WO2009123122A1 - 塩基発生剤、感光性樹脂組成物、当該感光性樹脂組成物からなるパターン形成用材料、当該感光性樹脂組成物を用いたパターン形成方法並びに物品 - Google Patents
塩基発生剤、感光性樹脂組成物、当該感光性樹脂組成物からなるパターン形成用材料、当該感光性樹脂組成物を用いたパターン形成方法並びに物品 Download PDFInfo
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- WO2009123122A1 WO2009123122A1 PCT/JP2009/056511 JP2009056511W WO2009123122A1 WO 2009123122 A1 WO2009123122 A1 WO 2009123122A1 JP 2009056511 W JP2009056511 W JP 2009056511W WO 2009123122 A1 WO2009123122 A1 WO 2009123122A1
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- resin composition
- photosensitive resin
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- base generator
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- 0 *c(c(*)c1*)c(*)c(C=CC(N(*)*)=O)c1O Chemical compound *c(c(*)c1*)c(*)c(C=CC(N(*)*)=O)c1O 0.000 description 1
- QVFKFFGNOQHGKL-ZHACJKMWSA-N CC(CCCC1C)N1C(/C=C/c1ccccc1O)=O Chemical compound CC(CCCC1C)N1C(/C=C/c1ccccc1O)=O QVFKFFGNOQHGKL-ZHACJKMWSA-N 0.000 description 1
- IITZCEJJNUEXJY-PKNBQFBNSA-N Oc1ccc(cccc2)c2c1/C=C/C(N1CCCCC1)=O Chemical compound Oc1ccc(cccc2)c2c1/C=C/C(N1CCCCC1)=O IITZCEJJNUEXJY-PKNBQFBNSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/22—Polybenzoxazoles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
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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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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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
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0387—Polyamides or polyimides
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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
- G03F7/20—Exposure; Apparatus therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/114—Initiator containing
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/114—Initiator containing
- Y10S430/12—Nitrogen compound containing
Definitions
- the present invention relates to a base generator that generates a base upon irradiation and heating of electromagnetic waves, and a photosensitive resin composition using the base generator, and in particular, a product formed through a patterning step or a curing acceleration step using electromagnetic waves.
- a photosensitive resin composition that can be suitably used as a material for a member, a pattern forming material comprising the photosensitive resin composition, a pattern forming method, and an article produced using the resin composition. is there.
- the photosensitive resin composition is used for, for example, an electronic component, an optical product, a molding material of an optical component, a layer forming material or an adhesive, and particularly preferably used for a product or a member formed through a patterning process using electromagnetic waves.
- polyimide which is a polymer material, exhibits top-class performance among organic materials such as heat resistance, dimensional stability, and insulation characteristics, so it is widely applied to insulating materials for electronic components. It has been actively used as a coating film, a base material for flexible printed wiring boards, and the like.
- polybenzoxazole which has low water absorption and low dielectric constant, and polybenzimidazole with excellent adhesion to the substrate, to which processing processes similar to polyimide are applied, etc. It has been studied energetically.
- polyimide is poorly soluble in a solvent and difficult to process.
- patterning is performed by exposure and development in the state of a polyimide precursor having excellent solvent solubility, and then heat treatment. For example, there is a method of obtaining a polyimide pattern by imidization by the method described above.
- a method of forming a pattern by providing a photosensitive resin as a resist layer on a polyimide precursor and (2) bonding or coordination of a photosensitive site to the polyimide precursor itself.
- a method of forming a pattern by its action Alternatively, a method in which a photosensitive component is mixed with a polyimide precursor to form a resin composition, and a pattern is formed by the action of the photosensitive component.
- a polyimide precursor polyamic acid acts as a dissolution inhibitor before exposure to electromagnetic waves, and after exposure, a carboxylic acid is formed to form a dissolution accelerator;
- the naphthoquinonediazide derivative is mixed, and pattern formation is performed by increasing the contrast of the dissolution rate of the exposed area and unexposed area to the developer, followed by imidization to obtain a polyimide pattern
- Patent Document 1 A methacryloyl group is introduced into the polyimide precursor via an ester bond or an ionic bond, a photo radical generator is added thereto, and the exposed area is crosslinked to dissolve the exposed and unexposed areas in the developer. The pattern is formed by increasing the contrast of the speed, and then imidization is performed to obtain a polyimide pattern. Etc. have been put into practical use (Patent Document 2).
- the method (2) does not require a resist layer and can greatly simplify the process.
- a naphthoquinonediazide derivative is used to increase the solubility contrast.
- the amount of addition is increased, there is a problem that the original physical properties of the polyimide cannot be obtained.
- the method (ii) has a problem that the structure of the polyimide precursor is restricted.
- a polyamic acid as a polyimide precursor is mixed with a photobase generator and heated after exposure to cause cyclization to proceed by the action of a base generated by exposure.
- a technique for obtaining a polyimide pattern by reducing the solubility, forming a pattern by increasing the contrast of the dissolution rate in the developing solution of the exposed part and the unexposed part, and then imidizing is reported ( Patent Document 3).
- photosensitive resin composition using the photobase generator examples include an epoxy compound (for example, Patent Document 4).
- an epoxy compound for example, Patent Document 4
- amines are generated in the layer containing the epoxy compound, so that the amines act as an initiator or a catalyst, and the epoxy compound can be cured only in the exposed area. Pattern formation can be performed.
- a photosensitive resin composition using a photobase generator is a resin composition because a photosensitive polymer precursor can be obtained simply by mixing a photobase generator at a certain ratio with an existing polymer precursor.
- the process for manufacturing is simple.
- a polyimide precursor in which the structure of a precursor compound used in the past is restricted has an advantage of high versatility because it can be applied to polyimide precursors having various structures.
- conventional photobase generators have low sensitivity, there has been a problem that the amount of electromagnetic wave irradiation increases. When the amount of electromagnetic wave irradiation increases, there is also a problem that the processing amount (throughput) per unit time decreases.
- a polyimide precursor when combined with a polyimide precursor, a polyimide precursor that is originally highly soluble in the developer due to the mechanism that only the exposed part is imidized by the catalytic action of the base generated by exposure and the part becomes insoluble in the developer.
- the dissolution rate of the exposed area is also fast, and there is a limit to increasing the solubility contrast of the exposed area and the unexposed area.
- the solubility contrast between the exposed area and the unexposed area increases, the remaining film ratio after development increases and a pattern having a better shape can be obtained.
- the process margin was reduced because it was necessary to adjust the concentration and amount of photobase generator and to add a dissolution accelerator.
- the present invention has been made in view of the above circumstances, and its main purpose is excellent in sensitivity and a base generator that can be used regardless of the type of the polymer precursor, and excellent in sensitivity and polymer precursor.
- a photosensitive resin composition capable of obtaining a pattern having a good shape while maintaining a sufficient process margin, with a large solubility contrast between the exposed and unexposed areas, regardless of the type. There is to do.
- the base generator according to the present invention is represented by the following chemical formula (1) and is characterized by generating a base upon irradiation with electromagnetic waves and heating.
- R 1 and R 2 are each independently hydrogen or a monovalent organic group, and may be the same or different.
- R 1 and R 2 are bonded to each other. May form a cyclic structure and may include a heteroatom bond, provided that at least one of R 1 and R 2 is a monovalent organic group
- R 3 , R 4 , R 5 And R 6 are each independently hydrogen, halogen, hydroxyl group, nitro group, nitroso group, mercapto group, silyl group, silanol group or monovalent organic group, and may be the same or different.
- 3 , R 4 , R 5, and R 6 may be bonded to each other to form a cyclic structure or may include a hetero atom bond.
- the base generator represented by the chemical formula (1) Since the base generator represented by the chemical formula (1) has the above specific structure, it generates a basic substance with a small amount of electromagnetic wave irradiation by combining irradiation with electromagnetic waves and heating, and thus has high sensitivity and high It can be used regardless of the type of molecular precursor and is a versatile base generator.
- the photosensitive resin composition according to the present invention relates to a polymer precursor whose reaction to the final product is accelerated by heating with a basic substance or in the presence of the basic substance, and the above-described present invention. It contains a base generator.
- the photosensitive resin composition according to the present invention is represented by the chemical formula (1) and generates a base upon irradiation with electromagnetic waves and heating, with a basic substance or by heating in the presence of a basic substance.
- the base generator preferably has a high sensitivity as a base generator, wherein the generated base is a secondary amine and / or heterocyclic compound having one NH group capable of forming an amide bond. Moreover, it is preferable from the viewpoint of strong basicity and large catalytic effect.
- the base generator is represented by the formula (1), wherein at least one of R 3 , R 4 , R 5 and R 6 is halogen, hydroxyl group, nitro group, nitroso group, mercapto group, silyl group, silanol. is a group or a monovalent organic group, or, R 3, R 4, 2 or more are bonded to R 5 and R 6, R 3, R 4, benzene R 5 and R 6 are attached Forming a condensed ring with the ring is preferable in that it can be adjusted so as to absorb a desired wavelength, and to improve solubility and compatibility with a polymer precursor to be combined.
- the base generator preferably has a boiling point of the generated base of 25 ° C. or higher and a weight loss at 350 ° C. of 80% or higher.
- the generated base has a boiling point of 25 ° C. or more, handling at room temperature becomes easy, and when the weight loss at 350 ° C. is 80% or more, it is easy to suppress the base from remaining in the cured polymer. Because.
- the structure of the generated base is represented by the following formula (2) from the viewpoint that the sensitivity as a base generator is high, the basicity is strong, and the catalytic effect is large. preferable.
- R 1 and R 2 are each independently a monovalent organic group having an alkyl group having 1 to 10 carbon atoms which may have a substituent, or a substituent. Or a cycloalkyl group having 4 to 12 carbon atoms, R 1 and R 2 may be the same or different, and R 1 and R 2 are bonded to form a cyclic structure. Or may contain a heteroatom bond.
- the base generator has absorption at at least one of the wavelengths of electromagnetic waves of 365 nm, 405 nm, or 436 nm from the viewpoint of further increasing the types of applicable polymer precursors.
- the polymer precursor includes a compound and polymer having an epoxy group, an isocyanate group, an oxetane group, or a thiirane group, a polysiloxane precursor, a polyimide precursor, and a polybenzo.
- One or more selected from the group consisting of oxazole precursors is preferably used.
- the polymer precursor is soluble in a basic solution because the solubility contrast between the exposed portion and the unexposed portion can be increased.
- a polyimide precursor such as polyamic acid or a polybenzoxazole precursor can be used as the polymer precursor of the photosensitive resin composition.
- a photosensitive resin composition having excellent physical properties such as heat resistance, dimensional stability, and insulating properties can be obtained.
- the polyimide precursor is preferably a polyamic acid from the viewpoint of easy availability of raw materials.
- the present invention also provides a pattern forming material comprising the photosensitive resin composition according to the present invention.
- this invention provides the pattern formation method using the said photosensitive resin composition.
- a coating film or a molded body is formed using the photosensitive resin composition, the coating film or the molded body is irradiated with electromagnetic waves in a predetermined pattern, and after irradiation or simultaneously with irradiation. It develops, after heating and changing the solubility of the said irradiation site
- a coating film or a molded body made of a photosensitive resin composition is used by combining a polymer precursor and a compound represented by the above formula (1) as a base generator.
- a pattern for performing development can be formed without using a resist film for protecting the surface from the developer.
- the present invention also provides a printed material, a paint, a sealant, an adhesive, a display device, a semiconductor device, an electronic component, a microelectromechanical system, light, which is at least partly formed of the photosensitive resin composition or a cured product thereof.
- a printed material a paint, a sealant, an adhesive, a display device, a semiconductor device, an electronic component, a microelectromechanical system, light, which is at least partly formed of the photosensitive resin composition or a cured product thereof.
- Articles of either shaped objects, optical members or building materials are also provided.
- the base generator of the present invention has a structure represented by the formula (1), a base is generated by irradiation with electromagnetic waves, and further generation of the base is promoted by heating. It has excellent sensitivity compared to the generator. Moreover, when using it for the photosensitive resin composition, it can be utilized combining regardless of the kind of polymer precursor.
- the base generator represented by the formula (1) included has a sensitivity superior to that of a conventionally used photobase generator. It is a composition.
- the photosensitive resin composition of the present invention has a phenolic hydroxyl group when the base is generated in addition to the change in solubility of the polymer precursor by the base derived from the base generator by irradiation and heating of electromagnetic waves.
- the photosensitive resin composition of the present invention can use the heating step in heating that promotes the generation of a base. , It has the advantage that the irradiation amount of electromagnetic waves can be reduced. Therefore, when used in a process including such a heating process, the photosensitive resin composition of the present invention can be streamlined compared to a conventional resin composition that generates a base only by electromagnetic wave irradiation.
- FIG. 1 is a graph showing the relationship between the thermosetting temperature after ultraviolet irradiation of a fully exposed coating film and an unexposed coating film prepared using the photosensitive resin composition (1), and the remaining amount of the polyimide precursor. is there.
- FIG. 2 is a graph showing the relationship between the exposure amount and the remaining film ratio, which was prepared using the photosensitive resin compositions (2), (3), and (4) and the comparative photosensitive resin composition (1). .
- (meth) acryloyl means acryloyl and / or methacryloyl
- (meth) acryl means acryl and / or methacryl
- (meth) acrylate means acrylate and / or methacrylate.
- the electromagnetic wave is not only an electromagnetic wave having a wavelength in the visible and invisible regions, but also a particle beam such as an electron beam, and radiation or a general term for the electromagnetic wave and the particle beam, unless the wavelength is specified. Contains ionizing radiation. In this specification, irradiation with electromagnetic waves is also referred to as exposure.
- the base generator according to the present invention is represented by the following formula (1), and generates a base by irradiation with electromagnetic waves and heating.
- R 1 and R 2 are each independently hydrogen or a monovalent organic group, and may be the same or different.
- R 1 and R 2 are bonded to each other. May form a cyclic structure and may include a heteroatom bond, provided that at least one of R 1 and R 2 is a monovalent organic group
- R 3 , R 4 , R 5 And R 6 are each independently hydrogen, halogen, hydroxyl group, nitro group, nitroso group, mercapto group, silyl group, silanol group or monovalent organic group, and may be the same or different.
- 3 , R 4 , R 5, and R 6 may be bonded to each other to form a cyclic structure or may include a hetero atom bond.
- the base generator of the present invention is a kind of photobase generator, and generates bases only by being irradiated with electromagnetic waves, but generation of bases is promoted by appropriate heating.
- the base generator of the present invention can efficiently generate a base with a small amount of electromagnetic wave irradiation by combining electromagnetic wave irradiation and heating, and has a higher sensitivity than conventional so-called photobase generators.
- the photobase generator refers to an agent that does not exhibit activity under normal conditions of normal temperature and pressure, but generates a base when electromagnetic waves are applied as an external stimulus.
- the base generator according to the present invention has the above specific structure, as shown by the following formula, (—CH ⁇ CH—C ( ⁇ O) — ) Moiety isomerizes to the cis form and further cyclized by heating to produce the base (NHR 1 R 2 ).
- the temperature at which the reaction when the polymer precursor becomes the final product can be lowered, or the curing reaction where the polymer precursor becomes the final product can be started.
- the base generator represented by the chemical formula (1) When the base generator represented by the chemical formula (1) is cyclized, the phenolic hydroxyl group disappears, the solubility changes, and in the case of a basic aqueous solution, the solubility decreases.
- the polymer precursor contained in the photosensitive resin composition according to the present invention is a polyimide precursor or a polybenzoxazole precursor, the solubility is further reduced due to the reaction of the precursor to the final product. It has a function of assisting, and it becomes possible to increase the solubility contrast between the exposed portion and the unexposed portion.
- R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group, and at least one of R 1 and R 2 is a monovalent organic group.
- NHR 1 R 2 is a base (in the present invention, “basic substance” is simply referred to as a base), but R 1 and R 2 are each an organic group that does not contain an amino group. Is preferred. If an amino group is contained in R 1 and R 2 , the base generator itself becomes a basic substance, which accelerates the reaction of the polymer precursor, resulting in a solubility contrast between the exposed and unexposed areas. There is a risk of the difference becoming smaller.
- the organic group of R 1 and R 2 contains an amino group.
- the monovalent organic group include a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, an aryl group, an aralkyl group, and a saturated or unsaturated halogenated alkyl group.
- These organic groups may contain bonds and substituents other than hydrocarbon groups such as heteroatoms in the organic group, and these may be linear or branched.
- R 1 and R 2 may be bonded to form a cyclic structure.
- the cyclic structure is a combination of two or more selected from the group consisting of saturated or unsaturated alicyclic hydrocarbons, heterocycles, and condensed rings, and the alicyclic hydrocarbons, heterocycles, and condensed rings. The structure which becomes may be sufficient.
- the substituent other than the hydrocarbon group in the organic group of R 1 and R 2 is not particularly limited, and is a halogen atom, a hydroxyl group, a mercapto group, a cyano group, a silyl group, a silanol group, an alkoxy group, an alkoxycarbonyl group, Nitro group, carboxyl group, acyl group, acyloxy group, sulfino group, sulfo group, saturated or unsaturated alkyl ether group, saturated or unsaturated alkyl thioether group, aryl ether group, aryl thioether group, amino group (-NH 2 , —NHR, —NRR ′: R and R ′ are each independently a hydrocarbon group.
- These groups may be linear, branched or cyclic.
- substituent other than the hydrocarbon group in the organic group of R 1 and R 2 include a halogen atom, a hydroxyl group, a mercapto group, a cyano group, a silyl group, a silanol group, an alkoxy group, an alkoxycarbonyl group, a nitro group, and an acyl group.
- An acyloxy group, a saturated or unsaturated alkyl ether group, a saturated or unsaturated alkyl thioether group, an aryl ether group, and an aryl thioether group are preferred.
- the generated base is NHR 1 R 2
- a primary amine, a secondary amine, or a heterocyclic compound is exemplified.
- the amine includes an aliphatic amine and an aromatic amine, respectively.
- the heterocyclic compound here means that NHR 1 R 2 has a cyclic structure and has aromaticity.
- Non-aromatic heterocyclic compounds that are not aromatic heterocyclic compounds are included herein as aliphatic amines as alicyclic amines.
- the NHR 1 R 2 to be produced is not only a base such as a monoamine having only one NH group capable of forming an amide bond, but also two or more NH groups capable of forming an amide bond such as diamine, triamine and tetraamine. It may be a base having.
- the generated NHR 1 R 2 is a base having two or more NH groups
- an NH group capable of forming an amide bond is formed at one or more terminals of R 1 and / or R 2 in the formula (1).
- bonded is mentioned.
- a residue other than R 1 and / or R 2 in the formula (1) is further bonded to one or more terminals of R 1 and / or R 2 in the formula (1). Structure.
- aliphatic primary amines include methylamine, ethylamine, propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, pentylamine, isoamylamine, tert-pentylamine Cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, cycloheptaneamine, octylamine, 2-octaneamine, 2,4,4-trimethylpentane-2-amine, cyclooctylamine and the like.
- aromatic primary amines examples include aniline, 2-aminophenol, 3-aminophenol, and 4-aminophenol.
- Aliphatic secondary amines include dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, ethylmethylamine, aziridine, azetidine, pyrrolidine, piperidine, azepan, azocan, methylaziridine, dimethylaziridine, methylazetidine, dimethyl Examples thereof include azetidine, trimethylazetidine, methylpyrrolidine, dimethylpyrrolidine, trimethylpyrrolidine, tetramethylpyrrolidine, methylpiperidine, dimethylpiperidine, trimethylpiperidine, tetramethylpiperidine, pentamethylpiperidine and the like, among which alicyclic amine is preferable.
- aromatic secondary amines examples include methylaniline, diphenylamine, and N-phenyl-1-naphthylamine.
- aromatic heterocyclic compound having an NH group capable of forming an amide bond an imino bond (—N ⁇ C (—R) —, —C ( ⁇ NR) —:
- R preferably has a hydrogen atom or a monovalent organic group), and examples thereof include imidazole, purine, triazole, and derivatives thereof.
- Bases having two or more NH groups capable of forming an amide bond include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7- Linear aliphatic alkylenediamines such as heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine; 1-butyl-1,2-ethanediamine, 1,1-dimethyl-1 , 4-butanediamine, 1-ethyl-1,4-butanediamine, 1,2-dimethyl-1,4-butanediamine, 1,3-dimethyl-1,4-butanediamine, 1,4-dimethyl-1 Branched aliphatic alkylenediamines such as 1,4-butanediamine and 2,3-dimethyl-1,4-butanediamine; cyclohexanediamine, methylcyclohexane Cycloaliphatic diamines such as s
- the thermal properties and basicity of the generated base are different. Catalytic action, such as lowering the reaction start temperature for the reaction from the polymer precursor to the final product, is more effective as a catalyst with a basic material having a higher basicity, and a lower temperature with a smaller amount of addition. Reaction to the final product is possible.
- secondary amines have higher basicity than primary amines, and their catalytic effect is greater.
- aliphatic amines are preferred over aromatic amines because they are more basic.
- the base generated in the present invention is a secondary amine and / or a heterocyclic compound
- the organic groups of R 1 and R 2 each independently preferably have 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly carbon atoms.
- the number is preferably 1 to 8.
- the base generated from the base generator represented by the chemical formula (1) preferably has one NH group capable of forming an amide bond.
- the base generator has two or more amide bonds that are cleaved by irradiation with electromagnetic waves and heating, for example, cinnamic acid derivatives
- photophores such as residues, per molecule.
- the molecular weight is usually increased, there is a problem that the solvent solubility is deteriorated.
- the base generated from the base generator represented by the chemical formula (1) is one having two or more NH groups capable of forming an amide bond. It can be suitably used because it can function not only as a curing accelerator but also as a curing agent.
- the structure of the generated secondary amine and / or heterocyclic compound is preferably represented by the following formula (2).
- R 1 and R 2 are each independently a monovalent organic group having an alkyl group having 1 to 10 carbon atoms which may have a substituent, or a substituent. Or a cycloalkyl group having 4 to 12 carbon atoms, R 1 and R 2 may be the same or different, and R 1 and R 2 are bonded to form a cyclic structure. Or may contain a heteroatom bond.
- the alkyl group may be linear or branched.
- the alkyl group preferably further has 1 to 8 carbon atoms
- the cycloalkyl group preferably further has 4 to 10 carbon atoms.
- An alicyclic amine having a cyclic structure having 4 to 12 carbon atoms, which R 1 and R 2 may be bonded to each other and may have a substituent, is also preferable.
- a heterocyclic compound having a cyclic structure having 2 to 12 carbon atoms which may have a substituent by bonding R 1 and R 2 is also preferable.
- R 3 , R 4 , R 5 and R 6 are each independently hydrogen, halogen, hydroxyl group, nitro group, nitroso group, mercapto group, silyl group, silanol group or monovalent organic group, and are the same May be different. Two or more of R 3 , R 4 , R 5, and R 6 may be bonded to form a cyclic structure, and may include a hetero atom bond. Examples of the halogen include fluorine, chlorine, bromine and the like.
- the monovalent organic group is not particularly limited, and examples thereof include a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, an aryl group, an aralkyl group, a saturated or unsaturated alkyl halide group, and a cyano group. .
- These organic groups may contain bonds and substituents other than hydrocarbon groups such as heteroatoms in the organic group, and these may be linear or branched.
- the bond other than the hydrocarbon group in the organic group of R 3 to R 6 is not particularly limited, and is an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, a carbonate bond, A sulfonyl bond etc. are mentioned.
- the substituent other than the hydrocarbon group in the organic group of R 3 to R 6 is not particularly limited, and is a halogen atom, hydroxyl group, mercapto group, cyano group, silyl group, silanol group, alkoxy group, nitro group, carboxyl group.
- R and R ′ are each independently a hydrocarbon group.
- substituents other than hydrocarbon groups in the organic groups of R 3 to R 6 include halogen atoms, hydroxyl groups, mercapto groups, cyano groups, silyl groups, silanol groups, alkoxy groups, alkoxycarbonyl groups, nitro groups, acyl groups.
- substituents other than hydrocarbon groups in the organic groups of R 3 to R 6 include halogen atoms, hydroxyl groups, mercapto groups, cyano groups, silyl groups, silanol groups, alkoxy groups, alkoxycarbonyl groups, nitro groups, acyl groups.
- Groups, acyloxy groups, saturated or unsaturated alkyl ether groups, saturated or unsaturated alkyl thioether groups, aryl ether groups, and aryl thioether groups are preferred.
- R 3 to R 6 may be bonded to form a cyclic structure.
- the cyclic structure is a combination of two or more selected from the group consisting of saturated or unsaturated alicyclic hydrocarbons, heterocycles, and condensed rings, and the alicyclic hydrocarbons, heterocycles, and condensed rings.
- the structure which becomes may be sufficient.
- R 3 ⁇ R 6 are formed two or more are bonded to them, naphthalene share atoms of the benzene ring of R 3 ⁇ R 6 are attached, anthracene, phenanthrene, and fused ring indene You may do it.
- R 3 , R 4 , R 5 and R 6 is preferably a halogen, a hydroxyl group, a nitro group, a nitroso group, a mercapto group, a silyl group, a silanol group or a monovalent organic group.
- the absorption wavelength can be shifted to a longer wavelength by introducing a substituent that extends the conjugated chain of the aromatic ring. It is also possible to improve the solubility and compatibility with the polymer precursor to be combined. Thereby, it is possible to improve the sensitivity of the photosensitive resin composition in consideration of the absorption wavelength of the polymer precursor to be combined.
- R 3 to R 6 include an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, a cycloalkenyl group having 4 to 13 carbon atoms, and an aryloxyalkyl group having 7 to 16 carbon atoms (—ROAr Group), an aralkyl group having 7 to 20 carbon atoms, an alkyl group having 2 to 11 carbon atoms having a cyano group, an alkyl group having 1 to 10 carbon atoms having a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, and 2 to 11 amide groups, C 1-10 alkylthio groups (—SR groups), C 1-10 acyl groups, C 2-11 ester groups, C 6-20 aryl groups, electron donating groups And / or an aryl group having 6 to 20 carbon atoms substituted with an electron-withdrawing group, a benzyl group substituted with an electron-donating group and / or an electron-with
- the alkyl moiety may be linear, branched or cyclic.
- R 3 to R 6 two or more of them are bonded to each other and a condensed ring such as naphthalene, anthracene, phenanthrene, or indene is formed by sharing the atoms of the benzene ring to which R 3 to R 6 are bonded. Even if it forms, it is preferable from the point which absorption wavelength becomes long.
- R 3, R 4, when at least one of R 5 and R 6 is a hydroxyl group, and R 3, R 4, R 5 and does not contain a hydroxyl group at R 6 Compound From the viewpoint of improving the solubility in a basic aqueous solution or the like and increasing the absorption wavelength.
- R 6 when R 6 is a phenolic hydroxyl group, a reaction site for cyclization of a compound isomerized to a cis isomer increases, which is preferable from the viewpoint of easy cyclization.
- the structure represented by the chemical formula (1) is a trans isomer and / or a cis isomer, and only the trans isomer may be used or a mixture of the trans isomer and the cis isomer may be used, but the solubility contrast is increased. Therefore, the ratio of the trans isomer is preferably 90 to 100%, and it is more preferable to use only the trans isomer.
- the temperature (5% when the weight is reduced by 5% from the initial weight by heating. % Weight reduction temperature) is preferably 100 ° C. or higher.
- a high boiling point solvent such as N-methyl-2-pyrrolidone
- the base generator of the present invention is a heating process (for example, after development) (for example, When the polymer to be combined is a polyimide precursor, it is preferably decomposed or volatilized by an imidization process).
- the temperature when the 50% weight is reduced from the initial weight (50% weight reduction temperature) is preferably 400 ° C. or less, and more preferably 350 ° C. or less.
- the boiling point of the generated base is 25 ° C. or more because the handleability at room temperature is improved.
- the boiling point of the generated base is not 25 ° C. or higher, when it is used as a coating film, the amine generated during drying tends to evaporate, which may make the operation difficult.
- the heating temperature for generating a base when using the base generator represented by the formula (1) is appropriately selected depending on the polymer precursor to be combined and the purpose, and is not particularly limited. Heating by the temperature (for example, room temperature) of the environment where the base generator is placed may be used, and in this case, the base is gradually generated. Further, since the base is also generated by heat generated as a by-product during irradiation with electromagnetic waves, heating may be performed substantially simultaneously with the heat generated as a by-product during irradiation with electromagnetic waves. From the viewpoint of increasing the reaction rate and generating the base efficiently, the heating temperature for generating the base is preferably 30 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 100 ° C.
- the suitable heating temperature is not limited to the above.
- the base generator represented by the formula (1) generates a base only by irradiation with an electromagnetic wave, but generation of the base is promoted by heating appropriately. Therefore, in order to generate a base efficiently, when using the base generator represented by the formula (1), the base is generated by heating after exposure or simultaneously with exposure. Exposure and heating may be performed alternately. The most efficient method is a method of heating simultaneously with exposure.
- the method for synthesizing the base generator represented by the chemical formula (1) of the present invention will be described by taking 2-hydroxycinnamic acid amide as an example, but the present invention is not limited to this.
- the base generator of the present invention can be synthesized by a plurality of conventionally known synthesis routes.
- 2-hydroxycinnamic amide can be synthesized, for example, by reacting 2-hydroxy cinnamic acid with cyclohexylamine.
- the desired product can be obtained by dissolving 2-hydroxycinnamic acid and cyclohexylamine in tetrahydrofuran in the presence of a condensing agent such as 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and stirring.
- Cinnamic acid into which each substituent is introduced can be synthesized by performing wittig reaction, Knoevenagel reaction, or Perkin reaction on hydroxybenzaldehyde having a corresponding substituent.
- the base generator represented by the chemical formula (1) of the present invention absorbs at least a part of the exposure wavelength in order to sufficiently exhibit the function of base generation for the polymer precursor to be the final product. It is necessary to have.
- the wavelength of a high-pressure mercury lamp that is a general exposure light source includes 365 nm, 405 nm, and 436 nm. For this reason, it is preferable that the base generator represented by the chemical formula (1) of the present invention absorbs at least one electromagnetic wave having a wavelength of 365 nm, 405 nm, or 436 nm. In such a case, it is preferable because the number of applicable polymer precursors is further increased.
- the base generator represented by the chemical formula (1) has a molar extinction coefficient of 100 or more at an electromagnetic wave wavelength of 365 nm, or 1 or more at 405 nm, and the number of applicable polymer precursors further increases. It is preferable from the point.
- the fact that the base generator represented by the chemical formula (1) of the present invention has absorption in the wavelength region is expressed by the chemical formula (1) in a solvent (for example, acetonitrile) that does not absorb in the wavelength region.
- concentration of the generated base generator is 1 ⁇ 10 ⁇ 4 mol / L or less (usually about 1 ⁇ 10 ⁇ 4 mol / L to 1 ⁇ 10 ⁇ 5 mol / L.
- an ultraviolet-visible spectrophotometer for example, UV-2550 (manufactured by Shimadzu Corporation)
- the base generator represented by the chemical formula (1) according to the present invention has excellent sensitivity as compared with conventionally used photobase generators, and therefore can be applied in various ways.
- a base such as an acid-base indicator is not limited to the combination with a polymer precursor whose reaction to the final product is accelerated by heating in the presence of a basic substance or in the presence of a basic substance, which will be described in detail later.
- various photosensitive compositions can be formed in combination with a compound whose structure and physical properties change.
- Such photosensitive compositions can be used for paints, printing inks, sealants or adhesives, display devices, semiconductor devices, electronic components, micro electro mechanical systems (MEMS), optical members, or architecture. It can be used as a material forming material.
- the photobase generator when an image forming layer is exposed in an image forming medium obtained by coating or impregnating a base material with an image forming layer containing at least a photobase generator and an acid-base indicator, the photobase generator However, it can also be applied to a display device such as an image forming medium characterized in that a base that reacts with an acid-base indicator is generated and an image is formed.
- the photosensitive resin composition according to the present invention includes a polymer precursor whose reaction to a final product is promoted by heating with a basic substance or in the presence of a basic substance, and the following chemical formula according to the present invention: It is represented by (1) and contains a base generator that generates a base by irradiation with electromagnetic waves and heating.
- R 1 and R 2 are each independently hydrogen or a monovalent organic group, and may be the same or different.
- R 1 and R 2 are bonded to each other. May form a cyclic structure and may include a heteroatom bond, provided that at least one of R 1 and R 2 is a monovalent organic group
- R 3 , R 4 , R 5 And R 6 are each independently hydrogen, halogen, hydroxyl group, nitro group, nitroso group, mercapto group, silyl group, silanol group or monovalent organic group, and may be the same or different.
- 3 , R 4 , R 5, and R 6 may be bonded to each other to form a cyclic structure or may include a hetero atom bond.
- the base generator represented by the formula (1) has the specific structure described above, and the (—CH ⁇ CH—C ( ⁇ O) —) moiety is converted into a cis isomer upon irradiation with electromagnetic waves. And then heated to generate a base (NHR 1 R 2 ). Further, when the base is generated, the structure represented by the formula (1) is cyclized. As a result, the phenolic hydroxyl group is lost, and the solubility of the basic aqueous solution in the developer is lowered. The polymer precursor is promoted to react with the final product by the action of a basic substance generated from the base generator.
- the photosensitive resin composition according to the present invention Due to such a change in solubility of the base generator and the polymer precursor, the photosensitive resin composition according to the present invention has a large difference in solubility between the exposed part and the unexposed part. The characteristic contrast increases, and pattern formation becomes possible.
- the photosensitive resin composition of the present invention has high sensitivity.
- the photosensitive resin composition of the present invention has a wide range of applicable polymer precursors, and is widely applied in fields where it is possible to make use of characteristics such as solubility changes of the polymer precursor and the base generator. The For example, it is suitably applied in a field where the characteristics of the photosensitive polyimide precursor resin composition and its imidized product can be utilized.
- the solubility contrast is increased by the change in solubility of the base generator and the polymer precursor, it is possible to suitably use a polyimide precursor that is originally highly soluble in a developer.
- the base generator used in the photosensitive resin composition according to the present invention is the same as the base generator according to the present invention. Since it can be used, explanation here is omitted. Therefore, the polymer precursor and other components that can be appropriately included as necessary will be described in order.
- the base generator and the polymer precursor one kind may be used alone, or two or more kinds may be mixed and used.
- the polymer precursor used in the photosensitive resin composition of the present invention means a substance that finally becomes a polymer exhibiting the desired physical properties by reaction, and the reaction includes intermolecular reaction and intramolecular reaction.
- the polymer precursor itself may be a relatively low molecular compound or a high molecular compound.
- the polymer precursor of the present invention is a compound whose reaction to the final product is promoted by a basic substance or by heating in the presence of the basic substance.
- the polymer precursor is obtained only by the action of the basic substance.
- the mode includes a mode in which the reaction temperature of the polymer precursor to the final product is lowered by the action of the basic substance as compared with the case where there is no action of the basic substance. . If there is a reaction temperature difference due to the presence or absence of such a basic substance, use the reaction temperature difference to select an appropriate temperature at which only the polymer precursor coexisting with the basic substance will react to the final product. By heating at, only the polymer precursor coexisting with the basic substance reacts with the final product, and the solubility in a solvent such as a developer changes. Therefore, the solubility of the polymer precursor in the solvent can be changed depending on the presence or absence of the basic substance, and thus patterning by development using the solvent as a developing solution becomes possible.
- the polymer precursor of the present invention can be used without particular limitation as long as the reaction to the final product is promoted by the basic substance as described above or by heating in the presence of the basic substance. is there.
- the following are typical examples, but the invention is not limited to these.
- Polymer precursor that becomes polymer by intermolecular reaction examples include a compound having a reactive substituent and a polymerization reaction, and a polymer, or a compound that forms a bond (crosslinking reaction) between molecules. And polymers.
- the reactive substituent include an epoxy group, an oxetane group, a thiirane group, an isocyanate group, a hydroxyl group, and a silanol group.
- the polymer precursor also includes a compound that undergoes hydrolysis and polycondensation between molecules, and the reactive substituent includes the polysiloxane precursor —SiX (where X is an alkoxy group, an acetoxy group, an oxime group).
- X is an alkoxy group, an acetoxy group, an oxime group.
- a hydrolyzable group selected from the group consisting of a group, an enoxy group, an amino group, an aminoxy group, an amide group, and a halogen).
- Examples of the compound having a reactive substituent and undergoing a polymerization reaction include a compound having one or more epoxy groups, a compound having one or more oxetane groups, and a compound having one or more thiirane groups.
- Examples of the polymer that has a reactive substituent and undergoes a polymerization reaction include a polymer having two or more epoxy groups (epoxy resin), a polymer having two or more oxetane groups, and two or more thiiranes. And a polymer having a group.
- the compounds and polymers having an epoxy group are specifically described below, but compounds and polymers having an oxetane group and a thiirane group can also be used in the same manner.
- the compound and polymer having one or more epoxy groups are not particularly limited as long as they have one or more epoxy groups in the molecule, and conventionally known compounds can be used.
- the base generator generally also has a function as a curing catalyst for a compound having one or more epoxy groups in the molecule.
- two functional groups having reactivity with the epoxy group are contained in the molecule.
- Two or more compounds may be used in combination.
- the functional group having reactivity with an epoxy group include a carboxyl group, a phenolic hydroxyl group, a mercapto group, a primary or secondary aromatic amino group, and the like. It is particularly preferable to have two or more of these functional groups in one molecule in consideration of three-dimensional curability.
- Examples of the polymer having one or more epoxy groups in the molecule include epoxy resins, bisphenol A type epoxy resins derived from bisphenol A and epichlorohydrin, bisphenol F type epoxy derived from bisphenol F and epichlorohydrin.
- Resin bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, Multifunctional epoxy resin such as naphthalene type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, trifunctional type epoxy resin and tetrafunctional type epoxy resin There are glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, hydantoin type epoxy resins, isocyanurate type epoxy resins, aliphatic chain epoxy resins, etc.
- epoxy resins may be halogenated and hydrogenated. May be.
- epoxy resin products for example, JER Coat 828, 1001, 801N, 806, 807, 152, 604, 630, 871, YX8000, YX8034, YX4000 manufactured by Japan Epoxy Resin Co., Ltd. 830, EXA835LV, HP4032D, HP820, EP4100 series, EP4000 series, EPU series, manufactured by ADEKA Corporation, Celoxide series (2021, 2021P, 2083, 2085, 3000, etc.) manufactured by Daicel Chemical Industries, Inc.
- examples of the compound that crosslinks between molecules include a combination of a compound having two or more isocyanate groups in the molecule and a compound having two or more hydroxyl groups in the molecule. By reacting with a hydroxyl group, a urethane bond is formed between the molecules, which can be a polymer.
- a polymer that undergoes a cross-linking reaction between molecules for example, a combination of a polymer having two or more isocyanate groups in the molecule (isocyanate resin) and a polymer having two or more hydroxyl groups in the molecule (polyol) Is mentioned. Further, a combination of a compound that undergoes a crosslinking reaction between molecules and a polymer may be used.
- a combination of a polymer (isocyanate resin) having two or more isocyanate groups in the molecule and a compound having two or more hydroxyl groups in the molecule, and a compound having two or more isocyanate groups in the molecule examples include a combination of polymers (polyols) having two or more hydroxyl groups in the molecule.
- any known compound can be used without particular limitation as long as it has two or more isocyanate groups in the molecule.
- examples of such compounds include low molecular weight compounds represented by p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate, oligomers,
- a polymer having an isocyanate group in the side chain or terminal of a polymer having a weight average molecular weight of 3,000 or more may be used.
- the compound and polymer having an isocyanate group are usually used in combination with a compound having a hydroxyl group in the molecule.
- the compound having such a hydroxyl group is not particularly limited as long as it has two or more hydroxyl groups in the molecule, and known compounds can be used.
- a polymer having a weight average molecular weight of 3,000 or more has a hydroxyl group in the side chain or terminal.
- a molecule may be used.
- Polysiloxane precursor examples of the compound that undergoes hydrolysis and polycondensation between molecules include polysiloxane precursors.
- the polysiloxane precursor Y n SiX (4-n) (where Y represents an alkyl group, fluoroalkyl group, vinyl group, phenyl group, or hydrogen which may have a substituent, and X is And a hydrolyzable group selected from the group consisting of an alkoxy group, an acetoxy group, an oxime group, an enoxy group, an amino group, an aminoxy group, an amide group, and a halogen, and n is an integer from 0 to 3. And the hydrolyzed polycondensate of the organosilicon compound.
- the hydrolyzable group is preferably an alkoxy group because the silica-dispersed oligomer solution is easily prepared and easily available.
- the organosilicon compound a well-known thing can be used without a restriction
- Polymer precursor that becomes polymer by intramolecular ring-closing reaction examples include a polyimide precursor and a polybenzoxazole precursor. These precursors may be a mixture of two or more separately synthesized polymer precursors.
- the polyimide precursor and polybenzoxazole precursor which are the preferable polymer precursors of this invention are demonstrated, this invention is not limited to these.
- Polyimide precursor As the polyimide precursor, a polyamic acid having a repeating unit represented by the following chemical formula (3) is preferably used.
- R 7 is a tetravalent organic group.
- R 8 is a divalent organic group.
- R 7 shows only the valence for bonding with an acid, it may have another substituent.
- R 8 indicates only the valence for bonding to the amine, but may have other substituents.
- Polyamic acid is preferable because it can be obtained by simply mixing acid dianhydride and diamine in a solution, so that it can be synthesized by a one-step reaction, can be easily synthesized, and can be obtained at low cost.
- the final curing temperature is less than 300 ° C., more preferably because the temperature required for imidization is low due to the catalytic effect of the basic substance. It can be lowered to 250 ° C. or lower.
- the final cure temperature had to be 300 ° C. or higher, so the use was limited. However, it became possible to lower the final cure temperature, so a wider range Applicable to usage.
- Polyamic acid is obtained by the reaction of acid dianhydride and diamine.
- R 7 or R 8 in the above chemical formula (3) Is preferably an aromatic compound, and R 7 and R 8 are more preferably aromatic compounds.
- R 7 of the chemical formula (3) four groups ((—CO—) 2 (—COOH) 2 ) bonded to R 7 may be bonded to the same aromatic ring. May be bonded to different aromatic rings.
- R 8 of the chemical formula (3) two groups ((—NH—) 2 ) bonded to R 8 may be bonded to the same aromatic ring or bonded to different aromatic rings. You may do it.
- the polyamic acid represented by the chemical formula (3) may be composed of a single repeating unit or may be composed of two or more kinds of repeating units.
- a conventionally known method can be applied. For example, (1) A method of synthesizing a polyamic acid as a precursor from an acid dianhydride and a diamine. (2) A polyimide precursor is synthesized by reacting a carboxylic acid such as an ester acid or an amic acid monomer with a monohydric alcohol, an amino compound, or an epoxy compound synthesized with an acid dianhydride.
- a carboxylic acid such as an ester acid or an amic acid monomer
- a monohydric alcohol such as an amino compound, or an epoxy compound synthesized with an acid dianhydride.
- the method is not limited to this.
- Examples of the acid dianhydride applicable to the reaction for obtaining the polyimide precursor of the present invention include ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, and methylcyclobutane.
- Aliphatic tetracarboxylic dianhydrides such as tetracarboxylic dianhydride and cyclopentanetetracarboxylic dianhydride; pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2,3 ′, 3,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic Acid dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,3', 3,4'-biphenyltetracarboxylic Dianhydride, 2,2 ′, 6,6′-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl)
- tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetra.
- the physical properties such as solubility and thermal expansion coefficient are adjusted without significantly impairing transparency. It is possible. Also, rigid acid dianhydrides such as pyromellitic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, etc. If used, the linear thermal expansion coefficient of the finally obtained polyimide becomes small, but it tends to inhibit the improvement of transparency, so it may be used in combination while paying attention to the copolymerization ratio.
- rigid acid dianhydrides such as pyromellitic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, etc. If used, the linear thermal expansion coefficient of the finally obtained polyimide becomes small, but it tends to inhibit the improvement of transparency, so it may be used in combination while paying attention to the copo
- the amine component can also be used alone or in combination of two or more diamines.
- the diamine component used is not limited, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl Sulfide, 4,4′-diaminodiphenylsulfide, 3,3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminobenzophenone, 4,4 ′ -Diaminobenzophenone, 3,4'-di
- guanamines examples include acetoguanamine, benzoguanamine, and the like, and some or all of the hydrogen atoms on the aromatic ring of the diamine are fluoro group, methyl group, methoxy group, trifluoromethyl group, or trifluoromethoxy group.
- Diamines substituted with substituents selected from the group can also be used.
- any one or more of ethynyl group, benzocyclobuten-4′-yl group, vinyl group, allyl group, cyano group, isocyanate group, and isopropenyl group serving as a crosslinking point may be used. Even if it introduce
- the diamine can be selected depending on the desired physical properties. If a rigid diamine such as p-phenylenediamine is used, the finally obtained polyimide has a low expansion coefficient.
- rigid diamines include p-phenylenediamine, m-phenylenediamine, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 2, 6 as diamines in which two amino groups are bonded to the same aromatic ring. -Diaminonaphthalene, 2,7-diaminonaphthalene, 1,4-diaminoanthracene and the like.
- diamines in which two or more aromatic rings are bonded by a single bond, and two or more amino groups are each bonded directly or as part of a substituent on a separate aromatic ring for example, there exists what is represented by following formula (4). Specific examples include benzidine and the like.
- a is a natural number of 1 or more, and the amino group is bonded to the meta position or the para position with respect to the bond between the benzene rings.
- the transmittance for electromagnetic waves having a wavelength of 1 ⁇ m or less can be improved by introducing fluorine as a substituent of the aromatic ring.
- the selected diamine is preferably an aromatic diamine from the viewpoint of heat resistance.
- the diamine may be an aliphatic diamine or siloxane within a range not exceeding 60 mol%, preferably not exceeding 40 mol%.
- Non-aromatic diamines such as diamines may be used.
- a polyimide precursor for example, while cooling a solution obtained by dissolving 4,4′-diaminodiphenyl ether as an amine component in an organic polar solvent such as N-methylpyrrolidone, an equimolar amount of 3,4 3 ′, 4,4′-biphenyltetracarboxylic dianhydride is gradually added and stirred to obtain a polyimide precursor solution.
- the polyimide precursor thus synthesized should have a copolymerization ratio of the aromatic acid component and / or aromatic amine component as large as possible when the final polyimide obtained is required to have heat resistance and dimensional stability. Is preferred.
- the proportion of the aromatic acid component in the acid component constituting the repeating unit of the imide structure is preferably 50 mol% or more, particularly preferably 70 mol% or more, and the amine component constituting the repeating unit of the imide structure
- the proportion of the aromatic amine component in the total is preferably 40 mol% or more, particularly preferably 60 mol% or more, and particularly preferably wholly aromatic polyimide.
- Polybenzoxazole precursor As the polybenzoxazole precursor used in the present invention, a polyamide alcohol having a repeating unit represented by the following chemical formula (5) is preferably used.
- Polyamide alcohol can be synthesized by a conventionally known method, and can be obtained, for example, by addition reaction of a dicarboxylic acid derivative such as dicarboxylic acid halide and dihydroxydiamine in an organic solvent.
- R 9 is a divalent organic group.
- R 10 is a tetravalent organic group.
- R 9 indicates only the valence for bonding with an acid, it may have another substituent.
- the tetravalent value of R 10 indicates only the valency for bonding with an amine and a hydroxyl group, but may have other substituents.
- Polyamide alcohol having a repeating unit represented by the chemical formula (5) gives excellent heat resistance and dimensional stability to the finally obtained polybenzoxazole.
- R 9 or R 10 is preferably an aromatic compound, and R 9 and R 10 are more preferably aromatic compounds.
- two groups (—CO—) 2 bonded to R 9 may be bonded to the same aromatic ring or bonded to different aromatic rings. May be.
- R 10 of the chemical formula (5) four groups ((—NH—) 2 (—OH) 2 ) bonded to R 10 may be bonded to the same aromatic ring, It may be bonded to different aromatic rings.
- the polyamide alcohol represented by the chemical formula (5) may be composed of a single repeating unit or may be composed of two or more kinds of repeating units.
- dicarboxylic acid and derivatives applicable to the reaction for obtaining the polybenzoxazole precursor examples include phthalic acid, isophthalic acid, terephthalic acid, 4,4′-benzophenone dicarboxylic acid, and 3,4′-benzophenone dicarboxylic acid.
- hydroxydiamine examples include, for example, 3,3′-dihydroxybenzidine, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, 3,3′-diamino-4,4′-dihydroxydiphenylsulfone, 4,4′-diamino-3,3′-dihydroxydiphenylsulfone, bis- (3-amino-4-hydroxyphenyl) methane, 2,2- Bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis- (4-amino-3-hydroxyphenyl) Hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, 2,2-bis- (4-amino-3) Hydroxyphenyl) propane, 4,4′-diamin
- Polymer precursors such as polyimide precursors and polybenzoxazole precursors have a film thickness of 1 ⁇ m in order to increase the sensitivity when used as a photosensitive resin composition and to obtain a pattern shape that accurately reproduces the mask pattern. Furthermore, it is preferable that the transmittance is at least 5% or more with respect to the exposure wavelength, and it is more preferable that the transmittance is 15% or more.
- the high transmittance of polymer precursors such as polyimide precursors and polybenzoxazole precursors with respect to the exposure wavelength means that there is little loss of electromagnetic waves, and a highly sensitive photosensitive resin composition is used. Obtainable.
- a transmittance with respect to an electromagnetic wave having a wavelength of at least 436 nm, 405 nm, and 365 nm is formed on a film having a thickness of 1 ⁇ m. Is preferably 5% or more, more preferably 15%, particularly preferably 50% or more.
- the weight average molecular weight of a polymer precursor such as a polyimide precursor or a polybenzoxazole precursor is preferably in the range of 3,000 to 1,000,000, depending on its use, and is preferably 5,000 to 500. Is more preferably in the range of 10,000 to 500,000.
- the weight average molecular weight is less than 3,000, it is difficult to obtain sufficient strength when a coating film or film is used. In addition, the strength of the film is reduced when heat treatment or the like is performed to obtain a polymer such as polyimide.
- the weight average molecular weight exceeds 1,000,000, the viscosity increases, the solubility tends to decrease, and it is difficult to obtain a coating film or film having a smooth surface and a uniform film thickness.
- the molecular weight used here is a value in terms of polystyrene measured by gel permeation chromatography (GPC), which may be the molecular weight of a polymer precursor itself such as a polyimide precursor, or chemical imidization with acetic anhydride or the like. It may be after processing.
- GPC gel permeation chromatography
- the solvent for the synthesis of the polyimide precursor or polybenzoxazole precursor is preferably a polar solvent, and representative examples include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide.
- examples include methylene sulfone, diethylene glycol dimethyl ether, cyclopentanone, ⁇ -butyrolactone, ⁇ -acetyl- ⁇ -butyrolactone, and these solvents are used alone or in combination of two or more.
- non-polar solvents such as benzene, benzonitrile, 1,4-dioxane, tetrahydrofuran, butyrolactone, xylene, toluene, cyclohexanone and the like can be used as a solvent, and these solvents are used as a raw material dispersion medium. It is used as a reaction regulator, a volatilization regulator of a solvent from the product, a film smoothing agent, and the like.
- the photosensitive resin composition of the present invention has an advantage that the solubility contrast between the exposed portion and the unexposed portion can be further increased.
- the photosensitive resin composition according to the present invention may be a simple mixture of the base generator represented by the chemical formula (1), one or more kinds of polymer precursors, and a solvent.
- a photosensitive resin composition may be prepared by blending a thermosetting component, a non-polymerizable binder resin other than the polymer precursor, and other components.
- Various general-purpose solvents can be used as a solvent for dissolving, dispersing or diluting the photosensitive resin composition.
- polyamic acid as a precursor, you may use the solution obtained by the synthesis reaction of polyamic acid as it is, and may mix other components there as needed.
- Usable general-purpose solvents include, for example, diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, and other ethers; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Glycol monoethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether (so-called cellosolves); ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclopentanone, cyclohexanone; acetic acid Ethyl, butyl acetate, N-propyl acid, i-propyl acetate, n-butyl acetate,
- N-methyl-2-pyrrolidone N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, dimethyl sulfoxide, hexa Polar solvents such as methylphosphoamide, N-acetyl-2-pyrrolidone, pyridine, dimethyl sulfone, tetramethylene sulfone, dimethyltetramethylene sulfone, diethylene glycol dimethyl ether, cyclopentanone, ⁇ -butyrolactone, ⁇ -acetyl- ⁇ -butyrolactone, etc. It is mentioned as a suitable thing.
- a compound having one or more ethylenically unsaturated bonds can be used.
- Aromatic vinyl compounds such as acrylate oligomers, epoxy (meth) acrylates, hydroxyl group-containing (meth) acrylates, and styrene can be exemplified.
- the use of an ethylenically unsaturated bond-containing compound having a tertiary amino group causes the carboxylic acid of the polyimide precursor to have an ionic bond.
- the photosensitive resin composition is formed, the contrast of the dissolution rate of the exposed area and the unexposed area is increased.
- a photoradical generator When using a photocurable compound having such an ethylenically unsaturated bond, a photoradical generator may be further added.
- the photo radical generator include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2 Acetophenones such as phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxyacetophenone, 1-hydroxycyclohexyl phenyl ketone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one
- Anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthra
- the photosensitive resin composition of the present invention may contain other photosensitive components that generate an acid or a base by light as an auxiliary role of the base generator of the present invention. good. Further, a base proliferating agent or a sensitizer may be added. Examples of compounds that generate an acid by light include photosensitive diazoquinone compounds having a 1,2-benzoquinonediazide or 1,2-naphthoquinonediazide structure. US Pat. Nos. 2,772,972, No. 213, No. 3,669,658.
- photoacid generators such as triazine and derivatives thereof, sulfonic acid oxime ester compounds, sulfonic acid iodonium salts, and sulfonic acid sulfonium salts can be used.
- the compound that generates a base by light examples include 2,6-dimethyl-3,5-dicyano-4- (2′-nitrophenyl) -1,4-dihydropyridine, 2,6-dimethyl-3,5-diacetyl.
- Examples include -4- (2'-nitrophenyl) -1,4-dihydropyridine, 2,6-dimethyl-3,5-diacetyl-4- (2 ', 4'-dinitrophenyl) -1,4-dihydropyridine it can.
- a base proliferating agent that generates a base by a decomposition or rearrangement reaction by the action of a small amount of base generated from the base generator may be used in combination.
- the base proliferating agent include a compound having 9-fluorenylmethyl carbamate bond, 1,1-dimethyl-2-cyanomethylcarbamate bond ((CN) CH 2 C (CH 3 ) 2 OC (O) NR 2 ), Compounds having a paranitrobenzyl carbamate bond, compounds having a 2,4-dichlorobenzyl carbamate bond, and other urethane compounds described in paragraphs 0010 to 0032 of JP 2000-330270 A And urethane compounds described in paragraphs 0033 to 0060 of JP-A-2008-250111.
- the addition of a sensitizer may be effective when it is desired to make the base generator sufficiently use the energy of electromagnetic waves having a wavelength that passes through the polymer to improve the sensitivity.
- a sensitizer may be effective when it is desired to make the base generator sufficiently use the energy of electromagnetic waves having a wavelength that passes through the polymer to improve the sensitivity.
- the absorption of the polyimide precursor is also at a wavelength of 360 nm or more, the effect of adding a sensitizer is great.
- sensitizers include thioxanthone and derivatives thereof such as diethylthioxanthone, coumarins and derivatives thereof, ketocoumarin and derivatives thereof, ketobiscoumarin and derivatives thereof, cyclopentanone and derivatives thereof , Cyclohexanone and derivatives thereof, thiopyrylium salts and derivatives thereof, thioxanthene series, xanthene series and derivatives thereof.
- coumarin, ketocoumarin and derivatives thereof include 3,3′-carbonylbiscoumarin, 3,3′-carbonylbis (5,7-dimethoxycoumarin), 3,3′-carbonylbis (7-acetoxycoumarin). ) And the like.
- thioxanthone and derivatives thereof include diethyl thioxanthone and isopropyl thioxanthone.
- various other organic or inorganic low molecular or high molecular compounds may be blended.
- dyes, surfactants, leveling agents, plasticizers, fine particles and the like can be used.
- the fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, inorganic fine particles such as colloidal silica, carbon, and layered silicate, and these may have a porous or hollow structure.
- the function or form includes pigments, fillers, fibers, and the like.
- the polymer precursor (solid content) is based on the entire solid content of the photosensitive resin composition from the viewpoint of film physical properties of the pattern to be obtained, particularly film strength and heat resistance. 30% by weight or more, preferably 50% by weight or more.
- the base generator represented by the chemical formula (1) is usually 0.1 to 95% by weight, preferably 0.5 to 60% by weight based on the solid content of the polymer precursor contained in the photosensitive resin composition. %. If it is less than 0.1% by weight, the solubility contrast between the exposed part and the unexposed part may not be sufficiently increased, and if it exceeds 95% by weight, the properties of the finally obtained cured resin will be reflected in the final product. It is hard to be done.
- the base generator represented by the chemical formula (1) is a solid content of the polymer precursor contained in the photosensitive resin composition.
- solid content of the photosensitive resin composition is all components other than a solvent, and a liquid monomer component is also contained in solid content.
- the blending ratio of optional components other than other solvents is preferably in the range of 0.1% by weight to 95% by weight with respect to the total solid content of the photosensitive resin composition.
- the amount is less than 0.1% by weight, the effect of adding the additive is hardly exhibited, and when it exceeds 95% by weight, the properties of the finally obtained resin cured product are not easily reflected in the final product.
- the photosensitive resin composition according to the present invention can be used in various coating processes and molding processes to produce films and molded articles having a three-dimensional shape.
- the resulting polyimide and polybenzoxazole have heat resistance, dimensional stability, and insulating properties.
- the 5% weight loss temperature measured in nitrogen of the polyimide and polybenzoxazole is preferably 250 ° C. or higher, more preferably 300 ° C. or higher.
- the 5% weight loss temperature is 300 ° C. or less, defects such as bubbles occur due to the decomposition gas generated in the solder reflow process. There is a fear.
- the 5% weight loss temperature means that when the weight loss is measured using a thermogravimetric analyzer, the weight of the sample is reduced by 5% from the initial weight (that is, the sample weight becomes 95% of the initial weight). Temperature).
- the 10% weight reduction temperature is a temperature at which the sample weight is reduced by 10% from the initial weight.
- the glass transition temperature of the polyimide and polybenzoxazole obtained from the photosensitive resin composition of the present invention is preferably as high as possible from the viewpoint of heat resistance, but in applications where a thermoforming process is considered like an optical waveguide,
- the glass transition temperature is preferably about 120 ° C. to 450 ° C., more preferably about 200 ° C. to 380 ° C.
- E ′′ loss elastic modulus (tan ⁇ ) by dynamic viscoelasticity measurement when polyimide and polybenzoxazole obtained from the photosensitive resin composition can be formed into a film shape.
- E ′′ loss elastic modulus (tan ⁇ ) by dynamic viscoelasticity measurement when polyimide and polybenzoxazole obtained from the photosensitive resin composition can be formed into a film shape.
- E ′′ loss elastic modulus (tan ⁇ ) by dynamic viscoelasticity measurement when polyimide and polybenzoxazole obtained from the photosensitive resin composition can be formed into a film shape.
- E ′′ loss elastic modulus (tan ⁇ ) by dynamic viscoelasticity measurement when polyimide and polybenzoxazole obtained from the photosensitive resin composition can be formed into a film shape
- the linear thermal expansion coefficient is preferably 60 ppm or less, and more preferably 40 ppm or less.
- 20 ppm or less is more preferable from the viewpoint of adhesion and warpage of the substrate.
- the linear thermal expansion coefficient in this invention can be calculated
- TMA thermomechanical analyzer
- the heating rate is 10 ° C./min
- the tensile load is 1 g / 25,000 ⁇ m so that the weight per cross-sectional area of the evaluation sample is the same. 2 is obtained.
- the photosensitive resin composition can be obtained by a simple method of simply mixing the base generator represented by the chemical formula (1) with the polymer precursor. Excellent cost performance.
- the aromatic component-containing carboxylic acid constituting the base generator represented by the chemical formula (1) and the basic substance can be obtained at low cost, and the price as the photosensitive resin composition can be suppressed.
- the photosensitive resin composition according to the present invention can be applied to promote the reaction of a wide variety of polymer precursors to the final product by the base generator represented by the chemical formula (1).
- the structure of the resulting polymer can be selected from a wide range.
- the base generator represented by the chemical formula (1) is cyclized when the base is generated and the phenolic hydroxyl group disappears, the solubility in a developer such as a basic solution is changed, and the polymer precursor is changed.
- a developer such as a basic solution
- the polymer precursor is changed.
- a polyimide precursor, a polybenzoxazole precursor or the like it helps to lower the solubility of the photosensitive resin composition and contributes to the improvement of the solubility contrast in the exposed and unexposed areas.
- the processing temperature required for reactions such as cyclization such as imidation from polyimide precursors or polybenzoxazole precursors to final products is reduced.
- the base generator of the present invention that generates a base by irradiation and heating of electromagnetic waves includes a heating step in the step of obtaining a final product from the polymer precursor, the heating step can be used. The amount can be reduced, and the process can be effectively used.
- the photosensitive resin composition according to the present invention is the same as the photosensitive resin composition according to the present invention in printing ink, paint, sealing agent, adhesive, electronic material, optical circuit component, molding material, resist material, building material, light. It can be used for all known fields and products in which resin materials are used, such as modeling and optical members. It can be suitably used both for applications that are used by exposing the entire surface, such as paints, sealants, and adhesives, and for applications that form patterns such as permanent films and release films.
- the photosensitive resin composition according to the present invention can be used in a wide range of fields, products such as heat resistance, dimensional stability, and insulation, such as paints, printing inks, sealants, or adhesives, or It is suitably used as a forming material for display devices, semiconductor devices, electronic components, micro-electro-mechanical systems (MEMS), optical members or building materials.
- a forming material for an electronic component a sealing material and a layer forming material can be used for a printed wiring board, an interlayer insulating film, a wiring covering film, and the like.
- a layer forming material or an image forming material can be used for a color filter, a film for flexible display, a resist material, an alignment film, and the like.
- a material for forming a semiconductor device a resist material, a layer forming material such as a buffer coat film, or the like can be used.
- a material for forming an optical component it can be used as an optical material or a layer forming material for holograms, optical waveguides, optical circuits, optical circuit components, antireflection films and the like.
- a building material it can use for a coating material, a coating agent, etc.
- a printed matter, a paint, a sealant, an adhesive, a display device, a semiconductor device, an electronic component, a microelectromechanical system, an optically shaped article, an optical member, or a building material is provided.
- the photosensitive resin composition according to the present invention can also be used as a pattern forming material.
- a photosensitive resin composition containing a polyimide precursor or a polybenzoxazole precursor is used as a pattern forming material (resist)
- the pattern formed thereby is a permanent film made of polyimide or polybenzoxazole.
- Functions as a component that imparts heat resistance and insulation such as color filters, flexible display films, electronic components, semiconductor devices, interlayer insulation films, wiring coating films, optical circuits, optical circuit components, antireflection films, etc. It is suitable for forming an optical member or an electronic member.
- the pattern forming method according to the present invention includes forming a coating film or a molded body made of the photosensitive resin composition according to the present invention, irradiating the coating film or the molded body with electromagnetic waves in a predetermined pattern, and after irradiation or It develops, after heating simultaneously with irradiation, changing the solubility of the said irradiation site
- the photosensitive resin composition according to the present invention is coated on some support to form a coating film, or a molded body is formed by a suitable molding method, and the coating film or molded body is formed into a predetermined pattern shape.
- the base generator represented by the above chemical formula (1) is isomerized and cyclized only in the exposed portion to produce a basic substance.
- the basic substance acts as a catalyst that promotes the reaction of the polymer precursor in the exposed area to the final product.
- a polymer precursor whose thermal curing temperature is lowered by the catalytic action of a base such as a polyimide precursor or a polybenzoxazole precursor
- a base such as a polyimide precursor or a polybenzoxazole precursor
- the part which wants to leave the pattern on the coating film or molded object of the photosensitive resin composition which combined the base generator represented by these is exposed.
- a basic substance is generated in the exposed portion, and the thermosetting temperature of that portion is selectively lowered.
- the exposed portion is heat-cured but the unexposed portion is heated at a processing temperature that is not heat-cured, and only the exposed portion is cured.
- the heating step for generating the basic substance and the heating step (post-exposure baking) for performing the reaction for curing only the exposed portion may be the same step or different steps.
- the unexposed portion is dissolved with a predetermined developer (such as an organic solvent or a basic aqueous solution) to form a pattern made of a thermoset. This pattern is further heated as necessary to complete thermosetting.
- a predetermined developer such as an organic solvent or a basic aqueous solution
- a polymer precursor that initiates the reaction by the catalytic action of a base such as a compound having an epoxy group or a cyanate group and a polymer
- first such a polymer precursor
- the part which wants to leave the pattern on the coating film or molded object of the photosensitive resin composition which combined the base generator represented by said Formula (1) is exposed.
- a basic substance is generated in the exposed area, the reaction of the compound having an epoxy group or cyanate group and a polymer in that area is initiated, and only the exposed area is cured.
- the heating step for generating the basic substance and the heating step (post-exposure bake) for performing the reaction for curing only the exposed portion may be the same step or different steps.
- thermosetting a desired negative two-dimensional resin pattern (general plane pattern) or a three-dimensional resin pattern (three-dimensionally shaped shape) is obtained.
- the photosensitive resin composition of the present invention includes N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N, N-diethylacetamide, N, N— Dimethylmethoxyacetamide, dimethylsulfoxide, hexamethylphosphoamide, N-acetyl-2-pyrrolidone, pyridine, dimethylsulfone, tetramethylenesulfone, dimethyltetramethylenesulfone, diethylene glycol dimethylether, cyclopentanone, ⁇ -butyrolactone, ⁇ -acetyl- After dissolving in a polar solvent such as ⁇ -butyrolactone, it is applied to the surface of a substrate such as a silicon wafer, a metal substrate, or a ceramic substrate by a dipping method, spray method, screen printing method, spin coating method, etc.
- a polar solvent such as ⁇ -but
- the thickness of the coating film is not particularly limited, but is preferably 0.5 to 50 ⁇ m, and more preferably 1.0 to 20 ⁇ m from the viewpoint of sensitivity and development speed.
- drying conditions for the applied coating include 80 to 100 ° C. and 1 to 20 minutes.
- This coating film is irradiated with electromagnetic waves through a mask having a predetermined pattern, and is exposed to a pattern. After heating, the unexposed portion of the film is developed and removed with an appropriate developer to obtain a desired pattern. A patterned film can be obtained.
- the exposure method and the exposure apparatus used in the exposure process are not particularly limited, and may be contact exposure or indirect exposure.
- a projector or a radiation source that can irradiate ultraviolet rays, visible rays, X-rays, electron beams, or the like can be used.
- the heating temperature for generating a heated base after exposure or simultaneously with exposure is appropriately selected depending on the polymer precursor to be combined and the purpose, and is not particularly limited. Heating by the temperature (for example, room temperature) of the environment where the photosensitive resin composition is placed may be used, and in that case, a base is gradually generated. Further, since the base is also generated by heat generated as a by-product during irradiation with electromagnetic waves, heating may be performed substantially simultaneously with the heat generated as a by-product during irradiation with electromagnetic waves. From the viewpoint of increasing the reaction rate and efficiently generating amine, the heating temperature for generating the base is preferably 30 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 100 ° C.
- a preferable heat treatment temperature range is appropriately selected depending on the type of the epoxy resin, but is usually about 100 ° C. to 150 ° C.
- the coating film of the photosensitive resin composition according to the present invention is a post-exposure bake (Post) between the exposure process and the development process in order to physically accelerate the crosslinking reaction or to perform a reaction to cure only the exposed area. It is preferable to perform exposure bake (PEB).
- the PEB is a temperature at which the reaction rate of the curing reaction such as the imidation rate differs between the site where the base is present and the site where the base is not present without irradiation due to the action of the base generated by irradiation and heating of electromagnetic waves. It is preferable to carry out with.
- the preferred heat treatment temperature range is usually about 60 ° C. to 200 ° C., more preferably 120 ° C. to 200 ° C.
- the heat treatment temperature is lower than 60 ° C., the imidization efficiency is poor, and it becomes difficult to cause a difference in the imidization ratio between the exposed and unexposed areas under realistic process conditions.
- the heat treatment temperature exceeds 200 ° C., imidization may proceed even in an unexposed portion where no amine is present, and it is difficult to cause a difference in solubility between the exposed portion and the unexposed portion.
- This heat treatment may be any known method as long as it is a known method, and specific examples thereof include heating with a circulating oven under a nitrogen atmosphere or a hot plate, or the like, but is not particularly limited.
- a base is generated from the base generator by irradiation with electromagnetic waves and heating, and the heating and PEB process for generating the base may be the same process or separate processes.
- the developer used in the development step is not particularly limited as long as the solvent that changes the solubility of the irradiated site is used as the developer, and is appropriately selected according to the polymer precursor to be used, such as a basic aqueous solution or an organic solvent. It is possible to select.
- the basic aqueous solution is not particularly limited.
- TMAH tetramethylammonium hydroxide
- aqueous solution having a concentration of 0.01% by weight to 10% by weight, preferably 0.05% by weight to 5% by weight.
- the aqueous solution include methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine, and tetramethylammonium.
- the solute may be one type or two or more types, and may contain 50% or more of the total weight, more preferably 70% or more, and an organic solvent or the like as long as water is contained.
- the organic solvent is not particularly limited, but polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, ⁇ -butyrolaclone, dimethylacrylamide, methanol, Alcohols such as ethanol and isopropanol, esters such as ethyl acetate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone, other tetrahydrofuran, chloroform, acetonitrile and the like alone or Two or more types may be added in combination. After development, washing is performed with water or a poor solvent. Also in this case, alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water.
- a patterned high heat resistant resin layer is formed by heating at a temperature of 180 to 500 ° C., preferably 200 to 350 ° C. for several tens of minutes to several hours.
- reaction solution was filtered to remove potassium carbonate, and the reaction solution was concentrated under reduced pressure. After concentration, 50 mL of 1N aqueous sodium hydroxide solution was added and stirred for 12 hours. After completion of the reaction, triphenylphosphine oxide was removed by filtration. Thereafter, concentrated hydrochloric acid was added dropwise to the reaction solution to make the reaction solution acidic, and a precipitate was generated. The precipitate was collected by filtration and washed with a small amount of chloroform to obtain 3.8 g of 2,4-dihydroxy-cinnamic acid.
- the synthesized base generators (1) to (16) and comparative base generator (1) were measured and evaluated as follows.
- the results of molar extinction coefficient and 5% weight loss temperature are shown in Table 1.
- Table 2 shows the results of the base generating ability.
- the base generation rate is a percentage of the number of moles of base generated relative to the number of moles of the base generator used, and the base generation rates of the base generators (1) to (16) are determined by light irradiation. And the ratio of heating.
- Base generation ability For each of the base generators (1) to (16), three 1 mg samples were prepared, and each was dissolved in deuterated dimethyl sulfoxide in a quartz NMR tube. Using a filter that transmits 20% of i-line and a high-pressure mercury lamp, one was irradiated with light at 2 J / cm 2 , and the other was irradiated with light at 20 J / cm 2 . The remaining one was not irradiated with light. 1 H NMR of each sample was measured to determine the isomerization ratio. Base generator (1) is 5.1% isomerization when 2J / cm 2 irradiation was 34.0% isomerization when 20 J / cm 2 irradiation.
- the base generators (1) to (16) of the present invention have a smaller molar extinction coefficient than the comparative base generator (1), but can generate a base efficiently.
- the base generator (9) having a methoxy group introduced into the cinnamic acid derivative site is particularly sensitive and can generate a base efficiently.
- the base generator (14) bonded with imidazole isomerizes very sensitively.
- the base generator (14) bonded with imidazole is characterized by low heat resistance compared to other base generators, a compound having an epoxy group or an isocyanate group having a low drying temperature or a low baking temperature after exposure is used. It is thought that it is suitable to use for the compound which has.
- a photosensitive resin composition (1) having the composition shown below was prepared.
- Polyimide precursor (1) 8 parts by weight
- Base generator (1) 2 parts by weight
- the photosensitive resin composition (1) was spin-coated on a chromium-plated glass so as to have a final film thickness of 1 ⁇ m, and dried on a hot plate at 100 ° C. for 5 minutes to obtain three coating films.
- One film was exposed at 2 J / cm 2 in terms of i-line.
- Another sheet was exposed in a pattern at 10 J / cm 2 in i-line conversion. The remaining one coating film was not exposed.
- a photosensitive resin composition (2) having the following composition was prepared using the base generator (3).
- Example 3 Preparation of photosensitive resin composition (3)
- a photosensitive resin composition (3) was prepared in the same manner as in Example 2, except that the base generator (9) was used instead of the base generator (3) in Example 2.
- Example 4 Preparation of photosensitive resin composition (4)
- a photosensitive resin composition (4) was prepared in the same manner as in Example 2, except that the base generator (16) was used instead of the base generator (3) in Example 2.
- Comparative Example 1 Preparation of comparative photosensitive resin composition (1)
- a comparative photosensitive resin composition (1) was prepared in the same manner as in Example 2, except that the comparative base generator (1) was used instead of the base generator (3) in Example 2.
- the photosensitive resin compositions (2), (3), (4) and the comparative photosensitive resin composition (1) were each spin-coated on a chrome-plated glass so as to have a final film thickness of 4 ⁇ m. Dry on a hot plate at 15 ° C. for 15 minutes, 5 coating films of photosensitive resin composition (2), 8 coating films of photosensitive resin compositions (3) and (4), respectively, and comparative photosensitivity 6 coating films of the conductive resin composition (1) were obtained. Except for one sheet, the entire surface was exposed with a high-pressure mercury lamp using a manual exposure machine. The four coating films of the photosensitive resin composition (2) were each exposed at 0, 500, 700, and 4000 mJ / cm 2 .
- the seven coating films of the photosensitive resin compositions (3) and (4) were respectively exposed at 0, 10, 30, 50, 100, 300, and 1000 mJ / cm 2 .
- the five coating films of the comparative photosensitive resin composition (1) were exposed at 0, 500, 1000, 2000, and 4000 mJ / cm 2 , respectively.
- the remaining one sheet was exposed in a pattern. Thereafter, each coating film was heated at 155 ° C. for 10 minutes.
- FIG. 1 shows the results of plotting the amount of decrease in peak intensity due to heating, based on the peak intensity of 1605 cm ⁇ 1 derived from the precursor before measurement. 1 that for Example 1, the difference in the imidization ratio between the two samples is maximum at around 160 ° C. Moreover, the spectrum derived from the polyimide precursor disappeared with the heating, and the peak derived from the polyimide appeared, so that it was confirmed that the reaction from the polyimide precursor to the polyimide proceeded.
- the photosensitive resin compositions (3) and (4) of the present invention have a normalized film thickness of about 1 at 50 mJ / cm 2
- the photosensitive resin composition (2) of the present invention has a normalized film of 500 mJ / cm 2.
- the thickness was about 1.
- Comparative photosensitive resin composition (1) is 500 mJ / in cm 2 residual film ratio is 0, the normalized thickness at 1000 mJ / cm 2 was about 1.
- the photosensitive resin composition of the present invention proceeds with imidization with a small exposure amount as compared with the comparative photosensitive resin composition, and it was shown that the sensitivity was high. It has been clarified that imidization proceeds with a particularly small exposure amount in the photosensitive resin compositions (3) and (4) of the present invention.
- tetramethylammonium hydroxide 2.38weight% aqueous solution and isopropanol are 9: 1. It was immersed in the mixed solution. As a result, a pattern was obtained in which the exposed portion remained undissolved in the developer. Furthermore, it was heated at 350 ° C. for 1 hour to perform imidization. From this result, it became clear that the photosensitive resin composition of the present invention can form a good pattern.
- the photosensitive resin composition (2) of the present invention formed a pattern at 500 mJ / cm 2
- the photosensitive resin compositions (3) and (4) formed a pattern at 100 mJ / cm 2 .
- the comparative photosensitive resin composition (1) was tested in the same manner, a pattern was finally formed at 2000 mJ / cm 2 .
- Two photosensitive resin compositions (5) and (6) weighing 500 mg each were prepared. Using a manual exposure machine, one side was exposed to 100 J / cm 2 in terms of i-line. All four examiners were heated at 160 ° C. for 30 minutes. As a result of NMR measurement of the sample after heating, formation of a new peak was confirmed in the sample irradiated with both the photosensitive resin compositions (5) and (6). Formation was not confirmed.
- the photosensitive resin compositions (5) and (6) were each spin-coated on a chrome-plated glass so as to have a final film thickness of 0.5 ⁇ m and dried on a hot plate at 80 ° C. for 15 minutes, Two coating films of each photosensitive resin composition were obtained. About one sheet of the coating film of each photosensitive resin composition, 10 J / cm ⁇ 2 > whole surface exposure was performed with the high pressure mercury lamp using the manual exposure machine. Thereafter, each coating film was heated at 160 ° C. for 30 minutes.
- Photosensitivity comprising 100 parts by weight of hexamethylene diisocyanate (manufactured by Kanto Chemical) as the isocyanate resin, 150 parts by weight of polytetrahydrofuran (manufactured by Aldrich) as the resin having a hydroxyl group, 10 parts by weight of the base generator (3), and 500 parts by weight of tetrahydrofuran.
- Resin composition (7) was prepared.
- the photosensitive resin composition (7) was spin-coated on chrome-plated glass to a final film thickness of 0.5 ⁇ m, and dried on a hot plate at 60 ° C. for 5 minutes to apply the photosensitive resin composition. One film was obtained. The obtained coating film was subjected to 1 J / cm 2 overall exposure with a high-pressure mercury lamp using a manual exposure machine. Then, when it heated at 120 degreeC for 10 minute (s) and cooled to room temperature, the low-elasticity solid substance was obtained and it confirmed that hardening with an isocyanate group and a hydroxyl group advanced.
- Example 8 Preparation of photosensitive resin composition (8)
- 100 parts by weight of the alkoxysilane condensate (1) and 10 parts by weight of the base generator (3) were mixed and then dissolved in 500 parts by weight of tetrahydrofuran as a solvent to prepare a photosensitive resin composition (8).
- the photosensitive resin composition (8) was spin-coated on chrome-plated glass to a final film thickness of 0.5 ⁇ m, and dried on an 80 ° C. hot plate for 5 minutes to apply the photosensitive resin composition. Two films were obtained. About one sheet of the coating film of each photosensitive resin composition, 10 J / cm ⁇ 2 > whole surface exposure was performed with the high pressure mercury lamp using the manual exposure machine. Thereafter, each of the exposed coating film and the unexposed coating film was heated at 120 ° C. for 30 minutes. Infrared absorption spectrum measurement was performed on each sample before and after heating.
Abstract
Description
例えば、高分子材料であるポリイミドは、耐熱性、寸法安定性、絶縁特性といった性能が有機物の中でもトップクラスの性能を示すため、電子部品の絶縁材料等へ広く適用され、半導体素子の中のチップコーティング膜や、フレキシブルプリント配線板の基材などとして盛んに利用されてきている。
また、近年、ポリイミドの有する課題を解決する為に、ポリイミドと類似の加工工程が適用される低吸水性で低誘電率を示すポリベンゾオキサゾールや、基板との密着性に優れるポリベンゾイミダゾール等も精力的に研究されている。
(1)ポリイミド前駆体にはパターン形成能力がなく、ポリイミド前駆体上に感光性樹脂をレジスト層として設けることによりパターンを形成する方法
(2)ポリイミド前駆体自身に感光性部位を結合や配位させて導入し、その作用により、パターンを形成する方法。または、ポリイミド前駆体に感光性成分を混合し樹脂組成物とし、その感光性成分の作用でパターンを形成する方法。
露光部と未露光部の間で溶解性のコントラストが大きければ大きいほど現像後の残膜率が大きく、更に形状も良好なパターンを得ることができるが、従来の感光性組成物では、現像液の濃度や光塩基発生剤の量を調整したり、溶解促進剤の添加が必要であり、プロセスマージンが小さくなってしまっていた。
本発明に係るパターン形成方法は、上記感光性樹脂組成物を用いて塗膜又は成形体を形成し、当該塗膜又は成形体を、所定パターン状に電磁波を照射し、照射後又は照射と同時に加熱し、前記照射部位の溶解性を変化させた後、現像することを特徴とする。
本発明の感光性樹脂組成物は、含まれる式(1)で表される塩基発生剤が、従来用いられていた光塩基発生剤と比べて優れた感度を有するため、感度の高い感光性樹脂組成物である。本発明の感光性樹脂組成物は、電磁波の照射と加熱により、塩基発生剤由来の塩基による高分子前駆体の溶解性の変化に加えて、塩基発生剤も塩基が発生する際にフェノール性水酸基が失われることにより塩基性水溶液に対する溶解性が変化するため、露光部、未露光部の溶解性の差をさらに大きくすることが可能である。露光部と未露光部とで大きな溶解性コントラストが得られる結果、十分なプロセスマージンを保ちつつ、形状が良好なパターンを得ることができる。
さらに本発明の感光性樹脂組成物においては、酸と異なり塩基が金属の腐食を起こさないため、より信頼性の高い硬化膜を得ることが出来る。
また、パターン形成工程に加熱工程を含む場合、本発明の感光性樹脂組成物は、塩基の発生を促進させる加熱において、前記加熱工程を利用することが可能であり、当該加熱工程を利用する分、電磁波の照射量を少なくできる利点を有する。そのためこの様な加熱工程を含む工程で用いる場合、本発明の感光性樹脂組成物は、電磁波照射のみで塩基を発生させる従来の樹脂組成物と比べ、工程の合理化も可能となる。
なお、本発明において(メタ)アクリロイルとは、アクリロイル及び/又はメタクリロイルを意味し、(メタ)アクリルとは、アクリル及び/又はメタクリルを意味し、(メタ)アクリレートとは、アクリレート及び/又はメタクリレートを意味する。
また、本発明において、電磁波とは、波長を特定した場合を除き、可視及び非可視領域の波長の電磁波だけでなく、電子線のような粒子線、及び、電磁波と粒子線を総称する放射線又は電離放射線が含まれる。本明細書では、電磁波の照射を露光ともいう。なお、波長365nm、405nm、436nmの電磁波をそれぞれ、i線、h線、g線とも表記することがある。
<塩基発生剤>
本発明に係る塩基発生剤は、下記式(1)で表わされ、且つ電磁波の照射と加熱により、塩基を発生する。
1価の有機基としては、飽和又は不飽和アルキル基、飽和又は不飽和シクロアルキル基、アリール基、アラルキル基、及び飽和又は不飽和ハロゲン化アルキル基等が挙げられる。これらの有機基は、当該有機基中にヘテロ原子等の炭化水素基以外の結合や置換基を含んでよく、これらは、直鎖状でも分岐状でも良い。
環状構造は、飽和又は不飽和の脂環式炭化水素、複素環、及び縮合環、並びに当該脂環式炭化水素、複素環、及び縮合環よりなる群から選ばれる2種以上が組み合されてなる構造であっても良い。
前記R1及びR2の有機基中の炭化水素基以外の置換基としては、ハロゲン原子、水酸基、メルカプト基、シアノ基、シリル基、シラノール基、アルコキシ基、アルコキシカルボニル基、ニトロ基、アシル基、アシルオキシ基、飽和又は不飽和アルキルエーテル基、飽和又は不飽和アルキルチオエーテル基、アリールエーテル基、及びアリールチオエーテル基が好ましい。
高分子前駆体から最終生成物への反応に対する反応開始温度を低下させる等の触媒作用は、塩基性の大きい塩基性物質の方が触媒としての効果が大きく、より少量の添加で、より低い温度での最終生成物への反応が可能となる。一般に1級アミンよりは2級アミンの方が塩基性は高く、その触媒効果が大きい。
また、芳香族アミンよりも脂肪族アミンの方が塩基性が強いため好ましい。
ハロゲンとしては、フッ素、塩素、臭素などが挙げられる。
1価の有機基としては、特に制限がなく、飽和又は不飽和アルキル基、飽和又は不飽和シクロアルキル基、アリール基、アラルキル基、及び飽和又は不飽和ハロゲン化アルキル基、シアノ基等が挙げられる。これらの有機基は、当該有機基中にヘテロ原子等の炭化水素基以外の結合や置換基を含んでよく、これらは、直鎖状でも分岐状でも良い。
中でも、R3~R6の有機基中の炭化水素基以外の置換基としては、ハロゲン原子、水酸基、メルカプト基、シアノ基、シリル基、シラノール基、アルコキシ基、アルコキシカルボニル基、ニトロ基、アシル基、アシルオキシ基、飽和又は不飽和アルキルエーテル基、飽和又は不飽和アルキルチオエーテル基、アリールエーテル基、及びアリールチオエーテル基が好ましい。
環状構造は、飽和又は不飽和の脂環式炭化水素、複素環、及び縮合環、並びに当該脂環式炭化水素、複素環、及び縮合環よりなる群から選ばれる2種以上が組み合されてなる構造であっても良い。例えば、R3~R6は、それらの2つ以上が結合して、R3~R6が結合しているベンゼン環の原子を共有してナフタレン、アントラセン、フェナントレン、インデン等の縮合環を形成していても良い。
また、R3~R6としては、それらの2つ以上が結合して、R3~R6が結合しているベンゼン環の原子を共有してナフタレン、アントラセン、フェナントレン、インデン等の縮合環を形成している場合も、吸収波長が長波長化する点から好ましい。
また、前記式(1)で表される塩基発生剤の塩基発生以外の分解を防ぐために、300℃以下で加熱することが好ましい。
各置換基を導入した桂皮酸の合成は、対応する置換基を有するヒドロキシベンズアルデヒドにwittig反応または、Knoevenagel反応、又はPerkin反応を行うことで合成できる。
例えば、光塩基発生剤と酸-塩基指示薬とを少なくとも含む画像形成層を、基材上に被覆又は基材に含浸させてなる画像形成媒体において、画像形成層を露光すると、前記光塩基発生剤が、酸-塩基指示薬と反応する塩基を生成し、画像が形成されることを特徴とする画像形成媒体のような表示装置などにも応用することができる。
本発明に係る感光性樹脂組成物は、塩基性物質によって又は塩基性物質の存在下での加熱によって最終生成物への反応が促進される高分子前駆体、及び、前記本発明に係る下記化学式(1)で表わされ且つ電磁波の照射と加熱により塩基を発生する塩基発生剤を含有することを特徴とする。
前記高分子前駆体は、前記塩基発生剤から発生した塩基性物質の作用によって最終生成物への反応が促進される。
塩基発生剤及び高分子前駆体としては、1種単独で用いても良いし、2種以上混合して用いても良い。
本発明の感光性樹脂組成物に用いる高分子前駆体とは、反応により最終的に目的の物性を示す高分子となる物質を意味し、当該反応には分子間反応及び分子内反応がある。高分子前駆体自体は、比較的低分子の化合物であっても高分子化合物であってもよい。
また、本発明の高分子前駆体は、塩基性物質によって又は塩基性物質の存在下での加熱によって最終生成物への反応が促進される化合物である。ここで、高分子前駆体が、塩基性物質によって又は塩基性物質の存在下での加熱によって最終生成物への反応が促進される態様には、高分子前駆体が塩基性物質の作用のみによって最終生成物に変化する態様のみならず、塩基性物質の作用によって高分子前駆体の最終生成物への反応温度が、塩基性物質の作用がない場合に比べて低下するような態様が含まれる。
このような塩基性物質の存在の有無により反応温度差が出来る場合には、反応温度差を利用して、塩基性物質と共存する高分子前駆体のみが最終生成物へと反応する適切な温度で加熱することにより、塩基性物質と共存する高分子前駆体のみが最終生成物へと反応し、現像液等の溶媒への溶解性が変化する。従って、塩基性物質の存在の有無によって、高分子前駆体の前記溶媒への溶解性を変化させることが可能となり、ひいては当該溶媒を現像液として用いて現像によるパターニングが可能になる。
分子間反応により目的の高分子となる高分子前駆体としては、反応性置換基を有し重合反応をする化合物及び高分子、又は、分子間に結合を形成する反応(架橋反応)をする化合物及び高分子がある。当該反応性置換基としては、エポキシ基、オキセタン基、チイラン基、イソシアネート基、ヒドロキシル基、シラノール基等が挙げられる。また、高分子前駆体には、分子間で加水分解・重縮合する化合物も含まれ、反応性置換基には、ポリシロキサン前駆体の-SiX(ここで、Xはアルコキシ基、アセトキシ基、オキシム基、エノキシ基、アミノ基、アミノキシ基、アミド基、及びハロゲンよりなる群から選択される加水分解性基)も挙げられる。
反応性置換基を有し重合反応をする高分子としては、例えば、2個以上のエポキシ基を有する高分子(エポキシ樹脂)、2個以上のオキセタン基を有する高分子、及び2個以上のチイラン基を有する高分子が挙げられる。下記に特にエポキシ基を有する化合物及び高分子について具体的に説明するが、オキセタン基、チイラン基を有する化合物及び高分子についても同様に用いることが可能である。
上記1個以上のエポキシ基を有する化合物及び高分子としては、分子内に1個以上のエポキシ基を有するものであれば特に制限なく、従来公知のものを使用できる。
前記塩基発生剤は、一般的には分子内に1個以上のエポキシ基を有する化合物の硬化触媒としての機能も有する。
また、重量平均分子量3,000~100,000のポリマー側鎖に上記官能基を導入したものを用いることが好ましい。3,000未満では膜強度の低下及び硬化膜表面にタック性が生じ、不純物等が付着しやすくなる恐れがある。また、100,000より大きいと粘度が増大する恐れがあり好ましくない。
分子間で架橋反応をする高分子としては、例えば、分子内に2個以上のイソシアネート基を有する高分子(イソシアネート樹脂)と分子内に2個以上のヒドロキシル基を有する高分子(ポリオール)の組み合わせが挙げられる。
また、分子間で架橋反応をする化合物と高分子の組み合わせを用いても良い。例えば、分子内に2個以上のイソシアネート基を有する高分子(イソシアネート樹脂)と分子内に2個以上のヒドロキシル基を有する化合物の組み合わせ、及び、分子内に2個以上のイソシアネート基を有する化合物と分子内に2個以上のヒドロキシル基を有する高分子(ポリオール)の組み合わせ等が挙げられる。
イソシアネート基をもつ化合物及び高分子としては、分子内に2個以上のイソシアネート基を有するものであれば特に制限なく、公知のものを使用できる。このような化合物としては、p-フェニレンジイソシアネート、2,4-トルエンジイソシアネート、2,6-トルエンジイソシアネート、1,5-ナフタレンジイソシアネート、ヘキサメチレンジイソシアネート等に代表される低分子化合物の他に、オリゴマー、重量平均分子分子量3,000以上のポリマーの側鎖又は末端にイソシアネート基が存在する高分子を用いてもよい。
前記イソシアネート基を持つ化合物及び高分子は、通常、分子内にヒドロキシル基を持つ化合物と組み合わせて用いられる。このようなヒドロキシル基を有する化合物としては、分子内に2個以上のヒドロキシル基を有するものであれば特に制限なく、公知のものを使用できる。このような化合物としては、エチレングリコール、プロピレングリコール、グリセリン、ジグリセリン、ペンタエリスリトール等の低分子化合物の他に、重量平均分子量3,000以上のポリマーの側鎖又は末端にヒドロキシル基が存在する高分子を用いてもよい。
分子間で加水分解・重縮合する化合物としては、たとえばポリシロキサン前駆体が挙げられる。
ポリシロキサン前駆体としては、YnSiX(4-n)(ここで、Yは置換基を有していても良いアルキル基、フルオロアルキル基、ビニル基、フェニル基、または水素を示し、Xはアルコキシ基、アセトキシ基、オキシム基、エノキシ基、アミノ基、アミノキシ基、アミド基、及びハロゲンよりなる群から選択される加水分解性基を示す。nは0~3までの整数である。) で示される有機ケイ素化合物及び当該有機ケイ素化合物の加水分解重縮合物が挙げられる。中でも、上記式においてnが0~2であるものが好ましい。また、シリカ分散オリゴマー溶液の調製がし易く入手も容易な点から、上記加水分解性基としては、アルコキシ基であるものが好ましい。
上記有機ケイ素化合物としては、特に制限なく、公知のものを使用できる。例えば、トリメトキシシラン、トリエトキシシラン、メチルトリクロルシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリイソプロポキシシラン、メチルトリt-ブトキシシラン、エチルトリブロムシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、n-プロピルトリエトキシシラン、n-ヘキシルトリメトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、テトラメトキシシラン、テトラエトキシシラン、テトラブトキシシラン、ジメトキシジエトキシシラン、ジメチルジクロルシラン、ジメチルジメトキシシラン、ジフェニルジメトキシシラン、ビニルトリメトキシシラン、トリフルオロプロピルトリメトキシシラン、γ-グリシドキシプロピルメチルジエトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、γ-メタアクリロキシプロピルメチルジメトキシシラン、γ-アミノプロピルメチルジメトキシシラン、γ-メルカプトプロピルメチルジエトキシシラン、γ-メルカプトプロピルトリメトキシシラン、β-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、フッ素系シランカップリング剤として知られたフルオロアルキルシラン、および、それらの加水分解縮合物もしくは共加水分解縮合物;並びに、それらの混合物を挙げることができる。
分子内閉環反応によって最終的に目的の物性を示す高分子となる高分子前駆体としてはポリイミド前駆体、ポリベンゾオキサゾール前駆体等がある。これらの前駆体は2種類以上の別々に合成した高分子前駆体の混合物でもよい。
以下、本発明の好ましい高分子前駆体であるポリイミド前駆体とポリベンゾオキサゾール前駆体について説明するが、本発明はこれらに限定されるものではない。
ポリイミド前駆体としては、下記化学式(3)で表される繰り返し単位を有するポリアミック酸が好適に用いられる。
m-フェニレンジアミン、o-フェニレンジアミン、3,3’-ジアミノジフェニルエーテル、3,4’-ジアミノジフェニルエーテル、4,4’-ジアミノジフェニルエーテル、3,3’-ジアミノジフェニルスルフィド、3,4’-ジアミノジフェニルスルフィド、4,4’-ジアミノジフェニルスルフィド、3,3’-ジアミノジフェニルスルホン、3,4’-ジアミノジフェニルスルホン、4,4’-ジアミノジフェニルスルホン、3,3’-ジアミノベンゾフェノン、4,4’-ジアミノベンゾフェノン、3,4’-ジアミノベンゾフェノン、3,3’-ジアミノジフェニルメタン、4,4’-ジアミノジフェニルメタン、3,4’-ジアミノジフェニルメタン、2,2-ジ(3-アミノフェニル)プロパン、2,2-ジ(4-アミノフェニル)プロパン、2-(3-アミノフェニル)-2-(4-アミノフェニル)プロパン、2,2-ジ(3-アミノフェニル)-1,1,1,3,3,3-ヘキサフルオロプロパン、2,2-ジ(4-アミノフェニル)-1,1,1,3,3,3-ヘキサフルオロプロパン、2-(3-アミノフェニル)-2-(4-アミノフェニル)-1,1,1,3,3,3-ヘキサフルオロプロパン、1,1-ジ(3-アミノフェニル)-1-フェニルエタン、1,1-ジ(4-アミノフェニル)-1-フェニルエタン、1-(3-アミノフェニル)-1-(4-アミノフェニル)-1-フェニルエタン、1,3-ビス(3-アミノフェノキシ)ベンゼン、1,3-ビス(4-アミノフェノキシ)ベンゼン、1,4-ビス(3-アミノフェノキシ)ベンゼン、1,4-ビス(4-アミノフェノキシ)ベンゼン、1,3-ビス(3-アミノベンゾイル)ベンゼン、1,3-ビス(4-アミノベンゾイル)ベンゼン、1,4-ビス(3-アミノベンゾイル)ベンゼン、1,4-ビス(4-アミノベンゾイル)ベンゼン、1,3-ビス(3-アミノ-α,α-ジメチルベンジル)ベンゼン、1,3-ビス(4-アミノ-α,α-ジメチルベンジル)ベンゼン、1,4-ビス(3-アミノ-α,α-ジメチルベンジル)ベンゼン、1,4-ビス(4-アミノ-α,α-ジメチルベンジル)ベンゼン、1,3-ビス(3-アミノ-α,α-ジトリフルオロメチルベンジル)ベンゼン、1,3-ビス(4-アミノ-α,α-ジトリフルオロメチルベンジル)ベンゼン、1,4-ビス(3-アミノ-α,α-ジトリフルオロメチルベンジル)ベンゼン、1,4-ビス(4-アミノ-α,α-ジトリフルオロメチルベンジル)ベンゼン、2,6-ビス(3-アミノフェノキシ)ベンゾニトリル、2,6-ビス(3-アミノフェノキシ)ピリジン、4,4’-ビス(3-アミノフェノキシ)ビフェニル、4,4’-ビス(4-アミノフェノキシ)ビフェニル、ビス[4-(3-アミノフェノキシ)フェニル]ケトン、ビス[4-(4-アミノフェノキシ)フェニル]ケトン、ビス[4-(3-アミノフェノキシ)フェニル]スルフィド、ビス[4-(4-アミノフェノキシ)フェニル]スルフィド、
具体例としては、2,2’-ジメチル-4,4’-ジアミノビフェニル、2,2’-ジトリフルオロメチル-4,4’-ジアミノビフェニル、3,3’-ジクロロ-4,4’-ジアミノビフェニル、3,3’-ジメトキシ-4,4’-ジアミノビフェニル、3,3’-ジメチル-4,4’-ジアミノビフェニル等が挙げられる。
ここで、選択されるジアミンは耐熱性の観点より芳香族ジアミンが好ましいが、目的の物性に応じてジアミンの全体の60モル%、好ましくは40モル%を超えない範囲で、脂肪族ジアミンやシロキサン系ジアミン等の芳香族以外のジアミンを用いても良い。
このようにして合成されるポリイミド前駆体は、最終的に得られるポリイミドに耐熱性及び寸法安定性を求める場合には、芳香族酸成分及び/又は芳香族アミン成分の共重合割合ができるだけ大きいことが好ましい。具体的には、イミド構造の繰り返し単位を構成する酸成分に占める芳香族酸成分の割合が50モル%以上、特に70モル%以上であることが好ましく、イミド構造の繰り返し単位を構成するアミン成分に占める芳香族アミン成分の割合が40モル%以上、特に60モル%以上であることが好ましく、全芳香族ポリイミドであることが特に好ましい。
本発明に用いられるポリベンゾオキサゾール前駆体としては、下記化学式(5)で表される繰り返し単位を有するポリアミドアルコールが好適に用いられる。
露光波長に対してポリイミド前駆体やポリベンゾオキサゾール前駆体等の高分子前駆体の透過率が高いということは、それだけ、電磁波のロスが少ないということであり、高感度の感光性樹脂組成物を得ることができる。
本発明に係る感光性樹脂組成物は、前記化学式(1)で表される塩基発生剤と、1種類以上の高分子前駆体と、溶媒の単純な混合物であってもよいが、さらに、光又は熱硬化性成分、高分子前駆体以外の非重合性バインダー樹脂、その他の成分を配合して、感光性樹脂組成物を調製してもよい。
光によって酸を発生させる化合物としては、1,2-ベンゾキノンジアジドあるいは1,2-ナフトキノンジアジド構造を有する感光性ジアゾキノン化合物があり、米国特許明細書第2,772,972号、第2,797,213号、第3,669,658号に提案されている。また、トリアジンやその誘導体、スルホン酸オキシムエステル化合物、スルホン酸ヨードニウム塩、スルホン酸スルフォニウム塩等、公知の光酸発生剤を用いることができる。光によって塩基を発生させる化合物としては、例えば2,6-ジメチル-3,5-ジシアノ-4-(2’-ニトロフェニル)-1,4-ジヒドロピリジン、2,6-ジメチル-3,5-ジアセチル-4-(2’-ニトロフェニル)-1,4-ジヒドロピリジン、2,6-ジメチル-3,5-ジアセチル-4-(2’,4’-ジニトロフェニル)-1,4-ジヒドロピリジンなどが例示できる。
特に、ポリイミド前駆体の吸収が360nm以上の波長にもある場合には、増感剤の添加による効果が大きい。増感剤と呼ばれる化合物の具体例としては、チオキサントン及び、ジエチルチオキサントンなどのその誘導体、クマリン系及び、その誘導体、ケトクマリン及び、その誘導体、ケトビスクマリン、及びその誘導体、シクロペンタノン及び、その誘導体、シクロヘキサノン及び、その誘導体、チオピリリウム塩及び、その誘導体、チオキサンテン系、キサンテン系及び、その誘導体などが挙げられる。
これらは、塩基発生剤との組み合わせによって、特に優れた効果を発揮する為、塩基発生剤の構造によって最適な増感作用を示す増感剤が適宜選択される。
前記化学式(1)で表される塩基発生剤は、感光性樹脂組成物に含まれる高分子前駆体の固形分に対し、通常、0.1~95重量%、好ましくは0.5~60重量%の範囲内で含有させる。0.1重量%未満であると露光部と未露光部の溶解性コントラストを十分に大きくできない恐れがあり、95重量%を超えると最終的に得られる樹脂硬化物の特性が最終生成物に反映されにくい。
エポキシ系化合物と組み合わせる場合など、硬化剤として用いられる場合には、硬化の程度にもよるが通常、0.1~95重量%、好ましくは0.5~60重量%の範囲内で含有させる。
一方、硬化促進剤として用いられる場合には、少量の添加で硬化が可能となり、前記化学式(1)で表される塩基発生剤は、感光性樹脂組成物に含まれる高分子前駆体の固形分に対し、通常、0.1~30重量%、好ましくは0.5~20重量%の範囲内で含有させることが好ましい。
なお、感光性樹脂組成物の固形分とは、溶剤以外の全成分であり、液状のモノマー成分も固形分に含まれる。
ここで、5%重量減少温度とは、熱重量分析装置を用いて重量減少を測定した時に、サンプルの重量が初期重量から5%減少した時点(すなわち、サンプル重量が初期の95%となった時点)の温度である。同様に10%重量減少温度とはサンプル重量が初期重量から10%減少した時点の温度である。
化学式(1)で表される塩基発生剤を構成する芳香族成分含有カルボン酸、並びに、塩基性物質は安価に入手することが可能で感光性樹脂組成物としての価格も抑えられる。
本発明に係る感光性樹脂組成物は、上記化学式(1)で表される塩基発生剤により、多種多様な高分子前駆体の最終生成物への反応促進に適用することができ、最終的に得られる高分子の構造を広範囲から選択することができる。
さらに、化学式(1)で表される塩基発生剤は、塩基の発生時に環化し、フェノール性水酸基を消失するため、塩基性溶液のような現像液への溶解性が変化し、高分子前駆体がポリイミド前駆体やポリベンゾオキサゾール前駆体等の場合に、感光性樹脂組成物の溶解性の低下を補助し、露光部と未露光部での溶解性コントラストの向上に寄与する。
また、電磁波の照射により発生したアミンなどの塩基性物質の触媒効果により、例えばポリイミド前駆体やポリベンゾオキサゾール前駆体から最終生成物へのイミド化などの環化等の反応に要する処理温度を低減できる為、プロセスへの負荷や製品への熱によるダメージを低減することが可能である。
さらに、電磁波の照射と加熱により塩基を発生する本発明の塩基発生剤は、高分子前駆体から最終生成物を得る工程に加熱工程が含まれる場合、当該加熱工程を利用できるため、電磁波の照射量を低減することが可能であり、工程の有効利用も可能である。
本発明に係るパターン形成方法は、前記本発明に係る感光性樹脂組成物からなる塗膜又は成形体を形成し、当該塗膜又は成形体を、所定パターン状に電磁波を照射し、照射後又は照射と同時に加熱し、前記照射部位の溶解性を変化させた後、現像することを特徴とする。
次に、所定の現像液(有機溶媒や塩基性水溶液等)で未露光部を溶解して熱硬化物からなるパターンを形成する。このパターンを、更に必要に応じ加熱して熱硬化を完結させる。以上の工程によって、通常ネガ型の所望の2次元樹脂パターン(一般的な平面パターン)又は3次元樹脂パターン(立体的に成形された形状)が得られる。
例えば、エポキシ樹脂の場合、好ましい熱処理の温度の範囲は、エポキシ樹脂の種類により適宜選択されるが、通常100℃~150℃程度である。
この熱処理は、公知の方法であればどの方法でもよく、具体的に例示すると、空気、又は窒素雰囲気下の循環オーブン、又はホットプレートによる加熱等が挙げられるが、特に限定されない。
本発明において、電磁波の照射と加熱により塩基発生剤から塩基が生ずるが、この塩基を発生させるための加熱とPEB工程は同一の工程としてもよいし、別の工程としてもよい。
現像工程に用いられる現像液としては、前記照射部位の溶解性が変化する溶剤を現像液として用いれば、特に限定されず、塩基性水溶液、有機溶剤など、用いられる高分子前駆体に合わせて適宜選択することが可能である。
溶質は、1種類でも2種類以上でも良く、全体の重量の50%以上、さらに好ましくは70%以上、水が含まれていれば有機溶媒等を含んでいても良い。
また、以下に示す装置を用いて各測定、実験を行った。
1H NMR測定:日本電子(株)製、JEOL JNM-LA400WB
手動露光:大日本科研製、MA-1100
吸光度測定:(株)島津製作所製、紫外可視分光光度計UV-2550
5%重量減少温度測定:(株)島津製作所製、示差熱・熱重量同時測定装置DTG-60
赤外線吸収スペクトル測定:バリアン・テクノロジーズ・ジャパン・リミテッド社製、FTS 7000
塗膜の加熱:アズワン(株)製、HOT PLATE EC-1200(本実施例中、ホットプレートと記載することがある)
ジ(4-アミノフェニル)エーテル10.0g(50mmol)を300mLの3つ口フラスコに投入し、105.4mLの脱水されたN,N-ジメチルアセトアミド(DMAc)に溶解させ窒素気流下、氷浴で冷却しながら撹拌した。そこへ、少しずつ3,3’,4,4’‐ビフェニルテトラカルボン酸3,4:3’,4’-二無水物14.7g(50mmol)を添加し、添加終了後、氷浴中で5時間撹拌し、その溶液を、脱水されたジエチルエーテルによって再沈殿し、その沈殿物を室温で減圧下、17時間乾燥し、重量平均分子量10,000のポリアミド酸(ポリイミド前駆体(1))を白色固体として定量的に得た。
冷却管をつけた100mlのフラスコにフェニルトリエトキシシラン5g、トリエトキシシラン10g、アンモニア水0.05g、水5ml及びプロピレングリコールモノメチルエーテルアセテート50mlを加えた。半円形型のメカニカルスターラーを用いて溶液を撹拌し、マントルヒーターで70℃で6時間反応させた。次いでエバポレーターを用いて水との縮合反応で生成したエタノールと残留水とを除去した。反応終了後、フラスコを室温になるまで放置し、アルコキシシランの縮合物(アルコキシシラン縮合物(1))を調製した。
窒素雰囲気下、300mL三口フラスコ中、o-クマリン酸(東京化成工業(株)製)1.00g(6.1mmol)を脱水テトラヒドロキシフラン100mLに溶解し、1-エチル-3-(3-ジメチルアミノプロピル)カルボジイミド塩酸塩(東京化成工業(株)製)1.17g(6.1mmol,1.0eq)を加えた。氷浴下で、シクロヘキシルアミン(関東化学(株)製)0.7ml(6.1mmol,1.0eq)を加えた後、室温で3日間攪拌した。反応液を食塩水で洗浄し、硫酸ナトリウムにて乾燥を行った。シリカゲルカラムクマトグラフィー(展開溶媒:クロロホルム/メタノール 1/0~20/1)により精製することにより、下記化学式(6)で表される塩基発生剤(1)を350mg得た。
100mLフラスコ中、炭酸カリウム2.00gをメタノール15mLに加えた。50mLフラスコ中、エトキシカルボニルメチル(トリフェニル)ホスホニウムブロミド(東京化成工業(株)製)4.29g(10mmol)、2-ヒドロキシ-4-メトキシベンズアルデヒド(東京化成工業(株)製)1.52g(10mmol)をメタノール10mLに溶解し、よく撹拌した炭酸カリウム溶液にゆっくり滴下した。3時間撹拌した後、薄層クロマトグラフィーにより反応の終了を確認したうえでろ過を行い炭酸カリウムを除き、減圧濃縮した。濃縮後、1Nの水酸化ナトリウム水溶液を50mL加え1時間撹拌した。反応終了後、沈殿物をろ過により除き、濃塩酸を滴下し反応液を酸性にした。沈殿物をろ過により集め、少量のクロロホルムにより洗浄することで2-ヒドロキシ-4-メトキシケイ皮酸を1.46g(7.52mmol)得た。
窒素雰囲気下、300mL三口フラスコ中、2-ヒドロキシ-4-メトキシケイ皮酸1.01g(5.2mmol)を脱水テトラヒドロキシフラン40mLに溶解し、氷浴下で1-エチル-3-(3-ジメチルアミノプロピル)カルボジイミド塩酸塩(東京化成工業(株)製)0.99g(5.2mmol)を加えた。30分後、1-ヒドロキシベンゾトリアゾール(東京化成工業(株)製)0.79g(5.2mmol)をゆっくり滴下した。室温に戻し30分程度撹拌した後、シクロヘキシルアミン(関東化学(株)製)0.5ml(4.2mmol)を加えた。10分後、4-(ジメチルアミノ)ピリジン0.10g(0.86mmol)を加えたのち終夜で攪拌した。反応終了後、反応溶液を濃縮し、水に溶解した。酢酸エチルで抽出した後、炭酸水素水溶液、1N塩酸、飽和食塩水で洗浄し、硫酸ナトリウムにて乾燥を行った。シリカゲルカラムクマトグラフィー(展開溶媒:クロロホルム/メタノール100/1~10/1)により精製することにより下記化学式(7)で表される塩基発生剤(2)を350mg得た。
窒素雰囲気下、100mL三口フラスコ中、o-クマリン酸(東京化成工業(株)製)0.50g(3.1mmol)を脱水テトラヒドロキシフラン40mLに溶解し、1-エチル-3-(3-ジメチルアミノプロピル)カルボジイミド塩酸塩(東京化成工業(株)製)0.59g(3.1mmol,1.0eq)を加えた。氷浴下で、ピペリジン(東京化成(株)製)0.3ml(3.1mmol,1.0eq)を加えた後、室温で一晩攪拌した。反応液を濃縮し、クロロホルムで抽出、希塩酸、飽和炭酸水素ナトリウム水溶液、食塩水で洗浄し、ろ過することにより、下記化学式(8)で表される塩基発生剤(3)を450mg得た。
窒素雰囲気下、100mL三口フラスコ中、o-クマリン酸(東京化成工業(株)製)1.00g(6.1mmol)を脱水テトラヒドロキシフラン40mLに溶解し、1-エチル-3-(3-ジメチルアミノプロピル)カルボジイミド塩酸塩(東京化成工業(株)製)1.4g(7.3mmol,1.2eq)を加えた。氷浴下で、ジプロピルアミン(東京化成(株)製)1.0ml(7.3mmol,1.2eq)を加えた後、室温で一晩攪拌した。反応液を濃縮し、クロロホルムで抽出、希塩酸、飽和炭酸水素ナトリウム水溶液、食塩水で洗浄し、ろ過することにより、下記化学式(9)で表される塩基発生剤(4)を171mg得た。
製造例4において、ジプロピルアミン(東京化成(株)製)1.0ml(7.3mmol,1.2eq)を用いる代わりに、ピロリジン(東京化成(株)製)0.6ml(7.3mmol,1.2eq)を用いた以外は、製造例4と同様にして、下記化学式(10)で表される塩基発生剤(5)を360mg得た。
製造例4において、ジプロピルアミン(東京化成(株)製)1.0ml(7.3mmol,1.2eq)を用いる代わりに、ヘキサメチレンイミン(東京化成(株)製)0.82ml(7.3mmol,1.2eq)を用いた以外は、製造例4と同様にして、下記化学式(11)で表される塩基発生剤(6)を379mg得た。
製造例4において、ジプロピルアミン(東京化成(株)製)1.0ml(7.3mmol,1.2eq)を用いる代わりに、ジエチルアミン(東京化成(株)製)1.0ml(7.3mmol,1.2eq)を用いた以外は、製造例4と同様にして、下記化学式(12)で表される塩基発生剤(7)を498mg得た。
100mLフラスコ中、2-ヒドロキシ-桂皮酸 500mg(3.0mmol)をジオキサン 20mlに溶解させ、塩化チオニル 200μl(2.8mmol、0.9eq)をゆっくり滴下した。10分撹拌した後、2,6-ジメチルピペリジン0.9ml(6.6mmol、2.2eq)を加えた。反応終了後、反応溶液を濃縮し、水に溶解した。クロロホルムで抽出した後、飽和炭酸水素ナトリウム水溶液、1N塩酸、飽和食塩水で洗浄したのちろ過することにより、下記化学式(13)で表される塩基発生剤(8)を64mg得た。
100mLフラスコ中、炭酸カリウム2.00gをメタノール15mLに加えた。50mLフラスコ中、エトキシカルボニルメチル(トリフェニル)ホスホニウム ブロミド2.67g(6.2mmol)、2-ヒドロキシ-4-メトキシベンズアルデヒド945mg(6.2 mmol)をメタノール10mLに溶解し、よく撹拌した炭酸カリウム溶液にゆっくり滴下した。3時間撹拌した後、TLCにより反応の終了を確認したうえでろ過を行い炭酸カリウムを除き、減圧濃縮した。濃縮後、1Nの水酸化ナトリウム水溶液を50mL加え1時間撹拌した。反応終了後、ろ過によりトリフェニルホスフィンオキシドを除いた後、濃塩酸を滴下し反応液を酸性にした。沈殿物をろ過により集め、少量のクロロホルムにより洗浄することで2-ヒドロキシ-4-メトキシケイ皮酸を1.00g得た。続いて、100mL三口フラスコ中、2-ヒドロキシ-4-メトキシケイ皮酸500mg(3.0 mmol)を脱水テトラヒドロキシフラン40mLに溶解し、1-エチル-3-(3-ジメチルアミノプロピル)カルボジイミド塩酸塩(EDC)0.586g(3.0mmol)を加えた。30分後、ピペリジン0.3ml(3.0mmol)を加えた。反応終了後、反応溶液を濃縮し、水に溶解した。ジエチルエーテルで抽出した後、飽和炭酸水素ナトリウム水溶液、1N塩酸、飽和食塩水で洗浄した。その後、シリカゲルカラムクマトグラフィー(展開溶媒:クロロホルム/メタノール 100/1~10/1)により精製することにより、下記化学式(14)で表される塩基発生剤(9)を64mg得た。
製造例9において、2-ヒドロキシ-4-メトキシベンズアルデヒド945mg(6.2 mmol)を用いる代わりに、3,5-ジ-tert-ブチルサリチルアルデヒド1.45g(6.2 mmol)を用いた以外は、製造例9と同様にして、2-ヒドロキシ-4-メトキシケイ皮酸の代わりに、3,5-ジ-tert-ブチル-2-ヒドロキシケイ皮酸を1.20 g得た。続いて、100 mL三口フラスコ中、3,5-ジ-tert-ブチル-2-ヒドロキシケイ皮酸500mg (1.8 mmol)を脱水テトラヒドロキシフラン20mLに溶解し、EDC 0.416g(2.2 mmol)を加えた。30分後、ピペリジン0.21mL(2.2mmol)を加え室温で一晩攪拌した。反応液を濃縮し、クロロホルムで抽出、希塩酸、飽和炭酸水素ナトリウム水溶液、食塩水で洗浄し、ろ過することにより、下記化学式(15)で表される塩基発生剤(10)を320mg得た。
製造例9において、2-ヒドロキシ-4-メトキシベンズアルデヒド945mg(6.2 mmol)を用いる代わりに、2-ヒドロキシ-1-ナフトアルデヒド1.07g(6.2 mmol)を用いた以外は、製造例9と同様にして、2-ヒドロキシ-4-メトキシケイ皮酸の代わりに、3-(2-ヒドロキシ-1-ナフタレニル)-アクリル酸を1.20g得た。続いて、100 mL三口フラスコ中、3-(2-ヒドロキシ-1-ナフタレニル)-アクリル酸1.00g(4.67mmol)を脱水テトラヒドロキシフラン20mLに溶解し、EDC 1.07g(5.60mmol)を加えた。30分後、シクロヘキシルアミン0.64mL(5.60mmol)を加え室温で一晩攪拌した。反応液を濃縮し、クロロホルムで抽出、希塩酸、飽和炭酸水素ナトリウム水溶液、食塩水で洗浄し、ろ過することにより、下記化学式(16)で表される塩基発生剤(11)を520mg得た。
製造例11と同様にして、3-(2-ヒドロキシ-1-ナフタレニル)-アクリル酸を1.20g得た。続いて、製造例11において、シクロヘキシルアミン0.64mL(5.60mmol)を用いる代わりに、ピペリジン0.65 ml (5.60 mmol)を用いる以外は、製造例11と同様にして、下記化学式(17)で表される塩基発生剤(12)を480mg得た。
製造例11と同様にして、3-(2-ヒドロキシ-1-ナフタレニル)-アクリル酸を1.20g得た。続いて、製造例11において、シクロヘキシルアミン0.64mL(5.60mmol)を用いる代わりに、ジプロピルアミン0.92 ml (5.60 mmol)を用いる以外は、製造例11と同様にして、下記化学式(18)で表される塩基発生剤(13)を620mg得た。
製造例4において、ジプロピルアミン(東京化成(株)製)1.0ml(7.3mmol,1.2eq)を用いる代わりに、イミダゾール(東京化成(株)製)0.37ml(5.5mmol,0.9eq)を用いた以外は、製造例4と同様にして、下記化学式(19)で表される塩基発生剤(14)を1.088g得た。
200 mLフラスコ中、炭酸カリウム10.0 g をメタノール75 mLに加えた。100 mLフラスコ中、エトキシカルボニルメチル(トリフェニル)ホスホニウム ブロミド(東京化成工業(株)製)21.5 g(50 mmol)、2,4-ジヒドロキシベンズアルデヒド(東京化成工業(株)製)6.9g(50 mmol)をメタノール50 mLに溶解し、よく撹拌した炭酸カリウム溶液にゆっくり滴下した。3時間撹拌した後、薄層クロマトグラフィー(TLC)により反応の終了を確認した。反応液のろ過を行い、炭酸カリウムを除き、反応液を減圧濃縮した。濃縮後、1Nの水酸化ナトリウム水溶液を50 mL加え、12時間撹拌した。反応終了後、ろ過によりトリフェニルホスフィンオキシドを除いた。その後、反応液に濃塩酸を滴下し、反応液を酸性にしたところ、沈殿物が発生した。当該沈殿物をろ過により集め、少量のクロロホルムにより洗浄することで2,4-ジヒドロキシ-ケイ皮酸を3.8 g得た。
製造例15において、シクロヘキシルアミン(東京化成(株)製)0.32mL(3.33mmol,1.2eq)を用いる代わりに、ピペリジン(東京化成(株)製)0.32mL(3.33mmol,1.2eq)を用いた以外は、製造例15と同様にして、下記化学式(21)で表される塩基発生剤(16)を360mg得た。
また、比較塩基発生剤(1)として、特開2006-189591号公報の記載に従い、Macromolecules A. Mochizuki, Vol.28, No.1, 1995に記載の方法により、下記化学式(22)で表される[(4,5-ジメトキシ-2-ニトロベンジル)オキシ]カルボニル-2,6-ジメチルピペリジン(以後、「DNCDP」と略称する場合がある)を合成した。
合成した塩基発生剤(1)~(16)、及び比較塩基発生剤(1)について、以下の測定を行い、評価した。モル吸光係数及び5%重量減少温度の結果を表1に示す。塩基発生能の結果を表2に示す。なお、表2において、塩基発生率とは、用いた塩基発生剤のモル数に対する発生した塩基のモル数の百分率であり、塩基発生剤(1)~(16)の塩基発生率は、光照射と加熱を合せた割合である。
塩基発生剤(1)~(16)、及び比較塩基発生剤(1)をそれぞれ、アセトニトリルに1×10-4mol/Lの濃度で溶解し、石英セル(光路長10mm)に溶液を満たし、吸光度を測定した。
塩基発生剤(1)~(16)、及び比較塩基発生剤(1)の耐熱性を評価するために、それぞれについて、試料重量3.4mg、昇温速度10℃/minの条件で5%重量減少温度を測定した。
塩基発生剤(1)~(16)についてそれぞれ、1mgの試料を3つ用意し、それぞれを石英製NMR管中で重ジメチルスルホキシドに溶解させた。i線を20%透過するフィルタと高圧水銀灯を用いて、1本には2J/cm2で光照射を行い、他の1本には20J/cm2で光照射を行った。残り1本には光照射を行わなかった。各サンプルの1H NMRを測定し、異性化の割合を求めた。
塩基発生剤(1)は2J/cm2照射すると5.1%異性化し、20J/cm2照射すると34.0%異性化した。異性化させたサンプルを160℃に加熱すると、異性化した化合物の98%が環化し、それにともない塩基が発生し、表2に示す塩基発生率となった。 塩基発生剤(2)~(16)についても同様にして、塩基発生率を求めた。結果は、表2にそれぞれ示す。塩基発生剤(12)及び(13)については塩基発生能が高く、20J/cm2照射するのではなく、6J/cm2照射した。
比較塩基発生剤(1)では2J/cm2の照射では塩基の発生が確認されなかった。20J/cm2照射すると4.8%の塩基を発生した。
これらのことから、本発明の塩基発生剤(1)~(16)は、比較塩基発生剤(1)と比較し、モル吸光係数は小さいが、効率良く塩基を発生できることがわかった。特に、桂皮酸誘導体部位にメトキシ基を導入した塩基発生剤(9)は、中でも感度が高く、効率良く塩基を発生できることがわかった。また、イミダゾールを結合させた塩基発生剤(14)は非常に感度よく異性化することがわかった。但し、イミダゾールを結合させた塩基発生剤(14)は他の塩基発生剤に比べて耐熱性が低いという特徴があるため、乾燥温度や露光後ベイク温度の低いエポキシ基を有する化合物やイソシアネート基を有する化合物に用いることが適していると考えられる。
下記に示す組成の感光性樹脂組成物(1)を調製した。
・ポリイミド前駆体(1):8重量部
・塩基発生剤(1):2重量部
・溶剤(DMAc(ジメチルアセトアミド)):90重量部
感光性樹脂組成物(1)を、クロムめっきされたガラス上に最終膜厚1μmになるようにスピンコートし、100℃のホットプレート上で5分間乾燥させて、塗膜を3枚得た。1枚の塗膜にはi線換算で、2J/cm2で全面露光を行った。別の1枚にはi線換算で、10J/cm2でパターン状に露光を行った。残り1枚の塗膜は露光を行わなかった。
塩基発生剤(3)を用いて、下記に示す組成の感光性樹脂組成物(2)を調製した。
・ポリイミド前駆体(1):85重量部
・塩基発生剤(3):15重量部
・溶剤(N-メチル-2-ピロリドン):733重量部
実施例2において塩基発生剤(3)の代わりに、塩基発生剤(9)を用いた以外は、実施例2と同様にして、感光性樹脂組成物(3)を調製した。
実施例2において塩基発生剤(3)の代わりに、塩基発生剤(16)を用いた以外は、実施例2と同様にして、感光性樹脂組成物(4)を調製した。
実施例2において塩基発生剤(3)の代わりに、比較塩基発生剤(1)を用いた以外は、実施例2と同様にして、比較感光性樹脂組成物(1)を調製した。
感光性樹脂組成物(2)、(3)、(4)及び比較感光性樹脂組成物(1)を、それぞれ、クロムめっきされたガラス上に最終膜厚4μmになるようにスピンコートし、80℃のホットプレート上で15分間乾燥させて、感光性樹脂組成物(2)の塗膜を5枚、感光性樹脂組成物(3)及び(4)の塗膜をそれぞれ8枚、並びに比較感光性樹脂組成物(1)の塗膜を6枚得た。1枚を除いて、手動露光機を用いて高圧水銀灯により全面露光を行った。感光性樹脂組成物(2)の4枚の塗膜に対しては、0、500、700、4000mJ/cm2でそれぞれ全面露光を行った。感光性樹脂組成物(3)及び(4)の7枚の塗膜に対しては、0、10、30、50、100、300、1000mJ/cm2でそれぞれ全面露光を行った。比較感光性樹脂組成物(1)の5枚の塗膜に対しては、0、500、1000、2000、4000mJ/cm2でそれぞれ全面露光を行った。残りの1枚は、それぞれパターン状に露光を行った。その後、それぞれの塗膜について、155℃で10分間加熱した。
(1)熱硬化温度
感光性樹脂組成物(1)を用いて作成した全面露光した塗膜及び未露光の塗膜について、それぞれ、室温から5℃/minで350℃まで加熱しながら赤外線吸収スペクトルを測定した。イミド化の進行状況を確認する為に、測定前の前駆体由来の1605cm-1のピーク強度を基準とし、加熱によるピーク強度の減少量をプロットした結果を図1に示す。
図1より、実施例1について、両サンプルのイミド化率の差が160℃付近で最大となることがわかる。また、加熱に伴い、ポリイミド前駆体由来のスペクトルが消失し、ポリイミド由来のピークが現れたことから、ポリイミド前駆体からポリイミドへの反応が進行したことが確認できた。
感光性樹脂組成物(2)、(3)、(4)及び比較感光性樹脂組成物(1)を用いて作成し、全面露光した塗膜をそれぞれ、テトラメチルアンモニウムハイドロオキサイド2.38重量%水溶液とイソプロパノールを9:1で混合した溶液に室温で10分間浸漬し、ガラス上の残存膜厚を測定した。結果を、図2に示す。なお、図中の規格化残膜率は、現像後膜厚×100/現像後の最高膜厚とした。
感光性樹脂組成物(1)を用いて作成したパターン状に露光した塗膜について、170℃のホットプレート上で5分間加熱した後、テトラメチルアンモニウムハイドロオキサイド2.38重量%水溶液とイソプロパノールを9:1で混合した溶液に浸漬した。その結果、露光部が現像液に溶解せず残存したパターンを得ることができた。さらに、それを350℃で1時間加熱しイミド化を行った。この結果より、本発明の感光性樹脂組成物は、良好なパターンを形成できることが明らかとなった。
また、感光性樹脂組成物(2)、(3)又は(4)を用いて作成したパターン状に露光した塗膜について、テトラメチルアンモニウムハイドロオキサイド2.38重量%水溶液とイソプロパノールを9:1で混合した溶液に浸漬した。その結果、露光部が現像液に溶解せず残存したパターンを得ることができた。さらに、それを350℃で1時間加熱しイミド化を行った。この結果より、本発明の感光性樹脂組成物は、良好なパターンを形成できることが明らかとなった。本発明の感光性樹脂組成物(2)は、500mJ/cm2でパターンを形成し、感光性樹脂組成物(3)及び(4)は、100mJ/cm2でパターンを形成した。それに対し、比較感光性樹脂組成物(1)は、同様に実験を行ったところ、2000mJ/cm2でようやくパターンを形成した。
塩基発生剤(5)又は(7)をそれぞれ用いて、下記に示す組成の感光性樹脂組成物(5)および(6)を調製した。
・エポキシ樹脂(jER828 ジャパンエポキシレジン社製):15重量部
・塩基発生剤(5)又は(7):15重量部
・溶剤(N-メチル-2-ピロリドン):370重量部
イソシアナート樹脂としてヘキサメチレンジイソシアナート(関東化学製)100重量部、水酸基を持つ樹脂としてポリテトラヒドロフラン(アルドリッチ製)150重量部、塩基発生剤(3)10重量部、テトラヒドロフラン500重量部からなる感光性樹脂組成物(7)を調製した。
アルコキシシラン縮合物(1) 100重量部と、塩基発生剤(3) 10重量部とを混合した後、溶剤であるテトラヒドロフラン500重量部に溶解させ、感光性樹脂組成物(8)を調製した。
Claims (14)
- 下記化学式(1)で表わされ且つ電磁波の照射と加熱により、塩基を発生することを特徴とする、塩基発生剤。
- 発生する塩基が、アミド結合を形成可能なNH基を1つ有する2級アミン及び/又は複素環式化合物であることを特徴とする、請求の範囲第1項に記載の塩基発生剤。
- 前記式(1)において、R3、R4、R5及びR6の少なくとも1つが、ハロゲン、水酸基、ニトロ基、ニトロソ基、メルカプト基、シリル基、シラノール基又は1価の有機基であるか、或いは、R3、R4、R5及びR6の2つ以上が結合して、R3、R4、R5及びR6が結合しているベンゼン環と縮合環を形成している、請求の範囲第1項又は第2項に記載の塩基発生剤。
- 発生する塩基の沸点が25℃以上であり、350℃における重量減少が80%以上であることを特徴とする、請求の範囲第1項~第3項のいずれかに記載の塩基発生剤。
- 365nm、405nm、436nmの電磁波の波長のうち少なくとも一つの波長に吸収を有することを特徴とする、請求の範囲第1項~第5項のいずれかに記載の塩基発生剤。
- 塩基性物質によって又は塩基性物質の存在下での加熱によって最終生成物への反応が促進される高分子前駆体、及び、前記請求の範囲第1項~第6項のいずれかに記載の塩基発生剤を含有することを特徴とする、感光性樹脂組成物。
- 前記高分子前駆体が、エポキシ基、イソシアネート基、オキセタン基、又はチイラン基を有する化合物及び高分子、ポリシロキサン前駆体、ポリイミド前駆体、並びにポリベンゾオキサゾール前駆体よりなる群から選択される1種以上を含むことを特徴とする、請求の範囲第7項に記載の感光性樹脂組成物。
- 前記高分子前駆体が、塩基性溶液に可溶であることを特徴とする、請求の範囲第7項又は第8項に記載の感光性樹脂組成物。
- 前記高分子前駆体が、ポリイミド前駆体又はポリベンゾオキサゾール前駆体であることを特徴とする、請求の範囲第7項~第9項のいずれかに記載の感光性樹脂組成物。
- 塗料、印刷インキ、シール剤、又は接着剤、或いは、表示装置、半導体装置、電子部品、微小電気機械システム、光造形物、光学部材又は建築材料の形成材料として用いられる請求の範囲第7項~第10項のいずれかに記載の感光性樹脂組成物。
- 前記請求の範囲第7項~第11項のいずれかに記載の感光性樹脂組成物からなるパターン形成用材料。
- 前記請求の範囲第7項~第11項のいずれかに記載の感光性樹脂組成物を用いて塗膜又は成形体を形成し、当該塗膜又は成形体を、所定パターン状に電磁波を照射し、照射後又は照射と同時に加熱し、前記照射部位の溶解性を変化させた後、現像することを特徴とするパターン形成方法。
- 前記請求の範囲第7項~第11項のいずれかに記載の感光性樹脂組成物又はその硬化物により少なくとも一部分が形成されている、印刷物、塗料、シール剤、接着剤、表示装置、半導体装置、電子部品、微小電気機械システム、光造形物、光学部材又は建築材料のいずれかの物品。
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Also Published As
Publication number | Publication date |
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CN101981154B (zh) | 2014-03-19 |
KR20110002018A (ko) | 2011-01-06 |
US8476444B2 (en) | 2013-07-02 |
KR101552464B1 (ko) | 2015-09-10 |
US20130309607A1 (en) | 2013-11-21 |
US8778596B2 (en) | 2014-07-15 |
KR101552371B1 (ko) | 2015-09-10 |
KR20150067383A (ko) | 2015-06-17 |
CN101981154A (zh) | 2011-02-23 |
US20110086311A1 (en) | 2011-04-14 |
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