KR20200037309A - Photosensitive resin composition, dry film, cured product, printed wiring board, semiconductor element and electronic component - Google Patents

Abstract

It provides a photosensitive resin composition, a dry film, a cured product, a printed wiring board, and electronic components that do not corrode metal wiring by curing at low temperatures below 300 ° C. The photosensitive resin composition of this invention contains (A) alkali-soluble resin, (B) photosensitive agent, and (C) at least one of the compound represented by general formula (1) and general formula (2). In the general formula (1), at least one of X ₁ to X ₃ is a -OH group or -OR (R is an organic group) group, and in the general formula (2), n is an integer of 1 to 1000.

Description

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

The present invention relates to a photosensitive resin composition, a dry film, a cured product, a printed wiring board, and a semiconductor element suitable for use in a protective film of a semiconductor device, an insulating film for a redistribution layer of a wafer level package (WLP), an insulating part of a passive component, and the like.

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

On the other hand, in order to prepare a positive photosensitive resin composition that can be cured at a low temperature, it has been considered to contain an acid catalyst such as sulfonic acid or onium salt as a cyclization catalyst and promote dehydration ring closure by the cyclization catalyst. For example, there is a thing containing an aliphatic sulfonic acid for a positive photosensitive resin composition capable of curing at a low temperature (Patent Document 1).

Japanese Patent Publication No. 2006-10781

However, the positive photosensitive resin composition described in Patent Literature 1 has a problem in that metal wiring, particularly, copper wiring is liable to be corroded by the generation of sulfonic acid.

Accordingly, 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 device, and electronic components that do not corrode metal wiring, especially copper wiring by curing at a low temperature of less than 300 ° C.

As a result of earnest examination, the present inventors discovered that the above-described problems can be solved by including a specific compound as a cyclization catalyst, and have achieved the present invention.

The photosensitive resin composition of the present invention is characterized by comprising (A) an alkali-soluble resin, (B) a photosensitive agent, 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 a -OH group or -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, it is preferable that the compound represented by the general formula (1) has two or more of the -OH group or the -OR group, and the compound represented by the general formula (2) is the In general formula (2), n is an integer of 2 or more, and is preferably a condensed phosphoric acid, and (A) preferably contains a polybenzoxazole precursor as the alkali-soluble resin, and contains a naphthoquinonediazide compound as the photosensitizer It is preferred.

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

The cured product of the present 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 is characterized by having the cured product.

The photosensitive resin composition of the present invention can be cured at a low temperature of less than 300 ° C. Moreover, by irradiating an active energy ray with respect to the photosensitive resin composition of this invention, metal wiring, especially hardened | cured material which does not corrode a copper wiring can be obtained. Moreover, the photosensitive resin composition of this invention can be obtained as said hardened | cured material by irradiating an active energy ray on the base material of a printed wiring board or a member of a semiconductor element.

Hereinafter, the photosensitive resin composition of the present invention, a dry film, a cured product, a printed wiring board, a semiconductor element, and electronic components will be described in more detail.

The photosensitive resin composition of the present invention comprises (A) an alkali-soluble resin, (B) a photosensitive agent, and (C) at least one of compounds represented by the general formulas (1) and (2). will be.

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

[(A) Alkali-soluble resin]

The photosensitive resin composition of this invention contains alkali-soluble resin.

The alkali-soluble resin (A) is a resin soluble in an aqueous alkali solution as a developing solution in the development after exposure by irradiation with active energy rays. As the alkali-soluble resin, an alkali-soluble polymer that has been used in conventional photosensitive resin compositions can be used. As an alkali-soluble polymer, what has an alkali-soluble group in a molecule | numerator, specifically, what has carboxyl group, phenolic hydroxyl group, sulfonic acid group, thiol group, etc. is mentioned. Among them, polymers having a phenolic hydroxyl group or a carboxyl group are preferable, and novolak resins, resol resins, polyimide precursors, polybenzoxazole precursors, and the like are mentioned. It is preferably a polyimide precursor or a polybenzoxazole precursor. When these polymers are heated at a predetermined temperature, they are dehydrated and closed to obtain heat-resistant resins in the form of polyimide or polybenzoxazole, or copolymerization of both.

(A) It is preferable that a polybenzoxazole precursor is polyhydroxyamic acid which has a repeating structure of the following general formula (3).

(Wherein, X represents a tetravalent organic group, Y represents a divalent organic group. N is an integer of 1 or more, preferably 10 to 50, more preferably 20 to 40.)

(A) When the polybenzoxazole precursor is synthesized by the above synthesis method, in the general formula (3), X is a residue of the dihydroxydiamines 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-hydroxy And phenyl) -1,1,1,3,3,3-hexafluoropropane. 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-butyl isophthalic 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-carboxy Dicarboxylic acids having aromatic rings such as phenyl) propane, 2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, oxalic acid, malonic acid, succinic acid, And aliphatic dicarboxylic acids such as 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and 1,3-cyclopentanedicarboxylic acid. Especially, 4,4'- dicarboxydiphenyl ether is preferable.

In the general formula (3), the tetravalent organic group represented by X may be either an aliphatic group or an aromatic group, but is preferably an aromatic group, and more preferably two hydroxy groups and two amino groups are positioned on the aromatic ring in an ortho position. The number of carbon atoms in the tetravalent aromatic group is preferably 6 to 30, and more preferably 6 to 24. Although the group shown below is mentioned as a specific example of the said tetravalent aromatic group, It is not limited to these, You may select the well-known aromatic group which can be contained in a polybenzoxazole precursor according to a use.

It is preferable that the said tetravalent aromatic group is the group shown below among the said aromatic groups.

In the general formula (3), the divalent organic group represented by Y may be either an aliphatic group or an aromatic group, but is preferably an aromatic group, and more preferably bonded to carbonyl in the general formula (3) on an aromatic ring. The number of carbon atoms in the divalent aromatic group is preferably 6 to 30, and more preferably 6 to 24. Although the group shown below is mentioned as a specific example of the said bivalent aromatic group, It is not limited to these, You may select the well-known aromatic group contained in a polybenzoxazole precursor according to a use.

(Wherein, A is a single bond, -CH _2- , -O-, -CO-, -S-, -SO _2- , -NHCO-, -C (CF ₃ ) _2- , -C (CH ₃ ) _It represents a divalent group selected from the group consisting of 2-.)

It is preferable that the said divalent organic group is the group shown below among the said aromatic groups.

(A) The polybenzoxazole precursor may contain 2 or more types of repeating structures of the said polyhydroxyamic acid. Moreover, the structure other than the repeating structure of the said polyhydroxyamic acid may be included, for example, the repeating structure of polyamic acid may be included.

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

(A) The polybenzoxazole precursor may be used individually by 1 type, or may be used in combination of 2 or more type.

(A) The method for synthesizing the polybenzoxazole precursor is not particularly limited and may be synthesized by a known method. For example, it can be obtained by reacting dihydroxydiamines as an amine component and dihalides of dicarboxylic acids such as dicarboxylic acid dichloride as an acid component.

(A) It is preferable that the compounding quantity of alkali-soluble resin is 60 to 90 mass% based on the total amount of solid content of a composition. When it contains 60 mass% or more, adhesiveness and surface hardenability become favorable. Moreover, the fall of crosslinking density in hardened | cured material can be prevented by including in 80 mass% or less, and coating film characteristics become favorable.

[(B) photosensitizer]

The photosensitive resin composition of this invention contains a photosensitive agent. (B) The photosensitive agent is not particularly limited, and a photo acid generator, photopolymerization initiator, or photobase generator can be used. The photo acid generator is a compound that generates acid by light irradiation such as ultraviolet light or visible light, the photopolymerization initiator is a compound that generates radicals and the like by the same light irradiation, and the photobase generator is by the same light irradiation It is a compound that produces one or more basic substances by changing the molecular structure or cleaving the molecule. In the present invention, as the photosensitive agent (B), a photo acid generator can be suitably used.

Examples of the photo acid generator include a naphthoquinone diazide compound, a diarylsulfonium salt, a triarylsulfonium salt, a dialkylphenacylsulfonium salt, a diaryl iodonium salt, an aryldiazonium salt, an aromatic tetracarboxylic acid ester, and aromatic sulfonic acid Esters, nitrobenzyl esters, aromatic N-oxyimidosulfonates, aromatic sulfamides, benzoquinone diazosulfonic acid esters, and the like. It is preferable that the photo acid generator is a dissolution inhibitor. Especially, it is preferable that it is a naphthoquinone diazide compound.

As a naphthoquinone diazide compound, specifically, for example, a naphthoquinone diazide adduct of tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene (for example, Sanbo Chemical Co., Ltd.) TS533, TS567, TS583, TS593 manufactured by the company, or a naphthoquinone diazide adduct of tetrahydroxybenzophenone (for example, BS550, BS570, BS599 manufactured by Sanbo Chemical Co., Ltd.), 4- {4- Naphthoquinone diazide adduct of [1,1-bis (4-hydroxyphenyl) ethyl] -α, α-dimethylbenzyl} phenol (eg, TKF-428, TKF- manufactured by Sanbo Chemical Co., Ltd.) 528).

As 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-based photopolymerization initiator, and a titanocene-based photopolymerization initiator. Can be used.

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

As said α-amino acetophenone type photoinitiator, specifically 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-dimethylamino acetophenone, etc. are mentioned, As a commercial item, BASF Japan company Irgacure 907, Irgacure 369, Irgacure 379, etc. can be used.

As the acylphosphine oxide-based photopolymerization initiator, specifically, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6 -Dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, and the like, and commercially available products include Irgacure TPO manufactured by BASF Japan and Omnirad (omnirad) 819 manufactured by IGM Resins. .

As said titanocene type photoinitiator, specifically, bis (cyclopentadienyl) -di-phenyl-titanium, bis (cyclopentadienyl) -di-chloro-titanium, bis (cyclopentadienyl) -bis (2, And 3,4,5,6 pentafluorophenyl) titanium, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyrrole-1-yl) phenyl) titanium, and the like. As a commercial item, Irgacure 784 by BASF Japan, etc. are mentioned.

Further, the photobase generator may be either an ionic photobase generator or a nonionic photobase generator, but the ionic photobase generator is preferable because the composition has high sensitivity and is advantageous for formation of a patterned film. As a basic substance, secondary amine and tertiary amine are mentioned, for example.

Examples of the ionic photobase generator include salts of aromatic carboxylic acids and tertiary amines, and WPBG-082, WPBG-167, WPBG-168, WPBG-266, and WPBG of ion type PBG manufactured by Wako Pure Chemical Industries, Ltd. -300 etc. can be used.

Examples of the non-ionic photobase generator include α-aminoacetophenone compounds, oxime ester compounds, N-formylated aromatic amino groups, N-acylated aromatic amino groups, nitrobenzyl carbamate groups, and alkoxybenzylcarba And compounds having a substituent such as a mate group. As other photobase generators, WPBG-018 (trade name: 9-anthrylmethyl N, N'-diethylcarbamate) manufactured by Wako Pure Chemical Industries, Ltd., WPBG-027 (trade name: (E) -1- [3- (2-hydroxyphenyl) -2-propenoyl] piperidine), WPBG-140 (trade name: 1- (anthraquinone-2-yl) ethyl imidazolecarboxylate), WPBG-165, etc. may also be used. have.

(B) The photosensitizer may be used individually by 1 type, or may be used in combination of 2 or more type. (B) It is preferable that the compounding quantity of a photosensitizer is 3-20 mass% based on the total amount of solid content of a composition. As described above, the photosensitive agent (B) is not limited to a positive type, and may be a negative type.

[At least one of the compounds represented by (C) general formula (1) and general formula (2)]

The photosensitive resin composition of this invention contains at least one of the compounds represented by general formula (1) and general formula (2).

First, the compound represented by the general formula (1) will be described.

In the general formula (1), at least one of X ₁ to X ₃ is a -OH group or -OR (R is an organic group) group. For example, X ₁ to X ₃ are both of a hydroxyl acid, X ₁ to X ₃ is a boronic acid (RB (OH) _{2) 2} OH in the dog, an -OR group all of X ₁ to X ₃ boric acid ester ( B (OR) ₃ ), boronic acid ester obtained by condensation reaction of boronic acid and alcohol (RB (OR) ₂ ), boric acid (R ₂ BOH) in which one of X ₁ to X ₃ is a hydroxyl group, condensation of boric acid and alcohol And boric acid esters (R ₂ BOR) obtained by the reaction.

The compound represented by the general formula (1) has a strong dehydration action, for example, a self-dehydration reaction from boric acid to boroxine. By 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.

In addition, the compound represented by the general formula (1) is not acidic and therefore does not corrode metal wiring such as copper or aluminum. Therefore, the photosensitive resin composition of this invention containing the compound represented by general formula (1) does not corrode a metal wiring.

In addition, the compound represented by the general formula (1) does not adversely affect the resolution of the photosensitive resin composition, nor does it adversely affect the thermal properties and mechanical properties.

In view of the above, the photosensitive resin composition of the present invention, which contains the compound represented by the general formula (1) as the component (C), does not degrade resolution, thermal properties, and mechanical properties, and at low temperature heating of less than 300 ° C. It can be hardened and does not corrode metal wiring such as aluminum wiring or copper wiring.

The compound represented by the general formula (1) is boric acid (B (OH) ₃ ), boronic acid (RB (OH) ₂ ), boric acid ester (B (OR) ₃ ), boronic acid ester (RB (OR) ₂ ) ), Boric acid (R ₂ BOH), and boric acid ester (R ₂ BOR).

Boronic acid (RB (OH) ₂ ) is exemplified by two hydroxyl groups among X ₁ to X ₃ in the general formula (1), that is, R is a phenyl group, trifluorophenyl group, thienyl group, methyl group or propenyl group. have. An alkyl group or an aryl group other than these may be used. Specific examples of boronic acid include phenylboronic acid, trifluorophenylboronic acid, 2-thiophenboronic acid, methylboronic acid, cis-propenylboronic acid, and trans-propenylboronic acid.

Boronic acid ester (RB (OR) ₂ ) is an ester of boronic acid and alcohol, and is produced by a condensation reaction of a boric acid ester and alcohol (including polyols such as diols). Examples of the alcohol used for the condensation reaction include pinacol, trimethylene glycol, and isopropanol. Except for two -OR groups of X ₁ to X ₃ in the general formula (1) of the boronic acid ester, that is, R may be the same as the boronic acid. Specific examples of the boronic ester include allylboronic acid pinacolato, 2-phenyl-1,3,2-dioxaborinane, and diisopropylmethylborane.

When the specific example of a boronic acid and the specific example of a boronic acid ester are shown by a structural formula, there are the following.

The compound represented by the general formula (1) can be used by mixing one or two or more of the above-described compounds.

In order to further promote cyclization, it is preferable that the compound represented by the general formula (1) has two or more of the -OH group or the -OR group. 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, in proportion to 100 parts by mass of the alkali-soluble resin (A) of the present invention. When included in 1 part by mass or more, the photosensitive resin composition can be sufficiently cured, and by being included in 5 parts by mass or less, it can be sufficiently mixed in the resin composition.

Moreover, as the compound which promotes cyclization of the alkali-soluble resin (A) similarly to the compound represented by the general formula (1), phosphoric acid and / or polyphosphoric acid can be used in combination with the compound represented by the general formula (1). .

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

For example, the compound represented by the general formula (2) has a strong dehydration action, such as a condensation dehydration reaction from orthophosphoric acid to condensed phosphoric acid. By 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.

In addition, the compound represented by the general formula (2) promotes cyclization of the alkali-soluble resin (A) by the action of a catalyst as an acid. The action of the catalyst as an acid and the above-described dehydration action are combined, and 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.

Since the action of the compound represented by the general formula (2) as an acid is not strong enough to corrode copper or copper alloy in the copper wiring, it does not corrode the copper wiring. Therefore, the photosensitive resin composition of this invention containing the compound represented by general formula (2) does not corrode a copper wiring.

In addition, the compound represented by the general formula (2) does not adversely affect the resolution of the photosensitive resin composition, nor does it adversely affect the thermal properties and mechanical properties.

In view of the above, the photosensitive resin composition of the present invention comprising the compound represented by the general formula (2) as the component (C) does not degrade resolution, thermal properties, or mechanical properties, and is cured at low temperature heating of less than 300 ° C. It does not corrode copper wiring.

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

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

The compound represented by the general formula (2) can be used by mixing one or two or more of the above-described compounds.

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

In addition, as the compound represented by the general formula (2) (A) as a compound that promotes the cyclization of the alkali-soluble resin, boric acid (B (OH) ₃ ), boronic acid (RB (OH) ₂ ), X ₁ to Boric acid esters (B (OR) ₃ ), boronic acid esters (RB (OR) ₂ ), boric acid (R ₂ BOH), and boric acid esters (R ₂ BOR), all of X ₃ are -OR groups. It can be used in combination with a compound represented by).

The photosensitive resin composition of this invention is a component other than at least one of the compound represented by the said (A) alkali-soluble resin, (B) photosensitive agent, and (C) general formula (1) and general formula (2) as needed. It may include. These components are described below.

[Silane coupling agent]

The photosensitive resin composition of the present invention may include 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. It is more preferable that it is a silane coupling agent which has an arylamino group from the point of excellent resolution.

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

It is preferable that the silane coupling agent having an arylamino group is a compound having a group represented by the following general formula (4).

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

In the general formula (4), it is preferable that R ³¹ to R ³⁵ are hydrogen atoms.

The silane coupling agent having an arylamino group is preferably a silicon atom and an arylamino group bonded to an organic group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms.

It is preferable that it is a compound shown below as a specific example of a silane coupling agent which has an arylamino group.

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

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

It is preferable that the following compound is a specific example of the silane coupling agent which has two or more trialkoxysilyl groups.

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 arylamino group mentioned above, and the silane coupling agent which has two or more trialkoxysilyl groups.

It is preferable that the compounding quantity of a silane coupling agent is 1-15 mass% based on the total amount of solid content of a composition. When it is 1 to 15 mass%, development residues of the exposed portion can be prevented.

[Sensitizer, adhesion aid, other ingredients]

In the photosensitive resin composition of the present invention, a sensitizer known for improving light sensitivity, a known adhesion aid for improving adhesion to a substrate, a crosslinking agent, and the like can be further blended in a range that does not impair the effects of the present invention. It might be.

Further, in order to impart processing characteristics and various functionalities to the photosensitive resin composition of the present invention, other various organic or inorganic low molecular or high molecular compounds may be blended. For example, surfactants, leveling agents, plasticizers, 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. in the photosensitive resin composition of this invention.

[solvent]

The solvent used in the photosensitive resin composition of the present invention includes (A) an alkali-soluble resin, (B) a photosensitizer, (C) at least one of the compounds represented by the general formulas (1) and (2) described above, and other The additive is not particularly limited as long as it is dissolved. Examples include N, N'-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N, N'-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, and γ- Butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphor And amide, 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 to be used can be appropriately determined depending on the thickness and viscosity of the coating film. For example, it can be used in the range of 50 to 9000 parts by mass based on 100 parts by mass of the alkali-soluble resin (A).

[Dry film]

The dry film of this invention has the resin layer obtained by apply | coating and drying the photosensitive resin composition of this invention to a carrier film. It is used by laminating the resin layer so as to contact the substrate.

In the dry film of the present invention, the photosensitive resin composition of the present invention is uniformly applied to a carrier film by a suitable method such as a blade coater, a lip coater, a comma coater, a film coater, and dried to form the above-mentioned resin layer, preferably It can be produced by laminating a cover film on it. The cover 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, as the film material of the carrier film and the cover film, any known material used for the dry film 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.

A polyethylene film, a polypropylene film, or the like can be used as the cover film, but the adhesive force with the resin layer is 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, and more preferably 5 to 50 µm.

[Carbide]

The cured product of the present invention is cured in a predetermined step using the photosensitive resin composition of the present invention described above. The patterned film, which is a cured product thereof, is produced, for example, by each of the following steps in the case of a positive photosensitive resin composition.

First, as a step 1, a coating film is obtained by applying and drying a photosensitive resin composition on a substrate, or by transferring a resin layer from a dry film onto the substrate. As a method of applying the photosensitive resin composition onto the substrate, a method conventionally used for the application of the photosensitive resin composition, for example, a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine or the like, or a spray coater The spray coating method, furthermore, an inkjet method or the like can be used. As a method for drying the coating film, a method such as air drying, heating drying by an oven or a hot plate, vacuum drying, or the like is used. Moreover, it is preferable to perform drying of a coating film on the condition in which the cyclization of (A) alkali-soluble resin in a photosensitive resin composition does not occur. Specifically, natural drying, blow drying or heat drying can be performed at 70 to 140 ° C. for 1 to 30 minutes. Preferably, drying is performed for 1 to 20 minutes on a hot plate. Moreover, vacuum drying is also possible, and in this case, it can be performed at room temperature for 20 minutes to 1 hour.

There is no particular limitation on the substrate on which the coating film of the photosensitive resin composition is formed, and it can be widely applied to semiconductor substrates such as silicon wafers, wiring substrates, various resins, and metals.

Next, as step 2, the coating film is exposed through a photomask having a pattern or directly. As the exposure light beam, those having a wavelength capable of activating the photo acid generator as the photosensitive agent (B) are used. Specifically, the exposure light beam preferably has a maximum wavelength in the range of 350 to 410 nm. As described above, light sensitivity can be prepared by appropriately blending the sensitizer. As an exposure apparatus, a contact aligner, a mirror projection, a stepper, a laser direct exposure apparatus, etc. can be used.

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

Next, as a step 4, the coating film is treated with a developer. Thereby, the exposed part in a coating film can be removed and the pattern film of the photosensitive resin composition of this invention can be formed.

As the method used for the development, any method can be selected from a conventionally known photoresist development method, for example, a rotating spray method, a paddle method, or an immersion method with ultrasonic treatment. As the developer, inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, and aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, and the like And aqueous solutions such as quaternary ammonium salts. Further, if necessary, an appropriate amount of a water-soluble organic solvent or surfactant, such as methanol, ethanol, or isopropyl alcohol, may be added. Then, if necessary, the coating film is washed with a rinse liquid to obtain a pattern film. As the rinse solution, 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.

Thereafter, as step 5, the pattern film is heated to obtain a cured coating film (cured product). The alkali developable resin (A) is cured by this heating, for example, the polybenzoxazole precursor is closed to obtain a polybenzoxazole. The heating temperature is appropriately set so that the pattern film of the alkali developable resin is curable. For example, heating is performed in an inert gas at 150 ° C or more and less 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 included as the component (C), and 180 to 180 when the compound represented by the general formula (2) is included. 250 ° C. Since the photosensitive resin composition of the present invention contains at least one of the compound represented by (C) the general formula (1) and the compound represented by the general formula (2), cyclization is promoted, and the heating temperature is less than 300 ° C. You can. Heating is performed, for example, by using a hot plate, an oven, and a temperature-rising oven capable of setting a temperature program. As the atmosphere (gas) at this time, air may be used, or an inert gas such as nitrogen or argon may be used.

Incidentally, when the photosensitive resin composition of the present invention is a negative photosensitive resin composition, (B) using a photopolymerization initiator or a photobase generator instead of a photoacid generator as the photosensitive agent, the coating film in step 4 is used as a developer. By processing, the unexposed portion in the coating film can be removed to form the 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 is suitably used, for example, as a coating material, a printing ink, or an adhesive, or a material for forming a display device, semiconductor element, semiconductor device, electronic component, optical component, or building material. Is used. Specifically, as a material for forming the display device, it can be used as a layer forming material or an image forming material as a color filter, a film for flexible displays, a resist material, an alignment film, or the like. Moreover, as a material for forming a semiconductor device, it can be used for a layer material such as a resist material or a buffer coating film. Moreover, as a material for forming an electronic component, it can be used for a printed wiring board, an interlayer insulating film, and a wiring coating film as a sealing material or a layer forming material. Moreover, as an optical component forming material, it can be used as an optical material or a layer forming material, such as a hologram, an optical waveguide, an optical circuit, an optical circuit component, and an antireflection film. Moreover, as a building material, it can be used for a coating material, a coating agent, etc.

The photosensitive resin composition of the present invention can be mainly used as a pattern forming material, and the pattern film as a cured product formed therefrom is a permanent film made of, for example, polybenzoxazole, etc., and functions as a component that provides heat resistance and insulation. In, in particular, surface protective films of semiconductor devices, display devices and light emitting devices, interlayer insulating films, insulating films for redistribution, protective films for flip chip devices, protective films for devices having bump structures, interlayer insulating films for multilayer circuits, insulating materials for passive components, solder It can be used suitably as a protective film of a printed wiring board, such as a resist or a coverlay film, and a liquid crystal aligning film. In particular, it is suitable for use in insulating films in contact with copper wiring or aluminum wiring.

Example

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to the examples. In addition, in the following, "parts" and "%" are all 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 added, and 28.00 g (76.5 mmol) of bis (3-amino-4-hydroxyamidophenyl) hexafluoropropane was stirred and dissolved. . Thereafter, the flask was immersed in an ice bath, and 25.00 g (83.2 mmol) of 4,4-diphenyl ether dicarboxylic acid chloride was added over a period of 30 minutes while maintaining the inside of the flask at 0 to 5 DEG C. And stirred for 30 minutes in an ice bath. Thereafter, stirring was continued at room temperature for 5 hours. The stirred solution was poured into 1 L of ion-exchanged water (specific resistance value of 18.2 MΩ · cm), and precipitates were recovered. Thereafter, the obtained solid was dissolved in 420 mL of acetone, and charged 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 repeating structure shown below at the terminal of the carboxyl group. 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 to 4)

With respect to 100 parts by mass of the benzoxazole precursor synthesized above, (B) naphthoquinone diazide compound B-1 (TKF-428 manufactured by Sanko Chemical Co., Ltd.) or B-2 (TKF-528 manufactured by Sanko Chemical Products) as a photosensitizer. 10 parts by mass, a silane coupling agent having an arylamino group (KBM-573 manufactured by Shin-Etsu Silicone Co., Ltd.) as a silane coupling agent, and 7 parts by mass of a C-1 or C-2 boric acid compound shown in Table 1 as a cyclization catalyst. After blending each 3 parts by mass, N-methylpyrrolidone (NMP) was added to make the benzoxazole precursor 30% by mass to prepare a varnish, and the photosensitive resin compositions of Examples 1 to 4 were adjusted.

(Comparative Examples 1 to 4)

In addition, as Comparative Examples 1 and 2, the photosensitive resin compositions of Comparative Examples 1 and 2 were adjusted in the same manner as in Examples 1 and 2, except that the above-described C-1 boric acid compound was not blended.

In addition, as the comparative example 3, the photosensitive resin composition of the comparative example 4 was adjusted like Example 1 except having mix | blended the organic phosphoric acid C-5 shown below instead of the above-mentioned boric acid compound C-1.

Moreover, as the comparative example 4, the photosensitive resin composition of the comparative example 3 was adjusted like Example 1 except having mixed the sulfonic acid C-8 shown below instead of the above-mentioned boric acid compound C-1.

The photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 to 4 thus prepared were evaluated for resolution, cyclization rate, Cu corrosion, and Al corrosion. The evaluation method is as follows.

(Method of producing a dry coating film for evaluation)

The photosensitive resin composition was applied on a silicon substrate with a spin coater. It dried at 120 degreeC for 3 minutes on the hot plate, and obtained the dry coating film of the photosensitive resin composition.

(Evaluation of resolution)

High-pressure mercury lamps were used in the obtained dry coating films of Examples 1 to 4 and Comparative Examples 1 to 4, and 300 mJ / cm ² of broad light was irradiated through a mask engraved with a pattern. After exposure, it was developed for 60 seconds with a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) and rinsed with water to obtain a positive pattern film. The resolution of this positive pattern film was measured.

Resolution: The pattern pattern after development was observed with an electron microscope (SEM "JSM-6010"), and the size of the minimum pattern capable of patterning the exposed portion without scum was defined as resolution (L (µm) / S (µm)).

(Conversion rate)

The obtained dried coating film was heated at a temperature of 200 ° C to 220 ° C on a hot plate for 1 hour, and the obtained cured product was subjected to waveform analysis by Fourier Transform InfraRed spectroscopy (FT-IR), and the following equation The conversion rate was calculated by.

As reference as aromatic ring C = C of the peak of the derived peak, i.e. a peak near 1595cm ^-1 I, and when the peak of the oxazole ring of the peak, that is, the vicinity of 1050cm ^-1 of CO derived hayeoteul Rafik II,

Conversion rate = {((II area / I area) ÷ (II area (100% conversion) / I area (100% conversion))} × 100

The evaluation of the cyclization rate in Table 1 was based on the following criteria.

◎: Currency conversion rate of 85% or more

○: The conversion rate is 80% or more and less than 85%.

△: Currency conversion rate was 75% or more and less than 80%.

×: conversion rate is 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 each of the Cu foil and the Al 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 the cured film was peeled from the Cu foil or the Al foil, corrosion of the Cu foil and the Al foil was observed by an optical microscope as a degree of discoloration.

Evaluation of Cu corrosion and Al corrosion was made into the following criteria.

○: no discoloration

×: discoloration

(Thermal and 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 evaluation results of resolution, cyclization rate, Cu corrosion, and Al corrosion are also described.

As can be seen from Table 1, Examples 1 to 4 containing a boric acid-based compound can sufficiently cure at a low temperature of 200 ° C or 220 ° C while having a resolution equivalent to that of a conventional photosensitive resin composition, and also Cu or Al was 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, since Comparative Examples 1 and 2 did not have a cyclization catalyst, it could hardly be hardened at the heating temperature of 220 degreeC. In addition, in Comparative Example 3, Al was corroded because the cyclization catalyst was organic phosphoric acid. In addition, in Comparative Example 4, because the cyclization catalyst was sulfonic acid, Cu and Al corroded.

(Examples 5 to 8)

With respect to 100 parts by mass of the benzoxazole precursor synthesized above, (B) naphthoquinone diazide compound B-1 (TKF-428 manufactured by Sanko Chemical Co., Ltd.) or B-2 (TKF-528 manufactured by Sanko Chemical Industry Co., Ltd.) as a photosensitizer. 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 condensed phosphoric acid of C-3 shown in Table 2 as a cyclization catalyst (n = 80 phosphorus pentoxide) % Or more) or 3 parts by mass of C-4 orthophosphoric acid, respectively, and then added as N-methylpyrrolidone (NMP) to make the benzoxazole precursor 30% by mass, to give a varnish. Examples 5 to 8 The photosensitive resin composition of was adjusted.

(Comparative Examples 5 to 10)

In addition, as Comparative Examples 5 and 6, the photosensitive resin compositions of Comparative Examples 5 and 6 were adjusted in the same manner as in Examples 5 and 6, except that the above-described condensed phosphoric acid C-3 was not blended.

Moreover, as the comparative example 7, the photosensitive resin composition of the comparative example 7 was adjusted like Example 5 except having mix | blended the organic phosphoric acid C-5 shown above in place of the above-mentioned condensed phosphoric acid C-3.

In Comparative Examples 8 and 9, Comparative Examples 8 and 9 were carried out in the same manner as in Example 5, except that the following organic phosphoric acid C-6 or C-7 was respectively blended instead of the above-mentioned condensed phosphoric acid C-3. The photosensitive resin composition of was adjusted.

In addition, as the comparative example 10, the photosensitive resin composition of the comparative example 10 was adjusted like Example 5 except having mix | blended the sulfonic acid C-8 shown below instead of the above-mentioned condensed phosphoric acid C-3.

The photosensitive resin compositions of Examples 5 to 8 and Comparative Examples 5 to 10 thus prepared were evaluated for resolution, cyclization rate, and Cu corrosion. The evaluation method is as follows.

(Method of producing a dry coating film for evaluation)

The photosensitive resin composition was applied on a silicon substrate with a spin coater. It dried at 120 degreeC for 3 minutes on the hot plate, and obtained the dry coating film of the photosensitive resin composition.

(Evaluation of resolution)

300 mJ / cm ² of broad light was irradiated through the mask on which the pattern was engraved using a high pressure mercury lamp in the dried coating films of Examples 5 to 8 and Comparative Examples 5 to 10 obtained. After exposure, it was developed for 60 seconds with a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) and rinsed with water to obtain a positive pattern film. The resolution of this positive pattern film was measured.

Resolution was determined by observing the pattern film after development with an electron microscope (SEM "JSM-6010"), and the size of the minimum pattern capable of patterning the exposed portion without scum was the resolution (L (µm) / S (µm)).

(Conversion rate)

The obtained dried coating film was heated at a temperature of 180 ° C to 200 ° C on a hot plate for 1 hour, and the obtained cured product was subjected to waveform analysis by Fourier Transform InfraRed spectroscopy (FT-IR), and the following equation The conversion rate was calculated by.

As reference as aromatic ring C = C of the peak of the derived peak, i.e. a peak near 1595cm ^-1 I, and when the peak of the oxazole ring of the peak, that is, the vicinity of 1050cm ^-1 of CO derived hayeoteul Rafik II,

Conversion rate = {((II area / I area) ÷ (II area (100% conversion) / I area (100% conversion))} × 100

The evaluation of the cyclization rate in Table 2 was based on the following criteria.

◎: Currency conversion rate of 85% or more

○: The conversion rate is 80% or more and less than 85%.

△: Currency conversion rate was 75% or more and less than 80%.

×: conversion rate is 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 the cured film was peeled from the Cu foil, corrosion of the Cu foil was observed by an optical microscope as a degree of discoloration.

Evaluation of Cu corrosion was made into the following criteria.

○: no discoloration

×: discoloration

(Thermal and 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 described.

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 a conventional photosensitive resin composition, and also do not corrode Cu. Did. In addition, Examples 5 to 8 had thermal and mechanical properties equivalent to those of the conventional photosensitive resin composition.

On the other hand, since Comparative Examples 5 and 6 did not have a cyclization catalyst, they could not be hardened sufficiently at a heating temperature of 200 ° C. In addition, in Comparative Examples 7 to 9, since the cyclization catalyst was organic phosphoric acid, it was not sufficiently curable at a heating temperature of 200C. 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 compounds represented by the general formulas (1) and (2).

(In General Formula (1), at least one of X ₁ to X ₃ is a -OH group or -OR (R is an organic group). In General Formula (2), n is an integer of 1 to 1000.) The photosensitive resin composition according to claim 1, wherein the compound represented by the general formula (1) has two or more of the -OH group or the -OR group. The photosensitive resin composition according to claim 1, wherein the compound represented by the general formula (2) is a 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 alkali-soluble resin (A). The photosensitive resin composition according to any one of claims 1 to 4, comprising a naphthoquinone diazide compound as the photosensitive agent. The dry film characterized by having the resin layer obtained by apply | coating and drying the photosensitive resin composition in any one of Claims 1-5 on a film. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 5 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.