WO2013191155A1 - Photosensitive resin composition, method for manufacturing cured film, cured film, organic el display device, and liquid crystal display device - Google Patents
Photosensitive resin composition, method for manufacturing cured film, cured film, organic el display device, and liquid crystal display device Download PDFInfo
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- WO2013191155A1 WO2013191155A1 PCT/JP2013/066657 JP2013066657W WO2013191155A1 WO 2013191155 A1 WO2013191155 A1 WO 2013191155A1 JP 2013066657 W JP2013066657 W JP 2013066657W WO 2013191155 A1 WO2013191155 A1 WO 2013191155A1
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- UFSFPRSMPJCKNE-UHFFFAOYSA-N CC(C)(C)NC(NCCN1CCOCC1)=S Chemical compound CC(C)(C)NC(NCCN1CCOCC1)=S UFSFPRSMPJCKNE-UHFFFAOYSA-N 0.000 description 1
- VVENCTDZUWPTMX-UHFFFAOYSA-N CCN(CC)CCNC(NC1CCCCC1)=S Chemical compound CCN(CC)CCNC(NC1CCCCC1)=S VVENCTDZUWPTMX-UHFFFAOYSA-N 0.000 description 1
- AKYYGBUVZFGJNI-UHFFFAOYSA-N S=C(NCCN1CCOCC1)NC1CCCCC1 Chemical compound S=C(NCCN1CCOCC1)NC1CCCCC1 AKYYGBUVZFGJNI-UHFFFAOYSA-N 0.000 description 1
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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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
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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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- 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
- G03F7/075—Silicon-containing compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
- G03F7/0751—Silicon-containing compounds used as adhesion-promoting additives or as means to improve adhesion
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
- G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
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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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/20—Changing the shape of the active layer in the devices, e.g. patterning
- H10K71/231—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers
- H10K71/233—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers by photolithographic etching
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/106—Binder containing
Definitions
- the present invention relates to a photosensitive resin composition (hereinafter sometimes simply referred to as “the composition of the present invention”). Moreover, it is related with the manufacturing method of the cured film using the said photosensitive resin composition, the cured film formed by hardening
- Organic EL display devices, liquid crystal display devices, and the like are provided with a patterned interlayer insulating film.
- photosensitive resin compositions are widely used because the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained.
- the interlayer insulating film in the above display device is desired to have high transparency. Yes. For this reason, it has been attempted to use an acrylic resin having excellent transparency as a film-forming component.
- acrylic resin having excellent transparency as a film-forming component.
- Patent Document 1 those described in Patent Document 1 are known.
- Patent Document 2 the thing of patent document 2 is also known as a photosensitive resin composition.
- adhesion to the substrate As an important characteristic of the photosensitive resin composition constituting the interlayer insulating film, adhesion to the substrate can be mentioned. In the development process, “film peeling” from the substrate may occur, which is one of the problems. Furthermore, in recent years, as display devices become higher performance and higher definition, it has become difficult to perform fine pattern processing, and improvement in adhesion of the interlayer insulating film material after curing is also required.
- the photosensitive resin composition is required to have adhesiveness with the base substrate during development and in the state of being a cured film.
- the substrate itself is made of a plurality of types of materials, the interlayer insulating film material formed on the surface thereof is provided with adhesion to the types of substrates.
- the object of the present invention is to provide a photosensitive resin composition that has good adhesion to a substrate.
- it aims at providing the formation method of a cured film using such a photosensitive resin composition, a cured film, an organic electroluminescence display, and a liquid crystal display device.
- ⁇ 5> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein the photoacid generator (B) is an oxime sulfonate compound.
- (F) The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 6>, comprising a crosslinking agent.
- ⁇ 8> (1) A step of applying the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 7> on a substrate, (2) removing the solvent from the applied photosensitive resin composition; (3) A step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays, (4) a step of developing the exposed photosensitive resin composition with an aqueous developer, and (5) A method for producing a cured film, comprising a post-baking step of thermosetting the developed photosensitive resin composition.
- the method for producing a cured film according to ⁇ 8> including a step of exposing the entire surface of the developed photosensitive resin composition after the developing step and before the post-baking step.
- ⁇ 10> A cured film formed by the method ⁇ 8> or ⁇ 9>.
- ⁇ 11> A cured film of ⁇ 10>, which is an interlayer insulating film.
- ⁇ 12> An organic EL display device or a liquid crystal display device having a cured film of ⁇ 10> or ⁇ 11>.
- the photosensitive resin composition according to any one of the above, wherein (A) the polymer component is 50 to 99.9 parts by mass with respect to 100 parts by mass of the total solid content, and (B) the nonionic photoacid.
- a composition comprising 0.1 to 10 parts by mass of a generator, 0.001 to 5 parts by mass of a compound represented by (C) the general formula (S), and 0.1 to 30 parts by mass of an alkoxysilane compound.
- the present invention it is possible to provide a photosensitive resin composition that can achieve high adhesion to a substrate during development and when used as a cured film.
- FIG. 1 is a conceptual diagram of a configuration of an example of a liquid crystal display device.
- the schematic sectional drawing of the active matrix substrate in a liquid crystal display device is shown, and it has the cured film 17 which is an interlayer insulation film.
- 1 shows a conceptual diagram of a configuration of an example of an organic EL display device.
- a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
- the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent.
- the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
- the photosensitive resin composition of the present invention (hereinafter sometimes referred to as “the composition of the present invention”) is preferably used as a positive photosensitive resin composition.
- the photosensitive resin composition of the present invention comprises (A) a polymer component containing a polymer that satisfies at least one of the following (1) and (2): (1) (a1) a polymer having a structural unit having an acid group protected with an acid-decomposable group, and (a2) a structural unit having a crosslinkable group, (2) (a1) a polymer having a structural unit having a group in which an acid group is protected with an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group, (B) a nonionic photoacid generator, (C) a compound represented by the above general formula (S), (D) a solvent, and (E) It contains an alkoxysilane compound. According to the present invention, it is possible to provide a photosensitive resin composition having excellent adhesion to
- the composition of the present invention comprises, as a polymer component, (1) (a1) a polymer having a structural unit having an acid group protected by an acid-decomposable group and (a2) a structural unit having a crosslinkable group, And (2) (a1) at least one of a polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group and (a2) a polymer having a structural unit having a crosslinkable group. Furthermore, polymers other than these may be included.
- the polymer component (A) in the present invention (hereinafter referred to as “component (A)”) is added in addition to the above (1) and / or (2) unless otherwise specified. Including those polymers.
- Component A has (a1) at least a structural unit having a group in which an acid group is protected with an acid-decomposable group.
- component (A) has the structural unit (a1), a highly sensitive photosensitive resin composition can be obtained.
- group in which the acid group is protected with an acid-decomposable group those known as an acid group and an acid-decomposable group can be used, and are not particularly limited.
- Specific examples of the acid group preferably include a carboxyl group and a phenolic hydroxyl group.
- the acid-decomposable group is a group that is relatively easily decomposed by an acid (for example, an acetal group such as an ester structure of a group represented by the formula (A1) described later, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group).
- a functional group or a group that is relatively difficult to decompose with an acid (for example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group).
- the structural unit having an acid group protected with an acid-decomposable group is a structural unit having a protected carboxyl group protected with an acid-decomposable group, or a protected phenolic group protected with an acid-decomposable group.
- a structural unit having a hydroxyl group is preferred.
- the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group and the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group will be described in order. To do.
- the structural unit (a1-1) having a protected carboxyl group protected by an acid-decomposable group is a protected carboxyl in which the carboxyl group of the structural unit having a carboxyl group is protected by an acid-decomposable group described in detail below.
- a structural unit having a group is not particularly limited, and a known structural unit can be used.
- a structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or an unsaturated tricarboxylic acid
- a structural unit (a1-1-2) having both an ethylenically unsaturated group and a structure derived from an acid anhydride.
- (a1-1-1) a structural unit derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule used as the structural unit having a carboxyl group, and (a1-1-2) ethylene
- the structural units having both the unsaturated group and the structure derived from the acid anhydride will be described in order.
- ⁇ (a1-1-1) Structural Unit Derived from Unsaturated Carboxylic Acid Having at least One Carboxyl Group in the Molecule >>>>>>>
- the unsaturated carboxylic acid used in the present invention as the structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule include those listed below. . That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, ⁇ -chloroacrylic acid, cinnamic acid, 2- (meth) acryloyloxyethyl-succinic acid, and 2- (meth) acrylic acid.
- Examples include leuoxyethyl hexahydrophthalic acid and 2- (meth) acryloyloxyethyl-phthalic acid.
- Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.
- the acid anhydride may be sufficient as unsaturated polycarboxylic acid used in order to obtain the structural unit which has a carboxyl group. Specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like.
- the unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester of a polyvalent carboxylic acid, such as succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2 -Methacryloyloxyethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like.
- the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both ends, and examples thereof include ⁇ -carboxypolycaprolactone monoacrylate and ⁇ -carboxypolycaprolactone monomethacrylate.
- unsaturated carboxylic acid acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used.
- the structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-phthalic acid, or unsaturated polycarboxylic acid anhydride It is preferable to use acrylic acid, methacrylic acid, and 2- (meth) acryloyloxyethyl hexahydrophthalic acid.
- the structural unit (a1-1-1) derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the molecule may be composed of one kind alone or two or more kinds. May be.
- (a1-1-2) Structural unit having both an ethylenically unsaturated group and a structure derived from an acid anhydride >>>>
- the structural unit (a1-1-2) having both an ethylenically unsaturated group and a structure derived from an acid anhydride is obtained by reacting a hydroxyl group present in the structural unit having an ethylenically unsaturated group with an acid anhydride.
- a unit derived from the obtained monomer is preferred.
- the acid anhydride known ones can be used, and specifically, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride, etc.
- phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferable from the viewpoint of developability.
- the reaction rate of the acid anhydride with respect to the hydroxyl group is preferably 10 to 100 mol%, more preferably 30 to 100 mol% from the viewpoint of developability.
- acid-decomposable group that can be used for the structural unit (a1-1) >>>>>
- the acid-decomposable group that can be used in the structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group the above-mentioned acid-decomposable group can be used.
- the carboxyl group is a protected carboxyl group protected in the form of an acetal, so that the basic physical properties of the photosensitive resin composition, in particular, sensitivity and pattern shape, contact hole formability, photosensitive resin It is preferable from the viewpoint of the storage stability of the composition.
- the carboxyl group is more preferably a protected carboxyl group protected in the form of an acetal represented by the following general formula (a1-10) from the viewpoint of sensitivity.
- the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following general formula (a1-10)
- the entire protected carboxyl group is — (C ⁇ O) —O—CR 101 It has a structure of R 102 (OR 103).
- R 101 and R 102 each independently represents a hydrogen atom or an alkyl group, except that R 101 and R 102 are both hydrogen atoms, and R 103 represents an alkyl group.
- R 101 or R 102 and R 103 may be linked to form a cyclic ether.
- R 101 to R 103 each independently represents a hydrogen atom or an alkyl group, and the alkyl group may be linear, branched or cyclic.
- both R 101 and R 102 do not represent a hydrogen atom, and at least one of R 101 and R 102 represents an alkyl group.
- R 101 , R 102 and R 103 represent an alkyl group
- the alkyl group may be linear, branched or cyclic.
- the linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms.
- methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n examples include -hexyl group, texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group and the like.
- the cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 4 to 6 carbon atoms.
- Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group.
- the alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group.
- R 101 , R 102 and R 103 When it has a halogen atom as a substituent, R 101 , R 102 and R 103 become a haloalkyl group, and when it has an aryl group as a substituent, R 101 , R 102 and R 103 become an aralkyl group.
- the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom or a chlorine atom is preferable.
- the aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, an ⁇ -methylphenyl group, and a naphthyl group.
- the alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and more preferably a methoxy group or an ethoxy group.
- the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group is a straight chain. Or a branched alkyl group, it may have a cycloalkyl group having 3 to 12 carbon atoms as a substituent. These substituents may be further substituted with the above substituents.
- R 101 , R 102 and R 103 represent an aryl group
- the aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. preferable.
- the aryl group may have a substituent, and preferred examples of the substituent include an alkyl group having 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group, a tolyl group, a silyl group, a cumenyl group, and a 1-naphthyl group.
- R 101 , R 102 and R 103 can be bonded together to form a ring together with the carbon atom to which they are bonded.
- Examples of the ring structure when R 101 and R 102 , R 101 and R 103 or R 102 and R 103 are bonded include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, an adamantyl group, and a tetrahydropyrani group. And the like.
- any one of R 101 and R 102 is preferably a hydrogen atom or a methyl group.
- radical polymerizable monomer used for forming the structural unit having a protected carboxyl group represented by the general formula (a1-10) a commercially available one may be used, or it may be synthesized by a known method. Things can also be used. For example, it can be synthesized by the synthesis method described in paragraph numbers 0037 to 0040 of JP2011-212494A.
- a first preferred embodiment of the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is a structural unit represented by the following general formula.
- R 1 and R 2 each represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 1 and R 2 is an alkyl group or an aryl group, and R 3 is an alkyl group or Represents an aryl group, R 1 or R 2 and R 3 may be linked to form a cyclic ether, R 4 represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group;
- R 1 and R 2 are alkyl groups, alkyl groups having 1 to 10 carbon atoms are preferred.
- R 1 and R 2 are aryl groups, a phenyl group is preferred.
- R 1 and R 2 are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- R 3 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.
- X represents a single bond or an arylene group, and a single bond is preferred.
- a second preferred embodiment of the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is a structural unit of the following general formula.
- R 121 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
- L 1 represents a carbonyl group or a phenylene group
- R 122 to R 128 each independently represents a hydrogen atom or 1 to 4 carbon atoms.
- Represents an alkyl group of R 121 is preferably a hydrogen atom or a methyl group.
- L 1 is preferably a carbonyl group.
- R 122 to R 128 are preferably hydrogen atoms.
- R represents a hydrogen atom or a methyl group.
- the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group is a protected phenolic group in which the structural unit having a phenolic hydroxyl group is protected by an acid-decomposable group described in detail below.
- ⁇ (a1-2-1) Structural unit having phenolic hydroxyl group Examples of the structural unit having a phenolic hydroxyl group include a hydroxystyrene structural unit and a structural unit in a novolac resin. Among these, a structural unit derived from hydroxystyrene or ⁇ -methylhydroxystyrene includes: It is preferable from the viewpoint of sensitivity. As the structural unit having a phenolic hydroxyl group, a structural unit represented by the following general formula (a1-20) is also preferable from the viewpoint of sensitivity.
- R 220 represents a hydrogen atom or a methyl group
- R 221 represents a single bond or a divalent linking group
- R 222 represents a halogen atom or a straight chain having 1 to 5 carbon atoms or Represents a branched alkyl group
- a represents an integer of 1 to 5
- b represents an integer of 0 to 4
- a + b is 5 or less, and when R 222 is 2 or more, these R 222 may be different or the same.
- R 220 represents a hydrogen atom or a methyl group, and is preferably a methyl group.
- R 221 represents a single bond or a divalent linking group. A single bond is preferable because the sensitivity can be improved and the transparency of the cured film can be further improved.
- the divalent linking group of R 221 may be exemplified alkylene groups, specific examples R 221 is an alkylene group, a methylene group, an ethylene group, a propylene group, isopropylene group, n- butylene group, isobutylene group, tert -Butylene group, pentylene group, isopentylene group, neopentylene group, hexylene group and the like. Among these, R 221 is preferably a single bond, a methylene group, or an ethylene group.
- the divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group.
- A represents an integer of 1 to 5, but a is preferably 1 or 2 and more preferably 1 from the viewpoint of the effects of the present invention and the ease of production.
- the bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4-position when the carbon atom bonded to R 221 is defined as the reference (first position).
- R 222 is a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms.
- a chlorine atom, a bromine atom, a methyl group, or an ethyl group is preferable from the viewpoint of easy production.
- B represents 0 or an integer of 1 to 4.
- the acid-decomposable group that can be used in the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group includes a structure having a protected carboxyl group protected with the acid-decomposable group. Similar to the acid-decomposable group that can be used for the unit (a1-1), known ones can be used and are not particularly limited.
- the structural unit having a protected phenolic hydroxyl group protected with acetal is a basic physical property of the photosensitive resin composition, particularly sensitivity and pattern shape, storage stability of the photosensitive resin composition, contact It is preferable from the viewpoint of hole formability. Furthermore, among the acid-decomposable groups, it is more preferable from the viewpoint of sensitivity that the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of an acetal represented by the general formula (a1-10).
- the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of the acetal represented by the general formula (a1-10)
- the entire protected phenolic hydroxyl group is —Ar—O—CR 101 R.
- the structure is 102 (OR 103 ).
- Ar represents an arylene group.
- Examples of the radical polymerizable monomer used to form a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected in the form of an acetal include, for example, paragraph number 0042 of JP-A No. 2011-215590. And the like.
- a 1-alkoxyalkyl protector of 4-hydroxyphenyl methacrylate and a tetrahydropyranyl protector of 4-hydroxyphenyl methacrylate are preferable from the viewpoint of transparency.
- acetal protecting group for the phenolic hydroxyl group examples include a 1-alkoxyalkyl group, such as a 1-ethoxyethyl group, a 1-methoxyethyl group, a 1-n-butoxyethyl group, and a 1-isobutoxyethyl group.
- 1- (2-chloroethoxy) ethyl group, 1- (2-ethylhexyloxy) ethyl group, 1-n-propoxyethyl group, 1-cyclohexyloxyethyl group, 1- (2-cyclohexylethoxy) ethyl group, 1 -A benzyloxyethyl group etc. can be mentioned, These can be used individually or in combination of 2 or more types.
- the radical polymerizable monomer used for forming the structural unit (a1-2) having a protected phenolic hydroxyl group protected by the acid-decomposable group a commercially available one may be used, or a known method may be used. What was synthesize
- combined by can also be used. For example, it can be synthesized by reacting a compound having a phenolic hydroxyl group with vinyl ether in the presence of an acid catalyst. In the above synthesis, a monomer having a phenolic hydroxyl group may be previously copolymerized with another monomer, and then reacted with vinyl ether in the presence of an acid catalyst.
- the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group the following structural units can be exemplified, but the present invention is not limited thereto.
- the structural unit (a1) is 20 to 100 in the polymer containing the structural unit (a1).
- the mol% is preferable, and 30 to 90 mol% is more preferable.
- the polymer containing the structural unit (a1) contains the following structural unit (a2)
- the single structural unit (a1) is contained in the polymer containing the structural unit (a1) and the structural unit (a2). From the viewpoint of sensitivity, it is preferably 3 to 70 mol%, more preferably 10 to 60 mol%.
- the acid-decomposable group that can be used in the structural unit (a1) is a structural unit having a protected carboxyl group in which the carboxyl group is protected in the form of an acetal
- the content is preferably 20 to 50 mol%.
- the structural unit (a1-1) having a protected carboxyl group protected with the acid-decomposable group is more developed than the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group. Is characterized by being fast. Therefore, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is preferred for rapid development. Conversely, when it is desired to delay development, it is preferable to use the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group.
- the structural unit (a1-1) having a protected carboxyl group protected with the acid-decomposable group is more developed than the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group. Is characterized by being fast. Therefore, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is preferred for rapid development. Conversely, when it is desired to delay development, it is preferable to use the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group.
- the component (A) has a structural unit (a2) having a crosslinkable group.
- the crosslinkable group is not particularly limited as long as it is a group that causes a curing reaction by heat treatment.
- Preferred embodiments of the structural unit having a crosslinkable group include an epoxy group, an oxetanyl group, a group represented by —NH—CH 2 —O—R (where R is an alkyl group having 1 to 20 carbon atoms), and ethylenically unsaturated groups.
- the component (A) preferably includes a structural unit containing at least one of an epoxy group and an oxetanyl group. In more detail, the following are mentioned.
- the polymer (A) preferably contains a structural unit (structural unit (a2-1)) having an epoxy group and / or an oxetanyl group.
- the 3-membered cyclic ether group is also called an epoxy group, and the 4-membered cyclic ether group is also called an oxetanyl group.
- the structural unit (a2-1) having an epoxy group and / or oxetanyl group may have at least one epoxy group or oxetanyl group in one structural unit.
- It may have an oxetanyl group, two or more epoxy groups, or two or more oxetanyl groups, and is not particularly limited, but preferably has a total of 1 to 3 epoxy groups and / or oxetanyl groups, It is more preferable to have one or two epoxy groups and / or oxetanyl groups in total, and it is even more preferable to have one epoxy group or oxetanyl group.
- radical polymerizable monomer used for forming the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl ⁇ -ethyl acrylate, and glycidyl ⁇ -n-propyl acrylate.
- radical polymerizable monomer used for forming the structural unit having an oxetanyl group include (meth) having an oxetanyl group described in paragraph Nos. 0011 to 0016 of JP-A No. 2001-330953, for example. Acrylic esters and the like are included, the contents of which are incorporated herein.
- radical polymerizable monomer used for forming the structural unit (a2-1) having the epoxy group and / or oxetanyl group include a monomer having a methacrylic ester structure and an acrylic ester structure. It is preferable that it is a monomer to contain.
- glycidyl methacrylate 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, methyl (3-ethyloxetane-3-yl) methacrylate, and methacrylic acid ( 3-ethyloxetane-3-yl) methyl.
- These structural units can be used individually by 1 type or in combination of 2 or more types.
- R represents a hydrogen atom or a methyl group.
- (a2-2) Structural unit having an ethylenically unsaturated group >>>
- One example of the structural unit (a2) having a crosslinkable group is a structural unit (a2-2) having an ethylenically unsaturated group (hereinafter also referred to as “structural unit (a2-2)”).
- the structural unit (a2-2) having an ethylenically unsaturated group is preferably a structural unit having an ethylenically unsaturated group in the side chain, having an ethylenically unsaturated group at the terminal, and having 3 to 16 carbon atoms.
- a structural unit having a side chain is more preferred, and a structural unit having a side chain represented by the following general formula (a2-2-1) is more preferred.
- R 301 represents a divalent linking group having 1 to 13 carbon atoms
- R 302 represents a hydrogen atom or a methyl group
- * represents a structural unit having a crosslinkable group ( It represents a site linked to the main chain of a2).
- R 301 is a divalent linking group having 1 to 13 carbon atoms and includes an alkenyl group, a cycloalkenyl group, an arylene group, or a combination of these, and includes an ester bond, an ether bond, an amide bond, a urethane bond, and the like. Bonds may be included.
- the divalent linking group may have a substituent such as a hydroxy group or a carboxyl group at an arbitrary position. Specific examples of R 301 include the following divalent linking groups.
- an aliphatic side chain including the divalent linking group represented by R 301 is preferable.
- the polymer used in the present invention is also preferably a structural unit (a2-3) having a group represented by —NH—CH 2 —O—R (R is an alkyl group having 1 to 20 carbon atoms).
- R is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
- the alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
- the structural unit (a2) is more preferably a structural unit having a group represented by the following general formula (a2-30).
- Formula (a2-30) (In general formula (a2-30), R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkyl group having 1 to 20 carbon atoms.) R 2 is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
- the alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
- R 2 include a methyl group, an ethyl group, an n-butyl group, an i-butyl group, a cyclohexyl group, and an n-hexyl group. Of these, i-butyl, n-butyl and methyl are preferred.
- the structural unit (a2) is 5 to 90% in the polymer containing the structural unit (a2).
- the mol% is preferable, and 20 to 80 mol% is more preferable.
- the polymer containing the structural unit (a2) contains the structural unit (a1)
- the single structural unit (a2) is contained in the polymer containing the structural unit (a1) and the structural unit (a2).
- it is preferably 3 to 70 mol%, more preferably 10 to 60 mol%.
- the structural unit (a2) is preferably contained in an amount of 3 to 70 mol%, more preferably 10 to 60 mol% in all the structural units of the component (A), regardless of any embodiment. preferable.
- the transparency and chemical resistance of the cured film obtained from the photosensitive resin composition are improved.
- the component (A) may have other structural units (a3) in addition to the structural units (a1) and / or (a2). These structural units may be contained in the polymer component (1) and / or (2). Further, apart from the polymer component (1) or (2), it may have a polymer component having other structural unit (a3) substantially not containing (a1) and (a2). . Apart from the polymer component (1) or (2), in the case of containing a polymer component having other structural unit (a3) substantially not containing (a1) and (a2), The blending amount is preferably 60% by mass or less, more preferably 40% by mass or less, and still more preferably 20% by mass or less in all polymer components.
- a monomer used as another structural unit (a3) For example, styrenes, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated Dicarboxylic acid diesters, bicyclounsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and other unsaturated compounds be able to.
- the monomer which becomes another structural unit (a3) can be used individually or in combination of 2 or more types.
- the other structural unit (a3) includes a structural unit containing at least an acid group.
- the structural unit (a3) specifically includes styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, ⁇ -methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, vinylbenzoic acid.
- styrenes and groups having an aliphatic cyclic skeleton are preferable from the viewpoint of electrical characteristics. Specifically, styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, ⁇ -methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, etc. Can be mentioned.
- (meth) acrylic acid alkyl ester is preferable from the viewpoint of adhesion.
- Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl (meth) acrylate, and methyl (meth) acrylate is more preferable.
- the content of the structural unit (a3) is preferably 60 mol% or less, more preferably 50 mol% or less, and further preferably 40 mol% or less.
- 0 mol% may be sufficient, it can be set as 1 mol% or more, for example, Furthermore, it can be set as 5 mol% or more. When it is within the above numerical range, various properties of the cured film obtained from the photosensitive resin composition are improved.
- the other structural unit (a3) preferably contains an acid group.
- the acid group in the present invention means a proton dissociable group having a pKa of less than 7.
- the acid group is usually incorporated into the polymer as a structural unit containing an acid group using a monomer capable of forming an acid group. By including such a structural unit containing an acid group in the polymer, the polymer tends to be easily dissolved in an alkaline developer.
- Acid groups used in the present invention include those derived from carboxylic acid groups, those derived from sulfonamide groups, those derived from phosphonic acid groups, those derived from sulfonic acid groups, those derived from phenolic hydroxyl groups, sulfones Amide groups, sulfonylimide groups and the like are exemplified, and those derived from carboxylic acid groups and / or those derived from phenolic hydroxyl groups are preferred.
- the structural unit containing an acid group used in the present invention is more preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, a structural unit derived from (meth) acrylic acid and / or an ester thereof. .
- the structural unit containing an acid group is preferably 1 to 80% by mole, more preferably 1 to 50% by mole, still more preferably 5 to 40% by mole, and particularly preferably 5 to 30% by mole of the structural unit of all polymer components. 5 to 20 mol% is particularly preferable.
- a polymer having other structural unit (a3) without substantially containing (a1) and (a2) may be included. .
- Such a polymer is preferably a resin having a carboxyl group in the side chain.
- a resin having a carboxyl group in the side chain For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048
- methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc. and side chain
- acidic cellulose derivatives having a carboxyl group those obtained by adding an acid anhydride to a polymer having a hydroxyl group
- high molecular polymers having a (meth) acryloyl group in the side chain examples thereof include acidic cellulose derivatives having a carboxyl group, those obtained by adding an acid anhydride to a
- benzyl (meth) acrylate / (meth) acrylic acid copolymer 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, described in JP-A-7-140654 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2 -Hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid
- Known polymer compounds described in JP-A-2003-233179, JP-A-2009-52020, and the like can be used, and the contents thereof are incorporated in the present specification. These polymers may contain only 1 type and may contain 2 or more types.
- SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F, SMA EF-30, SMA EF-40, SMA EF-60, SMA EF- are commercially available as these polymers.
- ARUFON UC-3000 ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (above, Toagosei Co., Ltd.)
- Joncryl 690, Joncryl 678, Joncryl 67, Joncryl 586 (above, manufactured by BASF) and the like can also be used.
- the molecular weight of the polymer (A) is a weight average molecular weight in terms of polystyrene, and is preferably 1,000 to 200,000, more preferably 2,000 to 50,000. Various characteristics are favorable in the range of said numerical value.
- the ratio (dispersity) between the number average molecular weight and the weight average molecular weight is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.
- the component (A) is used to form at least the structural units represented by the above (a1) and (a3). It can be synthesized by polymerizing a radical polymerizable monomer mixture containing a radical polymerizable monomer in an organic solvent using a radical polymerization initiator. It can also be synthesized by a so-called polymer reaction.
- the photosensitive resin composition of the present invention preferably contains the component (A) in a proportion of 50 to 99.9 parts by mass, and in a proportion of 70 to 98 parts by mass with respect to 100 parts by mass of the total solid content. More preferred.
- the photosensitive resin composition of the present invention contains (B) a nonionic photoacid generator.
- the nonionic photoacid generator also referred to as “component (B)” is a compound that generates an acid in response to actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm. Although preferred, it is not limited to its chemical structure.
- a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can be used as a sensitizer as long as it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.
- the photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and an acid of 2 or less. Most preferred are photoacid generators that generate.
- nonionic photoacid generators examples include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, it is preferable to use an oxime sulfonate compound from the viewpoint of insulation. These photoacid generators can be used singly or in combination of two or more. Specific examples of the trichloromethyl-s-triazines and diazomethane derivatives include the compounds described in paragraph numbers 0083 to 0088 of JP2011-221494A.
- oxime sulfonate compound that is, a compound having an oxime sulfonate structure
- a compound containing an oxime sulfonate structure represented by the following general formula (B1) can be preferably exemplified, and the contents thereof are incorporated in the present specification.
- R 21 represents an alkyl group or an aryl group.
- the wavy line represents a bond with another group.
- the alkyl group for R 21 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms.
- the alkyl group represented by R 21 is an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group or the like). It may be substituted with a cyclic group, preferably a bicycloalkyl group or the like.
- the aryl group for R 21 is preferably an aryl group having 6 to 11 carbon atoms, more preferably a phenyl group or a naphthyl group.
- the aryl group of R 21 may be substituted with a lower alkyl group, an alkoxy group, or a halogen atom.
- the above compound containing an oxime sulfonate structure represented by the above general formula (B1) is also preferably an oxime sulfonate compound represented by the following general formula (B2).
- R 42 represents an alkyl group or an aryl group
- X represents an alkyl group, an alkoxy group, or a halogen atom
- m4 represents an integer of 0 to 3
- m4 represents 2 or When it is 3, the plurality of X may be the same or different.
- the alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
- the alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
- the halogen atom as X is preferably a chlorine atom or a fluorine atom.
- m4 is preferably 0 or 1. In the above general formula (B2), m4 is 1, X is a methyl group, the substitution position of X is the ortho position, R 42 is a linear alkyl group having 1 to 10 carbon atoms, 7,7- A compound that is a dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferred.
- the compound containing an oxime sulfonate structure represented by the above general formula (B1) is also preferably an oxime sulfonate compound represented by the following general formula (B3).
- R 43 has the same meaning as R 42 in the formula (B2), and X 1 is a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, cyano Represents a group or a nitro group, and n4 represents an integer of 0 to 5.
- R 43 in the above general formula (B3) is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group.
- Perfluoro-n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferable, and n-octyl group is particularly preferable.
- X 1 is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
- n4 is preferably from 0 to 2, particularly preferably from 0 to 1.
- Specific examples of the compound represented by the general formula (B3) include ⁇ - (methylsulfonyloxyimino) benzyl cyanide, ⁇ - (ethylsulfonyloxyimino) benzyl cyanide, ⁇ - (n-propylsulfonyloxyimino).
- Benzyl cyanide ⁇ - (n-butylsulfonyloxyimino) benzyl cyanide, ⁇ - (4-toluenesulfonyloxyimino) benzyl cyanide, ⁇ -[(methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, ⁇ -[(ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, ⁇ -[(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, ⁇ -[(n-butylsulfonyloxyimino) -4- Methoxyphenyl] acetonitrile, ⁇ -[(4 It can be given toluenesulfonyl) -4-methoxyphenyl] acetonitrile.
- preferable oxime sulfonate compounds include the following compounds (i) to (viii), and the like can be used singly or in combination of two or more. Compounds (i) to (viii) can be obtained as commercial products. Moreover, it can also be used in combination with another kind of (B) photo-acid generator.
- the compound containing an oxime sulfonate structure represented by the above general formula (B1) is also preferably a compound represented by the following general formula (OS-1).
- R 101 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or Represents a heteroaryl group.
- R102 represents an alkyl group or an aryl group.
- X 101 represents —O—, —S—, —NH—, —NR 105 —, —CH 2 —, —CR 106 H—, or —CR 105 R 107 —, wherein R 105 to R 107 are alkyl groups.
- R 121 to R 124 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, Or an aryl group is represented. Two of R 121 to R 124 may be bonded to each other to form a ring.
- R 121 to R 124 are preferably a hydrogen atom, a halogen atom, and an alkyl group, and an embodiment in which at least two of R 121 to R 124 are bonded to each other to form an aryl group is also preferred. Among these, an embodiment in which R 121 to R 124 are all hydrogen atoms is preferable from the viewpoint of sensitivity. Any of the aforementioned functional groups may further have a substituent.
- the compound represented by the general formula (OS-1) is more preferably a compound represented by the following general formula (OS-2).
- R 101 , R 102 and R 121 to R 124 have the same meanings as in the formula (OS-1), and preferred examples thereof are also the same.
- R 101 in the general formula (OS-1) and the general formula (OS-2) is a cyano group or an aryl group is more preferable, and is represented by the general formula (OS-2).
- R 101 is most preferably a cyano group, a phenyl group or a naphthyl group.
- the steric structure (E, Z, etc.) of the oxime or benzothiazole ring may be either one or a mixture.
- the compound containing the oxime sulfonate structure represented by the above general formula (B1) includes the following general formula (OS-3), the following general formula (OS-4), or the following general formula (OS-5). It is preferable that it is an oxime sulfonate compound represented by these.
- R 22 , R 25 and R 28 each independently represents an alkyl group, an aryl group or a heteroaryl group
- R 23 , R 26 and R 29 Each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom
- R 24 , R 27 and R 30 each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group.
- X 1 to X 3 each independently represents an oxygen atom or a sulfur atom
- n 1 to n 3 each independently represents 1 or 2
- m 1 to m 3 each independently represents an integer of 0 to 6 Represents.
- the alkyl group, aryl group or heteroaryl group in R 22 , R 25 and R 28 may have a substituent.
- the alkyl group in R 22 , R 25 and R 28 is an alkyl group having 1 to 30 carbon atoms which may have a substituent. Is preferred.
- the aryl group in R 22 , R 25 and R 28 is an aryl group having 6 to 30 carbon atoms which may have a substituent. preferable.
- the heteroaryl group in R 1 is preferably a heteroaryl group having 4 to 30 carbon atoms in total which may have a substituent.
- At least one of the heteroaryl groups in R 22 , R 25 and R 28 may be a heteroaromatic ring, such as a heteroaromatic ring and benzene.
- the ring may be condensed.
- R 23 , R 26 and R 29 are preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group. preferable.
- one or two of R 23 , R 26 and R 29 present in the compound are an alkyl group, an aryl group or a halogen atom. It is more preferable that one is an alkyl group, an aryl group or a halogen atom, and it is particularly preferable that one is an alkyl group and the rest is a hydrogen atom.
- the alkyl group for R 23 , R 26 and R 29 is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and 1 to 1 carbon atoms which may have a substituent. More preferred is an alkyl group of 6.
- the aryl group for R 23 , R 26 and R 29 is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.
- X 1 to X 3 each independently represents O or S, and is preferably O.
- the ring containing X 1 to X 3 as a ring member is a 5-membered ring or a 6-membered ring.
- n 1 to n 3 each independently represents 1 or 2, and when X 1 to X 3 are O, n 1 to n 3 are each independently In addition, when X 1 to X 3 are S, n 1 to n 3 are each preferably 2 independently.
- R 24 , R 27 and R 30 each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group.
- R 24 , R 27 and R 30 are preferably each independently an alkyl group or an alkyloxy group.
- the alkyl group, alkyloxy group, sulfonic acid group, aminosulfonyl group and alkoxysulfonyl group in R 24 , R 27 and R 30 may have a substituent.
- the alkyl group in R 24 , R 27 and R 30 is an alkyl group having 1 to 30 carbon atoms which may have a substituent. It is preferable.
- the alkyloxy group in R 24 , R 27 and R 30 is an alkyloxy group having 1 to 30 carbon atoms which may have a substituent. Preferably there is.
- m 1 to m 3 each independently represents an integer of 0 to 6, preferably an integer of 0 to 2, preferably 0 or 1. More preferably, it is particularly preferably 0. Further, with respect to each of the substituents of (OS-3) to (OS-5) described above, the substitution of (OS-3) to (OS-5) described in paragraph numbers 0092 to 0109 of JP2011-221494A The preferred range of groups is likewise preferred.
- the compound containing the oxime sulfonate structure represented by the general formula (B1) is particularly an oxime sulfonate compound represented by any of the following general formulas (OS-6) to (OS-11). preferable.
- R 301 to R 306 represent an alkyl group, an aryl group, or a heteroaryl group
- R 307 represents a hydrogen atom or a bromine atom
- R 308 to R 310 , R 313 , R 316 and R 318 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group
- R 311 and R 314 each independently represent a hydrogen atom, a halogen atom, a methyl group or a methoxy group
- R 312 , R 315 , R 317 and R 319 each independently represent a hydrogen atom or a methyl group.
- oxime sulfonate compounds represented by the general formula (OS-3) to the general formula (OS-5) include compounds described in paragraph numbers 0114 to 0120 of JP2011-221494A. However, the present invention is not limited to these.
- the nonionic photoacid generator is 100 parts by mass of the total resin components (preferably the total solid content, more preferably the total of the polymer) in the photosensitive resin composition.
- 0.1 to 10 parts by mass is preferably used, and 0.5 to 10 parts by mass is more preferably used. Two or more kinds can be used in combination.
- (B ′) an ionic photoacid generator may be further included.
- (B ′) ionic photoacid generators include sulfonium salts, iodonium salts, quaternary ammonium salts, and the like. Among these, it is preferable to use an oxime sulfonate compound from the viewpoint of insulation. These ionic photoacid generators can be used singly or in combination of two or more.
- Specific examples of the diaryliodonium salts, triarylsulfonium salts, and quaternary ammonium salts include the compounds described in paragraph numbers 0083 to 0088 of JP2011-221494A.
- the photosensitive resin composition of the present invention when (B ′) an ionic photoacid generator is included, all the resin components in the photosensitive resin composition (preferably a solid content, preferably within a range not hindering the effects of the present invention). More preferably, it is used in an amount of 0 to 10 parts by weight, more preferably 0 to 5 parts by weight, based on 100 parts by weight of the total polymer. Further, the addition amount of (B ′) ionic photoacid generator is more preferably not more than the addition amount of (B) nonionic photoacid generator, and preferably not more than 10 mass%. However, in the present invention, an embodiment that substantially does not contain (B ') an ionic photoacid generator is preferred.
- composition of the present invention includes (C) a compound represented by the following general formula (S).
- General formula (S) (In general formula (S), R 1 represents a group containing at least one nitrogen atom, A represents a divalent linking group, and R 2 represents an organic group.)
- R 1 represents a group containing at least one nitrogen atom, preferably a group containing 1 to 3 nitrogen atoms, and more preferably a group represented by —NR 3 R 4 .
- R 1 is preferably a group composed of 1 to 10 carbon atoms, an oxygen atom, and 1 to 3 heteroatoms including at least one nitrogen atom.
- examples of the hetero atom include an oxygen atom and a sulfur atom, and an oxygen atom is preferable.
- R 1 is preferably a cyclic group, and more preferably a 5-membered or 6-membered cyclic group.
- R 3 and R 4 each represents an organic group.
- the organic group is preferably an alkyl group, an alkenyl group, or a group composed of at least one of —O—, —S— and —N—.
- R 3 and R 4 are each preferably a group having 1 to 3 carbon atoms. R 3 and R 4 may be bonded to each other to form a ring, and preferably forms a ring.
- R 1 Preferred embodiments of R 1 include the following embodiments. (1) An embodiment in which R 1 is a group represented by —NR 3 R 4 and R 3 and R 4 are bonded to each other to form a ring, or R 3 and R 4 are each The aspect which is an aliphatic hydrocarbon group. (2) Embodiment in which R 1 is a group represented by —NR 3 R 4 and R 3 and R 4 are bonded to each other to form a 5-membered or 6-membered ring, or R 3 and R 4 Are each a linear or branched aliphatic hydrocarbon group having 1 to 4 carbon atoms.
- R 1 is a group represented by —NR 3 R 4 , and R 3 and R 4 are bonded to each other to form two or more heteroatoms (at least one is a nitrogen atom and the rest are oxygen atoms or A mode in which a 5-membered ring or a 6-membered ring is formed, or a straight-chain aliphatic hydrocarbon group having 1 to 4 carbon atoms, each of R 3 and R 4 The aspect which is.
- R 1 examples include, for example, morpholino group, hydrazino group, pyridyl group, imidazolyl group, quinolyl group, piperidyl group, pyrrolidinyl group, pyrazonyl group, oxazolyl group, thiazolyl group, benzoxazolyl group, benzimidazolyl group, A benzthiazolyl group, a pyrazinyl group, a diethylamino group, etc. are mentioned. Of these, a morpholino group is preferable.
- R 2 represents an organic group.
- the organic group is preferably a hydrocarbon group or a group comprising a hydrocarbon group and at least one of —O— and —C ( ⁇ O) —.
- R 2 preferably has 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms.
- R 2 is more preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, or a group consisting of these and at least one combination of —O— and —C ( ⁇ O) —.
- These groups may have a substituent, and examples of the substituent include a halogen atom.
- R 2 is an alkyl group
- a linear or branched alkyl group having 1 to 8 carbon atoms or a cyclic alkyl group is preferable.
- R 2 is a cyclic alkyl group
- a 5-membered or 6-membered cyclic alkyl group is preferred.
- R 2 is an aryl group
- a phenyl group and a naphthyl group are exemplified, and a phenyl group is more preferable.
- R 2 include the following embodiments. (1) A mode of being a straight-chain alkylene group having 1 to 4 carbon atoms (preferably 2 or 3).
- A represents a divalent linking group, preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrocarbon group having 1 to 10 carbon atoms, and further preferably a hydrocarbon group having 2 to 6 carbon atoms.
- the hydrocarbon group include an alkylene group and an arylene group, and an alkylene group is preferable.
- the alkylene group include a methylene group, an ethylene group, a propylene group, a cyclohexylene group, and a cyclopentylene group.
- the arylene group include a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, and a naphthylene group.
- a methylene group, an ethylene group, and a propylene group are particularly preferable, and an ethylene group or a propylene group is more preferable.
- Preferred embodiments of A include the following embodiments. (1) An embodiment in which the alkyl group is a linear or branched alkyl group having 1 to 4 carbon atoms, a 5- or 6-membered cyclic alkyl group, or a phenyl group.
- the compound represented by the general formula (S) is exemplified as a particularly preferable embodiment in which the preferred embodiment of R 1 , the preferred embodiment of R 2 , and the preferred embodiment of A are combined.
- the compound represented by the general formula (S) is preferably represented by the general formula (S1).
- General formula (S1) (In general formula (S1), R 2 represents an organic group, and A represents a divalent linking group.) R 2 has the same meaning as R 2 in the formula (S), and the preferred range is also the same. A is synonymous with A in the above formula (S), and a preferred range is also synonymous.
- the following embodiments are preferable. (1) An embodiment in which A is a linear alkylene group having 1 to 4 carbon atoms, and R 2 is a linear, branched, or cyclic alkyl group. (2) A mode in which A is an alkylene group having 2 or 3 carbon atoms, and R 2 is a linear, branched or cyclic alkyl group having 2 to 6 carbon atoms.
- the photosensitive resin composition of the present invention preferably contains component (C) in a proportion of 0.001 to 5 parts by mass, and in a proportion of 0.003 to 2 parts by mass with respect to 100 parts by mass of the total solid content. More preferably, it is more preferably contained in a proportion of 0.005 to 1 part by mass. (C) Only 1 type may be sufficient as a component and 2 or more types may be sufficient as it. In the case of two or more types, the total is preferably in the above range.
- the photosensitive resin composition of the present invention contains (D) a solvent.
- the photosensitive resin composition of the present invention is preferably prepared as a solution in which the essential components of the present invention and optional components described below are dissolved in the solvent (D).
- known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene.
- Glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol Examples include monoalkyl ether acetates, esters, ketones, amides, lactones and the like.
- specific examples of the (D) solvent used in the photosensitive resin composition of the present invention include the solvents described in paragraph numbers 0174 to 0178 of JP2011-221494A, and the contents thereof are described in the present specification. Embedded in the book.
- the solvent that can be used in the present invention is a single type or a combination of two types, more preferably a combination of two types, propylene glycol monoalkyl ether acetates or dialkyl ethers, diacetates. And diethylene glycol dialkyl ethers or esters and butylene glycol alkyl ether acetates are more preferably used in combination.
- Component D is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof.
- Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), propylene glycol An example is methyl-n-propyl ether (boiling point 131 ° C.).
- Solvents having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), dipropylene glycol methyl ether acetate.
- the content of the solvent (D) in the photosensitive resin composition of the present invention is preferably 50 to 95 parts by mass, preferably 60 to 90 parts by mass, per 100 parts by mass of the total resin components in the photosensitive resin composition. More preferably it is.
- the photosensitive resin composition of the present invention is characterized by containing (E) an alkoxysilane compound (also referred to as “(E) component”).
- an alkoxysilane compound also referred to as “(E) component.
- the adhesion between the film formed from the photosensitive resin composition of the present invention and the substrate can be improved, or the properties of the film formed from the photosensitive resin composition of the present invention can be adjusted.
- Can do As the alkoxysilane compound, a dialkoxysilane compound or a trialkoxysilane compound is preferable, and a trialkoxysilane compound is more preferable.
- the alkoxy group contained in the alkoxysilane compound preferably has 1 to 5 carbon atoms.
- the (E) alkoxysilane compound that can be used in the photosensitive resin composition of the present invention is an inorganic material serving as a substrate, for example, silicon compounds such as silicon, silicon oxide, and silicon nitride, gold, copper, molybdenum, titanium, and aluminum. It is preferable that the compound improves the adhesion between the metal and the insulating film. Specifically, a known silane coupling agent or the like is also effective.
- silane coupling agents include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -glycidoxypropyltrialkoxysilane, ⁇ -glycidoxypropylalkyldialkoxysilane, and ⁇ -methacryloxy.
- ⁇ -glycidoxypropyltrialkoxysilane and ⁇ -methacryloxypropyltrialkoxysilane are more preferable, ⁇ -glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is more preferable. Further preferred. These can be used alone or in combination of two or more.
- Ph is a phenyl group.
- the (E) alkoxysilane compound in the photosensitive resin composition of the present invention is not particularly limited, and a known one can be used.
- the content of the (E) alkoxysilane compound in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by mass is more preferable.
- the photosensitive resin composition of the present invention in addition to the above components, (F) a crosslinking agent, (G) a sensitizer, (H) a basic compound, (I) a surfactant, J) An antioxidant can be preferably added. Further, the photosensitive resin composition of the present invention includes an acid proliferation agent, a development accelerator, a plasticizer, a thermal radical generator, a thermal acid generator, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor. Known additives such as can be added.
- the photosensitive resin composition of this invention contains a crosslinking agent as needed.
- a crosslinking agent is not limited as long as a crosslinking reaction is caused by heat.
- Excluding component A For example, a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, an alkoxymethyl group-containing crosslinking agent, a compound having at least one ethylenically unsaturated double bond, a blocked isocyanate compound, etc. Can be added.
- the addition amount of the crosslinking agent in the photosensitive resin composition of the present invention is preferably 0.01 to 50 parts by mass, and 0.1 to 30 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition.
- the amount is more preferably part by mass, and further preferably 0.5 to 20 parts by mass. By adding in this range, a cured film having excellent mechanical strength and solvent resistance can be obtained.
- a plurality of crosslinking agents may be used in combination. In that case, the content is calculated by adding all the crosslinking agents.
- bisphenol A type epoxy resins bisphenol F type epoxy resins, phenol novolac type epoxy resins, aliphatic epoxies, and aliphatic epoxy resins are more preferable, and bisphenol A type epoxy resins are particularly preferable.
- Aron oxetane OXT-121, OXT-221, OX-SQ, PNOX above, manufactured by Toagosei Co., Ltd.
- the compound containing an oxetanyl group is preferably used alone or mixed with a compound containing an epoxy group.
- alkoxymethyl group-containing crosslinking agents described in paragraphs 0107 to 0108 of JP2012-8223A and compounds having at least one ethylenically unsaturated double bond are also preferably used. The contents of which are incorporated herein by reference.
- alkoxymethyl group-containing crosslinking agent alkoxymethylated glycoluril is preferable.
- a blocked isocyanate compound can also be preferably employed as a crosslinking agent.
- the blocked isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanate group, but is preferably a compound having two or more blocked isocyanate groups in one molecule from the viewpoint of curability.
- the blocked isocyanate group in this invention is a group which can produce
- the group which reacted the blocking agent and the isocyanate group and protected the isocyanate group can illustrate preferably.
- the blocked isocyanate group is preferably a group capable of generating an isocyanate group by heat at 90 ° C. to 250 ° C.
- the skeleton of the blocked isocyanate compound is not particularly limited and may be any as long as it has two isocyanate groups in one molecule, and is aliphatic, alicyclic or aromatic.
- Polyisocyanates may be used, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene Diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2 2′-diethyl ether diisocyanate, diphenylmethane-4,4′-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1,3
- a compound and a prepolymer type skeleton compound derived from these compounds can be preferably used.
- tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are particularly preferable.
- Examples of the matrix structure of the blocked isocyanate compound in the photosensitive resin composition of the present invention include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.
- Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. be able to.
- a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferable.
- Examples of the oxime compound include oxime and ketoxime, and specific examples include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, benzophenone oxime, and acetoxime.
- Examples of the lactam compound include ⁇ -caprolactam and ⁇ -butyrolactam.
- Examples of the phenol compound include phenol, naphthol, cresol, xylenol, and halogen-substituted phenol.
- Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.
- Examples of the amine compound include primary amines and secondary amines, which may be aromatic amines, aliphatic amines, and alicyclic amines, and examples thereof include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.
- Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate and the like.
- Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole and the like.
- Examples of the mercaptan compound include alkyl mercaptans and aryl mercaptans.
- the blocked isocyanate compound that can be used in the photosensitive resin composition of the present invention is commercially available.
- Coronate AP Stable M Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (or more, Nippon Polyurethane Industry Co., Ltd.), Takenate B-830, B-815N, B-820NSU, B-842N, B-84N, B-870N, B-874N, B-882N (above, manufactured by Mitsui Chemicals, Inc.) ), Duranate 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (above , Manufactured by Asahi Kasei Chemicals Corporation, Death Module B 1100, BL1265 MPA / X, BL
- the photosensitive resin composition of the present invention preferably contains a sensitizer in order to promote its decomposition in combination with (B) a photoacid generator.
- the sensitizer absorbs actinic rays or radiation and enters an electronically excited state.
- the sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur.
- a photo-acid generator raise
- Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength ranges from 350 nm to 450 nm.
- Polynuclear aromatics eg, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene
- xanthenes Eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal
- xanthones eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone
- cyanines eg, thiacarbocyanine, oxacarbocyanine
- merocyanines For example, merocyanine, carbomerocyanine), rhodocyanines, oxonols, thiazines (eg, thionine, methylene blue, to
- polynuclear aromatics polynuclear aromatics, acridones, styryls, base styryls, and coumarins are preferable, and polynuclear aromatics are more preferable.
- polynuclear aromatics anthracene derivatives are most preferred.
- the addition amount of the sensitizer in the photosensitive resin composition of the present invention is preferably 0 to 1000 parts by mass with respect to 100 parts by mass of the photoacid generator of the photosensitive resin composition. More preferably, the amount is 50 to 200 parts by mass. Two or more kinds can be used in combination.
- the photosensitive resin composition of the present invention may further contain (H) a basic compound.
- the basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples thereof include compounds described in JP-A 2011-212494, paragraphs 0204 to 0207, the contents of which are incorporated herein.
- the basic compounds that can be used in the present invention may be used singly or in combination of two or more.
- the content of the (H) other basic compound in the photosensitive resin composition of the present invention, when containing another basic compound, is 0.1% relative to 100 parts by mass of the total solid content in the photosensitive resin composition.
- the amount is preferably 001 to 3 parts by mass, and more preferably 0.005 to 1 part by mass.
- the photosensitive resin composition of this invention contains the compound represented by general formula (S), it can also be set as the aspect which does not contain other basic compounds substantially.
- the photosensitive resin composition of the present invention may contain (I) a surfactant.
- a surfactant any of anionic, cationic, nonionic or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
- nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. .
- KP manufactured by Shin-Etsu Chemical Co., Ltd.
- Polyflow manufactured by Kyoeisha Chemical Co., Ltd.
- F-Top manufactured by JEMCO
- MegaFuck manufactured by DIC Corporation
- Florard Florard
- Asahi Guard Surflon (manufactured by Asahi Glass Co., Ltd.)
- PolyFox manufactured by OMNOVA
- SH-8400 Toray Dow Corning Silicone
- the surfactant contains the structural unit A and the structural unit B represented by the following general formula (I-1), and is converted to polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent.
- a copolymer having a weight average molecular weight (Mw) of 1,000 or more and 10,000 or less can be given as a preferred example.
- R 401 and R 403 each independently represent a hydrogen atom or a methyl group
- R 402 represents a linear alkylene group having 1 to 4 carbon atoms
- R 404 represents a hydrogen atom or Represents an alkyl group having 1 to 4 carbon atoms
- L represents an alkylene group having 3 to 6 carbon atoms
- p and q are mass percentages representing a polymerization ratio
- p is 10 mass% to 80 mass%.
- a numerical value is represented, q represents a numerical value of 20 mass% or more and 90 mass% or less, r represents an integer of 1 or more and 18 or less, and s represents an integer of 1 or more and 10 or less.
- L is preferably a branched alkylene group represented by the following general formula (I-2).
- R 405 in formula (I-2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability with respect to the coated surface. A number 2 or 3 alkyl group is more preferred.
- the weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
- the addition amount of (I) surfactant in the photosensitive resin composition of the present invention is preferably 10 parts by mass or less with respect to 100 parts by mass of the total solid content in the photosensitive resin composition, 0.001 More preferably, it is ⁇ 10 parts by mass, and further preferably 0.01-3 parts by mass.
- the photosensitive resin composition of the present invention may contain an antioxidant.
- an antioxidant a well-known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat-resistant transparency is excellent.
- antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, Examples thereof include nitrates, sulfites, thiosulfates, and hydroxylamine derivatives.
- phenol-based antioxidants amide-based antioxidants, hydrazide-based antioxidants, and sulfur-based antioxidants are particularly preferable from the viewpoint of coloring the cured film and reducing the film thickness. These may be used individually by 1 type and may mix 2 or more types. Examples of commercially available phenolic antioxidants include ADK STAB AO-15, ADK STAB AO-18, ADK STAB AO-20, ADK STAB AO-23, ADK STAB AO-30, ADK STAB AO-37, ADK STAB AO-40, and ADK STAB AO.
- ADK STAB AO-51 ADK STAB AO-60
- ADK STAB AO-70 ADK STAB AO-80
- ADK STAB AO-330 ADK STAB AO-412S
- ADK STAB AO-503 ADK STAB A-611, ADK STAB A-612, ADK STAB A -613, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-8W, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB PEP-36Z, ADK STAB HP-1 ADK STAB 2112, ADK STAB 260, ADK STAB 1522, ADK STAB 1178, ADK STAB 1500, ADK STAB C, ADK STAB 13510, ADK STAB 3010, ADK STAB CDA-1, ADK STAB CDA-6, ADK STAB ZS-27, ADK STAB ZS-90 -91 (above, manufactured by ADEKA Corporation), Irga
- the content of the antioxidant is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, based on the total solid content of the photosensitive resin composition. It is particularly preferably 5 to 4% by mass. By setting it in this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation can be improved.
- additives other than antioxidants various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators, and the like are used in the present invention. You may add to a resin composition.
- an acid proliferating agent in the photosensitive resin composition of the present invention, can be used for the purpose of improving sensitivity.
- the acid proliferating agent that can be used in the present invention is a compound that can further generate an acid by an acid-catalyzed reaction to increase the acid concentration in the reaction system, and is a compound that exists stably in the absence of an acid. is there.
- the acid strength is preferably 3 or less as an acid dissociation constant, pKa, and particularly preferably 2 or less.
- the acid proliferating agent examples include paragraph numbers 0203 to 0223 of JP-A-10-1508, paragraphs 0016 to 0055 of JP-A-10-282642, and page 39 of JP-T 9-512498.
- the compounds described on line 12 to page 47, line 2 can be mentioned, the contents of which are incorporated herein.
- the acid proliferating agent that can be used in the present invention include pKa such as dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, and phenylphosphonic acid, which are decomposed by an acid generated from the acid generator. Examples include compounds that generate 3 or less acids.
- the content of the acid proliferating agent in the photosensitive composition is 10 to 1,000 parts by mass with respect to 100 parts by mass of the photoacid generator, from the viewpoint of dissolution contrast between the exposed and unexposed parts. It is preferably 20 to 500 parts by mass.
- the photosensitive resin composition of the present invention can contain a development accelerator.
- a development accelerator the description in paragraphs 0171 to 0172 of JP2012-042837A can be referred to, and the contents thereof are incorporated in the present specification.
- a development accelerator may be used individually by 1 type, and can also use 2 or more types together.
- the addition amount of the development accelerator in the photosensitive resin composition of the present invention is preferably 0 to 30 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive composition, from the viewpoint of sensitivity and residual film ratio. 1 to 20 parts by mass is more preferable, and 0.5 to 10 parts by mass is most preferable.
- thermal radical generators described in paragraphs 0120 to 0121 of JP2012-8223A, nitrogen-containing compounds and thermal acid generators described in WO2011-133604A1 can be used. Is incorporated herein by reference.
- a resin composition can be prepared by preparing a solution in which components are dissolved in a solvent in advance and then mixing them in a predetermined ratio.
- the composition solution prepared as described above can be used after being filtered using a filter having a pore size of 0.2 ⁇ m or the like.
- the method for producing a cured film of the present invention preferably includes the following steps (1) to (5).
- substrate (2) A step of removing the solvent from the applied photosensitive resin composition; (3) A step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays; (4) A step of developing the exposed photosensitive resin composition with an aqueous developer; (5) A post-baking step of thermosetting the developed photosensitive resin composition.
- the photosensitive resin composition of the present invention is preferably applied onto a substrate to form a wet film containing a solvent.
- substrate cleaning such as alkali cleaning or plasma cleaning
- the method for treating the substrate surface with hexamethyldisilazane is not particularly limited, and examples thereof include a method in which the substrate is exposed to hexamethyldisilazane vapor.
- the substrate include inorganic substrates, resins, and resin composite materials.
- the inorganic substrate examples include glass, quartz, silicone, silicon nitride, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such a substrate.
- Resins include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, poly Fluorine resins such as benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, aromatic Made of synthetic resin such as aromatic ether, maleimide
- the coating method on the substrate is not particularly limited, and for example, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method, or the like can be used. Furthermore, it is also possible to apply a so-called pre-wet method as described in JP-A-2009-145395.
- the wet film thickness when applied is not particularly limited, and can be applied with a film thickness according to the application, but it is usually used in the range of 0.5 to 10 ⁇ m.
- the solvent removal step (2) the solvent is removed from the applied film by reducing pressure (vacuum) and / or heating to form a dry coating film on the substrate.
- the heating conditions for the solvent removal step are preferably 70 to 130 ° C. and about 30 to 300 seconds. When the temperature and time are in the above ranges, the pattern adhesiveness is better and the residue tends to be further reduced.
- the substrate provided with the coating film is irradiated with actinic rays through a mask having a predetermined pattern.
- the photoacid generator is decomposed to generate an acid. Due to the catalytic action of the generated acid, the acid-decomposable group contained in the coating film component is hydrolyzed to generate a carboxyl group or a phenolic hydroxyl group.
- a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, or the like can be used, and g-line (436 nm), i-line (365 nm), h-line ( Actinic rays having a wavelength of 300 nm to 450 nm, such as 405 nm), can be preferably used.
- irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.
- PEB Post Exposure Bake
- the temperature when performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C.
- the acid-decomposable group in the present invention has low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to generate a carboxyl group or a phenolic hydroxyl group, PEB is not necessarily performed.
- a positive image can also be formed by development.
- a polymer having a liberated carboxyl group or phenolic hydroxyl group is developed using an alkaline developer.
- a positive image is formed by removing an exposed area containing a resin composition having a carboxyl group or a phenolic hydroxyl group that is easily dissolved in an alkaline developer.
- the developer used in the development step preferably contains a basic compound.
- Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used.
- An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
- Preferred examples of the developer include a 0.4% aqueous solution, a 0.5% aqueous solution, a 0.7% aqueous solution, and a 2.38% aqueous solution of tetraethylammonium hydroxide.
- the pH of the developer is preferably 10.0 to 14.0.
- the development time is preferably 30 to 500 seconds, and the development method may be either a liquid piling method or a dipping method. After development, washing with running water is usually performed for 30 to 300 seconds to form a desired pattern.
- a rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like.
- a known method can be used as the rinsing method. For example, shower rinse and dip rinse can be mentioned.
- the acid-decomposable group is thermally decomposed to generate a carboxyl group or a phenolic hydroxyl group, and then crosslinked with a crosslinkable group, a crosslinking agent or the like.
- a cured film can be formed.
- This heating is performed using a heating device such as a hot plate or an oven at a predetermined temperature, for example, 180 to 250 ° C. for a predetermined time, for example, 5 to 90 minutes on the hot plate, 30 to 120 minutes for the oven. It is preferable to By proceeding such a crosslinking reaction, a protective film and an interlayer insulating film that are superior in heat resistance, hardness, and the like can be formed.
- post-baking can be performed after baking at a relatively low temperature (addition of a middle baking process).
- middle baking it is preferable to post-bake at a high temperature of 200 ° C. or higher after heating at 90 to 150 ° C. for 1 to 60 minutes.
- middle baking and post-baking can be heated in three or more stages. The taper angle of the pattern can be adjusted by devising such middle baking and post baking.
- These heating methods can use a known heating method such as a hot plate, an oven, or an infrared heater.
- the substrate on which the pattern was formed was re-exposed with actinic rays (post-exposure) and then post-baked to generate an acid from the photoacid generator present in the unexposed part, thereby performing a crosslinking step. It can function as a catalyst to promote, and can accelerate the curing reaction of the film.
- the preferred exposure amount in the case of including a post-exposure step preferably 100 ⁇ 3,000mJ / cm 2, particularly preferably 100 ⁇ 500mJ / cm 2.
- the cured film obtained from the photosensitive resin composition of the present invention can also be used as a dry etching resist.
- dry etching processes such as ashing, plasma etching, and ozone etching can be performed as the etching process.
- the cured film of the present invention is a cured film obtained by curing the photosensitive resin composition of the present invention.
- the cured film of the present invention can be suitably used as an interlayer insulating film.
- the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention.
- an interlayer insulating film having excellent insulation and high transparency even when baked at high temperatures can be obtained. Since the interlayer insulating film using the photosensitive resin composition of the present invention has high transparency and excellent cured film physical properties, it is useful for applications of organic EL display devices and liquid crystal display devices.
- the liquid crystal display device of the present invention comprises the cured film of the present invention.
- the liquid crystal display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and known liquid crystal displays having various structures.
- a device can be mentioned.
- specific examples of TFT (Thin-Film Transistor) included in the liquid crystal display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
- Liquid crystal driving methods that can be taken by the liquid crystal display device of the present invention include TN (Twisted Nematic) method, VA (Virtual Alignment) method, IPS (In-Place-Switching) method, FFS (Frings Field Switching) method, OCB (Optical). Compensated Bend) method and the like.
- the cured film of the present invention can also be used in a COA (Color Filter on Array) type liquid crystal display device.
- the organic insulating film (115) of JP-A-2005-284291, -346054 can be used as the organic insulating film (212).
- the alignment method of the liquid crystal alignment film that the liquid crystal display device of the present invention can take include a rubbing alignment method and a photo alignment method.
- the polymer orientation may be supported by a PSA (Polymer Sustained Alignment) technique described in Japanese Patent Application Laid-Open Nos. 2003-149647 and 2011-257734.
- the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, It can be used for various uses.
- a protective film for the color filter in addition to the planarization film and interlayer insulating film, a protective film for the color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state imaging device, etc.
- FIG. 1 is a conceptual cross-sectional view showing an example of an active matrix liquid crystal display device 10.
- the color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto.
- the elements of the TFT 16 corresponding to are arranged.
- Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17.
- an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
- the light source of the backlight is not particularly limited, and a known light source can be used.
- the liquid crystal display device may be a 3D (stereoscopic) type or a touch panel type. Further, it can be made flexible, and can be used as the second interphase insulating film (48) of JP 2011-145686 A or the interphase insulating film (520) of JP 2009-258758 A.
- the organic EL display device of the present invention comprises the cured film of the present invention.
- the organic EL display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various known structures having various structures. Examples thereof include an organic EL display device and a liquid crystal display device.
- specific examples of TFT (Thin-Film Transistor) included in the organic EL display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
- FIG. 2 is a conceptual diagram of an example of an organic EL display device.
- a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
- a bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si 3 N 4 is formed so as to cover the TFT 1.
- a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 ⁇ m) connected to the TFT 1 through the contact hole is formed on the insulating film 3.
- the wiring 2 is for connecting the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
- the flattening layer 4 is formed on the insulating film 3 in a state where the unevenness due to the wiring 2 is embedded.
- a bottom emission type organic EL element is formed on the planarizing film 4. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7.
- the first electrode 5 corresponds to the anode of the organic EL element.
- An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do. Further, although not shown in FIG.
- a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a second layer made of Al is formed on the entire surface above the substrate.
- An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving it.
- An EL display device is obtained.
- a resist pattern formed using the photosensitive resin composition of the present invention as a structural member of a MEMS device can be used as a partition wall or mechanically driven. Used as part of the part.
- MEMS devices include parts such as SAW filters, BAW filters, gyro sensors, display micro shutters, image sensors, electronic paper, inkjet heads, biochips, sealants, and the like. More specific examples are exemplified in JP-T-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.
- the photosensitive resin composition of the present invention is excellent in flatness and transparency, for example, the bank layer (16) and the planarization film (57) described in FIG. 2 of JP-A-2011-107476, JP-A-2010-
- MATHF 2-tetrahydrofuranyl methacrylate (synthetic product)
- MAEVE 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
- OXE-30 3-ethyl-3-oxetanylmethyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
- GMA Glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
- NBMA n-butoxymethylacrylamide (manufactured by Tokyo Chemical Industry)
- HEMA Hydroxyethyl methacrylate (Wako Pure Chemical Industries, Ltd.)
- MAA Methacrylic acid (manufactured by Wako Pure Chemical Industries)
- MMA Methyl methacrylate (Wako Pure Chemical Industries, Ltd.)
- St Styrene (Wako Pure Chemical Industries, Ltd.)
- DCPM Hydroxyethyl me
- the numerical values not indicated in the table are in mol%.
- the numerical value of a polymerization initiator and an additive is mol% when a monomer component is 100 mol%.
- the solid content concentration is shown as monomer mass / (monomer mass + solvent mass) ⁇ 100 (unit mass%).
- ⁇ Adjustment of photosensitive resin composition The polymer component, nonionic photoacid generator, sensitizer, compound represented by general formula (S), alkoxysilane compound, surfactant, general formula ( S) A basic compound other than the compound represented by S) and other components are dissolved and mixed in a solvent (MEDG) until the solid content concentration becomes 32%, and filtered through a polytetrafluoroethylene filter having a diameter of 0.2 ⁇ m.
- the photosensitive resin compositions of various examples and comparative examples were obtained.
- surface is the mass%.
- B-1 Structure shown below (synthesis example will be described later)
- B-2 PAG-103 (trade name, structure shown below, manufactured by BASF)
- B-3 ⁇ - (Hydroxyimino) -2-phenylacetonitrile (Synthesis example will be described later)
- reaction solution was allowed to react at room temperature for 1 hour.
- the obtained reaction solution was poured into water (150 mL) in which sodium hydroxide (1 g) was dissolved to completely dissolve it, and then ethyl acetate (100 ml) was added to separate the solution.
- ethyl acetate (100 ml) was added again, the aqueous layer was acidified with concentrated hydrochloric acid to pH 3 or lower, and the product was extracted and concentrated.
- the obtained crude crystals were washed with hexane to obtain ⁇ - (hydroxyimino) -2-phenylacetonitrile (4.6 g) in a yield of 63%.
- G-1 ⁇ -glycidoxypropyltrialkoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.)
- G-2 KBM-3103 (manufactured by Shin-Etsu Chemical Co., Ltd.)
- G-3 KBE-846 (manufactured by Shin-Etsu Chemical Co., Ltd.)
- G-4 KBM-3063 (manufactured by Shin-Etsu Chemical Co., Ltd.)
- H-1 2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
- H-2 1,5-diazabicyclo [4.3.0] -5-nonene (manufactured by Tokyo Chemical Industry Co., Ltd.)
- F-1 JER828 (manufactured by Mitsubishi Chemical Holdings Corporation)
- F-2 JER1007 (manufactured by Mitsubishi Chemical Holdings Corporation)
- F-3 JER157S65 (manufactured by Mitsubishi Chemical Holdings Corporation)
- F-4 Duranate 17B-60P (Asahi Kasei Chemicals Corporation)
- F-5 Celoxide 2021P (manufactured by Daicel Corporation)
- F-7 EPICLON EXA-4850-150 (manufactured by DIC Corporation)
- F-8 Takenate B-870N (Mitsui Chemicals)
- F-9 Nikarac MW-100LM (manufactured by Sanwa Chemical Co., Ltd.)
- F-10 Nikarac MX-270 (manufactured by Sanwa Chemical Co., Ltd.)
- F-11 Kayala
- J-1 ADK STAB AO-60 (manufactured by ADEKA Corporation)
- J-2 Irganox 1035 (manufactured by BASF)
- J-3 Irganox 1098 (BASF)
- 10 cm ⁇ 0.5 mm) is exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and each photosensitive resin composition solution is applied using a spin coater so that the dry film thickness becomes 3 ⁇ m.
- HMDS hexamethyldisilazane
- the whole surface was exposed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm 2 (illuminance: 20 mW / cm 2 , i-line), and then the substrate was heated in an oven at 230 ° C. for 30 minutes. Thus, a cured film was obtained.
- the cured film was cut using a cutter at intervals of 1 mm vertically and horizontally, and a tape peeling test (100 mask loss cut method: conforming to JIS 5600) was performed using a scotch tape. The adhesion between the cured film and the substrate was evaluated from the area of the cured film transferred to the back surface of the tape. The results are shown in the following table.
- ⁇ Hardened film adhesion Ti> A glass substrate (10 cm ⁇ 10 cm ⁇ 0.5 mm) on which a Ti (titanium) thin film was formed was exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and then each photosensitive resin composition was spin-coated. Then, the solvent was volatilized by pre-baking on a hot plate at 90 ° C. for 2 minutes to form a photosensitive resin composition layer having a thickness of 3 ⁇ m.
- HMDS hexamethyldisilazane
- the whole surface was exposed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm 2 (illuminance: 20 mW / cm 2 , i-line), and then the substrate was heated in an oven at 230 ° C. for 30 minutes. Thus, a cured film was obtained.
- the cured film was cut using a cutter at intervals of 1 mm vertically and horizontally, and a tape peeling test (100 mask loss cut method: conforming to JIS 5600) was performed using a scotch tape. The adhesion between the cured film and the substrate was evaluated from the area of the cured film transferred to the back surface of the tape. The results are shown in the following table.
- SiNx> A glass substrate (10 cm ⁇ 10 cm ⁇ 0.5 mm) on which a SiNx (silicon nitride) thin film is formed is exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and then each photosensitive resin composition is applied by spin coating. Then, the solvent was volatilized by pre-baking on a hot plate at 90 ° C. for 2 minutes to form a photosensitive resin composition layer having a thickness of 3 ⁇ m.
- HMDS hexamethyldisilazane
- the whole surface was exposed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm 2 (illuminance: 20 mW / cm 2 , i-line), and then the substrate was heated in an oven at 230 ° C. for 30 minutes. Thus, a cured film was obtained.
- the cured film was cut using a cutter at intervals of 1 mm vertically and horizontally, and a tape peeling test (100 mask loss cut method: conforming to JIS 5600) was performed using a scotch tape. The adhesion between the cured film and the substrate was evaluated from the area of the cured film transferred to the back surface of the tape. The results are shown in the following table.
- the photosensitive resin composition of the present invention has excellent adhesion during development, and the cured film of the photosensitive resin composition of the present invention also has excellent adhesion to the substrate. .
- the cured film of the photosensitive resin composition of the present invention since a plurality of types of substrates are all excellent in high cured film adhesion, they can be preferably used for wiring substrates such as display devices.
- having an adhesiveness of evaluation “A” with respect to the molybdenum substrate is extremely valuable.
- the cured film of the photosensitive resin composition of the present invention has an advantage of high chemical resistance.
- Example 65 was performed in the same manner as in Example 1 except that the exposure machine was changed from MPA 5500CF manufactured by Canon Inc. to FX-803M (gh-Line stepper) manufactured by Nikon Corporation. Evaluation of adhesion between the developed film and the cured film was the same level as in Example 1.
- Example 66 was carried out in the same manner as in Example 1 except that the developer was changed from an alkali developer (0.4 mass% TMAH aqueous solution) to an alkali developer (2.38 mass% TMAH aqueous solution). Evaluation of adhesion during development was the same level as in Example 1.
- Example 67 was performed in the same manner as in Example 1 except that the entire surface exposure step using the ultrahigh pressure mercury lamp before heating in the oven was omitted.
- the evaluation of the adhesion and chemical resistance of the cured film was the same level as in Example 1.
- Example 68 was performed in the same manner as in Example 1 except that the exposure machine was changed from an MPA 5500CF manufactured by Canon Inc. to a 355 nm laser exposure machine and 355 nm laser exposure was performed.
- the 355 nm laser exposure machine “AEGIS” manufactured by Buoy Technology Co., Ltd. was used (wavelength 355 nm, pulse width 6 nsec), and the exposure amount was measured using “PE10B-V2” manufactured by OPHIR. Evaluation of adhesion between the developed film and the cured film was the same level as in Example 1.
- Example 69 In the active matrix type liquid crystal display device shown in FIG. 1 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 69 was obtained. That is, using the photosensitive resin composition of Example 1, a cured film 17 was formed as an interlayer insulating film.
- liquid crystal display device When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
- Example 70 A liquid crystal display device similar to that of Example 69 was changed to obtain the same liquid crystal display device. That is, after the photosensitive resin composition of Example 1 was applied by a slit coating method, the solvent was removed by heating on a hot plate at 90 ° C./120 seconds to form a photosensitive resin composition layer having a thickness of 3.0 ⁇ m. Formed. The obtained coating film was flat and had a good surface shape without unevenness. Further, the performance as a liquid crystal display device was as good as in Example 69.
- Example 71 was performed in the same manner as in Example 1, except that the exposure machine was changed from MPA 5500CF manufactured by Canon Inc. to a UV-LED light source exposure machine. Evaluation of adhesion between the developed film and the cured film was the same level as in Example 1.
- the photosensitive resin compositions of the examples were excellent in the shape of the formed pattern regardless of the substrate and the exposure machine.
- Example 72> A liquid crystal display device similar to that of Example 69 was changed to obtain the same liquid crystal display device. That is, after the photosensitive resin composition of Example 1 was applied by a slit and spin method, the solvent was removed by heating on a hot plate at 90 ° C./120 seconds to form a photosensitive resin composition layer having a thickness of 3.0 ⁇ m. Formed. The obtained coating film was flat and had a good surface shape without unevenness. Further, the performance as a liquid crystal display device was as good as in Example 69.
- An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 2).
- a bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si 3 N 4 was formed so as to cover the TFT 1.
- a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 ⁇ m) connected to the TFT 1 through the contact hole is formed on the insulating film 3. .
- the wiring 2 is used to connect the TFT 1 with an organic EL element formed between TFTs 1 or in a later process.
- the planarizing film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded.
- the planarization film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 16 on a substrate, pre-baking (90 ° C./120 seconds) on a hot plate, and then applying high pressure from above the mask. After irradiating 45 mJ / cm 2 (illuminance 20 mW / cm 2 ) with i-line (365 nm) using a mercury lamp, a pattern was formed by developing with an alkaline aqueous solution, and heat treatment was performed at 230 ° C./30 minutes.
- the applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking. Furthermore, the average step of the wiring 2 was 500 nm, and the thickness of the prepared planarizing film 4 was 2,000 nm.
- a bottom emission type organic EL element was formed on the obtained flattening film 4.
- a first electrode 5 made of ITO was formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7.
- a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed.
- pattern processing was performed by wet etching using an ITO etchant.
- the resist pattern was stripped at 50 ° C. using a resist stripper (remover 100, manufactured by AZ Electronic Materials).
- the first electrode 5 thus obtained corresponds to the anode of the organic EL element.
- an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed.
- the photosensitive resin composition of Example 1 was used, and the insulating film 8 was formed by the same method as described above. By providing this insulating film 8, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in the subsequent process.
- a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus.
- a second electrode made of Al was formed on the entire surface above the substrate.
- substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the glass plate for sealing, and an ultraviolet curable epoxy resin.
- TFT Thin Film Transistor
- Wiring 3 Insulating film 4: Flattened film 5: First electrode 6: Glass substrate 7: Contact hole 8: Insulating film 10: Liquid crystal display device 12: Backlight unit 14, 15: Glass substrate 16: TFT 17: Cured film 18: Contact hole 19: ITO transparent electrode 20: Liquid crystal 22: Color filter
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Abstract
Description
さらに詳しくは、液晶表示装置、有機EL表示装置、集積回路素子、固体撮像素子などの電子部品の平坦化膜、保護膜や層間絶縁膜の形成に好適な、感光性樹脂組成物およびそれを用いた硬化膜の製造方法に関する。 The present invention relates to a photosensitive resin composition (hereinafter sometimes simply referred to as “the composition of the present invention”). Moreover, it is related with the manufacturing method of the cured film using the said photosensitive resin composition, the cured film formed by hardening | curing the photosensitive composition, and various image display apparatuses using the said cured film.
More specifically, a photosensitive resin composition suitable for forming a flattening film, a protective film, and an interlayer insulating film of electronic components such as a liquid crystal display device, an organic EL display device, an integrated circuit element, and a solid-state image sensor, and the use thereof The present invention relates to a method for producing a cured film.
本発明は上記課題を解決することを目的としたものであって、基板との密着性が良好な感光性樹脂組成物を提供することを目的とする。特に、現像時基板密着性および硬化後の各種基板に対する密着性が高い感光性樹脂組成物を提供することを目的とする。
さらに、このような感光性樹脂組成物を用いた硬化膜の形成方法、硬化膜、有機EL表示装置、および、液晶表示装置を提供することを目的とする。 As described above, the photosensitive resin composition is required to have adhesiveness with the base substrate during development and in the state of being a cured film. In particular, since the substrate itself is made of a plurality of types of materials, the interlayer insulating film material formed on the surface thereof is provided with adhesion to the types of substrates.
The object of the present invention is to provide a photosensitive resin composition that has good adhesion to a substrate. In particular, it is an object of the present invention to provide a photosensitive resin composition having high adhesion to a substrate during development and high adhesion to various substrates after curing.
Furthermore, it aims at providing the formation method of a cured film using such a photosensitive resin composition, a cured film, an organic electroluminescence display, and a liquid crystal display device.
<1>(A)下記(1)および(2)の少なくとも一方を満たす重合体を含む重合体成分、
(1)(a1)酸基が酸分解性基で保護された基を有する構成単位、および(a2)架橋性基を有する構成単位、を有する重合体、
(2)(a1)酸基が酸分解性基で保護された基を有する構成単位を有する重合体、および(a2)架橋性基を有する構成単位を有する重合体、
(B)非イオン性光酸発生剤、
(C)下記一般式(S)で表される化合物、
一般式(S)
(D)溶剤、ならびに、
(E)アルコキシシラン化合物
を含有する感光性樹脂組成物。
<2>一般式(S)において、R1が、-NR3R4で表される基である、<1>の感光性樹脂組成物(但し、R3およびR4は、それぞれ、有機基であり、互いに結合して環を形成していてもよい。)
<3>一般式(S)において、R1が、5員環または6員環の環状基である、<1>または<2>の感光性樹脂組成物。
<4>一般式(S)において、R1が、モルホリノ基である、<1>または<2>の感光性樹脂組成物。
<5>前記(B)の光酸発生剤が、オキシムスルホネート化合物である、<1>~<4>のいずれかの感光性樹脂組成物。
<6>アルコキシシラン化合物が、ジアルコキシシラン化合物またはトリアルコキシシラン化合物である、<1>~<5>のいずれかの感光性樹脂組成物。
<7>(F)架橋剤を含む<1>~<6>のいずれかの感光性樹脂組成物。
<8>(1)<1>~<7>のいずれかの感光性樹脂組成物を基板上に塗布する工程、
(2)塗布された感光性樹脂組成物から溶剤を除去する工程、
(3)溶剤が除去された感光性樹脂組成物を活性光線により露光する工程、
(4)露光された感光性樹脂組成物を水性現像液により現像する工程、および、
(5)現像された感光性樹脂組成物を熱硬化するポストベーク工程、を含む硬化膜の製造方法。
<9>前記現像工程後、前記ポストベーク工程前に、現像された感光性樹脂組成物を全面露光する工程を含む、<8>の硬化膜の製造方法。
<10><8>または<9>の方法により形成された硬化膜。
<11>層間絶縁膜である、<10>の硬化膜。
<12><10>または<11>の硬化膜を有する有機EL表示装置または液晶表示装置。 Specifically, the above-mentioned problem has been solved by the following solving means <1>, preferably <2> to <12>.
<1> (A) a polymer component containing a polymer that satisfies at least one of the following (1) and (2):
(1) (a1) a polymer having a structural unit having an acid group protected with an acid-decomposable group, and (a2) a structural unit having a crosslinkable group,
(2) (a1) a polymer having a structural unit having a group in which an acid group is protected with an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group,
(B) a nonionic photoacid generator,
(C) a compound represented by the following general formula (S),
General formula (S)
(D) a solvent, and
(E) A photosensitive resin composition containing an alkoxysilane compound.
<2> The photosensitive resin composition according to <1>, wherein R 1 is a group represented by —NR 3 R 4 in the general formula (S) (where R 3 and R 4 are each an organic group) And may be bonded to each other to form a ring.)
<3> The photosensitive resin composition according to <1> or <2>, wherein R 1 in the general formula (S) is a 5-membered or 6-membered cyclic group.
<4> The photosensitive resin composition according to <1> or <2>, wherein R 1 is a morpholino group in the general formula (S).
<5> The photosensitive resin composition according to any one of <1> to <4>, wherein the photoacid generator (B) is an oxime sulfonate compound.
<6> The photosensitive resin composition according to any one of <1> to <5>, wherein the alkoxysilane compound is a dialkoxysilane compound or a trialkoxysilane compound.
<7> (F) The photosensitive resin composition according to any one of <1> to <6>, comprising a crosslinking agent.
<8> (1) A step of applying the photosensitive resin composition according to any one of <1> to <7> on a substrate,
(2) removing the solvent from the applied photosensitive resin composition;
(3) A step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays,
(4) a step of developing the exposed photosensitive resin composition with an aqueous developer, and
(5) A method for producing a cured film, comprising a post-baking step of thermosetting the developed photosensitive resin composition.
<9> The method for producing a cured film according to <8>, including a step of exposing the entire surface of the developed photosensitive resin composition after the developing step and before the post-baking step.
<10> A cured film formed by the method <8> or <9>.
<11> A cured film of <10>, which is an interlayer insulating film.
<12> An organic EL display device or a liquid crystal display device having a cured film of <10> or <11>.
<13>上記いずれかに記載の感光性樹脂組成物であって、全固形分100質量部に対し、(A)重合体成分を50~99.9質量部、(B)非イオン性光酸発生剤を0.1~10質量部、(C)一般式(S)で表される化合物を0.001~5質量部、アルコキシシラン化合物を0.1~30質量部含む組成物。
<14>上記いずれかに記載の感光性樹脂組成物であって、一般式(S)で表される化合物中、R1が、-NR3R4で表される基であり、R3およびR4は、それぞれ、アルキル基、アルケニル基、または、これらと、-O-、-S-および-N-の少なくとも1つの組み合わせからなる基であり、
R1が、5員環または6員環の環状基である、組成物。 Further, the above-mentioned problem has been solved by the following means.
<13> The photosensitive resin composition according to any one of the above, wherein (A) the polymer component is 50 to 99.9 parts by mass with respect to 100 parts by mass of the total solid content, and (B) the nonionic photoacid. A composition comprising 0.1 to 10 parts by mass of a generator, 0.001 to 5 parts by mass of a compound represented by (C) the general formula (S), and 0.1 to 30 parts by mass of an alkoxysilane compound.
<14> The photosensitive resin composition according to any one of the above, wherein in the compound represented by the general formula (S), R 1 is a group represented by —NR 3 R 4 , and R 3 and Each of R 4 is an alkyl group, an alkenyl group, or a group consisting of these and at least one combination of —O—, —S— and —N—;
A composition wherein R 1 is a 5-membered or 6-membered cyclic group.
本発明の感光性樹脂組成物は、(A)下記(1)および(2)の少なくとも一方を満たす重合体を含む重合体成分、
(1)(a1)酸基が酸分解性基で保護された基を有する構成単位、および(a2)架橋性基を有する構成単位、を有する重合体、
(2)(a1)酸基が酸分解性基で保護された基を有する構成単位を有する重合体、および(a2)架橋性基を有する構成単位を有する重合体、
(B)非イオン性光酸発生剤、
(C)上記一般式(S)で表される化合物、
(D)溶剤、ならびに、
(E)アルコキシシラン化合物
を含有することを特徴とする。
本発明により、現像時、硬化膜として使用した際の基板との密着性に優れる感光性樹脂組成物を提供可能になる。さらに、耐薬品性も向上させることができる。
以下、本発明の組成物について詳細に説明する。 The photosensitive resin composition of the present invention (hereinafter sometimes referred to as “the composition of the present invention”) is preferably used as a positive photosensitive resin composition.
The photosensitive resin composition of the present invention comprises (A) a polymer component containing a polymer that satisfies at least one of the following (1) and (2):
(1) (a1) a polymer having a structural unit having an acid group protected with an acid-decomposable group, and (a2) a structural unit having a crosslinkable group,
(2) (a1) a polymer having a structural unit having a group in which an acid group is protected with an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group,
(B) a nonionic photoacid generator,
(C) a compound represented by the above general formula (S),
(D) a solvent, and
(E) It contains an alkoxysilane compound.
According to the present invention, it is possible to provide a photosensitive resin composition having excellent adhesion to a substrate when used as a cured film during development. Furthermore, chemical resistance can be improved.
Hereinafter, the composition of the present invention will be described in detail.
本発明の組成物は、重合体成分として、(1)(a1)酸基が酸分解性基で保護された基を有する構成単位および(a2)架橋性基を有する構成単位を有する重合体、ならびに(2)(a1)酸基が酸分解性基で保護された基を有する構成単位を有する重合体および(a2)架橋性基を有する構成単位を有する重合体、の少なくとも一方を含む。さらに、これら以外の重合体を含んでいてもよい。本発明における(A)重合体成分(以下、「(A)成分」というがある)は、特に述べない限り、上記(1)および/または(2)に加え、必要に応じて添加される他の重合体を含めたものを意味する。 <(A) Polymer component>
The composition of the present invention comprises, as a polymer component, (1) (a1) a polymer having a structural unit having an acid group protected by an acid-decomposable group and (a2) a structural unit having a crosslinkable group, And (2) (a1) at least one of a polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group and (a2) a polymer having a structural unit having a crosslinkable group. Furthermore, polymers other than these may be included. The polymer component (A) in the present invention (hereinafter referred to as “component (A)”) is added in addition to the above (1) and / or (2) unless otherwise specified. Including those polymers.
成分Aは、(a1)酸基が酸分解性基で保護された基を有する構成単位を少なくとも有する。(A)成分が構成単位(a1)を有することにより、極めて高感度な感光性樹脂組成物とすることができる。
本発明における「酸基が酸分解性基で保護された基」は、酸基および酸分解性基として公知のものを使用でき、特に限定されない。具体的な酸基としては、カルボキシル基、および、フェノール性水酸基が好ましく挙げられる。また、酸分解性基としては、酸により比較的分解し易い基(例えば、後述する式(A1)で表される基のエステル構造、テトラヒドロピラニルエステル基、または、テトラヒドロフラニルエステル基等のアセタール系官能基)や酸により比較的分解し難い基(例えば、tert-ブチルエステル基等の第三級アルキル基、tert-ブチルカーボネート基等の第三級アルキルカーボネート基)を用いることができる。 << Structural Unit (a1) >>
Component A has (a1) at least a structural unit having a group in which an acid group is protected with an acid-decomposable group. When the component (A) has the structural unit (a1), a highly sensitive photosensitive resin composition can be obtained.
As the “group in which the acid group is protected with an acid-decomposable group” in the present invention, those known as an acid group and an acid-decomposable group can be used, and are not particularly limited. Specific examples of the acid group preferably include a carboxyl group and a phenolic hydroxyl group. The acid-decomposable group is a group that is relatively easily decomposed by an acid (for example, an acetal group such as an ester structure of a group represented by the formula (A1) described later, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group). A functional group) or a group that is relatively difficult to decompose with an acid (for example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group).
以下、酸分解性基で保護された保護カルボキシル基を有する構成単位(a1-1)と、酸分解性基で保護された保護フェノール性水酸基を有する構成単位(a1-2)について、順にそれぞれ説明する。 (A1) The structural unit having an acid group protected with an acid-decomposable group is a structural unit having a protected carboxyl group protected with an acid-decomposable group, or a protected phenolic group protected with an acid-decomposable group. A structural unit having a hydroxyl group is preferred.
Hereinafter, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group and the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group will be described in order. To do.
上記酸分解性基で保護された保護カルボキシル基を有する構成単位(a1-1)は、カルボキシル基を有する構成単位のカルボキシル基が、以下で詳細に説明する酸分解性基によって保護された保護カルボキシル基を有する構成単位である。
上記酸分解性基で保護された保護カルボキシル基を有する構成単位(a1-1)に用いることができる上記カルボキシル基を有する構成単位としては、特に制限はなく公知の構成単位を用いることができる。例えば、不飽和モノカルボン酸、不飽和ジカルボン酸、不飽和トリカルボン酸などの、分子中に少なくとも1個のカルボキシル基を有する不飽和カルボン酸等に由来する構成単位(a1-1-1)や、エチレン性不飽和基と酸無水物由来の構造とを共に有する構成単位(a1-1-2)が挙げられる。
以下、上記カルボキシル基を有する構成単位として用いられる(a1-1-1)分子中に少なくとも1個のカルボキシル基を有する不飽和カルボン酸等に由来する構成単位と、(a1-1-2)エチレン性不飽和基と酸無水物由来の構造とを共に有する構成単位について、それぞれ順に説明する。 <<< (a1-1) Structural Unit Having a Protected Carboxyl Group Protected with an Acid-Decomposable Group >>>
The structural unit (a1-1) having a protected carboxyl group protected by an acid-decomposable group is a protected carboxyl in which the carboxyl group of the structural unit having a carboxyl group is protected by an acid-decomposable group described in detail below. A structural unit having a group.
The structural unit having a carboxyl group that can be used for the structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group is not particularly limited, and a known structural unit can be used. For example, a structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or an unsaturated tricarboxylic acid, And a structural unit (a1-1-2) having both an ethylenically unsaturated group and a structure derived from an acid anhydride.
Hereinafter, (a1-1-1) a structural unit derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule used as the structural unit having a carboxyl group, and (a1-1-2) ethylene The structural units having both the unsaturated group and the structure derived from the acid anhydride will be described in order.
上記分子中に少なくとも1個のカルボキシル基を有する不飽和カルボン酸等に由来する構成単位(a1-1-1)として本発明で用いられる不飽和カルボン酸としては以下に挙げるようなものが用いられる。すなわち、不飽和モノカルボン酸としては、例えば、アクリル酸、メタクリル酸、クロトン酸、α-クロロアクリル酸、けい皮酸、2-(メタ)アクリロイロキシエチル-コハク酸、2-(メタ)アクリロイロキシエチルヘキサヒドロフタル酸、2-(メタ)アクリロイロキシエチル-フタル酸、などが挙げられる。また、不飽和ジカルボン酸としては、例えば、マレイン酸、フマル酸、イタコン酸、シトラコン酸、メサコン酸などが挙げられる。また、カルボキシル基を有する構成単位を得るために用いられる不飽和多価カルボン酸は、その酸無水物であってもよい。具体的には、無水マレイン酸、無水イタコン酸、無水シトラコン酸などが挙げられる。また、不飽和多価カルボン酸は、多価カルボン酸のモノ(2-メタクリロイロキシアルキル)エステルであってもよく、例えば、コハク酸モノ(2-アクリロイロキシエチル)、コハク酸モノ(2-メタクリロイロキシエチル)、フタル酸モノ(2-アクリロイロキシエチル)、フタル酸モノ(2-メタクリロイロキシエチル)などが挙げられる。さらに、不飽和多価カルボン酸は、その両末端ジカルボキシポリマーのモノ(メタ)アクリレートであってもよく、例えば、ω-カルボキシポリカプロラクトンモノアクリレート、ω-カルボキシポリカプロラクトンモノメタクリレートなどが挙げられる。また、不飽和カルボン酸としては、アクリル酸-2-カルボキシエチルエステル、メタクリル酸-2-カルボキシエチルエステル、マレイン酸モノアルキルエステル、フマル酸モノアルキルエステル、4-カルボキシスチレン等も用いることができる。
中でも、現像性の観点から、上記分子中に少なくとも1個のカルボキシル基を有する不飽和カルボン酸等に由来する構成単位(a1-1-1)を形成するためには、アクリル酸、メタクリル酸、2-(メタ)アクリロイロキシエチル-コハク酸、2-(メタ)アクリロイロキシエチルヘキサヒドロフタル酸、2-(メタ)アクリロイロキシエチル-フタル酸、または不飽和多価カルボン酸の無水物等を用いることが好ましく、アクリル酸、メタクリル酸、2-(メタ)アクリロイロキシエチルヘキサヒドロフタル酸、を用いることがより好ましい。
上記分子中に少なくとも1個のカルボキシル基を有する不飽和カルボン酸等に由来する構成単位(a1-1-1)は、1種単独で構成されていてもよいし、2種以上で構成されていてもよい。 <<<<< (a1-1-1) Structural Unit Derived from Unsaturated Carboxylic Acid Having at least One Carboxyl Group in the Molecule >>>>
Examples of the unsaturated carboxylic acid used in the present invention as the structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule include those listed below. . That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, 2- (meth) acryloyloxyethyl-succinic acid, and 2- (meth) acrylic acid. Examples include leuoxyethyl hexahydrophthalic acid and 2- (meth) acryloyloxyethyl-phthalic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. Moreover, the acid anhydride may be sufficient as unsaturated polycarboxylic acid used in order to obtain the structural unit which has a carboxyl group. Specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. Further, the unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester of a polyvalent carboxylic acid, such as succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2 -Methacryloyloxyethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like. Further, the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both ends, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. As the unsaturated carboxylic acid, acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used.
Among them, from the viewpoint of developability, in order to form the structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-phthalic acid, or unsaturated polycarboxylic acid anhydride It is preferable to use acrylic acid, methacrylic acid, and 2- (meth) acryloyloxyethyl hexahydrophthalic acid.
The structural unit (a1-1-1) derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the molecule may be composed of one kind alone or two or more kinds. May be.
エチレン性不飽和基と酸無水物由来の構造とを共に有する構成単位(a1-1-2)は、エチレン性不飽和基を有する構成単位中に存在する水酸基と酸無水物とを反応させて得られたモノマーに由来する単位であることが好ましい。
上記酸無水物としては、公知のものが使用でき、具体的には、無水マレイン酸、無水コハク酸、無水イタコン酸、無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、無水クロレンド酸等の二塩基酸無水物;無水トリメリット酸、無水ピロメリット酸、ベンゾフェノンテトラカルボン酸無水物、ビフェニルテトラカルボン酸無水物などの酸無水物が挙げられる。これらの中では、現像性の観点から、無水フタル酸、テトラヒドロ無水フタル酸、または無水コハク酸、が好ましい。
上記酸無水物の水酸基に対する反応率は、現像性の観点から、好ましくは10~100モル%、より好ましくは30~100モル%である。 <<<< (a1-1-2) Structural unit having both an ethylenically unsaturated group and a structure derived from an acid anhydride >>>>
The structural unit (a1-1-2) having both an ethylenically unsaturated group and a structure derived from an acid anhydride is obtained by reacting a hydroxyl group present in the structural unit having an ethylenically unsaturated group with an acid anhydride. A unit derived from the obtained monomer is preferred.
As the acid anhydride, known ones can be used, and specifically, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride, etc. Dibasic acid anhydrides; acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic anhydride, and the like. Among these, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferable from the viewpoint of developability.
The reaction rate of the acid anhydride with respect to the hydroxyl group is preferably 10 to 100 mol%, more preferably 30 to 100 mol% from the viewpoint of developability.
上記酸分解性基で保護された保護カルボキシル基を有する構成単位(a1-1)に用いることができる上記酸分解性基としては上述の酸分解性基を用いることができる。
これらの酸分解性基の中でもカルボキシル基がアセタールの形で保護された保護カルボキシル基であることが、感光性樹脂組成物の基本物性、特に感度やパターン形状、コンタクトホールの形成性、感光性樹脂組成物の保存安定性の観点から好ましい。さらに酸分解性基の中でもカルボキシル基が下記一般式(a1-10)で表されるアセタールの形で保護された保護カルボキシル基であることが、感度の観点からより好ましい。なお、カルボキシル基が下記一般式(a1-10)で表されるアセタールの形で保護された保護カルボキシル基である場合、保護カルボキシル基の全体としては、-(C=O)-O-CR101R102(OR103)の構造となっている。 <<<< acid-decomposable group that can be used for the structural unit (a1-1) >>>>
As the acid-decomposable group that can be used in the structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group, the above-mentioned acid-decomposable group can be used.
Among these acid-decomposable groups, the carboxyl group is a protected carboxyl group protected in the form of an acetal, so that the basic physical properties of the photosensitive resin composition, in particular, sensitivity and pattern shape, contact hole formability, photosensitive resin It is preferable from the viewpoint of the storage stability of the composition. Further, among the acid-decomposable groups, the carboxyl group is more preferably a protected carboxyl group protected in the form of an acetal represented by the following general formula (a1-10) from the viewpoint of sensitivity. When the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following general formula (a1-10), the entire protected carboxyl group is — (C═O) —O—CR 101 It has a structure of R 102 (OR 103).
上記直鎖状または分岐鎖状のアルキル基としては、炭素数1~12であることが好ましく、炭素数1~6であることがより好ましく、炭素数1~4であることがさらに好ましい。具体的には、メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、i-ブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、ネオペンチル基、n-ヘキシル基、テキシル基(2,3-ジメチル-2-ブチル基)、n-ヘプチル基、n-オクチル基、2-エチルヘキシル基、n-ノニル基、n-デシル基等を挙げることができる。 In the general formula (a1-10), when R 101 , R 102 and R 103 represent an alkyl group, the alkyl group may be linear, branched or cyclic.
The linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n Examples include -hexyl group, texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group and the like.
上記ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が例示され、これらの中でもフッ素原子または塩素原子が好ましい。
また、上記アリール基としては、炭素数6~20のアリール基が好ましく、より好ましくは炭素数6~12であり、具体的には、フェニル基、α-メチルフェニル基、ナフチル基等が例示でき、アリール基で置換されたアルキル基全体、すなわち、アラルキル基としては、ベンジル基、α-メチルベンジル基、フェネチル基、ナフチルメチル基等が例示できる。
上記アルコキシ基としては、炭素数1~6のアルコキシ基が好ましく、より好ましくは炭素数1~4であり、メトキシ基またはエトキシ基がより好ましい。
また、上記アルキル基がシクロアルキル基である場合、上記シクロアルキル基は置換基として炭素数1~10の直鎖状または分岐鎖状のアルキル基を有していてもよく、アルキル基が直鎖状または分岐鎖状のアルキル基である場合には、置換基として炭素数3~12のシクロアルキル基を有していてもよい。
これらの置換基は、上記置換基でさらに置換されていてもよい。 The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group. When it has a halogen atom as a substituent, R 101 , R 102 and R 103 become a haloalkyl group, and when it has an aryl group as a substituent, R 101 , R 102 and R 103 become an aralkyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom or a chlorine atom is preferable.
The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, an α-methylphenyl group, and a naphthyl group. Examples of the entire alkyl group substituted with an aryl group, ie, an aralkyl group, include a benzyl group, an α-methylbenzyl group, a phenethyl group, and a naphthylmethyl group.
The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and more preferably a methoxy group or an ethoxy group.
In addition, when the alkyl group is a cycloalkyl group, the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group is a straight chain. Or a branched alkyl group, it may have a cycloalkyl group having 3 to 12 carbon atoms as a substituent.
These substituents may be further substituted with the above substituents.
R1およびR2がアルキル基の場合、炭素数は1~10のアルキル基が好ましい。R1およびR2がアリール基の場合、フェニル基が好ましい。R1およびR2は、それぞれ、水素原子または炭素数1~4のアルキル基が好ましい。
R3は、アルキル基またはアリール基を表し、炭素数1~10のアルキル基が好ましく、1~6のアルキル基がより好ましい。
Xは単結合またはアリーレン基を表し、単結合が好ましい。 A first preferred embodiment of the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is a structural unit represented by the following general formula.
When R 1 and R 2 are alkyl groups, alkyl groups having 1 to 10 carbon atoms are preferred. When R 1 and R 2 are aryl groups, a phenyl group is preferred. R 1 and R 2 are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R 3 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.
X represents a single bond or an arylene group, and a single bond is preferred.
R121は水素原子またはメチル基が好ましい。
L1はカルボニル基が好ましい。
R122~R128は、水素原子が好ましい。 A second preferred embodiment of the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is a structural unit of the following general formula.
R 121 is preferably a hydrogen atom or a methyl group.
L 1 is preferably a carbonyl group.
R 122 to R 128 are preferably hydrogen atoms.
上記酸分解性基で保護された保護フェノール性水酸基を有する構成単位(a1-2)は、フェノール性水酸基を有する構成単位が、以下で詳細に説明する酸分解性基によって保護された保護フェノール性水酸基を有する構成単位である。 <<< (a1-2) Structural unit having a protected phenolic hydroxyl group protected with an acid-decomposable group >>>
The structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group is a protected phenolic group in which the structural unit having a phenolic hydroxyl group is protected by an acid-decomposable group described in detail below. A structural unit having a hydroxyl group.
上記フェノール性水酸基を有する構成単位としては、ヒドロキシスチレン系構成単位やノボラック系の樹脂における構成単位が挙げられるが、これらの中では、ヒドロキシスチレン、またはα-メチルヒドロキシスチレンに由来する構成単位が、感度の観点から好ましい。またフェノール性水酸基を有する構成単位として、下記一般式(a1-20)で表される構成単位も、感度の観点から好ましい。 <<<< (a1-2-1) Structural unit having phenolic hydroxyl group >>>
Examples of the structural unit having a phenolic hydroxyl group include a hydroxystyrene structural unit and a structural unit in a novolac resin. Among these, a structural unit derived from hydroxystyrene or α-methylhydroxystyrene includes: It is preferable from the viewpoint of sensitivity. As the structural unit having a phenolic hydroxyl group, a structural unit represented by the following general formula (a1-20) is also preferable from the viewpoint of sensitivity.
また、R221は単結合または二価の連結基を示す。単結合である場合には、感度を向上させることができ、さらに硬化膜の透明性を向上させることができるので好ましい。R221の二価の連結基としてはアルキレン基が例示でき、R221がアルキレン基である具体例としては、メチレン基、エチレン基、プロピレン基、イソプロピレン基、n-ブチレン基、イソブチレン基、tert-ブチレン基、ペンチレン基、イソペンチレン基、ネオペンチレン基、ヘキシレン基等が挙げられる。中でも、R221が単結合、メチレン基、エチレン基であることが好ましい。また、上記二価の連結基は、置換基を有していてもよく、置換基としては、ハロゲン原子、水酸基、アルコキシ基等が挙げられる。また、aは1~5の整数を表すが、本発明の効果の観点や、製造が容易であるという点から、aは1または2であることが好ましく、aが1であることがより好ましい。
また、ベンゼン環における水酸基の結合位置は、R221と結合している炭素原子を基準(1位)としたとき、4位に結合していることが好ましい。
R222はハロゲン原子または炭素数1~5の直鎖または分岐鎖状のアルキル基である。具体的には、フッ素原子、塩素原子、臭素原子、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、イソブチル基、tert-ブチル基、ペンチル基、イソペンチル基、ネオペンチル基等が挙げられる。中でも製造が容易であるという点から、塩素原子、臭素原子、メチル基またはエチル基であることが好ましい。
また、bは0または1~4の整数を表す。 In the general formula (a1-20), R 220 represents a hydrogen atom or a methyl group, and is preferably a methyl group.
R 221 represents a single bond or a divalent linking group. A single bond is preferable because the sensitivity can be improved and the transparency of the cured film can be further improved. The divalent linking group of R 221 may be exemplified alkylene groups, specific examples R 221 is an alkylene group, a methylene group, an ethylene group, a propylene group, isopropylene group, n- butylene group, isobutylene group, tert -Butylene group, pentylene group, isopentylene group, neopentylene group, hexylene group and the like. Among these, R 221 is preferably a single bond, a methylene group, or an ethylene group. The divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group. A represents an integer of 1 to 5, but a is preferably 1 or 2 and more preferably 1 from the viewpoint of the effects of the present invention and the ease of production. .
Further, the bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4-position when the carbon atom bonded to R 221 is defined as the reference (first position).
R 222 is a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, fluorine atom, chlorine atom, bromine atom, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc. It is done. Among these, a chlorine atom, a bromine atom, a methyl group, or an ethyl group is preferable from the viewpoint of easy production.
B represents 0 or an integer of 1 to 4.
上記酸分解性基で保護された保護フェノール性水酸基を有する構成単位(a1-2)に用いることができる上記酸分解性基としては、上記酸分解性基で保護された保護カルボキシル基を有する構成単位(a1-1)に用いることができる上記酸分解性基と同様に、公知のものを使用でき、特に限定されない。酸分解性基の中でもアセタールで保護された保護フェノール性水酸基を有する構成単位であることが、感光性樹脂組成物の基本物性、特に感度やパターン形状、感光性樹脂組成物の保存安定性、コンタクトホールの形成性の観点から好ましい。さらに、酸分解性基の中でもフェノール性水酸基が上記一般式(a1-10)で表されるアセタールの形で保護された保護フェノール性水酸基であることが、感度の観点からより好ましい。なお、フェノール性水酸基が上記一般式(a1-10)で表されるアセタールの形で保護された保護フェノール性水酸基である場合、保護フェノール性水酸基の全体としては、-Ar-O-CR101R102(OR103)の構造となっている。
なお、Arはアリーレン基を表す。 <<<< acid-decomposable group that can be used for the structural unit (a1-2) >>>>
The acid-decomposable group that can be used in the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group includes a structure having a protected carboxyl group protected with the acid-decomposable group. Similar to the acid-decomposable group that can be used for the unit (a1-1), known ones can be used and are not particularly limited. Among the acid-decomposable groups, the structural unit having a protected phenolic hydroxyl group protected with acetal is a basic physical property of the photosensitive resin composition, particularly sensitivity and pattern shape, storage stability of the photosensitive resin composition, contact It is preferable from the viewpoint of hole formability. Furthermore, among the acid-decomposable groups, it is more preferable from the viewpoint of sensitivity that the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of an acetal represented by the general formula (a1-10). When the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of the acetal represented by the general formula (a1-10), the entire protected phenolic hydroxyl group is —Ar—O—CR 101 R. The structure is 102 (OR 103 ).
Ar represents an arylene group.
これらの中で、4-ヒドロキシフェニルメタクリレートの1-アルコキシアルキル保護体、4-ヒドロキシフェニルメタクリレートのテトラヒドロピラニル保護体、が透明性の観点から好ましい。 Examples of the radical polymerizable monomer used to form a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected in the form of an acetal include, for example, paragraph number 0042 of JP-A No. 2011-215590. And the like.
Among these, a 1-alkoxyalkyl protector of 4-hydroxyphenyl methacrylate and a tetrahydropyranyl protector of 4-hydroxyphenyl methacrylate are preferable from the viewpoint of transparency.
上記構成単位(a1)を含有する重合体が、実質的に、構成単位(a2)を含まない場合、構成単位(a1)は、該構成単位(a1)を含有する重合体中、20~100モル%が好ましく、30~90モル%がより好ましい。
上記構成単位(a1)を含有する重合体が、下記構成単位(a2)を含有する場合、単構成単位(a1)は、該構成単位(a1)と構成単位(a2)を含有する重合体中、感度の観点から3~70モル%が好ましく、10~60モル%がより好ましい。また、特に上記構成単位(a1)に用いることができる上記酸分解性基がカルボキシル基がアセタールの形で保護された保護カルボキシル基を有する構成単位である場合、20~50モル%が好ましい。 <<< Preferred Aspect of Structural Unit (a1) >>>
When the polymer containing the structural unit (a1) does not substantially contain the structural unit (a2), the structural unit (a1) is 20 to 100 in the polymer containing the structural unit (a1). The mol% is preferable, and 30 to 90 mol% is more preferable.
When the polymer containing the structural unit (a1) contains the following structural unit (a2), the single structural unit (a1) is contained in the polymer containing the structural unit (a1) and the structural unit (a2). From the viewpoint of sensitivity, it is preferably 3 to 70 mol%, more preferably 10 to 60 mol%. In particular, when the acid-decomposable group that can be used in the structural unit (a1) is a structural unit having a protected carboxyl group in which the carboxyl group is protected in the form of an acetal, the content is preferably 20 to 50 mol%.
上記酸分解性基で保護された保護カルボキシル基を有する構成単位(a1-1)は、上記酸分解性基で保護された保護フェノール性水酸基を有する構成単位(a1-2)に比べると、現像が速いという特徴がある。よって、速く現像したい場合には酸分解性基で保護された保護カルボキシル基を有する構成単位(a1-1)が好ましい。逆に現像を遅くしたい場合には酸分解性基で保護された保護フェノール性水酸基を有する構成単位(a1-2)を用いることが好ましい。 The structural unit (a1-1) having a protected carboxyl group protected with the acid-decomposable group is more developed than the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group. Is characterized by being fast. Therefore, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is preferred for rapid development. Conversely, when it is desired to delay development, it is preferable to use the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group.
The structural unit (a1-1) having a protected carboxyl group protected with the acid-decomposable group is more developed than the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group. Is characterized by being fast. Therefore, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is preferred for rapid development. Conversely, when it is desired to delay development, it is preferable to use the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group.
(A)成分は、架橋性基を有する構成単位(a2)を有する。上記架橋性基は、加熱処理で硬化反応を起こす基であれば特に限定はされない。好ましい架橋性基を有する構成単位の態様としては、エポキシ基、オキセタニル基、-NH-CH2-O-R(Rは炭素数1~20のアルキル基)で表される基およびエチレン性不飽和基よりなる群から選ばれた少なくとも1つを含む構成単位が挙げられ、エポキシ基、オキセタニル基、および、-NH-CH2-O-R(Rは炭素数1~20のアルキル基)で表される基から選ばれる少なくとも1種であることが好ましい。その中でも、本発明の感光性樹脂組成物は、上記(A)成分が、エポキシ基およびオキセタニル基のうち少なくとも1つを含む構成単位を含むことが好ましい。より詳細には、以下のものが挙げられる。 << (a2) Structural Unit Having Crosslinkable Group >>
The component (A) has a structural unit (a2) having a crosslinkable group. The crosslinkable group is not particularly limited as long as it is a group that causes a curing reaction by heat treatment. Preferred embodiments of the structural unit having a crosslinkable group include an epoxy group, an oxetanyl group, a group represented by —NH—CH 2 —O—R (where R is an alkyl group having 1 to 20 carbon atoms), and ethylenically unsaturated groups. A structural unit containing at least one member selected from the group consisting of groups, represented by an epoxy group, an oxetanyl group, and —NH—CH 2 —O—R (R is an alkyl group having 1 to 20 carbon atoms). It is preferable that it is at least 1 sort (s) chosen from the group made. Among them, in the photosensitive resin composition of the present invention, the component (A) preferably includes a structural unit containing at least one of an epoxy group and an oxetanyl group. In more detail, the following are mentioned.
上記(A)重合体は、エポキシ基および/またはオキセタニル基を有する構成単位(構成単位(a2-1))を含有することが好ましい。上記3員環の環状エーテル基はエポキシ基とも呼ばれ、4員環の環状エーテル基はオキセタニル基とも呼ばれる。
上記エポキシ基および/またはオキセタニル基を有する構成単位(a2-1)は、1つの構成単位中にエポキシ基またはオキセタニル基を少なくとも1つ有していればよく、1つ以上のエポキシ基および1つ以上オキセタニル基、2つ以上のエポキシ基、または、2つ以上のオキセタニル基を有していてもよく、特に限定されないが、エポキシ基および/またはオキセタニル基を合計1~3つ有することが好ましく、エポキシ基および/またはオキセタニル基を合計1または2つ有することがより好ましく、エポキシ基またはオキセタニル基を1つ有することがさらに好ましい。 <<< (a2-1) Structural Unit Having Epoxy Group and / or Oxetanyl Group >>>
The polymer (A) preferably contains a structural unit (structural unit (a2-1)) having an epoxy group and / or an oxetanyl group. The 3-membered cyclic ether group is also called an epoxy group, and the 4-membered cyclic ether group is also called an oxetanyl group.
The structural unit (a2-1) having an epoxy group and / or oxetanyl group may have at least one epoxy group or oxetanyl group in one structural unit. It may have an oxetanyl group, two or more epoxy groups, or two or more oxetanyl groups, and is not particularly limited, but preferably has a total of 1 to 3 epoxy groups and / or oxetanyl groups, It is more preferable to have one or two epoxy groups and / or oxetanyl groups in total, and it is even more preferable to have one epoxy group or oxetanyl group.
オキセタニル基を有する構成単位を形成するために用いられるラジカル重合性単量体の具体例としては、例えば、特開2001-330953号公報の段落番号0011~0016に記載のオキセタニル基を有する(メタ)アクリル酸エステルなどが挙げられ、これらの内容は本願明細書に組み込まれる。
上記エポキシ基および/またはオキセタニル基を有する構成単位(a2-1)を形成するために用いられるラジカル重合性単量体の具体例としては、メタクリル酸エステル構造を含有するモノマー、アクリル酸エステル構造を含有するモノマーであることが好ましい。 Specific examples of the radical polymerizable monomer used for forming the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, and glycidyl α-n-propyl acrylate. Glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexyl methacrylate Methyl, α-ethylacrylic acid-3,4-epoxycyclohexylmethyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, described in paragraph Nos. 0031 to 0035 of Japanese Patent No. 4168443 Alicyclic And compounds containing epoxy backbone can be cited, the contents of which are incorporated herein.
Specific examples of the radical polymerizable monomer used for forming the structural unit having an oxetanyl group include (meth) having an oxetanyl group described in paragraph Nos. 0011 to 0016 of JP-A No. 2001-330953, for example. Acrylic esters and the like are included, the contents of which are incorporated herein.
Specific examples of the radical polymerizable monomer used for forming the structural unit (a2-1) having the epoxy group and / or oxetanyl group include a monomer having a methacrylic ester structure and an acrylic ester structure. It is preferable that it is a monomer to contain.
上記架橋性基を有する構成単位(a2)の1つとして、エチレン性不飽和基を有する構成単位(a2-2)が挙げられる(以下、「構成単位(a2-2)」ともいう。)。上記エチレン性不飽和基を有する構成単位(a2-2)としては、側鎖にエチレン性不飽和基を有する構成単位が好ましく、末端にエチレン性不飽和基を有し、炭素数3~16の側鎖を有する構成単位がより好ましく、下記一般式(a2-2-1)で表される側鎖を有する構成単位がさらに好ましい。 <<< (a2-2) Structural unit having an ethylenically unsaturated group >>>
One example of the structural unit (a2) having a crosslinkable group is a structural unit (a2-2) having an ethylenically unsaturated group (hereinafter also referred to as “structural unit (a2-2)”). The structural unit (a2-2) having an ethylenically unsaturated group is preferably a structural unit having an ethylenically unsaturated group in the side chain, having an ethylenically unsaturated group at the terminal, and having 3 to 16 carbon atoms. A structural unit having a side chain is more preferred, and a structural unit having a side chain represented by the following general formula (a2-2-1) is more preferred.
本発明で用いる重合体は、-NH-CH2-O-R(Rは炭素数1~20のアルキル基)で表される基を有する構成単位(a2-3)も好ましい。構成単位(a2-3)を有することで、緩やかな加熱処理で硬化反応を起こすことができ、諸特性に優れた硬化膜を得ることができる。ここで、Rは炭素数1~9のアルキル基が好ましく、炭素数1~4のアルキル基がより好ましい。また、アルキル基は、直鎖、分岐または環状のアルキル基のいずれであってもよいが、好ましくは、直鎖または分岐のアルキル基である。構成単位(a2)は、より好ましくは、下記一般式(a2-30)で表される基を有する構成単位である。
一般式(a2-30)
R2は、炭素数1~9のアルキル基が好ましく、炭素数1~4のアルキル基がさらに好ましい。また、アルキル基は、直鎖、分岐または環状のアルキル基のいずれであってもよいが、好ましくは、直鎖または分岐のアルキル基である。
R2の具体例としては、メチル基、エチル基、n-ブチル基、i-ブチル基、シクロヘキシル基、およびn-ヘキシル基を挙げることができる。中でもi-ブチル基、n-ブチル基、メチル基が好ましい。 <<< Structural Unit Having a Group Represented by (a2-3) -NH—CH 2 —O—R (where R is an alkyl group having 1 to 20 carbon atoms) >>
The polymer used in the present invention is also preferably a structural unit (a2-3) having a group represented by —NH—CH 2 —O—R (R is an alkyl group having 1 to 20 carbon atoms). By having the structural unit (a2-3), a curing reaction can be caused by a mild heat treatment, and a cured film having excellent characteristics can be obtained. Here, R is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group. The structural unit (a2) is more preferably a structural unit having a group represented by the following general formula (a2-30).
Formula (a2-30)
R 2 is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
Specific examples of R 2 include a methyl group, an ethyl group, an n-butyl group, an i-butyl group, a cyclohexyl group, and an n-hexyl group. Of these, i-butyl, n-butyl and methyl are preferred.
上記構成単位(a2)を含有する重合体が、実質的に、構成単位(a1)を含まない場合、構成単位(a2)は、該構成単位(a2)を含有する重合体中、5~90モル%が好ましく、20~80モル%がより好ましい。
上記構成単位(a2)を含有する重合体が、上記構成単位(a1)を含有する場合、単構成単位(a2)は、該構成単位(a1)と構成単位(a2)を含有する重合体中、薬品耐性の観点から3~70モル%が好ましく、10~60モル%がより好ましい。
本発明では、さらに、いずれの態様にかかわらず、(A)成分の全構成単位中、構成単位(a2)を3~70モル%含有することが好ましく、10~60モル%含有することがより好ましい。 <<< Preferred Aspect of Structural Unit (a2) >>>
When the polymer containing the structural unit (a2) does not substantially contain the structural unit (a1), the structural unit (a2) is 5 to 90% in the polymer containing the structural unit (a2). The mol% is preferable, and 20 to 80 mol% is more preferable.
When the polymer containing the structural unit (a2) contains the structural unit (a1), the single structural unit (a2) is contained in the polymer containing the structural unit (a1) and the structural unit (a2). From the viewpoint of chemical resistance, it is preferably 3 to 70 mol%, more preferably 10 to 60 mol%.
In the present invention, the structural unit (a2) is preferably contained in an amount of 3 to 70 mol%, more preferably 10 to 60 mol% in all the structural units of the component (A), regardless of any embodiment. preferable.
本発明において、(A)成分は、上記構成単位(a1)および/または(a2)に加えて、これら以外の他の構成単位(a3)を有していてもよい。これらの構成単位は、上記重合体成分(1)および/または(2)が含んでいてもよい。また、上記重合体成分(1)または(2)とは別に、実質的に(a1)および(a2)を含まずに他の構成単位(a3)を有する重合体成分を有していてもよい。上記重合体成分(1)または(2)とは別に、実質的に(a1)および(a2)を含まずに他の構成単位(a3)を有する重合体成分を含む場合、該重合体成分の配合量は、全重合体成分中、60質量%以下であることが好ましく、40質量%以下であることがより好ましく、20質量%以下であることがさらに好ましい。 << (a3) Other structural units >>
In the present invention, the component (A) may have other structural units (a3) in addition to the structural units (a1) and / or (a2). These structural units may be contained in the polymer component (1) and / or (2). Further, apart from the polymer component (1) or (2), it may have a polymer component having other structural unit (a3) substantially not containing (a1) and (a2). . Apart from the polymer component (1) or (2), in the case of containing a polymer component having other structural unit (a3) substantially not containing (a1) and (a2), The blending amount is preferably 60% by mass or less, more preferably 40% by mass or less, and still more preferably 20% by mass or less in all polymer components.
重合体成分(1)が、さらに、1種または2種以上のその他の構成単位(a3)を有する態様。
(第2の実施形態)
重合体成分(2)の(a1)酸基が酸分解性基で保護された基を有する構成単位を有する重合体が、さらに、1種または2種以上のその他の構成単位(a3)を有する態様。
(第3の実施形態)
重合体成分(2)の(a2)架橋性基を有する構成単位を有する重合体が、さらに、1種または2種以上のその他の構成単位(a3)を有する態様。 (First embodiment)
The aspect in which the polymer component (1) further has one or more other structural units (a3).
(Second Embodiment)
The polymer having a structural unit having a group in which the (a1) acid group of the polymer component (2) is protected by an acid-decomposable group further has one or more other structural units (a3). Aspect.
(Third embodiment)
The aspect which the polymer which has a structural unit which has (a2) crosslinkable group of a polymer component (2) further has 1 type, or 2 or more types of other structural units (a3).
上記第1~第3の実施形態のいずれかにおいて、その他の構成単位(a3)として、少なくとも酸基を含む構成単位を含む態様。 (Fourth embodiment)
In any one of the first to third embodiments, the other structural unit (a3) includes a structural unit containing at least an acid group.
上記重合体成分(1)または(2)とは別に、さらに、実質的に(a1)および(a2)を含まずに他の構成単位(a3)を有する重合体を有する態様。 (Fifth embodiment)
In addition to the polymer component (1) or (2), an embodiment having a polymer having another structural unit (a3) substantially not containing (a1) and (a2).
上記第1~第5の実施形態の2以上の組み合わせからなる形態。
(第7の実施形態)
重合体成分(2)を少なくとも含む態様。特に、上記第1~第6の実施形態において、少なくとも重合体成分(2)を含む態様。 (Sixth embodiment)
A form comprising a combination of two or more of the first to fifth embodiments.
(Seventh embodiment)
An embodiment comprising at least the polymer component (2). In particular, in the first to sixth embodiments, at least the polymer component (2) is included.
本発明で用いられる酸基としては、カルボン酸基由来のもの、スルホンアミド基に由来のもの、ホスホン酸基に由来のもの、スルホン酸基に由来のもの、フェノール性水酸基に由来するもの、スルホンアミド基、スルホニルイミド基等が例示され、カルボン酸基由来のものおよび/またはフェノール性水酸基に由来のものが好ましい。
本発明で用いられる酸基を含む構成単位は、スチレンに由来する構成単位や、ビニル化合物に由来する構成単位、(メタ)アクリル酸および/またはそのエステルに由来する構成単位であることがより好ましい。 The other structural unit (a3) preferably contains an acid group. By containing an acid group, it becomes easy to dissolve in an alkaline developer, and the effects of the present invention are more effectively exhibited. The acid group in the present invention means a proton dissociable group having a pKa of less than 7. The acid group is usually incorporated into the polymer as a structural unit containing an acid group using a monomer capable of forming an acid group. By including such a structural unit containing an acid group in the polymer, the polymer tends to be easily dissolved in an alkaline developer.
Acid groups used in the present invention include those derived from carboxylic acid groups, those derived from sulfonamide groups, those derived from phosphonic acid groups, those derived from sulfonic acid groups, those derived from phenolic hydroxyl groups, sulfones Amide groups, sulfonylimide groups and the like are exemplified, and those derived from carboxylic acid groups and / or those derived from phenolic hydroxyl groups are preferred.
The structural unit containing an acid group used in the present invention is more preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, a structural unit derived from (meth) acrylic acid and / or an ester thereof. .
その他にも、特開平7-207211号公報、特開平8-259876号公報、特開平10-300922号公報、特開平11-140144号公報、特開平11-174224号公報、特開2000-56118号公報、特開2003-233179号公報、特開2009-52020号公報等に記載の公知の高分子化合物を使用することができ、これらの内容は本願明細書に組み込まれる。
これらの重合体は、1種類のみ含んでいてもよいし、2種類以上含んでいてもよい。 For example, benzyl (meth) acrylate / (meth) acrylic acid copolymer, 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, described in JP-A-7-140654 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2 -Hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid Copolymer and the like.
In addition, JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118 Known polymer compounds described in JP-A-2003-233179, JP-A-2009-52020, and the like can be used, and the contents thereof are incorporated in the present specification.
These polymers may contain only 1 type and may contain 2 or more types.
(A)重合体の分子量は、ポリスチレン換算重量平均分子量で、好ましくは1,000~200,000、より好ましくは2,000~50,000の範囲である。上記の数値の範囲内であると、諸特性が良好である。数平均分子量と重量平均分子量の比(分散度)は1.0~5.0が好ましく1.5~3.5がより好ましい。 << (A) Molecular Weight of Polymer >>
The molecular weight of the polymer (A) is a weight average molecular weight in terms of polystyrene, and is preferably 1,000 to 200,000, more preferably 2,000 to 50,000. Various characteristics are favorable in the range of said numerical value. The ratio (dispersity) between the number average molecular weight and the weight average molecular weight is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.
また、(A)成分の合成法についても、様々な方法が知られているが、一例を挙げると、少なくとも上記(a1)および上記(a3)で表される構成単位を形成するために用いられるラジカル重合性単量体を含むラジカル重合性単量体混合物を有機溶剤中、ラジカル重合開始剤を用いて重合することにより合成することができる。また、いわゆる高分子反応で合成することもできる。 << (A) Polymer Production Method >>
Various methods for synthesizing the component (A) are also known. For example, the component (A) is used to form at least the structural units represented by the above (a1) and (a3). It can be synthesized by polymerizing a radical polymerizable monomer mixture containing a radical polymerizable monomer in an organic solvent using a radical polymerization initiator. It can also be synthesized by a so-called polymer reaction.
本発明の感光性樹脂組成物は、(B)非イオン性光酸発生剤を含有する。本発明で使用される非イオン性光酸発生剤(「(B)成分」ともいう。)としては、波長300nm以上、好ましくは波長300~450nmの活性光線に感応し、酸を発生する化合物が好ましいが、その化学構造に制限されるものではない。また、波長300nm以上の活性光線に直接感応しない光酸発生剤についても、増感剤と併用することによって波長300nm以上の活性光線に感応し、酸を発生する化合物であれば、増感剤と組み合わせて好ましく用いることができる。本発明で使用される光酸発生剤としては、pKaが4以下の酸を発生する光酸発生剤が好ましく、pKaが3以下の酸を発生する光酸発生剤がより好ましく、2以下の酸を発生する光酸発生剤が最も好ましい。 <(B) Nonionic photoacid generator>
The photosensitive resin composition of the present invention contains (B) a nonionic photoacid generator. The nonionic photoacid generator (also referred to as “component (B)”) used in the present invention is a compound that generates an acid in response to actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm. Although preferred, it is not limited to its chemical structure. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can be used as a sensitizer as long as it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination. The photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and an acid of 2 or less. Most preferred are photoacid generators that generate.
R21のアルキル基としては、炭素数1~10の、直鎖状または分岐状アルキル基が好ましい。R21のアルキル基は、炭素数6~11のアリール基、炭素数1~10のアルコキシ基、または、シクロアルキル基(7,7-ジメチル-2-オキソノルボルニル基などの有橋式脂環基を含む、好ましくはビシクロアルキル基等)で置換されてもよい。
R21のアリール基としては、炭素数6~11のアリール基が好ましく、フェニル基またはナフチル基がより好ましい。R21のアリール基は、低級アルキル基、アルコキシ基あるいはハロゲン原子で置換されてもよい。 Any group may be substituted, and the alkyl group in R 21 may be linear, branched or cyclic. Acceptable substituents are described below.
The alkyl group for R 21 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group represented by R 21 is an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group or the like). It may be substituted with a cyclic group, preferably a bicycloalkyl group or the like.
The aryl group for R 21 is preferably an aryl group having 6 to 11 carbon atoms, more preferably a phenyl group or a naphthyl group. The aryl group of R 21 may be substituted with a lower alkyl group, an alkoxy group, or a halogen atom.
Xとしてのハロゲン原子は、塩素原子またはフッ素原子が好ましい。m4は、0または1が好ましい。上記一般式(B2)中、m4が1であり、Xがメチル基であり、Xの置換位置がオルト位であり、R42が炭素数1~10の直鎖状アルキル基、7,7-ジメチル-2-オキソノルボルニルメチル基、またはp-トルイル基である化合物が特に好ましい。 The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
The halogen atom as X is preferably a chlorine atom or a fluorine atom. m4 is preferably 0 or 1. In the above general formula (B2), m4 is 1, X is a methyl group, the substitution position of X is the ortho position, R 42 is a linear alkyl group having 1 to 10 carbon atoms, 7,7- A compound that is a dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferred.
X1としては、炭素数1~5のアルコキシ基が好ましく、メトキシ基がより好ましい。
n4としては、0~2が好ましく、0~1が特に好ましい。 R 43 in the above general formula (B3) is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group. Perfluoro-n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferable, and n-octyl group is particularly preferable.
X 1 is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
n4 is preferably from 0 to 2, particularly preferably from 0 to 1.
X101は-O-、-S-、-NH-、-NR105-、-CH2-、-CR106H-、または、-CR105R107-を表し、R105~R107はアルキル基、または、アリール基を表す。
R121~R124は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルケニル基、アルコキシ基、アミノ基、アルコキシカルボニル基、アルキルカルボニル基、アリールカルボニル基、アミド基、スルホ基、シアノ基、または、アリール基を表す。R121~R124のうち2つは、それぞれ互いに結合して環を形成してもよい。
R121~R124としては、水素原子、ハロゲン原子、および、アルキル基が好ましく、また、R121~R124のうち少なくとも2つが互いに結合してアリール基を形成する態様もまた、好ましく挙げられる。中でも、R121~R124がいずれも水素原子である態様が感度の観点から好ましい。
既述の官能基は、いずれも、さらに置換基を有していてもよい。 In the general formula (OS-1), R 101 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or Represents a heteroaryl group. R102 represents an alkyl group or an aryl group.
X 101 represents —O—, —S—, —NH—, —NR 105 —, —CH 2 —, —CR 106 H—, or —CR 105 R 107 —, wherein R 105 to R 107 are alkyl groups. Or an aryl group.
R 121 to R 124 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, Or an aryl group is represented. Two of R 121 to R 124 may be bonded to each other to form a ring.
R 121 to R 124 are preferably a hydrogen atom, a halogen atom, and an alkyl group, and an embodiment in which at least two of R 121 to R 124 are bonded to each other to form an aryl group is also preferred. Among these, an embodiment in which R 121 to R 124 are all hydrogen atoms is preferable from the viewpoint of sensitivity.
Any of the aforementioned functional groups may further have a substituent.
これらの中でも、上記一般式(OS-1)および上記一般式(OS-2)におけるR101がシアノ基、または、アリール基である態様がより好ましく、上記一般式(OS-2)で表され、R101がシアノ基、フェニル基またはナフチル基である態様が最も好ましい。 In the general formula (OS-2), R 101 , R 102 and R 121 to R 124 have the same meanings as in the formula (OS-1), and preferred examples thereof are also the same.
Among these, an embodiment in which R 101 in the general formula (OS-1) and the general formula (OS-2) is a cyano group or an aryl group is more preferable, and is represented by the general formula (OS-2). And R 101 is most preferably a cyano group, a phenyl group or a naphthyl group.
上記式(OS-3)~(OS-5)中、R22、R25およびR28におけるアルキル基としては、置換基を有していてもよい総炭素数1~30のアルキル基であることが好ましい。 In the general formulas (OS-3) to (OS-5), the alkyl group, aryl group or heteroaryl group in R 22 , R 25 and R 28 may have a substituent.
In the above formulas (OS-3) to (OS-5), the alkyl group in R 22 , R 25 and R 28 is an alkyl group having 1 to 30 carbon atoms which may have a substituent. Is preferred.
上記一般式(OS-3)~(OS-5)中、化合物中に2以上存在するR23、R26およびR29のうち、1つまたは2つがアルキル基、アリール基またはハロゲン原子であることが好ましく、1つがアルキル基、アリール基またはハロゲン原子であることがより好ましく、1つがアルキル基であり、かつ残りが水素原子であることが特に好ましい。 In the general formulas (OS-3) to (OS-5), R 23 , R 26 and R 29 are preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group. preferable.
In the above general formulas (OS-3) to (OS-5), one or two of R 23 , R 26 and R 29 present in the compound are an alkyl group, an aryl group or a halogen atom. It is more preferable that one is an alkyl group, an aryl group or a halogen atom, and it is particularly preferable that one is an alkyl group and the rest is a hydrogen atom.
上記一般式(OS-3)~(OS-5)において、X1~X3を環員として含む環は、5員環または6員環である。
上記一般式(OS-3)~(OS-5)中、n1~n3はそれぞれ独立に1または2を表し、X1~X3がOである場合、n1~n3はそれぞれ独立に1であることが好ましく、また、X1~X3がSである場合、n1~n3はそれぞれ独立に2であることが好ましい。 In the general formulas (OS-3) to (OS-5), X 1 to X 3 each independently represents O or S, and is preferably O.
In the general formulas (OS-3) to (OS-5), the ring containing X 1 to X 3 as a ring member is a 5-membered ring or a 6-membered ring.
In the general formulas (OS-3) to (OS-5), n 1 to n 3 each independently represents 1 or 2, and when X 1 to X 3 are O, n 1 to n 3 are each independently In addition, when X 1 to X 3 are S, n 1 to n 3 are each preferably 2 independently.
R24、R27およびR30におけるアルキル基、アルキルオキシ基、スルホン酸基、アミノスルホニル基およびアルコキシスルホニル基は、置換基を有していてもよい。
上記一般式(OS-3)~(OS-5)中、R24、R27およびR30におけるアルキル基としては、置換基を有していてもよい総炭素数1~30のアルキル基であることが好ましい。 In the general formulas (OS-3) to (OS-5), R 24 , R 27 and R 30 each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group. To express. Among them, R 24 , R 27 and R 30 are preferably each independently an alkyl group or an alkyloxy group.
The alkyl group, alkyloxy group, sulfonic acid group, aminosulfonyl group and alkoxysulfonyl group in R 24 , R 27 and R 30 may have a substituent.
In the general formulas (OS-3) to (OS-5), the alkyl group in R 24 , R 27 and R 30 is an alkyl group having 1 to 30 carbon atoms which may have a substituent. It is preferable.
また、上記(OS-3)~(OS-5)のそれぞれの置換基について、特開2011-221494号公報の段落番号0092~0109に記載の(OS-3)~(OS-5)の置換基の好ましい範囲も同様に好ましい。 In the general formulas (OS-3) to (OS-5), m 1 to m 3 each independently represents an integer of 0 to 6, preferably an integer of 0 to 2, preferably 0 or 1. More preferably, it is particularly preferably 0.
Further, with respect to each of the substituents of (OS-3) to (OS-5) described above, the substitution of (OS-3) to (OS-5) described in paragraph numbers 0092 to 0109 of JP2011-221494A The preferred range of groups is likewise preferred.
本発明の組成物は、(C)下記一般式(S)で表される化合物を含む。
一般式(S)
The composition of the present invention includes (C) a compound represented by the following general formula (S).
General formula (S)
R1は、1~10つの炭素原子と、酸素原子、少なくとも1つ以上の窒素原子を含むヘテロ原子1~3つから構成される基であることが好ましい。この場合のヘテロ原子としては、酸素原子、硫黄原子が挙げられ、酸素原子が好ましい。R1は環状基であることが好ましく、5員環または6員環の環状基であることがより好ましい。
R3およびR4は、それぞれ、有機基を表す。有機基としては、アルキル基、アルケニル基、または、これらと、-O-、-S-および-N-の少なくとも1つの組み合わせからなる基が好ましい。R3およびR4は、それぞれ、炭素数1~3の基であることが好ましい。R3およびR4は、互いに結合して、環を形成していてもよく、環を形成していることが好ましい。 R 1 represents a group containing at least one nitrogen atom, preferably a group containing 1 to 3 nitrogen atoms, and more preferably a group represented by —NR 3 R 4 .
R 1 is preferably a group composed of 1 to 10 carbon atoms, an oxygen atom, and 1 to 3 heteroatoms including at least one nitrogen atom. In this case, examples of the hetero atom include an oxygen atom and a sulfur atom, and an oxygen atom is preferable. R 1 is preferably a cyclic group, and more preferably a 5-membered or 6-membered cyclic group.
R 3 and R 4 each represents an organic group. The organic group is preferably an alkyl group, an alkenyl group, or a group composed of at least one of —O—, —S— and —N—. R 3 and R 4 are each preferably a group having 1 to 3 carbon atoms. R 3 and R 4 may be bonded to each other to form a ring, and preferably forms a ring.
(1)R1が-NR3R4で表される基であり、R3とR4が互いに結合して環を形成している態様、または、R3とR4が、ぞれぞれ、脂肪族炭化水素基である態様。
(2)R1が-NR3R4で表される基であり、R3とR4が互いに結合して5員環または6員環を形成している態様、または、R3とR4が、ぞれぞれ、炭素数1~4の直鎖または分岐の脂肪族炭化水素基である態様。
(3)R1が-NR3R4で表される基であり、R3とR4が互いに結合して2つ以上のヘテロ原子(少なくとも1つは窒素原子であり、残りは酸素原子または窒素原子が好ましい)を含む、5員環または6員環を形成している態様、または、R3とR4が、ぞれぞれ、炭素数1~4の直鎖の脂肪族炭化水素基である態様。 Preferred embodiments of R 1 include the following embodiments.
(1) An embodiment in which R 1 is a group represented by —NR 3 R 4 and R 3 and R 4 are bonded to each other to form a ring, or R 3 and R 4 are each The aspect which is an aliphatic hydrocarbon group.
(2) Embodiment in which R 1 is a group represented by —NR 3 R 4 and R 3 and R 4 are bonded to each other to form a 5-membered or 6-membered ring, or R 3 and R 4 Are each a linear or branched aliphatic hydrocarbon group having 1 to 4 carbon atoms.
(3) R 1 is a group represented by —NR 3 R 4 , and R 3 and R 4 are bonded to each other to form two or more heteroatoms (at least one is a nitrogen atom and the rest are oxygen atoms or A mode in which a 5-membered ring or a 6-membered ring is formed, or a straight-chain aliphatic hydrocarbon group having 1 to 4 carbon atoms, each of R 3 and R 4 The aspect which is.
R2は、炭素数1~20のアルキル基または炭素数6~12のアリール基、または、これらと-O-および-C(=O)-の少なくとも1つの組み合わせからなる基がさらに好ましい。これらの基は置換基を有していてもよく、置換基としてはハロゲン原子が例示される。
R2がアルキル基である場合、炭素数1~8の直鎖または分岐のアルキル基、または、環状アルキル基が好ましい。R2が環状アルキル基である場合、5員環または6員環の環状アルキル基が好ましい。
R2がアリール基である場合、フェニル基およびナフチル基が例示され、フェニル基がより好ましい。 R 2 represents an organic group. The organic group is preferably a hydrocarbon group or a group comprising a hydrocarbon group and at least one of —O— and —C (═O) —. R 2 preferably has 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms.
R 2 is more preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, or a group consisting of these and at least one combination of —O— and —C (═O) —. These groups may have a substituent, and examples of the substituent include a halogen atom.
When R 2 is an alkyl group, a linear or branched alkyl group having 1 to 8 carbon atoms or a cyclic alkyl group is preferable. When R 2 is a cyclic alkyl group, a 5-membered or 6-membered cyclic alkyl group is preferred.
When R 2 is an aryl group, a phenyl group and a naphthyl group are exemplified, and a phenyl group is more preferable.
(1)炭素数1~4(好ましくは2または3)の直鎖のアルキレン基である態様。 Preferred embodiments of R 2 include the following embodiments.
(1) A mode of being a straight-chain alkylene group having 1 to 4 carbon atoms (preferably 2 or 3).
アルキレン基としては、例えば、メチレン基、エチレン基、プロピレン基、シクロへキシレン基、シクロペンチレン基等が例示される。アリーレン基としては、例えば、1,2-フェニレン基、1,3-フェニレン基、1,4-フェニレン基、ナフチレン基等が例示される。本発明では特に、メチレン基、エチレン基、プロピレン基が好ましく、エチレン基またはプロピレン基がより好ましい。 A represents a divalent linking group, preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrocarbon group having 1 to 10 carbon atoms, and further preferably a hydrocarbon group having 2 to 6 carbon atoms. Examples of the hydrocarbon group include an alkylene group and an arylene group, and an alkylene group is preferable.
Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a cyclohexylene group, and a cyclopentylene group. Examples of the arylene group include a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, and a naphthylene group. In the present invention, a methylene group, an ethylene group, and a propylene group are particularly preferable, and an ethylene group or a propylene group is more preferable.
(1)炭素数1~4の直鎖または分岐のアルキル基、5員環または6員環の環状アルキル基、または、フェニル基である態様。 Preferred embodiments of A include the following embodiments.
(1) An embodiment in which the alkyl group is a linear or branched alkyl group having 1 to 4 carbon atoms, a 5- or 6-membered cyclic alkyl group, or a phenyl group.
R2は、上記式(S)におけるR2と同義であり、好ましい範囲も同義である。
Aは、上記式(S)におけるAと同義であり、好ましい範囲も同義である。
特に、一般式(S1)において、以下の態様が好ましい。
(1)Aは炭素数1~4の直鎖のアルキレン基であり、R2は、直鎖、分岐、または環状
のアルキル基である態様。
(2)Aは炭素数2または3のアルキレン基であり、R2は、炭素数2~6の直鎖、分岐、または環状のアルキル基である態様。 General formula (S1)
R 2 has the same meaning as R 2 in the formula (S), and the preferred range is also the same.
A is synonymous with A in the above formula (S), and a preferred range is also synonymous.
In particular, in the general formula (S1), the following embodiments are preferable.
(1) An embodiment in which A is a linear alkylene group having 1 to 4 carbon atoms, and R 2 is a linear, branched, or cyclic alkyl group.
(2) A mode in which A is an alkylene group having 2 or 3 carbon atoms, and R 2 is a linear, branched or cyclic alkyl group having 2 to 6 carbon atoms.
本発明の感光性樹脂組成物は、(D)溶剤を含有する。本発明の感光性樹脂組成物は、本発明の必須成分と、さらに後述の任意の成分を(D)溶剤に溶解した溶液として調製されることが好ましい。
本発明の感光性樹脂組成物に使用される(D)溶剤としては、公知の溶剤を用いることができ、エチレングリコールモノアルキルエーテル類、エチレングリコールジアルキルエーテル類、エチレングリコールモノアルキルエーテルアセテート類、プロピレングリコールモノアルキルエーテル類、プロピレングリコールジアルキルエーテル類、プロピレングリコールモノアルキルエーテルアセテート類、ジエチレングリコールジアルキルエーテル類、ジエチレングリコールモノアルキルエーテルアセテート類、ジプロピレングリコールモノアルキルエーテル類、ジプロピレングリコールジアルキルエーテル類、ジプロピレングリコールモノアルキルエーテルアセテート類、エステル類、ケトン類、アミド類、ラクトン類等が例示できる。また、本発明の感光性樹脂組成物に使用される(D)溶剤の具体例としては特開2011-221494号公報の段落番号0174~0178に記載の溶剤も挙げられ、これらの内容は本願明細書に組み込まれる。 <(D) Solvent>
The photosensitive resin composition of the present invention contains (D) a solvent. The photosensitive resin composition of the present invention is preferably prepared as a solution in which the essential components of the present invention and optional components described below are dissolved in the solvent (D).
As the solvent (D) used in the photosensitive resin composition of the present invention, known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene. Glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol Examples include monoalkyl ether acetates, esters, ketones, amides, lactones and the like. In addition, specific examples of the (D) solvent used in the photosensitive resin composition of the present invention include the solvents described in paragraph numbers 0174 to 0178 of JP2011-221494A, and the contents thereof are described in the present specification. Embedded in the book.
沸点130℃以上160℃未満の溶剤としては、プロピレングリコールモノメチルエーテルアセテート(沸点146℃)、プロピレングリコールモノエチルエーテルアセテート(沸点158℃)、プロピレングリコールメチル-n-ブチルエーテル(沸点155℃)、プロピレングリコールメチル-n-プロピルエーテル(沸点131℃)が例示できる。
沸点160℃以上の溶剤としては、3-エトキシプロピオン酸エチル(沸点170℃)、ジエチレングリコールメチルエチルエーテル(沸点176℃)、プロピレングリコールモノメチルエーテルプロピオネート(沸点160℃)、ジプロピレングリコールメチルエーテルアセテート(沸点213℃)、3-メトキシブチルエーテルアセテート(沸点171℃)、ジエチレングリコールジエチエルエーテル(沸点189℃)、ジエチレングリコールジメチルエーテル(沸点162℃)、プロピレングリコールジアセテート(沸点190℃)、ジエチレングリコールモノエチルエーテルアセテート(沸点220℃)、ジプロピレングリコールジメチルエーテル(沸点175℃)、1,3-ブチレングリコールジアセテート(沸点232℃)が例示できる。 Component D is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof.
Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), propylene glycol An example is methyl-n-propyl ether (boiling point 131 ° C.).
Solvents having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), dipropylene glycol methyl ether acetate. (Boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (Boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), 1,3-butylene glycol diacetate (boiling point 232 ° C) It can be.
本発明の感光性樹脂組成物は、(E)アルコキシシラン化合物(「(E)成分」ともいう)を含有することを特徴とする。アルコキシシラン化合物を用いると、本発明の感光性樹脂組成物により形成された膜と基板との密着性を向上できたり、本発明の感光性樹脂組成物により形成された膜の性質を調整することができる。アルコキシシラン化合物としては、ジアルコキシシラン化合物またはトリアルコキシシラン化合物が好ましく、トリアルコキシシラン化合物がより好ましい。アルコキシシラン化合物が有するアルコキシ基の炭素数は1~5が好ましい。
本発明の感光性樹脂組成物に用いることができる(E)アルコキシシラン化合物は、基材となる無機物、例えば、シリコン、酸化シリコン、窒化シリコン等のシリコン化合物、金、銅、モリブデン、チタン、アルミニウム等の金属と絶縁膜との密着性を向上させる化合物であることが好ましい。具体的には、公知のシランカップリング剤等も有効である。
シランカップリング剤としては、例えば、γ-アミノプロピルトリメトキシシラン、γ-アミノプロピルトリエトキシシラン、γ-グリシドキシプロピルトリアルコキシシラン、γ-グリシドキシプロピルアルキルジアルコキシシラン、γ-メタクリロキシプロピルトリアルコキシシラン、γ-メタクリロキシプロピルアルキルジアルコキシシラン、γ-クロロプロピルトリアルコキシシラン、γ-メルカプトプロピルトリアルコキシシラン、β-(3,4-エポキシシクロヘキシル)エチルトリアルコキシシラン、ビニルトリアルコキシシランが挙げられる。これらのうち、γ-グリシドキシプロピルトリアルコキシシランやγ-メタクリロキシプロピルトリアルコキシシランがより好ましく、γ-グリシドキシプロピルトリアルコキシシランがさらに好ましく、3-グリシドキシプロピルトリメトキシシランがよりさらに好ましい。これらは1種単独または2種以上を組み合わせて使用することができる。 (E) Alkoxysilane Compound The photosensitive resin composition of the present invention is characterized by containing (E) an alkoxysilane compound (also referred to as “(E) component”). When an alkoxysilane compound is used, the adhesion between the film formed from the photosensitive resin composition of the present invention and the substrate can be improved, or the properties of the film formed from the photosensitive resin composition of the present invention can be adjusted. Can do. As the alkoxysilane compound, a dialkoxysilane compound or a trialkoxysilane compound is preferable, and a trialkoxysilane compound is more preferable. The alkoxy group contained in the alkoxysilane compound preferably has 1 to 5 carbon atoms.
The (E) alkoxysilane compound that can be used in the photosensitive resin composition of the present invention is an inorganic material serving as a substrate, for example, silicon compounds such as silicon, silicon oxide, and silicon nitride, gold, copper, molybdenum, titanium, and aluminum. It is preferable that the compound improves the adhesion between the metal and the insulating film. Specifically, a known silane coupling agent or the like is also effective.
Examples of silane coupling agents include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropylalkyldialkoxysilane, and γ-methacryloxy. Propyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane Is mentioned. Of these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, γ-glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is more preferable. Further preferred. These can be used alone or in combination of two or more.
本発明の感光性樹脂組成物における(E)アルコキシシラン化合物の含有量は、感光性組成物中の全固形分100質量部に対して、0.1~30質量部が好ましく、0.5~20質量部がより好ましい。 The (E) alkoxysilane compound in the photosensitive resin composition of the present invention is not particularly limited, and a known one can be used.
The content of the (E) alkoxysilane compound in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by mass is more preferable.
本発明の感光性樹脂組成物には、上記成分に加えて、必要に応じて、(F)架橋剤、(G)増感剤、(H)塩基性化合物、(I)界面活性剤、(J)酸化防止剤を好ましく加えることができる。さらに本発明の感光性樹脂組成物には、酸増殖剤、現像促進剤、可塑剤、熱ラジカル発生剤、熱酸発生剤、紫外線吸収剤、増粘剤、および、有機または無機の沈殿防止剤などの公知の添加剤を加えることができる。 <Other ingredients>
In the photosensitive resin composition of the present invention, in addition to the above components, (F) a crosslinking agent, (G) a sensitizer, (H) a basic compound, (I) a surfactant, J) An antioxidant can be preferably added. Further, the photosensitive resin composition of the present invention includes an acid proliferation agent, a development accelerator, a plasticizer, a thermal radical generator, a thermal acid generator, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor. Known additives such as can be added.
本発明の感光性樹脂組成物は、必要に応じ、架橋剤を含有することが好ましい。架橋剤を添加することにより、本発明の感光性樹脂組成物により得られる硬化膜をより強固な膜とすることができる。
架橋剤としては、熱によって架橋反応が起こるものであれば制限は無い。(A成分を除く)。例えば、以下に述べる分子内に2個以上のエポキシ基またはオキセタニル基を有する化合物、アルコキシメチル基含有架橋剤、または、少なくとも1個のエチレン性不飽和二重結合を有する化合物、ブロックイソシアネート化合物等を添加することができる。
本発明の感光性樹脂組成物中における架橋剤の添加量は、感光性樹脂組成物の全固形分100質量部に対し、0.01~50質量部であることが好ましく、0.1~30質量部であることがより好ましく、0.5~20質量部であることがさらに好ましい。この範囲で添加することにより、機械的強度および耐溶剤性に優れた硬化膜が得られる。架橋剤は複数を併用することもでき、その場合は架橋剤を全て合算して含有量を計算する。 (F) Crosslinking agent It is preferable that the photosensitive resin composition of this invention contains a crosslinking agent as needed. By adding a crosslinking agent, the cured film obtained by the photosensitive resin composition of the present invention can be made a stronger film.
The crosslinking agent is not limited as long as a crosslinking reaction is caused by heat. (Excluding component A). For example, a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, an alkoxymethyl group-containing crosslinking agent, a compound having at least one ethylenically unsaturated double bond, a blocked isocyanate compound, etc. Can be added.
The addition amount of the crosslinking agent in the photosensitive resin composition of the present invention is preferably 0.01 to 50 parts by mass, and 0.1 to 30 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition. The amount is more preferably part by mass, and further preferably 0.5 to 20 parts by mass. By adding in this range, a cured film having excellent mechanical strength and solvent resistance can be obtained. A plurality of crosslinking agents may be used in combination. In that case, the content is calculated by adding all the crosslinking agents.
分子内に2個以上のエポキシ基を有する化合物の具体例としては、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、脂肪族エポキシ樹脂等を挙げることができる。 <Compound having two or more epoxy groups or oxetanyl groups in the molecule>
Specific examples of compounds having two or more epoxy groups in the molecule include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, aliphatic epoxy resins, and the like. Can do.
その他にも、ADEKA RESIN EP-4000S、同EP-4003S、同EP-4010S、同EP-4011S(以上、(株)ADEKA製)、NC-2000、NC-3000、NC-7300、XD-1000、EPPN-501、EPPN-502(以上、(株)ADEKA製)、デナコールEX-611、EX-612、EX-614、EX-614B、EX-622、EX-512、EX-521、EX-411、EX-421、EX-313、EX-314、EX-321、EX-211、EX-212、EX-810、EX-811、EX-850、EX-851、EX-821、EX-830、EX-832、EX-841、EX-911、EX-941、EX-920、EX-931、EX-212L、EX-214L、EX-216L、EX-321L、EX-850L、DLC-201、DLC-203、DLC-204、DLC-205、DLC-206、DLC-301、DLC-402(以上ナガセケムテック製)、YH-300、YH-301、YH-302、YH-315、YH-324、YH-325(以上新日鐵化学製)セロキサイド2021P、2081、3000、EHPE3150、エポリードGT400、セルビナースB0134、B0177((株)ダイセル)、EPICLON EXA-4850-150(DIC(株)製)、EPICLON EXA-4850-1000(DIC(株)製)、などが挙げられる。
これらは1種単独または2種以上を組み合わせて使用することができる。 These are available as commercial products. Examples thereof include commercially available products described in paragraph No. 0189 of JP2011-212494, such as JER157S70 and JER157S65 (manufactured by Mitsubishi Chemical Holdings Corporation).
In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX- 832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212L, EX- 14L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402 (manufactured by Nagase Chemtech), YH -300, YH-301, YH-302, YH-315, YH-324, YH-325 (manufactured by Nippon Steel Chemical Co., Ltd.) Celoxide 2021P, 2081, 3000, EHPE3150, Epolide GT400, Serbiners B0134, B0177 Daicel), EPICLON EXA-4850-150 (manufactured by DIC Corporation), EPICLON EXA-4850-1000 (manufactured by DIC Corporation), and the like.
These can be used alone or in combination of two or more.
本発明の感光性樹脂組成物では、架橋剤として、ブロックイソシアネート系化合物も好ましく採用できる。ブロックイソシアネート化合物は、ブロックイソシアネート基を有する化合物であれば特に制限はないが、硬化性の観点から、1分子内に2以上のブロックイソシアネート基を有する化合物であることが好ましい。
なお、本発明におけるブロックイソシアネート基とは、熱によりイソシアネート基を生成することが可能な基であり、例えば、ブロック剤とイソシアネート基とを反応させイソシアネート基を保護した基が好ましく例示できる。また、前記ブロックイソシアネート基は、90℃~250℃の熱によりイソシアネート基を生成することが可能な基であることが好ましい。
また、ブロックイソシアネート化合物としては、その骨格は特に限定されるものではなく、1分子中にイソシアネート基を2個有するものであればどのようなものでもよく、脂肪族、脂環族または芳香族のポリイソシアネートであってよいが、例えば2,4-トリレンジイソシアネート、2,6-トリレンジイソシアネート、イソホロンジイソシアネート、1,6-ヘキサメチレンジイソシアネート、1,3-トリメチレンジイソシアネート、1,4-テトラメチレンジイソシアネート、2,2,4-トリメチルヘキサメチレンジイソシアネート、2,4,4-トリメチルヘキサメチレンジイソシアネート、1,9-ノナメチレンジイソシアネート、1,10-デカメチレンジイソシアネート、1,4-シクロヘキサンジイソシアネート、2,2’-ジエチルエーテルジイソシアネート、ジフェニルメタン-4,4’-ジイソシアネート、o-キシレンジイソシアネート、m-キシレンジイソシアネート、p-キシレンジイソシアネート、メチレンビス(シクロヘキシルイソシアネート)、シクロヘキサン-1,3-ジメチレンジイソシアネート、シクロヘキサン-1,4-ジメチレレンジイソシアネート、1,5-ナフタレンジイソシアネート、p-フェニレンジイソシアネート、3,3’-メチレンジトリレン-4,4’-ジイソシアネート、4,4’-ジフェニルエーテルジイソシアネート、テトラクロロフェニレンジイソシアネート、ノルボルナンジイソシアネート、水素化1,3-キシリレンジイソシアネート、水素化1,4-キシリレンジイソシアネート等のイソシアネート化合物およびこれらの化合物から派生するプレポリマー型の骨格の化合物を好適に用いることができる。これらの中でも、トリレンジイソシアネート(TDI)やジフェニルメタンジイソシアネート(MDI)、ヘキサメチレンジイソシアネート(HDI)、イソホロンジイソシアネート(IPDI)が特に好ましい。 <Block isocyanate compound>
In the photosensitive resin composition of the present invention, a blocked isocyanate compound can also be preferably employed as a crosslinking agent. The blocked isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanate group, but is preferably a compound having two or more blocked isocyanate groups in one molecule from the viewpoint of curability.
In addition, the blocked isocyanate group in this invention is a group which can produce | generate an isocyanate group with a heat | fever, For example, the group which reacted the blocking agent and the isocyanate group and protected the isocyanate group can illustrate preferably. The blocked isocyanate group is preferably a group capable of generating an isocyanate group by heat at 90 ° C. to 250 ° C.
Further, the skeleton of the blocked isocyanate compound is not particularly limited and may be any as long as it has two isocyanate groups in one molecule, and is aliphatic, alicyclic or aromatic. Polyisocyanates may be used, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene Diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2 2′-diethyl ether diisocyanate, diphenylmethane-4,4′-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1 , 4-Dimethylylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3'-methyleneditolylene-4,4'-diisocyanate, 4,4'-diphenyl ether diisocyanate, tetrachlorophenylene diisocyanate, norbornane diisocyanate , Isocyanation of hydrogenated 1,3-xylylene diisocyanate, hydrogenated 1,4-xylylene diisocyanate, etc. A compound and a prepolymer type skeleton compound derived from these compounds can be preferably used. Among these, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are particularly preferable.
前記ブロックイソシアネート化合物のブロック構造を形成するブロック剤としては、オキシム化合物、ラクタム化合物、フェノール化合物、アルコール化合物、アミン化合物、活性メチレン化合物、ピラゾール化合物、メルカプタン化合物、イミダゾール系化合物、イミド系化合物等を挙げることができる。これらの中でも、オキシム化合物、ラクタム化合物、フェノール化合物、アルコール化合物、アミン化合物、活性メチレン化合物、ピラゾール化合物から選ばれるブロック剤が特に好ましい。 Examples of the matrix structure of the blocked isocyanate compound in the photosensitive resin composition of the present invention include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.
Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. be able to. Among these, a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferable.
前記ラクタム化合物としてはε-カプロラクタム、γ-ブチロラクタム等が例示できる。
前記フェノール化合物としては、フェノール、ナフトール、クレゾール、キシレノール、ハロゲン置換フェノール等が例示できる。
前記アルコール化合物としては、メタノール、エタノール、プロパノール、ブタノール、シクロヘキサノール、エチレングリコールモノアルキルエーテル、プロピレングリコールモノアルキルエーテル、乳酸アルキル等が例示できる。
前記アミン化合物としては、1級アミンおよび2級アミンが上げられ、芳香族アミン、脂肪族アミン、脂環族アミンいずれでもよく、アニリン、ジフェニルアミン、エチレンイミン、ポリエチレンイミン等が例示できる。
前記活性メチレン化合物としては、マロン酸ジエチル、マロン酸ジメチル、アセト酢酸エチル、アセト酢酸メチル等が例示できる。
前記ピラゾール化合物としては、ピラゾール、メチルピラゾール、ジメチルピラゾール等が例示できる、
前記メルカプタン化合物としては、アルキルメルカプタン、アリールメルカプタン等が例示できる。 Examples of the oxime compound include oxime and ketoxime, and specific examples include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, benzophenone oxime, and acetoxime.
Examples of the lactam compound include ε-caprolactam and γ-butyrolactam.
Examples of the phenol compound include phenol, naphthol, cresol, xylenol, and halogen-substituted phenol.
Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.
Examples of the amine compound include primary amines and secondary amines, which may be aromatic amines, aliphatic amines, and alicyclic amines, and examples thereof include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.
Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate and the like.
Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole and the like.
Examples of the mercaptan compound include alkyl mercaptans and aryl mercaptans.
本発明の感光性樹脂組成物は、(B)光酸発生剤との組み合わせにおいて、その分解を促進させるために、増感剤を含有することが好ましい。増感剤は、活性光線または放射線を吸収して電子励起状態となる。電子励起状態となった増感剤は、光酸発生剤と接触して、電子移動、エネルギー移動、発熱などの作用が生じる。これにより光酸発生剤は化学変化を起こして分解し、酸を生成する。好ましい増感剤の例としては、以下の化合物類に属しており、かつ350nmから450nmの波長域のいずれかに吸収波長を有する化合物を挙げることができる。 (G) Sensitizer The photosensitive resin composition of the present invention preferably contains a sensitizer in order to promote its decomposition in combination with (B) a photoacid generator. The sensitizer absorbs actinic rays or radiation and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a photo-acid generator raise | generates a chemical change and decomposes | disassembles and produces | generates an acid. Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength ranges from 350 nm to 450 nm.
これら増感剤の中でも、多核芳香族類、アクリドン類、スチリル類、ベーススチリル類、クマリン類が好ましく、多核芳香族類がより好ましい。多核芳香族類の中でもアントラセン誘導体が最も好ましい。 Polynuclear aromatics (eg, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene), xanthenes (Eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), xanthones (eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines ( For example, merocyanine, carbomerocyanine), rhodocyanines, oxonols, thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine oleoresin) Di, chloroflavin, acriflavine), acridones (eg, acridone, 10-butyl-2-chloroacridone), anthraquinones (eg, anthraquinone), squaliums (eg, squalium), styryls, base styryls ( For example, 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole), coumarins (for example, 7-diethylamino 4-methylcoumarin, 7-hydroxy 4-methylcoumarin, 2,3,6,7 -Tetrahydro-9-methyl-1H, 5H, 11H [1] benzopyrano [6,7,8-ij] quinolizine-11-non).
Among these sensitizers, polynuclear aromatics, acridones, styryls, base styryls, and coumarins are preferable, and polynuclear aromatics are more preferable. Of the polynuclear aromatics, anthracene derivatives are most preferred.
2種以上を併用することもできる。 The addition amount of the sensitizer in the photosensitive resin composition of the present invention is preferably 0 to 1000 parts by mass with respect to 100 parts by mass of the photoacid generator of the photosensitive resin composition. More preferably, the amount is 50 to 200 parts by mass.
Two or more kinds can be used in combination.
本発明の感光性樹脂組成物は、上記一般式(S)で表される化合物に加えて、さらに、(H)塩基性化合物を含有してもよい。(H)塩基性化合物としては、化学増幅レジストで用いられるものの中から任意に選択して使用することができる。例えば、脂肪族アミン、芳香族アミン、複素環式アミン、第四級アンモニウムヒドロキシド、カルボン酸の第四級アンモニウム塩等が挙げられる。これらの具体例としては、特開2011-221494号公報の段落番号0204~0207に記載の化合物が挙げられ、これらの内容は本願明細書に組み込まれる。 (H) Other Basic Compound In addition to the compound represented by the general formula (S), the photosensitive resin composition of the present invention may further contain (H) a basic compound. (H) The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples thereof include compounds described in JP-A 2011-212494, paragraphs 0204 to 0207, the contents of which are incorporated herein.
本発明の感光性樹脂組成物は、(I)界面活性剤を含有してもよい。(I)界面活性剤としては、アニオン系、カチオン系、ノニオン系、または、両性のいずれでも使用することができるが、好ましい界面活性剤はノニオン界面活性剤である。
ノニオン系界面活性剤の例としては、ポリオキシエチレン高級アルキルエーテル類、ポリオキシエチレン高級アルキルフェニルエーテル類、ポリオキシエチレングリコールの高級脂肪酸ジエステル類、シリコーン系、フッ素系界面活性剤を挙げることができる。また、以下商品名で、KP(信越化学工業(株)製)、ポリフロー(共栄社化学(株)製)、エフトップ(JEMCO社製)、メガファック(DIC(株)製)、フロラード(住友スリーエム(株)製)、アサヒガード、サーフロン(旭硝子(株)製)、PolyFox(OMNOVA社製)、SH-8400(東レ・ダウコーニングシリコーン)等の各シリーズを挙げることができる。
また、界面活性剤として、下記一般式(I-1)で表される構成単位Aおよび構成単位Bを含み、テトラヒドロフラン(THF)を溶剤とした場合のゲルパーミエーションクロマトグラフィーで測定されるポリスチレン換算の重量平均分子量(Mw)が1,000以上10,000以下である共重合体を好ましい例として挙げることができる。 (I) Surfactant The photosensitive resin composition of the present invention may contain (I) a surfactant. (I) As the surfactant, any of anionic, cationic, nonionic or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. . The following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by JEMCO), MegaFuck (manufactured by DIC Corporation), and Florard (Sumitomo 3M). Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), SH-8400 (Toray Dow Corning Silicone), and the like.
In addition, the surfactant contains the structural unit A and the structural unit B represented by the following general formula (I-1), and is converted to polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent. A copolymer having a weight average molecular weight (Mw) of 1,000 or more and 10,000 or less can be given as a preferred example.
本発明の感光性樹脂組成物における(I)界面活性剤の添加量は、感光性樹脂組成物中の全固形分100質量部に対して、10質量部以下であることが好ましく、0.001~10質量部であることがより好ましく、0.01~3質量部であることがさらに好ましい。 These surfactants can be used individually by 1 type or in mixture of 2 or more types.
The addition amount of (I) surfactant in the photosensitive resin composition of the present invention is preferably 10 parts by mass or less with respect to 100 parts by mass of the total solid content in the photosensitive resin composition, 0.001 More preferably, it is ˜10 parts by mass, and further preferably 0.01-3 parts by mass.
本発明の感光性樹脂組成物は、酸化防止剤を含有してもよい。酸化防止剤としては、公知の酸化防止剤を含有することができる。酸化防止剤を添加することにより、硬化膜の着色を防止できる、または、分解による膜厚減少を低減でき、また、耐熱透明性に優れるという利点がある。
このような酸化防止剤としては、例えば、リン系酸化防止剤、アミド類、ヒドラジド類、ヒンダードアミン系酸化防止剤、イオウ系酸化防止剤、フェノール系酸化防止剤、アスコルビン酸類、硫酸亜鉛、糖類、亜硝酸塩、亜硫酸塩、チオ硫酸塩、ヒドロキシルアミン誘導体などを挙げることができる。これらの中では、硬化膜の着色、膜厚減少の観点から特にフェノール系酸化防止剤、アミド系酸化防止剤、ヒドラジド系酸化防止剤、イオウ系酸化防止剤が好ましい。これらは1種単独で用いてもよいし、2種以上を混合してもよい。
フェノール系酸化防止剤の市販品としては、例えば、アデカスタブAO-15、アデカスタブAO-18、アデカスタブAO-20、アデカスタブAO-23、アデカスタブAO-30、アデカスタブAO-37、アデカスタブAO-40、アデカスタブAO-50、アデカスタブAO-51、アデカスタブAO-60、アデカスタブAO-70、アデカスタブAO-80、アデカスタブAO-330、アデカスタブAO-412S、アデカスタブAO-503、アデカスタブA-611、アデカスタブA-612、アデカスタブA-613、アデカスタブPEP-4C、アデカスタブPEP-8、アデカスタブPEP-8W、アデカスタブPEP-24G、アデカスタブPEP-36、アデカスタブPEP-36Z、アデカスタブHP-10、アデカスタブ2112、アデカスタブ260、アデカスタブ522A、アデカスタブ1178、アデカスタブ1500、アデカスタブC、アデカスタブ135A、アデカスタブ3010、アデカスタブTPP、アデカスタブCDA-1、アデカスタブCDA-6、アデカスタブZS-27、アデカスタブZS-90、アデカスタブZS-91(以上、(株)ADEKA製)、イルガノックス245FF、イルガノックス1010FF、イルガノックス1010、イルガノックスMD1024、イルガノックス1035FF、イルガノックス1035、イルガノックス1098、イルガノックス1330、イルガノックス1520L、イルガノックス3114、イルガノックス1726、イルガフォス168、イルガモッド295(BASF(株)製)などが挙げられる。中でも、アデカスタブAO-60、アデカスタブAO-80、イルガノックス1726、イルガノックス1035、イルガノックス1098を好適に使用することができる。 (J) Antioxidant The photosensitive resin composition of the present invention may contain an antioxidant. As an antioxidant, a well-known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat-resistant transparency is excellent.
Examples of such antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, Examples thereof include nitrates, sulfites, thiosulfates, and hydroxylamine derivatives. Among these, phenol-based antioxidants, amide-based antioxidants, hydrazide-based antioxidants, and sulfur-based antioxidants are particularly preferable from the viewpoint of coloring the cured film and reducing the film thickness. These may be used individually by 1 type and may mix 2 or more types.
Examples of commercially available phenolic antioxidants include ADK STAB AO-15, ADK STAB AO-18, ADK STAB AO-20, ADK STAB AO-23, ADK STAB AO-30, ADK STAB AO-37, ADK STAB AO-40, and ADK STAB AO. -50, ADK STAB AO-51, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-330, ADK STAB AO-412S, ADK STAB AO-503, ADK STAB A-611, ADK STAB A-612, ADK STAB A -613, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-8W, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB PEP-36Z, ADK STAB HP-1 ADK STAB 2112, ADK STAB 260, ADK STAB 1522, ADK STAB 1178, ADK STAB 1500, ADK STAB C, ADK STAB 13510, ADK STAB 3010, ADK STAB CDA-1, ADK STAB CDA-6, ADK STAB ZS-27, ADK STAB ZS-90 -91 (above, manufactured by ADEKA Corporation), Irganox 245FF, Irganox 1010FF, Irganox 1010, Irganox MD1024, Irganox 1035FF, Irganox 1035, Irganox 1098, Irganox 1330, Irganox 1520L, Irganox 3114, Irganox 1726, Irgafos 168, Irgamod 295 (BAS Co., Ltd.), and the like. Among them, ADK STAB AO-60, ADK STAB AO-80, IRGANOX 1726, IRGANOX 1035, and IRGANOX 1098 can be preferably used.
また、酸化防止剤以外の添加剤として、“高分子添加剤の新展開((株)日刊工業新聞社)”に記載の各種紫外線吸収剤や、金属不活性化剤等を本発明の感光性樹脂組成物に添加してもよい。 The content of the antioxidant is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, based on the total solid content of the photosensitive resin composition. It is particularly preferably 5 to 4% by mass. By setting it in this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation can be improved.
As additives other than antioxidants, various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators, and the like are used in the present invention. You may add to a resin composition.
本発明の感光性樹脂組成物は、感度向上を目的に、酸増殖剤を用いることができる。
本発明に用いることができる酸増殖剤は、酸触媒反応によってさらに酸を発生して反応系内の酸濃度を上昇させることができる化合物であり、酸が存在しない状態では安定に存在する化合物である。このような化合物は、1回の反応で1つ以上の酸が増えるため、反応の進行に伴って加速的に反応が進むが、発生した酸自体が自己分解を誘起するため、ここで発生する酸の強度は、酸解離定数、pKaとして3以下であるのが好ましく、特に2以下であるのが好ましい。
酸増殖剤の具体例としては、特開平10-1508号公報の段落番号0203~0223、特開平10-282642号公報の段落番号0016~0055、および、特表平9-512498号公報第39頁12行目~第47頁2行目に記載の化合物を挙げることができ、これらの内容は本願明細書に組み込まれる。
本発明で用いることができる酸増殖剤としては、酸発生剤から発生した酸によって分解し、ジクロロ酢酸、トリクロロ酢酸、メタンスルホン酸、ベンゼンスルホン酸、トリフルオロメタンスルホン酸、フェニルホスホン酸などのpKaが3以下の酸を発生させる化合物を挙げることができる。
具体的には
酸増殖剤の感光性組成物への含有量は、光酸発生剤100質量部に対して、10~1,000質量部とするのが、露光部と未露光部との溶解コントラストの観点から好ましく、20~500質量部とするのがさらに好ましい。 [Acid multiplication agent]
In the photosensitive resin composition of the present invention, an acid proliferating agent can be used for the purpose of improving sensitivity.
The acid proliferating agent that can be used in the present invention is a compound that can further generate an acid by an acid-catalyzed reaction to increase the acid concentration in the reaction system, and is a compound that exists stably in the absence of an acid. is there. In such a compound, since one or more acids increase in one reaction, the reaction proceeds at an accelerated rate as the reaction proceeds. However, the generated acid itself induces self-decomposition, and is generated here. The acid strength is preferably 3 or less as an acid dissociation constant, pKa, and particularly preferably 2 or less.
Specific examples of the acid proliferating agent include paragraph numbers 0203 to 0223 of JP-A-10-1508, paragraphs 0016 to 0055 of JP-A-10-282642, and page 39 of JP-T 9-512498. The compounds described on
Examples of the acid proliferating agent that can be used in the present invention include pKa such as dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, and phenylphosphonic acid, which are decomposed by an acid generated from the acid generator. Examples include compounds that generate 3 or less acids.
In particular
The content of the acid proliferating agent in the photosensitive composition is 10 to 1,000 parts by mass with respect to 100 parts by mass of the photoacid generator, from the viewpoint of dissolution contrast between the exposed and unexposed parts. It is preferably 20 to 500 parts by mass.
本発明の感光性樹脂組成物は、現像促進剤を含有することができる。
現像促進剤としては、特開2012-042837号公報の段落番号0171~0172の記載を参酌でき、かかる内容は本願明細書に組み込まれる。 [Development accelerator]
The photosensitive resin composition of the present invention can contain a development accelerator.
As the development accelerator, the description in paragraphs 0171 to 0172 of JP2012-042837A can be referred to, and the contents thereof are incorporated in the present specification.
本発明の感光性樹脂組成物における現像促進剤の添加量は、感度と残膜率の観点から、感光性組成物の全固形分100質量部に対し、0~30質量部が好ましく、0.1~20質量部がより好ましく、0.5~10質量部であることが最も好ましい。
また、その他の添加剤としては特開2012-8223号公報の段落番号0120~0121に記載の熱ラジカル発生剤、WO2011/136074A1に記載の窒素含有化合物および熱酸発生剤も用いることができ、これらの内容は本願明細書に組み込まれる。 A development accelerator may be used individually by 1 type, and can also use 2 or more types together.
The addition amount of the development accelerator in the photosensitive resin composition of the present invention is preferably 0 to 30 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive composition, from the viewpoint of sensitivity and residual film ratio. 1 to 20 parts by mass is more preferable, and 0.5 to 10 parts by mass is most preferable.
In addition, as other additives, thermal radical generators described in paragraphs 0120 to 0121 of JP2012-8223A, nitrogen-containing compounds and thermal acid generators described in WO2011-133604A1, can be used. Is incorporated herein by reference.
各成分を所定の割合でかつ任意の方法で混合し、撹拌溶解して感光性樹脂組成物を調製する。例えば、成分を、それぞれ予め溶剤に溶解させた溶液とした後、これらを所定の割合で混合して樹脂組成物を調製することもできる。以上のように調製した組成物溶液は、孔径0.2μmのフィルター等を用いてろ過した後に、使用に供することもできる。 <Method for preparing photosensitive resin composition>
Each component is mixed at a predetermined ratio and by any method, and dissolved by stirring to prepare a photosensitive resin composition. For example, a resin composition can be prepared by preparing a solution in which components are dissolved in a solvent in advance and then mixing them in a predetermined ratio. The composition solution prepared as described above can be used after being filtered using a filter having a pore size of 0.2 μm or the like.
次に、本発明の硬化膜の製造方法を説明する。
本発明の硬化膜の製造方法は、以下の(1)~(5)の工程を含むことが好ましい。
(1)本発明の感光性樹脂組成物を基板上に塗布する工程;
(2)塗布された感光性樹脂組成物から溶剤を除去する工程;
(3)溶剤が除去された感光性樹脂組成物を活性光線により露光する工程;
(4)露光された感光性樹脂組成物を水性現像液により現像する工程;
(5)現像された感光性樹脂組成物を熱硬化するポストベーク工程。
以下に各工程を順に説明する。 [Method for producing cured film]
Next, the manufacturing method of the cured film of this invention is demonstrated.
The method for producing a cured film of the present invention preferably includes the following steps (1) to (5).
(1) The process of apply | coating the photosensitive resin composition of this invention on a board | substrate;
(2) A step of removing the solvent from the applied photosensitive resin composition;
(3) A step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays;
(4) A step of developing the exposed photosensitive resin composition with an aqueous developer;
(5) A post-baking step of thermosetting the developed photosensitive resin composition.
Each step will be described below in order.
上記の基板としては、無機基板、樹脂、樹脂複合材料などが挙げられる。
無機基板としては、例えばガラス、石英、シリコーン、シリコンナイトライド、および、それらのような基板上にモリブデン、チタン、アルミ、銅などを蒸着した複合基板が挙げられる。
樹脂としては、ポリブチレンテレフタレート、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート、ポリスチレン、ポリカーボネート、ポリスルホン、ポリエーテルスルホン、ポリアリレート、アリルジグリコールカーボネート、ポリアミド、ポリイミド、ポリアミドイミド、ポリエーテルイミド、ポリベンズアゾール、ポリフェニレンサルファイド、ポリシクロオレフィン、ノルボルネン樹脂、ポリクロロトリフルオロエチレン等のフッ素樹脂、液晶ポリマー、アクリル樹脂、エポキシ樹脂、シリコーン樹脂、アイオノマー樹脂、シアネート樹脂、架橋フマル酸ジエステル、環状ポリオレフィン、芳香族エーテル、マレイミドーオレフィン、セルロース、エピスルフィド化合物等の合成樹脂からなる基板が挙げられる
これらの基板は、上記の形態のまま用いられる場合は少なく、通常、最終製品の形態によって、例えばTFT素子のような多層積層構造が形成されている。
基板への塗布方法は特に限定されず、例えば、スリットコート法、スプレー法、ロールコート法、回転塗布法、流延塗布法、スリットアンドスピン法等の方法を用いることができる。さらに、特開2009-145395号公報に記載されているような、所謂プリウェット法を適用することも可能である。
適用したときのウエット膜厚は特に限定されるものではなく、用途に応じた膜厚で塗布することができるが、通常は0.5~10μmの範囲で使用される。 In the application step (1), the photosensitive resin composition of the present invention is preferably applied onto a substrate to form a wet film containing a solvent. Before applying the photosensitive resin resin composition to the substrate, it is preferable to perform substrate cleaning such as alkali cleaning or plasma cleaning, and it is more preferable to treat the substrate surface with hexamethyldisilazane after substrate cleaning. By performing this treatment, the adhesiveness of the photosensitive resin composition to the substrate tends to be improved. The method for treating the substrate surface with hexamethyldisilazane is not particularly limited, and examples thereof include a method in which the substrate is exposed to hexamethyldisilazane vapor.
Examples of the substrate include inorganic substrates, resins, and resin composite materials.
Examples of the inorganic substrate include glass, quartz, silicone, silicon nitride, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such a substrate.
Resins include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, poly Fluorine resins such as benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, aromatic Made of synthetic resin such as aromatic ether, maleimide-olefin, cellulose, episulfide compound These substrates which may be mentioned are less if used while the above embodiment, normally, depending on the form of the final product, for example, multi-layered structure such as a TFT element is formed.
The coating method on the substrate is not particularly limited, and for example, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method, or the like can be used. Furthermore, it is also possible to apply a so-called pre-wet method as described in JP-A-2009-145395.
The wet film thickness when applied is not particularly limited, and can be applied with a film thickness according to the application, but it is usually used in the range of 0.5 to 10 μm.
活性光線による露光光源としては、低圧水銀灯、高圧水銀灯、超高圧水銀灯、ケミカルランプ、LED光源、エキシマレーザー発生装置などを用いることができ、g線(436nm)、i線(365nm)、h線(405nm)などの波長300nm以上450nm以下の波長を有する活性光線が好ましく使用できる。また、必要に応じて長波長カットフィルター、短波長カットフィルター、バンドパスフィルターのような分光フィルターを通して照射光を調整することもできる。
露光装置としては、ミラープロジェクションアライナー、ステッパー、スキャナー、プロキシミティ、コンタクト、マイクロレンズアレイ、レーザー露光、など各種方式の露光機を用いることができる。
酸触媒の生成した領域において、上記の加水分解反応を加速させるために、露光後加熱処理:Post Exposure Bake(以下、「PEB」ともいう。)を行うことができる。PEBにより、酸分解性基からのカルボキシル基またはフェノール性水酸基の生成を促進させることができる。PEBを行う場合の温度は、30℃以上130℃以下であることが好ましく、40℃以上110℃以下がより好ましく、50℃以上100℃以下が特に好ましい。
ただし、本発明における酸分解性基は、酸分解の活性化エネルギーが低く、露光による酸発生剤由来の酸により容易に分解し、カルボキシル基またはフェノール性水酸基を生じるため、必ずしもPEBを行うことなく、現像によりポジ画像を形成することもできる。 In the exposure step (3), the substrate provided with the coating film is irradiated with actinic rays through a mask having a predetermined pattern. In this step, the photoacid generator is decomposed to generate an acid. Due to the catalytic action of the generated acid, the acid-decomposable group contained in the coating film component is hydrolyzed to generate a carboxyl group or a phenolic hydroxyl group.
As an exposure light source using actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, or the like can be used, and g-line (436 nm), i-line (365 nm), h-line ( Actinic rays having a wavelength of 300 nm to 450 nm, such as 405 nm), can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, and a laser exposure can be used.
In order to accelerate the hydrolysis reaction in the region where the acid catalyst is generated, post-exposure heat treatment: Post Exposure Bake (hereinafter also referred to as “PEB”) can be performed. PEB can promote the formation of a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group. The temperature when performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C. or higher and 100 ° C. or lower.
However, since the acid-decomposable group in the present invention has low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to generate a carboxyl group or a phenolic hydroxyl group, PEB is not necessarily performed. A positive image can also be formed by development.
現像工程で使用する現像液には、塩基性化合物が含まれることが好ましい。塩基性化合物としては、例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物類;炭酸ナトリウム、炭酸カリウムなどのアルカリ金属炭酸塩類;重炭酸ナトリウム、重炭酸カリウムなどのアルカリ金属重炭酸塩類;テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、コリンヒドロキシド等のアンモニウムヒドロキシド類;ケイ酸ナトリウム、メタケイ酸ナトリウムなどの水溶液を使用することができる。また、上記アルカリ類の水溶液にメタノールやエタノールなどの水溶性有機溶剤や界面活性剤を適当量添加した水溶液を現像液として使用することもできる。
好ましい現像液として、テトラエチルアンモニウムヒドロキシドの0.4%水溶液、0.5%水溶液、0.7%水溶液、2.38%水溶液を挙げる事ができる。
現像液のpHは、好ましくは10.0~14.0である。
現像時間は、好ましくは30~500秒間であり、また、現像の手法は液盛り法、ディップ法等の何れでもよい。現像後は、流水洗浄を、通常、30~300秒間行い、所望のパターンを形成させることができる。 現像の後に、リンス工程を行うこともできる。リンス工程では、現像後の基板を純水などで洗うことで、付着している現像液除去、現像残渣除去を行う。リンス方法は公知の方法を用いることができる。例えばシャワーリンスやディップリンスなどを挙げる事ができる。 In the developing step (4), a polymer having a liberated carboxyl group or phenolic hydroxyl group is developed using an alkaline developer. A positive image is formed by removing an exposed area containing a resin composition having a carboxyl group or a phenolic hydroxyl group that is easily dissolved in an alkaline developer.
The developer used in the development step preferably contains a basic compound. Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
Preferred examples of the developer include a 0.4% aqueous solution, a 0.5% aqueous solution, a 0.7% aqueous solution, and a 2.38% aqueous solution of tetraethylammonium hydroxide.
The pH of the developer is preferably 10.0 to 14.0.
The development time is preferably 30 to 500 seconds, and the development method may be either a liquid piling method or a dipping method. After development, washing with running water is usually performed for 30 to 300 seconds to form a desired pattern. A rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like. A known method can be used as the rinsing method. For example, shower rinse and dip rinse can be mentioned.
ポストベークの前に、比較的低温でベークを行った後にポストベークすることもできる(ミドルベーク工程の追加)。ミドルベークを行う場合は、90~150℃で1~60分加熱した後に、200℃以上の高温でポストベークすることが好ましい。また、ミドルベーク、ポストベークを3段階以上の多段階に分けて加熱する事もできる。このようなミドルベーク、ポストベークの工夫により、パターンのテーパー角を調整することができる。これらの加熱は、ホットプレート、オーブン、赤外線ヒーターなど、公知の加熱方法を使用することができる。
なお、ポストベークに先立ち、パターンを形成した基板に活性光線により全面再露光(ポスト露光)した後、ポストベークすることにより未露光部分に存在する光酸発生剤から酸を発生させ、架橋工程を促進する触媒として機能させることができ、膜の硬化反応を促進することができる。ポスト露光工程を含む場合の好ましい露光量としては、100~3,000mJ/cm2が好ましく、100~500mJ/cm2が特に好ましい。 In the post-baking step of (5), by heating the obtained positive image, the acid-decomposable group is thermally decomposed to generate a carboxyl group or a phenolic hydroxyl group, and then crosslinked with a crosslinkable group, a crosslinking agent or the like. A cured film can be formed. This heating is performed using a heating device such as a hot plate or an oven at a predetermined temperature, for example, 180 to 250 ° C. for a predetermined time, for example, 5 to 90 minutes on the hot plate, 30 to 120 minutes for the oven. It is preferable to By proceeding such a crosslinking reaction, a protective film and an interlayer insulating film that are superior in heat resistance, hardness, and the like can be formed. Moreover, when performing heat processing, it can also improve transparency by performing in nitrogen atmosphere.
Prior to post-baking, post-baking can be performed after baking at a relatively low temperature (addition of a middle baking process). When performing middle baking, it is preferable to post-bake at a high temperature of 200 ° C. or higher after heating at 90 to 150 ° C. for 1 to 60 minutes. Moreover, middle baking and post-baking can be heated in three or more stages. The taper angle of the pattern can be adjusted by devising such middle baking and post baking. These heating methods can use a known heating method such as a hot plate, an oven, or an infrared heater.
Prior to post-baking, the substrate on which the pattern was formed was re-exposed with actinic rays (post-exposure) and then post-baked to generate an acid from the photoacid generator present in the unexposed part, thereby performing a crosslinking step. It can function as a catalyst to promote, and can accelerate the curing reaction of the film. The preferred exposure amount in the case of including a post-exposure step, preferably 100 ~ 3,000mJ / cm 2, particularly preferably 100 ~ 500mJ / cm 2.
本発明の硬化膜は、本発明の感光性樹脂組成物を硬化して得られた硬化膜である。
本発明の硬化膜は、層間絶縁膜として好適に用いることができる。また、本発明の硬化膜は、本発明の硬化膜の形成方法により得られた硬化膜であることが好ましい。
本発明の感光性樹脂組成物により、絶縁性に優れ、高温でベークされた場合においても高い透明性を有する層間絶縁膜が得られる。本発明の感光性樹脂組成物を用いてなる層間絶縁膜は、高い透明性を有し、硬化膜物性に優れるため、有機EL表示装置や液晶表示装置の用途に有用である。 [Curing film]
The cured film of the present invention is a cured film obtained by curing the photosensitive resin composition of the present invention.
The cured film of the present invention can be suitably used as an interlayer insulating film. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention.
With the photosensitive resin composition of the present invention, an interlayer insulating film having excellent insulation and high transparency even when baked at high temperatures can be obtained. Since the interlayer insulating film using the photosensitive resin composition of the present invention has high transparency and excellent cured film physical properties, it is useful for applications of organic EL display devices and liquid crystal display devices.
本発明の液晶表示装置は、本発明の硬化膜を具備することを特徴とする。
本発明の液晶表示装置としては、上記本発明の感光性樹脂組成物を用いて形成される平坦化膜や層間絶縁膜を有すること以外は特に制限されず、様々な構造をとる公知の液晶表示装置を挙げることができる。
例えば、本発明の液晶表示装置が具備するTFT(Thin-Film Transistor)の具体例としては、アモルファスシリコン-TFT、低温ポリシリコンーTFT、酸化物半導体TFT等が挙げられる。本発明の硬化膜は電気特性に優れるため、これらのTFTに組み合わせて好ましく用いることができる。
また、本発明の液晶表示装置が取りうる液晶駆動方式としてはTN(TwistedNematic)方式、VA(Virtical Alignment)方式、IPS(In-Place-Switching)方式、FFS(Frings Field Switching)方式、OCB(Optical Compensated Bend)方式などが挙げられる。
パネル構成においては、COA(Color Filter on Allay)方式の液晶表示装置でも本発明の硬化膜を用いることができ、例えば、特開2005-284291号公報の有機絶縁膜(115)や、特開2005-346054号公報の有機絶縁膜(212)として用いることができる。
また、本発明の液晶表示装置が取りうる液晶配向膜の具体的な配向方式としてはラビング配向法、光配向方などが挙げられる。また、特開2003-149647号公報や特開2011-257734号公報に記載のPSA(Polymer Sustained Alignment)技術によってポリマー配向支持されていてもよい。
また、本発明の感光性樹脂組成物および本発明の硬化膜は、上記用途に限定されず種々の用途に使用することができる。例えば、平坦化膜や層間絶縁膜以外にも、カラーフィルターの保護膜や、液晶表示装置における液晶層の厚みを一定に保持するためのスペーサーや固体撮像素子においてカラーフィルター上に設けられるマイクロレンズ等に好適に用いることができる。
図1は、アクティブマトリックス方式の液晶表示装置10の一例を示す概念的断面図である。このカラー液晶表示装置10は、背面にバックライトユニット12を有する液晶パネルであって、液晶パネルは、偏光フィルムが貼り付けられた2枚のガラス基板14,15の間に配置されたすべての画素に対応するTFT16の素子が配置されている。ガラス基板上に形成された各素子には、硬化膜17中に形成されたコンタクトホール18を通して、画素電極を形成するITO透明電極19が配線されている。ITO透明電極19の上には、液晶20の層とブラックマトリックスを配置したRGBカラーフィルター22が設けられている。
バックライトの光源としては、特に限定されず公知の光源を用いることができる。例えば白色LED、青色・赤色・緑色などの多色LED、蛍光灯(冷陰極管)、有機ELなどを挙げる事ができる。
また、液晶表示装置は、3D(立体視)型のものとしたり、タッチパネル型のものとしたりすることも可能である。さらにフレキシブル型にすることも可能であり、特開2011-145686号公報の第2相間絶縁膜(48)や、特開2009-258758号公報の相間絶縁膜(520)として用いることができる。 [Liquid Crystal Display]
The liquid crystal display device of the present invention comprises the cured film of the present invention.
The liquid crystal display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and known liquid crystal displays having various structures. A device can be mentioned.
For example, specific examples of TFT (Thin-Film Transistor) included in the liquid crystal display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
Liquid crystal driving methods that can be taken by the liquid crystal display device of the present invention include TN (Twisted Nematic) method, VA (Virtual Alignment) method, IPS (In-Place-Switching) method, FFS (Frings Field Switching) method, OCB (Optical). Compensated Bend) method and the like.
In the panel configuration, the cured film of the present invention can also be used in a COA (Color Filter on Array) type liquid crystal display device. For example, the organic insulating film (115) of JP-A-2005-284291, -346054 can be used as the organic insulating film (212).
Specific examples of the alignment method of the liquid crystal alignment film that the liquid crystal display device of the present invention can take include a rubbing alignment method and a photo alignment method. Further, the polymer orientation may be supported by a PSA (Polymer Sustained Alignment) technique described in Japanese Patent Application Laid-Open Nos. 2003-149647 and 2011-257734.
Moreover, the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, It can be used for various uses. For example, in addition to the planarization film and interlayer insulating film, a protective film for the color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state imaging device, etc. Can be suitably used.
FIG. 1 is a conceptual cross-sectional view showing an example of an active matrix liquid
The light source of the backlight is not particularly limited, and a known light source can be used. For example, a white LED, a multicolor LED such as blue, red, and green, a fluorescent lamp (cold cathode tube), and an organic EL can be used.
Further, the liquid crystal display device may be a 3D (stereoscopic) type or a touch panel type. Further, it can be made flexible, and can be used as the second interphase insulating film (48) of JP 2011-145686 A or the interphase insulating film (520) of JP 2009-258758 A.
本発明の有機EL表示装置は、本発明の硬化膜を具備することを特徴とする。
本発明の有機EL表示装置としては、上記本発明の感光性樹脂組成物を用いて形成される平坦化膜や層間絶縁膜を有すること以外は特に制限されず、様々な構造をとる公知の各種有機EL表示装置や液晶表示装置を挙げることができる。
例えば、本発明の有機EL表示装置が具備するTFT(Thin-Film Transistor)の具体例としては、アモルファスシリコン-TFT、低温ポリシリコンーTFT、酸化物半導体TFT等が挙げられる。本発明の硬化膜は電気特性に優れるため、これらのTFTに組み合わせて好ましく用いることができる。
図2は、有機EL表示装置の一例の構成概念図である。ボトムエミッション型の有機EL表示装置における基板の模式的断面図を示し、平坦化膜4を有している。
ガラス基板6上にボトムゲート型のTFT1を形成し、このTFT1を覆う状態でSi3N4から成る絶縁膜3が形成されている。絶縁膜3に、ここでは図示を省略したコンタクトホールを形成した後、このコンタクトホールを介してTFT1に接続される配線2(高さ1.0μm)が絶縁膜3上に形成されている。配線2は、TFT1間または、後の工程で形成される有機EL素子とTFT1とを接続するためのものである。
さらに、配線2の形成による凹凸を平坦化するために、配線2による凹凸を埋め込む状態で絶縁膜3上に平坦化層4が形成されている。
平坦化膜4上には、ボトムエミッション型の有機EL素子が形成されている。すなわち、平坦化膜4上に、ITOからなる第一電極5が、コンタクトホール7を介して配線2に接続させて形成されている。また、第一電極5は、有機EL素子の陽極に相当する。
第一電極5の周縁を覆う形状の絶縁膜8が形成されており、この絶縁膜8を設けることによって、第一電極5とこの後の工程で形成する第二電極との間のショートを防止することができる。
さらに、図2には図示していないが、所望のパターンマスクを介して、正孔輸送層、有機発光層、電子輸送層を順次蒸着して設け、次いで、基板上方の全面にAlから成る第二電極を形成し、封止用ガラス板と紫外線硬化型エポキシ樹脂を用いて貼り合わせることで封止し、各有機EL素子にこれを駆動するためのTFT1が接続されてなるアクティブマトリックス型の有機EL表示装置が得られる。 [Organic EL display device]
The organic EL display device of the present invention comprises the cured film of the present invention.
The organic EL display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various known structures having various structures. Examples thereof include an organic EL display device and a liquid crystal display device.
For example, specific examples of TFT (Thin-Film Transistor) included in the organic EL display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
FIG. 2 is a conceptual diagram of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
A bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating
Further, in order to flatten the unevenness due to the formation of the wiring 2, the flattening layer 4 is formed on the insulating
On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.
An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do.
Further, although not shown in FIG. 2, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a second layer made of Al is formed on the entire surface above the substrate. An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving it. An EL display device is obtained.
MATHF:2-テトラヒドロフラニルメタクリレート(合成品)
MAEVE:1-エトキシエチルメタクリレート(和光純薬工業社製)
OXE-30:3-エチル-3-オキセタニルメチルメタクリレート(大阪有機化学工業社製)
GMA:グリシジルメタクリレート(和光純薬工業社製)
NBMA:n-ブトキシメチルアクリルアミド(東京化成製)
HEMA:ヒドロキシエチルメタクリレート(和光純薬社製)
MAA:メタクリル酸(和光純薬工業社製)
MMA:メチルメタクリレート(和光純薬工業社製)
St:スチレン(和光純薬工業社製)
DCPM:ジシクロペンタニルメタクリレート
V-601:ジメチル-2,2’-アゾビス(2-メチルプロピオネート)(和光純薬工業社製)
V-65:2,2’-アゾビス(2,4-ジメチルバレロニトリル)(和光純薬工業社製)
MEDG:メチルエチルジグリコール(日本乳化剤(株)製)
PGMEA:メトキシプロピルアセテート(昭和電工社製) In the following synthesis examples, the following symbols represent the following compounds, respectively.
MATHF: 2-tetrahydrofuranyl methacrylate (synthetic product)
MAEVE: 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
OXE-30: 3-ethyl-3-oxetanylmethyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
GMA: Glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
NBMA: n-butoxymethylacrylamide (manufactured by Tokyo Chemical Industry)
HEMA: Hydroxyethyl methacrylate (Wako Pure Chemical Industries, Ltd.)
MAA: Methacrylic acid (manufactured by Wako Pure Chemical Industries)
MMA: Methyl methacrylate (Wako Pure Chemical Industries, Ltd.)
St: Styrene (Wako Pure Chemical Industries, Ltd.)
DCPM: Dicyclopentanyl methacrylate V-601: Dimethyl-2,2′-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.)
V-65: 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)
MEDG: methyl ethyl diglycol (manufactured by Nippon Emulsifier Co., Ltd.)
PGMEA: Methoxypropyl acetate (manufactured by Showa Denko)
メタクリル酸(86g、1mol)を15℃に冷却しておき、カンファースルホン酸(4.6g、0.02mol)添加した。その溶液に、2-ジヒドロフラン(71g、1mol、1.0当量)を滴下した。1時間撹拌した後に、飽和炭酸水素ナトリウム(500mL)を加え、酢酸エチル(500mL)で抽出し、硫酸マグネシウムで乾燥後、不溶物を濾過後40℃以下で減圧濃縮し、残渣の黄色油状物を減圧蒸留して沸点(bp.)54~56℃/3.5mmHg留分のメタクリル酸テトラヒドロ-2H-フラン-2-イル(MATHF)125gを無色油状物として得た(収率80%)。 <Synthesis of MATHF>
Methacrylic acid (86 g, 1 mol) was cooled to 15 ° C., and camphorsulfonic acid (4.6 g, 0.02 mol) was added. To the solution, 2-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was added dropwise. After stirring for 1 hour, saturated sodium bicarbonate (500 mL) was added, extracted with ethyl acetate (500 mL), dried over magnesium sulfate, insolubles were filtered and concentrated under reduced pressure at 40 ° C. or lower to give a residual yellow oily product. Distillation under reduced pressure gave 125 g of tetrahydro-2H-furan-2-yl methacrylate (MATHF) as a colorless oily substance (yield 80%) at a boiling point (bp.) Of 54 to 56 ° C./3.5 mmHg.
3つ口フラスコにPGMEA(89g)を入れ、窒素雰囲気下において90℃に昇温した。その溶液にMAA(全単量体成分中の9.5mol%となる量)、MATHF(全単量体成分中の43mol%となる量)、GMA(全単量体成分中の47.5mol%に相当)、V-65(全単量体成分の合計100mol%に対して4mol%に相当)を溶解させ、2時間かけて滴下した。滴下終了後2時間攪拌し、反応を終了させた。それにより重合体P-1を得た。なお、PGMEAとその他の成分の合計量の比を60:40とした。即ち、固形分濃度40%の重合体溶液を調製した。
モノマー種類等を下記表に示す通りに変更し、他の重合体を合成した。 <Synthesis Example of Polymer P-1>
PGMEA (89 g) was placed in a three-necked flask and heated to 90 ° C. in a nitrogen atmosphere. MAA (amount to be 9.5 mol% in all monomer components), MATH (amount to be 43 mol% in all monomer components), GMA (47.5 mol% in all monomer components) V-65 (corresponding to 4 mol% with respect to the total of 100 mol% of all monomer components) was dissolved and added dropwise over 2 hours. After completion of the dropwise addition, the mixture was stirred for 2 hours to complete the reaction. Thereby, a polymer P-1 was obtained. The ratio of the total amount of PGMEA and other components was 60:40. That is, a polymer solution having a solid content concentration of 40% was prepared.
Monomers and the like were changed as shown in the following table, and other polymers were synthesized.
下記表記載の固形分比となるように、重合体成分、非イオン性光酸発生剤、増感剤、一般式(S)で表される化合物、アルコキシシラン化合物、界面活性剤、一般式(S)で表される化合物以外の塩基性化合物、およびその他の成分を溶剤(MEDG)に固形分濃度32%になるまで溶解混合し、口径0.2μmのポリテトラフルオロエチレン製フィルターで濾過して、各種実施例および比較例の感光性樹脂組成物を得た。なお、表中の添加量は、質量%である。 <Adjustment of photosensitive resin composition>
The polymer component, nonionic photoacid generator, sensitizer, compound represented by general formula (S), alkoxysilane compound, surfactant, general formula ( S) A basic compound other than the compound represented by S) and other components are dissolved and mixed in a solvent (MEDG) until the solid content concentration becomes 32%, and filtered through a polytetrafluoroethylene filter having a diameter of 0.2 μm. The photosensitive resin compositions of various examples and comparative examples were obtained. In addition, the addition amount in a table | surface is the mass%.
P-21:Joncryl 67(BASF製)
P-22:ARUFON UC-3910(東亜合成(株)製)
P-23:SMA 1000P(CRAY VALLEY USA,LLC製)
P-24:SMA 2000P(CRAY VALLEY USA,LLC製)
P-25:SMA 3000P(CRAY VALLEY USA,LLC製)
P-26:SMA EF-30(CRAY VALLEY USA,LLC製)
P-27:SMA EF-40(CRAY VALLEY USA,LLC製)
P-28:SMA EF-60(CRAY VALLEY USA,LLC製)
P-29:SMA EF-80(CRAY VALLEY USA,LLC製)
P-30:SMA 2625P(CRAY VALLEY USA,LLC製)
P-31:SMA 3840F(CRAY VALLEY USA,LLC製) (Component (A) other than listed in Table 1)
P-21: Joncryl 67 (BASF)
P-22: ARUFON UC-3910 (manufactured by Toa Gosei Co., Ltd.)
P-23: SMA 1000P (manufactured by CRAY VALLEY USA, LLC)
P-24: SMA 2000P (manufactured by CRAY VALLEY USA, LLC)
P-25: SMA 3000P (manufactured by CRAY VALLEY USA, LLC)
P-26: SMA EF-30 (manufactured by CRAY VALLEY USA, LLC)
P-27: SMA EF-40 (CRAY VALLEY USA, LLC)
P-28: SMA EF-60 (CRAY VALLEY USA, LLC)
P-29: SMA EF-80 (manufactured by CRAY VALLEY USA, LLC)
P-30: SMA 2625P (manufactured by CRAY VALLEY USA, LLC)
P-31: SMA 3840F (manufactured by CRAY VALLEY USA, LLC)
B-1:下記に示す構造(合成例を後述する。)
B-2:PAG-103(商品名、下記に示す構造、BASF社製)
B-3:α-(ヒドロキシイミノ)-2-フェニルアセトニトリル(合成例を後述する。)
B-1: Structure shown below (synthesis example will be described later)
B-2: PAG-103 (trade name, structure shown below, manufactured by BASF)
B-3: α- (Hydroxyimino) -2-phenylacetonitrile (Synthesis example will be described later)
2-ナフトール(10g)、クロロベンゼン(30mL)の懸濁溶液に塩化アルミニウム(10.6g)、2-クロロプロピオニルクロリド(10.1g)を添加し、混合液を40℃に加熱して2時間反応させた。氷冷下、反応液に4NHCl水溶液(60mL)を滴下し、酢酸エチル(50mL)を添加して分液した。有機層に炭酸カリウム(19.2g)を加え、40℃で1時間反応させた後、2NHCl水溶液(60mL)を添加して分液し、有機層を濃縮後、結晶をジイソプロピルエーテル(10mL)でリスラリーし、ろ過、乾燥してケトン化合物(6.5g)を得た。
得られたケトン化合物(3.0g)、メタノール(30mL)の懸濁溶液に酢酸(7.3g)、50質量%ヒドロキシルアミン水溶液(8.0g)を添加し、加熱還流した。放冷後、水(50mL)を加え、析出した結晶をろ過、冷メタノール洗浄後、乾燥してオキシム化合物(2.4g)を得た。
得られたオキシム化合物(1.8g)をアセトン(20mL)に溶解させ、氷冷下トリエチルアミン(1.5g)、p-トルエンスルホニルクロリド(2.4g)を添加し、室温に昇温して1時間反応させた。反応液に水(50mL)を添加し、析出した結晶をろ過後、メタノール(20mL)でリスラリーし、ろ過、乾燥してB-1の化合物(上述の構造)(2.3g)を得た。
なお、B-1の1H-NMRスペクトル(300MHz、CDCl3)は、δ=8.3(d,1H),8.0(d,2H),7.9(d,1H),7.8(d,1H),7.6(dd,1H),7.4(dd,1H)7.3(d,2H),7.1(d.1H),5.6(q,1H),2.4(s,3H),1.7(d,3H)であった。 <Synthesis of B-1>
Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixture was heated to 40 ° C. for 2 hours. I let you. Under ice-cooling, 4N HCl aqueous solution (60 mL) was added dropwise to the reaction solution, and ethyl acetate (50 mL) was added for liquid separation. Potassium carbonate (19.2 g) was added to the organic layer, reacted at 40 ° C. for 1 hour, 2N HCl aqueous solution (60 mL) was added and separated, and the organic layer was concentrated. The crystals were diluted with diisopropyl ether (10 mL). The slurry was reslurried, filtered and dried to obtain a ketone compound (6.5 g).
Acetic acid (7.3 g) and a 50 mass% aqueous hydroxylamine solution (8.0 g) were added to a suspension of the obtained ketone compound (3.0 g) and methanol (30 mL), and the mixture was heated to reflux. After allowing to cool, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain an oxime compound (2.4 g).
The obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice cooling, and the temperature was raised to room temperature. Reacted for hours. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered, reslurried with methanol (20 mL), filtered and dried to obtain the compound of B-1 (the above structure) (2.3 g).
The 1H-NMR spectrum (300 MHz, CDCl3) of B-1 is δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 ( d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H) 7.3 (d, 2H), 7.1 (d.1H), 5.6 (q, 1H), 2 .4 (s, 3H), 1.7 (d, 3H).
フェニルアセトニトリル(5.85g、東京化成社製)をテトラヒドロフラン(50ml、和光純薬社製)に混合させ、氷浴につけ反応液を5℃以下に冷却した。次に、SM-28(ナトリウムメトキシド28%メタノール溶液、11.6g、和光純薬社製)を滴下し、氷浴下30分間攪拌し反応させた。次に、亜硝酸イソペンチル(7.03g、東京化成社製)を内温20度以下に保ちながら滴下し、滴下終了後に反応液を室温化1時間反応させた。得られた反応液を、水酸化ナトリウム(1g)を溶解させた水(150mL)に投入し完溶させ、次いで酢酸エチル(100ml)を添加して分液し、目的物を有する水層約180mlを得た。さらに再度酢酸エチル(100ml)を添加し、濃塩酸で水層をpH3以下の酸性とし、生成物を抽出、濃縮した。得られた粗結晶をヘキサンで洗浄すると、α-(ヒドロキシイミノ)-2-フェニルアセトニトリル(4.6g)が収率63%で得られた。 <Synthesis of B-3>
Phenylacetonitrile (5.85 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed with tetrahydrofuran (50 ml, manufactured by Wako Pure Chemical Industries, Ltd.), placed in an ice bath, and the reaction solution was cooled to 5 ° C. or lower. Next, SM-28 (sodium methoxide 28% methanol solution, 11.6 g, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise, and the mixture was allowed to react with stirring for 30 minutes in an ice bath. Next, isopentyl nitrite (7.03 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise while maintaining the internal temperature at 20 ° C. or less, and after completion of the addition, the reaction solution was allowed to react at room temperature for 1 hour. The obtained reaction solution was poured into water (150 mL) in which sodium hydroxide (1 g) was dissolved to completely dissolve it, and then ethyl acetate (100 ml) was added to separate the solution. Got. Further, ethyl acetate (100 ml) was added again, the aqueous layer was acidified with concentrated hydrochloric acid to
S-1:下記に示す構造
S-2:下記に示す構造
S-3:下記に示す構造
S-1: Structure shown below S-2: Structure shown below S-3: Structure shown below
MEDG:ハイソルブEDM(東邦化学工業社製)
1,3-BGDA:1,3-ブチレングリコールジアセテート((株)ダイセル製) (solvent)
MEDG: High Solve EDM (Toho Chemical Industries)
1,3-BGDA: 1,3-butylene glycol diacetate (manufactured by Daicel Corporation)
G-1:γ-グリシドキシプロピルトリアルコキシシラン(東京化成工業(株)製)
G-2:KBM-3103(信越化学工業(株)製)
G-3:KBE-846(信越化学工業(株)製)
G-4:KBM-3063(信越化学工業(株)製) (Alkoxysilane compound)
G-1: γ-glycidoxypropyltrialkoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.)
G-2: KBM-3103 (manufactured by Shin-Etsu Chemical Co., Ltd.)
G-3: KBE-846 (manufactured by Shin-Etsu Chemical Co., Ltd.)
G-4: KBM-3063 (manufactured by Shin-Etsu Chemical Co., Ltd.)
DBA:下記構造のジブトキシアントラセン(川崎化成社製)
DBA: Dibutoxyanthracene having the following structure (manufactured by Kawasaki Kasei Co., Ltd.)
H-1:2,4,5-トリフェニルイミダゾール(東京化成工業(株)製)
H-2:1,5-ジアザビシクロ[4.3.0]-5-ノネン(東京化成工業(株)製) (Other basic compounds)
H-1: 2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
H-2: 1,5-diazabicyclo [4.3.0] -5-nonene (manufactured by Tokyo Chemical Industry Co., Ltd.)
W-1:下記構造式で示されるパーフルオロアルキル基含有ノニオン界面活性剤(F-554,DIC製)
W-1: Perfluoroalkyl group-containing nonionic surfactant represented by the following structural formula (F-554, manufactured by DIC)
(架橋剤)
F-1:JER828((株)三菱ケミカルホールディングス製)
F-2:JER1007((株)三菱ケミカルホールディングス製)
F-3:JER157S65((株)三菱ケミカルホールディングス製)
F-4:デュラネート17B-60P(旭化成ケミカルズ(株)製)
F-5:セロキサイド2021P((株)ダイセル製)
F-6:デナコールEX-321L((株)ナガセケムテックス製)
F-7:EPICLON EXA-4850-150(DIC(株)製)
F-8:タケネートB-870N(三井化学(株)製)
F-9:ニカラックMW-100LM((株)三和ケミカル製)
F-10:ニカラックMX-270((株)三和ケミカル製)
F-11:カヤラッドDPHA(日本化薬(株)製) (Other ingredients)
(Crosslinking agent)
F-1: JER828 (manufactured by Mitsubishi Chemical Holdings Corporation)
F-2: JER1007 (manufactured by Mitsubishi Chemical Holdings Corporation)
F-3: JER157S65 (manufactured by Mitsubishi Chemical Holdings Corporation)
F-4: Duranate 17B-60P (Asahi Kasei Chemicals Corporation)
F-5: Celoxide 2021P (manufactured by Daicel Corporation)
F-6: Denacol EX-321L (manufactured by Nagase ChemteX Corporation)
F-7: EPICLON EXA-4850-150 (manufactured by DIC Corporation)
F-8: Takenate B-870N (Mitsui Chemicals)
F-9: Nikarac MW-100LM (manufactured by Sanwa Chemical Co., Ltd.)
F-10: Nikarac MX-270 (manufactured by Sanwa Chemical Co., Ltd.)
F-11: Kayalad DPHA (manufactured by Nippon Kayaku Co., Ltd.)
J-1:アデカスタブAO-60((株)ADEKA製)
J-2:イルガノックス1035(BASF製)
J-3:イルガノックス1098(BASF製) (Antioxidant)
J-1: ADK STAB AO-60 (manufactured by ADEKA Corporation)
J-2: Irganox 1035 (manufactured by BASF)
J-3: Irganox 1098 (BASF)
基板の一方の面の半分の領域(10cm×5cm)にMo(モリブデン)薄膜が成膜され、同じ面のもう半分の領域(10cm×5cm)にSiNx薄膜が成膜されたガラス基板(10cm×10cm×0.5mm)を、ヘキサメチルジシラザン(HMDS)蒸気下に30秒曝し、各感光性樹脂組成物溶液を、スピンコーターを用いて乾燥膜厚が3μmとなるように塗布した後、90℃で2分ホットプレート上でプリベークして溶剤を揮発させた。その後、10μmライン/10μmスペースを再現することのできるマスクを介して、超高圧水銀灯を用いて積算照射量40mJ/cm2(照度:20mW/cm2、i線)露光した後、アルカリ現像液(0.4質量%のTMAH水溶液)で、23℃、60秒間現像した後、超純水で1分間リンスした。得られた基板を光学顕微鏡で観察し、10μmライン/10μmスペースのパターンの欠け、剥がれをMo部とSiNx部を観察した。その結果を下記表に示した。剥がれが少ないほど好ましく、AまたはBが好ましい。
A:欠け、剥がれが全くない
B:欠け、剥がれが30%以下
C:欠け、剥がれが30%を超え60%以下
D:欠け、剥がれが60%を超え100%以下 <Evaluation of adhesion during development>
A glass substrate (10 cm × 10 cm) in which a Mo (molybdenum) thin film is formed on a half region (10 cm × 5 cm) of one surface of the substrate and a SiNx thin film is formed on the other half region (10 cm × 5 cm) of the same surface. 10 cm × 0.5 mm) is exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and each photosensitive resin composition solution is applied using a spin coater so that the dry film thickness becomes 3 μm. The solvent was volatilized by pre-baking on a hot plate at 2 ° C. for 2 minutes. Then, after exposure to an integrated dose of 40 mJ / cm 2 (illuminance: 20 mW / cm 2 , i-line) using an ultra-high pressure mercury lamp through a mask capable of reproducing a 10 μm line / 10 μm space, an alkali developer ( The film was developed at 23 ° C. for 60 seconds, and rinsed with ultrapure water for 1 minute. The obtained substrate was observed with an optical microscope, and the Mo part and the SiNx part were observed for chipping and peeling of the 10 μm line / 10 μm space pattern. The results are shown in the following table. Less peeling is preferable, and A or B is preferable.
A: No chipping or peeling B: Chipping or peeling 30% or less C: Chipping or peeling over 30% to 60% D: Chipping or peeling over 60% to 100% or less
Mo(モリブデン)薄膜が成膜されたガラス基板(10cm×10cm×0.5mm)を、ヘキサメチルジシラザン(HMDS)蒸気下に30秒曝し、その後、各感光性樹脂組成物をスピンコート塗布した後、90℃で2分ホットプレート上でプリベークして溶剤を揮発させ、膜厚3μmの感光性樹脂組成物層を形成した。続いて超高圧水銀灯を用いて積算照射量が300mJ/cm2(照度:20mW/cm2、i線)となるように全面露光し、その後、この基板をオーブンにて230℃で30分加熱して硬化膜を得た。
次に、硬化膜にカッターを用いて、縦横に1mmの間隔で切り込みを入れ、スコッチテープを用いてテープ剥離試験(100マスクロスカット法:JIS5600に準拠)を行った。テープ裏面に転写された硬化膜の面積から硬化膜と基板間の密着性を評価した。その結果を下記表に示した。数値としては小さいほど下地基板との密着性が高く、AまたはBが好ましい。
A:転写された面積が1%未満
B:転写された面積が1%以上5%未満
C:転写された面積が5%以上10%未満
D:転写された面積が10%以上50%未満
E:転写された面積が50%以上 <Hardened film adhesion: Mo>
A glass substrate (10 cm × 10 cm × 0.5 mm) on which a Mo (molybdenum) thin film was formed was exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and then each photosensitive resin composition was spin-coated. Then, the solvent was volatilized by pre-baking on a hot plate at 90 ° C. for 2 minutes to form a photosensitive resin composition layer having a thickness of 3 μm. Subsequently, the whole surface was exposed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm 2 (illuminance: 20 mW / cm 2 , i-line), and then the substrate was heated in an oven at 230 ° C. for 30 minutes. Thus, a cured film was obtained.
Next, the cured film was cut using a cutter at intervals of 1 mm vertically and horizontally, and a tape peeling test (100 mask loss cut method: conforming to JIS 5600) was performed using a scotch tape. The adhesion between the cured film and the substrate was evaluated from the area of the cured film transferred to the back surface of the tape. The results are shown in the following table. The smaller the numerical value, the higher the adhesion to the base substrate, and A or B is preferred.
A: The transferred area is less than 1% B: The transferred area is 1% or more and less than 5% C: The transferred area is 5% or more and less than 10% D: The transferred area is 10% or more and less than 50% E : The transferred area is 50% or more
Ti(チタン)薄膜が成膜されたガラス基板(10cm×10cm×0.5mm)を、ヘキサメチルジシラザン(HMDS)蒸気下に30秒曝し、その後、各感光性樹脂組成物をスピンコート塗布した後、90℃で2分ホットプレート上でプリベークして溶剤を揮発させ、膜厚3μmの感光性樹脂組成物層を形成した。続いて超高圧水銀灯を用いて積算照射量が300mJ/cm2(照度:20mW/cm2、i線)となるように全面露光し、その後、この基板をオーブンにて230℃で30分加熱して硬化膜を得た。
次に、硬化膜にカッターを用いて、縦横に1mmの間隔で切り込みを入れ、スコッチテープを用いてテープ剥離試験(100マスクロスカット法:JIS5600に準拠)を行った。テープ裏面に転写された硬化膜の面積から硬化膜と基板間の密着性を評価した。その結果を下記表に示した。数値としては小さいほど下地基板との密着性が高く、AまたはBが好ましい。
A:転写された面積が1%未満
B:転写された面積が1%以上5%未満
C:転写された面積が5%以上10%未満
D:転写された面積が10%以上50%未満
E:転写された面積が50%以上 <Hardened film adhesion: Ti>
A glass substrate (10 cm × 10 cm × 0.5 mm) on which a Ti (titanium) thin film was formed was exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and then each photosensitive resin composition was spin-coated. Then, the solvent was volatilized by pre-baking on a hot plate at 90 ° C. for 2 minutes to form a photosensitive resin composition layer having a thickness of 3 μm. Subsequently, the whole surface was exposed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm 2 (illuminance: 20 mW / cm 2 , i-line), and then the substrate was heated in an oven at 230 ° C. for 30 minutes. Thus, a cured film was obtained.
Next, the cured film was cut using a cutter at intervals of 1 mm vertically and horizontally, and a tape peeling test (100 mask loss cut method: conforming to JIS 5600) was performed using a scotch tape. The adhesion between the cured film and the substrate was evaluated from the area of the cured film transferred to the back surface of the tape. The results are shown in the following table. The smaller the numerical value, the higher the adhesion to the base substrate, and A or B is preferred.
A: The transferred area is less than 1% B: The transferred area is 1% or more and less than 5% C: The transferred area is 5% or more and less than 10% D: The transferred area is 10% or more and less than 50% E : The transferred area is 50% or more
SiNx(窒化シリコン)薄膜が成膜されたガラス基板(10cm×10cm×0.5mm)を、ヘキサメチルジシラザン(HMDS)蒸気下に30秒曝し、その後、各感光性樹脂組成物をスピンコート塗布した後、90℃で2分ホットプレート上でプリベークして溶剤を揮発させ、膜厚3μmの感光性樹脂組成物層を形成した。続いて超高圧水銀灯を用いて積算照射量が300mJ/cm2(照度:20mW/cm2、i線)となるように全面露光し、その後、この基板をオーブンにて230℃で30分加熱して硬化膜を得た。
次に、硬化膜にカッターを用いて、縦横に1mmの間隔で切り込みを入れ、スコッチテープを用いてテープ剥離試験(100マスクロスカット法:JIS5600に準拠)を行った。テープ裏面に転写された硬化膜の面積から硬化膜と基板間の密着性を評価した。その結果を下記表に示した。数値としては小さいほど下地基板との密着性が高く、AまたはBが好ましい。
A:転写された面積が1%未満
B:転写された面積が1%以上5%未満
C:転写された面積が5%以上10%未満
D:転写された面積が10%以上50%未満
E:転写された面積が50%以上 <Hardened film adhesion: SiNx>
A glass substrate (10 cm × 10 cm × 0.5 mm) on which a SiNx (silicon nitride) thin film is formed is exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and then each photosensitive resin composition is applied by spin coating. Then, the solvent was volatilized by pre-baking on a hot plate at 90 ° C. for 2 minutes to form a photosensitive resin composition layer having a thickness of 3 μm. Subsequently, the whole surface was exposed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm 2 (illuminance: 20 mW / cm 2 , i-line), and then the substrate was heated in an oven at 230 ° C. for 30 minutes. Thus, a cured film was obtained.
Next, the cured film was cut using a cutter at intervals of 1 mm vertically and horizontally, and a tape peeling test (100 mask loss cut method: conforming to JIS 5600) was performed using a scotch tape. The adhesion between the cured film and the substrate was evaluated from the area of the cured film transferred to the back surface of the tape. The results are shown in the following table. The smaller the numerical value, the higher the adhesion to the base substrate, and A or B is preferred.
A: The transferred area is less than 1% B: The transferred area is 1% or more and less than 5% C: The transferred area is 5% or more and less than 10% D: The transferred area is 10% or more and less than 50% E : The transferred area is 50% or more
ガラス基板(10cm×10cm×0.5mm)を、ヘキサメチルジシラザン(HMDS)蒸気下に30秒曝し、その後、各感光性樹脂組成物をスピンコート塗布した後、90℃で2分ホットプレート上でプリベークして溶剤を揮発させ、膜厚3μmの感光性樹脂組成物層を形成した。続いて超高圧水銀灯を用いて積算照射量が300mJ/cm2(照度:20mW/cm2、i線)となるように全面露光し、その後、この基板をオーブンにて230℃で30分加熱して硬化膜を得た。
得られた硬化膜の膜厚(T1)を測定した。そして、この硬化膜が形成された基板を60℃に温度制御されたジメチルスルホキシド:モノエタノールアミン=7:3溶液中に10分間浸漬させた後、浸漬後の硬化膜の膜厚(t1)を測定し、浸漬による膜厚変化率{|t1-T1|/T1}×100〔%〕を算出した。結果を下記表に示す。変化率は小さいほど好ましく、A、Bが実用上問題のないレベルである。
A:2%未満
B:2%以上3%未満
C:3%以上4%未満
D:4%以上6%未満
E:6%以上 <Evaluation of chemical resistance>
A glass substrate (10 cm × 10 cm × 0.5 mm) was exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and then each photosensitive resin composition was spin-coated and then heated at 90 ° C. for 2 minutes. Was pre-baked to volatilize the solvent to form a photosensitive resin composition layer having a thickness of 3 μm. Subsequently, the whole surface was exposed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm 2 (illuminance: 20 mW / cm 2 , i-line), and then the substrate was heated in an oven at 230 ° C. for 30 minutes. Thus, a cured film was obtained.
The film thickness (T 1 ) of the obtained cured film was measured. The temperature controlled dimethylsulfoxide The substrate, on which the cured film is formed 60 ° C.: monoethanolamine = 7: 3 After the solution was immersed 10 minutes, the film thickness of the cured film after immersion (t 1) The film thickness change rate {| t 1 −T 1 | / T 1 } × 100 [%] by immersion was calculated. The results are shown in the table below. The smaller the rate of change, the better. A and B are practically satisfactory levels.
A: Less than 2% B: 2% or more and less than 3% C: 3% or more and less than 4% D: 4% or more and less than 6% E: 6% or more
加えて、本発明の感光性樹脂組成物の硬化膜は、耐薬品性も高いというメリットがある。 As is clear from the above results, it was found that the photosensitive resin composition of the present invention has excellent adhesion during development, and the cured film of the photosensitive resin composition of the present invention also has excellent adhesion to the substrate. . In particular, since a plurality of types of substrates are all excellent in high cured film adhesion, they can be preferably used for wiring substrates such as display devices. Furthermore, having an adhesiveness of evaluation “A” with respect to the molybdenum substrate is extremely valuable.
In addition, the cured film of the photosensitive resin composition of the present invention has an advantage of high chemical resistance.
実施例65は、実施例1において、露光機を、キヤノン(株)製 MPA 5500CFから、Nikon(株)製FX-803M(gh-Line ステッパ)に変更した以外は同様に行った。現像時と硬化膜の密着性の評価は実施例1と同レベルであった。 <Example 65>
Example 65 was performed in the same manner as in Example 1 except that the exposure machine was changed from MPA 5500CF manufactured by Canon Inc. to FX-803M (gh-Line stepper) manufactured by Nikon Corporation. Evaluation of adhesion between the developed film and the cured film was the same level as in Example 1.
実施例66は、実施例1において、現像液をアルカリ現像液(0.4質量%のTMAH水溶液)からアルカリ現像液(2.38質量%のTMAH水溶液)に変更した以外は同様に行った。現像時の密着性の評価は実施例1と同レベルであった。 <Example 66>
Example 66 was carried out in the same manner as in Example 1 except that the developer was changed from an alkali developer (0.4 mass% TMAH aqueous solution) to an alkali developer (2.38 mass% TMAH aqueous solution). Evaluation of adhesion during development was the same level as in Example 1.
実施例67は、実施例1において、オーブンでの加熱前の超高圧水銀灯を用いた全面露光の工程を省いた以外は同様に行った。硬化膜の密着性と耐薬品性の評価は実施例1と同レベルであった。 <Example 67>
Example 67 was performed in the same manner as in Example 1 except that the entire surface exposure step using the ultrahigh pressure mercury lamp before heating in the oven was omitted. The evaluation of the adhesion and chemical resistance of the cured film was the same level as in Example 1.
実施例68は、実施例1において、露光機を、キヤノン(株)製 MPA 5500CFから、355nmレーザー露光機に変更して355nmレーザー露光を行った以外は同様に行った。ここで、355nmレーザー露光機としては、株式会社ブイテクノロジー社製の「AEGIS」を使用し(波長355nm、パルス幅6nsec)、露光量はOPHIR社製の「PE10B-V2」を用いて測定した。
現像時と硬化膜の密着性の評価は実施例1と同レベルであった。 <Example 68>
Example 68 was performed in the same manner as in Example 1 except that the exposure machine was changed from an MPA 5500CF manufactured by Canon Inc. to a 355 nm laser exposure machine and 355 nm laser exposure was performed. Here, as the 355 nm laser exposure machine, “AEGIS” manufactured by Buoy Technology Co., Ltd. was used (wavelength 355 nm, pulse width 6 nsec), and the exposure amount was measured using “PE10B-V2” manufactured by OPHIR.
Evaluation of adhesion between the developed film and the cured film was the same level as in Example 1.
特許第3321003号公報の図1に記載のアクティブマトリクス型液晶表示装置において、層間絶縁膜として硬化膜17を以下のようにして形成し、実施例69の液晶表示装置を得た。すなわち、実施例1の感光性樹脂組成物を用い、層間絶縁膜として硬化膜17を形成した。 <Example 69>
In the active matrix type liquid crystal display device shown in FIG. 1 of Japanese Patent No. 3321003, a cured
実施例69と以下の塗布プロセスのみ変更して、同様の液晶表示装置を得た。すなわち、実施例1の感光性樹脂組成物をスリットコート法にて塗布した後、90℃/120秒ホットプレート上で加熱により溶剤を除去し、膜厚3.0μmの感光性樹脂組成物層を形成した。得られた塗膜は、平坦でムラの無い良好な面状であった。また液晶表示装置としての性能も実施例69と同様に良好であった。 <Example 70>
A liquid crystal display device similar to that of Example 69 was changed to obtain the same liquid crystal display device. That is, after the photosensitive resin composition of Example 1 was applied by a slit coating method, the solvent was removed by heating on a hot plate at 90 ° C./120 seconds to form a photosensitive resin composition layer having a thickness of 3.0 μm. Formed. The obtained coating film was flat and had a good surface shape without unevenness. Further, the performance as a liquid crystal display device was as good as in Example 69.
実施例71は、実施例1において、露光機を、キヤノン(株)製 MPA 5500CFから、UV-LED光源露光機に変更した以外は同様に行った。現像時と硬化膜の密着性の評価は実施例1と同レベルであった。 <Example 71>
Example 71 was performed in the same manner as in Example 1, except that the exposure machine was changed from MPA 5500CF manufactured by Canon Inc. to a UV-LED light source exposure machine. Evaluation of adhesion between the developed film and the cured film was the same level as in Example 1.
実施例69と以下の塗布プロセスのみ変更して、同様の液晶表示装置を得た。すなわち、実施例1の感光性樹脂組成物をスリットアンドスピン法にて塗布した後、90℃/120秒ホットプレート上で加熱により溶剤を除去し、膜厚3.0μmの感光性樹脂組成物層を形成した。得られた塗膜は、平坦でムラの無い良好な面状であった。また液晶表示装置としての性能も実施例69と同様に良好であった。 <Example 72>
A liquid crystal display device similar to that of Example 69 was changed to obtain the same liquid crystal display device. That is, after the photosensitive resin composition of Example 1 was applied by a slit and spin method, the solvent was removed by heating on a hot plate at 90 ° C./120 seconds to form a photosensitive resin composition layer having a thickness of 3.0 μm. Formed. The obtained coating film was flat and had a good surface shape without unevenness. Further, the performance as a liquid crystal display device was as good as in Example 69.
薄膜トランジスター(TFT)を用いた有機EL表示装置を以下の方法で作製した(図2参照)。
ガラス基板6上にボトムゲート型のTFT1を形成し、このTFT1を覆う状態でSi3N4から成る絶縁膜3を形成した。次に、この絶縁膜3に、ここでは図示を省略したコンタクトホールを形成した後、このコンタクトホールを介してTFT1に接続される配線2(高さ1.0μm)を絶縁膜3上に形成した。この配線2は、TFT1間または、後の工程で形成される有機EL素子とTFT1とを接続するためのものである。 <Example 73>
An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 2).
A bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating
感光性樹脂組成物を塗布する際の塗布性は良好で、露光、現像、焼成の後に得られた硬化膜には、しわやクラックの発生は認められなかった。さらに、配線2の平均段差は500nm、作製した平坦化膜4の膜厚は2,000nmであった。 Further, in order to flatten the unevenness due to the formation of the wiring 2, the planarizing film 4 was formed on the insulating
The applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking. Furthermore, the average step of the wiring 2 was 500 nm, and the thickness of the prepared planarizing film 4 was 2,000 nm.
2:配線
3:絶縁膜
4:平坦化膜
5:第一電極
6:ガラス基板
7:コンタクトホール
8:絶縁膜
10:液晶表示装置
12:バックライトユニット
14,15:ガラス基板
16:TFT
17:硬化膜
18:コンタクトホール
19:ITO透明電極
20:液晶
22:カラーフィルター 1: TFT (Thin Film Transistor)
2: Wiring 3: Insulating film 4: Flattened film 5: First electrode 6: Glass substrate 7: Contact hole 8: Insulating film 10: Liquid crystal display device 12:
17: Cured film 18: Contact hole 19: ITO transparent electrode 20: Liquid crystal 22: Color filter
Claims (12)
- (A)下記(1)および(2)の少なくとも一方を満たす重合体を含む重合体成分、
(1)(a1)酸基が酸分解性基で保護された基を有する構成単位、および(a2)架橋性基を有する構成単位、を有する重合体、
(2)(a1)酸基が酸分解性基で保護された基を有する構成単位を有する重合体、および(a2)架橋性基を有する構成単位を有する重合体、
(B)非イオン性光酸発生剤、
(C)下記一般式(S)で表される化合物、
一般式(S)
(D)溶剤、ならびに、
(E)アルコキシシラン化合物
を含有する感光性樹脂組成物。 (A) a polymer component containing a polymer that satisfies at least one of the following (1) and (2):
(1) (a1) a polymer having a structural unit having an acid group protected with an acid-decomposable group, and (a2) a structural unit having a crosslinkable group,
(2) (a1) a polymer having a structural unit having a group in which an acid group is protected with an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group,
(B) a nonionic photoacid generator,
(C) a compound represented by the following general formula (S),
General formula (S)
(D) a solvent, and
(E) A photosensitive resin composition containing an alkoxysilane compound. - 一般式(S)において、R1が、-NR3R4で表される基である、請求項1に記載の感光性樹脂組成物(但し、R3およびR4は、それぞれ、有機基であり、互いに結合して環を形成していてもよい。) 2. The photosensitive resin composition according to claim 1, wherein in the general formula (S), R 1 is a group represented by —NR 3 R 4 (wherein R 3 and R 4 are each an organic group) And may be bonded to each other to form a ring.)
- 一般式(S)において、R1が、5員環または6員環の環状基である、請求項1または2に記載の感光性樹脂組成物。 The photosensitive resin composition of Claim 1 or 2 whose R < 1 > is a 5-membered ring or a 6-membered cyclic group in General formula (S).
- 一般式(S)において、R1が、モルホリノ基である、請求項1または2に記載の感光性樹脂組成物。 The photosensitive resin composition of Claim 1 or 2 whose R < 1 > is a morpholino group in general formula (S).
- 前記(B)の光酸発生剤が、オキシムスルホネート化合物である、請求項1~4のいずれか1項に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, wherein the photoacid generator (B) is an oxime sulfonate compound.
- アルコキシシラン化合物が、ジアルコキシシラン化合物またはトリアルコキシシラン化合物である、請求項1~5のいずれか1項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 5, wherein the alkoxysilane compound is a dialkoxysilane compound or a trialkoxysilane compound.
- (F)架橋剤を含む請求項1~6のいずれか1項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 6, comprising (F) a crosslinking agent.
- (1)請求項1~7のいずれか1項に記載の感光性樹脂組成物を基板上に塗布する工程、(2)塗布された感光性樹脂組成物から溶剤を除去する工程、
(3)溶剤が除去された感光性樹脂組成物を活性光線により露光する工程、
(4)露光された感光性樹脂組成物を水性現像液により現像する工程、および、
(5)現像された感光性樹脂組成物を熱硬化するポストベーク工程、を含む硬化膜の製造方法。 (1) a step of applying the photosensitive resin composition according to any one of claims 1 to 7 on a substrate; (2) a step of removing a solvent from the applied photosensitive resin composition;
(3) A step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays,
(4) a step of developing the exposed photosensitive resin composition with an aqueous developer, and
(5) A method for producing a cured film, comprising a post-baking step of thermosetting the developed photosensitive resin composition. - 前記現像工程後、前記ポストベーク工程前に、現像された感光性樹脂組成物を全面露光する工程を含む、請求項8に記載の硬化膜の製造方法。 The manufacturing method of the cured film of Claim 8 including the process of exposing the developed photosensitive resin composition to the whole surface after the said image development process and before the said post-baking process.
- 請求項8または9に記載の方法により形成された硬化膜。 A cured film formed by the method according to claim 8.
- 層間絶縁膜である、請求項10に記載の硬化膜。 The cured film of Claim 10 which is an interlayer insulation film.
- 請求項10または11に記載の硬化膜を有する有機EL表示装置または液晶表示装置。 An organic EL display device or a liquid crystal display device having the cured film according to claim 10 or 11.
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JP2017134355A (en) * | 2016-01-29 | 2017-08-03 | 富士フイルム株式会社 | Photosensitive resin composition, cured film, liquid crystal display device, organic electroluminescence display device and production method of cured film |
JP2017134246A (en) * | 2016-01-28 | 2017-08-03 | 富士フイルム株式会社 | Photosensitive resin composition, production method of cured film, cured film, touch panel, and display device |
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JP2002023374A (en) * | 2000-07-07 | 2002-01-23 | Fuji Photo Film Co Ltd | Positive type photoresist composition |
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