WO2022065337A1 - Resin composition, cured product, laminate, cured product production method, and semiconductor device - Google Patents
Resin composition, cured product, laminate, cured product production method, and semiconductor device Download PDFInfo
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- WO2022065337A1 WO2022065337A1 PCT/JP2021/034704 JP2021034704W WO2022065337A1 WO 2022065337 A1 WO2022065337 A1 WO 2022065337A1 JP 2021034704 W JP2021034704 W JP 2021034704W WO 2022065337 A1 WO2022065337 A1 WO 2022065337A1
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
- C08K5/3417—Five-membered rings condensed with carbocyclic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
Definitions
- the present invention relates to a resin composition, a cured product, a laminate, a method for producing a cured product, and a semiconductor device.
- Cyclic resin such as polyimide is applied to various applications because it has excellent heat resistance and insulating properties.
- the application is not particularly limited, and examples thereof include a semiconductor device for mounting as a material for an insulating film or a sealing material, or a protective film. It is also used as a base film and coverlay for flexible substrates.
- the cyclized resin such as polyimide is used in the form of a resin composition containing a precursor of a cyclized resin such as a polyimide precursor.
- a resin composition is applied to a substrate by coating, for example, to form a photosensitive film, and then exposed, developed, heated, etc., if necessary, to form a cured product on the substrate.
- the precursor of the cyclized resin such as the polyimide precursor is cyclized by heating, for example, and becomes a cyclized resin such as polyimide in the cured product.
- the resin composition can be applied by a known coating method or the like, for example, there is a high degree of freedom in designing the shape, size, application position, etc. of the applied resin composition at the time of application. It can be said that it is excellent in sex.
- the above-mentioned resin compositions are expected to be increasingly applied in industry from the viewpoint of excellent manufacturing adaptability.
- Patent Document 1 describes (A) a polyamide having a specific structural unit in a photosensitive resin composition containing a polyamide and an isocyanuric acid derivative having a photopolymerizable unsaturated bond as an essential component.
- (B) The isocyanuric acid derivative having a photopolymerizable unsaturated bond is a specific isocyanuric acid derivative, and (A) the content of (B) is 15 to 70 parts by mass with respect to 100 parts by mass.
- Patent Document 2 describes a monomer having a Diels-Alder reaction site and at least one acryloyl group, which can be polymerized by the acryloyl group.
- a cured product made of a resin composition it is required to improve the film strength (for example, breaking elongation) of the obtained cured product.
- the present invention relates to a resin composition having excellent film strength of the obtained cured product, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for producing the cured product, and the cured product or the cured product. It is an object of the present invention to provide a semiconductor device including the above-mentioned laminate.
- ⁇ 1> It has a plurality of polymerizable groups bonded via a linking group containing at least one structure selected from the group consisting of a cyclohexene structure and an acetal structure, and has a molecular weight of less than 1000.
- ⁇ 2> The resin composition according to ⁇ 1>, wherein the polymerizable group in the compound A is a group having an ethylenically unsaturated bond.
- ⁇ 3> The link according to any one of ⁇ 1> or ⁇ 2>, wherein the linking group in the compound A contains a plurality of at least one structures selected from the group consisting of a cyclohexene structure and an acetal structure.
- Resin composition. ⁇ 4> The resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein the linking group in the compound A contains a plurality of cyclohexene structures or a plurality of acetal structures.
- ⁇ 5> The resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein the compound A contains a compound represented by the following formula (2-1).
- R 1 , R 2 and R 3 each independently represent a monovalent organic group, and at least one of R 1 , R 2 and R 3 contains a group having a polymerizable group. .. ⁇ 6>
- R 4 independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and * is an oxygen atom contained in the formula (2-1).
- R 1 and R 2 each independently represent a monovalent organic group, and at least one of R 1 and R 2 contains a group having an ethylenically unsaturated bond.
- R 3 and R 4 each independently represent a monovalent organic group containing a group having an ethylenically unsaturated bond, and L represents a divalent linking group.
- ⁇ 15> The resin composition according to any one of ⁇ 1> to ⁇ 14>, which is used for forming an interlayer insulating film for a rewiring layer.
- ⁇ 16> A cured product obtained by curing the resin composition according to any one of ⁇ 1> to ⁇ 15>.
- ⁇ 17> A laminated body containing two or more layers made of the cured product according to ⁇ 16> and containing a metal layer between any of the cured products.
- ⁇ 18> A method for producing a cured product, which comprises a film forming step of applying the resin composition according to any one of ⁇ 1> to ⁇ 15> onto a substrate to form a film.
- ⁇ 19> The method for producing a cured product according to ⁇ 18>, which comprises an exposure step of selectively exposing the film and a developing step of developing the film with a developer to form a pattern.
- a semiconductor device comprising the cured product according to ⁇ 16> or the laminate according to ⁇ 17>.
- a resin composition having excellent film strength of the obtained cured product, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for producing the cured product, and the curing A semiconductor device including an object or the above-mentioned laminate is provided.
- the present invention is not limited to the specified embodiments.
- the numerical range represented by the symbol "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.
- the term "process” means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended action of the process can be achieved.
- the notation not describing substitution and non-substitution also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group).
- 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).
- exposure includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of the light used for exposure include emission line spectra of mercury lamps, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
- (meth) acrylate means both “acrylate” and “methacrylate”, or either
- (meth) acrylic means both “acrylic” and “methacrylic", or.
- Any, and “(meth) acryloyl” means both “acryloyl” and “methacrylic”, or either.
- Me in the structural formula represents a methyl group
- Et represents an ethyl group
- Bu represents a butyl group
- Ph represents a phenyl group.
- the total solid content means the total mass of all the components of the composition excluding the solvent.
- the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured by gel permeation chromatography (GPC) method and are defined as polystyrene-equivalent values unless otherwise specified.
- GPC gel permeation chromatography
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) for example, HLC-8220GPC (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. It can be obtained by connecting and using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) in series.
- the molecular weights shall be measured using THF (tetrahydrofuran) as an eluent.
- NMP N-methyl-2-pyrrolidone
- the detection in the GPC measurement shall be performed by using a detector having a wavelength of 254 nm of UV rays (ultraviolet rays).
- UV rays ultraviolet rays
- a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer and the other layer need not be in contact with each other.
- the direction in which the layers are stacked on the base material is referred to as "upper", or if there is a resin composition layer, the direction from the base material to the resin composition layer is referred to as "upper”. And the opposite direction is called "down". It should be noted that such a vertical setting is for convenience in the present specification, and in an actual embodiment, the "up" direction in the present specification may be different from the vertical upward direction.
- the composition may contain, as each component contained in the composition, two or more compounds corresponding to the component.
- the content of each component in the composition means the total content of all the compounds corresponding to the component.
- the temperature is 23 ° C.
- the atmospheric pressure is 101,325 Pa (1 atm)
- the relative humidity is 50% RH.
- a combination of preferred embodiments is a more preferred embodiment.
- the resin composition of the present invention has a plurality of polymerizable groups bonded via a linking group containing at least one structure selected from the group consisting of a cyclohexene structure and an acetal structure, and has a molecular weight.
- a linking group containing at least one structure selected from the group consisting of a cyclohexene structure and an acetal structure, and has a molecular weight.
- compound A hereinafter, also simply referred to as “compound A” having a value of less than 1000
- a precursor of a cyclization resin hereinafter, also referred to as “specific resin”.
- the resin composition of the present invention is preferably used for forming a photosensitive film to be subjected to exposure and development, and may be used for exposure and formation of a film to be subjected to development using a developing solution containing an organic solvent. preferable. Further, the resin composition of the present invention is preferably used for forming a photosensitive film to be subjected to negative type development.
- negative-type development refers to development in which a non-exposed portion is removed by development in exposure and development
- positive-type development refers to development in which an exposed portion is removed by development.
- the exposure method, the developer, and the developing method include, for example, the exposure method described in the exposure step in the description of the method for producing a cured product described later, the developer and the developing method described in the developing step. Is used.
- the resin composition of the present invention is excellent in the film strength of the obtained cured product.
- the mechanism by which the above effect is obtained is unknown, but it is presumed as follows.
- cyclization of the cyclized resin precursor and polymerization of the polymerizable compound can be promoted by heating or the like to obtain a cured product. It is done.
- the present inventors have made that the higher the density of the crosslinked structure formed by the above polymerization in the cured product, the lower the cyclization rate of the specific resin in the cured product, and the higher the film strength of the cured product. We have found that it may decrease. It is presumed that this is because if the density of the crosslinked structure becomes too high, the structural change in the precursor of the cyclized resin is hindered.
- the resin composition of the present invention has a plurality of polymerizable groups bonded via a linking group containing at least one structure selected from the group consisting of a cyclohexene structure and an acetal structure, and has a molecular weight.
- the inhibition of the structural change in the precursor of the above-mentioned cyclized resin is less likely to occur, and the cyclization rate of the specific resin in the cured product is increased, and as a result, the film strength of the cured product is improved.
- the cyclohexene structure or the acetal structure in the compound A is cleaved at the time of heating, but it is considered that a bond is formed again when the compound A is cooled to room temperature (23 ° C.) after heating, for example. Therefore, it is presumed that the cured product obtained by the resin composition of the present invention has excellent chemical resistance because a cyclized resin having a high cyclization rate is present in the cured product and the density of the crosslinked structure is high. Will be done.
- Patent Documents 1 and 2 do not describe the resin composition containing the compound A and the precursor of the cyclized resin.
- the resin composition of the present invention has a plurality of polymerizable groups bonded via a linking group containing at least one structure selected from the group consisting of a cyclohexene structure and an acetal structure, and has a molecular weight.
- a linking group containing at least one structure selected from the group consisting of a cyclohexene structure and an acetal structure, and has a molecular weight.
- the molecular weight of compound A is less than 1000, preferably 900 or less, and more preferably 800 or less.
- the lower limit of the molecular weight is not particularly limited, but is preferably 200 or more, for example.
- a radically polymerizable group is preferable because it is a group capable of undergoing a cross-linking reaction by the action of heat, radicals and the like.
- Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group and an amino group.
- a group having an ethylenically unsaturated bond is preferable.
- Examples of the group having an ethylenically unsaturated bond include a (meth) acryloxy group, a (meth) acrylamide group, a group in which a vinyl group is directly bonded to an aromatic ring such as a vinylphenyl group, an allyl group, a vinyl group and the like. From the viewpoint of reactivity, a (meth) acryloxy group is preferable.
- Compound A contains a plurality of polymerizable groups.
- Compound A may contain two or more polymerizable groups in total, such as containing one epoxy group and one (meth) acryloxy group, but is a group having an ethylenically unsaturated bond. It is preferable to include a plurality of.
- the number of polymerizable groups in compound A may be 2 or more, preferably 2 to 15, more preferably 2 to 10, further preferably 2 to 4, and 2. Is particularly preferred.
- the molar amount of the polymerizable group contained in 1 g of compound A is preferably 1.0 mmol / g or more, more preferably 1.5 mmol / g or more, and more preferably 2.0 mmol / g or more. More preferred.
- the upper limit of the molar amount is not particularly limited, but is preferably 8.0 mmol / g or less.
- Compound A has a cyclohexene structure and a plurality of polymerizable groups bonded via a linking group containing at least one structure selected from the group consisting of an acetal structure. That is, in compound A, the plurality of polymerizable groups are bonded via a linking group containing at least one structure selected from the group consisting of a cyclohexene structure and an acetal structure.
- the linking group preferably contains a plurality of at least one structure selected from the group consisting of a cyclohexene structure and an acetal structure, and may contain a plurality of cyclohexene structures or a plurality of acetal structures. More preferred.
- the number of at least one structure selected from the group consisting of the cyclohexene structure and the acetal structure in the linking group is preferably 1 to 10, more preferably 1 to 4, and 1 to 3. Further preferred, 2 is particularly preferred.
- the linking group includes at least one structure selected from the group consisting of the cyclohexene structure and the acetal structure described above, a hydrocarbon group which may be substituted, a (poly) alkyleneoxy group, -O-,-. It is preferably a group formed by a combination with at least one group selected from the group consisting of S-, -SO 2- , -CO- and -NHCO-.
- Examples of the above-mentioned hydrocarbon group include a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof, and a saturated aliphatic hydrocarbon group and an aromatic group. Group hydrocarbon groups or groups represented by combinations thereof are more preferable.
- examples of the substituent in the above hydrocarbon group include a halogen atom such as a fluorine atom.
- examples of the alkylene group in the (poly) alkyleneoxy group include an ethylene group, a propylene group, a trimethylene group, a butylene group and the like, and an ethylene group or a propylene group is preferable.
- the linking group may be a divalent or higher valent linking group, but is preferably a divalent to hexavalent linking group, more preferably a divalent to tetravalent linking group, and a divalent linking group. More preferred.
- the acetal structure or cyclohexene structure in the linking group is preferably a structure that is cleaved at 120 ° C to 230 ° C, and more preferably a structure that is cleaved at 130 ° C to 200 ° C.
- the compound A preferably contains a compound represented by the following formula (2-1).
- R 1 , R 2 and R 3 each independently represent a monovalent organic group, and at least one of R 1 , R 2 and R 3 contains a group having a polymerizable group. ..
- a hydrocarbon group is preferable, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, or an aralkyl group is more preferable, and an alkyl group is particularly preferable.
- an alkyl group an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group is further preferable.
- the aryl group an aryl group having 1 to 20 carbon atoms is preferable, an aryl group having 6 to 20 carbon atoms is more preferable, and a phenyl group is further preferable.
- the aryl group is preferably an aromatic hydrocarbon group.
- an alkenyl group having 2 to 10 carbon atoms is preferable, and an alkenyl group having 2 to 4 carbon atoms is more preferable.
- an alkynyl group an alkynyl group having 2 to 10 carbon atoms is preferable, and an alkynyl group having 2 to 4 carbon atoms is more preferable.
- the preferred embodiments of the alkyl group moiety and the aryl group moiety in the aralkyl group are the same as the preferred embodiments of the alkyl group and the aryl group described above.
- R 2 and R 3 are preferably groups having a polymerizable group independently.
- R 2 or R 3 is preferably a group represented by the following formula (P-1).
- L 1 represents an n + 1 valent linking group
- P 1 represents a polymerizable group
- n represents an integer of 1 or more
- * represents an oxygen atom in the formula (2-1). Represents the binding site of.
- examples of L 1 include the groups described in the above-mentioned linking group, and the same applies to preferred embodiments.
- n is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, further preferably 1 or 2, and particularly preferably 1.
- R 2 or R 3 is not a group having a polymerizable group, R 2 or R 3 is the same as R 1 in the above formula (2-1), and the preferred embodiment is also the same.
- R 2 and R 3 are independent groups having a partial structure represented by either the following formula (2-2) or the following formula (2-3), and R 2 and R 3 are preferable. It is more preferable that one of R3 is a group having a partial structure represented by the formula (2-2) and the other is a group having a partial structure represented by the formula ( 2-3 ).
- R 4 independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and * is an oxygen atom contained in the formula (2-1). Represents a binding site with, and L represents a divalent linking group.
- R4 is preferably a hydrogen atom or a methyl group.
- L the group described in the above-mentioned linking group can be mentioned, and the preferred embodiment is also the same.
- the compound represented by the formula (2-1) is preferably a compound represented by the following formula (2-4).
- R 4 independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
- L represents a divalent linking group.
- R4 is preferably a hydrogen atom or a methyl group.
- L the group described in the above-mentioned linking group can be mentioned, and an alkylene group, an alkyleneoxy group, or a group based on a combination thereof is more preferable.
- the alkylene group an alkylene group having 2 to 10 carbon atoms is preferable.
- alkyleneoxy group an ethyleneoxy group is preferable.
- the linking group in compound A contains a cyclohexene structure
- the linking group in compound A preferably contains a cyclohexene structure having a crosslinked ring structure or a fused ring structure.
- the cyclohexene structure having a crosslinked ring structure or a condensed ring structure is not particularly limited, and examples thereof include the following structures. In the following structures, * represents a binding site with another structure.
- compound A preferably contains a compound represented by the following formula (3-1).
- R 1 and R 2 each independently represent a monovalent organic group, and at least one of R 1 and R 2 contains a group having an ethylenically unsaturated bond.
- the preferred group in R 1 or R 2 includes the same group as the preferred group in R 2 in the above formula (2-1).
- the compound represented by the formula (3-1) is preferably a compound represented by the following formula (3-2).
- R 3 and R 4 each independently represent a monovalent organic group containing a group having an ethylenically unsaturated bond, and L represents a divalent linking group.
- R 3 and R 4 are preferably groups represented by the above formula (P-1).
- L the group described in the above-mentioned linking group can be mentioned, and an alkylene group, a polyalkyleneoxy group, or a group based on a combination thereof is more preferable.
- the alkylene group an alkylene group having 2 to 10 carbon atoms is preferable.
- the polyalkylene oxy group a polyethylene oxy group is preferable.
- the number of repetitions of the polyalkyleneoxy group is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 4.
- compound A examples include, but are not limited to, the following compounds.
- the content of compound A is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the resin composition of the present invention.
- the lower limit is more preferably 5% by mass or more.
- the upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.
- the resin composition of the present invention contains a precursor (specific resin) of a cyclized resin.
- the cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in the main chain structure.
- the main chain represents a relatively longest binding chain among resin molecules.
- the cyclization resin include polyimide, polybenzoxazole, and polyamideimide.
- the precursor of the cyclized resin refers to a resin that changes its chemical structure due to an external stimulus and becomes a cyclized resin, and a resin that changes its chemical structure due to heat and becomes a cyclized resin is preferable, and a ring closure reaction occurs due to heat.
- a resin that becomes a cyclization resin by forming a ring structure is more preferable.
- the precursor of the cyclization resin include a polyimide precursor, a polybenzoxazole precursor, a polyamide-imide precursor and the like. That is, the resin composition of the present invention is at least one selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor as the specific resin. It is preferable to contain a resin (specific resin).
- the resin composition of the present invention preferably contains polyimide or a polyimide precursor as the specific resin, and more preferably contains a polyimide precursor.
- the specific resin preferably has a polymerizable group, and more preferably contains a radically polymerizable group.
- the resin composition of the present invention preferably contains a radical polymerization initiator described later, contains a radical polymerization initiator described below, and contains a radical cross-linking agent described below. Is more preferable.
- a sensitizer described later can be included. From such a resin composition of the present invention, for example, a negative photosensitive film is formed.
- the specific resin may have a polar conversion group such as an acid-degradable group.
- the resin composition of the present invention preferably contains a photoacid generator described later. From such a resin composition of the present invention, for example, a chemically amplified positive type photosensitive film or a negative type photosensitive film is formed.
- the specific resin preferably contains a group capable of covalently bonding by reacting with the polymerizable group contained in the compound A.
- the compound A contains a group having an ethylenically unsaturated bond
- the specific resin also contains a group having an ethylenically unsaturated bond.
- the compound A contains an epoxy group
- the specific resin also contains an epoxy group. According to the above aspect, it is considered that a crosslink is formed between the compound A and the specific resin, and the chemical resistance of the obtained cured product is further improved.
- the polyimide precursor used in the present invention is not particularly specified, such as its type, but preferably contains a repeating unit represented by the following formula (2).
- a 1 and A 2 independently represent an oxygen atom or -NH-
- R 111 represents a divalent organic group
- R 115 represents a tetravalent organic group
- R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group.
- a 1 and A 2 in the formula (2) independently represent an oxygen atom or —NH—, and an oxygen atom is preferable.
- R 111 in the formula (2) represents a divalent organic group.
- the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group and a group containing an aromatic group, and a linear or branched aliphatic group having 2 to 20 carbon atoms and a carbon number of carbon atoms are exemplified.
- a cyclic aliphatic group having 3 to 20, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable.
- the hydrocarbon group in the chain may be substituted with a group containing a hetero atom, and in the cyclic aliphatic group and the aromatic group, the hydrocarbon group of the ring member is a hetero atom. It may be substituted with a group containing.
- Preferred embodiments of the present invention are exemplified by groups represented by -Ar- and -Ar-L-Ar-, and particularly preferably groups represented by -Ar-L-Ar-.
- Ar is an aromatic group independently
- L is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-,. -S-, -SO 2- or -NHCO-, or a group consisting of a combination of two or more of the above.
- R 111 is preferably derived from diamine.
- the diamine used for producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one kind of diamine may be used, or two or more kinds of diamines may be used. Specifically, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof. It is preferably a diamine containing, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms.
- the hydrocarbon group in the chain may be substituted with a group containing a hetero atom, and in the cyclic aliphatic group and the aromatic group, the hydrocarbon group of the ring member is a hetero atom. It may be substituted with a containing group.
- groups containing aromatic groups include:
- O)-, -S-, -SO 2- , -NHCO-, or a group selected from a combination thereof is preferable, and a single bond or a group having 1 to 3 carbon atoms which may be substituted with a fluorine atom may be used.
- * represents a binding site with another structure.
- diamine examples include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1 , 3-Diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-,1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4-) Aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- Or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl;
- diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/038598 are also preferable.
- a diamine having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017/038598 is also preferably used.
- R 111 is preferably represented by ⁇ Ar—L—Ar— from the viewpoint of the flexibility of the obtained organic film.
- Ar is an aromatic group independently
- L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—. , -SO 2- or -NHCO-, or a group consisting of a combination of two or more of the above.
- Ar is preferably a phenylene group
- L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S— or —SO2- . ..
- the aliphatic hydrocarbon group here is preferably an alkylene group.
- R 111 is preferably a divalent organic group represented by the following formula (51) or formula (61).
- a divalent organic group represented by the formula (61) is more preferable.
- Equation (51) In formula (51), R 50 to R 57 are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and at least one of R 50 to R 57 is a fluorine atom, a methyl group or trifluoro. It is a methyl group, and each of * independently represents a bonding site with a nitrogen atom in the formula (2).
- the monovalent organic group of R 50 to R 57 includes an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples thereof include an alkyl fluoride group.
- R 58 and R 59 are each independently a fluorine atom, a methyl group, or a trifluoromethyl group, and * is an independent binding site with a nitrogen atom in formula (2). show.
- Examples of the diamine giving the structure of the formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, and 2,2'-bis. (Fluoro) -4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl and the like can be mentioned. These may be used alone or in combination of two or more.
- R 115 in the formula (2) represents a tetravalent organic group.
- a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable.
- * independently represents a binding site with another structure.
- R 112 is a single bond or divalent linking group, which may be replaced with a single bond or a fluorine atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, —O—, It is preferably a group selected from -CO-, -S-, -SO 2- , and -NHCO-, and a combination thereof, and is a single bond, which may be substituted with a fluorine atom and has 1 to 1 carbon atoms.
- it is a group selected from 3 alkylene groups, -O-, -CO-, -S- and -SO 2- , and -CH 2- , -C (CF 3 ) 2- , -C ( CH 3 ) It is more preferably a divalent group selected from the group consisting of 2-, -O-, -CO-, -S- and -SO 2- .
- R 115 include tetracarboxylic acid residues remaining after removal of the anhydride group from the tetracarboxylic dianhydride.
- the polyimide precursor may contain only one type of tetracarboxylic dianhydride residue or two or more types as a structure corresponding to R 115 .
- the tetracarboxylic dianhydride is preferably represented by the following formula (O).
- R 115 represents a tetravalent organic group.
- the preferred range of R 115 is synonymous with R 115 in the formula (2), and the preferred range is also the same.
- tetracarboxylic acid dianhydride examples include pyromellitic acid dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-.
- PMDA pyromellitic acid dianhydride
- 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride 3,3', 4,4'-.
- tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598 are also mentioned as preferable examples.
- R 111 and R 115 has an OH group. More specifically, as R 111 , a residue of a bisaminophenol derivative can be mentioned.
- R 113 and R 114 in the formula (2) independently represent a hydrogen atom or a monovalent organic group, respectively.
- the monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group.
- at least one of R 113 and R 114 contains a polymerizable group, and it is more preferable that both contain a polymerizable group.
- at least one of R 113 and R 114 contains two or more polymerizable groups.
- the polymerizable group a radically polymerizable group is preferable because it is a group capable of undergoing a cross-linking reaction by the action of heat, radicals and the like.
- the polymerizable group examples include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group and an amino group. Be done.
- a group having an ethylenically unsaturated bond is preferable.
- Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group), and a (meth) acrylamide group.
- R200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and a hydrogen atom or a methyl group is preferable.
- * represents a binding site with another structure.
- R 201 represents an alkylene group having 2 to 12 carbon atoms, —CH 2 CH (OH) CH 2- , a cycloalkylene group or a polyalkyleneoxy group.
- R 201 examples include alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group and dodecamethylene group, 1,2-butanjiyl group, 1, 3-Butanjiyl group, -CH 2 CH (OH) CH 2- , polyalkyleneoxy group, alkylene group such as ethylene group, propylene group, -CH 2 CH (OH) CH 2- , cyclohexyl group, polyalkylene An oxy group is more preferable, and an alkylene group such as an ethylene group and a propylene group, or a polyalkylene oxy group is further preferable.
- alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group and dodecamethylene group, 1,2-butanjiyl group, 1, 3-Butanjiyl group,
- the polyalkyleneoxy group refers to a group to which two or more alkyleneoxy groups are directly bonded.
- the alkylene group in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
- the sequence of the alkyleneoxy groups in the polyalkyleneoxy group may be a random sequence or a sequence having a block. It may be an array having a pattern such as alternating.
- the carbon number of the alkylene group (including the carbon number of the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, and 2 to 6.
- the alkylene group may have a substituent.
- Preferred substituents include alkyl groups, aryl groups, halogen atoms and the like.
- the number of alkyleneoxy groups contained in the polyalkyleneoxy group is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.
- the polyalkyleneoxy group includes a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethylethyleneoxy group, a polytetramethyleneoxy group, or a plurality of ethyleneoxy groups and a plurality of propylenes from the viewpoint of solvent solubility and solvent resistance.
- a group bonded to an oxy group is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is further preferable.
- the ethyleneoxy groups and the propyleneoxy groups may be randomly arranged or may be arranged by forming a block. , Alternate or the like may be arranged in a pattern. The preferred embodiment of the number of repetitions of the ethyleneoxy group and the like in these groups is as described above.
- R 113 is a hydrogen atom or R 114 is a hydrogen atom
- R 113 is a hydrogen atom
- R 114 is a hydrogen atom
- the polyimide precursor forms a salt with a tertiary amine compound having an ethylenically unsaturated bond.
- the tertiary amine compound having such an ethylenically unsaturated bond include N, N-dimethylaminopropyl methacrylate.
- R 113 and R 114 may be a polar converting group such as an acid-degradable group.
- the acid-degradable group is not particularly limited as long as it decomposes by the action of an acid to produce an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but is not particularly limited, but is an acetal group, a ketal group, a silyl group, or a silyl ether group.
- a tertiary alkyl ester group or the like is preferable, and an acetal group or a ketal group is more preferable from the viewpoint of exposure sensitivity.
- the acid-degradable group examples include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group and tert-butoxycarbonylmethyl.
- examples include a group, a trimethylsilyl ether group and the like. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferable.
- the polyimide precursor has a fluorine atom in its structure.
- the fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.
- the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure.
- the diamine an embodiment using bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, or the like can be mentioned.
- the repeating unit represented by the formula (2) is preferably the repeating unit represented by the formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having a repeating unit represented by the formula (2-A). By including the repeating unit represented by the formula (2-A) in the polyimide precursor, it becomes possible to further widen the width of the exposure latitude. Equation (2-A) In formula (2-A), A 1 and A 2 represent oxygen atoms, R 111 and R 112 each independently represent a divalent organic group, and R 113 and R 114 each independently. Representing a hydrogen atom or a monovalent organic group, at least one of R 113 and R 114 is a group containing a polymerizable group, and it is preferable that both are groups containing a polymerizable group.
- a 1 , A 2 , R 111 , R 113 , and R 114 are independently synonymous with A 1 , A 2 , R 111 , R 113 , and R 114 in the formula (2), and the preferred ranges are also the same. .. R 112 has the same meaning as R 112 in the formula (5), and the preferred range is also the same.
- the polyimide precursor may contain one kind of repeating unit represented by the formula (2), but may contain two or more kinds. Further, it may contain a structural isomer of a repeating unit represented by the formula (2). Needless to say, the polyimide precursor may contain other types of repeating units in addition to the repeating units of the above formula (2).
- the content of the repeating unit represented by the formula (2) is 50 mol% or more of all the repeating units.
- the total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%.
- the upper limit of the total content is not particularly limited, and all the repeating units in the polyimide precursor except the terminal may be the repeating unit represented by the formula (2).
- the weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000.
- the number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.
- the degree of dispersion of the molecular weight of the polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and further preferably 2.0 or more.
- the upper limit of the dispersity of the molecular weight of the polyimide precursor is not particularly determined, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, still more preferably 6.0 or less.
- the degree of molecular weight dispersion is a value calculated by weight average molecular weight / number average molecular weight.
- the resin composition contains a plurality of types of polyimide precursors as the specific resin, it is preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion of at least one type of polyimide precursor are in the above range. Further, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by using the plurality of types of polyimide precursors as one resin are within the above ranges.
- the polybenzoxazole precursor used in the present invention is not particularly defined for its structure and the like, but preferably contains a repeating unit represented by the following formula (3).
- R 121 represents a divalent organic group
- R 122 represents a tetravalent organic group
- R 123 and R 124 each independently represent a hydrogen atom or a monovalent organic group. show.
- R 123 and R 124 are synonymous with R 113 in the formula (2), respectively, and the preferable range is also the same. That is, at least one is preferably a polymerizable group.
- R 121 represents a divalent organic group.
- the divalent organic group a group containing at least one of an aliphatic group and an aromatic group is preferable.
- the aliphatic group a linear aliphatic group is preferable.
- R 121 is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.
- a dicarboxylic acid residue a dicarboxylic acid containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferable, and a dicarboxylic acid residue containing an aromatic group is more preferable.
- a dicarboxylic acid containing an aliphatic group a dicarboxylic acid containing a linear or branched (preferably straight chain) aliphatic group is preferable, and a linear or branched (preferably straight chain) aliphatic group and two -COOH are preferable.
- a dicarboxylic acid consisting of is more preferable.
- the number of carbon atoms of the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, still more preferably 3 to 20, and 4 to 20. It is more preferably 15, and particularly preferably 5 to 10.
- the linear aliphatic group is preferably an alkylene group.
- dicarboxylic acid containing a linear aliphatic group examples include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2, 2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-Didimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimeric acid, sverin Acid, dodecafluorosveric acid, azelaic acid, sebacic acid, s
- Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6).
- dicarboxylic acid containing an aromatic group a dicarboxylic acid having the following aromatic groups is preferable, and a dicarboxylic acid consisting of only a group having the following aromatic groups and two -COOH is more preferable.
- A is -CH 2- , -O-, -S-, -SO 2- , -CO-, -NHCO-, -C (CF 3 ) 2- , and -C (CH 3 ) 2- Represents a divalent group selected from the group consisting of, and * represents a binding site with another structure independently.
- dicarboxylic acid containing an aromatic group examples include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.
- R 122 represents a tetravalent organic group.
- the tetravalent organic group has the same meaning as R 115 in the above formula (2), and the preferable range is also the same.
- R 122 is also preferably a group derived from a bisaminophenol derivative, and examples of the group derived from a bisaminophenol derivative include, for example, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'.
- bisaminophenol derivatives having the following aromatic groups are preferable.
- X 1 represents -O-, -S-, -C (CF 3 ) 2- , -CH 2- , -SO 2- , -NHCO-, and * and # represent other structures, respectively.
- R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom or an alkyl group. Further, it is also preferable that R 122 has a structure represented by the above formula.
- any two of the four * and # in total are the bonding sites with the nitrogen atom to which R 122 in the formula (3) is bonded, and The other two are preferably the bonding sites with the oxygen atom to which R 122 in the formula (3) is bonded, and the two * are the bonding sites with the oxygen atom to which the R 122 in the formula (3) is bonded.
- two # are the bonding sites with the nitrogen atom to which R 122 in the formula (3) is bonded, or two * are the bonding sites with the nitrogen atom to which R 122 in the formula (3) is bonded.
- the site is a site and the two #s are the bonding sites with the oxygen atom to which the R 122 in the formula (3) is bonded, and the two * are the oxygen to which the R 122 in the formula (3) is bonded. It is more preferable that it is a bond site with an atom and the two #s are bond sites with a nitrogen atom to which R 122 in the formula (3) is bonded.
- the bisaminophenol derivative is also preferably a compound represented by the formula (As).
- R 1 is a hydrogen atom, an alkylene, a substituted alkylene, -O-, -S-, -SO 2- , -CO-, -NHCO-, a single bond, or the following formula (A-). It is an organic group selected from the group of sc).
- R 2 is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different.
- R 3 is any of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different.
- R3 having a substituent at the ortho position of the phenolic hydroxy group , that is, R3 is considered to bring the distance between the carbonyl carbon of the amide bond and the hydroxy group closer, and at a low temperature. It is particularly preferable in that the effect of increasing the cyclization rate when cured is further enhanced.
- R 2 is an alkyl group and R 3 is an alkyl group has high transparency to i-rays and a high cyclization rate when cured at a low temperature. The effect can be maintained, which is preferable.
- R 1 is an alkylene or a substituted alkylene.
- the alkylene and the substituted alkylene according to R 1 include linear or branched alkyl groups having 1 to 8 carbon atoms, among which -CH 2- and -CH (CH 3 ).
- -, -C (CH 3 ) 2 has sufficient solubility in a solvent while maintaining the effects of high transparency to i-rays and high cyclization rate when cured at low temperature. It is more preferable in that an excellent polybenzoxazole precursor can be obtained.
- the polybenzoxazole precursor may contain other types of repeating units in addition to the repeating units of the above formula (3).
- the polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating unit in that the generation of warpage associated with ring closure can be suppressed.
- Z has an a structure and a b structure
- R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
- R 2s is a hydrocarbon group having 1 to 10 carbon atoms.
- at least one of R 3s , R 4s , R 5s , and R 6s is an aromatic group
- the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different.
- the polymerization of the a structure and the b structure may be block polymerization or random polymerization.
- the mol% of the Z portion is 5 to 95 mol% for the a structure, 95 to 5 mol% for the b structure, and 100 mol% for a + b.
- preferred Z includes those in which R 5s and R 6s in the b structure are phenyl groups.
- the molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000.
- the tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic dianhydride is further contained as the repeating unit.
- the repeating unit Is also preferable.
- examples of such a tetracarboxylic acid residue include the example of R 115 in the formula (2).
- the weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, preferably 18,000 to 30,000, more preferably 20,000 to 29,000, still more preferably 22,000 to 28, It is 000.
- the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.
- the degree of dispersion of the molecular weight of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, still more preferably 1.6 or more.
- the upper limit of the dispersity of the molecular weight of the polybenzoxazole precursor is not particularly determined, but for example, 2.6 or less is preferable, 2.5 or less is more preferable, 2.4 or less is further preferable, and 2.3 or less. Is more preferable, and 2.2 or less is even more preferable.
- the weight average molecular weight, the number average molecular weight, and the dispersity of at least one polybenzoxazole precursor may be within the above ranges. preferable. Further, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by using the plurality of types of polybenzoxazole precursors as one resin are within the above ranges.
- the polyamide-imide precursor preferably contains a repeating unit represented by the following formula (PAI-2).
- PAI-2 R 117 represents a trivalent organic group
- R 111 represents a divalent organic group
- a 2 represents an oxygen atom or -NH-
- R 113 represents a hydrogen atom or monovalent. Represents an organic group of.
- R 117 is composed of a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, a heteroaromatic group, or a single bond or a linking group.
- the above-mentioned linked groups are exemplified, and a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and a cyclic aliphatic group having 6 to 20 carbon atoms are exemplified.
- the aromatic group of the above, or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms by a single bond or a linking group is preferable.
- a group in which two or more of the above are combined is more preferable.
- a group is preferable, and an —O—, —S—, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group in which two or more of these are bonded is more preferable.
- an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is further preferable.
- halogenated alkylene group a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable.
- the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
- the halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with a halogen atom, but it is preferable that all of the hydrogen atoms are substituted with a halogen atom.
- preferred halogenated alkylene groups include (ditrifluoromethyl) methylene groups and the like.
- arylene group a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is further preferable.
- R 117 is derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated. Chlorination is preferable as the halogenation.
- a compound having three carboxy groups is referred to as a tricarboxylic acid compound. Of the three carboxy groups of the tricarboxylic acid compound, two carboxy groups may be acid anhydrideized.
- the halogenated tricarboxylic acid compound used in the production of the polyamide-imide precursor include branched chain aliphatic, cyclic aliphatic or aromatic tricarboxylic acid compounds. Only one kind of these tricarboxylic acid compounds may be used, or two or more kinds may be used.
- the tricarboxylic acid compound includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and a carbon number of carbon atoms.
- a tricarboxylic acid compound containing 6 to 20 aromatic groups or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms or carbon by a single bond or a linking group is preferable.
- a tricarboxylic acid compound containing a group in which two or more aromatic groups of the number 6 to 20 are combined is more preferable.
- the tricarboxylic acid compound examples include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and phthalic acid.
- (Or phthalic acid anhydride) and benzoic acid are single-bonded, -O-, -CH 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -SO 2- or a phenylene group. Examples thereof include linked compounds. These compounds may be compounds in which two carboxy groups are anhydrated (eg, trimellitic acid anhydride), or compounds in which at least one carboxy group is halogenated (eg, trimellitic acid anhydride). There may be.
- R 111 , A 2 , and R 113 are synonymous with R 111 , A 2 , and R 113 in the above formula (2), respectively, and the preferred embodiments are also the same.
- the polyamide-imide precursor may further contain other repeating units.
- the other repeating unit include a repeating unit represented by the above formula (2), a repeating unit represented by the following formula (PAI-1), and the like.
- R 116 represents a divalent organic group and R 111 represents a divalent organic group.
- R 116 is a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, a heteroaromatic group, or a single bond or a linking group.
- the above-mentioned linked groups are exemplified, and a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and a cyclic aliphatic group having 6 to 20 carbon atoms are exemplified.
- the aromatic group of the above, or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms by a single bond or a linking group is preferable.
- a group in which two or more of the above are combined is more preferable.
- a group is preferable, and an —O—, —S—, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group in which two or more of these are bonded is more preferable.
- an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is further preferable.
- halogenated alkylene group a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable.
- the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
- the halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with a halogen atom, but it is preferable that all of the hydrogen atoms are substituted with a halogen atom.
- preferred halogenated alkylene groups include (ditrifluoromethyl) methylene groups and the like.
- arylene group a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is further preferable.
- R 116 is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound.
- a compound having two carboxy groups is referred to as a dicarboxylic acid compound
- a compound having two halogenated carboxy groups is referred to as a dicarboxylic acid dihalide compound.
- the carboxy group in the dicarboxylic acid dihalide compound may be halogenated, but is preferably chlorinated, for example. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.
- Examples of the halogenated dicarboxylic acid compound or dicarboxylic acid dihalide compound used in the production of the polyamideimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compounds or dicarboxylic acids. Examples include aciddihalide compounds. Only one kind or two or more kinds of these dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used.
- the dicarboxylic acid compound or the dicarboxylic acid dihalide compound includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, and a cyclic fat having 3 to 20 carbon atoms.
- a dicarboxylic acid compound or a dicarboxylic acid dihalide compound containing a group group, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms is preferable.
- a dicarboxylic acid compound or a dicarboxylic acid dihalide compound containing a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group is more preferable.
- dicarboxylic acid compound examples include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, and methylsuccinic acid, 2,2-.
- R 111 has the same meaning as R 111 in the above formula (2), and the preferred embodiment is also the same.
- the polyamide-imide precursor has a fluorine atom in its structure.
- the fluorine atom content in the polyamide-imide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.
- the polyamide-imide precursor may be copolymerized with an aliphatic group having a siloxane structure.
- the diamine component an embodiment using bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, or the like can be mentioned.
- a repeating unit represented by the formula (PAI-2), a repeating unit represented by the formula (PAI-1), and a repeating unit represented by the formula (2) As one embodiment of the polyamide-imide precursor in the present invention, a repeating unit represented by the formula (PAI-2), a repeating unit represented by the formula (PAI-1), and a repeating unit represented by the formula (2).
- An embodiment in which the total content of the units is 50 mol% or more of all the repeating units can be mentioned.
- the total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%.
- the upper limit of the total content is not particularly limited, and all the repeating units in the polyamide-imide precursor except the terminal are represented by the repeating unit represented by the formula (PAI-2) and the formula (PAI-1). It may be either a repeating unit or a repeating unit represented by the formula (2).
- the total content of the repeating unit represented by the formula (PAI-2) and the repeating unit represented by the formula (PAI-1) is.
- An embodiment of 50 mol% or more of all repetition units can be mentioned.
- the total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%.
- the upper limit of the total content is not particularly limited, and all the repeating units in the polyamide-imide precursor except the terminal are represented by the repeating unit represented by the formula (PAI-2) or the formula (PAI-1). It may be any of the repeating units to be used.
- the weight average molecular weight (Mw) of the polyamide-imide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, still more preferably 10,000 to 50,000. ..
- the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.
- the degree of dispersion of the molecular weight of the polyamide-imide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more.
- the upper limit of the dispersity of the molecular weight of the polyamide-imide precursor is not particularly determined, but is preferably 7.0 or less, more preferably 6.5 or less, still more preferably 6.0 or less, for example.
- the weight average molecular weight, number average molecular weight, and dispersity of at least one type of polyamide-imide precursors are preferably in the above range. Further, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by using the plurality of types of polyamide-imide precursors as one resin are within the above ranges.
- the polyimide precursor and the like can be, for example, a method of reacting a tetracarboxylic acid dianhydride with a diamine at a low temperature, or reacting a tetracarboxylic acid dianhydride with a diamine at a low temperature to obtain a polyamic acid, and a condensing agent or an alkylating agent.
- the remaining dicarboxylic acid can be obtained by acid-halogenizing it with a halogenating agent and reacting it with a diamine.
- a method in which a diester is obtained from tetracarboxylic acid dianhydride and an alcohol, and then the remaining dicarboxylic acid is acid-halogenated with a halogenating agent and reacted with a diamine is more preferable.
- Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, Examples thereof include N'-disuccinimidyl carbonate and trifluoroacetic anhydride.
- Examples of the alkylating agent include N, N-dimethylformamide dimethylacetal, N, N-dimethylformamide diethylacetal, N, N-dialkylformamidedialkylacetal, trimethyl orthoformate, triethyl orthoformate and the like.
- halogenating agent examples include thionyl chloride, oxalyl chloride, phosphorus oxychloride and the like.
- an organic solvent in the reaction.
- the organic solvent may be one kind or two or more kinds.
- the organic solvent can be appropriately determined depending on the raw material, but is pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, ⁇ -butyrolactone and the like. Is exemplified.
- the basic compound may be one kind or two or more kinds.
- the basic compound can be appropriately determined depending on the raw material, but triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, N, N-dimethyl-4-amino. Examples thereof include pyridine and the like.
- -End sealant- In the method of producing a polyimide precursor or the like, it is preferable to seal the carboxylic acid anhydride, the acid anhydride derivative, or the amino group remaining at the resin terminal of the polyimide precursor or the like in order to further improve the storage stability.
- examples of the terminal encapsulant include monoalcohol, phenol, thiol, thiophenol, monoamine, etc., and are reactive and stable in the film. From the viewpoint of properties, it is more preferable to use monoalcohol, phenols and monoamines.
- Preferred compounds of monoalcohols include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol and flufuryl alcohol, and isopropanol.
- Preferred compounds of phenols include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol and hydroxystyrene.
- Preferred compounds of monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene and 1-hydroxy-6-.
- Aminonaphthalene 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1- Carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-amino Naphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4 -Aminobenzene sulfonic acid, 3-amino-4,6-di
- encapsulants for amino groups are carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, anhydrous sulfonic acids, sulfonic acid carboxylic acid anhydrides and the like, with carboxylic acid anhydrides and carboxylic acid chlorides being more preferred. preferable.
- Preferred compounds for carboxylic acid anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic acid anhydride, 5-norbornen-2,3-dicarboxylic acid anhydride and the like.
- Preferred compounds for the carboxylic acid chloride include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylate chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantancarbonyl chloride. , Heptafluorobutyryl chloride, stearate chloride, benzoyl chloride, and the like.
- a step of precipitating a solid may be included in the production of a polyimide precursor or the like. Specifically, the water-absorbing by-product of the dehydration condensing agent coexisting in the reaction solution was filtered off as necessary, and then obtained in a poor solvent such as water, an aliphatic lower alcohol, or a mixed solution thereof. By adding the polymer component and precipitating the polymer component, it is precipitated as a solid, and by drying, a polyimide precursor or the like can be obtained. In order to improve the degree of purification, operations such as redissolution, reprecipitation and drying of the polyimide precursor may be repeated. Further, a step of removing ionic impurities using an ion exchange resin may be included.
- the content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and more preferably 40% by mass or more, based on the total solid content of the resin composition. More preferably, it is more preferably 50% by mass or more. Further, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, and 98% by mass, based on the total solid content of the resin composition. % Or less, more preferably 97% by mass or less, and even more preferably 95% by mass or less.
- the resin composition of the present invention may contain only one type of specific resin, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.
- the resin composition of the present invention contains at least two kinds of resins.
- the resin composition of the present invention may contain two or more kinds of the specific resin and another resin described later in total, or may contain two or more kinds of the specific resin, but the specific resin may be contained. It is preferable to include two or more kinds.
- the resin composition of the present invention contains two or more kinds of specific resins, for example, two or more kinds of polyimides which are polyimide precursors and have different structures derived from dianhydride (R 115 in the above formula (2)). It is preferable to include a precursor.
- the resin composition of the present invention may contain the above-mentioned specific resin and another resin different from the specific resin (hereinafter, also simply referred to as “other resin”).
- Other resins include phenolic resin, polyamide, epoxy resin, polysiloxane, resin containing siloxane structure, (meth) acrylic resin, (meth) acrylamide resin, urethane resin, butyral resin, styryl resin, polyether resin, polyester resin. And so on.
- a (meth) acrylic resin a resin composition having excellent coatability can be obtained, and a pattern (cured product) having excellent solvent resistance can be obtained.
- a high polymerizable base value having a weight average molecular weight of 20,000 or less for example, the molar amount of the polymerizable group contained in 1 g of the resin. (1 ⁇ 10 -3 mol / g or more)
- a (meth) acrylic resin By adding a (meth) acrylic resin to the resin composition, the coatability of the resin composition, the solvent resistance of the pattern (cured product), etc. can be improved. can.
- the content of the other resin is preferably 0.01% by mass or more, preferably 0.05% by mass or more, based on the total solid content of the resin composition. It is more preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 5% by mass or more, and further preferably 10% by mass or more. More preferred. Further, the content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, and more preferably 70% by mass, based on the total solid content of the resin composition. It is more preferably 0% by mass or less, further preferably 60% by mass or less, and even more preferably 50% by mass or less.
- the content of the other resin may be low.
- the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and 10% by mass or less, based on the total solid content of the resin composition. Is more preferable, 5% by mass or less is further preferable, and 1% by mass or less is even more preferable.
- the lower limit of the content is not particularly limited, and may be 0% by mass or more.
- the resin composition of the present invention may contain only one kind of other resin, or may contain two or more kinds of other resins. When two or more kinds are contained, it is preferable that the total amount is within the above range.
- the resin composition of the present invention preferably contains a polymerizable compound.
- the polymerizable compound include radical cross-linking agents and other cross-linking agents.
- the resin composition of the present invention preferably contains a radical cross-linking agent.
- the radical cross-linking agent is a compound having a radically polymerizable group.
- a group containing an ethylenically unsaturated bond is preferable.
- Examples of the group containing an ethylenically unsaturated bond include a group having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, a (meth) acryloyl group, a maleimide group, and a (meth) acrylamide group.
- a (meth) acryloyl group As the group containing an ethylenically unsaturated bond, a (meth) acryloyl group, a (meth) acrylamide group and a vinylphenyl group are preferable, and from the viewpoint of reactivity, a (meth) acryloyl group is more preferable.
- the radical cross-linking agent is preferably a compound having one or more ethylenically unsaturated bonds, but more preferably a compound having two or more ethylenically unsaturated bonds.
- the radical cross-linking agent may have three or more ethylenically unsaturated bonds.
- As the compound having two or more ethylenically unsaturated bonds a compound having 2 to 15 ethylenically unsaturated bonds is preferable, and a compound having 2 to 10 ethylenically unsaturated bonds is more preferable, and 2 to 6 compounds are more preferable.
- the compound having is more preferable.
- the resin composition of the present invention comprises a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. It is also preferable to include.
- the molecular weight of the radical cross-linking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less.
- the lower limit of the molecular weight of the radical cross-linking agent is preferably 100 or more.
- radical cross-linking agent examples include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides, and are preferable.
- an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a sulfanyl group with a monofunctional or polyfunctional isocyanate group or an epoxy group, or a monofunctional or polyfunctional group.
- a dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
- an addition reaction product of an unsaturated carboxylic acid ester or amide having a polyelectron substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines and thiols, and a halogeno group.
- Substitution reaction products of unsaturated carboxylic acid esters or amides having a desorbing substituent such as tosyloxy group and monofunctional or polyfunctional alcohols, amines and thiols are also suitable.
- radical cross-linking agent a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable.
- examples are polyethylene glycol di (meth) acrylate, trimethyl ethanetri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol.
- Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with acrylic acid, and mixtures thereof.
- the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable.
- a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a cyclic ether group such as glycidyl (meth) acrylate and a compound having an ethylenically unsaturated bond can also be mentioned.
- a preferable radical cross-linking agent other than the above it has a fluorene ring and has an ethylenically unsaturated bond, which is described in JP-A-2010-160418, JP-A-2010-129825, Patent No. 4364216 and the like.
- Compounds having two or more groups and cardo resins can also be used.
- the compound described in JP-A No. 10-062986 together with specific examples as the formulas (1) and (2), which is obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated, is also available. It can be used as a radical cross-linking agent.
- dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nihon Kayaku Co., Ltd.) ), A-TMMT: Shin Nakamura Chemical Industry Co., Ltd.), Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; Nippon Kayaku Co., Ltd.), Dipentaerythritol hexa (meth) ) Acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and these (meth) acryloyl groups are mediated by ethylene glycol residues or propylene glycol residues. A structure that is bonded together is preferable.
- SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer
- SR-209 manufactured by Sartmer which is a bifunctional methacrylate having four ethyleneoxy chains.
- DPCA-60 a hexafunctional acrylate having 6 pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd.
- TPA-330 a trifunctional acrylate having 3 isobutyleneoxy chains
- urethane oligomer UAS-10 are examples of the radical cross-linking agent.
- UAB-140 (manufactured by Nippon Paper Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (Japan) Chemical Industry Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (manufactured by Nichiyu Co., Ltd.), etc. Can be mentioned.
- radical cross-linking agent examples include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Laid-Open No. 02-0322293, and Japanese Patent Laid-Open No. 02-016765.
- Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable.
- radical cross-linking agent compounds having an amino structure or a sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238, are used. You can also do it.
- the radical cross-linking agent may be a radical cross-linking agent having an acid group such as a carboxy group or a phosphoric acid group.
- the radical cross-linking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid group is obtained by reacting an unreacted hydroxy group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride.
- the radical cross-linking agent provided with the above is more preferable.
- the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Is a compound.
- examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
- the acid value of the radical cross-linking agent having an acid group is preferably 0.1 to 300 mgKOH / g, and particularly preferably 1 to 100 mgKOH / g.
- the acid value of the radical cross-linking agent is within the above range, it is excellent in manufacturable handling and further excellent in developability. Moreover, the polymerizability is good.
- the acid value is measured according to the description of JIS K 0070: 1992.
- the resin composition it is preferable to use bifunctional methacrylate or acrylate from the viewpoint of pattern resolution and film elasticity.
- Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate.
- the PEG200 diacrylate is a polyethylene glycol diacrylate having a polyethylene glycol chain formula of about 200.
- a monofunctional radical cross-linking agent can be preferably used as the radical cross-linking agent from the viewpoint of suppressing warpage associated with the control of the elastic modulus of the pattern (cured product).
- Examples of the monofunctional radical cross-linking agent include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, and cyclohexyl (meth). ) Acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc.
- N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allylglycidyl ether and the like are preferably used.
- the monofunctional radical cross-linking agent a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.
- the bifunctional or higher functional radical cross-linking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.
- the content thereof is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the resin composition of the present invention.
- the lower limit is more preferably 5% by mass or more.
- the upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.
- One type of radical cross-linking agent may be used alone, or two or more types may be mixed and used. When two or more types are used in combination, the total amount is preferably within the above range.
- the resin composition of the present invention contains another cross-linking agent different from the above-mentioned radical cross-linking agent.
- the other cross-linking agent refers to a cross-linking agent other than the above-mentioned radical cross-linking agent, and is a reaction of another compound in the composition or a reaction thereof by exposure to the above-mentioned photoacid generator or photobase generator.
- a compound having a plurality of groups in the molecule that promotes a reaction to form a covalent bond with the product is preferable, and a covalent bond is formed with another compound in the composition or a reaction product thereof.
- a compound having a plurality of groups in the molecule in which the reaction to be formed is promoted by the action of an acid or a base is preferable.
- the acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
- a compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group and an alkoxymethyl group is preferable, and the compound is selected from the group consisting of an acyloxymethyl group, a methylol group and an alkoxymethyl group.
- a compound having a structure in which at least one of the above groups is directly bonded to a nitrogen atom is more preferable.
- an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is changed to an acyloxymethyl group, a methylol group, or a methylol group.
- examples thereof include compounds having a structure substituted with an alkoxymethyl group.
- the method for producing these compounds is not particularly limited, and any compound having the same structure as the compound produced by the above method may be used. Further, it may be an oligomer formed by self-condensing the methylol groups of these compounds.
- the cross-linking agent using melamine is a melamine-based cross-linking agent
- the cross-linking agent using glycoluril, urea or alkylene urea is a urea-based cross-linking agent
- the cross-linking agent using alkylene urea is an alkylene urea-based cross-linking agent.
- a cross-linking agent using an agent or benzoguanamine is called a benzoguanamine-based cross-linking agent.
- the resin composition of the present invention preferably contains at least one compound selected from the group consisting of a urea-based cross-linking agent and a melamine-based cross-linking agent, and is preferably a glycoluril-based cross-linking agent and a melamine-based cross-linking agent described later. It is more preferred to include at least one compound selected from the group consisting of agents.
- the alkoxymethyl group or the acyloxymethyl group is directly substituted on the aromatic group or the nitrogen atom having the following urea structure, or on triazine.
- the alkoxymethyl group or acyloxymethyl group contained in the above compound preferably has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms.
- the total number of alkoxymethyl groups and acyloxymethyl groups contained in the above compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.
- the molecular weight of the above compound is preferably 1500 or less, preferably 180 to 1200.
- R 100 represents an alkyl group or an acyl group.
- R 101 and R 102 each independently represent a monovalent organic group and may be bonded to each other to form a ring.
- Examples of the compound in which the alkoxymethyl group or the acyloxymethyl group is directly substituted with the aromatic group include compounds as shown in the following general formula.
- X represents a single-bonded or divalent organic group
- each R 104 independently represents an alkyl group or an acyl group
- R 103 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group.
- R 103 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group.
- R 103 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group.
- R 103 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group.
- R 4 represents a group that decomposes by the action of an acid to produce an alkali-soluble group
- It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
- R5 represents a group desorbed by the action
- R 105 independently represents an alkyl group or an alkenyl group, a, b and c are independently 1 to 3, d is 0 to 4, e is 0 to 3, and f is 0 to 3. A + d is 5 or less, b + e is 4 or less, and c + f is 4 or less.
- R 5 in a group that decomposes by the action of an acid to produce an alkali-soluble group a group that is eliminated by the action of an acid, and a group represented by -C (R 4 ) 2 COOR 5 , for example, -C (R 36 ).
- R 36 to R 39 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
- R 36 and R 37 may be coupled to each other to form a ring.
- an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable.
- the alkyl group may be linear or branched.
- cycloalkyl group a cycloalkyl group having 3 to 12 carbon atoms is preferable, and a cycloalkyl group having 3 to 8 carbon atoms is more preferable.
- the cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a fused ring.
- the aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group.
- aralkyl group an aralkyl group having 7 to 20 carbon atoms is preferable, and an aralkyl group having 7 to 16 carbon atoms is more preferable.
- the above-mentioned aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as those of the above-mentioned preferred embodiments of alkyl and aryl groups.
- the alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms. Further, these groups may further have a known substituent as long as the effect of the present invention can be obtained.
- R 01 and R 02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
- the group that decomposes by the action of an acid to produce an alkali-soluble group, or the group that is desorbed by the action of an acid is preferably a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, or the like. More preferably, it is a tertiary alkyl ester group or an acetal group.
- Examples of the compound having an alkoxymethyl group include the following structures.
- Examples of the compound having an acyloxymethyl group include compounds in which the alkoxymethyl group of the following compound is changed to an acyloxymethyl group.
- Examples of the compound having an alkoxymethyl group or acyloxymethyl in the molecule include, but are not limited to, the following compounds.
- the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group a commercially available compound may be used, or a compound synthesized by a known method may be used. From the viewpoint of heat resistance, a compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring is preferable.
- melamine-based cross-linking agent examples include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine and the like.
- urea-based cross-linking agent examples include monohydroxymethylated glycol uryl, dihydroxymethylated glycol uryl, trihydroxymethylated glycol uryl, tetrahydroxymethylated glycol uryl, monomethoxymethylated glycol uryl, and dimethoxymethylated glycol.
- Uril trimethoxymethylated glycol uryl, tetramethoxymethylated glycol uryl, monoethoxymethylated glycol uryl, diethoxymethylated glycol uryl, triethoxymethylated glycol uryl, tetraethoxymethylated glycol uryl, monopropoxymethylated glycol uryl , Dipropoxymethylated glycol uryl, tripropoxymethylated glycol uryl, tetrapropoxymethylated glycol uryl, monobutoxymethylated glycol uryl, dibutoxymethylated glycol uryl, tributoxymethylated glycol uryl, or tetrabutoxymethylated glycol
- Glycoluril-based cross-linking agents such as uryl; Urea-based cross-linking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea, Monohydroxymethylated ethylene urea or dihydroxymethylated ethylene urea,
- benzoguanamine-based cross-linking agent examples include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, and trimethoxymethylated benzoguanamine.
- Tetramethoxymethylated benzoguanamine Tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetra Examples thereof include propoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine and the like.
- a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group at least one selected from the group consisting of a methylol group and an alkoxymethyl group on an aromatic ring (preferably a benzene ring).
- Compounds to which the group of the species is directly bonded are also preferably used. Specific examples of such compounds include benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, and hydroxymethylbenzoate hydroxymethylphenyl.
- suitable commercially available products include 46DMOC, 46DMOEP (all manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-PC, DML-PEP, DML-OC, and DML-OEP.
- the resin composition of the present invention contains at least one compound selected from the group consisting of an epoxy compound, an oxetane compound, and a benzoxazine compound as another cross-linking agent.
- the epoxy compound is preferably a compound having two or more epoxy groups in one molecule.
- the epoxy group undergoes a cross-linking reaction at 200 ° C. or lower, and the dehydration reaction derived from the cross-linking does not occur, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in suppressing low temperature curing and warpage of the resin composition of the present invention.
- the epoxy compound preferably contains a polyethylene oxide group.
- the polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.
- epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether. , Trimethylol propane Triglycidyl ether and other alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins; Polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; Polymethyl (glycidyloxypropyl) siloxane and other epoxy groups Examples include, but are not limited to, contained silicone.
- n is an integer of 1 to 5
- m is an integer of 1 to 20.
- n is preferably 1 to 2 and m is preferably 3 to 7 from the viewpoint of achieving both heat resistance and improvement in elongation.
- oxetane compound compound having an oxetanyl group
- the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis ⁇ [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene, and the like.
- examples thereof include 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester, and the like.
- Aron Oxetane series (for example, OXT-121, OXT-221) manufactured by Toagosei Co., Ltd. can be preferably used, and these can be used alone or in combination of two or more. good.
- benzoxazine compound examples include Pd-type benzoxazine, Fa-type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), a benzoxazine adduct of a polyhydroxystyrene resin, and a phenol novolac-type dihydrobenzo.
- examples include oxazine compounds. These may be used alone or in combination of two or more.
- the content of the other cross-linking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and 0. It is more preferably 5 to 15% by mass, and particularly preferably 1.0 to 10% by mass.
- the other cross-linking agent may be contained in only one kind, or may be contained in two or more kinds. When two or more other cross-linking agents are contained, the total is preferably in the above range.
- the resin composition of the present invention preferably contains a polymerization initiator that can initiate polymerization by light and / or heat.
- a photopolymerization initiator is preferably a radical polymerization initiator.
- the radical polymerization initiator is not particularly limited and may be appropriately selected from known radical polymerization initiators.
- a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable.
- it may be an active agent that causes some action with a photoexcited sensitizer and generates an active radical.
- the photoradical polymerization initiator contains at least one compound having a molar extinction coefficient of at least about 50 L ⁇ mol -1 ⁇ cm -1 within a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). Is preferable.
- the molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
- a known compound can be arbitrarily used.
- halogenated hydrocarbon derivatives for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
- acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime derivatives and the like.
- paragraphs 0165 to 0182 of JP2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219 can be referred to, and the contents thereof are incorporated in the present specification. Further, paragraphs 0065 to 0111 of JP-A-2014-130173, compounds described in Japanese Patent No.
- ketone compound for example, the compound described in paragraph 0087 of JP-A-2015-087611 is exemplified, and the content thereof is incorporated in the present specification.
- Kayacure-DETX-S manufactured by Nippon Kayaku Co., Ltd.
- Nippon Kayaku Co., Ltd. is also preferably used.
- a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be preferably used as the photoradical polymerization initiator. More specifically, for example, the aminoacetophenone-based initiator described in JP-A No. 10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, and the contents thereof are described in the present specification. Be incorporated.
- Examples of the ⁇ -hydroxyketone initiator include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, and DAROCUR 1173.
- Omnirad 184 Omnirad 1173
- Omnirad 2959 Omnirad 127
- IRGACURE 184 IRGACURE is a registered trademark
- DAROCUR 1173 DAROCUR 1173
- DAROCUR 1173 DAROCUR 1173.
- -2959, IRGACURE 127 (trade name: both manufactured by BASF) can be used.
- Omnirad 907 As the ⁇ -aminoketone-based initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369, and IRGACURE 369, all of which are IRGACURE 37. (Manufactured by the company) can be used.
- the aminoacetophenone-based initiator the compound described in JP-A-2009-191179, in which the maximum absorption wavelength is matched with a wavelength light source such as 365 nm or 405 nm, can also be used, and the contents thereof are incorporated in the present specification.
- acylphosphine oxide-based initiator examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
- Omnirad 819, Omnirad TPO (all manufactured by IGM Resins BV), IRGACURE-819 and IRGACURE-TPO (trade name: all manufactured by BASF) can be used.
- metallocene compound examples include IRGACURE-784, IRGACURE-784EG (all manufactured by BASF), Keycure VIS 813 (manufactured by King Brother Chem), and the like.
- the photoradical polymerization initiator is more preferably an oxime compound.
- the oxime compound By using the oxime compound, it becomes possible to improve the exposure latitude more effectively.
- the oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a photocuring accelerator.
- oxime compound examples include the compound described in JP-A-2001-233842, the compound described in JP-A-2000-080068, the compound described in JP-A-2006-342166, and J. Am. C. S. The compound according to Perkin II (1979, pp. 1653-1660), J. Mol. C. S. The compound described in Perkin II (1979, pp. 156-162), the compound described in Journal of Photopolisr Science and Technology (1995, pp. 202-232), the compound described in JP-A-2000-066385, the compound described in JP-A-2000-066385. Compounds described in JP-A-2004-534797, compounds described in JP-A-2017-109766, compounds described in Japanese Patent No.
- Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminovtan-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxy. Iminopentan-3-one, 2-acetoxyimimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one , And 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one and the like.
- an oxime compound (oxime-based photoradical polymerization initiator) as the photoradical polymerization initiator.
- IRGACURE OXE 01 IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), ADEKA PTOMER N-1919 (manufactured by ADEKA Corporation, JP-A-2012-014052).
- a radical polymerization initiator 2) is also preferably used.
- TR-PBG-304, TR-PBG-305 manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.
- Adeka Arkuru's NCI-730, NCI-831 and Adeka Arkuru's NCI-930 are also used. be able to.
- DFI-091 manufactured by Daito Chemix Co., Ltd.
- SpeedCure PDO manufactured by SARTOMER ARCEMA
- an oxime compound having the following structure can also be used.
- an oxime compound having a fluorene ring can also be used.
- Specific examples of the oxime compound having a fluorene ring include the compound described in JP-A-2014-137466 and the compound described in Japanese Patent No. 06636081, and the contents thereof are incorporated in the present specification.
- an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used.
- Specific examples of such oxime compounds include the compounds described in WO 2013/083505, the contents of which are incorporated herein.
- an oxime compound having a fluorine atom it is also possible to use an oxime compound having a fluorine atom.
- an oxime compound having a fluorine atom include the compounds described in JP-A-2010-262028, the compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013.
- Examples include compound (C-3) described in paragraph 0101 of JP-164471, the contents of which are incorporated herein.
- an oxime compound having a nitro group can be used as the photopolymerization initiator.
- the oxime compound having a nitro group is also preferably a dimer.
- Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP2013-114249A and paragraphs 0008-0012 and 0070-0079 of JP-A-2014-137466. Examples of the compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071 are incorporated herein by reference. Further, examples of the oxime compound having a nitro group include ADEKA ARKULS NCI-831 (manufactured by ADEKA Corporation).
- an oxime compound having a benzofuran skeleton can also be used.
- Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.
- an oxime compound in which a substituent having a hydroxy group is bonded to the carbazole skeleton can also be used.
- Examples of such a photopolymerization initiator include the compounds described in International Publication No. 2019/088055, and the contents thereof are incorporated in the present specification.
- an oxime compound having an aromatic ring group Ar OX1 having an electron-attracting group introduced into the aromatic ring (hereinafter, also referred to as oxime compound OX) can also be used.
- the electron-attracting group of the aromatic ring group Ar OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group and a cyano group.
- the benzoyl group may have a substituent.
- the substituent include a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group and an arylsulfanyl group.
- an acyl group or an amino group more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group or an amino group, and more preferably an alkoxy group or an alkyl group. It is more preferably a sulfanyl group or an amino group.
- the oxime compound OX is preferably at least one selected from the compound represented by the formula (OX1) and the compound represented by the formula (OX2), and more preferably the compound represented by the formula (OX2). preferable.
- RX1 is an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group.
- RX2 contains an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group and an aryl.
- RX3 to RX14 independently represent a hydrogen atom or a substituent. However, at least one of RX10 to RX14 is an electron-withdrawing group.
- RX12 is an electron-withdrawing group and RX10 , RX11 , RX13 and RX14 are hydrogen atoms.
- oxime compound OX examples include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated in the present specification.
- the most preferable oxime compound includes an oxime compound having a specific substituent shown in JP-A-2007-269779 and an oxime compound having a thioaryl group shown in JP-A-2009-191061. Incorporated herein.
- the photoradical polymerization initiator includes a trihalomethyltriazine compound, a benzyldimethylketal compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, and a triaryl.
- a trihalomethyltriazine compound Selected from the group consisting of imidazole dimer, onium salt compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, halomethyloxadiazole compound, 3-aryl substituted coumarin compound.
- Compounds are preferred.
- photoradical polymerization initiators are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds and acetophenone compounds.
- At least one compound selected from the group consisting of a trihalomethyltriazine compound, an ⁇ -aminoketone compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound is more preferable, and a metallocene compound or an oxime compound is further preferable. ..
- the photoradical polymerization initiator is N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone).
- 2-benzyl such as benzophenone
- -2-Dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-aromatic ketones such as morpholino-propanone-1, alkylanthraquinone, etc.
- benzoin ether compounds such as benzoin alkyl ether
- benzoin compounds such as benzoin and alkyl benzoin
- benzyl derivatives such as benzyl dimethyl ketal.
- a compound represented by the following formula (I) can also be used.
- R I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, and the like.
- RI01 is a group represented by the formula (II). It is the same group as RI00 , and RI02 to RI04 are independently alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, or halogen atoms.
- R I05 to R I07 are the same as R I 02 to R I 04 of the above formula (I).
- the photoradical polymerization initiator the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469 can also be used, and the contents thereof are incorporated in the present specification.
- a bifunctional or trifunctional or higher photoradical polymerization initiator may be used as the photoradical polymerization initiator.
- two or more radicals are generated from one molecule of the photoradical polymerization initiator, so that good sensitivity can be obtained.
- the crystallinity is lowered, the solubility in a solvent or the like is improved, the precipitation is less likely to occur with time, and the stability of the resin composition with time can be improved.
- Specific examples of the bifunctional or trifunctional or higher functional photo-radical polymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No.
- the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition of the present invention. It is more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more kinds of photopolymerization initiators are contained, the total amount is preferably in the above range. Since the photopolymerization initiator may also function as a thermal polymerization initiator, cross-linking with the photopolymerization initiator may be further promoted by heating an oven, a hot plate, or the like.
- the resin composition may contain a sensitizer.
- the sensitizer absorbs specific active radiation and becomes an electronically excited state.
- the sensitizer in the electron-excited state comes into contact with the thermal radical polymerization initiator, the photoradical polymerization initiator, and the like, and acts such as electron transfer, energy transfer, and heat generation occur.
- the thermal radical polymerization initiator and the photoradical polymerization initiator undergo a chemical change and decompose to generate a radical, an acid or a base.
- Usable sensitizers include benzophenone, Michler's ketone, coumarin, pyrazole azo, anilino azo, triphenylmethane, anthracinone, anthracene, anthrapyridone, benzylidene, oxonol, pyrazole triazole azo.
- Pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, penzopyran, indigo and the like can be used.
- sensitizer examples include Michler's ketone, 4,4'-bis (diethylamino) benzophenone, 2,5-bis (4'-diethylaminobenzal) cyclopentane, and 2,6-bis (4'-diethylaminobenzal).
- the content of the sensitizer is preferably 0.01 to 20% by mass, preferably 0.1 to 15% by mass, based on the total solid content of the resin composition. It is more preferably present, and even more preferably 0.5 to 10% by mass.
- the sensitizer may be used alone or in combination of two or more.
- the resin composition of the present invention may contain a chain transfer agent.
- Chain transfer agents are defined, for example, in the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, 2005), pp. 683-684.
- Examples of the chain transfer agent include RAFT (Reversible Addition Fragmentation chain Transfer), which is a group of compounds having -S-S-, -SO2 -S-, -NO-, SH, PH, SiH, and GeH in the molecule.
- Dithiobenzoate having a thiocarbonylthio group, trithiocarbonate, dithiocarbamate, xantate compound and the like used for polymerization are used. They can donate hydrogen to low-activity radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals.
- thiol compounds can be preferably used.
- the content of the chain transfer agent is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the resin composition of the present invention. 1 to 10 parts by mass is more preferable, and 0.5 to 5 parts by mass is further preferable.
- the chain transfer agent may be only one kind or two or more kinds. When there are two or more types of chain transfer agents, the total is preferably in the above range.
- the resin composition of the present invention preferably contains a photoacid generator.
- the photoacid generator represents a compound that generates at least one of Bronsted acid and Lewis acid by irradiation with light of 200 nm to 900 nm.
- the irradiated light is preferably light having a wavelength of 300 nm to 450 nm, and more preferably light having a wavelength of 330 nm to 420 nm.
- the photoacid generator is a photoacid generator capable of generating an acid by being exposed to light when used alone or in combination with a sensitizer.
- generated acids include hydrogen halide, carboxylic acid, sulfonic acid, sulfinic acid, thiosulfinic acid, phosphoric acid, phosphoric acid monoester, phosphoric acid diester, boron derivative, phosphorus derivative, antimony derivative, halogen peroxide, etc. Sulfonamide and the like are preferably mentioned.
- Examples of the photoacid generator used in the resin composition of the present invention include quinone diazide compounds, oxime sulfonate compounds, organic halogenated compounds, organic borate compounds, disulfone compounds, onium salt compounds and the like.
- Organic halogen compounds, oxime sulfonate compounds, and onium salt compounds are preferable from the viewpoint of sensitivity and storage stability, and oxime esters are preferable from the viewpoint of mechanical properties of the film to be formed.
- the quinone diazide compound is a monovalent or polyvalent hydroxy compound with an ester bond of quinone diazide sulfonic acid, a monovalent or polyvalent amino compound with quinone diazide sulfonic acid conjugated with a sulfonamide, and a polyhydroxypolyamino compound with quinone diazide.
- Examples thereof include those in which the sulfonic acid of the above is ester-bonded and / or sulfonic acid-bonded.
- All the functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxypolyamino compounds may not be substituted with quinonediazide, but it is preferable that 40 mol% or more of all the functional groups are substituted with quinonediazide on average. ..
- a quinone diazide compound By containing such a quinone diazide compound, it is possible to obtain a resin composition that is sensitive to i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of a mercury lamp which is a general ultraviolet ray. ..
- hydroxy compound phenol, trihydroxybenzophenone, 4methoxyphenol, isopropanol, octanol, t-Bu alcohol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP- PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylene Tris-FR -CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML -PFP, DML-PSBP, DML-MTrisPC, Tri
- the amino compounds include aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4.
- ′ -Diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfide and the like can be mentioned, but the present invention is not limited thereto.
- polyhydroxypolyamino compound examples include, but are not limited to, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 3,3'-dihydroxybenzidine. ..
- the quinone diazide compound contains an ester with a phenol compound and a 4-naphthoquinone diazidosulfonyl group. This makes it possible to obtain higher sensitivity to i-line exposure and higher resolution.
- the content of the quinonediazide compound used in the resin composition of the present invention is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the resin. It is preferable to set the content of the quinonediazide compound in this range because the contrast between the exposed portion and the unexposed portion can be obtained and the sensitivity can be further increased. Further, a sensitizer or the like may be added as needed.
- the photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as "oxime sulfonate compound").
- the oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but the following formula (OS-1), the formula (OS-103) described later, the formula (OS-104), or the formula (OS-). It is preferably the oxime sulfonate compound represented by 105).
- X3 represents an alkyl group, an alkoxy group, or a halogen atom. When a plurality of X3s exist, they may be the same or different from each other.
- the alkyl group and the alkoxy group in X3 may have a substituent.
- As the alkyl group in X3 a linear or branched alkyl group having 1 to 4 carbon atoms is preferable.
- As the alkoxy group in X3 a linear or branched alkoxy group having 1 to 4 carbon atoms is preferable.
- halogen atom in X3 a chlorine atom or a fluorine atom is preferable.
- m3 represents an integer of 0 to 3, and 0 or 1 is preferable. When m3 is 2 or 3 , the plurality of X3s may be the same or different.
- R 34 represents an alkyl group or an aryl group, which is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms, and carbon. It is preferably an alkoxy group of numbers 1 to 5, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W.
- W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms or an alkoxy halide having 1 to 5 carbon atoms.
- m3 is 3
- X3 is a methyl group
- the substitution position of X3 is the ortho position
- R34 is a linear alkyl group having 1 to 10 carbon atoms, 7,
- a compound having a 7-dimethyl-2-oxonorbornylmethyl group or a p-tolyl group is particularly preferable.
- oxime sulfonate compound represented by the formula (OS-1) are described in paragraphs 0064 to 0068 of JP2011-200969A and paragraph numbers 0158 to 0167 of JP2015-194674A. The following compounds are exemplified and their contents are incorporated herein.
- R s1 represents an alkyl group, an aryl group or a heteroaryl group
- R s2, which may be present in a plurality of R s2 independently represents a hydrogen atom, an alkyl group and an aryl group
- R s6 which represents a group or a halogen atom and may be present in a plurality, independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group
- Xs represents O or S.
- ns represents 1 or 2
- ms represents an integer from 0 to 6.
- an alkyl group represented by R s1 preferably 1 to 30 carbon atoms
- an aryl group preferably 6 to 30 carbon atoms
- a heteroaryl group carbon
- numbers 4 to 30 may have a known substituent as long as the effects of the present invention can be obtained.
- R s2 is preferably a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms) or an aryl group (preferably 6 to 30 carbon atoms).
- Hydrogen atom or alkyl group is more preferable.
- the Rs2 that may be present in two or more in the compound, one or two are preferably an alkyl group, an aryl group or a halogen atom, and one is more preferably an alkyl group, an aryl group or a halogen atom. It is particularly preferable that one is an alkyl group and the rest is a hydrogen atom.
- the alkyl group or aryl group represented by R s2 may have a known substituent as long as the effects of the present invention can be obtained.
- Xs represents O or S, and is preferably O.
- the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.
- ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is. It is preferably 2.
- the alkyl group represented by R s6 preferably having 1 to 30 carbon atoms
- the alkyloxy group preferably having 1 to 30 carbon atoms
- ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0. Is particularly preferable.
- the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111).
- the compound represented by the formula (OS-104) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is a compound represented by the following formula (OS-105). -108) or a compound represented by the formula (OS-109) is particularly preferable.
- R t1 represents an alkyl group, an aryl group or a heteroaryl group
- R t7 represents a hydrogen atom or a bromine atom
- R t8 represents a hydrogen atom and the number of carbon atoms. 1 to 8 alkyl groups, halogen atoms, chloromethyl groups, bromomethyl groups, bromoethyl groups, methoxymethyl groups, phenyl groups or chlorophenyl groups
- R t9 represents hydrogen atoms, halogen atoms, methyl groups or methoxy groups
- R t2 represents a hydrogen atom or a methyl group.
- R t7 represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
- R t8 is 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, and a phenyl group.
- it represents a chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. It is more preferable to have a methyl group, and it is particularly preferable to have a methyl group.
- R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
- R t2 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
- the three-dimensional structure (E, Z) of the oxime may be either one or a mixture.
- Specific examples of the oxime sulfonate compound represented by the above formulas (OS-103) to (OS-105) include paragraph numbers 008 to 0995 of JP2011-209692 and paragraphs of JP-A-2015-194674.
- the compounds of Nos. 0168 to 0194 are exemplified and their contents are incorporated herein.
- oxime sulfonate compound containing at least one oxime sulfonate group include compounds represented by the following formulas (OS-101) and (OS-102).
- Ru9 is 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, and the like. Represents an aryl group or a heteroaryl group.
- R u9 is a cyano group or an aryl group is more preferable, and the embodiment in which R u9 is a cyano group, a phenyl group or a naphthyl group is further preferable.
- Ru2a represents an alkyl group or an aryl group.
- Xu is -O-, -S-, -NH-, -NR u5- , -CH 2- , -CR u6 H- or CR u6 R u7.
- Ru1 to Ru4 are independently hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxy group, amino group, alkoxycarbonyl group and alkylcarbonyl group, respectively. , Arylcarbonyl group, amide group, sulfo group, cyano group or aryl group.
- Two of R u1 to R u4 may be bonded to each other to form a ring. At this time, the ring may be condensed to form a condensed ring together with the benzene ring.
- R u1 to Ru4 a hydrogen atom, a halogen atom or an alkyl group is preferable, and an embodiment in which at least two of Ru1 to Ru4 are bonded to each other to form an aryl group is also preferable. Above all, it is preferable that all of Ru1 to Ru4 are hydrogen atoms. Any of the above-mentioned substituents may further have a substituent.
- the compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102).
- the three-dimensional structure (E, Z, etc.) of the oxime and the benzothiazole ring may be either one or a mixture.
- Specific examples of the compound represented by the formula (OS-101) include the compounds described in paragraph numbers 0102 to 0106 of JP-A-2011-20969 and paragraph numbers 0195 to 0207 of JP-A-2015-194674. And these contents are incorporated herein.
- the following b-9, b-16, b-31, and b-33 are preferable.
- Examples of commercially available products include WPAG-336 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), WPAG-443 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), MBZ-101 (manufactured by Midori Kagaku Co., Ltd.), and the like. Can be done.
- organic halogenated compound examples include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605, JP-A. 48-36281, 55-32070, 60-239736, 61-169835, 61-169837, 62-58241, , Japanese Patent Application Laid-Open No. 62-212401, Japanese Patent Application Laid-Open No. 63-70243, Japanese Patent Application Laid-Open No. 63-298339, M.D. P.
- an oxazole compound substituted with a trihalomethyl group an S-triazine compound is given as a preferable example. More preferably, an s-triazine derivative in which at least one mono, di, or trihalogen-substituted methyl group is attached to the s-triazine ring, specifically, for example, 2,4,6-tris (monochromomethyl)-.
- Examples of the organic borate compound include JP-A-62-143044, JP-A-62-150242, JP-A-9-188685, JP-A-9-188686, and JP-A-9-188710.
- Japanese Patent Application Laid-Open No. 2000-131837 Japanese Patent Application Laid-Open No. 2002-107916, Japanese Patent Application Laid-Open No. 2764769, Japanese Patent Application Laid-Open No. 2002-116539, etc., and Kunz, Martin "Rad Tech '98.
- organic boron sulfonium complex or the organic boron oxosulfonium described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561.
- Specific examples thereof include organic boron transition metal coordination complexes of JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, JP-A-7-292014, and the like. Incorporated herein.
- disulfone compound examples include compounds described in JP-A-61-166544, Japanese Patent Application Laid-Open No. 2001-132318, and diazodisulfone compounds.
- onium salt compound examples include S. I. Schlesinger, Photogr. Sci. Eng. , 18,387 (1974), T.I. S. The diazonium salt described in Bal et al, Polymer, 21, 423 (1980), the ammonium salt described in US Pat. No. 4,069,055, JP-A-4-365049, etc., US Pat. No. 4,069 , 055, 4,069,056, European Patents 104, 143, US Patents 339, 049, 410, 201, Japanese Patent Application Laid-Open No. Iodonium salt described in Japanese Patent Application Laid-Open No. 2-150848, Japanese Patent Application Laid-Open No.
- onium salts examples include onium salts represented by the following general formulas (RI-I) to (RI-III).
- Ar 11 represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents are an alkyl group having 1 to 12 carbon atoms and 2 carbon atoms.
- Z 11 - represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinate ion, a thiosulfonic acid ion, and a sulfate ion, and is stable.
- perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, and sulfinate ion are preferable.
- Ar 21 and Ar 22 each represent an aryl group having 1 to 20 carbon atoms which may independently have 1 to 6 substituents, and preferred substituents have 1 to 12 carbon atoms.
- Z21 - represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinate ion, a thiosulfonic acid ion, and a sulfate ion, and is stable and reacts. From the viewpoint of sex, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion and carboxylate ion are preferable.
- R 31 , R 32 , and R 33 each have an aryl group or an alkyl group, an alkenyl group, or an alkynyl group having 6 to 20 carbon atoms, which may independently have 1 to 6 substituents. It is preferably an aryl group from the viewpoint of reactivity and stability.
- Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms.
- Examples thereof include an alkylamide group having 1 to 12 or an arylamide group, a carbonyl group, a carboxy group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms and a thioaryl group having 1 to 12 carbon atoms.
- Z 31 - represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinate ion, a thiosulfonic acid ion, a sulfate ion, and stability.
- perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion and carboxylate ion are preferable.
- preferable photoacid generators include the following.
- the photoacid generator is preferably used in an amount of 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, and more preferably 0.5 to 10% by mass, based on the total solid content of the resin composition. It is more preferably used, more preferably 0.5 to 3% by mass, and even more preferably 0.5 to 1.2% by mass.
- the photoacid generator may be used alone or in combination of two or more. In the case of a combination of a plurality of types, it is preferable that the total amount thereof is within the above range. It is also preferable to use it in combination with a sensitizer in order to impart photosensitivity to a desired light source.
- the resin composition of the present invention may contain a base generator.
- the base generator is a compound capable of generating a base by a physical or chemical action.
- Preferred base generators for the resin composition of the present invention include thermal base generators and photobase generators.
- the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition contains a base generator.
- the resin composition contains a thermal base generator, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties and chemical resistance of the cured product become good. The performance as an interlayer insulating film for a wiring layer is improved.
- the base generator may be an ionic base generator or a nonionic base generator.
- Examples of the base generated from the base generator include secondary amines and tertiary amines.
- the base generator according to the present invention is not particularly limited, and a known base generator can be used.
- Known base generators include, for example, carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetoamide compounds, carbamates compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, and amineimides.
- Compounds, pyridine derivative compounds, ⁇ -aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, ⁇ -lactone ring derivative compounds, amineimide compounds, phthalimide derivative compounds, acyloxyimino compounds and the like can be used.
- Specific examples of the compound of the nonionic base generator include a compound represented by the formula (B1), the formula (B2), or the formula (B3).
- Rb 1 , Rb 2 and Rb 3 are independently organic groups, halogen atoms or hydrogen atoms having no tertiary amine structure. However, Rb 1 and Rb 2 do not become hydrogen atoms at the same time. Further, none of Rb 1 , Rb 2 and Rb 3 has a carboxy group.
- the tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, this does not apply when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when an amide group is formed together with a nitrogen atom.
- Rb 1 , Rb 2 and Rb 3 contains a cyclic structure, and it is more preferable that at least two of them contain a cyclic structure.
- the cyclic structure may be either a monocyclic ring or a condensed ring, and a monocyclic ring or a condensed ring in which two monocyclic rings are condensed is preferable.
- the single ring is preferably a 5-membered ring or a 6-membered ring, and more preferably a 6-membered ring.
- a cyclohexane ring and a benzene ring are preferable, and a cyclohexane ring is more preferable.
- Rb 1 and Rb 2 are a hydrogen atom, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), and an alkenyl group (preferably 2 to 24 carbon atoms).
- 2-18 is more preferred, 3-12 is more preferred
- ⁇ 25 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable).
- Rb 1 and Rb 2 may be coupled to each other to form a ring.
- Rb 1 and Rb 2 are particularly linear, branched or cyclic alkyl groups which may have substituents (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms and even more preferably 3 to 12 carbon atoms). It is more preferably a cycloalkyl group which may have a substituent (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms) and having a substituent.
- substituents preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms and even more preferably 3 to 12 carbon atoms. It is more preferably a cycloalkyl group which may have a substituent (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms) and having a substituent.
- cyclohexyl groups are more preferred.
- Rb 3 examples include an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms) and an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 18).
- ⁇ 10 is more preferred
- alkoxy group preferably 2 to 24 carbon atoms, more preferably 2 to 12
- arylalkyl group preferably 7 to 23 carbon atoms, 7 to 19 more preferred.
- 7 to 12 are more preferable
- an arylalkenyl group preferably 8 to 24 carbon atoms, more preferably 8 to 20 carbon atoms, still more preferably 8 to 16 carbon atoms
- an alkoxyl group preferably 1 to 24 carbon atoms, 2 to 2 to 24.
- Rb 3 may further have a substituent as long as the effect of the present invention is exhibited.
- the compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).
- Rb 11 and Rb 12 , and Rb 31 and Rb 32 are the same as Rb 1 and Rb 2 in the formula (B1), respectively.
- Rb 13 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and a substituent may be provided as long as the effect of the present invention is exhibited.
- Rb 13 is preferably an arylalkyl group.
- Rb 33 and Rb 34 independently have a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms).
- Rb 33 and Rb 34 independently have a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms).
- 2 to 8 are more preferable, 2 to 3 are more preferable
- aryl groups (6 to 22 carbon atoms are preferable, 6 to 18 are more preferable, 6 to 10 are more preferable
- 23 is preferable, 7 to 19 is more preferable, and 7 to 11 is even more preferable), and a hydrogen atom is preferable.
- Rb 35 has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms) and an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 10 carbon atoms). 8 is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). , 7-12 is more preferable), and an aryl group is preferable.
- the compound represented by the formula (B1-1) is also preferable.
- Rb 11 and Rb 12 are synonymous with Rb 11 and Rb 12 in the formula (B1-1).
- Rb 15 and Rb 16 are a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms). More preferably, 2 to 3 are more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10), an arylalkyl group (preferably 7 to 23 carbon atoms, 7).
- Rb 17 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), and an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and an aryl group is particularly preferable.
- L is a divalent hydrocarbon group having a saturated hydrocarbon group on the path of the connecting chain connecting the adjacent oxygen atom and the carbon atom, and the number of atoms on the path of the connecting chain is Represents a hydrocarbon group having 3 or more.
- RN1 and RN2 each independently represent a monovalent organic group.
- linking chain refers to an atomic chain on a path connecting two atoms or a group of atoms to be linked, which is connected at the shortest (minimum number of atoms).
- L is composed of a phenylene ethylene group, has an ethylene group as a saturated hydrocarbon group, and the linking chain is composed of four carbon atoms, and is on the path of the linking chain. (That is, the number of atoms constituting the connecting chain, hereinafter also referred to as "linking chain length" or "connecting chain length”) is 4.
- the number of carbon atoms in L in the formula (B3) is preferably 3 to 24.
- the upper limit is more preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less.
- the lower limit is more preferably 4 or more.
- the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, still more preferably 6 or less, and 5 The following is particularly preferable.
- the chain length of L is preferably 4 or 5, and most preferably 4.
- Specific preferred compounds of the base generator include, for example, the compounds described in paragraphs 0102 to 0168 of International Publication No. 2020/06614 and the compounds described in paragraph numbers 0143 to 0177 of International Publication No. 2018/038002. Can be mentioned.
- the base generator contains a compound represented by the following formula (N1).
- RN1 and RN2 each independently represent a monovalent organic group
- RC1 represents a hydrogen atom or a protecting group
- L represents a divalent linking group
- L is a divalent linking group, preferably a divalent organic group.
- the linking chain length of the linking group is preferably 1 or more, and more preferably 2 or more.
- the upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less.
- the linking chain length is the number of atoms present in the atomic arrangement that is the shortest route between the two carbonyl groups in the equation.
- RN1 and RN2 each independently represent a monovalent organic group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), and a hydrocarbon group (preferably 3 to 12 carbon atoms). It is preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 10 carbon atoms), and specifically, an aliphatic hydrocarbon group (preferably 1 to 12 carbon atoms). Is more preferable) or an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), and an aliphatic hydrocarbon can be mentioned. Group is preferred.
- an aliphatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group are contained in the aliphatic hydrocarbon chain or the aromatic ring. It may have an oxygen atom in the substituent.
- an embodiment in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain is exemplified.
- a linear or branched chain alkyl group, a cyclic alkyl group, a group related to a combination of a chain alkyl group and a cyclic alkyl group, and an oxygen atom are contained in the chain.
- Examples thereof include alkyl groups having.
- the linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms.
- the linear or branched chain alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, or an isopropyl group.
- Examples thereof include a group, an isobutyl group, a secondary butyl group, a tertiary butyl group, an isopentyl group, a neopentyl group, a tertiary pentyl group, and an isohexyl group.
- the cyclic alkyl group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group and the like.
- the group related to the combination of the chain alkyl group and the cyclic alkyl group preferably has 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, and even more preferably 4 to 12 carbon atoms.
- Examples of the group related to the combination of the chain alkyl group and the cyclic alkyl group include a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, an ethylcyclohexylethyl group and the like.
- the alkyl group having an oxygen atom in the chain is preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms.
- the alkyl group having an oxygen atom in the chain may be chain-like or cyclic, and may be linear or branched. Among them, alkyl groups having 5 to 12 carbon atoms are preferable for RN1 and RN2 from the viewpoint of increasing the boiling point of the decomposition-generated base described later.
- a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable.
- RN1 and RN2 may be connected to each other to form an annular structure.
- oxygen atoms or the like may be contained in the chain.
- the cyclic structure formed by RN1 and RN2 may be a monocyclic ring or a condensed ring, but a monocyclic ring is preferable.
- a 5-membered ring or a 6-membered ring containing a nitrogen atom in the formula (N1) is preferable, and for example, a pyrrol ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, an imidazolidine ring, and the like.
- Examples thereof include a pyrazolidine ring, a piperidine ring, a piperazine ring, a morpholine ring and the like, and a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, a morpholine ring and the like are preferable.
- RC1 represents a hydrogen atom or a protecting group, and a hydrogen atom is preferable.
- the protecting group a protecting group that decomposes by the action of an acid or a base is preferable, and a protecting group that decomposes by an acid is preferable.
- the protecting group include a chain or cyclic alkyl group or a chain or cyclic alkyl group having an oxygen atom in the chain.
- the chain or cyclic alkyl group include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a cyclohexyl group and the like.
- Specific examples of the chain-like alkyl group having an oxygen atom in the chain include an alkyloxyalkyl group, and more specifically, a methyloxymethyl (MOM) group, an ethyloxyethyl (EE) group and the like. Can be mentioned.
- Examples of the cyclic alkyl group having an oxygen atom in the chain include an epoxy group, a glycidyl group, an oxetanyl group, a tetrahydrofuranyl group, a tetrahydropyranyl (THP) group and the like.
- the divalent linking group constituting L is not particularly specified, but a hydrocarbon group is preferable, and an aliphatic hydrocarbon group is more preferable.
- the hydrocarbon group may have a substituent, or may have an atom of a type other than a carbon atom in the hydrocarbon chain. More specifically, it is preferably a divalent hydrocarbon linking group which may have an oxygen atom in the chain, and a divalent aliphatic hydrocarbon which may have an oxygen atom in the chain. More preferably, a divalent aromatic hydrocarbon group, or a group relating to a combination of a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group.
- a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain is more preferable. It is preferable that these groups do not have an oxygen atom.
- the divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms.
- the divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.
- the divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms.
- the group (for example, an arylene alkyl group) relating to the combination of the divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group preferably has 7 to 22 carbon atoms, more preferably 7 to 18 carbon atoms, and 7 to 18 carbon atoms. 10 is more preferable.
- linking group L examples include a linear or branched chain alkylene group, a cyclic alkylene group, a group related to a combination of a chain alkylene group and a cyclic alkylene group, and an alkylene group having an oxygen atom in the chain.
- a linear or branched chain alkaneylene group, a cyclic alkaneylene group, an arylene group, or an arylene alkylene group is preferable.
- the linear or branched chain alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.
- the cyclic alkylene group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms.
- the group related to the combination of the chain alkylene group and the cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, and even more preferably 4 to 6 carbon atoms.
- the alkylene group having an oxygen atom in the chain may be chain-like or cyclic, and may be linear or branched.
- the alkylene group having an oxygen atom in the chain is preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms.
- the linear or branched chain-like alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 3 carbon atoms.
- the cyclic alkenylene group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms.
- the arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms.
- the arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms.
- a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkenylene group, an arylene group and an arylene alkylene group are preferable, and a 1,2-ethylene group and a propandiyl group (particularly 1, 3-Propanediyl group), cyclohexanediyl group (especially 1,2-cyclohexanediyl group), vinylene group (especially cisvinylene group), phenylene group (1,2-phenylene group), phenylene methylene group (especially 1,2-phenylene) Methylene group) and ethyleneoxyethylene group (particularly 1,2-ethyleneoxy-1,2-ethylene group) are more preferable.
- Examples of the base generator include the following, but the present invention is not construed as being limited thereto.
- the molecular weight of the non-ionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less.
- the lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.
- Specific preferable compounds of the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of International Publication No. 2018/038002.
- ammonium salt examples include, but are not limited to, the following compounds.
- iminium salt examples include, but are not limited to, the following compounds.
- the content of the base generator is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the resin in the resin composition of the present invention.
- the lower limit is more preferably 0.3 parts by mass or more, and further preferably 0.5 parts by mass or more.
- the upper limit is more preferably 30 parts by mass or less, further preferably 20 parts by mass or less, further preferably 10 parts by mass or less, 5 parts by mass or less, or 4 parts by mass or less.
- the base generator one kind or two or more kinds can be used. When two or more types are used, the total amount is preferably in the above range.
- the resin composition of the present invention preferably contains a solvent.
- a solvent a known solvent can be arbitrarily used.
- the solvent is preferably an organic solvent.
- the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas and alcohols.
- esters include ethyl acetate, -n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and ⁇ -butyrolactone.
- alkylalkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, etc.) Ethyl propionate, etc.)
- 3-alkyloxypropionate alkyl esters eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.) (eg, methyl 3-methoxypropionate, 3-methoxypropionate, etc.) Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)
- 2-alkyloxypropionate alkyl esters eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, ethyl 2-alkyl
- ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether.
- ketones for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone and the like are preferable.
- cyclic hydrocarbons for example, aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene are preferable.
- sulfoxides for example, dimethyl sulfoxide is preferable.
- N, N, N', N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone and the like are preferable.
- Alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, Diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, Examples thereof include ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.
- the solvent is preferably a mixture of two or more types from the viewpoint of improving the properties of the coated surface.
- the solvent content is preferably such that the total solid content concentration of the resin composition of the present invention is 5 to 80% by mass, and is preferably 5 to 75% by mass. It is more preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass.
- the solvent content may be adjusted according to the desired thickness of the coating film and the coating method.
- the resin composition of the present invention may contain only one type of solvent, or may contain two or more types of solvent. When two or more kinds of solvents are contained, the total is preferably in the above range.
- the resin composition of the present invention preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like.
- a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like.
- the metal adhesion improver include a silane coupling agent having an alkoxysilyl group, an aluminum-based adhesive aid, a titanium-based adhesive aid, a compound having a sulfone amide structure and a compound having a thiourea structure, a phosphoric acid derivative compound, and a ⁇ -ketoester. Examples thereof include compounds and amino compounds.
- silane coupling agent examples include the compound described in paragraph 0167 of International Publication No. 2015/199219, the compound described in paragraphs 0062 to 0073 of JP-A-2014-191002, paragraph of International Publication No. 2011/080992.
- examples thereof include the compounds described in paragraph 0055 and the compounds described in paragraphs 0067 to 0078 of JP-A-2018-173573, the contents of which are incorporated herein by reference.
- silane coupling agents examples include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycid.
- Aluminum-based adhesive aid examples include aluminum tris (ethyl acetoacetate), aluminum tris (acetyl acetonate), ethyl acetoacetate aluminum diisopropylate, and the like.
- the content of the metal adhesive improving agent is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and further preferably 0. It is in the range of 5 to 5 parts by mass.
- the metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more types are used, it is preferable that the total is in the above range.
- the resin composition of the present invention preferably further contains a migration inhibitor.
- a migration inhibitor By including the migration inhibitor, it is possible to effectively suppress the movement of metal ions derived from the metal layer (metal wiring) into the membrane.
- the migration inhibitor is not particularly limited, but has a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isooxazole ring, isothiazole ring, tetrazole ring, pyridine ring, etc.
- a heterocyclic ring pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isooxazole ring, isothiazole ring, tetrazole ring, pyridine ring, etc.
- triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 1H-tetrazole, 5- Tetrazole-based compounds such as phenyltetrazole and 5-amino-1H-tetrazole can be preferably used.
- an ion trap agent that traps anions such as halogen ions can also be used.
- Examples of other migration inhibitors include the rust preventive agent described in paragraph 0094 of JP2013-015701, the compound described in paragraphs 0073 to 0076 of JP2009-283711, and JP-A-2011-059656.
- the compounds described in paragraph 0052, the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520A, the compounds described in paragraph 0166 of International Publication No. 2015/199219, and the like can be used. The content is incorporated herein.
- the migration inhibitor include the following compounds.
- the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the resin composition of the present invention. , 0.05 to 2.0% by mass, more preferably 0.1 to 1.0% by mass.
- the migration inhibitor may be only one kind or two or more kinds. When there are two or more types of migration inhibitors, the total is preferably in the above range.
- the resin composition of the present invention preferably contains a polymerization inhibitor.
- the polymerization inhibitor include phenol-based compounds, quinone-based compounds, amino-based compounds, N-oxyl-free radical compound-based compounds, nitro-based compounds, nitroso-based compounds, heteroaromatic ring-based compounds, and metal compounds.
- Specific compounds of the polymerization inhibitor include p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1, 4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenyl Hydroxyamine primary cerium salt, N-nitroso-N-phenylhydroxyamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine tetraacetic acid, 2, 6-Di-tert-butyl-4-methylphenol
- polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compound described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used, and the contents thereof are described in the present specification. Be incorporated.
- the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, preferably 0 to 20% by mass, based on the total solid content of the resin composition of the present invention. It is more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass.
- the polymerization inhibitor may be only one kind or two or more kinds. When there are two or more types of polymerization inhibitors, the total is preferably in the above range.
- the resin composition of the present invention preferably contains an acid scavenger in order to reduce the change in performance over time from exposure to heating.
- the acid scavenger refers to a compound that can capture the generated acid by being present in the system, and is preferably a compound having low acidity and high pKa.
- the acid trapping agent a compound having an amino group is preferable, a primary amine, a secondary amine, a tertiary amine, an ammonium salt, a tertiary amine and the like are preferable, and a primary amine, a secondary amine, a tertiary amine and an ammonium salt are preferable.
- the acid scavenger include a compound having an imidazole structure, a diazabicyclo structure, an onium structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline having a hydroxyl group and / or an ether bond. Derivatives and the like can be preferably mentioned.
- the acid scavenger is a salt having a cation selected from ammonium, diazonium, iodonium, sulfonium, phosphonium, pyridinium and the like, and an anion of an acid having a lower acidity than the acid generated by the acid generator. Is preferable.
- Examples of the acid scavenger having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, 2-phenylbenzimidazole and the like.
- As an acid scavenger having a diazabicyclo structure 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] nona-5-ene, 1,8-diazabicyclo [5,4] , 0] Undekar 7-En and the like.
- Examples of the acid trapping agent having an onium structure include tetrabutylammonium hydroxide, triarylsulfoniumhydroxydo, phenacylsulfoniumhydroxydo, sulfoniumhydroxydo having a 2-oxoalkyl group, specifically triphenylsulfoniumhydroxydo and tris (specifically, triphenylsulfonium hydroxide, tris ( Examples thereof include t-butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide.
- Examples of the acid scavenger having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine.
- Examples of the acid scavenger having an aniline structure include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like.
- Examples of the acid scavenger having a pyridine structure include pyridine, 4-methylpyridine and the like.
- alkylamine derivative having a hydroxyl group and / or an ether bond examples include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, tris (methoxyethoxyethyl) amine and the like.
- aniline derivative having a hydroxyl group and / or an ether bond examples include N, N-bis (hydroxyethyl) aniline and the like.
- preferred acid trapping agents include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N.
- N-dimethylaniline diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo [2.2.2] octane), N, N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N-methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N, N-diethylethylenediamine, N, N, N', N'-tetrabutyl-1,6-hexanediamine, spermidin, diaminocyclohexane, bis (2-methoxyethyl) amine, piperidine, methylpiperidin
- the composition according to the present invention may or may not contain an acid scavenger, but when it is contained, the content of the acid scavenger is usually 0.001 to 0 based on the total solid content of the composition. It is 10% by mass, preferably 0.01 to 5% by mass.
- the acid generator / acid scavenger (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.
- the resin composition of the present invention comprises various additives such as a surfactant, a higher fatty acid derivative, a thermal polymerization initiator, an inorganic particle, and an ultraviolet absorber, if necessary, as long as the effects of the present invention can be obtained.
- Organic titanium compounds, antioxidants, antiaggregating agents, phenolic compounds, other polymer compounds, plasticizers and other auxiliaries eg, antifoaming agents, flame retardant agents, etc.
- properties such as film physical characteristics can be adjusted.
- the total blending amount is preferably 3% by mass or less of the solid content of the resin composition of the present invention.
- surfactant various surfactants such as a fluorine-based surfactant, a silicone-based surfactant, and a hydrocarbon-based surfactant can be used.
- the surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.
- the liquid characteristics (particularly, fluidity) when prepared as a coating liquid are further improved, and the uniformity of the coating thickness and the liquid saving property are further improved. can do. That is, when a film is formed by using a coating liquid to which a composition containing a surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, and the wettability to the surface to be coated is improved. , The applicability to the surface to be coated is improved. Therefore, it is possible to more preferably form a film having a uniform thickness with small thickness unevenness.
- fluorine-based surfactant examples include Megafuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, and F479.
- F482, F554, F780, RS-72-K above, manufactured by DIC Co., Ltd.
- Florard FC430, FC431, FC171, Novek FC4430, FC4432 aboveve, manufactured by 3M Japan Ltd.
- the compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 and the compounds described in paragraphs 0117 to 0132 of JP-A-2011-132503 can also be used. Incorporated herein.
- a block polymer can also be used as the fluorine-based surfactant, and specific examples thereof include compounds described in JP-A-2011-89090, the contents of which are incorporated in the present specification.
- the fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth).
- a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.
- the weight average molecular weight of the above compounds is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.
- a fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as the fluorine-based surfactant. Specific examples thereof include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP2010-164965, the contents of which are incorporated in the present specification. Examples of commercially available products include Megafuck RS-101, RS-102, and RS-718K manufactured by DIC Corporation.
- the fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass.
- a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity in the thickness of the coating film and liquid saving, and has good solubility in the composition.
- silicone-based surfactant examples include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 (all, Toray Dow Corning Co., Ltd.). ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials), KP-341, KF6001, KF6002 (all manufactured by Shinetsu Silicone Co., Ltd.) ), BYK307, BYK323, BYK330 (all manufactured by Big Chemie Co., Ltd.) and the like.
- hydrocarbon-based surfactant examples include Pionin A-76, Newcalgen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin D-3605, and Pionin.
- Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ethers, polyoxyethylene stearyl ethers, etc. Examples thereof include polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester.
- organosiloxane polymer KP-341 manufactured by Shin-Etsu Chemical Co., Ltd.
- (meth) acrylic acid-based (co) polymer Polyflow No. 75, No. 77, No. 90, No. 95 manufactured by Kyoeisha Chemical Co., Ltd.
- W001 manufactured by Yusho Co., Ltd.
- anion-type surfactant examples include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Industries, Ltd.) and the like.
- the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.
- the resin composition of the present invention is added with a higher fatty acid derivative such as behenic acid or behenic acid amide, and the resin composition of the present invention is dried in the process of drying after application. It may be unevenly distributed on the surface of.
- the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass with respect to the total solid content of the resin composition of the present invention.
- the higher fatty acid derivative may be only one kind or two or more kinds. When there are two or more higher fatty acid derivatives, the total is preferably in the above range.
- the resin composition of the present invention may contain a thermal polymerization initiator, and in particular, a thermal radical polymerization initiator may be contained.
- the thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. Since the polymerization reaction of the resin and the polymerizable compound can be promoted by adding the thermal radical polymerization initiator, the solvent resistance can be further improved. Further, the above-mentioned photopolymerization initiator may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.
- thermal radical polymerization initiator examples include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated in the present specification.
- the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition of the present invention. , More preferably 0.5 to 15% by mass. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more kinds of thermal polymerization initiators are contained, the total amount is preferably in the above range.
- the resin composition of the present invention may contain inorganic particles.
- specific examples of the inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.
- the average particle size of the inorganic particles is preferably 0.01 to 2.0 ⁇ m, more preferably 0.02 to 1.5 ⁇ m, further preferably 0.03 to 1.0 ⁇ m, and 0.04 to 0.5 ⁇ m. Especially preferable.
- the average particle size of the inorganic particles is a primary particle size and a volume average particle size.
- the volume average particle size can be measured by a dynamic light scattering method using Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurement is difficult, it can be measured by a centrifugal sedimentation light transmission method, an X-ray transmission method, or a laser diffraction / scattering method.
- the composition of the present invention may contain an ultraviolet absorber.
- an ultraviolet absorber such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, or triazine-based can be used.
- salicylate-based ultraviolet absorbers include phenylsalicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate and the like
- benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-.
- Methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2- Hydroxyl-4-octoxybenzophenone and the like can be mentioned.
- benzotriazole-based ultraviolet absorbers include 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole and 2- (2'-hydroxy-3).
- Examples of the substituted acrylonitrile-based ultraviolet absorber include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and the like.
- the triazine-based ultraviolet absorber 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) )-1,3,5-Triazine, 2- [4-[(2-Hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) Mono (hydroxyphenyl) triazine compounds such as -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin
- the above-mentioned various ultraviolet absorbers may be used alone or in combination of two or more.
- the composition of the present invention may or may not contain an ultraviolet absorber, but when it is contained, the content of the ultraviolet absorber is 0.001% by mass with respect to the total solid content mass of the composition of the present invention. It is preferably 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less.
- the resin composition of the present embodiment may contain an organic titanium compound. Since the resin composition contains an organic titanium compound, a resin layer having excellent chemical resistance can be formed even when cured at a low temperature.
- Examples of the organic titanium compound that can be used include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.
- Specific examples of the organic titanium compound are shown in I) to VII) below:
- I) Titanium chelate compound Among them, a titanium chelate compound having two or more alkoxy groups is more preferable because the resin composition has good storage stability and a good curing pattern can be obtained.
- Specific examples include titanium bis (triethanolamine) diisopropoxyside, titanium di (n-butoxide) bis (2,4-pentanegenate), and titanium diisopropoxiside bis (2,4-pentanegeonate).
- Titanium Alkoxy Titanium Compounds For example, Titanium Tetra (n-Butoxide), Titanium Tetraethoxide, Titanium Tetra (2-ethylhexoxyside), Titanium Tetraisobutoxide, Titanium Tetraisopropoxyside, Titanium Tetramethoxide , Titanium Tetramethoxypropoxyside, Titanium Tetramethylphenoxide, Titanium Tetra (n-Noniloxide), Titanium Tetra (n-Propoxide), Titanium Tetrasteeryloxyside, Titanium Tetrakiss [Bis ⁇ 2,2- (Aryloxymethyl) Butokiside ⁇ ] etc.
- Titanocene compounds for example, pentamethylcyclopentadienyl titanium trimethoxide, bis ( ⁇ 5-2,4-cyclopentadiene-1-yl) bis (2,6-difluorophenyl) titanium, bis ( ⁇ 5-2, 2). 4-Cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium and the like.
- Monoalkoxytitanium compound For example, titaniumtris (dioctylphosphate) isopropoxyside, titaniumtris (dodecylbenzenesulfonate) isopropoxyside and the like.
- Titanium oxide compound For example, titanium oxide bis (pentanionate), titanium oxide bis (tetramethylheptandionate), phthalocyanine titanium oxide and the like.
- the organic titanium compound at least one compound selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanocene compound has better chemical resistance. It is preferable from the viewpoint of playing.
- -Pyrrole-1-yl) phenyl) titanium is preferred.
- the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the specific resin.
- the blending amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are more effectively exhibited in the obtained curing pattern, while when it is 10 parts by mass or less, the storage stability of the composition Excellent.
- the composition of the present invention may contain an antioxidant.
- an antioxidant By containing an antioxidant as an additive, it is possible to improve the elongation characteristics of the film after curing and the adhesion with a metal material.
- the antioxidant include phenol compounds, phosphite ester compounds, thioether compounds and the like.
- the phenol compound any phenol compound known as a phenolic antioxidant can be used.
- Preferred phenolic compounds include hindered phenolic compounds.
- a compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxy group is preferable.
- a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable.
- a compound having a phenol group and a phosphite ester group in the same molecule is also preferable.
- a phosphorus-based antioxidant can also be preferably used.
- antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, and Adekastab AO-80. , ADEKA STAB AO-330 (above, manufactured by ADEKA Corporation) and the like.
- the antioxidant the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used, and the contents thereof are incorporated in the present specification.
- the composition of the present invention may contain a latent antioxidant, if necessary.
- the latent antioxidant is a compound in which the site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst. This includes compounds in which the protecting group is desorbed and functions as an antioxidant.
- Examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219, the contents of which are incorporated in the present specification.
- Examples of commercially available products of latent antioxidants include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation).
- preferred antioxidants include 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and compounds of formula (3).
- R 5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), and R 6 represents an alkylene having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). Represents a group.
- R 7 represents a 1- to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), an oxygen atom, and a nitrogen atom.
- k represents an integer of 1 to 4.
- the compound represented by the formula (3) suppresses the oxidative deterioration of the aliphatic group and the phenolic hydroxyl group of the resin.
- metal oxidation can be suppressed by the rust preventive action on the metal material.
- R 7 includes an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an arylether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group and a heterocyclic group.
- -O-, -NH-, -NHNH-, a combination thereof and the like can be mentioned, and may further have a substituent.
- alkyl ether group and -NH- from the viewpoint of solubility in a developing solution and metal adhesion
- -NH- is preferable from the viewpoint of interaction with a resin and metal adhesion due to metal complex formation. More preferred.
- Examples of the compound represented by the general formula (3) include the following, but the compound is not limited to the following structure.
- the amount of the antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to the resin.
- the addition amount is 0.1 part by mass or more, the effect of improving the elongation property and the adhesion to the metal material can be easily obtained even in a high temperature and high humidity environment, and when the addition amount is 10 parts by mass or less, for example, the emulsion is exposed.
- the interaction with the agent improves the sensitivity of the resin composition.
- Only one kind of antioxidant may be used, or two or more kinds may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.
- the resin composition of the present embodiment may contain an anti-aggregation agent, if necessary.
- the antiaggregating agent include sodium polyacrylate and the like.
- one type of anti-aggregation agent may be used alone, or two or more types may be used in combination.
- the composition of the present invention may or may not contain an anti-aggregation agent, but when it is contained, the content of the anti-aggregation agent is 0.01% by mass with respect to the total solid content mass of the composition of the present invention. It is preferably 10% by mass or less, and more preferably 0.02% by mass or more and 5% by mass or less.
- the resin composition of the present embodiment may contain a phenolic compound, if necessary.
- phenolic compound include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, and BisP-CP.
- one type of phenolic compound may be used alone, or two or more types may be used in combination.
- the composition of the present invention may or may not contain a phenolic compound, but when it is contained, the content of the phenolic compound is 0.01% by mass with respect to the total solid content mass of the composition of the present invention. It is preferably 30% by mass or more, and more preferably 0.02% by mass or more and 20% by mass or less.
- Examples of other polymer compounds include siloxane resins, (meth) acrylic polymers copolymerized with (meth) acrylic acid, novolak resins, resole resins, polyhydroxystyrene resins and copolymers thereof.
- the other polymer compound may be a modified product into which a cross-linking group such as a methylol group, an alkoxymethyl group, or an epoxy group is introduced.
- one type of other polymer compound may be used alone, or two or more types may be used in combination.
- the composition of the present invention may or may not contain other polymer compounds, but when it is contained, the content of the other polymer compounds is 0 with respect to the total solid content mass of the composition of the present invention. It is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less.
- the viscosity of the resin composition of the present invention can be adjusted by adjusting the solid content concentration of the resin composition. From the viewpoint of the coating film thickness, 1,000 mm 2 / s to 12,000 mm 2 / s is preferable, 2,000 mm 2 / s to 10,000 mm 2 / s is more preferable, and 2,500 mm 2 / s to 8,000 mm. 2 / s is more preferable. Within the above range, it becomes easy to obtain a highly uniform coating film.
- the water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved. Examples of the method for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.
- the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, still more preferably less than 0.5 mass ppm.
- the metal include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel and the like, but metals contained as a complex of an organic compound and a metal are excluded. When a plurality of metals are contained, it is preferable that the total of these metals is in the above range.
- the resin composition of the present invention selects a raw material having a low metal content as the raw material constituting the resin composition of the present invention.
- examples thereof include a method of filtering the raw materials constituting the product by a filter, a method of lining the inside of the device with polytetrafluoroethylene or the like, and performing distillation under conditions in which contamination is suppressed as much as possible.
- the resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and less than 200 mass ppm from the viewpoint of wiring corrosiveness. Is more preferable. Among them, those existing in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm.
- the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total amount of chlorine atom and bromine atom, or chlorine ion and bromine ion is in the above range, respectively.
- ion exchange treatment and the like are preferably mentioned.
- a conventionally known storage container can be used as the storage container for the resin composition of the present invention.
- a multi-layer bottle having a container inner wall made of 6 types and 6 layers of resin and 6 types of resin are used as the storage container. It is also preferable to use a bottle having a 7-layer structure. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.
- the cured product of the present invention is a cured product obtained by curing the resin composition of the present invention.
- the curing of the resin composition is preferably by heating, more preferably the heating temperature is in the range of 120 ° C to 400 ° C, further preferably in the range of 140 ° C to 380 ° C, and 170 ° C. It is particularly preferable that the temperature is in the range of about 350 ° C.
- the form of the cured product of the resin composition is not particularly limited, and can be selected according to the intended use, such as a film shape, a rod shape, a spherical shape, and a pellet shape.
- the cured product is preferably in the form of a film.
- this cured product can be used for forming a protective film on the wall surface, forming via holes for conduction, adjusting impedance, capacitance or internal stress, and imparting a heat dissipation function. You can also choose the shape.
- the film thickness of this cured product (film made of the cured product) is preferably 0.5 ⁇ m or more and 150 ⁇ m or less.
- the shrinkage rate of the resin composition of the present invention when cured is preferably 50% or less, more preferably 45% or less, still more preferably 40% or less.
- the imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more. If it is 70% or more, it may be a cured product having excellent mechanical properties.
- the elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, still more preferably 50% or more.
- the glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180 ° C. or higher, more preferably 210 ° C. or higher, and even more preferably 230 ° C. or higher.
- the resin composition of the present invention can be prepared by mixing each of the above components.
- the mixing method is not particularly limited, and a conventionally known method can be used. For mixing, mixing with a stirring blade, mixing with a ball mill, mixing by rotating the tank itself, or the like can be adopted.
- the temperature during mixing is preferably 10 to 30 ° C, more preferably 15 to 25 ° C.
- the filter hole diameter may be, for example, 5 ⁇ m or less, preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, still more preferably 0.1 ⁇ m or less.
- the filter material is preferably polytetrafluoroethylene, polyethylene or nylon. When the material of the filter is polyethylene, it is more preferable to use HDPE (high density polyethylene).
- the filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel for use.
- filters having different pore diameters or materials may be used in combination.
- the connection mode include a mode in which an HDPE filter having a hole diameter of 1 ⁇ m is connected in series as the first stage and an HDPE filter having a hole diameter of 0.2 ⁇ m is connected in series as the second stage.
- various materials may be filtered a plurality of times. When filtering multiple times, circulation filtration may be used. Moreover, you may pressurize and perform filtration.
- the pressure to be pressurized is, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, and more preferably 0.05 MPa or more and 0.7 MPa or less. , 0.05 MPa or more and 0.5 MPa or less is more preferable.
- impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined.
- the adsorbent a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
- the resin composition filled in the bottle may be placed under reduced pressure to perform a step of degassing.
- the method for producing a cured product of the present invention preferably includes a film forming step of applying a resin composition onto a substrate to form a film. Further, in the method for producing a cured product of the present invention, the film forming step, the exposure step of selectively exposing the film formed by the film forming step, and the film exposed by the exposure step are developed using a developing solution. It is more preferable to include a developing step of forming a pattern.
- the method for producing a cured product of the present invention includes the film forming step, the exposure step, the developing step, and the heating step for heating the pattern obtained by the developing step and the post-development for exposing the pattern obtained by the developing step.
- the production method of the present invention includes the above-mentioned film forming step and the above-mentioned step of heating the film.
- the production method of the present invention includes the above-mentioned film forming step and the above-mentioned step of heating the film.
- the resin composition of the present invention can be applied to a substrate to form a film and can be used in a film forming step.
- the method for producing a cured product of the present invention preferably includes a film forming step of applying a resin composition onto a substrate to form a film.
- the type of the base material can be appropriately determined depending on the application, but semiconductor-made base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin-film transistor, Either a magnetic film, a reflective film, a metal substrate such as Ni, Cu, Cr, or Fe (for example, a substrate formed of metal, or a substrate in which a metal layer is formed by, for example, plating or thin film deposition, etc.). (May be good), paper, SOG (Spin On Glass), TFT (thin film transistor) array base material, mold base material, electrode plate of plasma display panel (PDP), and the like, and are not particularly limited.
- semiconductor-made base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin-film transistor, Either a magnetic film, a reflective film, a metal substrate such as Ni, Cu, Cr, or Fe (for
- a semiconductor-made base material is particularly preferable, and a silicon base material, a Cu base material, and a molded base material are more preferable. Further, these substrates may be provided with a layer such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) or the like on the surface thereof.
- the shape of the base material is not particularly limited, and may be circular or rectangular. The size of the base material is, for example, 100 to 450 mm in diameter, preferably 200 to 450 mm in a circular shape. If it is rectangular, for example, the length of the short side is 100 to 1000 mm, preferably 200 to 700 mm.
- a plate-shaped base material (substrate), preferably a panel-shaped base material (board) is used as the base material.
- a resin composition when a resin composition is applied to the surface of a resin layer (for example, a layer made of a cured product) or the surface of a metal layer to form a film, the resin layer or the metal layer becomes a base material.
- Coating is preferable as a means for applying the resin composition of the present invention on a substrate.
- the means to be applied include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, and a slit coating method.
- An inkjet method and the like are exemplified. From the viewpoint of film thickness uniformity, a spin coating method, a slit coating method, a spray coating method, or an inkjet method is more preferable, and spin coating is performed from the viewpoint of film thickness uniformity and productivity.
- the method and the slit coating method are preferable. By adjusting the solid content concentration and the coating conditions of the resin composition according to the method, a film having a desired thickness can be obtained.
- the coating method can be appropriately selected depending on the shape of the substrate.
- a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular substrate, a slit coating method or a spray coating method is preferable.
- the method, the inkjet method and the like are preferable.
- the spin coating method for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. Further, it is also possible to apply a method of transferring a coating film previously applied onto a temporary support by the above-mentioned application method onto a substrate.
- the production method described in paragraphs 0023 and 0036 to 0051 of JP-A-2006-023696 and paragraphs 0090 to 0108 of JP-A-2006-047592 can be suitably used in the present invention.
- a step of removing the excess film at the end of the base material may be performed. Examples of such a process include edge bead rinse (EBR), back rinse and the like.
- EBR edge bead rinse
- a pre-wet step of applying various solvents to the base material before applying the resin composition to the base material to improve the wettability of the base material and then applying the resin composition may be adopted.
- the film may be subjected to a step (drying step) of drying the film (layer) formed to remove the solvent after the film forming step (layer forming step). That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed by the film forming step. Further, it is preferable that the drying step is performed after the film forming step and before the exposure step.
- the drying temperature of the film in the drying step is preferably 50 to 150 ° C, more preferably 70 ° C to 130 ° C, still more preferably 90 ° C to 110 ° C. Further, drying may be performed by reducing the pressure.
- the drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, more preferably 2 minutes to 7 minutes.
- the film may be subjected to an exposure step of selectively exposing the film. That is, the method for producing a cured product of the present invention may include an exposure step of selectively exposing the film formed by the film forming step. Selective exposure means exposing a part of the film. Further, by selectively exposing the film, an exposed region (exposed portion) and an unexposed region (non-exposed portion) are formed on the film.
- the exposure amount is not particularly determined as long as the resin composition of the present invention can be cured, but for example, it is preferably 50 to 10,000 mJ / cm 2 in terms of exposure energy at a wavelength of 365 nm, and 200 to 8,000 mJ / cm 2 . Is more preferable.
- the exposure wavelength can be appropriately set in the range of 190 to 1,000 nm, preferably 240 to 550 nm.
- the exposure wavelengths are as follows: (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength).
- the resin composition of the present invention is particularly preferably exposed to a high-pressure mercury lamp, and above all, to be exposed to i-rays.
- the exposure method is not particularly limited as long as it is a method in which at least a part of the film made of the resin composition of the present invention is exposed, but exposure using a photomask, exposure by a laser direct imaging method, or the like is possible. Can be mentioned.
- the film may be subjected to a step of heating after exposure (post-exposure heating step). That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the film exposed by the exposure step.
- the post-exposure heating step can be performed after the exposure step and before the developing step.
- the heating temperature in the post-exposure heating step is preferably 50 ° C to 140 ° C, more preferably 60 ° C to 120 ° C.
- the heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.
- the heating rate in the post-exposure heating step is preferably 1 to 12 ° C./min, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min from the temperature at the start of heating to the maximum heating temperature. Further, the heating rate may be appropriately changed during heating.
- the heating means in the post-exposure heating step is not particularly limited, and a known hot plate, oven, infrared heater, or the like can be used. Further, it is also preferable to carry out the heating in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium or argon.
- the film after exposure may be subjected to a developing step of developing with a developing solution to form a pattern.
- the method for producing a cured product of the present invention may include a developing step of developing a film exposed by the exposure step with a developing solution to form a pattern.
- a developing step of developing a film exposed by the exposure step with a developing solution to form a pattern By performing the development, one of the exposed portion and the non-exposed portion of the film is removed, and a pattern is formed.
- the development in which the non-exposed portion of the film is removed by the developing step is called negative type development
- the development in which the exposed portion of the film is removed by the developing step is called positive type development.
- Examples of the developing solution used in the developing step include an alkaline aqueous solution or a developing solution containing an organic solvent.
- the developing solution is an alkaline aqueous solution
- examples of the basic compound that the alkaline aqueous solution can contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts.
- TMAH Tetramethylammonium Hydroxide
- potassium hydroxide sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine , Dimethylethanolamine, Triethanolamine, Tetraethylammonium Hydroxide, Tetrapropylammonium Hydroxide, Tetrabutylammonium Hydroxide, Tetrapentyl Ammonium Hydroxide, Tetrahexyl Ammonium Hydroxide, Tetraoctyl Ammonium Hydroxide, Ethyltrimethylammonium Hydroxide , Butyltrimethylammonium Hydroxide, Methyltriamylammonium Hydroxide, Dibutyldipentylammonium Hydroxide, dimethylbis (2-Hydroxyethyl) Ammonium Hydroxide, tri
- the content of the basic compound in the developing solution is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and 0.3 to 3% by mass in the total mass of the developing solution. Is more preferable.
- the organic solvent may be, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, etc.
- alkyl alkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxy
- Ethyl, etc. methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, etc.
- Ethyl glycol monomethyl ether ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene Glycol monoethyl ether acetate, propylene Glycolmonopropyl ether acetate and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and as cyclic hydrocarbons, for example, for example.
- ketones for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-h
- Aromatic hydrocarbons such as toluene, xylene, and anisole, cyclic terpenes such as limonene, dimethylsulfoxide as sulfoxides, and methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, and diethylene glycol as alcohols.
- Preferable examples thereof include propylene glycol, methylisobutylcarbinol, triethyleneglycol and the like
- examples of the amides include N-methylpyrrolidone, N-ethylpyrrolidone and dimethylformamide.
- the developer contains an organic solvent
- one type or a mixture of two or more types of organic solvent can be used.
- a developer containing at least one selected from the group consisting of cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferable, and cyclopentanone and ⁇ -butyrolactone are preferable.
- a developer containing at least one selected from the group consisting of dimethyl sulfoxide and dimethyl sulfoxide is more preferable, and a developer containing cyclopentanone is most preferable.
- the content of the organic solvent with respect to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, and more preferably 80% by mass or more. Is more preferable, and 90% by mass or more is particularly preferable. Further, the content may be 100% by mass.
- the developer may further contain other components.
- other components include known surfactants and known defoaming agents.
- the method of supplying the developing solution is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material on which the film is formed in the developing solution and the method of supplying the developing solution to the film formed on the base material using a nozzle.
- the type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
- the method of supplying the developing solution with a straight nozzle or the method of continuously supplying the developing solution with a spray nozzle is preferable. From the viewpoint of permeability, the method of supplying with a spray nozzle is more preferable. Further, after the developer is continuously supplied by the straight nozzle, the base material is spun to remove the developer from the base material, and after spin drying, the developer is continuously supplied by the straight nozzle again, and then the base material is spun to use the developer as the base material. A step of removing from the top may be adopted, or this step may be repeated a plurality of times.
- the method of supplying the developer in the developing process includes a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept in a substantially stationary state on the substrate, and a process in which the developer is superposed on the substrate.
- a process of vibrating with a sound wave or the like and a process of combining them can be adopted.
- the development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes.
- the temperature of the developing solution at the time of development is not particularly determined, but is preferably 10 to 45 ° C, more preferably 18 ° C to 30 ° C.
- the pattern may be further washed (rinsed) with the rinsing solution. Further, a method such as supplying a rinse liquid before the developer in contact with the pattern is completely dried may be adopted.
- the developing solution is an alkaline aqueous solution
- water can be used as the rinsing solution.
- the developer is a developer containing an organic solvent, for example, a solvent different from the solvent contained in the developer (for example, water or an organic solvent different from the organic solvent contained in the developer) is used as the rinse solution. be able to.
- the esters include, for example, ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate.
- alkyl alkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, methoxyacetic acid) Eth
- 2-alkyloxypropionate alkyl esters eg, methyl 2-alkyl
- Ethylene glycol monomethyl ether Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), Propylene glycol monoethyl ether acetate, propionate Lopyrene glycol monopropyl ether acetate and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and as cyclic hydrocarbons, for example.
- ketones for example, methyl ethyl ketone, cyclohexanone,
- Aromatic hydrocarbons such as toluene, xylene, anisole, cyclic terpenes such as limonene, dimethylsulfoxide as sulfoxides, and methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol as alcohols.
- Propylene glycol, methylisobutylcarbinol, triethyleneglycol and the like, and examples of the amides include N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide and the like.
- the rinsing liquid contains an organic solvent
- one type or a mixture of two or more types of organic solvent can be used.
- cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA and PGME are particularly preferable, cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, PGMEA and PGME are more preferable, and cyclohexanone and PGMEA are more preferable. More preferred.
- the rinsing liquid contains an organic solvent
- 50% by mass or more of the rinsing liquid is preferably an organic solvent, 70% by mass or more is more preferably an organic solvent, and 90% by mass or more is an organic solvent. Is more preferable.
- the rinse liquid may be 100% by mass of an organic solvent.
- the rinse solution may further contain other components.
- other components include known surfactants and known defoaming agents.
- the method of supplying the rinsing liquid is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material in the rinsing liquid, the method of supplying the rinsing liquid to the base material by filling, and the method of supplying the rinsing liquid to the base material by a shower.
- the method of supplying the rinse liquid with a shower nozzle, a straight nozzle, a spray nozzle, etc. there is a method of supplying the rinse liquid with a spray nozzle is preferable. From the viewpoint of the permeability of the rinse liquid into the image portion, the method of supplying with a spray nozzle is more preferable.
- the type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
- the rinsing step is preferably a step of supplying the rinsing liquid to the exposed film by a straight nozzle or continuously, and more preferably a step of supplying the rinsing liquid by a spray nozzle.
- a method of supplying the rinse liquid in the rinsing step a step of continuously supplying the rinse liquid to the base material, a step of keeping the rinse liquid in a substantially stationary state on the base material, and a step of superimposing the rinse liquid on the base material.
- a process of vibrating with a sonic or the like and a process of combining them can be adopted.
- the rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes.
- the temperature of the rinsing liquid at the time of rinsing is not particularly determined, but is preferably 10 to 45 ° C, more preferably 18 ° C to 30 ° C.
- the pattern obtained by the developing step (in the case of performing the rinsing step, the pattern after rinsing) may be subjected to a heating step of heating the pattern obtained by the above-mentioned development. That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained by the developing step. Further, the method for producing a cured product of the present invention may include a pattern obtained by another method without performing a developing step, or a heating step of heating the film obtained by the film forming step. In the heating step, the resin such as the polyimide precursor is cyclized to become the resin such as polyimide.
- the heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450 ° C, more preferably 150 to 350 ° C, further preferably 150 to 250 ° C, further preferably 160 to 250 ° C, and particularly preferably 160 to 230 ° C. preferable.
- the heating step is preferably a step of promoting the cyclization reaction of the polyimide precursor in the pattern by the action of the base or the like generated from the base generator by heating.
- the heating in the heating step is preferably performed at a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature.
- the temperature rising rate is more preferably 2 to 10 ° C./min, even more preferably 3 to 10 ° C./min.
- the temperature at the start of heating it is preferable to carry out from the temperature at the start of heating to the maximum heating temperature at a heating rate of 1 to 8 ° C./sec, more preferably 2 to 7 ° C./sec, and 3 to 6 ° C. °C / sec is more preferable.
- the temperature at the start of heating is preferably 20 ° C to 150 ° C, more preferably 20 ° C to 130 ° C, and even more preferably 25 ° C to 120 ° C.
- the temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature is started.
- the resin composition of the present invention when applied onto a substrate and then dried, it is the temperature of the film (layer) after drying, for example, from the boiling point of the solvent contained in the resin composition of the present invention.
- the heating time (heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.
- the heating temperature is preferably 30 ° C. or higher, more preferably 80 ° C. or higher, still more preferably 100 ° C. or higher, from the viewpoint of adhesion between layers. It is particularly preferable that the temperature is 120 ° C. or higher.
- the upper limit of the heating temperature is preferably 350 ° C. or lower, more preferably 250 ° C. or lower, and even more preferably 240 ° C. or lower.
- Heating may be performed in stages. As an example, the temperature is raised from 25 ° C. to 120 ° C. at 3 ° C./min and held at 120 ° C. for 60 minutes, the temperature is raised from 120 ° C. to 180 ° C. at 2 ° C./min, and the temperature is kept at 180 ° C. for 120 minutes. , And so on. It is also preferable to perform the treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547. It is possible to improve the characteristics of the film by such a pretreatment step.
- the pretreatment step may be performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes.
- the pretreatment may be performed in two or more steps, for example, the first pretreatment step may be performed in the range of 100 to 150 ° C., and then the second pretreatment step may be performed in the range of 150 to 200 ° C. good. Further, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.
- the heating step is preferably carried out in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium or argon or under reduced pressure in order to prevent decomposition of the specific resin.
- the oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
- the heating means in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared furnace, an electric heating oven, a hot air oven, and an infrared oven.
- the method for producing a cured product of the present invention may include a post-development exposure step for exposing the pattern obtained by the developing step.
- the method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of a heating step and a post-development exposure step.
- the post-development exposure step for example, a reaction in which cyclization of a polyimide precursor or the like is promoted by exposure to a photobase generator, a reaction in which desorption of an acid-degradable group is promoted by exposure to a photoacid generator, etc. are promoted. can do.
- the post-development exposure step at least a part of the pattern obtained in the development step may be exposed, but it is preferable that all of the above patterns are exposed.
- the exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ / cm 2 and more preferably 100 to 15,000 mJ / cm 2 in terms of exposure energy at a wavelength at which the photosensitive compound has sensitivity. preferable.
- the post-development exposure step can be performed using, for example, the light source in the above-mentioned exposure step, and it is preferable to use broadband light.
- the pattern obtained by the developing step may be subjected to the metal layer forming step of forming the metal layer on the pattern.
- the method for producing a cured product of the present invention includes a metal layer forming step of forming a metal layer on a pattern obtained by a developing step (preferably one provided in at least one of a heating step and a post-development exposure step). Is preferable.
- metal layer existing metal species can be used without particular limitation, and examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are more preferred, and copper is even more preferred.
- the method for forming the metal layer is not particularly limited, and an existing method can be applied.
- the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, JP-A-2004-101850, US Pat. No. 7,788,181B2, US Pat. No. 9,177,926B2 are used. can do.
- photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electrolytic plating, electroless plating, etching, printing, and a combination of these can be considered.
- a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electrolytic plating can be mentioned.
- Preferred embodiments of plating include electrolytic plating using a copper sulfate or copper cyanide plating solution.
- the thickness of the metal layer is preferably 0.01 to 50 ⁇ m, more preferably 1 to 10 ⁇ m in the thickest portion.
- Examples of the method for producing a cured product of the present invention or the applicable field of the cured product of the present invention include an insulating film for an electronic device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like.
- Other examples include forming a pattern by etching on a sealing film, a substrate material (base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above. For these applications, for example, Science & Technology Co., Ltd.
- the method for producing a cured product of the present invention, or the cured product of the present invention is used for manufacturing a plate surface such as an offset plate surface or a screen plate surface, using it for etching molded parts, protective lacquer and dielectric in electronics, especially microelectronics. It can also be used for layer production and the like.
- the laminated body of the present invention refers to a structure having a plurality of layers made of the cured product of the present invention.
- the laminated body of the present invention is a laminated body containing two or more layers made of a cured product, and may be a laminated body in which three or more layers are laminated.
- the two or more layers made of the cured product contained in the laminated body at least one is a layer made of the cured product of the present invention, which causes shrinkage of the cured product or deformation of the cured product due to the shrinkage. From the viewpoint of suppressing, it is also preferable that the layer made of all the cured products contained in the laminated body is the layer made of the cured product of the present invention.
- the method for producing a laminated body of the present invention preferably includes the method for producing a cured product of the present invention, and more preferably includes repeating the method for producing a cured product of the present invention a plurality of times.
- the laminated body of the present invention contains two or more layers made of a cured product and contains a metal layer between any of the layers made of the cured product.
- the metal layer is preferably formed by the metal layer forming step. That is, it is preferable that the method for producing a laminated body of the present invention further includes a metal layer forming step of forming a metal layer on a layer made of the cured product between the methods for producing a cured product which is performed a plurality of times.
- the preferred embodiment of the metal layer forming step is as described above.
- a laminate including at least a layer structure in which three layers of a layer made of a first cured product, a metal layer, and a layer made of a second cured product are laminated in this order is preferable. Be done. It is preferable that the layer made of the first cured product and the layer made of the second cured product are both layers made of the cured product of the present invention.
- the resin composition of the present invention used for forming the layer made of the first cured product and the resin composition of the present invention used for forming the layer made of the second cured product have the same composition. It may be a product or a composition having a different composition.
- the metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.
- the method for producing a laminated body of the present invention preferably includes a laminating step.
- the laminating step means that (a) a film forming step (layer forming step), (b) an exposure step, (c) a developing step, (d) a heating step and development are performed again on the surface of a pattern (resin layer) or a metal layer. It is a series of steps including performing at least one of the post-exposure steps in this order. However, it may be an embodiment in which at least one of the film forming step (a), the heating step and the post-development exposure step (d) is repeated. Further, (e) a metal layer forming step may be included after at least one of the (d) heating step and the post-development exposure step. Needless to say, the laminating step may further include the above-mentioned drying step and the like as appropriate.
- the surface activation treatment step may be further performed after the exposure step, the heating step, or the metal layer forming step.
- Plasma treatment is exemplified as the surface activation treatment. Details of the surface activation treatment will be described later.
- the laminating step is preferably performed 2 to 20 times, more preferably 2 to 9 times.
- a structure having two or more and 20 or less resin layers such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferable, and a structure having two or more and 9 or less layers is more preferable. ..
- the composition, shape, film thickness, etc. of each of the above layers may be the same or different.
- a cured product (resin layer) of the resin composition of the present invention so as to further cover the metal layer after the metal layer is provided.
- a film forming step an exposure step, (c) a developing step, (d) at least one of a heating step and a post-development exposure step (e) a metal layer forming step is repeated in this order.
- a film forming step an exposure step
- a developing step a developing step
- a metal layer forming step is repeated in this order.
- a film forming step, (d) at least one of a heating step and a post-development exposure step, and (e) a metal layer forming step is repeated in this order.
- the method for producing a laminate of the present invention preferably includes a surface activation treatment step of surface activating at least a part of the metal layer and the resin composition layer.
- the surface activation treatment step is usually performed after the metal layer forming step, but after the development step (preferably after at least one of the heating step and the post-development exposure step), the surface activation treatment of the resin composition layer is performed.
- the metal layer forming step may be performed.
- the surface activation treatment may be performed on at least a part of the metal layer, on at least a part of the exposed resin composition layer, or on the metal layer and the exposed resin composition layer. For both, you may go to at least part of each.
- the surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable to perform the surface activation treatment on a part or all of the region forming the resin composition layer on the surface of the metal layer.
- the surface activation treatment is performed on a part or all of the resin composition layer (resin layer) after exposure. As described above, by performing the surface activation treatment on the surface of the resin composition layer, it is possible to improve the adhesion to the metal layer or the resin layer provided on the surface of the surface activation treatment.
- the resin composition layer when the resin composition layer is cured, such as when negative type development is performed, it is less likely to be damaged by the surface treatment and the adhesion is likely to be improved.
- Specific examples of the surface activation treatment include plasma treatment of various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixed gas, argon / oxygen mixed gas, etc.), corona discharge treatment, and CF 4 / O 2 .
- the energy is preferably 500 to 200,000 J / m 2 , more preferably 1000 to 100,000 J / m 2 , and most preferably 10,000 to 50,000 J / m 2 .
- the present invention also discloses a semiconductor device containing the cured product of the present invention or the laminate of the present invention.
- the present invention also discloses a method for producing a cured product of the present invention, or a method for producing a semiconductor device including a method for producing a laminate of the present invention.
- the semiconductor device in which the resin composition of the present invention is used to form the interlayer insulating film for the rewiring layer the description in paragraphs 0213 to 0218 and FIG. 1 of JP-A-2016-0273557 can be referred to. These contents are incorporated in the present specification.
- reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) of pyridine and 90 mL of N-methylpyrrolidone were added.
- the reaction mixture was then cooled to ⁇ 10 ° C. and 16.12 g (135.5 mmol) of SOCL 2 was added over 10 minutes while keeping the temperature at ⁇ 10 ⁇ 4 ° C. Viscosity increased while SOCL 2 was added. After diluting with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours.
- the polyimide precursor was filtered off, stirred again in 4 liters of water for 30 minutes and filtered again.
- the resulting polyimide precursor was then dried under reduced pressure at 45 ° C. for 3 days.
- the weight average molecular weight of this polyimide precursor was 18,000.
- ⁇ Synthesis example 4> [4,4'-oxydiphthalic anhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (orthotridin) and polyimide precursor from 2-hydroxyethyl methacrylate (A-4: having a radically polymerizable group) Synthesis of polyimide precursor)] 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140 ° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, and 0.05 g of hydroquinone.
- the polybenzoxazole precursor was then precipitated in 6 liters of water and the water-polybenzoxazole precursor mixture was stirred at a rate of 5000 rpm for 15 minutes.
- the polybenzoxazole precursor was removed by filtration, stirred again in 6 liters of water for 30 minutes and filtered again.
- the resulting polybenzoxazole precursor was then dried under reduced pressure at 45 ° C. for 3 days.
- the weight average molecular weight of this polybenzoxazole precursor was 15,000.
- the obtained reaction solution was added to 3 liters of ethyl alcohol to form a precipitate composed of a crude polymer.
- the produced crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution.
- the obtained crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer, and the obtained precipitate was collected by filtration and then vacuum dried to obtain a powdery polymer A-6.
- the weight average molecular weight (Mw) of this polymer A-6 was measured and found to be 20,000.
- ⁇ Synthesis example 7> [3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 4,4'-diaminodiphenyl ether, and polyimide precursor from 2-hydroxyethyl methacrylate (A-7: Polyimide having a radically polymerizable group) Synthesis of precursor)] Synthesis Example 6 except that 147.1 g of 3,3'4,4'-biphenyltetracarboxylic dianhydride was used in place of 155.1 g of 4,4'-oxydiphthalic acid dianhydride in Synthesis Example 7. The reaction was carried out in the same manner as described in 1. Polymer A-7 was obtained. The weight average molecular weight (Mw) of this polymer A-7 was measured and found to be 22,000.
- [Polymerizable compound] -C-1 A compound having the following structure-C-2: M-327 (3 mol-modified caprolactone of isocyanuric acid ethylene oxide-modified triacrylate manufactured by Toagosei Co., Ltd.
- N-Phenyldiethanolamine-J-2 Compound with the following structure
- a resin composition or a comparative composition was applied onto a silicon wafer by a spin coating method to form a resin layer.
- the silicon wafer on which the resin layer was formed was dried on a hot plate at 100 ° C. for 4 minutes to obtain a resin composition layer having a uniform thickness of 20 ⁇ m on the silicon wafer.
- the resin composition layer on the silicon wafer was exposed to an exposure energy of 400 mJ / cm 2 using a broadband exposure machine (manufactured by Ushio, Inc .: UX-1000SN-EH01), and the exposed resin composition layer was exposed.
- the temperature was raised at a heating rate of 5 ° C./min under a nitrogen atmosphere, and after reaching 180 ° C., heating was performed at this temperature for 2 hours.
- the heated resin composition layer and the silicon wafer were immersed in a 3 mass% hydrofluoric acid aqueous solution, and the heated resin composition layer was peeled off from the silicon wafer. The peeled and heated resin composition layer was used as a cured product.
- the evaluation was performed according to the following evaluation criteria, and the evaluation results are described in the "Chemical resistance" column of the table. It can be said that the smaller the value of the dissolution rate, the better the chemical resistance of the cured product.
- D The dissolution rate is 500 nm / min or more.
- a resin composition or a comparative composition was applied onto a silicon wafer by a spin coating method to form a resin composition layer.
- the silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a uniform resin composition layer having a thickness of about 15 ⁇ m on the silicon wafer.
- the entire surface of the obtained resin composition layer was exposed to i-line with an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C).
- the resin composition layer (resin layer) after the exposure was heated at a heating rate of 10 ° C./min under a nitrogen atmosphere, reached 230 ° C., and then heated for 3 hours.
- the cured resin layer (cured product) was immersed in a 4.9 mass% hydrofluoric acid aqueous solution, and the cured product was peeled off from the silicon wafer.
- the peeled cured product was punched out using a punching machine to prepare a test piece having a sample width of 3 mm and a sample length of 30 mm.
- the obtained test piece was subjected to a film using a tensile tester (Tencilon) at a crosshead speed of 300 mm / min in an environment of 25 ° C.
- Teencilon tensile tester
- the resin and the resin composition containing the compound A according to the present invention are excellent in the film strength of the obtained cured product.
- the compositions according to Comparative Examples 1 and 2 do not contain compound A. It can be seen that the compositions according to Comparative Examples 1 and 2 are inferior in the film strength of the obtained cured product. Further, from the above results, it can be seen that the resin and the resin composition containing the compound A according to the present invention are excellent in chemical resistance of the obtained cured product.
- the resin compositions according to Comparative Examples 1 and 2 do not contain compound A. It can be seen that the resin compositions according to Comparative Examples 1 and 2 are inferior in the chemical resistance of the obtained cured product.
- Example 101 The resin composition used in Example 1 was applied in a layered manner on the surface of the copper thin layer of the resin substrate having the copper thin layer formed on the surface by a spin coating method, dried at 100 ° C. for 4 minutes, and the film thickness was increased. After forming a 20 ⁇ m photosensitive film, exposure was performed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). Exposure was performed via a mask (a binary mask with a pattern of 1: 1 line and space and a line width of 10 ⁇ m) at a wavelength of 365 nm. After the exposure, it was heated at 100 ° C. for 4 minutes.
- NSR1505 i6 a binary mask with a pattern of 1: 1 line and space and a line width of 10 ⁇ m
- the temperature was raised at a heating rate of 10 ° C./min under a nitrogen atmosphere, and after reaching 230 ° C., the temperature was maintained at 230 ° C. for 120 minutes to form an interlayer insulating film for the rewiring layer.
- the interlayer insulating film for the rewiring layer was excellent in insulating property. Moreover, when a semiconductor device was manufactured using these interlayer insulating films for the rewiring layer, it was confirmed that the semiconductor device operated without any problem.
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Abstract
Description
このような樹脂組成物を、例えば塗布等により基材に適用して感光膜を形成し、その後、必要に応じて露光、現像、加熱等を行うことにより、硬化物を基材上に形成することができる。
上記ポリイミド前駆体等の環化樹脂の前駆体は、例えば加熱により環化され、硬化物中でポリイミド等の環化樹脂となる。
樹脂組成物は、公知の塗布方法等により適用可能であるため、例えば、適用される樹脂組成物の適用時の形状、大きさ、適用位置等の設計の自由度が高いなど、製造上の適応性に優れるといえる。ポリイミド等の環化樹脂が有する高い性能に加え、このような製造上の適応性に優れる観点から、上述の樹脂組成物の産業上の応用展開がますます期待されている。 For example, in the above-mentioned applications, the cyclized resin such as polyimide is used in the form of a resin composition containing a precursor of a cyclized resin such as a polyimide precursor.
Such a resin composition is applied to a substrate by coating, for example, to form a photosensitive film, and then exposed, developed, heated, etc., if necessary, to form a cured product on the substrate. be able to.
The precursor of the cyclized resin such as the polyimide precursor is cyclized by heating, for example, and becomes a cyclized resin such as polyimide in the cured product.
Since the resin composition can be applied by a known coating method or the like, for example, there is a high degree of freedom in designing the shape, size, application position, etc. of the applied resin composition at the time of application. It can be said that it is excellent in sex. In addition to the high performance of cyclized resins such as polyimide, the above-mentioned resin compositions are expected to be increasingly applied in industry from the viewpoint of excellent manufacturing adaptability.
特許文献2には、Diels-Alder反応部位と、少なくとも一つのアクリロイル基とを有し、上記アクリロイル基により重合可能であることを特徴とする単量体が記載されている。 For example, Patent Document 1 describes (A) a polyamide having a specific structural unit in a photosensitive resin composition containing a polyamide and an isocyanuric acid derivative having a photopolymerizable unsaturated bond as an essential component. , (B) The isocyanuric acid derivative having a photopolymerizable unsaturated bond is a specific isocyanuric acid derivative, and (A) the content of (B) is 15 to 70 parts by mass with respect to 100 parts by mass. A characteristic photosensitive resin composition is described.
Patent Document 2 describes a monomer having a Diels-Alder reaction site and at least one acryloyl group, which can be polymerized by the acryloyl group.
<1> シクロヘキセン構造、及び、アセタール構造からなる群より選択される少なくとも1種の構造を含む連結基を介して結合している複数の重合性基を有し、かつ、分子量が1000未満である化合物A、並びに、
環化樹脂の前駆体を含む、
樹脂組成物。
<2> 上記化合物Aにおける重合性基が、エチレン性不飽和結合を有する基である、<1>に記載の樹脂組成物。
<3> 上記化合物Aにおける連結基が、シクロヘキセン構造、及び、アセタール構造よりなる群より選択される少なくとも1種の構造を複数個含む、<1>又は<2>のいずれか1つに記載の樹脂組成物。
<4> 上記化合物Aにおける連結基が、シクロヘキセン構造を複数個含むか、又は、アセタール構造を複数個含む、<1>~<3>のいずれか1つに記載の樹脂組成物。
<5> 上記化合物Aが、下記式(2-1)で表される化合物を含む、<1>~<4>のいずれか1つに記載の樹脂組成物。
式(2-1)中、R1、R2及びR3はそれぞれ独立に、1価の有機基を表し、R1、R2及びR3の少なくとも1つは重合性基を有する基を含む。
<6> 上記R2、R3が下記式(2-2)又は下記式(2-3)のいずれかで表される部分構造を有する基である、<5>に記載の樹脂組成物。
式(2-2)、式(2-3)中、R4はそれぞれ独立に、水素原子または炭素数1~5のアルキル基を表し、*は、式(2-1)に含まれる酸素原子との結合部位を表し、Lは2価の連結基を表す。
<7> 上記式(2-1)で表される化合物が下記式(2-4)で表される化合物である、<5>に記載の樹脂組成物。
式(2-4)中、R4はそれぞれ独立に、水素原子または炭素数1~5のアルキル基を表し、Lは2価の連結基を表す。
<8> 上記化合物Aにおける連結基が、架橋環構造又は縮合環構造を有するシクロヘキセン構造を含む、<1>~<7>のいずれか1つに記載の樹脂組成物。
<9> 上記化合物Aが、下記式(3-1)で表される化合物を含む、<1>~<8>のいずれか1つに記載の樹脂組成物。
式(3-1)中、R1、R2はそれぞれ独立に1価の有機基を表し、R1、R2の少なくとも1つはエチレン性不飽和結合を有する基を含む。
<10> 上記式(3-1)で表される化合物が下記式(3-2)で表される化合物である、<9>に記載の樹脂組成物。
式(3-2)中、R3及びR4はそれぞれ独立に、エチレン性不飽和結合を有する基を含む1価の有機基を表し、Lは2価の連結基を表す。
<11> 上記環化樹脂の前駆体として、ポリイミド前駆体を含む、<1>~<10>のいずれか1つに記載の樹脂組成物。
<12> 上記ポリイミド前駆体が下記式(2)で表される繰返し単位を有する、<11>に記載の樹脂組成物;
式(2)中、A1及びA2は、それぞれ独立に、酸素原子又は-NH-を表し、R111は、2価の有機基を表し、R115は、4価の有機基を表し、R113及びR114は、それぞれ独立に、水素原子又は1価の有機基を表す。
<13> 上記式(2)におけるR113及びR114の少なくとも一方がラジカル重合性基を含む、<12>に記載の樹脂組成物。
<14> ラジカル重合開始剤を更に含む、<1>~<13>のいずれか1つに記載の樹脂組成物。
<15> 再配線層用層間絶縁膜の形成に用いられる、<1>~<14>のいずれか1つに記載の樹脂組成物。
<16> <1>~<15>のいずれか1つに記載の樹脂組成物を硬化してなる硬化物。
<17> <16>に記載の硬化物からなる層を2層以上含み、上記硬化物同士のいずれかの間に金属層を含む積層体。
<18> <1>~<15>のいずれか1つに記載の樹脂組成物を基材上に適用して膜を形成する膜形成工程を含む、硬化物の製造方法。
<19> 上記膜を選択的に露光する露光工程及び上記膜を現像液を用いて現像してパターンを形成する現像工程を含む、<18>に記載の硬化物の製造方法。
<20> 上記膜を50~450℃で加熱する加熱工程を含む、<18>又は<19>に記載の硬化物の製造方法。
<21> <16>に記載の硬化物又は<17>に記載の積層体を含む、半導体デバイス。 Examples of typical embodiments of the present invention are shown below.
<1> It has a plurality of polymerizable groups bonded via a linking group containing at least one structure selected from the group consisting of a cyclohexene structure and an acetal structure, and has a molecular weight of less than 1000. Compound A, and
Contains precursors of cyclized resin,
Resin composition.
<2> The resin composition according to <1>, wherein the polymerizable group in the compound A is a group having an ethylenically unsaturated bond.
<3> The link according to any one of <1> or <2>, wherein the linking group in the compound A contains a plurality of at least one structures selected from the group consisting of a cyclohexene structure and an acetal structure. Resin composition.
<4> The resin composition according to any one of <1> to <3>, wherein the linking group in the compound A contains a plurality of cyclohexene structures or a plurality of acetal structures.
<5> The resin composition according to any one of <1> to <4>, wherein the compound A contains a compound represented by the following formula (2-1).
In formula (2-1), R 1 , R 2 and R 3 each independently represent a monovalent organic group, and at least one of R 1 , R 2 and R 3 contains a group having a polymerizable group. ..
<6> The resin composition according to <5>, wherein R 2 and R 3 are groups having a partial structure represented by either the following formula (2-2) or the following formula (2-3).
In the formula (2-2) and the formula (2-3), R 4 independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and * is an oxygen atom contained in the formula (2-1). Represents a binding site with, and L represents a divalent linking group.
<7> The resin composition according to <5>, wherein the compound represented by the above formula (2-1) is a compound represented by the following formula (2-4).
In formula (2-4), R 4 independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and L represents a divalent linking group.
<8> The resin composition according to any one of <1> to <7>, wherein the linking group in the compound A contains a cyclohexene structure having a crosslinked ring structure or a condensed ring structure.
<9> The resin composition according to any one of <1> to <8>, wherein the compound A contains a compound represented by the following formula (3-1).
In formula (3-1), R 1 and R 2 each independently represent a monovalent organic group, and at least one of R 1 and R 2 contains a group having an ethylenically unsaturated bond.
<10> The resin composition according to <9>, wherein the compound represented by the above formula (3-1) is a compound represented by the following formula (3-2).
In formula (3-2), R 3 and R 4 each independently represent a monovalent organic group containing a group having an ethylenically unsaturated bond, and L represents a divalent linking group.
<11> The resin composition according to any one of <1> to <10>, which comprises a polyimide precursor as the precursor of the cyclized resin.
<12> The resin composition according to <11>, wherein the polyimide precursor has a repeating unit represented by the following formula (2);
In formula (2), A 1 and A 2 independently represent an oxygen atom or -NH-, R 111 represents a divalent organic group, and R 115 represents a tetravalent organic group. R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group.
<13> The resin composition according to <12>, wherein at least one of R 113 and R 114 in the above formula (2) contains a radically polymerizable group.
<14> The resin composition according to any one of <1> to <13>, further comprising a radical polymerization initiator.
<15> The resin composition according to any one of <1> to <14>, which is used for forming an interlayer insulating film for a rewiring layer.
<16> A cured product obtained by curing the resin composition according to any one of <1> to <15>.
<17> A laminated body containing two or more layers made of the cured product according to <16> and containing a metal layer between any of the cured products.
<18> A method for producing a cured product, which comprises a film forming step of applying the resin composition according to any one of <1> to <15> onto a substrate to form a film.
<19> The method for producing a cured product according to <18>, which comprises an exposure step of selectively exposing the film and a developing step of developing the film with a developer to form a pattern.
<20> The method for producing a cured product according to <18> or <19>, which comprises a heating step of heating the film at 50 to 450 ° C.
<21> A semiconductor device comprising the cured product according to <16> or the laminate according to <17>.
本明細書において「~」という記号を用いて表される数値範囲は、「~」の前後に記載される数値をそれぞれ下限値及び上限値として含む範囲を意味する。
本明細書において「工程」との語は、独立した工程だけではなく、その工程の所期の作用が達成できる限りにおいて、他の工程と明確に区別できない工程も含む意味である。
本明細書における基(原子団)の表記において、置換及び無置換を記していない表記は、置換基を有しない基(原子団)と共に置換基を有する基(原子団)をも包含する。例えば、「アルキル基」とは、置換基を有しないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含する。
本明細書において「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線、イオンビーム等の粒子線を用いた露光も含む。また、露光に用いられる光としては、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線(EUV光)、X線、電子線等の活性光線又は放射線が挙げられる。
本明細書において、「(メタ)アクリレート」は、「アクリレート」及び「メタクリレート」の両方、又は、いずれかを意味し、「(メタ)アクリル」は、「アクリル」及び「メタクリル」の両方、又は、いずれかを意味し、「(メタ)アクリロイル」は、「アクリロイル」及び「メタクリロイル」の両方、又は、いずれかを意味する。
本明細書において、構造式中のMeはメチル基を表し、Etはエチル基を表し、Buはブチル基を表し、Phはフェニル基を表す。
本明細書において、全固形分とは、組成物の全成分から溶剤を除いた成分の総質量をいう。また本明細書において、固形分濃度とは、組成物の総質量に対する、溶剤を除く他の成分の質量百分率である。
本明細書において、重量平均分子量(Mw)及び数平均分子量(Mn)は、特に述べない限り、ゲル浸透クロマトグラフィ(GPC)法を用いて測定した値であり、ポリスチレン換算値として定義される。本明細書において、重量平均分子量(Mw)及び数平均分子量(Mn)は、例えば、HLC-8220GPC(東ソー(株)製)を用い、カラムとしてガードカラムHZ-L、TSKgel Super HZM-M、TSKgel Super HZ4000、TSKgel Super HZ3000、及び、TSKgel Super HZ2000(以上、東ソー(株)製)を直列に連結して用いることによって求めることができる。それらの分子量は特に述べない限り、溶離液としてTHF(テトラヒドロフラン)を用いて測定したものとする。ただし、溶解性が低い場合など、溶離液としてTHFが適していない場合にはNMP(N-メチル-2-ピロリドン)を用いることもできる。また、GPC測定における検出は特に述べない限り、UV線(紫外線)の波長254nm検出器を使用したものとする。
本明細書において、積層体を構成する各層の位置関係について、「上」又は「下」と記載したときには、注目している複数の層のうち基準となる層の上側又は下側に他の層があればよい。すなわち、基準となる層と上記他の層の間に、更に第3の層や要素が介在していてもよく、基準となる層と上記他の層は接している必要はない。また、特に断らない限り、基材に対し層が積み重なっていく方向を「上」と称し、又は、樹脂組成物層がある場合には、基材から樹脂組成物層へ向かう方向を「上」と称し、その反対方向を「下」と称する。なお、このような上下方向の設定は、本明細書中における便宜のためであり、実際の態様においては、本明細書における「上」方向は、鉛直上向きと異なることもありうる。
本明細書において、特段の記載がない限り、組成物は、組成物に含まれる各成分として、その成分に該当する2種以上の化合物を含んでもよい。また、特段の記載がない限り、組成物における各成分の含有量とは、その成分に該当する全ての化合物の合計含有量を意味する。
本明細書において、特に述べない限り、温度は23℃、気圧は101,325Pa(1気圧)、相対湿度は50%RHである。
本明細書において、好ましい態様の組み合わせは、より好ましい態様である。 Hereinafter, the main embodiments of the present invention will be described. However, the present invention is not limited to the specified embodiments.
In the present specification, the numerical range represented by the symbol "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.
As used herein, the term "process" means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended action of the process can be achieved.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, 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).
As used herein, the term "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of the light used for exposure include emission line spectra of mercury lamps, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
As used herein, "(meth) acrylate" means both "acrylate" and "methacrylate", or either, and "(meth) acrylic" means both "acrylic" and "methacrylic", or. , Any, and "(meth) acryloyl" means both "acryloyl" and "methacrylic", or either.
In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
As used herein, the total solid content means the total mass of all the components of the composition excluding the solvent. Further, in the present specification, the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured by gel permeation chromatography (GPC) method and are defined as polystyrene-equivalent values unless otherwise specified. In the present specification, for the weight average molecular weight (Mw) and the number average molecular weight (Mn), for example, HLC-8220GPC (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. It can be obtained by connecting and using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) in series. Unless otherwise specified, their molecular weights shall be measured using THF (tetrahydrofuran) as an eluent. However, NMP (N-methyl-2-pyrrolidone) can also be used when THF is not suitable as the eluent, such as when the solubility is low. Further, unless otherwise specified, the detection in the GPC measurement shall be performed by using a detector having a wavelength of 254 nm of UV rays (ultraviolet rays).
In the present specification, when the positional relationship of each layer constituting the laminated body is described as "upper" or "lower", the other layer is on the upper side or the lower side of the reference layer among the plurality of layers of interest. All you need is. That is, a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer and the other layer need not be in contact with each other. Unless otherwise specified, the direction in which the layers are stacked on the base material is referred to as "upper", or if there is a resin composition layer, the direction from the base material to the resin composition layer is referred to as "upper". And the opposite direction is called "down". It should be noted that such a vertical setting is for convenience in the present specification, and in an actual embodiment, the "up" direction in the present specification may be different from the vertical upward direction.
Unless otherwise specified in the present specification, the composition may contain, as each component contained in the composition, two or more compounds corresponding to the component. Further, unless otherwise specified, the content of each component in the composition means the total content of all the compounds corresponding to the component.
In the present specification, unless otherwise specified, the temperature is 23 ° C., the atmospheric pressure is 101,325 Pa (1 atm), and the relative humidity is 50% RH.
As used herein, a combination of preferred embodiments is a more preferred embodiment.
本発明の樹脂組成物は、シクロヘキセン構造、及び、アセタール構造からなる群より選択される少なくとも1種の構造を含む連結基を介して結合している複数の重合性基を有し、かつ、分子量が1000未満である化合物A(以下、単に「化合物A」ともいう。)、並びに、環化樹脂の前駆体(以下、「特定樹脂」ともいう。)を含む。 (Resin composition)
The resin composition of the present invention has a plurality of polymerizable groups bonded via a linking group containing at least one structure selected from the group consisting of a cyclohexene structure and an acetal structure, and has a molecular weight. Contains compound A (hereinafter, also simply referred to as “compound A”) having a value of less than 1000, and a precursor of a cyclization resin (hereinafter, also referred to as “specific resin”).
また、本発明の樹脂組成物は、ネガ型現像に供される感光膜の形成に用いられることが好ましい。
本発明において、ネガ型現像とは、露光及び現像において、現像により非露光部が除去される現像をいい、ポジ型現像とは、現像により露光部が除去される現像をいう。
上記露光の方法、上記現像液、及び、上記現像の方法としては、例えば、後述する硬化物の製造方法の説明における露光工程において説明された露光方法、現像工程において説明された現像液及び現像方法が使用される。 The resin composition of the present invention is preferably used for forming a photosensitive film to be subjected to exposure and development, and may be used for exposure and formation of a film to be subjected to development using a developing solution containing an organic solvent. preferable.
Further, the resin composition of the present invention is preferably used for forming a photosensitive film to be subjected to negative type development.
In the present invention, negative-type development refers to development in which a non-exposed portion is removed by development in exposure and development, and positive-type development refers to development in which an exposed portion is removed by development.
The exposure method, the developer, and the developing method include, for example, the exposure method described in the exposure step in the description of the method for producing a cured product described later, the developer and the developing method described in the developing step. Is used.
上記効果が得られるメカニズムは不明であるが、下記のように推測される。 The resin composition of the present invention is excellent in the film strength of the obtained cured product.
The mechanism by which the above effect is obtained is unknown, but it is presumed as follows.
本発明者らは、鋭意検討した結果、硬化物中で上記重合により形成される架橋構造の密度が高くなるほど、硬化物中での特定樹脂の環化率が低くなり、硬化物の膜強度が低下する場合があることを見出した。これは、上記架橋構造の密度が高くなりすぎると、環化樹脂の前駆体における構造変化が阻害されてしまうためであると推測される。
このような構造変化の阻害は、特に、露光等により、加熱前に重合性化合物の重合を進行させた場合に顕著に表れると考えられる。
本発明の樹脂組成物は、シクロヘキセン構造、及び、アセタール構造からなる群より選択される少なくとも1種の構造を含む連結基を介して結合している複数の重合性基を有し、かつ、分子量が1000未満である化合物Aを有する。
上記化合物Aは、例えば露光、加熱等により重合性基の重合が進行したとしても、加熱時にはシクロヘキセン構造、又は、アセタール構造が分解すると考えられる。そのため、上述の環化樹脂の前駆体における構造変化の阻害が起こりにくくなり、硬化物中の特定樹脂の環化率が高くなる結果、硬化物の膜強度が向上すると考えられる。
また、上記化合物Aにおけるシクロヘキセン構造、又は、アセタール構造は、加熱時には切断されているが、加熱後に例えば室温(23℃)まで冷却された際に再度結合が形成されると考えられる。
そのため、本発明の樹脂組成物により得られる硬化物は、硬化物中に環化率の高い環化樹脂が存在し、かつ、架橋構造の密度が高くなるため、耐薬品性にも優れると推測される。 Conventionally, in a resin composition containing a cyclized resin precursor and a polymerizable compound, cyclization of the cyclized resin precursor and polymerization of the polymerizable compound can be promoted by heating or the like to obtain a cured product. It is done.
As a result of diligent studies, the present inventors have made that the higher the density of the crosslinked structure formed by the above polymerization in the cured product, the lower the cyclization rate of the specific resin in the cured product, and the higher the film strength of the cured product. We have found that it may decrease. It is presumed that this is because if the density of the crosslinked structure becomes too high, the structural change in the precursor of the cyclized resin is hindered.
It is considered that such inhibition of the structural change is particularly remarkable when the polymerization of the polymerizable compound is promoted before heating by exposure or the like.
The resin composition of the present invention has a plurality of polymerizable groups bonded via a linking group containing at least one structure selected from the group consisting of a cyclohexene structure and an acetal structure, and has a molecular weight. Has compound A in which is less than 1000.
It is considered that the cyclohexene structure or the acetal structure of the compound A is decomposed at the time of heating even if the polymerization of the polymerizable group proceeds by, for example, exposure or heating. Therefore, it is considered that the inhibition of the structural change in the precursor of the above-mentioned cyclized resin is less likely to occur, and the cyclization rate of the specific resin in the cured product is increased, and as a result, the film strength of the cured product is improved.
Further, the cyclohexene structure or the acetal structure in the compound A is cleaved at the time of heating, but it is considered that a bond is formed again when the compound A is cooled to room temperature (23 ° C.) after heating, for example.
Therefore, it is presumed that the cured product obtained by the resin composition of the present invention has excellent chemical resistance because a cyclized resin having a high cyclization rate is present in the cured product and the density of the crosslinked structure is high. Will be done.
本発明の樹脂組成物は、シクロヘキセン構造、及び、アセタール構造からなる群より選択される少なくとも1種の構造を含む連結基を介して結合している複数の重合性基を有し、かつ、分子量が1000未満である化合物Aを含む。
化合物Aの分子量は1000未満であり、900以下であることが好ましく、800以下であることがより好ましい。上記分子量の下限は特に限定されないが、例えば、200以上であることが好ましい。 <Compound A>
The resin composition of the present invention has a plurality of polymerizable groups bonded via a linking group containing at least one structure selected from the group consisting of a cyclohexene structure and an acetal structure, and has a molecular weight. Contains compound A in which is less than 1000.
The molecular weight of compound A is less than 1000, preferably 900 or less, and more preferably 800 or less. The lower limit of the molecular weight is not particularly limited, but is preferably 200 or more, for example.
化合物Aに含まれる重合性基としては、熱、ラジカル等の作用により架橋反応することが可能な基であって、ラジカル重合性基が好ましい。重合性基の具体例としては、エチレン性不飽和結合を有する基、アルコキシメチル基、ヒドロキシメチル基、アシルオキシメチル基、エポキシ基、オキセタニル基、ベンゾオキサゾリル基、ブロックイソシアネート基、アミノ基が挙げられ、エチレン性不飽和結合を有する基が好ましい。
エチレン性不飽和結合を有する基としては、(メタ)アクリロキシ基、(メタ)アクリルアミド基、ビニルフェニル基等の芳香環に直接ビニル基が結合した基、アリル基、ビニル基等が挙げられるが、反応性の観点からは(メタ)アクリロキシ基が好ましい。 [Polymerizable group]
As the polymerizable group contained in the compound A, a radically polymerizable group is preferable because it is a group capable of undergoing a cross-linking reaction by the action of heat, radicals and the like. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group and an amino group. A group having an ethylenically unsaturated bond is preferable.
Examples of the group having an ethylenically unsaturated bond include a (meth) acryloxy group, a (meth) acrylamide group, a group in which a vinyl group is directly bonded to an aromatic ring such as a vinylphenyl group, an allyl group, a vinyl group and the like. From the viewpoint of reactivity, a (meth) acryloxy group is preferable.
化合物Aは、例えば、エポキシ基1つと(メタ)アクリロキシ基1つとを含むというように、2種以上の重合性基を合計で複数となるよう含んでもよいが、エチレン性不飽和結合を有する基を複数含むことが好ましい。 Compound A contains a plurality of polymerizable groups.
Compound A may contain two or more polymerizable groups in total, such as containing one epoxy group and one (meth) acryloxy group, but is a group having an ethylenically unsaturated bond. It is preferable to include a plurality of.
1gの化合物Aに含まれる重合性基のモル量は、1.0mmol/g以上であることが好ましく、1.5mmol/g以上であることがより好ましく、2.0mmol/g以上であることが更に好ましい。上記モル量の上限は特に限定されないが、8.0mmol/g以下であることが好ましい。 The number of polymerizable groups in compound A may be 2 or more, preferably 2 to 15, more preferably 2 to 10, further preferably 2 to 4, and 2. Is particularly preferred.
The molar amount of the polymerizable group contained in 1 g of compound A is preferably 1.0 mmol / g or more, more preferably 1.5 mmol / g or more, and more preferably 2.0 mmol / g or more. More preferred. The upper limit of the molar amount is not particularly limited, but is preferably 8.0 mmol / g or less.
化合物Aは、シクロヘキセン構造、及び、アセタール構造からなる群より選択される少なくとも1種の構造を含む連結基を介して結合している複数の重合性基を有する。すなわち、化合物Aにおいて、複数の重合性基は、シクロヘキセン構造、及び、アセタール構造からなる群より選択される少なくとも1種の構造を含む連結基を介して結合している。 [Connecting group]
Compound A has a cyclohexene structure and a plurality of polymerizable groups bonded via a linking group containing at least one structure selected from the group consisting of an acetal structure. That is, in compound A, the plurality of polymerizable groups are bonded via a linking group containing at least one structure selected from the group consisting of a cyclohexene structure and an acetal structure.
上記連結基におけるシクロヘキセン構造、及び、アセタール構造よりなる群より選択される少なくとも1種の構造の個数は、1~10であることが好ましく、1~4であることがより好ましく、1~3が更に好ましく、2が特に好ましい。 The linking group preferably contains a plurality of at least one structure selected from the group consisting of a cyclohexene structure and an acetal structure, and may contain a plurality of cyclohexene structures or a plurality of acetal structures. More preferred.
The number of at least one structure selected from the group consisting of the cyclohexene structure and the acetal structure in the linking group is preferably 1 to 10, more preferably 1 to 4, and 1 to 3. Further preferred, 2 is particularly preferred.
上記炭化水素基としては、飽和脂肪族炭化水素基、不飽和脂肪族炭化水素基、芳香族炭化水素基、又は、これらの組み合わせにより表される基が挙げられ、飽和脂肪族炭化水素基、芳香族炭化水素基、又は、これらの組み合わせにより表される基がより好ましい。
また、上記炭化水素基における置換基としては、フッ素原子等のハロゲン原子が挙げられる。
上記(ポリ)アルキレンオキシ基におけるアルキレン基としては、エチレン基、プロピレン基、トリメチレン基、ブチレン基等が挙げられ、エチレン基又はプロピレン基が好ましい。
上記連結基は、2価以上の連結基であればよいが、2~6価の連結基であることが好ましく、2~4価の連結基であることが更に好ましく、2価の連結基がより好ましい。 The linking group includes at least one structure selected from the group consisting of the cyclohexene structure and the acetal structure described above, a hydrocarbon group which may be substituted, a (poly) alkyleneoxy group, -O-,-. It is preferably a group formed by a combination with at least one group selected from the group consisting of S-, -SO 2- , -CO- and -NHCO-.
Examples of the above-mentioned hydrocarbon group include a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof, and a saturated aliphatic hydrocarbon group and an aromatic group. Group hydrocarbon groups or groups represented by combinations thereof are more preferable.
Further, examples of the substituent in the above hydrocarbon group include a halogen atom such as a fluorine atom.
Examples of the alkylene group in the (poly) alkyleneoxy group include an ethylene group, a propylene group, a trimethylene group, a butylene group and the like, and an ethylene group or a propylene group is preferable.
The linking group may be a divalent or higher valent linking group, but is preferably a divalent to hexavalent linking group, more preferably a divalent to tetravalent linking group, and a divalent linking group. More preferred.
式(2-1)中、R1、R2及びR3はそれぞれ独立に、1価の有機基を表し、R1、R2及びR3の少なくとも1つは重合性基を有する基を含む。 When the linking group contains an acetal structure, the compound A preferably contains a compound represented by the following formula (2-1).
In formula (2-1), R 1 , R 2 and R 3 each independently represent a monovalent organic group, and at least one of R 1 , R 2 and R 3 contains a group having a polymerizable group. ..
上記アルキル基としては、炭素数1~10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く、メチル基が更に好ましい。
上記アリール基としては、炭素数1~20のアリール基が好ましく、炭素数6~20のアリール基がより好ましく、フェニル基が更に好ましい。また、上記アリール基は、芳香族炭化水素基であることが好ましい。
上記アルケニル基としては、炭素数2~10のアルケニル基が好ましく、炭素数2~4のアルケニル基がより好ましい。
上記アルキニル基としては、炭素数2~10のアルキニル基が好ましく、炭素数2~4のアルキニル基がより好ましい。
上記アラルキル基におけるアルキル基部分、アリール基部分の好ましい態様は、上述のアルキル基、アリール基の好ましい態様と同様である。 In the formula (2-1), as R1 , a hydrocarbon group is preferable, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, or an aralkyl group is more preferable, and an alkyl group is particularly preferable.
As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group is further preferable.
As the aryl group, an aryl group having 1 to 20 carbon atoms is preferable, an aryl group having 6 to 20 carbon atoms is more preferable, and a phenyl group is further preferable. Further, the aryl group is preferably an aromatic hydrocarbon group.
As the alkenyl group, an alkenyl group having 2 to 10 carbon atoms is preferable, and an alkenyl group having 2 to 4 carbon atoms is more preferable.
As the alkynyl group, an alkynyl group having 2 to 10 carbon atoms is preferable, and an alkynyl group having 2 to 4 carbon atoms is more preferable.
The preferred embodiments of the alkyl group moiety and the aryl group moiety in the aralkyl group are the same as the preferred embodiments of the alkyl group and the aryl group described above.
R2又はR3が重合性基を有する基である場合、R2又はR3は下記式(P-1)で表される基であることが好ましい。
式(P-1)中、L1はn+1価の連結基を表し、P1は重合性基を表し、nは1以上の整数を表し、*は式(2-1)中の酸素原子との結合部位を表す。
式(P-1)中、L1としては上述の連結基において説明した基が挙げられ、好ましい態様も同様である。
式(P-1)中、P1としては上述の重合性基において説明した基が挙げられ、好ましい態様も同様である。
式(P-1)中、nは1~10の整数であることが好ましく、1~5の整数であることがより好ましく、1又は2であることが更に好ましく、1が特に好ましい。
R2又はR3が重合性基を有する基ではない場合、R2又はR3は上述の式(2-1)におけるR1と同様であり、好ましい態様も同様である。 In formula (2-1), R 2 and R 3 are preferably groups having a polymerizable group independently.
When R 2 or R 3 is a group having a polymerizable group, R 2 or R 3 is preferably a group represented by the following formula (P-1).
In the formula (P-1), L 1 represents an n + 1 valent linking group, P 1 represents a polymerizable group, n represents an integer of 1 or more, and * represents an oxygen atom in the formula (2-1). Represents the binding site of.
In the formula (P-1), examples of L 1 include the groups described in the above-mentioned linking group, and the same applies to preferred embodiments.
In the formula (P-1), as P 1 , the group described in the above-mentioned polymerizable group can be mentioned, and the preferred embodiment is also the same.
In the formula (P-1), n is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, further preferably 1 or 2, and particularly preferably 1.
When R 2 or R 3 is not a group having a polymerizable group, R 2 or R 3 is the same as R 1 in the above formula (2-1), and the preferred embodiment is also the same.
式(2-2)又は式(2-3)中、R4はそれぞれ独立に、水素原子または炭素数1~5のアルキル基を表し、*は、式(2-1)に含まれる酸素原子との結合部位を表し、Lは2価の連結基を表す。
式(2-2)又は式(2-3)中、R4は水素原子又はメチル基が好ましい。
式(2-2)又は式(2-3)中、Lとしては上述の連結基において説明した基が挙げられ、好ましい態様も同様である。 Among these, it is preferable that R 2 and R 3 are independent groups having a partial structure represented by either the following formula (2-2) or the following formula (2-3), and R 2 and R 3 are preferable. It is more preferable that one of R3 is a group having a partial structure represented by the formula (2-2) and the other is a group having a partial structure represented by the formula ( 2-3 ).
In the formula (2-2) or the formula (2-3), R 4 independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and * is an oxygen atom contained in the formula (2-1). Represents a binding site with, and L represents a divalent linking group.
In the formula (2-2) or the formula (2-3), R4 is preferably a hydrogen atom or a methyl group.
In the formula (2-2) or the formula (2-3), as L, the group described in the above-mentioned linking group can be mentioned, and the preferred embodiment is also the same.
式(2-4)中、R4はそれぞれ独立に、水素原子または炭素数1~5のアルキル基を表し、Lは2価の連結基を表す。
式(2-4)中、R4は水素原子又はメチル基が好ましい。
式(2-4)中、Lとしては上述の連結基において説明した基が挙げられ、アルキレン基、アルキレンオキシ基、又はこれらの組み合わせによる基がより好ましい。
上記アルキレン基としては、炭素数2~10のアルキレン基が好ましい。
上記アルキレンオキシ基としては、エチレンオキシ基が好ましい。 The compound represented by the formula (2-1) is preferably a compound represented by the following formula (2-4).
In formula (2-4), R 4 independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and L represents a divalent linking group.
In formula (2-4), R4 is preferably a hydrogen atom or a methyl group.
In the formula (2-4), as L, the group described in the above-mentioned linking group can be mentioned, and an alkylene group, an alkyleneoxy group, or a group based on a combination thereof is more preferable.
As the alkylene group, an alkylene group having 2 to 10 carbon atoms is preferable.
As the alkyleneoxy group, an ethyleneoxy group is preferable.
架橋環構造又は縮合環構造を有するシクロヘキセン構造としては、特に限定されないが、下記構造が挙げられる。下記構造中、*はそれぞれ、他の構造との結合部位を表す。
The cyclohexene structure having a crosslinked ring structure or a condensed ring structure is not particularly limited, and examples thereof include the following structures. In the following structures, * represents a binding site with another structure.
式(3-1)中、R1及びR2はそれぞれ独立に、1価の有機基を表し、R1及びR2の少なくとも1つはエチレン性不飽和結合を有する基を含む。 Among these, compound A preferably contains a compound represented by the following formula (3-1).
In formula (3-1), R 1 and R 2 each independently represent a monovalent organic group, and at least one of R 1 and R 2 contains a group having an ethylenically unsaturated bond.
式(3-2)中、R3及びR4はそれぞれ独立に、エチレン性不飽和結合を有する基を含む1価の有機基を表し、Lは2価の連結基を表す。 The compound represented by the formula (3-1) is preferably a compound represented by the following formula (3-2).
In formula (3-2), R 3 and R 4 each independently represent a monovalent organic group containing a group having an ethylenically unsaturated bond, and L represents a divalent linking group.
式(3-2)中、Lとしては上述の連結基において説明した基が挙げられ、アルキレン基、ポリアルキレンオキシ基、又はこれらの組み合わせによる基がより好ましい。
上記アルキレン基としては、炭素数2~10のアルキレン基が好ましい。
上記ポリアルキレンオキシ基としては、ポリエチレンオキシ基が好ましい。
上記ポリアルキレンオキシ基の繰り返し数は、2~20が好ましく、2~10がより好ましく、2~4が更に好ましい。 In formula (3-2), R 3 and R 4 are preferably groups represented by the above formula (P-1).
In the formula (3-2), as L, the group described in the above-mentioned linking group can be mentioned, and an alkylene group, a polyalkyleneoxy group, or a group based on a combination thereof is more preferable.
As the alkylene group, an alkylene group having 2 to 10 carbon atoms is preferable.
As the polyalkylene oxy group, a polyethylene oxy group is preferable.
The number of repetitions of the polyalkyleneoxy group is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 4.
本発明の樹脂組成物は、環化樹脂の前駆体(特定樹脂)を含む。
環化樹脂は、主鎖構造中にイミド環構造又はオキサゾール環構造を含む樹脂であることが好ましい。
本発明において、主鎖とは、樹脂分子中で相対的に最も長い結合鎖を表す。
環化樹脂としては、ポリイミド、ポリベンゾオキサゾール、ポリアミドイミド等が挙げられる。
環化樹脂の前駆体とは、外部刺激により化学構造の変化を生じて環化樹脂となる樹脂をいい、熱により化学構造の変化を生じて環化樹脂となる樹脂が好ましく、熱により閉環反応を生じて環構造が形成されることにより環化樹脂となる樹脂がより好ましい。
環化樹脂の前駆体としては、ポリイミド前駆体、ポリベンゾオキサゾール前駆体、ポリアミドイミド前駆体等が挙げられる。
すなわち、本発明の樹脂組成物は、特定樹脂として、ポリイミド、ポリイミド前駆体、ポリベンゾオキサゾール、ポリベンゾオキサゾール前駆体、ポリアミドイミド、及び、ポリアミドイミド前駆体よりなる群から選ばれた少なくとも1種の樹脂(特定樹脂)を含むことが好ましい。
本発明の樹脂組成物は、特定樹脂として、ポリイミド又はポリイミド前駆体を含むことが好ましく、ポリイミド前駆体を含むことがより好ましい。
また、特定樹脂は重合性基を有することが好ましく、ラジカル重合性基を含むことがより好ましい。
特定樹脂がラジカル重合性基を有する場合、本発明の樹脂組成物は、後述のラジカル重合開始剤を含むことが好ましく、後述のラジカル重合開始剤を含み、かつ、後述のラジカル架橋剤を含むことがより好ましい。さらに必要に応じて、後述の増感剤を含むことができる。このような本発明の樹脂組成物からは、例えば、ネガ型感光膜が形成される。
また、特定樹脂は、酸分解性基等の極性変換基を有していてもよい。
特定樹脂が酸分解性基を有する場合、本発明の樹脂組成物は、後述の光酸発生剤を含むことが好ましい。このような本発明の樹脂組成物からは、例えば、化学増幅型であるポジ型感光膜又はネガ型感光膜が形成される。
また、特定樹脂は、化合物Aに含まれる重合性基と反応して共有結合可能な基を含むことが好ましい。
例えば、化合物Aがエチレン性不飽和結合を有する基を含む場合、特定樹脂もエチレン性不飽和結合を有する基を含むことが好ましい。
また、化合物Aがエポキシ基を含む場合、特定樹脂もエポキシ基を含むことが好ましい。
上記態様によれば、化合物Aと特定樹脂の間にも架橋が形成され、得られる硬化物の耐薬品性がより向上すると考えられる。 <Specific resin>
The resin composition of the present invention contains a precursor (specific resin) of a cyclized resin.
The cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in the main chain structure.
In the present invention, the main chain represents a relatively longest binding chain among resin molecules.
Examples of the cyclization resin include polyimide, polybenzoxazole, and polyamideimide.
The precursor of the cyclized resin refers to a resin that changes its chemical structure due to an external stimulus and becomes a cyclized resin, and a resin that changes its chemical structure due to heat and becomes a cyclized resin is preferable, and a ring closure reaction occurs due to heat. A resin that becomes a cyclization resin by forming a ring structure is more preferable.
Examples of the precursor of the cyclization resin include a polyimide precursor, a polybenzoxazole precursor, a polyamide-imide precursor and the like.
That is, the resin composition of the present invention is at least one selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor as the specific resin. It is preferable to contain a resin (specific resin).
The resin composition of the present invention preferably contains polyimide or a polyimide precursor as the specific resin, and more preferably contains a polyimide precursor.
Further, the specific resin preferably has a polymerizable group, and more preferably contains a radically polymerizable group.
When the specific resin has a radically polymerizable group, the resin composition of the present invention preferably contains a radical polymerization initiator described later, contains a radical polymerization initiator described below, and contains a radical cross-linking agent described below. Is more preferable. Further, if necessary, a sensitizer described later can be included. From such a resin composition of the present invention, for example, a negative photosensitive film is formed.
Further, the specific resin may have a polar conversion group such as an acid-degradable group.
When the specific resin has an acid-degradable group, the resin composition of the present invention preferably contains a photoacid generator described later. From such a resin composition of the present invention, for example, a chemically amplified positive type photosensitive film or a negative type photosensitive film is formed.
Further, the specific resin preferably contains a group capable of covalently bonding by reacting with the polymerizable group contained in the compound A.
For example, when the compound A contains a group having an ethylenically unsaturated bond, it is preferable that the specific resin also contains a group having an ethylenically unsaturated bond.
When the compound A contains an epoxy group, it is preferable that the specific resin also contains an epoxy group.
According to the above aspect, it is considered that a crosslink is formed between the compound A and the specific resin, and the chemical resistance of the obtained cured product is further improved.
本発明で用いるポリイミド前駆体は、その種類等特に定めるものではないが、下記式(2)で表される繰返し単位を含むことが好ましい。
式(2)中、A1及びA2は、それぞれ独立に、酸素原子又は-NH-を表し、R111は、2価の有機基を表し、R115は、4価の有機基を表し、R113及びR114は、それぞれ独立に、水素原子又は1価の有機基を表す。 [Polyimide precursor]
The polyimide precursor used in the present invention is not particularly specified, such as its type, but preferably contains a repeating unit represented by the following formula (2).
In formula (2), A 1 and A 2 independently represent an oxygen atom or -NH-, R 111 represents a divalent organic group, and R 115 represents a tetravalent organic group. R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group.
式(2)におけるR111は、2価の有機基を表す。2価の有機基としては、直鎖又は分岐の脂肪族基、環状の脂肪族基及び芳香族基を含む基が例示され、炭素数2~20の直鎖又は分岐の脂肪族基、炭素数3~20の環状の脂肪族基、炭素数3~20の芳香族基、又は、これらの組み合わせからなる基が好ましく、炭素数6~20の芳香族基を含む基がより好ましい。上記直鎖又は分岐の脂肪族基は鎖中の炭化水素基がヘテロ原子を含む基で置換されていてもよく、上記環状の脂肪族基および芳香族基は環員の炭化水素基がヘテロ原子を含む基で置換されていてもよい。本発明の好ましい実施形態として、-Ar-および-Ar-L-Ar-で表される基であることが例示され、特に好ましくは-Ar-L-Ar-で表される基である。但し、Arは、それぞれ独立に、芳香族基であり、Lは、単結合、フッ素原子で置換されていてもよい炭素数1~10の脂肪族炭化水素基、-O-、-CO-、-S-、-SO2-又は-NHCO-、あるいは、上記の2つ以上の組み合わせからなる基である。これらの好ましい範囲は、上述のとおりである。 A 1 and A 2 in the formula (2) independently represent an oxygen atom or —NH—, and an oxygen atom is preferable.
R 111 in the formula (2) represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group and a group containing an aromatic group, and a linear or branched aliphatic group having 2 to 20 carbon atoms and a carbon number of carbon atoms are exemplified. A cyclic aliphatic group having 3 to 20, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable. In the linear or branched aliphatic group, the hydrocarbon group in the chain may be substituted with a group containing a hetero atom, and in the cyclic aliphatic group and the aromatic group, the hydrocarbon group of the ring member is a hetero atom. It may be substituted with a group containing. Preferred embodiments of the present invention are exemplified by groups represented by -Ar- and -Ar-L-Ar-, and particularly preferably groups represented by -Ar-L-Ar-. However, Ar is an aromatic group independently, and L is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-,. -S-, -SO 2- or -NHCO-, or a group consisting of a combination of two or more of the above. These preferred ranges are as described above.
具体的には、炭素数2~20の直鎖又は分岐の脂肪族基、炭素数3~20の環状の脂肪族基、炭素数3~20の芳香族基、又は、これらの組み合わせからなる基を含むジアミンであることが好ましく、炭素数6~20の芳香族基を含むジアミンであることがより好ましい。上記直鎖又は分岐の脂肪族基は鎖中の炭化水素基がヘテロ原子を含む基で置換されていてもよく上記環状の脂肪族基および芳香族基は環員の炭化水素基がヘテロ原子を含む基で置換されていてもよい。芳香族基を含む基の例としては、下記が挙げられる。 R 111 is preferably derived from diamine. Examples of the diamine used for producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one kind of diamine may be used, or two or more kinds of diamines may be used.
Specifically, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof. It is preferably a diamine containing, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. In the linear or branched aliphatic group, the hydrocarbon group in the chain may be substituted with a group containing a hetero atom, and in the cyclic aliphatic group and the aromatic group, the hydrocarbon group of the ring member is a hetero atom. It may be substituted with a containing group. Examples of groups containing aromatic groups include:
式中、Aは単結合又は2価の連結基を表し、単結合、又は、フッ素原子で置換されていてもよい炭素数1~10の脂肪族炭化水素基、-O-、-C(=O)-、-S-、-SO2-、-NHCO-、又は、これらの組み合わせから選択される基であることが好ましく、単結合、フッ素原子で置換されていてもよい炭素数1~3のアルキレン基、-O-、-C(=O)-、-S-、又は、-SO2-から選択される基であることがより好ましく、-CH2-、-O-、-S-、-SO2-、-C(CF3)2-、又は、-C(CH3)2-であることが更に好ましい。
式中、*は他の構造との結合部位を表す。
In the formula, A represents a single bond or a divalent linking group, which is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —C (=). O)-, -S-, -SO 2- , -NHCO-, or a group selected from a combination thereof is preferable, and a single bond or a group having 1 to 3 carbon atoms which may be substituted with a fluorine atom may be used. It is more preferable that the group is selected from the alkylene group of -O-, -C (= O)-, -S-, or -SO2- , and -CH 2- , -O-, -S-. , -SO 2- , -C (CF 3 ) 2- , or -C (CH 3 ) 2- , more preferably.
In the formula, * represents a binding site with another structure.
式(51)
式(51)中、R50~R57は、それぞれ独立に、水素原子、フッ素原子又は1価の有機基であり、R50~R57の少なくとも1つは、フッ素原子、メチル基又はトリフルオロメチル基であり、*はそれぞれ独立に、式(2)中の窒素原子との結合部位を表す。
R50~R57の1価の有機基としては、炭素数1~10(好ましくは炭素数1~6)の無置換のアルキル基、炭素数1~10(好ましくは炭素数1~6)のフッ化アルキル基等が挙げられる。
式(61)中、R58及びR59は、それぞれ独立に、フッ素原子、メチル基、又はトリフルオロメチル基であり、*はそれぞれ独立に、式(2)中の窒素原子との結合部位を表す。
式(51)又は(61)の構造を与えるジアミンとしては、2,2’-ジメチルベンジジン、2,2’-ビス(トリフルオロメチル)-4,4’-ジアミノビフェニル、2,2’-ビス(フルオロ)-4,4’-ジアミノビフェニル、4,4’-ジアミノオクタフルオロビフェニル等が挙げられる。これらは1種で又は2種以上を組み合わせて用いてもよい。 Further, from the viewpoint of i-ray transmittance, R 111 is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, a divalent organic group represented by the formula (61) is more preferable.
Equation (51)
In formula (51), R 50 to R 57 are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and at least one of R 50 to R 57 is a fluorine atom, a methyl group or trifluoro. It is a methyl group, and each of * independently represents a bonding site with a nitrogen atom in the formula (2).
The monovalent organic group of R 50 to R 57 includes an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples thereof include an alkyl fluoride group.
In formula (61), R 58 and R 59 are each independently a fluorine atom, a methyl group, or a trifluoromethyl group, and * is an independent binding site with a nitrogen atom in formula (2). show.
Examples of the diamine giving the structure of the formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, and 2,2'-bis. (Fluoro) -4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl and the like can be mentioned. These may be used alone or in combination of two or more.
式(5)又は式(6)中、*はそれぞれ独立に、他の構造との結合部位を表す。
式(5)中、R112は単結合又は2価の連結基であり、単結合、又は、フッ素原子で置換されていてもよい炭素数1~10の脂肪族炭化水素基、-O-、-CO-、-S-、-SO2-、及び-NHCO-、ならびに、これらの組み合わせから選択される基であることが好ましく、単結合、フッ素原子で置換されていてもよい炭素数1~3のアルキレン基、-O-、-CO-、-S-及び-SO2-から選択される基であることがより好ましく、-CH2-、-C(CF3)2-、-C(CH3)2-、-O-、-CO-、-S-及び-SO2-からなる群から選択される2価の基であることが更に好ましい。 R 115 in the formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable.
In formula (5) or formula (6), * independently represents a binding site with another structure.
In formula (5), R 112 is a single bond or divalent linking group, which may be replaced with a single bond or a fluorine atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, —O—, It is preferably a group selected from -CO-, -S-, -SO 2- , and -NHCO-, and a combination thereof, and is a single bond, which may be substituted with a fluorine atom and has 1 to 1 carbon atoms. More preferably, it is a group selected from 3 alkylene groups, -O-, -CO-, -S- and -SO 2- , and -CH 2- , -C (CF 3 ) 2- , -C ( CH 3 ) It is more preferably a divalent group selected from the group consisting of 2-, -O-, -CO-, -S- and -SO 2- .
テトラカルボン酸二無水物は、下記式(O)で表されることが好ましい。
式(O)中、R115は、4価の有機基を表す。R115の好ましい範囲は式(2)におけるR115と同義であり、好ましい範囲も同様である。 Specific examples of R 115 include tetracarboxylic acid residues remaining after removal of the anhydride group from the tetracarboxylic dianhydride. The polyimide precursor may contain only one type of tetracarboxylic dianhydride residue or two or more types as a structure corresponding to R 115 .
The tetracarboxylic dianhydride is preferably represented by the following formula (O).
In formula (O), R 115 represents a tetravalent organic group. The preferred range of R 115 is synonymous with R 115 in the formula (2), and the preferred range is also the same.
エチレン性不飽和結合を有する基としては、ビニル基、アリル基、イソアリル基、2-メチルアリル基、ビニル基と直接結合した芳香環を有する基(例えば、ビニルフェニル基など)、(メタ)アクリルアミド基、(メタ)アクリロイルオキシ基、下記式(III)で表される基などが挙げられ、下記式(III)で表される基が好ましい。 R 113 and R 114 in the formula (2) independently represent a hydrogen atom or a monovalent organic group, respectively. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. Further, it is preferable that at least one of R 113 and R 114 contains a polymerizable group, and it is more preferable that both contain a polymerizable group. It is also preferred that at least one of R 113 and R 114 contains two or more polymerizable groups. As the polymerizable group, a radically polymerizable group is preferable because it is a group capable of undergoing a cross-linking reaction by the action of heat, radicals and the like. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group and an amino group. Be done. As the radically polymerizable group of the polyimide precursor, a group having an ethylenically unsaturated bond is preferable.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group), and a (meth) acrylamide group. , (Meta) acryloyloxy group, a group represented by the following formula (III), and the like, and a group represented by the following formula (III) is preferable.
式(III)において、*は他の構造との結合部位を表す。
式(III)において、R201は、炭素数2~12のアルキレン基、-CH2CH(OH)CH2-、シクロアルキレン基又はポリアルキレンオキシ基を表す。
好適なR201の例は、エチレン基、プロピレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基、オクタメチレン基、ドデカメチレン基等のアルキレン基、1,2-ブタンジイル基、1,3-ブタンジイル基、-CH2CH(OH)CH2-、ポリアルキレンオキシ基が挙げられ、エチレン基、プロピレン基等のアルキレン基、-CH2CH(OH)CH2-、シクロヘキシル基、ポリアルキレンオキシ基がより好ましく、エチレン基、プロピレン基等のアルキレン基、又はポリアルキレンオキシ基が更に好ましい。
本発明において、ポリアルキレンオキシ基とは、アルキレンオキシ基が2以上直接結合した基をいう。ポリアルキレンオキシ基に含まれる複数のアルキレンオキシ基におけるアルキレン基は、それぞれ同一であっても異なっていてもよい。
ポリアルキレンオキシ基が、アルキレン基が異なる複数種のアルキレンオキシ基を含む場合、ポリアルキレンオキシ基におけるアルキレンオキシ基の配列は、ランダムな配列であってもよいし、ブロックを有する配列であってもよいし、交互等のパターンを有する配列であってもよい。
上記アルキレン基の炭素数(アルキレン基が置換基を有する場合、置換基の炭素数を含む)は、2以上であることが好ましく、2~10であることがより好ましく、2~6であることがより好ましく、2~5であることが更に好ましく、2~4であることが一層好ましく、2又は3であることが特に好ましく、2であることが最も好ましい。
また、上記アルキレン基は、置換基を有していてもよい。好ましい置換基としては、アルキル基、アリール基、ハロゲン原子等が挙げられる。
また、ポリアルキレンオキシ基に含まれるアルキレンオキシ基の数(ポリアルキレンオキシ基の繰返し数)は、2~20が好ましく、2~10がより好ましく、2~6が更に好ましい。
ポリアルキレンオキシ基としては、溶剤溶解性及び耐溶剤性の観点からは、ポリエチレンオキシ基、ポリプロピレンオキシ基、ポリトリメチレンオキシ基、ポリテトラメチレンオキシ基、又は、複数のエチレンオキシ基と複数のプロピレンオキシ基とが結合した基が好ましく、ポリエチレンオキシ基又はポリプロピレンオキシ基がより好ましく、ポリエチレンオキシ基が更に好ましい。上記複数のエチレンオキシ基と複数のプロピレンオキシ基とが結合した基において、エチレンオキシ基とプロピレンオキシ基とはランダムに配列していてもよいし、ブロックを形成して配列していてもよいし、交互等のパターン状に配列していてもよい。これらの基におけるエチレンオキシ基等の繰返し数の好ましい態様は上述の通りである。 In formula (III), R200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and a hydrogen atom or a methyl group is preferable.
In formula (III), * represents a binding site with another structure.
In formula (III), R 201 represents an alkylene group having 2 to 12 carbon atoms, —CH 2 CH (OH) CH 2- , a cycloalkylene group or a polyalkyleneoxy group.
Examples of suitable R 201 include alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group and dodecamethylene group, 1,2-butanjiyl group, 1, 3-Butanjiyl group, -CH 2 CH (OH) CH 2- , polyalkyleneoxy group, alkylene group such as ethylene group, propylene group, -CH 2 CH (OH) CH 2- , cyclohexyl group, polyalkylene An oxy group is more preferable, and an alkylene group such as an ethylene group and a propylene group, or a polyalkylene oxy group is further preferable.
In the present invention, the polyalkyleneoxy group refers to a group to which two or more alkyleneoxy groups are directly bonded. The alkylene group in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
When the polyalkyleneoxy group contains a plurality of types of alkyleneoxy groups having different alkylene groups, the sequence of the alkyleneoxy groups in the polyalkyleneoxy group may be a random sequence or a sequence having a block. It may be an array having a pattern such as alternating.
The carbon number of the alkylene group (including the carbon number of the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, and 2 to 6. Is more preferable, 2 to 5 is more preferable, 2 to 4 is more preferable, 2 or 3 is particularly preferable, and 2 is most preferable.
Further, the alkylene group may have a substituent. Preferred substituents include alkyl groups, aryl groups, halogen atoms and the like.
The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repetitions of the polyalkyleneoxy group) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.
The polyalkyleneoxy group includes a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethylethyleneoxy group, a polytetramethyleneoxy group, or a plurality of ethyleneoxy groups and a plurality of propylenes from the viewpoint of solvent solubility and solvent resistance. A group bonded to an oxy group is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is further preferable. In the group in which the plurality of ethyleneoxy groups and the plurality of propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be randomly arranged or may be arranged by forming a block. , Alternate or the like may be arranged in a pattern. The preferred embodiment of the number of repetitions of the ethyleneoxy group and the like in these groups is as described above.
酸分解性基の具体例としては、tert-ブトキシカルボニル基、イソプロポキシカルボニル基、テトラヒドロピラニル基、テトラヒドロフラニル基、エトキシエチル基、メトキシエチル基、エトキシメチル基、トリメチルシリル基、tert-ブトキシカルボニルメチル基、トリメチルシリルエーテル基などが挙げられる。露光感度の観点からは、エトキシエチル基、又は、テトラヒドロフラニル基が好ましい。 In formula (2), at least one of R 113 and R 114 may be a polar converting group such as an acid-degradable group. The acid-degradable group is not particularly limited as long as it decomposes by the action of an acid to produce an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but is not particularly limited, but is an acetal group, a ketal group, a silyl group, or a silyl ether group. , A tertiary alkyl ester group or the like is preferable, and an acetal group or a ketal group is more preferable from the viewpoint of exposure sensitivity.
Specific examples of the acid-degradable group include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group and tert-butoxycarbonylmethyl. Examples include a group, a trimethylsilyl ether group and the like. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferable.
式(2-A)
式(2-A)中、A1及びA2は、酸素原子を表し、R111及びR112は、それぞれ独立に、2価の有機基を表し、R113及びR114は、それぞれ独立に、水素原子又は1価の有機基を表し、R113及びR114の少なくとも一方は、重合性基を含む基であり、両方が重合性基を含む基であることが好ましい。 The repeating unit represented by the formula (2) is preferably the repeating unit represented by the formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having a repeating unit represented by the formula (2-A). By including the repeating unit represented by the formula (2-A) in the polyimide precursor, it becomes possible to further widen the width of the exposure latitude.
Equation (2-A)
In formula (2-A), A 1 and A 2 represent oxygen atoms, R 111 and R 112 each independently represent a divalent organic group, and R 113 and R 114 each independently. Representing a hydrogen atom or a monovalent organic group, at least one of R 113 and R 114 is a group containing a polymerizable group, and it is preferable that both are groups containing a polymerizable group.
R112は、式(5)におけるR112と同義であり、好ましい範囲も同様である。 A 1 , A 2 , R 111 , R 113 , and R 114 are independently synonymous with A 1 , A 2 , R 111 , R 113 , and R 114 in the formula (2), and the preferred ranges are also the same. ..
R 112 has the same meaning as R 112 in the formula (5), and the preferred range is also the same.
上記ポリイミド前駆体の分子量の分散度は、1.5以上が好ましく、1.8以上がより好ましく、2.0以上であることが更に好ましい。ポリイミド前駆体の分子量の分散度の上限値は特に定めるものではないが、例えば、7.0以下が好ましく、6.5以下がより好ましく、6.0以下が更に好ましい。
本明細書において、分子量の分散度とは、重量平均分子量/数平均分子量により算出される値である。
また、樹脂組成物が特定樹脂として複数種のポリイミド前駆体を含む場合、少なくとも1種のポリイミド前駆体の重量平均分子量、数平均分子量、及び、分散度が上記範囲であることが好ましい。また、上記複数種のポリイミド前駆体を1つの樹脂として算出した重量平均分子量、数平均分子量、及び、分散度が、それぞれ、上記範囲内であることも好ましい。 The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. The number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.
The degree of dispersion of the molecular weight of the polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and further preferably 2.0 or more. The upper limit of the dispersity of the molecular weight of the polyimide precursor is not particularly determined, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, still more preferably 6.0 or less.
In the present specification, the degree of molecular weight dispersion is a value calculated by weight average molecular weight / number average molecular weight.
When the resin composition contains a plurality of types of polyimide precursors as the specific resin, it is preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion of at least one type of polyimide precursor are in the above range. Further, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by using the plurality of types of polyimide precursors as one resin are within the above ranges.
本発明で用いるポリベンゾオキサゾール前駆体は、その構造等について特に定めるものではないが、好ましくは下記式(3)で表される繰返し単位を含む。
式(3)中、R121は、2価の有機基を表し、R122は、4価の有機基を表し、R123及びR124は、それぞれ独立に、水素原子又は1価の有機基を表す。 [Polybenzoxazole precursor]
The polybenzoxazole precursor used in the present invention is not particularly defined for its structure and the like, but preferably contains a repeating unit represented by the following formula (3).
In formula (3), R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, and R 123 and R 124 each independently represent a hydrogen atom or a monovalent organic group. show.
式(3)において、R121は、2価の有機基を表す。2価の有機基としては、脂肪族基及び芳香族基の少なくとも一方を含む基が好ましい。脂肪族基としては、直鎖の脂肪族基が好ましい。R121は、ジカルボン酸残基が好ましい。ジカルボン酸残基は、1種のみ用いてもよいし、2種以上用いてもよい。 In the formula (3), R 123 and R 124 are synonymous with R 113 in the formula (2), respectively, and the preferable range is also the same. That is, at least one is preferably a polymerizable group.
In formula (3), R 121 represents a divalent organic group. As the divalent organic group, a group containing at least one of an aliphatic group and an aromatic group is preferable. As the aliphatic group, a linear aliphatic group is preferable. R 121 is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.
脂肪族基を含むジカルボン酸としては、直鎖又は分岐(好ましくは直鎖)の脂肪族基を含むジカルボン酸が好ましく、直鎖又は分岐(好ましくは直鎖)の脂肪族基と2つの-COOHからなるジカルボン酸がより好ましい。直鎖又は分岐(好ましくは直鎖)の脂肪族基の炭素数は、2~30であることが好ましく、2~25であることがより好ましく、3~20であることが更に好ましく、4~15であることが一層好ましく、5~10であることが特に好ましい。直鎖の脂肪族基はアルキレン基であることが好ましい。
直鎖の脂肪族基を含むジカルボン酸としては、マロン酸、ジメチルマロン酸、エチルマロン酸、イソプロピルマロン酸、ジ-n-ブチルマロン酸、スクシン酸、テトラフルオロスクシン酸、メチルスクシン酸、2,2-ジメチルスクシン酸、2,3-ジメチルスクシン酸、ジメチルメチルスクシン酸、グルタル酸、ヘキサフルオログルタル酸、2-メチルグルタル酸、3-メチルグルタル酸、2,2-ジメチルグルタル酸、3,3-ジメチルグルタル酸、3-エチル-3-メチルグルタル酸、アジピン酸、オクタフルオロアジピン酸、3-メチルアジピン酸、ピメリン酸、2,2,6,6-テトラメチルピメリン酸、スベリン酸、ドデカフルオロスベリン酸、アゼライン酸、セバシン酸、ヘキサデカフルオロセバシン酸、1,9-ノナン二酸、ドデカン二酸、トリデカン二酸、テトラデカン二酸、ペンタデカン二酸、ヘキサデカン二酸、ヘプタデカン二酸、オクタデカン二酸、ノナデカン二酸、エイコサン二酸、ヘンエイコサン二酸、ドコサン二酸、トリコサン二酸、テトラコサン二酸、ペンタコサン二酸、ヘキサコサン二酸、ヘプタコサン二酸、オクタコサン二酸、ノナコサン二酸、トリアコンタン二酸、ヘントリアコンタン二酸、ドトリアコンタン二酸、ジグリコール酸、更に下記式で表されるジカルボン酸等が挙げられる。 As the dicarboxylic acid residue, a dicarboxylic acid containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferable, and a dicarboxylic acid residue containing an aromatic group is more preferable.
As the dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a linear or branched (preferably straight chain) aliphatic group is preferable, and a linear or branched (preferably straight chain) aliphatic group and two -COOH are preferable. A dicarboxylic acid consisting of is more preferable. The number of carbon atoms of the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, still more preferably 3 to 20, and 4 to 20. It is more preferably 15, and particularly preferably 5 to 10. The linear aliphatic group is preferably an alkylene group.
Examples of the dicarboxylic acid containing a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2, 2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-Didimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimeric acid, sverin Acid, dodecafluorosveric acid, azelaic acid, sebacic acid, hexadecafluorosevacinic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid , Octadecandioic acid, Nonadecandioic acid, Eikosandioic acid, Heneikosandioic acid, Docosandioic acid, Tricosanedioic acid, Tetracosandioic acid, Pentacosandioic acid, Hexacosandioic acid, Heptakosandioic acid, Octakosandioic acid, Nonakosandioic acid, Tria Examples thereof include contandioic acid, hentoria-contandioic acid, dotoria-contanedioic acid, diglycolic acid, and dicarboxylic acid represented by the following formula.
(式中、Zは炭素数1~6の炭化水素基であり、nは1~6の整数である。)
(In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6).
式中、Aは-CH2-、-O-、-S-、-SO2-、-CO-、-NHCO-、-C(CF3)2-、及び、-C(CH3)2-からなる群から選択される2価の基を表し、*はそれぞれ独立に、他の構造との結合部位を表す。
In the formula, A is -CH 2- , -O-, -S-, -SO 2- , -CO-, -NHCO-, -C (CF 3 ) 2- , and -C (CH 3 ) 2- Represents a divalent group selected from the group consisting of, and * represents a binding site with another structure independently.
R122は、また、ビスアミノフェノール誘導体由来の基であることが好ましく、ビスアミノフェノール誘導体由来の基としては、例えば、3,3’-ジアミノ-4,4’-ジヒドロキシビフェニル、4,4’-ジアミノ-3,3’-ジヒドロキシビフェニル、3,3’-ジアミノ-4,4’-ジヒドロキシジフェニルスルホン、4,4’-ジアミノ-3,3’-ジヒドロキシジフェニルスルホン、ビス-(3-アミノ-4-ヒドロキシフェニル)メタン、2,2-ビス(3-アミノ-4-ヒドロキシフェニル)プロパン、2,2-ビス-(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン、2,2-ビス-(4-アミノ-3-ヒドロキシフェニル)ヘキサフルオロプロパン、ビス-(4-アミノ-3-ヒドロキシフェニル)メタン、2,2-ビス-(4-アミノ-3-ヒドロキシフェニル)プロパン、4,4’-ジアミノ-3,3’-ジヒドロキシベンゾフェノン、3,3’-ジアミノ-4,4’-ジヒドロキシベンゾフェノン、4,4’-ジアミノ-3,3’-ジヒドロキシジフェニルエーテル、3,3’-ジアミノ-4,4’-ジヒドロキシジフェニルエーテル、1,4-ジアミノ-2,5-ジヒドロキシベンゼン、1,3-ジアミノ-2,4-ジヒドロキシベンゼン、1,3-ジアミノ-4,6-ジヒドロキシベンゼンなどが挙げられる。これらのビスアミノフェノールは、単独にて、あるいは混合して使用してもよい。 In formula (3), R 122 represents a tetravalent organic group. The tetravalent organic group has the same meaning as R 115 in the above formula (2), and the preferable range is also the same.
R 122 is also preferably a group derived from a bisaminophenol derivative, and examples of the group derived from a bisaminophenol derivative include, for example, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'. -Diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis- (3-amino- 4-Hydroxyphenyl) methane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis- (4-Amino-3-hydroxyphenyl) hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, 2,2-bis- (4-amino-3-hydroxyphenyl) propane, 4,4'-Diamino-3,3'-dihydroxybenzophenone,3,3'-diamino-4,4'-dihydroxybenzophenone,4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4, Examples thereof include 4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene and 1,3-diamino-4,6-dihydroxybenzene. These bis-aminophenols may be used alone or in combination.
式中、X1は、-O-、-S-、-C(CF3)2-、-CH2-、-SO2-、-NHCO-を表し、*及び#はそれぞれ、他の構造との結合部位を表す。Rは水素原子又は1価の置換基を表し、水素原子又は炭化水素基が好ましく、水素原子又はアルキル基がより好ましい。また、R122は、上記式により表される構造であることも好ましい。R122が、上記式により表される構造である場合、計4つの*及び#のうち、いずれか2つが式(3)中のR122が結合する窒素原子との結合部位であり、かつ、別の2つが式(3)中のR122が結合する酸素原子との結合部位であることが好ましく、2つの*が式(3)中のR122が結合する酸素原子との結合部位であり、かつ、2つの#が式(3)中のR122が結合する窒素原子との結合部位であるか、又は、2つの*が式(3)中のR122が結合する窒素原子との結合部位であり、かつ、2つの#が式(3)中のR122が結合する酸素原子との結合部位であることがより好ましく、2つの*が式(3)中のR122が結合する酸素原子との結合部位であり、かつ、2つの#が式(3)中のR122が結合する窒素原子との結合部位であることが更に好ましい。
In the formula, X 1 represents -O-, -S-, -C (CF 3 ) 2- , -CH 2- , -SO 2- , -NHCO-, and * and # represent other structures, respectively. Represents the binding site of. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom or an alkyl group. Further, it is also preferable that R 122 has a structure represented by the above formula. When R 122 has a structure represented by the above formula, any two of the four * and # in total are the bonding sites with the nitrogen atom to which R 122 in the formula (3) is bonded, and The other two are preferably the bonding sites with the oxygen atom to which R 122 in the formula (3) is bonded, and the two * are the bonding sites with the oxygen atom to which the R 122 in the formula (3) is bonded. , And two # are the bonding sites with the nitrogen atom to which R 122 in the formula (3) is bonded, or two * are the bonding sites with the nitrogen atom to which R 122 in the formula (3) is bonded. It is more preferable that the site is a site and the two #s are the bonding sites with the oxygen atom to which the R 122 in the formula (3) is bonded, and the two * are the oxygen to which the R 122 in the formula (3) is bonded. It is more preferable that it is a bond site with an atom and the two #s are bond sites with a nitrogen atom to which R 122 in the formula (3) is bonded.
ポリベンゾオキサゾール前駆体は、閉環に伴う反りの発生を抑制できる点で、下記式(SL)で表されるジアミン残基を他の種類の繰返し単位として含むことが好ましい。 The polybenzoxazole precursor may contain other types of repeating units in addition to the repeating units of the above formula (3).
The polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating unit in that the generation of warpage associated with ring closure can be suppressed.
式(SL)中、Zは、a構造とb構造を有し、R1sは、水素原子又は炭素数1~10の炭化水素基であり、R2sは炭素数1~10の炭化水素基であり、R3s、R4s、R5s、R6sのうち少なくとも1つは芳香族基で、残りは水素原子又は炭素数1~30の有機基で、それぞれ同一でも異なっていてもよい。a構造及びb構造の重合は、ブロック重合でもランダム重合でもよい。Z部分のモル%は、a構造は5~95モル%、b構造は95~5モル%であり、a+bは100モル%である。
In formula (SL), Z has an a structure and a b structure, R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R 2s is a hydrocarbon group having 1 to 10 carbon atoms. Yes, at least one of R 3s , R 4s , R 5s , and R 6s is an aromatic group, and the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. The mol% of the Z portion is 5 to 95 mol% for the a structure, 95 to 5 mol% for the b structure, and 100 mol% for a + b.
上記ポリベンゾオキサゾール前駆体の分子量の分散度は、1.4以上であることが好ましく、1.5以上がより好ましく、1.6以上であることが更に好ましい。ポリベンゾオキサゾール前駆体の分子量の分散度の上限値は特に定めるものではないが、例えば、2.6以下が好ましく、2.5以下がより好ましく、2.4以下が更に好ましく、2.3以下が一層好ましく、2.2以下がより一層好ましい。
また、樹脂組成物が特定樹脂として複数種のポリベンゾオキサゾール前駆体を含む場合、少なくとも1種のポリベンゾオキサゾール前駆体の重量平均分子量、数平均分子量、及び、分散度が上記範囲であることが好ましい。また、上記複数種のポリベンゾオキサゾール前駆体を1つの樹脂として算出した重量平均分子量、数平均分子量、及び、分散度が、それぞれ、上記範囲内であることも好ましい。 The weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, preferably 18,000 to 30,000, more preferably 20,000 to 29,000, still more preferably 22,000 to 28, It is 000. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.
The degree of dispersion of the molecular weight of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, still more preferably 1.6 or more. The upper limit of the dispersity of the molecular weight of the polybenzoxazole precursor is not particularly determined, but for example, 2.6 or less is preferable, 2.5 or less is more preferable, 2.4 or less is further preferable, and 2.3 or less. Is more preferable, and 2.2 or less is even more preferable.
When the resin composition contains a plurality of polybenzoxazole precursors as the specific resin, the weight average molecular weight, the number average molecular weight, and the dispersity of at least one polybenzoxazole precursor may be within the above ranges. preferable. Further, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by using the plurality of types of polybenzoxazole precursors as one resin are within the above ranges.
ポリアミドイミド前駆体は、下記式(PAI-2)で表される繰返し単位を含むことが好ましい。
式(PAI-2)中、R117は3価の有機基を表し、R111は2価の有機基を表し、A2は酸素原子又は-NH-を表し、R113は水素原子又は1価の有機基を表す。 [Polyamide-imide precursor]
The polyamide-imide precursor preferably contains a repeating unit represented by the following formula (PAI-2).
In formula (PAI-2), R 117 represents a trivalent organic group, R 111 represents a divalent organic group, A 2 represents an oxygen atom or -NH-, and R 113 represents a hydrogen atom or monovalent. Represents an organic group of.
上記連結基としては、-O-、-S-、-C(=O)-、-S(=O)2-、アルキレン基、ハロゲン化アルキレン基、アリーレン基、又はこれらを2以上結合した連結基が好ましく、-O-、-S-、アルキレン基、ハロゲン化アルキレン基、アリーレン基、又はこれらを2以上結合した連結基がより好ましい。
上記アルキレン基としては、炭素数1~20のアルキレン基が好ましく、炭素数1~10のアルキレン基がより好ましく、炭素数1~4のアルキレン基が更に好ましい。
上記ハロゲン化アルキレン基としては、炭素数1~20のハロゲン化アルキレン基が好ましく、炭素数1~10のハロゲン化アルキレン基がより好ましく、炭素数1~4のハロゲン化アルキレン基がより好ましい。また、上記ハロゲン化アルキレン基におけるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられ、フッ素原子が好ましい。上記ハロゲン化アルキレン基は、水素原子を有していても、水素原子の全てがハロゲン原子で置換されていてもよいが、水素原子の全てがハロゲン原子で置換されていることが好ましい。好ましいハロゲン化アルキレン基の例としては、(ジトリフルオロメチル)メチレン基等が挙げられる。
上記アリーレン基としては、フェニレン基又はナフチレン基が好ましく、フェニレン基がより好ましく、1,3-フェニレン基又は1,4-フェニレン基が更に好ましい。 In formula (PAI-2), R 117 is composed of a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, a heteroaromatic group, or a single bond or a linking group. The above-mentioned linked groups are exemplified, and a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and a cyclic aliphatic group having 6 to 20 carbon atoms are exemplified. The aromatic group of the above, or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms by a single bond or a linking group is preferable. A group in which two or more of the above are combined is more preferable.
The linking group includes -O-, -S-, -C (= O)-, -S (= O) 2- , an alkylene group, a halogenated alkylene group, an arylene group, or a link in which two or more of these are bonded. A group is preferable, and an —O—, —S—, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group in which two or more of these are bonded is more preferable.
As the alkylene group, an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is further preferable.
As the halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable. Examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable. The halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with a halogen atom, but it is preferable that all of the hydrogen atoms are substituted with a halogen atom. Examples of preferred halogenated alkylene groups include (ditrifluoromethyl) methylene groups and the like.
As the arylene group, a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is further preferable.
本発明において、カルボキシ基を3つ有する化合物をトリカルボン酸化合物という。
上記トリカルボン酸化合物の3つのカルボキシ基のうち2つのカルボキシ基は酸無水物化されていてもよい。
ポリアミドイミド前駆体の製造に用いられるハロゲン化されていてもよいトリカルボン酸化合物としては、分岐鎖状の脂肪族、環状の脂肪族又は芳香族のトリカルボン酸化合物などが挙げられる。
これらのトリカルボン酸化合物は、1種のみ用いてもよいし、2種以上用いてもよい。 Further, it is preferable that R 117 is derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated. Chlorination is preferable as the halogenation.
In the present invention, a compound having three carboxy groups is referred to as a tricarboxylic acid compound.
Of the three carboxy groups of the tricarboxylic acid compound, two carboxy groups may be acid anhydrideized.
Examples of the halogenated tricarboxylic acid compound used in the production of the polyamide-imide precursor include branched chain aliphatic, cyclic aliphatic or aromatic tricarboxylic acid compounds.
Only one kind of these tricarboxylic acid compounds may be used, or two or more kinds may be used.
これらの化合物は、2つのカルボキシ基が無水物化した化合物(例えば、トリメリット酸無水物)であってもよいし、少なくとも1つのカルボキシ基がハロゲン化した化合物(例えば、無水トリメリット酸クロリド)であってもよい。 Specific examples of the tricarboxylic acid compound include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and phthalic acid. (Or phthalic acid anhydride) and benzoic acid are single-bonded, -O-, -CH 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -SO 2- or a phenylene group. Examples thereof include linked compounds.
These compounds may be compounds in which two carboxy groups are anhydrated (eg, trimellitic acid anhydride), or compounds in which at least one carboxy group is halogenated (eg, trimellitic acid anhydride). There may be.
他の繰返し単位としては、上述の式(2)で表される繰返し単位、下記式(PAI-1)で表される繰返し単位等が挙げられる。
Examples of the other repeating unit include a repeating unit represented by the above formula (2), a repeating unit represented by the following formula (PAI-1), and the like.
式(PAI-1)中、R116は、直鎖状又は分岐鎖状の脂肪族基、環状の脂肪族基、及び芳香族基、複素芳香族基、又は単結合若しくは連結基によりこれらを2以上連結した基が例示され、炭素数2~20の直鎖の脂肪族基、炭素数3~20の分岐の脂肪族基、炭素数3~20の環状の脂肪族基、炭素数6~20の芳香族基、又は、単結合若しくは連結基によりこれらを2以上組み合わせた基が好ましく、炭素数6~20の芳香族基、又は、単結合若しくは連結基により炭素数6~20の芳香族基を2以上組み合わせた基がより好ましい。
上記連結基としては、-O-、-S-、-C(=O)-、-S(=O)2-、アルキレン基、ハロゲン化アルキレン基、アリーレン基、又はこれらを2以上結合した連結基が好ましく、-O-、-S-、アルキレン基、ハロゲン化アルキレン基、アリーレン基、又はこれらを2以上結合した連結基がより好ましい。
上記アルキレン基としては、炭素数1~20のアルキレン基が好ましく、炭素数1~10のアルキレン基がより好ましく、炭素数1~4のアルキレン基が更に好ましい。
上記ハロゲン化アルキレン基としては、炭素数1~20のハロゲン化アルキレン基が好ましく、炭素数1~10のハロゲン化アルキレン基がより好ましく、炭素数1~4のハロゲン化アルキレン基がより好ましい。また、上記ハロゲン化アルキレン基におけるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられ、フッ素原子が好ましい。上記ハロゲン化アルキレン基は、水素原子を有していても、水素原子の全てがハロゲン原子で置換されていてもよいが、水素原子の全てがハロゲン原子で置換されていることが好ましい。好ましいハロゲン化アルキレン基の例としては、(ジトリフルオロメチル)メチレン基等が挙げられる。
上記アリーレン基としては、フェニレン基又はナフチレン基が好ましく、フェニレン基がより好ましく、1,3-フェニレン基又は1,4-フェニレン基が更に好ましい。 In formula (PAI-1), R 116 represents a divalent organic group and R 111 represents a divalent organic group.
In formula (PAI-1), R 116 is a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, a heteroaromatic group, or a single bond or a linking group. The above-mentioned linked groups are exemplified, and a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and a cyclic aliphatic group having 6 to 20 carbon atoms are exemplified. The aromatic group of the above, or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms by a single bond or a linking group is preferable. A group in which two or more of the above are combined is more preferable.
The linking group includes -O-, -S-, -C (= O)-, -S (= O) 2- , an alkylene group, a halogenated alkylene group, an arylene group, or a link in which two or more of these are bonded. A group is preferable, and an —O—, —S—, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group in which two or more of these are bonded is more preferable.
As the alkylene group, an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is further preferable.
As the halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable. Examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable. The halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with a halogen atom, but it is preferable that all of the hydrogen atoms are substituted with a halogen atom. Examples of preferred halogenated alkylene groups include (ditrifluoromethyl) methylene groups and the like.
As the arylene group, a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is further preferable.
本発明において、カルボキシ基を2つ有する化合物をジカルボン酸化合物、ハロゲン化されたカルボキシ基を2つ有する化合物をジカルボン酸ジハライド化合物という。
ジカルボン酸ジハライド化合物におけるカルボキシ基は、ハロゲン化されていればよいが、例えば、塩素化されていることが好ましい。すなわち、ジカルボン酸ジハライド化合物は、ジカルボン酸ジクロリド化合物であることが好ましい。
ポリアミドイミド前駆体の製造に用いられるハロゲン化されていてもよいジカルボン酸化合物又はジカルボン酸ジハライド化合物としては、直鎖状又は分岐鎖状の脂肪族、環状の脂肪族又は芳香族ジカルボン酸化合物又はジカルボン酸ジハライド化合物などが挙げられる。
これらのジカルボン酸化合物又はジカルボン酸ジハライド化合物は、1種のみ用いてもよいし、2種以上用いてもよい。 Further, R 116 is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound.
In the present invention, a compound having two carboxy groups is referred to as a dicarboxylic acid compound, and a compound having two halogenated carboxy groups is referred to as a dicarboxylic acid dihalide compound.
The carboxy group in the dicarboxylic acid dihalide compound may be halogenated, but is preferably chlorinated, for example. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.
Examples of the halogenated dicarboxylic acid compound or dicarboxylic acid dihalide compound used in the production of the polyamideimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compounds or dicarboxylic acids. Examples include aciddihalide compounds.
Only one kind or two or more kinds of these dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used.
ジカルボン酸ジハライド化合物の具体例としては、上記ジカルボン酸化合物の具体例における2つのカルボキシ基をハロゲン化した構造の化合物が挙げられる。 Specific examples of the dicarboxylic acid compound include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, and methylsuccinic acid, 2,2-. Didimethyl succinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3, 3-Didimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimeric acid, suberic acid, Dodecafluorosveric acid, azelaic acid, sebacic acid, hexadecafluorosevacinic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecane Diacid, Nonadecandioic acid, Eikosandioic acid, Heneikosandioic acid, Docosandioic acid, Tricosanedioic acid, Tetracosandioic acid, Pentacosanedioic acid, Hexacosandioic acid, Heptakosandioic acid, Octakosandioic acid, Nonakosandioic acid, Triacanthani Acid, Hentria Contanedioic Acid, Dotoria Contanedioic Acid, Diglycolic Acid, phthalic Acid, Isophthalic Acid, Telephthalic Acid, 4,4'-biphenylcarboxylic Acid, 4,4'-biphenylcarboxylic Acid, 4,4'- Examples thereof include dicarboxydiphenyl ether and benzophenone-4,4'-dicarboxylic acid.
Specific examples of the dicarboxylic acid dihalide compound include compounds having a structure in which two carboxy groups are halogenated in the specific examples of the dicarboxylic acid compound.
また、本発明におけるポリアミドイミド前駆体の別の一実施形態として、式(PAI-2)で表される繰返し単位、及び、式(PAI-1)で表される繰返し単位の合計含有量が、全繰返し単位の50モル%以上である態様が挙げられる。上記合計含有量は、70モル%以上であることがより好ましく、90モル%以上であることが更に好ましく、90モル%超であることが特に好ましい。上記合計含有量の上限は、特に限定されず、末端を除くポリアミドイミド前駆体における全ての繰返し単位が、式(PAI-2)で表される繰返し単位、又は、式(PAI-1)で表される繰返し単位のいずれかであってもよい。 As one embodiment of the polyamide-imide precursor in the present invention, a repeating unit represented by the formula (PAI-2), a repeating unit represented by the formula (PAI-1), and a repeating unit represented by the formula (2). An embodiment in which the total content of the units is 50 mol% or more of all the repeating units can be mentioned. The total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all the repeating units in the polyamide-imide precursor except the terminal are represented by the repeating unit represented by the formula (PAI-2) and the formula (PAI-1). It may be either a repeating unit or a repeating unit represented by the formula (2).
Further, as another embodiment of the polyamide-imide precursor in the present invention, the total content of the repeating unit represented by the formula (PAI-2) and the repeating unit represented by the formula (PAI-1) is. An embodiment of 50 mol% or more of all repetition units can be mentioned. The total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all the repeating units in the polyamide-imide precursor except the terminal are represented by the repeating unit represented by the formula (PAI-2) or the formula (PAI-1). It may be any of the repeating units to be used.
ポリアミドイミド前駆体の分子量の分散度は、1.5以上が好ましく、1.8以上がより好ましく、2.0以上であることが更に好ましい。ポリアミドイミド前駆体の分子量の分散度の上限値は特に定めるものではないが、例えば、7.0以下が好ましく、6.5以下がより好ましく、6.0以下が更に好ましい。また、樹脂組成物が特定樹脂として複数種のポリアミドイミド前駆体を含む場合、少なくとも1種のポリアミドイミド前駆体の重量平均分子量、数平均分子量、及び、分散度が上記範囲であることが好ましい。また、上記複数種のポリアミドイミド前駆体を1つの樹脂として算出した重量平均分子量、数平均分子量、及び、分散度が、それぞれ、上記範囲内であることも好ましい。 The weight average molecular weight (Mw) of the polyamide-imide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, still more preferably 10,000 to 50,000. .. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.
The degree of dispersion of the molecular weight of the polyamide-imide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the dispersity of the molecular weight of the polyamide-imide precursor is not particularly determined, but is preferably 7.0 or less, more preferably 6.5 or less, still more preferably 6.0 or less, for example. When the resin composition contains a plurality of types of polyamide-imide precursors as the specific resin, the weight average molecular weight, number average molecular weight, and dispersity of at least one type of polyamide-imide precursors are preferably in the above range. Further, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by using the plurality of types of polyamide-imide precursors as one resin are within the above ranges.
ポリイミド前駆体等は、例えば、低温中でテトラカルボン酸二無水物とジアミンを反応させる方法、低温中でテトラカルボン酸二無水物とジアミンを反応させてポリアミック酸を得、縮合剤又はアルキル化剤を用いてエステル化する方法、テトラカルボン酸二無水物とアルコールとによりジエステルを得て、その後ジアミンと縮合剤の存在下で反応させる方法、テトラカルボン酸二無水物とアルコールとによりジエステルを得、その後残りのジカルボン酸をハロゲン化剤を用いて酸ハロゲン化し、ジアミンと反応させる方法、などの方法を利用して得ることができる。上記製造方法のうち、テトラカルボン酸二無水物とアルコールとによりジエステルを得、その後残りのジカルボン酸をハロゲン化剤を用いて酸ハロゲン化し、ジアミンと反応させる方法がより好ましい。
上記縮合剤としては、例えばジシクロヘキシルカルボジイミド、ジイソプロピルカルボジイミド、1-エトキシカルボニル-2-エトキシ-1,2-ジヒドロキノリン、1,1-カルボニルジオキシ-ジ-1,2,3-ベンゾトリアゾール、N,N’-ジスクシンイミジルカーボネート、無水トリフルオロ酢酸等が挙げられる。
上記アルキル化剤としては、N,N-ジメチルホルムアミドジメチルアセタール、N,N-ジメチルホルムアミドジエチルアセタール、N,N-ジアルキルホルムアミドジアルキルアセタール、オルトギ酸トリメチル、オルトギ酸トリエチル等が挙げられる。
上記ハロゲン化剤としては、塩化チオニル、塩化オキサリル、オキシ塩化リン等が挙げられる。
ポリイミド前駆体等の製造方法では、反応に際し、有機溶剤を用いることが好ましい。有機溶剤は1種でもよいし、2種以上でもよい。
有機溶剤としては、原料に応じて適宜定めることができるが、ピリジン、ジエチレングリコールジメチルエーテル(ジグリム)、N-メチルピロリドン、N-エチルピロリドン、プロピオン酸エチル、ジメチルアセトアミド、ジメチルホルムアミド、テトラヒドロフラン、γ-ブチロラクトン等が例示される。
ポリイミド前駆体等の製造方法では、反応に際し、塩基性化合物を添加することが好ましい。塩基性化合物は1種でもよいし、2種以上でもよい。
塩基性化合物は、原料に応じて適宜定めることができるが、トリエチルアミン、ジイソプロピルエチルアミン、ピリジン、1,8-ジアザビシクロ[5.4.0]ウンデカ-7-エン、N,N-ジメチル-4-アミノピリジン等が例示される。 [Manufacturing method of polyimide precursor, etc.]
The polyimide precursor and the like can be, for example, a method of reacting a tetracarboxylic acid dianhydride with a diamine at a low temperature, or reacting a tetracarboxylic acid dianhydride with a diamine at a low temperature to obtain a polyamic acid, and a condensing agent or an alkylating agent. A method of esterifying with tetracarboxylic acid dianhydride and alcohol to obtain a diester, and then reacting with diamine in the presence of a condensing agent, a method of obtaining a diester with tetracarboxylic acid dianhydride and alcohol. After that, the remaining dicarboxylic acid can be obtained by acid-halogenizing it with a halogenating agent and reacting it with a diamine. Among the above-mentioned production methods, a method in which a diester is obtained from tetracarboxylic acid dianhydride and an alcohol, and then the remaining dicarboxylic acid is acid-halogenated with a halogenating agent and reacted with a diamine is more preferable.
Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, Examples thereof include N'-disuccinimidyl carbonate and trifluoroacetic anhydride.
Examples of the alkylating agent include N, N-dimethylformamide dimethylacetal, N, N-dimethylformamide diethylacetal, N, N-dialkylformamidedialkylacetal, trimethyl orthoformate, triethyl orthoformate and the like.
Examples of the halogenating agent include thionyl chloride, oxalyl chloride, phosphorus oxychloride and the like.
In the method for producing a polyimide precursor or the like, it is preferable to use an organic solvent in the reaction. The organic solvent may be one kind or two or more kinds.
The organic solvent can be appropriately determined depending on the raw material, but is pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone and the like. Is exemplified.
In the method for producing a polyimide precursor or the like, it is preferable to add a basic compound during the reaction. The basic compound may be one kind or two or more kinds.
The basic compound can be appropriately determined depending on the raw material, but triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, N, N-dimethyl-4-amino. Examples thereof include pyridine and the like.
ポリイミド前駆体等の製造方法に際し、保存安定性をより向上させるため、ポリイミド前駆体等の樹脂末端に残存するカルボン酸無水物、酸無水物誘導体、或いは、アミノ基を封止することが好ましい。樹脂末端に残存するカルボン酸無水物、及び酸無水物誘導体を封止する際、末端封止剤としては、モノアルコール、フェノール、チオール、チオフェノール、モノアミン等が挙げられ、反応性、膜の安定性から、モノアルコール、フェノール類やモノアミンを用いることがより好ましい。モノアルコールの好ましい化合物としては、メタノール、エタノール、プロパノール、ブタノール、ヘキサノール、オクタノール、ドデシノール、ベンジルアルコール、2-フェニルエタノール、2-メトキシエタノール、2-クロロメタノール、フルフリルアルコール等の1級アルコール、イソプロパノール、2-ブタノール、シクロヘキシルアルコール、シクロペンタノール、1-メトキシ-2-プロパノール等の2級アルコール、t-ブチルアルコール、アダマンタンアルコール等の3級アルコールが挙げられる。フェノール類の好ましい化合物としては、フェノール、メトキシフェノール、メチルフェノール、ナフタレン-1-オール、ナフタレン-2-オール、ヒドロキシスチレン等のフェノール類などが挙げられる。また、モノアミンの好ましい化合物としては、アニリン、2-エチニルアニリン、3-エチニルアニリン、4-エチニルアニリン、5-アミノ-8-ヒドロキシキノリン、1-ヒドロキシ-7-アミノナフタレン、1-ヒドロキシ-6-アミノナフタレン、1-ヒドロキシ-5-アミノナフタレン、1-ヒドロキシ-4-アミノナフタレン、2-ヒドロキシ-7-アミノナフタレン、2-ヒドロキシ-6-アミノナフタレン、2-ヒドロキシ-5-アミノナフタレン、1-カルボキシ-7-アミノナフタレン、1-カルボキシ-6-アミノナフタレン、1-カルボキシ-5-アミノナフタレン、2-カルボキシ-7-アミノナフタレン、2-カルボキシ-6-アミノナフタレン、2-カルボキシ-5-アミノナフタレン、2-アミノ安息香酸、3-アミノ安息香酸、4-アミノ安息香酸、4-アミノサリチル酸、5-アミノサリチル酸、6-アミノサリチル酸、2-アミノベンゼンスルホン酸、3-アミノベンゼンスルホン酸、4-アミノベンゼンスルホン酸、3-アミノ-4,6-ジヒドロキシピリミジン、2-アミノフェノール、3-アミノフェノール、4-アミノフェノール、2-アミノチオフェノール、3-アミノチオフェノール、4-アミノチオフェノールなどが挙げられる。これらを2種以上用いてもよく、複数の末端封止剤を反応させることにより、複数の異なる末端基を導入してもよい。
また、樹脂末端のアミノ基を封止する際、アミノ基と反応可能な官能基を有する化合物で封止することが可能である。アミノ基に対する好ましい封止剤は、カルボン酸無水物、カルボン酸クロリド、カルボン酸ブロミド、スルホン酸クロリド、無水スルホン酸、スルホン酸カルボン酸無水物などが好ましく、カルボン酸無水物、カルボン酸クロリドがより好ましい。カルボン酸無水物の好ましい化合物としては、無水酢酸、無水プロピオン酸、無水シュウ酸、無水コハク酸、無水マレイン酸、無水フタル酸、無水安息香酸、5-ノルボルネン-2,3-ジカルボン酸無水物などが挙げられる。また、カルボン酸クロリドの好ましい化合物としては、塩化アセチル、アクリル酸クロリド、プロピオニルクロリド、メタクリル酸クロリド、ピバロイルクロリド、シクロヘキサンカルボニルクロリド、2-エチルヘキサノイルクロリド、シンナモイルクロリド、1-アダマンタンカルボニルクロリド、ヘプタフルオロブチリルクロリド、ステアリン酸クロリド、ベンゾイルクロリド、などが挙げられる。 -End sealant-
In the method of producing a polyimide precursor or the like, it is preferable to seal the carboxylic acid anhydride, the acid anhydride derivative, or the amino group remaining at the resin terminal of the polyimide precursor or the like in order to further improve the storage stability. When encapsulating the carboxylic acid anhydride and the acid anhydride derivative remaining at the resin terminal, examples of the terminal encapsulant include monoalcohol, phenol, thiol, thiophenol, monoamine, etc., and are reactive and stable in the film. From the viewpoint of properties, it is more preferable to use monoalcohol, phenols and monoamines. Preferred compounds of monoalcohols include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol and flufuryl alcohol, and isopropanol. , 2-Butanol, cyclohexyl alcohol, cyclopentanol, 1-methoxy-2-propanol and other secondary alcohols, t-butyl alcohol, adamantan alcohol and other tertiary alcohols. Preferred compounds of phenols include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol and hydroxystyrene. Preferred compounds of monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene and 1-hydroxy-6-. Aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1- Carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-amino Naphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4 -Aminobenzene sulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Can be mentioned. Two or more of these may be used, or a plurality of different end groups may be introduced by reacting a plurality of terminal encapsulants.
Further, when sealing the amino group at the end of the resin, it is possible to seal with a compound having a functional group capable of reacting with the amino group. Preferred encapsulants for amino groups are carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, anhydrous sulfonic acids, sulfonic acid carboxylic acid anhydrides and the like, with carboxylic acid anhydrides and carboxylic acid chlorides being more preferred. preferable. Preferred compounds for carboxylic acid anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic acid anhydride, 5-norbornen-2,3-dicarboxylic acid anhydride and the like. Can be mentioned. Preferred compounds for the carboxylic acid chloride include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylate chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantancarbonyl chloride. , Heptafluorobutyryl chloride, stearate chloride, benzoyl chloride, and the like.
ポリイミド前駆体等の製造に際し、固体を析出する工程を含んでいてもよい。具体的には、反応液中に共存している脱水縮合剤の吸水副生物を必要に応じて濾別した後、水、脂肪族低級アルコール、又はその混合液等の貧溶媒に、得られた重合体成分を投入し、重合体成分を析出させることで、固体として析出させ、乾燥させることでポリイミド前駆体等を得ることができる。精製度を向上させるために、ポリイミド前駆体等を再溶解、再沈析出、乾燥等の操作を繰返してもよい。さらに、イオン交換樹脂を用いてイオン性不純物を除去する工程を含んでいてもよい。 -Solid precipitation-
A step of precipitating a solid may be included in the production of a polyimide precursor or the like. Specifically, the water-absorbing by-product of the dehydration condensing agent coexisting in the reaction solution was filtered off as necessary, and then obtained in a poor solvent such as water, an aliphatic lower alcohol, or a mixed solution thereof. By adding the polymer component and precipitating the polymer component, it is precipitated as a solid, and by drying, a polyimide precursor or the like can be obtained. In order to improve the degree of purification, operations such as redissolution, reprecipitation and drying of the polyimide precursor may be repeated. Further, a step of removing ionic impurities using an ion exchange resin may be included.
本発明の樹脂組成物における特定樹脂の含有量は、樹脂組成物の全固形分に対し20質量%以上であることが好ましく、30質量%以上であることがより好ましく、40質量%以上であることが更に好ましく、50質量%以上であることが一層好ましい。また、本発明の樹脂組成物における樹脂の含有量は、樹脂組成物の全固形分に対し、99.5質量%以下であることが好ましく、99質量%以下であることがより好ましく、98質量%以下であることが更に好ましく、97質量%以下であることが一層好ましく、95質量%以下であることがより一層好ましい。
本発明の樹脂組成物は、特定樹脂を1種のみ含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合、合計量が上記範囲となることが好ましい。 〔Content〕
The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and more preferably 40% by mass or more, based on the total solid content of the resin composition. More preferably, it is more preferably 50% by mass or more. Further, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, and 98% by mass, based on the total solid content of the resin composition. % Or less, more preferably 97% by mass or less, and even more preferably 95% by mass or less.
The resin composition of the present invention may contain only one type of specific resin, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.
具体的には、本発明の樹脂組成物は、特定樹脂と、後述する他の樹脂とを合計で2種以上含んでもよいし、特定樹脂を2種以上含んでいてもよいが、特定樹脂を2種以上含むことが好ましい。
本発明の樹脂組成物が特定樹脂を2種以上含む場合、例えば、ポリイミド前駆体であって、二無水物由来の構造(上述の式(2)でいうR115)が異なる2種以上のポリイミド前駆体を含むことが好ましい。 Further, it is also preferable that the resin composition of the present invention contains at least two kinds of resins.
Specifically, the resin composition of the present invention may contain two or more kinds of the specific resin and another resin described later in total, or may contain two or more kinds of the specific resin, but the specific resin may be contained. It is preferable to include two or more kinds.
When the resin composition of the present invention contains two or more kinds of specific resins, for example, two or more kinds of polyimides which are polyimide precursors and have different structures derived from dianhydride (R 115 in the above formula (2)). It is preferable to include a precursor.
本発明の樹脂組成物は、上述した特定樹脂と、特定樹脂とは異なる他の樹脂(以下、単に「他の樹脂」ともいう)とを含んでもよい。
他の樹脂としては、フェノール樹脂、ポリアミド、エポキシ樹脂、ポリシロキサン、シロキサン構造を含む樹脂、(メタ)アクリル樹脂、(メタ)アクリルアミド樹脂、ウレタン樹脂、ブチラール樹脂、スチリル樹脂、ポリエーテル樹脂、ポリエステル樹脂等が挙げられる。
例えば、(メタ)アクリル樹脂を更に加えることにより、塗布性に優れた樹脂組成物が得られ、また、耐溶剤性に優れたパターン(硬化物)が得られる。
例えば、後述する重合性化合物に代えて、又は、後述する重合性化合物に加えて、重量平均分子量が20,000以下の重合性基価の高い(例えば、樹脂1gにおける重合性基の含有モル量が1×10-3モル/g以上である)(メタ)アクリル樹脂を樹脂組成物に添加することにより、樹脂組成物の塗布性、パターン(硬化物)の耐溶剤性等を向上させることができる。 <Other resins>
The resin composition of the present invention may contain the above-mentioned specific resin and another resin different from the specific resin (hereinafter, also simply referred to as “other resin”).
Other resins include phenolic resin, polyamide, epoxy resin, polysiloxane, resin containing siloxane structure, (meth) acrylic resin, (meth) acrylamide resin, urethane resin, butyral resin, styryl resin, polyether resin, polyester resin. And so on.
For example, by further adding a (meth) acrylic resin, a resin composition having excellent coatability can be obtained, and a pattern (cured product) having excellent solvent resistance can be obtained.
For example, instead of the polymerizable compound described later, or in addition to the polymerizable compound described later, a high polymerizable base value having a weight average molecular weight of 20,000 or less (for example, the molar amount of the polymerizable group contained in 1 g of the resin). (1 × 10 -3 mol / g or more) By adding a (meth) acrylic resin to the resin composition, the coatability of the resin composition, the solvent resistance of the pattern (cured product), etc. can be improved. can.
また、本発明の樹脂組成物における、他の樹脂の含有量は、樹脂組成物の全固形分に対し、80質量%以下であることが好ましく、75質量%以下であることがより好ましく、70質量%以下であることが更に好ましく、60質量%以下であることが一層好ましく、50質量%以下であることがより一層好ましい。
また、本発明の樹脂組成物の好ましい一態様として、他の樹脂の含有量が低含有量である態様とすることもできる。上記態様において、他の樹脂の含有量は、樹脂組成物の全固形分に対し、20質量%以下であることが好ましく、15質量%以下であることがより好ましく、10質量%以下であることが更に好ましく、5質量%以下であることが一層好ましく、1質量%以下であることがより一層好ましい。上記含有量の下限は特に限定されず、0質量%以上であればよい。
本発明の樹脂組成物は、他の樹脂を1種のみ含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合、合計量が上記範囲となることが好ましい。 When the resin composition of the present invention contains another resin, the content of the other resin is preferably 0.01% by mass or more, preferably 0.05% by mass or more, based on the total solid content of the resin composition. It is more preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 5% by mass or more, and further preferably 10% by mass or more. More preferred.
Further, the content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, and more preferably 70% by mass, based on the total solid content of the resin composition. It is more preferably 0% by mass or less, further preferably 60% by mass or less, and even more preferably 50% by mass or less.
Further, as a preferred embodiment of the resin composition of the present invention, the content of the other resin may be low. In the above embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and 10% by mass or less, based on the total solid content of the resin composition. Is more preferable, 5% by mass or less is further preferable, and 1% by mass or less is even more preferable. The lower limit of the content is not particularly limited, and may be 0% by mass or more.
The resin composition of the present invention may contain only one kind of other resin, or may contain two or more kinds of other resins. When two or more kinds are contained, it is preferable that the total amount is within the above range.
本発明の樹脂組成物は、重合性化合物を含むことが好ましい。
重合性化合物としては、ラジカル架橋剤、又は、他の架橋剤が挙げられる。 <Polymerizable compound>
The resin composition of the present invention preferably contains a polymerizable compound.
Examples of the polymerizable compound include radical cross-linking agents and other cross-linking agents.
本発明の樹脂組成物は、ラジカル架橋剤を含むことが好ましい。
ラジカル架橋剤は、ラジカル重合性基を有する化合物である。ラジカル重合性基としては、エチレン性不飽和結合を含む基が好ましい。上記エチレン性不飽和結合を含む基としては、ビニル基、アリル基、ビニルフェニル基、(メタ)アクリロイル基、マレイミド基、(メタ)アクリルアミド基などのエチレン性不飽和結合を有する基が挙げられる。
これらの中でも、上記エチレン性不飽和結合を含む基としては、(メタ)アクリロイル基、(メタ)アクリルアミド基、ビニルフェニル基が好ましく、反応性の観点からは、(メタ)アクリロイル基がより好ましい。 [Radical cross-linking agent]
The resin composition of the present invention preferably contains a radical cross-linking agent.
The radical cross-linking agent is a compound having a radically polymerizable group. As the radically polymerizable group, a group containing an ethylenically unsaturated bond is preferable. Examples of the group containing an ethylenically unsaturated bond include a group having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, a (meth) acryloyl group, a maleimide group, and a (meth) acrylamide group.
Among these, as the group containing an ethylenically unsaturated bond, a (meth) acryloyl group, a (meth) acrylamide group and a vinylphenyl group are preferable, and from the viewpoint of reactivity, a (meth) acryloyl group is more preferable.
上記エチレン性不飽和結合を2個以上有する化合物としては、エチレン性不飽和結合を2~15個有する化合物が好ましく、エチレン性不飽和結合を2~10個有する化合物がより好ましく、2~6個有する化合物が更に好ましい。
また、得られるパターン(硬化物)の膜強度の観点からは、本発明の樹脂組成物は、エチレン性不飽和結合を2個有する化合物と、上記エチレン性不飽和結合を3個以上有する化合物とを含むことも好ましい。 The radical cross-linking agent is preferably a compound having one or more ethylenically unsaturated bonds, but more preferably a compound having two or more ethylenically unsaturated bonds. The radical cross-linking agent may have three or more ethylenically unsaturated bonds.
As the compound having two or more ethylenically unsaturated bonds, a compound having 2 to 15 ethylenically unsaturated bonds is preferable, and a compound having 2 to 10 ethylenically unsaturated bonds is more preferable, and 2 to 6 compounds are more preferable. The compound having is more preferable.
Further, from the viewpoint of the film strength of the obtained pattern (cured product), the resin composition of the present invention comprises a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. It is also preferable to include.
具体的な化合物としては、トリエチレングリコールジアクリレート、トリエチレングリコールジメタクリレート、テトラエチレングリコールジメタクリレート、テトラエチレングリコールジアクリレート、PEG(ポリエチレングリコール)200ジアクリレート、PEG200ジメタクリレート、PEG600ジアクリレート、PEG600ジメタクリレート、ポリテトラエチレングリコールジアクリレート、ポリテトラエチレングリコールジメタクリレート、ネオペンチルグリコールジアクリレート、ネオペンチルグリコールジメタクリレート、3-メチル-1,5-ペンタンジオールジアクリレート、1,6-ヘキサンジオールジアクリレート、1,6ヘキサンジオールジメタクリレート、ジメチロール-トリシクロデカンジアクリレート、ジメチロール-トリシクロデカンジメタクリレート、ビスフェノールAのEO(エチレンオキシド)付加物ジアクリレート、ビスフェノールAのEO付加物ジメタクリレート、ビスフェノールAのPO(プロピレンオキシド)付加物ジアクリレート、ビスフェノールAのPO付加物ジメタクリレート、2-ヒドロキシー3-アクリロイロキシプロピルメタクリレート、イソシアヌル酸EO変性ジアクリレート、イソシアヌル酸変性ジメタクリレート、その他ウレタン結合を有する2官能アクリレート、ウレタン結合を有する2官能メタクリレートを使用することができる。これらは必要に応じ、2種以上を混合し使用することができる。
なお、例えばPEG200ジアクリレートとは、ポリエチレングリコールジアクリレートであって、ポリエチレングリコール鎖の式量が200程度のものをいう。
本発明の樹脂組成物は、パターン(硬化物)の弾性率制御に伴う反り抑制の観点から、ラジカル架橋剤として、単官能ラジカル架橋剤を好ましく用いることができる。単官能ラジカル架橋剤としては、n-ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリレート、ブトキシエチル(メタ)アクリレート、カルビトール(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、ベンジル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、N-メチロール(メタ)アクリルアミド、グリシジル(メタ)アクリレート、ポリエチレングリコールモノ(メタ)アクリレート、ポリプロピレングリコールモノ(メタ)アクリレート等の(メタ)アクリル酸誘導体、N-ビニルピロリドン、N-ビニルカプロラクタム等のN-ビニル化合物類、アリルグリシジルエーテル等が好ましく用いられる。単官能ラジカル架橋剤としては、露光前の揮発を抑制するため、常圧下で100℃以上の沸点を持つ化合物も好ましい。
その他、2官能以上のラジカル架橋剤としては、ジアリルフタレート、トリアリルトリメリテート等のアリル化合物類が挙げられる。 As the resin composition, it is preferable to use bifunctional methacrylate or acrylate from the viewpoint of pattern resolution and film elasticity.
Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate. Meacrylate, Polytetraethylene glycol dimethacrylate, Polytetraethylene glycol dimethacrylate, Neopentyl glycol diacrylate, Neopentyl glycol dimethacrylate, 3-Methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6 hexanediol dimethacrylate, dimethyrol-tricyclodecanediacrylate, dimethyrol-tricyclodecanedimethacrylate, EO (ethylene oxide) adacrylate diacrylate of bisphenol A, EO adacrylate dimethacrylate of bisphenol A, PO of bisphenol A ( (Propropylene oxide) Additive Diacrylate, PO Additive Dimethacrylate of Bisphenol A, 2-Hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, and other bifunctional acrylates having a urethane bond, Bifunctional methacrylate having a urethane bond can be used. If necessary, two or more of these can be mixed and used.
For example, the PEG200 diacrylate is a polyethylene glycol diacrylate having a polyethylene glycol chain formula of about 200.
In the resin composition of the present invention, a monofunctional radical cross-linking agent can be preferably used as the radical cross-linking agent from the viewpoint of suppressing warpage associated with the control of the elastic modulus of the pattern (cured product). Examples of the monofunctional radical cross-linking agent include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, and cyclohexyl (meth). ) Acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc. (meth) Acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allylglycidyl ether and the like are preferably used. As the monofunctional radical cross-linking agent, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.
Other examples of the bifunctional or higher functional radical cross-linking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.
本発明の樹脂組成物は、上述したラジカル架橋剤とは異なる、他の架橋剤を含むことも好ましい。
本発明において、他の架橋剤とは、上述したラジカル架橋剤以外の架橋剤をいい、上述の光酸発生剤、又は、光塩基発生剤の感光により、組成物中の他の化合物又はその反応生成物との間で共有結合を形成する反応が促進される基を分子内に複数個有する化合物であることが好ましく、組成物中の他の化合物又はその反応生成物との間で共有結合を形成する反応が酸又は塩基の作用によって促進される基を分子内に複数個有する化合物が好ましい。
上記酸又は塩基は、露光工程において、光酸発生剤又は光塩基発生剤から発生する酸又は塩基であることが好ましい。
他の架橋剤としては、アシルオキシメチル基、メチロール基及びアルコキシメチル基よりなる群から選ばれた少なくとも1種の基を有する化合物が好ましく、アシルオキシメチル基、メチロール基及びアルコキシメチル基よりなる群から選ばれた少なくとも1種の基が窒素原子に直接結合した構造を有する化合物がより好ましい。
他の架橋剤としては、例えば、メラミン、グリコールウリル、尿素、アルキレン尿素、ベンゾグアナミンなどのアミノ基含有化合物にホルムアルデヒド又はホルムアルデヒドとアルコールを反応させ、上記アミノ基の水素原子をアシルオキシメチル基、メチロール基又はアルコキシメチル基で置換した構造を有する化合物が挙げられる。これらの化合物の製造方法は特に限定されず、上記方法により製造された化合物と同様の構造を有する化合物であればよい。また、これらの化合物のメチロール基同士が自己縮合してなるオリゴマーであってもよい。
上記のアミノ基含有化合物として、メラミンを用いた架橋剤をメラミン系架橋剤、グリコールウリル、尿素又はアルキレン尿素を用いた架橋剤を尿素系架橋剤、アルキレン尿素を用いた架橋剤をアルキレン尿素系架橋剤、ベンゾグアナミンを用いた架橋剤をベンゾグアナミン系架橋剤という。
これらの中でも、本発明の樹脂組成物は、尿素系架橋剤及びメラミン系架橋剤よりなる群から選ばれた少なくとも1種の化合物を含むことが好ましく、後述するグリコールウリル系架橋剤及びメラミン系架橋剤よりなる群から選ばれた少なくとも1種の化合物を含むことがより好ましい。 [Other cross-linking agents]
It is also preferable that the resin composition of the present invention contains another cross-linking agent different from the above-mentioned radical cross-linking agent.
In the present invention, the other cross-linking agent refers to a cross-linking agent other than the above-mentioned radical cross-linking agent, and is a reaction of another compound in the composition or a reaction thereof by exposure to the above-mentioned photoacid generator or photobase generator. A compound having a plurality of groups in the molecule that promotes a reaction to form a covalent bond with the product is preferable, and a covalent bond is formed with another compound in the composition or a reaction product thereof. A compound having a plurality of groups in the molecule in which the reaction to be formed is promoted by the action of an acid or a base is preferable.
The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
As the other cross-linking agent, a compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group and an alkoxymethyl group is preferable, and the compound is selected from the group consisting of an acyloxymethyl group, a methylol group and an alkoxymethyl group. A compound having a structure in which at least one of the above groups is directly bonded to a nitrogen atom is more preferable.
As another cross-linking agent, for example, an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is changed to an acyloxymethyl group, a methylol group, or a methylol group. Examples thereof include compounds having a structure substituted with an alkoxymethyl group. The method for producing these compounds is not particularly limited, and any compound having the same structure as the compound produced by the above method may be used. Further, it may be an oligomer formed by self-condensing the methylol groups of these compounds.
As the above amino group-containing compound, the cross-linking agent using melamine is a melamine-based cross-linking agent, the cross-linking agent using glycoluril, urea or alkylene urea is a urea-based cross-linking agent, and the cross-linking agent using alkylene urea is an alkylene urea-based cross-linking agent. A cross-linking agent using an agent or benzoguanamine is called a benzoguanamine-based cross-linking agent.
Among these, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of a urea-based cross-linking agent and a melamine-based cross-linking agent, and is preferably a glycoluril-based cross-linking agent and a melamine-based cross-linking agent described later. It is more preferred to include at least one compound selected from the group consisting of agents.
上記化合物が有するアルコキシメチル基又はアシルオキシメチル基は、炭素数2~5が好ましく、炭素数2又は3が好ましく、炭素数2がより好ましい。
上記化合物が有するアルコキシメチル基及びアシルオキシメチル基の総数は1~10が好ましく、より好ましくは2~8、特に好ましくは3~6である。
上記化合物の分子量は好ましくは1500以下であり、180~1200が好ましい。 As the compound containing at least one of the alkoxymethyl group and the acyloxymethyl group in the present invention, the alkoxymethyl group or the acyloxymethyl group is directly substituted on the aromatic group or the nitrogen atom having the following urea structure, or on triazine. Can be mentioned as a structural example.
The alkoxymethyl group or acyloxymethyl group contained in the above compound preferably has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms.
The total number of alkoxymethyl groups and acyloxymethyl groups contained in the above compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.
The molecular weight of the above compound is preferably 1500 or less, preferably 180 to 1200.
R101及びR102は、それぞれ独立に、一価の有機基を表し、互いに結合して環を形成してもよい。 R 100 represents an alkyl group or an acyl group.
R 101 and R 102 each independently represent a monovalent organic group and may be bonded to each other to form a ring.
R105は各々独立にアルキル基又はアルケニル基を示し、a、b及びcは各々独立に1~3であり、dは0~4であり、eは0~3であり、fは0~3であり、a+dは5以下であり、b+eは4以下であり、c+fは4以下である。
酸の作用により分解し、アルカリ可溶性基を生じる基、酸の作用により脱離する基、-C(R4)2COOR5で表される基におけるR5については、例えば、-C(R36)(R37)(R38)、-C(R36)(R37)(OR39)、-C(R01)(R02)(OR39)等を挙げることができる。
式中、R36~R39は、各々独立に、アルキル基、シクロアルキル基、アリール基、アラルキル基又はアルケニル基を表す。R36とR37とは、互いに結合して環を形成してもよい。
上記アルキル基としては、炭素数1~10のアルキル基が好ましく、炭素数1~5のアルキル基がより好ましい。
上記アルキル基は、直鎖状、分岐鎖状のいずれであってもよい。
上記シクロアルキル基としては、炭素数3~12のシクロアルキル基が好ましく、炭素数3~8のシクロアルキル基がより好ましい。
上記シクロアルキル基は単環構造であってもよいし、縮合環等の多環構造であってもよい。
上記アリール基は炭素数6~30の芳香族炭化水素基であることが好ましく、フェニル基であることがより好ましい。
上記アラルキル基としては、炭素数7~20のアラルキル基が好ましく、炭素数7~16のアラルキル基がより好ましい。
上記アラルキル基はアルキル基により置換されたアリール基を意図しており、これらのアルキル基及びアリール基の好ましい態様は、上述のアルキル基及びアリール基の好ましい態様と同様である。
上記アルケニル基は炭素数3~20のアルケニル基が好ましく、炭素数3~16のアルケニル基がより好ましい。
また、これらの基は本発明の効果が得られる範囲内で、公知の置換基を更に有していてもよい。 In the formula, X represents a single-bonded or divalent organic group, each R 104 independently represents an alkyl group or an acyl group, and R 103 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group. , Or a group that decomposes by the action of an acid to produce an alkali-soluble group (for example, a group that is desorbed by the action of an acid, a group represented by -C (R 4 ) 2 COOR 5 (R 4 is independent of each other). It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R5 represents a group desorbed by the action of an acid.)).
R 105 independently represents an alkyl group or an alkenyl group, a, b and c are independently 1 to 3, d is 0 to 4, e is 0 to 3, and f is 0 to 3. A + d is 5 or less, b + e is 4 or less, and c + f is 4 or less.
For R 5 in a group that decomposes by the action of an acid to produce an alkali-soluble group, a group that is eliminated by the action of an acid, and a group represented by -C (R 4 ) 2 COOR 5 , for example, -C (R 36 ). ) (R 37 ) (R 38 ), -C (R 36 ) (R 37 ) (OR 39 ), -C (R 01 ) (R 02 ) (OR 39 ) and the like.
In the formula, R 36 to R 39 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R 36 and R 37 may be coupled to each other to form a ring.
As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable.
The alkyl group may be linear or branched.
As the cycloalkyl group, a cycloalkyl group having 3 to 12 carbon atoms is preferable, and a cycloalkyl group having 3 to 8 carbon atoms is more preferable.
The cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a fused ring.
The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group.
As the aralkyl group, an aralkyl group having 7 to 20 carbon atoms is preferable, and an aralkyl group having 7 to 16 carbon atoms is more preferable.
The above-mentioned aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as those of the above-mentioned preferred embodiments of alkyl and aryl groups.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms.
Further, these groups may further have a known substituent as long as the effect of the present invention can be obtained.
耐熱性の観点で、アルコキシメチル基又はアシルオキシメチル基が、直接芳香環やトリアジン環上に置換した化合物が好ましい。 As the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group, a commercially available compound may be used, or a compound synthesized by a known method may be used.
From the viewpoint of heat resistance, a compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring is preferable.
ビスメトキシメチル尿素、ビスエトキシメチル尿素、ビスプロポキシメチル尿素、ビスブトキシメチル尿素等の尿素系架橋剤、
モノヒドロキシメチル化エチレン尿素又はジヒドロキシメチル化エチレン尿素、モノメトキシメチル化エチレン尿素、ジメトキシメチル化エチレン尿素、モノエトキシメチル化エチレン尿素、ジエトキシメチル化エチレン尿素、モノプロポキシメチル化エチレン尿素、ジプロポキシメチル化エチレン尿素、モノブトキシメチル化エチレン尿素、又は、ジブトキシメチル化エチレン尿素などのエチレン尿素系架橋剤、
モノヒドロキシメチル化プロピレン尿素、ジヒドロキシメチル化プロピレン尿素、モノメトキシメチル化プロピレン尿素、ジメトキシメチル化プロピレン尿素、モノエトキシメチル化プロピレン尿素、ジエトキシメチル化プロピレン尿素、モノプロポキシメチル化プロピレン尿素、ジプロポキシメチル化プロピレン尿素、モノブトキシメチル化プロピレン尿素、又は、ジブトキシメチル化プロピレン尿素などのプロピレン尿素系架橋剤、
1,3-ジ(メトキシメチル)4,5-ジヒドロキシ-2-イミダゾリジノン、1,3-ジ(メトキシメチル)-4,5-ジメトキシ-2-イミダゾリジノンなどが挙げられる。 Specific examples of the urea-based cross-linking agent include monohydroxymethylated glycol uryl, dihydroxymethylated glycol uryl, trihydroxymethylated glycol uryl, tetrahydroxymethylated glycol uryl, monomethoxymethylated glycol uryl, and dimethoxymethylated glycol. Uril, trimethoxymethylated glycol uryl, tetramethoxymethylated glycol uryl, monoethoxymethylated glycol uryl, diethoxymethylated glycol uryl, triethoxymethylated glycol uryl, tetraethoxymethylated glycol uryl, monopropoxymethylated glycol uryl , Dipropoxymethylated glycol uryl, tripropoxymethylated glycol uryl, tetrapropoxymethylated glycol uryl, monobutoxymethylated glycol uryl, dibutoxymethylated glycol uryl, tributoxymethylated glycol uryl, or tetrabutoxymethylated glycol Glycoluril-based cross-linking agents such as uryl;
Urea-based cross-linking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea,
Monohydroxymethylated ethylene urea or dihydroxymethylated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethyl Ethyleneurea-based cross-linking agents such as ethyleneurea, monobutoxymethylated, or dibutoxymethylated ethyleneurea,
Monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethyl A propylene urea-based cross-linking agent such as propylene dioxide, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea,
Examples thereof include 1,3-di (methoxymethyl) 4,5-dihydroxy-2-imidazolidinone and 1,3-di (methoxymethyl) -4,5-dimethoxy-2-imidazolidinone.
このような化合物の具体例としては、ベンゼンジメタノール、ビス(ヒドロキシメチル)クレゾール、ビス(ヒドロキシメチル)ジメトキシベンゼン、ビス(ヒドロキシメチル)ジフェニルエーテル、ビス(ヒドロキシメチル)ベンゾフェノン、ヒドロキシメチル安息香酸ヒドロキシメチルフェニル、ビス(ヒドロキシメチル)ビフェニル、ジメチルビス(ヒドロキシメチル)ビフェニル、ビス(メトキシメチル)ベンゼン、ビス(メトキシメチル)クレゾール、ビス(メトキシメチル)ジメトキシベンゼン、ビス(メトキシメチル)ジフェニルエーテル、ビス(メトキシメチル)ベンゾフェノン、メトキシメチル安息香酸メトキシメチルフェニル、ビス(メトキシメチル)ビフェニル、ジメチルビス(メトキシメチル)ビフェニル、4,4’,4’’-エチリデントリス[2,6-ビス(メトキシメチル)フェノール]、5,5’-[2,2,2‐トリフルオロ‐1‐(トリフルオロメチル)エチリデン]ビス[2‐ヒドロキシ‐1,3‐ベンゼンジメタノール]、3,3’,5,5’-テトラキス(メトキシメチル)-1,1’-ビフェニル-4,4’-ジオール等が挙げられる。 In addition, as a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group, at least one selected from the group consisting of a methylol group and an alkoxymethyl group on an aromatic ring (preferably a benzene ring). Compounds to which the group of the species is directly bonded are also preferably used.
Specific examples of such compounds include benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, and hydroxymethylbenzoate hydroxymethylphenyl. , Bis (hydroxymethyl) biphenyl, dimethylbis (hydroxymethyl) biphenyl, bis (methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxybenzene, bis (methoxymethyl) diphenyl ether, bis (methoxymethyl) Benzenephenone, methoxymethylphenyl methoxymethylbenzoate, bis (methoxymethyl) biphenyl, dimethylbis (methoxymethyl) biphenyl, 4,4', 4''-ethylidentris [2,6-bis (methoxymethyl) phenol], 5 , 5'-[2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] bis [2-hydroxy-1,3-benzenedimethanol], 3,3', 5,5'-tetrakis ( Examples thereof include methoxymethyl) -1,1'-biphenyl-4,4'-diol and the like.
エポキシ化合物としては、一分子中にエポキシ基を2以上有する化合物であることが好ましい。エポキシ基は、200℃以下で架橋反応し、かつ、架橋に由来する脱水反応が起こらないため膜収縮が起きにくい。このため、エポキシ化合物を含有することは、本発明の樹脂組成物の低温硬化及び反りの抑制に効果的である。 -Epoxy compound (compound having an epoxy group)-
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group undergoes a cross-linking reaction at 200 ° C. or lower, and the dehydration reaction derived from the cross-linking does not occur, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in suppressing low temperature curing and warpage of the resin composition of the present invention.
オキセタン化合物としては、一分子中にオキセタン環を2つ以上有する化合物、3-エチル-3-ヒドロキシメチルオキセタン、1,4-ビス{[(3-エチル-3-オキセタニル)メトキシ]メチル}ベンゼン、3-エチル-3-(2-エチルヘキシルメチル)オキセタン、1,4-ベンゼンジカルボン酸-ビス[(3-エチル-3-オキセタニル)メチル]エステル等を挙げることができる。具体的な例としては、東亞合成(株)製のアロンオキセタンシリーズ(例えば、OXT-121、OXT-221)が好適に使用することができ、これらは単独で、又は2種以上混合してもよい。 -Oxetane compound (compound having an oxetanyl group)-
Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, and the like. Examples thereof include 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester, and the like. As a specific example, Aron Oxetane series (for example, OXT-121, OXT-221) manufactured by Toagosei Co., Ltd. can be preferably used, and these can be used alone or in combination of two or more. good.
ベンゾオキサジン化合物は、開環付加反応に由来する架橋反応のため、硬化時に脱ガスが発生せず、更に熱収縮を小さくして反りの発生が抑えられることから好ましい。 -Benzoxazine compound (compound having a benzoxazolyl group)-
Since the benzoxazine compound is a cross-linking reaction derived from the cycloaddition reaction, degassing does not occur at the time of curing, and heat shrinkage is further reduced to suppress the occurrence of warpage, which is preferable.
本発明の樹脂組成物は、光及び/又は熱により重合を開始させることができる重合開始剤を含むことが好ましい。特に光重合開始剤を含むことが好ましい。
重合開始剤は、ラジカル重合開始剤であることが好ましい。ラジカル重合開始剤としては、特に制限はなく、公知のラジカル重合開始剤の中から適宜選択することができる。例えば、紫外線領域から可視領域の光線に対して感光性を有する光ラジカル重合開始剤が好ましい。また、光励起された増感剤と何らかの作用を生じ、活性ラジカルを生成する活性剤であってもよい。 [Polymer initiator]
The resin composition of the present invention preferably contains a polymerization initiator that can initiate polymerization by light and / or heat. In particular, it is preferable to include a photopolymerization initiator.
The polymerization initiator is preferably a radical polymerization initiator. The radical polymerization initiator is not particularly limited and may be appropriately selected from known radical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. Further, it may be an active agent that causes some action with a photoexcited sensitizer and generates an active radical.
Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), ADEKA PTOMER N-1919 (manufactured by ADEKA Corporation, JP-A-2012-014052). A radical polymerization initiator 2) is also preferably used. In addition, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.), Adeka Arkuru's NCI-730, NCI-831 and Adeka Arkuru's NCI-930 (manufactured by ADEKA Corporation) are also used. be able to. Further, DFI-091 (manufactured by Daito Chemix Co., Ltd.) and SpeedCure PDO (manufactured by SARTOMER ARCEMA) can be used. Further, an oxime compound having the following structure can also be used.
式中、RX1は、アルキル基、アルケニル基、アルコキシ基、アリール基、アリールオキシ基、複素環基、複素環オキシ基、アルキルスルファニル基、アリールスルファニル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、アシル基、アシルオキシ基、アミノ基、ホスフィノイル基、カルバモイル基またはスルファモイル基を表し、
RX2は、アルキル基、アルケニル基、アルコキシ基、アリール基、アリールオキシ基、複素環基、複素環オキシ基、アルキルスルファニル基、アリールスルファニル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、アシルオキシ基またはアミノ基を表し、
RX3~RX14は、それぞれ独立して水素原子または置換基を表す。
ただし、RX10~RX14のうち少なくとも一つは、電子求引性基である。 The oxime compound OX is preferably at least one selected from the compound represented by the formula (OX1) and the compound represented by the formula (OX2), and more preferably the compound represented by the formula (OX2). preferable.
In the formula, RX1 is an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group. Represents a group, arylsulfonyl group, acyl group, acyloxy group, amino group, phosphinoyl group, carbamoyl group or sulfamoyl group.
RX2 contains an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group and an aryl. Represents a sulfonyl group, an acyloxy group or an amino group
RX3 to RX14 independently represent a hydrogen atom or a substituent.
However, at least one of RX10 to RX14 is an electron-withdrawing group.
なお、光重合開始剤は熱重合開始剤としても機能する場合があるため、オーブンやホットプレート等の加熱によって光重合開始剤による架橋を更に進行させられる場合がある。 When the photopolymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition of the present invention. It is more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more kinds of photopolymerization initiators are contained, the total amount is preferably in the above range.
Since the photopolymerization initiator may also function as a thermal polymerization initiator, cross-linking with the photopolymerization initiator may be further promoted by heating an oven, a hot plate, or the like.
樹脂組成物は、増感剤を含んでいてもよい。増感剤は、特定の活性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、熱ラジカル重合開始剤、光ラジカル重合開始剤などと接触して、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、熱ラジカル重合開始剤、光ラジカル重合開始剤は化学変化を起こして分解し、ラジカル、酸又は塩基を生成する。
使用可能な増感剤として、ベンゾフェノン系、ミヒラーズケトン系、クマリン系、ピラゾールアゾ系、アニリノアゾ系、トリフェニルメタン系、アントラキノン系、アントラセン系、アントラピリドン系、ベンジリデン系、オキソノール系、ピラゾロトリアゾールアゾ系、ピリドンアゾ系、シアニン系、フェノチアジン系、ピロロピラゾールアゾメチン系、キサンテン系、フタロシアニン系、ペンゾピラン系、インジゴ系等の化合物を使用することができる。
増感剤としては、例えば、ミヒラーズケトン、4,4’-ビス(ジエチルアミノ)ベンゾフェノン、2,5-ビス(4’-ジエチルアミノベンザル)シクロペンタン、2,6-ビス(4’-ジエチルアミノベンザル)シクロヘキサノン、2,6-ビス(4’-ジエチルアミノベンザル)-4-メチルシクロヘキサノン、4,4’-ビス(ジメチルアミノ)カルコン、4,4’-ビス(ジエチルアミノ)カルコン、p-ジメチルアミノシンナミリデンインダノン、p-ジメチルアミノベンジリデンインダノン、2-(p-ジメチルアミノフェニルビフェニレン)-ベンゾチアゾール、2-(p-ジメチルアミノフェニルビニレン)ベンゾチアゾール、2-(p-ジメチルアミノフェニルビニレン)イソナフトチアゾール、1,3-ビス(4’-ジメチルアミノベンザル)アセトン、1,3-ビス(4’-ジエチルアミノベンザル)アセトン、3,3’-カルボニル-ビス(7-ジエチルアミノクマリン)、3-アセチル-7-ジメチルアミノクマリン、3-エトキシカルボニル-7-ジメチルアミノクマリン、3-ベンジロキシカルボニル-7-ジメチルアミノクマリン、3-メトキシカルボニル-7-ジエチルアミノクマリン、3-エトキシカルボニル-7-ジエチルアミノクマリン(7-(ジエチルアミノ)クマリン-3-カルボン酸エチル)、N-フェニル-N’-エチルエタノールアミン、N-フェニルジエタノールアミン、N-p-トリルジエタノールアミン、N-フェニルエタノールアミン、4-モルホリノベンゾフェノン、ジメチルアミノ安息香酸イソアミル、ジエチルアミノ安息香酸イソアミル、2-メルカプトベンズイミダゾール、1-フェニル-5-メルカプトテトラゾール、2-メルカプトベンゾチアゾール、2-(p-ジメチルアミノスチリル)ベンズオキサゾール、2-(p-ジメチルアミノスチリル)ベンゾチアゾール、2-(p-ジメチルアミノスチリル)ナフト(1,2-d)チアゾール、2-(p-ジメチルアミノベンゾイル)スチレン、ジフェニルアセトアミド、ベンズアニリド、N-メチルアセトアニリド、3‘,4’-ジメチルアセトアニリド等が挙げられる。
また、他の増感色素を用いてもよい。
増感色素の詳細については、特開2016-027357号公報の段落0161~0163の記載を参酌でき、この内容は本明細書に組み込まれる。 [Sensitizer]
The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in the electron-excited state comes into contact with the thermal radical polymerization initiator, the photoradical polymerization initiator, and the like, and acts such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal radical polymerization initiator and the photoradical polymerization initiator undergo a chemical change and decompose to generate a radical, an acid or a base.
Usable sensitizers include benzophenone, Michler's ketone, coumarin, pyrazole azo, anilino azo, triphenylmethane, anthracinone, anthracene, anthrapyridone, benzylidene, oxonol, pyrazole triazole azo. , Pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, penzopyran, indigo and the like can be used.
Examples of the sensitizer include Michler's ketone, 4,4'-bis (diethylamino) benzophenone, 2,5-bis (4'-diethylaminobenzal) cyclopentane, and 2,6-bis (4'-diethylaminobenzal). Cyclohexanone, 2,6-bis (4'-diethylaminobenzal) -4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone, p-dimethylaminocinnamyl Denindanone, p-dimethylaminobenzylideneindanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p-dimethylaminophenylbinylene) benzothiazole, 2- (p-dimethylaminophenylbinylene) iso Naftthiazole, 1,3-bis (4'-dimethylaminobenzal) acetone, 1,3-bis (4'-diethylaminobenzal) acetone, 3,3'-carbonyl-bis (7-diethylaminocoumarin), 3 -Acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylamino Kumarin (7- (diethylamino) coumarin-3-carboxylate ethyl), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, Isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethyl) Aminostyryl) benzothiazole, 2- (p-dimethylaminostyryl) naphtho (1,2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3', 4 '-Dimethylacetanilide and the like can be mentioned.
Moreover, you may use other sensitizing dyes.
For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP-A-2016-027355 can be referred to, and the content thereof is incorporated in the present specification.
本発明の樹脂組成物は、連鎖移動剤を含有してもよい。連鎖移動剤は、例えば高分子辞典第三版(高分子学会編、2005年)683-684頁に定義されている。連鎖移動剤としては、例えば、分子内に-S-S-、-SO2-S-、-N-O-、SH、PH、SiH、及びGeHを有する化合物群、RAFT(Reversible Addition Fragmentation chain Transfer)重合に用いられるチオカルボニルチオ基を有するジチオベンゾアート、トリチオカルボナート、ジチオカルバマート、キサンタート化合物等が用いられる。これらは、低活性のラジカルに水素を供与して、ラジカルを生成するか、若しくは、酸化された後、脱プロトンすることによりラジカルを生成しうる。特に、チオール化合物を好ましく用いることができる。 [Chain transfer agent]
The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, 2005), pp. 683-684. Examples of the chain transfer agent include RAFT (Reversible Addition Fragmentation chain Transfer), which is a group of compounds having -S-S-, -SO2 -S-, -NO-, SH, PH, SiH, and GeH in the molecule. ) Dithiobenzoate having a thiocarbonylthio group, trithiocarbonate, dithiocarbamate, xantate compound and the like used for polymerization are used. They can donate hydrogen to low-activity radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals. In particular, thiol compounds can be preferably used.
本発明の樹脂組成物は、光酸発生剤を含むことが好ましい。
光酸発生剤とは、200nm~900nmの光照射により、ブレンステッド酸、及び、ルイス酸の少なくとも一方を発生させる化合物を表す。照射される光は、好ましくは波長300nm~450nmの光であり、より好ましくは330nm~420nmの光である。光酸発生剤単独または増感剤との併用において、感光して酸を発生させることが可能な光酸発生剤であることが好ましい。
発生する酸の例としては、ハロゲン化水素、カルボン酸、スルホン酸、スルフィン酸、チオスルフィン酸、リン酸、リン酸モノエステル、リン酸ジエステル、ホウ素誘導体、リン誘導体、アンチモン誘導体、過酸化ハロゲン、スルホンアミド等が好ましく挙げられる。 [Photoacid generator]
The resin composition of the present invention preferably contains a photoacid generator.
The photoacid generator represents a compound that generates at least one of Bronsted acid and Lewis acid by irradiation with light of 200 nm to 900 nm. The irradiated light is preferably light having a wavelength of 300 nm to 450 nm, and more preferably light having a wavelength of 330 nm to 420 nm. It is preferable that the photoacid generator is a photoacid generator capable of generating an acid by being exposed to light when used alone or in combination with a sensitizer.
Examples of generated acids include hydrogen halide, carboxylic acid, sulfonic acid, sulfinic acid, thiosulfinic acid, phosphoric acid, phosphoric acid monoester, phosphoric acid diester, boron derivative, phosphorus derivative, antimony derivative, halogen peroxide, etc. Sulfonamide and the like are preferably mentioned.
感度、保存安定性の観点から、有機ハロゲン化合物、オキシムスルホネート化合物、オニウム塩化合物が好ましく、形成する膜の機械特性等から、オキシムエステルが好ましい。 Examples of the photoacid generator used in the resin composition of the present invention include quinone diazide compounds, oxime sulfonate compounds, organic halogenated compounds, organic borate compounds, disulfone compounds, onium salt compounds and the like.
Organic halogen compounds, oxime sulfonate compounds, and onium salt compounds are preferable from the viewpoint of sensitivity and storage stability, and oxime esters are preferable from the viewpoint of mechanical properties of the film to be formed.
オキシムスルホネート化合物は、オキシムスルホネート基を有していれば特に制限はないが、下記式(OS-1)、後述する式(OS-103)、式(OS-104)、又は、式(OS-105)で表されるオキシムスルホネート化合物であることが好ましい。 The photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as "oxime sulfonate compound").
The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but the following formula (OS-1), the formula (OS-103) described later, the formula (OS-104), or the formula (OS-). It is preferably the oxime sulfonate compound represented by 105).
式(OS-1)中、m3は、0~3の整数を表し、0又は1が好ましい。m3が2又は3であるとき、複数のX3は同一でも異なっていてもよい。
式(OS-1)中、R34は、アルキル基又はアリール基を表し、炭素数1~10のアルキル基、炭素数1~10のアルコキシ基、炭素数1~5のハロゲン化アルキル基、炭素数1~5のハロゲン化アルコキシ基、Wで置換されていてもよいフェニル基、Wで置換されていてもよいナフチル基又はWで置換されていてもよいアントラニル基であることが好ましい。Wは、ハロゲン原子、シアノ基、ニトロ基、炭素数1~10のアルキル基、炭素数1~10のアルコキシ基、炭素数1~5のハロゲン化アルキル基又は炭素数1~5のハロゲン化アルコキシ基、炭素数6~20のアリール基、炭素数6~20のハロゲン化アリール基を表す。 In formula (OS- 1 ), X3 represents an alkyl group, an alkoxy group, or a halogen atom. When a plurality of X3s exist, they may be the same or different from each other. The alkyl group and the alkoxy group in X3 may have a substituent. As the alkyl group in X3 , a linear or branched alkyl group having 1 to 4 carbon atoms is preferable. As the alkoxy group in X3 , a linear or branched alkoxy group having 1 to 4 carbon atoms is preferable. As the halogen atom in X3 , a chlorine atom or a fluorine atom is preferable.
In the formula (OS-1), m3 represents an integer of 0 to 3, and 0 or 1 is preferable. When m3 is 2 or 3 , the plurality of X3s may be the same or different.
In the formula (OS-1), R 34 represents an alkyl group or an aryl group, which is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms, and carbon. It is preferably an alkoxy group of numbers 1 to 5, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W. W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms or an alkoxy halide having 1 to 5 carbon atoms. Represents a group, an aryl group having 6 to 20 carbon atoms, and an aryl halide group having 6 to 20 carbon atoms.
式(OS-103)~式(OS-105)中、Rs1で表されるアルキル基(炭素数1~30が好ましい)、アリール基(炭素数6~30が好ましい)又はヘテロアリール基(炭素数4~30が好ましい)は、本発明の効果が得られる範囲で公知の置換基を有していてもよい。 In formulas (OS-103) to (OS-105), R s1 represents an alkyl group, an aryl group or a heteroaryl group, and R s2, which may be present in a plurality of R s2 , independently represents a hydrogen atom, an alkyl group and an aryl group. R s6 , which represents a group or a halogen atom and may be present in a plurality, independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, and Xs represents O or S. Represented, ns represents 1 or 2, ms represents an integer from 0 to 6.
In formulas (OS-103) to (OS-105), an alkyl group represented by R s1 (preferably 1 to 30 carbon atoms), an aryl group (preferably 6 to 30 carbon atoms) or a heteroaryl group (carbon). (Preferably numbers 4 to 30) may have a known substituent as long as the effects of the present invention can be obtained.
式(OS-103)、式(OS-104)、又は、式(OS-105)中、XsはO又はSを表し、Oであることが好ましい。上記式(OS-103)~(OS-105)において、Xsを環員として含む環は、5員環又は6員環である。 In the formulas (OS-103) to (OS-105), R s2 is preferably a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms) or an aryl group (preferably 6 to 30 carbon atoms). , Hydrogen atom or alkyl group is more preferable. Of the Rs2 that may be present in two or more in the compound, one or two are preferably an alkyl group, an aryl group or a halogen atom, and one is more preferably an alkyl group, an aryl group or a halogen atom. It is particularly preferable that one is an alkyl group and the rest is a hydrogen atom. The alkyl group or aryl group represented by R s2 may have a known substituent as long as the effects of the present invention can be obtained.
In the formula (OS-103), the formula (OS-104), or the formula (OS-105), Xs represents O or S, and is preferably O. In the above formulas (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.
式(OS-103)~式(OS-105)中、Rs6で表されるアルキル基(炭素数1~30が好ましい)及びアルキルオキシ基(炭素数1~30が好ましい)は、置換基を有していてもよい。
式(OS-103)~式(OS-105)中、msは0~6の整数を表し、0~2の整数であることが好ましく、0又は1であることがより好ましく、0であることが特に好ましい。 In the formulas (OS-103) to (OS-105), ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is. It is preferably 2.
In the formulas (OS-103) to (OS-105), the alkyl group represented by R s6 (preferably having 1 to 30 carbon atoms) and the alkyloxy group (preferably having 1 to 30 carbon atoms) are substituted groups. You may have.
In the formulas (OS-103) to (OS-105), ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0. Is particularly preferable.
式(OS-106)~式(OS-111)中、Rt7は、水素原子又は臭素原子を表し、水素原子であることが好ましい。 In formulas (OS-106) to (OS-111), R t1 represents an alkyl group, an aryl group or a heteroaryl group, R t7 represents a hydrogen atom or a bromine atom, and R t8 represents a hydrogen atom and the number of carbon atoms. 1 to 8 alkyl groups, halogen atoms, chloromethyl groups, bromomethyl groups, bromoethyl groups, methoxymethyl groups, phenyl groups or chlorophenyl groups, R t9 represents hydrogen atoms, halogen atoms, methyl groups or methoxy groups, and R t2 represents a hydrogen atom or a methyl group.
In the formulas (OS-106) to (OS-111), R t7 represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
Rt2は、水素原子又はメチル基を表し、水素原子であることが好ましい。
また、上記オキシムスルホネート化合物において、オキシムの立体構造(E,Z)については、いずれか一方であっても、混合物であってもよい。
上記式(OS-103)~式(OS-105)で表されるオキシムスルホネート化合物の具体例としては、特開2011-209692号公報の段落番号0088~0095、特開2015-194674号公報の段落番号0168~0194に記載の化合物が例示され、これらの内容は本明細書に組み込まれる。 In the formulas (OS-106) to (OS-111), R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
R t2 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
Further, in the above-mentioned oxime sulfonate compound, the three-dimensional structure (E, Z) of the oxime may be either one or a mixture.
Specific examples of the oxime sulfonate compound represented by the above formulas (OS-103) to (OS-105) include paragraph numbers 008 to 0995 of JP2011-209692 and paragraphs of JP-A-2015-194674. The compounds of Nos. 0168 to 0194 are exemplified and their contents are incorporated herein.
式(OS-101)又は式(OS-102)中、Ru2aは、アルキル基又はアリール基を表す。
式(OS-101)又は式(OS-102)中、Xuは、-O-、-S-、-NH-、-NRu5-、-CH2-、-CRu6H-又はCRu6Ru7-を表し、Ru5~Ru7はそれぞれ独立に、アルキル基又はアリール基を表す。 In the formula (OS-101) or the formula (OS-102), Ru9 is 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, and the like. Represents an aryl group or a heteroaryl group. The embodiment in which R u9 is a cyano group or an aryl group is more preferable, and the embodiment in which R u9 is a cyano group, a phenyl group or a naphthyl group is further preferable.
In formula (OS-101) or formula (OS-102), Ru2a represents an alkyl group or an aryl group.
In formula (OS-101) or formula (OS-102), Xu is -O-, -S-, -NH-, -NR u5- , -CH 2- , -CR u6 H- or CR u6 R u7. -Represents-, and R u5 to R u7 independently represent an alkyl group or an aryl group.
また、上記オキシムスルホネート化合物において、オキシムやベンゾチアゾール環の立体構造(E,Z等)についてはそれぞれ、いずれか一方であっても、混合物であってもよい。
式(OS-101)で表される化合物の具体例としては、特開2011-209692号公報の段落番号0102~0106、特開2015-194674号公報の段落番号0195~0207に記載の化合物が例示され、これらの内容は本明細書に組み込まれる。
上記化合物の中でも、下記b-9、b-16、b-31、b-33が好ましい。
市販品としては、WPAG-336(富士フイルム和光純薬(株)製)、WPAG-443(富士フイルム和光純薬(株)製)、MBZ-101(みどり化学(株)製)等を挙げることができる。 The compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102).
Further, in the above-mentioned oxime sulfonate compound, the three-dimensional structure (E, Z, etc.) of the oxime and the benzothiazole ring may be either one or a mixture.
Specific examples of the compound represented by the formula (OS-101) include the compounds described in paragraph numbers 0102 to 0106 of JP-A-2011-20969 and paragraph numbers 0195 to 0207 of JP-A-2015-194674. And these contents are incorporated herein.
Among the above compounds, the following b-9, b-16, b-31, and b-33 are preferable.
Examples of commercially available products include WPAG-336 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), WPAG-443 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), MBZ-101 (manufactured by Midori Kagaku Co., Ltd.), and the like. Can be done.
より好適には、少なくとも一つのモノ、ジ、又はトリハロゲン置換メチル基がs-トリアジン環に結合したs-トリアジン誘導体、具体的には、例えば、2,4,6-トリス(モノクロロメチル)-s-トリアジン、2,4,6-トリス(ジクロロメチル)-s-トリアジン、2,4,6-トリス(トリクロロメチル)-s-トリアジン、2-メチル-4,6-ビス(トリクロロメチル)-s-トリアジン、2―n-プロピル-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(α,α,β-トリクロロエチル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-フェニル-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(p-メトキシフェニル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(3,4-エポキシフェニル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(p-クロロフェニル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-〔1-(p-メトキシフェニル)-2,4-ブタジエニル〕-4,6-ビス(トリクロロメチル)-s-トリアジン、2-スチリル-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(p-メトキシスチリル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(p-i-プロピルオキシスチリル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(p-トリル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(4-ナトキシナフチル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-フェニルチオ-4,6-ビス(トリクロロメチル)-s-トリアジン、2-ベンジルチオ-4,6-ビス(トリクロロメチル)-s-トリアジン、2,4,6-トリス(ジブロモメチル)-s-トリアジン、2,4,6-トリス(トリブロモメチル)-s-トリアジン、2-メチル-4,6-ビス(トリブロモメチル)-s-トリアジン、2-メトキシ-4,6-ビス(トリブロモメチル)-s-トリアジン等が挙げられる。 Specific examples of the organic halogenated compound include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605, JP-A. 48-36281, 55-32070, 60-239736, 61-169835, 61-169837, 62-58241, , Japanese Patent Application Laid-Open No. 62-212401, Japanese Patent Application Laid-Open No. 63-70243, Japanese Patent Application Laid-Open No. 63-298339, M.D. P. The compounds described in Hutt “Jurnal of Heterocyclic Chemistry” 1 (No3), (1970) and the like are mentioned, and the contents thereof are incorporated in the present specification. In particular, an oxazole compound substituted with a trihalomethyl group: an S-triazine compound is given as a preferable example.
More preferably, an s-triazine derivative in which at least one mono, di, or trihalogen-substituted methyl group is attached to the s-triazine ring, specifically, for example, 2,4,6-tris (monochromomethyl)-. s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl)- s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine , 2-Phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4-epoxy) Phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- [1- (p-methoxyphenyl) -2,4-Butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4 , 6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine , 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s- Examples thereof include triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) -s-triazine and the like.
式(RI-I)中、Ar11は置換基を1~6有していても良い炭素数20以下のアリール基を表し、好ましい置換基としては炭素数1~12のアルキル基、炭素数2~12のアルケニル基、炭素数2~12のアルキニル基、炭素数6~12のアリール基、炭素数1~12のアルコキシ基、炭素数1~12のアリーロキシ基、ハロゲン原子、炭素数1~12のアルキルアミノ基、炭素数2~12のジアルキルアミノ基、アルキル基の炭素数が1~12のアルキルアミド基又はアリール基の炭素数が6~20のアリールアミド基、カルボニル基、カルボキシ基、シアノ基、スルホニル基、炭素数1~12のチオアルキル基、炭素数1~12のチオアリール基が挙げられる。Z11 -は1価の陰イオンを表し、ハロゲンイオン、過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、チオスルホン酸イオン、硫酸イオンであり、安定性の面から過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオンが好ましい。式(RI-II)中、Ar21、Ar22は各々独立に置換基を1~6有していてもよい炭素数1~20のアリール基を表し、好ましい置換基としては炭素数1~12のアルキル基、炭素数2~12のアルケニル基、炭素数2~12のアルキニル基、炭素数1~12のアリール基、炭素数1~12のアルコキシ基、炭素数1~12のアリーロキシ基、ハロゲン原子、炭素数1~12のモノアルキルアミノ基、アルキル基の炭素数がそれぞれ独立に1~12のジアルキルアミノ基、アルキル基の炭素数が炭素数1~12のアルキルアミド基又はアリールアミド基、カルボニル基、カルボキシ基、シアノ基、スルホニル基、炭素数1~12のチオアルキル基、炭素数1~12のチオアリール基が挙げられる。Z21-は1価の陰イオンを表し、ハロゲンイオン、過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、チオスルホン酸イオン、硫酸イオンであり、安定性、反応性の面から過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、カルボン酸イオンが好ましい。式(RI-III)中、R31、R32、R33は各々独立に置換基を1~6有していても良い炭素数6~20のアリール基又はアルキル基、アルケニル基、アルキニル基を表し、好ましくは反応性、安定性の面から、アリール基であることが望ましい。好ましい置換基としては炭素数1~12のアルキル基、炭素数2~12のアルケニル基、炭素数2~12のアルキニル基、炭素数1~12のアリール基、炭素数1~12のアルコキシ基、炭素数1~12のアリーロキシ基、ハロゲン原子、炭素数1~12のモノアルキルアミノ基、アルキル基の炭素数がそれぞれ独立に炭素数1~12のジアルキルアミノ基、アルキル基の炭素数が炭素数1~12のアルキルアミド基又はアリールアミド基、カルボニル基、カルボキシ基、シアノ基、スルホニル基、炭素数1~12のチオアルキル基、炭素数1~12のチオアリール基が挙げられる。Z31 -は1価の陰イオンを表し、ハロゲンイオン、過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、チオスルホン酸イオン、硫酸イオンであり、安定性、反応性の面から過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、カルボン酸イオンが好ましい。 Examples of the onium salt include onium salts represented by the following general formulas (RI-I) to (RI-III).
In the formula (RI-I), Ar 11 represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents are an alkyl group having 1 to 12 carbon atoms and 2 carbon atoms. ~ 12 alkenyl groups, alkynyl groups with 2-12 carbon atoms, aryl groups with 6-12 carbon atoms, alkoxy groups with 1-12 carbon atoms, allyloxy groups with 1-12 carbon atoms, halogen atoms, 1-12 carbon atoms Alkylamino group, dialkylamino group with 2 to 12 carbon atoms, alkylamide group with 1 to 12 carbon atoms or arylamide group with 6 to 20 carbon atoms, carbonyl group, carboxy group, cyano Examples thereof include a group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z 11 - represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinate ion, a thiosulfonic acid ion, and a sulfate ion, and is stable. From the aspect, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, and sulfinate ion are preferable. In the formula (RI-II), Ar 21 and Ar 22 each represent an aryl group having 1 to 20 carbon atoms which may independently have 1 to 6 substituents, and preferred substituents have 1 to 12 carbon atoms. Alkyl group, alkenyl group with 2 to 12 carbon atoms, alkynyl group with 2 to 12 carbon atoms, aryl group with 1 to 12 carbon atoms, alkoxy group with 1 to 12 carbon atoms, allyloxy group with 1 to 12 carbon atoms, halogen An atom, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms independently of the alkyl group, an alkylamide group or an arylamide group having 1 to 12 carbon atoms in the alkyl group, Examples thereof include a carbonyl group, a carboxy group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z21 - represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinate ion, a thiosulfonic acid ion, and a sulfate ion, and is stable and reacts. From the viewpoint of sex, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion and carboxylate ion are preferable. In formula (RI-III), R 31 , R 32 , and R 33 each have an aryl group or an alkyl group, an alkenyl group, or an alkynyl group having 6 to 20 carbon atoms, which may independently have 1 to 6 substituents. It is preferably an aryl group from the viewpoint of reactivity and stability. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms. An aryloxy group having 1 to 12 carbon atoms, a halogen atom, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms independently of each other, and an alkyl group having 1 to 12 carbon atoms. Examples thereof include an alkylamide group having 1 to 12 or an arylamide group, a carbonyl group, a carboxy group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms and a thioaryl group having 1 to 12 carbon atoms. Z 31 - represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinate ion, a thiosulfonic acid ion, a sulfate ion, and stability. From the viewpoint of reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion and carboxylate ion are preferable.
光酸発生剤は、1種単独で使用されても、複数種の組み合わせで使用されてもよい。複数種の組み合わせの場合には、それらの合計量が上記範囲にあることが好ましい。
また、所望の光源に対して、感光性を付与する為、増感剤と併用することも好ましい。 The photoacid generator is preferably used in an amount of 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, and more preferably 0.5 to 10% by mass, based on the total solid content of the resin composition. It is more preferably used, more preferably 0.5 to 3% by mass, and even more preferably 0.5 to 1.2% by mass.
The photoacid generator may be used alone or in combination of two or more. In the case of a combination of a plurality of types, it is preferable that the total amount thereof is within the above range.
It is also preferable to use it in combination with a sensitizer in order to impart photosensitivity to a desired light source.
本発明の樹脂組成物は、塩基発生剤を含んでもよい。ここで、塩基発生剤とは、物理的または化学的な作用によって塩基を発生することができる化合物である。本発明の樹脂組成物にとって好ましい塩基発生剤としては、熱塩基発生剤および光塩基発生剤が挙げられる。
特に、樹脂組成物が環化樹脂の前駆体を含む場合、樹脂組成物は塩基発生剤を含むことが好ましい。樹脂組成物が熱塩基発生剤を含有することによって、例えば加熱により前駆体の環化反応を促進でき、硬化物の機械特性や耐薬品性が良好なものとなり、例えば半導体パッケージ中に含まれる再配線層用層間絶縁膜としての性能が良好となる。
塩基発生剤としては、イオン型塩基発生剤でもよく、非イオン型塩基発生剤でもよい。塩基発生剤から発生する塩基としては、例えば、2級アミン、3級アミンが挙げられる。
本発明に係る塩基発生剤について特に制限はなく、公知の塩基発生剤を用いることができる。公知の塩基発生剤としては、例えば、カルバモイルオキシム化合物、カルバモイルヒドロキシルアミン化合物、カルバミン酸化合物、ホルムアミド化合物、アセトアミド化合物、カルバメート化合物、ベンジルカルバメート化合物、ニトロベンジルカルバメート化合物、スルホンアミド化合物、イミダゾール誘導体化合物、アミンイミド化合物、ピリジン誘導体化合物、α-アミノアセトフェノン誘導体化合物、4級アンモニウム塩誘導体化合物、ピリジニウム塩、α-ラクトン環誘導体化合物、アミンイミド化合物、フタルイミド誘導体化合物、アシルオキシイミノ化合物、などを用いることができる。
非イオン型塩基発生剤の具体的な化合物としては、式(B1)、式(B2)、又は式(B3)で表される化合物が挙げられる。
The resin composition of the present invention may contain a base generator. Here, the base generator is a compound capable of generating a base by a physical or chemical action. Preferred base generators for the resin composition of the present invention include thermal base generators and photobase generators.
In particular, when the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition contains a base generator. When the resin composition contains a thermal base generator, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties and chemical resistance of the cured product become good. The performance as an interlayer insulating film for a wiring layer is improved.
The base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines.
The base generator according to the present invention is not particularly limited, and a known base generator can be used. Known base generators include, for example, carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetoamide compounds, carbamates compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, and amineimides. Compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amineimide compounds, phthalimide derivative compounds, acyloxyimino compounds and the like can be used.
Specific examples of the compound of the nonionic base generator include a compound represented by the formula (B1), the formula (B2), or the formula (B3).
Rb13はアルキル基(炭素数1~24が好ましく、2~18がより好ましく、3~12が更に好ましい)、アルケニル基(炭素数2~24が好ましく、2~18がより好ましく、3~12が更に好ましい)、アリール基(炭素数6~22が好ましく、6~18がより好ましく、6~12が更に好ましい)、アリールアルキル基(炭素数7~23が好ましく、7~19がより好ましく、7~12が更に好ましい)であり、本発明の効果を奏する範囲で置換基を有していてもよい。中でも、Rb13はアリールアルキル基が好ましい。 In the formula, Rb 11 and Rb 12 , and Rb 31 and Rb 32 are the same as Rb 1 and Rb 2 in the formula (B1), respectively.
Rb 13 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and a substituent may be provided as long as the effect of the present invention is exhibited. Among them, Rb 13 is preferably an arylalkyl group.
Rb15及びRb16は水素原子、アルキル基(炭素数1~12が好ましく、1~6がより好ましく、1~3が更に好ましい)、アルケニル基(炭素数2~12が好ましく、2~6がより好ましく、2~3が更に好ましい)、アリール基(炭素数6~22が好ましく、6~18がより好ましく、6~10が更に好ましい)、アリールアルキル基(炭素数7~23が好ましく、7~19がより好ましく、7~11が更に好ましい)であり、水素原子又はメチル基が好ましい。
Rb17はアルキル基(炭素数1~24が好ましく、1~12がより好ましく、3~8が更に好ましい)、アルケニル基(炭素数2~12が好ましく、2~10がより好ましく、3~8が更に好ましい)、アリール基(炭素数6~22が好ましく、6~18がより好ましく、6~12が更に好ましい)、アリールアルキル基(炭素数7~23が好ましく、7~19がより好ましく、7~12が更に好ましい)であり、中でもアリール基が好ましい。 Rb 11 and Rb 12 are synonymous with Rb 11 and Rb 12 in the formula (B1-1).
Rb 15 and Rb 16 are a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms). More preferably, 2 to 3 are more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10), an arylalkyl group (preferably 7 to 23 carbon atoms, 7). ~ 19 is more preferable, and 7 to 11 are more preferable), and a hydrogen atom or a methyl group is preferable.
Rb 17 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), and an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and an aryl group is particularly preferable.
環状アルキル基は、炭素数3~12のものが好ましく、3~6がより好ましい。環状アルキル基は、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロオクチル基等が挙げられる。
鎖状アルキル基と環状アルキル基の組合せに係る基は、炭素数4~24のものが好ましく、4~18がより好ましく、4~12がさらに好ましい。鎖状アルキル基と環状アルキル基の組合せに係る基は、例えば、シクロヘキシルメチル基、シクロヘキシルエチル基、シクロヘキシルプロピル基、メチルシクロヘキシルメチル基、エチルシクロヘキシルエチル基等が挙げられる。
酸素原子を鎖中に有するアルキル基は、炭素数2~12のものが好ましく、2~6がより好ましく、2~4がさらに好ましい。酸素原子を鎖中に有するアルキル基は、鎖状でも環状でもよく、直鎖でも分岐でもよい。
なかでも、後述する分解生成塩基の沸点を高める観点で、RN1およびRN2は炭素数5~12のアルキル基が好ましい。ただし、金属(例えば銅)の層と積層する際の密着性を重視する処方においては、環状のアルキル基を有する基や炭素数1~8のアルキル基であることが好ましい。 As the aliphatic hydrocarbon group constituting RN1 and RN2 , a linear or branched chain alkyl group, a cyclic alkyl group, a group related to a combination of a chain alkyl group and a cyclic alkyl group, and an oxygen atom are contained in the chain. Examples thereof include alkyl groups having. The linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms. The linear or branched chain alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, or an isopropyl group. Examples thereof include a group, an isobutyl group, a secondary butyl group, a tertiary butyl group, an isopentyl group, a neopentyl group, a tertiary pentyl group, and an isohexyl group.
The cyclic alkyl group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group and the like.
The group related to the combination of the chain alkyl group and the cyclic alkyl group preferably has 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, and even more preferably 4 to 12 carbon atoms. Examples of the group related to the combination of the chain alkyl group and the cyclic alkyl group include a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, an ethylcyclohexylethyl group and the like.
The alkyl group having an oxygen atom in the chain is preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms. The alkyl group having an oxygen atom in the chain may be chain-like or cyclic, and may be linear or branched.
Among them, alkyl groups having 5 to 12 carbon atoms are preferable for RN1 and RN2 from the viewpoint of increasing the boiling point of the decomposition-generated base described later. However, in a formulation that emphasizes adhesion when laminated with a metal (for example, copper) layer, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable.
2価の炭化水素連結基は、炭素数1~24のものが好ましく、2~12がより好ましく、2~6がさらに好ましい。2価の脂肪族炭化水素基は、炭素数1~12のものが好ましく、2~6がより好ましく、2~4がさらに好ましい。2価の芳香族炭化水素基は、炭素数6~22のものが好ましく、6~18がより好ましく、6~10がさらに好ましい。2価の脂肪族炭化水素基と2価の芳香族炭化水素基の組み合わせに係る基(例えば、アリーレンアルキル基)は、炭素数7~22のものが好ましく、7~18がより好ましく、7~10がさらに好ましい。 The divalent linking group constituting L is not particularly specified, but a hydrocarbon group is preferable, and an aliphatic hydrocarbon group is more preferable. The hydrocarbon group may have a substituent, or may have an atom of a type other than a carbon atom in the hydrocarbon chain. More specifically, it is preferably a divalent hydrocarbon linking group which may have an oxygen atom in the chain, and a divalent aliphatic hydrocarbon which may have an oxygen atom in the chain. More preferably, a divalent aromatic hydrocarbon group, or a group relating to a combination of a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group. A divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain is more preferable. It is preferable that these groups do not have an oxygen atom.
The divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms. The group (for example, an arylene alkyl group) relating to the combination of the divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group preferably has 7 to 22 carbon atoms, more preferably 7 to 18 carbon atoms, and 7 to 18 carbon atoms. 10 is more preferable.
直鎖または分岐の鎖状アルキレン基は、炭素数1~12のものが好ましく、2~6がより好ましく、2~4がさらに好ましい。
環状アルキレン基は、炭素数3~12のものが好ましく、3~6がより好ましい。
鎖状アルキレン基と環状アルキレン基の組み合わせに係る基は、炭素数4~24のものが好ましく、4~12がより好ましく、4~6がさらに好ましい。
酸素原子を鎖中に有するアルキレン基は、鎖状でも環状でもよく、直鎖でも分岐でもよい。酸素原子を鎖中に有するアルキレン基は、炭素数1~12のものが好ましく、1~6がより好ましく、1~3がさらに好ましい。 Specific examples of the linking group L include a linear or branched chain alkylene group, a cyclic alkylene group, a group related to a combination of a chain alkylene group and a cyclic alkylene group, and an alkylene group having an oxygen atom in the chain. , A linear or branched chain alkaneylene group, a cyclic alkaneylene group, an arylene group, or an arylene alkylene group is preferable.
The linear or branched chain alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.
The cyclic alkylene group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms.
The group related to the combination of the chain alkylene group and the cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, and even more preferably 4 to 6 carbon atoms.
The alkylene group having an oxygen atom in the chain may be chain-like or cyclic, and may be linear or branched. The alkylene group having an oxygen atom in the chain is preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms.
環状のアルケニレン基は、炭素数3~12のものが好ましく、3~6がより好ましい。環状のアルケニレン基は、C=C結合の数は1~6が好ましく、1~4がより好ましく、1~2がさらに好ましい。
アリーレン基は、炭素数6~22のものが好ましく、6~18がより好ましく、6~10がさらに好ましい。
アリーレンアルキレン基は、炭素数7~23のものが好ましく、7~19がより好ましく、7~11がさらに好ましい。
中でも、鎖状アルキレン基、環状アルキレン基、酸素原子を鎖中に有するアルキレン基、鎖状のアルケニレン基、アリーレン基、アリーレンアルキレン基が好ましく、1,2-エチレン基、プロパンジイル基(特に1,3-プロパンジイル基)、シクロヘキサンジイル基(特に1,2-シクロヘキサンジイル基)、ビニレン基(特にシスビニレン基)、フェニレン基(1,2-フェニレン基)、フェニレンメチレン基(特に1,2-フェニレンメチレン基)、エチレンオキシエチレン基(特に1,2-エチレンオキシ-1,2-エチレン基)がより好ましい。 The linear or branched chain-like alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 3 carbon atoms. The linear or branched chain-like alkenylene group preferably has 1 to 10 C = C bonds, more preferably 1 to 6, and even more preferably 1 to 3.
The cyclic alkenylene group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms. For the cyclic alkenylene group, the number of C = C bonds is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 2.
The arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms.
The arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms.
Among them, a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkenylene group, an arylene group and an arylene alkylene group are preferable, and a 1,2-ethylene group and a propandiyl group (particularly 1, 3-Propanediyl group), cyclohexanediyl group (especially 1,2-cyclohexanediyl group), vinylene group (especially cisvinylene group), phenylene group (1,2-phenylene group), phenylene methylene group (especially 1,2-phenylene) Methylene group) and ethyleneoxyethylene group (particularly 1,2-ethyleneoxy-1,2-ethylene group) are more preferable.
塩基発生剤は、1種又は2種以上を用いることができる。2種以上を用いる場合は、合計量が上記範囲であることが好ましい。 When the resin composition of the present invention contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the resin in the resin composition of the present invention. The lower limit is more preferably 0.3 parts by mass or more, and further preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, further preferably 20 parts by mass or less, further preferably 10 parts by mass or less, 5 parts by mass or less, or 4 parts by mass or less.
As the base generator, one kind or two or more kinds can be used. When two or more types are used, the total amount is preferably in the above range.
本発明の樹脂組成物は、溶剤を含むことが好ましい。
溶剤は、公知の溶剤を任意に使用できる。溶剤は有機溶剤が好ましい。有機溶剤としては、エステル類、エーテル類、ケトン類、環状炭化水素類、スルホキシド類、アミド類、ウレア類、アルコール類などの化合物が挙げられる。 <Solvent>
The resin composition of the present invention preferably contains a solvent.
As the solvent, a known solvent can be arbitrarily used. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas and alcohols.
本発明の樹脂組成物は、電極や配線などに用いられる金属材料との接着性を向上させるための金属接着性改良剤を含んでいることが好ましい。金属接着性改良剤としては、アルコキシシリル基を有するシランカップリング剤、アルミニウム系接着助剤、チタン系接着助剤、スルホンアミド構造を有する化合物及びチオウレア構造を有する化合物、リン酸誘導体化合物、βケトエステル化合物、アミノ化合物等が挙げられる。 <Metal adhesion improver>
The resin composition of the present invention preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like. Examples of the metal adhesion improver include a silane coupling agent having an alkoxysilyl group, an aluminum-based adhesive aid, a titanium-based adhesive aid, a compound having a sulfone amide structure and a compound having a thiourea structure, a phosphoric acid derivative compound, and a β-ketoester. Examples thereof include compounds and amino compounds.
シランカップリング剤としては、例えば、国際公開第2015/199219号の段落0167に記載の化合物、特開2014-191002号公報の段落0062~0073に記載の化合物、国際公開第2011/080992号の段落0063~0071に記載の化合物、特開2014-191252号公報の段落0060~0061に記載の化合物、特開2014-041264号公報の段落0045~0052に記載の化合物、国際公開第2014/097594号の段落0055に記載の化合物、特開2018-173573の段落0067~0078に記載の化合物が挙げられ、これらの内容は本明細書に組み込まれる。また、特開2011-128358号公報の段落0050~0058に記載のように異なる2種以上のシランカップリング剤を用いることも好ましい。また、シランカップリング剤は、下記化合物を用いることも好ましい。以下の式中、Meはメチル基を、Etはエチル基を表す。 〔Silane coupling agent〕
Examples of the silane coupling agent include the compound described in paragraph 0167 of International Publication No. 2015/199219, the compound described in paragraphs 0062 to 0073 of JP-A-2014-191002, paragraph of International Publication No. 2011/080992. The compounds described in 0063 to 0071, the compounds described in paragraphs 0060 to 0061 of JP-A-2014-191252, the compounds described in paragraphs 0045-0052 of JP-A-2014-041264, International Publication No. 2014/097594. Examples thereof include the compounds described in paragraph 0055 and the compounds described in paragraphs 0067 to 0078 of JP-A-2018-173573, the contents of which are incorporated herein by reference. Further, it is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358. Further, it is also preferable to use the following compounds as the silane coupling agent. In the following formula, Me represents a methyl group and Et represents an ethyl group.
アルミニウム系接着助剤としては、例えば、アルミニウムトリス(エチルアセトアセテート)、アルミニウムトリス(アセチルアセトネート)、エチルアセトアセテートアルミニウムジイソプロピレート等を挙げることができる。 [Aluminum-based adhesive aid]
Examples of the aluminum-based adhesive aid include aluminum tris (ethyl acetoacetate), aluminum tris (acetyl acetonate), ethyl acetoacetate aluminum diisopropylate, and the like.
本発明の樹脂組成物は、マイグレーション抑制剤を更に含むことが好ましい。マイグレーション抑制剤を含むことにより、金属層(金属配線)由来の金属イオンが膜内へ移動することを効果的に抑制可能となる。 <Migration inhibitor>
The resin composition of the present invention preferably further contains a migration inhibitor. By including the migration inhibitor, it is possible to effectively suppress the movement of metal ions derived from the metal layer (metal wiring) into the membrane.
本発明の樹脂組成物は、重合禁止剤を含むことが好ましい。重合禁止剤としてはフェノール系化合物、キノン系化合物、アミノ系化合物、N-オキシルフリーラジカル化合物系化合物、ニトロ系化合物、ニトロソ系化合物、ヘテロ芳香環系化合物、金属化合物などが挙げられる。 <Polymerization inhibitor>
The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of the polymerization inhibitor include phenol-based compounds, quinone-based compounds, amino-based compounds, N-oxyl-free radical compound-based compounds, nitro-based compounds, nitroso-based compounds, heteroaromatic ring-based compounds, and metal compounds.
本発明の樹脂組成物は、露光から加熱までの経時による性能変化を低減するために、酸捕捉剤を含有することが好ましい。ここで酸捕捉剤とは、系中に存在することで発生酸を捕捉することができる化合物を指し、酸性度が低くpKaの高い化合物であることが好ましい。酸捕捉剤としては、アミノ基を有する化合物が好ましく、1級アミン、2級アミン、3級アミン、アンモニウム塩、3級アミドなどが好ましく、1級アミン、2級アミン、3級アミン、アンモニウム塩が好ましく、2級アミン、3級アミン、アンモニウム塩がより好ましい。
酸捕捉剤としては、イミダゾール構造、ジアザビシクロ構造、オニウム構造、トリアルキルアミン構造、アニリン構造又はピリジン構造を有する化合物、水酸基及び/又はエーテル結合を有するアルキルアミン誘導体、水酸基及び/又はエーテル結合を有するアニリン誘導体等を好ましく挙げることができる。オニウム構造を有する場合、酸捕捉剤はアンモニウム、ジアゾニウム、ヨードニウム、スルホニウム、ホスホニウム、ピリジニウムなどから選択されるカチオンと、酸発生剤が発生する酸より酸性度の低い酸のアニオンとを有する塩であることが好ましい。 <Acid scavenger>
The resin composition of the present invention preferably contains an acid scavenger in order to reduce the change in performance over time from exposure to heating. Here, the acid scavenger refers to a compound that can capture the generated acid by being present in the system, and is preferably a compound having low acidity and high pKa. As the acid trapping agent, a compound having an amino group is preferable, a primary amine, a secondary amine, a tertiary amine, an ammonium salt, a tertiary amine and the like are preferable, and a primary amine, a secondary amine, a tertiary amine and an ammonium salt are preferable. Is preferable, and secondary amines, tertiary amines, and ammonium salts are more preferable.
Examples of the acid scavenger include a compound having an imidazole structure, a diazabicyclo structure, an onium structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline having a hydroxyl group and / or an ether bond. Derivatives and the like can be preferably mentioned. When having an onium structure, the acid scavenger is a salt having a cation selected from ammonium, diazonium, iodonium, sulfonium, phosphonium, pyridinium and the like, and an anion of an acid having a lower acidity than the acid generated by the acid generator. Is preferable.
本発明に係る組成物は、酸捕捉剤を含有してもしなくてもよいが、含有する場合、酸捕捉剤の含有量は、組成物の全固形分を基準として、通常は0.001~10質量%であり、好ましくは0.01~5質量%である。 These acid scavengers may be used alone or in combination of two or more.
The composition according to the present invention may or may not contain an acid scavenger, but when it is contained, the content of the acid scavenger is usually 0.001 to 0 based on the total solid content of the composition. It is 10% by mass, preferably 0.01 to 5% by mass.
本発明の樹脂組成物は、本発明の効果が得られる範囲で、必要に応じて、各種の添加物、例えば、界面活性剤、高級脂肪酸誘導体、熱重合開始剤、無機粒子、紫外線吸収剤、有機チタン化合物、酸化防止剤、凝集防止剤、フェノール系化合物、他の高分子化合物、可塑剤及びその他の助剤類(例えば、消泡剤、難燃剤など)等を配合することができる。これらの成分を適宜含有させることにより、膜物性などの性質を調整することができる。これらの成分は、例えば、特開2012-003225号公報の段落番号0183以降(対応する米国特許出願公開第2013/0034812号明細書の段落番号0237)の記載、特開2008-250074号公報の段落番号0101~0104、0107~0109等の記載を参酌でき、これらの内容は本明細書に組み込まれる。これらの添加剤を配合する場合、その合計配合量は本発明の樹脂組成物の固形分の3質量%以下とすることが好ましい。 <Other additives>
The resin composition of the present invention comprises various additives such as a surfactant, a higher fatty acid derivative, a thermal polymerization initiator, an inorganic particle, and an ultraviolet absorber, if necessary, as long as the effects of the present invention can be obtained. Organic titanium compounds, antioxidants, antiaggregating agents, phenolic compounds, other polymer compounds, plasticizers and other auxiliaries (eg, antifoaming agents, flame retardant agents, etc.) can be blended. By appropriately containing these components, properties such as film physical characteristics can be adjusted. These components are described in, for example, paragraph No. 0183 or later of JP2012-003225A (paragraph number 0237 of the corresponding US Patent Application Publication No. 2013/0034812), paragraph 2008-250074. The description of numbers 0101 to 0104, 0107 to 0109, etc. can be taken into consideration, and these contents are incorporated in the present specification. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the resin composition of the present invention.
界面活性剤としては、フッ素系界面活性剤、シリコーン系界面活性剤、炭化水素系界面活性剤などの各種界面活性剤を使用できる。界面活性剤はノニオン型界面活性剤であってもよく、カチオン型界面活性剤であってもよく、アニオン型界面活性剤であってもよい。 [Surfactant]
As the surfactant, various surfactants such as a fluorine-based surfactant, a silicone-based surfactant, and a hydrocarbon-based surfactant can be used. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.
フッ素系界面活性剤は、フッ素原子を有する(メタ)アクリレート化合物に由来する繰り返し単位と、アルキレンオキシ基(好ましくはエチレンオキシ基、プロピレンオキシ基)を2以上(好ましくは5以上)有する(メタ)アクリレート化合物に由来する繰り返し単位と、を含む含フッ素高分子化合物も好ましく用いることができ、下記化合物も本発明で用いられるフッ素系界面活性剤として例示される。
The fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.
フッ素系界面活性剤は、エチレン性不飽和基を側鎖に有する含フッ素重合体をフッ素系界面活性剤として用いることもできる。具体例としては、特開2010-164965号公報の段落0050~0090および段落0289~0295に記載された化合物が挙げられ、この内容は本明細書に組み込まれる。また、市販品としては、例えばDIC(株)製のメガファックRS-101、RS-102、RS-718K等が挙げられる。 The weight average molecular weight of the above compounds is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.
As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as the fluorine-based surfactant. Specific examples thereof include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP2010-164965, the contents of which are incorporated in the present specification. Examples of commercially available products include Megafuck RS-101, RS-102, and RS-718K manufactured by DIC Corporation.
界面活性剤の含有量は、組成物の全固形分に対して、0.001~2.0質量%が好ましく、0.005~1.0質量%がより好ましい。 Only one type of surfactant may be used, or two or more types may be combined.
The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.
本発明の樹脂組成物は、酸素に起因する重合阻害を防止するために、ベヘン酸やベヘン酸アミドのような高級脂肪酸誘導体を添加して、塗布後の乾燥の過程で本発明の樹脂組成物の表面に偏在させてもよい。 [Higher fatty acid derivative]
In order to prevent polymerization inhibition caused by oxygen, the resin composition of the present invention is added with a higher fatty acid derivative such as behenic acid or behenic acid amide, and the resin composition of the present invention is dried in the process of drying after application. It may be unevenly distributed on the surface of.
本発明の樹脂組成物は、熱重合開始剤を含んでもよく、特に熱ラジカル重合開始剤を含んでもよい。熱ラジカル重合開始剤は、熱のエネルギーによってラジカルを発生し、重合性を有する化合物の重合反応を開始又は促進させる化合物である。熱ラジカル重合開始剤を添加することによって樹脂及び重合性化合物の重合反応を進行させることもできるので、より耐溶剤性を向上できる。また、上述した光重合開始剤も熱により重合を開始する機能を有する場合があり、熱重合開始剤として添加することができる場合がある。 [Thermal polymerization initiator]
The resin composition of the present invention may contain a thermal polymerization initiator, and in particular, a thermal radical polymerization initiator may be contained. The thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. Since the polymerization reaction of the resin and the polymerizable compound can be promoted by adding the thermal radical polymerization initiator, the solvent resistance can be further improved. Further, the above-mentioned photopolymerization initiator may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.
本発明の樹脂組成物は、無機粒子を含んでもよい。無機粒子として、具体的には、炭酸カルシウム、リン酸カルシウム、シリカ、カオリン、タルク、二酸化チタン、アルミナ、硫酸バリウム、フッ化カルシウム、フッ化リチウム、ゼオライト、硫化モリブデン、ガラス等を含むことができる。 [Inorganic particles]
The resin composition of the present invention may contain inorganic particles. Specific examples of the inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.
無機粒子の上記平均粒子径は、一次粒子径であり、また体積平均粒子径である。体積平均粒子径は、Nanotrac WAVE II EX-150(日機装社製)による動的光散乱法で測定できる。
上記測定が困難である場合は、遠心沈降光透過法、X線透過法、レーザー回折・散乱法で測定することもできる。 The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further preferably 0.03 to 1.0 μm, and 0.04 to 0.5 μm. Especially preferable.
The average particle size of the inorganic particles is a primary particle size and a volume average particle size. The volume average particle size can be measured by a dynamic light scattering method using Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.).
If the above measurement is difficult, it can be measured by a centrifugal sedimentation light transmission method, an X-ray transmission method, or a laser diffraction / scattering method.
本発明の組成物は、紫外線吸収剤を含んでいてもよい。紫外線吸収剤としては、サリシレート系、ベンゾフェノン系、ベンゾトリアゾール系、置換アクリロニトリル系、トリアジン系などの紫外線吸収剤を使用することができる。
サリシレート系紫外線吸収剤の例としては、フェニルサリシレート、p-オクチルフェニルサリシレート、p-t-ブチルフェニルサリシレートなどが挙げられ、ベンゾフェノン系紫外線吸収剤の例としては、2,2’-ジヒドロキシ-4-メトキシベンゾフェノン、2,2’-ジヒドロキシ-4,4’-ジメトキシベンゾフェノン、2,2’,4,4’-テトラヒドロキシベンゾフェノン、2-ヒドロキシ-4-メトキシベンゾフェノン、2,4-ジヒドロキシベンゾフェノン、2-ヒドロキシ-4-オクトキシベンゾフェノンなどが挙げられる。また、ベンゾトリアゾール系紫外線吸収剤の例としては、2-(2’-ヒドロキシ-3’,5’-ジ-tert-ブチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’-tert-ブチル-5’-メチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’-tert-アミル-5’-イソブチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’-イソブチル-5’-メチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’-イソブチル-5’-プロピルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’,5’-ジ-tert-ブチルフェニル)ベンゾトリアゾール、2-(2’-ヒドロキシ-5’-メチルフェニル)ベンゾトリアゾール、2-[2’-ヒドロキシ-5’-(1,1,3,3-テトラメチル)フェニル]ベンゾトリアゾールなどが挙げられる。 [UV absorber]
The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, an ultraviolet absorber such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, or triazine-based can be used.
Examples of salicylate-based ultraviolet absorbers include phenylsalicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate and the like, and examples of benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-. Methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2- Hydroxyl-4-octoxybenzophenone and the like can be mentioned. Examples of benzotriazole-based ultraviolet absorbers include 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole and 2- (2'-hydroxy-3). '-Tert-Butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2-( 2'-Hydroxy-3'-isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole, 2 -(2'-Hydroxy-3', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- [2'-hydroxy-5' -(1,1,3,3-tetramethyl) phenyl] benzotriazole and the like can be mentioned.
本発明の組成物は、紫外線吸収剤を含んでも含まなくてもよいが、含む場合、紫外線吸収剤の含有量は、本発明の組成物の全固形分質量に対して、0.001質量%以上1質量%以下であることが好ましく、0.01質量%以上0.1質量%以下であることがより好ましい。 In the present invention, the above-mentioned various ultraviolet absorbers may be used alone or in combination of two or more.
The composition of the present invention may or may not contain an ultraviolet absorber, but when it is contained, the content of the ultraviolet absorber is 0.001% by mass with respect to the total solid content mass of the composition of the present invention. It is preferably 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less.
本実施形態の樹脂組成物は、有機チタン化合物を含有してもよい。樹脂組成物が有機チタン化合物を含有することにより、低温で硬化した場合であっても耐薬品性に優れる樹脂層を形成できる。 [Organic titanium compound]
The resin composition of the present embodiment may contain an organic titanium compound. Since the resin composition contains an organic titanium compound, a resin layer having excellent chemical resistance can be formed even when cured at a low temperature.
有機チタン化合物の具体例を、以下のI)~VII)に示す:
I)チタンキレート化合物:中でも、樹脂組成物の保存安定性がよく、良好な硬化パターンが得られることから、アルコキシ基を2個以上有するチタンキレート化合物がより好ましい。具体的な例は、チタニウムビス(トリエタノールアミン)ジイソプロポキサイド、チタニウムジ(n-ブトキサイド)ビス(2,4-ペンタンジオネート)、チタニウムジイソプロポキサイドビス(2,4-ペンタンジオネート)、チタニウムジイソプロポキサイドビス(テトラメチルヘプタンジオネート)、チタニウムジイソプロポキサイドビス(エチルアセトアセテート)等である。
II)テトラアルコキシチタン化合物:例えば、チタニウムテトラ(n-ブトキサイド)、チタニウムテトラエトキサイド、チタニウムテトラ(2-エチルヘキソキサイド)、チタニウムテトライソブトキサイド、チタニウムテトライソプロポキサイド、チタニウムテトラメトキサイド、チタニウムテトラメトキシプロポキサイド、チタニウムテトラメチルフェノキサイド、チタニウムテトラ(n-ノニロキサイド)、チタニウムテトラ(n-プロポキサイド)、チタニウムテトラステアリロキサイド、チタニウムテトラキス[ビス{2,2-(アリロキシメチル)ブトキサイド}]等である。
III)チタノセン化合物:例えば、ペンタメチルシクロペンタジエニルチタニウムトリメトキサイド、ビス(η5-2,4-シクロペンタジエン-1-イル)ビス(2,6-ジフルオロフェニル)チタニウム、ビス(η5-2,4-シクロペンタジエン-1-イル)ビス(2,6-ジフルオロ-3-(1H-ピロール-1-イル)フェニル)チタニウム等である。
IV)モノアルコキシチタン化合物:例えば、チタニウムトリス(ジオクチルホスフェート)イソプロポキサイド、チタニウムトリス(ドデシルベンゼンスルホネート)イソプロポキサイド等である。
V)チタニウムオキサイド化合物:例えば、チタニウムオキサイドビス(ペンタンジオネート)、チタニウムオキサイドビス(テトラメチルヘプタンジオネート)、フタロシアニンチタニウムオキサイド等である。
VI)チタニウムテトラアセチルアセトネート化合物:例えば、チタニウムテトラアセチルアセトネート等である。
VII)チタネートカップリング剤:例えば、イソプロピルトリドデシルベンゼンスルホニルチタネート等である。 Examples of the organic titanium compound that can be used include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.
Specific examples of the organic titanium compound are shown in I) to VII) below:
I) Titanium chelate compound: Among them, a titanium chelate compound having two or more alkoxy groups is more preferable because the resin composition has good storage stability and a good curing pattern can be obtained. Specific examples include titanium bis (triethanolamine) diisopropoxyside, titanium di (n-butoxide) bis (2,4-pentanegenate), and titanium diisopropoxiside bis (2,4-pentanegeonate). ), Titanium diisopropoxyside bis (tetramethylheptandionate), titanium diisopropoxyside bis (ethylacetacetate) and the like.
II) Titanium Alkoxy Titanium Compounds: For example, Titanium Tetra (n-Butoxide), Titanium Tetraethoxide, Titanium Tetra (2-ethylhexoxyside), Titanium Tetraisobutoxide, Titanium Tetraisopropoxyside, Titanium Tetramethoxide , Titanium Tetramethoxypropoxyside, Titanium Tetramethylphenoxide, Titanium Tetra (n-Noniloxide), Titanium Tetra (n-Propoxide), Titanium Tetrasteeryloxyside, Titanium Tetrakiss [Bis {2,2- (Aryloxymethyl) Butokiside}] etc.
III) Titanocene compounds: for example, pentamethylcyclopentadienyl titanium trimethoxide, bis (η5-2,4-cyclopentadiene-1-yl) bis (2,6-difluorophenyl) titanium, bis (η5-2, 2). 4-Cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium and the like.
IV) Monoalkoxytitanium compound: For example, titaniumtris (dioctylphosphate) isopropoxyside, titaniumtris (dodecylbenzenesulfonate) isopropoxyside and the like.
V) Titanium oxide compound: For example, titanium oxide bis (pentanionate), titanium oxide bis (tetramethylheptandionate), phthalocyanine titanium oxide and the like.
VI) Titanium tetraacetylacetonate compound: For example, titanium tetraacetylacetonate and the like.
VII) Titanate Coupling Agent: For example, isopropyltridodecylbenzenesulfonyl titanate and the like.
本発明の組成物は、酸化防止剤を含んでいてもよい。添加剤として酸化防止剤を含有することで、硬化後の膜の伸度特性や、金属材料との密着性を向上させることができる。酸化防止剤としては、フェノール化合物、亜リン酸エステル化合物、チオエーテル化合物などが挙げられる。フェノール化合物としては、フェノール系酸化防止剤として知られる任意のフェノール化合物を使用することができる。好ましいフェノール化合物としては、ヒンダードフェノール化合物が挙げられる。フェノール性ヒドロキシ基に隣接する部位(オルト位)に置換基を有する化合物が好ましい。上述の置換基としては炭素数1~22の置換又は無置換のアルキル基が好ましい。また、酸化防止剤は、同一分子内にフェノール基と亜リン酸エステル基を有する化合物も好ましい。また、酸化防止剤は、リン系酸化防止剤も好適に使用することができる。リン系酸化防止剤としてはトリス[2-[[2,4,8,10-テトラキス(1,1-ジメチルエチル)ジベンゾ[d,f][1,3,2]ジオキサホスフェピン-6-イル]オキシ]エチル]アミン、トリス[2-[(4,6,9,11-テトラ-tert-ブチルジベンゾ[d,f][1,3,2]ジオキサホスフェピン-2-イル)オキシ]エチル]アミン、亜リン酸エチルビス(2,4-ジ-tert-ブチル-6-メチルフェニル)などが挙げられる。酸化防止剤の市販品としては、例えば、アデカスタブ AO-20、アデカスタブ AO-30、アデカスタブ AO-40、アデカスタブ AO-50、アデカスタブ AO-50F、アデカスタブ AO-60、アデカスタブ AO-60G、アデカスタブ AO-80、アデカスタブ AO-330(以上、(株)ADEKA製)などが挙げられる。また、酸化防止剤は、特許第6268967号公報の段落番号0023~0048に記載された化合物を使用することもでき、この内容は本明細書に組み込まれる。また、本発明の組成物は、必要に応じて、潜在酸化防止剤を含有してもよい。潜在酸化防止剤としては、酸化防止剤として機能する部位が保護基で保護された化合物であって、100~250℃で加熱するか、又は酸/塩基触媒存在下で80~200℃で加熱することにより保護基が脱離して酸化防止剤として機能する化合物が挙げられる。潜在酸化防止剤としては、国際公開第2014/021023号、国際公開第2017/030005号、特開2017-008219号公報に記載された化合物が挙げられ、この内容は本明細書に組み込まれる。潜在酸化防止剤の市販品としては、アデカアークルズGPA-5001((株)ADEKA製)等が挙げられる。
好ましい酸化防止剤の例としては、2,2-チオビス(4-メチル-6-t-ブチルフェノール)、2,6-ジ-t-ブチルフェノールおよび式(3)で表される化合物が挙げられる。 〔Antioxidant〕
The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, it is possible to improve the elongation characteristics of the film after curing and the adhesion with a metal material. Examples of the antioxidant include phenol compounds, phosphite ester compounds, thioether compounds and the like. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxy group is preferable. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Further, as the antioxidant, a compound having a phenol group and a phosphite ester group in the same molecule is also preferable. Further, as the antioxidant, a phosphorus-based antioxidant can also be preferably used. As a phosphorus-based antioxidant, Tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphepine-6] -Il] Oxy] Ethyl] amine, Tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphepin-2-yl] ) Oxy] ethyl] amine, ethylbis phosphite (2,4-di-tert-butyl-6-methylphenyl) and the like. Commercially available products of antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, and Adekastab AO-80. , ADEKA STAB AO-330 (above, manufactured by ADEKA Corporation) and the like. Further, as the antioxidant, the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used, and the contents thereof are incorporated in the present specification. In addition, the composition of the present invention may contain a latent antioxidant, if necessary. The latent antioxidant is a compound in which the site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst. This includes compounds in which the protecting group is desorbed and functions as an antioxidant. Examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219, the contents of which are incorporated in the present specification. Examples of commercially available products of latent antioxidants include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation).
Examples of preferred antioxidants include 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and compounds of formula (3).
本実施形態の樹脂組成物は、必要に応じて凝集防止剤を含有してもよい。凝集防止剤としては、ポリアクリル酸ナトリウム等が挙げられる。 [Anti-coagulation agent]
The resin composition of the present embodiment may contain an anti-aggregation agent, if necessary. Examples of the antiaggregating agent include sodium polyacrylate and the like.
本発明の組成物は、凝集防止剤を含んでも含まなくてもよいが、含む場合、凝集防止剤の含有量は、本発明の組成物の全固形分質量に対して、0.01質量%以上10質量%以下であることが好ましく、0.02質量%以上5質量%以下であることがより好ましい。 In the present invention, one type of anti-aggregation agent may be used alone, or two or more types may be used in combination.
The composition of the present invention may or may not contain an anti-aggregation agent, but when it is contained, the content of the anti-aggregation agent is 0.01% by mass with respect to the total solid content mass of the composition of the present invention. It is preferably 10% by mass or less, and more preferably 0.02% by mass or more and 5% by mass or less.
本実施形態の樹脂組成物は、必要に応じてフェノール系化合物を含有してもよい。フェノール系化合物としては、Bis-Z、BisP-EZ、TekP-4HBPA、TrisP-HAP、TrisP-PA、BisOCHP-Z、BisP-MZ、BisP-PZ、BisP-IPZ、BisOCP-IPZ、BisP-CP、BisRS-2P、BisRS-3P、BisP-OCHP、メチレントリス-FR-CR、BisRS-26X(以上、商品名、本州化学工業(株)製)、BIP-PC、BIR-PC、BIR-PTBP、BIR-BIPC-F(以上、商品名、旭有機材工業(株)製)等が挙げられる。 [Phenolic compounds]
The resin composition of the present embodiment may contain a phenolic compound, if necessary. Examples of the phenolic compound include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, and BisP-CP. BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR -BIPC-F (above, trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.) and the like can be mentioned.
本発明の組成物は、フェノール系化合物を含んでも含まなくてもよいが、含む場合、フェノール系化合物の含有量は、本発明の組成物の全固形分質量に対して、0.01質量%以上30質量%以下であることが好ましく、0.02質量%以上20質量%以下であることがより好ましい。 In the present invention, one type of phenolic compound may be used alone, or two or more types may be used in combination.
The composition of the present invention may or may not contain a phenolic compound, but when it is contained, the content of the phenolic compound is 0.01% by mass with respect to the total solid content mass of the composition of the present invention. It is preferably 30% by mass or more, and more preferably 0.02% by mass or more and 20% by mass or less.
他の高分子化合物としては、シロキサン樹脂、(メタ)アクリル酸を共重合した(メタ)アクリルポリマー、ノボラック樹脂、レゾール樹脂、ポリヒドロキシスチレン樹脂およびそれらの共重合体などが挙げられる。他の高分子化合物はメチロール基、アルコキシメチル基、エポキシ基などの架橋基が導入された変性体であってもよい。 [Other polymer compounds]
Examples of other polymer compounds include siloxane resins, (meth) acrylic polymers copolymerized with (meth) acrylic acid, novolak resins, resole resins, polyhydroxystyrene resins and copolymers thereof. The other polymer compound may be a modified product into which a cross-linking group such as a methylol group, an alkoxymethyl group, or an epoxy group is introduced.
本発明の組成物は、他の高分子化合物を含んでも含まなくてもよいが、含む場合、他の高分子化合物の含有量は、本発明の組成物の全固形分質量に対して、0.01質量%以上30質量%以下であることが好ましく、0.02質量%以上20質量%以下であることがより好ましい。 In the present invention, one type of other polymer compound may be used alone, or two or more types may be used in combination.
The composition of the present invention may or may not contain other polymer compounds, but when it is contained, the content of the other polymer compounds is 0 with respect to the total solid content mass of the composition of the present invention. It is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less.
本発明の樹脂組成物の粘度は、樹脂組成物の固形分濃度により調整できる。塗布膜厚の観点から、1,000mm2/s~12,000mm2/sが好ましく、2,000mm2/s~10,000mm2/sがより好ましく、2,500mm2/s~8,000mm2/sが更に好ましい。上記範囲であれば、均一性の高い塗布膜を得ることが容易になる。1,000mm2/s以上であれば、例えば再配線用絶縁膜として必要とされる膜厚で塗布することが容易であり、12,000mm2/s以下であれば、塗布面状に優れた塗膜が得られる。 <Characteristics of resin composition>
The viscosity of the resin composition of the present invention can be adjusted by adjusting the solid content concentration of the resin composition. From the viewpoint of the coating film thickness, 1,000 mm 2 / s to 12,000 mm 2 / s is preferable, 2,000 mm 2 / s to 10,000 mm 2 / s is more preferable, and 2,500 mm 2 / s to 8,000 mm. 2 / s is more preferable. Within the above range, it becomes easy to obtain a highly uniform coating film. If it is 1,000 mm 2 / s or more, it is easy to apply it with a film thickness required for, for example, an insulating film for rewiring, and if it is 12,000 mm 2 / s or less, the coating surface is excellent. A coating film is obtained.
本発明の樹脂組成物の含水率は、2.0質量%未満であることが好ましく、1.5質量%未満であることがより好ましく、1.0質量%未満であることが更に好ましい。2.0%未満であれば、樹脂組成物の保存安定性が向上する。
水分の含有量を維持する方法としては、保管条件における湿度の調整、保管時の収容容器の空隙率低減などが挙げられる。 <Restrictions on substances contained in the resin composition>
The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved.
Examples of the method for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.
ハロゲン原子の含有量を調節する方法としては、イオン交換処理などが好ましく挙げられる。 Considering the use as a semiconductor material, the resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and less than 200 mass ppm from the viewpoint of wiring corrosiveness. Is more preferable. Among them, those existing in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total amount of chlorine atom and bromine atom, or chlorine ion and bromine ion is in the above range, respectively.
As a method for adjusting the content of halogen atoms, ion exchange treatment and the like are preferably mentioned.
本発明の樹脂組成物を硬化することにより、この樹脂組成物の硬化物を得ることができる。
本発明の硬化物は、本発明の樹脂組成物を硬化してなる硬化物である。
樹脂組成物の硬化は加熱によるものであることが好ましく、加熱温度が120℃~400℃の範囲内であることがより好ましく、140℃~380℃の範囲内にあることが更に好ましく、170℃~350℃の範囲内にあることが特に好ましい。樹脂組成物の硬化物の形態は、特に限定されず、フィルム状、棒状、球状、ペレット状など、用途に合わせて選択することができる。本発明において、この硬化物は、フィルム状であることが好ましい。また、樹脂組成物のパターン加工によって、壁面への保護膜の形成、導通のためのビアホール形成、インピーダンスや静電容量あるいは内部応力の調整、放熱機能付与など、用途にあわせて、この硬化物の形状を選択することもできる。この硬化物(硬化物からなる膜)の膜厚は、0.5μm以上150μm以下であることが好ましい。
本発明の樹脂組成物を硬化した際の収縮率は、50%以下が好ましく、45%以下がより好ましく、40%以下が更に好ましい。ここで、収縮率は、樹脂組成物の硬化前後の体積変化の百分率を指し、下記の式より算出することができる。
収縮率[%]=100-(硬化後の体積÷硬化前の体積)×100 <Cured product of resin composition>
By curing the resin composition of the present invention, a cured product of this resin composition can be obtained.
The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention.
The curing of the resin composition is preferably by heating, more preferably the heating temperature is in the range of 120 ° C to 400 ° C, further preferably in the range of 140 ° C to 380 ° C, and 170 ° C. It is particularly preferable that the temperature is in the range of about 350 ° C. The form of the cured product of the resin composition is not particularly limited, and can be selected according to the intended use, such as a film shape, a rod shape, a spherical shape, and a pellet shape. In the present invention, the cured product is preferably in the form of a film. In addition, by pattern processing of the resin composition, this cured product can be used for forming a protective film on the wall surface, forming via holes for conduction, adjusting impedance, capacitance or internal stress, and imparting a heat dissipation function. You can also choose the shape. The film thickness of this cured product (film made of the cured product) is preferably 0.5 μm or more and 150 μm or less.
The shrinkage rate of the resin composition of the present invention when cured is preferably 50% or less, more preferably 45% or less, still more preferably 40% or less. Here, the shrinkage ratio refers to the percentage of the volume change of the resin composition before and after curing, and can be calculated from the following formula.
Shrinkage rate [%] = 100- (volume after curing ÷ volume before curing) x 100
本発明の樹脂組成物の硬化物のイミド化反応率は、70%以上が好ましく、80%以上がより好ましく、90%以上が更に好ましい。70%以上であれば、機械特性に優れた硬化物となる場合がある。
本発明の樹脂組成物の硬化物の破断伸びは、30%以上が好ましく、40%以上がより好ましく、50%以上が更に好ましい。
本発明の樹脂組成物の硬化物のガラス転移温度(Tg)は、180℃以上であることが好ましく、210℃以上であることがより好ましく、230℃以上であることがさらに好ましい。 <Characteristics of cured product of resin composition>
The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more. If it is 70% or more, it may be a cured product having excellent mechanical properties.
The elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, still more preferably 50% or more.
The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180 ° C. or higher, more preferably 210 ° C. or higher, and even more preferably 230 ° C. or higher.
本発明の樹脂組成物は、上記各成分を混合して調製することができる。混合方法は特に限定はなく、従来公知の方法で行うことができる。
混合は撹拌羽による混合、ボールミルによる混合、タンク自身を回転させる混合などを採用することができる。
混合中の温度は10~30℃が好ましく、15~25℃がより好ましい。 <Preparation of resin composition>
The resin composition of the present invention can be prepared by mixing each of the above components. The mixing method is not particularly limited, and a conventionally known method can be used.
For mixing, mixing with a stirring blade, mixing with a ball mill, mixing by rotating the tank itself, or the like can be adopted.
The temperature during mixing is preferably 10 to 30 ° C, more preferably 15 to 25 ° C.
フィルターを用いたろ過の他、吸着材を用いた不純物の除去処理を行ってもよい。フィルターろ過と吸着材を用いた不純物除去処理とを組み合わせてもよい。吸着材としては、公知の吸着材を用いることができる。例えば、シリカゲル、ゼオライトなどの無機系吸着材、活性炭などの有機系吸着材が挙げられる。
更にフィルターを用いたろ過後、ボトルに充填した樹脂組成物を減圧下に置き、脱気する工程を施しても良い。 Further, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the resin composition of the present invention. The filter hole diameter may be, for example, 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, still more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene or nylon. When the material of the filter is polyethylene, it is more preferable to use HDPE (high density polyethylene). The filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel for use. When using a plurality of types of filters, filters having different pore diameters or materials may be used in combination. Examples of the connection mode include a mode in which an HDPE filter having a hole diameter of 1 μm is connected in series as the first stage and an HDPE filter having a hole diameter of 0.2 μm is connected in series as the second stage. In addition, various materials may be filtered a plurality of times. When filtering multiple times, circulation filtration may be used. Moreover, you may pressurize and perform filtration. When pressurizing and filtering, the pressure to be pressurized is, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, and more preferably 0.05 MPa or more and 0.7 MPa or less. , 0.05 MPa or more and 0.5 MPa or less is more preferable.
In addition to filtration using a filter, impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
Further, after filtration using a filter, the resin composition filled in the bottle may be placed under reduced pressure to perform a step of degassing.
本発明の硬化物の製造方法は、樹脂組成物を基材上に適用して膜を形成する膜形成工程を含むことが好ましい。
また、本発明の硬化物の製造方法は、上記膜形成工程、膜形成工程により形成された膜を選択的に露光する露光工程、及び、露光工程により露光された膜を現像液を用いて現像してパターンを形成する現像工程を含むことがより好ましい。
本発明の硬化物の製造方法は、上記膜形成工程、上記露光工程、上記現像工程、並びに、現像工程により得られたパターンを加熱する加熱工程及び現像工程により得られたパターンを露光する現像後露光工程の少なくとも一方を含むことが特に好ましい。
また、本発明の製造方法は、上記膜形成工程、及び、上記膜を加熱する工程を含むことも好ましい。
以下、各工程の詳細について説明する。 (Manufacturing method of cured product)
The method for producing a cured product of the present invention preferably includes a film forming step of applying a resin composition onto a substrate to form a film.
Further, in the method for producing a cured product of the present invention, the film forming step, the exposure step of selectively exposing the film formed by the film forming step, and the film exposed by the exposure step are developed using a developing solution. It is more preferable to include a developing step of forming a pattern.
The method for producing a cured product of the present invention includes the film forming step, the exposure step, the developing step, and the heating step for heating the pattern obtained by the developing step and the post-development for exposing the pattern obtained by the developing step. It is particularly preferred to include at least one of the exposure steps.
Moreover, it is also preferable that the production method of the present invention includes the above-mentioned film forming step and the above-mentioned step of heating the film.
Hereinafter, details of each step will be described.
本発明の樹脂組成物は、基材上に適用して膜を形成する膜形成工程に用いることができる。
本発明の硬化物の製造方法は、樹脂組成物を基材上に適用して膜を形成する膜形成工程を含むことが好ましい。 <Membrane formation process>
The resin composition of the present invention can be applied to a substrate to form a film and can be used in a film forming step.
The method for producing a cured product of the present invention preferably includes a film forming step of applying a resin composition onto a substrate to form a film.
基材の種類は、用途に応じて適宜定めることができるが、シリコン、窒化シリコン、ポリシリコン、酸化シリコン、アモルファスシリコンなどの半導体作製基材、石英、ガラス、光学フィルム、セラミック材料、蒸着膜、磁性膜、反射膜、Ni、Cu、Cr、Feなどの金属基材(例えば、金属から形成された基材、及び、金属層が例えばめっきや蒸着等により形成された基材のいずれであってもよい)、紙、SOG(Spin On Glass)、TFT(薄膜トランジスタ)アレイ基材、モールド基材、プラズマディスプレイパネル(PDP)の電極板などが挙げられ、特に制約されない。本発明では、特に、半導体作製基材が好ましく、シリコン基材、Cu基材およびモールド基材がより好ましい。
また、これらの基材にはヘキサメチルジシラザン(HMDS)等による密着層や酸化層などの層が表面に設けられていてもよい。
また、基材の形状は特に限定されず、円形状であってもよく、矩形状であってもよい。
基材のサイズとしては、円形状であれば、例えば直径が100~450mmであり、好ましくは200~450mmである。矩形状であれば、例えば短辺の長さが100~1000mmであり、好ましくは200~700mmである。
また、基材としては、例えば板状、好ましくはパネル状の基材(基板)が用いられる。 〔Base material〕
The type of the base material can be appropriately determined depending on the application, but semiconductor-made base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin-film transistor, Either a magnetic film, a reflective film, a metal substrate such as Ni, Cu, Cr, or Fe (for example, a substrate formed of metal, or a substrate in which a metal layer is formed by, for example, plating or thin film deposition, etc.). (May be good), paper, SOG (Spin On Glass), TFT (thin film transistor) array base material, mold base material, electrode plate of plasma display panel (PDP), and the like, and are not particularly limited. In the present invention, a semiconductor-made base material is particularly preferable, and a silicon base material, a Cu base material, and a molded base material are more preferable.
Further, these substrates may be provided with a layer such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) or the like on the surface thereof.
Further, the shape of the base material is not particularly limited, and may be circular or rectangular.
The size of the base material is, for example, 100 to 450 mm in diameter, preferably 200 to 450 mm in a circular shape. If it is rectangular, for example, the length of the short side is 100 to 1000 mm, preferably 200 to 700 mm.
Further, as the base material, for example, a plate-shaped base material (substrate), preferably a panel-shaped base material (board) is used.
また、あらかじめ仮支持体上に上記付与方法によって付与して形成した塗膜を、基材上に転写する方法を適用することもできる。
転写方法に関しては特開2006-023696号公報の段落0023、0036~0051や、特開2006-047592号公報の段落0096~0108に記載の作製方法を本発明においても好適に用いることができる。
また、基材の端部において余分な膜の除去を行なう工程を行なってもよい。このような工程の例には、エッジビードリンス(EBR)、バックリンスなどが挙げられる。
また樹脂組成物を基材に塗布する前に基材を種々の溶剤を塗布し、基材の濡れ性を向上させた後に樹脂組成物を塗布するプリウェット工程を採用しても良い。 Specifically, the means to be applied include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, and a slit coating method. An inkjet method and the like are exemplified. From the viewpoint of film thickness uniformity, a spin coating method, a slit coating method, a spray coating method, or an inkjet method is more preferable, and spin coating is performed from the viewpoint of film thickness uniformity and productivity. The method and the slit coating method are preferable. By adjusting the solid content concentration and the coating conditions of the resin composition according to the method, a film having a desired thickness can be obtained. Further, the coating method can be appropriately selected depending on the shape of the substrate. For a circular substrate such as a wafer, a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular substrate, a slit coating method or a spray coating method is preferable. The method, the inkjet method and the like are preferable. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes.
Further, it is also possible to apply a method of transferring a coating film previously applied onto a temporary support by the above-mentioned application method onto a substrate.
Regarding the transfer method, the production method described in paragraphs 0023 and 0036 to 0051 of JP-A-2006-023696 and paragraphs 0090 to 0108 of JP-A-2006-047592 can be suitably used in the present invention.
Further, a step of removing the excess film at the end of the base material may be performed. Examples of such a process include edge bead rinse (EBR), back rinse and the like.
Further, a pre-wet step of applying various solvents to the base material before applying the resin composition to the base material to improve the wettability of the base material and then applying the resin composition may be adopted.
上記膜は、膜形成工程(層形成工程)の後に、溶剤を除去するために形成された膜(層)を乾燥する工程(乾燥工程)に供されてもよい。
すなわち、本発明の硬化物の製造方法は、膜形成工程により形成された膜を乾燥する乾燥工程を含んでもよい。
また、上記乾燥工程は膜形成工程の後、露光工程の前に行われることが好ましい。
乾燥工程における膜の乾燥温度は50~150℃であることが好ましく、70℃~130℃がより好ましく、90℃~110℃が更に好ましい。また、減圧により乾燥を行っても良い。乾燥時間としては、30秒~20分が例示され、1分~10分が好ましく、2分~7分がより好ましい。 <Drying process>
The film may be subjected to a step (drying step) of drying the film (layer) formed to remove the solvent after the film forming step (layer forming step).
That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed by the film forming step.
Further, it is preferable that the drying step is performed after the film forming step and before the exposure step.
The drying temperature of the film in the drying step is preferably 50 to 150 ° C, more preferably 70 ° C to 130 ° C, still more preferably 90 ° C to 110 ° C. Further, drying may be performed by reducing the pressure. The drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, more preferably 2 minutes to 7 minutes.
上記膜は、膜を選択的に露光する露光工程に供されてもよい。
すなわち、本発明の硬化物の製造方法は、膜形成工程により形成された膜を選択的に露光する露光工程を含んでもよい。
選択的に露光するとは、膜の一部を露光することを意味している。また、選択的に露光することにより、膜には露光された領域(露光部)と露光されていない領域(非露光部)が形成される。
露光量は、本発明の樹脂組成物を硬化できる限り特に定めるものではないが、例えば、波長365nmでの露光エネルギー換算で50~10,000mJ/cm2が好ましく、200~8,000mJ/cm2がより好ましい。 <Exposure process>
The film may be subjected to an exposure step of selectively exposing the film.
That is, the method for producing a cured product of the present invention may include an exposure step of selectively exposing the film formed by the film forming step.
Selective exposure means exposing a part of the film. Further, by selectively exposing the film, an exposed region (exposed portion) and an unexposed region (non-exposed portion) are formed on the film.
The exposure amount is not particularly determined as long as the resin composition of the present invention can be cured, but for example, it is preferably 50 to 10,000 mJ / cm 2 in terms of exposure energy at a wavelength of 365 nm, and 200 to 8,000 mJ / cm 2 . Is more preferable.
また、露光の方式は特に限定されず、本発明の樹脂組成物からなる膜の少なくとも一部が露光される方式であればよいが、フォトマスクを使用した露光、レーザーダイレクトイメージング法による露光等が挙げられる。 The exposure wavelengths are as follows: (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength). 436 nm), h line (wavelength 405 nm), i line (wavelength 365 nm), broad (3 wavelengths of g, h, i line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm) ), F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, etc. Will be. The resin composition of the present invention is particularly preferably exposed to a high-pressure mercury lamp, and above all, to be exposed to i-rays. As a result, particularly high exposure sensitivity can be obtained.
The exposure method is not particularly limited as long as it is a method in which at least a part of the film made of the resin composition of the present invention is exposed, but exposure using a photomask, exposure by a laser direct imaging method, or the like is possible. Can be mentioned.
上記膜は、露光後に加熱する工程(露光後加熱工程)に供されてもよい。
すなわち、本発明の硬化物の製造方法は、露光工程により露光された膜を加熱する露光後加熱工程を含んでもよい。
露光後加熱工程は、露光工程後、現像工程前に行うことができる。
露光後加熱工程における加熱温度は、50℃~140℃であることが好ましく、60℃~120℃であることがより好ましい。
露光後加熱工程における加熱時間は、30秒間~300分間が好ましく、1分間~10分間がより好ましい。
露光後加熱工程における昇温速度は、加熱開始時の温度から最高加熱温度まで1~12℃/分が好ましく、2~10℃/分がより好ましく、3~10℃/分が更に好ましい。
また、昇温速度は加熱途中で適宜変更してもよい。
露光後加熱工程における加熱手段としては、特に限定されず、公知のホットプレート、オーブン、赤外線ヒーター等を用いることができる。
また、加熱に際し、窒素、ヘリウム、アルゴンなどの不活性ガスを流す等により、低酸素濃度の雰囲気で行うことも好ましい。 <Heating process after exposure>
The film may be subjected to a step of heating after exposure (post-exposure heating step).
That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the film exposed by the exposure step.
The post-exposure heating step can be performed after the exposure step and before the developing step.
The heating temperature in the post-exposure heating step is preferably 50 ° C to 140 ° C, more preferably 60 ° C to 120 ° C.
The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.
The heating rate in the post-exposure heating step is preferably 1 to 12 ° C./min, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min from the temperature at the start of heating to the maximum heating temperature.
Further, the heating rate may be appropriately changed during heating.
The heating means in the post-exposure heating step is not particularly limited, and a known hot plate, oven, infrared heater, or the like can be used.
Further, it is also preferable to carry out the heating in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium or argon.
露光後の上記膜は、現像液を用いて現像してパターンを形成する現像工程に供されてもよい。
すなわち、本発明の硬化物の製造方法は、露光工程により露光された膜を現像液を用いて現像してパターンを形成する現像工程を含んでもよい。現像を行うことにより、膜の露光部及び非露光部のうち一方が除去され、パターンが形成される。
ここで、膜の非露光部が現像工程により除去される現像をネガ型現像といい、膜の露光部が現像工程により除去される現像をポジ型現像という。 <Development process>
The film after exposure may be subjected to a developing step of developing with a developing solution to form a pattern.
That is, the method for producing a cured product of the present invention may include a developing step of developing a film exposed by the exposure step with a developing solution to form a pattern. By performing the development, one of the exposed portion and the non-exposed portion of the film is removed, and a pattern is formed.
Here, the development in which the non-exposed portion of the film is removed by the developing step is called negative type development, and the development in which the exposed portion of the film is removed by the developing step is called positive type development.
現像工程において用いられる現像液としては、アルカリ水溶液、又は、有機溶剤を含む現像液が挙げられる。 [Developer]
Examples of the developing solution used in the developing step include an alkaline aqueous solution or a developing solution containing an organic solvent.
他の成分としては、例えば、公知の界面活性剤や公知の消泡剤等が挙げられる。 The developer may further contain other components.
Examples of other components include known surfactants and known defoaming agents.
現像液の供給方法は、所望のパターンを形成できれば特に制限は無く、膜が形成された基材を現像液に浸漬する方法、基材上に形成された膜にノズルを用いて現像液を供給するパドル現像、または、現像液を連続供給する方法がある。ノズルの種類は特に制限は無く、ストレートノズル、シャワーノズル、スプレーノズル等が挙げられる。
現像液の浸透性、非画像部の除去性、製造上の効率の観点から、現像液をストレートノズルで供給する方法、又はスプレーノズルにて連続供給する方法が好ましく、画像部への現像液の浸透性の観点からは、スプレーノズルで供給する方法がより好ましい。
また、現像液をストレートノズルにて連続供給後、基材をスピンし現像液を基材上から除去し、スピン乾燥後に再度ストレートノズルにて連続供給後、基材をスピンし現像液を基材上から除去する工程を採用してもよく、この工程を複数回繰り返しても良い。
また現像工程における現像液の供給方法としては、現像液が連続的に基材に供給され続ける工程、基材上で現像液が略静止状態で保たれる工程、基材上で現像液を超音波等で振動させる工程及びそれらを組み合わせた工程などが採用可能である。 [Method of supplying developer]
The method of supplying the developing solution is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material on which the film is formed in the developing solution and the method of supplying the developing solution to the film formed on the base material using a nozzle. There is a method of paddle development or a method of continuously supplying a developer. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
From the viewpoint of the permeability of the developing solution, the removability of the non-image area, and the manufacturing efficiency, the method of supplying the developing solution with a straight nozzle or the method of continuously supplying the developing solution with a spray nozzle is preferable. From the viewpoint of permeability, the method of supplying with a spray nozzle is more preferable.
Further, after the developer is continuously supplied by the straight nozzle, the base material is spun to remove the developer from the base material, and after spin drying, the developer is continuously supplied by the straight nozzle again, and then the base material is spun to use the developer as the base material. A step of removing from the top may be adopted, or this step may be repeated a plurality of times.
The method of supplying the developer in the developing process includes a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept in a substantially stationary state on the substrate, and a process in which the developer is superposed on the substrate. A process of vibrating with a sound wave or the like and a process of combining them can be adopted.
現像液がアルカリ水溶液である場合、リンス液としては、例えば水を用いることができる。現像液が有機溶剤を含む現像液である場合、リンス液としては、例えば、現像液に含まれる溶剤とは異なる溶剤(例えば、水、現像液に含まれる有機溶剤とは異なる有機溶剤)を用いることができる。 [Rinse liquid]
When the developing solution is an alkaline aqueous solution, for example, water can be used as the rinsing solution. When the developer is a developer containing an organic solvent, for example, a solvent different from the solvent contained in the developer (for example, water or an organic solvent different from the organic solvent contained in the developer) is used as the rinse solution. be able to.
他の成分としては、例えば、公知の界面活性剤や公知の消泡剤等が挙げられる。 The rinse solution may further contain other components.
Examples of other components include known surfactants and known defoaming agents.
リンス液の供給方法は、所望のパターンを形成できれば特に制限は無く、基材をリンス液に浸漬する方法、基材に液盛りによりリンス液を供給する方法、基材にリンス液をシャワーで供給する方法、基材上にストレートノズル等の手段によりリンス液を連続供給する方法がある。
リンス液の浸透性、非画像部の除去性、製造上の効率の観点から、リンス液をシャワーノズル、ストレートノズル、スプレーノズルなどで供給する方法があり、スプレーノズルにて連続供給する方法が好ましく、画像部へのリンス液の浸透性の観点からは、スプレーノズルで供給する方法がより好ましい。ノズルの種類は特に制限は無く、ストレートノズル、シャワーノズル、スプレーノズル等が挙げられる。
すなわち、リンス工程は、リンス液を上記露光後の膜に対してストレートノズルにより供給、又は、連続供給する工程であることが好ましく、リンス液をスプレーノズルにより供給する工程であることがより好ましい。
またリンス工程におけるリンス液の供給方法としては、リンス液が連続的に基材に供給され続ける工程、基材上でリンス液が略静止状態で保たれる工程、基材上でリンス液を超音波等で振動させる工程及びそれらを組み合わせた工程などが採用可能である。 [Supplying method of rinse liquid]
The method of supplying the rinsing liquid is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material in the rinsing liquid, the method of supplying the rinsing liquid to the base material by filling, and the method of supplying the rinsing liquid to the base material by a shower. There is a method of continuously supplying the rinse liquid onto the substrate by means such as a straight nozzle.
From the viewpoint of the permeability of the rinse liquid, the removability of non-image areas, and the efficiency of manufacturing, there is a method of supplying the rinse liquid with a shower nozzle, a straight nozzle, a spray nozzle, etc., and a method of continuously supplying the rinse liquid with a spray nozzle is preferable. From the viewpoint of the permeability of the rinse liquid into the image portion, the method of supplying with a spray nozzle is more preferable. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
That is, the rinsing step is preferably a step of supplying the rinsing liquid to the exposed film by a straight nozzle or continuously, and more preferably a step of supplying the rinsing liquid by a spray nozzle.
Further, as a method of supplying the rinse liquid in the rinsing step, a step of continuously supplying the rinse liquid to the base material, a step of keeping the rinse liquid in a substantially stationary state on the base material, and a step of superimposing the rinse liquid on the base material. A process of vibrating with a sonic or the like and a process of combining them can be adopted.
現像工程により得られたパターン(リンス工程を行う場合は、リンス後のパターン)は、上記現像により得られたパターンを加熱する加熱工程に供されてもよい。
すなわち、本発明の硬化物の製造方法は、現像工程により得られたパターンを加熱する加熱工程を含んでもよい。
また、本発明の硬化物の製造方法は、現像工程を行わずに他の方法で得られたパターン、又は、膜形成工程により得られた膜を加熱する加熱工程を含んでもよい。
加熱工程において、ポリイミド前駆体等の樹脂は環化してポリイミド等の樹脂となる。
また、特定樹脂、又は特定樹脂以外の架橋剤における未反応の架橋性基の架橋なども進行する。
加熱工程における加熱温度(最高加熱温度)としては、50~450℃が好ましく、150~350℃がより好ましく、150~250℃が更に好ましく、160~250℃が一層好ましく、160~230℃が特に好ましい。 <Heating process>
The pattern obtained by the developing step (in the case of performing the rinsing step, the pattern after rinsing) may be subjected to a heating step of heating the pattern obtained by the above-mentioned development.
That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained by the developing step.
Further, the method for producing a cured product of the present invention may include a pattern obtained by another method without performing a developing step, or a heating step of heating the film obtained by the film forming step.
In the heating step, the resin such as the polyimide precursor is cyclized to become the resin such as polyimide.
In addition, cross-linking of unreacted cross-linking groups with a specific resin or a cross-linking agent other than the specific resin also proceeds.
The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450 ° C, more preferably 150 to 350 ° C, further preferably 150 to 250 ° C, further preferably 160 to 250 ° C, and particularly preferably 160 to 230 ° C. preferable.
加えて、急速加熱可能なオーブンの場合、加熱開始時の温度から最高加熱温度まで1~8℃/秒の昇温速度で行うことが好ましく、2~7℃/秒がより好ましく、3~6℃/秒が更に好ましい。 The heating in the heating step is preferably performed at a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature. The temperature rising rate is more preferably 2 to 10 ° C./min, even more preferably 3 to 10 ° C./min. By setting the temperature rise rate to 1 ° C./min or more, it is possible to prevent excessive volatilization of the acid or solvent while ensuring productivity, and by setting the temperature rise rate to 12 ° C./min or less, curing is possible. The residual stress of the object can be relaxed.
In addition, in the case of an oven capable of rapid heating, it is preferable to carry out from the temperature at the start of heating to the maximum heating temperature at a heating rate of 1 to 8 ° C./sec, more preferably 2 to 7 ° C./sec, and 3 to 6 ° C. ℃ / sec is more preferable.
上記加熱温度の上限は、350℃以下であることが好ましく、250℃以下であることがより好ましく、240℃以下であることが更に好ましい。 In particular, when forming a multi-layered laminate, the heating temperature is preferably 30 ° C. or higher, more preferably 80 ° C. or higher, still more preferably 100 ° C. or higher, from the viewpoint of adhesion between layers. It is particularly preferable that the temperature is 120 ° C. or higher.
The upper limit of the heating temperature is preferably 350 ° C. or lower, more preferably 250 ° C. or lower, and even more preferably 240 ° C. or lower.
更に、加熱後冷却してもよく、この場合の冷却速度としては、1~5℃/分であることが好ましい。 Heating may be performed in stages. As an example, the temperature is raised from 25 ° C. to 120 ° C. at 3 ° C./min and held at 120 ° C. for 60 minutes, the temperature is raised from 120 ° C. to 180 ° C. at 2 ° C./min, and the temperature is kept at 180 ° C. for 120 minutes. , And so on. It is also preferable to perform the treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547. It is possible to improve the characteristics of the film by such a pretreatment step. The pretreatment step may be performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps, for example, the first pretreatment step may be performed in the range of 100 to 150 ° C., and then the second pretreatment step may be performed in the range of 150 to 200 ° C. good.
Further, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.
加熱工程における加熱手段としては、特に限定されないが、例えばホットプレート、赤外炉、電熱式オーブン、熱風式オーブン、赤外線オーブンなどが挙げられる。 The heating step is preferably carried out in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium or argon or under reduced pressure in order to prevent decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
The heating means in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared furnace, an electric heating oven, a hot air oven, and an infrared oven.
現像工程により得られた(リンス工程を行う場合は、リンス後のパターン)は、上記加熱工程に代えて、又は、上記加熱工程に加えて、現像工程後のパターンを露光する現像後露光工程に供されてもよい。
すなわち、本発明の硬化物の製造方法は、現像工程により得られたパターンを露光する現像後露光工程を含んでもよい。本発明の硬化物の製造方法は、加熱工程及び現像後露光工程を含んでもよいし、加熱工程及び現像後露光工程の一方のみを含んでもよい。
現像後露光工程においては、例えば、光塩基発生剤の感光によってポリイミド前駆体等の環化が進行する反応や、光酸発生剤の感光によって酸分解性基の脱離が進行する反応などを促進することができる。
現像後露光工程においては、現像工程において得られたパターンの少なくとも一部が露光されればよいが、上記パターンの全部が露光されることが好ましい。
現像後露光工程における露光量は、感光性化合物が感度を有する波長における露光エネルギー換算で、50~20,000mJ/cm2であることが好ましく、100~15,000mJ/cm2であることがより好ましい。
現像後露光工程は、例えば、上述の露光工程における光源を用いて行うことができ、ブロードバンド光を用いることが好ましい。 <Exposure process after development>
The obtained by the developing step (in the case of performing the rinsing step, the pattern after rinsing) is used in the post-development exposure step of exposing the pattern after the developing step in place of the above heating step or in addition to the above heating step. It may be offered.
That is, the method for producing a cured product of the present invention may include a post-development exposure step for exposing the pattern obtained by the developing step. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of a heating step and a post-development exposure step.
In the post-development exposure step, for example, a reaction in which cyclization of a polyimide precursor or the like is promoted by exposure to a photobase generator, a reaction in which desorption of an acid-degradable group is promoted by exposure to a photoacid generator, etc. are promoted. can do.
In the post-development exposure step, at least a part of the pattern obtained in the development step may be exposed, but it is preferable that all of the above patterns are exposed.
The exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ / cm 2 and more preferably 100 to 15,000 mJ / cm 2 in terms of exposure energy at a wavelength at which the photosensitive compound has sensitivity. preferable.
The post-development exposure step can be performed using, for example, the light source in the above-mentioned exposure step, and it is preferable to use broadband light.
現像工程により得られたパターン(加熱工程及び露光後現像工程の少なくとも一方に供されたものが好ましい)は、パターン上に金属層を形成する金属層形成工程に供されてもよい。
すなわち、本発明の硬化物の製造方法は、現像工程により得られたパターン(加熱工程及び現像後露光工程少なくとも一方に供されたものが好ましい)上に金属層を形成する金属層形成工程を含むことが好ましい。 <Metal layer forming process>
The pattern obtained by the developing step (preferably those subjected to at least one of the heating step and the post-exposure developing step) may be subjected to the metal layer forming step of forming the metal layer on the pattern.
That is, the method for producing a cured product of the present invention includes a metal layer forming step of forming a metal layer on a pattern obtained by a developing step (preferably one provided in at least one of a heating step and a post-development exposure step). Is preferable.
本発明の硬化物の製造方法、又は、本発明の硬化物の適用可能な分野としては、電子デバイスの絶縁膜、再配線層用層間絶縁膜、ストレスバッファ膜などが挙げられる。そのほか、封止フィルム、基板材料(フレキシブルプリント基板のベースフィルムやカバーレイ、層間絶縁膜)、又は上記のような実装用途の絶縁膜をエッチングでパターン形成することなどが挙げられる。これらの用途については、例えば、サイエンス&テクノロジー(株)「ポリイミドの高機能化と応用技術」2008年4月、柿本雅明/監修、CMCテクニカルライブラリー「ポリイミド材料の基礎と開発」2011年11月発行、日本ポリイミド・芳香族系高分子研究会/編「最新ポリイミド 基礎と応用」エヌ・ティー・エス,2010年8月等を参照することができる。 <Use>
Examples of the method for producing a cured product of the present invention or the applicable field of the cured product of the present invention include an insulating film for an electronic device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like. Other examples include forming a pattern by etching on a sealing film, a substrate material (base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above. For these applications, for example, Science & Technology Co., Ltd. "High-performance and applied technology of polyimide" April 2008, Masaaki Kakimoto / supervision, CMC technical library "Basics and development of polyimide materials" November 2011 You can refer to "Latest Polyimide Basics and Applications", NTS, August 2010, etc., published by Japan Polyimide / Aromatic Polymer Research Association / ed.
本発明の積層体とは、本発明の硬化物からなる層を複数層有する構造体をいう。
本発明の積層体は、硬化物からなる層を2層以上含む積層体であり、3層以上積層した積層体としてもよい。
上記積層体に含まれる2層以上の上記硬化物からなる層のうち、少なくとも1つが本発明の硬化物からなる層であり、硬化物の収縮、又は、上記収縮に伴う硬化物の変形等を抑制する観点からは、上記積層体に含まれる全ての硬化物からなる層が本発明の硬化物からなる層であることも好ましい。 (Laminated body and method for manufacturing the laminated body)
The laminated body of the present invention refers to a structure having a plurality of layers made of the cured product of the present invention.
The laminated body of the present invention is a laminated body containing two or more layers made of a cured product, and may be a laminated body in which three or more layers are laminated.
Of the two or more layers made of the cured product contained in the laminated body, at least one is a layer made of the cured product of the present invention, which causes shrinkage of the cured product or deformation of the cured product due to the shrinkage. From the viewpoint of suppressing, it is also preferable that the layer made of all the cured products contained in the laminated body is the layer made of the cured product of the present invention.
すなわち、本発明の積層体の製造方法は、複数回行われる硬化物の製造方法の間に、硬化物からなる層上に金属層を形成する金属層形成工程を更に含むことが好ましい。金属層形成工程の好ましい態様は上述の通りである。
上記積層体としては、例えば、第一の硬化物からなる層、金属層、第二の硬化物からなる層の3つの層がこの順に積層された層構造を少なくとも含む積層体が好ましいものとして挙げられる。
上記第一の硬化物からなる層及び上記第二の硬化物からなる層は、いずれも本発明の硬化物からなる層であることが好ましい。上記第一の硬化物からなる層の形成に用いられる本発明の樹脂組成物と、上記第二の硬化物からなる層の形成に用いられる本発明の樹脂組成物とは、組成が同一の組成物であってもよいし、組成が異なる組成物であってもよい。本発明の積層体における金属層は、再配線層などの金属配線として好ましく用いられる。 It is preferable that the laminated body of the present invention contains two or more layers made of a cured product and contains a metal layer between any of the layers made of the cured product. The metal layer is preferably formed by the metal layer forming step.
That is, it is preferable that the method for producing a laminated body of the present invention further includes a metal layer forming step of forming a metal layer on a layer made of the cured product between the methods for producing a cured product which is performed a plurality of times. The preferred embodiment of the metal layer forming step is as described above.
As the above-mentioned laminate, for example, a laminate including at least a layer structure in which three layers of a layer made of a first cured product, a metal layer, and a layer made of a second cured product are laminated in this order is preferable. Be done.
It is preferable that the layer made of the first cured product and the layer made of the second cured product are both layers made of the cured product of the present invention. The resin composition of the present invention used for forming the layer made of the first cured product and the resin composition of the present invention used for forming the layer made of the second cured product have the same composition. It may be a product or a composition having a different composition. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.
本発明の積層体の製造方法は、積層工程を含むことが好ましい。
積層工程とは、パターン(樹脂層)又は金属層の表面に、再度、(a)膜形成工程(層形成工程)、(b)露光工程、(c)現像工程、(d)加熱工程及び現像後露光工程の少なくとも一方を、この順に行うことを含む一連の工程である。ただし、(a)の膜形成工程および(d)加熱工程及び現像後露光工程の少なくとも一方を繰り返す態様であってもよい。また、(d)加熱工程及び現像後露光工程の少なくとも一方の後には(e)金属層形成工程を含んでもよい。積層工程には、更に、上記乾燥工程等を適宜含んでいてもよいことは言うまでもない。 <Laminating process>
The method for producing a laminated body of the present invention preferably includes a laminating step.
The laminating step means that (a) a film forming step (layer forming step), (b) an exposure step, (c) a developing step, (d) a heating step and development are performed again on the surface of a pattern (resin layer) or a metal layer. It is a series of steps including performing at least one of the post-exposure steps in this order. However, it may be an embodiment in which at least one of the film forming step (a), the heating step and the post-development exposure step (d) is repeated. Further, (e) a metal layer forming step may be included after at least one of the (d) heating step and the post-development exposure step. Needless to say, the laminating step may further include the above-mentioned drying step and the like as appropriate.
例えば、樹脂層/金属層/樹脂層/金属層/樹脂層/金属層のように、樹脂層を2層以上20層以下とする構成が好ましく、2層以上9層以下とする構成が更に好ましい。
上記各層はそれぞれ、組成、形状、膜厚等が同一であってもよいし、異なっていてもよい。 The laminating step is preferably performed 2 to 20 times, more preferably 2 to 9 times.
For example, a structure having two or more and 20 or less resin layers, such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferable, and a structure having two or more and 9 or less layers is more preferable. ..
The composition, shape, film thickness, etc. of each of the above layers may be the same or different.
本発明の積層体の製造方法は、上記金属層および樹脂組成物層の少なくとも一部を表面活性化処理する、表面活性化処理工程を含むことが好ましい。
表面活性化処理工程は、通常、金属層形成工程の後に行うが、上記現像工程の後(好ましくは、加熱工程及び現像後露光工程の少なくとも一方の後)、樹脂組成物層に表面活性化処理工程を行ってから、金属層形成工程を行ってもよい。
表面活性化処理は、金属層の少なくとも一部のみに行ってもよいし、露光後の樹脂組成物層の少なくとも一部のみに行ってもよいし、金属層および露光後の樹脂組成物層の両方について、それぞれ、少なくとも一部に行ってもよい。表面活性化処理は、金属層の少なくとも一部について行うことが好ましく、金属層のうち、表面に樹脂組成物層を形成する領域の一部または全部に表面活性化処理を行うことが好ましい。このように、金属層の表面に表面活性化処理を行うことにより、その表面に設けられる樹脂組成物層(膜)との密着性を向上させることができる。
また、表面活性化処理は、露光後の樹脂組成物層(樹脂層)の一部または全部についても行うことが好ましい。このように、樹脂組成物層の表面に表面活性化処理を行うことにより、表面活性化処理した表面に設けられる金属層や樹脂層との密着性を向上させることができる。特にネガ型現像を行う場合など、樹脂組成物層が硬化されている場合には、表面処理によるダメージを受けにくく、密着性が向上しやすい。
表面活性化処理としては、具体的には、各種原料ガス(酸素、水素、アルゴン、窒素、窒素/水素混合ガス、アルゴン/酸素混合ガスなど)のプラズマ処理、コロナ放電処理、CF4/O2、NF3/O2、SF6、NF3、NF3/O2によるエッチング処理、紫外線(UV)オゾン法による表面処理、塩酸水溶液に浸漬して酸化皮膜を除去した後にアミノ基とチオール基を少なくとも一種有する化合物を含む有機表面処理剤への浸漬処理、ブラシを用いた機械的な粗面化処理から選択され、プラズマ処理が好ましく、特に原料ガスに酸素を用いた酸素プラズマ処理が好ましい。コロナ放電処理の場合、エネルギーは、500~200,000J/m2が好ましく、1000~100,000J/m2がより好ましく、10,000~50,000J/m2が最も好ましい。 (Surface activation treatment process)
The method for producing a laminate of the present invention preferably includes a surface activation treatment step of surface activating at least a part of the metal layer and the resin composition layer.
The surface activation treatment step is usually performed after the metal layer forming step, but after the development step (preferably after at least one of the heating step and the post-development exposure step), the surface activation treatment of the resin composition layer is performed. After performing the step, the metal layer forming step may be performed.
The surface activation treatment may be performed on at least a part of the metal layer, on at least a part of the exposed resin composition layer, or on the metal layer and the exposed resin composition layer. For both, you may go to at least part of each. The surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable to perform the surface activation treatment on a part or all of the region forming the resin composition layer on the surface of the metal layer. By performing the surface activation treatment on the surface of the metal layer in this way, the adhesion to the resin composition layer (film) provided on the surface can be improved.
Further, it is preferable that the surface activation treatment is performed on a part or all of the resin composition layer (resin layer) after exposure. As described above, by performing the surface activation treatment on the surface of the resin composition layer, it is possible to improve the adhesion to the metal layer or the resin layer provided on the surface of the surface activation treatment. In particular, when the resin composition layer is cured, such as when negative type development is performed, it is less likely to be damaged by the surface treatment and the adhesion is likely to be improved.
Specific examples of the surface activation treatment include plasma treatment of various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixed gas, argon / oxygen mixed gas, etc.), corona discharge treatment, and CF 4 / O 2 . , NF 3 / O 2 , SF 6 , NF 3 , NF 3 / O 2 , etching treatment, surface treatment by ultraviolet (UV) ozone method, immersion in hydrochloric acid aqueous solution to remove oxide film, then amino group and thiol group It is selected from a dipping treatment in an organic surface treatment agent containing at least one compound and a mechanical roughening treatment using a brush, and plasma treatment is preferable, and oxygen plasma treatment using oxygen as a raw material gas is particularly preferable. In the case of the corona discharge treatment, the energy is preferably 500 to 200,000 J / m 2 , more preferably 1000 to 100,000 J / m 2 , and most preferably 10,000 to 50,000 J / m 2 .
また、本発明は、本発明の硬化物、又は、本発明の積層体を含む半導体デバイスも開示する。
また、本発明は、本発明の硬化物の製造方法、又は、本発明の積層体の製造方法を含む半導体デバイスの製造方法も開示する。本発明の樹脂組成物を再配線層用層間絶縁膜の形成に用いた半導体デバイスの具体例としては、特開2016-027357号公報の段落0213~0218の記載及び図1の記載を参酌でき、これらの内容は本明細書に組み込まれる。 (Manufacturing method of electronic device)
The present invention also discloses a semiconductor device containing the cured product of the present invention or the laminate of the present invention.
The present invention also discloses a method for producing a cured product of the present invention, or a method for producing a semiconductor device including a method for producing a laminate of the present invention. As specific examples of the semiconductor device in which the resin composition of the present invention is used to form the interlayer insulating film for the rewiring layer, the description in paragraphs 0213 to 0218 and FIG. 1 of JP-A-2016-0273557 can be referred to. These contents are incorporated in the present specification.
3口丸底フラスコに、ジエチレングリコールジビニルエーテル 23.73g(0.150mol)、メタクリル酸 77.84g (0.900mol)、乾燥塩化メチレン 100ml、及び、4-メトキシフェノール 39mgを加え20℃以下で撹拌しながらCSA(10-カンファースルホン酸) 125mmg(0.54mmol)を添加した。一時的に40℃程度まで上昇するが直ぐに低下し25℃で4時間撹拌した。反応終了後、反応液を炭酸水素ナトリウム 60gを含む水 500mlと酢酸エチル 300mlの混合液に注ぎ、30分間攪拌した。有機相を分離し、飽和炭酸水素ナトリウム水溶液 300mlで2回、飽和食塩水 200mlで1回洗浄した。有機相を硫酸ナトリウムで乾燥した後、4-メトキシフェノール 25mgを加え減圧下で濃縮し、目的物であるB-1の油状物を46.31g、収率93.4%で得た。
化合物B-1のH1-NMR測定結果は下記の通りである。
6.16(2H)、6.01(2H)、5.60(2H)、3.81(2H)、3.71(2H)、3.65(4H)、1.95(6H)、1.46(6H)
To a 3-necked round bottom flask, add 23.73 g (0.150 mol) of diethylene glycol divinyl ether, 77.84 g (0.900 mol) of methacrylic acid, 100 ml of dry methylene chloride, and 39 mg of 4-methoxyphenol, and stir at 20 ° C or lower. However, 125 mmg (0.54 mmol) of CSA (10-camphorsulfonic acid) was added. The temperature temporarily increased to about 40 ° C., but immediately decreased, and the mixture was stirred at 25 ° C. for 4 hours. After completion of the reaction, the reaction solution was poured into a mixture of 500 ml of water containing 60 g of sodium hydrogen carbonate and 300 ml of ethyl acetate, and the mixture was stirred for 30 minutes. The organic phase was separated and washed twice with 300 ml of saturated aqueous sodium hydrogen carbonate solution and once with 200 ml of saturated brine. After drying the organic phase with sodium sulfate, 25 mg of 4-methoxyphenol was added and concentrated under reduced pressure to obtain 46.31 g of the target oil of B-1 in a yield of 93.4%.
The H1 - NMR measurement results of compound B-1 are as follows.
6.16 (2H), 6.01 (2H), 5.60 (2H), 3.81 (2H), 3.71 (2H), 3.65 (4H), 1.95 (6H), 1 .46 (6H)
特開2010-224558号公報に記載の方法を参照し、下記化合物B-2を合成した。
The following compound B-2 was synthesized with reference to the method described in JP-A-2010-224558.
特開2014-169384号公報に記載の方法を参照し、下記化合物B-3を合成した。
The following compound B-3 was synthesized with reference to the method described in JP-A-2014-169384.
特開2005-232412号公報に記載の方法を参照し、下記化合物B-4を合成した。
The following compound B-4 was synthesized with reference to the method described in JP-A-2005-232912.
化合物B-1の合成において、メタクリル酸を等モル量の下記化合物B-5aに変更した以外は、化合物B-1と同様の方法により、下記化合物B-5を合成した。
In the synthesis of compound B-1, the following compound B-5 was synthesized by the same method as that of compound B-1, except that methacrylic acid was changed to the following compound B-5a in an equimolar amount.
〔ピロメリット酸二無水物、4,4’-ジアミノジフェニルエーテル及びベンジルアルコールからのポリイミド前駆体(A-1:ラジカル重合性基を有さないポリイミド前駆体)の合成〕
14.06g(64.5ミリモル)のピロメリット酸二無水物(140℃で12時間乾燥)と、14.22g(131.58ミリモル)のベンジルアルコールを、50mLのN-メチルピロリドンに懸濁させ、モレキュラーシーブで乾燥させた。懸濁液を100℃で3時間加熱した。反応混合物を室温に冷却し、21.43g(270.9ミリモル)のピリジン及び90mLのN-メチルピロリドンを加えた。次いで、反応混合物を-10℃に冷却し、温度を-10±4℃に保ちながら16.12g(135.5ミリモル)のSOCl2を10分かけて加えた。SOCl2を加えている間、粘度が増加した。50mLのN-メチルピロリドンで希釈した後、反応混合物を室温で2時間撹拌した。次いで、100mLのN-メチルピロリドンに11.08g(58.7ミリモル)の4,4’-ジアミノジフェニルエーテルを溶解させた溶液を、-5~0℃の温度範囲に調整しつつ、20分かけて反応混合物に滴下した。次いで、反応混合物を0℃で1時間反応させたのち、エタノールを70g加えて、室温で1晩撹拌した。次いで、5リットルの水の中でポリイミド前駆体を沈殿させ、水-ポリイミド前駆体混合物を5,000rpmの速度で15分間撹拌した。ポリイミド前駆体をろ過して除き、4リットルの水の中で再度30分間撹拌し再びろ過した。次いで、得られたポリイミド前駆体を減圧下で、45℃で3日間乾燥した。このポリイミド前駆体の重量平均分子量は、18,000であった。
[Synthesis of polyimide precursor (A-1: polyimide precursor having no radical polymerizable group) from pyromellitic acid dianhydride, 4,4'-diaminodiphenyl ether and benzyl alcohol]
14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C. for 12 hours) and 14.22 g (131.58 mmol) of benzyl alcohol were suspended in 50 mL of N-methylpyrrolidone. , Dryed in a molecular sieve. The suspension was heated at 100 ° C. for 3 hours. The reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) of pyridine and 90 mL of N-methylpyrrolidone were added. The reaction mixture was then cooled to −10 ° C. and 16.12 g (135.5 mmol) of SOCL 2 was added over 10 minutes while keeping the temperature at −10 ± 4 ° C. Viscosity increased while SOCL 2 was added. After diluting with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, a solution prepared by dissolving 11.08 g (58.7 mmol) of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was prepared over 20 minutes while adjusting the temperature range to -5 to 0 ° C. It was added dropwise to the reaction mixture. Then, the reaction mixture was reacted at 0 ° C. for 1 hour, 70 g of ethanol was added, and the mixture was stirred overnight at room temperature. The polyimide precursor was then precipitated in 5 liters of water and the water-polyimide precursor mixture was stirred at a rate of 5,000 rpm for 15 minutes. The polyimide precursor was filtered off, stirred again in 4 liters of water for 30 minutes and filtered again. The resulting polyimide precursor was then dried under reduced pressure at 45 ° C. for 3 days. The weight average molecular weight of this polyimide precursor was 18,000.
〔ピロメリット酸二無水物、4,4’-ジアミノジフェニルエーテル及び2-ヒドロキシエチルメタクリレートからのポリイミド前駆体(A-2:ラジカル重合性基を有するポリイミド前駆体)の合成〕
14.06g(64.5ミリモル)のピロメリット酸二無水物(140℃で12時間乾燥した)と、16.8g(129ミリモル)の2-ヒドロキシエチルメタクリレートと、0.05gのハイドロキノンと、20.4g(258ミリモル)のピリジンと、100gのダイグライム(ジエチレングリコールジメチルエーテル)を混合し、60℃の温度で18時間撹拌して、ピロメリット酸と2-ヒドロキシエチルメタクリレートのジエステルを製造した。次いで、得られたジエステルをSOCl2により塩素化した後、合成例1と同様の方法で4,4’-ジアミノジフェニルエーテルでポリイミド前駆体に変換し、合成例1と同様の方法でポリイミド前駆体を得た。このポリイミド前駆体の重量平均分子量は、19,000であった。
[Synthesis of polyimide precursor (A-2: polyimide precursor having a radically polymerizable group) from pyromellitic acid dianhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate]
14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, and 20 .4 g (258 mmol) of pyridine and 100 g of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at a temperature of 60 ° C. for 18 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Next, the obtained diester was chlorinated with SOCL 2 , converted to a polyimide precursor with 4,4'-diaminodiphenyl ether by the same method as in Synthesis Example 1, and the polyimide precursor was obtained by the same method as in Synthesis Example 1. Obtained. The weight average molecular weight of this polyimide precursor was 19,000.
〔4,4’-オキシジフタル酸無水物、4,4’-ジアミノジフェニルエーテル及び2-ヒドロキシエチルメタクリレートからのポリイミド前駆体(A-3:ラジカル重合性基を有するポリイミド前駆体)の合成〕
20.0g(64.5ミリモル)の4,4’-オキシジフタル酸無水物(140℃で12時間乾燥した)と、16.8g(129ミリモル)の2-ヒドロキシエチルメタクリレートと、0.05gのハイドロキノンと、20.4g(258ミリモル)のピリジンと、100gのダイグライムとを混合し、60℃の温度で18時間撹拌して、4,4’-オキシジフタル酸と2-ヒドロキシエチルメタクリレートのジエステルを製造した。次いで、得られたジエステルをSOCl2により塩素化した後、合成例1と同様の方法で4,4’-ジアミノジフェニルエーテルでポリイミド前駆体に変換し、合成例1と同様の方法でポリイミド前駆体を得た。このポリイミド前駆体の重量平均分子量は、18,000であった。
[Synthesis of polyimide precursor (A-3: polyimide precursor having radical polymerizable group) from 4,4'-oxydiphthalic anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate]
20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140 ° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, and 0.05 g of hydroquinone. , 20.4 g (258 mmol) of pyridine and 100 g of diglime were mixed and stirred at a temperature of 60 ° C. for 18 hours to prepare a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. .. Next, the obtained diester was chlorinated with SOCL 2 , converted to a polyimide precursor with 4,4'-diaminodiphenyl ether by the same method as in Synthesis Example 1, and the polyimide precursor was obtained by the same method as in Synthesis Example 1. Obtained. The weight average molecular weight of this polyimide precursor was 18,000.
〔4,4’-オキシジフタル酸無水物、4,4’-ジアミノ-2,2’-ジメチルビフェニル(オルトトリジン)及び2-ヒドロキシエチルメタクリレートからのポリイミド前駆体(A-4:ラジカル重合性基を有するポリイミド前駆体)の合成〕
20.0g(64.5ミリモル)の4,4’-オキシジフタル酸無水物(140℃で12時間乾燥した)と、16.8g(129ミリモル)の2-ヒドロキシエチルメタクリレートと、0.05gのハイドロキノンと、20.4g(258ミリモル)のピリジンと、100gのダイグライムとを混合し、60℃の温度で18時間撹拌して、4,4’-オキシジフタル酸と2-ヒドロキシエチルメタクリレートのジエステルを製造した。次いで、得られたジエステルをSOCl2により塩素化した後、合成例1と同様の方法で4,4’-ジアミノ-2,2’-ジメチルビフェニルでポリイミド前駆体に変換し、合成例1と同様の方法でポリイミド前駆体を得た。このポリイミド前駆体の重量平均分子量は、19,000であった。
[4,4'-oxydiphthalic anhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (orthotridin) and polyimide precursor from 2-hydroxyethyl methacrylate (A-4: having a radically polymerizable group) Synthesis of polyimide precursor)]
20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140 ° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, and 0.05 g of hydroquinone. , 20.4 g (258 mmol) of pyridine and 100 g of diglime were mixed and stirred at a temperature of 60 ° C. for 18 hours to prepare a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. .. Next, the obtained diester was chlorinated with SOCL 2 , and then converted into a polyimide precursor with 4,4'-diamino-2,2'-dimethylbiphenyl by the same method as in Synthesis Example 1, and the same as in Synthesis Example 1. A polyimide precursor was obtained by the above method. The weight average molecular weight of this polyimide precursor was 19,000.
〔2,2'-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン及び4,4'-オキシジベンゾイルクロリドからのポリベンゾオキサゾール前駆体(A-5)の合成〕
N-メチル-2-ピロリドン100mLに、2,2'-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン13.92gを添加し、撹拌溶解した。続いて、温度を0~5℃に保ちながら、11.21gの4,4'-オキシジベンゾイルクロリドを10分間で滴下した後、60分間撹拌を続けた。次いで、6リットルの水の中でポリベンゾオキサゾール前駆体を沈殿させ、水-ポリベンゾオキサゾール前駆体混合物を5000rpmの速度で15分間撹拌した。ポリベンゾオキサゾール前駆体を濾過して除き、6リットルの水の中で再度30分間撹拌し再び濾過した。次いで、得られたポリベンゾオキサゾール前駆体を減圧下で、45℃で3日間乾燥した。このポリベンゾオキサゾール前駆体の重量平均分子量は、15,000であった。
[Synthesis of polybenzoxazole precursor (A-5) from 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4,4'-oxydibenzoyl chloride]
To 100 mL of N-methyl-2-pyrrolidone, 13.92 g of 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added and dissolved by stirring. Subsequently, 11.21 g of 4,4'-oxydibenzoyl chloride was added dropwise over 10 minutes while maintaining the temperature at 0 to 5 ° C., and then stirring was continued for 60 minutes. The polybenzoxazole precursor was then precipitated in 6 liters of water and the water-polybenzoxazole precursor mixture was stirred at a rate of 5000 rpm for 15 minutes. The polybenzoxazole precursor was removed by filtration, stirred again in 6 liters of water for 30 minutes and filtered again. The resulting polybenzoxazole precursor was then dried under reduced pressure at 45 ° C. for 3 days. The weight average molecular weight of this polybenzoxazole precursor was 15,000.
〔4,4’-オキシジフタル酸二無水物、4,4’-ジアミノジフェニルエーテル、及び2-ヒドロキシエチルメタクリレートからのポリイミド前駆体(A-6:ラジカル重合性基を有するポリイミド前駆体)の合成〕
4,4’-オキシジフタル酸二無水物(ODPA)155.1gをセパラブルフラスコに入れ、2-ヒドロキシエチルメタクリレート(HEMA)134.0g及びγ-ブチロラクトン400mlを加えた。室温下で撹拌しながら、ピリジン79.1gを加えることにより、反応混合物を得た。反応による発熱の終了後、室温まで放冷し、更に16時間静置した。 <Synthesis example 6>
[Synthesis of polyimide precursor (A-6: polyimide precursor having a radically polymerizable group) from 4,4'-oxydiphthalic acid dianhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate]
155.1 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) was placed in a separable flask, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added. A reaction mixture was obtained by adding 79.1 g of pyridine while stirring at room temperature. After the exotherm by the reaction was completed, the mixture was allowed to cool to room temperature and allowed to stand for another 16 hours.
〔3,3’,4,4’-ビフェニルテトラカルボン酸二無水物、4,4’-ジアミノジフェニルエーテル、及び2-ヒドロキシエチルメタクリレートからのポリイミド前駆体(A-7:ラジカル重合性基を有するポリイミド前駆体)の合成〕
合成例7において、4,4’-オキシジフタル酸二無水物155.1gに代えて、3,3’4,4’-ビフェニルテトラカルボン酸二無水物147.1gを用いた以外は、合成例6に記載の方法と同様にして反応を行うことにより、ポリマーA-7を得た。このポリマーA-7の重量平均分子量(Mw)を測定したところ、22,000であった。 <Synthesis example 7>
[3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 4,4'-diaminodiphenyl ether, and polyimide precursor from 2-hydroxyethyl methacrylate (A-7: Polyimide having a radically polymerizable group) Synthesis of precursor)]
Synthesis Example 6 except that 147.1 g of 3,3'4,4'-biphenyltetracarboxylic dianhydride was used in place of 155.1 g of 4,4'-oxydiphthalic acid dianhydride in Synthesis Example 7. The reaction was carried out in the same manner as described in 1. Polymer A-7 was obtained. The weight average molecular weight (Mw) of this polymer A-7 was measured and found to be 22,000.
各実施例において、それぞれ、下記表に記載の成分を混合し、各樹脂組成物を得た。また、各比較例において、それぞれ、下記表に記載の成分を混合し、各比較用組成物を得た。
具体的には、表の「溶剤」以外の欄に記載の成分の含有量は、表の「質量部」に記載の量とし、表の「溶剤」の欄に記載の成分の含有量は、組成物の固形分濃度が表に記載の値となる量とした。
また、例えば表の「溶剤」の「I-1/I-2」「80/20」の記載は、I-1とI-2の含有量の比が、質量比でI-1:I-2=80:20であることを示している。
得られた樹脂組成物及び比較用組成物を、細孔の幅が0.8μmのポリテトラフルオロエチレン製フィルターを通して加圧ろ過した。
また、表中、「-」の記載は該当する成分を組成物が含有していないことを示している。 <Examples and comparative examples>
In each example, the components listed in the table below were mixed to obtain each resin composition. Further, in each comparative example, the components listed in the following table were mixed to obtain each comparative composition.
Specifically, the content of the component described in the column other than "solvent" in the table shall be the amount described in "part by mass" of the table, and the content of the component described in the column "solvent" of the table shall be the amount. The solid content concentration of the composition was set to the value shown in the table.
Further, for example, in the description of "I-1 / I-2" and "80/20" of "solvent" in the table, the ratio of the contents of I-1 and I-2 is the mass ratio of I-1: I-. It shows that 2 = 80:20.
The obtained resin composition and comparative composition were pressure-filtered through a filter made of polytetrafluoroethylene having a pore width of 0.8 μm.
Further, in the table, the description of "-" indicates that the composition does not contain the corresponding component.
・A-1~A-7:上記で合成したA-1~A-7 [Cyclic resin or its precursor]
-A-1 to A-7: A-1 to A-7 synthesized above
・B-1~B-5:上記で合成したB-1~B-5
・B-6:下記構造の化合物
B-1 to B-5: B-1 to B-5 synthesized above
B-6: Compounds with the following structure
・C-1:下記構造の化合物
・C-2:M-327(東亞合成株式会社製イソシアヌル酸エチレンオキシド変性トリアクリレートのカプロラクトン3モル変性品
-C-1: A compound having the following structure-C-2: M-327 (3 mol-modified caprolactone of isocyanuric acid ethylene oxide-modified triacrylate manufactured by Toagosei Co., Ltd.
・J-1:N-フェニルジエタノールアミン
・J-2:下記構造の化合物
-J-1: N-Phenyldiethanolamine-J-2: Compound with the following structure
・D-1及びD-2:下記構造の化合物
-D-1 and D-2: Compounds with the following structures
・F-1~F-3:下記構造の化合物
・F-3:2-ニトロソ-1-ナフト-ル(東京化成工業(株)製)
・ F-1 to F-3: Compounds with the following structure ・ F-3: 2-nitroso-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.)
・G-1~G-3:下記構造の化合物
G-1 to G-3: Compounds with the following structure
・H-1~H-3:下記構造の化合物
-H-1 to H-3: Compounds having the following structure
I-1:γ-ブチロラクトン(三和油化社製)
I-2:ジメチルスルホキシド(富士フイルム和光純薬(株)製)
I-3:N-メチル-2-ピロリドン(Ashland社製)
I-4:乳酸エチル(東京化成工業(株)製) 〔solvent〕
I-1: γ-Butyrolactone (manufactured by Sanwa Yuka Co., Ltd.)
I-2: Dimethyl sulfoxide (manufactured by Wako Pure Chemical Industries, Ltd.)
I-3: N-methyl-2-pyrrolidone (manufactured by Ashland)
I-4: Ethyl lactate (manufactured by Tokyo Chemical Industry Co., Ltd.)
〔硬化物の製造〕
各実施例及び比較例において、それぞれ、樹脂組成物又は比較用組成物をシリコンウェハ上にスピンコート法により適用し、樹脂層を形成した。上記樹脂層が形成されたシリコンウェハをホットプレート上で、100℃で4分間乾燥し、シリコンウェハ上に20μmの均一な厚さの樹脂組成物層とした。
シリコンウェハ上の樹脂組成物層を、ブロードバンド露光機(ウシオ電機(株)製:UX-1000SN-EH01)を用いて、400mJ/cm2の露光エネルギーで露光し、露光した樹脂組成物層を、窒素雰囲気下で、5℃/分の昇温速度で昇温し、180℃に達した後、この温度で2時間加熱した。上記加熱後の樹脂組成物層及びシリコンウェハを3質量%フッ化水素酸水溶液に浸漬し、シリコンウェハから加熱後の樹脂組成物層を剥離した。上記剥離した加熱後の樹脂組成物層を硬化物とした。 <Evaluation>
[Manufacturing of cured product]
In each Example and Comparative Example, a resin composition or a comparative composition was applied onto a silicon wafer by a spin coating method to form a resin layer. The silicon wafer on which the resin layer was formed was dried on a hot plate at 100 ° C. for 4 minutes to obtain a resin composition layer having a uniform thickness of 20 μm on the silicon wafer.
The resin composition layer on the silicon wafer was exposed to an exposure energy of 400 mJ / cm 2 using a broadband exposure machine (manufactured by Ushio, Inc .: UX-1000SN-EH01), and the exposed resin composition layer was exposed. The temperature was raised at a heating rate of 5 ° C./min under a nitrogen atmosphere, and after reaching 180 ° C., heating was performed at this temperature for 2 hours. The heated resin composition layer and the silicon wafer were immersed in a 3 mass% hydrofluoric acid aqueous solution, and the heated resin composition layer was peeled off from the silicon wafer. The peeled and heated resin composition layer was used as a cured product.
得られた硬化物を下記の薬液に下記の条件で浸漬し、溶解速度を算定した。
薬液:ジメチルスルホキシド(DMSO)と25質量%のテトラメチルアンモニウムヒドロキシド(TMAH)水溶液の90:10(質量比)の混合物
評価条件:薬液中に硬化物を75℃で15分間浸漬して浸漬前後の膜厚を比較し、溶解速度(nm/分)を算出した。膜厚測定は、エリプソメーター(Foothill社製KT-22)で塗布面10点の膜厚測定を実施し、その平均値を算術平均値として求めた。
評価は下記評価基準に従って行い、評価結果は表の「耐薬品性」の欄に記載した。溶解速度の値が小さいほど、硬化物は耐薬品性に優れるといえる。
-評価基準-
A:溶解速度が200nm/分未満である。
B:溶解速度が200nm/分以上350nm/分未満である。
C:溶解速度が350nm/分以上500nm/分未満である。
D:溶解速度が500nm/分以上である。 〔chemical resistance〕
The obtained cured product was immersed in the following chemical solution under the following conditions, and the dissolution rate was calculated.
Chemical solution: Mixture of dimethylsulfoxide (DMSO) and 25% by mass tetramethylammonium hydroxide (TMAH) aqueous solution at 90:10 (mass ratio) Evaluation conditions: Immerse the cured product in the chemical solution at 75 ° C. for 15 minutes before and after immersion. The dissolution rate (nm / min) was calculated by comparing the film thicknesses of the above. For the film thickness measurement, the film thickness was measured at 10 points on the coated surface with an ellipsometer (KT-22 manufactured by Footill), and the average value was obtained as an arithmetic mean value.
The evaluation was performed according to the following evaluation criteria, and the evaluation results are described in the "Chemical resistance" column of the table. It can be said that the smaller the value of the dissolution rate, the better the chemical resistance of the cured product.
-Evaluation criteria-
A: The dissolution rate is less than 200 nm / min.
B: The dissolution rate is 200 nm / min or more and less than 350 nm / min.
C: The dissolution rate is 350 nm / min or more and less than 500 nm / min.
D: The dissolution rate is 500 nm / min or more.
各実施例及び比較例において、それぞれ、樹脂組成物又は比較用組成物をスピンコート法でシリコンウェハ上に適用して樹脂組成物層を形成した。得られた樹脂組成物層を適用したシリコンウェハをホットプレート上で、100℃で5分間乾燥し、シリコンウェハ上に約15μmの厚さの均一な樹脂組成物層を得た。
得られた樹脂組成物層の全面に対して、ステッパー(Nikon NSR 2005 i9C)を用いて、500mJ/cm2の露光エネルギーでi線露光した。
上記露光後の樹脂組成物層(樹脂層)を、窒素雰囲気下で、10℃/分の昇温速度で昇温し、230℃に達した後、3時間加熱した。硬化後の樹脂層(硬化物)を4.9質量%フッ化水素酸水溶液に浸漬し、シリコンウェハから硬化物を剥離した。剥離した硬化物を、打ち抜き機を用いて打ち抜いて、試料幅3mm、試料長30mmの試験片を作製した。得られた試験片を、引張り試験機(テンシロン)を用いて、クロスヘッドスピード300mm/分で、25℃、65%RH(相対湿度)の環境下にて、JIS-K6251に準拠してフィルムの長手方向の破断伸び率を測定した。評価は各5回ずつ実施し、フィルムが破断した時の伸び率(破断伸び率)について、その算術平均値を指標値として用いた。
上記指標値を下記評価基準に従って評価し、評価結果は表の「破断伸び」の欄に記載した。上記指標値が大きいほど、得られる硬化物の膜強度(破断伸び)に優れるといえる。
-評価基準-
A:上記指標値が60%以上であった。
B:上記指標値が55%以上60%未満であった。
C:上記指標値が50%以上55%未満であった。
D:上記指標値が50%未満であった。 [Breaking elongation]
In each Example and Comparative Example, a resin composition or a comparative composition was applied onto a silicon wafer by a spin coating method to form a resin composition layer. The silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a uniform resin composition layer having a thickness of about 15 μm on the silicon wafer.
The entire surface of the obtained resin composition layer was exposed to i-line with an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C).
The resin composition layer (resin layer) after the exposure was heated at a heating rate of 10 ° C./min under a nitrogen atmosphere, reached 230 ° C., and then heated for 3 hours. The cured resin layer (cured product) was immersed in a 4.9 mass% hydrofluoric acid aqueous solution, and the cured product was peeled off from the silicon wafer. The peeled cured product was punched out using a punching machine to prepare a test piece having a sample width of 3 mm and a sample length of 30 mm. The obtained test piece was subjected to a film using a tensile tester (Tencilon) at a crosshead speed of 300 mm / min in an environment of 25 ° C. and 65% RH (relative humidity) in accordance with JIS-K6251. The elongation at break in the longitudinal direction was measured. The evaluation was carried out 5 times each, and the arithmetic mean value of the elongation rate (breaking elongation rate) when the film was broken was used as an index value.
The above index values were evaluated according to the following evaluation criteria, and the evaluation results are described in the "break elongation" column of the table. It can be said that the larger the index value is, the better the film strength (break elongation) of the obtained cured product is.
-Evaluation criteria-
A: The above index value was 60% or more.
B: The index value was 55% or more and less than 60%.
C: The above index value was 50% or more and less than 55%.
D: The above index value was less than 50%.
比較例1~2に係る組成物は、化合物Aを含有しない。この比較例1~2に係る組成物は、得られる硬化物の膜強度に劣ることが分かる。
また、以上の結果から、本発明に係る、樹脂、及び、化合物Aを含む樹脂組成物は、得られる硬化物の耐薬品性に優れることが分かる。
比較例1~2に係る樹脂組成物は、化合物Aを含有しない。この比較例1~2に係る樹脂組成物は、得られる硬化物の耐薬品性に劣ることが分かる。 From the above results, it can be seen that the resin and the resin composition containing the compound A according to the present invention are excellent in the film strength of the obtained cured product.
The compositions according to Comparative Examples 1 and 2 do not contain compound A. It can be seen that the compositions according to Comparative Examples 1 and 2 are inferior in the film strength of the obtained cured product.
Further, from the above results, it can be seen that the resin and the resin composition containing the compound A according to the present invention are excellent in chemical resistance of the obtained cured product.
The resin compositions according to Comparative Examples 1 and 2 do not contain compound A. It can be seen that the resin compositions according to Comparative Examples 1 and 2 are inferior in the chemical resistance of the obtained cured product.
実施例1において使用した樹脂組成物を、表面に銅薄層が形成された樹脂基材の銅薄層の表面にスピンコート法により層状に適用して、100℃で4分間乾燥し、膜厚20μmの感光膜を形成した後、ステッパー((株)ニコン製、NSR1505 i6)を用いて露光した。露光はマスク(パターンが1:1ラインアンドスペースであり、線幅が10μmであるバイナリマスク)を介して、波長365nmで行った。露光後、100℃で4分間加熱した。上記加熱後、シクロヘキサノンで2分間現像し、PGMEAで30秒間リンスし、層のパターンを得た。
次いで、窒素雰囲気下で、10℃/分の昇温速度で昇温し、230℃に達した後、230℃で120分間維持して、再配線層用層間絶縁膜を形成した。この再配線層用層間絶縁膜は、絶縁性に優れていた。
また、これらの再配線層用層間絶縁膜を使用して半導体デバイスを製造したところ、問題なく動作することを確認した。 <Example 101>
The resin composition used in Example 1 was applied in a layered manner on the surface of the copper thin layer of the resin substrate having the copper thin layer formed on the surface by a spin coating method, dried at 100 ° C. for 4 minutes, and the film thickness was increased. After forming a 20 μm photosensitive film, exposure was performed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). Exposure was performed via a mask (a binary mask with a pattern of 1: 1 line and space and a line width of 10 μm) at a wavelength of 365 nm. After the exposure, it was heated at 100 ° C. for 4 minutes. After the above heating, it was developed with cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern.
Next, the temperature was raised at a heating rate of 10 ° C./min under a nitrogen atmosphere, and after reaching 230 ° C., the temperature was maintained at 230 ° C. for 120 minutes to form an interlayer insulating film for the rewiring layer. The interlayer insulating film for the rewiring layer was excellent in insulating property.
Moreover, when a semiconductor device was manufactured using these interlayer insulating films for the rewiring layer, it was confirmed that the semiconductor device operated without any problem.
Claims (21)
- シクロヘキセン構造、及び、アセタール構造からなる群より選択される少なくとも1種の構造を含む連結基を介して結合している複数の重合性基を有し、かつ、分子量が1000未満である化合物A、並びに、
環化樹脂の前駆体を含む、
樹脂組成物。 Compound A, which has a plurality of polymerizable groups bonded via a linking group containing at least one structure selected from the group consisting of a cyclohexene structure and an acetal structure, and has a molecular weight of less than 1000. and,
Contains precursors of cyclized resin,
Resin composition. - 前記化合物Aにおける重合性基が、エチレン性不飽和結合を有する基である、請求項1に記載の樹脂組成物。 The resin composition according to claim 1, wherein the polymerizable group in the compound A is a group having an ethylenically unsaturated bond.
- 前記化合物Aにおける連結基が、シクロヘキセン構造、及び、アセタール構造よりなる群より選択される少なくとも1種の構造を複数個含む、請求項1又は2に記載の樹脂組成物。 The resin composition according to claim 1 or 2, wherein the linking group in the compound A contains a plurality of at least one structures selected from the group consisting of a cyclohexene structure and an acetal structure.
- 前記化合物Aにおける連結基が、シクロヘキセン構造を複数個含むか、又は、アセタール構造を複数個含む、請求項1~3のいずれか1項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 3, wherein the linking group in the compound A contains a plurality of cyclohexene structures or a plurality of acetal structures.
- 前記化合物Aが、下記式(2-1)で表される化合物を含む、請求項1~4のいずれか1項に記載の樹脂組成物。
式(2-1)中、R1、R2及びR3はそれぞれ独立に、1価の有機基を表し、R1、R2及びR3の少なくとも1つは重合性基を有する基を含む。 The resin composition according to any one of claims 1 to 4, wherein the compound A contains a compound represented by the following formula (2-1).
In formula (2-1), R 1 , R 2 and R 3 each independently represent a monovalent organic group, and at least one of R 1 , R 2 and R 3 contains a group having a polymerizable group. .. - 前記R2、R3が下記式(2-2)又は下記式(2-3)のいずれかで表される部分構造を有する基である、請求項5に記載の樹脂組成物。
式(2-2)、式(2-3)中、R4はそれぞれ独立に、水素原子または炭素数1~5のアルキル基を表し、*は、式(2-1)に含まれる酸素原子との結合部位を表し、Lは2価の連結基を表す。 The resin composition according to claim 5, wherein R 2 and R 3 are groups having a partial structure represented by either the following formula (2-2) or the following formula (2-3).
In the formula (2-2) and the formula (2-3), R 4 independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and * is an oxygen atom contained in the formula (2-1). Represents a binding site with, and L represents a divalent linking group. - 前記式(2-1)で表される化合物が下記式(2-4)で表される化合物である、請求項5に記載の樹脂組成物。
式(2-4)中、R4はそれぞれ独立に、水素原子または炭素数1~5のアルキル基を表し、Lは2価の連結基を表す。 The resin composition according to claim 5, wherein the compound represented by the formula (2-1) is a compound represented by the following formula (2-4).
In formula (2-4), R 4 independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and L represents a divalent linking group. - 前記化合物Aにおける連結基が、架橋環構造又は縮合環構造を有するシクロヘキセン構造を含む、請求項1~7のいずれか1項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 7, wherein the linking group in the compound A contains a cyclohexene structure having a crosslinked ring structure or a condensed ring structure.
- 前記化合物Aが、下記式(3-1)で表される化合物を含む、請求項1~8のいずれか1項に記載の樹脂組成物。
式(3-1)中、R1、R2はそれぞれ独立に1価の有機基を表し、R1、R2の少なくとも1つはエチレン性不飽和結合を有する基を含む。 The resin composition according to any one of claims 1 to 8, wherein the compound A contains a compound represented by the following formula (3-1).
In formula (3-1), R 1 and R 2 each independently represent a monovalent organic group, and at least one of R 1 and R 2 contains a group having an ethylenically unsaturated bond. - 前記式(3-1)で表される化合物が下記式(3-2)で表される化合物である、請求項9に記載の樹脂組成物。
式(3-2)中、R3及びR4はそれぞれ独立に、エチレン性不飽和結合を有する基を含む1価の有機基を表し、Lは2価の連結基を表す。 The resin composition according to claim 9, wherein the compound represented by the formula (3-1) is a compound represented by the following formula (3-2).
In formula (3-2), R 3 and R 4 each independently represent a monovalent organic group containing a group having an ethylenically unsaturated bond, and L represents a divalent linking group. - 前記環化樹脂の前駆体として、ポリイミド前駆体を含む、請求項1~10のいずれか1項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 10, which comprises a polyimide precursor as the precursor of the cyclized resin.
- 前記ポリイミド前駆体が下記式(2)で表される繰返し単位を有する、請求項11に記載の樹脂組成物;
式(2)中、A1及びA2は、それぞれ独立に、酸素原子又は-NH-を表し、R111は、2価の有機基を表し、R115は、4価の有機基を表し、R113及びR114は、それぞれ独立に、水素原子又は1価の有機基を表す。 The resin composition according to claim 11, wherein the polyimide precursor has a repeating unit represented by the following formula (2).
In formula (2), A 1 and A 2 independently represent an oxygen atom or -NH-, R 111 represents a divalent organic group, and R 115 represents a tetravalent organic group. R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group. - 前記式(2)におけるR113及びR114の少なくとも一方がラジカル重合性基を含む、請求項12に記載の樹脂組成物。 The resin composition according to claim 12, wherein at least one of R 113 and R 114 in the formula (2) contains a radically polymerizable group.
- ラジカル重合開始剤を更に含む、請求項1~13のいずれか1項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 13, further comprising a radical polymerization initiator.
- 再配線層用層間絶縁膜の形成に用いられる、請求項1~14のいずれか1項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 14, which is used for forming an interlayer insulating film for a rewiring layer.
- 請求項1~15のいずれか1項に記載の樹脂組成物を硬化してなる硬化物。 A cured product obtained by curing the resin composition according to any one of claims 1 to 15.
- 請求項16に記載の硬化物からなる層を2層以上含み、前記硬化物同士のいずれかの間に金属層を含む積層体。 A laminated body containing two or more layers made of the cured product according to claim 16 and containing a metal layer between any of the cured products.
- 請求項1~15のいずれか1項に記載の樹脂組成物を基材上に適用して膜を形成する膜形成工程を含む、硬化物の製造方法。 A method for producing a cured product, which comprises a film forming step of applying the resin composition according to any one of claims 1 to 15 onto a substrate to form a film.
- 前記膜を選択的に露光する露光工程及び前記膜を現像液を用いて現像してパターンを形成する現像工程を含む、請求項18に記載の硬化物の製造方法。 The method for producing a cured product according to claim 18, further comprising an exposure step of selectively exposing the film and a developing step of developing the film with a developer to form a pattern.
- 前記膜を50~450℃で加熱する加熱工程を含む、請求項18又は19に記載の硬化物の製造方法。 The method for producing a cured product according to claim 18 or 19, which comprises a heating step of heating the film at 50 to 450 ° C.
- 請求項16に記載の硬化物又は請求項17に記載の積層体を含む、半導体デバイス。 A semiconductor device comprising the cured product according to claim 16 or the laminate according to claim 17.
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JP2009109987A (en) * | 2007-10-09 | 2009-05-21 | Chisso Corp | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
JP2009185213A (en) * | 2008-02-07 | 2009-08-20 | Chisso Corp | Thermosetting composition |
JP2010053323A (en) * | 2008-08-29 | 2010-03-11 | Chisso Corp | Thermosetting composition, method for producing the same, and use of the same |
JP2011237755A (en) * | 2009-09-18 | 2011-11-24 | Jnc Corp | Liquid crystal aligning agent, liquid crystal alignment layer, method for producing liquid crystal alignment layer, and liquid crystal display element |
WO2012002512A1 (en) * | 2010-06-30 | 2012-01-05 | 日産化学工業株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, manufacturing method for liquid crystal display element, and polymerisable compound |
WO2018155639A1 (en) * | 2017-02-23 | 2018-08-30 | 日立化成デュポンマイクロシステムズ株式会社 | Resin composition, cured product, pattern cured product, cured product production method, interlayer insulating film, surface protection film and electronic component |
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JP4789657B2 (en) | 2006-03-13 | 2011-10-12 | 旭化成イーマテリアルズ株式会社 | Photosensitive resin composition |
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JP2009109987A (en) * | 2007-10-09 | 2009-05-21 | Chisso Corp | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
JP2009185213A (en) * | 2008-02-07 | 2009-08-20 | Chisso Corp | Thermosetting composition |
JP2010053323A (en) * | 2008-08-29 | 2010-03-11 | Chisso Corp | Thermosetting composition, method for producing the same, and use of the same |
JP2011237755A (en) * | 2009-09-18 | 2011-11-24 | Jnc Corp | Liquid crystal aligning agent, liquid crystal alignment layer, method for producing liquid crystal alignment layer, and liquid crystal display element |
WO2012002512A1 (en) * | 2010-06-30 | 2012-01-05 | 日産化学工業株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, manufacturing method for liquid crystal display element, and polymerisable compound |
WO2018155639A1 (en) * | 2017-02-23 | 2018-08-30 | 日立化成デュポンマイクロシステムズ株式会社 | Resin composition, cured product, pattern cured product, cured product production method, interlayer insulating film, surface protection film and electronic component |
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