WO2015019802A1 - 感光性樹脂組成物、そのレリーフパターン膜、レリーフパターン膜の製造方法、レリーフパターン膜を含む電子部品又は光学製品、及び感光性樹脂組成物を含む接着剤 - Google Patents
感光性樹脂組成物、そのレリーフパターン膜、レリーフパターン膜の製造方法、レリーフパターン膜を含む電子部品又は光学製品、及び感光性樹脂組成物を含む接着剤 Download PDFInfo
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- 0 CC(C(c1c(*)c(*)c(*)c(*)c1*)=C)N1C(CCC2)N2CCC1 Chemical compound CC(C(c1c(*)c(*)c(*)c(*)c1*)=C)N1C(CCC2)N2CCC1 0.000 description 4
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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
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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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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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
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on 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 C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0387—Polyamides or polyimides
Definitions
- the present invention relates to a polymer precursor having a polyamic acid or polyamic acid ester repeating unit at least partially, and a nonionic photoreactive latent that generates a strongly basic tertiary amine by irradiation with actinic rays.
- Photosensitive resin composition containing basic substance, relief pattern film (polymer film) using the same, method for producing relief pattern film, and electron having relief pattern film as surface protective film layer and / or interlayer insulating film
- the present invention relates to an adhesive including a component or an optical product and a photosensitive resin composition.
- the polyimide developed by DuPont in 1955 in the United States is widely applied in various fields based on excellent properties such as high insulation, heat resistance, and high mechanical strength.
- it is being applied to coating films for semiconductor elements, flexible printed wiring boards, and heat-resistant insulating interlayers.
- high workability is also required for polyimide.
- polyimide has an aspect that it is difficult to process due to poor thermoplasticity and solubility in organic solvents. For this reason, polyimide is widely used by a method in which photosensitivity is imparted to a polyimide precursor, and a desired pattern is formed by irradiation with actinic rays, and then the ring is closed at a high temperature.
- photosensitive polyimide which has improved processability by imparting photosensitivity to the polyimide precursor, has the feature of shortening complicated processes, so from the viewpoint of productivity and process simplification. Higher utility than non-photosensitive polyimide.
- the conventional photosensitive polyimide makes the polyimide precursor imidize by performing the heating process of 300 degreeC or more after image development (for example, refer patent document 1, 2).
- a photosensitive resin composition capable of forming a polyimide film by imidizing a polyimide precursor at a low temperature is disclosed (for example, see Patent Document 3).
- An object of the present invention is made in view of the above background, and is a photosensitive resin composition capable of easily forming a highly accurate pattern in a low-temperature process without having the disadvantages of the prior art.
- Relief pattern film polymer film
- the present inventor has paid attention to a photosensitive polyimide composition using a photobase generator, and as a result of intensive research, generates a strongly basic tertiary amine by irradiation with actinic rays. It has been found that the object of the present invention can be achieved by a combination of a nonionic photoreactive latent basic substance and a specific polymer precursor.
- the photosensitive resin composition according to the present invention comprises (A) a polymer precursor having a polyamic acid or polyamic acid ester repeating unit in at least a part thereof, and (B) a strongly basic compound by irradiation with actinic rays. And a nonionic photoreactive latent basic substance that generates a tertiary amine.
- the latent basic substance (B) a nonionic substance that generates a strong base by changing its chemical structure upon irradiation with actinic rays is used. Specifically, the latent basic substance (B) is excited by irradiation with actinic rays, and the chemical structure is changed to generate a strongly basic tertiary amine. And the strong basic tertiary amine which generate
- the latent basic substance (B) acts as a very effective photosensitive component on the polymer precursor (A), and facilitates development with a developer. Specifically, the imidization of the exposed part is promoted to make it have almost no solubility. On the other hand, since the unexposed portion remains soluble in the solution, development with a developer is facilitated.
- the polymer precursor (A) is preferably a compound represented by the following general formula (1).
- R 1 is a tetravalent organic group
- R 2 is a divalent organic group
- X is a divalent organic group
- R 3 and R 4 may be the same or different from each other, and are a hydrogen atom, a monovalent organic group or a functional group having silicon
- m is an integer greater than or equal to 1
- n is 0 or an integer of 1 or more.
- the latent basic substance (B) is preferably a compound represented by the general formula (2).
- R 5 is unsubstituted or one or more alkyl, alkenyl, alkynyl, haloalkyl, NR 12 R 13 , CN, OR 14 , SR 15 , COR 16 , COOR 17 , Halogen or formula (3)
- An aromatic or heteroaromatic group substituted by: or R 5 is a group of formula (4)
- a group represented by R 6 and R 7 are, independently of one another, hydrogen, alkyl, alkenyl, alkynyl, or phenyl which is unsubstituted or substituted by one or more alkyl, CN, OR 14 , SR 15 , halogen or haloalkyl ;
- R 9 is alkyl or NR 14A R 15A ;
- R 14A and R 15A are both unsubstituted or form an alkylene bridge substituted with one or more alkyls;
- R 8 , R 10 , R 11 , R 12 and R 13 are, independently of one another, hydrogen or alkyl; or R 8 and R 10 are both unsubstituted or by one or more alkyl Form a substituted alkylene bridge; or
- R 9 and R 11 independently of R 8 and R 10 , together form an alkylene bridge that is unsubstituted or substituted by one or more alkyls.
- R 14 , R 15 and R 17 are independently of each other hydrogen or alkyl;
- R 16 is hydrogen or alkyl; or is unsubstituted or one or more alkyl, alkenyl, alkynyl, haloalkyl, NR 12 R 13 , CN, OR 14 , SR 15 , COR 14 , COOR 17 , or An aromatic or heteroaromatic group substituted by halogen;
- R 18 is unsubstituted or aromatic substituted by one or more alkyl, alkenyl, alkynyl, haloalkyl, NR 12 R 13 , CN, OR 14 , SR 15 , COR 16 , COOR 17 , or halogen Or a heteroaromatic group;
- R 19 is hydrogen or alkyl;
- R 20 is hydrogen, alkyl, or unsubstituted, or one or more alkyl, vinyl, alkenyl, alkynyl, haloalkyl, pheny
- the latent basic substance (B) represented by the formula (2) is preferably a compound represented by the formula (5).
- x is an integer from 1 to 5; y and z are each independently an integer of 0 to 6; R 21 and R 22 are each independently an alkyl group having 1 to 4 carbon atoms; A is a carbon or nitrogen atom.
- the latent basic substance (B) represented by the formula (2) is more preferably a compound represented by the formula (6-1) or the formula (6-2).
- the boiling point of the strongly basic tertiary amine generated from the latent basic substance (B) is preferably 100 ° C. or higher, and more preferably 150 ° C. or higher.
- the pKa of the conjugate acid of the strongly basic tertiary amine generated from the latent basic substance (B) is preferably 9 or more, and more preferably 12 or more.
- the wavelength of the high-pressure mercury lamp which is a general exposure light source, is 436 nm, 405 nm, 365 nm, and the wavelength of the KrF laser is 248 nm, so the latent basic substance (B) is in the range of 240 nm to 450 nm. It is preferable to have absorption at any wavelength.
- the polymer precursor (A) of the present invention is not particularly limited in structure, but when developing with a developer, it is soluble in the developer, for example, when developing with an alkali developer. Is preferably a polyamic acid.
- the photosensitive resin composition of the present invention can form a pattern well at 200 ° C. or lower.
- the relief pattern film of the present invention is a coating film formed by drying the above-mentioned photosensitive resin composition on a substrate, irradiating the coating film with actinic rays in a pattern, and irradiating the coating film with actinic rays. It is manufactured by heating at 200 ° C. or less and developing the heated coating film.
- the photosensitive resin composition of the present invention can be used as an adhesive component, and the relief pattern film obtained by imidizing the photosensitive resin composition is a surface protective film for electronic parts or optical products. It is suitably used as a layer and / or an interlayer insulating film.
- a strongly basic tertiary amine is generated by irradiating an actinic ray to the nonionic photoreactive latent basic substance (B).
- the imidization of the polymer precursor (A) was achieved at a low temperature (200 ° C. or less).
- the relief pattern film thus obtained is a material having both tensile strength and pattern formability.
- the photosensitive resin composition according to the present invention can be imidized even at 200 ° C. or lower, it can be applied to a wider range of applications in the technical field using polyimide, and the possibility of use as a material for various members is expanded. did.
- the present invention it is possible to overcome a technical problem related to a conventional polyimide precursor, in which it is difficult to obtain a solubility contrast between an exposed portion and an unexposed portion, and a good pattern shape can be obtained.
- the photosensitive resin composition according to the present invention can select a polymer precursor (A) having a wide range of structures, the polymer obtained thereby has functions such as heat resistance, dimensional stability, and insulation. Can be given.
- the photosensitive resin composition according to the present invention is mainly used as a pattern forming material, and the pattern formed thereby functions as a component that imparts heat resistance and insulation as a permanent film, such as a color filter.
- a pattern forming material such as a color filter.
- Flexible substrate members liquid crystal alignment films, semiconductor devices, electronic components, interlayer insulation films, wiring coating films such as solder resists and coverlays, solder dams, optical circuits, optical circuit components, antireflection films, other optical members, Or it is suitable for forming building materials.
- the photosensitive resin composition of the present invention comprises (A) a polymer precursor having at least a part of a polyamic acid or polyamic acid ester repeating unit, and (B) a strongly basic tertiary compound by irradiation with actinic rays. Contains a nonionic photoreactive latent basic substance that generates amines.
- the polymer precursor (A) used in the present invention is preferably represented by the following general formula (1).
- R 1 is a tetravalent organic group
- R 2 is a divalent organic group
- X is a divalent organic group.
- X include a phenol group, an alkylphenol group, a (meth) acrylate group, a cyclic alkyl group, a cyclic alkenyl group, a hydroxyamide acid group, an aromatic or aliphatic ester group, an amide group, an amidoimide group, a carbonate ester group, and a siloxane.
- M is an integer of 1 or more, and n is 0 or an integer of 1 or more.
- the preferred number average molecular weight of the polymer precursor (A) is from 1,000 to 1,000,000, more preferably from 5,000 to 500,000, and even more preferably from 10,000 to 200,000.
- R 1 and R 2 are aromatic groups, preferably aromatic groups having 6 to 32 carbon atoms, or aliphatic groups, preferably aliphatic groups having 4 to 20 carbon atoms, depending on the application. Selected from the group. R 1 and R 2 are preferably the following acid dianhydrides used in the production of the polymer precursor (A) and substituents R 1 and R 2 contained in the diamine.
- R 1 and R 2 when patterning the photosensitive resin composition with short wavelength light, it is preferable to use an aliphatic group as R 1 and R 2 from the viewpoint of the absorption characteristics of the polymer.
- R 1 and R 2 when a group containing fluorine is used as R 1 and R 2 , the wavelength of light absorption can be reduced or the dielectric properties can be improved.
- the structure of the polymer precursor (A) can be selected according to the application.
- R 1 shows only the valence for bonding with an acid
- R 1 may have a substituent
- the divalent value of R 2 indicates only the valence for bonding with the amine, but may have other substituents.
- R 3 and R 4 are a hydrogen atom, a monovalent organic group, or a functional group having silicon.
- R 3 and R 4 are monovalent organic groups
- examples include alkyl groups, alkenyl groups, alkynyl groups, and aryl groups.
- R 3 and R 4 are functional groups having monovalent silicon, for example, a siloxane group, a silane group, a silanol group, and the like can be given. Further, only a part of R 3 and R 4 can be hydrogen or a monovalent organic group, whereby the solubility can be controlled.
- a polyamic acid in which R 3 and R 4 are hydrogen atoms is preferably used. Thereby, alkali developability becomes favorable and a favorable pattern is obtained.
- the polyamic acid can be prepared by applying a conventionally known method. For example, it can be prepared simply by mixing acid dianhydride and diamine in a solution. It is preferably used because it can be synthesized by a one-step reaction, can be obtained easily and at low cost, and does not require further modification. Although the synthesis method of a polymer precursor (A) is not specifically limited, A well-known method is applicable.
- tetracarboxylic dianhydrides examples include those represented by the following formula (8).
- the specific examples shown below are merely examples, and it goes without saying that known ones can be used as long as they do not contradict the gist of the present invention.
- R 1 group in the repeating unit of the polyamic acid according to the present embodiment is preferably derived from R 1 of the tetracarboxylic dianhydride used as a raw material for polyamic acid production.
- Examples of the acid dianhydride applicable to the production of the polymer precursor (A) include ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetra.
- Aliphatic tetracarboxylic dianhydrides such as carboxylic 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 ′, 6,6′-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane
- 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 plurality of carboxyl groups of the acid dianhydride may be present on a single aromatic ring or a plurality of aromatic rings.
- the compound represented by the formula (9) is a single aromatic ring or a plurality of aromatic rings.
- An acid dianhydride represented by the formula can be used. From the viewpoint of transparency and mechanical properties, it is preferable to use the above acid dianhydride.
- Examples of amines that can be used in the present invention include diamines represented by the following formula (10). However, the following are examples, and it goes without saying that known ones can be used as long as they do not contradict the gist of the present invention.
- diamines when the R 2 group is a divalent aromatic group include paraphenylenediamine, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4 ′.
- Examples of diamines when the R 2 group is a divalent aliphatic group include 1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylene Diamine, Octamethylenediamine, Nonamethylenediamine, 4,4-Diaminoheptamethylenediamine, 1,4-Diaminocyclohexane, Isophoronediamine, Tetrahydrodicyclopentadienylenediamine, Hexahydro-4,7-methanoindanylenediethylenediamine And tricyclo [6.2.1.02,7] -undecylenedimethyldiamine, 4,4′-methylenebis (cyclohexylamine), and isophoronediamine.
- diaminopolysiloxane represented by the following formula (11).
- R 28 and R 29 each independently represent a divalent hydrocarbon group
- R 30 and R 31 each independently represent a monovalent hydrocarbon group.
- p is 1 or more, preferably an integer of 1 to 10.
- R 28 and R 29 in the above formula (11) are an alkylene group having 1 to 7 carbon atoms such as a methylene group, an ethylene group or a propylene group, or an arylene group having 6 to 18 carbon atoms such as a phenylene group.
- R 30 and R 31 include an alkyl group having 1 to 7 carbon atoms such as a methyl group and an ethyl group, and an aryl group having 6 to 12 carbon atoms such as a phenyl group.
- the ester of polyamic acid can be obtained by a known method.
- an acid anhydride such as 3,3′-benzophenonetetracarboxylic dianhydride and an alcohol such as ethanol are reacted to form a half ester.
- the half ester is converted to diester diacid chloride using thionyl chloride.
- An ester of polyamic acid can be obtained by reacting the diester diacid chloride with a diamine such as 3,5-diaminobenzoic acid.
- At least a part of the polymer precursor (A) having a polyamic acid or polyamic acid ester repeating unit may be a single type of material or a mixture of a plurality of types. It may be used as Further, it may be a copolymer in which R 1 and / or R 2 each have a plurality of structures.
- the nonionic photoreactive latent basic substance (B) generates a strongly basic tertiary amine by irradiation with actinic rays.
- the latent basic substance (B) changes its chemical structure by light irradiation and generates a strongly basic tertiary amine.
- the strongly basic tertiary amine generated is preferably, for example, amidine or guanidine.
- the tertiary amine generated by irradiation with actinic rays is more preferably a cyclic structure.
- visible light, ultraviolet rays, electron beams, X-rays and the like can be irradiated as active rays for the latent basic substance (B), and ultraviolet rays, particularly ultraviolet rays of 248 nm, 365 nm, 405 nm, and 436 nm. Is preferably used.
- the amount of the latent basic substance (B) to be used is appropriately selected according to the film thickness, the type of the latent basic substance (B), the type of the polymer precursor (A), and the like.
- the amount of the latent basic substance (B) added is 1 to 40 parts by mass with respect to 100 parts by mass of the polymer precursor (A). More preferred is 5 to 35 parts by mass, and still more preferred is 10 to 30 parts by mass.
- the polymer precursor (A) can be imidized satisfactorily by the added amount of the latent basic substance (B).
- the latent basic substance (B) of the present invention is nonionic unlike conventional ionic photobase generators, it may be added to the photosensitive resin composition as a catalyst. In addition to excellent solubility in an organic solvent and easy handling, a composition and a polymer film obtained therefrom can be obtained uniformly.
- the latent basic substance (B) that generates a strongly basic tertiary amine upon irradiation with actinic rays is preferably a compound represented by the general formula (2).
- R 5 can absorb light in the wavelength range of 200 to 650 nm, is unsubstituted, or is one or more alkyl, alkenyl, alkynyl, haloalkyl, NR 12 R 13 , CN, OR 14 , SR 15 , COR 16 , COOR 17 , halogen or
- R 6 and R 7 are, independently of one another, hydrogen, alkyl, alkenyl, alkynyl, or phenyl which is unsubstituted or substituted by one or more alkyl, CN, OR 14 , SR 15 , halogen or haloalkyl ;
- R 9 is alkyl or NR 14A R 15A ;
- R 14A and R 15A are both unsubstituted or form an alkylene bridge substituted with one or more alkyls;
- R 8 , R 10 , R 11 , R 12 and R 13 are, independently of one another, hydrogen or alkyl; or R 8 and R 10 are both unsubstituted or by one or more alkyl Form a substituted alkylene bridge; or
- R 9 and R 11 independently of R 8 and R 10 , together form an alkylene bridge that is unsubstituted or substituted by one or more alkyls.
- R 14 , R 15 and R 17 are independently of each other hydrogen or alkyl;
- R 16 is hydrogen or alkyl; or is capable of absorbing light in the wavelength range of 200 to 650 nm, is unsubstituted, or is one or more alkyl, alkenyl, alkynyl, haloalkyl, NR 12 R 13 , CN, OR 14 , SR 15 , COR 14 , COOR 17 , or an aromatic or heteroaromatic group substituted by halogen;
- R 18 is capable of absorbing light in the wavelength range of 200-650 nm and is unsubstituted or one or more alkyl, alkenyl, alkynyl, haloalkyl, NR 12 R 13 , CN, OR 14 , SR 15 , COR 16 , COOR 17 , or an aromatic or heteroaromatic group substituted by halogen;
- R 19 is hydrogen or alkyl;
- R 20 is hydrogen, alkyl, or
- the latent basic substance (B) represented by the formula (2) is a compound represented by the formula (5).
- x is an integer from 1 to 5; y and z are each independently an integer of 0 to 6; R 21 and R 22 are each independently an alkyl group having 1 to 4 carbon atoms; A is a carbon or nitrogen atom; R 5 , R 6 and R 7 are as defined above)
- the latent basic substance (B) represented by the formula (2) is preferably represented by the formula (6-1) or the formula (6-2).
- R 23 to R 27 are each independently a hydrogen atom or a monovalent organic group, and may contain oxygen or sulfur in addition to carbon. Two or more of R 23 to R 27 are the same. Or all of them may be different, or two or more of R 23 to R 27 may be bonded to form a cyclic structure.
- the boiling point of the strongly basic tertiary amine from which the latent basic substance (B) is generated is preferably 100 ° C. or higher, and more preferably 150 ° C. or higher.
- the strongly basic tertiary amine from which the latent basic substance (B) is generated preferably has a pKa of the conjugate acid of 9 or more, more preferably 12 or more.
- a strongly basic tertiary amine having a PKa in the range of 11 to 14, particularly 12.3 to 13.7 by irradiation with actinic rays is preferable in both handling and imidization.
- a strongly basic tertiary amine having a boiling point of 100 ° C. or higher evaporation of the strongly basic tertiary amine during the imidation reaction can be suppressed, and the boiling point of the strongly basic tertiary amine is When it is 150 ° C. or higher, it is possible to suppress evaporation at post-cure after imidization.
- imidization can be easily performed when the pKa of the conjugate acid of the strongly basic tertiary amine is 9 or more. Furthermore, imidation can be performed more easily and rapidly by setting the pKa of the conjugate acid of a strongly basic tertiary amine to 12 or more.
- the latent basic substance (B) is in the range of 240 nm to 450 nm.
- the combination and addition amount of (B) are appropriately selected according to the coating film thickness and the like. It is preferable to use a polymer precursor (A) having a small absorption with respect to the wavelength of the actinic ray so as to achieve a low exposure amount and can cope with a thick film.
- the absorption characteristics can be appropriately changed. For example, in order to shift the absorption region to a short wavelength, the polymer precursor (A) having an aromatic group is used, the conjugated system such as R 1 or / and R 2 is shortened, or the charge transfer complex It is useful to prevent the formation of.
- the solvent (C) in the photosensitive resin composition is not particularly limited as long as it dissolves the polymer precursor (A), the latent basic substance (B), and other additives.
- Examples include N, N′-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N, N′-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, ⁇ -butyrolactone, ⁇ -acetyl- ⁇ - Examples include butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, ⁇ -butyrolactone, and diethylene glycol monomethyl ether. These may be used alone or in combination of two or more.
- the amount of the solvent used can be in the range of 50 to 9000 parts by mass with respect to 100 parts by mass
- a sensitizer (D) may be added to the photosensitive resin composition according to the present embodiment in order to further improve the photosensitivity.
- the sensitizer (D) include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzal) cyclopentane, and 2,6-bis (4′-diethylaminobenzene).
- thioxanthones such as thioxanthen-9-one. These can be used alone or in combination of 2 to 5 kinds. It is preferable to use 0.1 to 10 parts by mass with respect to 100 parts by mass of the sensitizer (D) and the polymer precursor (A).
- an adhesion assistant may be added to the photosensitive resin composition according to Embodiment 1 to improve the adhesion to the substrate.
- Any known adhesion assistant can be used as long as it is not contrary to the gist of the present invention.
- the addition amount of the adhesion assistant is preferably in the range of 0.5 to 10 parts by mass with respect to 100 parts by mass of the polymer precursor (A).
- a base proliferating agent may be added to the photosensitive resin composition of the present invention.
- the decomposition rate of the latent basic substance (B) of the same degree is required from the surface to the bottom.
- the addition of a base proliferating agent is preferable.
- the base proliferating agents disclosed in JP2012-237776, JP2006-282657 and the like can be used.
- produces an acid or a base with light in the range which does not impair the film
- a photo radical generator may be added.
- 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.
- Specific materials for obtaining a porous shape or a hollow structure include various pigments, fillers, fibers, and the like.
- Step 1 a photosensitive resin composition is applied on a substrate and dried to obtain a coating film.
- a method for coating the photosensitive resin composition on the substrate methods conventionally used for coating the photosensitive resin composition, such as spin coater, bar coater, blade coater, curtain coater, screen printer, etc.
- coating, the method of spray-coating with a spray coater, Furthermore, the inkjet method etc. can be used.
- a method for drying the coating film methods such as air drying, heat drying with an oven or hot plate, and vacuum drying are used.
- natural drying, air drying, or heat drying can be performed at 20 ° C. to 140 ° C. for 1 minute to 1 hour.
- drying is performed on a hot plate for 1 to 5 minutes.
- Vacuum drying is also possible, and in this case, it can be carried out at room temperature for 1 minute to 1 hour.
- the base material is not particularly limited, and can be widely applied to silicon wafers, wiring boards, various resins, metals, and passivation protective films for semiconductor devices.
- step 2 the coating film is exposed through a photomask having a pattern or directly.
- the exposure light having a wavelength capable of activating the latent basic substance (B) to be changed into a strongly basic tertiary amine is used.
- the photosensitivity can be adjusted by appropriately using a sensitizer.
- a contact aligner, mirror projection, stepper, laser direct exposure apparatus, or the like can be used.
- step 3 heating is performed so as to promote imidization of the coating film by the base generated in the coating film.
- the base generated in the exposed portion in Step 2 serves as a catalyst, and the polymer precursor (A) is partially imidized.
- the heating time and the heating temperature are appropriately changed depending on the polymer precursor (A) to be used, the coating film thickness, and the type of the latent basic substance (B). Typically, in the case of a coating film thickness of about 10 ⁇ m, it is about 2 to 10 minutes at 110 to 200 ° C. If the heating temperature is too low, partial imidization cannot be achieved efficiently. On the other hand, if the heating temperature is too high, imidization of the unexposed area proceeds to reduce the difference in solubility between the exposed area and the unexposed area, which may cause a problem in pattern formation.
- step 4 the coating film is treated with a developer. Thereby, the unexposed part in a coating film is removed and the pattern which consists of a polymer precursor (A) and a partially imidized polyimide can be formed on a base material.
- an arbitrary method can be selected from conventionally known photoresist development methods such as a rotary spray method, a paddle method, an immersion method involving ultrasonic treatment, and the like.
- Developers include inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide.
- aqueous solution of quaternary ammonium salts such as Further, if necessary, a water-soluble organic solvent such as methanol, ethanol, isopropyl alcohol, or a surfactant can be used in an appropriate amount as an aqueous solution. Thereafter, the coating film is washed with a rinse solution as necessary to obtain a pattern coating film.
- a rinse solution as necessary to obtain a pattern coating film.
- rinsing liquid distilled water, methanol, ethanol, isopropanol or the like can be used alone or in combination. Moreover, you may use the said solvent (C) as a developing solution.
- the coating film patterned in Step 5 is heated.
- the heating temperature is appropriately set so that the polyimide pattern can be cured.
- heating is performed in an inert gas at 150 to 300 ° C. for about 5 to 120 minutes.
- a more preferable range of the heating temperature is 150 to 250 ° C, and a more preferable range is 180 to 220 ° C.
- the heating is performed by using, for example, a hot plate, an oven, or a temperature rising oven in which a temperature program can be set.
- the atmosphere (gas) may be air, or an inert gas such as nitrogen or argon.
- the photosensitive resin composition according to the present invention is a known resin material such as printing ink, adhesive, filler, electronic material, optical circuit component, molding material, resist material, building material, three-dimensional modeling, and optical member.
- resin material such as printing ink, adhesive, filler, electronic material, optical circuit component, molding material, resist material, building material, three-dimensional modeling, and optical member.
- the photosensitive resin according to the present invention is suitably used as a material for forming semiconductor devices, electronic components, interlayer insulating films, wiring coating films, optical circuits, optical circuit components, antireflection films, holograms, optical members or building materials.
- the photosensitive resin composition containing the polymer precursor (A) is mainly used as a pattern forming material (resist), and the pattern formed thereby has a heat resistance and insulating property as a permanent film made of polyimide.
- a pattern forming material resist
- the pattern formed thereby has a heat resistance and insulating property as a permanent film made of polyimide.
- nonionic photoreactive latent basic substance 1 8-benzyl-1,8-diazabicyclo [5.4.0] undecane 1,8-diazabicyclo [5. 4.0] Undecane was produced.
- the reaction mixture was poured into 200 mL of water, and the organic phase solvent separated by the separation funnel was removed by a rotary evaporator. To the remaining yellowish liquid, 500 mL of hexane was added. The precipitated salt was removed by filtration and the solvent was distilled off on a rotary evaporator. After standing, the solution slowly solidified, and 8-benzyl-1,8-diazabicyclo [5.4.0] undecane was obtained as a pale yellowish oil.
- nonionic photoreactive latent basic substance 3 5-methylstyrene-1,5-diazabicyclo [4.3.0] nonane 5-methylstyrene-1, 5-Diazabicyclo [4.3.0] nonane was prepared.
- Polymer precursor In a 500 mL three-necked flask, 12.01 g (60 mmol) of 4,4′-diaminodiphenyl ether was added to 141.3 g of dehydrated N-methyl-2-pyrrolidone (NMP). Stir at room temperature to dissolve. To this solution, pyromellitic dianhydride (13.09 g, 60 mmol) was gradually added. After the addition was completed, the solution was stirred at room temperature for 12 hours under a nitrogen stream to obtain a polyamic acid solution as a polymer precursor. .
- NMP N-methyl-2-pyrrolidone
- photosensitive resin composition 1 photosensitive resin composition 1 of the present invention.
- photosensitive resin composition 2 71.6 mg of the nonionic photoreactive latent basic substance 2 was dissolved in 3 g of the polymer precursor solution to obtain a photosensitive resin composition (photosensitive resin composition 2) of the present invention.
- photosensitive resin composition 4 71.6 mg of the following photosensitive material 4 was dissolved in 3 g of the polymer precursor solution to obtain a photosensitive resin composition (photosensitive resin composition 4) of a comparative example.
- photosensitive resin composition 6 71.6 mg of the following photosensitive material 6 was dissolved in 3 g of the polymer precursor solution to obtain a photosensitive resin composition (photosensitive resin composition 6) of a comparative example.
- a comparative photosensitive resin composition (photosensitive resin composition 7) consisting only of 3 g of the polymer precursor solution was obtained.
- Ultraviolet irradiation / low temperature heating test (1-1) Preparation of cured samples according to Examples 1 and 2 and Comparative Example 4 (ultraviolet irradiation and low temperature heating) Photosensitive resin compositions 1 and 2 (Examples 1 and 2) and photosensitive resin composition 7 (Comparative Example 4) were applied on a copper plate to a final film thickness of 1 ⁇ m. These were dried on a hot plate at 100 ° C. for 15 minutes, and then irradiated with 10 J ultraviolet rays in terms of h-line in an exposure apparatus (manufactured by Oak Manufacturing Co., Ltd.) equipped with a metal halide lamp.
- an exposure apparatus manufactured by Oak Manufacturing Co., Ltd.
- each symbol has the following meaning: a: (CN) Absorbance at 1374 cm-1 b: (COC) Absorbance at 1237 cm-1 (a / b)
- PI Ratio of height of CN-derived peak to peak from COC of standard cured sample (a / b)
- PAA, init Ratio of height of the peak derived from CN of the dried sample to the peak derived from COC (a / b) sample : From the CN of the cured sample according to Examples 1 and 2 and Comparative Example 4 Peak COC-derived peak height ratio
- the imidization ratio of the photosensitive resin composition was calculated at each temperature. The result is as shown in FIG. In the photosensitive resin compositions 1 and 2 (Examples 1 and 2), imidization occurred at a lower temperature than the photosensitive resin composition 7 (Comparative Example 4), and the photosensitive resin compositions 1 and 7 (implemented). It was found that the difference in imidization ratio between Example 1 and Comparative Example 4) was maximized at around 170 ° C. Furthermore, the imidation ratio of the photosensitive resin composition 1 reaches 100% around 180 ° C. On the other hand, the imidation ratio of the photosensitive resin composition 7 was 75% up to 200 ° C.
- Photosensitive resin compositions 1, 2, and 4, 5 (Examples 1 and 2 and Comparative Examples 1 and 2) were placed on electrolytic copper foil (Furukawa Electric, GTS-treated product). The film was applied to a final film thickness of 50 ⁇ m and dried with a hot air circulating dryer at 80 ° C. for 30 minutes. Thereto, 10J UV irradiation was performed in terms of h-line conversion with an exposure apparatus (manufactured by Oak Manufacturing Co., Ltd.) equipped with a metal halide lamp, and then each sample was heated at 180 ° C. for 1 hour for imidization.
- an exposure apparatus manufactured by Oak Manufacturing Co., Ltd.
- the photosensitive resin composition 1 (Example 1) had a tensile elastic modulus of 2.2 GPa and a tensile elongation of 26%, and exhibited good physical properties.
- the photosensitive resin compositions 4 and 5 (Comparative Examples 1 and 2) were not easily tested because cracks were easily generated.
- the photosensitive resin compositions 1 to 3 (Examples 1 to 3) were able to obtain good patterns because the exposed areas were not dissolved in the developer.
- the photosensitive resin composition 6 (Comparative Example 3) was difficult to dissolve in the unexposed part and the dissolution rate contrast was insufficient.
- imidization was performed by heating the patterns obtained from the photosensitive resin compositions 1 to 3 at 180 ° C. for 1 hour.
- the photosensitive resin composition of the present invention can form a good pattern.
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Abstract
Description
R1は4価の有機基であり
R2は2価の有機基であり、
Xは2価の有機基であり
R3及びR4は、相互に同一でも異なってもよく、水素原子又は1価の有機基またはケイ素を有する官能基であり、
mは1以上の整数であり、
nは0または1以上の整数である。)
R6およびR7は、互いに独立して、水素、アルキル、アルケニル、アルキニルであるか、非置換または1つ以上のアルキル、CN、OR14、SR15、ハロゲンまたはハロアルキルによって置換されたフェニルであり;
R9は、アルキルまたはNR14AR15Aであり; R14AおよびR15Aは、ともに、非置換であるか、または1つ以上のアルキルによって置換されたアルキレンブリッジを形成し;
R8、R10、R11、R12およびR13は、互いに独立して、水素またはアルキルであり;あるいは
R8およびR10は、ともに、非置換であるか、または1つ以上のアルキルによって置換されたアルキレンブリッジを形成し;あるいは
R9およびR11は、R8およびR10から独立して、ともに、非置換であるか、または1つ以上のアルキルによって置換されたアルキレンブリッジを形成し;
R14、R15およびR17は、互いに独立して、水素またはアルキルであり;
R16は水素又はアルキルであり;あるいは、非置換であるか、または1つ以上のアルキル、アルケニル、アルキニル、ハロアルキル、NR12R13、CN、OR14、SR15、COR14、COOR17、またはハロゲンによって置換された芳香族または複素芳香族基であり;
R18は、非置換であるか、または1つ以上のアルキル、アルケニル、アルキニル、ハロアルキル、NR12R13、CN、OR14、SR15、COR16、COOR17、またはハロゲンによって置換された芳香族または複素芳香族基であり;
R19は、水素またはアルキルであり;
R20は、水素、アルキル、あるいは非置換であるか、または1つ以上のアルキル、ビニル、アルケニル、アルキニル、ハロアルキル、フェニル、NR12R13、CN、OR14、SR15、COR16、COOR17またはハロゲンによって置換されたフェニルである。)
ポリアミック酸は、従来公知の手法を適用することにより調製可能である。例えば、酸二無水物とジアミンを溶液中で混合するのみで調製できる。1段階の反応で合成することができ、容易かつ低コストで得られ、更なる修飾が不要であるため、好ましく使われている。高分子前駆体(A)の合成方法は特に限定されないが、公知の手法が適用可能である。
R6およびR7は、互いに独立して、水素、アルキル、アルケニル、アルキニルであるか、非置換または1つ以上のアルキル、CN、OR14、SR15、ハロゲンまたはハロアルキルによって置換されたフェニルであり;
R9は、アルキルまたはNR14AR15Aであり; R14AおよびR15Aは、ともに、非置換であるか、または1つ以上のアルキルによって置換されたアルキレンブリッジを形成し;
R8、R10、R11、R12およびR13は、互いに独立して、水素またはアルキルであり;あるいは
R8およびR10は、ともに、非置換であるか、または1つ以上のアルキルによって置換されたアルキレンブリッジを形成し;あるいは
R9およびR11は、R8およびR10から独立して、ともに、非置換であるか、または1つ以上のアルキルによって置換されたアルキレンブリッジを形成し;
R14、R15およびR17は、互いに独立して、水素またはアルキルであり;
R16は水素又はアルキルであり;あるいは200~650nmの波長範囲で光を吸収することが可能であり、非置換であるか、または1つ以上のアルキル、アルケニル、アルキニル、ハロアルキル、NR12R13、CN、OR14、SR15、COR14、COOR17、またはハロゲンによって置換された芳香族または複素芳香族基であり;
R18は、200~650nmの波長範囲で光を吸収することが可能であり、非置換であるか、または1つ以上のアルキル、アルケニル、アルキニル、ハロアルキル、NR12R13、CN、OR14、SR15、COR16、COOR17、またはハロゲンによって置換された芳香族または複素芳香族基であり;
R19は、水素またはアルキルであり;
R20は、水素、アルキル、あるいは非置換であるか、または1つ以上のアルキル、ビニル、アルケニル、アルキニル、ハロアルキル、フェニル、NR12R13、CN、OR14、SR15、COR16、COOR17またはハロゲンによって置換されたフェニルである。)
xは1~5の整数であり;
y及びzは、互いに独立して、0~6の整数であり;
R21及びR22は、互いに独立して、炭素数1~4のアルキル基であり;
Aは炭素又は窒素原子であり;
R5、R6及びR7は、以上に定義されている通りである)
[合成例1]
以下の手順により、下式により示される1,8-ジアザビシクロ[5.4.0]ウンデカンを製造した。
2.5Lのフラスコに、tert-ブチルメチルエーテル1470mLと1,8-ジアザビシクロ[5.4.0]ウンデカ-7-エン152 g(1mol)を装填した。その後、水素化リチウムアルミニウム18.97g(0.5 mol)を数回に分けてフラスコの中に導入し、生じたエマルジョンを室温で1時間攪拌した。続いて反応混合物を2時間にわたり55~57℃に加温し、その後室温にて一晩攪拌した。薄層クロマトグラフィーにより、反応完了を確認した。反応混合物を0℃に冷却し、注意して水19mLおよび次に濃度10%の水酸化ナトリウム溶液19mLを添加した。さらに水57mLを添加した。得られた混合物を1時間攪拌した後、ろ過し、吸引フィルタ上の生成物をtert-ブチルメチルエーテル200mL、および塩化メチレン200mL×2回によって洗浄した。洗浄液を硫酸ナトリウム上で乾燥させ、回転蒸発器で溶媒を留去した。1,8-ジアザビシクロ[5.4.0]ウンデカンが黄色を帯びた油状物として得られた
750mLフラスコの中で、水酸化ナトリウム21.0g(0.525mol)およびヨウ化カリウム5.81g(0.035 mol)をジクロロメタン350 mLに懸濁した。次に塩化ベンジル44.31g(0.35 mol)および上記により得られた1,8-ジアザビシクロ[5.4.0]ウンデカン54.00g(0.35 mol)を添加し、懸濁液を室温にて24時間攪拌した。1H-NMRスペクトルには塩化ベンジル中のベンジル性プロトンのピークはもはや確認できなかった。
[合成例2]
1,8-ジアザビシクロ[5.4.0]ウンデカ-7-エンの代わりに1,5-ジアザビシクロ[4.3.0]ノン-5-エンを用いた以外は合成例1と同様の手順によって下記式により示される5-ベンジル-1,5-ジアザビシクロ[4.3.0]ノナン(pKa=7.46)を調製した。生成物は、淡い黄色を帯びた油状物として得られた。構造の確認は1H-NMRを用いて行った。5-ベンジル-1,5-ジアザビシクロ[4.3.0]ノナンのpKa値は、上記文献に記載の方法に基づいている。
[合成例3]
以下の手順により、下式により示される5-メチルスチレン-1,5-ジアザビシクロ[4.3.0]ノナンを製造した。
[合成例4]
500mLの3つ口フラスコ中で、141.3gの脱水N-メチル-2-ピロリドン(NMP)に4,4’-ジアミノジフェニルエーテル 12.01g (60mmol)を添加し、窒素気流下、室温で撹拌し、溶解させた。この溶液に、ピロメリット酸二無水物13.09 g(60mmol)を徐々に添加し、添加終了後、窒素気流下、室温で12時間撹拌し、高分子前駆体であるポリアミック酸溶液を得た。
[比較例1]
(1)紫外線照射・低温加熱試験
(1-1)実施例1、2、及び比較例4による硬化サンプルの作製(紫外線照射及び低温加熱)
感光性樹脂組成物1と2(実施例1及び2)及び感光性樹脂組成物7(比較例4)を、それぞれ銅板の上に最終膜厚1μmになるように塗布した。これらに対し、100℃でホットプレートの上で15分間乾燥させた後、さらにメタルハライドランプを搭載した露光装置(株式会社オーク製作所製)でh線換算、10J紫外線照射を行った。
(1-2)標準硬化サンプルの作製(高温加熱)
感光性樹脂組成物7(比較例4)を、ウェハーの上に最終膜厚1μmになるように塗布し、これをホットプレートで100℃30分、200℃30分、250℃30分、300℃1時間加熱した。これにより、イミド化させ標準イミド膜を得た。
(1-3)乾燥サンプルの作製
感光性樹脂組成物7(比較例4)を、ウェハーの上に最終膜厚1μmになるように塗布し、これを100℃にて15分加熱して乾燥サンプルとした。
但し、式1中、各符号は以下の意味を有する:
a: (C-N)1374 cm-1の吸光度
b: (C-O-C)1237 cm-1の吸光度
(a/b)PI: 標準硬化サンプルのC-N由来のピークのC-O-C由来のピークに対する高さの比
(a/b)PAA,init : 乾燥サンプルのC-N由来のピークのC-O-C由来のピークに対する高さの比
(a/b)sample : 実施例1、2、及び比較例4による硬化サンプルのC-N由来のピークのC-O-C由来のピークの高さの比
感光性樹脂組成物1、2、及び4、5(実施例1、2、及び比較例1、2)を、電解銅箔(古河電工製、GTS処理品)上に最終膜厚50μmになるように塗布し、80℃の熱風循環乾燥機で30分間乾燥させた。そこへ、メタルハライドランプを搭載した露光装置(株式会社オーク製作所製)でh線換算、10J紫外線照射を行い、その後、各サンプルを180℃で1時間加熱しイミド化を行った。
(2-1)自立膜形成
感光性樹脂組成物1と2(実施例1と2)より平坦かつ均一な自立した硬化膜が得られた。それに対して、感光性樹脂組成物4と5では、脆くて自立膜ができなかった。硬化膜の性質が違った理由は、活性光線の照射によって発生した2級塩基が、イミド化促進効果が弱く、かつ2級アミンの活性水素がポリアミック酸と何らかの反応を生じたためと考えられる。
(2-2)引張試験結果
感光性樹脂組成物1(実施例1)、並びに感光性樹脂組成物4及び5(比較例1及び2)の硬化膜を10×40×0.05(mm)の試験片として、SHIMADZU AG-X(引張試験機)を使用し、引張速度1mm/minにて引張試験を行った。この結果を図2に示した。感光性樹脂組成物1(実施例1)は、引張弾性率が2.2GPa、引張伸度が26%であり、良好な物性を示した。一方、感光性樹脂組成物4及び5(比較例1及び2)では、容易に亀裂が生じたため、試験ができなかった。
感光性樹脂組成物1~3及び6(実施例1~3、比較例3)を、ウェハー上に最終膜厚1μmになるようにスピンコートし、80℃のホットプレート上で30分間乾燥させた。これに対し、メタルハライドランプを搭載した露光装置(株式会社オーク製作所製)でh線換算、10J紫外線照射を行い、その後、170℃のホットプレート上で5分加熱した後、テトラメチルアンモニウムハイドロオキサイド2.38%溶液に浸漬した。その結果、感光性樹脂組成物1から3(実施例1~3)は、露光部が現像液に溶解せず良好なパターンを得ることができた。これに対して、感光性樹脂組成物6(比較例3)は、未露光部が溶けにくく、溶解速度のコントラストが不十分であることがわかった。さらに、感光性樹脂組成物1~3から得られたパターンを180℃で1時間加熱しイミド化を行った。
Claims (14)
- (A)少なくとも一部にポリアミック酸、又は、ポリアミック酸エステルの繰り返し単位を有する高分子前駆体と、
(B)活性光線の照射によって強塩基性第3級アミンを発生する非イオン性光反応型潜在性塩基性物質と、
を含有することを特徴とする感光性樹脂組成物。 - 前記潜在性塩基性物質(B)が一般式(2)で表される化合物である請求項1または2に記載の感光性樹脂組成物。
R5は、非置換であるか、または、1つ以上のアルキル、アルケニル、アルキニル、ハロアルキル、NR12R13、CN、OR14、SR15、COR16、COOR17、ハロゲンまたは式(3)
R5は、式(4)
R6およびR7は、互いに独立して、水素、アルキル、アルケニル、アルキニルであるか、非置換または1つ以上のアルキル、CN、OR14、SR15、ハロゲンまたはハロアルキルによって置換されたフェニルであり;
R9は、アルキルまたはNR14AR15Aであり; R14AおよびR15Aは、ともに、非置換であるか、または1つ以上のアルキルによって置換されたアルキレンブリッジを形成し;
R8、R10、R11、R12およびR13は、互いに独立して、水素またはアルキルであり;あるいは
R8およびR10は、ともに、非置換であるか、または1つ以上のアルキルによって置換されたアルキレンブリッジを形成し;あるいは
R9およびR11は、R8およびR10から独立して、ともに、非置換であるか、または1つ以上のアルキルによって置換されたアルキレンブリッジを形成し;
R14、R15およびR17は、互いに独立して、水素またはアルキルであり;
R16は水素又はアルキルであり;あるいは、非置換であるか、または1つ以上のアルキル、アルケニル、アルキニル、ハロアルキル、NR12R13、CN、OR14、SR15、COR14、COOR17、またはハロゲンによって置換された芳香族または複素芳香族基であり;
R18は、非置換であるか、または1つ以上のアルキル、アルケニル、アルキニル、ハロアルキル、NR12R13、CN、OR14、SR15、COR16、COOR17、またはハロゲンによって置換された芳香族または複素芳香族基であり;
R19は、水素またはアルキルであり;
R20は、水素、アルキル、あるいは非置換であるか、または1つ以上のアルキル、ビニル、アルケニル、アルキニル、ハロアルキル、フェニル、NR12R13、CN、OR14、SR15、COR16、COOR17またはハロゲンによって置換されたフェニルである。) - 前記潜在性塩基性物質(B)が発生する強塩基性第3級アミンの共役酸のpKaが、9以上である請求項1または2に記載の感光性樹脂組成物。
- 前記潜在性塩基性物質(B)は、240nm~450nmの範囲のいずれかの波長に吸収を有することを特徴とする請求項1または2に記載の感光性樹脂組成物。
- 前記高分子前駆体(A)が、アルカリ溶液に可溶であることを特徴とする請求項1または2に記載の感光性樹脂組成物。
- 前記高分子前駆体(A)が、ポリアミック酸である請求項1または2に記載の感光性樹脂組成物。
- 200℃以下でパターンを形成することが可能である請求項1または2に記載の感光性樹脂組成物。
- 請求項1または2に記載の感光性樹脂組成物から得られるレリーフパターン膜。
- 請求項1または2に記載した感光性樹脂組成物を乾燥してなる塗膜を基材上に形成し、
前記塗膜に活性光線をパターン状に照射し、
前記活性光線を照射した塗膜を200℃以下で加熱し、
前記加熱された塗膜を現像することを特徴とするレリーフパターン膜の製造方法。 - 請求項11に記載のレリーフパターン膜を表面保護膜層及び/又は層間絶縁膜として有する電子部品又は光学製品。
- 請求項1または2に記載の感光性樹脂組成物を含む接着剤。
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