JP7081138B2 - A negative photosensitive resin composition for forming a permanent film, a cured film of the composition, and an electric / electronic device provided with the cured film. - Google Patents

Description

The present invention relates to a negative photosensitive resin composition for forming a permanent film, a cured film of the composition, and an electric / electronic device provided with the cured film.

In the manufacture of electrical and electronic equipment, photosensitive resin compositions may be used to form permanent films (films that remain in final products). Specifically, various studies have been conducted on photosensitive resin compositions for forming permanent films (typically cured films) such as interlayer films, surface protective films, and dam materials (Patent Document 1).

Japanese Unexamined Patent Publication No. 2012-63788

The photosensitive resin composition can be broadly divided into a positive type, that is, a photosensitive resin composition in which the exposed portion dissolves when developed with an alkaline developer, and a negative type, that is, when developed with an alkaline developer or an organic solvent. There is a photosensitive resin composition in which an unexposed portion is dissolved. Here, in the negative type photosensitive resin composition, a cross-linking reaction occurs typically by the action of an acid (acid catalyst) or a radical generated by exposure in the resin film formed by the photosensitive resin composition, resulting in the result. , The resin film of the exposed part is insoluble (cured) in the developing solution.
When the cross-linking reaction is sufficiently advanced with the negative photosensitive resin composition, as a result, the adhesion between the cured film and the substrate is enhanced, and as a result, the reliability as a permanent film (reliability of the semiconductor device) is enhanced. Tend to be.

However, if the cross-linking reaction is sufficiently advanced, there is a problem that the resolution tends to decrease as a trade-off. This is because the cross-linking reaction is generally an acid-catalyzed reaction. That is, the cross-linking reaction proceeds by the diffusion of the acid generated from the photosensitive agent in the resin film formed of the negative photosensitive resin composition, but it is difficult to micro-control the "diffusion" of the acid. ..
For example, when the resin membrane is heated in order to sufficiently proceed the cross-linking reaction, the cross-linking reaction certainly proceeds. However, at the same time, the diffusion of acid in the resin film becomes active. Then, the acid diffuses to the unexposed area in the resin film. As a result, the cross-linking reaction proceeds even in the unexposed region of the resin film, and the resolution deteriorates.

In particular, in the recent production of electrical and electronic devices, compatibility between adhesion and resolution in a copper (Cu) substrate is required, but according to the knowledge of the present inventor, a conventional negative photosensitive resin composition is required. The product had insufficient performance in terms of both adhesion and resolution in a copper substrate.

The present invention has been made in view of such circumstances. That is, it provides a negative photosensitive resin composition for forming a permanent film, which can achieve both adhesion and resolution in a copper substrate.

The present inventor has diligently studied to solve the above problems. As a result, it has been found that the above-mentioned problems can be achieved by a negative photosensitive resin composition containing a compound having a nitrogen atom and a silanol group or a group that generates a silanol group by hydrolysis in one molecule. ..

According to the present invention
Phenol formaldehyde (A),
Photosensitizer (B),
A compound (D) containing a group having a cross-linking agent (C) and a nitrogen atom and a silanol group or a group that generates a silanol group by hydrolysis in one molecule.
Including
The photosensitive agent (B) contains a compound that generates an acid when irradiated with active light.
The nitrogen atom in the compound (D) is a negative photosensitive resin composition for forming a permanent film containing a nitrogen atom having a basicity capable of inactivating the acid .
The negative photosensitive resin composition is
(I) Only the phenol resin (A) is contained as the resin, or the resin is contained.
(Ii) The resin contains the phenol resin (A) and a resin (A') other than the phenol (A).
In the case of (ii), the content of the resin (A') is 0.1 to 50 parts by mass when the content of the phenol resin (A) is 100 parts by mass, which is a negative photosensitive resin composition. object
Is provided.

Further, according to the present invention, there is provided a cured film obtained by curing the above negative photosensitive resin composition.

Further, according to the present invention, an electric / electronic device provided with the above-mentioned cured film is provided.

According to the present invention, it is possible to obtain a negative photosensitive resin composition for forming a permanent film, which can achieve both adhesion and resolution in a copper substrate.
That is, according to the present invention, the negative photosensitive resin composition has sufficient adhesion even on a Cu substrate for which sufficient adhesion has not been obtained in the conventional negative photosensitive resin composition, and the resolution is also good. Can be obtained.

Hereinafter, embodiments will be described.
The notation "a to b" indicates a or more and b or less unless otherwise specified. Further, in the notation of a group (atomic group) in the present specification, the notation that does not indicate whether it is substituted or unsubstituted 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 negative photosensitive resin composition according to this embodiment is
Phenol formaldehyde (A),
Photosensitizer (B),
A compound (D) containing a group having a cross-linking agent (C) and a nitrogen atom and a silanol group or a group that generates a silanol group by hydrolysis in one molecule.
It is a negative type photosensitive resin composition for forming a permanent film containing.

The reason why the above-mentioned negative photosensitive resin composition can achieve both adhesion and resolution in a copper substrate is not always clear, but it is presumed as follows.
Due to the basicity of the nitrogen atom in the compound (D) (hereinafter, also simply referred to as compound (D)) containing a group having a nitrogen atom and a silanol group or a group that generates a silanol group by hydrolysis in one molecule. The acid (acid catalyst) generated from the photosensitizer (B) is inactivated. Then, in the resin film formed by the negative photosensitive resin composition, the acid is suppressed from diffusing to the unexposed region, and as a result, the resolving power is improved. In particular, the compound (D) has a silanol group or a group that generates a silanol group by hydrolysis, and since this group has a property of binding to a substrate or the like, a part of the compound (D) is "" in the resin film. "Fixed". That is, the compound (D) itself does not diffuse in the resin film. Then, the compound (D) can "ambush" the acid that tends to diffuse into the unexposed region in the resin film, and as a result, the diffusion of the acid is suppressed more effectively.
Further, it is considered that the compound (D) reacts with the copper substrate in the exposed portion to form a bond between the substrate and the resin film, and the adhesion to the substrate is improved.

Hereinafter, the components contained in or may be contained in the negative photosensitive resin composition according to the present embodiment will be described.

<Phenol resin (A)>
The negative photosensitive resin composition according to this embodiment contains a phenol resin (A).
The phenolic resin (A) has a structural unit derived from a phenol compound and at least one compound selected from the group consisting of an aldehyde compound, a dimethylol compound, a dimethoxymethyl compound and a dihaloalkyl compound. In other words, the phenol resin (A) is obtained by reacting a phenol compound with at least one compound selected from the group consisting of an aldehyde compound, a dimethylol compound, a dimethoxymethyl compound and a dihaloalkyl compound.
Specifically, as the phenol resin (A), a reaction product of a phenol compound such as phenol novolac resin, cresol novolak resin, bisphenol novolak resin, resole-type phenol resin, and an aldehyde compound; a phenol compound such as phenol aralkyl and phenol biphenyl aralkyl. And a reaction product with at least one compound selected from the group consisting of a dimethylol compound, a dimethoxymethyl compound and a dihaloalkyl compound. Only one kind of phenol resin (A) may be used, or two or more kinds may be used in combination.

Among these, the phenol resin (A) is one selected from a reaction product of a phenol compound and an aldehyde compound and a reaction product of a phenol compound and a compound selected from a dimethanol compound, a dimethoxymethyl compound, and a dihaloalkyl compound. It is preferable to contain two or more kinds.

The phenol compound is not limited to the phenol compound used in the reaction product of the phenol compound and the aldehyde compound or the reaction product of the phenol compound and the compound selected from the dimethanol compound, the dimethoxymethyl compound and the dihaloalkyl compound. Specifically, as the phenol compound, cresols such as phenol, o-cresol, m-cresol, 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, fluoroglucolcinol; biphenyl-based phenols such as 4,4'-biphenol. These may be used alone or in combination of two or more.

Further, the aldehyde compound used in the reaction product of the phenol compound and the aldehyde compound is not particularly limited. Specific examples thereof include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and salicylaldehyde. These may be used alone or in combination of two or more.

Further, the dimethanol compound, the dimethoxymethyl compound and the dihaloalkyl compound used in the reaction product of the phenol compound and the compound selected from the dimethanol compound, the dimethoxymethyl compound and the dihaloalkyl compound are not particularly limited. Specifically, 1,4-benzenedimethanol, 1,3-benzenedimethanol, 4,4'-biphenyldimethanol, 3,4'-biphenyldimethanol, 3,3'-biphenyldimethanol, 2, Dimethanol compounds such as 6-naphthalenedimethanol, 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, etc. , 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, 4,4'-bis (bromomethyl) biphenyl, 3,4'-bis (bromomethyl) Biphenyl or bis (hargenoalkyl) compounds such as 3,3'-bis (bromomethyl) biphenyl, biphenyl aralkyl compounds such as 4,4'-bis (methoxymethyl) biphenyl and 4,4'-bis (methoxymethyl) biphenyl And so on.

In the present embodiment, as one embodiment, it is preferable that the phenol resin (A) is a cresol novolac resin or a phenol novolac resin.
Further, as another embodiment, it is preferable that the phenol resin (A) contains at least one of the following structural units (i) to (iii).
(I) Structural unit having a biphenol skeleton (ii) Structural unit having a bisphenol skeleton (iii) Structural unit having a biphenyl skeleton

(I) More specifically, as the structural unit having a biphenol skeleton, a structural unit represented by the following general formula (A1) can be mentioned.

In the general formula (A1),
R ¹¹ and R ¹² each independently consist of a hydroxyl group, a halogen atom, a carboxyl group, an alkyl group, an alkenyl group, an alkyl ether group, a saturated or unsaturated alicyclic group and an organic group having an aromatic structure. It is a monovalent group selected from, and these may be bonded via an ester bond, an ether bond, an amide bond, or a carbonyl bond.
X ¹ and Y ¹ are independently selected from the group consisting of an aliphatic group which may have a single bond or an unsaturated bond, an alicyclic group and an organic group having an aromatic structure. It is the basis of the price. Here, Y ¹ is bonded to one of the two benzene rings.
p and q each independently represent an integer of 0 to 3.

The alkyl group, alkenyl group and alkyl ether group of R ¹¹ and R ¹² have preferably 1 to 20 carbon atoms.
The saturated or unsaturated alicyclic groups of R ¹¹ and R ¹² preferably have 3 to 20 carbon atoms.
The organic group having an aromatic structure of R ¹¹ and R ¹² preferably has 6 to 20 carbon atoms.
The aliphatic group which may have an unsaturated bond of X ¹ and Y ¹ has preferably 1 to 10 carbon atoms.
The alicyclic groups of X ¹ and Y ¹ preferably have 3 to 20 carbon atoms.
The preferred number of carbon atoms of the organic group having an aromatic structure of X ¹ and Y ¹ is 6 to 20.

(Ii) More specifically, as the structural unit having a bisphenol skeleton, a structural unit represented by the following general formula (A2) can be mentioned.

In the general formula (A2),
The R ²¹ is a group consisting of a hydroxyl group, a halogen atom, a carboxyl group, an alkyl group, an alkenyl group, an alkyl ether group, a saturated or unsaturated alicyclic group and an organic group having an aromatic structure independently of each other when there are a plurality of them. It is a monovalent group selected from, and these may be bonded via an ester bond, an ether bond, an amide bond, or a carbonyl bond.
X ² is at least one divalent group selected from an alkylene group, an alicyclic group, an aromatic group, an ether group, an ester group, a thioether group, a sulfide group and a carbonyl group.
Y ² and Z ² are divalently selected from the group consisting of an aliphatic group which may have a single bond or an unsaturated bond, an alicyclic group and an organic group having an aromatic structure, respectively. Is the basis of. Here, Z ² is bonded to one of the two benzene rings.
p and q each independently represent an integer of 0 to 3.

The alkyl group, alkenyl group and alkyl ether group of R ²¹ preferably have 1 to 20 carbon atoms.
The saturated or unsaturated alicyclic group of R ²¹ has preferably 3 to 20 carbon atoms.
The organic group having an aromatic structure of R ²¹ preferably has 6 to 20 carbon atoms.
The alkylene group of X ² may be linear or branched, and the preferred number of carbon atoms is 1 to 6.
The alicyclic group of X ² may be monocyclic or polycyclic, and the preferred number of carbon atoms is 3 to 12.
The preferred number of carbon atoms of the aromatic group of X2 is 6 to ²⁰ .
The aliphatic group which may have an unsaturated bond of Y ² and Z ² has preferably 1 to 10 carbon atoms.
The alicyclic groups of Y ² and Z ² preferably have 3 to 20 carbon atoms.
The organic group having an aromatic structure of Y ² and Z ² has a preferable carbon number of 6 to 20.

(Iii) More specifically, as the structural unit having a biphenyl skeleton, a structural unit represented by the following general formula (A3) can be mentioned.

In the general formula (A3),
R ³¹ , R ³² and R ³³ independently have a halogen atom, a carboxyl group, a hydroxyl group, an aliphatic group which may have an unsaturated bond, and 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 to 3.
When p is 2 or more, each R ³² may be the same or different.
When q is 2 or more, each R ³¹ may be the same or different.
When r is 2 or more, each R ³³ may be the same or different.
s is an integer from 1 to (5-r), preferably 1 or 2.

The aliphatic group which may have an unsaturated bond of R ³¹ , R ³² and R ³³ has preferably 1 to 10 carbon atoms.
The alicyclic group which may have unsaturated bonds of R ³¹ , R ³² and R ³³ has preferably 3 to 10 carbon atoms.
The aromatic groups of R ³¹ , R ³² and R ³³ have preferably 6 to 20 carbon atoms.
Hydrogen atoms contained in these aliphatic groups, alicyclic groups and aromatic groups may be substituted with substituents. Examples of the substituent include a halogen atom, a carboxyl group, a hydroxyl group and the like.

The R ³¹ , R ³² and R ³³ are preferably any of hydrogen, fluorine, a methyl group and a trifluoromethyl group. Further, in the general formula (A3), the biphenyldiyl structure is preferably connected at positions 4,4-. By satisfying these conditions, the mechanical properties (stretchability, etc.) of the permanent film can be improved.

When the phenol resin (A) contains at least one of the structural units (i) to (iii), the content of the structural units (i) to (iii) in the phenol resin (A) is not particularly limited. , (I) to (iii) are preferably 10 to 100 mol% in terms of surely obtaining the effect of the structural unit.

As the phenol resin (A), only one type may be used, or two or more types may be used in combination.
Further, the negative photosensitive resin composition according to the present embodiment may or may not contain a resin (A') other than the phenol resin (A). When the negative type photosensitive resin composition contains the resin (A'), the content thereof is 0.1 when the content of the phenol resin (A) in the negative type photosensitive resin composition is 100 parts by mass. It is about 50 parts by mass, preferably 0.1 to 20 parts by mass.

<Photosensitive agent (B)>
The negative photosensitive resin composition according to this embodiment contains a photosensitive agent (B).
As the photosensitive agent (B), an acid generator, that is, a compound that generates an acid by irradiation with an active light ray (for example, g-ray or i-ray) can be preferably mentioned.
Specifically, as the photosensitizer (B), a photosensitive diazoquinone compound, onium salt (sulfonium salt, iodonium salt, etc.), sulfonic acid ester compound, oxime sulfonate compound, diazodisulfone compound, 2-nitrobenzyl ester compound, N- Examples thereof include iminosulfonate compounds, imidesulfonate compounds, 2,6-bis (trichloromethyl) -1,3,5-triazine compounds, dihydropyridine compounds and the like.
As the photosensitive agent (B), only one type may be used, or two or more types may be used in combination.

In the present embodiment, the photosensitizer (B) preferably contains at least one compound selected from a triazine compound, a sulfonium salt, an iodonium salt and a sulfonic acid ester. By using any of these compounds as the photosensitive agent (B), a negative photosensitive resin composition having good storage stability and sufficiently high sensitivity for practical use can be obtained.

The photosensitizer (B) is a relatively acid whose generated acid is sulfonic acid, disulfonylimide acid, hexafluorophosphate, fluoroantimonic acid, tetrafluoroboric acid, tetrakis (pentafluorophenyl) boric acid and the like. It is preferably a strong acid. This makes it possible to further increase the sensitivity.

Further, in the present embodiment, as one aspect, it is also preferable to use a photosensitive agent represented by the following general formula (BI).
A ⁺ _XP- ⁽ BI)

In the general formula (BI),
A ⁺ represents a sulfonium cation or an iodonium cation.
^XP- _is an anion containing a disulfonylimide structure.

The A ⁺ sulfonium cation is preferably a triarylsulfonium cation, and more preferably a triphenylsulfonium cation. The aryl group or phenyl group of these cations may have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an arylthio group and the like.
The A ⁺ iodonium cation is preferably a diallyl iodonium cation, and more preferably a diphenyl iodonium cation. The aryl group or phenyl group of these cations may have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an arylthio group and the like.

Examples of the anion containing the disulfonylimide structure of XP ⁻ include the disulfonylimide ^anion represented by ₍ Rf _— SO2-) _2N− . Here, Rf is a fluorine atom or an organic group substituted with a fluorine atom (alkyl group (for example, 1 to 10 carbon atoms), cycloalkyl group (for example, 3 to 10 carbon atoms), aryl group (for example, 6 to 10 carbon atoms). ) Etc.). The plurality of Rfs may be the same or different.

Commercially available products of the photosensitizer (B) include, for example, CPI-100P, CPI-101A, CPI-200K, CPI-210S manufactured by San-Apro, and a photoacid generator manufactured by DSP Gokyo Food & Chemical Co., Ltd. Can be mentioned.

The content of the photosensitive agent (B) in the negative-type photosensitive resin composition is usually 0.1 to 20 when the content of the phenol resin (A) in the negative-type photosensitive resin composition is 100 parts by mass. It is by mass, preferably 0.1 to 10 parts by mass, and more preferably 1 to 5 parts by mass. Within this range, a sufficient amount of acid can be secured for the cross-linking reaction, and a permanent film can be stably obtained.

<Crosslinking agent (C)>
The negative photosensitive resin composition according to this embodiment contains a cross-linking agent (C). The cross-linking agent (C) typically has a group (cross-linking group) capable of forming a covalent bond between the phenol resin (A) and the cross-linking agent (C). Then, the cross-linking reaction proceeds due to the action of the acid generated from the photosensitive agent (B).

The cross-linking agent (C) typically contains two or more cross-linking groups in one molecule. As a result, a crosslinked structure is formed, and the resin film is cured (insoluble in the developing solution). The number of crosslinkable groups contained in one molecule of the crosslinker (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, so that the properties of the finally obtained cured film can be adjusted. Examples of the crosslinkable group include reactive groups contained in the compounds (1) to (5) described later.

Preferred cross-linking agent (C) includes, for example, the following compounds (1) to (5).
As the cross-linking agent (C), only one type may be used, or a plurality of types may be used in combination.

(1) Cross-linking agent having an alkoxymethyl group and / or a methylol group (-CH ₂ OH): for example, benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, Bis (hydroxymethyl) benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis (hydroxymethyl) biphenyl, dimethylbis (hydroxymethyl) biphenyl, bis (methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxy Benzene, bis (methoxymethyl) diphenyl ether, bis (methoxymethyl) benzophenone, methoxymethylbenzoate methoxymethylphenyl, bis (methoxymethyl) biphenyl, dimethylbis (methoxymethyl) biphenyl; as commercial products, Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (manufactured by Mitsui Cytec Co., Ltd.), Nicarac MX-270,- 280, -290, Nicarac MS-11, Nicarac 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 (manufactured by Asahi Organic Materials Industry Co., Ltd.) ), DML-MBPC, 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-diacetoximel-p-cresol, TriML-P, TriML-35XL, TriML-TrisCR-HAP, HML-TPPHBA, HML- TPHA P, HMOM-TPPHBA, HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.) and the like can be mentioned.

(2) Compounds 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. , Glycopolyglycidyl ether, sorbitol polyglycidyl ether, glycidyl ether such as 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) ) Alicyclic epoxy such as adipate, dicyclopentanediene oxide, bis (2,3-epoxycyclopentyl) ether, celoxide 2021, celoxide 2081, celoxside 2083, celoxide 2085, celoxide 8000, and epiride GT401 manufactured by Daicel Co., Ltd. , 2,2'-(((((1- (4- (2- (4- (oxylan-2-ylmethoxy) phenyl) propan-2-yl) phenyl) ether-1,1-diyl) bis (4) , 1-phenylene)) bis (oxy)) bis (methylene)) bis (oxylan)) (for example, Techmore VG3101L (manufactured by Printec Co., Ltd.)), Epolite 100MF (manufactured by Kyoeisha Chemical Industry Co., Ltd.), Epiol TMP Aliper polyglycidyl ether (manufactured by Nichiyu Co., Ltd.), 1,1,3,3,5,5-hexamethyl-1,5-bis (3- (oxylan-2-ylmethoxy) propyl) tri-siloxane (For example, DMS-E09 (manufactured by Gerest)) and the like can be mentioned.

(3) Compounds having an oxetanyl group: For example, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, bis [1-ethyl (3-oxetanyl)] methyl ether, 4,4'-. Bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl, 4,4'-bis (3-ethyl-3-oxetanylmethoxy) biphenyl, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, diethylene glycol Bis (3-ethyl-3-oxetanylmethyl) ether, bis (3-ethyl-3-oxetanylmethyl) diphenoate, trimethylolpropanetris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl- 3-Oxetanylmethyl) ether, poly [[3-[(3-ethyl-3-oxetanyl) methoxy] propyl] silaseskioxane] derivative, oxetanyl silicate, phenol novolac-type oxetane, 1,3-bis [(3-ethyl) Oxetane-3-yl) methoxy] benzene and the like can be mentioned.

(4) 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 and the like. Can be mentioned.

(5) Compounds having a bismaleimide group: For example, 4,4'-diphenylmethanebismaleimide, phenylmethanemaleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl. -4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, 4,4'-diphenyl ether bismaleimide, Examples thereof include 4,4'-diphenylsulphonbismaleimide, 1,3-bis (3-maleimidephenoxy) benzene, and 1,3-bis (4-maleimidephenoxy) benzene.

The content of the cross-linking agent (C) in the negative photosensitive resin composition is 1 to 100 parts by mass, preferably 20 to 70 parts by mass with respect to 100 parts by mass of the phenol resin (A). When the content is 1 part by mass or more, a cured film having sufficient mechanical strength can be obtained, and when the content is 100 parts by mass or less, the stability of the negative photosensitive resin composition in a varnish state can be improved. Can be enhanced.

<Compound (D) containing a group having a nitrogen atom and a silanol group or a group that generates a silanol group by hydrolysis in one molecule>
The negative photosensitive resin composition according to the present embodiment is a compound (D) containing a group having a nitrogen atom and a silanol group or a group that generates a silanol group by hydrolysis in one molecule (in the present specification). Simply referred to as compound (D)).

The group having a nitrogen atom of the compound (D) is preferably a group containing a structure represented by the following general formula (I) or a group containing a nitrogen-containing heterocyclic structure. As a result, it is possible to achieve both resolution and substrate adhesion at a higher level.
R ¹ R ² N- (I)
In the general formula (I), R ¹ and R ² independently represent a hydrogen atom, an alkyl group, an alicyclic group or an aryl group, respectively. R ¹ and R ² may be connected to each other to form a ring structure.
The alkyl groups of R ¹ and R ² may be linear or branched, preferably having 1 to 12 carbon atoms and more preferably 1 to 6 carbon atoms.
The alicyclic groups of R ¹ and R ² have preferably 3 to 20 carbon atoms.
The aryl group of R ¹ and R ² has preferably 6 to 20 carbon atoms.

When the group having a nitrogen atom of the compound (D) is a group having a structure represented by the general formula (I), it is preferable that at least one of R ¹ and R ² is not a hydrogen atom. That is, at least one of R ¹ and R ² is preferably an alkyl group, an alicyclic group or an aryl group. As a result, the basic strength of the compound (D) is optimized, so that it is possible to suppress a decrease in sensitivity while obtaining the effects of resolution and adhesion.

When the group having a nitrogen atom of the compound (D) is a group containing a nitrogen-containing heterocyclic structure, the nitrogen-containing heterocyclic structure is not particularly limited. For example, it may have an unsaturated structure or a saturated structure, and may have a monocyclic structure or a polycyclic structure. Further, the heterocycle may contain a heteroatom other than the nitrogen atom.

Examples of nitrogen-containing heterocyclic structures include pyrrolidine structure, piperidine structure, pyridine structure, azole structure, imidazole structure, pyrazole structure, oxazole structure, thiazole structure, imidazoline structure, pyrazine structure, morpholin structure, thiazine structure, and indole structure. , Isoindole structure, benzoimidazole structure, quinoline structure, isoquinoline structure, quinoxalin structure and the like. Among these, the pyridine structure is preferable. This is because the strength of basicity is optimal, and it is possible to suppress the decrease in sensitivity while obtaining the effects of resolution and adhesion.

The compound (D) preferably contains a compound represented by the following general formula (II). As a result, it is possible to achieve both resolution and substrate adhesion at a higher level.

In general formula (II),
RN represents a group having a ^nitrogen atom.
X represents a single bond or a divalent linking group.
R independently represents a hydrogen atom or a monovalent organic group.

Examples of the group having a ^nitrogen atom of RN include the above-mentioned group containing a structure represented by the general formula (I) or a group containing a nitrogen-containing heterocyclic structure, and the same applies to preferred embodiments.

Examples of the divalent linking group of X include an alkylene group, an alicyclic group, an aromatic group, an ether group, an ester group, a thioether group, a sulfide group, a carbonyl group, an amide group (-CONH-), and these. A group in which two or more of them are linked can be mentioned. The alkylene group may be linear or branched, preferably having 1 to 12 carbon atoms and more preferably 1 to 6 carbon atoms. The alicyclic group may be monocyclic or polycyclic, and the preferred number of carbon atoms is 3 to 12. The preferred number of carbon atoms of the aromatic group is 6 to 20.
X includes at least one group selected from the group consisting of (i) an alkylene group, or (ii) an ether group, an ester group, a thioether group, a sulfide group, a carbonyl group and an amide group (-CONH-), and an alkylene. It is preferable that the group is linked to the group.
In particular, X is preferably the group of (ii) above (especially when RN is an amino group ₍ ^H2N− )). In particular, it is preferable that the portion of X linked to the ^RN (amino group or the like) is at least one selected from the group consisting of an ester group, a carbonyl group and an amide group (-CONH-). As a result, the basic strength of the nitrogen atom can be optimized, and it can be expected that the effects of resolution and adhesion can be obtained while suppressing the decrease in sensitivity.

Examples of the monovalent organic group of R include an alkyl group, an alkenyl group, a saturated or unsaturated alicyclic group, and a group having an aromatic structure. The number of carbon atoms of the alkyl group and the alkenyl group is preferably 1 to 10, more preferably 1 to 4. The saturated or unsaturated alicyclic group may be monocyclic or polycyclic, and the preferred number of carbon atoms is 3 to 12. The preferred number of carbon atoms of the aromatic group is 6 to 20.
As R, an alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
The plurality of Rs may be the same as or different from each other.

Specific examples of the compound (D) include, for example, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and γ-aminopropylmethyldi. Ethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ- Aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, N-phenyl-γ-amino-propyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxy Silane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-) Butylidene) Propylamine, N-phenyl-3-aminopropyltrimethoxysilane and the like can be mentioned.

Further, a compound obtained by reacting a silicon compound having an amino group with an isocyanate compound or a carbonic acid ester derivative described in JP-A-2000-344940 can also be mentioned.

The content of the compound (D) in the negative photosensitive resin composition is preferably 0.01 to 30 parts by mass, preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the phenol resin (A). It is more preferably present, and even more preferably 0.5 to 5 parts by mass. By setting the content to these lower limit values or more, it becomes easy to obtain the effect of achieving both resolution and substrate adhesion. Further, by setting the content to these upper limit values or less, it is possible to achieve both resolution and substrate adhesion without lowering the sensitivity.
When the compound (D) has a group that generates a silanol group by hydrolysis, the compound (D) has a silanol group by hydrolysis during storage or transportation after preparation of the negative photosensitive resin composition. The groups that generate the above can be hydrolyzed. The above content is not the blending amount of the compound (D) at the time of preparing the negative photosensitive resin composition, but the total amount of the compound (D) actually contained in the negative photosensitive resin composition at the time of its use or the like. Means.
The compound (D) may be used alone or in combination of two or more.

<Surfactant (E)>
The negative photosensitive resin composition according to this embodiment preferably contains a surfactant (E). By containing the surfactant (E), the coatability when obtaining the resin film by the negative photosensitive resin composition becomes good, and the resin film having a uniform thickness can be obtained. In addition, it is possible to prevent residues and pattern floating when developing the resin film. As the surfactant (E), a nonionic surfactant is particularly preferable.

Examples of the surfactant (E) 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 this embodiment, nonionic, fluorine-based surfactants or silicone-based surfactants are preferable. Examples of the fluorine-based surfactant include Megafuck F-171, F-173, F-444, F-470, F-471, F-475, F-482, F-477, and F manufactured by DIC Corporation. -554, F-556, F-557, R-40 and R-41, Novec FC4430 manufactured by Sumitomo 3M Ltd., FC4432 and the like, but are not limited thereto.

When the negative photosensitive resin composition contains the surfactant (E), the content thereof is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the phenol resin (A). By setting the content in this range, the effect of the surfactant can be sufficiently obtained while the effect of the other components can be obtained.
When the surfactant (E) is used, only one type may be used, or two or more types may be used in combination.

<Phenol compound (F)>
The negative photosensitive resin composition according to this embodiment preferably contains a phenol compound (F). By including this, the effect of adjusting / optimizing the solubility (developability) and reducing scum can be expected.

As the phenol compound (F), for example, a compound having 1 to 6 phenolic hydroxyl groups in one molecule is preferable. From another viewpoint, for example, a low molecular weight compound having a molecular weight of 1000 or less, preferably a molecular weight of 750 or less, and more preferably a molecular weight of 500 or less is preferable. Although there is no particular lower limit on the molecular weight, it is typically 50 or more.

Specific examples of the phenol compound (F) include biphenol, 4-ethylresorcinol, 2-propylresorcinol, 4-butylresorcinol, 4-hexylresorcinol, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4 -Hydroxybenzoic acid, 4,4'-dihydroxydiphenylsulfide, 3,3'-dihydroxydiphenyldisulfide, 4,4'-dihydroxydiphenylsulphon, 2,2'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylmethane, 2, 2'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ether, biphenol, 4,4'-(1,3-dimethylbutylidene) diphenol, 4,4'-(2-ethylhexylidene) diphenol, 4 , 4'-Etilidene bisphenol, 2,2'-ethylenedioxydiphenol, 3,3'-ethylenedioxydiphenol, 1,5-bis (o-hydroxyphenoxy) -3-oxapentane, bisphenol A, bisphenol Examples thereof include F, fluoroglucolside, α, α, α'-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene and the like.

When the negative photosensitive resin composition contains the phenol compound (F), the content thereof is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the phenol resin (A). By setting the content in this range, it becomes easy to obtain the effects of adjusting / optimizing the solubility (developability) and reducing scum while obtaining the effects of other components.
When the phenol compound (F) is used, only one kind may be used, or two or more kinds may be used in combination.

<Solvent (G)>
The negative photosensitive resin composition according to this embodiment preferably contains a solvent (G). That is, the negative photosensitive resin composition according to the present embodiment preferably contains a phenol resin (A), a photosensitive agent (B), a cross-linking agent (C), a compound (D), and an optional component as required. Is preferably dissolved or dispersed in the solvent (G).
The solvent (G) is typically an organic solvent. Hereinafter, the case where the solvent (G) is an organic solvent will be described.

Examples of the organic solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and 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 and the like can be mentioned. As the organic solvent, only one kind may be used, or two or more kinds may be mixed and used.

The content of the solvent (G) in the negative photosensitive resin composition is 50 parts by mass to 1000 parts by mass, preferably 100 parts by mass to 500 parts by mass with respect to 100 parts by mass of the phenol resin (A). By using a solvent in the above range, it is possible to prepare a negative photosensitive resin composition having excellent handleability in which each component is sufficiently dissolved.
When the solvent (G) is used, only one type may be used, or two or more types may be used in combination.

<Other ingredients>
The negative photosensitive resin composition according to the present embodiment contains, if necessary, a cross-linking reaction accelerator (pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole and the like). Additives such as nitrogen complex five-membered ring compound), dissolution accelerator, antioxidant, filler, thermoacid generator, terminal encapsulant, sensitizer, etc. are further included to the extent that the effects of the present invention are not impaired. May be good.

<Preparation of negative photosensitive resin composition>
The method for preparing the negative photosensitive resin composition according to the present embodiment is not particularly limited. A known method can be appropriately adopted depending on the components finally contained in the negative photosensitive resin composition.

<Use>
The negative photosensitive resin composition according to the present embodiment is used for forming a film for electrical / electronic devices such as a permanent film and a resist film. "Electrical / electronic equipment" refers to electronic devices such as semiconductor chips, semiconductor elements, printed wiring boards, electric circuits, display devices such as television receivers and monitors, information and communication terminals, light emitting diodes, physical batteries, and chemical batteries. It refers to elements, devices, final products, and other electrical equipment in general that apply engineering technology.
The negative photosensitive resin composition according to the present embodiment is preferably used for permanent film forming, particularly from the viewpoint of good adhesion. Since it exhibits good adhesion, it can contribute to improving the reliability and durability of electrical and electronic devices.
Further, although the negative photosensitive resin composition according to the present embodiment contains the compound (D), there is little drawback of performance due to the compound (D), and in this respect as well, it can be preferably used for permanent film forming applications. For example, the negative photosensitive resin composition according to the present embodiment exhibits the same or higher performance as the conventional one in terms of "elongability", which is one of the performances required for permanent film forming applications.

<Manufacturing method of electrical and electronic equipment>
Using the negative photosensitive resin composition according to this embodiment, for example, the following steps:
A step of providing a negative photosensitive resin composition on a substrate,
A step of heating and drying the negative photosensitive resin composition to obtain a photosensitive resin film,
The process of exposing the photosensitive resin film with active light,
A step of developing the exposed photosensitive resin film to obtain a patterned resin film, and a step of heating the patterned resin film to obtain a cured film.
A cured film obtained by curing the negative photosensitive resin composition according to the present embodiment and an electric / electronic device provided with the cured film can be produced.

The process of providing the negative 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 substrate, a SiN substrate, and a GaN substrate. The substrate includes, for example, a substrate on which a semiconductor element or a display element is formed on the surface, in addition to the raw substrate. In order to improve the adhesiveness, the surface of the substrate may be treated with an adhesive auxiliary such as a silane coupling agent. In addition, in this embodiment, in particular, when a substrate in which Si (more specifically, SiN) or Cu is exposed on the surface is used, it is possible to achieve both resolution and adhesion to a high degree.
The step of providing the negative photosensitive resin composition can be performed by rotary coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, an inkjet method, or the like.

A step (also referred to as a prebaking step) of heating and drying a negative photosensitive resin composition to obtain a photosensitive resin film will be described.
The temperature of heat drying is usually 80 to 140 ° C, preferably 90 to 130 ° C. By heating and drying at this temperature, the cross-linking reaction before exposure can be suppressed, and the patterning property (resolution, etc.) can be improved.
The heating and drying time is usually about 30 to 600 seconds, preferably about 60 to 300 seconds. A photosensitive resin film is formed by removing the solvent by this heat drying. Heating is typically performed on a hot plate, an oven, or the like. The thickness of this photosensitive resin film is preferably 1 to 500 μm.

The process of exposing the photosensitive resin film with the active light beam will be described.
As the active ray, for example, X-ray, electron beam, ultraviolet ray, visible light and the like can be used. In terms of wavelength, active light rays having a wavelength of 200 to 500 nm are preferable. From the viewpoint of pattern resolution and handleability, the light source is preferably g-line, h-line or i-line of a mercury lamp. Further, two or more light rays may be mixed and used. As the exposure apparatus, a contact aligner, a mirror projection or a stepper is preferable. After the exposure, the photosensitive resin film may be heated again if necessary, and the temperature and time thereof are, for example, about 80 to 140 ° C. and 10 to 300 seconds.

A step (development step) of developing an exposed photosensitive resin film to obtain a patterned resin film will be described.
In the developing step, development can be carried out using a suitable developer, for example, by a method such as a dipping method, a paddle method, or a rotary spray method. By development, the unexposed portion is eluted and removed from the photosensitive resin film.

The developer that can be used is not particularly limited. For example, an alkaline aqueous solution or an organic solvent can be used. Specific examples of the alkaline aqueous solution include (i) an inorganic alkaline aqueous solution such as sodium hydroxide, sodium carbonate, sodium silicate and ammonia, (ii) an organic amine aqueous solution such as ethylamine, diethylamine, triethylamine and triethanolamine, and (iiii). ) Examples thereof include an aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide. Specific examples of the organic solvent include a ketone solvent such as cyclopentanone, an ester solvent such as propylene glycol monomethyl ether acetate (PGMEA) and butyl acetate, and an ether solvent such as propylene glycol monomethyl ether.
A water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added to the developing solution.
As the developing solution, an aqueous solution of tetramethylammonium hydroxide 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 developing step, washing is preferably performed with a rinsing solution to remove the developing solution. Thereby, a patterned resin film can be obtained. Examples of the rinsing solution include distilled water, methanol, ethanol, isopropanol, propylene glycol monomethyl ether and the like. These may be used alone or in combination of two or more.

The process of heating the patterned resin film to obtain a cured film will be described.
A cured film can be obtained by heating the patterned resin film obtained as described above. This heating temperature is typically 150 to 400 ° C, preferably 170 to 300 ° C, and more preferably 170 to 250 ° C. By setting this temperature range, it is considered that the entire membrane can be uniformly crosslinked. The heating time is not particularly limited, but is, for example, in the range of 15 to 300 minutes. This heat treatment can be performed by a hot plate, an oven, a temperature-increasing oven in which a temperature program can be set, or the like. The atmospheric gas for heat treatment may be air or an inert gas such as nitrogen or argon. Further, it may be heated under reduced pressure.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted. Modifications, improvements, etc. to the extent that the object of the present invention can be achieved are included in the present invention.
Hereinafter, an example of the reference form will be added.
1. 1.
Phenol formaldehyde (A),
Photosensitizer (B),
Crosslinker (C) and
A compound (D) containing a group having a nitrogen atom and a silanol group or a group that generates a silanol group by hydrolysis in one molecule (D).
A negative photosensitive resin composition for forming a permanent film.
2. 2.
1. 1. The negative photosensitive resin composition according to the above.
A negative photosensitive resin composition in which the group having a nitrogen atom of the compound (D) is a group having a structure represented by the following general formula (I) or a group having a nitrogen-containing heterocyclic structure.
R ¹ R ² N- (I)
In the general formula (I), R ¹ and R ² independently represent a hydrogen atom, an alkyl group, an alicyclic group or an aryl group, respectively. R ¹ and R ² may be connected to each other to form a ring structure.
3. 3.
1. 1. Or 2. The negative photosensitive resin composition according to the above.
A negative photosensitive resin composition in which the compound (D) contains the compound represented by the above-mentioned general formula (II).
In the above general formula (II),
RN represents a group having a nitrogen atom ^.
X represents a single bond or a divalent linking group.
R independently represents a hydrogen atom or a monovalent organic group.
4.
1. 1. ~ 3. The negative type photosensitive resin composition according to any one of the above.
A negative photosensitive resin composition in which the content of the compound (D) is 0.01 to 30 parts by mass with respect to 100 parts by mass of the phenol resin (A).
5.
1. 1. ~ 4. The negative type photosensitive resin composition according to any one of the above.
A negative photosensitive resin composition in which the photosensitizer (B) contains at least one compound selected from a triazine compound, a sulfonium salt, an iodonium salt and a sulfonic acid ester.
6.
1. 1. ~ 5. The negative type photosensitive resin composition according to any one of the above.
A negative photosensitive resin composition used for forming an interlayer film, a surface protective film, or a permanent film used as a dam material.
7.
1. 1. From 6. The cured film of the negative type photosensitive resin composition according to any one of the above.
8.
7. An electrical / electronic device provided with the cured film described in 1.

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

<Synthesis example 1: Synthesis of phenolic resin (A-3)>
In a four-necked glass round-bottom flask equipped with a thermometer, stirrer, raw material inlet and dry nitrogen gas inlet, 186.2 g (1.00 mol) of 4,4'-biphenol and p-cresol 86. 5 g (0.8 mol), 24.0 g (0.8 mol) of formaldehyde, 11.3 g (0.09 mol) of oxalic acid / dihydrate, and 308 g of γ-butyrolactone were charged.
Next, the round-bottom flask was bathed in oil while flowing nitrogen, and a polycondensation reaction was carried out at 100 ° C. for 6 hours while refluxing the reaction solution.
Then, the obtained reaction solution was cooled to room temperature, 411 g of acetone was added, and the mixture was stirred and mixed until uniform.
Then, the reaction solution in the round-bottom flask was dropped and mixed with 10 L of water to precipitate the resin component. The precipitated resin component was separated by filtration and recovered, and then vacuum dried at 60 ° C. to obtain a phenol resin represented by the formula (A-3) described later. In the formula (A-3) described later, the bond bonded to the biphenol structure is bonded to either one of the two benzene rings.
The weight average molecular weight of the obtained phenol resin (A-3) was 11000.

<Synthesis Example 2: Synthesis of Phenol Formaldehyde (A-4)>
110.1 g (1.00 mol) of resorcinol and 4,4-bis (methoxymethyl) biphenyl in a four-necked glass round-bottom flask equipped with a thermometer, stirrer, raw material inlet and dry nitrogen gas inlet tube. 193.9 g (0.8 mol), 7.7 g (0.05 mol) of diethyl sulfate, and 500 g of γ-butyrolactone were charged.
Next, the round-bottom flask was bathed in oil while flowing nitrogen, and the polycondensation reaction was carried out at 100 ° C. for 6 hours while refluxing the reaction solution.
Then, the obtained reaction solution was cooled to room temperature, 323 g of acetone was added, and the mixture was stirred and mixed until uniform.
Then, the reaction solution in the round-bottom flask was dropped and mixed with 10 L of water to precipitate the resin component. The precipitated resin component was separated by filtration and recovered, and then vacuum dried at 60 ° C. to obtain a phenol resin represented by the formula (A-4) described later.
The weight average molecular weight of the obtained phenol resin (A-4) was 7000.

<Preparation of photosensitive resin composition>
The photosensitive resin compositions of Examples 1 to 9 and Comparative Example 1 were prepared as follows.

First, each component blended according to Table 1 below was stirred and mixed in a nitrogen atmosphere.
Then, it was 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 Table 1 are as follows. The unit of the component amount in Table 1 is a mass part.

・ Phenol resin (A)
(A-1) Cresol Novolac Resin (PR-56001 manufactured by Sumitomo Bakelite Co., Ltd., polystyrene-equivalent weight average molecular weight (Mw) = 11000)
(A-2) Phenolic novolak resin (PR-50731 manufactured by Sumitomo Bakelite Co., Ltd., polystyrene-equivalent weight average molecular weight (Mw) = 11000)
(A-3) Phenol resin obtained by Synthetic Example 1 (A-4) Phenol resin obtained by Synthetic Example 2

・ Photosensitizer (B)
(B-1) CPI-310B (manufactured by Sun Appro Co., Ltd., structure below)
(B-2) ZK-1232 (manufactured by DSP Gokyo Food & Chemical Co., Ltd., structure below)

・ Crosslinking agent (C)
(C-1) Nicarac MX-270 (manufactured by Sanwa Chemical Co., Ltd., structure below)
(C-2) TML-BPA (manufactured by Honshu Chemical Industry Co., Ltd., structure below)
(C-3) Cellokiside 2021P (manufactured by Daicel Corporation, structure below)

-Compound (D)
(D-1) X-12-989MS (manufactured by Shinetsu Silicone Co., Ltd., hereinafter structure)
(D-2) Z-6120 (manufactured by Toray Dow Corning Co., Ltd., hereinafter structure)
(D-3) KBM-573 (manufactured by Shinetsu Silicone Co., Ltd., hereinafter structure)
(D-4) KBM-403E (manufactured by Shinetsu Silicone Co., Ltd., following structure, comparative compound)

-Surfactant (E)
(E-1) F444 (manufactured by DIC Corporation, perfluoroalkylethylene oxide adduct)

・ Phenolic compound (F)
(F-1) Fluorogluside (manufactured by Kanto Chemical Co., Inc., hereinafter structure)
(F-2) Biphenol (manufactured by Honshu Chemical Industry Co., Ltd., hereinafter structure)

・ Solvent (G)
(G-1) γ-Butyrolactone (abbreviation: GBL)
(G-2) Propylene Glycol Monomethyl Ether Acetate (abbreviation: PGMEA)

<Evaluation of sensitivity>
The prepared photosensitive resin compositions were each applied on an 8-inch silicon wafer using a spin coater. After coating, it was prebaked on a hot plate at 120 ° C. for 3 minutes to obtain a coating film having a film thickness of about 9.0 μm.
This coating film was irradiated with i-line through a mask manufactured by Toppan Printing Co., Ltd. (test chart No. 1: a residual pattern having a width of 1.0 to 100 μm and a punching pattern are drawn). An i-line stepper (NSR-4425i manufactured by Nikon Corporation) was used for irradiation.
After the exposure, the wafer was placed on a hot plate and baked at 100 ° C. for 2 minutes.
Then, paddle development was carried out twice for 30 seconds using a 2.38% aqueous solution of tetramethylammonium hydroxide as a developing solution. Then, it was rinsed with pure water for 10 seconds. This gave a negative pattern.

Patterning evaluation was performed a plurality of times by changing the exposure amount, and the minimum exposure amount at which a line pattern having a width of 50 μm was formed by a mask opening having a width of 50 μm was defined as sensitivity (mJ / cm ² ). The lower the sensitivity, the better in terms of throughput.

<Evaluation of resolution>
A pattern was formed by the same process as <evaluation of sensitivity> except that the exposure was performed with the above "minimum exposure amount" + 100 mJ / cm ² . The resolution of the line pattern at this time was evaluated.
The results are shown in Table 2 as "pattern resolution (μm)". The resolution should be small when creating fine wiring.

<Substrate adhesion evaluation (silicon nitride substrate and copper substrate)>
The photosensitive resin composition was applied onto a silicon wafer having silicon nitride on its surface and a silicon wafer having copper plating formed on it by using a spin coater. Then, it was prebaked on a hot plate at 120 ° C. for 3 minutes to obtain a coating film having a film thickness of about 10 μm.
The obtained coating film was irradiated with ultraviolet rays of 1000 mJ / cm ² in terms of i-line using a high-pressure mercury lamp. Then, while keeping the oxygen concentration at 1000 ppm or less, it was heated in an oven at 200 ° C. for 60 minutes to obtain a cured film of the photosensitive resin composition.
The adhesion of this cured film was evaluated by a so-called grid tape test. Specifically, first, the blades of the cutter were inserted into the cured film at intervals of 1 mm in length and width, and 100 patterns of 1 mm × 1 mm were created. Next, cellophane tape (registered trademark) having a peel strength of 3.0 mN / 10 mm was often attached to the surface of the pattern with an eraser. Then, the cellophane tape (registered trademark) was peeled off vertically.
The number of peeled patterns was counted and used as an index of substrate adhesion. The smaller the number of peels, the better the adhesion to silicon nitride and copper.

<Tensile elongation (elongability)>
The photosensitive resin composition was applied to a silicon wafer using a spin coater. Then, it was prebaked on a hot plate at 120 ° C. for 3 minutes to obtain a coating film having a film thickness of about 10 μm.

The obtained coating film was irradiated with ultraviolet rays of 1000 mJ / cm ² in terms of i-line using a high-pressure mercury lamp. Then, while keeping the oxygen concentration at 1000 ppm or less, it was heated in an oven at 200 ° C. for 60 minutes to obtain a cured film of the photosensitive resin composition.

The obtained cured film was diced, cut into a size of 10 mm × 60 mm, immersed in a 2% hydrofluoric acid aqueous solution to peel off the cured film, and dried at 60 ° C. for 10 hours to prepare 10 test pieces. A tensile test (stretching speed: 5 mm / min) was carried out on each of the 10 test pieces using a tensile tester (Tensilon RTC-1210A) manufactured by Orientec Co., Ltd. in an atmosphere of 23 ° C.

After the test was carried out, the tensile elongation was calculated from the breaking distance and the initial distance using the following formulas, and the average value of 10 test pieces was taken as the tensile elongation. The unit is%.
Formula: Tensile elongation (%) = {(breaking distance-initial distance) / initial distance} x 100

<Manufacturing of semiconductor devices>
Using a simulated device wafer provided with a copper plating circuit on the surface, the photosensitive resin compositions of Examples 1 to 9 were each applied so as to have a final film thickness of 5 μm. After that, processing such as exposure and development was performed to perform pattern processing, and the film was cured.

Then, the wafer was divided into chip sizes and mounted on a lead frame for 16-pin DIP (Dual Inline Package) using a conductive paste. Then, it was sealed and molded with an epoxy resin for semiconductor encapsulation (EME-6300H manufactured by Sumitomo Bakelite Co., Ltd.) to obtain a semiconductor device.

The obtained semiconductor device (semiconductor package) was treated at 85 ° C. and 85% humidity for 168 hours. Then, it was immersed in a solder bath at 260 ° C. for 10 seconds, and then subjected to a high temperature and high humidity pressure cooker treatment (125 ° C., 2.3 atm, 100% relative humidity) to check for open defects of the copper plating circuit.
No corrosion or the like occurred in the obtained semiconductor device. That is, it was confirmed that the semiconductor device provided with the resin film produced by using the photosensitive resin compositions of Examples 1 to 9 can be practically used without any problem.

The formulation and evaluation results of each composition are summarized in Table 1 below.

As shown in Table 1, the photosensitive resin compositions of Examples 1 to 9 containing compound (D) and other components had significantly better pattern resolution than Comparative Example 1 containing no compound (D). In addition, the adhesion to the Cu substrate was remarkably better than that of Comparative Example 1. That is, from Examples 1 to 9 and Comparative Example 1, it was shown that the photosensitive resin composition according to the present embodiment can achieve both resolution and substrate adhesion.
In addition, the photosensitive resin compositions of Examples 1 to 9 had sufficiently good results in terms of adhesion to the silicon nitride substrate and tensile elongation.
A detailed analysis reveals the following trends.

-Analysis of Examples 1 to 3 (same composition except that compound (D) was changed):
In the above-mentioned general formula (II), X is linked to at least one group selected from the group consisting of an ether group, an ester group, a thioether group, a sulfide group, a carbonyl group and an amide group (-CONH-) and an alkylene group. In the examples using the compound (D-1) or (D-2) which is the "group", the sensitivity is better than that of the compound (D-3) in which X is the "alkylene group".

-Analysis of Examples 4 to 6 (same composition except that the phenol resin (A) was changed):
The resolution is improved by using a phenolic resin containing a structural unit having a biphenyl skeleton.

-Analysis of Examples 7 and 8 (change in content of compound (D)):
When the content of the compound (D) is increased, the pattern resolution tends to be further improved. On the other hand, when the content of the compound (D) is reduced, the decrease in sensitivity tends to be suppressed.
Even if the content of the compound (D) is small, a remarkable effect on the adhesion to the Cu substrate is obtained.

Claims (8)

Phenol formaldehyde (A),
Photosensitizer (B),
A compound (D) containing a group having a cross-linking agent (C) and a nitrogen atom and a silanol group or a group that generates a silanol group by hydrolysis in one molecule.
Including
The photosensitive agent (B) contains a compound that generates an acid when irradiated with active light.
The nitrogen atom in the compound (D) is a negative photosensitive resin composition for forming a permanent film containing a nitrogen atom having a basicity capable of inactivating the acid .
The negative photosensitive resin composition is
(I) Only the phenol resin (A) is contained as the resin, or the resin is contained.
(Ii) The resin contains the phenol resin (A) and a resin (A') other than the phenol (A).
In the case of (ii), the content of the resin (A') is 0.1 to 50 parts by mass when the content of the phenol resin (A) is 100 parts by mass, which is a negative photosensitive resin composition. thing. The negative photosensitive resin composition according to claim 1.
A negative photosensitive resin composition in which the group having a nitrogen atom of the compound (D) is a group having a structure represented by the following general formula (I) or a group having a nitrogen-containing heterocyclic structure.
R ¹ R ² N- (I)
In the general formula (I), R ¹ and R ² independently represent a hydrogen atom, an alkyl group, an alicyclic group or an aryl group, respectively. R ¹ and R ² may be connected to each other to form a ring structure. The negative photosensitive resin composition according to claim 1 or 2.
A negative photosensitive resin composition in which the compound (D) contains a compound represented by the following general formula (II).

In general formula (II),
RN represents a group having a ^nitrogen atom.
X represents a single bond or a divalent linking group.
R independently represents a hydrogen atom or a monovalent organic group. The negative photosensitive resin composition according to any one of claims 1 to 3.
A negative photosensitive resin composition in which the content of the compound (D) is 0.01 to 30 parts by mass with respect to 100 parts by mass of the phenol resin (A). The negative photosensitive resin composition according to any one of claims 1 to 4.
A negative photosensitive resin composition in which the photosensitizer (B) contains at least one compound selected from a triazine compound, a sulfonium salt, an iodonium salt and a sulfonic acid ester. The negative photosensitive resin composition according to any one of claims 1 to 5.
A negative photosensitive resin composition used for forming an interlayer film, a surface protective film, or a permanent film used as a dam material. The cured film of the negative photosensitive resin composition according to any one of claims 1 to 6. An electrical / electronic device comprising the cured film according to claim 7.