JP2018173473A - Photosensitive resin composition, electric/electronic apparatus having cured film of photosensitive resin composition, and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition that is sufficiently cured in a treatment condition of a relatively low temperature (about 200°C) and can give a cured film having good mechanical properties under the treatment condition.SOLUTION: A photosensitive resin composition used for forming a cured film constituting an electric/electronic apparatus contains (A) an alkali-soluble resin, (B) a photoacid generator, (C) a crosslinking agent, (D) a heat acid generator and (E) an organic solvent and has an exothermic peak in a temperature region of 130 to 240°C in a DTA curve obtained by differential thermal analysis at a programming rate of 10°C/min by use of a mixture produced by uniformly mixing 100 pts.mass of the alkali-soluble resin (A), 30 pts.mass of the crosslinking agent (C) and 10 pts.mass of the heat acid generator (D) as a measurement target.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin composition, an electric / electronic device provided with a cured film of the photosensitive resin composition, and a manufacturing method thereof.

  In the production of electrical and electronic equipment, photosensitive resin compositions are sometimes used and are being actively studied. The photosensitive resin composition typically becomes a permanent film such as an interlayer film or a surface protective film after being cured by heat treatment (Patent Document 1, etc.).

International Publication No. 2013/088852

With the miniaturization, complexity, and diversification of electrical and electronic equipment, various characteristics are required for photosensitive resin compositions. For example, from the viewpoint of protection of electric / electronic devices, a photosensitive resin composition that is sufficiently cured by heat treatment at a relatively low temperature (about 200 ° C.) may be required. In addition, there is a case where a cured film having good mechanical properties such as stretchability is required instead of simply curing. Furthermore, both curability at a relatively low temperature and good mechanical properties of the cured film may be required.
However, it is not always easy to design a photosensitive resin composition that can be cured at a relatively low temperature and that has a good mechanical property of a cured film cured under a low temperature condition. Specifically, when a photosensitive resin composition is designed with priority given to ease of curing at low temperatures, the mechanical properties (stretchability, etc.) of the finally obtained cured film tend to be inferior. On the other hand, when a photosensitive resin composition is designed giving priority to good mechanical properties, it tends to be difficult to appropriately cure the photosensitive resin composition under low temperature conditions.

  The present invention has been made in view of such circumstances. That is, the present invention provides a photosensitive resin composition that can be sufficiently cured under relatively low temperature (about 200 ° C.) processing conditions and can obtain a cured film having good mechanical properties under the processing conditions.

  The present inventors diligently studied to solve the above problems. As a result, in the photosensitive resin composition containing the alkali-soluble resin (A), the photoacid generator (B), the crosslinking agent (C), the thermal acid generator (D), and the organic solvent (E), the composition Of a DTA curve obtained when differential thermal analysis (DTA) of a mixture of only the alkali-soluble resin (A), the crosslinking agent (C) and the thermal acid generator (D) used in the product is performed. The present inventors have found that a composition having a peak position within a specific temperature range solves the above-mentioned problems, and has completed the present invention.

According to the present invention,
Alkali-soluble resin (A),
Photoacid generator (B),
Cross-linking agent (C),
Thermal acid generator (D) and organic solvent (E)
Containing
10 ° C. using a mixture in which 100 parts by mass of the alkali-soluble resin (A), 30 parts by mass of the cross-linking agent (C), and 10 parts by mass of the thermal acid generator (D) are uniformly mixed. A photosensitive resin composition is provided in which a DTA curve obtained by differential thermal analysis at a rate of temperature increase per minute has an exothermic peak in the temperature range of 130 to 240 ° C.

Moreover, according to the present invention,
An electric / electronic device provided with a cured film of the above-described photosensitive resin composition is provided.

Furthermore, according to the present invention,
A step of providing the photosensitive resin composition described above on a substrate;
A step of heating and drying the photosensitive resin composition to obtain a photosensitive resin film;
Exposing the photosensitive resin film with actinic rays;
Developing the exposed photosensitive resin film to obtain a patterned resin film; and heating the patterned resin film to obtain a cured film;
A method for manufacturing an electrical / electronic device is provided.

  According to the present invention, there is obtained a photosensitive resin composition that can be sufficiently cured under relatively low temperature (about 200 ° C.) processing conditions and obtain a cured film having good mechanical properties (such as stretchability) under the processing conditions. be able to.

Hereinafter, embodiments will be described.
Note that the notation “a to b” represents “a” to “b” unless otherwise specified. In addition, in the description of groups (atomic groups) in this specification, the description that does not indicate substitution or non-substitution includes both those having no substituent and those having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The photosensitive resin composition according to the present embodiment is a photosensitive resin composition used for forming a cured film constituting an electric / electronic device, and includes an alkali-soluble resin (A), a photoacid generator (B), Contains a crosslinking agent (C), a thermal acid generator (D) and an organic solvent (E), 100 parts by mass of an alkali-soluble resin (A), 30 parts by mass of a crosslinking agent (C), and 10 parts by mass of A DTA curve obtained by differential thermal analysis at a heating rate of 10 ° C./min using a mixture in which the thermal acid generator (D) is uniformly mixed as a measurement target has an exothermic peak in a temperature range of 130 to 240 ° C. It is an adhesive resin composition.
Here, the DTA curve preferably has an exothermic peak in a temperature range of 172 to 230 ° C. from the viewpoint of further enhancing the effects of the present invention. Here, the “exothermic peak” means that if the DTA curve is recognized to have a plurality of maximums, the highest peak among the plurality of maximums is set as the “exothermic peak”, and the exothermic peak is 130 to 240. It needs to be in the region of ° C.

  The reason why a photosensitive resin composition satisfying the above parameters is sufficiently cured at a relatively low temperature (around 200 ° C.) and a cured film having good mechanical properties under the processing conditions is not necessarily clear. There is not, but it is guessed as follows.

  As one method for realizing curing by heating at a relatively low temperature (around 200 ° C.), a method of adding a thermal acid generator (D) to the photosensitive resin composition can be considered. This is because additional acid is generated by heating and the curing reaction can be accelerated.

  However, it is necessary to prepare a photosensitive resin composition that can be cured at a relatively low temperature (around 200 ° C.) and obtain a cured film having good mechanical properties under the curing conditions, and to generate a suitable thermal acid. In general, it is difficult to select an agent or the like. The reason for this is that, according to the inventor's thought, the ease of the curing reaction and the mechanical properties of the finally obtained cured film are such that the thermal acid generator (D) itself is susceptible to acid generation and the acid generated. It is not determined only by the acid strength of the resin, but may be a complex one determined by the “correlation” between the thermal acid generator and the resin or crosslinking agent in the resin film.

Based on the above idea, the present inventor, when using the thermal acid generator (D), achieves both curing at a relatively low temperature (around 200 ° C.) and good mechanical properties under the curing conditions. Various indicators for preparing possible compositions were investigated. As a result of the examination,
(I) “A DTA curve obtained when a mixture of an alkali-soluble resin (A), a crosslinking agent (C) and a thermal acid generator (D) used in the composition is subjected to differential thermal analysis, as defined in the present invention `` Peak exothermic peak position '' as an index,
(Ii) specifying a combination of an alkali-soluble resin (A), a crosslinking agent (C) and a thermal acid generator (D) whose index (temperature) is within a specific range, and such an alkali By preparing (selecting) the composition using the soluble resin (A), the crosslinking agent (C) and the thermal acid generator (D), a composition capable of solving the problems of the present invention can be obtained. I found it.

The reason why the problem of the present invention can be solved by using the thermal acid generator (D) and the like and setting the “exothermic peak position of the DTA curve” defined in the present invention within a specific range is considered as follows. It is done.
The exothermic peak position of the DTA curve of the mixture of the alkali-soluble resin (A), the crosslinking agent (C) and the thermal acid generator (D) used in the composition is the thermal decomposition of the thermal acid generator (D) “single”. It is considered that the behavior of the thermal acid generator (D) in “in the resin film” is reflected instead of the ease. That is, the exothermic peak position of the DTA curve is considered to be one index for visualizing and quantifying the above-mentioned “correlation”. By setting such an index within a certain numerical range, there is a “balance” between curing at a relatively low temperature (around 200 ° C.) and obtaining a film having good mechanical properties under the processing conditions. It can be taken.

It supplements about said "balance".
In order to obtain a film that is sufficiently cured even at a relatively low temperature (around 200 ° C.), curing (crosslinking reaction) by the acid generated from the thermal acid generator tends to proceed, that is, the photosensitivity of the crosslinking reaction is “fast”. It is considered necessary to design a resin composition. However, if the speed of the cross-linking reaction is too fast, the cross-linking reaction in the film tends to proceed “locally”. If it does so, uniform hardening (crosslinking reaction) will not be performed in the whole film | membrane, but the mechanical physical property of a cured film will become a bad thing. That is, for solving the problems of the present invention, the speed of the cross-linking reaction is “moderately fast”, and the speed of the cross-linking reaction (curability at low temperature) and the uniform curing throughout the film are highly compatible. It may be necessary to design the composition.

  As described above, the exothermic peak position of the DTA curve defined in the present invention is an index representing the “correlation” between the thermal acid generator and the resin or crosslinking agent in the resin film. Therefore, when a photosensitive resin composition is prepared by selecting a combination of an alkali-soluble resin, a crosslinking agent and a thermal acid generator so that the exothermic peak position is within a specific temperature range, a curing temperature of about 200 ° C. is obtained. It is considered that both the speed of the crosslinking reaction and the uniform curing of the entire film can be achieved.

In order to set the exothermic peak position of the DTA curve defined in the present invention within a specific temperature range, the combination of the alkali-soluble resin (A), the crosslinking agent (C) and the thermal acid generator (D) is appropriate. Select each component as follows. The guidelines for selecting more specific components are as follows.
Alkali-soluble resin (A): Appropriate selection of resin structure, molecular weight, density of sites capable of reacting with the crosslinking agent (C), glass transition temperature, mass average molecular weight, etc. Crosslinking agent (C): site to be crosslinked (crosslinking The chemical structure and reactivity of the functional group) and the number of crosslinkable groups per molecule (functional group number) should be selected appropriately. Thermal acid generator (D): Thermal decomposability (thermal stability), acid generated By appropriately adjusting these, the exothermic peak position of the DTA curve defined in the present invention is within a specific temperature range (130 to 240 ° C., preferably 172 to 230). The photosensitive resin composition containing a combination of the alkali-soluble resin (A), the crosslinking agent (C) and the thermal acid generator (D) at a temperature of ° C), and further these components can be obtained.

The DTA curve can be obtained, for example, by the measurement method described in the examples described later.
In addition, when the photosensitive resin composition contains, for example, two kinds of alkali-soluble resins (a1 and a2) by equal mass, a sample for differential heat measurement is obtained by using 50 parts by mass of a1 and a2, respectively. The same applies to the other components.

  Further, in the photosensitive resin composition, the 5% mass reduction temperature of a cured film obtained by heat treatment at 200 ° C. for 60 minutes is preferably 300 ° C. or higher, and 300 ° C. or higher and 400 ° C. or lower. Is more preferable. By designing the photosensitive resin composition so as to obtain such a cured film, deterioration can be suppressed even when the cured film is exposed to severe conditions such as high temperature and high humidity.

Moreover, it is preferable that the glass transition temperature of the cured film obtained by heat-processing the photosensitive resin composition on 200 degreeC and the conditions for 60 minutes is 200 degreeC or more, and it is more preferable that it is 200-300 degreeC.
A glass transition temperature of 200 ° C. or higher means that the temperature cycle reliability is high, that is, the cured film is stable against repeated heating / falling, and the reliability of electric / electronic equipment. Contributes to improvement.
In general, a high glass transition temperature means that the resin structure is rigid and the mechanical properties (elongation, etc.) are poor. However, in the present embodiment, as described above, it is considered that the entire film is uniformly cured. As a result, it is considered that good mechanical properties can be obtained while achieving a high glass transition temperature.

  As described above, the photosensitive resin composition includes an alkali-soluble resin (A), a photoacid generator (B), a crosslinking agent (C), a thermal acid generator (D), and an organic solvent (E). Moreover, you may contain another arbitrary component. In the present embodiment, the photosensitive resin composition has, for example, a varnish shape. Hereinafter, each of these components will be described.

<Alkali-soluble resin (A)>
The photosensitive resin composition according to the present embodiment contains an alkali-soluble resin (A) (hereinafter also referred to as component (A) or the like). Examples of the alkali-soluble resin (A) include phenol resins, hydroxystyrene resins, acrylic / methacrylic resins, cyclic olefin resins, precursors having amide bonds such as polybenzoxazole precursors and polyimide precursors, and the precursors. Examples thereof include resins obtained by dehydrating and ring-closing the body. Two or more alkali-soluble resins (A) may be mixed and used.

  In this embodiment, it is desirable that the alkali-soluble resin (A) includes a phenol resin. Thereby, the further improvement of the mechanical physical property (stretchability etc.) of a cured film can be anticipated. When the alkali-soluble resin (A) contains a phenol resin, the content of the phenol resin with respect to the total amount of the alkali-soluble resin (A) is preferably 50% by mass or more, more preferably 75% by mass or more, and further preferably 90% by mass or more. Preferably, it is 100 mass%, and it is especially preferable. By doing so, the effect expected from the phenol resin is sufficiently exhibited.

  Specific examples of the phenol resin include novolac type phenol resins such as phenol novolac resin, cresol novolac resin, bisphenol novolac resin, phenol-biphenyl novolac resin; phenol compounds such as novolac type phenol resin, resol type phenol resin, cresol novolac resin and the like. Reaction product with aldehyde compound; reaction product of phenol compound such as phenol aralkyl resin and dimethanol compound.

  Among these, the phenol resin preferably contains one or more selected from a reaction product of a phenol compound and an aldehyde compound and a reaction product of a phenol compound and a dimethanol compound.

  The phenol compound used for the reaction product of the phenol compound and the aldehyde compound or the reaction product of the phenol compound and the dimethanol compound is not limited. Specific examples of the phenol compound include cresols such as phenol, o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, Xylenols such as 3,4-xylenol and 3,5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol and p-ethylphenol; alkylphenols such as isopropylphenol, butylphenol and p-tert-butylphenol Polyhydric phenols such as resorcinol, catechol, hydroquinone, pyrogallol and phloroglucinol; biphenyl phenols such as 4,4′-biphenol; These may use only 1 type and may use 2 or more types together.

  Moreover, the aldehyde compound used for the reaction material of a phenol compound and an aldehyde compound is not specifically limited. Specific examples include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, salicylaldehyde and the like. These may use only 1 type and may use 2 or more types together.

  Moreover, the dimethanol compound used for the reaction material of a phenol compound and a dimethanol compound is not specifically limited. Specifically, 1,4-benzenedimethanol, 1,3-benzenedimethanol, 4,4′-biphenyldimethanol, 3,4′-biphenyldimethanol, 3,3′-biphenyldimethanol, 2, Dimethanol compounds such as 6-naphthalenediethanol and 2,6-bis (hydroxymethyl) -p-cresol; 1,4-bis (methoxymethyl) benzene, 1,3-bis (methoxymethyl) benzene, 4,4 Bis (alkoxymethyl) compounds such as' -bis (methoxymethyl) biphenyl, 3,4'-bis (methoxymethyl) biphenyl, 3,3'-bis (methoxymethyl) biphenyl, methyl 2,6-naphthalenedicarboxylate Or 1,4-bis (chloromethyl) benzene, 1,3-bis (chloromethyl) benzene, 1,4-bis (bromomethyl) Benzene, 1,3-bis (bromomethyl) benzene, 4,4′-bis (chloromethyl) biphenyl, 3,4′-bis (chloromethyl) biphenyl, 3,3′-bis (chloromethyl) biphenyl, 4, Bis (hargenoalkyl) compounds such as 4′-bis (bromomethyl) biphenyl, 3,4′-bis (bromomethyl) biphenyl or 3,3′-bis (bromomethyl) biphenyl, 4,4′-bis (methoxymethyl) And biphenyl aralkyl compounds such as biphenyl and 4,4′-bis (methoxymethyl) biphenyl. These may use only 1 type and may use 2 or more types together.

  In the present embodiment, as one aspect, the alkali-soluble resin (A) preferably contains a phenol resin having a biphenyldiyl skeleton in the molecule. More specifically, the alkali-soluble resin (A) preferably contains a phenol resin having a structural unit represented by the following general formula (1). This can be expected to further improve the mechanical properties (such as stretchability) of the cured film.

In general formula (1),
R ¹ , R ² and R ³ each independently represent a halogen atom, a carboxyl group, a hydroxyl group, an aliphatic group which may have an unsaturated bond, or an alicyclic group which may have an unsaturated bond And at least one group selected from the group consisting of aromatic groups.
p and q are each independently an integer of 0 to 4.
r is an integer of 0-3.
When p is 2 or more, each R ¹ may be the same or different.
When q is 2 or more, each R ² may be the same or different.
When r is 2 or more, each R ³ may be the same or different.

The preferable carbon number of the aliphatic group which may have an unsaturated bond of R ¹ , R ² and R ³ is 1-10. ^Further, R 1, ^{R 2} and of ^{R 3,} preferred carbon number of good alicyclic group which may have an unsaturated bond is 3 to 10. ^Further, preferable number of carbon atoms of the aromatic group of R 1, ^{R 2} and ^{R 3} are 6-20. The hydrogen atom contained in these aliphatic group, alicyclic group and aromatic group may be substituted with a substituent. Examples of the substituent include a halogen atom, a carboxyl group, and a hydroxyl group.

R ¹ , R ² and R ³ are preferably any one of hydrogen, fluorine, a methyl group and a trifluoromethyl group. Moreover, in General formula (1), it is preferable that the biphenyldiyl structure is connected in the 4,4-position. By satisfying these, the mechanical properties (stretchability, etc.) of the cured film can be improved.

  When the phenol resin has a structural unit represented by the general formula (1), the content of the structural unit of the general formula (1) in the entire phenol resin is preferably 20% by mass or more, and more preferably 30% by mass or more. . As an upper limit, all structural units (that is, 100%) in the phenol resin may be structural units of the general formula (1). Thereby, the mechanical properties of the cured film can be further improved.

  The weight average molecular weight of the alkali-soluble resin (A) is typically 1000 to 100,000, preferably 2000 to 50000, more preferably 3000 to 30000. By setting this numerical value range, the solubility in an organic solvent (E) described later and the solubility in a developer can be improved, and the mechanical properties of the cured film can be improved. it can. Further, the molecular weight distribution of the alkali-soluble resin (A) is typically 1.2 to 7, preferably 1.2 to 4, and more preferably 1.2 to 2. By making it into this numerical range, it can be expected to improve the resolution of the photosensitive resin composition.

<Photoacid generator (B)>
The photosensitive resin composition according to the present embodiment contains a photoacid generator (B), that is, a compound that generates an acid upon irradiation with actinic rays.
Specific examples of the photoacid generator (B) include photosensitive diazoquinone compounds, onium salts (sulfonium salts, iodonium salts, etc.), sulfonic acid ester compounds, oxime sulfonate compounds, diazodisulfone compounds, 2-nitrobenzyl ester compounds, N-iminosulfonate compounds, imidosulfonate compounds, 2,6-bis (trichloromethyl) -1,3,5-triazine compounds, dihydropyridine compounds and the like can be mentioned. In the present specification, photoacid generators having an oxime sulfonate structure are classified as “oxime sulfonate compounds”, not “sulfonic acid ester compounds”.
Only 1 type may be used for a photo-acid generator (B), and 2 or more types may be used together.

  When the photosensitive resin composition is a positive type (the exposed portion dissolves when developed with an alkali developer after pattern exposure), the photoacid generator (B) includes a diazoquinone compound as one embodiment. As a result, a positive pattern with good sensitivity and resolution can be obtained. Further, a diazoquinone compound and an onium salt (such as a triarylsulfonium salt or a sulfonium borate salt) may be used in combination.

  As a diazoquinone compound, 1 type, or 2 or more types of compounds can be used among the things shown below, for example.

In each of the above diazoquinone compounds, Q is any one of the structures represented by the following formula (a), the following formula (b), and the following formula (c), or a hydrogen atom. However, at least one of Q of each diazoquinone compound is one of structures represented by the following formula (a), the following formula (b), and the following formula (c). Moreover, n is an integer of 1-5.
The Q of the diazoquinone compound preferably includes the following formula (a) or the following formula (b). Thereby, the transparency of the photosensitive resin composition can be improved. Therefore, the appearance of the photosensitive resin composition can be improved.

  The content of the photoacid generator (B) in the photosensitive resin composition is preferably 1 to 30 parts by mass when the content of the alkali-soluble resin (A) in the composition is 100 parts by mass. 2 to 20 parts by mass is more preferable. Thereby, the photosensitive resin composition can be adjusted to a practically appropriate sensitivity.

<Crosslinking agent (C)>
The photosensitive resin composition according to the present embodiment contains a crosslinking agent (C). The crosslinking agent (C) typically has a group (crosslinkable group) that can react with the alkali-soluble resin (A). When a resin film is produced using the photosensitive resin composition of the present embodiment containing the crosslinking agent (C), patterned by exposure and development, and then cured by heating, the crosslinking agent (C) becomes an acid generator (B Crosslinks with the alkali-soluble resin (A) by the action of an acid generated from the above) or heat.

  The crosslinking agent (C) typically contains two or more crosslinkable groups in one molecule. Thereby, the crosslinked structure which connects the principal chains of alkali-soluble resin (A) is formed, and a resin film hardens | cures. The number of crosslinkable groups contained in one molecule of the crosslinking agent (C) is usually 2 to 8, preferably 2 to 6, and more preferably 2 to 4. By appropriately selecting this number, the crosslinked structure in the resin film can be controlled, and it can be expected to obtain a film having better mechanical properties. In addition, as a crosslinkable group, the reactive group which the compound of the below-mentioned (1)-(4) has is mentioned.

  Preferred examples of the crosslinking agent (C) include the following compounds (1) to (4). In addition, a crosslinking agent (C) may use only 1 type and may use multiple types together.

  (1) Crosslinking agent having alkoxymethyl group and / or methylol group: for example, benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone Hydroxymethylphenyl hydroxybenzoate, bis (hydroxymethyl) biphenyl, dimethylbis (hydroxymethyl) biphenyl, bis (methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxybenzene, bis (methoxymethyl) ) Diphenyl ether, bis (methoxymethyl) benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis (methoxymethyl) biphenyl, dimethyl Bis (methoxymethyl) biphenyl; commercial products include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (Mitsui Cytec Co., Ltd.), Nicalak MX-270, -280, -290, Nicalack MS-11, Nicalak MW-30, -100, -300, -390, -750 (manufactured by Sanwa Chemical Co., Ltd.) ), 1,4-bis (methoxymethyl) benzene, 4,4′-biphenyldimethanol, 4,4′-bis (methoxymethyl) biphenyl, commercially available 26DMPC, 46DMOC, DM-BIPC-F, DM- BIOC-F, TM-BIP-A (Asahi Organic Materials Co., Ltd.), DML-MBP C, DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, DML-OC, dimethylol-Bis-C, dimethylol-BisOC-P, DML-BisOC-Z, DML-BisOCHP-Z, DML-PFP, DML-PSBP, DML-MB25, DML-MTrisPC, DML-Bis25X-34XL, DML-Bis25X-PCHP, 2,6-dimethoxymethyl-4-t -Butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymer-p-cresol, TriML-P, TriML-35XL, TriML-TrisCR-HAP, HML-TPPHBA, HML-TPPHAP, HMOM- TPPH A, HMOM-TPHAP (manufactured by Honshu Chemical Industry Co.) and the like. In this embodiment, the mechanical properties (stretchability, etc.) of the film can be further improved by using a crosslinking agent having an alkoxymethyl group and / or a methylol group.

(2) Compound having an epoxy group: for example, n-butyl glycidyl ether, 2-ethoxyhexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether Glycidyl ether such as glycerol polyglycidyl ether, sorbitol polyglycidyl ether, glycidyl ether of bisphenol A (or F), glycidyl ester such as adipic acid diglycidyl ester, o-phthalic acid diglycidyl ester, 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexane) carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl (3,4 Epoxy-6-methylcyclohexane) carboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, dicyclopentanediene oxide, bis (2,3-epoxycyclopentyl) ether, and Daicel Corporation Alicyclic epoxy such as Celoxide 2021, Celoxide 2081, Celoxide 2083, Celoxide 2085, Celoxide 8000, Epolide GT401, 2,2 '-(((((1- (4- (2- (4- (oxirane-2- (Ilmethoxy) phenyl) propan-2-yl) phenyl) ethane-1,1-diyl) bis (4,1-phenylene)) bis (oxy)) bis (methylene)) bis (oxirane)) (e.g. Techmore VG3101L ( (Made by Printec Co., Ltd.)), Aliphatic polyglycidyl ether such as Epolite 100MF (manufactured by Kyoeisha Chemical Industry 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 Gerest)) and the like.
(3) Compound having an isocyanate group: for example, 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, 1,3-phenylene bismethylene diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, etc. Is mentioned.
(4) Compounds having a bismaleimide group: for example, 4,4′-diphenylmethane bismaleimide, phenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3′-dimethyl-5,5′-diethyl -4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, 4,4'-diphenyl ether bismaleimide, Examples include 4,4′-diphenylsulfone bismaleimide, 1,3-bis (3-maleimidophenoxy) benzene, 1,3-bis (4-maleimidophenoxy) benzene, and the like.

  Content of the crosslinking agent (C) in the photosensitive resin composition is 1-100 mass parts with respect to 100 mass parts of alkali-soluble resin (A), Preferably, it is 5-50 mass parts. By setting the content to 1 part by mass or more, a cured film having sufficient mechanical strength can be obtained, and by setting the content to 100 parts by mass or less, the stability of the photosensitive resin composition in the varnish state is improved. Can do.

<Thermal acid generator (D)>
The photosensitive resin composition according to this embodiment contains a thermal acid generator (D), that is, a compound that generates an acid by heating (more specifically, heating at about 200 ° C.). Since the composition contains a thermal acid generator (D), additional acid is generated when the film is thermally cured, and a sufficient amount of acid is secured, so that the entire film is cured more evenly (cross-linking). Reaction), and the mechanical properties of the cured film can be further enhanced. Moreover, using an appropriate amount of an appropriate thermal decomposable (thermal stable) thermal acid generator is an effective means for designing a composition in which the exothermic peak position of the DTA curve is within a predetermined temperature range. One. Only 1 type may be used for a thermal acid generator (D), and 2 or more types may be used together.

The thermal acid generator (D) is not particularly limited, and for example, onium salts (sulfonium salts, iodonium salts, etc.), sulfonic acid ester compounds, oxime sulfonate compounds, diazodisulfone compounds, and the like can be used. Among these, sulfonium salts and sulfonic acid ester compounds are preferable from the viewpoint of improving the mechanical properties of the cured film.
In the present specification, thermal acid generators having an oxime sulfonate structure are classified as “oxime sulfonate compounds”, not “sulfonic acid ester compounds”.

  As another viewpoint, the thermal acid generator (D) preferably includes a thermal acid generator having a naphthalene skeleton. More specifically, for example, an onium salt (sulfonium salt, iodonium salt) having a naphthalene skeleton in the cation portion can be given. The reason is unknown, but when the composition contains such a thermal acid generator (D), there is an effect that wrinkles are not generated in the cured film even when the obtained cured film is aged under high temperature and high humidity conditions. . Moreover, corrosion reduction of Si, Cu, Al, etc. on the semiconductor substrate can be expected.

  As another aspect, the acid generated from the thermal acid generator (D) is sulfonic acid, disulfonylimide acid, hexafluorophosphoric acid, fluoroantimonic acid, tetrafluoroboric acid, tetrakis (pentafluorophenyl) boric acid, etc. It is preferable that the acid has a relatively strong acid strength. By selecting such a thermal acid generator (D), curing (crosslinking reaction) can be ensured.

  Examples of the thermal acid generator (D) include the following compounds. In addition, these compounds are available through DSP Gokyo Food & Chemical Co., Ltd., Sanshin Chemical Co., Ltd., Wako Pure Chemical Industries, Ltd., Tokyo Chemical Industry Co., Ltd., etc., for example.

  The content of the thermal acid generator (D) in the photosensitive resin composition is 0.1 to 50 parts by mass, preferably 1 to 20 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (A). It is. When the composition contains the thermal acid generator (D) within the above range, the effect of the thermal acid generator (D) can be sufficiently obtained. In addition, the exothermic peak position of the DTA curve can be easily placed in a predetermined temperature range.

In the present embodiment, the photoacid generator (B) and the thermal acid generator (D) are separate compounds. One compound generates an acid upon irradiation with actinic rays (that is, has a function as a photoacid generator (B)) and also generates an acid upon heating (that is, a thermal acid generator (D)) In the present embodiment, a photosensitive resin composition is prepared using different compounds as the photoacid generator (B) and the thermal acid generator (D), respectively. .
In particular, when the photosensitive resin composition is a positive type, the composition contains the aforementioned diazoquinone compound as the photoacid generator (B), and an onium salt (sulfonium salt, iodonium salt) as the thermal acid generator (D). Etc.), a sulfonic acid ester compound, an oxime sulfonate compound and a diazodisulfone compound.

<Organic solvent (E)>
The photosensitive resin composition according to the present embodiment includes an organic solvent (E). That is, the photosensitive resin composition is obtained by dissolving or dispersing an alkali-soluble resin (A), an acid generator (B), a crosslinking agent (C) and the like in an organic solvent. Organic solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl 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-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate and methyl-3-methoxypro Pionate etc. are mentioned. Only one organic solvent may be used, or two or more organic solvents may be mixed and used.

  Content of the organic solvent (E) in the photosensitive resin composition is 50 mass parts-1000 mass parts with respect to 100 mass parts of alkali-soluble resin (A), Preferably it is 100 mass parts-500 mass parts. By using an organic solvent in the above range, a photosensitive resin composition having excellent handling properties in which each component is sufficiently dissolved can be produced. As another aspect, the organic solvent (E) is used in an amount such that the viscosity of the photosensitive resin composition is usually 100 to 1000 mPa · s, preferably 200 to 800 mPa · s.

<Silane coupling agent (F)>
The photosensitive resin composition according to the present embodiment may include a silane coupling agent (F). By including the silane coupling agent (F), when the resin film is formed on the substrate with the photosensitive resin composition, the adhesion between the resin film and the substrate is improved.

  Examples of the silane coupling agent (F) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3- Methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (amino Ethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane Methoxy Lan, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxypropyl) tetrasulfide, 3-isocyanate Examples thereof include, but are not limited to, propyltriethoxysilane, and silicon compounds obtained by reacting an amino group-containing silicon compound with an acid dianhydride or acid anhydride. Silane coupling agents can be used alone or in combination.

  The compounding quantity of the silane coupling agent (F) in the photosensitive resin composition is 0.1-30 mass parts with respect to 100 mass parts of alkali-soluble resin (A), Preferably, it is 1-20 mass parts. is there. By using the silane coupling agent (F) within the above range, both the adhesion to the substrate and the preservability of the photosensitive resin composition can be achieved.

<Surfactant (G)>
The photosensitive resin composition according to the present embodiment may contain a surfactant (G). By including the surfactant (G), the coating property when the photosensitive resin composition is applied onto a substrate to obtain a resin film is improved, and a coating film having a uniform thickness can be obtained. Further, it is possible to prevent residues and pattern floating when the coating film is developed. As the surfactant (G), a nonionic surfactant is particularly preferable.

  Examples of the surfactant (G) include a compound containing a fluorine-containing group (for example, a fluorinated alkyl group) or a silanol group, or a compound having a siloxane bond as a main skeleton. In the present embodiment, a nonionic fluorine-based surfactant or silicone-based surfactant is preferable. Examples of the fluorosurfactant include Megafac F-171, F-173, F-444, F-470, F-471, F-475, F-482, F-477, F manufactured by DIC Corporation. -554, F-556 and F-557, Sumitomo 3M Co., Ltd. Novec FC4430, FC4432 etc. are mentioned, However It is not limited to these.

  When using surfactant, as its content, 0.01-10 mass parts is preferable with respect to 100 mass parts of alkali-soluble resin (A).

<Reaction accelerator (H)>
The photosensitive resin composition according to the present embodiment may include a reaction accelerator (H). By including the reaction accelerator (H), crosslinking between the alkali-soluble resin (A) and the crosslinking agent can be promoted. Examples of the reaction accelerator (H) include a hetero five-membered ring compound containing nitrogen. Specific examples include pyrrole, pyrazole, imidazole, 1,2,3-triazole, and 1,2,4-triazole.

<Other additives>
If necessary, the photosensitive resin composition according to the present embodiment includes additives such as a dissolution accelerator, an antioxidant, a filler, a photopolymerization initiator, a terminal blocker, and a sensitizer. It may further be included within a range that does not impair.

<Preparation of photosensitive resin composition>
The method for preparing the photosensitive resin composition according to this embodiment is not particularly limited. A well-known method can be suitably employ | adopted according to the component which the photosensitive resin composition finally contains. For example, each of the above components can be prepared by mixing or dissolving or dispersing in the organic solvent (E). Thereby, a varnish-like photosensitive resin composition is obtained.

<Electrical and electronic equipment>
The electric / electronic device provided with the cured film of the photosensitive resin composition according to the present embodiment has high reliability because the cured film has good mechanical properties (such as expansion / contraction rate).
Here, “electrical / electronic device” means a semiconductor chip, a semiconductor element, a printed wiring board, an electric circuit, a display device such as a television receiver or a monitor, an information communication terminal, a light emitting diode, a physical battery, a chemical battery, etc. This refers to devices, devices, final products, and other equipment related to electricity that apply engineering technology.
The photosensitive resin composition according to the present embodiment can be cured sufficiently even at a relatively low temperature and can form a cured film having good mechanical properties. Therefore, it is suitable for electric / electronic devices including heat-sensitive elements. Is also preferably applicable.
In addition, the cured film of the photosensitive resin composition according to the present embodiment is applied as, for example, a protective film, an insulating film, a dam material, or the like in an electric / electronic device.

<Manufacturing method of electrical / electronic equipment>
The manufacturing method of the electric / electronic device provided with the cured film of the photosensitive resin composition according to the present embodiment will be described.
For example, the following steps:
A step of providing the above-described photosensitive resin composition on a substrate;
A step of heating and drying the photosensitive resin composition to obtain a photosensitive resin film;
Exposing the photosensitive resin film with actinic rays;
Developing the exposed photosensitive resin film to obtain a patterned resin film, and heating the patterned resin film to obtain a cured film;
Thus, an electric / electronic device provided with the cured film of the photosensitive resin composition according to the present embodiment can be manufactured.
When the above-described photosensitive resin composition is used, a cured film having good physical properties can be finally obtained, so that a highly reliable electric / electronic device can be obtained.

The process of providing the above-mentioned photosensitive resin composition on the substrate will be described.
The substrate is not particularly limited, and examples thereof include a silicon wafer, a ceramic substrate, an aluminum substrate, a SiC wafer, and a GaN wafer. The substrate includes, in addition to an unprocessed substrate, for example, a substrate on which a semiconductor element or a display element is formed. In order to improve adhesion, the substrate surface may be treated with an adhesion aid such as a silane coupling agent.
The step of providing the photosensitive resin composition can be performed by spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, an inkjet method, or the like.

A process of obtaining a photosensitive resin film by heating and drying the photosensitive resin composition (also referred to as a prebaking process) will be described.
The temperature for heat drying is usually 80 to 140 ° C, preferably 90 to 120 ° C. In particular, in the present embodiment, this temperature is preferably lower than the peak temperature of the exothermic peak in the above DTA curve. As another aspect, the temperature for heat drying is preferably 5 to 10 ° C lower than the peak temperature of the exothermic peak in the DTA curve, and more preferably 10 to 20 ° C. By carrying out like this, the crosslinking reaction before exposure can be suppressed and patterning property can be made favorable.
Moreover, the heat drying time is usually about 30 to 600 seconds, preferably about 30 to 300 seconds. By removing the solvent by this heat drying, a photosensitive resin film is formed. Heating is typically performed with a hot plate, oven, or the like. The thickness of the photosensitive resin film is preferably 1 to 500 μm.

The process of exposing the photosensitive resin film with actinic rays will be described.
As the actinic ray for exposure, for example, X-ray, electron beam, ultraviolet ray, visible ray and the like can be used. In terms of wavelength, an actinic ray of 200 to 500 nm is preferable. From the viewpoint of pattern resolution and handleability, the light source is preferably a g-line, h-line or i-line of a mercury lamp. Two or more light beams may be mixed and used. As the exposure apparatus, a contact aligner, mirror projection or stepper is preferable.
In addition, after the exposure, the photosensitive resin film may be heated again as necessary (post-exposure bake). The temperature is, for example, 80 to 150 ° C, preferably 90 to 120 ° C. The time is, for example, 30 to 600 seconds, preferably 30 to 300 seconds.

A process (developing process) of developing the exposed photosensitive resin film to obtain a patterned resin film will be described.
In the development step, development can be performed using a suitable developer, for example, by a method such as an immersion method, a paddle method, or a rotary spray method. By development, an exposed portion (in the case of a positive type) or an unexposed portion (in the case of a negative type) is eluted and removed from the coating film, and a patterned resin film can be obtained.

The developer that can be used is not particularly limited. For example, alkaline aqueous solution, more specifically, (i) inorganic alkaline aqueous solution such as sodium hydroxide, sodium carbonate, sodium silicate, ammonia, (ii) organic amine aqueous solution such as ethylamine, diethylamine, triethylamine, triethanolamine, (Iii) An aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide or tetrabutylammonium hydroxide may be used. An organic solvent such as cyclopentanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate can also be used.
For example, a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added to the developer.
As the developer, a tetramethylammonium hydroxide aqueous solution is preferable. The concentration of tetramethylammonium hydroxide in this aqueous solution is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass.

  After the development step, the developer is preferably removed by rinsing with a rinse solution. Thereby, a patterned resin film can be obtained. Examples of the rinsing liquid include distilled water, methanol, ethanol, isopropanol, and propylene glycol monomethyl ether. These can be used alone or in combination of two or more.

A process of obtaining a cured film by heating the patterned resin film will be described.
A cured film can be obtained by heating the patterned resin film obtained as described above. The heating temperature is typically about 150 to 400 ° C, but in the present embodiment, 160 to 300 ° C is particularly preferable, and 180 to 200 ° C is more preferable. By setting it as this temperature range, it is thought that the speed | rate of crosslinking reaction (curability at low temperature) and the uniform hardening in the whole film | membrane can be made to make highly compatible. Although heating time is not specifically limited, For example, it exists in the range of 15 to 300 minutes. This heat treatment can be performed by a hot plate, an oven, a temperature rising oven in which a temperature program can be set, or the like. The atmospheric gas for performing the heat treatment may be air or an inert gas such as nitrogen or argon. Moreover, you may heat under reduced pressure.

  As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are employable. Modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely with reference to an Example, this invention is not limited to an Example.

<Preparation of photosensitive resin composition>
About each of Examples 1-14 and Comparative Examples 1 and 2, the photosensitive resin composition was prepared as follows.
Each component blended according to Table 2 was stirred under a nitrogen atmosphere and then filtered through a polyethylene filter having a pore size of 0.2 μm to obtain a varnish-like photosensitive resin composition. The details of each component in the table are as follows. Moreover, the unit in a table | surface is a mass part.

・ Alkali-soluble resin (A)
A-1: Phenolic resin having the following structural units (weight average molecular weight: 11,000)

  A-2: Phenolic resin having the following structural units (100% of the structural units in the resin are the following structural units, weight average molecular weight: 10,000)

・光酸発生剤（Ｂ）
Ｂ−１：以下構造のジアゾキノン化合物
（Ｑは、水素原子、または、前掲の式（ａ）のジアゾ含有骨格である。）

・ Photoacid generator (B)
B-1: Diazoquinone compound having the following structure (Q is a hydrogen atom or a diazo-containing skeleton of the above formula (a)).

・ Crosslinking agent (C)
C-1: Compound having the following structure (Nikarak MX-270, manufactured by Sanwa Chemical Co., Ltd.)

・ Heat acid generator (D)
The compounds listed in Table 1 above were used.
・ Organic solvent (E)
E-1: γ-butyrolactone / silane coupling agent (F)
F-1: Compound having the following structure (KBM503 manufactured by Shin-Etsu Silicone Co., Ltd.)

・ Surfactant (G)
G-1: FC4430 manufactured by 3M Japan

<Measurement of exothermic peak>
The procedure was as follows. The following (1) and (2) were performed under a yellow lamp in order to prevent decomposition of the thermal acid generator.
(1) 100 parts by mass of the alkali-soluble resin used in the compositions of Examples and Comparative Examples, 30 parts by mass of the crosslinking agent, and 10 parts by mass of the thermal acid generator were weighed. For example, in Example 1, 100 parts by mass of the alkali-soluble resin A-1, 30 parts by mass of the crosslinking agent C-1, and 10 parts by mass of the thermal acid generator D-1 were weighed.
(2) Each component weighed above was uniformly mixed in a mortar to obtain a sample for exothermic peak measurement.
(3) About 5 mg of the sample obtained above was subjected to DTA measurement using a TG / DTA apparatus (STA7200RV, manufactured by Hitachi High-Tech Science Co., Ltd.) to obtain a chart.
The measurement conditions are 30 to 400 ° C. (temperature increase at 10 ° C./min), nitrogen = 200 mL / min.

<Production of cured film>
A cured film for evaluation was obtained by the following procedure.
(1) The composition was applied onto a 6 inch silicon wafer using a spin coater.
(2) Prebaked at 120 ° C. for 3 minutes on a hot plate to obtain a resin film having a thickness of about 10 to 12 μm.
(3) The mixture was put in a heating oven, heated from room temperature to 200 ° C. at 5 ° C./min while flowing nitrogen, and then directly heated at 200 ° C. for 60 minutes. Then, it cooled to room temperature.

<Evaluation of elongation>
The wafer with a cured film obtained by the above procedure is cut into a width of 4.5 mm and a length of 9 cm with a dicing machine, and then the film is peeled off from the silicon wafer in a 2% hydrofluoric acid aqueous solution and washed with pure water. And dried at 60 ° C. for 10 hours to obtain a test piece.
The obtained test piece was set on a tensile tester (Orientec Co., Ltd., Tensilon RTC-1210A) so that the distance between chucks was 20 mm, and then a tensile test was performed at 23 ° C. and 5 mm / min. The tensile elongation of the test piece was calculated from the following formula.
Tensile elongation (%) = {(distance between chucks at break / distance between initial chucks) -1} × 100
The tensile elongation is preferably a high value from the viewpoint of preventing the film from cracking in the electric / electronic device.
The stretch rate was evaluated five times. The average value of 20% or more was ◎ (particularly good), the one that was 10% or more and less than 20% was ◯ (good), greater than 0% and less than 10% What was was made into x (bad).

<Evaluation of glass transition temperature of cured film>
In the same manner as in the above <Evaluation of elongation>, a test piece having a width of 4.5 mm × a length of 9 mm or more was obtained from the cured film. About this test piece, the glass transition temperature was calculated | required by the thermomechanical analysis (TMA, apparatus: Seiko Instruments Inc. TMA / SS6000).
Measurement: 1st run: 30 ° C. to 160 ° C. (temperature increase 10 ° C./min) 2nd run: 160 ° C. to 10 ° C. (temperature decrease 10 ° C./min) 3rd run: 10 ° C. to 400 ° C. (temperature increase 10 ° C./min) Min), nitrogen = 200 mL / min, and a load of 30 N. The inflection point was read from the curve data in the result of the 3rd run obtained and used as the glass transition temperature. A sample having a glass transition temperature of 200 ° C. or higher was evaluated as “good”, and a sample having a glass transition temperature of 100 ° C. or higher and lower than 200 ° C. was evaluated as “poor”.

<Evaluation of 5% mass reduction temperature>
The test piece was cut out from the cured film in the same manner as in the above <evaluation of expansion / contraction ratio>, and a measurement sample of about 10 mg was obtained. For this sample, using differential thermogravimetric simultaneous measurement device (manufactured by Hitachi High-Tech Science Ltd. STA7200RV), it was measured 5% thermal mass loss temperature (Td _5).
The measurement conditions were 30 to 700 ° C. (temperature increase at 10 ° C./min) and Air = 200 mL / min.
In order to eliminate the influence of moisture in the film, the mass at 100 ° C. was recorded, and the temperature when the mass decreased by 5% was defined as Td ₅ .

<Evaluation of film appearance after high temperature and high humidity test>
The procedure was as follows.
(1) A photosensitive resin composition of each example and comparative example using a spin coater on each of a silicon substrate, a substrate on which a silicon substrate is coated with Cu, and a substrate on which a silicon substrate is coated with Al. Was applied.
(2) Each substrate was pre-baked at 120 ° C. for 3 minutes on a hot plate to obtain a resin film having a thickness of 10 to 12 μm.
(3) The resin film obtained above is put into a heating oven together with the substrate, heated from room temperature to 200 ° C. at 5 ° C./min while flowing nitrogen, and then subjected to heat treatment at 200 ° C. for 60 minutes as it is, Cooled to room temperature to obtain a cured film.
(4) The cured film obtained above was treated for 168 hours (one week) under the conditions of a temperature of 125 ° C., a humidity of 100%, and a pressure of 2.3 atm. This process is performed by Hastest Solutions Inc. PC-R8D.

After the treatment, the cured film was observed with an optical microscope and evaluated as follows.
○: Appearance of cured film is good △: Appearance of cured film is partially defective, but is not problematic for application to electronic / electronic equipment ×: Appearance of cured film is poor, to electronic / electronic equipment In addition, in this evaluation, in the same photosensitive resin composition, the evaluation with a silicon substrate, the evaluation with a substrate in which Cu is coated on the silicon substrate, and the surface coating with Al on the silicon substrate are performed. There was no significant difference between the evaluation with the substrate used.

As shown in the table above, by using the photosensitive resin composition according to the present embodiment, it is sufficiently cured under relatively low temperature (about 200 ° C.) processing conditions, and mechanical properties (elongation) under the processing conditions. However, an excellent cured film could be obtained. Moreover, it was shown that the glass transition temperature of the cured film is high and the temperature cycle reliability is high.
Furthermore, the film appearance after the high-temperature and high-humidity test was good particularly in the composition using a thermal acid generator having a naphthalene skeleton.

Claims (12)

A photosensitive resin composition used for forming a cured film constituting an electric / electronic device,
Alkali-soluble resin (A),
Photoacid generator (B),
Cross-linking agent (C),
Thermal acid generator (D) and organic solvent (E)
Containing
10 ° C. using a mixture in which 100 parts by mass of the alkali-soluble resin (A), 30 parts by mass of the cross-linking agent (C), and 10 parts by mass of the thermal acid generator (D) are uniformly mixed. The photosensitive resin composition in which the DTA curve obtained by the differential thermal analysis of the temperature increase rate of / min has an exothermic peak in the temperature range of 130-240 degreeC. The photosensitive resin composition according to claim 1,
The photosensitive resin composition whose 5% mass reduction | decrease temperature of the cured film obtained by heat-processing on 200 degreeC and the conditions for 60 minutes is 300 degreeC or more. The photosensitive resin composition according to claim 1 or 2,
The photosensitive resin composition in which the DTA curve has an exothermic peak in a temperature range of 172 to 230 ° C. It is the photosensitive resin composition of any one of Claims 1-3, Comprising:
A photosensitive resin composition in which the thermal acid generator (D) contains a sulfonium salt or a sulfonic acid ester compound. It is the photosensitive resin composition of any one of Claims 1-4, Comprising:
The photosensitive resin composition in which the thermal acid generator (D) includes a thermal acid generator having a naphthalene skeleton. It is the photosensitive resin composition of any one of Claims 1-5,
The photosensitive resin composition in which the alkali-soluble resin (A) contains a phenol resin. It is the photosensitive resin composition of any one of Claims 1-6, Comprising:
The photosensitive resin composition in which the alkali-soluble resin (A) includes a phenol resin having a biphenyldiyl skeleton in the molecule. It is the photosensitive resin composition of any one of Claims 1-7,
The photosensitive resin composition in which the said alkali-soluble resin (A) contains the phenol resin which has a structural unit represented by following General formula (1).

In general formula (1),
R ¹ , R ² and R ³ each independently represent a halogen atom, a carboxyl group, a hydroxyl group, an aliphatic group which may have an unsaturated bond, or an alicyclic group which may have an unsaturated bond And at least one group selected from the group consisting of aromatic groups.
p and q are each independently an integer of 0 to 4.
r is an integer of 0-3.
When p is 2 or more, each R ¹ may be the same or different.
When q is 2 or more, each R ² may be the same or different.
When r is 2 or more, each R ³ may be the same or different. It is the photosensitive resin composition of any one of Claims 1-8, Comprising:
The photosensitive resin composition in which the said crosslinking agent (C) contains the crosslinking agent which has an alkoxymethyl group and / or a methylol group.   The electrical / electronic device provided with the cured film of the photosensitive resin composition of any one of Claims 1-9. The process of providing the photosensitive resin composition of any one of Claims 1-9 on a board | substrate,
A step of heating and drying the photosensitive resin composition to obtain a photosensitive resin film;
Exposing the photosensitive resin film with actinic rays;
Developing the exposed photosensitive resin film to obtain a patterned resin film; and heating the patterned resin film to obtain a cured film;
A method for manufacturing an electric / electronic device. In the manufacturing method of the electric / electronic device according to claim 11,
The step of obtaining a photosensitive resin film by heating and drying the photosensitive resin composition is a step of drying by heating at a temperature lower than the peak temperature of the exothermic peak of the photosensitive resin composition. Production method.