JPWO2019026772A1 - Photosensitive resin composition, dry film, cured product, printed wiring board, semiconductor element and electronic component - Google Patents

Abstract

Provided are a photosensitive resin composition, a dry film, a cured product, a printed wiring board and an electronic component which are hardened at a low temperature of less than 300° C. and do not corrode metal wiring. The photosensitive resin composition of the present invention comprises (A) an alkali-soluble resin, (B) a photosensitizer, and (C) at least one of the compounds represented by the general formulas (1) and (2). Including. In the general formula (1), at least one of X1 to X3 is an —OH group or an —OR (R is an organic group) group, and in the general formula (2), n is an integer of 1 to 1000. Is.

Description

The present invention provides a photosensitive resin composition, a dry film, a cured product, and a printed wiring board suitable for use as a protective film for semiconductor devices, an insulating film for rewiring layers of wafer level packages (WLP), an insulating portion of passive components, and the like. And a semiconductor device.

A photosensitive heat resistant resin such as photosensitive polyimide or polybenzoxazole (PBO) is used for the buffer coat film of the LSI and the insulating film for the redistribution layer of the wafer level package (WLP). These photosensitive heat-resistant resins are cured by a heat treatment for cyclizing a resin precursor. Conventional heat treatment was performed at 300° C. or higher, but in recent years, it has been required to cure the precursor of the photosensitive heat-resistant resin at a low temperature in order to suppress heat damage to the semiconductor element.

On the other hand, conventionally, in order to obtain a low-temperature curable positive-type photosensitive resin composition, it has been considered to include an acid catalyst such as sulfonic acid or an onium salt as a cyclization catalyst, and to promote dehydration ring closure by this cyclization catalyst. Has been done. For example, there is a positive-type photosensitive resin composition curable at low temperature that contains an aliphatic sulfonic acid (Patent Document 1).

JP, 2006-10781, A

However, the positive photosensitive resin composition described in Patent Document 1 has a problem that metal wiring, especially copper wiring, is easily corroded due to generation of sulfonic acid.

Therefore, an object of the present invention is to provide a photosensitive resin composition, a dry film, a cured product, a printed wiring board, a semiconductor element and an electronic component which are hardened at a low temperature of less than 300° C. and do not corrode metal wiring, especially copper wiring. To provide.

As a result of intensive studies, the present inventors have found that the photosensitive resin composition can solve the above problems by including a specific compound as a cyclization catalyst, and have completed the present invention.

上記一般式（１）中、Ｘ_１〜Ｘ_３のうち少なくとも一つは、−ＯＨ基または−ＯＲ（Ｒは有機基）基である。一般式（２）中、ｎは、１〜１０００の整数である。The photosensitive resin composition of the present invention comprises (A) an alkali-soluble resin, (B) a photosensitizer, and (C) at least one of the compounds represented by the general formulas (1) and (2). It is characterized by including.

In the general formula (1), at least one of X _{1 to} X ₃ is an —OH group or an —OR (R is an organic group) group. In general formula (2), n is an integer of 1 to 1000.

In the photosensitive resin composition of the present invention, the compound represented by the general formula (1) preferably has two or more —OH groups or the above —OR groups, and is represented by the general formula (2). It is preferable that the compound is condensed phosphoric acid in which n is an integer of 2 or more in the general formula (2), and it is preferable that the compound (A) contains a polybenzoxazole precursor as the alkali-soluble resin. It is preferable to include a naphthoquinonediazide compound as

The dry film of the present invention is characterized by having a resin layer obtained by applying the above-mentioned photosensitive resin composition to the film and drying the film.
The cured product of the invention is characterized by being obtained by curing the photosensitive resin composition or the resin layer of the dry film.
The printed wiring board, semiconductor element and electronic component of the present invention are characterized by having the above-mentioned cured product.

The photosensitive resin composition of the present invention can be cured at a low temperature of less than 300°C. Further, by irradiating the photosensitive resin composition of the present invention with an active energy ray, it is possible to obtain a cured product that does not corrode metal wiring, especially copper wiring. Further, the photosensitive resin composition of the present invention can be contained as the above-mentioned cured product by irradiating the base material of the printed wiring board or the member of the semiconductor element with active energy rays.

上記一般式（１）中、Ｘ_１〜Ｘ_３のうち少なくとも一つは、−ＯＨ基または−ＯＲ（Ｒは有機基）基であり、上記一般式（２）中、ｎは、１〜１０００の整数である。Hereinafter, the photosensitive resin composition, the dry film, the cured product, the printed wiring board, the semiconductor element and the electronic component of the present invention will be described more specifically.
The photosensitive resin composition of the present invention comprises (A) an alkali-soluble resin, (B) a photosensitizer, and (C) at least one of the compounds represented by the general formulas (1) and (2). It is characterized by including.

In the general formula (1), at least one of X _{1 to} X ₃ is an —OH group or an —OR (R is an organic group) group, and in the general formula (2), n is 1 to 1000. Is an integer.

[(A) Alkali-soluble resin]
The photosensitive resin composition of the present invention contains an alkali-soluble resin.
The alkali-soluble resin (A) is a resin that is soluble in an alkaline aqueous solution as a developing solution in the development after exposure by irradiation with active energy rays. As the alkali-soluble resin, the alkali-soluble polymer that has been used in the photosensitive resin composition up to now 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 them, a polymer having a phenolic hydroxyl group or a carboxyl group is preferable, and examples thereof include novolac resin, resole resin, polyimide precursor, and polybenzoxazole precursor. Preferred are a polyimide precursor and a polybenzoxazole precursor. When these polymers are heated at a predetermined temperature, dehydration and ring closure occur, and a heat resistant resin is obtained in the form of polyimide, polybenzoxazole, or a copolymer 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 (A) is preferably a polyhydroxyamide acid having a repeating structure represented by the following general formula (3).

(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 (A) is synthesized by the above synthesis method, in the general formula (3), X is a residue of the dihydroxydiamine, and Y is a residue of the dicarboxylic acid. ..

Examples of the 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 Fluoropropane and the like can be mentioned. Among them, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane is preferable.

Examples of the dicarboxylic acid include isophthalic acid, terephthalic acid, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′. -Dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxytetraphenylsilane, bis(4-carboxyphenyl) sulfone, 2,2-bis(p-carboxyphenyl)propane, 2,2 -Dicarboxylic acid 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 thereof include aliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and 1,3-cyclopentanedicarboxylic acid. Of these, 4,4'-dicarboxydiphenyl ether is preferable.

In the general formula (3), the tetravalent organic group represented by X may be an aliphatic group or an aromatic group, but is preferably an aromatic group, and two hydroxy groups and two amino groups are in the ortho position. More preferably, it is located on the aromatic ring. The tetravalent aromatic group preferably has 6 to 30 carbon atoms, and more preferably has 6 to 24 carbon atoms. Specific examples of the above tetravalent aromatic group include the groups shown below, but the present invention is not limited thereto, and a known aromatic group that can be contained in the polybenzoxazole precursor is selected according to the application. do it.

The tetravalent aromatic group is preferably a group shown below among the aromatic groups.

In the general formula (3), 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 in the general formula (3) on the aromatic ring is preferable. More preferably, it is bound to The divalent aromatic group preferably has 6 to 30 carbon atoms, and more preferably 6 to 24 carbon atoms. Specific examples of the above divalent aromatic group include the groups shown below, but the present invention is not limited thereto, and a known aromatic group contained in the polybenzoxazole precursor may be selected according to the application. Good.

（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 radical selected from the group consisting of).

The divalent organic group is preferably a group shown below among the aromatic groups.

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

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

As the polybenzoxazole precursor (A), one type may be used alone, or two or more types may be used in combination.
The method for synthesizing the (A) polybenzoxazole precursor is not particularly limited and may be a known method. 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 blending amount of the (A) alkali-soluble resin is preferably 60 to 90 mass% based on the total solid content of the composition. When the content is 60% by mass or more, the adhesiveness and surface curability are improved. Further, when the content is 80% by mass or less, it is possible to prevent a decrease in the crosslink density in the cured product and to improve the coating film characteristics.

[(B) Photosensitizer]
The photosensitive resin composition of the present invention contains a photosensitizer. The photosensitizer (B) is not particularly limited, and photoacid generators, photopolymerization initiators, and photobase generators can be used. The photo-acid generator is a compound that generates an acid upon irradiation with light such as ultraviolet rays or visible light, the photopolymerization initiator is a compound that generates a radical upon irradiation with similar light, and the photo-base generator is the same. Is a compound that changes its molecular structure by irradiation with light or cleaves a molecule to produce one or more basic substances. In the present invention, a photoacid generator can be preferably used as the (B) photosensitizer.
As the photoacid generator, a naphthoquinonediazide compound, a diarylsulfonium salt, a triarylsulfonium salt, a dialkylphenacylsulfonium salt, a diaryliodonium salt, an aryldiazonium salt, an aromatic tetracarboxylic acid ester, an aromatic sulfonic acid ester, a nitrobenzyl ester , Aromatic N-oxyimide sulfonate, aromatic sulfamide, benzoquinone diazosulfonic acid ester, and the like. The photo-acid generator is preferably a dissolution inhibitor. Of these, a naphthoquinonediazide compound is preferable.

Specific examples of the naphthoquinonediazide compound include naphthoquinonediazide adducts of tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene (for example, TS533, TS567, TS583, TS593 manufactured by Sanpo Chemical Laboratory Co., Ltd.). ), tetranaphthobenzophenone naphthoquinonediazide adduct (for example, BS550, BS570, BS599 manufactured by Sanpo Chemical Laboratory Co., Ltd.) and 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]-α A naphthoquinonediazide adduct of α-dimethylbenzyl}phenol (for example, TKF-428 and TKF-528 manufactured by Sanpo Chemical Laboratory Co., Ltd.) can be used.

As the photopolymerization initiator, a conventionally known one can be used, and examples thereof include an oxime ester photopolymerization initiator having an oxime ester group, an α-aminoacetophenone photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator. An initiator, a titanocene-based photopolymerization initiator, or the like 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 manufactured by ADEKA, and NCI-831.

Specific examples of the α-aminoacetophenone photopolymerization initiator include 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 and the like, and commercially available products such as Irgacure 907, Irgacure 369 and Irgacure 379 manufactured by BASF Japan Ltd. can be used.

Specific examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and bis(2,6). -Dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide and the like, and commercially available products include Irgacure TPO manufactured by BASF Japan Ltd., Omnirad (Omnilad) 819 manufactured by IGM Resins. it can.

Specific examples of the titanocene-based photopolymerization initiator include bis(cyclopentadienyl)-di-phenyl-titanium, bis(cyclopentadienyl)-di-chloro-titanium, and bis(cyclopentadienyl). -Bis(2,3,4,5,6 pentafluorophenyl)titanium, bis(cyclopentadienyl)-bis(2,6-difluoro-3-(pyrrol-1-yl)phenyl)titanium and the like. .. Examples of commercially available products include Irgacure 784 manufactured by BASF Japan.

Further, the photobase generator may be an ionic photobase generator or a nonionic photobase generator, but the ionic photobase generator has a higher sensitivity of the composition and can form a pattern film. It is preferable because it becomes advantageous. Examples of the basic substance include secondary amines and tertiary amines.

Examples of the ionic photobase generator include salts of aromatic component-containing carboxylic acids and tertiary amines, and Wako Pure Chemical Industries, Ltd. ionic PBG WPBG-082, WPBG-167, WPBG-168, WPBG-. 266, WPBG-300 or the like 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, nitrobenzylcarbamate groups, and alkoxyoxybenzyl. Examples thereof include compounds having a substituent such as a carbamate group. As other photobase generators, WPBG-018 (trade name: 9-anthrylmethyl N, N'-diethylcarbamate), WPBG-027 (trade name: (E)-1-[3-(2) manufactured by Wako Pure Chemical Industries, Ltd. -Hydroxyphenyl)-2-propenoyl]piperidine), WPBG-140 (trade name: 1-(anthraquinon-2-yl)ethyl imidazolecarboxylate), WPBG-165 and the like can also be used.

As the photosensitizer (B), one type may be used alone, or two or more types may be used in combination. The compounding amount of the photosensitizer (B) is preferably 3 to 20% by mass based on the total solid content of the composition. As described above, the photosensitizer (B) is not limited to the voluminous type, but may be the negative type.

まず、一般式（１）で表される化合物について説明する。
上記一般式（１）中、Ｘ_１〜Ｘ_３のうち少なくとも一つは、−ＯＨ基または−ＯＲ（Ｒは有機基）基である。例えば、Ｘ_１〜Ｘ_３のいずれもが水酸基であるホウ酸、Ｘ_１〜Ｘ_３のうちの２個が水酸基であるボロン酸（ＲＢ（ＯＨ）_２）、Ｘ_１〜Ｘ_３のいずれもが−ＯＲ基であるホウ酸エステル（Ｂ（ＯＲ）_３）、ボロン酸とアルコールとの縮合反応により得られるボロン酸エステル（ＲＢ（ＯＲ）_２）、Ｘ_１〜Ｘ_３のうちの１個が水酸基であるボリン酸（Ｒ_２ＢＯＨ）、ボリン酸とアルコールとの縮合反応により得られるボリン酸エステル（Ｒ_２ＢＯＲ）を挙げることができる。[(C) At least one of the compounds represented by the general formula (1) and the general formula (2)]
The photosensitive resin composition of the present invention contains at least one of the compounds represented by the general formula (1) and the general formula (2).

First, the compound represented by formula (1) will be described.
In the general formula (1), at least one of X _{1 to} X ₃ is an —OH group or an —OR (R is an organic group) group. For _example, boric acid both of X 1 to X ₃ is a hydroxyl _group, two boronic acid is a hydroxyl group of _{X 1 ~X 3 (RB (OH} ) 2), any of X 1 to X ₃ is A borate ester (B(OR) ₃ ), which is an —OR group, a boronate ester (RB(OR) ₂ ), which is obtained by a condensation reaction of a boronic acid and an alcohol, and _one of X _{1 to} X ₃ is a hydroxyl group. borinic acid _(R 2 BOH) is, may be mentioned borinic acid ester obtained by condensation reaction of a borinic acid with an alcohol _(R 2 BOR).

For example, the compound represented by the above general formula (1) has a strong dehydrating action, such as a self-dehydrating reaction from boric acid to boroxine. Due to this dehydration action, the compound represented by the general formula (1) promotes cyclization of the alkali-soluble resin (A). As a result, the photosensitive resin composition of the present invention containing the compound represented by the general formula (1) can be cured at a low temperature of less than 300°C.

Further, the compound represented by the general formula (1) is not acidic and therefore does not corrode metal wiring such as copper and aluminum. Therefore, the photosensitive resin composition of the present invention containing the compound represented by the general formula (1) does not corrode metal wiring.
Further, the compound represented by the general formula (1) does not adversely affect the resolution of the photosensitive resin composition, and does not adversely affect the thermal characteristics and mechanical characteristics.
From the above, the photosensitive resin composition of the present invention containing the compound represented by the general formula (1) as the component (C) can be treated at 300° C. without lowering the resolution, thermal characteristics and mechanical characteristics. It can be cured by heating at a low temperature of less than 1, and does not corrode metal wiring such as aluminum wiring and copper wiring.

The compound represented by the general formula (1) is the above-mentioned boric acid (B(OH) ₃ ), boronic acid (RB(OH) ₂ ), boric acid ester (B(OR) ₃ ), boronic acid ester (RB). (OR) ₂ ), borinic acid (R ₂ BOH), and borinic acid ester (R ₂ BOR).
Boronic acid (RB(OH) ₂ ) is other than two hydroxyl groups of X _{1 to} X _{3 in} the general formula (1), that is, R is a phenyl group, a triflurophenyl group, a thienyl group, a methyl group or propenyl. A group etc. can be illustrated. It may be an alkyl group or an aryl group other than these. Specific examples of the boronic acid include phenylboronic acid, trifluorophenylboronic acid, 2-thiopheneboronic acid, methylboronic acid, cis-propenylboronic acid and trans-propenylboronic acid.
The boronic acid ester (RB(OR) ₂ ) is an ester of boronic acid and an alcohol, and is produced by a condensation reaction between a boric acid ester and an alcohol (including a polyol such as a diol). Examples of the alcohol used in the condensation reaction include pinacol, trimethylene glycol, isopropanol and the like. Examples of the boronic acid ester other than two —OR groups among X _{1 to} X _{3 in} the general formula (1), that is, R, are the same as those of the above boronic acid. Specific examples of the boronic acid ester include allylboronic acid pinacolate, 2-phenyl-1,3,2-dioxaborinane, diisopropylmethylborane and the like.
Specific examples of the boronic acid and the boronic acid ester are shown below by structural formulas.

The compound represented by the general formula (1) can be used alone or in combination of two or more.
In order to further promote cyclization, the compound represented by the general formula (1) preferably has two or more —OH groups or —OR groups. More preferred is boric acid B(OH) ₃ .

As the component (C), the compounding amount of the compound represented by the general formula (1) is preferably 1 to 5 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (A) of the present invention. When the amount is 1 part by mass or more, the photosensitive resin composition can be sufficiently cured, and when the amount is 5 parts by mass or less, the photosensitive resin composition can be sufficiently mixed in the resin composition.

Further, as in the case of the compound represented by the general formula (1), phosphoric acid and/or polyphosphoric acid is used as the compound for promoting the cyclization of the alkali-soluble resin (A), and the compound represented by the general formula (1) is used. Can be used together.

Next, the compound represented by formula (2) will be described.

For example, as in the condensation dehydration reaction from orthophosphoric acid to condensed phosphoric acid, the compound represented by the general formula (2) has a strong dehydration action. Due to this dehydration action, the compound represented by the general formula (2) promotes cyclization of the alkali-soluble resin (A). As a result, the photosensitive resin composition of the present invention containing the compound represented by the general formula (2) can be cured at a low temperature of less than 300°C.

The compound represented by the general formula (2) promotes cyclization of the (A) alkali-soluble resin by the action of the catalyst as an acid. The photosensitive resin composition of the present invention containing the compound represented by the general formula (2) in combination with the action of the catalyst as an acid and the above-described dehydration action can be cured at a low temperature of less than 300°C. ..
The action of the compound represented by the general formula (2) as an acid does not corrode the copper wiring because it is not strong enough to corrode the copper or copper alloy of the copper wiring. Therefore, the photosensitive resin composition of the present invention containing the compound represented by the general formula (2) does not corrode the copper wiring.
Furthermore, the compound represented by the general formula (2) does not adversely affect the resolution of the photosensitive resin composition, and does not adversely affect the thermal characteristics and mechanical characteristics.
From the above, the photosensitive resin composition of the present invention containing the compound represented by the general formula (2) as the component (C) is less than 300° C. without deteriorating the resolution, thermal characteristics and mechanical characteristics. Can be hardened by low temperature heating and does not corrode copper wiring.

Examples of the compound represented by the general formula (2) include the above-mentioned orthophosphoric acid (H ₃ PO ₄ ), pyrophosphoric acid (H ₄ P ₂ O ₇ ), and other condensed phosphoric acid.

Since condensed phosphoric acid has a greater effect of promoting cyclization of the alkali-soluble resin (A) than orthophosphoric acid, the photosensitive resin composition of the present invention has the above general formula (2) in the above formula (2) from the viewpoint of low temperature curing. A condensed phosphoric acid in which n is an integer of 2 or more is preferable.

The compound represented by the general formula (2) can be used alone or in combination of two or more.

The compounding amount of the compound represented by the general formula (2) is preferably 1 to 5 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin of the present invention. When the amount is 1 part by mass or more, the photosensitive resin composition can be sufficiently cured, and when the amount is 5 parts by mass or less, the photosensitive resin composition can be sufficiently mixed in the resin composition.

Further, similar to the compound represented by the general formula (2), boric acid (B(OH) ₃ ), boronic acid (RB(OH) ₂ ), Each of X _{1 to} X ₃ is a —OR group, a borate ester (B(OR) ₃ ), a boronate ester (RB(OR) ₂ ), a borinic acid (R ₂ BOH), a borinate ester (R ₂ BOR) can be used in combination with the compound represented by the general formula (2).

The photosensitive resin composition of the present invention is, if necessary, the above-mentioned (A) alkali-soluble resin, (B) photosensitizer, (C) compound represented by the general formula (1) and the general formula (2). It is possible to include components other than at least one of the above. Such components are described below.

[Silane coupling agent]
The photosensitive resin composition of the present invention may contain a silane coupling agent. The silane coupling agent is preferably a silane coupling agent having an arylamino group and a silane coupling agent having two or more trialkoxysilyl groups. A silane coupling agent having an arylamino group is more preferable because it has excellent resolution.

The silane coupling agent having an arylamino group will be described. The aryl group of the arylamino group, aromatic hydrocarbon groups such as phenyl group, tolyl group, xylyl group, condensed polycyclic aromatic groups such as naphthyl group, anthracenyl group, phenanthrenyl group, thienyl group, aromatic such as indolyl group. Group heterocyclic groups are mentioned.

（式中、Ｒ^３１〜Ｒ^３５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 (4).

(In the formula, R ^{31 to} R ³⁵ each independently represent a hydrogen atom or an organic group.)

In the general formula (4), R ^{31 to} R ³⁵ are preferably hydrogen atoms.

In the silane coupling agent having an arylamino group, it is preferable that the silicon atom and the arylamino group are bound by 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 arylamino group are preferably the compounds shown below.

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

In the silane coupling agent having two or more trialkoxysilyl groups, at least two silicon atoms are preferably bonded with 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.

The silane coupling agent may be used alone or in combination of two or more. Moreover, you may contain the silane coupling agent other than the silane coupling agent which has the above-mentioned arylamino group, and the silane coupling agent which has two or more trialkoxy silyl groups.
The content of the silane coupling agent is preferably 1 to 15% by mass based on the total solid content of the composition. When the content is 1 to 15% by mass, the undeveloped portion in the exposed area can be prevented.

[Sensitizer, adhesion aid, other ingredients]
In the photosensitive resin composition of the present invention, a known sensitizer for further improving the photosensitivity and a known adhesion aid for improving the adhesiveness to the base material within the range that does not impair the effects of the present invention. Alternatively, a cross-linking agent or the like can be added.
Further, 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 added. For example, a surfactant, a leveling agent, a plasticizer, fine particles and the like 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 silicate. Moreover, you may mix|blend various coloring agents, fibers, etc. with the photosensitive resin composition of this invention.

[solvent]
The solvent used in the photosensitive resin composition of the present invention is (A) an alkali-soluble resin, (B) a photosensitizer, (C) at least the compound represented by the general formula (1) and the general formula (2) described above. There is no particular limitation as long as it dissolves one and other additives. As an example, N,N'-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N,N'-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ- Examples thereof include 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 the solvent used can be appropriately determined according to the coating film thickness and the viscosity. For example, it can be used in the range of 50 to 9000 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin.

[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 it. 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 is a uniform coating of the photosensitive resin composition of the present invention on a carrier film by a blade coater, a lip coater, a comma coater, a film coater or the like, followed by drying to form the above resin layer. It can be manufactured by forming and preferably laminating a cover film thereon. The cover film and the carrier film may be the same film material or different films.

In the dry film of the present invention, as the film material of the carrier film and the cover film, any of those known as those used for dry films can be used.
As the carrier film, for example, 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, a polyethylene film, a polypropylene film, or the like 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 5 to 50 μm.

[Cured product]
The cured product of the present invention is obtained by curing the photosensitive resin composition of the present invention described above in a predetermined step. For example, in the case of a positive type photosensitive resin composition, the pattern film which is the cured product is manufactured by the following steps.

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. The method for applying the photosensitive resin composition onto the substrate is a method that has been conventionally used for applying the photosensitive resin composition, for example, a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, or the like. Can be used, a spray coating method using a spray coater, and an inkjet method can be used. As a method for drying the coating film, air drying, heat drying using an oven or a hot plate, vacuum drying and the like are used. Further, it is desirable to dry the coating film under the condition that the (A) alkali-soluble resin in the photosensitive resin composition does not cause ring closure. Specifically, natural drying, blast drying, or heat drying can be performed at 70 to 140° C. for 1 to 30 minutes. Preferably, it is dried on a hot plate for 1 to 20 minutes. Vacuum drying is also possible, and in this case, it can be 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 it can be widely applied to semiconductor base materials such as silicon wafers, wiring boards, various resins and metals.

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

Subsequently, in step 3, if necessary, the coating film may be heated for a short time to ring-close a part of the alkali-soluble resin (A) in the unexposed portion. Here, the ring closure rate is about 30%. The heating time and heating temperature are appropriately changed depending on the type of (A) alkali-soluble resin, coating film thickness, and (B) type of photosensitizer.

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

As a method used for development, any method can be selected from conventionally known photoresist development methods, for example, a rotary spray method, a paddle method, and a dipping method accompanied by ultrasonic treatment. Examples of the developer include inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia water, organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide. Examples thereof include aqueous solutions of quaternary ammonium salts and the like. If necessary, a water-soluble organic solvent such as methanol, ethanol or isopropyl alcohol, or a surfactant may be added in an appropriate amount. Then, if necessary, the coating film is washed with a rinse liquid to obtain a patterned film. As the rinse liquid, distilled water, methanol, ethanol, isopropyl alcohol, or the like can be used alone or in combination. Moreover, you may use the said solvent as a developing solution.

Then, in step 5, the pattern film is heated to obtain a cured coating film (cured product). By this heating, the alkali developable resin (A) is cured and, for example, the polybenzoxazole precursor is ring-closed to obtain polybenzoxazole. The heating temperature is appropriately set so that the pattern film of the alkali developing resin can be cured. For example, heating is performed in an inert gas at 150° C. or higher and lower than 300° C. for about 5 to 120 minutes. A more preferable range of the heating temperature is 200 to 250° C. when the compound represented by the general formula (1) is contained as the component (C), and 180 when the compound represented by the general formula (2) is contained. ~250°C. The photosensitive resin composition of the present invention contains (C) at least one of the compound represented by the general formula (1) and the compound represented by the general formula (2). The heating temperature can be less than. The heating is performed by using, for example, a hot plate, an oven, or a temperature rising type 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.

When the photosensitive resin composition of the present invention is a negative photosensitive resin composition, a photopolymerization initiator or a photobase generator is used as the photosensitizer (B) instead of the photoacid generator, and the above steps are performed. By treating the coating film with a developing solution in 4, the unexposed portion 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 examples thereof include paints, printing inks, or adhesives, or display devices, semiconductor elements, semiconductor devices, electronic components, optical components, or building material forming materials. Is preferably used as. Specifically, as a material for forming a display device, a layer forming material or an image forming material, a color filter, a film for flexible display, a resist material, an alignment film, or the like can be used. As a material for forming a semiconductor device, a resist material, a layer forming material such as a buffer coat film, or the like can be used. Further, as a material for forming an electronic component, a sealing material or a layer forming material can be used for a printed wiring board, an interlayer insulating film, a wiring coating film, or the like. Furthermore, as a material for forming an optical component, a hologram, an optical waveguide, an optical circuit, an optical circuit component, an antireflection film or the like can be used as an optical material or a layer forming material. Furthermore, as a building material, it can be used in paints, coating agents and the like.

The photosensitive resin composition of the present invention is mainly used as a pattern forming material, and a pattern film as a cured product formed by the composition is provided with heat resistance and insulation as a permanent film made of, for example, polybenzoxazole. Functioning as a component, in particular, a surface protective film for semiconductor devices, display devices and light emitting devices, an interlayer insulating film, an insulating film for rewiring, a protective film for flip-chip devices, a protective film for a device having a bump structure, and a multilayer. It can be suitably used as an interlayer insulating film for a circuit, an insulating material for passive components, a protective film for a printed wiring board 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 or the like in contact with copper wiring or aluminum wiring.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. In the following, "parts" and "%" are based on mass 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 charged, and 28.00 g (76.5 mmol) of bis(3-amino-4-hydroxyamidophenyl)hexafluoropropane was dissolved by stirring. .. Then, 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-diphenyletherdicarboxylic acid chloride was added as a solid over 5 minutes by 5 g, and the ice bath was added. Stir in 30 minutes. Then, stirring was continued at room temperature for 5 hours. The stirred solution was poured into 1 L of ion-exchanged water (specific resistance value 18.2 MΩ·cm), and the precipitate was collected. Then, the obtained solid was dissolved in 420 mL of acetone and poured into 1 L of ion-exchanged water. The precipitated solid was collected and dried under reduced pressure to obtain a polybenzoxazole (PBO) precursor A-1 having a carboxyl group terminal and the repeating structure shown below. The polybenzoxazole precursor A-1 had a number average molecular weight (Mn) of 12,900, a weight average molecular weight (Mw) of 29,300, and Mw/Mn of 2.28.

(Examples 1 to 4)
With respect to 100 parts by mass of the benzoxazole precursor synthesized above, (B) a naphthoquinonediazide compound B-1 (TKF-428 manufactured by Sanpo Chemical Co., Ltd.) or B-2 (TKF-528 manufactured by Sanpo Chemical Co., Ltd.) was used. 10 parts by mass, 7 parts by mass of a silane coupling agent having an arylamino group (KBM-573 manufactured by Shin-Etsu Silicone Co., Ltd.) as a silane coupling agent, and C-1 or C- shown in Table 1 as a cyclization catalyst. After blending 3 parts by mass of each of the boric acid-based compound of 2 and N-methylpyrrolidone (NMP) so that the benzoxazole precursor is 30% by mass to form a varnish, the photosensitive resin compositions of Examples 1 to 4 I adjusted things.

(Comparative Examples 1 to 4)
Further, as Comparative Examples 1 and 2, the photosensitive resin compositions of Comparative Examples 1 and 2 were prepared in the same manner as in Examples 1 and 2 except that the above-mentioned C-1 boric acid compound was not blended.
Further, as Comparative Example 3, the photosensitive resin composition of Comparative Example 4 was prepared in the same manner as in Example 1 except that the organic phosphoric acid C-5 shown below was added instead of the boric acid compound C-1 described above. It was adjusted.

Further, as Comparative Example 4, the photosensitive resin composition of Comparative Example 3 was prepared in the same manner as in Example 1 except that the sulfonic acid C-8 shown below was blended in place of the boric acid compound C-1 described above. did.

The resolution, cyclization rate, Cu corrosion, and Al corrosion of the photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 to 4 thus prepared were evaluated. 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 with a spin coater. It was dried at 120° C. for 3 minutes on a hot plate to obtain a dry coating film of the photosensitive resin composition.
(Evaluation of resolution)
The dry coating films obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were irradiated with broad light of 300 mJ/cm ² through a mask having a pattern engraved using a high pressure mercury lamp. After the exposure, it was developed with a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds and rinsed with water to obtain a positive pattern film. The resolution of this positive pattern film was measured.
Regarding the resolution, the pattern film after development is observed by an electron microscope (SEM "JSM-6010") and the size of the smallest pattern that can pattern the exposed area without scum is resolved (L (μm)/S (μm)). ).

(Cyclization rate)
The obtained dried coating film is heated on a hot plate at a temperature of 200°C to 220°C for 1 hour, and the obtained cured product is subjected to waveform analysis by Fourier Transform InfraRed spectroscopy (FT-IR). Then, the cyclization rate was calculated by the following formula.
As a reference, when the peak derived from C=C of the aromatic ring, that is, the peak near 1595 cm ⁻¹ is defined as peak I, and the peak derived from C—O of the oxazole ring, that is, the peak near 1050 cm ⁻¹ is defined as peak II,
Cyclization rate={(area of II/area of I)÷(area of II (100% cyclization)/area of I (100% cyclization))}×100
The evaluation of the cyclization rate in Table 1 was based on the following criteria.
⊚: Cyclization rate of 85% or more ○: Cyclization rate of 80% or more and less than 85% Δ: Cyclization rate of 75% or more and less than 80% ×: Cyclization rate of less than 75%

(Cu corrosion, Al corrosion)
The photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 to 4 were applied to Cu foil and Al foil, respectively, dried at 120° C. for 3 minutes on a hot plate, and then heated at 200° C. for 1 hour. A cured film was obtained. After peeling the cured film from the Cu foil or Al foil, corrosion of the Cu foil and Al foil was observed by an optical microscope as the degree of discoloration.
The following criteria were used for evaluation of Cu corrosion and Al corrosion.
○: No discoloration ×: Discoloration (thermal/mechanical properties)
The thermo-mechanical properties (Tg, elongation, elastic modulus, strength) of the cured film obtained by heating were specified.

In Table 1, the heating temperature at the time of heating is shown, and the evaluation results of resolution, cyclization rate, Cu corrosion, and Al corrosion are also shown.

As can be seen from Table 1, Examples 1 to 4 containing a boric acid-based compound can be sufficiently cured at a low temperature of 200° C. or 220° C. while having a resolution equivalent to that of a conventional photosensitive resin composition. Moreover, Cu and Al were not corroded. In addition, Examples 1 to 4 had thermal and mechanical properties equivalent to those of the conventional photosensitive resin composition.

On the other hand, Comparative Examples 1 and 2 did not have a cyclization catalyst, and therefore could not be sufficiently cured at a heating temperature of 220°C. In Comparative Example 3, Al was corroded because the cyclization catalyst was organic phosphoric acid. Furthermore, in Comparative Example 4, since the cyclization catalyst was sulfonic acid, Cu and Al were corroded.

(Examples 5 to 8)
With respect to 100 parts by mass of the benzoxazole precursor synthesized above, (B) a naphthoquinonediazide compound B-1 (TKF-428 manufactured by Sanpo Chemical Co., Ltd.) or B-2 (TKF-528 manufactured by Sanpo Chemical Co., Ltd.) was used. 10 parts by mass, 7 parts by mass of a silane coupling agent having an arylamino group (KBM-573 manufactured by Shin-Etsu Silicone Co., Ltd.) as a silane coupling agent, and C-3 condensed phosphorus shown in Table 2 as a cyclization catalyst. Acid (n=diphosphorus pentoxide 80% or more) or 3 parts by mass of C-4 orthophosphoric acid, and then N-methylpyrrolidone (NMP) is added so that the benzoxazole precursor becomes 30% by mass. Using a varnish, the photosensitive resin compositions of Examples 5 to 8 were prepared.

(Comparative Examples 5-10)
Further, as Comparative Examples 5 and 6, the photosensitive resin compositions of Comparative Examples 5 and 6 were prepared in the same manner as in Examples 5 and 6 except that the above-described condensed phosphoric acid C-3 was not added.

Further, as Comparative Example 7, the photosensitive resin of Comparative Example 7 was prepared in the same manner as in Example 5 except that the above-mentioned organic phosphoric acid C-5 was blended in place of the above-mentioned condensed phosphoric acid C-3. The composition was adjusted.
In addition, as Comparative Examples 8 and 9, a comparison was made in the same manner as in Example 5 except that the following organic phosphoric acid C-6 or C-7 was added instead of the above-mentioned condensed phosphoric acid C-3. The photosensitive resin compositions of Examples 8 and 9 were prepared.

Further, as Comparative Example 10, a photosensitive resin composition of Comparative Example 10 was prepared in the same manner as in Example 5 except that the sulfonic acid C-8 shown below was blended in place of the above-mentioned condensed phosphoric acid C-3. ..

The resolution, cyclization rate, and Cu corrosion of the photosensitive resin compositions of Examples 5-8 and Comparative Examples 5-10 thus prepared were evaluated. 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 with a spin coater. It was dried at 120° C. for 3 minutes on a hot plate to obtain a dry coating film of the photosensitive resin composition.
(Evaluation of resolution)
The dry coating films obtained in Examples 5 to 8 and Comparative Examples 5 to 10 were irradiated with broad light of 300 mJ/cm ² through a mask in which a pattern was engraved using a high pressure mercury lamp. After the exposure, it was developed with a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds and rinsed with water to obtain a positive pattern film. The resolution of this positive pattern film was measured.
For the resolution, the pattern film after development is observed with an electron microscope (SEM “JSM-6010”) and the size of the smallest pattern that can pattern the exposed portion without scum is defined as the resolution (L (μm)/S (μm)). did.

(Cyclization rate)
The obtained dried coating film was heated on a hot plate at a temperature of 180° C. to 200° C. for 1 hour, and the obtained cured product was subjected to waveform analysis by Fourier Transform InfraRed spectroscopy (FT-IR). Then, the cyclization rate was calculated by the following formula.
As a reference, when the peak derived from C=C of the aromatic ring, that is, the peak near 1595 cm ⁻¹ is defined as peak I, and the peak derived from C—O of the oxazole ring, that is, the peak near 1050 cm ⁻¹ is defined as peak II,
Cyclization rate={(area of II/area of I)÷(area of II (100% cyclization)/area of I (100% cyclization))}×100
The evaluation of the cyclization rate in Table 2 was based on the following criteria.
⊚: Cyclization rate of 85% or more ○: Cyclization rate of 80% or more and less than 85% Δ: Cyclization rate of 75% or more and less than 80% ×: Cyclization rate of less than 75%

(Cu corrosion)
The photosensitive resin compositions of Examples 5 to 8 and Comparative Examples 5 to 10 were applied to Cu foil, dried on a hot plate at 120°C for 3 minutes, and then heated at 200°C for 1 hour to obtain a cured film. .. After peeling the cured film from the Cu foil, corrosion of the Cu foil was observed as an extent of discoloration with an optical microscope.
The evaluation of Cu corrosion was based on the following criteria.
○: No discoloration ×: Discoloration (thermal/mechanical properties)
The thermo-mechanical properties (Tg, elongation, elastic modulus, strength) of the cured film obtained by heating were specified.

In Table 2, the heating temperature at the time of heating is shown, and the evaluation results of resolution, cyclization rate, and Cu corrosion are also shown.

表２から分かるように、リン酸を含む実施例５〜８は、従来の感光性樹脂組成物と同等の解像度を有しながら１８０℃や２００℃といった低温で十分に硬化させることができ、しかも、Ｃｕを腐食させることがなかった。また、実施例５〜８は、従来の感光性樹脂組成物と同等の熱、機械的特性を有していた。

As can be seen from Table 2, Examples 5 to 8 containing phosphoric acid can be sufficiently cured at a low temperature of 180° C. or 200° C. while having a resolution equivalent to that of the conventional photosensitive resin composition, and , Cu was not corroded. Further, Examples 5 to 8 had thermal and mechanical properties equivalent to those of the conventional photosensitive resin composition.

On the other hand, Comparative Examples 5 and 6 did not have a cyclization catalyst, and therefore could not be sufficiently cured at a heating temperature of 200°C. Further, in Comparative Examples 7 to 9, since the cyclization catalyst was organic phosphoric acid, it could not be sufficiently cured at a heating temperature of 200°C. Furthermore, in Comparative Example 10, Cu was corroded because the cyclization catalyst was sulfonic acid.

Claims (10)

A photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a photosensitizer, and (C) at least one of the compounds represented by the general formulas (1) and (2).

(In the general formula (1), at least one of X _{1 to} X ₃ is an —OH group or an —OR (R is an organic group) group. In the general formula (2), n is 1 to 1000. It is an integer.) The photosensitive resin composition according to claim 1, wherein the compound represented by the general formula (1) has two or more —OH groups or two or —OR groups. The photosensitive resin composition according to claim 1, wherein the compound represented by the general formula (2) is condensed phosphoric acid in which n is an integer of 2 or more in the general formula (2). The photosensitive resin composition according to any one of claims 1 to 3, comprising a polybenzoxazole precursor as the (A) alkali-soluble resin. The photosensitive resin composition according to claim 1, comprising a naphthoquinonediazide compound as the photosensitizer. A dry film having a resin layer obtained by applying the photosensitive resin composition according to any one of claims 1 to 5 to a film and drying the film. A cured product obtained by curing the photosensitive resin composition according to claim 1 or the resin layer of the dry film according to claim 6. A printed wiring board comprising the cured product according to claim 7. A semiconductor device comprising the cured product according to claim 7. An electronic component comprising the cured product according to claim 7.