JP2019032489A - Photosensitive resin composition, dry film, cured product, printed wiring board, and semiconductor element - Google Patents

Abstract

A photosensitive resin composition having high mechanical properties and storage stability while having a short curing time and low-temperature curing, good adhesion to a copper substrate, and capable of obtaining high resolution, and use thereof A dry film, a cured product, a printed wiring board having the cured product, and a semiconductor element are provided. (A) An alkali-soluble resin having an unsaturated group at the terminal, (B) a photosensitive agent, (C) a compound other than (B) having at least two or more azide groups, and (D) an antioxidant. including. [Selection figure] None

Description

  The present invention relates to a photosensitive resin composition, a dry film, a cured product, a printed wiring board, and a semiconductor element.

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

  On the other hand, in photosensitive resin compositions used for applications such as printed wiring boards and semiconductor elements, in addition to basic properties such as resolution, high mechanical properties and wiring even when the final curing temperature is low. Good adhesion to the copper used is required.

  On the other hand, Patent Document 1 discloses a positive photosensitive resin composition having improved mechanical properties by a low-temperature curing at 210 ° C. for 120 minutes using a combination of a polyamide resin, a photosensitive diazonaphthoquinone compound, a phenol compound, and a bisazide compound. Has been. Moreover, what designated the polyamide of the terminal (alkenyl group and alkynyl group) as a polyamide resin is also indicated.

  In the invention described in Patent Document 2, an alkali-soluble resin and photosensitivity in which an unsaturated group (alkenyl group and alkynyl group) is introduced into one end group, and pyrazole, triazole or tetrazole are introduced into the other end and side chain. There is disclosed a positive photosensitive resin composition which is a combination of diazonaphthoquinone compounds and is improved in adhesion to copper and copper alloy metal wiring by low-temperature curing at 220 ° C. for 90 minutes.

JP-A-2005-292160 International Publication No. 2013/141212

  However, in the invention described in Patent Document 1, mechanical properties are improved by reacting and crosslinking an unsaturated group and an azide compound, but those having an unsaturated group introduced at the terminal are antioxidants. Otherwise, the storage stability is poor, and there is a concern that it reacts with the decomposed product of the photosensitive diazonaphthoquinone compound being added and becomes inactive, resulting in a decrease in mechanical properties. And, since the terminal becomes inactive, a large amount of the azide compound remains in the film, decomposes at the time of curing and releases nitrogen, and serious peeling due to bubble generation is sufficiently expected, as well as the curing time. However, there is a problem that the process time is longer than that of a general one. Further, attention has not been paid to the problems of resolution and adhesion on a metal substrate.

  On the other hand, in the invention described in Patent Document 2, adhesion is achieved by the interaction of side-chain pyrazole, triazole, and tetrazole with the surface of copper and copper alloy. However, since these functional groups are eliminated during imidization and oxazolization at the time of curing, there is a problem of large film slipping, resulting in poor pattern shape and low resolution. .

  Therefore, an object of the present invention is to provide a photosensitive resin composition having a short curing time, low temperature curing yet having high mechanical properties and storage stability, good adhesion to a copper substrate, and excellent resolution. It is an object to provide a dry film, a cured product, a printed wiring board having the cured product, and a semiconductor element using the same.

  As a result of intensive studies, the present inventors have found that the above-mentioned problems associated with conventional photosensitive resin compositions containing a polyamide resin, a photosensitive diazonaphthoquinone compound, a phenol compound, and a bisazide compound can be solved by adding an antioxidant. The headline and the present invention were completed.

  That is, the photosensitive resin composition of the present invention comprises (A) an alkali-soluble resin having an unsaturated group at the terminal, (B) a photosensitive agent, and (C) a compound other than (B) having at least two or more azide groups. (D) An antioxidant is included.

  In the photosensitive resin composition of the present invention, the (D) antioxidant is preferably an alicyclic enol compound.

  In the photosensitive resin composition of the present invention, the alkali-soluble resin having an unsaturated group at the terminal (A) is preferably a polyamide resin.

  In the photosensitive resin composition of the present invention, the unsaturated group at the terminal of the alkali-soluble resin having an unsaturated group at the terminal (A) is preferably an alkynyl group or an alkenyl group.

  In the photosensitive resin composition of the present invention, the (B) photosensitive agent is preferably a photosensitive diazonaphthoquinone compound.

  The photosensitive resin composition of the present invention preferably further comprises (E) a thiol compound.

  The photosensitive resin composition of the present invention preferably uses (F) an ester solvent.

  The dry film of the present invention has a resin layer obtained from the photosensitive resin composition of the present invention.

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

  The printed wiring board and the semiconductor element of the present invention are characterized by having the cured product of the present invention.

  According to the present invention, (D) by using an antioxidant, (A) the terminal unsaturated group of the alkali-soluble resin having an unsaturated group at the terminal while maintaining properties such as curing at low temperature and high mechanical properties It becomes possible to maintain the active state. As a result, it is possible to provide a photosensitive resin composition with improved storage stability, reduced mechanical properties, and improved pattern shape by suppressing film slippage. The photosensitive resin composition is improved in adhesion with copper and has a short curing time because the reaction between the resin and the unsaturated terminal at the copper interface is accelerated.

  The photosensitive resin composition of the present invention comprises (A) an alkali-soluble resin having an unsaturated group at the terminal, (B) a photosensitive agent, (C) a compound other than (B) having at least two or more azide groups, ( D) An antioxidant is included. Below, each component of the curable composition of this invention is demonstrated.

(A) Alkali-soluble resin having an unsaturated group at the terminal]
Examples of the alkali-soluble resin having an unsaturated group at the terminal (A) of the present invention include acrylic resins such as a cresol type novolak resin, a hydroxystyrene resin, a methacrylic acid resin, and a methacrylic ester resin, a hydroxyl group, a carboxyl group, and the like. Examples thereof include cyclic olefin resins, polyimidazole resins, polyamide resins, and the like. Of these, polyamide resins are preferred. Specific examples include polybenzoxazole precursors, polyimide precursors, polythiazole precursors, and the like. It is preferable to have a hydroxyl group, carboxyl group, ether bond or ester bond, thiol group, thioether bond or thioester bond in the main chain or side chain of these resins. Furthermore, a part of the main chain of these resins may have a polybenzoxazole structure, a polyimide structure, or a polybenzthiazole structure.

式中、Ｘは２〜４価の有機基を示し、Ｙは２〜４価の有機基を示す。ｎは１以上の整数であり、好ましくは１０〜７０である。Ｒ_１、Ｒ_２は１価以上の官能基を示す。ｉ、ｊは０〜８の整数である。Ｒ_３は１価の有機基である。 (A) The method of synthesizing the alkali-soluble resin having an unsaturated group at the terminal is not particularly limited, and may be synthesized by a known method. For example, it is obtained by reacting a diamine as an amine component with a dicarboxylic acid dihalide as an acid component and then adding a monoamine having an unsaturated group or a monofunctional acid anhydride having an unsaturated group as a terminal component. be able to. As such a polyamide resin, the polyamide-type resin shown by following (1) can be mentioned, for example.

In the formula, X represents a divalent to tetravalent organic group, and Y represents a divalent to tetravalent organic group. n is an integer greater than or equal to 1, Preferably it is 10-70. R ₁ and R _{2 each} represent a monovalent or higher functional group. i and j are integers of 0-8. R ₃ is a monovalent organic group.

（式中、Ａは単結合、−ＣＨ_２−、−Ｏ−、−ＣＯ−、−Ｓ−、−ＳＯ_２−、−ＮＨＣＯ−、−Ｃ（ＣＦ_３）_２−からなる群から選択される２価の基を表す。） In the general formula (1), the divalent to tetravalent organic group represented by X may be an aliphatic group or an aromatic group, but is preferably an aromatic group. The number of carbon atoms of the divalent to tetravalent aromatic group is preferably 6 to 30, and more preferably 6 to 24. Specific examples of the tetravalent aromatic group include the following groups, but are not limited thereto, and a known aromatic group that can be included in the aromatic polyamide resin is selected according to the use. Good.

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

  Diamine is mentioned as a compound which can be used when the valence of X is bivalent. Examples of the diamine include diaminoisophorone (3-aminomethyl-3,5,5-trimethylcyclohexylamine), toluenediamine, 4,4'-methylenediphenyldiamine, hexamethylenediamine, and the like. Moreover, diamine is not limited to these.

In the general formula (1), examples of the organic group represented by R ₁ include a hydroxyl group, an alkyl ether, a thiol, and a thioether, and among them, a hydroxyl group is preferable. i is an integer from 0 to 8, preferably 0 to 2. The monomer of the above formula may be used alone, or two or more kinds of copolymers may be used.

（式中、Ａは単結合、−ＣＨ_２−、−Ｏ−、−ＣＯ−、−Ｓ−、−ＳＯ_２−、−ＮＨＣＯ−、−Ｃ（ＣＦ_３）_２−からなる群から選択される２価の基を表す。） In the general formula (1), the divalent to tetravalent organic group represented by Y may be an aliphatic group or an aromatic group, but when Y is divalent, it is preferably an aromatic group, and an aromatic ring It is more preferable that it is bonded to the carbonyl in the general formula (1) above. The number of carbon atoms of the divalent to tetravalent aromatic group is preferably 6 to 30, and more preferably 6 to 24. Specific examples of the divalent to tetravalent aromatic group include the following groups, but are not limited thereto, and publicly known aromatic groups that can be included in the aromatic polyamide resin as shown below. What is necessary is just to select according to a use.

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

  The compound that can be used when Y is tetravalent is preferably a carboxylic acid anhydride, and more preferably a tetracarboxylic dianhydride. Specifically, aliphatic such as ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride Tetracarboxylic dianhydride; pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2,3 ′, 3,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic acid Dianhydride, 2,3 ′, 3,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 6,6′-biphenyltetracarboxylic dianhydride, 2 2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride Bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, Bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2 , 2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 1,3-bis [(3,4-dicarboxy) benzoyl] benzene Dianhydride, , 4-bis [(3,4-dicarboxy) benzoyl] benzene dianhydride, 2,2-bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} propane dianhydride, 2, 2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} propane dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, Bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, 4,4′-bis [4- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, 4, 4′-bis [3- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, bis {4- [3- (1,2-dicarboxyl ) Phenoxy] phenyl} ketone dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} sulfone dianhydride, bis {4- [3- (1,2-dicarboxy) phenoxy ] Phenyl} sulfone dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} sulfide dianhydride, bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl } Sulphide dianhydride, 2,2-bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} -1,1,1,3,3,3-hexafluoropropane dianhydride, 2 , 2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,6,7- Naphthalene tetracarboxylic acid 1,1,1,3,3,3-hexafluoro-2,2-bis (2,3- or 3,4-dicarboxyphenyl) propane dianhydride, 1,4,5,8-naphthalene Tetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 1,2,4,5-benzenetetracarboxylic Acid dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic acid Dianhydride, pyridinetetracarboxylic dianhydride, sulfonyldiphthalic anhydride, m-terphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, p-terphenyl-3,3' , 4,4'-Tetracarboxylic Aromatic tetracarboxylic dianhydrides such as dianhydrides, 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] Examples include furan-1,3-dione.

  Among the above acid dianhydrides, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4 ′ as tetracarboxylic dianhydride -Biphenyltetracarboxylic dianhydride, 2,2 ', 6,6'-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3 4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 1,2,4,5-benzenetetracarboxylic dianhydride, 1,3,3a, 4 5,9b-Hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione is preferred.

In the general formula (1), examples of the organic group represented by R ₂ include a carboxylic acid group, a carboxylic ester bond, and a thioester bond. i is an integer from 0 to 8, preferably 0 to 2. The monomer of the above formula may be used alone, or two or more kinds of copolymers may be used.

In the general formula (1), R ₃ is an organic group having an unsaturated bond. Thereby, mechanical properties such as tensile strength of the cured film can be improved.

これらの中で特に好ましいものとしては、式（２−１）、式（２−２）および式（２−７）であり、これらは単独で用いてもよく、２種以上用いても良い。 Examples of such unsaturated groups include compounds containing an aliphatic group or aromatic group having at least one alkenyl group or alkynyl group, and an alicyclic compound group. Examples of such a group derived from an acid anhydride containing an aliphatic group or a cyclic compound group having at least one alkenyl group or alkynyl group after reacting with an amino group or a carboxylic acid group include, for example, formula (2) The unsaturated group etc. which are shown by these can be mentioned.

Among these, particularly preferred are formula (2-1), formula (2-2) and formula (2-7), which may be used alone or in combination of two or more.

  (A) The alkali-soluble resin having an unsaturated group at the terminal may contain two or more of the above polyamide repeating structures. In addition, a structure other than the above-mentioned polyamide repeating structure may be included, and for example, a cresol-type novolac resin structure may be included.

  (A) One type of alkali-soluble resin having an unsaturated group at the terminal may be used alone, or two or more types may be combined.

[(B) Photosensitive agent]
(B) Photosensitive agent of the present invention includes naphthoquinonediazide compounds, diarylsulfonium salts, triarylsulfonium salts, dialkylphenacylsulfonium salts, diaryliodonium salts, aryldiazonium salts, aromatic tetracarboxylic acid esters, aromatic sulfonic acid esters Nitrobenzyl ester, aromatic N-oxyimide sulfonate, aromatic sulfamide, benzoquinone diazosulfonic acid ester, and the like. Of these, naphthoquinonediazide compounds are preferred.

Specific examples of the naphthoquinone diazide compound include, for example, naphthoquinone diazide adduct of tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene (for example, TS533, TS567, TS583, TS593 manufactured by Sanpo Chemical Laboratory Co., Ltd.). ), Naphthoquinonediazide adducts of tetrahydroxybenzophenone (for example, BS550, BS570, BS599, manufactured by Sanpo Chemical Laboratory Co., Ltd.), 4- {4- [1,1-bis (4-hydroxyphenyl) ethyl]- A naphthoquinone diazide adduct of α, α-dimethylbenzyl} phenol (for example, TKF-428, TKF-528 manufactured by Sanpo Chemical Laboratory Co., Ltd.) or the like can be used.
Here, the addition of naphthoquinonediazide may be performed by, for example, reacting o-quinonediazidesulfonyl chloride with a hydroxy compound or an amino compound.

  (B) A photosensitive agent may be used individually by 1 type, and may be used in combination of 2 or more type. (B) It is preferable that the compounding quantity of a photosensitive agent is 3-20 mass% on the basis of composition solid content whole quantity.

上記（３）式中ｋおよびｌおよびｈは２〜１００の整数であり、１０〜５０であることが好ましい。 [(C) Compound other than (B) having at least two or more azide groups]
Specific examples of the compound (C) other than (B) having at least two or more azide groups in the present invention include the azide compounds shown in the following (3).

In the above formula (3), k, l and h are integers of 2 to 100, preferably 10 to 50.

  (C) The compounds other than (B) having at least two or more azide groups may include those described above, but are not limited thereto. Two or more types may be used.

  (C) The amount of the compound other than (B) having at least two or more azide groups is preferably 0.5 to 20% by mass based on the total amount of the solid content of the composition, and preferably 0.5 to 10% by mass. It is more preferable that With such a blending ratio, a composition having better mechanical properties after curing at low temperature can be obtained.

[(D) Antioxidant]
As described above, the present invention uses (D) an antioxidant, and (A) absorbs free radicals of terminal unsaturated groups of an alkali-soluble resin having an unsaturated group at the terminal. While maintaining properties such as curing at low temperature and high mechanical properties, it becomes possible to maintain the active state of the terminal unsaturated group of the alkali-soluble resin having an unsaturated group at the terminal (A), thereby improving storage stability. Improvement, suppression of deterioration of mechanical properties, improvement of pattern shape by prevention of film peeling, improvement of adhesion with copper, and shortening of curing time can be achieved.

  (D) As the antioxidant, normal antioxidants such as hydroquinones and phosphoric acid compounds can be used, and among them, alicyclic enol compounds are preferred. When an alicyclic enol compound is used, a compound having a terminal unsaturated group and an azide group is bonded to promote the formation of a triazine ring that improves the adhesion with copper, thereby further improving the copper adhesion. Moreover, since many OH groups contained in the alicyclic enol compound dissolve the polyamide, the resolution is further improved.

  Examples of the alicyclic enol compound suitable for the antioxidant (D) of the present invention include vitamin C and erythorbic acid.

  The addition amount of (D) antioxidant used in the present invention is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass based on the total amount of the solid component of the composition. If it exists in such a mixture ratio, the active state of the terminal unsaturated group of alkali-soluble resin can be fully maintained.

[(E) Thiol compound]
In the present invention, by further using the (E) thiol compound as a dissolution accelerator, the solubility in the developer can be further improved, and the sensitivity and resolution can be further improved while maintaining the mechanical properties.

  (E) Thiol compounds suitable for the present invention include D, L-dithiothreitol.

  The addition amount of the (E) thiol compound used in the present invention is 0.01 to 20 parts by mass with respect to 100 parts by mass of the alkali-soluble resin having an unsaturated group at the terminal (A). More preferably, it is 0.1-10 mass%. If it is the said range, generation | occurrence | production of a scum can be suppressed more reliably.

[(F) Solvent]
In the photosensitive thermosetting resin composition of the present invention, an organic solvent can be used for preparing the resin composition or adjusting the viscosity when applied to a substrate or a carrier film. In the present invention, since it is necessary to dissolve (C) the azide group of a compound other than (B) having at least two or more azide groups, an ester solvent or an amide solvent is preferable, and the end group is deactivated. Most preferred are ester solvents.

  Examples of the (F) solvent that can be used in the present invention include N, N′-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N, N′-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ- Butyrolactone, α-acetyl-γ-butyrolactone, propylene glycol monomethyl ether acetate, ethyl butyrate, methyl butyrate, ethyl lactate, methyl lactate, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone Dimethyl sulfoxide, hexamethylphosphoramide, pyridine, γ-butyrolactone, and diethylene glycol monomethyl ether. Of these, γ-butyrolactone, α-acetyl-γ-butyrolactone, propylene glycol monomethyl ether acetate, ethyl butyrate, methyl butyrate, ethyl lactate, and ethyl lactate are more preferred.

  (F) A solvent may be used individually by 1 type and may be used in combination of 2 or more type. The compounding quantity of these solvents can be used in the range of 50-9000 mass parts with respect to 100 mass parts of alkali-soluble resin which has an unsaturated group in (A) terminal according to a coating film thickness or a viscosity.

  (F) Solvent is (C) Toluene, tetrahydrofuran, dioxane, cyclohexanone, pyridine, o-xylene, m-xylene, anisole, etc., depending on the solubility of the compound other than (B) having at least two or more azide groups A small amount may be used. The blending of these solvents may be used in the range of 50 to 3000 parts by mass with respect to 100 parts by mass of the compound other than (C) having (C) at least two or more azide groups, depending on the coating film thickness and viscosity. it can.

[Sensitizer, adhesion aid, other ingredients]
The photosensitive resin composition of the present invention includes a known sensitizer for improving photosensitivity and a known adhesion assistant for improving adhesion to a substrate within a range not impairing the effects of the present invention. Etc. can also be blended.

  In addition, various organic or inorganic low-molecular or high-molecular compounds may be added to the photosensitive resin composition of the present invention in order to impart processing characteristics and various functionalities. 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, fiber, etc. with the photosensitive resin composition of this invention.

[Dry film]
The dry film of the present invention has a resin layer obtained by drying after applying the photosensitive resin composition of the present invention.

  In the dry film of the present invention, the photosensitive resin composition of the present invention is uniformly applied to a carrier film (support film) by an appropriate method using a blade coater, a lip coater, a comma coater, a film coater, etc., and dried. The above-described resin layer is formed, and preferably, a cover film (protective film) is laminated 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 for the carrier film and the cover film, any known materials 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 a cover film having a smaller adhesive force than the carrier film is preferable.

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

  For example, in the case of a positive photosensitive resin composition, a pattern film that is a cured product of the photosensitive resin composition of the present invention is produced as follows.

  First, as Step 1, a photosensitive resin composition is applied on a substrate and dried, or a resin layer is transferred (laminated) from a dry film onto a substrate to obtain a coating film. As a method for coating the photosensitive resin composition on the substrate, methods conventionally used for coating the photosensitive resin composition, such as spin coater, bar coater, blade coater, curtain coater, screen printer, etc. The method of apply | coating, the method of spray-coating with a spray coater, Furthermore, the inkjet method etc. can be used. As a method for drying the coating film, methods such as air drying, heat drying with an oven or hot plate, and vacuum drying are used. Moreover, it is desirable to dry the coating film under conditions such that ring closure of an alkali-soluble resin having an unsaturated group at the terminal (A) in the photosensitive resin composition, such as a polybenzoxazole precursor, does not occur. Specifically, natural drying, air drying, or heat drying can be performed at 70 to 140 ° C. for 1 to 30 minutes. Preferably, drying is performed on a hot plate for 1 to 20 minutes. Moreover, vacuum drying is also possible, and in this case, it can be carried out at room temperature for 20 minutes to 1 hour.

  The base material is not particularly limited, and can be widely applied to a semiconductor base material such as a silicon wafer, a wiring board, and a base material made of various resins or metals.

  Next, as Step 2, the coating film is exposed through a photomask having a pattern or directly. As the exposure light beam, one having a wavelength capable of activating the photoacid generator (B) as a photosensitizer to generate an acid is used. 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 using a sensitizer. As the exposure apparatus, a contact aligner, mirror projection, stepper, laser direct exposure apparatus, or the like can be used.

  Subsequently, as Step 3, heating may be performed to partially close the (A) polybenzoxazole precursor in the unexposed portion. Here, the ring closure rate is about 30%. The heating time and heating temperature are appropriately changed depending on (A) the polybenzoxazole precursor, the coating film thickness, and (B) the type of the photoacid generator as the photosensitive agent.

  Next, in 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 | membrane of the photosensitive resin composition of this invention can be formed.

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

  Thereafter, in step 5, the pattern film is heated to obtain a cured coating film (cured product). At this time, (A) the polybenzoxazole precursor may be closed to obtain polybenzoxazole. The heating temperature is appropriately set so that the pattern film of polybenzoxazole can be cured. For example, heating is performed at 150 to 350 ° C. for about 5 to 120 minutes in an inert gas. A more preferable range of the heating temperature is 200 to 300 ° C. The heating is performed by using, for example, a hot plate, an oven, or a temperature rising oven in which a temperature program can be set. At this time, the atmosphere (gas) may be air, or an inert gas such as nitrogen or argon.

  In the case where the photosensitive resin composition of the present invention is a negative photosensitive resin composition, (B) a photopolymerization initiator or a photobase generator is used instead of the photoacid generator as the photosensitive agent, and the above steps By processing a coating film with a developing solution in 4, the unexposed part in a coating film can be removed and the pattern film | membrane of the photosensitive resin composition of this invention can be formed.

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

  The photosensitive resin composition of the present invention is mainly used as a pattern forming material, and the pattern film formed thereby functions as a component imparting heat resistance and insulation as a permanent film made of, for example, polybenzoxazole. In particular, surface protective films for semiconductor devices, display devices and light emitting devices, interlayer insulating films, insulating films for rewiring, protective films for flip chip devices, protective films for devices having bump structures, and interlayer insulating films for multilayer circuits It can be suitably used as an insulating material for passive parts, a protective film for printed wiring boards such as a solder resist and a coverlay film, and a liquid crystal alignment film.

  EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following description, “parts” and “%” are all based on mass unless otherwise specified.

(Synthesis of polybenzoxazole precursor A-1)
40.3 g (0.11 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane was added to a four-necked separable flask equipped with a thermometer, a stirrer, a raw material charging port and a nitrogen gas inlet. ) Was dissolved in 1500 g of N-methyl-2-pyrrolidone, and 35.4 g (0.12 mol) of diphenyl ether-4,4′-dicarboxylic acid dichloride was added while stirring the reaction system at a temperature of 0 to 5 ° C., followed by stirring. Then, the temperature of the reaction system was returned to room temperature over 30 minutes and stirred as it was for 6 hours. Thereafter, 7.0 g (0.06 mol) of 4-ethynylaniline was added, and the mixture was further reacted at 40 ° C. for 1 hour. After completion of the reaction, the reaction solution was added dropwise to 2000 g of pure water. The precipitate was collected by filtration and washed, followed by vacuum drying to obtain a polybenzoxazole precursor (A-1) having an unsaturated hydrocarbon bond at the terminal (A).

(Synthesis of polybenzoxazole precursor P-1)
In a 0.5 liter flask equipped with a stirrer and a thermometer, 212 g of N-methylpyrrolidone was charged, and 30.47 g (83.2 mmol) of bis (3-amino-4-hydroxyamidophenyl) hexafluoropropane was stirred and dissolved. Thereafter, the flask was immersed in an ice bath, and while maintaining the inside of the flask at 0 to 5 ° C., 22.57 g (76.5 mmol) of 4,4-diphenyl ether dicarboxylic acid chloride was added in 5 g portions as a solid over 30 minutes. Stir in for 30 minutes. Thereafter, stirring was continued at room temperature for 2 hours. Thereafter, the solution was poured into 1 L of ion exchange water (specific resistance value: 18.2 MΩ · cm), and the precipitate was collected. Thereafter, the obtained solid was dissolved in 420 mL of acetone and poured into 1 L of ion exchange water. The precipitated solid was collected and then dried under reduced pressure to obtain a carboxylic acid-terminated polybenzoxazole precursor (P-1). The weight average molecular weight calculated | required by GPC method standard polystyrene conversion was 29,300.

(Examples 1-2)
(A) 20 mass parts of B-1 as (B) photosensitive agent of (A) alkali-soluble resin A-1 which has the terminal unsaturated group synthesize | combined above as (B) photosensitive agent of (C) As a compound other than (B) having at least two or more azide groups, C-1 is 2 parts by mass, (D) as an antioxidant, D-1 or D-2 is 0.1 part by mass, (E) After blending 3 parts by mass of E-1 as a thiol compound, γ-butyrolactone was added to form a varnish so that the polymer would be 30% by mass, and the photosensitive resin compositions of Examples 1 and 2 were prepared.

(Comparative Examples 1-3)
As Comparative Example 1, the photosensitive resin of Comparative Example 1 was the same as Example 1 except that no compound other than (C) (C) other than (B) having at least two azide groups was added. The composition was adjusted.
Moreover, as Comparative Example 2, the photosensitive resin composition of Comparative Example 2 was prepared in the same manner as in Example 1 except that the above-described D-1 (D) antioxidant was not blended.
Moreover, as Comparative Example 3, a photosensitive resin composition of Comparative Example 3 was prepared in the same manner as in Example 1 except that P-1 described above was blended in place of A-1 as an alkali-soluble resin.
About the photosensitive resin compositions of Examples 1-2 and Comparative Examples 1-3 thus prepared, resolution, film thickness shrinkage ratio, elongation at break after curing at 220 ° C. for 60 minutes (mechanical characteristics), storage stability The adhesion with copper was evaluated. The evaluation method is as follows. These evaluation results are also shown in Table 1.

(Resolution)
The various photosensitive resin compositions were applied onto a silicon wafer using a spin coater and dried on a hot plate at 120 ° C. for 3 minutes to obtain a dry coating film of the photosensitive resin composition. The obtained dried coating film was irradiated with 300 mJ / cm ² of broad light through a mask in which a pattern was carved using a high-pressure mercury lamp. After exposure, the resist film was developed with a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution for a predetermined time and rinsed with water to obtain a positive pattern. Each positive pattern is observed using a scanning electron microscope (JSM-JSM-610), and L (μm) / S (μm) (line / space) where the pattern can be created without scum after development is resolved. It was sex.

(Elongation at 220 ° C. for 60 minutes, elongation at break (mechanical characteristics) and film thickness shrinkage)
The various photosensitive resin compositions were applied onto a silicon wafer using a spin coater and heated at 120 ° C. for 30 minutes to form a coating film having a thickness of 30 μm. Thereafter, the coating film was heated in an inert gas oven at 150 ° C. for 30 minutes in a nitrogen atmosphere, and then heated at 220 ° C. for 60 minutes to obtain a cured film. Next, using a PCT apparatus, the cured film was peeled off under conditions of 121 ° C., 100% RH, 60 minutes, and then film physical properties such as elongation at break were examined. The elongation at break was determined from a tensile test using EZ-SX manufactured by Shimadzu Corporation.
Moreover, the film thickness before hardening and the film thickness after hardening were measured, and the film thickness shrinkage ratio was computed by the following formula | equation.
Film thickness shrinkage = (film thickness after curing / μm) / (film thickness before curing / μm) × 100

(Adhesion with copper)
Copper was sputtered onto a silicon wafer, and a substrate (copper sputter substrate) having a metal material layer formed on each surface with a thickness of 200 to 500 nm was prepared. On the substrate, the various photosensitive resin compositions were applied by a spin coating method, and then baked on a hot plate at 120 ° C. for 4 minutes using a hot plate to finally form a pre-baked film having a thickness of 5 μm. Using a clean oven (CLH-21CD-S manufactured by Koyo Thermo System Co., Ltd.), this membrane was heated at 150 ° C. for 30 minutes under a nitrogen stream (oxygen concentration of 10 ppm or less), then further heated to 220 ° C. for 60 minutes Curing was performed to obtain a cured polyamide film. The substrate was divided into two, and each substrate was cut into 10 rows and 10 columns in a grid pattern at intervals of 2 mm using a single blade on the cured film. Among these, about one sample board | substrate, the peeling test which investigates the number of squares which peeled among 100 squares by peeling with a cellophane (trademark) was done. The other sample substrate was subjected to a PCT treatment using a PCT apparatus under a saturation condition of 121 ° C. and 2 atm for 100 hours, and then the above-described peeling test was performed. The evaluation criteria are as follows.
◎: When the number of peeling was less than 5 in the peeling test for any substrate ○: When the number of peeling was less than 10 ×: When the number was 10 or more

(Storage stability)
The above various photosensitive resin compositions were measured for viscosity at 25 ° C. using a viscometer (TPE-100, manufactured by Toki Sangyo Co., Ltd.), allowed to stand at room temperature for 2 weeks, then measured for viscosity again, and the rate of change ( (Thickening rate) was calculated. The evaluation criteria are as follows.
A: Change in viscosity is less than ± 5% ○: Less than ± 10% ×: More than ± 10%

Ａ−１：上記で合成したポリベンゾオキサゾール前駆体Ａ−１
Ｐ−１：上記で合成したポリベンゾオキサゾール前駆体Ｐ−１
Ｂ−１：三宝化学研究所社製：ＴＫＦ−４２８
Ｃ−１：（２，６−ビス（４−アジドベンジリデン）シクロヘキサノン（約３０％水湿潤品））（東京化成工業株式会社製ＡＺ１）

Ｄ−１：ビタミンＣ（東京化成工業株式会社製）

Ｄ−２：チオジメチレンビス〔３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート〕（東京化成工業株式会社製）

Ｅ−１：Ｄ，Ｌ−ジチオトレイトール（和光純薬工業株式製）

A-1: Polybenzoxazole precursor A-1 synthesized above
P-1: Polybenzoxazole precursor P-1 synthesized above
B-1: Sanpo Chemical Laboratory, Inc .: TKF-428
C-1: (2,6-bis (4-azidobenzylidene) cyclohexanone (about 30% water-wet product)) (Tokyo Chemical Industry Co., Ltd. AZ1)

D-1: Vitamin C (manufactured by Tokyo Chemical Industry Co., Ltd.)

D-2: Thiodimethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (manufactured by Tokyo Chemical Industry Co., Ltd.)

E-1: D, L-dithiothreitol (manufactured by Wako Pure Chemical Industries, Ltd.)

From the results shown in Table 1, in the present invention, it is possible to improve storage stability, improve pattern shape by suppressing film slipping, and improve adhesion to copper while obtaining high mechanical properties. I understand that. Moreover, when an alicyclic enol compound is used as antioxidant, it turns out that adhesiveness and resolution with copper improve more.

Claims (11)

  (A) An alkali-soluble resin having an unsaturated group at the terminal, (B) a photosensitizer, (C) a compound other than (B) having at least two azide groups, and (D) an antioxidant. A photosensitive resin composition.   The photosensitive resin composition according to claim 1, wherein the (D) antioxidant is an alicyclic enol compound.   The photosensitive resin composition according to claim 1 or 2, wherein the alkali-soluble resin having an unsaturated group at the terminal (A) is a polyamide resin.   The photosensitive resin composition according to any one of claims 1 to 3, wherein the unsaturated group at the terminal of the alkali-soluble resin having an unsaturated group at the terminal (A) is an alkynyl group or an alkenyl group.   The photosensitive resin composition according to claim 1, wherein the (B) photosensitive agent is a photosensitive diazonaphthoquinone compound.   (E) The photosensitive resin composition as described in any one of Claims 1-5 which further contains a thiol compound.   (F) The photosensitive resin composition as described in any one of Claims 1-6 using an ester solvent.   It has a resin layer obtained from the photosensitive resin composition as described in any one of Claims 1-7, The dry film characterized by the above-mentioned.   A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 7 or the resin layer of the dry film according to claim 8.   A printed wiring board comprising the cured product according to claim 9. A semiconductor device comprising the cured product according to claim 9.