WO2017122744A1 - 感光性樹脂組成物、ドライフィルム、硬化物およびプリント配線板 - Google Patents
感光性樹脂組成物、ドライフィルム、硬化物およびプリント配線板 Download PDFInfo
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- WO2017122744A1 WO2017122744A1 PCT/JP2017/000876 JP2017000876W WO2017122744A1 WO 2017122744 A1 WO2017122744 A1 WO 2017122744A1 JP 2017000876 W JP2017000876 W JP 2017000876W WO 2017122744 A1 WO2017122744 A1 WO 2017122744A1
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- Prior art keywords
- group
- polyamic acid
- resin composition
- photosensitive resin
- acid ester
- Prior art date
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- 0 C*(*)C(C=CC(C(*=I)=C(*)**1)=C1OC)=O Chemical compound C*(*)C(C=CC(C(*=I)=C(*)**1)=C1OC)=O 0.000 description 1
Classifications
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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
-
- 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
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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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
- C08G73/1075—Partially aromatic polyimides
-
- 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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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
- H05K3/287—Photosensitive compositions
Definitions
- the present invention relates to a photosensitive resin composition, a dry film, a cured product, and a printed wiring board.
- Polyimide is widely applied in various fields based on excellent properties such as high insulation, heat resistance, and high mechanical strength. For example, it is not limited to the aerospace field where it was first applied, but is being applied to coating films for semiconductor elements, flexible printed wiring boards, and heat-resistant insulating interlayer materials.
- Polyimide has an aspect that it is difficult to process due to poor thermoplasticity and solubility in organic solvents. For this reason, polyimide develops a desired pattern film
- Patent Document 1 describes a photosensitive resin composition containing a polyamic acid ester and a photosensitive base generator.
- Patent Document 2 describes a negative photosensitive resin composition containing a polyamic acid derivative containing both an amic acid moiety and an amic acid ester moiety and a compound that generates a basic substance upon irradiation.
- an object of the present invention is to provide a photosensitive resin composition having excellent resolution, a dry film having a resin layer obtained from the composition, a cured product of the composition or the resin layer of the dry film, and the curing It is providing the printed wiring board which has a thing.
- the photosensitive resin composition of the present invention is a photosensitive resin composition containing (A) a polyamic acid ester and (B) a photobase generator, wherein the (A) polyamic acid ester is It has a structure represented by the following general formula (1).
- R 1 is a tetravalent organic group
- R 2 is a group having an alicyclic skeleton, a phenylene group, a group having a bisphenylene skeleton bonded by an alkylene group, and an alkylene group.
- X is a divalent organic group
- R 3 and R 4 may be the same or different from each other, and are a monovalent organic group or a functional group having silicon
- m is 1 or more.
- polyamic acid ester in the photosensitive resin composition of this invention does not contain an amic acid part substantially. That is, the polyamic acid ester (A) in the photosensitive resin composition of the present invention includes a polyamic acid derivative containing both an amic acid moiety and an amic acid ester moiety, as described in JP-A-2003-084435. Are different.
- R 1 in the general formula (1) is a tetravalent organic group containing a condensed ring of an aromatic ring and an aliphatic hydrocarbon ring, an aromatic group and an alicyclic group. It is preferably a tetravalent organic group containing a hydrocarbon group or a tetravalent organic group containing a fluorine atom.
- the (A) polyamic acid ester preferably has a structure represented by at least one of the following general formulas (1-1) and (1-2).
- R 2 is any one of a group having an alicyclic skeleton, a phenylene group, a group having a bisphenylene skeleton bonded by an alkylene group, and an alkylene group
- X is a divalent group.
- R 3 and R 4 which may be the same or different from each other, are a monovalent organic group or a functional group having silicon, m is an integer of 1 or more, and n is 0 or 1 (It is an integer above.)
- R 2 is any one of a group having an alicyclic skeleton, a phenylene group, a group having a bisphenylene skeleton bonded by an alkylene group, and an alkylene group
- X is a divalent organic group
- R 3 and R 4 may be the same or different from each other, and are 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 (B) photobase generator is preferably an ionic photobase generator.
- the dry film of the present invention is characterized by having a resin layer obtained by applying the photosensitive resin composition to a film and drying it.
- the cured product of the present invention is obtained by curing the photosensitive resin composition or the resin layer of the dry film.
- the printed wiring board of the present invention is characterized by having the cured product.
- a photosensitive resin composition having excellent resolution a dry film having a resin layer obtained from the composition, a cured product of the composition or the resin layer of the dry film, and the cured product
- the printed wiring board which has can be provided.
- the (A) polyamic acid ester used in the present invention has a structure represented by the following general formula (1).
- R 1 is a tetravalent organic group
- R 2 is a group having an alicyclic skeleton, a phenylene group, a group having a bisphenylene skeleton bonded by an alkylene group, and an alkylene group.
- X is a divalent organic group
- R 3 and R 4 may be the same or different from each other, and are a monovalent organic group or a functional group having silicon
- m is 1 or more.
- It is an integer
- n is 0 or an integer of 1 or more.
- the number average molecular weight of the polyamic acid ester is preferably 1,000 to 1,000,000, more preferably 5,000 to 500,000, and even more preferably 10,000 to 200,000.
- the tetravalent organic group represented by R 1 is not particularly limited, and may be selected according to the application.
- an aromatic group preferably an aromatic group having 6 to 32 carbon atoms, or an aliphatic group, preferably an aliphatic group having 4 to 20 carbon atoms.
- R 1 is preferably a substituent R 1 contained in an acid dianhydride described later used in the production of (A) polyamic acid ester.
- R 1 represents a tetravalent organic group containing a condensed ring of an aromatic ring and an aliphatic hydrocarbon ring, an aromatic group and an alicyclic hydrocarbon group. It is preferably a tetravalent organic group containing or a tetravalent organic group containing a fluorine atom.
- Z 1 is an unsaturated hydrocarbon group having 4 to 12 carbon atoms that forms an aromatic ring (preferably a benzene ring, a naphthalene ring, particularly a benzene ring) together with an ethylene group common to Z 2.
- aromatic ring preferably a benzene ring, a naphthalene ring, particularly a benzene ring
- Z 2 is an aliphatic carbon atom having 3 to 10 carbon atoms (preferably 4 to 6, particularly 4 atoms) that forms an aliphatic hydrocarbon ring (alicyclic hydrocarbon) together with an ethylene group common to Z 1.
- R 6 is generally a hydrogen atom, an alkyl group (1 to 4 carbon atoms), an alkoxy group (1 to 4 carbon atoms), a hydroxy group or a halogen atom, preferably a hydrogen atom.
- Z 3 is an unsaturated hydrocarbon group having 4 to 12 carbon atoms that forms an aromatic ring (preferably a benzene ring, a naphthalene ring, particularly a benzene ring) together with an ethylene group common to Z 4.
- aromatic ring preferably a benzene ring, a naphthalene ring, particularly a benzene ring
- Z 4 is an aliphatic carbon atom having 3 to 10 carbon atoms (preferably 4 to 6, particularly 4 atoms) that forms an aliphatic hydrocarbon ring (alicyclic hydrocarbon) with an ethylene group common to Z 3.
- An aliphatic hydrocarbon ring having at least one alkyl group (1 to 4 carbon atoms), alkoxy group (1 to 4 carbon atoms), aryl group (6 to 6 carbon atoms) as a substituent. 10), a hydroxy group and a halogen atom.
- Two monovalent bonds represented by “-” one set of bonds, one set of bonds on the right side of Z 4 or one set of bonds on the left side
- a pair of bonds may be arranged adjacent to each other, or may be arranged with at least one carbon atom from each other if the ring is large.
- Z 5 is an unsaturated hydrocarbon group having 4 to 12 carbon atoms that forms an aromatic ring (preferably a benzene ring, a naphthalene ring, particularly a benzene ring) with an ethylene group common to Z 6.
- aromatic ring preferably a benzene ring, a naphthalene ring, particularly a benzene ring
- Two monovalent bonds represented by “-” are bonded to adjacent carbons, but combinations of two adjacent monovalent bonds represented by “-” are also adjacent to each other. If the ring is large, they may be arranged with at least one carbon atom from each other.
- R 7 is generally a hydrogen atom, an alkyl group (1 to 4 carbon atoms), an alkoxy group (1 to 4 carbon atoms), a hydroxy group or a halogen atom, preferably a hydrogen atom.
- Z 6 is an aliphatic group having 3 to 10 carbon atoms (preferably 4 to 6, particularly 4) which forms an aliphatic hydrocarbon ring (alicyclic hydrocarbon ring) together with an ethylene group common to Z 5.
- Z 7 is an unsaturated hydrocarbon group having 4 to 12 carbon atoms that forms an aromatic ring (preferably a benzene ring, a naphthalene ring, particularly a benzene ring) with an ethylene group common to Z 8, and is an aromatic ring Has at least one alkyl group (1 to 4 carbon atoms), alkoxy group (1 to 4 carbon atoms), aryl group (6 to 10 carbon atoms), hydroxy group, halogen atom as a substituent. You may have.
- Two "-" monovalent bond represented by (right bond Z 7 or the left bond of Z 7) is bonded to the carbon adjacent each pair of The bonds may be arranged adjacent to each other, or may be arranged with at least one carbon atom from each other if the ring is large.
- Z 8 is a saturated group having 3 to 10 carbon atoms (preferably 4 to 6, particularly 4) that forms an aliphatic hydrocarbon ring (alicyclic hydrocarbon ring) together with an ethylene group common to Z 7.
- a hydrocarbon group, and the saturated hydrocarbon ring is substituted with at least one alkyl group (1 to 4 carbon atoms), alkoxy group (1 to 4 carbon atoms), aryl group (6 to 6 carbon atoms). 10), a hydroxy group and a halogen atom.
- the organic groups represented by the formulas (1-1) and (1-2) are preferable, and the organic group represented by the formula (1-1) is particularly preferable. preferable.
- the tetravalent organic group containing a fluorine atom preferably has an aromatic group (preferably a phenyl group, a naphthalene group, particularly a phenyl group), and preferably has a trifluoromethyl group and an aromatic group.
- the (A) polyamic acid ester preferably has a structure represented by at least one of the following general formulas (1-1) and (1-2).
- (1-1) R 2 to R 4 , X, m and n are the same as in formula (1).
- R 2 in the formula (1) is any one of a group having an alicyclic skeleton, a phenylene group, a group having a bisphenylene skeleton bonded by an alkylene group, and an alkylene group.
- the phenylene group and the alkylene group are directly bonded to the two nitrogen atoms bonded to R 2 in the formula (1).
- the alicyclic skeleton and the bisphenylene skeleton bonded by the alkylene group may or may not be directly bonded to the two nitrogen atoms bonded to R 2 in the formula (1).
- R 2 is preferably a substituent R 2 contained in a diamine or diisocyanate described later used in the production of (A) polyamic acid ester.
- the group having the alicyclic skeleton in R 2 may have a substituent and may form a condensed ring.
- the group having an alicyclic skeleton is preferably represented by the following general formula (2-1).
- n1 represents an integer of 0 to 10
- R 10 represents an aliphatic group, preferably an alkylene group having 1 to 5 carbon atoms, more preferably a methylene group
- 11 is independently an aliphatic group or an aromatic group, and preferably represents an aliphatic group such as a methyl group or an ethyl group.
- the phenylene group in R 2 may have a substituent and may form a condensed ring.
- the phenylene group is preferably represented by the following general formula (2-2).
- n2 represents an integer of 0 to 4
- R 12 each independently represents an aliphatic group or an aromatic group, preferably an aliphatic group such as a methyl group or an ethyl group. .
- the group having a bisphenylene skeleton bonded to the alkylene group in R 2 may have a substituent and may form a condensed ring.
- the group having a bisphenylene skeleton bonded by an alkylene group is preferably represented by the following general formula (2-3).
- (2-3) represents an integer of 0 to 4 each independently n3 and n4, respectively
- R 13 and R 14 are independently an aliphatic group or an aromatic group, preferably a methyl group, ethyl Represents an aliphatic group such as a group, and R 15 represents an alkylene group having 1 to 5 carbon atoms.
- the alkylene group for R 15 in formula (2-3) may have a substituent such as an aliphatic group or an aromatic group.
- the alkylene group for R 2 is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 to 8 carbon atoms.
- the alkylene group for R 2 may have a substituent such as an aliphatic group or an aromatic group.
- R 2 is preferably a group having an alicyclic skeleton, and more preferably a group having an alicyclic skeleton and no aromatic skeleton because of excellent resolution.
- R 3 and R 4 in the formula (1) are each independently a monovalent organic group or a functional group having silicon.
- the monovalent organic group in R 3 and R 4 include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group.
- the functional group having monovalent silicon in R 3 and R 4 include a siloxane group, a silane group, and a silanol group.
- R 3 and R 4 in the formula (1) are preferably alkyl groups from the viewpoint of solubility during the synthesis of the polyamic acid ester.
- the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
- the alkyl group is preferably a butyl group, a pentyl group, or a hexyl group.
- X in the formula (1) is a divalent organic group such as an aromatic or aliphatic ester group, an amide group, an amidoimide group, a siloxane group, an epoxy group, or an oxetanyl group.
- Polyamic acid ester may be used individually by 1 type, and may use 2 or more types together. Further, it may be a copolymer in which at least one of R 1 and R 2 has a plurality of structures.
- the blending amount of the polyamic acid ester may be used in the range of 5 to 30% by mass based on the total amount of the composition, for example, depending on the coating film thickness and viscosity.
- the polyamic acid ester can be synthesized using a conventionally known method. For example, an acid anhydride such as 3,3′-benzophenonetetracarboxylic dianhydride is reacted with an alcohol such as ethanol to form a half ester. The half ester is converted to diester diacid chloride using thionyl chloride.
- the polyamic acid ester (A) can be obtained by reacting the diester diacid chloride with a diamine such as 3,5-diaminobenzoic acid.
- a polyamic acid ester may be obtained by reacting a half ester obtained by reacting the above acid anhydride and alcohol with a diisocyanate such as isophorone diisocyanate.
- a diisocyanate such as isophorone diisocyanate.
- the synthesis method using diisocyanate can synthesize
- the acid anhydride that can be used for the synthesis of the polyamic acid ester is preferably a carboxylic dianhydride, and more preferably a tetracarboxylic dianhydride.
- a carboxylic dianhydride and more preferably a tetracarboxylic dianhydride.
- a tetracarboxylic dianhydride As an example, what is represented by the following general formula (3) can be mentioned.
- acid dianhydride applicable to the synthesis of the polyamic acid ester (A) include ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, methyl Aliphatic tetracarboxylic dianhydrides such as cyclobutanetetracarboxylic dianhydride and cyclopentanetetracarboxylic dianhydride; pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2,3 ′, 3,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetra Carboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracar
- the tetravalent organic containing R 1 in the formula (3) is a tetravalent organic group or an aromatic group and an alicyclic hydrocarbon group, including fused rings and aromatic ring and aliphatic hydrocarbon rings
- the cycloaliphatic skeleton is preferably a cyclohexane skeleton.
- the acid anhydride preferably does not have an alkyl group (for example, a t-butyl group) on the aromatic skeleton.
- the acid anhydride preferably has an acid anhydride group having a succinic anhydride structure.
- Examples of the acid anhydride group having a succinic anhydride structure include the following acid anhydride groups.
- the following compounds are preferable.
- the molecular weight of the acid anhydride is preferably 600 or less, more preferably 500 or less, and even more preferably 400 or less.
- the lower limit of the molecular weight is preferably 250 or more.
- 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
- Examples of the diamine that can be used to obtain a polyamic acid ester include diamines represented by the following general formula (4). However, the following are examples, and known ones can be used as long as they do not contradict the gist of the present invention.
- diamine examples include diaminoisophorone (3-aminomethyl-3,5,5-trimethylcyclohexylamine), toluenediamine, 4,4'-methylenediphenyldiamine, hexamethylenediamine and the like.
- diisocyanate examples include isophorone diisocyanate (ITI), toluene diisocyanate (TDI), methylene diphenyl 4,4′-diisocyanate (MDI), 2,2-bis (4-isocyanatophenyl) hexafluoropropane, hexamethylene diisocyanate. (HMDI) and the like.
- photobase generator (B) One or more photobase generators can function as a catalyst for the ring-closing reaction of a polyamic acid ester by changing the molecular structure upon irradiation with light such as ultraviolet light or visible light, or by cleaving the molecule. It is a compound that produces a basic substance.
- the photobase generator may be an ionic photobase generator or a nonionic photobase generator, but the ionic photobase generator has higher composition sensitivity and excellent resolution. This is preferable because it is advantageous for forming a pattern film. Examples of basic substances include secondary amines and tertiary amines.
- Nonionic photobase generators include, for example, ⁇ -aminoacetophenone compounds, oxime ester compounds, N-formylated aromatic amino groups, N-acylated aromatic amino groups, nitrobenzyl carbamate groups, alcohols, and the like. Examples thereof include compounds having a substituent such as an oxybenzyl carbamate group.
- WPBG-018 (trade name: 9-anthrylmethylN, N'-diethylcarbamate)
- WPBG-027 trade name: (E) -1- [3- (2-hydroxyphenyl) -2-propenoyl piperidine
- WPBG-140 (trade name: 1- (anthraquinon-2-yl) ethyl imidazolecarboxylate)
- WPBG-165 and the like can also be used.
- the ⁇ -aminoacetophenone compound has a benzoin ether bond in the molecule, and when irradiated with light, cleavage occurs in the molecule to produce a basic substance (amine) that exhibits a curing catalytic action.
- ⁇ -aminoacetophenone compounds include (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane (Irgacure 369, trade name, manufactured by BASF Japan Ltd.) and 4- (methylthiobenzoyl) -1-methyl.
- -1-morpholinoethane (Irgacure 907, trade name, manufactured by BASF Japan Ltd.), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl]-
- a commercially available compound such as 1-butanone (Irgacure 379, trade name, manufactured by BASF Japan Ltd.) or a solution thereof can be used.
- Any oxime ester compound can be used as long as it is a compound that generates a basic substance by light irradiation.
- oxime ester compounds those having a group represented by the following general formula (6) are preferable.
- R 16 is a hydrogen atom, an unsubstituted or alkyl group having 1 to 6 carbon atoms, a phenyl group or a phenyl group substituted with a halogen atom, an unsubstituted or 1 carbon atom substituted with one or more hydroxyl groups.
- An alkyl group of ⁇ 20 the alkyl group interrupted by one or more oxygen atoms, unsubstituted, an alkyl group of 1 to 6 carbon atoms or a cycloalkyl group of 5 to 8 carbon atoms substituted by a phenyl group, unsubstituted Or an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group, R 17 represents an unsubstituted or alkyl group having 1 to 6 carbon atoms, a phenyl group substituted with a phenyl group or a halogen atom, an unsubstituted or alkyl group having 1 to 20 carbon atoms substituted with one or more hydroxyl groups,
- the oxime ester compound may have a group represented by the following formula (7).
- R 18 and R 19 are each independently hydrogen or a monovalent organic group, and they may be the same or different. In addition, the two may combine to form a cyclic structure. May be.
- oxime ester photobase generators examples include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by BASF Japan, N-1919, and NCI-831 manufactured by Adeka.
- numerator described in the patent 4344400 gazette can also be used suitably.
- (B) photobase generator a photobase generator having a carbamate structure represented by the following general formula (8), or a photobase generator represented by the following general formulas (9) and (10) may be used. .
- R 20 , R 21 , R 22 and R 23 each independently have hydrogen, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or a substituent.
- R 24 and R 25 are each independently hydrogen, an optionally substituted alkyl group having 1 to 6 carbon atoms, or a substituent.
- R 26 represents an optionally substituted nitrophenyl group
- R 27 and R 28 each independently represents hydrogen, or a substituent.
- R 29 and R 30 are each independently hydrogen or a monovalent organic group, and may be the same or different.
- R 29 and R 30 are bonded to form a cyclic structure.
- at least one of R 29 and R 30 is a monovalent organic group
- R 31 , R 32 , R 33 and R 34. are each independently hydrogen, halogen, hydroxyl, nitro, nitroso group, a mercapto group, a silyl group, a silanol group or a monovalent organic group, it may be different even in the same .
- R 31, R 32 , R 33, and R 34 may be bonded to each other to form a cyclic structure, and may include a hetero atom bond.
- R 35 is unsubstituted or one or more alkyl, alkenyl, alkynyl, haloalkyl, NR 42 R 43 , CN, OR 44 , SR 45 , COR 46 , COOR 47 , Halogen or formula (11) Or an aromatic or heteroaromatic group substituted by: R 35 is a group of formula (12)
- a group represented by R 36 and R 37 are, independently of one another, hydrogen, alkyl, alkenyl, alkynyl, unsubstituted or substituted with one or more alkyl, CN, OR 44, SR 45, phenyl substituted by halogen or haloalkyl ;
- R 39 is alkyl or NR 44A R 45A ;
- R 44A and R 45A together form an alkylene bridge that is unsubstituted or substituted by one or more alkyls;
- R 38 , R 40 , R 41 , R 42 and R 43 are independently of each other hydrogen or
- R 44 , R 45 and R 47 are, independently of one another, hydrogen or alkyl;
- R 46 is hydrogen or alkyl; alternatively, unsubstituted or one or more alkyl, alkenyl, alkynyl, haloalkyl, NR 42 R 43 , CN, OR 44 , SR 45 , COR 44 , COOR 47 , or An aromatic or heteroaromatic group substituted by halogen;
- R 48 is an aromatic that is unsubstituted or substituted by one or more alkyl, alkenyl, alkynyl, haloalkyl, NR 42 R 43 , CN, OR 44 , SR 45 , COR 46 , COOR 47 , or halogen.
- R 49 is hydrogen or alkyl
- R 50 is hydrogen, alkyl, or unsubstituted, or one or more alkyl, vinyl, alkenyl, alkynyl, haloalkyl, phenyl, NR 42 R 43 , CN, OR 44 , SR 45 , COR 46 , COOR 47 Or phenyl substituted by halogen.
- Examples of the ionic type (B) photobase generator include salts of an aromatic component-containing carboxylic acid represented by the following general formula (13) and a tertiary amine, the following general formulas (14) to (18), Photobase generators represented by (23) and (24), WPBG-082, WPBG-167, WPBG-168, WPBG-266, WPBG- manufactured by Wako Pure Chemical Industries, Ltd. represented by the following structural formula 300 or the like can be used.
- R 51 to R 60 are each independently hydrogen or a monovalent organic group.
- Ar represents any of the groups selected from the group consisting of acenaphthenyl group represented by coumarinyl group represented by the following general formula [I] and the following general formula, [II], Y + is A group represented by the following general formula [III], a group represented by the following general formula [IV], a group represented by the following formula [V], a group represented by the following formula [VI], and the following general formula [VII]
- Z ⁇ represents a halogen anion, a borate anion, an N, N-dimethylcarbamate anion, an N, N-dimethyldithiocarbamate anion, a thiocyanate anion, a cyanate anion, represents benzoic acid anion or benzoyl formic acid anions
- R 61 and R 62 are each independently a hydrogen atom, C 1 -C 10 straight, branched youth Or a cyclic alkyl group or a phenyl group which may have a
- m R 63 and n R 64 each independently represent a halogen atom, a linear, branched or cyclic alkylcarbonyl group having 2 to 10 carbon atoms. Or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, m represents an integer of 0 to 5, and n represents an integer of 0 to 7.
- R 65 to R 67 each independently represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.
- A represents a nitrogen atom.
- R 68 represents a hydrogen atom or a hydroxyl group
- R 69 and R 70 are each independently a hydrogen atom or a straight chain having 1 to 10 carbon atoms. Represents a chain, branched or cyclic alkyl group.
- R 71 , R 72 and R 73 are each independently a hydrogen atom or an organic group, and may be the same or different.
- R 71 , R 72 And R 73 may be bonded to each other to form a cyclic structure, and may contain a hetero atom bond, provided that at least one of R 71 , R 72 and R 73 is an organic group.
- R 74 , R 76 and R 77 each independently represents a hydrogen atom or an organic group, and may be the same or different, and R 75 represents a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, silyl group, a silanol group, a nitro group, a nitroso group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, an ammonio group or an organic group .
- R 74, R 75, R 76 and R 77 may be bonded to each other to form a cyclic structure, and may contain a heteroatom bond, and R 78 and R 79 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, Mercapto group, sulfide group, silyl group, silanol group, nitro group, nitro
- R 85 and R 86 represent an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, and 6 to 6 carbon atoms.
- R 14 aryl group, nitro group, hydroxyl group, cyano group, alkoxy group represented by OR 87 , amino group represented by NR 88 R 89 , acyl group represented by R 90 CO, represented by R 91 COO acyloxy group, an alkylthio group or an arylthio group represented by SR 92 or halogen atom
- R 87, R 90, R 91 and R 92 is an alkyl group or an aryl group having 6 to 12 carbon atoms having 1 to 8 carbon atoms
- R 88 and R 89 are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms
- n is an integer of 0 to 7
- m is an integer of 0 to 9.
- Y + is Formula (1 ) To (22), Q is a nitrogen atom or methine group (CH), t and u are 2 or 3, w is an integer of 0 to 2, and A is hydrogen An atom, a hydroxyl group or a halogen atom, and R 93 to R 95 are an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an aryl group having 6 to 14 carbon atoms, R 85 or R 86 and CH 2 -Y + X - it may be bonded to the same benzene ring and may be attached to different benzene rings .
- X - is a counter anion selected from borate anions, phenolate anion and a carboxylate anion is there.
- X 1 and X 2 independently represent an oxygen atom or a sulfur atom.
- R 96 to R 104 independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, a silyl group, or a silanol. group, or a monovalent represents an organic group .
- R 105, R 106, R 107 represents a hydrogen atom or a monovalent organic group. provided that at least one of R 105, R 106, R 107 is a monovalent Organic group.
- R 108 ⁇ R 117 are each independently hydrogen or a monovalent organic group, can have even different all be two or more of them identical. Also, they And R 118 to R 120 each independently represent hydrogen or a monovalent organic group, and two or more of them may be the same or different. Two or more of them may be bonded to form a cyclic structure, R 121 is hydrogen or a monovalent organic group, and A is a compound that can be an anion or Element.
- the photobase generator may be used alone or in combination of two or more.
- the blending amount of the (B) photobase generator is preferably 5 to 50% by mass based on the total amount of the composition. When the content is 5 to 50% by mass, the resolution is excellent.
- the combination and addition amount are appropriately selected according to the coating film thickness and the like. It is preferable to use a polyamic acid ester (A) having a small absorption with respect to the wavelength of the actinic ray so that low exposure can be achieved and the film thickness can be increased.
- the (A) polyamic acid ester having an aromatic group is used, the conjugated system such as R 1 and / or R 2 is shortened, or the charge transfer complex It is useful to prevent formation.
- the solvent that can be used in the photosensitive resin composition of the present invention is not particularly limited as long as it dissolves (A) polyamic acid ester, (B) photobase generator, 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.
- the amount of the solvent to be used is not particularly limited. For example, it may be used in the range of 50 to 9000 parts by mass with respect to 100 parts by mass of (A) polyamic acid ester, depending on the coating film thickness and viscosity.
- a sensitizer can also be added to the photosensitive resin composition of the present invention in order to further improve the photosensitivity.
- the sensitizer include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzal) cyclopentane, and 2,6-bis (4′-diethylaminobenzal) cyclohexanone.
- thioxanthones such as 9H-thioxanthen-9-one. These can be used alone or in combination of 2 to 5 kinds.
- the sensitizer is preferably used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the (A) polyamic acid ester.
- an adhesion aid can be blended with the photosensitive resin composition of the present invention in order 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 blending 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 (A) polyamic acid ester.
- a base proliferating agent may be added to the photosensitive resin composition of the present invention.
- the decomposition rate of the photobase generator (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 JP 2012-237776 A, JP 2006-282657 A, and the like can be used.
- photosensitive resin composition of this invention may be added to the photosensitive resin composition of this invention the other photosensitive component which generates an acid 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.
- the dry film of the present invention has a resin layer obtained by applying and drying the photosensitive resin composition of the present invention on a carrier film (support).
- the dry film is formed by diluting the photosensitive resin composition of the present invention with the above-mentioned organic solvent and adjusting the viscosity to an appropriate viscosity, followed by a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer coater. Apply a uniform thickness on a carrier film with a roll coater, gravure coater, spray coater, etc. Thereafter, the applied photosensitive resin composition is usually dried at a temperature of 50 to 130 ° C. for 1 to 30 minutes to form a resin layer.
- the coating film thickness is not particularly limited, but in general, the film thickness after drying is appropriately selected in the range of 10 to 150 ⁇ m, preferably 20 to 60 ⁇ m.
- a plastic film As the carrier film, a plastic film is used, and a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is preferably used.
- the thickness of the carrier film is not particularly limited, but is generally appropriately selected within the range of 10 to 150 ⁇ m.
- a peelable cover film is further formed on the film surface for the purpose of preventing dust from adhering to the film surface. It is preferable to laminate.
- the peelable cover film for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used.
- a cover film what is necessary is just a thing smaller than the adhesive force of a resin layer and a carrier film when peeling a cover film.
- 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. Moreover, it is desirable to perform drying of a coating film on the conditions that the imidation of (A) polyamic acid ester in the photosensitive resin composition does not occur.
- natural drying, blast drying, or heat drying can be performed at 20 to 140 ° C. for 1 minute to 1 hour.
- drying is performed on a hot plate for 1 to 20 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 (B) photobase generator to generate a base 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 (A) the polyamic acid ester is partially imidized.
- the heating time and the heating temperature are appropriately changed depending on the type of (A) polyamic acid ester, coating film thickness, and (B) photobase generator used. 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.
- the pattern film which consists of (A) polyamic acid ester and the 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, and an immersion method involving ultrasonic treatment.
- Developers include inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide.
- 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 liquid as necessary to obtain a pattern film.
- a rinse liquid as necessary to obtain a pattern film.
- distilled water, methanol, ethanol, isopropanol or the like can be used alone or in combination.
- Examples of the developer include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, ⁇ -butyrolactone, hexamethylphosphoryl tri Amide, methanol, ethanol, isopropyl alcohol, methyl carbitol, ethyl carbitol, toluene, xylene, ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate, ethyl-3-ethoxypropio Organic solvents such as nate, 2-heptanone, ethyl acetate, diacetone alcohol may be used.
- the pattern film is heated.
- the heating temperature is appropriately set so that the polyimide pattern film 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 use of the photosensitive resin composition of the present invention is not particularly limited. For example, printing ink, adhesive, filler, electronic material, optical circuit component, molding material, resist material, building material, three-dimensional modeling, optical member, etc. And various known fields and products in which resin materials are used.
- the photosensitive resin composition of the present invention containing (A) a polyamic acid ester is mainly used as a pattern forming material (resist), and the pattern film formed thereby is heat resistant as a permanent film made of polyimide.
- a pattern forming material resist
- the pattern film formed thereby is heat resistant as a permanent film made of polyimide.
- the solution including the precipitate was filtered and dried to obtain a polymer precursor polymer.
- the obtained polymer was dissolved in DMAc (N, N-dimethylacetamide) and reprecipitated with MeOH. Filtration and drying were performed to prepare a 15% by mass polyamic acid ester A-1 solution using dehydrated DMAc as a solvent.
- Synthesis Example 10 Synthesis of polyamic acid ester A-10
- the polyamic acid ester A-10 was the same as Synthesis Example 1 except that 6FDA was changed to PMDA as the acid dianhydride and anhydrous ITI was changed to anhydrous HMDI (hexamethylene diisocyanate) shown in the following table as the diisocyanate. A solution was made.
- 6FDA was changed to PMDA as the acid dianhydride
- anhydrous ITI was changed to anhydrous HMDI (hexamethylene diisocyanate) shown in the following table as the diisocyanate.
- HMDI hexamethylene diisocyanate
- Examples 1 to 28, Comparative Examples 1 to 3 In the blending ratio (mass ratio) described in Tables 23 and 24 below, the photobase generator was blended and dissolved in the polyamic acid ester and polyamic acid solution obtained above. Examples and Comparative Examples A photosensitive resin composition was obtained. The photobase generator was added so as to be 10% by mass based on the total amount of the photosensitive resin composition. In addition, the compounding quantity of the polyamic acid ester and polyamic acid in a table
- Each photosensitive resin composition of Examples and Comparative Examples was spin-coated on a wafer so as to have a film thickness of 5 ⁇ m after drying, and was dried on an 80 ° C. hot plate for 20 minutes.
- a pattern mask was placed on the resulting dried film, and broad exposure was performed with a table-type exposure apparatus (manufactured by Mitsunaga Electric Co., Ltd.) with the exposure amounts shown in Tables 23 and 24.
- the wafer was heated on a hot plate at 150 ° C.
- the photosensitive resin composition of the present invention provides a pattern film. Moreover, the composition containing an ionic photobase generator was more sensitive and had better resolution than the nonionic photobase generator. Furthermore, by using polyamic acid Tert-butyl ester and alkali development, there was an effect of accelerating dissolution of unexposed areas, and better pattern formation was achieved. On the other hand, in the photosensitive resin composition of Comparative Example in which another polyamic acid or polyamic acid ester was blended in place of the specific polyamic acid ester in the present invention, it was difficult to form a pattern film.
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Abstract
Description
(式(1)中、R1は4価の有機基であり、R2は脂環式骨格を有する基、フェニレン基、アルキレン基で結合されたビスフェニレン骨格を有する基、および、アルキレン基のいずれかであり、Xは2価の有機基であり、R3およびR4は、相互に同一でも異なってもよく、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。)
なお、本発明の感光性樹脂組成物における(A)ポリアミック酸エステルは、実質的にアミック酸部分を含まない。即ち、本発明の感光性樹脂組成物における(A)ポリアミック酸エステルは、特開2003-084435号公報に記載されているような、アミック酸部分およびアミック酸エステル部分の両方を含むポリアミド酸誘導体とは異なるものである。
(式(1-1)中、R2は脂環式骨格を有する基、フェニレン基、アルキレン基で結合されたビスフェニレン骨格を有する基、および、アルキレン基のいずれかであり、Xは2価の有機基であり、R3およびR4は、相互に同一でも異なってもよく、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。)
(式(1-2)中、
R2は脂環式骨格を有する基、フェニレン基、アルキレン基で結合されたビスフェニレン骨格を有する基、および、アルキレン基のいずれかであり、
Xは2価の有機基であり、
R3およびR4は、相互に同一でも異なってもよく、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。)
本発明に使用される(A)ポリアミック酸エステルは、下記一般式(1)で表される構造を有するものである。
(式(1)中、R1は4価の有機基であり、R2は脂環式骨格を有する基、フェニレン基、アルキレン基で結合されたビスフェニレン骨格を有する基、および、アルキレン基のいずれかであり、Xは2価の有機基であり、R3およびR4は、相互に同一でも異なってもよく、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。)
Z1は、Z2と共通するエチレン基と共に芳香族環(好ましくはベンゼン環、ナフタレン環、特にベンゼン環)を形成する炭素原子数4~12個の不飽和炭化水素基であり、芳香族環は置換基として少なくとも1個のアルキル基(炭素原子数1~4個)、アルコキシ基(炭素原子数1~4個)、アリール基(炭素原子数6~10個)、ヒドロキシ基、ハロゲン原子を有していてもよい。
Z3は、Z4と共通するエチレン基と共に芳香族環(好ましくはベンゼン環、ナフタレン環、特にベンゼン環)を形成する炭素原子数4~12個の不飽和炭化水素基であり、芳香族環は置換基として少なくとも1個のアルキル基(炭素原子数1~4個)、アルコキシ基(炭素原子数1~4個)、アリール基(炭素原子数6~10個)、ヒドロキシ基、ハロゲン原子を有していてもよい。
Z5は、Z6と共通するエチレン基と共に芳香族環(好ましくはベンゼン環、ナフタレン環、特にベンゼン環)を形成する炭素原子数4~12個の不飽和炭化水素基であり、芳香族環は置換基として少なくとも1個のアルキル基(炭素原子数1~4個)、アルコキシ基(炭素原子数1~4個)、アリール基(炭素原子数6~10個)、ヒドロキシ基、ハロゲン原子を有していてもよい。2個の「-」で表される1価の結合手は、隣接する炭素に結合しているが、2個の「-」で表される隣接する1価の結合手の組み合わせ同士も隣接して配置されてもよいし、環が大きければ、相互に少なくとも1個の炭素原子をおいて配置されてもよい。2個の「-」で表される1価の結合手は、隣接する炭素に結合しているが、「=CR7-」で表される2価の結合手は、「-」の結合手が結合する炭素の少なくとも1個の炭素原子をおいて隣の炭素原子に結合していることが好ましい。R7は一般に水素原子、アルキル基(炭素原子数1~4個)、アルコキシ基(炭素原子数1~4個)、ヒドロキシ基、ハロゲン原子であり、水素原子が好ましい。
Z7は、Z8と共通するエチレン基と共に芳香族環(好ましくはベンゼン環、ナフタレン環、特にベンゼン環)を形成する炭素原子数4~12個の不飽和炭化水素基であり、芳香族環は置換基として少なくとも1個のアルキル基(炭素原子数1~4個)、アルコキシ基(炭素原子数1~4個)、アリール基(炭素原子数6~10個)、ヒドロキシ基、ハロゲン原子を有していてもよい。2個の「-」で表される1価の結合手(Z7の右側の結合手、または、Z7の左側の結合手)は、それぞれ隣接する炭素に結合しているが、一組の結合手同士も隣接して配置されてもよいし、環が大きければ、相互に少なくとも1個の炭素原子をおいて配置されてもよい。
(式(1-1)中、R2~R4、X、mおよびnは式(1)と同様である。)
(式(1-2)中、R2~R4、X、mおよびnは式(1)と同様である。)
(式(2-1)中、n1は0~10の整数を表し、R10は脂肪族基であり、好ましくは炭素数1~5のアルキレン基であり、より好ましくはメチレン基を表し、R11はそれぞれ独立に、脂肪族基または芳香族基であり、好ましくはメチル基、エチル基などの脂肪族基を表す。)
(式(2-2)中、n2は0~4の整数を表し、R12はそれぞれ独立に、脂肪族基または芳香族基であり、好ましくはメチル基、エチル基などの脂肪族基を表す。)
(式(2-3)中、n3およびn4はそれぞれ独立に0~4の整数を表し、R13およびR14はそれぞれ独立に、脂肪族基または芳香族基であり、好ましくはメチル基、エチル基などの脂肪族基を表し、R15は炭素数1~5のアルキレン基を表す。)
(B)光塩基発生剤は、紫外線や可視光等の光照射により分子構造が変化するか、または、分子が開裂することにより、ポリアミック酸エステルの閉環反応の触媒として機能しうる1種以上の塩基性物質を生成する化合物である。(B)光塩基発生剤は、イオン型光塩基発生剤でもよく、非イオン型光塩基発生剤でもよいが、イオン型光塩基発生剤の方が組成物の感度が高く、解像性に優れ、パターン膜の形成に有利になるので好ましい。塩基性物質として、例えば2級アミン、3級アミンが挙げられる。
非イオン型の(B)光塩基発生剤として、例えば、α-アミノアセトフェノン化合物、オキシムエステル化合物や、N-ホルミル化芳香族アミノ基、N-アシル化芳香族アミノ基、ニトロベンジルカーバメイト基、アルコオキシベンジルカーバメート基等の置換基を有する化合物等が挙げられる。
(式中、R16は、水素原子、無置換または炭素数1~6のアルキル基、フェニル基もしくはハロゲン原子で置換されたフェニル基、無置換または1個以上の水酸基で置換された炭素数1~20のアルキル基、1個以上の酸素原子で中断された該アルキル基、無置換または炭素数1~6のアルキル基もしくはフェニル基で置換された炭素数5~8のシクロアルキル基、無置換または炭素数1~6のアルキル基もしくはフェニル基で置換された炭素数2~20のアルカノイル基またはベンゾイル基を表し、
R17は、無置換または炭素数1~6のアルキル基、フェニル基もしくはハロゲン原子で置換されたフェニル基、無置換または1個以上の水酸基で置換された炭素数1~20のアルキル基、1個以上の酸素原子で中断された該アルキル基、無置換または炭素数1~6のアルキル基もしくはフェニル基で置換された炭素数5~8のシクロアルキル基、無置換または炭素数1~6のアルキル基もしくはフェニル基で置換された炭素数2~20のアルカノイル基またはベンゾイル基を表す。)
(式中、R18およびR19は、それぞれ独立に水素または1価の有機基であり、それらは同一であっても異なっていてもよい。また、それら2つが結合して環状構造を形成していてもよい。)
によって置換された芳香族または複素芳香族基であり;あるいは
R35は、式(12)
によって表わされる基であり;
R36およびR37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、OR44、SR45、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;
R39は、アルキルまたはNR44AR45Aであり;R44AおよびR45A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;
R38、R40、R41、R42およびR43は、互いに独立して、水素またはアルキルであり;あるいは
R38およびR40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
R39およびR41は、R38およびR40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;
R44、R45およびR47は、互いに独立して、水素またはアルキルであり;
R46は水素またはアルキルであり;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、NR42R43、CN、OR44、SR45、COR44、COOR47、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;
R48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、NR42R43、CN、OR44、SR45、COR46、COOR47、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;
R49は、水素またはアルキルであり;
R50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、NR42R43、CN、OR44、SR45、COR46、COOR47またはハロゲンによって置換されたフェニルである。)
イオン型の(B)光塩基発生剤としては、例えば、下記一般式(13)で表される芳香族成分含有カルボン酸と3級アミンとの塩、下記一般式(14)~(18)、(23)および(24)で表される光塩基発生剤、下記構造式で表される和光純薬社製イオン型PBGのWPBG-082、WPBG-167、WPBG-168、WPBG-266、WPBG-300等を用いることができる。
(式[I]および式[II]中、m個のR63およびn個のR64はそれぞれ独立して、ハロゲン原子、炭素数2~10の直鎖状、分枝状若しくは環状のアルキルカルボニル基または炭素数1~10の直鎖状、分枝状若しくは環状のアルキル基を表す。mは、0~5の整数を表し、nは、0~7の整数を表す。)
(式[III]中、R65~R67はそれぞれ独立して、炭素数1~10の直鎖状、分枝状若しくは環状のアルキル基を表す。式[IV]中、Aは、窒素原子またはメチン基(CH基)を表し、R68は、水素原子またはヒドロキシル基を表す。一般式[VII]中、R69およびR70はそれぞれ独立して、水素原子または炭素数1~10の直鎖状、分枝状若しくは環状のアルキル基を表す。)
また、現像液としては、例えば、N-メチル-2-ピロリドン、N-アセチル-2-ピロリドン、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、ジメチルスルホキシド、γ-ブチロラクトン、ヘキサメチルホスホルトリアミド、メタノール、エタノール、イソプロピルアルコール、メチルカルビトール、エチルカルビトール、トルエン、キシレン、乳酸エチル、ピルビン酸エチル、プロピレングリコールモノメチルエーテルアセテート、メチル-3-メトキシプロピオネート、エチル-3-エトキシプロピオネート、2-ヘプタノン、酢酸エチル、ジアセトンアルコールなど有機溶剤を使用してもよい。
酸二無水物として6FDA(4,4’-(ヘキサフルオロイソプロピリデン)ジフタル酸無水物)5gに乾燥MeOH約25gを加えて還流した。還流開始後約30分ほぼ透明な液が得られた。更に、約5時間還流し、冷却し、ポアーサイズ0.7μmのフィルタで濾過し不純物を除いた。減圧乾燥してMeOHを完全に除去し、白い結晶として、表1に記載する酸無水物のハーフエステルを得た。
容量100mlの三口フラスコに、表1に記載する酸無水物のハーフエステル5mmolと無水3-メチル-1-フェニル-2-ホスホレン1-オキシド0.0125mmolを投入した後、窒素を流しながら、10mlの脱水スルホランで溶解させた。ジイソシアネートとして無水ITI(ジイソシアン酸イソホロン)5mmolを5ml脱水スルホランで溶解させ、フラスコに約5分間で滴下した。混合溶液を200℃、3時間で反応させ、MeOH 500mlで沈殿した。沈殿を含めた溶液を濾過し、乾燥を行って、高分子前駆体ポリマーを得た。得られたポリマーをDMAc(N,N-ジメチルアセトアミド)に溶解し、MeOHで再沈殿した。濾過、乾燥を行って、脱水DMAcを溶媒として15質量%のポリアミック酸エステルA-1溶液を作製した。
酸二無水物として、6FDAをPMDA(ピロメリット酸無水物)に変更した以外は、合成例1と同様にしてポリアミック酸エステルA-2溶液を作製した。
ジイソシアネートとして、無水ITIを下記表に記載の無水MDI(4,4’-ジイソシアン酸メチレンジフェニル)に変更した以外は、合成例1と同様にしてポリアミック酸エステルA-3溶液を作製した。
酸二無水物として、6FDAをPMDAに変更し、ジイソシアネートとして、無水ITIを下記表に記載の無水MDIに変更した以外は、合成例1と同様にしてポリアミック酸エステルA-4溶液を作製した。
ジイソシアネートとして、無水ITIを下記表に記載の無水TDI-1(2,4-トルエンジイソシアネート)に変更した以外は、合成例1と同様にしてポリアミック酸エステルA-5溶液を作製した。
酸二無水物として、6FDAをPMDAに変更し、ジイソシアネートとして、無水ITIを下記表に記載の無水TDI-1に変更した以外は、合成例1と同様にしてポリアミック酸エステルA-6溶液を作製した。
酸二無水物として、6FDAをTDA(1,3,3a,4,5,9b-ヘキサヒドロ-5(テトラヒドロ-2,5-ジオキソ-3-フラニル)ナフト[1,2-c]フラン-1,3-ジオン)に変更し、ジイソシアネートとして、無水ITIを下記表に記載の無水TDI-2(2,4-トルエンジイソシアネートと2,6-トルエンジイソシアネートの混合物(80:20)に変更した以外は、合成例1と同様にしてポリアミック酸エステルA-7溶液を作製した。
酸二無水物として、6FDAをTDAに変更し、ジイソシアネートとして、無水ITIを下記表に記載の無水MDIに変更した以外は、合成例1と同様にしてポリアミック酸エステルA-8溶液を作製した。
酸二無水物として、6FDAをTDAに変更した以外は、合成例1と同様にしてポリアミック酸エステルA-9溶液を作製した。
酸二無水物として、6FDAをPMDAに変更し、ジイソシアネートとして、無水ITIを下記表に記載の無水HMDI(ヘキサメチレンジイソシアネート)に変更した以外は、合成例1と同様にしてポリアミック酸エステルA-10溶液を作製した。
合成例1においてMeOHをtert-ブチルアルコールに変更した以外は、合成例1と同様にしてポリアミック酸エステルA-11溶液を作製した。
合成例2においてMeOHをtert-ブチルアルコールに変更した以外は、合成例2と同様にしてポリアミック酸エステルA-12溶液を作製した。
合成例3においてMeOHをtert-ブチルアルコールに変更した以外は、合成例3と同様にしてポリアミック酸エステルA-13溶液を作製した。
合成例4においてMeOHをtert-ブチルアルコールに変更した以外は、合成例4と同様にしてポリアミック酸エステルA-14溶液を作製した。
合成例5においてMeOHをtert-ブチルアルコールに変更した以外は、合成例5と同様にしてポリアミック酸エステルA-15溶液を作製した。
合成例6においてMeOHをtert-ブチルアルコールに変更した以外は、合成例6と同様にしてポリアミック酸エステルA-16溶液を作製した。
合成例7においてMeOHをtert-ブチルアルコールに変更した以外は、合成例7と同様にしてポリアミック酸エステルA-17溶液を作製した。
合成例8においてMeOHをtert-ブチルアルコールに変更した以外は、合成例8と同様にしてポリアミック酸エステルA-18溶液を作製した。
合成例9においてMeOHをtert-ブチルアルコールに変更した以外は、合成例9と同様にしてポリアミック酸エステルA-19溶液を作製した。
合成例10においてMeOHをtert-ブチルアルコールに変更した以外は、合成例10と同様にしてポリアミック酸エステルA-20溶液を作製した。
容量300mlのセパラブルフラスコに、下記表に記載のジアミン30mmolを投入した後、窒素を流しながら、脱水DMAc(N,N-ジメチルアセトアミド)でジアミンを溶解させた。ジアミンを全て溶解させた後、酸無水物として、下記表に記載の6FDA30mmolを徐々に加えた。少量のDMAcでフラスコの壁に付着した6FDAを反応溶液に流し入れた後、24時間、室温で撹拌して反応させ、15質量%のポリアミック酸の溶液を得た。脱水DMAcの投入量はポリアミック酸の溶液の量の75質量%であった。
酸無水物として、6FDAを下記表に記載のPMDAに変更した以外は、比較合成例1と同様にしてポリアミック酸R-2溶液を作製した。
特開2003-084435号公報の比較例2の記載に合成手順に従って、3,3’,4,4’-ジフェニルエーテルテトラカルボン酸二無水物(ODPA)と4,4’-ジアミノジフェニルエーテル(DDE,ODA)とエタノール(EtOH)とを使用して、100%エステル化したポリアミック酸エステルを合成し、ポリアミック酸エステルR-3溶液を作製した。
下記表23、24に記載の配合比(質量比)で、上記で得られたポリアミック酸エステル、ポリアミック酸の溶液に対して、光塩基発生剤を配合し、溶解させて、実施例および比較例の感光性樹脂組成物を得た。光塩基発生剤は、感光性樹脂組成物全量基準で10質量%となるように加えた。尚、表中のポリアミック酸エステル、ポリアミック酸の配合量は、固形分量を示す。
実施例および比較例の各感光性樹脂組成物を、ウェハー上に乾燥後の膜厚5μmになるようにスピンコートし、80℃のホットプレート上で20分間乾燥させた。
得られた乾燥膜上にパターンマスクを配置して卓上型露光装置(三永電機社製)で表23、24中に記載の露光量でブロード露光を行った。
そのウェハーを、150℃のホットプレート上で6分加熱した後、有機溶剤現像液(DMAc(ジメチルアセトアミド))、またはアルカリ現像液(2.38質量%TMAH(テトラメチルアンモニウムハイドロオキサイド)水溶液と2‐プロパノールの1:1重量比混合溶液)に浸漬し、現像した。
解像度の評価として、上記現像後のパターンを電子顕微鏡で観察し、パターン形成したなかで良好に解像された最少形状のサイズを評価した。
数値: 最少パターンサイズ(μm)
×: パターン形成不可
一方、本発明における特定のポリアミック酸エステルにかえて、他のポリアミック酸またはポリアミック酸エステルを配合した比較例の感光性樹脂組成物は、パターン膜の形成が困難なものであった。
Claims (7)
- 前記一般式(1)中のR1が、芳香族環と脂肪族炭化水素環との縮合環を含む4価の有機基、芳香族基と脂環式炭化水素基とを含む4価の有機基、またはフッ素原子を含む4価の有機基であることを特徴とする請求項1記載の感光性樹脂組成物。
- 前記(A)ポリアミック酸エステルが、下記一般式(1-1)および(1-2)の少なくともいずれか一方で表される構造を有することを特徴とする請求項1記載の感光性樹脂組成物。
(式(1-1)中、
R2は脂環式骨格を有する基、フェニレン基、アルキレン基で結合されたビスフェニレン骨格を有する基、および、アルキレン基のいずれかであり、
Xは2価の有機基であり、
R3およびR4は、相互に同一でも異なってもよく、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。)
(式(1-2)中、
R2は脂環式骨格を有する基、フェニレン基、アルキレン基で結合されたビスフェニレン骨格を有する基、および、アルキレン基のいずれかであり、
Xは2価の有機基であり、
R3およびR4は、相互に同一でも異なってもよく、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。) - 前記(B)光塩基発生剤が、イオン型光塩基発生剤であることを特徴とする請求項1記載の感光性樹脂組成物。
- 請求項1記載の感光性樹脂組成物を、フィルムに塗布、乾燥して得られる樹脂層を有することを特徴とするドライフィルム。
- 請求項1~4のいずれか1項記載の感光性樹脂組成物または請求項5記載のドライフィルムの樹脂層を、硬化して得られることを特徴とする硬化物。
- 請求項6記載の硬化物を有することを特徴とするプリント配線板。
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JP2009265637A (ja) * | 2008-03-31 | 2009-11-12 | Dainippon Printing Co Ltd | 感光性樹脂組成物、物品、及びパターン形成方法 |
JP2010186134A (ja) * | 2009-02-13 | 2010-08-26 | Asahi Kasei E-Materials Corp | 感光性樹脂組成物及びそれを用いた回路基板 |
WO2015019802A1 (ja) * | 2013-08-09 | 2015-02-12 | 太陽ホールディングス株式会社 | 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 |
JP2015141303A (ja) * | 2014-01-28 | 2015-08-03 | 太陽インキ製造株式会社 | 感光性熱硬化性樹脂組成物およびフレキシブルプリント配線板 |
JP2016130836A (ja) * | 2015-01-13 | 2016-07-21 | 太陽ホールディングス株式会社 | 感光性樹脂組成物、そのドライフィルム及び硬化物、硬化物を含む電子部品又は光学製品、並びに感光性樹脂組成物を含む接着剤 |
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CN108475023B (zh) | 2022-02-25 |
JP6738353B2 (ja) | 2020-08-12 |
KR20180102622A (ko) | 2018-09-17 |
JPWO2017122744A1 (ja) | 2018-11-01 |
TWI735508B (zh) | 2021-08-11 |
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