WO2018056013A1 - Positive photosensitive resin composition, dry film, cured product, printed wiring board and semiconductor element - Google Patents

Positive photosensitive resin composition, dry film, cured product, printed wiring board and semiconductor element Download PDF

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Publication number
WO2018056013A1
WO2018056013A1 PCT/JP2017/031248 JP2017031248W WO2018056013A1 WO 2018056013 A1 WO2018056013 A1 WO 2018056013A1 JP 2017031248 W JP2017031248 W JP 2017031248W WO 2018056013 A1 WO2018056013 A1 WO 2018056013A1
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Prior art keywords
resin composition
photosensitive resin
silane coupling
coupling agent
film
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PCT/JP2017/031248
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French (fr)
Japanese (ja)
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真歩 秋元
成強 許
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太陽ホールディングス株式会社
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Application filed by 太陽ホールディングス株式会社 filed Critical 太陽ホールディングス株式会社
Priority to JP2018540942A priority Critical patent/JP7011591B2/en
Priority to CN201780057125.XA priority patent/CN109716235B/en
Priority to KR1020197011002A priority patent/KR102385641B1/en
Publication of WO2018056013A1 publication Critical patent/WO2018056013A1/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings

Definitions

  • the present invention relates to a positive photosensitive resin composition, a dry film, a cured product, a printed wiring board, and a semiconductor element.
  • a positive photosensitive resin composition that can be developed with an alkaline aqueous solution
  • a composition containing a polybenzoxazole (PBO) precursor and a photoacid generator such as a naphthoquinonediazide compound is used.
  • the polybenzoxazole cured product obtained by thermosetting such a composition is excellent in heat resistance and electrical insulation, so that a surface protective film of an electrical material or an interlayer insulation film, for example, a coating film of a semiconductor element, Application to flexible printed wiring board materials and heat-resistant insulating interlayer materials is underway.
  • an object of the present invention is to provide a positive photosensitive resin composition having an excellent residual film ratio, 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 the curing
  • An object of the present invention is to provide a printed wiring board having an object and a semiconductor element having the cured product.
  • the positive photosensitive resin composition of the present invention includes (A) a polybenzoxazole precursor, (B) a photoacid generator, (C) a melamine-based crosslinking agent, and (D) a silane coupling agent.
  • the positive photosensitive resin composition of the present invention preferably contains a silane coupling agent having an arylamino group as the (D) silane coupling agent.
  • the dry film of the present invention is characterized by having a resin layer obtained by applying the photosensitive resin composition to a film and drying it.
  • the cured product of the present invention is obtained by curing the photosensitive resin composition or the resin layer of the dry film.
  • the printed wiring board of the present invention is characterized by having the cured product.
  • the semiconductor element of the present invention is characterized by having the cured product.
  • a positive photosensitive resin composition having an excellent residual film ratio, 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 the cured product
  • a printed wiring board having a semiconductor device and a semiconductor element having the cured product can be provided.
  • the positive 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 dihalide of a dicarboxylic acid such as dicarboxylic acid dichloride as an acid component.
  • the polybenzoxazole precursor is preferably a polyhydroxyamide acid having the following repeating structure.
  • X represents a tetravalent organic group and Y represents a divalent organic group.
  • N is an integer of 1 or more, preferably 10 to 50, more preferably 20 to 40.
  • dihydroxydiamines examples 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. Of these, 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane is preferred.
  • dicarboxylic acid examples 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 acids such as 1,4-cyclohexanedicarboxylic
  • the tetravalent organic group represented by X may be an aliphatic group or an aromatic group, but is preferably an aromatic group, and two hydroxy groups and two amino groups are in the ortho position. More preferably, it is located on the aromatic ring.
  • the tetravalent aromatic group preferably has 6 to 30 carbon atoms, and more preferably 6 to 24 carbon atoms.
  • 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.
  • 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
  • the divalent aromatic group preferably has 6 to 30 carbon atoms, and more preferably 6 to 24 carbon atoms. 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.
  • A is a single bond, —CH 2 —, —O—, —CO—, —S—, —SO 2 —, —NHCO—, —C (CF 3 ) 2 —, —C (CH 3 )) 2 represents a divalent group selected from the group consisting of-.
  • the divalent organic group is preferably the following group among the aromatic groups.
  • the polybenzoxazole precursor may contain two or more repeating structures of the above polyhydroxyamide acid. Further, it may contain a structure other than the above-mentioned repeating structure of polyhydroxyamic acid, for example, it may contain a repeating structure of polyamic acid.
  • the number average molecular weight (Mn) of the polybenzoxazole precursor is preferably 5,000 to 100,000, and more preferably 8,000 to 50,000.
  • the number average molecular weight is a numerical value measured by (GPC) and converted by standard polystyrene.
  • the weight average molecular weight (Mw) of the (A) polybenzoxazole precursor is preferably 10,000 to 200,000, more preferably 16,000 to 100,000.
  • the weight average molecular weight is a value measured by (GPC) and converted to standard polystyrene.
  • Mw / Mn is preferably from 1 to 5, and more preferably from 1 to 3.
  • the blending amount of the (A) polybenzoxazole precursor is preferably 60 to 90% by mass based on the total amount of the solid content of the composition.
  • (B) Photoacid generator As a photoacid generator, a naphthoquinonediazide compound, a diarylsulfonium salt, a triarylsulfonium salt, a dialkylphenacylsulfonium salt, a diaryliodonium salt, an aryldiazonium salt, an aromatic tetracarboxylic acid ester, an aromatic sulfonic acid ester, Examples thereof include nitrobenzyl ester, aromatic N-oxyimide sulfonate, aromatic sulfamide, and benzoquinone diazosulfonic acid ester.
  • the photoacid generator is preferably a dissolution inhibitor. Of these, a naphthoquinonediazide compound is preferable.
  • naphthoquinonediazide compound examples include, for example, naphthoquinonediazide 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.
  • naphthoquinonediazide compound examples include, for example, naphthoquinonediazide adduct of tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene (for example, TS533, TS567, TS583, TS593 manufactured by Sanpo Chemical Laboratory Co., Ltd.).
  • One photoacid generator may be used alone, or two or more photoacid generators may be used in combination.
  • the blending amount of the (B) photoacid generator is preferably 3 to 20% by mass based on the total amount of the solid content of the composition.
  • (C) Melamine-based crosslinking agent (C) Although it will not specifically limit if it is a crosslinking agent which has a melamine structure as a melamine type crosslinking agent, It is preferable that it is a melamine type crosslinking agent represented by following General formula (2).
  • R 21A , R 22A , R 23A , R 24A , R 25A and R 26A are each independently preferably an alkylene group having 1 to 3 carbon atoms.
  • R 21B , R 22B , R 23B , R 24B R 25B and R 26B are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • R 21A , R 22A , R 23A , R 24A , R 25A and R 26A are each preferably a methylene group.
  • R 21B , R 22B , R 23B , R 24B , R 25B and R 26B are more preferably each independently a methyl group or a hydrogen atom.
  • (C) One type of melamine-based crosslinking agent may be used alone, or two or more types may be used in combination.
  • the blending amount of the (C) melamine crosslinking agent is preferably 1 to 15% by mass based on the total amount of the solid content of the composition. When the content is 1 to 15% by mass, the remaining film ratio in the unexposed area can be increased, and the development remaining in the exposed area can be prevented.
  • the positive photosensitive resin composition of the present invention preferably contains a crosslinking agent other than (C) the melamine-based crosslinking agent, and is at least one of the following crosslinking agent 2, crosslinking agent 5 and crosslinking agent 6. It is preferable to contain.
  • (C) By including a melamine-based crosslinking agent and at least one of the crosslinking agent 2, the crosslinking agent 5, and the crosslinking agent 6, a dissolution promoting effect is obtained, and the developability is improved.
  • the amount of the crosslinking agent other than the melamine-based crosslinking agent is preferably 1 to 15% by mass based on the total amount of the solid content of the composition.
  • the total amount of the crosslinking agent 2, the crosslinking agent 5 and the crosslinking agent 6 is preferably 1 to 15% by mass based on the total amount of the solid content of the composition.
  • the positive photosensitive resin composition of the present invention is (D) at least one silane coupling agent selected from a silane coupling agent having an arylamino group and a silane coupling agent having two or more trialkoxysilyl groups. Including species.
  • aryl group of the arylamino group examples include aromatic hydrocarbon groups such as phenyl group, tolyl group and xylyl group, condensed polycyclic aromatic groups such as naphthyl group, anthracenyl group and phenanthrenyl group, thienyl group and indolyl group.
  • aromatic heterocyclic group is mentioned.
  • the silane coupling agent having an arylamino group is preferably a compound having a group represented by the following general formula (3). (Wherein R 31 to R 35 each independently represents a hydrogen atom or an organic group.)
  • R 31 to R 35 are preferably hydrogen atoms.
  • a silicon atom and an arylamino group are preferably bonded with an organic group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms.
  • silane coupling agent having an arylamino group are preferably the following compounds.
  • the trialkoxysilyl group 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.
  • the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Among them, a methoxy group and an ethoxy group are preferable.
  • the silane coupling agent having two or more trialkoxysilyl groups at least two silicon atoms are bonded by an organic group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms. preferable.
  • silane coupling agent having two or more trialkoxysilyl groups are preferably the following compounds.
  • the silane coupling agent is preferably a silane coupling agent having an arylamino group because of its excellent resolution.
  • silane coupling agent may be used alone, or two or more silane coupling agents may be used in combination.
  • the amount of the silane coupling agent is preferably 1 to 15% by mass based on the total amount of the solid content of the composition. When it is 1 to 15% by mass, it is possible to prevent undeveloped residues in the exposed area.
  • the positive photosensitive resin composition of the present invention may contain other silane coupling agents as long as the effects of the present invention are not impaired.
  • the positive photosensitive resin composition of the present invention preferably contains t-butylcatechol.
  • t-butylcatechol By containing t-butylcatechol, the development residue (scum) is small and the developability is excellent.
  • the blending amount of t-butylcatechol is preferably 0.1 to 2% by mass based on the total amount of the solid content of the composition.
  • a solvent can be blended in the positive photosensitive resin composition of the present invention. Any solvent that dissolves (A) a polybenzoxazole precursor, (B) a photoacid generator, (C) a melamine-based crosslinking agent, (D) a silane coupling agent, and other additives can be used. There is no particular limitation.
  • Examples include N, N′-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N, N′-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, ⁇ -butyrolactone, ⁇ -acetyl- ⁇ - Examples include butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, ⁇ -butyrolactone, and diethylene glycol monomethyl ether. These may be used alone or in combination of two or more.
  • the amount of the solvent used can be in the range of 50 to 9000 parts by mass with respect to 100 parts by mass of the (A) polybenzoxazole precursor, depending on the coating film thickness and viscosity.
  • a known sensitizer can be blended in order to further improve the photosensitivity.
  • a known adhesion assistant can be added to the positive photosensitive resin composition of the present invention in order to improve the adhesion to the substrate.
  • various organic or inorganic low-molecular or high-molecular compounds may be blended.
  • 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.
  • the dry film of the present invention has a resin layer obtained by applying and then drying the positive photosensitive resin composition of the present invention.
  • the dry film of the present invention is used by laminating a resin layer so as to be in contact with a substrate.
  • the dry film of the present invention is obtained by uniformly applying the positive photosensitive resin composition of the present invention to a carrier film by an appropriate method such as a blade coater, a lip coater, a comma coater, or a film coater, and drying the resin. It can be produced by forming a layer and preferably laminating a cover film thereon.
  • the cover film and the carrier film may be the same film material or different films.
  • any known materials used for dry films can be used.
  • thermoplastic film such as a polyester film such as polyethylene terephthalate having a thickness of 2 to 150 ⁇ m is used.
  • cover film a polyethylene film, a polypropylene film or the like can be used, but it is preferable that the adhesive force with the resin layer is smaller than that of the carrier film.
  • the film thickness of the resin layer on the dry film of the present invention is preferably 100 ⁇ m or less, and more preferably in the range of 5 to 50 ⁇ m.
  • the pattern film that is a cured product of the positive photosensitive resin composition of the present invention is produced, for example, as follows.
  • Step 1 a positive photosensitive resin composition is applied on a substrate and dried, or a resin layer is transferred from a dry film onto the substrate to obtain a coating film.
  • a method for applying the positive photosensitive resin composition on the substrate methods conventionally used for applying the photosensitive resin composition, for example, spin coater, bar coater, blade coater, curtain coater, screen printing, etc.
  • a coating method using a machine, a spray coating method using a spray coater, an ink jet method or the like can be used.
  • 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.
  • the coating film under conditions such that ring closure of the (A) polybenzoxazole precursor in the photosensitive resin composition does not occur.
  • natural drying, air drying, or heat drying can be performed at 70 to 140 ° C. for 1 to 30 minutes.
  • drying is performed on a hot plate for 1 to 20 minutes.
  • Vacuum drying is also possible, and in this case, it can be performed at room temperature for 20 minutes to 1 hour.
  • the base material there is no particular limitation on the base material, and it can be widely applied to semiconductor base materials such as silicon wafers, wiring boards, various resins, metals, and the like.
  • the coating film is exposed through a photomask having a pattern or directly.
  • the exposure light beam having a wavelength capable of activating the photoacid generator (B) and generating an acid is used.
  • the exposure light beam preferably has a maximum wavelength in the range of 350 to 410 nm.
  • the photosensitivity can be adjusted by appropriately using a sensitizer.
  • a contact aligner, mirror projection, stepper, laser direct exposure apparatus, or the like can be used as the exposure apparatus.
  • Step 3 heating may be performed to cyclize a part of the (A) polybenzoxazole precursor in the unexposed area.
  • 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.
  • 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 positive photosensitive resin composition of this invention can be formed.
  • an arbitrary method can be selected from conventionally known photoresist development methods such as a rotary spray method, a paddle method, an immersion method involving ultrasonic treatment, and the like.
  • 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.
  • 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.
  • a rinse liquid as necessary to obtain a pattern film.
  • a 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.
  • step 5 the pattern film is heated to obtain a cured coating film (cured product).
  • 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.
  • heating is performed in an inert gas at 150 to 350 ° C. for about 5 to 120 minutes.
  • 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.
  • the atmosphere (gas) may be air, or an inert gas such as nitrogen or argon.
  • the use of the positive photosensitive resin composition of the present invention is not particularly limited.
  • printing ink, adhesive, filler, electronic material, optical circuit component, molding material, resist material, building material, three-dimensional modeling, optical Examples include various known fields and products in which resin materials are used, such as members.
  • It is suitably used as a coating material for printed wiring boards such as coating films, electronic components, interlayer insulating films, solder resists, optical circuits, optical circuit components, antireflection films, holograms, optical members, or building materials.
  • the positive photosensitive resin composition of the present invention is mainly used as a pattern forming material (resist), and the pattern film formed thereby imparts heat resistance and insulation as a permanent film made of polybenzoxazole.
  • a pattern forming material resist
  • the pattern film formed thereby imparts heat resistance and insulation as a permanent film made of polybenzoxazole.
  • Example 1 and 2 and Comparative Examples 1 to 11 After blending 10 parts by mass of diazonaphthoquinone (DNQ), 5 parts by mass of the crosslinking agent described in Table 1 below and 5 parts by mass of the silane coupling agent with respect to 100 parts by mass of the benzoxazole precursor synthesized above, benzoxazole N-methylpyrrolidone (NMP) was added so that the precursor would be 30% by mass to form a varnish, which was applied onto a silicon substrate using a spin coater. It was dried at 120 ° C. for 3 minutes on a hot plate to obtain a dry coating film of the photosensitive resin composition.
  • NMP benzoxazole N-methylpyrrolidone
  • the resulting dried coating film was irradiated with broad light of 200 mJ / cm 2 through a mask in which a pattern was engraved using a high-pressure mercury lamp. After the exposure, the film was developed with an aqueous 2.38% tetramethylammonium hydroxide (TMAH) solution for 60 seconds and rinsed with water to obtain a positive pattern film.
  • TMAH tetramethylammonium hydroxide
  • crosslinker 1 (Nikalac MW390, manufactured by Sanwa Chemical Co., Ltd.) was used as the melamine-based crosslinker.
  • silane coupling agents having an arylamino group and silane coupling agents having two or more trialkoxysilyl groups coupling agents 1 (KBM-573 manufactured by Shin-Etsu Silicone) and 2 (Shin-Etsu Silicone) KBM-3066) was used.
  • Crosslinker 1 Crosslinker 2
  • Crosslinker 3 Crosslinker 4
  • Crosslinker 5 Crosslinker 6
  • Coupling agent 1 Coupling agent 2 Coupling agent 3 Coupling agent 4 Coupling agent 5 Coupling agent 6 Coupling agent 7 Coupling agent 8
  • Examples 3 to 6 Based on 100 parts by mass of the benzoxazole precursor synthesized above, 10 parts by mass of diazonaphthoquinone (DNQ), 5 parts by mass of each cross-linking agent described in Table 2 below, 5 parts by mass of silane coupling agent, t-butylcatechol 0 After blending 0.5 parts by mass, N-methylpyrrolidone (NMP) was added so that the benzoxazole precursor was 30% by mass to form a varnish, which was applied onto a silicon substrate using a spin coater. It was dried at 120 ° C. for 3 minutes on a hot plate to obtain a dry coating film of the photosensitive resin composition.
  • NMP N-methylpyrrolidone
  • the resulting dried coating film was irradiated with broad light of 200 mJ / cm 2 through a mask in which a pattern was engraved using a high-pressure mercury lamp. After the exposure, the film was developed with an aqueous 2.38% tetramethylammonium hydroxide (TMAH) solution for 60 seconds and rinsed with water to obtain a positive pattern film.
  • TMAH tetramethylammonium hydroxide
  • the said crosslinking agent 1 (Sanwa Chemical Co., Ltd. product Nikalac MW390) was used as a melamine type crosslinking agent. Further, the above coupling agent 1 (KBM-573 manufactured by Shin-Etsu Silicone Co., Ltd.) was used as a silane coupling agent having an arylamino group. As other crosslinking agents other than the melamine-based crosslinking agent, the above-mentioned crosslinking agents 2, 5 and 6 were used.
  • Example 1 The photosensitive resin composition of Example 1 in Table 1 was also evaluated in the same manner, and the results are shown in Table 2 together with Examples 3 to 6.
  • Examples 7 and 8, Comparative Examples 12 to 25 With respect to 100 parts by mass of the benzoxazole precursor synthesized above, 10 parts by mass of diazonaphthoquinone (DNQ), 5 parts by mass of a crosslinking agent described in Table 3 below, 5 parts by mass of a silane coupling agent, 0. After blending 5 parts by mass, N-methylpyrrolidone (NMP) was added so that the benzoxazole precursor was 30% by mass to form a varnish, which was applied onto a silicon substrate using a spin coater. It was dried at 120 ° C. for 3 minutes on a hot plate to obtain a dry coating film of the photosensitive resin composition.
  • NMP N-methylpyrrolidone
  • the resulting dried coating film was irradiated with broad light of 200 mJ / cm 2 through a mask in which a pattern was engraved using a high-pressure mercury lamp. After the exposure, the film was developed with an aqueous 2.38% tetramethylammonium hydroxide (TMAH) solution for 60 seconds and rinsed with water to obtain a positive pattern film.
  • TMAH tetramethylammonium hydroxide
  • the said crosslinking agent 1 (Sanwa Chemical Co., Ltd. product Nikalac MW390) was used as a melamine type crosslinking agent.
  • the silane coupling agent having an arylamino group and the silane coupling agent having two or more trialkoxysilyl groups the above coupling agents 1 (KBM-573 manufactured by Shin-Etsu Silicone Co., Ltd.) and 2 (Shin-Etsu Silicone), respectively. KBM-3066) was used.
  • Coupling agent 9 Coupling agent 10 Coupling agent 11

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Abstract

Provided are: a positive photosensitive resin composition having excellent film retention ratio; a dry film having a resin layer that is obtained from this composition; a cured product of this composition or the resin layer of this dry film; a printed wiring board having this cured product; and a semiconductor element having this cured product. A positive photosensitive resin composition which contains (A) a polybenzoxazole precursor, (B) a photoacid generator, (C) a melamine-based crosslinking agent and (D) a silane coupling agent, and which is characterized in that at least one silane coupling agent selected from among silane coupling agents having an arylamino group and silane coupling agents having two or more trialkoxysilyl groups is contained as the silane coupling agent (D); and the like.

Description

ポジ型感光性樹脂組成物、ドライフィルム、硬化物、プリント配線板および半導体素子Positive photosensitive resin composition, dry film, cured product, printed wiring board, and semiconductor element
　本発明はポジ型感光性樹脂組成物、ドライフィルム、硬化物、プリント配線板および半導体素子に関する。 The present invention relates to a positive photosensitive resin composition, a dry film, a cured product, a printed wiring board, and a semiconductor element.
　アルカリ水溶液で現像可能なポジ型感光性樹脂組成物として、ポリベンゾオキサゾール（ＰＢＯ）前駆体とナフトキノンジアジド化合物等の光酸発生剤を配合した組成物が用いられている。このような組成物を熱硬化して得られるポリベンゾオキサゾール硬化物は、耐熱性および電気絶縁性に優れることから、電気材料の表面保護膜や層間絶縁膜、例えば、半導体素子のコーティング膜や、フレキシブルプリント配線板材料、耐熱絶縁性層間材への適用が進められている。 As a positive photosensitive resin composition that can be developed with an alkaline aqueous solution, a composition containing a polybenzoxazole (PBO) precursor and a photoacid generator such as a naphthoquinonediazide compound is used. The polybenzoxazole cured product obtained by thermosetting such a composition is excellent in heat resistance and electrical insulation, so that a surface protective film of an electrical material or an interlayer insulation film, for example, a coating film of a semiconductor element, Application to flexible printed wiring board materials and heat-resistant insulating interlayer materials is underway.
　上記のようなポリベンゾオキサゾール前駆体を含有するポジ型感光性樹脂組成物を熱硬化させるためには高温で処理する必要があるが、耐熱性に乏しい材料にも用いられるようにするために、また、環境面、コスト面、安全面における要求から、処理温度を低減することが求められている。そのような手段として、従来、架橋剤を配合することが知られている（例えば、特許文献１、２）。 In order to thermally cure the positive photosensitive resin composition containing the polybenzoxazole precursor as described above, it is necessary to process at a high temperature, but in order to be used for a material having poor heat resistance, In addition, the processing temperature is required to be reduced due to environmental, cost, and safety requirements. As such means, it is conventionally known to add a crosslinking agent (for example, Patent Documents 1 and 2).
特開２００９－２６５５２０号公報JP 2009-265520 A 特開２０１１－０５３４５８号公報JP 2011-053458 A
　しかしながら、架橋剤を配合すると、アルカリ現像後の未露光部の残膜率が低下するという問題があった。 However, when a crosslinking agent is blended, there is a problem that the remaining film ratio of the unexposed part after alkali development is lowered.
　そこで本発明の目的は、残膜率に優れたポジ型感光性樹脂組成物、該組成物から得られる樹脂層を有するドライフィルム、該組成物または該ドライフィルムの樹脂層の硬化物、該硬化物を有するプリント配線板および該硬化物を有する半導体素子を提供することにある。 Accordingly, an object of the present invention is to provide a positive photosensitive resin composition having an excellent residual film ratio, 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 the curing An object of the present invention is to provide a printed wiring board having an object and a semiconductor element having the cured product.
　本発明者等は上記に鑑み鋭意検討した結果、特定の架橋剤とシランカップリング剤を用いることによって、上記課題を解決しうることを見出し、本発明を完成するに至った。 As a result of intensive studies in view of the above, the present inventors have found that the above problems can be solved by using a specific crosslinking agent and silane coupling agent, and have completed the present invention.
　即ち、本発明のポジ型感光性樹脂組成物は、（Ａ）ポリベンゾオキサゾール前駆体、（Ｂ）光酸発生剤、（Ｃ）メラミン系架橋剤、および、（Ｄ）シランカップリング剤を含むポジ型感光性樹脂組成物であって、前記（Ｄ）シランカップリング剤として、アリールアミノ基を有するシランカップリング剤および二つ以上のトリアルコキシシリル基を有するシランカップリング剤から選ばれる少なくとも１種を含むことを特徴とするものである。 That is, the positive photosensitive resin composition of the present invention includes (A) a polybenzoxazole precursor, (B) a photoacid generator, (C) a melamine-based crosslinking agent, and (D) a silane coupling agent. A positive photosensitive resin composition, wherein the (D) silane coupling agent is at least one selected from a silane coupling agent having an arylamino group and a silane coupling agent having two or more trialkoxysilyl groups. It is characterized by including seeds.
　本発明のポジ型感光性樹脂組成物は、前記（Ｄ）シランカップリング剤として、アリールアミノ基を有するシランカップリング剤を含むことが好ましい。 The positive photosensitive resin composition of the present invention preferably contains a silane coupling agent having an arylamino group as the (D) silane coupling agent.
　本発明のドライフィルムは、前記感光性樹脂組成物を、フィルムに塗布、乾燥して得られる樹脂層を有することを特徴とするものである。 The dry film of the present invention is characterized by having a resin layer obtained by applying the photosensitive resin composition to a film and drying it.
　本発明の硬化物は、前記感光性樹脂組成物または前記ドライフィルムの樹脂層を、硬化して得られることを特徴とするものである。 The cured product of the present invention is obtained by curing the photosensitive resin composition or the resin layer of the dry film.
　本発明のプリント配線板は、前記硬化物を有することを特徴とするものである。 The printed wiring board of the present invention is characterized by having the cured product.
　本発明の半導体素子は、前記硬化物を有することを特徴とするものである。 The semiconductor element of the present invention is characterized by having the cured product.
　本発明によれば、残膜率に優れたポジ型感光性樹脂組成物、該組成物から得られる樹脂層を有するドライフィルム、該組成物または該ドライフィルムの樹脂層の硬化物、該硬化物を有するプリント配線板および該硬化物を有する半導体素子を提供することができる。 According to the present invention, a positive photosensitive resin composition having an excellent residual film ratio, 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 the cured product A printed wiring board having a semiconductor device and a semiconductor element having the cured product can be provided.
実施例におけるスカムの確認方法の評価〇の評価例を示す写真図である。It is a photograph figure which shows the evaluation example of evaluation (circle) of the confirmation method of the scum in an Example. 実施例におけるスカムの確認方法の評価△の評価例を示す写真図である。It is a photograph figure which shows the evaluation example of evaluation (triangle | delta) of the confirmation method of the scum in an Example. 実施例におけるスカムの確認方法の評価×の評価例を示す写真図である。It is a photograph figure which shows the evaluation example of evaluation x of the confirmation method of the scum in an Example.
　以下、本発明のポジ型感光性樹脂組成物が含有する成分について詳述する。 Hereinafter, components contained in the positive photosensitive resin composition of the present invention will be described in detail.
［（Ａ）ポリベンゾオキサゾール前駆体］
　本発明のポジ型感光性樹脂組成物は、（Ａ）ポリベンゾオキサゾール前駆体を含有する。（Ａ）ポリベンゾオキサゾール前駆体を合成する方法は特に限定されず、公知の方法で合成すればよい。例えば、アミン成分としてジヒドロキシジアミン類と、酸成分としてジカルボン酸ジクロリド等のジカルボン酸のジハライドとを反応させて得ることができる。 [(A) Polybenzoxazole precursor]
The positive 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 dihalide of a dicarboxylic acid such as dicarboxylic acid dichloride as an acid component.
　（Ａ）ポリベンゾオキサゾール前駆体は、下記の繰り返し構造を有するポリヒドロキシアミド酸であることが好ましい。
Figure JPOXMLDOC01-appb-I000001
（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 acid having the following repeating structure.
Figure JPOXMLDOC01-appb-I000001
(In the formula, X represents a tetravalent organic group and Y represents a divalent organic group. N is an integer of 1 or more, preferably 10 to 50, more preferably 20 to 40.)
　（Ａ）ポリベンゾオキサゾール前駆体を上記の合成方法で合成する場合、前記一般式（１）中、Ｘは、前記ジヒドロキシジアミン類の残基であり、Ｙは、前記ジカルボン酸の残基である。 (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. .
　前記ジヒドロキシジアミン類としては、３，３’－ジアミノ－４，４’－ジヒドロキシビフェニル、４，４’－ジアミノ－３，３’－ジヒドロキシビフェニル、ビス（３－アミノ－４－ヒドロキシフェニル）プロパン、ビス（４－アミノ－３－ヒドロキシフェニル）プロパン、ビス（３－アミノ－４－ヒドロキシフェニル）スルホン、ビス（４－アミノ－３－ヒドロキシフェニル）スルホン、２，２－ビス（３－アミノ－４－ヒドロキシフェニル）－１，１，１，３，３，３－ヘキサフルオロプロパン、２，２－ビス（４－アミノ－３－ヒドロキシフェニル）－１，１，１，３，３，３－ヘキサフルオロプロパン等が挙げられる。中でも、２，２－ビス（３－アミノ－４－ヒドロキシフェニル）－１，１，１，３，３，３－ヘキサフルオロプロパンが好ましい。 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. Of these, 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane is preferred.
　前記ジカルボン酸としては、イソフタル酸、テレフタル酸、５－ｔｅｒｔ－ブチルイソフタル酸、５－ブロモイソフタル酸、５－フルオロイソフタル酸、５－クロロイソフタル酸、２，６－ナフタレンジカルボン酸、４，４’－ジカルボキシビフェニル、４，４’－ジカルボキシジフェニルエーテル、４，４’－ジカルボキシテトラフェニルシラン、ビス（４－カルボキシフェニル）スルホン、２，２－ビス（ｐ－カルボキシフェニル）プロパン、２，２－ビス（４－カルボキシフェニル）－１，１，１，３，３，３－ヘキサフルオロプロパン等の芳香環を有するジカルボン酸、シュウ酸、マロン酸、コハク酸、１，２－シクロブタンジカルボン酸、１，４－シクロヘキサンジカルボン酸、１，３－シクロペンタンジカルボン酸等の脂肪族系ジカルボン酸が挙げられる。中でも、４，４’－ジカルボキシジフェニルエーテルが好ましい。 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 acids such as 1,4-cyclohexanedicarboxylic acid and 1,3-cyclopentanedicarboxylic acid Include the dicarboxylic acid. Of these, 4,4'-dicarboxydiphenyl ether is preferable.
　前記一般式（１）中、Ｘが示す４価の有機基は脂肪族基でも芳香族基でもよいが、芳香族基であることが好ましく、２つのヒドロキシ基と２つのアミノ基がオルト位に芳香環上に位置することがより好ましい。前記４価の芳香族基の炭素原子数は、６～３０であることが好ましく、６～２４であることがより好ましい。前記４価の芳香族基の具体例としては下記の基が挙げられるが、これらに限定されるものではなく、ポリベンゾオキサゾール前駆体に含まれうる公知の芳香族基を用途に応じて選択すればよい。 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 tetravalent aromatic group preferably has 6 to 30 carbon atoms, and more preferably 6 to 24 carbon atoms. 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.
Figure JPOXMLDOC01-appb-I000002
Figure JPOXMLDOC01-appb-I000002
　前記４価の芳香族基は、前記芳香族基の中でも下記の基であることが好ましい。
Figure JPOXMLDOC01-appb-I000003
The tetravalent aromatic group is preferably the following group among the aromatic groups.
Figure JPOXMLDOC01-appb-I000003
　前記一般式（１）中、Ｙが示す２価の有機基は脂肪族基でも芳香族基でもよいが、芳香族基であることが好ましく、芳香環上で前記一般式（１）中のカルボニルと結合していることがより好ましい。前記２価の芳香族基の炭素原子数は、６～３０であることが好ましく、６～２４であることがより好ましい。前記２価の芳香族基の具体例としては下記の基が挙げられるが、これらに限定されるものではなく、ポリベンゾオキサゾール前駆体に含まれる公知の芳香族基を用途に応じて選択すればよい。 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 divalent aromatic group preferably has 6 to 30 carbon atoms, and more preferably 6 to 24 carbon atoms. 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.
Figure JPOXMLDOC01-appb-I000004
（式中、Ａは単結合、－ＣＨ２－、－Ｏ－、－ＣＯ－、－Ｓ－、－ＳＯ２－、－ＮＨＣＯ－、－Ｃ（ＣＦ３）２－、－Ｃ（ＣＨ３）２－からなる群から選択される２価の基を表す。）
Figure JPOXMLDOC01-appb-I000004
(Wherein A is a single bond, —CH 2 —, —O—, —CO—, —S—, —SO 2 —, —NHCO—, —C (CF 3 ) 2 —, —C (CH 3 )) 2 represents a divalent group selected from the group consisting of-.
　前記２価の有機基は、前記芳香族基の中でも下記の基であることが好ましい。
Figure JPOXMLDOC01-appb-I000005
The divalent organic group is preferably the following group among the aromatic groups.
Figure JPOXMLDOC01-appb-I000005
　（Ａ）ポリベンゾオキサゾール前駆体は、上記のポリヒドロキシアミド酸の繰り返し構造を２種以上含んでいてもよい。また、上記のポリヒドロキシアミド酸の繰り返し構造以外の構造を含んでいてもよく、例えば、ポリアミド酸の繰り返し構造を含んでいてもよい。 (A) The polybenzoxazole precursor may contain two or more repeating structures of the above polyhydroxyamide acid. Further, it may contain a structure other than the above-mentioned repeating structure of polyhydroxyamic acid, for example, it may contain a repeating structure of polyamic acid.
　（Ａ）ポリベンゾオキサゾール前駆体の数平均分子量（Ｍｎ）は５，０００～１００，０００であることが好ましく、８，０００～５０，０００であることがより好ましい。ここで数平均分子量は、（ＧＰＣ）で測定し、標準ポリスチレンで換算した数値である。また、（Ａ）ポリベンゾオキサゾール前駆体の重量平均分子量（Ｍｗ）は１０，０００～２００，０００であることが好ましく、１６，０００～１００，０００であることがより好ましい。ここで重量平均分子量は、（ＧＰＣ）で測定し、標準ポリスチレンで換算した数値である。Ｍｗ／Ｍｎは１～５であることが好ましく、１～３であることがより好ましい。 (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 (GPC) and converted by standard polystyrene. The weight average molecular weight (Mw) of the (A) polybenzoxazole precursor is preferably 10,000 to 200,000, more preferably 16,000 to 100,000. Here, the weight average molecular weight is a value measured by (GPC) and converted to standard polystyrene. Mw / Mn is preferably from 1 to 5, and more preferably from 1 to 3.
　（Ａ）ポリベンゾオキサゾール前駆体は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。（Ａ）ポリベンゾオキサゾール前駆体の配合量は、組成物固形分全量基準で６０～９０質量％であることが好ましい。 (A) One polybenzoxazole precursor may be used alone, or two or more may be used in combination. The blending amount of the (A) polybenzoxazole precursor is preferably 60 to 90% by mass based on the total amount of the solid content of the composition.
［（Ｂ）光酸発生剤］
　（Ｂ）光酸発生剤としては、ナフトキノンジアジド化合物、ジアリールスルホニウム塩、トリアリールスルホニウム塩、ジアルキルフェナシルスルホニウム塩、ジアリールヨードニウム塩、アリールジアゾニウム塩、芳香族テトラカルボン酸エステル、芳香族スルホン酸エステル、ニトロベンジルエステル、芳香族Ｎ－オキシイミドスルフォネート、芳香族スルファミド、ベンゾキノンジアゾスルホン酸エステル等を挙げることができる。（Ｂ）光酸発生剤は、溶解阻害剤であることが好ましい。中でもナフトキノンジアジド化合物であることが好ましい。 [(B) Photoacid generator]
(B) As a photoacid generator, a naphthoquinonediazide compound, a diarylsulfonium salt, a triarylsulfonium salt, a dialkylphenacylsulfonium salt, a diaryliodonium salt, an aryldiazonium salt, an aromatic tetracarboxylic acid ester, an aromatic sulfonic acid ester, Examples thereof include nitrobenzyl ester, aromatic N-oxyimide sulfonate, aromatic sulfamide, and benzoquinone diazosulfonic acid ester. (B) The photoacid generator is preferably a dissolution inhibitor. Of these, a naphthoquinonediazide compound is preferable.
　ナフトキノンジアジド化合物としては、具体的には例えば、トリス（４－ヒドロキシフェニル）－１－エチル－４－イソプロピルベンゼンのナフトキノンジアジド付加物（例えば、三宝化学研究所社製のＴＳ５３３，ＴＳ５６７，ＴＳ５８３，ＴＳ５９３）や、テトラヒドロキシベンゾフェノンのナフトキノンジアジド付加物（例えば、三宝化学研究所社製のＢＳ５５０，ＢＳ５７０，ＢＳ５９９）等を使用することができる。 Specific examples of the naphthoquinonediazide compound include, for example, naphthoquinonediazide 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.
　（Ｂ）光酸発生剤は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。（Ｂ）光酸発生剤の配合量は、組成物固形分全量基準で３～２０質量％であることが好ましい。 (B) One photoacid generator may be used alone, or two or more photoacid generators may be used in combination. The blending amount of the (B) photoacid generator is preferably 3 to 20% by mass based on the total amount of the solid content of the composition.
［（Ｃ）メラミン系架橋剤］
　（Ｃ）メラミン系架橋剤としては、メラミン構造を有する架橋剤であれば特に限定されないが、下記一般式（２）で表されるメラミン系架橋剤であることが好ましい。
Figure JPOXMLDOC01-appb-I000006
（式中、Ｒ２１Ａ、Ｒ２２Ａ、Ｒ２３Ａ、Ｒ２４Ａ、Ｒ２５ＡおよびＲ２６Ａはそれぞれ独立に炭素数１～３のアルキレン基であることが好ましい。Ｒ２１Ｂ、Ｒ２２Ｂ、Ｒ２３Ｂ、Ｒ２４Ｂ、Ｒ２５ＢおよびＲ２６Ｂはそれぞれ独立に水素原子、または、炭素数１～３のアルキル基であることが好ましい。） [(C) Melamine-based crosslinking agent]
(C) Although it will not specifically limit if it is a crosslinking agent which has a melamine structure as a melamine type crosslinking agent, It is preferable that it is a melamine type crosslinking agent represented by following General formula (2).
Figure JPOXMLDOC01-appb-I000006
(Wherein R 21A , R 22A , R 23A , R 24A , R 25A and R 26A are each independently preferably an alkylene group having 1 to 3 carbon atoms. R 21B , R 22B , R 23B , R 24B R 25B and R 26B are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)
　上記一般式（２）中、Ｒ２１Ａ、Ｒ２２Ａ、Ｒ２３Ａ、Ｒ２４Ａ、Ｒ２５ＡおよびＲ２６Ａはそれぞれメチレン基であることがより好ましい。また、Ｒ２１Ｂ、Ｒ２２Ｂ、Ｒ２３Ｂ、Ｒ２４Ｂ、Ｒ２５ＢおよびＲ２６Ｂはそれぞれ独立にメチル基または水素原子であることがより好ましい。 In the general formula (2), R 21A , R 22A , R 23A , R 24A , R 25A and R 26A are each preferably a methylene group. R 21B , R 22B , R 23B , R 24B , R 25B and R 26B are more preferably each independently a methyl group or a hydrogen atom.
　（Ｃ）メラミン系架橋剤は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。（Ｃ）メラミン系架橋剤の配合量は、組成物固形分全量基準で１～１５質量％であることが好ましい。１～１５質量％であると、未露光部の残膜率を高くでき、露光部の現像残りを防止することができる。 (C) One type of melamine-based crosslinking agent may be used alone, or two or more types may be used in combination. The blending amount of the (C) melamine crosslinking agent is preferably 1 to 15% by mass based on the total amount of the solid content of the composition. When the content is 1 to 15% by mass, the remaining film ratio in the unexposed area can be increased, and the development remaining in the exposed area can be prevented.
　本発明のポジ型感光性樹脂組成物は、（Ｃ）メラミン系架橋剤以外の他の架橋剤を含有することが好ましく、以下の架橋剤２、架橋剤５および架橋剤６の少なくともいずれか一種を含有することが好ましい。（Ｃ）メラミン系架橋剤と、架橋剤２、架橋剤５および架橋剤６の少なくともいずれか一種とを含むことにより、溶解促進効果が得られ、現像性が良好となる。 The positive photosensitive resin composition of the present invention preferably contains a crosslinking agent other than (C) the melamine-based crosslinking agent, and is at least one of the following crosslinking agent 2, crosslinking agent 5 and crosslinking agent 6. It is preferable to contain. (C) By including a melamine-based crosslinking agent and at least one of the crosslinking agent 2, the crosslinking agent 5, and the crosslinking agent 6, a dissolution promoting effect is obtained, and the developability is improved.
架橋剤２
Figure JPOXMLDOC01-appb-I000007
架橋剤５　　　　　　  　　　　　　　　
Figure JPOXMLDOC01-appb-I000008
架橋剤６
Figure JPOXMLDOC01-appb-I000009
Crosslinker 2
Figure JPOXMLDOC01-appb-I000007
Crosslinker 5
Figure JPOXMLDOC01-appb-I000008
Crosslinker 6
Figure JPOXMLDOC01-appb-I000009
　（Ｃ）メラミン系架橋剤以外の他の架橋剤の配合量は、組成物固形分全量基準で１～１５質量％であることが好ましい。特に、架橋剤２、架橋剤５および架橋剤６の合計配合量が、組成物固形分全量基準で１～１５質量％であることが好ましい。 (C) The amount of the crosslinking agent other than the melamine-based crosslinking agent is preferably 1 to 15% by mass based on the total amount of the solid content of the composition. In particular, the total amount of the crosslinking agent 2, the crosslinking agent 5 and the crosslinking agent 6 is preferably 1 to 15% by mass based on the total amount of the solid content of the composition.
［（Ｄ）シランカップリング剤］
　本発明のポジ型感光性樹脂組成物は、（Ｄ）シランカップリング剤として、アリールアミノ基を有するシランカップリング剤および二つ以上のトリアルコキシシリル基を有するシランカップリング剤から選ばれる少なくとも１種を含む。 [(D) Silane coupling agent]
The positive photosensitive resin composition of the present invention is (D) at least one silane coupling agent selected from a silane coupling agent having an arylamino group and a silane coupling agent having two or more trialkoxysilyl groups. Including species.
　前記アリールアミノ基のアリール基としては、フェニル基、トリル基、キシリル基等の芳香族炭化水素基、ナフチル基、アントラセニル基、フェナントレニル基等の縮合多環芳香族基、チエニル基、インドリル基等の芳香族複素環基が挙げられる。 Examples of the aryl group of the arylamino group include aromatic hydrocarbon groups such as phenyl group, tolyl group and xylyl group, condensed polycyclic aromatic groups such as naphthyl group, anthracenyl group and phenanthrenyl group, thienyl group and indolyl group. An aromatic heterocyclic group is mentioned.
　前記アリールアミノ基を有するシランカップリング剤は、下記一般式（３）で示される基を有する化合物であることが好ましい。
Figure JPOXMLDOC01-appb-I000010
（式中、Ｒ３１～Ｒ３５はそれぞれ独立に水素原子または有機基を表す。） The silane coupling agent having an arylamino group is preferably a compound having a group represented by the following general formula (3).
Figure JPOXMLDOC01-appb-I000010
(Wherein R 31 to R 35 each independently represents a hydrogen atom or an organic group.)
　前記一般式（３）中、Ｒ３１～Ｒ３５が水素原子であることが好ましい。 In the general formula (3), R 31 to R 35 are preferably hydrogen atoms.
　前記アリールアミノ基を有するシランカップリング剤は、ケイ素原子とアリールアミノ基とが、炭素数１～１０の有機基、好ましくは炭素数１～１０のアルキレン基で結合していることが好ましい。 In the silane coupling agent having an arylamino group, a silicon atom and an arylamino group are preferably bonded with an organic group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms.
　前記アリールアミノ基を有するシランカップリング剤の具体例としては下記の化合物であることが好ましい。
Figure JPOXMLDOC01-appb-I000011
Specific examples of the silane coupling agent having an arylamino group are preferably the following compounds.
Figure JPOXMLDOC01-appb-I000011
　前記二つ以上のトリアルコキシシリル基を有するシランカップリング剤が有するトリアルコキシシリル基はそれぞれ同じでも異なっていてもよく、また、これらの基が有するアルコキシ基はそれぞれ同じでも異なっていてもよい。アルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等が挙げられるが、中でも、メトキシ基、エトキシ基であることが好ましい。 The trialkoxysilyl group 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. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Among them, a methoxy group and an ethoxy group are preferable.
　前記二つ以上のトリアルコキシシリル基を有するシランカップリング剤は、少なくとも二つのケイ素原子が、炭素数１～１０の有機基、好ましくは炭素数１～１０のアルキレン基で結合していることが好ましい。 In the silane coupling agent having two or more trialkoxysilyl groups, at least two silicon atoms are bonded by an organic group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms. preferable.
　前記二つ以上のトリアルコキシシリル基を有するシランカップリング剤の具体例としては下記の化合物であることが好ましい。
Figure JPOXMLDOC01-appb-I000012
Specific examples of the silane coupling agent having two or more trialkoxysilyl groups are preferably the following compounds.
Figure JPOXMLDOC01-appb-I000012
　（Ｄ）シランカップリング剤は、解像性に優れることから、アリールアミノ基を有するシランカップリング剤であることが好ましい。 (D) The silane coupling agent is preferably a silane coupling agent having an arylamino group because of its excellent resolution.
　（Ｄ）シランカップリング剤は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。（Ｄ）シランカップリング剤の配合量は、組成物固形分全量基準で１～１５質量％であることが好ましい。１～１５質量％であると露光部の現像残りを防止することができる。 (D) One silane coupling agent may be used alone, or two or more silane coupling agents may be used in combination. (D) The amount of the silane coupling agent is preferably 1 to 15% by mass based on the total amount of the solid content of the composition. When it is 1 to 15% by mass, it is possible to prevent undeveloped residues in the exposed area.
　本発明のポジ型感光性樹脂組成物は、本発明の効果を損なわない範囲で、他のシランカップリング剤を含有してもよい。 The positive photosensitive resin composition of the present invention may contain other silane coupling agents as long as the effects of the present invention are not impaired.
　以下に、本発明のポジ型感光性樹脂組成物に配合可能な他の成分を説明する。 Hereinafter, other components that can be blended in the positive photosensitive resin composition of the present invention will be described.
（ｔ－ブチルカテコール）
　本発明のポジ型感光性樹脂組成物は、ｔ－ブチルカテコールを含有することが好ましい。ｔ－ブチルカテコールを含有することにより、現像残渣（スカム）が少なく現像性に優れる。 (T-butylcatechol)
The positive photosensitive resin composition of the present invention preferably contains t-butylcatechol. By containing t-butylcatechol, the development residue (scum) is small and the developability is excellent.
　ｔ－ブチルカテコールの配合量は、組成物固形分全量基準で０．１～２質量％であることが好ましい。 The blending amount of t-butylcatechol is preferably 0.1 to 2% by mass based on the total amount of the solid content of the composition.
　本発明のポジ型感光性樹脂組成物には、溶媒を配合することができる。溶媒としては、（Ａ）ポリベンゾオキサゾール前駆体、（Ｂ）光酸発生剤、（Ｃ）メラミン系架橋剤、（Ｄ）シランカップリング剤、および、他の添加剤を溶解させるものであれば特に限定されない。一例としては、Ｎ，Ｎ’－ジメチルホルムアミド、Ｎ－メチルピロリドン、Ｎ－エチル－２－ピロリドン、Ｎ，Ｎ’－ジメチルアセトアミド、ジエチレングリコールジメチルエーテル、シクロペンタノン、γ－ブチロラクトン、α－アセチル－γ－ブチロラクトン、テトラメチル尿素、１，３－ジメチル－２－イミダゾリノン、Ｎ－シクロヘキシル－２－ピロリドン、ジメチルスルホキシド、ヘキサメチルホスホルアミド、ピリジン、γ－ブチロラクトン、ジエチレングリコールモノメチルエーテルを挙げることができる。これらは単独で用いても、二種以上を混合して用いてもかまわない。使用する溶媒の量は、塗布膜厚や粘度に応じて、（Ａ）ポリベンゾオキサゾール前駆体１００質量部に対し、５０～９０００質量部の範囲で用いることができる。 A solvent can be blended in the positive photosensitive resin composition of the present invention. Any solvent that dissolves (A) a polybenzoxazole precursor, (B) a photoacid generator, (C) a melamine-based crosslinking agent, (D) a silane coupling agent, and other additives can be used. There is no particular limitation. Examples include N, N′-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N, N′-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ- Examples include butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, γ-butyrolactone, and diethylene glycol monomethyl ether. These may be used alone or in combination of two or more. The amount of the solvent used can be in the range of 50 to 9000 parts by mass with respect to 100 parts by mass of the (A) polybenzoxazole precursor, depending on the coating film thickness and viscosity.
　本発明のポジ型感光性樹脂組成物には、更に光感度を向上させるために公知の増感剤を配合することもできる。 In the positive photosensitive resin composition of the present invention, a known sensitizer can be blended in order to further improve the photosensitivity.
　また、本発明のポジ型感光性樹脂組成物には、基材との接着性向上のため公知の接着助剤を添加することもできる。 In addition, a known adhesion assistant can be added to the positive photosensitive resin composition of the present invention in order to improve the adhesion to the substrate.
　本発明のポジ型感光性樹脂組成物に加工特性や各種機能性を付与するために、その他に様々な有機または無機の低分子または高分子化合物を配合してもよい。例えば、界面活性剤、レベリング剤、可塑剤、微粒子等を用いることができる。微粒子には、ポリスチレン、ポリテトラフルオロエチレン等の有機微粒子、コロイダルシリカ、カーボン、層状珪酸塩等の無機微粒子が含まれる。また、本発明のポジ型感光性樹脂組成物に各種着色剤および繊維等を配合してもよい。 In order to impart processing characteristics and various functionalities to the positive photosensitive resin composition of the present invention, various organic or inorganic low-molecular or high-molecular compounds may be blended. 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 positive photosensitive resin composition of this invention.
［ドライフィルム］
　本発明のドライフィルムは、本発明のポジ型感光性樹脂組成物を塗布後、乾燥して得られる樹脂層を有する。本発明のドライフィルムは、樹脂層を、基材に接するようにラミネートして使用される。 [Dry film]
The dry film of the present invention has a resin layer obtained by applying and then drying the positive photosensitive resin composition of the present invention. The dry film of the present invention is used by laminating a resin layer so as to be in contact with a substrate.
　本発明のドライフィルムは、キャリアフィルムに本発明のポジ型感光性樹脂組成物をブレードコーター、リップコーター、コンマコーター、フィルムコーター等の適宜の方法により均一に塗布し、乾燥して、前記した樹脂層を形成し、好ましくはその上にカバーフィルムを積層することにより、製造することができる。カバーフィルムとキャリアフィルムは同一のフィルム材料であっても、異なるフィルムを用いてもよい。 The dry film of the present invention is obtained by uniformly applying the positive photosensitive resin composition of the present invention to a carrier film by an appropriate method such as a blade coater, a lip coater, a comma coater, or a film coater, and drying the resin. It can be produced by forming a layer and preferably laminating a cover film thereon. The cover film and the carrier film may be the same film material or different films.
　本発明のドライフィルムにおいて、キャリアフィルムおよびカバーフィルムのフィルム材料は、ドライフィルムに用いられるものとして公知のものをいずれも使用することができる。 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.
　キャリアフィルムとしては、例えば２～１５０μｍの厚さのポリエチレンテレフタレート等のポリエステルフィルム等の熱可塑性フィルムが用いられる。 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.
　カバーフィルムとしては、ポリエチレンフィルム、ポリプロピレンフィルム等を使用することができるが、樹脂層との接着力が、キャリアフィルムよりも小さいものが良い。 As the cover film, a polyethylene film, a polypropylene film or the like can be used, but it is preferable that the adhesive force with the resin layer is smaller than that of the carrier film.
　本発明のドライフィルム上の樹脂層の膜厚は、１００μｍ以下が好ましく、５～５０μｍの範囲がより好ましい。 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.
　本発明のポジ型感光性樹脂組成物を用いて、その硬化物であるパターン膜は、例えば下記のように製造する。 The pattern film that is a cured product of the positive photosensitive resin composition of the present invention is produced, for example, as follows.
　まず、ステップ１として、ポジ型感光性樹脂組成物を基材上に塗布、乾燥する、或いはドライフィルムから樹脂層を基材上に転写することにより塗膜を得る。ポジ型感光性樹脂組成物を基材上に塗布する方法としては、従来から感光性樹脂組成物の塗布に用いられていた方法、例えば、スピンコーター、バーコーター、ブレードコーター、カーテンコーター、スクリーン印刷機等で塗布する方法、スプレーコーターで噴霧塗布する方法、さらにはインクジェット法等を用いることができる。塗膜の乾燥方法としては、風乾、オーブンまたはホットプレートによる加熱乾燥、真空乾燥等の方法が用いられる。また、塗膜の乾燥は、感光性樹脂組成物中の（Ａ）ポリベンゾオキサゾール前駆体の閉環が起こらないような条件で行うことが望ましい。具体的には、自然乾燥、送風乾燥、あるいは加熱乾燥を、７０～１４０℃で１～３０分の条件で行うことができる。好ましくは、ホットプレート上で１～２０分乾燥を行う。また、真空乾燥も可能であり、この場合は、室温で２０分～１時間の条件で行うことができる。 First, as Step 1, a positive photosensitive resin composition is applied on a substrate and dried, or a resin layer is transferred from a dry film onto the substrate to obtain a coating film. As a method for applying the positive photosensitive resin composition on the substrate, methods conventionally used for applying the photosensitive resin composition, for example, spin coater, bar coater, blade coater, curtain coater, screen printing, etc. A coating method using a machine, a spray coating method using a spray coater, an ink jet method or the like 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. Vacuum drying is also possible, and in this case, it can be performed at room temperature for 20 minutes to 1 hour.
　基材に特に制限はなく、シリコンウェハー等の半導体基材、配線基板、各種樹脂、金属等に広く適用できる。 There is no particular limitation on the base material, and it can be widely applied to semiconductor base materials such as silicon wafers, wiring boards, various resins, metals, and the like.
　次に、ステップ２として、上記塗膜を、パターンを有するフォトマスクを介して、あるいは、直接露光する。露光光線は、（Ｂ）光酸発生剤を活性化させ、酸を発生させることができる波長のものを用いる。具体的には、露光光線は、最大波長が３５０～４１０ｎｍの範囲にあるものが好ましい。上述したように、適宜増感剤を用いると、光感度を調製することができる。露光装置としては、コンタクトアライナー、ミラープロジェクション、ステッパー、レーザーダイレクト露光装置等を用いることができる。 Next, as step 2, the coating film is exposed through a photomask having a pattern or directly. The exposure light beam having a wavelength capable of activating the photoacid generator (B) and generating 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.
　続いて、ステップ３として、加熱し、未露光部の（Ａ）ポリベンゾオキサゾール前駆体の一部を閉環してもよい。ここで、閉環率は、３０％程度である。加熱時間および加熱温度は、（Ａ）ポリベンゾオキサゾール前駆体、塗布膜厚、（Ｂ）光酸発生剤の種類によって適宜変更する。 Subsequently, as Step 3, heating may be performed to cyclize a part of the (A) polybenzoxazole precursor in the unexposed area. 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.
　次いで、ステップ４として、塗膜を現像液で処理する。これにより、塗膜中の露光部分を除去して、本発明のポジ型感光性樹脂組成物のパターン膜を形成することができる。 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 of the positive photosensitive resin composition of this invention can be formed.
　現像に用いる方法としては、従来知られているフォトレジストの現像方法、例えば回転スプレー法、パドル法、超音波処理を伴う浸せき法等の中から任意の方法を選択することができる。現像液としては、水酸化ナトリウム、炭酸ナトリウム、ケイ酸ナトリウム、アンモニア水等の無機アルカリ類、エチルアミン、ジエチルアミン、トリエチルアミン、トリエタノールアミン等の有機アミン類、テトラメチルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド等の四級アンモニウム塩類等の水溶液を挙げることができる。また、必要に応じて、これらにメタノール、エタノール、イソプロピルアルコール等の水溶性有機溶媒や界面活性剤を適当量添加してもよい。その後、必要に応じて塗膜をリンス液により洗浄してパターン膜を得る。リンス液としては、蒸留水、メタノール、エタノール、イソプロピルアルコール等を単独または組み合わせて用いることができる。また、現像液として上記溶媒を使用してもよい。 As a method used for development, an arbitrary method can be selected from conventionally known photoresist development methods such as a rotary spray method, a paddle method, an immersion method involving ultrasonic treatment, and the like. 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.
　その後、ステップ５として、パターン膜を加熱して硬化塗膜（硬化物）を得る。このとき、（Ａ）ポリベンゾオキサゾール前駆体を閉環し、ポリベンゾオキサゾールを得ればよい。加熱温度は、ポリベンゾオキサゾールのパターン膜を硬化可能なように適宜設定する。例えば、不活性ガス中で、１５０～３５０℃で５～１２０分程度の加熱を行う。加熱温度のより好ましい範囲は、２００～３００℃である。加熱は、例えば、ホットプレート、オーブン、温度プログラムを設定できる昇温式オーブンを用いることにより行う。このときの雰囲気（気体）としては空気を用いてもよく、窒素、アルゴン等の不活性ガスを用いてもよい。 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 in an inert gas at 150 to 350 ° C. for about 5 to 120 minutes. 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.
　本発明のポジ型感光性樹脂組成物の用途は特に限定されず、例えば、印刷インキ、接着剤、充填剤、電子材料、光回路部品、成形材料、レジスト材料、建築材料、３次元造形、光学部材等、樹脂材料が用いられる公知の種々の分野・製品などが挙げられる。特にポリベンゾオキサゾール膜の耐熱性、寸法安定性、絶縁性等の特性が有効とされる広範な分野・製品、例えば、塗料または印刷インキ、或いは、カラーフィルター、フレキシブルディスプレー用フィルム、半導体素子の被覆膜、電子部品、層間絶縁膜、ソルダーレジストなどのプリント配線板の被覆膜、光回路、光回路部品、反射防止膜、ホログラム、光学部材または建築材料の形成材料として好適に用いられる。 The use of the positive photosensitive resin composition of the present invention is not particularly limited. For example, printing ink, adhesive, filler, electronic material, optical circuit component, molding material, resist material, building material, three-dimensional modeling, optical Examples include various known fields and products in which resin materials are used, such as members. In particular, a wide range of fields and products in which the polybenzoxazole film is effective in heat resistance, dimensional stability, insulation, etc., such as paints or printing inks, color filters, flexible display films, semiconductor device coatings, etc. It is suitably used as a coating material for printed wiring boards such as coating films, electronic components, interlayer insulating films, solder resists, optical circuits, optical circuit components, antireflection films, holograms, optical members, or building materials.
　特に、本発明のポジ型感光性樹脂組成物は、主にパターン形成材料（レジスト）として用いられ、それによって形成されたパターン膜は、ポリベンゾオキサゾールからなる永久膜として耐熱性や絶縁性を付与する成分として機能し、例えば、カラーフィルター、フレキシブルディスプレー用フィルム、電子部品、半導体素子の被覆膜、層間絶縁膜、ソルダーレジストやカバーレイ膜などのプリント配線板の被覆膜、ソルダーダム、光回路、光回路部品、反射防止膜、その他の光学部材または電子部材を形成するのに適している。 In particular, the positive photosensitive resin composition of the present invention is mainly used as a pattern forming material (resist), and the pattern film formed thereby imparts heat resistance and insulation as a permanent film made of polybenzoxazole. For example, color filters, films for flexible displays, electronic components, coating films for semiconductor elements, interlayer insulation films, coating films for printed wiring boards such as solder resists and coverlay films, solder dams, optical circuits It is suitable for forming optical circuit components, antireflection films, other optical members or electronic members.
　以下、本発明を、実施例を用いてより詳細に説明するが、本発明は下記実施例に限定されるものではない。なお、以下において「部」および「％」とあるのは、特に断りのない限り全て質量基準である。 Hereinafter, the present invention will be described in more detail with reference to 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.
（ポリベンゾオキサゾール（ＰＢＯ）前駆体の合成）
　攪拌機、温度計を備えた０．５リットルのフラスコ中にＮ－メチルピロリドン２１２ｇ仕込み、ビス（３－アミノ－４－ヒドロキシアミドフェニル）ヘキサフルオロプロパン２８．００ｇ（７６．５ｍｍｏｌ）を撹拌溶解した。その後、フラスコを氷浴に浸し、フラスコ内を０～５℃に保ちながら、４，４－ジフェニルエーテルジカルボン酸クロリド２５．００ｇ（８３．２ｍｍｏｌ）を固体のまま５ｇずつ３０分間かけて加え、氷浴中で３０分間撹拌した。その後、室温で５時間撹拌を続けた。撹拌した溶液を１Ｌのイオン交換水（比抵抗値１８．２ＭΩ・ｃｍ）に投入し、析出物を回収した。その後、得られた固体をアセトン４２０ｍＬに溶解させ、１Ｌのイオン交換水に投入した。析出した個体を回収後、減圧乾燥してカルボキシル基末端の下記の繰り返し構造を有するポリベンゾオキサゾール（ＰＢＯ）前駆体Ａ１を得た。ポリベンゾオキサゾール前駆体Ａ１の数平均分子量（Ｍｎ）は１２，９００、重量平均分子量（Ｍｗ）は２９，３００、Ｍｗ／Ｍｎは２．２８であった。 (Synthesis of polybenzoxazole (PBO) precursor)
In a 0.5 liter flask equipped with a stirrer and a thermometer, 212 g of N-methylpyrrolidone was charged and 28.00 g (76.5 mmol) of bis (3-amino-4-hydroxyamidophenyl) hexafluoropropane was 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., 25.00 g (83.2 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 collected and dried under reduced pressure to obtain a polybenzoxazole (PBO) precursor A1 having the following repeating structure at the carboxyl group end. The number average molecular weight (Mn) of the polybenzoxazole precursor A1 was 12,900, the weight average molecular weight (Mw) was 29,300, and Mw / Mn was 2.28.
Figure JPOXMLDOC01-appb-I000013
Figure JPOXMLDOC01-appb-I000013
（実施例１、２、比較例１～１１）
　上記で合成したベンゾオキサゾール前駆体１００質量部に対して、ジアゾナフトキノン（ＤＮＱ）１０質量部と下記表１に記載の架橋剤５質量部、シランカップリング剤５質量部を配合した後、ベンゾオキサゾール前駆体が３０質量％になるようにＮ－メチルピロリドン（ＮＭＰ）を加えてワニスとし、スピンコーターを用いてシリコン基板上に塗布した。ホットプレートで１２０℃３分乾燥させ、感光性樹脂組成物の乾燥塗膜を得た。得られた乾燥塗膜に高圧水銀ランプを用い、パターンが刻まれたマスクを介して２００ｍＪ／ｃｍ２のブロード光を照射した。露光後２．３８％テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）水溶液にて６０秒現像し、水でリンスし、ポジ型パターン膜を得た。 (Examples 1 and 2 and Comparative Examples 1 to 11)
After blending 10 parts by mass of diazonaphthoquinone (DNQ), 5 parts by mass of the crosslinking agent described in Table 1 below and 5 parts by mass of the silane coupling agent with respect to 100 parts by mass of the benzoxazole precursor synthesized above, benzoxazole N-methylpyrrolidone (NMP) was added so that the precursor would be 30% by mass to form a varnish, which was applied onto a silicon substrate using a spin coater. It was dried at 120 ° C. for 3 minutes on a hot plate to obtain a dry coating film of the photosensitive resin composition. The resulting dried coating film was irradiated with broad light of 200 mJ / cm 2 through a mask in which a pattern was engraved using a high-pressure mercury lamp. After the exposure, the film was developed with an aqueous 2.38% tetramethylammonium hydroxide (TMAH) solution for 60 seconds and rinsed with water to obtain a positive pattern film.
　尚、下記表１中、メラミン系架橋剤として架橋剤１（三和ケミカル社製ニカラックＭＷ３９０）を用いた。また、アリールアミノ基を有するシランカップリング剤、および、二つ以上のトリアルコキシシリル基を有するシランカップリング剤として、それぞれカップリング剤１（信越シリコーン社製ＫＢＭ－５７３）および２（信越シリコーン社製ＫＢＭ－３０６６）を用いた。 In Table 1 below, crosslinker 1 (Nikalac MW390, manufactured by Sanwa Chemical Co., Ltd.) was used as the melamine-based crosslinker. As silane coupling agents having an arylamino group and silane coupling agents having two or more trialkoxysilyl groups, coupling agents 1 (KBM-573 manufactured by Shin-Etsu Silicone) and 2 (Shin-Etsu Silicone) KBM-3066) was used.
（未露光部残膜率の評価）
　現像後のパターン膜において膜厚を測定し、現像前の膜厚との比をとることで未露光部残膜率をそれぞれ求め、下記基準で評価した。
○：未露光部残膜率が７５％以上
×：未露光部残膜率が７５％未満 (Evaluation of unexposed area remaining film rate)
The film thickness was measured in the pattern film after development, and the ratio of the film thickness before development was determined to determine the unexposed portion residual film ratio, and evaluated according to the following criteria.
○: Unexposed portion remaining film rate is 75% or more ×: Unexposed portion remaining film rate is less than 75%
（解像度の評価）
　現像後のパターン膜を電子顕微鏡（ＳＥＭ“ＪＳＭ－６０１０”）で観察し露光部をスカムなくパターニングできる最少パターンの大きさを解像度（Ｌ（μｍ）／Ｓ（μｍ））とした。 (Resolution evaluation)
The developed pattern film was observed with an electron microscope (SEM “JSM-6010”), and the resolution (L (μm) / S (μm)) was defined as the minimum pattern size that can pattern the exposed portion without scum.
Figure JPOXMLDOC01-appb-T000014
 ＊：現像後に残膜しなかった。
Figure JPOXMLDOC01-appb-T000014
 *: No film remained after development.
架橋剤１　　　　　　　　　　　　　　架橋剤２
Figure JPOXMLDOC01-appb-I000015
架橋剤３　　　　　　　　　　　　　　架橋剤４
Figure JPOXMLDOC01-appb-I000016
架橋剤５　　　　　　　　　　　　　　架橋剤６
Figure JPOXMLDOC01-appb-I000017
Crosslinker 1 Crosslinker 2
Figure JPOXMLDOC01-appb-I000015
Crosslinker 3 Crosslinker 4
Figure JPOXMLDOC01-appb-I000016
Crosslinker 5 Crosslinker 6
Figure JPOXMLDOC01-appb-I000017
カップリング剤１　　　　　　　　　　
Figure JPOXMLDOC01-appb-I000018
カップリング剤２
Figure JPOXMLDOC01-appb-I000019
カップリング剤３
Figure JPOXMLDOC01-appb-I000020
カップリング剤４
Figure JPOXMLDOC01-appb-I000021
カップリング剤５
Figure JPOXMLDOC01-appb-I000022
カップリング剤６
Figure JPOXMLDOC01-appb-I000023
カップリング剤７
Figure JPOXMLDOC01-appb-I000024
カップリング剤８
Figure JPOXMLDOC01-appb-I000025
Coupling agent 1
Figure JPOXMLDOC01-appb-I000018
Coupling agent 2
Figure JPOXMLDOC01-appb-I000019
Coupling agent 3
Figure JPOXMLDOC01-appb-I000020
Coupling agent 4
Figure JPOXMLDOC01-appb-I000021
Coupling agent 5
Figure JPOXMLDOC01-appb-I000022
Coupling agent 6
Figure JPOXMLDOC01-appb-I000023
Coupling agent 7
Figure JPOXMLDOC01-appb-I000024
Coupling agent 8
Figure JPOXMLDOC01-appb-I000025
　表１に示す結果から、前記の特定の架橋剤とシランカップリング剤を含有する本発明のポジ型感光性樹脂組成物は、残膜率に優れることがわかる。 From the results shown in Table 1, it can be seen that the positive photosensitive resin composition of the present invention containing the specific crosslinking agent and the silane coupling agent is excellent in the remaining film ratio.
（実施例３～６）
　上記で合成したベンゾオキサゾール前駆体１００質量部に対して、ジアゾナフトキノン（ＤＮＱ）１０質量部と下記表２に記載の各架橋剤５質量部、シランカップリング剤５質量部、ｔ－ブチルカテコール０．５質量部を配合した後、ベンゾオキサゾール前駆体が３０質量％になるようにＮ－メチルピロリドン（ＮＭＰ）を加えてワニスとし、スピンコーターを用いてシリコン基板上に塗布した。ホットプレートで１２０℃３分乾燥させ、感光性樹脂組成物の乾燥塗膜を得た。得られた乾燥塗膜に高圧水銀ランプを用い、パターンが刻まれたマスクを介して２００ｍＪ／ｃｍ２のブロード光を照射した。露光後２．３８％テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）水溶液にて６０秒現像し、水でリンスし、ポジ型パターン膜を得た。 (Examples 3 to 6)
Based on 100 parts by mass of the benzoxazole precursor synthesized above, 10 parts by mass of diazonaphthoquinone (DNQ), 5 parts by mass of each cross-linking agent described in Table 2 below, 5 parts by mass of silane coupling agent, t-butylcatechol 0 After blending 0.5 parts by mass, N-methylpyrrolidone (NMP) was added so that the benzoxazole precursor was 30% by mass to form a varnish, which was applied onto a silicon substrate using a spin coater. It was dried at 120 ° C. for 3 minutes on a hot plate to obtain a dry coating film of the photosensitive resin composition. The resulting dried coating film was irradiated with broad light of 200 mJ / cm 2 through a mask in which a pattern was engraved using a high-pressure mercury lamp. After the exposure, the film was developed with an aqueous 2.38% tetramethylammonium hydroxide (TMAH) solution for 60 seconds and rinsed with water to obtain a positive pattern film.
　尚、下記表２中、メラミン系架橋剤として上記架橋剤１（三和ケミカル社製ニカラックＭＷ３９０）を用いた。また、アリールアミノ基を有するシランカップリング剤として、上記カップリング剤１（信越シリコーン社製ＫＢＭ－５７３）を用いた。メラミン系架橋剤以外の他の架橋剤として、上記架橋剤２、５および６を用いた。 In addition, in the following Table 2, the said crosslinking agent 1 (Sanwa Chemical Co., Ltd. product Nikalac MW390) was used as a melamine type crosslinking agent. Further, the above coupling agent 1 (KBM-573 manufactured by Shin-Etsu Silicone Co., Ltd.) was used as a silane coupling agent having an arylamino group. As other crosslinking agents other than the melamine-based crosslinking agent, the above-mentioned crosslinking agents 2, 5 and 6 were used.
　下記表２中、上記と同様の方法で未露光部残膜率および解像度を評価した。 In Table 2 below, the unexposed portion residual film ratio and resolution were evaluated in the same manner as described above.
（スカムの確認方法）
　現像後パターンの断面画像を確認し、パターンの裾引きがなくスカムがきれいになくなっているものを〇、パターンの裾引きはあるがシリコン基板面まで現像できているものを△、スカムが残っているものを×とした。また、〇、△、×の評価例をそれぞれ図１～３に示す。 (How to check scum)
Check the cross-sectional image of the pattern after development. If the pattern does not have a skirt and the scum is not clean, it is ◯. If the pattern is skirted but is developed to the silicon substrate surface, the scum remains. The thing was set as x. Moreover, evaluation examples of ○, Δ, and × are shown in FIGS. 1 to 3, respectively.
　表１中の実施例１の感光性樹脂組成物についても同様に評価し、実施例３～６と共に結果を表２に示す。 The photosensitive resin composition of Example 1 in Table 1 was also evaluated in the same manner, and the results are shown in Table 2 together with Examples 3 to 6.
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000026
ｔ－ブチルカテコール
Figure JPOXMLDOC01-appb-I000027
t-Butylcatechol
Figure JPOXMLDOC01-appb-I000027
（実施例７、８、比較例１２～２５）
　上記で合成したベンゾオキサゾール前駆体１００質量部に対して、ジアゾナフトキノン（ＤＮＱ）１０質量部と下記表３に記載の架橋剤５質量部、シランカップリング剤５質量部、ｔ－ブチルカテコール０．５質量部を配合した後、ベンゾオキサゾール前駆体が３０質量％になるようにＮ－メチルピロリドン（ＮＭＰ）を加えてワニスとし、スピンコーターを用いてシリコン基板上に塗布した。ホットプレートで１２０℃３分乾燥させ、感光性樹脂組成物の乾燥塗膜を得た。得られた乾燥塗膜に高圧水銀ランプを用い、パターンが刻まれたマスクを介して２００ｍＪ／ｃｍ２のブロード光を照射した。露光後２．３８％テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）水溶液にて６０秒現像し、水でリンスし、ポジ型パターン膜を得た。 (Examples 7 and 8, Comparative Examples 12 to 25)
With respect to 100 parts by mass of the benzoxazole precursor synthesized above, 10 parts by mass of diazonaphthoquinone (DNQ), 5 parts by mass of a crosslinking agent described in Table 3 below, 5 parts by mass of a silane coupling agent, 0. After blending 5 parts by mass, N-methylpyrrolidone (NMP) was added so that the benzoxazole precursor was 30% by mass to form a varnish, which was applied onto a silicon substrate using a spin coater. It was dried at 120 ° C. for 3 minutes on a hot plate to obtain a dry coating film of the photosensitive resin composition. The resulting dried coating film was irradiated with broad light of 200 mJ / cm 2 through a mask in which a pattern was engraved using a high-pressure mercury lamp. After the exposure, the film was developed with an aqueous 2.38% tetramethylammonium hydroxide (TMAH) solution for 60 seconds and rinsed with water to obtain a positive pattern film.
　尚、下記表３中、メラミン系架橋剤として上記架橋剤１（三和ケミカル社製ニカラックＭＷ３９０）を用いた。また、アリールアミノ基を有するシランカップリング剤、および、二つ以上のトリアルコキシシリル基を有するシランカップリング剤として、それぞれ上記カップリング剤１（信越シリコーン社製ＫＢＭ－５７３）および２（信越シリコーン社製ＫＢＭ－３０６６）を用いた。 In addition, in the following Table 3, the said crosslinking agent 1 (Sanwa Chemical Co., Ltd. product Nikalac MW390) was used as a melamine type crosslinking agent. Further, as the silane coupling agent having an arylamino group and the silane coupling agent having two or more trialkoxysilyl groups, the above coupling agents 1 (KBM-573 manufactured by Shin-Etsu Silicone Co., Ltd.) and 2 (Shin-Etsu Silicone), respectively. KBM-3066) was used.
　下記表３中、上記と同様の方法で未露光部残膜率、解像度およびスカムを評価した。 In Table 3 below, the unexposed remaining film ratio, resolution and scum were evaluated in the same manner as described above.
Figure JPOXMLDOC01-appb-T000028
 ＊：現像後に残膜しなかった。
Figure JPOXMLDOC01-appb-T000028
 *: No film remained after development.
カップリング剤９
Figure JPOXMLDOC01-appb-I000029
カップリング剤１０
Figure JPOXMLDOC01-appb-I000030
カップリング剤１１
Figure JPOXMLDOC01-appb-I000031
Coupling agent 9
Figure JPOXMLDOC01-appb-I000029
Coupling agent 10
Figure JPOXMLDOC01-appb-I000030
Coupling agent 11
Figure JPOXMLDOC01-appb-I000031
　表２、３に示す結果からも、前記の特定の架橋剤とシランカップリング剤を含有する本発明のポジ型感光性樹脂組成物は、残膜率に優れることがわかる。また、本発明のポジ型感光性樹脂組成物にｔ－ブチルカテコールを配合することによって、現像残渣が少なく、現像性がより優れることがわかる。さらに、本発明のポジ型感光性樹脂組成物に他の架橋剤を配合することによって、現像性がより優れることがわかる。
  From the results shown in Tables 2 and 3, it can be seen that the positive photosensitive resin composition of the present invention containing the specific crosslinking agent and the silane coupling agent is excellent in the remaining film ratio. It can also be seen that by adding t-butylcatechol to the positive photosensitive resin composition of the present invention, there are few development residues and the developability is more excellent. Furthermore, it turns out that developability is more excellent by mix | blending another crosslinking agent with the positive photosensitive resin composition of this invention.

Claims (7)

  1. 　（Ａ）ポリベンゾオキサゾール前駆体、
    　（Ｂ）光酸発生剤、
    　（Ｃ）メラミン系架橋剤、および、
    　（Ｄ）シランカップリング剤
    　を含むポジ型感光性樹脂組成物であって、
    　前記（Ｄ）シランカップリング剤として、アリールアミノ基を有するシランカップリング剤および二つ以上のトリアルコキシシリル基を有するシランカップリング剤から選ばれる少なくとも１種を含むことを特徴とするポジ型感光性樹脂組成物。     (A) a polybenzoxazole precursor,
    (B) a photoacid generator,
    (C) a melamine-based crosslinking agent, and
    (D) a positive photosensitive resin composition containing a silane coupling agent,
    The positive photosensitivity comprising (D) at least one selected from a silane coupling agent having an arylamino group and a silane coupling agent having two or more trialkoxysilyl groups as the silane coupling agent. Resin composition.
  2. 　前記（Ｄ）シランカップリング剤として、アリールアミノ基を有するシランカップリング剤を含むことを特徴とする請求項１に記載のポジ型感光性樹脂組成物。 The positive photosensitive resin composition according to claim 1, wherein the silane coupling agent (D) includes a silane coupling agent having an arylamino group.
  3. 　さらに、ｔ－ブチルカテコールを含むことを特徴とする請求項１に記載のポジ型感光性樹脂組成物。 The positive photosensitive resin composition according to claim 1, further comprising t-butylcatechol.
  4. 　請求項１記載のポジ型感光性樹脂組成物を、フィルムに塗布、乾燥して得られる樹脂層を有することを特徴とするドライフィルム。 A dry film comprising a resin layer obtained by applying the positive photosensitive resin composition according to claim 1 to a film and drying the film.
  5. 　請求項１～３のいずれか一項に記載のポジ型感光性樹脂組成物または請求項４記載のドライフィルムの樹脂層を、硬化して得られることを特徴とする硬化物。 A cured product obtained by curing the positive photosensitive resin composition according to any one of claims 1 to 3 or the resin layer of the dry film according to claim 4.
  6. 　請求項５記載の硬化物を有することを特徴とするプリント配線板。 A printed wiring board comprising the cured product according to claim 5.
  7. 　請求項５記載の硬化物を有することを特徴とする半導体素子。
          A semiconductor device comprising the cured product according to claim 5.
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