TW202003695A - Photosensitive resin composition, dry film, cured product, printed wiring board, and semiconductor element - Google Patents

Abstract

Provided are: a photosensitive resin composition from which a cured product having both an improved chemical resistance and elongation rate can be obtained by curing at a low temperature of less than 300 DEG C; a dry film having a resin layer which is obtained from said composition; a cured product of a resin layer of the composition or the dry film; a semiconductor element having said cured product; a printed wiring board; and an electronic component. This photosensitive resin composition is characterized by including (A) an alkali-soluble resin, (B) a photosensitive agent, and (C) a polyester compound including 100-10,000 polymerization units represented by general formula (1). (In general formula (1), X represents an alkylene group having 1-10 carbon atoms.).

Description

Photosensitive resin composition, dry film, cured product, printed wiring board and semiconductor element

The present invention relates to a photosensitive resin composition, dry film, hardened material, printed wiring board suitable for a protective film of a semiconductor device, an insulating film for a redistribution layer of a wafer level package (WLP), an insulating portion of a passive part, etc. And semiconductor components.

For the buffer coating film of LSI or the insulating film for the redistribution layer of wafer level packaging (WLP), a photosensitive resin containing a heat-resistant resin precursor such as polyimide or polybenzoxazole (PBO) can be used The cured film of the composition. These photosensitive resin compositions are hardened by heat treatment to cyclize the heat-resistant resin precursor. Conventional heat treatment is 300°C or higher, but in recent years, in order to suppress thermal damage of semiconductor elements, it is required to harden the precursor of the heat-resistant resin at a low temperature.

In contrast, in the past, it has been discussed that, as a photosensitive resin composition that can be hardened at a low temperature, a crosslinking agent having a hydroxymethyl group in the structure is included, so that the crosslinking agent can proceed with the resin at a low temperature Crosslinking to improve the properties of the cured film. For example, the positive photosensitive resin composition that can be hardened at a low temperature includes a melamine-based or urea-based crosslinking agent (Patent Document 1).

On the other hand, the hardened product of the above-mentioned photosensitive resin composition also requires elongation (breaking elongation) in order to ensure mechanical and thermal shock reliability. [Prior Technical Literature] [Patent Literature]

Patent Document 1: Patent No. 4046563

[Problems to be solved by the invention]

If a melamine-based or urea-based crosslinking agent is blended, although it can be hardened at low temperature, more crosslinking agent must be added to have sufficient chemical resistance. As a result, the crosslinking density increases and the elongation decreases. .

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

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

(一般式(1)中，X表示碳數1～10之伸烷基。)That is, the photosensitive resin composition of the present invention comprises (A) an alkali-soluble resin, (B) a photosensitizer, and (C) a polyether compound containing 100 to 10,000 polymerization units represented by general formula (1).

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

(一般式(2)中，Y表示碳數1～10之伸烷基。惟，排除與一般式(1)中之X相同的情況。)In the photosensitive resin composition of the present invention, it is preferred that the polyether compound (C) further contains 1 to 1,000 polymerization units represented by general formula (2).

(In general formula (2), Y represents an alkylene group having 1 to 10 carbon atoms. However, the same situation as X in general formula (1) is excluded.)

(一般式(3)中，Z表示側鏈具有反應性官能基或苯基的碳數1～10之伸烷基。)The photosensitive resin composition of the present invention is preferably one in which the polyether compound (C) further contains 1 to 1,000 polymerization units represented by general formula (3).

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

The photosensitive resin composition of the present invention is preferably one containing a polybenzoxazole precursor in the aforementioned (A) alkali-soluble resin.

The photosensitive resin composition of the present invention is preferably one containing a diazonaphthoquinone compound in the aforementioned (B) photosensitive agent.

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

The cured product of the present invention is characterized 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 aforementioned cured product.

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

The electronic component of the present invention is characterized by having the aforementioned hardened product. [Effect of invention]

According to the present invention, it is possible to provide a photosensitive resin composition capable of obtaining a cured product which is cured at a low temperature of not more than 300°C and has improved chemical resistance and elongation, a dry film having a resin layer obtained from the composition, The cured product of the composition or the resin layer of the dry film, the semiconductor element having the cured product, the printed wiring board, and the electronic parts.

Hereinafter, the components contained in the photosensitive resin composition of the present invention will be described 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 alkaline aqueous solution as a developing solution in the developed image after exposure to active energy rays. As the alkali-soluble resin, alkali-soluble polymers that have hitherto been used in photosensitive resin compositions can be used. Alkali-soluble polymers are those having an alkali-soluble group in the molecule, and specific examples include those having a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group. Among them, a polymer having a phenolic hydroxyl group or a carboxyl group is preferred, and examples thereof include novolak resins, soluble phenolic resins, polyimide precursors, and polybenzoxazole precursors. Preferred are polyimide precursors and polybenzoxazole precursors. If these polymers are heated at a predetermined temperature, they will be dehydrated and closed, and a heat-resistant resin will be obtained in the form of copolymerization of polyimide, polybenzoxazole, or both.

(式中，X表示4價之有機基，Y表示2價之有機基。n為1以上之整數，較佳為10～50，更佳為20～40。)The polybenzoxazole precursor is preferably a polyhydroxyamide having a repeating structure of general formula (4) described later.

(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, and more preferably 20 to 40.)

When the polybenzoxazole precursor is synthesized by the above-mentioned synthesis method, in the above general formula (4), X is the residue of the above dihydroxydiamine, and Y is the 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), bis(4- Amino-3-hydroxyphenyl) ash, 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-hexafluoropropane, etc. Among them, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane is more preferable.

For the above dicarboxylic acids, 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-carboxyl Phenyl) ash, 2,2-bis(p-carboxyphenyl)propane, 2,2-bis(4-carboxyphenyl)-1,1,1,3,3,3-hexafluoropropane, etc. Aromatic ring dicarboxylic acids, oxalic acid, malonic acid, succinic acid, 1,2-cyclobutane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 1,3-cyclopentane dicarboxylic acid, etc. Aliphatic dicarboxylic acid. Among them, 4,4'-dicarboxydiphenyl ether is more preferable.

In the above general formula (4), the tetravalent organic group represented by X may be an aliphatic group or an aromatic group, but an aromatic group is preferred, and two hydroxyl groups and two amine groups are adjacent to and located at Those with aromatic rings are better. The number of carbon atoms of the above-mentioned tetravalent aromatic group is preferably 6-30, and more preferably 6-24. The specific examples of the above-mentioned tetravalent aromatic group include the groups shown below, but they are not limited to these. Depending on the application, a known aromatic group that can be contained in the polybenzoxazole precursor is selected That's it.

Even if the above-mentioned tetravalent aromatic group is among the above-mentioned aromatic groups, the group shown below is preferable.

In the above general formula (4), the divalent organic group represented by Y may be an aliphatic group or an aromatic group, but an aromatic group is preferred, and an aromatic ring is the same as the carbonyl group in the above general formula (4) Bonders are better. The number of carbon atoms of the divalent aromatic group is preferably 6-30, and more preferably 6-24. The specific examples of the above-mentioned divalent aromatic group include the groups shown below, but it is not limited to these. Depending on the application, a known aromatic group that can be contained in the polybenzoxazole precursor is selected That's it.

(式中，A表示單鍵、-CH₂ -、-O-、-CO-、-S-、 -SO₂ -、-NHCO-、-C(CF₃ )₂ -、-C(CH₃ )₂ -所成之群選出的2價之基。)

(In the formula, A represents a single bond, -CH ₂ -, -O-, -CO-, -S-, -SO ₂ -, -NHCO-, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -The base of the 2 price selected by the group.)

The above-mentioned divalent organic group, even among the above-mentioned aromatic groups, is preferably the group shown below.

The polybenzoxazole precursor may also contain a repeating structure of two or more of the above polyhydroxyamides. In addition, it may include a structure other than the repeating structure of the above-mentioned polyhydroxyamide, for example, 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, and more preferably 8,000 to 50,000. Here, the number average molecular weight is measured by colloidal permeation chromatography (GPC) and converted to standard polystyrene. In addition, the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 10,000 to 200,000, and more preferably 16,000 to 100,000. Here, the weight average molecular weight is measured by GPC and converted to standard polystyrene. Mw/Mn is preferably 1-5, more preferably 1-3.

The polybenzoxazole precursor may be used alone or in combination of two or more. The method of synthesizing the polybenzoxazole precursor is not particularly limited, and it may be synthesized by a known method. For example, it can be obtained by reacting dihydroxy diamines as amine components with dihalides of dicarboxylic acids such as dicarboxylic acid dichloride as acid components.

(A) The blending amount of the alkali-soluble resin is preferably 60 to 90% by mass based on the total solid content of the composition. By including 60% by mass or more, adhesion and surface hardening property are good. In addition, by including 90% by mass or less, it is possible to prevent the crosslink density in the cured product from decreasing, and the coating film characteristics are improved.

[(B) Sensitizer] The photosensitive resin composition of the present invention contains a photosensitizer. (B) The photosensitive agent is not particularly limited, and a photoacid generator, photopolymerization initiator, or photobase generator can be used. The photo-acid generator is a compound that generates an acid by irradiation with ultraviolet light or visible light, etc. The photopolymerization initiator is a compound that generates free radicals and the like by irradiation with the same light, and the photo-base generator is produced by the same Irradiation of light changes the molecular structure or cracks the molecule, thereby generating a compound of more than one basic substance. In the present invention, it is preferable to use a photoacid generator as the (B) photosensitizer. Examples of photoacid generators include naphthoquinonediazide compounds, diarylammonium salts, triarylammonium salts, dialkylbenzylmethylammonium salts, diarylphosphonium salts, and aryldiazonium salts. , Aromatic tetracarboxylic acid esters, aromatic sulfonate esters, nitrobenzyl esters, aromatic N-oxyl imide sulfonate, aromatic sulfonamide, benzoquinone diazide sulfonate, etc. The photoacid generator is preferably one that dissolves the inhibitor. Among them, naphthoquinonediazide compounds are preferred.

For naphthoquinonediazide compounds, specifically, naphthoquinonediazide adducts of ginseng (4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene (for example, Sambo TS533, TS567, TS583, TS593 manufactured by the Institute of Chemistry, naphthoquinone diazide adducts of tetrahydroxybenzophenone (e.g., BS550, BS570, BS599 manufactured by Sambo Institute of Chemistry), 4-{ 4-[1,1-bis(4-hydroxyphenyl)ethyl]-α,α-dimethylbenzyl}phenol naphthoquinone diazide adduct (for example, manufactured by Sambo Chemical Research Institute) TKF-428, TKF-528) etc.

In addition, for the photopolymerization initiator, conventionally known ones can be used, for example, an oxime ester-based photopolymerization initiator having an oxime ester group, an α-aminoacetophenone-based photopolymerization initiator, an acylphosphine oxide Series photopolymerization initiator, titanocene series photopolymerization initiator, etc.

As for the aforementioned oxime ester-based photopolymerization initiator, commercially available products include CGI-325, IRGACURE-OXE01, IRGACURE-OXE02 manufactured by BASF JAPAN, N-1919, NCI-831 manufactured by ADEKA, and the like.

For the aforementioned α-aminoacetophenone-based photopolymerization initiator, specifically, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylacetone- 1. 2-Benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butane-1-one, 2-(dimethylamino)-2-[(4- Methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoacetophenone, etc., for commercial products, then There are Omnirad 907, Omnirad 369, Omnirad 379, etc. manufactured by IGM Resins.

As for the above-mentioned acylphosphine oxide-based photopolymerization initiator, specifically, 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-tri Methylbenzyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzyl)-2,4,4-trimethyl-pentylphosphine oxide, etc., and commercially available In terms of products, Omnirad TPO and Omnirad 819 made by IGM Resins can be used.

In terms of the above-mentioned titanocene-based photopolymerization initiator, specifically, bis(cyclolocenyl)-di-phenyl-titanium, bis(cyclolocenyl)-di-chloro-titanium, bis(cyclolocenyl)- Bis(2, 3, 4, 5, 6 pentafluorophenyl) titanium, bis(cyclopentyl)-bis(2,6-difluoro-3-(pyrrol-1-yl)phenyl) titanium, etc. In terms of commercially available products, Omnirad 784 manufactured by IGM Resins and the like can be cited.

In addition, the photobase generator may be an ionic photobase generator or a non-ionic photobase generator. However, the ionic photobase generator has a high sensitivity to the composition, which is beneficial to the patterned film. It is better formed. As for the alkaline substance, for example, a secondary amine or a tertiary amine can be mentioned.

For the ionic photobase generator, for example, a salt formed by a carboxylic acid containing an aromatic component and a tertiary amine, or WPBG-082, WPBG-167, WPBG-168 of ionic PBG manufactured by Wako Pure Chemical Industries, Ltd. , WPBG-266, WPBG-300, etc.

Non-ionic photobase generators include, for example, α-aminoacetophenone compounds, oxime ester compounds, or having N-methylated aromatic amine groups, N-acetylated aromatic amine groups, and nitrobenzyl Compounds such as substituents such as aminocarbamate groups, alkoxybenzylcarbamate groups, etc. For other photobase generators, WPBG-018 (trade name: 9-anthrylmethyl N, N'-diethylcarbamate) and WPBG-027 (trade name: (E)-1-[3- (2-hydroxyphenyl)-2-propenoyl] piperidine), WPBG-140 (trade name: 1-(anthraquinon-2-yl) ethyl imidazolecarboxylate), WPBG-165, etc.

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

(一般式(1)中，X表示碳數1～10之伸烷基。)[Polyether compound containing 100 to 10,000 (C) polymerization units represented by general formula (1)] The photosensitive resin composition of the present invention includes 100 to 10,000 (C) polymerization units represented by general formula (1) Polyether compound (hereinafter referred to simply as "(C) polyether compound").

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

(C) The polyether compound has high compatibility with the (A) alkali-soluble resin, and even in a high molecular weight body containing a polymerization unit of 100 or more in general formula (1), it will maintain a uniform form during drying or curing. As a result, the photosensitive resin composition of the present invention containing the (C) polyether compound can have sufficient chemical resistance and mechanical properties even if it is cured at a low temperature of less than 300°C.

Furthermore, since the compound represented by the general formula (1) is hydrophilic, it does not hinder the solubility in the alkali developing solution. As a result, the photosensitive resin composition of the present invention containing the (C) polyether compound can have the same resolution as the conventional photosensitive resin composition.

As can be seen from the above description, the photosensitive resin composition of the present invention containing the (C) polyether compound does not reduce the chemical resistance, mechanical properties, and resolution. It can be heated under a low temperature of less than 300°C. Its hardened.

By containing more than 100 polymerized units represented by general formula (1), the photosensitive resin composition of the present invention can exhibit sufficient chemical resistance and mechanical properties even when cured at a low temperature of less than 300°C性性。 Sexual characteristics. In addition, if the polymerization unit is 10,000 or less, the solubility in a solvent is good, and it is suitable for the production of a photosensitive resin composition. More preferably, it is 1,000 to 10,000. By including polymerization units of 1,000 or more, the contrast of the dissolution rate difference between the unexposed part and the exposed part is improved, and it shows good resolution.

(C) Both ends of the polyether compound are preferably -OR (R represents a hydrogen atom or an alkylene group having 1 to 10 carbon atoms). The alkylene group having 1 to 10 carbon atoms represented by R may be the same as X in the general formula (1). By making the end the same as the main chain skeleton, the change in compatibility due to the difference in molecular weight can be reduced. (C) Both ends of the polyether compound are preferably -OH. By this, good solubility in alkali developing solution will be shown.

In the general formula (1), the alkylene group having 1 to 10 carbon atoms represented by X includes methylene, ethylidene, trimethylene, and propylidene (=-CH ₂ CH(CH ₃ ) Linear or branched chain alkylene such as tetramethylene, 1,1-dimethyltetramethylene, butylene, octyl, decyl, etc. Among these, from the viewpoint of high hydrophilicity and developability with respect to an alkaline aqueous solution, alkylene having 2 to 4 carbon atoms is more preferred, and ethylidene is more preferred.

(一般式(2)中，Y表示碳數1～10之伸烷基。惟，排除與一般式(1)中之X相同的情況。)(C) The polyether compound may be a copolymer such as a random copolymer or a block copolymer. For other polymerization units, for example, the polymerization unit represented by the general formula (2) may be mentioned.

(In general formula (2), Y represents an alkylene group having 1 to 10 carbon atoms. However, the same situation as X in general formula (1) is excluded.)

In the general formula (2), the alkylene group having 1 to 10 carbon atoms represented by Y may be the same as X in the general formula (1). Among them, the branched chain alkylene group is more preferred, because the degree of crystallinity will be lower, the compatibility with the (A) alkali-soluble resin is high, and a more uniform form will be formed. When the photosensitive resin composition is cured at a low temperature of less than 300°C, it can have better mechanical properties. Among these, branched chain alkylene having 3 to 5 carbon atoms is more preferable, and propylene is even better.

(C) The number of polymerization units represented by the general formula (2) contained in the polyether compound is preferably 1 to 1,000, and more preferably 10 to 100. In addition, the ratio of the number of polymerization units shown in the general formula (2) to the number of polymerization units shown in the general formula (1) is for a period of 10% or less.

In addition, other polymerization units that may contain the (C) polyether compound include, for example, polymerization units represented by general formula (3).

(一般式(3)中，Z表示側鏈具有反應性官能基或苯基的碳數1～10之伸烷基。前述反應性官能基方面，可舉出醛基、醯基、胺甲醯基、異氰酸酯基、咪唑基、矽烷醇基、烷氧基矽基、羥甲基、烷氧基甲基、環氧基、氧雜環丁烷基、乙烯基、乙炔基、烯丙基、丙烯醯基、甲基丙烯醯基等。)藉由在側鏈具有前述反應性官能基，在硬化時因會與(A)鹼可溶性樹脂反應之故，可在硬化後維持均一形態。又，藉由在側鏈含有苯基，而得以提高與含多數芳香環之(A)鹼可溶性樹脂的相溶性。

(In the general formula (3), Z represents a C 1-10 alkylene group having a reactive functional group or phenyl group in the side chain. The reactive functional group includes aldehyde group, acetyl group, and carbamoyl group. Group, isocyanate group, imidazolyl group, silanol group, alkoxysilyl group, methylol group, alkoxymethyl group, epoxy group, oxetanyl group, vinyl group, ethynyl group, allyl group, propylene group Acyl group, methacryl group, etc.) By having the above-mentioned reactive functional group in the side chain, it can react with (A) alkali-soluble resin during curing, so it can maintain a uniform form after curing. Moreover, by containing a phenyl group in the side chain, the compatibility with (A) alkali-soluble resin containing many aromatic rings can be improved.

(C) The polymerization unit represented by general formula (3) contained in the polyether compound is preferably 1 to 1,000, and more preferably 10 to 100.

(C) Of the polymerization units contained in the polyether compound, the ratio of the polymerization units represented by the general formula (1) is preferably 70% or more, more preferably 80% or more, and more than 90% good.

In addition, among the polymerization units contained in the (C) polyether compound, the ratio of the polymerization unit represented by the general formula (2) is preferably 1-50%, more preferably 3-20%, 5- 10% is better.

In addition, among the polymerization units contained in the (C) polyether compound, the ratio of the total of the polymerization units represented by the general formula (1) and the polymerization units represented by the general formula (2) is preferably at least 80% , More than 90% is better. In addition, the molecular weight occupied by the side chain becomes smaller, and the mechanical properties can be further improved by moderate interaction with the (A) alkali-soluble resin, which can also have good solubility in alkali developing solution, so it is greater than 98 % Is better, 100% is particularly good.

(C) Specific compounds of polyether compounds include, for example, polyethylene oxide (PEO) and polypropylene oxide (PPO), and ethylene oxide/propylene oxide copolymer (P(EO/PO)) , Others include polyethers obtained by copolymerizing ethylene oxide with vinyl and phenyl on the side chain on P(EO/PO).

Among the above-mentioned polyethers, as described above, PEO is preferable in terms of higher hydrophilicity than PPO and developability with respect to an alkaline aqueous solution. For the same reason, in P(EO/PO), the ratio of PO to EO is 10% or less.

Also, as described above, P(EO/PO) has a lower degree of crystallinity than PEO. Compared with PEO, P(EO/PO) has higher compatibility with (A) alkali-soluble resin and forms a more uniform 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 as described above, preferably a polymer or copolymer of ethylene oxide or propylene oxide. In addition, (C) the polyether compound is formed by the polymerization unit of the general formula (1) consisting only of X as the polymerization unit, and the polymerization unit of the general formula (2) where Y is the propyl group. Polyether compounds are better.

(C) The polyether compound may be a commercially available product, for example, PEO (Mn=5,000) manufactured by SIGMA-ALDRICH, PEO (Mn=8,000, 20,000, 100,000, 200,000) manufactured by Wako Pure Chemical Industries, Ltd., manufactured by Mingcheng Chemical Co., Ltd. Polyether compounds such as ALKOX EP-1010N, CP-A2H, CP-B2, ZEOSPAN 8100, 8030, 8010, etc. manufactured by ZEON Corporation of Japan.

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

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

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

(Silane coupling agent) The photosensitive resin composition of the present invention may contain a silane coupling agent. The silane coupling agent is not particularly limited. A silane coupling agent having an arylamine group and a silane coupling agent having two or more trialkoxysilyl groups are preferred. From the viewpoint of excellent resolution, it is better to use a silane coupling agent having an arylamine group.

The silane coupling agent having an arylamine group will be described. Examples of the aryl group of the arylamino group include aromatic hydrocarbon groups such as phenyl, tolyl, and xylyl, condensed polycyclic aromatic groups such as naphthyl, anthryl, and phenanthryl, thienyl, and indolyl. Etc. aromatic heterocyclic groups.

(式中，R⁵¹ ～R⁵⁵ 各自獨立地表示氫原子或有機基。)The silane coupling agent having an arylamine 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.

The silane coupling agent having an arylamine group is preferably a silicon atom and an arylamine group through 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 an arylamine group are preferably the compounds shown below.

Next, a silane coupling agent having two or more trialkoxysilyl groups will be described. Silane coupling agent having two or more trialkoxysilyl groups, the trialkoxysilyl groups may be the same or different, and the alkoxy groups of these groups may be the same or different different. As for the alkoxy group, methoxy, ethoxy, propoxy, butoxy and the like can be mentioned. Among them, methoxy and ethoxy are more preferable.

A silane coupling agent having two or more trialkoxysilyl groups is composed of at least two silicon atoms through an organic group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms. good.

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

The silane coupling agent may be used alone or in combination of two or more. In addition, it may contain a silane coupling agent other than the silane coupling agent having an arylamine group and a silane coupling agent having two or more trialkoxysilyl groups.

The blending amount of the silane coupling agent is based on the total solid content of the composition, preferably 1 to 15% by mass. If it is 1 to 15% by mass, the development of the exposed portion can be prevented.

[Sensitizer, adhesion aid, other ingredients] In the photosensitive resin composition of the present invention, a well-known sensitizer may be blended in order to further improve the photosensitivity, and a well-known sensitizer may be blended in order to improve the adhesion to the substrate Adhesion aid or cross-linking agent. In addition, in order to impart processing characteristics or various functions 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 may contain organic fine particles such as polystyrene and polytetrafluoroethylene, inorganic fine particles such as colloidal silica, carbon, and layered silicate. In addition, the photosensitive resin composition of the present invention may be blended with various coloring agents and fibers.

[Solvent] If the solvent used in the photosensitive resin composition of the present invention is (A) an alkali-soluble resin, (B) a photosensitizer, (C) the compound represented by the general formula (1) and other additives, and No particular limitation. As an example, N,N'-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N,N'-dimethylacetamide, diethylene glycol di Methyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolidinone, N-cyclohexyl- 2-pyrrolidone, dimethylsulfonate, hexamethylphosphoramide, pyridine, γ-butyrolactone, diethylene glycol monomethyl ether. These can be used alone, and it is no problem to mix two or more. The amount of the solvent used can be appropriately determined according to the thickness or viscosity of the coating film. For example, it can be used in the range of 50 to 9000 parts by mass with respect to 100 parts by mass of (A) alkali-soluble resin.

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

[Dry film] The dry film of the present invention has a resin layer obtained by applying the photosensitive resin composition of the present invention to a carrier film and then drying. This resin layer is used by being laminated so as to be in contact with the base material.

The dry film of the present invention can be applied to the carrier film to uniformly apply the photosensitive resin composition of the present invention by a suitable method such as a blade coater, a lip coater, a corner wheel coater, a film coater, etc. The above-mentioned resin layer is formed by drying and drying, and it is preferably produced by laminating a coating film thereon. The coating film and the carrier film may be the same film material, or different films may be used.

In the dry film of the present invention, the film material of the carrier film and the coating film can be any known film as the film used in the dry film. For the carrier film, a thermoplastic film such as a polyester film such as polyethylene terephthalate having a thickness of 2 to 150 μm can be used. As for the covering film, although polyethylene film, polypropylene film, etc. can be used, the adhesive force with the resin layer is preferably smaller than 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.

[Hardened] The cured product of the present invention is one which uses the above-mentioned photosensitive resin composition of the present invention and is cured at a predetermined pitch. The patterned film of the cured product may be produced by a well-known and common manufacturing method. For example, (A) in the case of a positive photosensitive resin composition containing a polybenzoxazole precursor in the alkali-soluble resin, it can be borrowed It is manufactured by the following steps.

First, in step 1, the photosensitive resin composition is applied to the substrate and dried, or the resin layer is transferred onto the substrate from a dry film to obtain a coating film. For the method of coating the photosensitive resin composition on the substrate, the method used for coating the photosensitive resin composition since ancient times can be used, for example, a spin coater, a rod coater, a blade coater, For a method of coating by a curtain coater, a screen printing machine, etc., and a method of spray coating by a spray coater, an inkjet method can also be used. For the drying method of the coating film, methods such as air drying, heating drying by an oven or a hot plate, and vacuum drying can be used. In addition, the drying of the coating film is desirably performed under the condition that the ring closure of the polybenzoxazole precursor in the photosensitive resin composition does not occur. Specifically, it is performed under the conditions of natural drying, air drying or heat drying at 70 to 140° C. for 1 to 30 minutes. Preferably, it is dried on a hot plate for 1 to 20 minutes. In addition, vacuum drying can be performed, in which case it is performed at room temperature for 20 minutes to 1 hour. The base material on which the coating film of the photosensitive resin composition is formed is not particularly limited, and can be widely applied to semiconductor base materials such as silicon wafers, wiring boards, various resins, metals, and the like.

Next, in step 2, the coating film is passed through a patterned mask or directly exposed. The exposure light is a wavelength that activates the photoacid generator as the (B) sensitizer. Specifically, the exposure light preferably has a maximum wavelength in the range of 350 to 410 nm. As described above, by appropriately blending the sensitizer, the light sensitivity can be modulated. For the exposure device, a contact aligner, mirror projection, stepper, laser direct exposure device, etc. can be used.

Next, in step 3, if necessary, the coating film may be heated for a short time, or a part of the polybenzoxazole precursor in the unexposed portion may be closed. Here, the closed-loop rate is about 30%. The heating time and the heating temperature can be appropriately changed according to the type of polybenzoxazole precursor, the thickness of the coating film, and the type of (B) photosensitive agent.

On the other hand, in Step 4, the above coating film is treated with a developing solution. By this, the exposed portion of the coating film is removed, and the patterned film of the photosensitive resin composition of the present invention can be formed.

As for the method used for the development, any conventionally known method for developing a photoresist, for example, a rotary spray method, a paddle stirring method, an immersion method with ultrasonic treatment, etc., can be selected. In terms of developer, inorganic bases such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia, organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine, and tetramethyl Aqueous solutions of quaternary ammonium salts such as ammonium hydroxide and tetrabutylammonium hydroxide. In addition, water-soluble organic solvents such as methanol, ethanol, and isopropyl alcohol or surfactants may be appropriately added to these as needed. After that, if necessary, the coating film is washed with a rinse solution to obtain a patterned film. For the rinse solution, distilled water, methanol, ethanol, isopropyl alcohol, etc. can be used alone or in combination. In addition, as the developing solution, the above-mentioned solvent can also be used.

Then, step 5 is to heat the patterned film to obtain a cured coating film (cured product). By this heating, the polybenzoxazole precursor is ring-closed to obtain polybenzoxazole. The heating temperature may be appropriately set so that the patterned film of the photosensitive resin composition can be cured. For example, heating may be performed in an inert gas at a temperature of 150°C or higher but not higher than 300°C for about 5 to 120 minutes. The preferred heating temperature range is 180 to 250°C. Since the photosensitive resin composition of the present invention contains (C) a polyether compound, cyclization can be promoted, and a heating temperature less than 300°C can be selected. The heating can be performed using, for example, a hot plate, an oven, and a temperature-increasing oven in which a thermometer can be set. At this time, the atmosphere (gas) may be air, 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-type photosensitive resin composition, (B) for the sensitizer, a photopolymerization initiator or a photobase generator may be used instead of the photoacid generator, by the above steps In step 4, the coating film is treated with a developing solution to remove unexposed parts of the coating film 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. For example, it is suitably used as a forming material for paint, printing ink, or adhesive, or display device, semiconductor device, electronic component, optical component, or building material. Specifically, as a forming material of a display device, it can be used as a layer forming material or an image forming material for color filters, films for flexible displays, resist materials, alignment films, and the like. In addition, the formation material of the semiconductor device can be used as a layer formation material such as a resist material and a buffer coating film. In addition, the forming material of electronic parts can be used as a sealing material or a layer forming material for printed wiring boards, interlayer insulating films, wiring coating films, and the like. Furthermore, as for the forming material of optical parts, it can be used for holographic optics, optical waveguides, optical circuits, optical circuit parts, anti-reflection films, etc. as optical materials or layer forming materials. In addition, for building materials, it can be used for paints, coating agents, etc.

The photosensitive resin composition of the present invention is mainly used as a pattern-forming material, and the patterned film formed therefrom, for example, a permanent film made of polybenzoxazole, etc., can be used to impart heat resistance due to its function It is suitable for the protection of semiconductor devices, display devices and light-emitting devices as surface protective films, interlayer insulating films, rewiring insulating films, flip-chip device protective films, and devices with bump structures. Films, interlayer insulating films for multilayer circuits, insulating materials for passive parts, solder resists, protective film for printed wiring boards, etc., protective films for liquid crystal alignment films, etc. It is especially suitable for insulating films in contact with copper wiring or aluminum wiring. [Example]

Hereinafter, although the present invention will be described in more detail with examples, the present invention is not limited to the examples. In addition, in the following, "parts" and "%" are all quality standards unless otherwise specified.

(Synthesis of polybenzoxazole (PBO) precursor) In a 0.5 liter flask equipped with a stirrer and a thermometer, 212 g of N-methylpyrrolidone was placed, and 28.00 g (76.5 mmol) of bis(3-amino-4-hydroxyamidophenyl)hexafluoropropane was dissolved by stirring. After that, the flask was immersed in an ice bath, and while keeping the flask inside at 0 to 5°C, 4,4-diphenyl ether dicarboxylic acid chloride 25.00 g (83.2 mmol) was directly added as a solid every 30 minutes Add 5g and stir for 30 minutes in an ice bath. After that, 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) to collect precipitates. After that, the obtained solid was dissolved in 420 mL of acetone and poured into 1 L of ion-exchanged water. After recovering the precipitated solid, it was dried under reduced pressure to obtain a polybenzoxazole (PBO) precursor A-1 having a carboxyl terminal and a repeating structure shown below. The number average molecular weight (Mn) of the polybenzoxazole precursor A-1 was 12,900, the weight average molecular weight (Mw) was 29,300, and Mw/Mn was 2.28.

(Examples 1-9) Relative to 100 parts by mass of the polybenzoxazole precursor synthesized above, 10 parts by mass of naphthoquinonediazide compound B-1 (TKF-428 manufactured by Sambo Chemical Co., Ltd.) as a (B) sensitizer is coupled as silane 7 parts by mass of a silane coupling agent (KBM-573 manufactured by Shin-Etsu Silicone Co., Ltd.) having an arylamine group and each of the following polyether compounds of C-1 to C-4 are blended to make benzox Γ-butyrolactone (GBL) was added as a paint so that the azole precursor was 30% by mass, and the photosensitive resin compositions of Examples 1 to 9 were prepared. In addition, PEO (Mn=5,000) made by SIGMA-ALDRICH as C-1, PEO (Mn=8,000, 20,000, 100,000, 200,000) made by Wako Pure Chemical Industries, and ALKOX EP-made by Mingcheng Chemical Company as C-2 were used. 1010N (random copolymer of ethylene oxide and propylene oxide, m:n=12:1, Mn=about 100,000), ALKOX CP-A2H (allyl epoxypropyl ether) manufactured by Mingcheng Chemical Co., Ltd. as C-3 Random copolymer with ethylene oxide and propylene oxide, l:m:n=96:1:3, Mn=approximately 80,000), ALKOX CP-B2 (ethylene oxide and propylene oxide) manufactured by Mingcheng Chemical Company of C-4 , Random copolymer of phenyl epoxypropyl ether, n:m:l=97:1:2, Mn=about 100,000).

(Comparative Examples 1 to 6) In addition, in Comparative Example 1, the photosensitive resin composition of Comparative Example 1 was prepared in the same manner as in Example 1, except that the C-1 (C) polyether compound was not blended. In addition, in Comparative Examples 2 to 6, in addition to blending the melamine-based or urea-based crosslinking agents C-5 to C-8 shown below to replace the (C) polyether compounds C-1 to C-4, the rest This was carried out in the same manner as in Examples 1 to 5, and the photosensitive resin compositions of Comparative Examples 2 to 6 were prepared.

The photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 6 prepared in this way were evaluated for resolution, chemical resistance, and breaking elongation. The evaluation method is as follows.

(Production method of dry coating film for evaluation) The above-mentioned photosensitive resin composition was applied on a silicon substrate with a spin coater. This was dried on a hot plate at 120°C for 3 minutes to obtain a dried coating film of the photosensitive resin composition.

(Evaluation of chemical resistance) The dry coating film obtained above was heated on a hot plate at a temperature of 240° C. for 1 hour, and the resulting cured product was immersed in γ-butyrolactone (GBL) for 10 minutes to evaluate the change in film thickness and the presence or absence of cracks. The evaluation of chemical resistance in Tables 1 and 2 is based on the following. Change in film thickness ○: The change in film thickness is less than ±1% △: The change in film thickness is more than ±1% but not more than 5% ×: The change in film thickness is ±5% or more crack ○: No crack in 1cm division △: No more than 10 cracks in 1cm zoning ×: More than 10 cracks in 1cm division

(Evaluation of breaking extension) The dried coating film obtained above was heated on a hot plate at 240°C for 1 hour, using a PCT device (HAST SYSTEM TPC-412MD manufactured by ESPEC), after 168 hours at 121°C, saturation, and 0.2 MPa, the The peeled cured film with a thickness of 30 μm was cut into a length of 50 mm × a width of 5 mm, and a tensile test was carried out by “EZ-SX” manufactured by Shimadzu Corporation. The distance between the jigs was 30 mm, the drawing speed was 3 mm/mm, and the measurement was performed 7 times. Among them, the average of the top 3 was taken as the breaking extension. The evaluation of breaking elongation in Table 1 and Table 2 is based on the following. ◎: more than 20% ○: 15% or more but less than 20% △: More than 10% and less than 15% ×: less than 10%

In addition to showing the heating temperature during heating, Table 1 and Table 2 also record the evaluation results of the chemical resistance and breaking elongation.

It can be seen from Tables 1 and 2 that Examples 1 to 9 containing (C) polyether compounds having a polymerization unit of 100 to 10,000 can be sufficiently hardened at a low temperature of 240°C, and exhibit sufficient chemical resistance and Broken extension. Furthermore, in the case of (C) polyether compounds, Example 6 containing the C-2 compound can further improve the breaking elongation. In addition, Examples 1 to 9 have the same resolution as the conventional photosensitive resin composition.

In contrast, in Comparative Example 1, since the (C) polyether compound was not blended, it could not be sufficiently cured at a heating temperature of 240°C. In Comparative Examples 2 to 5, additives other than the (C) polyether compound were blended as a crosslinking agent, but sufficient chemical resistance could not be obtained. In addition, in Comparative Example 6, the increase in the amount of the melamine-based crosslinking agent improved the chemical resistance, but compared with the conventional photosensitive resin composition, the elongation at break was reduced.

Claims (10)

A photosensitive resin composition characterized by comprising (A) an alkali-soluble resin, (B) a photosensitizer, and (C) a polyether compound containing 100 to 10,000 polymerization units represented by general formula (1),

(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 polymerization units represented by general formula (2),

(In the general formula (2), Y represents an alkylene group having 1 to 10 carbon atoms, but the same case as X in the general formula (1) is excluded). The photosensitive resin composition according to claim 1, wherein the polyether compound (C) further contains 1 to 1,000 polymerization units represented by general formula (3),

(In general formula (3), Z represents a C 1-10 alkylene group having a reactive functional group or phenyl group in the side chain). The photosensitive resin composition according to claim 1, wherein the aforementioned (A) alkali-soluble resin contains a polybenzoxazole precursor. The photosensitive resin composition according to claim 1, wherein the aforementioned (B) photosensitive agent contains a diazonaphthoquinone compound. A dry film characterized by having a resin layer obtained by applying the photosensitive resin composition of claim 1 to a film and drying. A hardened product characterized by hardening the photosensitive resin composition of any one of claims 1 to 5 or the resin layer of the dry film of claim 6. A printed wiring board characterized by having the hardened product of claim 7. A semiconductor device characterized by having the hardened product of claim 7. An electronic part characterized by the hardened product of claim 7.