomes favorable. The temperature and time of heating after exposure are, for example, about 50 to 200° C. for 10 to 600 seconds.

(Development step: Figure 1C) In the development step, the photosensitive resin film exposed in the exposure step is developed using a developer. Thereby, a part of the photosensitive resin film 3 can be removed, and the resin film 3A provided with the opening 5 can be obtained. The photosensitive resin composition of this embodiment is usually a negative type. Therefore, the opening 5 is provided in a portion corresponding to the light shielding portion of the photomask 20 . The developing step can be performed by, for example, a dipping method, a liquid coating method, a spin spray method, or the like.

In this embodiment, it is preferable that the developer contains an organic solvent. More specifically, it is preferable that the developer is a developer containing an organic solvent as a main component (95% by mass or more of the components is an organic solvent). By developing with a developing solution containing an organic solvent, compared with the case of developing with an alkaline developing solution (aqueous), pattern swelling and the like caused by the developing solution can be suppressed. That is, it is easier to obtain a clear pattern.

Specific examples of the organic solvent usable in the developer include ketone-based solvents such as cyclopentanone, ester-based solvents such as propylene glycol monomethyl ether acetate (PGMEA) and butyl acetate, and propylene glycol monomethyl ether. and other ether-based solvents, etc. As the developer, an organic solvent developer composed of only an organic solvent and containing only impurities that are inevitably contained can be used. In addition, there are metal elements as impurities that are inevitably contained, but from the viewpoint of preventing contamination of electronic devices, the less impurities that are inevitably contained, the better.

The time of the developing step is usually about 5 to 300 seconds, preferably about 10 to 120 seconds, and can be appropriately adjusted according to the thickness of the resin film, the shape of the pattern to be formed, and the like.

Between the development step and the subsequent step, for example, there may be a hardening step of hardening the resin film 3A. Hardening can be performed, for example, by heat treatment at 150 to 250° C. for 30 to 240 minutes.

(Additional rewiring step: Figure 1D) A portion of the opening 5 provided in the developing step may be provided with a Cu redistribution line 11 different from the level difference 10 (eg, Cu redistribution line). By improving the flatness of the upper surface of the resin film 3A, the fine Cu rewiring 11 can be provided precisely.

The embodiments of the present invention have been described above, but these are merely examples of the present invention, and various configurations other than those described above may be employed. In addition, this invention is not limited to the above-mentioned embodiment, The deformation|transformation, improvement, etc. within the range which can achieve the objective of this invention are all included in this invention. [Example]

Embodiments of the present invention will be described in detail based on Examples and Comparative Examples. The present invention is not limited only to the Examples, which are explained beforehand for the sake of prudence.

<Example using epoxy resin> (Manufacture of photosensitive resin composition) First, a homogeneous mixture of the composition shown in Table 1 below was obtained.

[Table 1] material ratio display Epoxy Resin-1 EPPN-201 18.0% by mass Epoxy-2 LX-01 4.4% by mass Phenoxy resin PKHA 6.7% by mass Sensitizer (photocationic polymerization initiator) CPI-310B 0.6 mass % Surfactant FC4432 0.03% by mass Adhesion Auxiliary X-12-967C 0.27% by mass solvent Propylene Glycol Monomethyl Ether Acetate 70.0% by mass

The epoxy resin EPPN-201 is a compound represented by the following chemical formula manufactured by Nippon Kayaku Co., Ltd.. The epoxy resin LX-01 is a compound represented by the following chemical formula, manufactured by OSAKA SODA CO., LTD. The phenoxy resin PKHA is a compound represented by the following chemical formula manufactured by Gabriel Phenoxies. Sensitizer (photocationic polymerization initiator) CPI-310B is a photoacid generator manufactured by San-Apro Ltd., cationic structure: triaryl (phenyl) sulfonium, anionic structure: B(C ₆ F ₅ ) ₄ . The surfactant FC4432 is a nonionic fluorine-based surfactant manufactured by 3M. The adhesion adjuvant X-12-967C is 3-trimethoxysilylpropyl succinic anhydride manufactured by Shin-Etsu Chemical Co., Ltd.

The above-mentioned mixture was filtered under any of the following conditions of Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-2. Then, the photosensitive resin composition was manufactured.

Example 1-1 The mixture was passed through a hollow fiber membrane filter (model: F70SC12F-L8, pore size: 0.2 μm, material: polypropylene, membrane area: 20000 cm ² ) of KITZ MICRO FILTER CORPORATION at a flow rate of 100 g/min. filtered. Example 1-2 First, the mixture was filtered through a membrane filter (Model: PIAA01P01, pore size: 1.0 μm, material: polyethylene, membrane area: 8000 cm ² ) of Entegris Corporation at a flow rate of 100 g/min, and then This was filtered through a hollow fiber membrane filter (Model: F70SC12F-L8, pore diameter: 0.2 μm, material: polypropylene, membrane area: 20000 cm ² ) of KITZ MICRO FILTER CORPORATION at a flow rate of 100 g/min. Example 1-3 First, the mixture was filtered three times at a flow rate of 1000 g/min using a membrane filter (model: PIAH01P01, pore size: 0.5 μm, material: polyethylene, membrane area: 8000 cm ² ) from Entegris. . The mixture after the circulating filtration was passed through a hollow fiber membrane filter (Model: F70SC12F-L8, pore diameter: 0.2 μm, material: polypropylene, membrane area: 20000 cm ² ) of KITZ MICRO FILTER CORPORATION at a flow rate of 500 g/min. filtered.

Comparative Example 1-1 The mixture was filtered at a flow rate of 100 g/min through a membrane filter (model: PIAG01P01, pore diameter: 0.2 μm, material: ultra-high molecular weight polyethylene, membrane area: 8800 cm ² ) manufactured by Entegris. Comparative Example 1-2 First, the mixture was filtered at a flow rate of 100 g/min through a membrane filter (Model: PIAA01P01, pore size: 1.0 μm, material: polyethylene, membrane area: 8000 cm ² ) manufactured by Entegris, and then This was filtered through a membrane filter (model: PIAG01P01, pore diameter: 0.2 μm, material: ultra-high molecular weight polyethylene, membrane area: 8800 cm ² ) manufactured by Entegris at a flow rate of 100 g/min.

(measurement of particle number) Each photosensitive resin composition was flowed through a particle counter using a light scattering method of light having a wavelength of 780 nm at a flow rate of 3 g/min, and the number of particles with a diameter of 0.5 to 20 μm counted in 1 minute of measurement was counted. As a particle counter, RION Co., Ltd. "KS-42 Kai" was used.

(Evaluation of tensile elongation properties) Each photosensitive resin composition was applied on a Si wafer, and the solvent was dried to form a resin film having a thickness of 10 μm. The resin film was cured under the conditions of 170° C. and 2 hours to obtain a cured film. After cooling to room temperature, the entire wafer was cut into 5 mm×20 mm, and the cured film was peeled off from the wafer with an aqueous hydrofluoric acid solution. The peeled cured film was placed in a universal testing machine, and a tensile test was performed at room temperature at a speed of 5 mm/min. Thereafter, the elongation at break point was measured. The measurement was performed 10 times for each of the Examples and Comparative Examples. The average value of the elongation at break point obtained by 10 measurements is described in the table below.

(Evaluation of Adhesion with Metal) An evaluation sample was produced by the following process. Each photosensitive resin composition was applied on a Cu wafer, and the solvent was dried to form a resin film having a thickness of 5 μm. Then, through-holes were formed in the photosensitive resin film by exposure and image development, and it was made to harden on the conditions of 170 degreeC and 2 hours, and the cured film was obtained. Next, the scum remaining on the resin film was removed by O ₂ plasma. Next, a Ti layer (thickness: 50 nm) and a Cu layer (300 nm) were formed on the substrate by sputtering, and then a resist (TMMR (registered trademark) P-W1000T PM TOKYO OHKA KOGYO CO., LTD. made), then copper plating was performed, the through holes were filled with copper plating, and the resist was stripped with a resist stripping solution (manufactured by ST-120 TOKYO OHKA KOGYO CO., LTD.) to obtain an evaluation sample.

Next, the adhesiveness with the metal was evaluated by the following evaluation method. A simple reflow process was performed on the evaluation samples. After heating on a 260°C hot plate for 5 seconds, it was taken out from the hot plate and cooled to room temperature. The operation of heating and cooling was performed 10 times. The confirmation of the adhesion state with the metal was implemented by FIB-SEM. The through-hole portion filled with copper plating was subjected to FIB processing, and the cross section was observed by SEM to confirm whether or not the interface between the resin film and Cu was peeled off.

The measurement results of the particle number, the evaluation results of the tensile elongation properties, and the evaluation results of the adhesion with metals are summarized in the following table.

[Table 2] Example and comparative example number Number of particles Tensile elongation properties (elongation at break point (%), average of 10 times) Adhesion to metal Example 1-1 9 43 good Example 1-2 5 43 good Examples 1-3 7 37 good Comparative Example 1-1 319 32 bad Comparative Example 1-2 323 30 bad

As shown in the above table, the cured film (permanent film) formed from the photosensitive resin composition having a small number of particles has better tensile elongation properties than those formed from the photosensitive resin composition having a large particle number. Moreover, the cured film (permanent film) formed from the photosensitive resin composition with a small particle number shows favorable adhesiveness with a metal.

(Evaluation of Pattern Formability) For the sake of prudence, the photosensitive resin composition using the above-mentioned epoxy resin was confirmed to have pattern formability as a "photosensitive resin composition" as follows.

The photosensitive resin composition of Example 1-1 was coated on an 8-inch silicon wafer using a spin coater. After the coating, in the atmosphere, a hot plate was used for prebaking at 120° C. for 3 minutes to obtain a resin film having a film thickness of about 9 μm. The resin film was irradiated with i-rays through a mask made by TOPPAN INC. (with a residual pattern and a punching pattern having a width of 1.0 to 100 μm drawn). For the irradiation, an i-ray stepper (manufactured by Nikon Corporation, NSR-4425i) was used. After exposure, the wafer was placed on a hot plate and baked at 70° C. for 5 minutes in the atmosphere. Then, the unexposed part was melt|dissolved and removed by performing spray image development for 30 second using propylene glycol monomethyl ether acetate as a developer. Through the above steps, a pattern in which only the unexposed portion in the film is selectively removed is obtained. That is, it was confirmed that a "pattern" can be formed by exposure using a mask.

Moreover, the pattern was obtained similarly using the photosensitive resin composition of Example 1-2 and 1-3 instead of the photosensitive resin composition of Example 1-1.

<Example using polyimide/polyimide resin> (Synthesis of polymer (A-1)) First, 2,2'-bis(trifluoromethyl)-4,4'-diamine Biphenyl (hereinafter, also referred to as TFMB) 64.1g (0.20 mol) and benzophenone-3,3',4,4'-tetracarboxylic dianhydride (hereinafter, also referred to as BTDA) 70.9g (0.22 moles) into an appropriately sized reaction vessel with a stirrer and cooling tubes. Then, GBL500g was added to the reaction container further. After nitrogen gas was introduced for 10 minutes, the temperature was raised to 60°C while stirring, and the reaction was performed for 1.5 hours. Then, the reaction was further performed at 180° C. for 3 hours to polymerize the diamine and the acid dianhydride to prepare a polyimide solution. The obtained polyimide solution was diluted with acetone to prepare a diluted solution, and the diluted solution was then added dropwise to a mixed solution of water/methanol=3/1 to precipitate a white solid. The obtained white solid was recovered and vacuum-dried at a temperature of 120°C. Through the above steps, a polyimide powder having an acid anhydride at the terminal, that is, a polymer (A-1) was obtained. The weight average molecular weight (Mw) of the polymer (A-1) measured by GPC measurement was 25,000. Furthermore, the polymer (A-1) was subjected to ¹ H-NMR measurement, and the imidization ratio (defined as above) was calculated from the quantitative value of the polyimide amide peak relative to the aromatic ring peak. The imidization rate is over 99%.

The chemical formula of the polymer (A-1) is shown below.

(Manufacture of photosensitive resin composition) First, each of the following materials is uniformly mixed to obtain a mixture. ·Resin 100 parts by mass of the above (A-1) ·Multifunctional (meth)acrylate compound Viscoat #802 (manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD., a structure represented by the following chemical formula) 80 parts by mass

·Photosensitive agent Irugacure OXE02 (manufactured by BASF, oxime ester type photoradical generator) 10 parts by mass · Thermal free radical generator PERKADOX BC (manufactured by Nouryon, organic peroxide, cumyl peroxide) 10 parts by mass ·Epoxy resin TECHMORE VG3101L (manufactured by Printec Corporation) 7 parts by mass CELLOXIDE 2021P (manufactured by Daicel Corporation) 3 parts by mass · Hardening catalyst 4,4'-Sulfonyl diphenol tetraphenylphosphonium 3 parts by mass The synthesis method of the above-mentioned hardening catalyst is as follows. 37.5 g (0.15 mol) of 4,4'-bisphenol S and 100 mL of methanol were put into a separable flask with a stirring device, and the mixture was stirred and dissolved at room temperature. A solution obtained by dissolving 4.0 g (0.1 mol) of sodium in 50 mL of methanol. Next, a solution obtained by dissolving 41.9 g (0.1 mol) of tetraphenylphosphine bromide in 150 mL of methanol in advance was added. After continuing stirring for a while and adding 300 mL of methanol, the solution in the flask was added dropwise to a large amount of water while stirring to obtain a white precipitate. The precipitate was filtered and dried. Through the above steps, the target product was obtained as white crystals. · Adhesion Auxiliary (Silane Coupling Agent) KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd., 3-methacryloyloxypropyltrimethoxysilane) 5 parts by mass X-12-967C (manufactured by Shin-Etsu Chemical Co., Ltd., the structure is as described above) 2 parts by mass · Surfactant FC4432 (manufactured by 3M, fluorine-based) 0.1 parts by mass 2 parts by mass of water ·Solvent (organic solvent) Ethyl lactate (EL) 259 parts by mass γ-Butyrolactone (GBL) 259 parts by mass

The above mixture was filtered under one of the following conditions in Example 2-1 or Comparative Example 2-1. Then, the photosensitive resin composition was manufactured. Example 2-1 The mixture was passed through a hollow fiber membrane filter of KITZ MICRO FILTER CORPORATION (model: F50C12T-L2, pore size: 0.2 μm, material: polypropylene, membrane area: 20000 cm ² ) at a flow rate of 50 g/min. filtered. Comparative Example 2-1 The mixture was filtered at a flow rate of 50 g/min through a membrane filter (model: CWUGOS1S3, pore diameter: 0.2 μm, material: ultra-high molecular weight polyethylene, membrane area: 8800 cm ² ) manufactured by Entegris.

(measurement of particle number) Measurements were carried out in the same manner as in the examples using epoxy resins.

(Evaluation of tensile elongation properties) Each photosensitive resin composition was applied on a Si wafer, and the solvent was dried to form a resin film having a thickness of 7 μm. This resin film was hardened under the conditions of 200 degreeC, 2 hours, and nitrogen atmosphere (oxygen concentration 1000 ppm or less), and the cured film was obtained. After cooling to room temperature, the entire wafer was cut into 5 mm×20 mm, and the cured film was peeled off from the wafer with an aqueous hydrofluoric acid solution. The peeled cured film was placed in a universal testing machine, and a tensile test was performed at room temperature at a speed of 5 mm/min. Thereafter, the elongation at break point was measured. The measurement was performed 10 times for each of the Examples and Comparative Examples. The average value of the elongation at break point obtained by 10 measurements is described in the table below.

The measurement results of the particle number and the evaluation results of the tensile elongation characteristics are summarized in the following table.

[table 3] Example and comparative example number Number of particles Tensile elongation properties (elongation at break point (%), average of 10 times) Example 2-1 1 27 Comparative Example 2-1 129 18

As shown in the above table, in the polyimide/polyimide resin system, the cured film (permanent film) formed of the photosensitive resin composition with a small number of particles has a higher tensile elongation property than a photosensitive resin composition with a large number of particles. Resin composition formers are good. From this result and the result of the above-mentioned epoxy resin system, it turns out that the tensile elongation characteristic of a permanent film (cured film) becomes favorable because the number of particles in the photosensitive resin composition is small, regardless of the type of resin.

(Evaluation of Pattern Formability) For the sake of prudence, the photosensitive resin composition using the above-mentioned polyimide/polyimide resin was confirmed to have pattern formability as a "photosensitive resin composition".

The photosensitive resin composition using the above-mentioned polyimide/polyimide resin was applied on an 8-inch silicon wafer using a spin coater so that the film thickness after drying was 5 μm. Then, it dried at 100 degreeC for 3 minutes with a hotplate, and obtained the photosensitive resin film. Using an i-ray stepper (NSR-4425i, manufactured by Nikon Corporation), while changing the exposure amount, a mask (test pattern No. 1: a residual pattern and a punching pattern with a width of 0.5 to 50 μm are drawn) made by TOPPAN INC. The photosensitive resin film was irradiated with i-rays. Then, using cyclopentanone as a developer, development was performed for 30 seconds, and it was rotated at 2500 revolutions for 10 seconds, and dried. Through the above steps, a through hole of 10 μmΦ can be opened in the resin film. That is, it was confirmed that a "pattern" can be formed by exposure using a mask.

This application claims priority based on Japanese Application No. 2020-121920 filed on Jul. 16, 2020 and Japanese Application No. 2021-113582 filed on Jul. 8, 2021, and discloses the same All content referenced here.

1: Substrate 3: Photosensitive resin film 3A: Resin film 5: Opening 10: Stage difference 11: Cu rewiring 20: Photomask

[FIG. 1] It is a figure for demonstrating the manufacturing method of an electronic device.

1: Substrate

3: Photosensitive resin film

3A: Resin film

5: Opening

10: Stage difference

11: Cu rewiring

20: Photomask

Claims (13)

A photosensitive resin composition, which is a thermosetting photosensitive resin composition for permanent film formation, and Contains resin and sensitizer, The number of particles with a diameter of 0.5 to 20 μm counted by a particle counter using a light scattering method of light having a wavelength of 780 nm in one minute of measurement at a flow rate of 3 g/min was 100 or less. The photosensitive resin composition of claim 1, wherein, The aforementioned resin contains one or two or more selected from the group consisting of epoxy resins, polyimide resins, and polyimide resins. The photosensitive resin composition according to claim 1 or 2, wherein the resin contains a structural unit represented by the following general formula (PA-1) and/or a structural unit represented by the following general formula (PI-1),

In the general formulae (PA-1) and (PI-1), X is a divalent organic group, and Y is a tetravalent organic group. The photosensitive resin composition of claim 3, wherein, In the aforementioned general formulae (PA-1) and (PI-1), at least one of X and Y is a group containing a fluorine atom. The photosensitive resin composition of claim 1 or 2, wherein, The aforementioned photosensitizer contains a photocationic polymerization initiator. The photosensitive resin composition according to claim 1 or 2, which further contains a phenoxy resin. The photosensitive resin composition according to claim 1 or 2, which further contains an adhesion assistant. The photosensitive resin composition of claim 1 or 2 is negative type. The photosensitive resin composition of claim 1 or 2 is of a chemically amplified type. The photosensitive resin composition according to claim 1 or 2, which is used to form a permanent film provided in contact with a metal member. A method of manufacturing an electronic device, comprising: A film forming step, using the photosensitive resin composition of any one of claims 1 to 9 to form a photosensitive resin film; an exposure step, exposing the photosensitive resin film; and In the developing step, the exposed photosensitive resin film is developed. An electronic device provided with a permanent film formed of the photosensitive resin composition of any one of claims 1 to 9. A method for producing a photosensitive resin composition, which is the method for producing a photosensitive resin composition according to any one of claims 1 to 9, and includes a filtration step through a hollow fiber membrane filter having a pore size of 0.5 μm or less .

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