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WO2018056013A1 - Composition de résine photosensible positive, film sec, produit durci, carte de circuits imprimés et élément semi-conducteur - Google Patents

Composition de résine photosensible positive, film sec, produit durci, carte de circuits imprimés et élément semi-conducteur 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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WIPO (PCT)
Prior art keywords
resin composition
photosensitive resin
silane coupling
coupling agent
film
Prior art date
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Ceased
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PCT/JP2017/031248
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English (en)
Japanese (ja)
Inventor
真歩 秋元
成強 許
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Taiyo Holdings Co Ltd
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Taiyo Holdings Co Ltd
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Filing date
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Priority to JP2018540942A priority Critical patent/JP7011591B2/ja
Priority to CN201780057125.XA priority patent/CN109716235B/zh
Priority to KR1020197011002A priority patent/KR102385641B1/ko
Publication of WO2018056013A1 publication Critical patent/WO2018056013A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials For Photolithography (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

L'invention concerne : une composition de résine photosensible positive ayant un excellent rapport de rétention de film ; un film sec ayant une couche de résine qui est obtenue à partir de cette composition ; un produit durci de cette composition ou de la couche de résine de ce film sec ; une carte de circuit imprimé ayant ce produit durci ; et un élément semi-conducteur ayant ce produit durci. Une composition de résine photosensible positive qui contient (A) un précurseur de polybenzoxazole, (B) un générateur de photoacide, (C) un agent de réticulation à base de mélamine et (D) un agent de couplage silane, et qui est caractérisé en ce qu'au moins un agent de couplage silane choisi parmi des agents de couplage silane ayant un groupe arylamino et des agents de couplage silane ayant deux groupes trialcoxysilyle ou plus est contenu en tant qu'agent de couplage silane (D) ; et analogues.
PCT/JP2017/031248 2016-09-20 2017-08-30 Composition de résine photosensible positive, film sec, produit durci, carte de circuits imprimés et élément semi-conducteur Ceased WO2018056013A1 (fr)

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JP2018540942A JP7011591B2 (ja) 2016-09-20 2017-08-30 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
CN201780057125.XA CN109716235B (zh) 2016-09-20 2017-08-30 正型感光性树脂组合物、干膜、固化物、印刷电路板及半导体元件
KR1020197011002A KR102385641B1 (ko) 2016-09-20 2017-08-30 포지티브형 감광성 수지 조성물, 드라이 필름, 경화물, 프린트 배선판 및 반도체 소자

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JP7011591B2 (ja) 2022-01-26
TWI743196B (zh) 2021-10-21
CN109716235A (zh) 2019-05-03
CN109716235B (zh) 2022-11-18

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