Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/22—Polybenzoxazoles
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/05—Alcohols; Metal alcoholates
• • 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
  • C08K5/13—Phenols; Phenolates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • 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
• • 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
• • 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
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/075—Silicon-containing compounds

Definitions

• the present invention relates to a resin composition, a method for producing the same, and a method for producing a pattern-forming composition.
• a resin having a polymerizable group has been synthesized in an organic solvent to obtain a synthetic reaction solution containing the resin having a polymerizable group.
• the resin is used in the form of a powdery, granular or pellet-shaped resin composition containing the resin and the organic solvent by removing a part of the organic solvent from the synthetic reaction solution by drying.
• a method of redissolving the resin composition in a solvent may be performed.
• Patent Document 1 includes a reflector, a lead frame embedded in the reflector, a recess, and a base in which a part of the lead frame is exposed on the bottom surface of the recess.
• the reflector is a silica powder having an average particle size of 9 to 25 ⁇ m and a proportion of particles having a particle size of 6 ⁇ m or less of 25 to 40% by volume.
• Patent Document 2 describes a temperature-sensitive color-changing resin composition comprising a microcapsule containing a reversible heat-coloring material, an ultraviolet absorber, and an antioxidant in a resin.
• a powdery, granular or pellet-shaped resin composition containing a resin having a polymerizable group improvement in filterability when redissolved in a solvent is required.
• a pattern-forming composition prepared by redissolving the above resin composition it is required to be able to form a finer pattern.
• the ability of the pattern-forming composition to form a finer pattern is also referred to as "excellent in pattern-forming property".
• the present invention relates to a resin composition having excellent filterability when redissolved in a solvent and excellent pattern forming property when a pattern forming composition is prepared by redissolving, a method for producing the same, and a pattern forming composition.
• the purpose is to provide a manufacturing method.
• the content of the agent is 0.1% by mass to 10,000% by mass with respect to the content of the above resin.
• ⁇ 3> The resin composition according to ⁇ 1> or ⁇ 2>, wherein the total content of the resin, the antioxidant, and the organic solvent with respect to the total mass of the resin composition is 95% by mass or more. thing.
• ⁇ 4> The resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein the resin contains a polyimide precursor.
• ⁇ 5> The resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein the resin contains a repeating unit represented by the following formula (2) or (3).
• Equation (2) Equation (3)
• 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 independently represents a hydrogen atom or a monovalent organic group.
• R 121 represents a divalent organic group
• R 122 represents a tetravalent organic group
• R 123 and R 124 independently represent a hydrogen atom or a monovalent organic group. .. ⁇ 6>
• the antioxidant is at least selected from the group consisting of phenol-based compounds, alcohol-based compounds, aldehyde-based compounds, amine-based compounds, nitroso-based compounds, phosphorus-based compounds, sulfur-based compounds, and ketone-based compounds.
• the organic solvent is a hydrocarbon compound, an alcohol compound, a carboxylic acid, a ketone compound, an ester compound, an ether compound, a nitrile compound, an amide compound, an amine compound, a sulfone compound and a sulfoxide compound.
• a method for producing a resin composition which comprises an addition step of adding the antioxidant to the production composition containing the organic solvent and the resin.
• ⁇ 13> The method for producing a resin composition according to ⁇ 11> or ⁇ 12>, which comprises a re-settling step of re-settling the resin after the addition step.
• ⁇ 14> The method for producing a resin composition according to ⁇ 13>, wherein after the reprecipitation step, a drying step of removing the organic solvent is performed.
• a method for producing a pattern-forming composition which comprises a mixing step of mixing the resin composition according to any one of ⁇ 1> to ⁇ 10> with a solvent.
• ⁇ 16> The method for producing a pattern-forming composition according to ⁇ 15>, wherein the photosensitive agent is further mixed in the above mixing step.
• a resin composition excellent in filterability when redissolved in a solvent and pattern forming property when a pattern forming composition is prepared by redissolving, a method for producing the same, and a pattern forming composition 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 the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, 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 defined as polystyrene-equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified.
• GPC measurement 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 using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation).
• the direction in which the layers are stacked on the base material is referred to as "upper", or if there is a photosensitive layer, the direction from the base material to the photosensitive layer is referred to as “upper”.
• the opposite direction is referred to as "down”.
• 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 is at least one resin selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, and is a resin having a polymerizable group (hereinafter, also referred to as "specific resin”). ), Contains an antioxidant and an organic solvent, and the content of the antioxidant is 0.1% by mass to 10,000% by mass with respect to the content of the resin, and is in the form of powder. It is in the form of granules or pellets.
• the resin composition of the present invention is excellent in filterability when redissolved in a solvent and pattern-forming property when a pattern-forming composition is prepared.
• the mechanism by which the above effect is obtained is unknown, but it is presumed as follows.
• a powdery, granular or pellet-like composition containing a resin having a polymerizable group and an organic solvent
• the peroxide, powder, granule or pellet contained in the organic solvent is produced or stored.
• the polymerization of the polymerizable group contained in the resin having a polymerizable group may proceed due to the peroxide or the like generated from the powder or the pellet.
• the polymerization proceeds in the powdery, granular or pelletized composition, and therefore, when the powdery, granular or pelletized composition is redissolved in the solvent, filtration occurs. In some cases, the sex was reduced.
• the polyimide precursor or the polybenzoxazole precursor (particularly, the polyimide precursor) has low solubility in a solvent, and if the resin polymerization proceeds as described above, the composition after re-dissolution The filterability may be significantly reduced. Therefore, as a result of diligent studies by the present inventors, the filterability is improved by containing the antioxidant in the composition at a content of 0.1% by mass or more with respect to the content of the specific resin. I found. It is presumed that this is because if the antioxidant is 0.1% by mass or more, the polymerization of the above-mentioned polymerizable group is suppressed.
• the content of the antioxidant is set to 10,000 mass ppm or less with respect to the content of the resin. It has been found that even when a composition for pattern formation is prepared, the pattern forming property is excellent. It is presumed that this is because the content of the antioxidant is set within the above range to prevent the polymerization in the pattern-forming composition from being excessively suppressed.
• Patent Documents 1 and 2 do not describe or suggest that the resin composition in the form of powder, granules or pellets contains the antioxidant in a specific content.
• the fact that the resin composition is in the form of powder means that the resin composition is fine solid particles and the average value of the length in the major axis direction is less than 30 ⁇ m.
• the fact that the resin composition is in the form of granules means that the resin composition is fine solid particles and the average value of the length in the major axis direction is 30 ⁇ m or more and 1 mm or less.
• the particulate resins may come into contact with each other to form an aggregate to form larger particles, or an aggregate containing the particulate resin may be formed.
• the fact that the resin composition is in the form of pellets means that the resin composition is molded in the form of a lump.
• the size of the pellet is not particularly limited, and the size may be determined according to the use of the resin composition.
• the components contained in the curable resin composition of the present invention will be described in detail.
• the resin composition of the present invention is at least one resin selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, and contains a resin having a polymerizable group (specific resin).
• the polyimide precursor and the polybenzoxazole precursor are cyclized by, for example, heating or chemical treatment to become polyimide and polybenzoxazole, respectively. Since polyimide or polybenzoxazole is excellent in heat resistance, insulating property, etc., a pattern-forming composition obtained by redissolving the resin composition of the present invention in a solvent by containing a specific resin in the resin composition of the present invention.
• the thing can be applied to various uses.
• 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 can also be used as a base film or a coverlay for a flexible substrate.
• Examples of the polymerizable group include known polymerizable groups such as a radically polymerizable group, an epoxy group, an oxetanyl group, a methylol group and an alkoxymethyl group, and a radically polymerizable group is preferable.
• a group having an ethylenically unsaturated bond is preferable.
• Examples of the group having an ethylenically unsaturated bond include a group having a vinyl group which may be substituted and directly bonded to an aromatic ring such as a vinyl group, an allyl group and a vinylphenyl group, a (meth) acrylamide group and a (meth) group. Examples thereof include an acryloyloxy group, and a (meth) acryloyloxy group is preferable.
• the resin composition of the present invention contains a polyimide precursor as a specific resin.
• the resin of the present invention preferably contains a repeating unit represented by the formula (2) or the formula (3) described later, and more preferably contains a repeating unit represented by the formula (2).
• 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). Further, the polyimide precursor used in the present invention has a polymerizable group. The polymerizable group may be contained in the repeating unit represented by the following formula (2), may be contained in another repeating unit, or may be contained at the end of the polyimide precursor. .. One of the preferred embodiments of the present invention is an embodiment in which the polymerizable group is contained in the repeating unit represented by the following formula (2).
• R 111 , R 113 or R 114 in the following formula (2) is a polymerizable group
• the embodiment in which at least one of R 113 or R 114 is a polymerizable group is more preferable.
• R 113 and R 114 are polymerizable groups is more preferable.
• Equation (2) In 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, and R 113. And R 114 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 6 to 20, an aromatic group having 6 to 20 carbon atoms, or a group composed of a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable.
• a group represented by —L—Ar— is exemplified.
• 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.
• 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 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group consisting of a combination thereof.
• the diamine containing the above is preferable, and the diamine containing a group consisting of an aromatic group having 6 to 20 carbon atoms is more preferable.
• aromatic groups include:
• 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.
• diamines can also be preferably used.
• 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, and 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 a phenylene group is preferably, L is an aliphatic hydrocarbon group having a fluorine atom are carbon atoms and optionally 1 or substituted by 2, -O -, - CO - , - S- or SO 2 - are preferred.
• 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 each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R 50 to R 57 is a fluorine atom, a methyl group or a trifluoro. It is a methyl group.
• 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 independently fluorine atoms or trifluoromethyl groups, respectively.
• Examples of the diamine compound giving the structure of the formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2'-. Examples thereof include bis (fluoro) -4,4'-diaminobiphenyl and 4,4'-diaminooctafluorobiphenyl. These may be used alone or in combination of two or more.
• R 111 may have a structure containing a polymerizable group.
• R 111 may have a structure derived from a diamine compound having a polymerizable group.
• the diamine compound having a polymerizable group is not particularly limited, but is preferably a compound containing an aromatic ring structure, and is a compound having a structure in which a structure containing an amino group and a polymerizable group is directly linked to the aromatic ring structure. Is more preferable.
• a group having an ethylenically unsaturated bond, a cyclic ether group, a methylol group or a group containing an alkoxymethyl group is preferable, and a vinyl group, a (meth) allyl group, a (meth) acrylamide group and a (meth) acryloxy are preferable.
• a group, a maleimide group, a vinylphenyl group, an epoxy group, an oxetanyl group, a methylol group or an alkoxymethyl group is more preferable, and a (meth) acryloxy group, a (meth) acrylamide group, an epoxy group, a methylol group or an alkoxymethyl group is further preferable.
• 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 an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be single-bonded or substituted with a fluorine atom, —O—, —CO—, —S—, —SO.
• NHCO- and preferably a group selected from a combination thereof, a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO. More preferably, it is a group selected from-, -S- and SO 2- , -CH 2- , -C (CF 3 ) 2- , -C (CH 3 ) 2-, -O-, -CO. -, - and more preferably a divalent radical selected from the group consisting of - S-, and SO 2.
• R 115 include tetracarboxylic acid residues remaining after removal of the anhydride group from the tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used.
• the tetracarboxylic dianhydride is preferably represented by the following formula (O).
• R 115 represents a tetravalent organic group.
• a preferred range of R 115 has the same meaning as R 115 in formula (2), and preferred ranges are 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
• 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 independently represent a hydrogen atom or a monovalent organic group, and it is preferable that at least one of R 113 and R 114 contains a polymerizable group, and both contain a polymerizable group. preferable.
• 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 in the specific resin 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 a methylol.
• examples include a group and an amino group.
• the radically polymerizable group of the polyimide precursor or the like a group having an ethylenically unsaturated bond is preferable.
• Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, a group represented by the following formula (III) and the like, and a group represented by the following formula (III) is preferable.
• R200 represents a hydrogen atom or a methyl group, and a hydrogen atom 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- or a polyalkyleneoxy group. Examples of suitable R 201 are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butandyl group, 1,3-butanjiyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group.
• the polyalkyleneoxy group means a group in 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. 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 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 and R 114 are each independently a hydrogen atom or a monovalent organic group.
• the monovalent organic group include an aromatic group and an aralkyl group in which an acidic group is bonded to one, two or three carbons constituting the aryl group, preferably one.
• Specific examples thereof include an aromatic group having an acidic group having 6 to 20 carbon atoms and an aralkyl group having an acidic group having 7 to 25 carbon atoms. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group can be mentioned.
• the acidic group is preferably an OH group. It is also more preferable that R 113 or R 114 is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl.
• R 113 or R 114 is preferably a monovalent organic group.
• the monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and an alkyl group substituted with an aromatic group is more preferable.
• the alkyl group preferably has 1 to 30 carbon atoms.
• the alkyl group may be linear, branched or cyclic.
• linear or branched alkyl group examples include 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, a dodecyl group, a tetradecyl group and an octadecyl group.
• Isobutyl group isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, 2-ethylhexyl group 2- (2- (2-methoxyethoxy) ethoxy) ethoxy group, 2- (2- (2) -Ethoxyethoxy) ethoxy) ethoxy) ethoxy group, 2- (2- (2- (2-methoxyethoxy) ethoxy) ethoxy) ethoxy group, and 2- (2- (2- (2- (2-ethoxyethoxy) ethoxy) ) Ethoxy group is mentioned.
• the cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group.
• Examples of the cyclic alkyl group of the monocycle include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group.
• Examples of the polycyclic cyclic alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a phenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group and a pinenyl group. Can be mentioned. Of these, the cyclohexyl group is most preferable from the viewpoint of achieving high sensitivity. Further, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described later is preferable.
• aromatic group examples include substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, inden ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, and anthracene.
• the benzene ring is most preferred.
• 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.
• the polyimide precursor has a fluorine atom in the structural unit.
• 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 component include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylpentasiloxane.
• 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 and the like used in the present invention is a precursor having a repeating unit represented by the formula (2-A). With such a structure, the width of the exposure latitude can be further widened. 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 polymerizable groups.
• a 1, A 2, R 111 , R 113 and R 114 each independently have the same meaning as A 1, A 2, R 111 , R 113 and R 114 in formula (2), and preferred ranges are also the same .
• R 112 has the same meaning as R 112 in formula (5), and preferred ranges are also the same.
• the polyimide precursor may contain one kind of repeating structural unit represented by the formula (2), but may also 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 structural units in addition to the repeating unit of the above formula (2).
• polyimide precursor in the present invention a polyimide precursor in which 50 mol% or more, more 70 mol% or more, particularly 90 mol% or more of all repeating units is a repeating unit represented by the formula (2) is used. Illustrated.
• the weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and even more preferably 22,000 to 25,000.
• 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 polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and further preferably 2.8 or more.
• the upper limit of the dispersity of the molecular weight of the polyimide precursor is not particularly determined, but for example, 4.5 or less is preferable, 4.0 or less is more preferable, 3.8 or less is further preferable, and 3.2 or less is further preferable. Preferably, 3.1 or less is even more preferable, 3.0 or less is even more preferable, and 2.95 or less is particularly preferable.
• the degree of molecular weight dispersion is a value calculated by weight average molecular weight / number average molecular weight.
• 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). Further, the polybenzoxazole precursor used in the present invention has a polymerizable group. The polymerizable group may be contained in a repeating unit represented by the following formula (3), may be contained in another repeating unit, or may be contained at the terminal of a polybenzoxazole precursor. May be good.
• One of the preferred embodiments of the present invention is an embodiment in which the polymerizable group is contained in the repeating unit represented by the following formula (3).
• R 123 or R 124 in the following formula (3) is a polymerizable group
• R 123 and R 124 are polymerizable groups is further preferable.
• Equation (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.
• 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 carbon number 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 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 preferably R 122 in another 2 Exemplary ethynylphenylbiadamantane derivatives (3) is a binding site to the oxygen atom bonding, two * is a bond sites with an oxygen atom R 122 are attached in the formula (3) , 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.
• 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.
• 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.
• phenolic hydroxy original ortho i.e., to have also substituent R 3 is believed to closer the distance of the carbonyl carbon and hydroxy original amide bond, It is particularly preferable in that the effect of increasing the cyclization rate when cured at a low temperature 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 structural units in addition to the repeating unit of the above formula (3). It is preferable to include a diamine residue represented by the following formula (SL) as another type of repeating structural unit in that the occurrence of warpage due to ring closure can be suppressed.
• SL diamine residue represented by the following formula
• 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 used as the repeating structural unit. It is also preferable to include it. 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 preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and further, when used in a composition described later, for example. It is preferably 22,000 to 28,000.
• 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.
• a polyimide precursor or the like is used as an end-capping agent such as an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound. It is preferable to seal the end of the resin. It is more preferable to use monoamine as the terminal encapsulant, and preferred compounds of monoamine are aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-.
• the content of the specific resin in the resin composition of the present invention is preferably 80% by mass or more, more preferably 85% by mass or more, and 90% by mass or more with respect to the total solid content of the resin composition. Is even more preferable. 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. It is more preferably% or less, and even more preferably 97% by mass or less.
• the 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 an antioxidant.
• the content of the antioxidant is 0.1 mass ppm to 10,000 mass ppm, preferably 10 to 1,000 mass ppm, and 50 to 500 mass ppm with respect to the content of the resin. It is more preferable to have.
• the resin composition of the present invention may contain one type of antioxidant alone or two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.
• the redox potential of the antioxidant is preferably 0.91 V or less, more preferably 0.65 V or less, and 0.45 V or less. Is more preferable.
• the lower limit of the redox potential is not particularly limited, but is preferably ⁇ 2.00 V or higher.
• the redox potential is measured by the method described in Examples described later. When the redox potential is within the above range, it is considered that the above-mentioned peroxide has excellent reducing property and the filterability when redissolved in a solvent is improved.
• antioxidant at least one selected from the group consisting of phenol-based compounds, alcohol-based compounds, aldehyde-based compounds, amine-based compounds, nitroso-based compounds, phosphorus-based compounds, sulfur-based compounds, and ketone-based compounds. Compounds are preferred.
• phenolic compound examples include hydroquinone, o-methoxyphenol, p-methoxyphenol, 2,6-di-methoxyphenol, pyrogallol and the like.
• alcohol compounds examples include ascorbic acid and glucose.
• aldehyde compound examples include formaldehyde, acetaldehyde, benzaldehyde, p-methoxybenzaldehyde and the like.
• Examples of the amine compound include 2-methoxyaniline, 4-methoxyaniline, 4-hydroxyaniline, p-phenylenediamine and the like.
• nitroso compound examples include 4-nitrosoanisole and 4-nitrosodimethylaniline.
• Examples of the phosphorus compound include triethylphosphine and triphenylphosphine.
• sulfur-based compound examples include thiophenol, 4-hydroxythiophenol, cysteine and the like.
• Examples of the ketone compound include 3-bromo- ⁇ -rapacon and the like.
• a phenol-based compound having an unsaturated degree of 1 or more or an alcohol-based compound having an unsaturated degree of 1 or more is preferable from the viewpoint of filterability when redissolved in a solvent.
• the degree of unsaturation is a number represented by (2C + 2-H-X + N) / 2, where C is the number of carbon atoms, H is the number of hydrogen atoms, X is the number of halogen atoms, and N is the number of nitrogen atoms. Is.
• the degree of unsaturation is preferably 1 to 5, more preferably 2 to 4.
• the resin composition of the present invention contains an organic solvent.
• the content of the organic solvent is not particularly limited, but is preferably more than 0 and 10% by mass or less, more preferably 0.1 to 8% by mass or less, based on the total mass of the resin composition. It is more preferably 1 to 6% by mass or less.
• the organic solvent is 10% by mass or less (preferably 8% by mass or less, more preferably 6% by mass or less)
• the resin composition of the present invention may contain one type of organic solvent alone, or may contain two or more types of organic solvent. When two or more kinds are contained, it is preferable that the total amount is within the above range.
• the organic solvent consists of a group consisting of hydrocarbon compounds, alcohol compounds, carboxylic acids, ketone compounds, ester compounds, ether compounds, nitrile compounds, amide compounds, amine compounds, sulfone compounds and sulfoxide compounds. It is preferable to contain at least one selected species.
• hydrocarbon compound examples include aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene.
• Examples of the alcohol compound include methanol, ethanol, propanol, isopropanol, butanol and the like.
• carboxylic acid examples include formic acid, acetic acid, propionic acid, lactic acid and the like.
• ketone compound examples include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like.
• Ester compounds include ethyl acetate, -n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone, ⁇ -caprolactone.
• alkylalkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)
• 3-Alkyloxypropionate alkyl esters eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-).
• 2-alkyloxypropionate alkyl esters eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate
• Etc. eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxy
• Methyl acid and ethyl 2-alkyloxy-2-methylpropionate eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.
• ether compounds include diethylene glycol dimethyl ether, tetrahydrofuran, 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, and propylene glycol.
• examples thereof include monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.
• nitrile compound examples include acetonitrile, propionitrile, benzonitrile and the like.
• amide compound examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like.
• amine-based compounds include monomethanolamine, dimethanolamine, trimethanolamine, monoethanolamine, diethanolamine, triethanolamine, dimethylamine and the like.
• sulfone compound examples include sulfolane and the like.
• Examples of the sulfoxide compound include dimethyl sulfoxide and the like.
• the resin composition of the present invention preferably contains an amide compound, an ether compound, a ketone compound, or an ester compound, and is preferably a lactam compound, a cyclic ether compound, a cyclic ketone compound, or a cyclic ketone compound. , It is more preferable to contain a lactone-based solvent.
• the resin composition of the present invention may further contain a specific resin, an antioxidant, and other components other than the organic solvent.
• the resin composition of the present invention may also be in an embodiment that does not substantially contain other components.
• the total content of the specific resin, the antioxidant, and the organic solvent with respect to the total mass of the resin composition is preferably 90% by mass or more, and more preferably 95% by mass or more.
• Examples of other components include nitrogen-containing compounds and compounds having a polymerizable group.
• the nitrogen-containing compound include a compound containing a urea structure, a compound containing a carbodiimide structure, and a compound containing an isourea structure.
• the nitrogen-containing compound includes a compound represented by the following formula (1-1), a compound represented by the following formula (1-2), a compound represented by the following formula (1-3), and the like. Can be mentioned.
• R 11 and R 12 are independently aliphatic hydrocarbons having 1 to 7 carbon atoms which may have a substituent.
• R 21 and R 22 each independently represent an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent
• R 31 and R 32 each independently have a substituent. It represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent
• R 33 represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent.
• R 11 and R 12 are independently unsubstituted aliphatic hydrocarbon groups having 1 to 7 carbon atoms, or primary amine salt structures and secondary amine salts as substituents.
• An aliphatic hydrocarbon group having 1 to 7 carbon atoms having at least one substituent selected from the group consisting of a structure, a tertiary amino group, a tertiary amine salt structure, and a quaternary ammonium group is preferable.
• An unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms is more preferable.
• an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms in R 11 and R 12 an unsubstituted saturated aliphatic hydrocarbon group having 1 to 7 carbon atoms is preferable, and an unsubstituted aliphatic hydrocarbon group having 2 to 7 carbon atoms is preferable.
• Saturated aliphatic hydrocarbon groups are more preferable, and ethyl groups, isopropyl groups, t-butyl groups or cyclohexyl groups are more preferable.
• R 11 and R 12 each independently have 2 to 2 carbon atoms having at least one substituent selected from the group consisting of a hydroxy group, an alkoxy group, a thiol group, and an alkylthio group. It may be an aliphatic hydrocarbon group of 7. The aliphatic hydrocarbon group having 2 to 7 carbon atoms may have two or more of the substituents, but an embodiment having only one substituent is also one of the preferred embodiments of the present invention.
• R 21 and R 22 each independently represent an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent.
• R 21 and R 22 have an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms or an amino group or a quaternary ammonium group as a substituent and have 1 to 7 carbon atoms.
• the aliphatic hydrocarbon group of 1 to 7 is preferable, and an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms is more preferable.
• the unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms in R 21 and R 22 or the aliphatic hydrocarbon group having 1 to 7 carbon atoms having the substituent is preferable.
• the embodiments are the same as those shown in the description of R 11 and R 12, respectively.
• R 31 and R 32 have an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms or an amino group or a quaternary ammonium group as a substituent and have 1 to 7 carbon atoms.
• the aliphatic hydrocarbon group of 1 to 7 is preferable, and an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms is more preferable.
• the unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms in R 31 and R 32 , or the aliphatic hydrocarbon group having 1 to 7 carbon atoms having the substituent is preferable.
• the embodiments are the same as those shown in the description of R 11 and R 12, respectively.
• R 33 represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, and is an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms. It is more preferable that it is an unsubstituted saturated aliphatic hydrocarbon group having 1 to 7 carbon atoms, and more preferably it is a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms.
• R 33 a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or a t-butyl group is preferable, and an ethyl group is more preferable.
• the resin composition of the present invention may contain a compound having a polymerizable group as another component.
• the polymerizable group include groups similar to the polymerizable group in the above-mentioned specific resin, and preferred embodiments are also the same.
• the compound having a polymerizable group may be contained, for example, as an unreacted component among the raw materials for introducing the polymerizable group into the above-mentioned polyimide or polybenzoxazole.
• a compound having a polymerizable group and a hydroxy group is preferable, and hydroxymethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, and glycerinji (meth).
• the content of the other components is not particularly limited, but is preferably 10% by mass or less, and more preferably 5% by mass or less.
• the lower limit is not particularly limited and may be 0% by mass.
• the resin composition of the present invention may contain other components alone or in combination of two or more. When two or more kinds are used in combination, the total amount is preferably within the above range.
• the method for producing a resin composition of the present invention includes an addition step of adding the antioxidant to the production composition containing the organic solvent and the specific resin.
• the amount of the antioxidant added may be such that the content of the antioxidant in the resin composition is within the above range.
• the method for producing a resin composition of the present invention preferably includes a synthesis step of reacting a raw material in a solvent to obtain a reaction solution containing a specific resin.
• the synthesis step may be carried out by a known method.
• the specific resin is a polyimide precursor or a polybenzoxazole precursor
• known methods can be used without particular limitation.
• a method of halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then reacting with a diamine to obtain a specific resin can be mentioned. It is also preferable to synthesize using a non-halogen catalyst without using the above-mentioned halogenating agent.
• a non-halogen catalyst a known amidation catalyst containing no halogen atom can be used without particular limitation.
• a boroxin compound, an N-hydroxy compound, a tertiary amine, a phosphoric acid ester, or an amine can be used. Examples thereof include carbodiimide compounds such as salts and urea compounds.
• carbodiimide compound examples include N, N'-diisopropylcarbodiimide, N, N'-dicyclohexylcarbodiimide and the like.
• the solvent used in the above synthesis step can be appropriately determined depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone. Further, the organic solvent in the above-mentioned resin composition may be used. It is also preferable to remove the precipitates generated in the reaction solution by filtration in the synthesis step.
• the above reaction solution may be used as the above-mentioned production composition, but the specific resin solution after the reprecipitation / redissolution step described later is used as the above-mentioned production composition. Is preferable. That is, as one of the preferred embodiments of the method for producing a resin composition of the present invention, a specific resin solution obtained by a reprecipitation / redissolving step including a synthesis step and a reprecipitation / redissolution step is used as the production composition. An embodiment in which the addition step is performed using the above can be mentioned.
• the method for producing a resin composition of the present invention comprises a reprecipitation / redissolution step in which the specific resin in the reaction solution is reprecipitated, the reprecipitated specific resin is redissolved in the organic solvent, and a specific resin solution is obtained. It is preferable to include it.
• a reprecipitation method a reaction solution containing a specific resin such as a polyimide precursor and the above solvent is supplied to a poor solvent such as water or alcohol (a solvent having a low solubility of the specific resin). Can sink.
• the reprecipitated specific resin can be obtained by, for example, a method such as filtration.
• the organic solvent used for redissolution may be any good solvent for the resin (solvent having high solubility of the specific resin), and is preferably the organic solvent described in the above resin composition.
• Conditions such as the temperature at the time of re-precipitation or re-dissolution are not particularly limited, and known methods may be followed.
• the reprecipitation step can be performed by the same method as the reprecipitation in the reprecipitation redissolution step described above.
• the re-settled specific resin can be obtained by a method such as filtration. That is, by the reprecipitation step, the specific resin is obtained in a form containing a small amount of the organic solvent.
• the drying conditions are not particularly limited, but for example, it can be dried at 25 to 45 ° C. for 1 hour to 7 days under reduced pressure.
• the drying means is not particularly limited, and for example, a known vacuum dryer can be used.
• the degree of drying is not particularly limited as long as it is dry in which at least a part of the organic solvent is removed, and the content of the organic solvent is within the above range with respect to the total mass of the resin composition. It is preferable to dry it.
• the method for producing a pattern-forming composition of the present invention preferably includes a mixing step of mixing the resin composition of the present invention with a solvent.
• the mixing method is not particularly limited, and a conventionally known method can be used. Further, in the method for producing a pattern-forming composition of the present invention, it is preferable to further mix the photosensitive agent in the above mixing step. Further, in the method for producing a pattern-forming composition of the present invention, other components may be further mixed in the above mixing step.
• the content of the specific resin in the pattern-forming composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and 40% by mass or more with respect to the total solid content of the resin composition.
• the resin content in the composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, and 98% by mass or less, based on the total solid content of the composition. It is more preferably 97% by mass or less, and even more preferably 95% by mass or less.
• the pattern-forming composition of the present invention may contain only one type of the specific resin, or may contain two or more types of the specific resin. When two or more kinds are contained, it is preferable that the total amount is within the above range.
• the pattern-forming composition contains two or more kinds of specific resins
• a resin composition containing two or more kinds of specific resins may be used, or a resin composition containing a specific resin and another specific resin are contained. It may be used in combination with a resin composition.
• the filter hole diameter is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, still more preferably 0.1 ⁇ m or less. On the other hand, from the viewpoint of productivity, 5 ⁇ m or less is preferable, 3 ⁇ m or less is more preferable, and 1 ⁇ m or less is further preferable.
• the filter material is preferably polytetrafluoroethylene, polyethylene or nylon.
• 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.
• various materials may be filtered a plurality of times.
• circulation filtration may be used.
• you may pressurize and perform filtration.
• the pressurizing pressure is preferably 0.05 MPa or more and 0.3 MPa or less.
• 0.01 MPa or more and 1.0 MPa or less is preferable, 0.03 MPa or more and 0.9 MPa or less is more preferable, and 0.05 MPa or more and 0.7 MPa or less is further preferable.
• impurities may be removed using an adsorbent.
• Filter filtration and impurity removal treatment using an adsorbent may be combined.
• 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 solvent, the photosensitive agent, and other components contained in the pattern-forming composition obtained by the method for producing the pattern-forming composition of the present invention will be described as the components contained in the pattern-forming composition.
• a pattern-forming composition can be obtained by mixing these components as necessary.
• the pattern-forming 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.
• alkyl oxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, etc.) Ethyl ethoxyacetate, etc.)
• alkyl oxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, etc.) Ethyl ethoxyacetate, etc.)
• 3-alkyloxypropionate alkyl esters eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
• ethers include diethylene glycol dimethyl ether, tetrahydrofuran, 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, and propylene glycol.
• Suitable examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, and propylene glycol monopropyl ether acetate.
• 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 mixed solvent to be mixed is preferable.
• the combined use of dimethyl sulfoxide and ⁇ -butyrolactone is particularly preferred.
• a combination of N-methyl-2-pyrrolidone and ethyl lactate, N-methyl-2-pyrrolidone and ethyl lactate, diacetone alcohol and ethyl lactate, cyclopentanone and ⁇ -butyrolactone is also preferable.
• the solvent content is preferably such that the total solid content concentration of the pattern-forming composition is 5 to 80% by mass, and more preferably 5 to 75% by mass. It is preferable that the amount is 10 to 70% by mass, more preferably 40 to 70% by mass, and even more preferably 40 to 70% by mass.
• the solvent content may be adjusted according to the desired thickness of the coating film and the coating method.
• the solvent may be contained in only one kind, or may be contained in two or more kinds. When two or more kinds of solvents are contained, the total is preferably in the above range.
• the pattern-forming composition preferably contains a photosensitive agent.
• a photosensitive agent a photopolymerization initiator is preferable.
• the pattern-forming composition preferably contains a photopolymerization initiator as the photosensitive agent.
• the photopolymerization initiator is preferably a photoradical polymerization initiator.
• the photoradical polymerization initiator is not particularly limited and may be appropriately selected from known photoradical 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 the oxime compound described later is preferable.
• 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 the range of about 300 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 as the photoradical polymerization initiator.
• 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.
• Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azido compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. Can be mentioned.
• the description in paragraphs 0165 to 0182 of JP-A-2016-027357 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.
• 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 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.
• IRGACURE 184 (IRGACURE is a registered trademark)
• DAROCUR 1173 As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF) can be used.
• aminoacetophenone-based initiator commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.
• the compound described in JP-A-2009-191179 in which the absorption maximum wavelength is matched with a wavelength light source such as 365 nm or 405 nm, can also be used.
• acylphosphine-based initiator examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) can be used.
• metallocene compound examples include IRGACURE-784 and IRGACURE-784EG (both manufactured by BASF).
• 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.
• the compound described in JP-A-2001-233842 the compound described in JP-A-2000-080068, and the compound described in JP-A-2006-342166 can be used.
• 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-phenylpropan-1-one and the like.
• an oxime compound (oxime-based photopolymerization 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 manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.
• ADEKA ARCULDS NCI-831 and ADEKA ARCULDS NCI-930 manufactured by ADEKA Corporation
• DFI-091 manufactured by Daito Chemix Co., Ltd.
• 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.
• 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 an oxime compound include the compounds described in International Publication No. 2013/083505.
• an oxime compound having a fluorine atom includes 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 thereof include the compound (C-3) described in paragraph 0101 of Japanese Patent Publication No. 164471.
• Examples of the most preferable oxime compound include 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.
• 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, an oxime compound, a triarylimidazole dimer, and a benzophenone compound is more preferable, a metallocene compound or an oxime compound is further preferable, and an oxime compound is further preferable. Is even more 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).
• -Aromatic ketones such as -2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanol-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.
• R I01 is a group represented by formula (II), the same as R I00
• the groups, R I02 to R I 04, are independently alkyls having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, or halogens, respectively.
• R I05 to R I07 are the same as R I 02 to R I 04 of the above formula (I).
• the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469 can also be used.
• 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 pattern-forming composition. 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.
• the pattern-forming composition contains a photoacid generator as a photosensitive agent.
• a photoacid generator for example, acid is generated in the exposed part of the photosensitive film, the solubility of the exposed part in the developing solution (for example, an alkaline aqueous solution) is increased, and the exposed part is removed by the developing solution.
• a positive pattern can be obtained.
• the pattern-forming composition contains a photoacid generator and a cross-linking agent other than the radical cross-linking agent described later, for example, the cross-linking reaction of the cross-linking agent is promoted by the acid generated in the exposed portion. It is also possible to make the exposed portion more difficult to be removed by the developing solution than the non-exposed portion. According to such an embodiment, a negative pattern can be obtained.
• the photoacid generator is not particularly limited as long as it generates an acid by exposure, but is an onium salt compound such as a quinonediazide compound, a diazonium salt, a phosphonium salt, a sulfonium salt, or an iodonium salt, an imide sulfonate, and an oxime.
• onium salt compound such as a quinonediazide compound, a diazonium salt, a phosphonium salt, a sulfonium salt, or an iodonium salt, an imide sulfonate, and an oxime.
• examples thereof include sulfonate compounds such as sulfonate, diazodisulfone, disulfone, and o-nitrobenzylsulfonate.
• the quinone-diazide compound includes a polyhydroxy compound in which quinone-diazide sulfonic acid is ester-bonded, a polyamino compound in which quinone-diazide sulfonic acid is conjugated with a sulfonamide, and a polyhydroxypolyamino compound in which quinone-diazide sulfonic acid is ester-bonded and a sulfonamide bond.
• Examples include those bonded by at least one of the above. In the present invention, for example, it is preferable that 50 mol% or more of all the functional groups of these polyhydroxy compounds and polyamino compounds are substituted with quinonediazide.
• the quinone diazide either a 5-naphthoquinone diazidosulfonyl group or a 4-naphthoquinone diazidosulfonyl group is preferably used.
• the 4-naphthoquinone diazidosulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure.
• the 5-naphthoquinone diazidosulfonyl ester compound has absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure.
• a naphthoquinone diazidosulfonyl ester compound having a 4-naphthoquinone diazidosulfonyl group and a 5-naphthoquinone diazidosulfonyl group may be contained in the same molecule, or a 4-naphthoquinone diazidosulfonyl ester compound and a 5-naphthoquinone diazidosulfonyl ester compound may be contained. It may be contained.
• the naphthoquinone diazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxy group and a quinone diazido sulfonic acid compound, and can be synthesized by a known method. By using these naphthoquinone diazide compounds, the resolution, sensitivity, and residual film ratio are further improved.
• Examples of the naphthoquinone diazide compound include 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid, and salts or ester compounds of these compounds. Be done.
• Examples of the onium salt compound or the sulfonate compound include the compounds described in paragraphs 0064 to 0122 of JP-A-2008-013646.
• the photoacid generator is also preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as “oxime sulfonate compound”).
• 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).
• X 3 is an alkyl group, an alkoxyl group, or a halogen atom. If X 3 there are a plurality, each be the same or may be different. Alkyl group and an alkoxyl group represented by X 3 may have a substituent.
• the halogen atom in the X 3, 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, a plurality of X 3 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 alkoxyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms, and carbon. It is preferably an alkoxyl 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 alkoxyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms or an alkoxyl halide having 1 to 5 carbon atoms.
• 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 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 preferably numbers 4 to 30
• R s1 preferably 1 to 30 carbon atoms
• aryl group preferably 6 to 30 carbon atoms
• heteroaryl group preferably numbers 4 to 30
• T may have a substituent T.
• 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 substituent T.
• 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 alkoxyl 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.
• R u5 to R u7 each independently represent an alkyl group or an aryl group.
• Ru1 to Ru4 are independently hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxyl group, amino group, alkoxycarbonyl group and alkylcarbonyl group, respectively. , Arylcarbonyl group, amide group, sulfo group, cyano group or aryl group. 2 in turn, each may be bonded to each other to form a ring of the R u1 ⁇ R u4. At this time, the ring may be condensed to form a fused ring together with the benzene ring.
• R u1 ⁇ R u4 a hydrogen atom, preferably a halogen atom or an alkyl group, also aspects to form the at least two aryl groups bonded to each other of R u1 ⁇ R u4 preferred.
• 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.
• b-9, b-16, b-31, and b-33 are preferable.
• a commercially available product may be used as the photoacid generator.
• Commercially available products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-376, WPAG-370, WPAG-443, WPAG-469, WPAG-638, and WPAG-690 (any of which).
• Fujifilm Wako Pure Chemical Industries, Ltd. Omnicat 250, Omnicat 270 (all manufactured by IGM Resins BV), Irgacure 250, Irgacure 270, Irgacure 290 (all manufactured by BASF), MBZ-101 (all manufactured by BASF). (Made by Midori Chemical Industries, Ltd.) and the like.
• an organic halogenated compound can also be applied.
• 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, JP-A-55-3207, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62- 212401, JP-A-63-70243, JP-A-63-298339, M.D. P.
• S-triazine compounds S-triazine compounds
• an organic borate compound can also be applied.
• the organic borate compound include JP-A-62-143044, JP-A-62-150242, JP-A-9-188685, JP-A-9-188686, JP-A-9-188710, and JP-A-2000. -131837, JP-A-2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, etc., and Kunz, Martin "Rad Tech'98. Proceeding Compound 19-22, 1998, Chicago", etc.
• Japanese Patent Laid-Open No. 6-175553 Organic Boron Iodonium Complex
• Japanese Patent Application Laid-Open No. 9-188710 Organic Boron Phosphorium Complex
• JP-A-7-128785 JP-A.
• Specific examples thereof include organic boron transition metal coordination complexes of JP-A-7-140589, JP-A-7-306527, and JP-A-7-292014.
• a disulfone compound can also be applied as a photoacid generator.
• examples of the disulfone compound 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, Phosphonium salts described in 055 and 4,069,056, European Patents 104 and 143, US Patents 339,049, 410 and 201, JP-A-2. -150848, Iodonium salt described in JP-A-2-296514, European Patent Nos.
• onium salts examples include onium salts represented by the following general formulas (RI-I) to (RI-III).
• Ar11 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 1 to 12 carbon atoms.
• Z11 - represents a monovalent anion, a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, surface stability
• Perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion are preferable.
• Ar21 and Ar22 each represent an aryl group having 20 or less carbon atoms which may independently have 1 to 6 substituents, and a preferable substituent is an alkyl group having 1 to 12 carbon atoms.
• Alkylamino group with 1 to 12 carbon atoms dialkylamino group with 1 to 12 carbon atoms, alkylamide group or arylamide group with 1 to 12 carbon atoms, carbonyl group, carboxyl group, cyano group, sulfonyl group, 1 to 12 carbon atoms
• Examples thereof include a thioalkyl group of 1 to 12 and a thioaryl group having 1 to 12 carbon atoms.
• Z21 - represents a monovalent anion, a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, stability, reaction From the viewpoint of sex, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion and carboxylate ion are preferable.
• R31, R32, and R33 each represent an aryl group or an alkyl group having 20 or less carbon atoms, an alkenyl group, and an alkynyl group, which may independently have 1 to 6 substituents, and are preferable. From the viewpoint of reactivity and stability, an aryl group is desirable.
• Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 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 a 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.
• Z31 - represents a monovalent anion, a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, stability, reaction From the viewpoint of sex, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion and carboxylate ion are preferable.
• 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 pattern-forming composition. It is more preferably 2 to 15% by mass. Only one type of photoacid generator may be contained, or two or more types may be contained. When two or more photoacid generators are contained, the total is preferably in the above range.
• the pattern-forming composition may contain a photobase generator as the photosensitive agent.
• a photobase generator as the photosensitive agent.
• the cross-linking reaction of the cross-linking agent is promoted by promoting the cyclization of the specific resin by the base generated in the exposed portion. It is also possible to make the exposed portion more difficult to be removed by the developing solution than the non-exposed portion due to such an action. According to such an aspect, a negative type relief pattern can be obtained.
• the photobase generator is not particularly limited as long as it generates a base by exposure, and known ones can be used.
• M. Shirai, and M. Tsunooka Prog. Polym. Sci. , 21, 1 (1996); Masahiro Kakuoka, Polymer Processing, 46, 2 (1997); C.I. Kutal, Code. Chem. Rev. , 211,353 (2001); Y. Kaneko, A. Sarker, and D. Neckers, Chem. Mother. , 11, 170 (1999); H. Tachi, M. et al. Shirai, and M. Tsunooka, J.M. Photopolym. Sci. Technol. , 13, 153 (2000); Winkle, and K. Graziano, J.M.
• Ionic compounds whose base components are neutralized by forming salts and nonionic compounds whose base components are latent by urethane bonds or oxime bonds such as carbamate derivatives, oxime ester derivatives, and acyl compounds.
• carbamate derivatives, amide derivatives, imide derivatives, ⁇ -cobalt complexes, imidazole derivatives, cinnamic acid amide derivatives, oxime derivatives and the like are more preferable examples of the photobase generator.
• the basic substance generated from the photobase generator is not particularly limited, and examples thereof include compounds having an amino group, particularly monoamines, polyamines such as diamines, and amidines. From the viewpoint of the imidization rate, it is preferable that the basic substance has a large pKa in DMSO (dimethyl sulfoxide) of the conjugate acid.
• the pKa is preferably 1 or more, and more preferably 3 or more.
• the upper limit of the above pKa is not particularly limited, but is preferably 20 or less.
• pKa represents the logarithm of the reciprocal of the first dissociation constant of acid
• pKa represents the logarithm of the reciprocal of the first dissociation constant of acid
• the photobase generator is preferably a photobase generator that does not contain a salt in the structure, and the nitrogen atom of the base portion generated in the photobase generator is preferable. It is preferable that there is no charge on the top.
• the photobase generator it is preferable that the generated base is latent using a covalent bond, and the mechanism of base generation is such that the covalent bond between the nitrogen atom of the generated base portion and the adjacent atom is cleaved. It is preferable that the base is generated.
• the photobase generator does not contain a salt in the structure, the photobase generator can be neutralized, so that the solvent solubility is better and the pot life is improved.
• the amine generated from the photobase generator used in the present invention is preferably a primary amine or a secondary amine.
• the photobase generator is preferably a photobase generator containing a salt in the structure.
• the base generated as described above is latent using a covalent bond, and the generated base has an amide bond, a carbamate bond, and an oxime bond. It is preferably latent using.
• the photobase generator according to the present invention include a photobase generator having a cinnamon acid amide structure as disclosed in JP-A-2009-080452 and International Publication No. 2009/123122, JP-A-2006-189591.
• Examples thereof include a photobase generator having an oxime structure, but the present invention is not limited to these, and other known photobase generator structures can be used.
• the photobase generator the compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 of JP2012-093746, and the compounds described in paragraphs 0022 to 0069 of JP2013-194205.
• Examples thereof include the compounds described in paragraphs 0026 to 0074 of JP2013-204319A, and the compounds described in paragraph number 0052 of International Publication No. 2010/064631.
• a commercially available product may be used as the photobase generator.
• Commercially available products include WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-207, WPBG-018, WPGB-015, WPBG-041, WPGB-172, WPGB-174, WPBG. -166, WPGB-158, WPGB-025, WPGB-168, WPGB-167, WPBG-082 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), A2502, B5085, N0528, N1052, O0396, O0447, O0448 ( (Made by Tokyo Chemical Industry Co., Ltd.) and the like.
• 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 pattern-forming composition. It is more preferably 2 to 15% by mass. Only one type of photobase generator may be contained, or two or more types may be contained. When two or more photobase generators are contained, the total is preferably in the above range.
• the pattern-forming composition 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. By adding the thermal radical polymerization initiator, the polymerization reaction of the resin and the cross-linking agent can be promoted in the heating step for obtaining the cured product, so that the solvent resistance can be further improved.
• thermal radical polymerization initiator examples include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.
• 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 pattern-forming composition. More preferably, it is 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 pattern-forming composition may contain a thermoacid generator.
• the thermoacid generator generates an acid by heating and promotes a cross-linking reaction of at least one compound selected from a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxetane compound and a benzoxazine compound. It has the effect of making it.
• the thermal decomposition start temperature of the thermal acid generator is preferably 50 ° C. to 270 ° C., more preferably 50 ° C. to 250 ° C. Further, no acid is generated during drying (pre-baking: about 70 to 140 ° C.) after applying the pattern-forming composition to the substrate, and final heating (cure: about 100 to 400) after patterning in subsequent exposure and development. It is preferable to select an agent that generates an acid at (° C.)) as the thermal acid generator because it can suppress a decrease in sensitivity during development.
• the thermal decomposition start temperature is determined as the peak temperature of the exothermic peak, which is the lowest temperature when the thermal acid generator is heated to 500 ° C. at 5 ° C./min in a pressure-resistant capsule. Examples of the device used for measuring the thermal decomposition start temperature include Q2000 (manufactured by TA Instruments).
• the acid generated from the thermal acid generator is preferably a strong acid, for example, aryl sulfonic acid such as p-toluene sulfonic acid and benzene sulfonic acid, alkyl sulfonic acid such as methane sulfonic acid, ethane sulfonic acid and butane sulfonic acid, or trifluoromethane.
• aryl sulfonic acid such as p-toluene sulfonic acid and benzene sulfonic acid
• alkyl sulfonic acid such as methane sulfonic acid, ethane sulfonic acid and butane sulfonic acid
• haloalkyl sulfonic acid such as sulfonic acid is preferable.
• thermoacid generator include those described in paragraph 0055 of JP2013-072935.
• those that generate an alkyl sulfonic acid having 1 to 4 carbon atoms or a haloalkyl sulfonic acid having 1 to 4 carbon atoms are more preferable from the viewpoint that there is little residue in the organic film and it is difficult to deteriorate the physical properties of the organic film.
• thermoacid generator the compound described in paragraph 0059 of JP2013-167742A is also preferable as the thermoacid generator.
• the content of the thermoacid generator is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more with respect to 100 parts by mass of the specific resin.
• the content of the thermoacid generator is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more with respect to 100 parts by mass of the specific resin.
• the pattern-forming composition may further contain an onium salt.
• an onium salt when the pattern-forming composition contains a polyimide precursor or a polybenzoxazole precursor as the specific resin, it is preferable to contain an onium salt.
• the type of onium salt and the like are not particularly specified, but ammonium salt, iminium salt, sulfonium salt, iodonium salt or phosphonium salt are preferably mentioned.
• an ammonium salt or an iminium salt is preferable from the viewpoint of high thermal stability, and a sulfonium salt, an iodonium salt or a phosphonium salt is preferable from the viewpoint of compatibility with a polymer.
• the onium salt is a salt of a cation and an anion having an onium structure, and the cation and the anion may or may not be bonded via a covalent bond. .. That is, the onium salt may be an intramolecular salt having a cation part and an anion part in the same molecular structure, or a cation molecule and an anion molecule, which are different molecules, are ionically bonded. It may be an intermolecular salt, but it is preferably an intermolecular salt. Further, in the pattern-forming composition, the cation portion or the cation molecule and the anion portion or the anion molecule may be bonded or dissociated by an ionic bond.
• an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation is preferable, and at least one cation selected from the group consisting of a tetraalkylammonium cation, a sulfonium cation and an iodonium cation is more preferable.
• the onium salt used in the present invention may be a thermal base generator described later.
• the thermal base generator refers to a compound that generates a base by heating, and examples thereof include a compound that generates a base when heated to 40 ° C. or higher.
• Examples of the onium salt include the onium salt described in paragraphs 0122 to 0138 of International Publication No. 2018/043262.
• onium salts used in the field of polyimide precursors can be used without particular limitation.
• the content of the onium salt is preferably 0.1 to 50% by mass with respect to the total solid content of the pattern-forming composition.
• the lower limit is more preferably 0.5% by mass or more, further preferably 0.85% by mass or more, and even more preferably 1% by mass or more.
• the upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less, further preferably 10% by mass or less, 5% by mass or less, or 4% by mass or less.
• the onium salt one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.
• the pattern-forming composition may further contain a thermal base generator.
• a thermal base generator when the pattern-forming composition contains a polyimide precursor or a polybenzoxazole precursor as the specific resin, it is preferable to include a thermal base generator.
• the other thermobase generator may be a compound corresponding to the above-mentioned onium salt, or may be a thermobase generator other than the above-mentioned onium salt.
• the thermobase generator other than the above-mentioned onium salt include nonionic thermobase generators.
• the nonionic thermal base generator include compounds represented by the formula (B1) or the formula (B2).
• 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 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, still more preferably 3 to 12). 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, still more preferably 3 to 12
• 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 carbon atoms). ⁇ 10 is more preferable), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, 7 to 19 carbon atoms are more preferable).
• 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).
• 18 is more preferred, 3 to 12 are more preferred), aryloxy groups (6 to 22 carbon atoms are preferred, 6 to 18 are more preferred, 6 to 12 are even more preferred), or arylalkyloxy groups (7 to 12 carbon atoms are preferred).
• 23 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable).
• a cycloalkyl group (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferable.
• 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 has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms) and 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 preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12), 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 have the same meanings as 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 carbon atoms), and 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.
• the molecular weight of the nonionic thermal 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.
• thermo base generators or specific examples of thermal base generators other than the above-mentioned onium salts include the following compounds.
• the content of the other thermal base generator is preferably 0.1 to 50% by mass with respect to the total solid content of the pattern-forming composition.
• the lower limit is more preferably 0.5% by mass or more, further preferably 1% by mass or more.
• the upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less.
• the thermal base generator one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.
• the pattern-forming composition preferably contains a cross-linking agent.
• the cross-linking agent include radical cross-linking agents and other cross-linking agents.
• the pattern-forming composition preferably further 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.
• 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 and a (meth) acryloyl group.
• the (meth) acryloyl group is preferable as the group containing the ethylenically unsaturated bond, and the (meth) acryloyl group is more preferable from the viewpoint of reactivity.
• the radical cross-linking agent may be a compound having one or more ethylenically unsaturated bonds, but is more preferably a compound having two or more ethylenically unsaturated bonds.
• the compound having two ethylenically unsaturated bonds is preferably a compound having two groups containing the ethylenically unsaturated bond.
• the pattern-forming composition preferably contains a compound having three or more ethylenically unsaturated bonds as a radical cross-linking agent.
• the compound having 3 or more ethylenically unsaturated bonds a compound having 3 to 15 ethylenically unsaturated bonds is preferable, and a compound having 3 to 10 ethylenically unsaturated bonds is more preferable, and 3 to 6 compounds are more preferable.
• the compound having is more preferable.
• the compound having 3 or more ethylenically unsaturated bonds is preferably a compound having 3 or more groups containing the ethylenically unsaturated bond, and more preferably a compound having 3 to 15 ethylenically unsaturated bonds.
• a compound having 3 to 10 is more preferable, and a compound having 3 to 6 is particularly preferable.
• the pattern-forming composition contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. ..
• 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.
• a compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylated, is described in JP-A-48-041708, JP-A-50-006034, and JP-A-51-0379193.
• Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with acids, 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) Chemicals (manufactured by Kayaku 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 40 mgKOH / g, and particularly preferably 5 to 30 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 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 is measured according to the description of JIS K 0070: 1992.
• bifunctional methacrylate or acrylate as the pattern-forming composition.
• Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, and polytetraethylene.
• Glycoglycyl diacrylate 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 adduct diacrylate of bisphenol A, EO adux glycol dimethacrylate of bisphenol A, PO adduct diacrylate of bisphenol A, PO of bisphenol A Additives dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, other bifunctional acrylates having a ure
• a monofunctional radical cross-linking agent can be preferably used as the radical cross-linking agent.
• 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).
• N-vinyl compounds such as acrylic acid derivatives, N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allylglycidyl ether, diallyl phthalate and triallyl trimellitate 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 content thereof is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the pattern-forming composition.
• 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 radical cross-linking agent may be used alone or in combination of two or more. When two or more kinds are used in combination, the total amount is preferably in the above range.
• the pattern-forming composition preferably 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 exposed to the above-mentioned photosensitive agent to form a pattern with another compound in the pattern-forming composition or a reaction product thereof.
• a compound having a plurality of groups in the molecule that promotes a reaction for forming a covalent bond is preferable, and a reaction for forming a covalent bond with another compound in the pattern-forming composition or a reaction product thereof.
• a compound having a plurality of groups in the molecule 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 which is a photosensitizer in the exposure step.
• a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is preferable, and at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is preferable.
• a compound having a structure 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 a methylol group or an alkoxymethyl group.
• examples thereof include compounds having a substituted structure.
• 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 pattern-forming composition 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 preferable to contain at least one compound selected from the group consisting of.
• 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 uryl.
• Glycol-uryl-based cross-linking agent 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, monodiethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propy
• 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, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxy Examples thereof include methylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine and the like.
• the 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 hydroxymethylphenyl hydroxymethylbenzoate.
• 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 pattern-forming composition 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.
• 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 pattern-forming composition.
• 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.
• Examples include, but are not limited to, the contained silicone.
• 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.
• the Aron Oxetane series manufactured by Toagosei Co., Ltd. (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, and these can be used alone. Alternatively, two or more types may be mixed.
• 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 during curing, and heat shrinkage is further reduced to suppress the occurrence of warpage, which is preferable.
• benzoxazine compound are BA type benzoxazine, Bm type benzoxazine, Pd type benzoxazine, FA type benzoxazine (above, trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), poly.
• examples thereof include a benzoxazine adduct of a hydroxystyrene resin and a phenol novolac type dihydrobenzoxazine compound. 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 0.5 by mass, based on the total solid content of the pattern-forming composition. It is more preferably 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 pattern-forming composition further comprises at least one compound selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure. It is preferable to include it.
• the sulfonamide structure is a structure represented by the following formula (S-1).
• R represents a hydrogen atom or an organic group
• R may be bonded to another structure to form a ring structure
• * may independently form a binding site with another structure. show.
• the R is preferably the same group as R 2 in the following formula (S-2).
• the compound having a sulfonamide structure may be a compound having two or more sulfonamide structures, but is preferably a compound having one sulfonamide structure.
• the compound having a sulfonamide structure is preferably a compound represented by the following formula (S-2).
• R 1 , R 2 and R 3 each independently represent a hydrogen atom or a monovalent organic group, and two or more of R 1 , R 2 and R 3 are bonded to each other. It may form a ring structure. It is preferable that R 1 , R 2 and R 3 are independently monovalent organic groups.
• R 1 , R 2 and R 3 include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, and a carboxy group.
• examples thereof include a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a group in which two or more of these are combined.
• the alkyl group an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.
• alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, a 2-ethylhexyl group and the like.
• a cycloalkyl group having 5 to 10 carbon atoms is preferable, and a cycloalkyl group having 6 to 10 carbon atoms is more preferable.
• examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.
• an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms is more preferable.
• Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group and the like.
• As the alkoxysilyl group an alkoxysilyl group having 1 to 10 carbon atoms is preferable, and an alkoxysilyl group having 1 to 4 carbon atoms is more preferable.
• Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group and a butoxysilyl group.
• aryl group an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 12 carbon atoms is more preferable.
• the aryl group may have a substituent such as an alkyl group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group and the like.
• heterocyclic group examples include a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring and a pyrimididin ring.
• R 1 is an aryl group and R 2 and R 3 are independently hydrogen atoms or alkyl groups are preferable.
• Examples of compounds having a sulfonamide structure include benzenesulfonamide, dimethylbenzenesulfonamide, N-butylbenzenesulfonamide, sulfanylamide, o-toluenesulfonamide, p-toluenesulfonamide, hydroxynaphthalenesulfonamide, naphthalene-1.
• the thiourea structure is a structure represented by the following formula (T-1).
• R 4 and R 5 each independently represent a hydrogen atom or a monovalent organic group, and R 4 and R 5 may be bonded to form a ring structure, where R 4 is. * it is may form a ring structure and other structures that bind, R 5 may form a ring structure and other structures that bind *, * is independently other Represents the site of connection with the structure of.
• R 4 and R 5 are independently hydrogen atoms.
• R 4 and R 5 include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxy group, and a carbonyl group.
• examples thereof include an allyl group, a vinyl group, a heterocyclic group, or a group in which two or more of these are combined.
• the alkyl group an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.
• alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, a 2-ethylhexyl group and the like.
• a cycloalkyl group having 5 to 10 carbon atoms is preferable, and a cycloalkyl group having 6 to 10 carbon atoms is more preferable.
• examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.
• an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms is more preferable.
• Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group and the like.
• As the alkoxysilyl group an alkoxysilyl group having 1 to 10 carbon atoms is preferable, and an alkoxysilyl group having 1 to 4 carbon atoms is more preferable.
• Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group and a butoxysilyl group.
• aryl group an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 12 carbon atoms is more preferable.
• the aryl group may have a substituent such as an alkyl group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group and the like.
• heterocyclic group examples include a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring and a pyrimididin ring.
• the compound having a thiourea structure may be a compound having two or more thiourea structures, but a compound having one thiourea structure is preferable.
• the compound having a thiourea structure is preferably a compound represented by the following formula (T-2).
• R 4 to R 7 each independently represent a hydrogen atom or a monovalent organic group, and at least two of R 4 to R 7 are bonded to each other to form a ring structure. You may.
• R 4 and R 5 have the same meanings as R 4 and R 5 in formula (T-1), a preferable embodiment thereof is also the same.
• R 6 and R 7 are independently monovalent organic groups.
• the preferred embodiment of the monovalent organic group in R 6 and R 7 is the same as the preferred embodiment of the monovalent organic group in R 4 and R 5 in the formula (T-1). ..
• Examples of compounds having a thiourea structure include N-acetylthiourea, N-allyl thiourea, N-allyl-N'-(2-hydroxyethyl) thiourea, 1-adamantyl thiourea, N-benzoylthiourea, N, N'-.
• Diphenylthiourea 1-benzyl-phenylthiourea, 1,3-dibutylthiourea, 1,3-diisopropylthiourea, 1,3-dicyclohexylthiourea, 1- (3- (trimethoxysilyl) propyl) -3-methylthiourea, trimethyl Examples thereof include thiourea, tetramethylthiourea, N, N-diphenylthiourea, ethylenethiourea (2-imidazolinthione), carbimazole, and 1,3-dimethyl-2-thiohydrantin.
• the total content of the compound having a sulfonamide structure and the compound having a thiourea structure is preferably 0.05 to 10% by mass, preferably 0.1 to 5% by mass, based on the total mass of the pattern-forming composition. More preferably, it is more preferably 0.2 to 3% by mass.
• the pattern-forming composition may contain only one compound selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure, or may contain two or more compounds. When only one kind is contained, the content of the compound is preferably in the above range, and when two or more kinds are contained, the total amount thereof is preferably in the above range.
• the pattern-forming composition 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 photosensitive film.
• the migration inhibitor is not particularly limited, but has a heterocyclic ring (pyran ring, furan ring, thiophene ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrazole ring, isooxazole ring, isothiazole ring, tetrazole ring, etc.
• a heterocyclic ring pyran ring, furan ring, thiophene ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrazole ring, isooxazole ring, isothiazole ring, tetrazole ring, etc.
• 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 compound described in paragraph 0052, the compound described in paragraphs 0114, 0116 and 0118 of JP2012-194520A, the compound described in paragraph 0166 of International Publication No. 2015/199219 and the like can be used.
• 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 pattern-forming composition, and is 0. It is more preferably 0.05 to 2.0% by mass, and even 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 pattern-forming composition preferably contains a polymerization inhibitor.
• polymerization inhibitor examples include hydroquinone, o-methoxyphenol, methoxyhydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol (t-butylcatechol), 1, 4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso- N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine tetraacetic acid, 2,6-di-tert-butyl-4 -Methylphenol,
• the content of the polymerization inhibitor is 0.01 to 20.0% by mass, 0.01 to 20.0% by mass, based on the total solid content of the pattern-forming composition. It is preferably ⁇ 5% by mass, more preferably 0.02 to 3% by mass, and even more preferably 0.05 to 2.5% 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 pattern-forming composition preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring, and the like.
• the metal adhesiveness improving agent include a silane coupling agent, an aluminum-based adhesive aid, a titanium-based adhesive aid, a compound having a sulfonamide structure and a compound having a thiourea structure, a phosphoric acid derivative compound, a ⁇ -ketoester compound, an amino compound and the like. And so on.
• 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 include the compounds described in paragraph 0055.
• Et represents an ethyl group.
• 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 compounds described in paragraphs 0046 to 0049 of JP2014-186186A and the sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935 can also be used. ..
• the content of the metal adhesive improving agent is preferably in the range of 0.1 to 30 parts by mass, more preferably 0.5 to 15 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 kinds are used, it is preferable that the total is in the above range.
• the pattern-forming composition 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 adhesiveness improving agent the compounds described in paragraphs 0046 to 0049 of JP2014-186186A and the sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935 can also be used.
• the content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further, with respect to 100 parts by mass of the heterocycle-containing polymer precursor. It is preferably in the range of 0.5 to 5 parts by mass.
• the metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more kinds are used, it is preferable that the total is in the above range.
• the pattern-forming composition is, if necessary, various additives such as a sensitizer, a chain transfer agent, a surfactant, a higher fatty acid derivative, an inorganic particle, and a curing agent, as long as the effects of the present invention can be obtained.
• various additives such as a sensitizer, a chain transfer agent, a surfactant, a higher fatty acid derivative, an inorganic particle, and a curing agent, as long as the effects of the present invention can be obtained.
• Curing catalyst, filler, antioxidant, ultraviolet absorber, anti-aggregation agent and the like can be blended.
• the total blending amount is preferably 3% by mass or less of the solid content of the pattern-forming composition.
• the pattern-forming composition may contain a sensitizer.
• the sensitizer absorbs specific active radiation and becomes an electronically excited state.
• the sensitizer in the electronically excited state comes into contact with the thermal curing accelerator, 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 curing accelerator, 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.
• sensitizer examples include Michler's ketone, 4,4'-bis (diethylamino) benzophenone, 2,5-bis (4'-diethylaminobenzal) cyclopentane, and 2,6-bis (4'-diethylaminobenzal).
• a sensitizing dye may be used as the sensitizer.
• 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.
• the content of the sensitizer is preferably 0.01 to 20% by mass, preferably 0.1 to 20% by mass, based on the total solid content of the pattern-forming composition. It is more preferably 15% by mass, and even more preferably 0.5 to 10% by mass.
• the sensitizer may be used alone or in combination of two or more.
• the pattern-forming composition 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.
• As the chain transfer agent for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is 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 pattern-forming composition, preferably 1 to 10 parts by mass. Parts are more preferable, and 1 to 5 parts by mass are 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.
• a surfactant may be added to the pattern-forming composition from the viewpoint of further improving the coatability.
• various types of surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
• the following surfactants are also preferable.
• the parentheses indicating the repeating unit of the main chain indicate the content (mol%) of each repeating unit
• the parentheses indicating the repeating unit of the side chain indicate the number of repetitions of each repeating unit.
• the surfactant the compound described in paragraphs 0159 to 0165 of International Publication No.
• 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 compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP2010-164965, such as Megafuck RS-101, RS-102, RS-718K manufactured by DIC Corporation. Can be mentioned.
• 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), KP341, KF6001, KF6002 (all manufactured by Shin-Etsu Silicone Co., Ltd.) ), BYK307, BYK323, BYK330 (all manufactured by Big Chemie Co., Ltd.) and the like.
• hydrocarbon-based surfactant examples include Pionin A-76, New Calgen 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.
• organosiloxane polymer KP341 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, based on the total solid content of the pattern-forming composition. It is preferably 0.005 to 1.0% by mass.
• the surfactant may be only one kind or two or more kinds. When there are two or more types of surfactant, the total is preferably in the above range.
• a higher fatty acid derivative such as behenic acid or behenic acid amide is added in order to prevent polymerization inhibition due to oxygen, and the surface of the pattern-forming composition is dried in the process of drying after application. It may be unevenly distributed in.
• 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 pattern-forming composition.
• 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 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 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 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 negative photosensitive resin composition has good storage stability and a good curing pattern can be obtained.
• Specific examples are titanium bis (triethanolamine) diisopropoxiside, titanium di (n-butoxide) bis (2,4-pentanegenate, 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.
• Titanosen 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 (pentangionate), 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) titanosen compound has better chemical resistance. It is preferable from the viewpoint of playing.
• -Pyrrole-1-yl) phenyl) titanium is preferred.
• the blending amount thereof 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 precursor of the cyclized resin. ..
• the blending amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited in the obtained curing pattern, while when it is 10 parts by mass or less, the storage stability of the composition is 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 a phenol compound, a phosphite ester compound, a thioether compound 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. Further, as the antioxidant, the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used. 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.
• 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 represented by the general formula (3).
• R5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms
• R6 represents an alkylene group having 2 or more carbon atoms
• R7 represents a 1- to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms, an O atom, and an N atom
• k represents an integer of 1 to 4.
• the compound represented by the general formula (3) suppresses 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.
• k is more preferably an integer of 2 to 4.
• R7 include 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, a heterocyclic group, and-.
• R7 include 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, a heterocyclic group, and-.
• Examples thereof include O-, -NH-, -NHNH-, and combinations thereof, and may further have a substituent.
• alkyl ether and -NH- from the viewpoint of solubility in a developing solution and metal adhesion, and -NH- is more preferable from the viewpoint of interaction with a resin and metal adhesion due to metal complex formation. preferable.
• Examples of the compound represented by the following 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 less than 0.1 part by mass, it is difficult to obtain the effect of improving the elongation property after reliability and the adhesion to the metal material, and when the addition amount is more than 10 parts by mass, it is due to the interaction with the photosensitizer. , There is a risk of reducing 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 kinds are used, it is preferable that the total amount thereof is within the above range.
• the water content of the pattern-forming composition is preferably less than 5% by mass, more preferably less than 1% by mass, still more preferably less than 0.6% by mass, from the viewpoint of the properties of the coated surface.
• Examples of the method for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container.
• the metal content of the pattern-forming composition 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, from the viewpoint of insulating properties.
• the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are contained, it is preferable that the total of these metals is in the above range.
• a pattern-forming composition is configured in which a raw material having a low metal content is selected as a raw material constituting the pattern-forming composition. Examples thereof include a method of filtering the raw material to be subjected to a filter, a method of lining the inside of the apparatus with polytetrafluoroethylene or the like, and performing distillation under conditions in which contamination is suppressed as much as possible.
• the pattern-forming composition 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. More preferred. 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 pattern-forming composition.
• a multi-layer bottle having the inner wall of the container composed of 6 types and 6 layers of resin and 7 types of resin are used as the storage container. It is also preferable to use a bottle having a layered structure. Examples of such a container include the container described in JP-A-2015-123351.
• the pattern-forming composition is preferably used for forming an interlayer insulating film for the rewiring layer. In addition, it can also be used for forming an insulating film of a semiconductor device, forming a stress buffer film, and the like.
• a resin composition or a comparative composition was produced according to the following production method.
• the types and contents of the specific resin, acid value inhibitor, other inclusions (other components) contained in the obtained resin composition or comparative composition, and the oxidation-reduction potential of the antioxidant will be described later. Listed in the table.
• the redox potential of the antioxidant was measured by the following method. Cyclic voltammetry measurements were performed using the WaveNano potentiometer (Pine Research Instrumentation). The following materials were used as the reference electrode, counter electrode, and working electrode.
• Reference electrode in a freshly prepared solution of 5 mmol / L silver nitrate in anhydrous acetonitrile, including the use of an acetonitrile solution of silver / silver nitrate (0.1 mol / L tetraalkylammonium tetrafluoroborate as electrolyte).
• Silver wire soaked in)
• Counter electrode Platinum wire
• Working electrode Platinum disc (diameter 1.6 mm)
• the oxidation potential of each antioxidant was measured using a solution of each antioxidant in a THF (THF) solution (5 mmol / L).
• THF THF
• As the supporting electrolyte 1 mol / L tetrabutylammonium perchlorate (TBAP) was used.
• Reduction scans were measured with 0.1 mol / L TBAP acetonitrile solution relative to the THF solution (5 mmol / L) of each antioxidant. Typically, 3 cycles (6 divisions) were performed at a sweep rate of 20 mV / sec. The energy level was modified with an offset of 4.7 V to convert to vacuum level.
• a voltamogram was measured for each antioxidant solution in tetrahydrofuran (THF) (THF) (5 mmol / L), and the redox potential was determined as the half-wave potential obtained from the voltamogram. Further, in the table, the description of "-" means that the corresponding component is not contained.
• Example 1 21.2 g of 4,4'-oxydiphthalic acid dianhydride (ODPA), 18.0 g of 2-hydroxyethylmethacrylate (HEMA), 23.9 g of pyridine, 0.10 g of water and 250 ml of diglyme. was mixed and stirred at a temperature of 60 ° C. for 4 hours to produce a diester of ODPA and HEMA. The reaction mixture was then cooled to ⁇ 10 ° C. and 17.0 g of SOCL 2 was added over 60 minutes while keeping the temperature at ⁇ 10 ⁇ 5 ° C.
• ODPA 4,4'-oxydiphthalic acid dianhydride
• HEMA 2-hydroxyethylmethacrylate
• This polymer A-1 had a weight average molecular weight of 26,000.
• the structure of the obtained polymer A-1 is presumed to be the structure represented by the following formula (A-1).
• ODPA 4,4'-oxydiphthalic acid dianhydride
• HEMA 2-hydroxyethyl methacrylate
• the resulting reaction was added to 3 liters of ethyl alcohol to produce a crude polymer.
• the crude polymer was collected by filtration, dissolved in 1.5 liters of tetrahydrofuran, and then 0.3 g of p-methoxyphenol was mixed to obtain a crude polymer solution.
• the resulting crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer and the water-polymer mixture was stirred at a rate of 5000 rpm for 15 minutes.
• the polymer was filtered off again and dried under reduced pressure at 45 ° C. for 3 days to give a powdery resin composition.
• This polymer A-2 had a weight average molecular weight (Mw) of 20,000.
• Mw weight average molecular weight
• Example 3 14.9 g of pyromellitic anhydride, 18.0 g of 2-hydroxyethyl methacrylate (HEMA), 23.9 g of pyridine, 0.10 g of water and 250 ml of diglyme were mixed and mixed at 60 ° C. Stirring at temperature for 4 hours produced a diester of pyromellitic acid anhydride and HEMA. The reaction mixture was then cooled to ⁇ 10 ° C. and 17.0 g of SOCL 2 was added over 60 minutes while keeping the temperature at ⁇ 10 ⁇ 5 ° C.
• HEMA 2-hydroxyethyl methacrylate
• This polymer A-3 had a weight average molecular weight of 21,000.
• the structure of the obtained polymer A-3 is presumed to be the structure represented by the following formula (A-3).
• Example 4 147.1 g of 2,2'-biphthalic anhydride was placed in a 2 liter volume separable flask, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of ⁇ -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. Next, under ice-cooling, a solution prepared by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of ⁇ -butyrolactone was added to the reaction mixture over 40 minutes with stirring.
• DCC dicyclohexylcarbodiimide
• the crude polymer was collected by filtration, dissolved in 1.5 liters of tetrahydrofuran, and then 0.3 g of p-methoxyphenol was mixed to obtain a crude polymer solution.
• the resulting crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer and the water-polymer mixture was stirred at a rate of 5000 rpm for 15 minutes.
• the polymer was filtered off again and dried under reduced pressure at 45 ° C. for 3 days to give a powdery resin composition.
• This polymer A-4 had a weight average molecular weight (Mw) of 20,500.
• Mw weight average molecular weight
• the structure of the obtained polymer A-4 is presumed to be a structure represented by the following formula (A-4).
• Example 5 22.0 g of 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 18.0 g of 2-hydroxyethylmethacrylate (HEMA), 23.9 g of pyridine and 0.10 g of water.
• HEMA 2-hydroxyethylmethacrylate
• 250 ml of digrim was mixed and stirred at a temperature of 60 ° C. for 4 hours to produce a diester of 3,3', 4,4'-benzophenonetetracarboxylic dianhydride and HEMA.
• the reaction mixture was then cooled to ⁇ 10 ° C. and 17.0 g of SOCL 2 was added over 60 minutes while keeping the temperature at ⁇ 10 ⁇ 5 ° C.
• This polymer A-5 had a weight average molecular weight of 22,000.
• the structure of the obtained polymer A-5 is presumed to be the structure represented by the following formula (A-5).
• ODPA 4,4'-oxydiphthalic acid dianhydride
• HEMA 2-hydroxyethylmethacrylate
• This polymer A-6 had a weight average molecular weight of 20,000.
• the structure of the obtained polymer A-6 is presumed to be the structure represented by the following formula (A-6).
• HEMA 2-hydroxyethyl methacrylate
• This polymer A-7 had a weight average molecular weight of 20,000.
• the structure of the obtained polymer A-7 is presumed to be the structure represented by the following formula (A-7).
• Example 8 > 21.2 g of 4,4'-oxydiphthalic acid dianhydride (ODPA), 18.0 g of 2-hydroxyethylmethacrylate (HEMA), 23.9 g of pyridine, 0.10 g of water and 250 ml of diglyme. was mixed and stirred at a temperature of 60 ° C. for 4 hours to produce a diester of ODPA and HEMA. The reaction mixture was then cooled to ⁇ 10 ° C. and 17.0 g of SOCL 2 was added over 60 minutes while keeping the temperature at ⁇ 10 ⁇ 5 ° C.
• ODPA 4,4'-oxydiphthalic acid dianhydride
• HEMA 2-hydroxyethylmethacrylate
• This polymer A-8 had a weight average molecular weight of 25,000.
• the structure of the obtained polymer A-8 is presumed to be the structure represented by the following formula (A-8).
• Example 9 > 21.2 g of 4,4'-oxydiphthalic acid dianhydride (ODPA), 18.0 g of 2-hydroxyethylmethacrylate (HEMA), 23.9 g of pyridine, 0.10 g of water and 250 ml of diglyme. was mixed and stirred at a temperature of 60 ° C. for 4 hours to produce a diester of ODPA and HEMA. The reaction mixture was then cooled to ⁇ 10 ° C. and 17.0 g of SOCL 2 was added over 60 minutes while keeping the temperature at ⁇ 10 ⁇ 5 ° C.
• ODPA 4,4'-oxydiphthalic acid dianhydride
• HEMA 2-hydroxyethylmethacrylate
• This polymer A-9 had a weight average molecular weight of 20,000.
• the structure of the obtained polymer A-9 is presumed to be the structure represented by the following formula (A-9).
• HEMA 2-hydroxyethyl methacrylate
• This polymer A-10 had a weight average molecular weight of 22,000.
• the structure of the obtained polymer A-10 is presumed to be a structure represented by the following formula (A-10).
• Example 11 The powdery resin compositions synthesized in Examples 2 and 4 were mixed in the same amount to obtain a powdery resin composition containing two kinds of resins, an antioxidant and a solvent.
• Example 12 A crude polymer was obtained by the same operation as in Example 8. The crude polymer was dissolved in 380 ml of N-methylpyrrolidone and 0.5 g of p-methoxyphenol and 0.5 g of ascorbic acid were mixed. The resulting solution was added to 3 liters of water to precipitate the polymer and the water-polymer mixture was stirred at a rate of 5000 rpm for 15 minutes. The polymer was filtered off again and dried under reduced pressure at 45 ° C. for 3 days to give a powdery resin composition. This polymer A-8 had a weight average molecular weight of 25,000. The structure of the obtained polymer A-8 is presumed to be the structure represented by the above formula (A-8).
• Example 13 A crude polymer was obtained by the same operation as in Example 2. After dissolving the crude polymer in 1.5 liters of tetrahydrofuran, 0.3 g of p-methoxyphenol and 7.5 g of diethanolamine were mixed to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer and the water-polymer mixture was stirred at a rate of 5000 rpm for 15 minutes. The polymer was filtered off again and dried under reduced pressure at 45 ° C. for 3 days to give a powdery resin composition. This polymer A-2 had a weight average molecular weight (Mw) of 20,000. The structure of the obtained polymer A-2 is presumed to be the structure represented by the above formula (A-2).
• Example 14 The crude polymer was synthesized by the same procedure as in Example 1. The crude polymer was dissolved in 380 ml of tetrahydrofuran and mixed with 0.1 g of 2,6-di-tert-butyl-p-cresol. The resulting solution was added to 3 liters of water to precipitate the polymer and the water-polymer mixture was stirred at a rate of 5000 rpm for 15 minutes. The polymer was filtered off again and dried under reduced pressure at 45 ° C. for 3 days to give a powdery resin composition.
• Example 15 The crude polymer was synthesized by the same procedure as in Example 1. The crude polymer was dissolved in 500 ml of N-methylpyrrolidone and mixed with 0.05 g of p-methoxyphenol. The resulting solution was added to 2 liters of water to precipitate the polymer and the water-polymer mixture was stirred at a rate of 5000 rpm for 15 minutes. The polymer was filtered off again and dried under reduced pressure at 45 ° C. for 3 days to give a powdery comparative composition.
• Example 1 The crude polymer was synthesized by the same procedure as in Example 1. The crude polymer was dissolved in 380 ml of tetrahydrofuran. The resulting solution was added to 3 liters of water to precipitate the polymer and the water-polymer mixture was stirred at a rate of 5000 rpm for 15 minutes. The polymer was filtered off again and dried under reduced pressure at 45 ° C. for 3 days to give a powdery comparative composition.
• Example 2 The crude polymer was synthesized by the same procedure as in Example 1. The crude polymer was dissolved in 380 ml of tetrahydrofuran and mixed with 5.0 g of hydroquinone. The resulting solution was added to 3 liters of water to precipitate the polymer and the water-polymer mixture was stirred at a rate of 5000 rpm for 15 minutes. The polymer was filtered off again and dried under reduced pressure at 45 ° C. for 3 days to give a powdery comparative composition.
• composition of photosensitive resin composition 32 parts by mass of the resin composition or comparative composition prepared in each Example or Comparative Example
• Photoradical polymerization initiator IRGACURE OXE 01 (manufactured by BASF) 1.2 parts by mass Radical polymerizable compound: The following compound (in parentheses) Subscripts represent the number of repetitions) 5.6 parts by mass Polymerization inhibitor: 0.08 parts by mass of p-benzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.)
• Migration inhibitor 0.12 parts by mass of the following compound
• Metal adhesion improver 0.6 parts by mass of the following compound (Et represents an ethyl group)
• Base generator 0.4 parts by mass of the following compound (Et represents an ethyl group)
• Solvent ⁇ -butyrolactone (manufactured by Sanwa Yuka Industry Co., Ltd.) 45 parts by mass and dimethyl sulfoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
• Each photosensitive resin composition was pressure-filtered at a pressure of 0.3 MPa through a filter having a pore width of 0.8 ⁇ m, and then applied onto a silicon wafer by a spin coating method.
• the silicon wafer coated with the photosensitive resin composition layer was dried on a hot plate at 100 ° C. for 5 minutes to form a photosensitive resin composition layer having a uniform film thickness of 10 ⁇ m on the silicon wafer.
• the photosensitive resin composition layer on the silicon wafer was exposed using a stepper (Nikon NSR 2005 i9C).
• the exposure is performed by i-line, and a 1: 1 line-and-space pattern is formed from 5 ⁇ m to 25 ⁇ m in 1 ⁇ m increments at each exposure energy of 200, 300, 400, 500, 600, 700, 800 mJ / cm 2 at a wavelength of 365 nm.
• the resin layer was obtained by exposure using the photomask.
• the resin layer obtained above was negatively developed with cyclopentanone for 60 seconds and rinsed with propylene glycol monomethyl ether acetate (PGMEA).
• PMEA propylene glycol monomethyl ether acetate
• the smallest line width was used as the index value. Evaluation was performed according to the following evaluation criteria using the above index values, and the evaluation results are described in the "Pattern formation" column of the table. The smaller the line width of the obtained resin layer (pattern), the larger the difference in solubility between the light-irradiated portion and the light-non-irradiated portion in the developing solution, which is a preferable result.
• the measurement limit is 5 ⁇ m.
• the resin composition of the present invention is excellent in filterability when redissolved in a solvent and pattern formation property when a pattern-forming composition is prepared by redissolution.
• the comparative composition according to Comparative Example 1 does not contain an antioxidant. It can be seen that in such a composition, the filterability is lowered after being dissolved in the solvent.
• the comparative composition according to Comparative Example 2 contains an antioxidant in an amount exceeding 10,000 mass ppm with respect to the content of the specific resin. It can be seen that when a pattern-forming composition (photosensitive resin composition) is prepared using such a composition, the pattern-forming property is lowered.
• Example 101 The photosensitive 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, and dried at 100 ° C. for 4 minutes. After forming a curable resin composition layer having a film thickness of 20 ⁇ m, 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 3 hours 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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