JP7360380B2 - Photosensitive resin compositions, dry films, cured products, printed wiring boards and semiconductor devices - Google Patents

Description

The present invention relates to photosensitive resin compositions, dry films, cured products, and printed wiring boards suitable for use in protective films of semiconductor devices, insulating films for rewiring layers of wafer level packages (WLP), insulating parts of passive components, etc. and related to semiconductor devices.

Cured films of photosensitive resin compositions containing precursors of heat-resistant resins such as polyimide and polybenzoxazole (PBO) are used as buffer coat films for LSIs and insulating films for redistribution layers in wafer-level packages (WLPs). ing. These photosensitive resin compositions are cured by heat treatment to cyclize a heat-resistant resin precursor. Conventional heat treatment was carried out at temperatures of 300° C. or higher, but in recent years there has been a demand for heat-resistant resin precursors to be cured at low temperatures in order to suppress thermal damage to semiconductor elements.

Conventionally, in order to create a photosensitive resin composition that can be cured at low temperatures, a crosslinking agent containing a methylol group in its structure is added, and this crosslinking agent crosslinks with the resin at low temperatures to improve the properties of the cured film. This is being considered. For example, some positive photosensitive resin compositions that can be cured at low temperatures contain melamine-based or urea-based crosslinking agents (Patent Document 1).

On the other hand, elongation (elongation at break) is also required for the cured product of the photosensitive resin composition as described above in order to ensure mechanical and thermal shock reliability.

Patent No. 4046563

Adding a melamine-based or urea-based crosslinking agent enables low-temperature curing, but in order to provide sufficient chemical resistance, a large amount of crosslinking agent must be added, resulting in an increase in crosslinking density. Therefore, there was a problem that the elongation rate decreased.

Therefore, the object of the present invention is to provide a photosensitive resin composition that can be cured at a low temperature of less than 300°C and obtain a cured product with improved chemical resistance and elongation. The object of the present invention is to provide a film, a cured product of the resin layer of the composition or the dry film, and a semiconductor element, a printed wiring board, and an electronic component having the cured product.

As a result of extensive studies, the present inventors have found that the above-mentioned problems can be solved by including a specific polyether compound in the photosensitive resin composition, and have completed the present invention.

（一般式（１）中、Ｘは、炭素数１～１０のアルキレン基を示す。）That is, the photosensitive resin composition of the present invention comprises (A) an alkali-soluble resin, (B) a photosensitizer, and (C) a polyether containing 100 to 10,000 polymerized units represented by general formula (1). It is characterized by containing a compound.

(In general formula (1), X represents an alkylene group having 1 to 10 carbon atoms.)

（一般式（２）中、Ｙは、炭素数１～１０のアルキレン基を示す。ただし、一般式（１）中のＸと同一である場合を除く。）In the photosensitive resin composition of the present invention, the polyether compound (C) preferably further contains 1 to 1,000 polymerized units represented by general formula (2).

(In general formula (2), Y represents an alkylene group having 1 to 10 carbon atoms. However, this excludes cases where it is the same as X in general formula (1).)

（一般式（３）中、Ｚは、反応性官能基またはフェニル基を側鎖に有する炭素数１～１０のアルキレン基を示す。）In the photosensitive resin composition of the present invention, it is preferable that the polyether compound (C) further contains 1 to 1,000 polymerized units represented by general formula (3).

(In the general formula (3), Z represents a reactive functional group or an alkylene group having 1 to 10 carbon atoms having a phenyl group in the side chain.)

The photosensitive resin composition of the present invention preferably contains a polybenzoxazole precursor as the alkali-soluble resin (A).

The photosensitive resin composition of the present invention preferably contains a naphthoquinone diazide compound as the photosensitive agent (B).

The dry film of the present invention is characterized by having a resin layer obtained by coating and drying the photosensitive resin composition on a film.

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

The printed wiring board of the present invention is characterized by having the cured product.

The semiconductor element of the present invention is characterized by having the cured product.

The electronic component of the present invention is characterized by having the cured product.

According to the present invention, there is provided a photosensitive resin composition that can be cured at a low temperature of less than 300° C. to obtain a cured product with improved chemical resistance and elongation, and a dry film having a resin layer obtained from the composition. , a cured product of the resin layer of the composition or the dry film, and a semiconductor element, a printed wiring board, and an electronic component having the cured product can be provided.

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

[(A) Alkali-soluble resin]
The photosensitive resin composition of the present invention contains an alkali-soluble resin. The alkali-soluble resin is a resin that is soluble in an aqueous alkali solution as a developer during development after exposure to active energy rays. As the alkali-soluble resin, alkali-soluble polymers that have been used in conventional photosensitive resin compositions can be used. Examples of the alkali-soluble polymer include those having an alkali-soluble group in the molecule, specifically those having a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a thiol group, and the like. Among these, polymers having a phenolic hydroxyl group or a carboxyl group are preferred, and examples thereof include novolac resins, resol resins, polyimide precursors, and polybenzoxazole precursors. Preferred are polyimide precursors and polybenzoxazole precursors. When these polymers are heated at a predetermined temperature, they undergo dehydration and ring closure, and a heat-resistant resin is obtained in the form of polyimide, polybenzoxazole, or a copolymerization of both.

（式中、Ｘは４価の有機基を示し、Ｙは２価の有機基を示す。ｎは１以上の整数であり、好ましくは１０～５０、より好ましくは２０～４０である。）The polybenzoxazole precursor is preferably a polyhydroxyamic acid having a repeating structure represented by the following general formula (4).

(In the formula, X represents a tetravalent organic group, and Y represents a divalent organic group. n is an integer of 1 or more, preferably 10 to 50, more preferably 20 to 40.)

When the polybenzoxazole precursor is synthesized by the above synthesis method, in the above general formula (4), X is a residue of the above dihydroxydiamine, and Y is a residue of the above dicarboxylic acid.

The above dihydroxydiamines include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis(3-amino-4-hydroxyphenyl)propane, Bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 2,2-bis(3-amino-4 -hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl)-1,1,1,3,3,3-hexa Examples include fluoropropane. Among them, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane is preferred.

Examples of the dicarboxylic acids include isophthalic acid, terephthalic acid, 5-tert-butyl isophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalene dicarboxylic acid, 4,4' -Dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxytetraphenylsilane, bis(4-carboxyphenyl)sulfone, 2,2-bis(p-carboxyphenyl)propane, 2,2 -Dicarboxylic acids having an aromatic ring such as -bis(4-carboxyphenyl)-1,1,1,3,3,3-hexafluoropropane, oxalic acid, malonic acid, succinic acid, 1,2-cyclobutanedicarboxylic acid, Examples include aliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and 1,3-cyclopentanedicarboxylic acid. Among them, 4,4'-dicarboxydiphenyl ether is preferred.

In the above general formula (4), the tetravalent organic group represented by More preferably, it is located on an aromatic ring. The number of carbon atoms in the tetravalent aromatic group is preferably 6 to 30, more preferably 6 to 24. Specific examples of the above-mentioned tetravalent aromatic group include the groups shown below, but are not limited to these. Known aromatic groups that can be included in the polybenzoxazole precursor are selected depending on the purpose. do it.

Among the aromatic groups described above, the tetravalent aromatic group is preferably a group shown below.

In the above general formula (4), the divalent organic group represented by Y may be an aliphatic group or an aromatic group, but is preferably an aromatic group, and the carbonyl group in the above general formula (4) is preferably an aromatic group. More preferably, it is combined with. The number of carbon atoms in the divalent aromatic group is preferably 6 to 30, more preferably 6 to 24. Specific examples of the above-mentioned divalent aromatic group include the groups shown below, but are not limited to these. Known aromatic groups contained in the polybenzoxazole precursor may be selected depending on the purpose. Bye.

（式中、Ａは単結合、－ＣＨ_２－、－Ｏ－、－ＣＯ－、－Ｓ－、－ＳＯ_２－、－ＮＨＣＯ－、－Ｃ（ＣＦ_３）_２－、－Ｃ（ＣＨ_３）_２－からなる群から選択される２価の基を表す。）

(In the formula, A is a single bond, -CH ₂ -, -O-, -CO-, -S-, -SO ₂ -, -NHCO-, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ represents a divalent group selected from the group consisting of -)

Among the aromatic groups, the divalent organic group is preferably the group shown below.

The polybenzoxazole precursor may contain two or more types of repeating structures of the above polyhydroxyamic acid. Further, it may contain a structure other than the repeating structure of polyhydroxyamic acid described above, for example, it may contain a repeating structure of polyamic acid.

The number average molecular weight (Mn) of the polybenzoxazole precursor is preferably 5,000 to 100,000, more preferably 8,000 to 50,000. Here, the number average molecular weight is a value measured by gel permeation chromatography (GPC) and converted to standard polystyrene. Further, the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 10,000 to 200,000, more preferably 16,000 to 100,000. Here, the weight average molecular weight is a value measured by GPC and converted to standard polystyrene. Mw/Mn is preferably 1-5, more preferably 1-3.

One type of polybenzoxazole precursor may be used alone, or two or more types may be used in combination.
The method for synthesizing the polybenzoxazole precursor is not particularly limited, and any known method may be used. For example, it can be obtained by reacting dihydroxydiamines as an amine component with a dihalide of a dicarboxylic acid such as dicarboxylic acid dichloride as an acid component.

The amount of the alkali-soluble resin (A) blended is preferably 60 to 90% by mass based on the total solid content of the composition. By containing it in an amount of 60% by mass or more, adhesiveness and surface hardening properties become good. Moreover, by containing it in an amount of 90% by mass or less, it is possible to prevent a decrease in the crosslinking density in the cured product, and the coating film properties become good.

[(B) Photosensitizer]
The photosensitive resin composition of the present invention contains a photosensitizer. (B) There are no particular limitations on the photosensitizer, and photoacid generators, photopolymerization initiators, and photobase generators can be used. A photoacid generator is a compound that generates an acid when irradiated with light such as ultraviolet rays or visible light, a photopolymerization initiator is a compound that generates radicals etc. when irradiated with light, and a photobase generator is a compound that generates an acid when irradiated with light such as ultraviolet rays or visible light. It is a compound whose molecular structure changes or whose molecules are cleaved to produce one or more basic substances when irradiated with light. In the present invention, a photoacid generator can be suitably used as the (B) photosensitizer.
Examples of photoacid generators include naphthoquinonediazide compounds, diarylsulfonium salts, triarylsulfonium salts, dialkylphenacylsulfonium salts, diaryliodonium salts, aryldiazonium salts, aromatic tetracarboxylic acid esters, aromatic sulfonic acid esters, and nitrobenzyl esters. , aromatic N-oxyimidosulfonate, aromatic sulfamide, benzoquinonediazosulfonic acid ester, and the like. Preferably, the photoacid generator is a dissolution inhibitor. Among these, naphthoquinone diazide compounds are preferred.

Specifically, the naphthoquinonediazide compound includes, for example, a naphthoquinonediazide adduct of tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene (for example, TS533, TS567, TS583, TS593 manufactured by Sanpo Chemical Research Institute). ), naphthoquinonediazide adducts of tetrahydroxybenzophenone (for example, BS550, BS570, BS599 manufactured by Sanpo Chemical Research Institute), and 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]-α , α-dimethylbenzyl}phenol and naphthoquinone diazide adducts (for example, TKF-428 and TKF-528 manufactured by Sanpo Chemical Research Institute), etc. can be used.

Further, as the photopolymerization initiator, commonly known ones can be used, such as oxime ester photopolymerization initiators having an oxime ester group, α-aminoacetophenone photopolymerization initiators, and acylphosphine oxide photopolymerization initiators. An initiator, a titanocene photopolymerization initiator, etc. can be used.

As the oxime ester photopolymerization initiator, commercially available products include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by BASF Japan, N-1919 and NCI-831 manufactured by ADEKA.

Specifically, the α-aminoacetophenone photopolymerization initiator is 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1,2-benzyl-2-dimethylamino- 1-(4-morpholinophenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone , N,N-dimethylaminoacetophenone, etc., and commercially available products include Omnirad 907, Omnirad 369, and Omnirad 379 manufactured by IGM Resins.

Specifically, the acylphosphine oxide photopolymerization initiator includes 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and bis(2,6-trimethylbenzoyl)-phenylphosphine oxide. -dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, etc., and commercially available products include Omnirad TPO and Omnirad 819 manufactured by IGM Resins.

Specifically, the titanocene photopolymerization initiator includes bis(cyclopentadienyl)-diphenyl-titanium, bis(cyclopentadienyl)-di-chloro-titanium, and bis(cyclopentadienyl). -bis(2,3,4,5,6pentafluorophenyl)titanium, bis(cyclopentadienyl)-bis(2,6-difluoro-3-(pyrrol-1-yl)phenyl)titanium, etc. . Commercially available products include Omnirad 784 manufactured by IGM Resins.

The photobase generator may be either an ionic photobase generator or a nonionic photobase generator, but the ionic photobase generator has higher composition sensitivity and is more effective in forming patterned films. This is preferable because it is advantageous. Examples of the basic substance include secondary amines and tertiary amines.

Examples of ionic photobase generators include salts of aromatic component-containing carboxylic acids and tertiary amines, and ionic PBGs manufactured by Wako Pure Chemical Industries, Ltd. such as WPBG-082, WPBG-167, WPBG-168, and WPBG-. 266, WPBG-300, etc. can be used.

Examples of nonionic photobase generators include α-aminoacetophenone compounds, oxime ester compounds, N-formylated aromatic amino groups, N-acylated aromatic amino groups, nitrobenzyl carbamate groups, alkoxybenzyl Examples include compounds having substituents such as carbamate groups. Other photobase generators include WPBG-018 (product name: 9-anthrylmethyl N,N'-diethylcarbamate) and WPBG-027 (product name: (E)-1-[3-(2) manufactured by Wako Pure Chemical Industries, Ltd. －ｈｙｄｒｏｘｙｐｈｅｎｙｌ）－２－ｐｒｏｐｅｎｏｙｌ］ｐｉｐｅｒｉｄｉｎｅ）、ＷＰＢＧ－１４０（商品名：１－（ａｎｔｈｒａｑｕｉｎｏｎ－２－ｙｌ）ｅｔｈｙｌ ｉｍｉｄａｚｏｌｅｃａｒｂｏｘｙｌａｔｅ）、ＷＰＢＧ－１６５等を使用することもできる。

(B) The photosensitizers may be used alone or in combination of two or more. The amount of the photosensitizer (B) is preferably 3 to 20% by mass based on the total solid content of the composition.

（一般式（１）中、Ｘは、炭素数１～１０のアルキレン基を示す。）[(C) Polyether compound containing 100 to 10,000 polymerized units represented by general formula (1)]
The photosensitive resin composition of the present invention comprises (C) a polyether compound containing 100 to 10,000 polymerized units represented by general formula (1) (hereinafter also simply referred to as "(C) polyether compound"). include.

(In general formula (1), X represents an alkylene group having 1 to 10 carbon atoms.)

(C) Polyether compound has high compatibility with (A) alkali-soluble resin, so even in a high molecular weight product containing 100 or more polymerized units represented by general formula (1), it is uniform during drying and curing process. maintains good morphology. As a result, the photosensitive resin composition of the present invention containing the polyether compound (C) can have sufficient chemical resistance and mechanical properties even when cured at a low temperature of less than 300°C.

Furthermore, since the compound represented by the above general formula (1) is hydrophilic, it does not inhibit solubility in an alkaline developer. As a result, the photosensitive resin composition of the present invention containing the polyether compound (C) can have resolution equivalent to that of conventional photosensitive resin compositions.

From the above, the photosensitive resin composition of the present invention containing the polyether compound (C) can be cured by heating at a low temperature of less than 300°C without deteriorating chemical resistance, mechanical properties, or resolution. can.

By containing 100 or more polymerized units represented by general formula (1), the photosensitive resin composition of the present invention has sufficient chemical resistance and mechanical properties even when cured at a low temperature of less than 300°C. Characteristics are shown. Further, when the number of polymerized units is 10,000 or less, the solubility in a solvent is good and it is suitable for producing a photosensitive resin composition. More preferably, it is 1,000 to 10,000. By containing 1,000 or more polymerized units, the contrast, which is the difference in dissolution rate between the unexposed area and the exposed area, is improved and good resolution is exhibited.

Both ends of the polyether compound (C) are preferably -OR (R represents a hydrogen atom or an alkylene group having 1 to 10 carbon atoms). Examples of the alkylene group having 1 to 10 carbon atoms that R can include include those similar to X in the above general formula (1). By making the terminals similar to the main chain skeleton, changes in compatibility due to differences in molecular weight can be reduced. (C) Both ends of the polyether compound are preferably -OH. This results in good solubility in alkaline developers.

In the above general _formula (1), the alkylene group having 1 to ₁₀ carbon atoms represented by , 1,1-dimethyltetramethylene group, butylene group, octylene group, decylene group, and other linear or branched alkylene groups. Among these, alkylene groups having 2 to 4 carbon atoms are preferred, and ethylene groups are more preferred, from the viewpoint of high hydrophilicity and developability in alkaline aqueous solutions.

（一般式（２）中、Ｙは、炭素数１～１０のアルキレン基を示す。ただし、一般式（１）中のＸと同一である場合を除く。）(C) The polyether compound may be a copolymer such as a random copolymer or a block copolymer. Examples of other polymerized units include a polymerized unit represented by general formula (2).

(In general formula (2), Y represents an alkylene group having 1 to 10 carbon atoms. However, this excludes cases where it is the same as X in general formula (1).)

In the above general formula (2), examples of the alkylene group having 1 to 10 carbon atoms represented by Y include the same groups as X in the above general formula (1). Among these, a branched alkylene group is preferable, and the photosensitive resin composition of the present invention has a low crystallinity, high compatibility with the alkali-soluble resin (A), and forms a more uniform morphology. It also has better mechanical properties when the product is cured at lower temperatures below 300°C. Among them, branched alkylene groups having 3 to 5 carbon atoms are more preferred, and propylene groups are even more preferred.

The number of polymerized units represented by the above general formula (2) contained in the polyether compound (C) is preferably 1 to 1,000, more preferably 10 to 100. Further, the ratio of the number of polymerized units represented by the above general formula (2) to the number of polymerized units represented by the above general formula (1) is preferably 10% or less.

Further, as other polymerized units that the polyether compound (C) may include, for example, a polymerized unit represented by general formula (3) can be mentioned.

（一般式（３）中、Ｚは、反応性官能基またはフェニル基を側鎖に有する炭素数１～１０のアルキレン基を示す。前記反応性官能基としては、アルデヒド基、アシル基、カルバモイル基、イソシアネート基、イミダゾール基、シラノール基、アルコキシシリル基、メチロール基、アルコキシメチル基、エポキシ基、オキセタニル基、ビニル基、エチニル基、アリル基、アクリル基、メタクリル基等が挙げられる。）前記反応性官能基を側鎖に有することで、硬化時に（Ａ）アルカリ可溶性樹脂と反応することで、硬化後における均一なモルフォロジーを維持する。また、側鎖にフェニル基を含むことで、芳香環を多く含む（Ａ）アルカリ可溶性樹脂との相溶性を高めることができる。

(In the general formula (3), Z represents a reactive functional group or an alkylene group having 1 to 10 carbon atoms having a phenyl group in the side chain. The reactive functional group includes an aldehyde group, an acyl group, a carbamoyl group, , isocyanate group, imidazole group, silanol group, alkoxysilyl group, methylol group, alkoxymethyl group, epoxy group, oxetanyl group, vinyl group, ethynyl group, allyl group, acrylic group, methacryl group, etc.) The above-mentioned reactivity By having a functional group in the side chain, it reacts with the alkali-soluble resin (A) during curing, thereby maintaining uniform morphology after curing. Moreover, by including a phenyl group in the side chain, compatibility with the alkali-soluble resin (A) containing many aromatic rings can be improved.

The number of polymerized units represented by the general formula (3) contained in the polyether compound (C) is preferably 1 to 1,000, more preferably 10 to 100.

(C) Among the polymerized units contained in the polyether compound, the proportion of the polymerized units represented by general formula (1) is preferably 70% or more, more preferably 80% or more, and 90%. It is more preferable that it is above.

Further, among the polymerized units contained in the polyether compound (C), the proportion of the polymerized units represented by general formula (2) is preferably 1 to 50%, more preferably 3 to 20%. It is preferably 5% to 10%, more preferably 5% to 10%.

Furthermore, among the polymerized units contained in the polyether compound (C), the total ratio of the polymerized units represented by general formula (1) and the polymerized units represented by general formula (2) is 80% or more. It is preferably 90% or more, and more preferably 90% or more. In addition, the molecular weight occupied by the side chain becomes smaller, and by moderate interaction with (A) alkali-soluble resin, mechanical properties are further improved, and good solubility in alkaline developers can be achieved. More preferably, it is larger, and particularly preferably 100%.

(C) Specific examples of the polyether compound include polyethylene oxide (PEO), polypropylene oxide (PPO), ethylene oxide/propylene oxide copolymer (P(EO/PO)), and P(EO/PO). Examples include polyethers obtained by copolymerizing ethylene oxide (PO) with vinyl groups and phenyl groups in the side chains.

Among the above polyethers, as mentioned above, PEO has higher hydrophilicity than PPO, and from the viewpoint of developability with an aqueous alkaline solution, PEO is preferable. For the same reason, in P(EO/PO), it is desirable that the ratio of PO to EO is 10% or less.

In addition, as mentioned above, since P(EO/PO) has a lower crystallinity than PEO, P(EO/PO) has higher compatibility with (A) alkali-soluble resin than PEO and has a more uniform morphology. form. As a result, P(EO/PO) has better mechanical properties than PEO even when the photosensitive resin composition of the present invention is cured at a low temperature of less than 300°C.

(C) The polyether compound is preferably a polymer or copolymer of ethylene oxide or propylene oxide as described above. The (C) polyether compound is composed of only the polymerized units of general formula (1) in which X is an ethylene group and the polymerized units of general formula (2) in which Y is a propylene group. More preferably, it is an ether compound.

(C) The polyether compound may be a commercially available product, such as PEO manufactured by SIGMA-ALDRICH (Mn = 5,000), PEO manufactured by Wako Pure Chemical Industries, Ltd. (Mn = 8,000, 20,000, 100,000, 200,000), Alcox EP-1010N, CP-A2H, and CP-B2 manufactured by Meisei Chemical Co., Ltd., and ZEOSPAN 8100, 8030, and 8010 manufactured by Zeon Corporation.

The polyether compound (C) preferably has a number average molecular weight (Mn) of 3,000 to 300,000, more preferably 5,000 to 200,000.

(C) The polyether compound may be used alone or in combination of two or more.

The blending amount of the polyether compound (C) is preferably 1 to 20 parts by weight, more preferably 3 to 15 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A). Further, it is more preferably 7 to 15 parts by mass, and by containing it in an amount of 7 parts by mass or more, the mechanical properties can be further improved when the photosensitive resin composition is cured at a low temperature. Moreover, by including it in an amount of 15 parts by mass or less, it can be sufficiently mixed into the resin composition.

(Silane coupling agent)
The photosensitive resin composition of the present invention can contain a silane coupling agent. The silane coupling agent is not particularly limited, but a silane coupling agent having an arylamino group and a silane coupling agent having two or more trialkoxysilyl groups are preferred. A silane coupling agent having an arylamino group is more preferable since it has excellent resolution.

A silane coupling agent having an arylamino group will be explained. Examples of the aryl group of the arylamino group include aromatic hydrocarbon groups such as phenyl, tolyl, and xylyl groups, fused polycyclic aromatic groups such as naphthyl, anthracenyl, and phenanthrenyl groups, and aromatic groups such as thienyl and indolyl groups. and group heterocyclic groups.

（式中、Ｒ^５１～Ｒ^５５はそれぞれ独立に水素原子または有機基を表す。）The silane coupling agent having an arylamino group is preferably a compound having a group represented by the following general formula (5).

(In the formula, R ⁵¹ to R ⁵⁵ each independently represent a hydrogen atom or an organic group.)

In the above general formula (5), R ⁵¹ to R ⁵⁵ are preferably hydrogen atoms.

In the silane coupling agent having an arylamino group, the silicon atom and the arylamino group are preferably bonded via an organic group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms.

As specific examples of the silane coupling agent having an arylamino group, the following compounds are preferred.

Next, a silane coupling agent having two or more trialkoxysilyl groups will be explained. The trialkoxysilyl groups possessed by the silane coupling agent having two or more trialkoxysilyl groups may be the same or different, and the alkoxy groups possessed by these groups may be the same or different, respectively. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, and among them, methoxy group and ethoxy group are preferable.

In the silane coupling agent having two or more trialkoxysilyl groups, at least two silicon atoms are preferably bonded via an organic group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms. .

Specific examples of the silane coupling agent having two or more trialkoxysilyl groups are preferably the following compounds.

One type of silane coupling agent may be used alone, or two or more types may be used in combination. Further, it may contain a silane coupling agent other than the above-mentioned silane coupling agent having an arylamino group and a silane coupling agent having two or more trialkoxysilyl groups.

The amount of the silane coupling agent blended is preferably 1 to 15% by mass based on the total solid content of the composition. When the amount is 1 to 15% by mass, it is possible to prevent undeveloped portions of exposed areas.

[Sensitizer, adhesion aid, other ingredients]
The photosensitive resin composition of the present invention may contain a known sensitizer to further improve photosensitivity and a known adhesion aid to improve adhesion to the substrate, within a range that does not impair the effects of the present invention. A crosslinking agent or the like may also be added. Furthermore, in order to impart processing characteristics and various functionalities to the photosensitive resin composition of the present invention, various other organic or inorganic low-molecular or high-molecular compounds may be blended. For example, surfactants, leveling agents, plasticizers, fine particles, etc. can be used. The fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, and inorganic fine particles such as colloidal silica, carbon, and layered silicates. Furthermore, various coloring agents, fibers, etc. may be added to the photosensitive resin composition of the present invention.

[solvent]
The solvent used in the photosensitive resin composition of the present invention contains (A) an alkali-soluble resin, (B) a photosensitizer, (C) the compound represented by the aforementioned general formula (1), and other additives. It is not particularly limited as long as it can be dissolved. Examples include N,N'-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N,N'-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ- Mention may be made of butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, γ-butyrolactone, and diethylene glycol monomethyl ether. These may be used alone or in combination of two or more. The amount of solvent to be used can be appropriately determined depending on the coating film thickness and viscosity. For example, it can be used in an amount of 50 to 9,000 parts by mass based on 100 parts by mass of the alkali-soluble resin (A).

The photosensitive resin composition of the present invention is preferably of positive type.

[Dry film]
The dry film of the present invention has a resin layer obtained by coating the photosensitive resin composition of the present invention on a carrier film and then drying the coated photosensitive resin composition. This resin layer is used by laminating it in contact with a base material.

The dry film of the present invention can be produced by uniformly applying the photosensitive resin composition of the present invention to a carrier film using an appropriate method such as a blade coater, lip coater, comma coater, film coater, etc., and drying it to form the above-described resin layer. It can be manufactured by forming a cover film and preferably laminating a cover film thereon. The cover film and the carrier film may be the same film material or may be different films.

In the dry film of the present invention, any film material known for use in dry films can be used for the carrier film and the cover film.
As the carrier film, a thermoplastic film such as a polyester film such as polyethylene terephthalate having a thickness of 2 to 150 μm is used.
As the cover film, polyethylene film, polypropylene film, etc. can be used, but it is preferable that the adhesive force with the resin layer is smaller than that of the carrier film.

The thickness of the resin layer on the dry film of the present invention is preferably 100 μm or less, more preferably in the range of 5 to 50 μm.

[Cured product]
The cured product of the present invention is obtained by curing the above-described photosensitive resin composition of the present invention in a predetermined step. The pattern film, which is the cured product, may be manufactured by a known and commonly used manufacturing method. For example, in the case of a positive photosensitive resin composition containing a polybenzoxazole precursor as the alkali-soluble resin (A), each of the following steps is performed. Manufactured by

First, in step 1, a coating film is obtained by applying a photosensitive resin composition onto a substrate and drying it, or by transferring a resin layer from a dry film onto the substrate. Methods for applying the photosensitive resin composition onto the substrate include methods conventionally used for applying photosensitive resin compositions, such as spin coaters, bar coaters, blade coaters, curtain coaters, screen printers, etc. A coating method using a spray coater, a spray coating method using a spray coater, an inkjet method, etc. can be used. As a method for drying the coating film, methods such as air drying, heating drying using an oven or hot plate, and vacuum drying are used. Further, it is desirable that the coating film be dried under conditions that do not cause ring closure of the polybenzoxazole precursor in the photosensitive resin composition. Specifically, natural drying, blow drying, or heat drying can be performed at 70 to 140° C. for 1 to 30 minutes. Preferably, drying is performed on a hot plate for 1 to 20 minutes. Vacuum drying is also possible, and in this case it can be carried out at room temperature for 20 minutes to 1 hour.
There is no particular restriction on the substrate on which the coating film of the photosensitive resin composition is formed, and it can be widely applied to semiconductor substrates such as silicon wafers, wiring boards, various resins, metals, etc.

Next, in step 2, the coating film is exposed to light through a patterned photomask or directly. The exposure light beam used has a wavelength that can activate the photoacid generator (B) as a photosensitizer. Specifically, the exposure light preferably has a maximum wavelength in the range of 350 to 410 nm. As mentioned above, photosensitivity can be adjusted by appropriately blending a sensitizer. As the exposure device, a contact aligner, mirror projection, stepper, laser direct exposure device, etc. can be used.

Subsequently, in Step 3, the coating film may be heated for a short time as necessary to ring-close a portion of the polybenzoxazole precursor in the unexposed area. Here, the ring closure rate is about 30%. The heating time and heating temperature are appropriately changed depending on the type of polybenzoxazole precursor, the coating film thickness, and the type of (B) photosensitizer.

Next, in step 4, the coating film is treated with a developer. Thereby, the exposed portion in the coating film can be removed to form a patterned film of the photosensitive resin composition of the present invention.

As the method used for development, any method can be selected from conventionally known photoresist development methods, such as a rotary spray method, a paddle method, and an immersion method accompanied by ultrasonic treatment. Examples of developing solutions include inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, and aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine, and tetramethylammonium hydroxide and tetrabutylammonium hydroxide. Examples include aqueous solutions of quaternary ammonium salts such as . Further, if necessary, a suitable amount of a water-soluble organic solvent such as methanol, ethanol, isopropyl alcohol, or a surfactant may be added to these. Thereafter, if necessary, the coating film is washed with a rinsing liquid to obtain a patterned film. As the rinsing liquid, distilled water, methanol, ethanol, isopropyl alcohol, etc. can be used alone or in combination. Further, the above-mentioned solvents may be used as the developer.

Thereafter, in step 5, the patterned film is heated to obtain a cured coating film (cured product). This heating causes ring closure of the polybenzoxazole precursor to obtain polybenzoxazole. The heating temperature is appropriately set so that the patterned film of the photosensitive resin composition can be cured. For example, heating is performed in an inert gas at a temperature of 150° C. or more and less than 300° C. for about 5 to 120 minutes. A more preferable heating temperature range is 180 to 250°C. Since the photosensitive resin composition of the present invention contains the polyether compound (C), cyclization is promoted and the heating temperature can be lower than 300°C. Heating is performed, for example, by using a hot plate, an oven, or a heating oven in which a temperature program can be set. As the atmosphere (gas) at this time, air may be used, or an inert gas such as nitrogen or argon may be used.

In addition, when the photosensitive resin composition of the present invention is a negative photosensitive resin composition, the above step is performed using a photopolymerization initiator or a photobase generator instead of the photoacid generator as the photosensitizer (B). By treating the coating film with a developer in step 4, unexposed portions in the coating film can be removed to form a patterned film of the photosensitive resin composition of the present invention.

The use of the photosensitive resin composition of the present invention is not particularly limited, and for example, it can be suitably used as a paint, printing ink, or adhesive, or as a forming material for display devices, semiconductor devices, electronic components, optical components, or building materials. used. Specifically, as a material for forming a display device, it can be used as a layer-forming material or an image-forming material, such as a color filter, a flexible display film, a resist material, an alignment film, and the like. Further, as a material for forming a semiconductor device, it can be used as a resist material, a layer forming material such as a buffer coat film, and the like. Further, as a material for forming electronic components, it can be used as a sealing material or a layer forming material for printed wiring boards, interlayer insulating films, wiring coating films, etc. Furthermore, as a material for forming optical components, it can be used as an optical material or a layer forming material for holograms, optical waveguides, optical circuits, optical circuit components, antireflection films, and the like. Furthermore, as a building material, it can be used as a paint, a coating agent, etc.

The photosensitive resin composition of the present invention is mainly used as a pattern forming material, and the pattern film formed thereby functions as a component that imparts heat resistance and insulation as a permanent film made of polybenzoxazole, etc. Therefore, it is particularly suitable for surface protection films for semiconductor devices, display devices, and light emitting devices, interlayer insulation films, rewiring insulation films, protection films for flip-chip devices, protection films for devices with bump structures, and interlayer insulation for multilayer circuits. It can be suitably used as a film, an insulating material for passive components, a protective film for printed wiring boards such as a solder resist or a coverlay film, and a liquid crystal alignment film. In particular, it is suitable for use as an insulating film in contact with copper wiring or aluminum wiring.

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

(Synthesis of polybenzoxazole (PBO) precursor)
212 g of N-methylpyrrolidone was placed in a 0.5 liter flask equipped with a stirrer and a thermometer, and 28.00 g (76.5 mmol) of bis(3-amino-4-hydroxyamidophenyl)hexafluoropropane was dissolved with stirring. . Thereafter, the flask was immersed in an ice bath, and while keeping the inside of the flask at 0 to 5°C, 25.00 g (83.2 mmol) of 4,4-diphenyl ether dicarboxylic acid chloride was added as a solid in 5 g portions over 30 minutes. The mixture was stirred for 30 minutes. Thereafter, stirring was continued for 5 hours at room temperature. The stirred solution was poured into 1 L of ion-exchanged water (specific resistance value: 18.2 MΩ·cm), and the precipitate was collected. Thereafter, the obtained solid was dissolved in 420 mL of acetone and poured into 1 L of ion-exchanged water. After collecting the precipitated solid, it was dried under reduced pressure to obtain a polybenzoxazole (PBO) precursor A-1 having a carboxyl group-terminated repeating structure shown below. The number average molecular weight (Mn) of polybenzoxazole precursor A-1 was 12,900, the weight average molecular weight (Mw) was 29,300, and the Mw/Mn was 2.28.

(Examples 1 to 9)
To 100 parts by mass of the polybenzoxazole precursor synthesized above, (B) 10 parts by mass of naphthoquinonediazide compound B-1 (TKF-428 manufactured by Sanbo Chemical Co., Ltd.) as a photosensitizer, and aryl as a silane coupling agent. After blending 7 parts by mass of a silane coupling agent having an amino group (KBM-573 manufactured by Shin-Etsu Silicone Co., Ltd.) and each of the C-1 to C-4 polyether compounds shown below, 30 parts by mass of the benzoxazole precursor was added. % of gamma-butyrolactone (GBL) to prepare a varnish, and photosensitive resin compositions of Examples 1 to 9 were prepared. In addition, as C-1, PEO manufactured by SIGMA-ALDRICH (Mn = 5,000), as PEO manufactured by Wako Pure Chemical Industries, Ltd. (Mn = 8,000, 20,000, 100,000, 200,000), as C-2. Alcox EP-1010N manufactured by Meisei Chemical Co., Ltd. (random copolymer of ethylene oxide and propylene oxide, m:n = 12:1, Mn = approximately 100,000), Alcox CP-A2H manufactured by Meisei Chemical Co., Ltd. as C-3 ( Random copolymer of allyl glycidyl ether, ethylene oxide, and propylene oxide, l:m:n = 96:1:3, Mn = approximately 80,000), Alcox CP-B2 manufactured by Meisei Chemical Co., Ltd. (ethylene oxide) as C-4 and a random copolymer of propylene oxide and phenyl glycidyl ether, n:m:l=97:1:2, Mn=about 100,000).

(Comparative Examples 1 to 6)
Further, as Comparative Example 1, a photosensitive resin composition of Comparative Example 1 was prepared in the same manner as in Example 1 except that the above-mentioned (C) polyether compound of C-1 was not blended.
In addition, Comparative Examples 2 to 6 were carried out except that the following melamine-based or urea-based crosslinking agents C-5 to C-8 were blended instead of the above-mentioned (C) polyether compounds C-1 to C-4. Photosensitive resin compositions of Comparative Examples 2 to 6 were prepared in the same manner as Examples 1 to 5.

The photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 6 thus prepared were evaluated for resolution, chemical resistance, and elongation at break. The evaluation method is as follows.

(Method for producing dry coating film for evaluation)
The above photosensitive resin composition was applied onto a silicon substrate using a spin coater. It was dried on a hot plate at 120° C. for 3 minutes to obtain a dry coating film of the photosensitive resin composition.

(Evaluation of chemical resistance)
The dried coating film obtained above was heated on a hot plate at a temperature of 240° C. for 1 hour, and the obtained cured product was immersed in gamma-butyrolactone (GBL) for 10 minutes, and the change in film thickness and the presence or absence of cracks were evaluated. The evaluation of chemical resistance in Tables 1 and 2 was based on the following criteria.
Film thickness change ○: Film thickness change less than ±1% △: Film thickness change more than ±1% and less than 5% ×: Film thickness change more than ±5% Crack ○: No crack in 1 cm section △: Crack in 1 cm section 1 or more and less than 10 cracks ×: 10 or more cracks in a 1 cm section

(Evaluation of elongation at break)
The dried coating film obtained above was heated on a hot plate for 1 hour at a temperature of 240°C, and then tested at 168°C under the conditions of 121°C, saturation, and 0.2 MPa using a PCT device (HAST SYSTEM TPC-412MD manufactured by Espec). After a period of time had elapsed, the peeled cured film with a thickness of 30 μm was cut into pieces of 50 mm in length and 5 mm in width, and a tensile test was conducted using “EZ-SX” manufactured by Shimadzu Corporation. The distance between the grips was 30 mm, the tensile speed was 3 mm/mm, and the measurements were performed seven times, and the average of the top three measurements was taken as the elongation at break.
The evaluation of elongation at break in Tables 1 and 2 was based on the following criteria.
◎: 20% or more ○: 15% or more and less than 20% △: 10% or more and less than 15% ×: less than 10%

Tables 1 and 2 show the heating temperature during heating, and also show the evaluation results of chemical resistance and elongation at break.

As can be seen from Tables 1 and 2, Examples 1 to 9 containing (C) a polyether compound having 100 to 10,000 polymerized units can be sufficiently cured at a low temperature of 240°C, and have a sufficient It showed chemical resistance and elongation at break. Furthermore, Example 6 containing the compound C-2 as the polyether compound (C) was able to further improve the elongation at break. Note that Examples 1 to 9 had resolutions equivalent to those of conventional photosensitive resin compositions.

On the other hand, in Comparative Example 1, since the polyether compound (C) was not blended, sufficient curing could not be achieved at the heating temperature of 240°C. Furthermore, in Comparative Examples 2 to 5, additives other than the polyether compound (C) were blended as a crosslinking agent, but sufficient chemical resistance could not be obtained. Furthermore, in Comparative Example 6, the chemical resistance was improved by increasing the amount of the melamine crosslinking agent added, but the elongation at break was lower than that of the conventional photosensitive resin composition.

Claims (8)

A photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a photosensitizer, and (C) a polyether compound containing 100 to 10,000 polymerized units represented by general formula (1). hand,
The alkali-soluble resin (A) is a polybenzoxazole precursor, and the amount thereof is 60 to 90% by mass based on the total solid content of the photosensitive resin composition,
A photosensitive resin composition comprising a naphthoquinone diazide compound as the photosensitive agent (B) .

(In general formula (1), X represents an alkylene group having 1 to 10 carbon atoms.) The photosensitive resin composition according to claim 1, wherein the polyether compound (C) further contains 1 to 1,000 polymerized units represented by general formula (2).

(In general formula (2), Y represents an alkylene group having 1 to 10 carbon atoms. However, this excludes cases where it is the same as X in general formula (1).) The photosensitive resin composition according to claim 1, wherein the polyether compound (C) further contains 1 to 1,000 polymerized units represented by general formula (3).

(In the general formula (3), Z represents a reactive functional group or an alkylene group having 1 to 10 carbon atoms having a phenyl group in the side chain.) A dry film comprising a resin layer obtained by applying the photosensitive resin composition according to claim 1 onto a film and drying it. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 3 or the resin layer of the dry film according to claim 4 . A printed wiring board comprising the cured product according to claim 5 . A semiconductor device comprising the cured product according to claim 5 . An electronic component comprising the cured product according to claim 5 .