JP2019012223A - Photosensitive resin composition, dry film, cured product, printed wiring board and semiconductor element - Google Patents

Abstract

To provide a photosensitive resin composition that is excellent in developability (residual film rate) and resolution, and has excellent adhesion to both copper and silicon, a dry film having a resin layer obtained from the composition, a cured product of the composition or the resin layer of the dry film, and a printed wiring board and a semiconductor element having the cured product.SOLUTION: The present invention provides a photosensitive resin composition containing (A) a polybenzoxazole precursor, (B) a photosensitizer, and (C) an alkoxysilane containing triazine thiol derivative, and a dry film, a cured product, a printed wiring board and a semiconductor element using the same.SELECTED DRAWING: 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.

As a photosensitive resin composition that can be developed with an alkaline aqueous solution, a composition in which a polybenzoxazole (hereinafter also referred to as “PBO”) precursor and a photoacid generator such as a naphthoquinonediazide compound are blended is used. The polybenzoxazole cured product obtained by thermosetting such a composition is excellent in various properties such as heat resistance and electrical insulation, so that it can be used for printed wiring board materials, surface protection films for semiconductor elements, interlayer insulation films, etc. Application to is progressing.
On the other hand, in the photosensitive resin composition used for applications such as printed wiring boards and semiconductor elements, in addition to basic characteristics such as developability, both copper used for wiring and silicon used for the substrate are used. Good adhesion is required.

  In contrast, conventionally, as a photosensitive resin composition using a polybenzoxazole precursor, for example, in Patent Document 1, a photosensitive resin composition in which a pyrimidine skeleton compound containing an S atom is blended with a polybenzoxazole precursor. It is disclosed.

Japanese Patent No. 4759613

  However, since the photosensitive resin composition according to Patent Document 1 has a low molecular weight compound containing S atoms, the stability is poor, and the developability of the coated film after exposure and the mechanical properties of the cured film are deteriorated. There are difficulties and resolution has not been studied.

  Accordingly, an object of the present invention is to provide a photosensitive resin composition having excellent developability (residual film ratio) and resolution, and excellent adhesion to both copper and silicon, and a dry layer having a resin layer obtained from the composition. The object is to provide a cured product of a resin layer of a film, the composition or the dry film, a printed wiring board having the cured product, and a semiconductor element.

  As a result of intensive studies, the present inventor has found that the above problems can be solved by blending a PBO precursor with a triazine thiol derivative having an alkoxysilane moiety (alkoxysilane-containing triazine thiol derivative). It came to be completed.

  That is, the photosensitive resin composition of the present invention is characterized by containing (A) a polybenzoxazole precursor, (B) a photosensitizer, and (C) an alkoxysilane-containing triazine thiol derivative.

  In the photosensitive resin composition of the present invention, the (C) alkoxysilane-containing triazine thiol derivative is preferably an ethoxysilane-containing triazine thiol.

  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 comprises the photosensitive resin composition or the resin layer of the dry film.

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

  According to the present invention, a photosensitive resin composition having excellent developability (residual film ratio) and resolution, and excellent adhesion to both copper and silicon, and a dry film having a resin layer obtained from the composition Further, a cured product of the resin layer of the composition or the dry film, a printed wiring board having the cured product, and a semiconductor element can be provided.

Hereinafter, embodiments of the present invention will be described in detail.
The photosensitive resin composition of the present invention has the greatest feature in that (C) an alkoxysilane-containing triazine thiol derivative is blended. Thus, by blending the (C) alkoxysilane-containing triazine thiol derivative with the photosensitive resin composition containing the PBO precursor, it is excellent in developability (residual film ratio) and resolution, and copper and silicon. Excellent adhesion to both can also be ensured. In addition, the (C) alkoxysilane-containing triazine thiol derivative has high stability, so that the physical properties of the cured product are not deteriorated.

  Hereinafter, each component which comprises the photosensitive resin composition of this invention is explained in full detail.

[(A) Polybenzoxazole precursor]
The photosensitive resin composition of the present invention contains (A) a polybenzoxazole precursor. (A) The method of synthesizing the polybenzoxazole precursor is not particularly limited, and may be synthesized by a known method. For example, it can be obtained by reacting a dihydroxydiamine as an amine component with a dicarboxylic acid dihalide such as dicarboxylic acid dichloride as an acid component.

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

(In the formula, 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 (1), X is a residue of the dihydroxydiamine, and Y is a residue of the dicarboxylic acid. .

  Examples of the dihydroxydiamines include 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) propane, Bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 2,2-bis (3-amino-4) -Hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) -1,1,1,3,3,3-hexa Examples include fluoropropane. Among these, 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane is preferable.

  Examples of the dicarboxylic acid include isophthalic acid, terephthalic acid, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4 ′ -Dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2-bis (p-carboxyphenyl) propane, 2,2 -Dicarboxylic acid having an aromatic ring such as bis (4-carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, oxalic acid, malonic acid, succinic acid, 1,2-cyclobutanedicarboxylic acid, Aliphatic systems such as 1,4-cyclohexanedicarboxylic acid and 1,3-cyclopentanedicarboxylic acid And a carboxylate. Of these, 4,4'-dicarboxydiphenyl ether is preferable.

  In the general formula (1), the tetravalent organic group represented by X may be an aliphatic group or an aromatic group, but is preferably an aromatic group, and two hydroxy groups and two amino groups are in the ortho position. More preferably, it is located on the aromatic ring. The number of carbon atoms of the tetravalent aromatic group is preferably 6-30, and more preferably 6-24. 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 polybenzoxazole precursor is selected according to the use. That's fine.

The tetravalent aromatic group is preferably the following group among the aromatic groups.

  In the general formula (1), the divalent organic group represented by Y may be an aliphatic group or an aromatic group, but is preferably an aromatic group, and the carbonyl in the general formula (1) on the aromatic ring. It is more preferable that it is couple | bonded with. The number of carbon atoms of the divalent aromatic group is preferably 6-30, and more preferably 6-24. Specific examples of the divalent aromatic group include the following groups, but are not limited thereto, and a known aromatic group contained in the polybenzoxazole precursor may be selected according to the use. Good.

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

(In the formula, A represents a single bond, —CH ₂ —, —O—, —CO—, —S—, —SO ₂ —, —NHCO;
It represents a divalent group selected from the group consisting of —, —C (CF ₃ ) ₂ —, and —C (CH ₃ ) ₂ —. )

The divalent organic group is preferably the following group among the aromatic groups.

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

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

  (A) A polybenzoxazole precursor may be used individually by 1 type, and may be used in combination of 2 or more type. (A) It is preferable that the compounding quantity of a polybenzoxazole precursor is 60-90 mass% on the basis of composition solid content whole quantity, and it is more preferable that it is 70-80 mass%.

[(B) Photosensitive agent]
(B) There is no restriction | limiting in particular as a photosensitive agent, A photo-acid generator, a photoinitiator, and a photobase generator can be used. A photoacid generator is a compound that generates an acid upon irradiation with light such as ultraviolet light or visible light, a photopolymerization initiator is a compound that generates a radical or the like by the same light irradiation, and a photobase generator is the same. Is a compound that changes its molecular structure upon irradiation with light or generates one or more basic substances by cleavage of the molecule. In the present invention, a photoacid generator can be suitably used as the photosensitive agent (B).

  Photoacid generators include naphthoquinonediazide compounds, diarylsulfonium salts, triarylsulfonium salts, dialkylphenacylsulfonium salts, diaryliodonium salts, aryldiazonium salts, aromatic tetracarboxylic acid esters, aromatic sulfonic acid esters, nitrobenzyl esters , Aromatic N-oxyimide sulfonate, aromatic sulfamide, benzoquinone diazosulfonic acid ester and the like. The photoacid generator is preferably a dissolution inhibitor. Of these, a naphthoquinonediazide compound is preferable.

  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.) and the like can be used.

  Further, as the photopolymerization initiator, conventionally known ones can be used. For example, an oxime ester photopolymerization initiator having an oxime ester group, an α-aminoacetophenone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator. An initiator, a titanocene photopolymerization initiator, or the like can be used.

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

  Specific examples of the α-aminoacetophenone photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone N, N-dimethylaminoacetophenone and the like, and as commercially available products, Irgacure 907, Irgacure 369, Irgacure 379, etc. manufactured by BASF Japan Ltd. can be used.

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

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

  The photobase generator may be an ionic photobase generator or a non-ionic photobase generator, but the ionic photobase generator is more sensitive to the composition and can be used to form a pattern film. This is preferable because it is advantageous. Examples of basic substances include secondary amines and tertiary amines.

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

  Nonionic photobase generators include, for example, α-aminoacetophenone compounds, oxime ester compounds, N-formylated aromatic amino groups, N-acylated aromatic amino groups, nitrobenzyl carbamate groups, alcoholoxybenzyls. Examples thereof include compounds having a substituent such as a carbamate group. Other photobase generators include WPBG-018 (trade name: 9-anthrylmethyl N, N'-diethylcarbamate), WPBG-027 (trade name: (E) -1- [3- (2 -Hydroxyphenyl) -2-propenoyl] piperidine), WPBG-140 (trade name: 1- (anthraquinon-2-yl) ethyl imidazolecarboxylate), WPBG-165, and the like can also be used.

  (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 photosensitizer is 3-20 mass% on the basis of composition solid content whole quantity, and it is more preferable that it is 5-20 mass%.

[(C) Alkoxysilane-containing triazine thiol derivative]
(C) Although it does not specifically limit as an alkoxysilane containing triazine thiol derivative, For example, what has a structure represented by following General formula (2)-(4) is mentioned. Here, in the (C) alkoxysilane-containing triazine thiol derivative according to the present invention, when the “alkoxysilane moiety” substantially improves the adhesion to silicon, the “triazine thiol moiety” is positive. This eliminates the film residue in the exposed area, improves the developability (residual film ratio) and resolution, and improves the adhesion with copper.

In the general formula (2), R ¹ is H—, CH ₃ —, C ₂ H ₅ —, CH ₂ ═CHCH ₂ —, C ₄ H ₉ —, C ₆ H ₅ —, or C ₆ H ₁₃ —. Yes, R ² is —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ SCH ₂ CH ₂ — or —CH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ —, wherein X is CH ₃ —, C ₂ H ₅ —, n—C ₃ H ₇ —, i—C ₃ H ₇ —, n—C ₄ H ₉ —, _{i-C 4 H 9 -,} t-C 4 H 9 - or _C 6 _{H 5} - a and, Y _{is, CH 3 O-, C 2 H} 5 O-, n-C 3 H 7 O-, i- _{C 3 H 7 O-, n-} C 4 H 9 O-, i-C 4 H 9 O-, t-C 4 H 9 O- or _C 6 _H 5 is O-, n Is an integer from 1 to 3.

In the general formula (3), R ³ is — (CH ₂ CH ₂ ) ₂ CHOCONHCH ₂ CH ₂ CH ₂ — or — (CH ₂ CH ₂ ) ₂ N—CH ₂ CH ₂ CH ₂ —. , N and R ^{3 form a} cyclic structure. X, Y and n represent the same as in the general formula (2).

In the general formula (4), R ⁴ represents —S—, —O—, —NHCH ₂ C ₆ H ₄ O—, —NHC ₆ H ₄ O—, —NHC ₆ H ₃ (Cl) O—, —NHCH. _{2 C 6 H 3 (NO 2} ) O -, - NHC 6 H 3 (NO 2) O -, - NHC 6 H 3 (CN) O -, - NHC 6 H 2 (NO 2) 2 O -, - NHC _{6 H 3 (COOCH 3) O} -, - NHC 10 H 6 O -, - NHC 10 H 5 (NO 2) O -, - NHC 10 H 4 (NO 2) 2 O -, - NHC 6 H 4 S- _{, -NHC 6 H 3 (Cl)} S -, - NHCH 2 C 6 H 3 (NO 2) S -, - NHC 6 H 3 (NO 2) S -, - NHC 6 H 3 (CN) S -, - _{NHC 6 H 2 (NO 2)} 2 S -, - NHC 6 H 3 (COOCH 3) S -, - NHC 10 _{6 S -, - NHC 10 H} 5 (NO 2) S- or _{-NHC 10 H 4 (NO 2)} 2 is S-, Z is an alkoxy group, j is an integer from 1 to 6.

In the present invention, among the above, it is preferable to use an ethoxysilane-containing triazinethiol derivative as the (C) alkoxysilane-containing triazinethiol derivative from the viewpoint of obtaining the effects of the present invention better. Examples of the ethoxysilane-containing triazine thiol derivative include 6- [3- (triethoxysilyl) propylamino] -1,3,5-triazine-2,4-dithiol represented by the following structural formula.

  (C) An alkoxysilane containing triazine thiol derivative may be used individually by 1 type, and may be used in combination of 2 or more type. (C) The compounding amount of the alkoxysilane-containing triazine thiol derivative is preferably 1 to 20% by mass, and more preferably 3 to 10% by mass based on the total solid content of the composition. By setting it as the said range, the outstanding developability (residual film rate) and resolution, and the adhesiveness excellent in copper and silicon can be made compatible more highly.

  A solvent can be mix | blended with the photosensitive resin composition of this invention. The solvent is not particularly limited as long as it dissolves (A) a polybenzoxazole precursor, (B) a photosensitizing agent, (C) an alkoxysilane-containing triazine thiol derivative, and other optional additives. Specific examples of the solvent include N, N′-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N, N′-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl. -Γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, γ-butyrolactone, diethylene glycol monomethyl ether it can. These may be used alone or in combination of two or more. The quantity of the solvent to be used can be used in the range of 50-9000 mass parts with respect to 100 mass parts of (A) polybenzoxazole precursor according to a coating film thickness and a viscosity.

  In the photosensitive resin composition of the present invention, a known crosslinking agent, sensitizer, adhesion aid and the like can be blended within a range not impairing the effects of the present invention.

  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. Furthermore, you may mix | blend various coloring agents, fiber, etc. with the photosensitive resin composition of this invention.

  The photosensitive resin composition of the present invention may be a positive type or a negative type, but in the case of a positive type, a more remarkable effect can be obtained, which is preferable.

[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 the (A) polybenzoxazole precursor in the photosensitive resin composition 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 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 a bump structure, interlayer insulating films for multilayer circuits, passive It can be suitably used as an insulating material for parts, a protective film for printed wiring boards such as solder resist and coverlay film, and a liquid crystal alignment film.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to the following Example. In the following description, “parts” and “%” are all based on mass unless otherwise specified.

(Synthesis of polybenzoxazole (PBO) precursor)
A 0.5-liter flask equipped with a stirrer and a thermometer was charged with 212 g of N-methylpyrrolidone, and 17.55 g (47.93 mmol) of bis (3-amino-4-hydroxyamidophenyl) hexafluoropropane was stirred and dissolved. . Thereafter, the flask was immersed in an ice bath, and while keeping the inside of the flask at 0 to 5 ° C., 15.00 g (50.83 mmol) of 4,4-diphenyl ether dicarboxylic acid chloride was added as a solid in 5 g portions over 30 minutes. Stir in for 30 minutes. Thereafter, stirring was continued at room temperature for 5 hours. The stirred 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 recovered and then dried under reduced pressure to obtain a polybenzoxazole (PBO) precursor (A-1) having the following repeating structure at the carboxyl group end. The number average molecular weight (Mn) of the polybenzoxazole precursor (A-1) was 17,300, the weight average molecular weight (Mw) was 42,100, and Mw / Mn was 2.45.

(Example 1, Comparative Examples 1-3)
With respect to 100 parts by mass of the benzoxazole precursor (A-1), 10 parts by mass of diazonaphthoquinone (DNQ) represented by the following structural formula (B-1) as a photosensitizer and various additions described in Table 1 below After blending the agent, N-methylpyrrolidone (NMP) was added so that the benzoxazole precursor was 30% by mass to obtain a varnish, and the photosensitive resin compositions of Example 1 and Comparative Examples 1 to 3 were prepared. .
Thus, about the photosensitive resin composition of Example 1 and Comparative Examples 1-3 prepared, the sensitivity, the resolution, the remaining film rate (developability), and adhesiveness were evaluated. The evaluation method is as follows.

(Test method)
The various photosensitive resin compositions were applied onto a copper-coated wafer with a spin coater and dried on a hot plate at 120 ° C. for 3 minutes to obtain a dried film of the photosensitive resin composition. The obtained dried film was irradiated with an exposure dose of 100 to 1000 mJ / cm ² through a mask with a pattern engraved using a high-pressure mercury lamp. After the exposure, the film was developed with an aqueous 2.38% tetramethylammonium hydroxide (TMAH) solution for 30 seconds and rinsed with water to obtain a positive pattern.
Similarly, a positive pattern was obtained on the silicon substrate.
(Evaluation of sensitivity and resolution)
Exposure ^{100mJ / cm 2, 200mJ / cm} 2, 300mJ / cm 2, 400mJ / cm 2, 500mJ / cm 2, 600mJ / cm 2, 700mJ / cm 2, 800mJ / cm 2, 900mJ / cm 2, 1000mJ / cm ^{In FIG. 2} , 10 positive patterns obtained by irradiation are observed with an electron microscope (SEM “JSM-6010”), and the minimum exposure amount that can pattern an exposed portion without scum (development residue) is determined by sensitivity (mJ / cm ² ), and the minimum pattern size (μm) was evaluated as resolution.

(Evaluation of remaining film ratio (developability))
In the above test, for the post-exposure coating film obtained with the minimum exposure amount that could be patterned without scum, the pre-development film thickness and post-development film thickness of the unexposed part were measured, and the remaining film ratio was calculated according to the following formula: And evaluated. The film thickness before development was 5 μm in all examples.

(Evaluation of adhesion after curing)
After applying the above various photosensitive resin compositions to a copper substrate or a silicon substrate using a spin coater, drying on a hot plate at 120 ° C. for 3 minutes, and applying heat treatment at 150 ° C. for 30 minutes / 320 ° C. for 1 hour to cure. Thus, a cured film of the photosensitive resin composition was obtained. With respect to the obtained cured film, a square of 1 × 1 (mm) size was formed with a cutter knife to form a total of 100 grids in 10 rows vertically and horizontally. The sample was subjected to a pressure cooker (PCT) test (conditions: continuous treatment at a temperature of 121 ° C. and a humidity of 100% for 24 hours), and then the grids were peeled off with tape. Adhesion was evaluated by counting the number of peeled grids.

  These evaluation results are also shown in Table 1.

As is clear from the results shown in Table 1, in the examples using (C) (C), which is an alkoxysilane-containing triazine thiol derivative, excellent residual film rate (developability) and resolution, copper It was confirmed that the adhesiveness to both silicon and silicon was compatible.

Claims (6)

(A) a polybenzoxazole precursor,
(B) a photosensitive agent, and
(C) The photosensitive resin composition characterized by including the alkoxysilane containing triazine thiol derivative.   The photosensitive resin composition according to claim 1, wherein the (C) alkoxysilane-containing triazine thiol derivative is ethoxysilane-containing triazine thiol.   A dry film comprising a resin layer obtained by applying and drying the photosensitive resin composition according to claim 1 on a film.   A cured product comprising the photosensitive resin composition according to claim 1 or 2 or the resin layer of the dry film according to claim 3.   A printed wiring board comprising the cured product according to claim 4.   A semiconductor device comprising the cured product according to claim 4.