WO2018003725A1 - Negative photosensitive resin composition, cured film, method for producing cured film, semiconductor device, method for producing laminate, method for producing semiconductor device, and polyimide precursor - Google Patents
Negative photosensitive resin composition, cured film, method for producing cured film, semiconductor device, method for producing laminate, method for producing semiconductor device, and polyimide precursor Download PDFInfo
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- WO2018003725A1 WO2018003725A1 PCT/JP2017/023341 JP2017023341W WO2018003725A1 WO 2018003725 A1 WO2018003725 A1 WO 2018003725A1 JP 2017023341 W JP2017023341 W JP 2017023341W WO 2018003725 A1 WO2018003725 A1 WO 2018003725A1
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0387—Polyamides or polyimides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/065—Polyamides; Polyesteramides; Polyimides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
Definitions
- the present invention relates to a negative photosensitive resin composition, a cured film, a method for producing a cured film, a semiconductor device, a method for producing a laminate, a method for producing a semiconductor device, and a polyimide precursor.
- Thermosetting resins that are cured by cyclization are used for insulating layers of semiconductor devices and the like because they are excellent in heat resistance and insulation. Moreover, since polyimide resin has low solubility in a solvent, it is used in the state of a precursor (polyimide precursor) before cyclization reaction, applied to a substrate, etc., and then heated to cyclize the polyimide precursor. A cured film is also formed.
- Patent Document 1 discloses (A) a substituent having a repeating unit represented by the general formula (1) in the main chain and a photopolymerizable carbon-carbon double bond at both molecular ends.
- a polyimide precursor having an actinic functional group having a structure modified with an aminobenzene or a trimellitic acid derivative (B) a photo-assisting agent having a photopolymerizable functional group, and (C) N-aryl
- a resin composition containing a photopolymerization initiator containing an ⁇ -amino acid and a thioxanthone, wherein the content of the photopolymerization initiator is 7 to 15 parts by mass with respect to 100 parts by mass of the polyimide precursor Part of the photosensitive resin composition is described.
- R 1 is a tetravalent organic group
- R 2 is a divalent organic group.
- Patent Document 1 Since Patent Document 1 has a polyamic acid structure, it is susceptible to hydrolysis by water. Therefore, the stability over time is low, and furthermore, the synthesized resin cannot be purified in an aqueous system, so that it is difficult to apply it in semiconductor applications that require high quality.
- an object of the present invention is to provide a negative photosensitive resin composition excellent in resolution. Moreover, it is providing the cured film using said negative photosensitive resin composition, the manufacturing method of a cured film, a semiconductor device, the manufacturing method of a laminated body, the manufacturing method of a semiconductor device, and a polyimide precursor.
- the present inventors can improve the resolution by providing a polymerizable group at the end of the polyimide precursor and setting the weight average molecular weight of the polyimide precursor to 50000 or less.
- the present invention has been completed. Accordingly, the present invention provides the following.
- ⁇ 1> includes a polyimide precursor, a photopolymerization initiator, and a solvent,
- the polyimide precursor has a repeating unit represented by the formula (1), has a structure represented by the formula (2) at at least one end, and has a weight average molecular weight of 50000 or less, and is a negative photosensitive.
- Resin composition In formula (1), X represents a divalent organic group, Y represents a tetravalent organic group, and R 1 and R 2 are each independently a non-polymerizable organic group; (A) l -L 1- * (2) In the formula (2), A represents a polymerizable group, L 1 represents a single bond or an l + 1 valent organic group, l represents an integer of 1 to 10, and * represents a bonding site with another site. ⁇ 2> The negative photosensitive resin composition according to ⁇ 1>, wherein l in formula (2) is an integer of 2 to 5.
- ⁇ 6> The negative photosensitive resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the polyimide precursor has a weight average molecular weight of 5000 or more.
- ⁇ 7> The negative photosensitive resin composition according to any one of ⁇ 1> to ⁇ 6>, further comprising a polyfunctional radical polymerizable monomer.
- ⁇ 8> The negative photosensitive resin composition according to any one of ⁇ 1> to ⁇ 7>, further comprising a thermal base generator.
- ⁇ 9> The negative photosensitive resin composition according to any one of ⁇ 1> to ⁇ 8>, wherein the photopolymerization initiator is at least one selected from an oxime compound and a metallocene compound.
- ⁇ 10> The negative photosensitive resin composition according to any one of ⁇ 1> to ⁇ 9>, which is used for forming an interlayer insulating film for a rewiring layer.
- ⁇ 11> A cured film obtained by curing the negative photosensitive resin composition according to any one of ⁇ 1> to ⁇ 10>.
- ⁇ 12> The cured film according to ⁇ 11>, wherein the film thickness is 1 to 30 ⁇ m.
- ⁇ 13> a photosensitive resin composition layer forming step in which the negative photosensitive resin composition according to any one of ⁇ 1> to ⁇ 10> is applied to a substrate to form a layer; An exposure step of exposing the negative photosensitive resin composition layer; A development processing step of performing development processing on the exposed photosensitive resin composition layer; The manufacturing method of the cured film which has this.
- ⁇ 15> A semiconductor device having the cured film according to ⁇ 11> or ⁇ 12>.
- ⁇ 16> A method for producing a laminate including the method for producing a cured film according to ⁇ 13> or ⁇ 14>.
- ⁇ 17> A method for producing a semiconductor device, comprising the method for producing a cured film according to ⁇ 13> or ⁇ 14>.
- X represents a divalent organic group
- Y represents a tetravalent organic group
- R 1 and R 2 are each independently a non-polymerizable organic group;
- A represents a polymerizable group
- L 1 represents a single bond or an l + 1 valent organic group
- l represents an integer of 1 to 10
- * represents a bonding site with another site.
- a negative photosensitive resin composition excellent in resolution.
- a cured film, a cured film manufacturing method, a semiconductor device, a laminate manufacturing method, a semiconductor device manufacturing method, and a polyimide precursor using the negative photosensitive resin composition.
- the description of the components in the present invention described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.
- the notation which does not describe substitution and unsubstituted includes the group which has a substituent with the group which does not have a substituent.
- the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
- exposure includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams.
- the light used for exposure generally includes active rays or radiation such as an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
- active rays or radiation such as an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
- a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
- “(meth) acrylate” represents both and / or “acrylate” and “methacrylate”
- (meth) acryl” represents both “acryl” and “methacryl”
- (Meth) acryloyl” represents either or both of “acryloyl” and “methacryloyl”.
- solid content concentration is the mass percentage of the other component except a solvent with respect to the gross mass of a composition. Moreover, solid content concentration says the density
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene conversion values according to gel permeation chromatography (GPC) measurement unless otherwise specified.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) are HLC-8220 (manufactured by Tosoh Corporation), and guard columns TSK guard column Super AW-H and TSK Super AWM-H (Tosoh Corporation) ))).
- the eluent was measured using N-methyl-2-pyrrolidone (NMP) unless otherwise stated.
- NMP N-methyl-2-pyrrolidone
- RI differential refractive index
- the negative photosensitive resin composition of the present invention includes a polyimide precursor, a photopolymerization initiator, and a solvent. It has a structure represented by Formula (2) mentioned later at least at one terminal, and has a weight average molecular weight of 50000 or less.
- the composition of this invention can be set as the negative photosensitive resin composition excellent in resolution. It is assumed that the mechanism for obtaining such an effect is as follows. According to the study by the present inventors, it was found that the glass transition temperature (Tg) can be improved by providing a polymerizable group at the terminal of the polyimide precursor. So far, polyimide precursors have generally been provided with a polymerizable group in the side chain because the polymerizable group can be introduced at a high density. However, it has been found that when a polymerizable group is added to the side chain of the polyimide precursor, the polymerizable group of the side chain may be detached during the cyclization of the polyimide precursor.
- Tg glass transition temperature
- the resolution during development was inferior. This was thought to be due to the relatively small amount of polymerizable groups relative to the polyimide precursor. Therefore, by setting the weight average molecular weight of the polyimide precursor to 50000 or less, the amount of the polymerizable group relative to the polyimide precursor can be relatively increased, and as a result, the resolution has been successfully improved. is there. Furthermore, according to the present invention, it is possible to improve the resolution while maintaining a high Tg of the cured film of the negative photosensitive resin composition.
- R 1 and R 2 in the formula (1) are non-polymerizable groups having 1 to 4 carbon atoms, whereby the rate of remaining film after thermosetting can be improved. That is, when polyimide is cyclized, the R 1 and R 2 portions of the formula (1) are easily detached, and the film is reduced when it is detached.
- the R 1 and R 2 portions of the formula (1) are non-polymerizable groups having 1 to 4 carbon atoms, so that even when these groups are eliminated by cyclization, the film can be more effectively reduced. Can be suppressed. That is, the remaining film ratio after thermosetting can be maintained higher.
- the lower limit value of the glass transition temperature measured by the method described in Examples described later is preferably 226 ° C or higher, more preferably 228 ° C or higher, and 230 ° C or higher. Is more preferable. If the glass transition temperature is equal to or higher than the above value, an improvement in reliability in a high temperature process such as a vapor deposition process for forming a metal wiring or a bonding process between electrodes can be expected.
- the upper limit value of the glass transition temperature is not particularly defined, but for example, the desired performance is sufficiently exhibited even at 350 ° C. or lower.
- the exposed film residual film ratio is preferably 50% or more, more preferably 70% or more, and further preferably 90% or more.
- the exposed portion residual film ratio is a value defined as follows. The details of the measurement method can be referred to the description of Examples described later.
- Exposed part residual film ratio (%) [film thickness after development of exposed part / film thickness of unexposed part before development] ⁇ 100
- the residual film ratio after thermosetting is preferably 70% or more, more preferably 80% or more, and further preferably 85% or more.
- the composition of the present invention has a repeating unit represented by the formula (1), has a structure represented by the formula (2) at at least one end, and has a weight average molecular weight of 50,000 or less. Containing.
- This polyimide precursor is also the polyimide precursor of the present invention.
- X represents a divalent organic group
- Y represents a tetravalent organic group
- R 1 and R 2 are each independently a non-polymerizable organic group
- A represents a polymerizable group
- L 1 represents a single bond or an l + 1 valent organic group
- l represents an integer of 1 to 10
- * represents a bonding site with another site.
- Examples of the divalent organic group represented by X in the formula (1) include a linear or branched aliphatic group, a group containing a cyclic aliphatic group, and an aromatic group.
- a branched aliphatic group, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof is preferable, and includes an aromatic group having 6 to 20 carbon atoms. Groups are more preferred.
- a particularly preferred embodiment includes a group represented by “—Ar—L—Ar—”.
- Ar is each independently an aromatic group
- 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—, and a group consisting of a combination of two or more of the above.
- Ar is preferably a phenylene group.
- L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S— or —SO 2 —.
- the aliphatic hydrocarbon group here is preferably an alkylene group.
- the divalent organic group represented by X in the formula (1) is preferably a group derived from diamine.
- the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamine.
- One type of diamine may be used, or two or more types may be used.
- the divalent organic group represented by X is a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, or an aromatic group having 6 to 20 carbon atoms.
- a diamine containing a group or a group consisting of a combination thereof is preferred, and a diamine containing an aromatic group having 6 to 20 carbon atoms is more preferred.
- the following aromatic groups are mentioned as an example of an aromatic group.
- A represents a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —C ( ⁇ O) —, —S—. , —S ( ⁇ O) 2 —, —NHCO—, and 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, It is more preferably a group selected from —O—, —C ( ⁇ O) —, —S—, —SO 2 —, —CH 2 —, —O—, —S—, —SO 2 —, More preferably, it is a divalent group selected from the group consisting of —C (CF 3 ) 2 — and —C (CH 3 ) 2 —.
- 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; meta and paraphenylenediamine, diaminotoluene, 4,4'- and 3 , 3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether
- diamines (DA-1) to (DA-18) shown below are also preferable.
- a diamine having at least two alkylene glycol units in the main chain is also a preferred example.
- Preferred is a diamine containing two or more ethylene glycol chains or propylene glycol chains in one molecule, and more preferred is a diamine containing no aromatic ring.
- Specific examples include Jeffermin (registered trademark) KH-511, Jeffermin (registered trademark) ED-600, Jeffermin (registered trademark) ED-900, Jeffermin (registered trademark) ED-2003, Jeffermin (registered trademark).
- EDR-148 Jeffamine (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (above trade names, manufactured by HUNTSMAN), 1- (2- (2- (2- (2- Aminopropoxy) ethoxy) propoxy) propan-2-amine, 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propan-2-amine, and the like, but is not limited thereto. .
- x, y, and z are average values.
- the divalent organic group represented by X in the formula (1) is also preferably a divalent organic group represented by the following formula (51) or formula (61) from the viewpoint of i-line transmittance.
- a divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-line transmittance and availability.
- Formula (51) In the formula (51), R 10 to R 17 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R 10 to R 17 is a fluorine atom, a methyl group or a trifluoromethyl group. It is.
- Examples of the monovalent organic group represented by R 10 to R 17 include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorine atom having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Alkyl group and the like.
- Formula (61) In formula (61), R 18 and R 19 are each independently a fluorine atom or a trifluoromethyl group.
- Examples of the diamine compound that gives the structure of formula (51) or (61) include 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diamino.
- Biphenyl 2,2′-bis (fluoro) -4,4′-diaminobiphenyl, 4,4′-diaminooctafluorobiphenyl and the like can be mentioned. These may be used alone or in combination of two or more.
- R 112 represents a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—, —SO.
- -, - NHCO- is preferably a group selected from these combinations, a single bond, an alkylene group which ⁇ 1 carbon atoms which may be 3-substituted by fluorine atoms, -O -, - CO- More preferably a group selected from -S- and -SO 2- , -CH 2- , -C (CF 3 ) 2- , -C (CH 3 ) 2- , -O-, -CO More preferred is a divalent group selected from the group consisting of —, —S— and —SO 2 —.
- tetravalent organic group represented by Y in Formula (1) examples include a tetracarboxylic acid residue remaining after the removal of the acid dianhydride group from tetracarboxylic dianhydride. Only one tetracarboxylic dianhydride may be used, or two or more tetracarboxylic dianhydrides may be used.
- the tetracarboxylic dianhydride is preferably a compound represented by the following formula (O).
- tetracarboxylic dianhydride examples include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl sulfide tetra Carboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4 4'-diphenylmethanetetracarboxylic dianhydride, 2,2 ', 3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,3 , 3 ′, 4′-benzophenonetetracarboxylic dianhydride, 4,4′-oxydi
- tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below are also preferable examples.
- At least one of X and Y in the formula (1) has a hydroxyl group.
- the non-polymerizable organic group represented by R 1 and R 2 in the formula (1) is preferably a group not containing a carbon-carbon unsaturated double bond.
- a linear or branched alkyl group, a cyclic alkyl group, and an aromatic group are preferable.
- the aromatic group include an aryl group and an aralkyl group.
- the non-polymerizable organic group represented by R 1 and R 2 is more preferably a non-polymerizable organic group having 1 to 4 carbon atoms, and is a linear or branched alkyl group having 1 to 4 carbon atoms. Is more preferable.
- non-polymerizable organic group examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, octadecyl group.
- Group, sec-butyl group and tert-butyl group are preferable, methyl group and ethyl group are more preferable, and methyl group is more preferable.
- the polyimide precursor of the present invention has a structure represented by the formula (2) at least at one end.
- A represents a polymerizable group
- L 1 represents a single bond or an l + 1 valent organic group
- l represents an integer of 1 to 10
- * represents a bonding site with another site.
- the polymerizable group represented by A in the formula (2) is preferably a group containing a carbon-carbon unsaturated double bond. Specific examples include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a group represented by the following formula (A-1), and a group represented by the formula (A-2).
- * represents a bonding site with L 1 and equation (2).
- R 3 represents a hydrogen atom or a methyl group
- Z represents an oxygen atom or NH.
- L 1 represents a single bond or an l + 1 valent organic group, preferably an l + 1 valent organic group.
- the l + 1 valent organic group is composed of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. Groups. Specific examples of the l + 1 valent organic group include the following structural units or a group formed by combining two or more of the following structural units (which may form a ring structure).
- l represents an integer of 1 to 10, preferably an integer of 2 to 10, more preferably an integer of 2 to 8, and further preferably an integer of 2 to 5. According to this aspect, the remaining film ratio after development in the exposed portion can be increased.
- the structure represented by Formula (2) is preferably a structure represented by Formula (3) or Formula (4), and more preferably a structure represented by Formula (3). According to this aspect, the remaining film ratio after development in the exposed portion can be increased.
- R 3 represents a hydrogen atom or a methyl group
- Z represents an oxygen atom or NH
- L 2 represents a single bond or an m + 1 valent organic group
- m represents an integer of 1 to 10.
- * Indicates a binding site with another site.
- L 3 represents a single bond or an n + 1 valent organic group
- n represents an integer of 1 to 10
- * represents a bonding site with another site.
- the m + 1 valent organic group represented by L 2 in Formula (3) and the n + 1 valent organic group represented by L 3 in Formula (4) are the groups described for the l + 1 valent organic group represented by L 1 in Formula (2).
- the preferable range is also the same.
- m represents an integer of 1 to 10, preferably an integer of 2 to 10, more preferably an integer of 2 to 8, and further preferably an integer of 2 to 5. According to this aspect, the remaining film ratio in the exposed portion can be increased.
- n represents an integer of 1 to 10, preferably an integer of 2 to 10, more preferably an integer of 2 to 8, and further preferably an integer of 2 to 5. According to this aspect, the remaining film ratio in the exposed portion can be increased.
- the polyimide precursor of the present invention has a fluorine atom in the repeating unit.
- the fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.
- the polyimide precursor of the present invention may further contain a repeating unit containing an aliphatic group having a siloxane structure for the purpose of improving adhesion to the substrate.
- a repeating unit containing an aliphatic group having a siloxane structure for the purpose of improving adhesion to the substrate.
- the diamine component for introducing an aliphatic group having a siloxane structure include bis (3-aminopropyl) tetramethyldisiloxane and bis (paraaminophenyl) octamethylpentasiloxane.
- the repeating unit represented by the formula (1) may be one type or two or more types. Moreover, the polyimide precursor may contain the structural isomer of the repeating unit represented by Formula (1). The polyimide precursor may also contain other types of repeating units in addition to the repeating unit represented by the formula (1).
- the polyimide precursor of the present invention preferably contains 50 mol% or more of the repeating units represented by the formula (1), more preferably 70 mol% or more, more preferably 90 mol% or more of all repeating units. More preferably.
- the weight average molecular weight (Mw) of the polyimide precursor is 50000 or less, preferably 40000 or less, and more preferably 35000 or less.
- the lower limit is preferably more than 2000, more preferably 5000 or more, further preferably 6000 or more, and further preferably 7000 or more. If the weight average molecular weight of a polyimide precursor is 50000 or less, it is excellent in developability. Moreover, if the weight average molecular weight of a polyimide precursor is 5000 or more, the mechanical strength of the obtained cured film is favorable.
- the degree of dispersion (Mw / Mn) 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 degree of dispersion of the polyimide precursor is not particularly defined, but is, for example, preferably 4.5 or less, more preferably 4.0 or less, still more preferably 3.8 or less, and still more preferably 3.2 or less, 3.1 or less is even more preferable, 3.0 or less is even more preferable, and 2.95 or less is even more preferable.
- the content of the polyimide precursor in the composition of the present invention is preferably 10 to 99% by mass, more preferably 50 to 98% by mass, and further preferably 70 to 96% by mass of the total solid content of the composition of the present invention.
- the composition of the present invention has a repeating unit represented by the formula (1), and has a structure represented by “(A) 1 -L 1- *” at least at one end;
- the content of the polyimide precursor having a weight average molecular weight of 50000 or less is preferably 10 to 99% by mass, more preferably 50 to 98% by mass, and further 70 to 96% by mass based on the total solid content of the composition of the present invention. preferable.
- the carboxyl group is esterified. Can be manufactured.
- the reaction product is further reacted with a compound having a polymerizable group. it can.
- the molar ratio of tetracarboxylic dianhydride or derivative thereof to the above alcohol is 0.9 to 1.1: 2.1 to 1.
- the molar ratio of tetracarboxylic dianhydride or derivative thereof to diamine is 0.8 to 1.2: 1.2 to 0. .8 is preferable, and 1.001 to 1.2: 0.999 to 0.8 is more preferable.
- the reaction temperature of the above reaction is preferably ⁇ 20 to 60 ° C.
- the reaction time is preferably 30 minutes to 10 hours.
- the molecular weight of the alcohol to be reacted with tetracarboxylic dianhydride is preferably 30 to 150, more preferably 30 to 80, and further preferably 30 to 65.
- the alcohol to be reacted with tetracarboxylic dianhydride is preferably an alcohol having 1 to 8 carbon atoms, more preferably an alcohol having 1 to 4 carbon atoms, still more preferably an alcohol having 1 to 3 carbon atoms, and an alcohol having 1 or 2 carbon atoms.
- Alcohol is more preferable, and alcohol having 1 carbon (methanol) is even more preferable.
- Specific examples of the alcohol include methanol, ethanol, propanol, and n-butanol, and methanol is particularly preferable.
- the compound having a polymerizable group is preferably a compound having 1 to 10 polymerizable groups, more preferably a compound having 2 to 8 polymerizable groups, and still more preferably a compound having 2 to 5 polymerizable groups.
- a group containing a carbon-carbon unsaturated double bond is preferable.
- a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a styryl group, a group represented by the above formula (A-1) and a group represented by the above formula (A-2) Is mentioned.
- the molecular weight of the compound having a polymerizable group is preferably from 100 to 2000, more preferably from 100 to 1500, and further preferably from 100 to 1000. If the molecular weight of the compound having a polymerizable group is within the above range, specific examples of the compound in which a polyimide precursor excellent in resolution can be easily obtained include pentaerythritol trimethyl when an acid dianhydride is excessively used.
- EO ethylene oxide
- 2-isocyanatoethyl (meth) acrylate and 1,1- (bisacryloyloxymethyl) ethyl isocyanate are exemplified.
- an organic solvent is preferably used for the reaction.
- One or more organic solvents may be used.
- the organic solvent can be appropriately determined according to the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.
- one end of the main chain of the precursor is sealed with an end-capping agent such as an acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound in order to further improve storage stability. You may stop. Of these, it is more preferable to use a monoamine.
- the monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, and 1-hydroxy-7.
- -Aminonaphthalene 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2, -Hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6- Aminonaphthalene, 2-carbo Ci-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-amino Benzenesulfonic acid, 4-amino
- a step of depositing a solid may be included. Specifically, solid precipitation can be performed by precipitating the polyimide precursor in the reaction solution in a poor solvent such as water or alcohol. Then, a polyimide precursor can be dried and a powdery polyimide precursor can be obtained.
- the composition of the present invention contains a photopolymerization initiator.
- the photopolymerization initiator include a photocationic polymerization initiator and a photoradical polymerization initiator, and a photoradical polymerization initiator is preferred.
- the composition of the present invention contains a photo radical polymerization initiator
- the composition of the present invention is applied to a substrate such as a semiconductor wafer to form a negative photosensitive resin composition layer, and then irradiated with light. Curing due to radicals occurs, and the solubility in the light irradiation part can be reduced. For this reason, for example, by exposing a negative photosensitive resin composition layer through a photomask having a pattern for masking only the electrode portion, it is possible to easily produce regions having different solubility according to the electrode pattern. There are advantages.
- a photoinitiator having photosensitivity to light in the ultraviolet region to the visible region is preferable. Further, it may be an activator that generates some active radicals by generating some action with the photoexcited sensitizer.
- the photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 to 800 nm (preferably 330 to 500 nm). The molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.
- halogenated hydrocarbon derivatives for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group
- acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime derivatives, etc.
- ketone compounds include the compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated herein.
- Kaya Cure DETX manufactured by Nippon Kayaku Co., Ltd.
- Nippon Kayaku Co., Ltd. is also preferably used.
- hydroxyacetophenone compounds As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
- 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.
- aminoacetophenone-based initiator compounds described in JP-A-2009-191179 in which the absorption maximum wavelength is matched with a wavelength light source of 365 nm or 405 nm can also be used.
- the acylphosphine initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
- IRGACURE-819 and IRGACURE-TPO which are commercially available products can be used.
- the metallocene compound include IRGACURE-784 (manufactured by BASF).
- More preferred examples of the photopolymerization initiator include oxime compounds.
- the exposure latitude can be improved more effectively.
- Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as a thermal base generator.
- Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
- Preferable oxime compounds include, for example, compounds having the following structures, 3-benzooxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxy Iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
- IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), Adekaoptomer N-1919 (manufactured by ADEKA Corporation, light described in JP2012-14052A) A polymerization initiator 2) is also preferably used.
- TR-PBG-304 manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.
- Adeka Arkles NCI-831 and Adeka Arkles NCI-930 made by ADEKA
- DFI-091 manufactured by Daitokemix Co., Ltd.
- an oxime compound having a fluorine atom examples include compounds described in JP 2010-262028 A, compounds 24, 36 to 40 described in paragraph 0345 of JP 2014-500852 A, and JP 2013. And the compound (C-3) described in paragraph 0101 of JP-A No. 164471.
- oxime compounds having a specific substituent as disclosed in JP-A-2007-267979 there are oxime compounds having a thioaryl group as disclosed in JP-A-2009-191061, and the like.
- Photopolymerization initiators are trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryls from the viewpoint of exposure sensitivity.
- Selected from the group consisting of imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds. are preferred.
- More preferred photopolymerization initiators are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, 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, and a metallocene compound or an oxime compound is more preferable, and an oxime compound. Is particularly preferred.
- Photopolymerization initiators include N, N′-tetraalkyl-4,4′-diaminobenzophenone, 2-benzyl-, such as benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), and the like.
- Aromatic ketones such as 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, alkyl anthraquinones, etc.
- benzoin ether compounds such as benzoin alkyl ether
- benzoin compounds such as benzoin and alkylbenzoin
- benzyl derivatives such as benzyldimethyl ketal.
- a compound represented by the following formula (I) can also be used.
- R 50 represents 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; An alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, and 2 to 2 carbon atoms interrupted by one or more oxygen atoms A phenyl group substituted with at least one of 18 alkyl groups and an alkyl group having 1 to 4 carbon atoms; or biphenylyl, and R 51 is the group represented by formula (II) or the same as R 50
- Each of R 52 to R 54 is independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or halogen.
- R 55 is the alkyl
- the content of the photopolymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.1 to 30% by mass with respect to the total solid content of the composition of the present invention. 10% by mass.
- the photoinitiator may contain only 1 type and may contain 2 or more types. When two or more photopolymerization initiators are contained, the total is preferably in the above range.
- the composition of the present invention contains a solvent.
- a known solvent can be arbitrarily used as the solvent.
- the solvent is preferably an organic solvent.
- Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.
- esters 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, and ⁇ -caprolactone , ⁇ -valerolactone, alkyl oxyacetates (for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.
- alkyl oxyacetates for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl al
- 3-alkyloxypropionic acid alkyl esters for example, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (for example, methyl 3-methoxypropionate, 3-methoxypropionate)) Ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)
- 2-alkyloxypropionic acid alkyl esters for example, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2 -Propyl alkyloxypropionate and the like (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)
- 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, propylene glycol Preferred examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.
- ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone.
- aromatic hydrocarbons include toluene, xylene, anisole, limonene and the like.
- Suitable examples of the sulfoxides include dimethyl sulfoxide.
- Preferable examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like.
- the solvent is preferably in the form of a mixture of two or more from the viewpoint of improving the properties of the coated surface.
- a mixed solution composed of two or more selected from dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable.
- the combined use of dimethyl sulfoxide and ⁇ -butyrolactone is particularly preferred.
- the content of the solvent is preferably such that the total solid concentration of the composition of the present invention is 5 to 80% by mass, more preferably 5 to 70% by mass, and more preferably 10 to 60% by mass from the viewpoint of applicability. % Is particularly preferred.
- the solvent content may be adjusted depending on the desired thickness and coating method. For example, if the coating method is spin coating or slit coating, the content of the solvent having a solid content concentration in the above range is preferable. In the case of spray coating, the amount is preferably 0.1% by mass to 50% by mass, and more preferably 1.0% by mass to 25% by mass.
- a photosensitive resin composition layer having a desired thickness can be uniformly formed by adjusting the amount of solvent by the coating method.
- the solvent may contain only 1 type and may contain 2 or more types. When two or more solvents are contained, the total is preferably in the above range.
- the composition of the present invention preferably contains a polyfunctional radically polymerizable monomer (hereinafter also referred to as a polymerizable monomer). By setting it as such a structure, the cured film excellent in heat resistance can be formed.
- a polyfunctional radically polymerizable monomer hereinafter also referred to as a polymerizable monomer.
- a compound having a radical polymerizable group can be used as the polymerizable monomer.
- the radical polymerizable group include groups having an ethylenically unsaturated bond such as a styryl group, a vinyl group, a (meth) acryloyl group, and a (meth) allyl group.
- the radical polymerizable group is preferably a (meth) acryloyl group.
- the polymerizable monomer preferably has two or more radical polymerizable groups, more preferably three or more.
- the upper limit is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.
- the molecular weight of the polymerizable monomer is preferably 2000 or less, more preferably 1500 or less, and even more preferably 900 or less.
- the lower limit of the molecular weight of the polymerizable monomer is preferably 100 or more.
- the composition of the present invention preferably contains at least one bifunctional or higher polymerizable monomer containing two or more polymerizable groups, and preferably contains at least one trifunctional or higher polymerizable monomer. Is more preferable. Further, it may be a mixture of a bifunctional polymerizable monomer and a trifunctional or higher functional polymerizable monomer.
- the number of functional groups of the polymerizable monomer means the number of radical polymerizable groups in one molecule.
- the polymerizable monomer examples include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides. These are esters of saturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds. Also, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
- unsaturated carboxylic acids for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
- esters thereof are esters of saturated carboxylic acids and polyhydric alcohol compounds
- an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine, or thiol, and a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable.
- the description in paragraphs 0113 to 0122 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated in the present specification.
- the polymerizable monomer is also preferably a compound having a boiling point of 100 ° C. or higher under normal pressure.
- Examples include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol.
- polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid, and mixtures thereof described in JP-B 52-30490. it can. Also suitable are the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970.
- polyfunctional (meth) acrylate etc. which are obtained by making the compound which has cyclic ether groups, such as glycidyl (meth) acrylate, and an ethylenically unsaturated group, react with polyfunctional carboxylic acid can also be mentioned.
- preferable polymerizable monomers include groups having a fluorene ring and an ethylenically unsaturated bond described in JP2010-160418A, JP2010-129825A, Japanese Patent No. 4364216, and the like. It is also possible to use a compound having two or more or a cardo resin. Other examples include specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and JP-A-2-25493. And vinyl phosphonic acid compounds. Also, compounds containing a perfluoroalkyl group described in JP-A-61-22048 can be used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photopolymerizable monomers and oligomers, can also be used.
- polymerizable monomers represented by the following formulas (MO-1) to (MO-5) can also be suitably used.
- T is an oxyalkylene group
- the terminal on the carbon atom side is bonded to R.
- n is an integer from 0 to 14, and m is an integer from 0 to 8.
- a plurality of R and T present in the molecule may be the same or different.
- the compounds described in paragraphs 0248 to 0251 of JP-A No. 2007-267979 can be used. .
- dipentaerythritol triacrylate (as a commercially available product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercially available product, as KAYARAD D-320; Nippon Kayaku Co., Ltd.) ), A-TMMT: Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (As commercial products, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.), and these (meth) acryloyl groups are bonded via ethylene glycol and prop
- Examples of commercially available polymerizable monomers include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer, SR-209, manufactured by Sartomer, which is a bifunctional methacrylate having four ethyleneoxy chains, DPCA-60, a 6-functional acrylate having 6 pentyleneoxy chains, TPA-330, a 3-functional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS-10, UAB-140 manufactured by Nippon Kayaku Co., Ltd.
- NK ester M-40G (Manufactured by Sanyo Kokusaku Pulp), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (Nippon Kayaku ( UA-306H, UA-306T, UA-306I, AH-600 T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (NOF Co., Ltd.), and the like.
- Polymerizable monomers include urethane acrylates such as those described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765.
- Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable.
- compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used as polymerizable monomers. You can also.
- the polymerizable monomer may be a polymerizable monomer having an acid group such as a carboxyl group, a sulfo group, or a phosphoric acid group.
- the polymerizable monomer having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. More preferred is a polymerizable monomer.
- the aliphatic polyhydroxy compound is pentaerythritol and / or diester. It is a compound that is pentaerythritol.
- examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
- the polymerizable monomer having an acid group one kind may be used alone, or two or more kinds may be mixed and used.
- a preferable acid value of the polymerizable monomer having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g.
- the acid value of the polymerizable monomer is within the above range, the production and handling properties are excellent, and further, the developability is excellent. Also, the polymerizability is good.
- the content of the polymerizable monomer is preferably 1 to 50% by mass with respect to the total solid content of the composition of the present invention from the viewpoint of good polymerizability and heat resistance.
- the lower limit is more preferably 5% by mass or more.
- the upper limit is more preferably 30% by mass or less.
- As the polymerizable monomer one kind may be used alone, or two or more kinds may be mixed and used.
- the mass ratio of the polyimide precursor to the polymerizable monomer is preferably 98/2 to 10/90, more preferably 95/5 to 30/70, and 90/10 to 50 / 50 is most preferred. If the mass ratio of a polyimide precursor and a polymerizable monomer is in the above range, a cured film that is superior in polymerizability and heat resistance can be formed.
- a monofunctional polymerizable monomer can be preferably used from the viewpoint of warpage suppression by controlling the elastic modulus of the cured film.
- Monofunctional polymerizable monomers include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, cyclohexyl (meth) ) Acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc.
- N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, etc. Goods and the like are preferably used.
- the monofunctional polymerizable monomer a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.
- composition of this invention can further contain other polymerizable compounds other than the polyimide precursor and polymerizable monomer mentioned above.
- Other polymerizable compounds include compounds having a hydroxymethyl group, alkoxymethyl group or acyloxymethyl group; epoxy compounds; oxetane compounds; benzoxazine compounds.
- R 4 represents a t-valent organic group having 1 to 200 carbon atoms
- R 5 represents a group represented by —OR 6 or —OCO—R 7.
- R 6 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms
- R 7 represents an organic group having 1 to 10 carbon atoms.
- the content of the compound represented by the formula (AM1) is preferably 5 to 40 parts by mass with respect to 100 parts by mass of the polyimide precursor. More preferably, it is 10 to 35 parts by mass. Further, the compound represented by the following formula (AM4) is contained in the total amount of other polymerizable compounds in an amount of 10 to 90% by mass, and the compound represented by the following formula (AM5) is contained in an amount of 10 to 90% by mass. Is also preferable.
- R 4 represents a divalent organic group having 1 to 200 carbon atoms
- R 5 represents a group represented by —OR 6 or —OCO—R 7
- R 6 represents a hydrogen atom or a carbon atom.
- R 7 represents an organic group having 1 to 10 carbon atoms.
- R 4 represents a u-valent organic group having 1 to 200 carbon atoms
- R 5 represents a group represented by —OR 6 or —OCO—R 7.
- R 6 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms
- R 7 represents an organic group having 1 to 10 carbon atoms.
- the occurrence of cracks can be more effectively suppressed when the composition of the present invention is applied to an uneven substrate. Moreover, it is excellent in pattern workability and can form the cured film which has high heat resistance from which 5% mass reduction
- Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (trade name, manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML.
- Specific examples of the compound represented by the formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.), NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW-100LM (trade name, manufactured by Sanwa Chemical Co., Ltd.).
- 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 less and does not cause a dehydration reaction derived from the cross-linking, so that film shrinkage hardly occurs. For this reason, containing an epoxy compound is effective for low-temperature curing and warping of the composition.
- the epoxy compound preferably contains a polyethylene oxide group. Thereby, an elasticity modulus falls more and also curvature can be suppressed. Moreover, the film
- 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 compound examples include bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resin such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resin such as polypropylene glycol diglycidyl ether; polymethyl (glycidyl Examples include, but are not limited to, epoxy group-containing silicones such as (roxypropyl) siloxane.
- Epicron (registered trademark) 850-S Epicron (registered trademark) HP-4032, Epicron (registered trademark) HP-7200, Epicron (registered trademark) HP-820, Epicron (registered trademark) HP-4700, Epicron (registered trademark) EXA-4710, Epicron (registered trademark) HP-4770, Epicron (registered trademark) EXA-859CRP, Epicron (registered trademark) EXA-1514, Epicron (registered trademark) EXA-4880, Epicron (registered trademark) EXA-4850-150, Epicron EXA-4850-1000, Epicron (registered trademark) EXA-4816, Epicron (registered trademark) EXA-4822 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.), Rica Resin (registered trademark) ) BEO-60E (trade name, Shin Nippon Rika ( )), EP-4003S, EP-4000S (trade name, manufactured by
- an epoxy resin containing a polyethylene oxide group is preferable in terms of suppressing warpage and excellent heat resistance.
- Epicron (registered trademark) EXA-4880, Epicron (registered trademark) EXA-4822, and Licaredin (registered trademark) BEO-60E are preferable because they contain a polyethylene oxide group.
- the content of the epoxy compound is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and still more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the polyimide precursor. If the content of the epoxy compound is 5 parts by mass or more, warpage of the obtained cured film can be further suppressed, and if it is 50 parts by mass or less, pattern filling caused by reflow during curing can be further suppressed.
- oxetane compound compound having 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, Examples include 3-ethyl-3- (2-ethylhexylmethyl) oxetane and 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester.
- Aron Oxetane series (for example, OXT-121, OXT-221, OXT-191, OXT-223) manufactured by Toagosei Co., Ltd. can be preferably used. Two or more kinds may be mixed.
- the content of the oxetane compound is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and still more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the polyimide precursor.
- a benzoxazine compound (compound having a benzoxazolyl group))
- a benzoxazine compound is preferable because it is a cross-linking reaction derived from a ring-opening addition reaction, so that degassing does not occur during curing, and thermal contraction is further reduced to suppress warpage.
- benzoxazine compound examples include Ba type benzoxazine, Bm type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, phenol novolac type dihydrobenzoxazine. Compounds. These may be used alone or in combination of two or more.
- the content of the benzoxazine compound is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and still more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the polyimide precursor.
- the composition of the present invention preferably further contains a metal discoloration inhibitor.
- a metal discoloration prevention agent it can suppress effectively that the metal ion derived from a metal layer (metal wiring) moves into a negative photosensitive resin composition layer.
- the metal discoloration inhibitor is not particularly limited, but a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring , Pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thioureas and mercapto groups, hindered phenols Compounds, salicylic acid derivative compounds, and hydrazide derivative compounds.
- triazole compounds such as triazole and benzotriazole, and tetrazole compounds such as tetrazole and benzotetrazole can be preferably used.
- an ion trapping agent that traps anions such as halogen ions can be used.
- Examples of other metal discoloration inhibitors include rust preventives described in paragraph 0094 of JP2013-15701A, compounds described in paragraphs 0073 to 0076 of JP2009-283711A, and JP2011-59656A. And the compounds described in paragraphs 0114, 0116 and 0118 of JP 2012-194520 A, and the like.
- metal discoloration inhibitor examples include the following compounds.
- the content of the metal discoloration inhibitor is preferably 0.01 to 5.0% by mass relative to the total solid content of the composition of the present invention. 05 to 2.0% by mass is more preferable, and 0.1 to 1.0% by mass is more preferable. Only one type of metal discoloration inhibitor may be used, or two or more types may be used. When two or more metal discoloration inhibitors are used, the total is preferably within the above range.
- the composition of the present invention preferably contains a polymerization inhibitor.
- the polymerization inhibitor include hydroquinone, paramethoxyphenol, di-tert-butyl-paracresol, pyrogallol, para-tert-butylcatechol, parabenzoquinone, diphenyl-parabenzoquinone, 4,4′-thiobis (3-methyl).
- a polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and compounds described in paragraphs 0031 to 0046 of international publication WO2015 / 125469 can also be used. Further, the following compounds can be used (Me is a methyl group).
- the content of the polymerization inhibitor is preferably 0.01 to 5% by mass relative to the total solid content of the composition of the present invention. Only one polymerization inhibitor may be used, or two or more polymerization inhibitors may be used. When two or more polymerization inhibitors are used, the total is preferably within the above range.
- the composition of the present invention preferably contains a thermal base generator.
- the type of the thermal base generator is not particularly defined, but is selected from an acidic compound that generates a base when heated to 40 ° C. or higher, and an ammonium salt having an anion having an pKa1 of 0 to 4 and an ammonium cation. It is preferable to include a thermal base generator containing at least one kind.
- pKa1 represents the logarithm ( ⁇ Log 10 Ka) of the reciprocal of the dissociation constant (Ka) of the first proton of the acid, and will be described in detail later.
- the base generated from these compounds can promote the cyclization reaction of the polyimide precursor and the like. Can be carried out at low temperatures. In addition, even if these compounds coexist with a polyimide precursor that is cured by cyclization with a base, since the cyclization of the polyimide precursor hardly proceeds unless heated, a composition having excellent storage stability can be obtained. Can be prepared.
- the solution obtained by stirring means a compound having a value measured at 20 ° C. of less than 7 using a pH (power of hydrogen) meter.
- the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40 ° C. or higher, more preferably 120 to 200 ° C.
- the upper limit of the base generation temperature is preferably 190 ° C. or lower, more preferably 180 ° C. or lower, and further preferably 165 ° C. or lower.
- the lower limit of the base generation temperature is preferably 130 ° C or higher, and more preferably 135 ° C or higher. If the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 120 ° C. or higher, a base is unlikely to be generated during storage, so that a composition having excellent stability can be prepared.
- the base generation temperature of the acidic compound (A1) and ammonium salt (A2) is 200 ° C. or lower, the cyclization temperature of the polyimide precursor or the like can be lowered.
- the base generation temperature is measured, for example, by using differential scanning calorimetry, heating the compound to 250 ° C. at 5 ° C./min in a pressure capsule, reading the peak temperature of the lowest exothermic peak, and measuring the peak temperature as the base generation temperature. can do.
- the base generated by the thermal base generator is preferably a secondary amine or a tertiary amine, more preferably a tertiary amine. Since tertiary amine has high basicity, cyclization temperature of a polyimide precursor, a polybenzoxazole precursor, etc. can be made lower.
- the base generated by the thermal base generator preferably has a boiling point of 80 ° C. or higher, more preferably 100 ° C. or higher, and further preferably 140 ° C. or higher.
- the molecular weight of the generated base is preferably 80 to 2000.
- the lower limit is more preferably 100 or more.
- the upper limit is more preferably 500 or less.
- the molecular weight value is a theoretical value obtained from the structural formula.
- the acidic compound (A1) preferably contains one or more selected from an ammonium salt and a compound represented by the formula (101) or (102) described later.
- the ammonium salt (A2) is preferably an acidic compound.
- the ammonium salt (A2) may be a compound containing an acidic compound that generates a base when heated to 40 ° C. or higher (preferably 120 to 200 ° C.), or 40 ° C. or higher (preferably 120 to 200 ° C.). ) May be a compound excluding an acidic compound that generates a base when heated.
- the ammonium salt means a salt of an ammonium cation represented by the following formula (101) or formula (102) and an anion.
- the anion may be bonded to any part of the ammonium cation via a covalent bond, and may be outside the molecule of the ammonium cation, but may be outside the molecule of the ammonium cation. preferable.
- numerator of an ammonium cation means the case where an ammonium cation and an anion are not couple
- the anion outside the molecule of the cation moiety is also referred to as a counter anion.
- R 1 to R 6 each independently represents a hydrogen atom or a hydrocarbon group
- R 7 represents a hydrocarbon group
- R 1 and R 2 , R 3 and R 4 , R 5 and R 6 , R 5 and R 7 in Formula (101) and Formula (102) may be bonded to form a ring.
- the ammonium cation is preferably represented by any of the following formulas (Y1-1) to (Y1-5).
- R 101 represents an n-valent organic group
- R 1 and R 7 have the same meanings as in formula (101) or formula (102).
- Ar 101 and Ar 102 each independently represent an aryl group
- n represents an integer of 1 or more
- m represents an integer of 0 to 5 .
- the ammonium salt preferably has an anion having an pKa1 of 0 to 4 and an ammonium cation.
- the upper limit of the anion pKa1 is more preferably 3.5 or less, and even more preferably 3.2 or less.
- the lower limit is preferably 0.5 or more, and more preferably 1.0 or more. If the pKa1 of the anion is in the above range, a polyimide precursor or the like can be cyclized at a low temperature, and the stability of the composition can be improved. If pKa1 is 4 or less, the stability of the thermal base generator is good, the generation of a base without heating can be suppressed, and the stability of the composition is good.
- the kind of anion is preferably one selected from a carboxylate anion, a phenol anion, a phosphate anion, and a sulfate anion, and a carboxylate anion is more preferable because both the stability of the salt and the thermal decomposability can be achieved. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion.
- the carboxylic acid anion is preferably a divalent or higher carboxylic acid anion having two or more carboxyl groups, and more preferably a divalent carboxylic acid anion.
- the stability, curability and developability of the composition can be further improved by using an anion of a divalent carboxylic acid.
- the carboxylic acid anion is preferably a carboxylic acid anion having a pKa1 of 4 or less.
- pKa1 is more preferably 3.5 or less, and even more preferably 3.2 or less.
- the stability of the composition can be further improved.
- pKa1 represents the logarithm of the reciprocal of the dissociation constant of the first proton of the acid, and the determination of Organic Structures by Physical Methods (author: Brown, HC, McDaniel, D.H., Hafliger Ed .: Braude, EA, Nachod, FC; Academic Press, New York, 1955), and Data for Biochemical Research (author: Dawson, R. M.). al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, values calculated from the structural formula using software of ACD / pKa (manufactured by ACD / Labs) are used.
- the carboxylate anion is preferably represented by the following formula (X1).
- EWG represents an electron withdrawing group.
- the electron-withdrawing group means a group in which Hammett's substituent constant ⁇ m exhibits a positive value.
- ⁇ m is a review by Yusuke Tono, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965) p. 631-642.
- the electron withdrawing group in this embodiment is not limited to the substituent described in the said literature.
- Me represents a methyl group
- Ac represents an acetyl group
- Ph represents a phenyl group.
- EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).
- R x1 to R x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group or a carboxyl group, and Ar represents an aromatic group Represents.
- the carboxylate anion is preferably represented by the following formula (XA).
- Formula (XA) In the formula (XA), L 10 represents a single bond or a divalent linking group selected from an alkylene group, an alkenylene group, an aromatic group, —NR X —, and a combination thereof, and R X represents a hydrogen atom Represents an alkyl group, an alkenyl group or an aryl group.
- carboxylate anion examples include a maleate anion, a phthalate anion, an N-phenyliminodiacetic acid anion, and an oxalate anion. These can be preferably used.
- thermal base generator examples include the following compounds.
- the content of the thermal base generator is preferably 0.1 to 50% by mass relative to the total solid content of the composition of the present invention.
- the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
- the upper limit is more preferably 30% by mass or less, and further preferably 20% by mass or less.
- 1 type (s) or 2 or more types can be used for a thermal base generator. When using 2 or more types, it is preferable that a total amount is the said range.
- the composition of this invention contains the metal adhesive improvement agent for improving the adhesiveness with the metal material used for an electrode, wiring, etc.
- metal adhesion improvers include silane coupling agents.
- silane coupling agent examples include compounds described in paragraphs 0062 to 0073 of JP-A No. 2014-191002, compounds described in paragraphs 0063 to 0071 of international publication WO 2011 / 080992A1, and JP-A No. 2014-191252. Examples thereof include compounds described in paragraphs 0060 to 0061, compounds described in paragraphs 0045 to 0052 of JP 2014-41264 A, and compounds described in paragraph 0055 of international publication WO 2014/097594. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A. Moreover, it is also preferable to use the following compound for a silane coupling agent. In the following formula, Et represents an ethyl group.
- the content of the metal adhesion improving agent is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the polyimide precursor. Adhesiveness between the cured film and the metal layer after the curing process becomes good by setting it to 0.1 parts by mass or more, and heat resistance and mechanical properties of the cured film after the curing process are good by setting it to 30 parts by mass or less. Become. Only one type of metal adhesion improver may be used, or two or more types may be used. When using 2 or more types, it is preferable that the sum total is the said range.
- the composition of the present invention is various additives, for example, a photobase generator, a thermal polymerization initiator, a thermal acid generator, a sensitizing dye, a chain transfer, as necessary, as long as the effects of the present invention are not impaired.
- An agent, a surfactant, a higher fatty acid derivative, inorganic particles, a curing agent, a curing catalyst, a filler, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, and the like can be blended.
- the total blending amount is preferably 3% by mass or less of the solid content of the composition.
- the composition of the present invention may contain a photobase generator.
- a photobase generator is a compound that generates a base upon exposure and does not exhibit activity under normal conditions of room temperature and normal pressure. However, when an electromagnetic wave is irradiated and heated as an external stimulus, a base (basic substance) is generated. If it is a compound which generate
- the content of the photobase generator is not particularly limited as long as a desired resin pattern can be formed, and can be a general content.
- the photobase generator is preferably in the range of 0.01 parts by weight to less than 30 parts by weight with respect to 100 parts by weight of the polyimide precursor, and is in the range of 0.05 parts by weight to 25 parts by weight. Is more preferable, and is more preferably in the range of 0.1 to 20 parts by mass. Only one photobase generator may be used, or two or more photobase generators may be used. When there are two or more photobase generators, the total is preferably in the above range.
- a known compound can be used as a photobase generator.
- M.M. Shirai, and M.M. Tsunooka Prog. Polym. Sci. , 21, 1 (1996); Masahiro Kadooka, polymer processing, 46, 2 (1997); Kutal, Coord. Chem. Rev. , 211, 353 (2001); Kaneko, A .; Sarker, and D. Neckers, Chem. Mater. 11, 170 (1999); Tachi, M .; Shirai, and M.M. Tsunooka, J. et al. Photopolym. Sci. Technol. , 13, 153 (2000); Winkle, and K.K. Graziano, J. et al.
- An ionic compound neutralized by forming a salt with a base component, or a nonionic compound in which the base component is made latent by a urethane bond or an oxime bond such as a carbamate derivative, an oxime ester derivative, or an acyl compound can be mentioned.
- the photobase generator carbamate derivatives, amide derivatives, imide derivatives, ⁇ -cobalt complexes, imidazole derivatives, cinnamic acid amide derivatives, oxime derivatives, and the like can also be used. Further, the photobase generator having a cinnamic acid amide structure described in Japanese Patent Application Laid-Open No. 2009-80452 and International Publication No. WO2009 / 123122, and Japanese Patent Application Laid-Open No. 2006-189591 and Japanese Patent Application Laid-Open No. 2008-247747.
- a photobase generator having a carbamate structure, or a photobase generator having an oxime structure or a carbamoyloxime structure described in JP2007-249013A and JP2008-003581A can also be used.
- Other photobase generators include compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 of JP2012-93746A, compounds described in paragraphs 0022 to 0069 of JP2013-194205, Examples thereof include the compounds described in paragraphs 0026 to 0074 of JP2013-204019A and the compound described in paragraph 0052 of WO2010 / 064631.
- the composition of the present invention may contain a thermal polymerization initiator (preferably a thermal radical polymerization initiator).
- a thermal radical polymerization initiator a known thermal radical polymerization initiator can be used.
- the thermal radical polymerization initiator is a compound that generates radicals by heat energy and initiates or accelerates a polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the polyimide precursor can be advanced together with the cyclization of the polyimide precursor, so that higher heat resistance can be achieved.
- Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-63554.
- the content of the thermal radical polymerization initiator is preferably 0.1 to 50% by mass, based on the total solid content of the composition of the present invention, 0.1 to 30% by mass is more preferable, and 0.1-20% by mass is particularly preferable. Further, the thermal radical polymerization initiator is preferably contained in an amount of 0.1 to 50 parts by mass, more preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the polyimide precursor. According to this aspect, it is easy to form a cured film having more excellent heat resistance. Only one type of thermal radical polymerization initiator may be used, or two or more types may be used. When there are two or more thermal radical polymerization initiators, the total is preferably in the above range.
- the composition of the present invention may contain a thermal acid generator.
- the thermal acid generator generates an acid by heating, promotes cyclization of the polyimide precursor, and further improves the mechanical properties of the cured film.
- Examples of the thermal acid generator include compounds described in paragraph 0059 of JP2013-167742A.
- 0.01 mass part or more is preferable with respect to 100 mass parts of polyimide precursors, and, as for content of a thermal acid generator, 0.1 mass part or more is more preferable.
- the content of the thermal acid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and particularly preferably 10 parts by mass or less from the viewpoint of electrical insulation of the cured film.
- One type of thermal acid generator may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.
- the composition of the present invention may contain a sensitizing dye.
- a sensitizing dye absorbs specific actinic radiation and enters an electronically excited state.
- the sensitizing dye in an electronically excited state comes into contact with a base generator, a thermal radical polymerization initiator, a photopolymerization initiator, and the like, and effects such as electron transfer, energy transfer, and heat generation occur.
- the base generator, the thermal radical polymerization initiator, and the photopolymerization initiator are decomposed by causing a chemical change to generate radicals, acids, or bases. Details of the sensitizing dye can be referred to the descriptions in paragraphs 0161 to 0163 of JP-A-2016-027357, the contents of which are incorporated herein.
- the content of the sensitizing dye is preferably 0.01 to 20% by mass, and preferably 0.1 to 15% by mass with respect to the total solid content of the composition of the present invention. Is more preferable, and 0.5 to 10% by mass is even more preferable.
- a sensitizing dye may be used individually by 1 type, and may use 2 or more types together.
- the composition of the present invention may contain a chain transfer agent.
- the chain transfer agent is defined, for example, in Polymer Dictionary 3rd Edition (edited by the Polymer Society, 2005) pages 683-684.
- As the chain transfer agent for example, a compound group having SH, PH, SiH, GeH in the molecule is used. These can generate hydrogen by donating hydrogen to a low activity radical to generate a radical, or after being oxidized and deprotonated.
- thiol compounds for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.
- 2-mercaptobenzimidazoles for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.
- 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 composition of the present invention, and 1 to 10 parts by mass. Part is more preferable, and 1 to 5 parts by mass is more preferable. Only one type of chain transfer agent may be used, or two or more types may be used. When there are two or more chain transfer agents, the total is preferably in the above range.
- surfactant Various kinds of surfactants may be added to the composition of the present invention from the viewpoint of further improving applicability.
- the surfactant various types of surfactants such as a fluorosurfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used.
- the following surfactants are also preferable.
- the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0%, based on the total solid content of the composition of the present invention. 0.005 to 1.0 mass%. Only one surfactant may be used, or two or more surfactants may be used. When there are two or more surfactants, the total is preferably in the above range.
- the composition of the present invention is added with a higher fatty acid derivative such as behenic acid or behenic acid amide, and is unevenly distributed on the surface of the composition in the process of drying after coating. May be.
- a higher fatty acid derivative such as behenic acid or behenic acid amide
- 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 composition of the present invention. Only one higher fatty acid derivative may be used, or two or more higher fatty acid derivatives may be used. When two or more higher fatty acid derivatives are used, the total is preferably within the above range.
- the water content of the composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and particularly preferably less than 0.6% by mass from the viewpoint of the coated surface properties.
- the metal content of the composition of the present invention is preferably less than 5 ppm by weight (parts per million), more preferably less than 1 ppm by weight, and particularly preferably less than 0.5 ppm by weight from the viewpoint of insulation.
- the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are included, the total of these metals is preferably in the above range.
- a raw material having a low metal content is selected as a raw material constituting the composition of the present invention.
- the raw material to be filtered may be filtered, or the inside of the apparatus may be lined with polytetrafluoroethylene or the like, and distillation may be performed under a condition in which contamination is suppressed as much as possible.
- the halogen atom content is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and particularly preferably less than 200 ppm by mass from the viewpoint of wiring corrosion.
- a halogen ion is less than 5 mass ppm, More preferably, it is less than 1 mass ppm, Especially less than 0.5 mass ppm is preferable.
- the halogen atom include a chlorine atom and a bromine atom. The total of chlorine atoms and bromine atoms, or chloride ions and bromide ions is preferably in the above range.
- the composition of the present invention can be prepared by mixing the above components.
- the mixing method is not particularly limited, and can be performed by a conventionally known method.
- the filter pore size is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, and even more preferably 0.1 ⁇ m or less.
- the material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.
- a filter that has been washed in advance with an organic solvent may be used.
- a plurality of types of filters may be connected in series or in parallel.
- filters having different pore diameters and / 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 filter.
- the pressure applied is preferably 0.05 MPa or more and 0.3 MPa or less.
- impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined.
- the adsorbent a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
- the cured film of the present invention is formed by curing the composition of the present invention.
- the thickness of the cured film of the present invention can be, for example, 1 ⁇ m or more, and can be 5 ⁇ m or more. Moreover, as an upper limit, it can be set to 100 micrometers or less, and can also be set to 30 micrometers or less.
- a laminate may be obtained by laminating two or more cured films of the present invention.
- Such a laminate preferably has a metal layer between the cured films.
- Such a metal layer is preferably used as a metal wiring such as a rewiring layer.
- Fields to which the cured film of the present invention can be applied include insulating films for semiconductor devices, interlayer insulating films for rewiring layers, and the like. Particularly, since the resolution is good, it can be preferably used for an interlayer insulating film for a rewiring layer in a three-dimensional mounting device.
- the cured film in the present invention can also be used for electronic photoresists, galvanic resists, galvanic resists, etching resists, solder top resists, and the like.
- the cured film of the present invention can also be used for the production of printing plates such as offset printing plates or screen printing plates, the use for etching molded parts, the production of protective lacquers and dielectric layers in electronics, in particular microelectronics.
- the method for producing a cured film of the present invention includes using the composition of the present invention.
- the negative photosensitive resin composition of the present invention is applied to a substrate to form a layer, a negative photosensitive resin composition layer forming step, an exposure step of exposing the negative photosensitive resin composition layer, And a development process for the exposed negative photosensitive resin composition layer.
- the production method of the present invention may include a step of heating the developed negative photosensitive resin composition layer at a temperature of 50 to 500 ° C. after the development processing step. Since the cured film of the present invention has excellent heat resistance, good performance can be maintained even when heated at 150 to 500 ° C.
- the method for producing a laminate of the present invention includes the method for producing a cured film of the present invention.
- a negative photosensitive resin composition layer forming step, an exposure step, and a development processing step are performed again. It is preferable to carry out again in the above order.
- the negative photosensitive resin composition layer forming step, the exposure step, and the development processing step are preferably performed 2 to 5 times in the above order (that is, 3 to 6 times in total).
- a laminated body can be obtained by laminating a cured film.
- the present invention also discloses a semiconductor device including the cured film of the present invention.
- a semiconductor device including the cured film of the present invention.
- an embodiment of a semiconductor device using the composition of the present invention as an interlayer insulating film for a rewiring layer will be described.
- a semiconductor device 100 shown in FIG. 1 is a so-called three-dimensional mounting device, and a stacked body 101 in which a plurality of semiconductor elements (semiconductor chips) 101 a to 101 d are stacked is arranged on a wiring board 120.
- the number of stacked semiconductor elements (semiconductor chips) is not particularly limited. It may be a layer, 8 layers, 16 layers, 32 layers, or the like. Moreover, one layer may be sufficient.
- the plurality of semiconductor elements 101a to 101d are each made of a semiconductor wafer such as a silicon substrate.
- the uppermost semiconductor element 101a does not have a through electrode, and an electrode pad (not shown) is formed on one surface thereof.
- the semiconductor elements 101b to 101d have through electrodes 102b to 102d, and connection pads (not shown) provided integrally with the through electrodes are provided on both surfaces of each semiconductor element.
- the stacked body 101 has a structure in which a semiconductor element 101a having no through electrode and flip-chip connection of semiconductor elements 101b to 101d having through electrodes 102b to 102d are connected. That is, the electrode pad of the semiconductor element 101a having no through electrode and the connection pad on the semiconductor element 101a side of the semiconductor element 101b having the adjacent through electrode 102b are connected by the metal bump 103a such as a solder bump, The connection pad on the other side of the semiconductor element 101b having the electrode 102b is connected to the connection pad on the semiconductor element 101b side of the semiconductor element 101c having the adjacent through electrode 102c by a metal bump 103b such as a solder bump.
- connection pad on the other side of the semiconductor element 101c having the through electrode 102c is connected to the connection pad on the semiconductor element 101c side of the semiconductor element 101d having the adjacent through electrode 102d by the metal bump 103c such as a solder bump.
- An underfill layer 110 is formed in the gaps between the semiconductor elements 101a to 101d, and the semiconductor elements 101a to 101d are stacked via the underfill layer 110.
- the laminated body 101 is laminated on the wiring board 120.
- the wiring substrate 120 for example, a multilayer wiring substrate using an insulating substrate such as a resin substrate, a ceramic substrate, or a glass substrate as a base material is used.
- the wiring board 120 to which the resin board is applied include a multilayer copper-clad laminate (multilayer printed wiring board).
- a surface electrode 120 a is provided on one surface of the wiring board 120.
- An insulating layer 115 in which a rewiring layer 105 is formed is disposed between the wiring substrate 120 and the stacked body 101, and the wiring substrate 120 and the stacked body 101 are electrically connected via the rewiring layer 105. It is connected.
- the insulating layer 115 is formed using the composition of the present invention. That is, one end of the rewiring layer 105 is connected to an electrode pad formed on the surface of the semiconductor element 101d on the rewiring layer 105 side through a metal bump 103d such as a solder bump.
- the other end of the rewiring layer 105 is connected to the surface electrode 120a of the wiring board via a metal bump 103e such as a solder bump.
- An underfill layer 110 a is formed between the insulating layer 115 and the stacked body 101.
- an underfill layer 110 b is formed between the insulating layer 115 and the wiring substrate 120.
- the cured film of the present invention can be widely used in various applications using polyimide.
- polyimide is resistant to heat
- the cured film in the present invention is used for plastic substrates and interlayer insulation films for liquid crystal displays, organic EL displays, electronic paper and other display devices, automotive parts, heat resistant paints, coating agents, and films. Can also be suitably used.
- the polyimide precursor of this invention can also be used for a positive photosensitive resin composition.
- ODPA 4,4′-oxydiphthalic dianhydride
- the structure of the obtained polyimide precursor (P-1) was confirmed by 1 H-NMR (nuclear magnetic resonance spectrum) (DMSO (dimethyl sulfoxide) -d6 solution). 10.6 to 10.3 ppm (m, 2H), 8.2 to 6.7 ppm (m, 14 H), 6.4 to 6.2 ppm (m, 1 H), 6.2 to 6.0 ppm (m, 1 H) ), 6.0 to 5.8 ppm (m, 0.9H), 4.4 to 4.0 ppm (m, 3H), 3.9 to 3.6 ppm (s, 6H).
- DMSO dimethyl sulfoxide
- the weight average molecular weight of the obtained P-1 was 50,000.
- the measurement conditions are as follows. Column: 1 TSK guardcolumn Super AW-H (4.6 mm ID. ⁇ 35 mm) 1 TSK Super AWM-H (6.0 mm ID.
- the obtained mixed solution was diluted with NMP, and the weight average molecular weight measured by GPC was 50,000.
- the polyimide precursor was precipitated in a mixed solvent of 3 liters of water and 3 liters of acetone. The polyimide precursor was filtered off and stirred again in 4 liters of water for 30 minutes and filtered again.
- the obtained polyimide precursor was dried at room temperature under reduced pressure for 2 days.
- the obtained solid was dissolved in NMP, and the weight average molecular weight measured by GPC was 20000. It was thought that it decomposed in the purification process.
- ODPA Tokyo Chemical Industry BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, Tokyo Chemical Industry ODA: Tokyo Chemical Industry Benzidine (4,4′-diaminobiphenyl): Tokyo Chemical Industry Manufactured by Ethanol: Wako Pure Chemical Industries, Ltd. n-Butanol: Wako Pure Chemical Industries, Ltd. n-Octanol: Wako Pure Chemical Industries, Ltd.
- DPHA Nippon Kayaku
- KAYARAD DPHA M-305 Pentaerythritol triacrylate, manufactured by Toagosei Co., Ltd.
- Aronix M-305 701 Glycerol dimethacrylate, Shin-Nakamura Chemical Co., Ltd.
- Hydroxyethyl acrylate Wako Pure Chemical Industries, Ltd.
- M-215 Isocyanuric acid ethylene oxide (EO) modified diacrylate, manufactured by Toagosei Co., Ltd., Aronix M-215 Karenz BEI: 1,1- (bisacryloyloxymethyl) ethyl isocyanate, manufactured by Showa Denko Karenz MOI: 2-isocyanatoethyl methacrylate, manufactured by Showa Denko 4-Aminostyrene: manufactured by Tokyo Chemical Industry
- the negative photosensitive resin composition is filtered under pressure at a pressure of 3.0 MPa through a filter having a pore width of 0.8 ⁇ m, and then the negative photosensitive resin composition is applied onto a silicon wafer by spin coating.
- a negative photosensitive resin composition layer was formed by applying in layers.
- the obtained silicon wafer to which the negative photosensitive resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to form a uniform negative photosensitive resin composition layer having a thickness of 15 ⁇ m on the silicon wafer. Obtained.
- the negative photosensitive resin composition layer on the silicon wafer was exposed with an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C).
- Exposed part residual film ratio (%) [film thickness after development of exposed part / film thickness of unexposed part before development] ⁇ 100 5: 90% or more 4: 70% or more and less than 90% 3: 50% or more and less than 70% 2: 30% or more and less than 50% 1: less than 30% Evaluation of 3 or more is practically preferable.
- the negative photosensitive resin composition is filtered under pressure at a pressure of 3.0 MPa through a filter having a pore width of 0.8 ⁇ m, and then the negative photosensitive resin composition is applied onto a silicon wafer by spin coating.
- a negative photosensitive resin composition layer was formed by applying in layers.
- the silicon wafer to which the obtained negative photosensitive resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes, and a uniform negative photosensitive resin composition layer having a thickness of 15 ⁇ m was formed on the silicon wafer. did. This was developed with cyclopentanone for 60 seconds, and the unexposed portion residual film ratio was determined from the change in film thickness before and after development.
- Unexposed area remaining film ratio (%) [(film thickness after development of unexposed area) / film thickness before development of unexposed area] ⁇ 100 5: Less than 5% 4: 5% or more but less than 20% 3: 20% or more but less than 50% 2: 50% or more but less than 90% 1: 90% or more Evaluation of 3 or more is practically preferable.
- the negative photosensitive resin composition is filtered under pressure at a pressure of 3.0 MPa through a filter having a pore width of 0.8 ⁇ m, and then the negative photosensitive resin composition is applied onto a silicon wafer by spin coating.
- a negative photosensitive resin composition layer was formed by applying in layers.
- the silicon wafer to which the obtained negative photosensitive resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes, and a uniform negative photosensitive resin composition layer having a thickness of 15 ⁇ m was formed on the silicon wafer. did.
- the negative photosensitive resin composition layer on the silicon wafer was exposed at an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C), and the exposed negative photosensitive resin composition layer (resin layer) was heated at a rate of temperature increase of 10 ° C./min in a nitrogen atmosphere, and was maintained for 3 hours after reaching 230 ° C., and the remaining film ratio after heating was determined from the change in film thickness before and after heating.
- Residual film ratio after thermosetting (%) [film thickness after thermosetting / film thickness before thermosetting] ⁇ 100 5: 85% or more 4: 80% or more and less than 85% 3: 70% or more and less than 80% 2: 60% or more and less than 70% 1: less than 60% Evaluation of 2 or more is practically preferable.
- the negative photosensitive resin composition is filtered under pressure at a pressure of 3.0 MPa through a filter having a pore width of 0.8 ⁇ m, and then the negative photosensitive resin composition is applied onto a silicon wafer by spin coating.
- a negative photosensitive resin composition layer was formed by applying in layers.
- the obtained silicon wafer to which the negative photosensitive resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to form a uniform negative photosensitive resin composition layer having a thickness of 15 ⁇ m on the silicon wafer. Obtained.
- the negative photosensitive resin composition layer on the silicon wafer was exposed at an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C), and the exposed negative photosensitive resin composition layer (resin layer) was heated at a rate of temperature increase of 10 ° C./min in a nitrogen atmosphere, and was maintained for 3 hours after reaching 230 ° C.
- the cured resin layer was immersed in a 4.9% by mass hydrofluoric acid solution, and the resin layer was peeled off from the silicon wafer to obtain a resin film.
- the obtained resin film was set in a viscoelasticity measuring device (Rhegel E4000, manufactured by UBM Co., Ltd.), and the temperature was increased from 0 ° C. to 350 ° C. at a frequency of 1 Hz and a temperature increase rate of 10 ° C./min. , Tg (° C.) was determined from the peak temperature of tan ⁇ .
- Example 1 ⁇ Other Examples and Comparative Examples>
- one or more of the polyimide precursor, photopolymerization initiator, radical polymerizable monomer, polymerization inhibitor, metal discoloration inhibitor, silane coupling agent, and solvent are changed as shown in Table 4 or Table 5.
- some examples were blended with a thermal base generator, and others were performed in the same manner.
- G-1 the following compound
- G-2 the following compound
- G-3 the following compound
- G-4 the following compound
- DMSO dimethyl sulfoxide
- GBL ⁇ -butyrolactone
- NMP N-methyl-2-pyrrolidone ethyl lactate
- the Tg was high and the resolution was excellent.
- the glass transition temperature was 230 ° C. or higher, which was 5 ° C. higher than those of Comparative Examples 1 and 2.
- An increase in Tg of 5 ° C. can be said to be a very remarkable effect from the viewpoint of improving reliability in a high-temperature process such as a vapor deposition process for forming a metal wiring or a bonding process between electrodes.
- R 1 and R 2 of formula (1) an organic group of a non-polymerizable group having 1 to 4 carbon atoms
- Example 100 Manufacture of laminated body 1>
- the photosensitive resin composition of Example 3 was subjected to pressure filtration through a filter having a pore width of 0.8 ⁇ m, and then a photosensitive resin composition layer was formed on a silicon wafer by spin coating.
- the obtained silicon wafer to which the photosensitive resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a uniform photosensitive resin composition layer having a thickness of 15 ⁇ m on the silicon wafer.
- the photosensitive resin composition layer on the silicon wafer was exposed with an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C), and the exposed photosensitive resin composition layer (resin layer) was Development was performed with cyclopentanone for 60 seconds to form a 10 ⁇ m diameter hole.
- the temperature was raised at a rate of 10 ° C./min in a nitrogen atmosphere, and after reaching 230 ° C., the temperature was maintained for 3 hours.
- After cooling to room temperature again using the same type of photosensitive resin composition as the photosensitive resin composition on the surface of the resin layer, filtration of the photosensitive resin composition in the same manner as described above, 3 of the patterned film was performed.
- the procedure up to the time heating was performed again to form a laminate 1 having two resin layers.
- Example 3 The photosensitive resin composition of Example 3 was subjected to pressure filtration through a filter having a pore width of 0.8 ⁇ m, and then a photosensitive resin composition layer was formed on a silicon wafer by spin coating. The obtained silicon wafer to which the photosensitive resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a uniform photosensitive resin composition layer having a thickness of 15 ⁇ m on the silicon wafer.
- the photosensitive resin composition layer on the silicon wafer was exposed with an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C), and the exposed photosensitive resin composition layer (resin layer) was subjected to cyclopenta
- a hole having a diameter of 10 ⁇ m was formed by developing for 60 seconds in a non-process.
- the temperature was raised at a rate of 10 ° C./min in a nitrogen atmosphere, and after reaching 230 ° C., the temperature was maintained for 3 hours.
- a 2 ⁇ m thick copper thin film (metal layer) was applied to a part of the surface of the photosensitive resin composition layer by vapor deposition so as to cover the hole portion.
- the photosensitive resin composition of Example 3 was filtered in the same manner as described above, and then the patterned film was used for 3 hours. The procedure up to the heating was performed again to produce a laminate 3 composed of resin layer / metal layer / resin layer.
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Abstract
Description
<1>ポリイミド前駆体と、光重合開始剤と、溶剤とを含み、
ポリイミド前駆体は、式(1)で表される繰り返し単位を有し、少なくとも一方の末端に式(2)で表される構造を有し、重量平均分子量が50000以下である、ネガ型感光性樹脂組成物;
(A)l-L1-* (2)
式(2)中、Aは重合性基を表し、L1は単結合またはl+1価の有機基を表し、lは1~10の整数を表し、*は他の部位との結合部位を示す。
<2>式(2)におけるlが、2~5の整数である、<1>に記載のネガ型感光性樹脂組成物。
<3>R1およびR2はそれぞれ独立に、炭素数1~4の非重合性の有機基である、<1>または<2>に記載のネガ型感光性樹脂組成物。
<4>式(2)中のAは、炭素-炭素不飽和二重結合を含む基である、<1>~<3>のいずれか1つに記載のネガ型感光性樹脂組成物。
<5>式(2)で表される構造は、式(3)または式(4)で表わされる構造である、<1>~<4>のいずれか1つに記載のネガ型感光性樹脂組成物;
式(4)中、L3は単結合またはn+1価の有機基を表し、nは1~10の整数を表し、*は他の部位との結合部位を示す。
<6>ポリイミド前駆体の重量平均分子量が5000以上である、<1>~<5>のいずれか1つに記載のネガ型感光性樹脂組成物。
<7>さらに、多官能ラジカル重合性モノマーを含む、<1>~<6>のいずれか1つに記載のネガ型感光性樹脂組成物。
<8>さらに、熱塩基発生剤を含む、<1>~<7>のいずれか1つに記載のネガ型感光性樹脂組成物。
<9>光重合開始剤がオキシム化合物およびメタロセン化合物から選ばれる少なくとも1種である、<1>~<8>のいずれか1つに記載のネガ型感光性樹脂組成物。
<10>再配線層用層間絶縁膜形成用である、<1>~<9>のいずれか1つに記載のネガ型感光性樹脂組成物。
<11><1>~<10>のいずれか1つに記載のネガ型感光性樹脂組成物を硬化してなる硬化膜。
<12>膜厚が1~30μmである、<11>に記載の硬化膜。
<13><1>~<10>のいずれか1つに記載のネガ型感光性樹脂組成物を基板に適用して層状にする感光性樹脂組成物層形成工程と、
ネガ型感光性樹脂組成物層を露光する露光工程と、
露光された感光性樹脂組成物層に対して、現像処理を行う現像処理工程と、
を有する硬化膜の製造方法。
<14>現像処理工程後に、現像されたネガ型感光性樹脂組成物層を50~500℃の温度で加熱する加熱工程を含む、<13>に記載の硬化膜の製造方法。
<15><11>または<12>に記載の硬化膜を有する半導体デバイス。
<16><13>または<14>に記載の硬化膜の製造方法を含む、積層体の製造方法。
<17><13>または<14>に記載の硬化膜の製造方法を含む、半導体デバイスの製造方法。
<18>式(1)で表される繰り返し単位を有し、少なくとも一方の末端に式(2)で表される構造を有し、重量平均分子量が50000以下であるポリイミド前駆体;
(A)l-L1-* (2)
式(2)中、Aは重合性基を表し、L1は単結合またはl+1価の有機基を表し、lは1~10の整数を表し、*は他の部位との結合部位を示す。
<19>R1およびR2はそれぞれ独立に、炭素数1~4の非重合性の有機基である、<18>に記載のポリイミド前駆体。
<20>式(2)中のAは、炭素-炭素不飽和二重結合を含む基である、<18>または<19>に記載のポリイミド前駆体。
<21>式(2)におけるlが、2~5の整数である、<18>~<20>のいずれか1つに記載のポリイミド前駆体。 As a result of intensive studies, the present inventors can improve the resolution by providing a polymerizable group at the end of the polyimide precursor and setting the weight average molecular weight of the polyimide precursor to 50000 or less. As a result, the present invention has been completed. Accordingly, the present invention provides the following.
<1> includes a polyimide precursor, a photopolymerization initiator, and a solvent,
The polyimide precursor has a repeating unit represented by the formula (1), has a structure represented by the formula (2) at at least one end, and has a weight average molecular weight of 50000 or less, and is a negative photosensitive. Resin composition;
(A) l -L 1- * (2)
In the formula (2), A represents a polymerizable group, L 1 represents a single bond or an l + 1 valent organic group, l represents an integer of 1 to 10, and * represents a bonding site with another site.
<2> The negative photosensitive resin composition according to <1>, wherein l in formula (2) is an integer of 2 to 5.
<3> The negative photosensitive resin composition according to <1> or <2>, wherein R 1 and R 2 are each independently a non-polymerizable organic group having 1 to 4 carbon atoms.
<4> The negative photosensitive resin composition according to any one of <1> to <3>, wherein A in the formula (2) is a group containing a carbon-carbon unsaturated double bond.
<5> The negative photosensitive resin according to any one of <1> to <4>, wherein the structure represented by formula (2) is a structure represented by formula (3) or formula (4): Composition;
In the formula (4), L 3 represents a single bond or an n + 1 valent organic group, n represents an integer of 1 to 10, and * represents a bonding site with another site.
<6> The negative photosensitive resin composition according to any one of <1> to <5>, wherein the polyimide precursor has a weight average molecular weight of 5000 or more.
<7> The negative photosensitive resin composition according to any one of <1> to <6>, further comprising a polyfunctional radical polymerizable monomer.
<8> The negative photosensitive resin composition according to any one of <1> to <7>, further comprising a thermal base generator.
<9> The negative photosensitive resin composition according to any one of <1> to <8>, wherein the photopolymerization initiator is at least one selected from an oxime compound and a metallocene compound.
<10> The negative photosensitive resin composition according to any one of <1> to <9>, which is used for forming an interlayer insulating film for a rewiring layer.
<11> A cured film obtained by curing the negative photosensitive resin composition according to any one of <1> to <10>.
<12> The cured film according to <11>, wherein the film thickness is 1 to 30 μm.
<13> a photosensitive resin composition layer forming step in which the negative photosensitive resin composition according to any one of <1> to <10> is applied to a substrate to form a layer;
An exposure step of exposing the negative photosensitive resin composition layer;
A development processing step of performing development processing on the exposed photosensitive resin composition layer;
The manufacturing method of the cured film which has this.
<14> The method for producing a cured film according to <13>, further comprising a heating step of heating the developed negative photosensitive resin composition layer at a temperature of 50 to 500 ° C. after the development processing step.
<15> A semiconductor device having the cured film according to <11> or <12>.
<16> A method for producing a laminate including the method for producing a cured film according to <13> or <14>.
<17> A method for producing a semiconductor device, comprising the method for producing a cured film according to <13> or <14>.
<18> A polyimide precursor having a repeating unit represented by formula (1), having a structure represented by formula (2) at at least one end, and having a weight average molecular weight of 50,000 or less;
(A) l -L 1- * (2)
In the formula (2), A represents a polymerizable group, L 1 represents a single bond or an l + 1 valent organic group, l represents an integer of 1 to 10, and * represents a bonding site with another site.
<19> The polyimide precursor according to <18>, wherein R 1 and R 2 are each independently a non-polymerizable organic group having 1 to 4 carbon atoms.
<20> The polyimide precursor according to <18> or <19>, wherein A in the formula (2) is a group containing a carbon-carbon unsaturated double bond.
<21> The polyimide precursor according to any one of <18> to <20>, wherein l in formula (2) is an integer of 2 to 5.
本明細書における基(原子団)の表記において、置換および無置換を記していない表記は、置換基を有さない基と共に置換基を有する基をも包含する。例えば、「アルキル基」とは、置換基を有さないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含する。
本明細書において「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線、イオンビーム等の粒子線を用いた描画も露光に含める。また、露光に用いられる光としては、一般的に、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線(EUV光)、X線、電子線等の活性光線または放射線が挙げられる。
本明細書において、「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
本明細書において、「(メタ)アクリレート」は、「アクリレート」および「メタクリレート」の双方、または、いずれかを表し、「(メタ)アクリル」は、「アクリル」および「メタクリル」の双方、または、いずれかを表し、「(メタ)アクリロイル」は、「アクリロイル」および「メタクリロイル」の双方、または、いずれかを表す。
本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。
本明細書において、固形分濃度とは、組成物の総質量に対する、溶剤を除く他の成分の質量百分率である。また、固形分濃度は、特に述べない限り25℃における濃度をいう。
本明細書において、重量平均分子量(Mw)および数平均分子量(Mn)は、特に述べない限り、ゲル浸透クロマトグラフィー(GPC)測定に従い、ポリスチレン換算値として定義される。本明細書において、重量平均分子量(Mw)および数平均分子量(Mn)は、HLC-8220(東ソー(株)製)を用い、カラムとしてガードカラムTSKguardcolumn SuperAW-H、TSK SuperAWM-H(東ソー(株)製)を用いることによって求めることができる。溶離液は特に述べない限り、N-メチル-2-ピロリドン(NMP)を用いて測定したものとする。また、検出は特に述べない限り、示差屈折率(RI)検出器を使用したものとする。 The description of the components in the present invention described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.
In the notation of a group (atomic group) in this specification, the notation which does not describe substitution and unsubstituted includes the group which has a substituent with the group which does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, unless otherwise specified, “exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. The light used for exposure generally includes active rays or radiation such as an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present specification, “(meth) acrylate” represents both and / or “acrylate” and “methacrylate”, and “(meth) acryl” represents both “acryl” and “methacryl”, or “(Meth) acryloyl” represents either or both of “acryloyl” and “methacryloyl”.
In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
In this specification, solid content concentration is the mass percentage of the other component except a solvent with respect to the gross mass of a composition. Moreover, solid content concentration says the density | concentration in 25 degreeC unless there is particular mention.
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene conversion values according to gel permeation chromatography (GPC) measurement unless otherwise specified. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are HLC-8220 (manufactured by Tosoh Corporation), and guard columns TSK guard column Super AW-H and TSK Super AWM-H (Tosoh Corporation) ))). The eluent was measured using N-methyl-2-pyrrolidone (NMP) unless otherwise stated. Unless otherwise stated, a differential refractive index (RI) detector is used for detection.
本発明のネガ型感光性樹脂組成物(以下、本発明の組成物ともいう)は、ポリイミド前駆体と、光重合開始剤と、溶剤とを含み、ポリイミド前駆体は、後述する式(1)で表される繰り返し単位を有し、少なくとも一方の末端に後述する式(2)で表される構造を有し、重量平均分子量が50000以下であることを特徴とする。 <Negative photosensitive resin composition>
The negative photosensitive resin composition of the present invention (hereinafter also referred to as the composition of the present invention) includes a polyimide precursor, a photopolymerization initiator, and a solvent. It has a structure represented by Formula (2) mentioned later at least at one terminal, and has a weight average molecular weight of 50000 or less.
本発明者らの検討によれば、ポリイミド前駆体の末端に重合性基を設けることにより、ガラス転移温度(Tg)を向上可能であることが分かった。これまで、ポリイミド前駆体は、重合性基を高密度に導入可能という理由から、側鎖に重合性基が設けられるのが一般的であった。しかしながら、ポリイミド前駆体の側鎖に重合性基を入れると、ポリイミド前駆体の環化の際に、上記側鎖の重合性基が脱離してしまう場合があることが分かった。これに対し、ポリイミド前駆体の末端に重合性基を導入すると、環化しても、重合性基の脱離は起こらない。
しかしながら、末端に重合性基のみを設けると、現像時の解像性が劣ることが分かった。これは、ポリイミド前駆体に対する重合性基の量が相対的に少ないためであると考えられた。そこで、ポリイミド前駆体の重量平均分子量を50000以下とすることで、ポリイミド前駆体に対する重合性基の量を相対的に高めることができ、その結果、解像性を向上させることに成功したものである。
さらに、本発明によれば、ネガ型感光性樹脂組成物の硬化膜の高いTgを維持しつつ、解像性を向上させることができる。 According to the composition of this invention, it can be set as the negative photosensitive resin composition excellent in resolution. It is assumed that the mechanism for obtaining such an effect is as follows.
According to the study by the present inventors, it was found that the glass transition temperature (Tg) can be improved by providing a polymerizable group at the terminal of the polyimide precursor. So far, polyimide precursors have generally been provided with a polymerizable group in the side chain because the polymerizable group can be introduced at a high density. However, it has been found that when a polymerizable group is added to the side chain of the polyimide precursor, the polymerizable group of the side chain may be detached during the cyclization of the polyimide precursor. In contrast, when a polymerizable group is introduced at the end of the polyimide precursor, the polymerizable group is not eliminated even when cyclized.
However, it was found that when only the polymerizable group was provided at the terminal, the resolution during development was inferior. This was thought to be due to the relatively small amount of polymerizable groups relative to the polyimide precursor. Therefore, by setting the weight average molecular weight of the polyimide precursor to 50000 or less, the amount of the polymerizable group relative to the polyimide precursor can be relatively increased, and as a result, the resolution has been successfully improved. is there.
Furthermore, according to the present invention, it is possible to improve the resolution while maintaining a high Tg of the cured film of the negative photosensitive resin composition.
露光部残膜率(%)=[露光部の現像後の膜厚/未露光部の現像前の膜厚]×100 In the composition of the present invention, the exposed film residual film ratio is preferably 50% or more, more preferably 70% or more, and further preferably 90% or more. The exposed portion residual film ratio is a value defined as follows. The details of the measurement method can be referred to the description of Examples described later.
Exposed part residual film ratio (%) = [film thickness after development of exposed part / film thickness of unexposed part before development] × 100
熱硬化後の残膜率(%)=[熱硬化後の膜厚/熱硬化前の膜厚]×100 In the composition of the present invention, the residual film ratio after thermosetting is preferably 70% or more, more preferably 80% or more, and further preferably 85% or more. In addition, the remaining film rate after thermosetting is a value defined by the following. The details of the measurement method can be referred to the description of Examples described later.
Residual film ratio after thermosetting (%) = [film thickness after thermosetting / film thickness before thermosetting] × 100
本発明の組成物は、式(1)で表される繰り返し単位を有し、少なくとも一方の末端に式(2)で表される構造を有し、重量平均分子量が50000以下であるポリイミド前駆体を含有する。このポリイミド前駆体は、本発明のポリイミド前駆体でもある。
(A)l-L1-* (2)
式(2)中、Aは重合性基を表し、L1は単結合またはl+1価の有機基を表し、lは1~10の整数を表し、*は他の部位との結合部位を示す。 << Polyimide precursor >>
The composition of the present invention has a repeating unit represented by the formula (1), has a structure represented by the formula (2) at at least one end, and has a weight average molecular weight of 50,000 or less. Containing. This polyimide precursor is also the polyimide precursor of the present invention.
(A) l -L 1- * (2)
In the formula (2), A represents a polymerizable group, L 1 represents a single bond or an l + 1 valent organic group, l represents an integer of 1 to 10, and * represents a bonding site with another site.
具体的には、Xが表す2価の有機基は、炭素数2~20の直鎖または分岐の脂肪族基、炭素数6~20の環状の脂肪族基、炭素数6~20の芳香族基、または、これらの組み合わせからなる基を含むジアミンであることが好ましく、炭素数6~20の芳香族基を含むジアミンであることがより好ましい。芳香族基の例としては、下記の芳香族基が挙げられる。 The divalent organic group represented by X in the formula (1) is preferably a group derived from diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamine. One type of diamine may be used, or two or more types may be used.
Specifically, the divalent organic group represented by X is a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, or an aromatic group having 6 to 20 carbon atoms. A diamine containing a group or a group consisting of a combination thereof is preferred, and a diamine containing an aromatic group having 6 to 20 carbon atoms is more preferred. The following aromatic groups are mentioned as an example of an aromatic group.
ジェファーミン(登録商標)KH-511、ジェファーミン(登録商標)ED-600、ジェファーミン(登録商標)ED-900、ジェファーミン(登録商標)ED-2003、ジェファーミン(登録商標)EDR-148、ジェファーミン(登録商標)EDR-176の構造を以下に示す。 A diamine having at least two alkylene glycol units in the main chain is also a preferred example. Preferred is a diamine containing two or more ethylene glycol chains or propylene glycol chains in one molecule, and more preferred is a diamine containing no aromatic ring. Specific examples include Jeffermin (registered trademark) KH-511, Jeffermin (registered trademark) ED-600, Jeffermin (registered trademark) ED-900, Jeffermin (registered trademark) ED-2003, Jeffermin (registered trademark). ) EDR-148, Jeffamine (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (above trade names, manufactured by HUNTSMAN), 1- (2- (2- (2- (2- Aminopropoxy) ethoxy) propoxy) propan-2-amine, 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propan-2-amine, and the like, but is not limited thereto. .
Jeffermin (registered trademark) KH-511, Jeffermin (registered trademark) ED-600, Jeffermin (registered trademark) ED-900, Jeffermin (registered trademark) ED-2003, Jeffermin (registered trademark) EDR-148, The structure of Jeffamine (registered trademark) EDR-176 is shown below.
式(51)
R10~R17の1価の有機基として、炭素数1~10(好ましくは炭素数1~6)の無置換のアルキル基、炭素数1~10(好ましくは炭素数1~6)のフッ化アルキル基等が挙げられる。
式(61)
式(51)または(61)の構造を与えるジアミン化合物としては、2,2’-ジメチル-4,4’-ジアミノビフェニル、2,2’-ビス(トリフルオロメチル)-4,4’-ジアミノビフェニル、2,2’-ビス(フルオロ)-4,4’-ジアミノビフェニル、4,4’-ジアミノオクタフルオロビフェニル等が挙げられる。これらは1種を用いるか、または2種以上を組み合わせて用いてもよい。 The divalent organic group represented by X in the formula (1) is also preferably a divalent organic group represented by the following formula (51) or formula (61) from the viewpoint of i-line transmittance. In particular, a divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-line transmittance and availability.
Formula (51)
Examples of the monovalent organic group represented by R 10 to R 17 include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorine atom having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Alkyl group and the like.
Formula (61)
Examples of the diamine compound that gives the structure of formula (51) or (61) include 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diamino. Biphenyl, 2,2′-bis (fluoro) -4,4′-diaminobiphenyl, 4,4′-diaminooctafluorobiphenyl and the like can be mentioned. These may be used alone or in combination of two or more.
式(5)
Formula (5)
式(O)
Formula (O)
(A)l-L1-* (2)
式(2)中、Aは重合性基を表し、L1は単結合またはl+1価の有機基を表し、lは1~10の整数を表し、*は他の部位との結合部位を示す。 The polyimide precursor of the present invention has a structure represented by the formula (2) at least at one end.
(A) l -L 1- * (2)
In the formula (2), A represents a polymerizable group, L 1 represents a single bond or an l + 1 valent organic group, l represents an integer of 1 to 10, and * represents a bonding site with another site.
l+1価の有機基の具体例として、以下の構造単位または以下の構造単位が2以上組み合わさって構成される基(環構造を形成していてもよい)を挙げることができる。 In the formula (2), L 1 represents a single bond or an l + 1 valent organic group, preferably an l + 1 valent organic group. The l + 1 valent organic group is composed of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. Groups.
Specific examples of the l + 1 valent organic group include the following structural units or a group formed by combining two or more of the following structural units (which may form a ring structure).
式(4)中、L3は単結合またはn+1価の有機基を表し、nは1~10の整数を表し、*は他の部位との結合部位を示す。 The structure represented by Formula (2) is preferably a structure represented by Formula (3) or Formula (4), and more preferably a structure represented by Formula (3). According to this aspect, the remaining film ratio after development in the exposed portion can be increased.
In the formula (4), L 3 represents a single bond or an n + 1 valent organic group, n represents an integer of 1 to 10, and * represents a bonding site with another site.
また、本発明の組成物における、式(1)で表される繰り返し単位を有し、かつ、少なくとも一方の末端に「(A)l-L1-*」で表される構造を有し、重量平均分子量が50000以下であるポリイミド前駆体の含有量は、本発明の組成物の全固形分の10~99質量%が好ましく、50~98質量%がより好ましく、70~96質量%がさらに好ましい。 The content of the polyimide precursor in the composition of the present invention is preferably 10 to 99% by mass, more preferably 50 to 98% by mass, and further preferably 70 to 96% by mass of the total solid content of the composition of the present invention. .
The composition of the present invention has a repeating unit represented by the formula (1), and has a structure represented by “(A) 1 -L 1- *” at least at one end; The content of the polyimide precursor having a weight average molecular weight of 50000 or less is preferably 10 to 99% by mass, more preferably 50 to 98% by mass, and further 70 to 96% by mass based on the total solid content of the composition of the present invention. preferable.
本発明では、テトラカルボン酸二無水物またはその誘導体と、上記アルコールの原料モル比(テトラカルボン酸二無水物またはその誘導体:アルコール)は、0.9~1.1:2.1~1.9が好ましい。
本発明では、また、テトラカルボン酸二無水物またはその誘導体と、ジアミンの原料モル比(テトラカルボン酸二無水物またはその誘導体:ジアミン)は、0.8~1.2:1.2~0.8が好ましく、1.001~1.2:0.999~0.8がより好ましい。このように、テトラカルボン酸二無水物またはその誘導体をわずかにリッチにすることにより、重合性基を有する化合物添加前の末端は酸無水物構造となり、水酸基またはアミノ基と重合性基を有する化合物によって、重合性基を確実に導入することができる。
上記の反応の反応温度は、-20~60℃が好ましい。また、反応時間は30分~10時間が好ましい。 In the polyimide precursor of the present invention, after reacting a diamine with tetracarboxylic dianhydride or a derivative thereof, and further reacting a compound having a polymerizable group with this reaction product, the carboxyl group is esterified. Can be manufactured. As another method, after reacting a diamine with an ester of a tetracarboxylic dianhydride or the like and an alcohol, the reaction product is further reacted with a compound having a polymerizable group. it can.
In the present invention, the molar ratio of tetracarboxylic dianhydride or derivative thereof to the above alcohol (tetracarboxylic dianhydride or derivative thereof: alcohol) is 0.9 to 1.1: 2.1 to 1. 9 is preferred.
In the present invention, the molar ratio of tetracarboxylic dianhydride or derivative thereof to diamine (tetracarboxylic dianhydride or derivative thereof: diamine) is 0.8 to 1.2: 1.2 to 0. .8 is preferable, and 1.001 to 1.2: 0.999 to 0.8 is more preferable. Thus, by slightly enriching the tetracarboxylic dianhydride or its derivative, the terminal before addition of the compound having a polymerizable group becomes an acid anhydride structure, and the compound having a hydroxyl group or an amino group and a polymerizable group Thus, the polymerizable group can be reliably introduced.
The reaction temperature of the above reaction is preferably −20 to 60 ° C. The reaction time is preferably 30 minutes to 10 hours.
テトラカルボン酸二無水物と反応させるアルコールは、炭素数1~8のアルコールが好ましく、炭素数1~4のアルコールがより好ましく、炭素数1~3のアルコールがさらに好ましく、炭素数1または2のアルコールが一層好ましく、炭素数1のアルコール(メタノール)がより一層好ましい。
上記アルコールの具体例としては、メタノール、エタノール、プロパノール、n-ブタノールが挙げられ、メタノールが特に好ましい。 Further, the molecular weight of the alcohol to be reacted with tetracarboxylic dianhydride is preferably 30 to 150, more preferably 30 to 80, and further preferably 30 to 65. When the molecular weight of the alcohol to be reacted with tetracarboxylic dianhydride is in the above range, a polyimide precursor having excellent resolution is easily obtained.
The alcohol to be reacted with tetracarboxylic dianhydride is preferably an alcohol having 1 to 8 carbon atoms, more preferably an alcohol having 1 to 4 carbon atoms, still more preferably an alcohol having 1 to 3 carbon atoms, and an alcohol having 1 or 2 carbon atoms. Alcohol is more preferable, and alcohol having 1 carbon (methanol) is even more preferable.
Specific examples of the alcohol include methanol, ethanol, propanol, and n-butanol, and methanol is particularly preferable.
また、重合性基を有する化合物の分子量は、100~2000が好ましく、100~1500がより好ましく、100~1000がさらに好ましい。重合性基を有する化合物の分子量が上述の範囲であれば、解像性に優れたポリイミド前駆体が得られやすい化合物の具体例としては、酸二無水物を過剰に用いる場合は、ペンタエリスリトールトリ(メタ)アクリレート、グリセロールジ(メタ)アクリレート、イソシアヌル酸エチレンオキシド(EO)変性ジ(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、4-アミノスチレンが例示され、ジアミンを過剰に用いる場合には、2-イソシアナトエチル(メタ)アクリレート、1,1-(ビスアクリロイルオキシメチル)エチルイソシアネートが例示される。 The compound having a polymerizable group is preferably a compound having 1 to 10 polymerizable groups, more preferably a compound having 2 to 8 polymerizable groups, and still more preferably a compound having 2 to 5 polymerizable groups. As the polymerizable group, a group containing a carbon-carbon unsaturated double bond is preferable. Specifically, a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a styryl group, a group represented by the above formula (A-1) and a group represented by the above formula (A-2) Is mentioned.
The molecular weight of the compound having a polymerizable group is preferably from 100 to 2000, more preferably from 100 to 1500, and further preferably from 100 to 1000. If the molecular weight of the compound having a polymerizable group is within the above range, specific examples of the compound in which a polyimide precursor excellent in resolution can be easily obtained include pentaerythritol trimethyl when an acid dianhydride is excessively used. (Meth) acrylate, glycerol di (meth) acrylate, isocyanuric acid ethylene oxide (EO) modified di (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) Examples include acrylate and 4-aminostyrene. When diamine is used in excess, 2-isocyanatoethyl (meth) acrylate and 1,1- (bisacryloyloxymethyl) ethyl isocyanate are exemplified.
有機溶剤としては、原料に応じて適宜定めることができるが、ピリジン、ジエチレングリコールジメチルエーテル(ジグリム)、N-メチルピロリドンおよびN-エチルピロリドンが例示される。 In the method for producing a polyimide precursor, an organic solvent is preferably used for the reaction. One or more organic solvents may be used.
The organic solvent can be appropriately determined according to the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.
本発明の組成物は、光重合開始剤を含有する。光重合開始剤は、光カチオン重合開始剤、光ラジカル重合開始剤などが挙げられ、光ラジカル重合開始剤が好ましい。本発明の組成物が光ラジカル重合開始剤を含むことにより、本発明の組成物を半導体ウエハなどの基板に適用してネガ型感光性樹脂組成物層を形成した後、光を照射することで、ラジカルに起因する硬化が起こり、光照射部における溶解性を低下させることができる。このため、例えば、電極部のみをマスクするパターンを持つフォトマスクを介してネガ型感光性樹脂組成物層を露光することで、電極のパターンにしたがって、溶解性の異なる領域を簡便に作製できるという利点がある。 << photopolymerization initiator >>
The composition of the present invention contains a photopolymerization initiator. Examples of the photopolymerization initiator include a photocationic polymerization initiator and a photoradical polymerization initiator, and a photoradical polymerization initiator is preferred. When the composition of the present invention contains a photo radical polymerization initiator, the composition of the present invention is applied to a substrate such as a semiconductor wafer to form a negative photosensitive resin composition layer, and then irradiated with light. Curing due to radicals occurs, and the solubility in the light irradiation part can be reduced. For this reason, for example, by exposing a negative photosensitive resin composition layer through a photomask having a pattern for masking only the electrode portion, it is possible to easily produce regions having different solubility according to the electrode pattern. There are advantages.
光重合開始剤は、約300~800nm(好ましくは330~500nm)の範囲内に少なくとも約50のモル吸光係数を有する化合物を、少なくとも1種含有していることが好ましい。化合物のモル吸光係数は、公知の方法を用いて測定することができる。例えば、紫外可視分光光度計(Varian社製Cary-5 spectrophotometer)にて、酢酸エチル溶剤を用い、0.01g/Lの濃度で測定することが好ましい。 There is no restriction | limiting in particular as a photoinitiator, It can select suitably from well-known photoinitiators. For example, a photopolymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferable. Further, it may be an activator that generates some active radicals by generating some action with the photoexcited sensitizer.
The photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 to 800 nm (preferably 330 to 500 nm). The molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.
ヒドロキシアセトフェノン系開始剤としては、IRGACURE-184(IRGACUREは登録商標)、DAROCUR-1173、IRGACURE-500、IRGACURE-2959、IRGACURE-127(商品名:いずれもBASF社製)を用いることができる。
アミノアセトフェノン系開始剤としては、市販品であるIRGACURE-907、IRGACURE-369、および、IRGACURE-379(商品名:いずれもBASF社製)を用いることができる。
アミノアセトフェノン系開始剤として、365nmまたは405nm等の波長光源に吸収極大波長がマッチングされた特開2009-191179号公報に記載の化合物も用いることができる。
アシルホスフィン系開始剤としては、2,4,6-トリメチルベンゾイル-ジフェニル-ホスフィンオキサイドなどが挙げられる。また、市販品であるIRGACURE-819やIRGACURE-TPO(商品名:いずれもBASF社製)を用いることができる。
メタロセン化合物としては、IRGACURE-784(BASF社製)などが例示される。 As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
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.
As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, compounds described in JP-A-2009-191179 in which the absorption maximum wavelength is matched with a wavelength light source of 365 nm or 405 nm can also be used.
Examples of the acylphosphine initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) which are commercially available products can be used.
Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF).
オキシム化合物の具体例としては、特開2001-233842号公報に記載の化合物、特開2000-80068号公報に記載の化合物、特開2006-342166号公報に記載の化合物を用いることができる。
好ましいオキシム化合物としては、例えば、下記の構造の化合物や、3-ベンゾオキシイミノブタン-2-オン、3-アセトキシイミノブタン-2-オン、3-プロピオニルオキシイミノブタン-2-オン、2-アセトキシイミノペンタン-3-オン、2-アセトキシイミノ-1-フェニルプロパン-1-オン、2-ベンゾイルオキシイミノ-1-フェニルプロパン-1-オン、3-(4-トルエンスルホニルオキシ)イミノブタン-2-オン、および2-エトキシカルボニルオキシイミノ-1-フェニルプロパン-1-オンなどが挙げられる。
さらに、また、フッ素原子を有するオキシム化合物を用いることも可能である。そのようなオキシム化合物の具体例としては、特開2010-262028号公報に記載されている化合物、特表2014-500852号公報の段落0345に記載されている化合物24、36~40、特開2013-164471号公報の段落0101に記載されている化合物(C-3)などが挙げられる。
最も好ましいオキシム化合物としては、特開2007-269779号公報に示される特定置換基を有するオキシム化合物や、特開2009-191061号公報に示されるチオアリール基を有するオキシム化合物などが挙げられる。 More preferred examples of the photopolymerization initiator include oxime compounds. By using the oxime compound, the exposure latitude can be improved more effectively. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as a thermal base generator.
Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
Preferable oxime compounds include, for example, compounds having the following structures, 3-benzooxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxy Iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
Furthermore, it is also possible to use an oxime compound having a fluorine atom. Specific examples of such oxime compounds include compounds described in JP 2010-262028 A, compounds 24, 36 to 40 described in paragraph 0345 of JP 2014-500852 A, and JP 2013. And the compound (C-3) described in paragraph 0101 of JP-A No. 164471.
As the most preferred oxime compounds, there are oxime compounds having a specific substituent as disclosed in JP-A-2007-267979, oxime compounds having a thioaryl group as disclosed in JP-A-2009-191061, and the like.
さらに好ましい光重合開始剤は、トリハロメチルトリアジン化合物、α-アミノケトン化合物、アシルホスフィン化合物、フォスフィンオキサイド化合物、メタロセン化合物、オキシム化合物、トリアリールイミダゾールダイマー、オニウム塩化合物、ベンゾフェノン化合物、アセトフェノン化合物であり、トリハロメチルトリアジン化合物、α-アミノケトン化合物、オキシム化合物、トリアリールイミダゾールダイマー、ベンゾフェノン化合物からなる群より選ばれる少なくとも1種の化合物が一層好ましく、メタロセン化合物またはオキシム化合物を用いるのがより一層好ましく、オキシム化合物が特に好ましい。
また、光重合開始剤は、ベンゾフェノン、N,N’-テトラメチル-4,4’-ジアミノベンゾフェノン(ミヒラーケトン)等のN,N’-テトラアルキル-4,4’-ジアミノベンゾフェノン、2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)-ブタノン-1、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルフォリノ-プロパノン-1等の芳香族ケトン、アルキルアントラキノン等の芳香環と縮環したキノン類、ベンゾインアルキルエーテル等のベンゾインエーテル化合物、ベンゾイン、アルキルベンゾイン等のベンゾイン化合物、ベンジルジメチルケタール等のベンジル誘導体などを用いることもできる。また、下記式(I)で表される化合物を用いることもできる。
More preferred photopolymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, acetophenone compounds, At least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound is more preferable, and a metallocene compound or an oxime compound is more preferable, and an oxime compound. Is particularly preferred.
Photopolymerization initiators include N, N′-tetraalkyl-4,4′-diaminobenzophenone, 2-benzyl-, such as benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), and the like. Aromatic ketones such as 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, alkyl anthraquinones, etc. It is also possible to use quinones fused with an aromatic ring, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, and benzyl derivatives such as benzyldimethyl ketal. A compound represented by the following formula (I) can also be used.
本発明の組成物は、溶剤を含有する。溶剤は、公知の溶剤を任意に使用できる。溶剤は有機溶剤が好ましい。有機溶剤としては、エステル類、エーテル類、ケトン類、芳香族炭化水素類、スルホキシド類、アミド類などの化合物が挙げられる。
エステル類として、例えば、酢酸エチル、酢酸-n-ブチル、酢酸イソブチル、ギ酸アミル、酢酸イソアミル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、乳酸メチル、乳酸エチル、γ-ブチロラクトン、ε-カプロラクトン、δ-バレロラクトン、アルキルオキシ酢酸アルキル(例えば、アルキルオキシ酢酸メチル、アルキルオキシ酢酸エチル、アルキルオキシ酢酸ブチル(例えば、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル等))、3-アルキルオキシプロピオン酸アルキルエステル類(例えば、3-アルキルオキシプロピオン酸メチル、3-アルキルオキシプロピオン酸エチル等(例えば、3-メトキシプロピオン酸メチル、3-メトキシプロピオン酸エチル、3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル等))、2-アルキルオキシプロピオン酸アルキルエステル類(例えば、2-アルキルオキシプロピオン酸メチル、2-アルキルオキシプロピオン酸エチル、2-アルキルオキシプロピオン酸プロピル等(例えば、2-メトキシプロピオン酸メチル、2-メトキシプロピオン酸エチル、2-メトキシプロピオン酸プロピル、2-エトキシプロピオン酸メチル、2-エトキシプロピオン酸エチル))、2-アルキルオキシ-2-メチルプロピオン酸メチルおよび2-アルキルオキシ-2-メチルプロピオン酸エチル(例えば、2-メトキシ-2-メチルプロピオン酸メチル、2-エトキシ-2-メチルプロピオン酸エチル等)、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、2-オキソブタン酸メチル、2-オキソブタン酸エチル等が好適に挙げられる。
エーテル類として、例えば、ジエチレングリコールジメチルエーテル、テトラヒドロフラン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート等が好適に挙げられる。
ケトン類として、例えば、メチルエチルケトン、シクロヘキサノン、シクロペンタノン、2-ヘプタノン、3-ヘプタノン等が好適に挙げられる。
芳香族炭化水素類として、例えば、トルエン、キシレン、アニソール、リモネン等が好適に挙げられる。
スルホキシド類として、例えば、ジメチルスルホキシドが好適に挙げられる。
アミド類として、N-メチル-2-ピロリドン、N -エチル-2-ピロリドン、N,N-ジメチルアセトアミド、N,N-ジメチルホルムアミド等が好適に挙げられる。 << Solvent >>
The composition of the present invention contains a solvent. A known solvent can be arbitrarily used as the solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.
Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, and ε-caprolactone , Δ-valerolactone, alkyl oxyacetates (for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc. )), 3-alkyloxypropionic acid alkyl esters (for example, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (for example, methyl 3-methoxypropionate, 3-methoxypropionate)) Ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (for example, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2 -Propyl alkyloxypropionate and the like (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyl Methyl oxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate , Pyruvic acid Chill, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, 2-ethyl-oxobutanoate can be preferably used.
Examples of 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, propylene glycol Preferred examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.
Preferred examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone.
Preferable examples of aromatic hydrocarbons include toluene, xylene, anisole, limonene and the like.
Suitable examples of the sulfoxides include dimethyl sulfoxide.
Preferable examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like.
溶剤は1種のみ含有していてもよいし、2種以上含有していてもよい。溶剤を2種以上含有する場合は、その合計が上記範囲であることが好ましい。 The content of the solvent is preferably such that the total solid concentration of the composition of the present invention is 5 to 80% by mass, more preferably 5 to 70% by mass, and more preferably 10 to 60% by mass from the viewpoint of applicability. % Is particularly preferred. The solvent content may be adjusted depending on the desired thickness and coating method. For example, if the coating method is spin coating or slit coating, the content of the solvent having a solid content concentration in the above range is preferable. In the case of spray coating, the amount is preferably 0.1% by mass to 50% by mass, and more preferably 1.0% by mass to 25% by mass. A photosensitive resin composition layer having a desired thickness can be uniformly formed by adjusting the amount of solvent by the coating method.
The solvent may contain only 1 type and may contain 2 or more types. When two or more solvents are contained, the total is preferably in the above range.
本発明の組成物は、多官能ラジカル重合性モノマー(以下、重合性モノマーともいう)を含むことが好ましい。このような構成とすることにより、耐熱性に優れた硬化膜を形成することができる。 << Polyfunctional radical polymerizable monomer >>
The composition of the present invention preferably contains a polyfunctional radically polymerizable monomer (hereinafter also referred to as a polymerizable monomer). By setting it as such a structure, the cured film excellent in heat resistance can be formed.
また、その他の好ましい重合性モノマーとして、特開2010-160418号公報、特開2010-129825号公報、特許第4364216号等に記載される、フルオレン環を有し、エチレン性不飽和結合を有する基を2個以上有する化合物や、カルド樹脂も使用することが可能である。
さらに、その他の例としては、特公昭46-43946号公報、特公平1-40337号公報、特公平1-40336号公報に記載の特定の不飽和化合物や、特開平2-25493号公報に記載のビニルホスホン酸系化合物等もあげることができる。また、特開昭61-22048号公報に記載のペルフルオロアルキル基を含む化合物を用いることもできる。さらに日本接着協会誌 vol.20、No.7、300~308ページ(1984年)に光重合性モノマーおよびオリゴマーとして紹介されているものも使用することができる。 The polymerizable monomer is also preferably a compound having a boiling point of 100 ° C. or higher under normal pressure. Examples include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol. Many such as penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin and trimethylolethane A compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylated, JP-B-48-4170 Urethane (meth) acrylates, as described in JP-A Nos. 50-6034 and 51-37193, JP-A 48-64183, JP-B 49-43191, Mention may be made of polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid, and mixtures thereof described in JP-B 52-30490. it can. Also suitable are the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970. Moreover, the polyfunctional (meth) acrylate etc. which are obtained by making the compound which has cyclic ether groups, such as glycidyl (meth) acrylate, and an ethylenically unsaturated group, react with polyfunctional carboxylic acid can also be mentioned.
Other preferable polymerizable monomers include groups having a fluorene ring and an ethylenically unsaturated bond described in JP2010-160418A, JP2010-129825A, Japanese Patent No. 4364216, and the like. It is also possible to use a compound having two or more or a cardo resin.
Other examples include specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and JP-A-2-25493. And vinyl phosphonic acid compounds. Also, compounds containing a perfluoroalkyl group described in JP-A-61-22048 can be used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photopolymerizable monomers and oligomers, can also be used.
上記式(MO-1)~(MO-5)で表される重合性化合物の各々において、複数のRの内の少なくとも1つは、-OC(=O)CH=CH2、または、-OC(=O)C(CH3)=CH2で表される基を表す。
上記式(MO-1)~(MO-5)で表される、重合性モノマーの具体例としては、特開2007-269779号公報の段落0248~0251に記載されている化合物を用いることができる。 In the above formulas, n is an integer from 0 to 14, and m is an integer from 0 to 8. A plurality of R and T present in the molecule may be the same or different.
In each of the polymerizable compounds represented by the above formulas (MO-1) to (MO-5), at least one of a plurality of R is —OC (═O) CH═CH 2 or —OC (= O) represents a group represented by C (CH 3 ) ═CH 2 .
As specific examples of the polymerizable monomer represented by the above formulas (MO-1) to (MO-5), the compounds described in paragraphs 0248 to 0251 of JP-A No. 2007-267979 can be used. .
また、上記式(MO-1)、式(MO-2)のペンタエリスリトール誘導体および/またはジペンタエリスリトール誘導体も好ましい例として挙げられる。 As a polymerizable monomer, dipentaerythritol triacrylate (as a commercially available product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercially available product, as KAYARAD D-320; Nippon Kayaku Co., Ltd.) ), A-TMMT: Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (As commercial products, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.), and these (meth) acryloyl groups are bonded via ethylene glycol and propylene glycol residues. A structure is preferred. These oligomer types can also be used.
Further, preferred examples include pentaerythritol derivatives and / or dipentaerythritol derivatives of the above formulas (MO-1) and (MO-2).
酸基を有する重合性モノマーは、1種を単独で用いてもよいが、2種以上を混合して用いてもよい。また、必要に応じて酸基を有しない重合性モノマーと酸基を有する重合性モノマーを併用してもよい。
酸基を有する重合性モノマーの好ましい酸価は、0.1~40mgKOH/gであり、特に好ましくは5~30mgKOH/gである。重合性モノマーの酸価が上記範囲であれば、製造や取扱性に優れ、さらには、現像性に優れる。また、重合性が良好である。 The polymerizable monomer may be a polymerizable monomer having an acid group such as a carboxyl group, a sulfo group, or a phosphoric acid group. The polymerizable monomer having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. More preferred is a polymerizable monomer. Particularly preferably, in the polymerizable monomer in which a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound to give an acid group, the aliphatic polyhydroxy compound is pentaerythritol and / or diester. It is a compound that is pentaerythritol. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
As the polymerizable monomer having an acid group, one kind may be used alone, or two or more kinds may be mixed and used. Moreover, you may use together the polymerizable monomer which does not have an acid group, and the polymerizable monomer which has an acid group as needed.
A preferable acid value of the polymerizable monomer having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When the acid value of the polymerizable monomer is within the above range, the production and handling properties are excellent, and further, the developability is excellent. Also, the polymerizability is good.
また、ポリイミド前駆体と重合性モノマーとの質量割合(ポリイミド前駆体/重合性モノマー)は、98/2~10/90が好ましく、95/5~30/70がより好ましく、90/10~50/50が最も好ましい。ポリイミド前駆体と重合性モノマーとの質量割合が上記範囲であれば、重合性および耐熱性により優れた硬化膜を形成できる。 The content of the polymerizable monomer is preferably 1 to 50% by mass with respect to the total solid content of the composition of the present invention from the viewpoint of good polymerizability and heat resistance. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 30% by mass or less. As the polymerizable monomer, one kind may be used alone, or two or more kinds may be mixed and used.
The mass ratio of the polyimide precursor to the polymerizable monomer (polyimide precursor / polymerizable monomer) is preferably 98/2 to 10/90, more preferably 95/5 to 30/70, and 90/10 to 50 / 50 is most preferred. If the mass ratio of a polyimide precursor and a polymerizable monomer is in the above range, a cured film that is superior in polymerizability and heat resistance can be formed.
本発明の組成物は、上述したポリイミド前駆体および重合性モノマー以外の他の重合性化合物をさらに含むことができる。他の重合性化合物としては、ヒドロキシメチル基、アルコキシメチル基またはアシルオキシメチル基を有する化合物;エポキシ化合物;オキセタン化合物;ベンゾオキサジン化合物が挙げられる。 << Other polymerizable compounds >>
The composition of this invention can further contain other polymerizable compounds other than the polyimide precursor and polymerizable monomer mentioned above. Other polymerizable compounds include compounds having a hydroxymethyl group, alkoxymethyl group or acyloxymethyl group; epoxy compounds; oxetane compounds; benzoxazine compounds.
ヒドロキシメチル基、アルコキシメチル基またはアシルオキシメチル基を有する化合物としては、下記式(AM1)で示される化合物が好ましい。 (Compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group)
As the compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, a compound represented by the following formula (AM1) is preferable.
エポキシ化合物としては、一分子中にエポキシ基を2以上有する化合物であることが好ましい。エポキシ基は、200℃以下で架橋反応し、かつ、架橋に由来する脱水反応が起こらないため膜収縮が起きにくい。このため、エポキシ化合物を含有することは、組成物の低温硬化および反りの抑制に効果的である。 (Epoxy compound (compound having an epoxy group))
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group undergoes a cross-linking reaction at 200 ° C. or less and does not cause a dehydration reaction derived from the cross-linking, so that film shrinkage hardly occurs. For this reason, containing an epoxy compound is effective for low-temperature curing and warping of the composition.
オキセタン化合物としては、一分子中にオキセタン環を2つ以上有する化合物、3-エチル-3-ヒドロキシメチルオキセタン、1,4-ビス{[(3-エチル-3-オキセタニル)メトキシ]メチル}ベンゼン、3-エチル-3-(2-エチルヘキシルメチル)オキセタン、1,4-ベンゼンジカルボン酸-ビス[(3-エチル-3-オキセタニル)メチル]エステル等を挙げることができる。具体的な例としては、東亞合成株式会社製のアロンオキセタンシリーズ(例えば、OXT-121、OXT-221、OXT-191、OXT-223)が好適に使用することができ、これらは単独で、あるいは2種以上混合してもよい。 (Oxetane compound (compound having 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, Examples include 3-ethyl-3- (2-ethylhexylmethyl) oxetane and 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester. As specific examples, Aron Oxetane series (for example, OXT-121, OXT-221, OXT-191, OXT-223) manufactured by Toagosei Co., Ltd. can be preferably used. Two or more kinds may be mixed.
ベンゾオキサジン化合物は、開環付加反応に由来する架橋反応のため、キュア時に脱ガスが発生せず、さらに熱収縮を小さくして反りの発生が抑えられることから好ましい。 (Benzoxazine compound (compound having a benzoxazolyl group))
A benzoxazine compound is preferable because it is a cross-linking reaction derived from a ring-opening addition reaction, so that degassing does not occur during curing, and thermal contraction is further reduced to suppress warpage.
本発明の組成物は、さらに金属変色防止剤を含むことが好ましい。本発明の組成物が金属変色防止剤を含むことにより、金属層(金属配線)由来の金属イオンがネガ型感光性樹脂組成物層内へ移動することを効果的に抑制できる。
金属変色防止剤としては、特に制限はないが、複素環(ピロール環、フラン環、チオフェン環、イミダゾール環、オキサゾール環、チアゾール環、ピラゾール環、イソオキサゾール環、イソチアゾール環、テトラゾール環、ピリジン環、ピリダジン環、ピリミジン環、ピラジン環、ピペリジン環、ピペラジン環、モルホリン環、2H-ピラン環および6H-ピラン環、トリアジン環)を有する化合物、チオ尿素類およびメルカプト基を有する化合物、ヒンダードフェノール系化合物、サリチル酸誘導体系化合物、ヒドラジド誘導体系化合物が挙げられる。特に、トリアゾール、ベンゾトリアゾール等のトリアゾール系化合物、テトラゾール、ベンゾテトラゾール等のテトラゾール系化合物が好ましく使用できる。 << Metal discoloration inhibitor >>
The composition of the present invention preferably further contains a metal discoloration inhibitor. When the composition of this invention contains a metal discoloration prevention agent, it can suppress effectively that the metal ion derived from a metal layer (metal wiring) moves into a negative photosensitive resin composition layer.
The metal discoloration inhibitor is not particularly limited, but a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring , Pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thioureas and mercapto groups, hindered phenols Compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as triazole and benzotriazole, and tetrazole compounds such as tetrazole and benzotetrazole can be preferably used.
本発明の組成物は、重合禁止剤を含むことが好ましい。
重合禁止剤としては、例えば、ヒドロキノン、パラメトキシフェノール、ジ-tert-ブチル-パラクレゾール、ピロガロール、パラ-tert-ブチルカテコール、パラベンゾキノン、ジフェニル-パラベンゾキノン、4,4′-チオビス(3-メチル-6-tert-ブチルフェノール)、2,2′-メチレンビス(4-メチル-6-tert-ブチルフェノール)、N-ニトロソ-N-フェニルヒドロキシアミンアルミニウム塩、フェノチアジン、N-ニトロソジフェニルアミン、N-フェニルナフチルアミン、エチレンジアミン四酢酸、1,2-シクロヘキサンジアミン四酢酸、グリコールエーテルジアミン四酢酸、2,6-ジ-tert-ブチル-4-メチルフェノール、5-ニトロソ-8-ヒドロキシキノリン、1-ニトロソ-2-ナフトール、2-ニトロソ-1-ナフトール、2-ニトロソ-5-(N-エチル-N-スルフォプロピルアミノ)フェノール、N-ニトロソ-N-(1-ナフチル)ヒドロキシアミンアンモニウム塩、ビス(4-ヒドロキシ-3,5-tert-ブチル)フェニルメタンなどが好適に用いられる。また、特開2015-127817号公報の段落0060に記載の重合禁止剤、および、国際公開WO2015/125469号の段落0031~0046に記載の化合物を用いることもできる。
また、下記化合物用いることができる(Meはメチル基である)。
重合禁止剤は1種のみでもよいし、2種以上であってもよい。重合禁止剤が2種以上の場合は、その合計が上記範囲であることが好ましい。 << Polymerization inhibitor >>
The composition of the present invention preferably contains a polymerization inhibitor.
Examples of the polymerization inhibitor include hydroquinone, paramethoxyphenol, di-tert-butyl-paracresol, pyrogallol, para-tert-butylcatechol, parabenzoquinone, diphenyl-parabenzoquinone, 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, Ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso 2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, bis ( 4-hydroxy-3,5-tert-butyl) phenylmethane and the like are preferably used. In addition, a polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and compounds described in paragraphs 0031 to 0046 of international publication WO2015 / 125469 can also be used.
Further, the following compounds can be used (Me is a methyl group).
Only one polymerization inhibitor may be used, or two or more polymerization inhibitors may be used. When two or more polymerization inhibitors are used, the total is preferably within the above range.
本発明の組成物は、熱塩基発生剤を含むことが好ましい。
熱塩基発生剤としては、その種類等は特に定めるものではないが、40℃以上に加熱すると塩基を発生する酸性化合物、および、pKa1が0~4のアニオンとアンモニウムカチオンとを有するアンモニウム塩から選ばれる少なくとも1種を含む熱塩基発生剤を含むことが好ましい。ここで、pKa1とは、酸の第一のプロトンの解離定数(Ka)の逆数の対数(-Log10Ka)を表し、詳細は後述する。 << thermal base generator >>
The composition of the present invention preferably contains a thermal base generator.
The type of the thermal base generator is not particularly defined, but is selected from an acidic compound that generates a base when heated to 40 ° C. or higher, and an ammonium salt having an anion having an pKa1 of 0 to 4 and an ammonium cation. It is preferable to include a thermal base generator containing at least one kind. Here, pKa1 represents the logarithm (−Log 10 Ka) of the reciprocal of the dissociation constant (Ka) of the first proton of the acid, and will be described in detail later.
なお、本明細書において、酸性化合物とは、化合物を容器に1g採取し、イオン交換水とテトラヒドロフランとの混合液(質量比は水/テトラヒドロフラン=1/4)を50mL加えて、室温で1時間撹拌して得られた溶液を、pH(power of hydrogen)メーターを用いて、20℃にて測定した値が7未満である化合物を意味する。 Since the acidic compound (A1) and the ammonium salt (A2) generate a base when heated, the base generated from these compounds can promote the cyclization reaction of the polyimide precursor and the like. Can be carried out at low temperatures. In addition, even if these compounds coexist with a polyimide precursor that is cured by cyclization with a base, since the cyclization of the polyimide precursor hardly proceeds unless heated, a composition having excellent storage stability can be obtained. Can be prepared.
In the present specification, an acidic compound means that 1 g of a compound is collected in a container, and 50 mL of a mixed solution of ion-exchanged water and tetrahydrofuran (mass ratio is water / tetrahydrofuran = 1/4) is added to the mixture at room temperature for 1 hour. The solution obtained by stirring means a compound having a value measured at 20 ° C. of less than 7 using a pH (power of hydrogen) meter.
酸性化合物(A1)およびアンモニウム塩(A2)の塩基発生温度が120℃以上であれば、保存中に塩基が発生しにくいので、安定性に優れた組成物を調製することができる。酸性化合物(A1)およびアンモニウム塩(A2)の塩基発生温度が200℃以下であれば、ポリイミド前駆体などの環化温度を低くできる。塩基発生温度は、例えば、示差走査熱量測定を用い、化合物を耐圧カプセル中5℃/分で250℃まで加熱し、最も温度が低い発熱ピークのピーク温度を読み取り、ピーク温度を塩基発生温度として測定することができる。 In this embodiment, the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40 ° C. or higher, more preferably 120 to 200 ° C. The upper limit of the base generation temperature is preferably 190 ° C. or lower, more preferably 180 ° C. or lower, and further preferably 165 ° C. or lower. The lower limit of the base generation temperature is preferably 130 ° C or higher, and more preferably 135 ° C or higher.
If the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 120 ° C. or higher, a base is unlikely to be generated during storage, so that a composition having excellent stability can be prepared. If the base generation temperature of the acidic compound (A1) and ammonium salt (A2) is 200 ° C. or lower, the cyclization temperature of the polyimide precursor or the like can be lowered. The base generation temperature is measured, for example, by using differential scanning calorimetry, heating the compound to 250 ° C. at 5 ° C./min in a pressure capsule, reading the peak temperature of the lowest exothermic peak, and measuring the peak temperature as the base generation temperature. can do.
式(101) 式(102)
Formula (101) Formula (102)
式(Y1-1)~(Y1-4)において、Ar101およびAr102は、それぞれ独立に、アリール基を表し、nは、1以上の整数を表し、mは、0~5の整数を表す。 In formulas (Y1-1) to (Y1-5), R 101 represents an n-valent organic group, and R 1 and R 7 have the same meanings as in formula (101) or formula (102).
In formulas (Y1-1) to (Y1-4), Ar 101 and Ar 102 each independently represent an aryl group, n represents an integer of 1 or more, and m represents an integer of 0 to 5 .
アニオンの種類は、カルボン酸アニオン、フェノールアニオン、リン酸アニオンおよび硫酸アニオンから選ばれる1種が好ましく、塩の安定性と熱分解性を両立させられるという理由からカルボン酸アニオンがより好ましい。すなわち、アンモニウム塩は、アンモニウムカチオンとカルボン酸アニオンとの塩がより好ましい。
カルボン酸アニオンは、2個以上のカルボキシル基を持つ2価以上のカルボン酸のアニオンが好ましく、2価のカルボン酸のアニオンがより好ましい。この態様によれば、組成物の安定性、硬化性および現像性をより向上できる熱塩基発生剤とすることができる。特に、2価のカルボン酸のアニオンを用いることで、組成物の安定性、硬化性および現像性をさらに向上できる。
本実施形態において、カルボン酸アニオンは、pKa1が4以下のカルボン酸のアニオンであることが好ましい。pKa1は、3.5以下がより好ましく、3.2以下が一層好ましい。この態様によれば、組成物の安定性をより向上できる。
ここでpKa1とは、酸の第一のプロトンの解離定数の逆数の対数を表し、Determination of Organic Structures by Physical Methods(著者:Brown, H. C., McDaniel, D. H., Hafliger, O., Nachod, F. C.; 編纂:Braude, E. A., Nachod, F. C.; Academic Press, New York, 1955)や、Data for Biochemical Research(著者:Dawson, R.M.C.et al; Oxford, Clarendon Press, 1959)に記載の値を参照することができる。これらの文献に記載の無い化合物については、ACD/pKa(ACD/Labs製)のソフトを用いて構造式より算出した値を用いることとする。 In this embodiment, the ammonium salt preferably has an anion having an pKa1 of 0 to 4 and an ammonium cation. The upper limit of the anion pKa1 is more preferably 3.5 or less, and even more preferably 3.2 or less. The lower limit is preferably 0.5 or more, and more preferably 1.0 or more. If the pKa1 of the anion is in the above range, a polyimide precursor or the like can be cyclized at a low temperature, and the stability of the composition can be improved. If pKa1 is 4 or less, the stability of the thermal base generator is good, the generation of a base without heating can be suppressed, and the stability of the composition is good. If pKa1 is 0 or more, the generated base is hardly neutralized, and the cyclization efficiency of the polyimide precursor or the like is good.
The kind of anion is preferably one selected from a carboxylate anion, a phenol anion, a phosphate anion, and a sulfate anion, and a carboxylate anion is more preferable because both the stability of the salt and the thermal decomposability can be achieved. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion.
The carboxylic acid anion is preferably a divalent or higher carboxylic acid anion having two or more carboxyl groups, and more preferably a divalent carboxylic acid anion. According to this aspect, it is possible to provide a thermal base generator that can further improve the stability, curability and developability of the composition. In particular, the stability, curability and developability of the composition can be further improved by using an anion of a divalent carboxylic acid.
In the present embodiment, the carboxylic acid anion is preferably a carboxylic acid anion having a pKa1 of 4 or less. pKa1 is more preferably 3.5 or less, and even more preferably 3.2 or less. According to this aspect, the stability of the composition can be further improved.
Here, pKa1 represents the logarithm of the reciprocal of the dissociation constant of the first proton of the acid, and the determination of Organic Structures by Physical Methods (author: Brown, HC, McDaniel, D.H., Hafliger Ed .: Braude, EA, Nachod, FC; Academic Press, New York, 1955), and Data for Biochemical Research (author: Dawson, R. M.). al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, values calculated from the structural formula using software of ACD / pKa (manufactured by ACD / Labs) are used.
σmが正の値を示す置換基の例としては例えば、CF3基(σm=0.43)、CF3CO基(σm=0.63)、HC≡C基(σm=0.21)、CH2=CH基(σm=0.06)、Ac基(σm=0.38)、MeOCO基(σm=0.37)、MeCOCH=CH基(σm=0.21)、PhCO基(σm=0.34)、H2NCOCH2基(σm=0.06)などが挙げられる。なお、Meはメチル基を表し、Acはアセチル基を表し、Phはフェニル基を表す。 In the present embodiment, the electron-withdrawing group means a group in which Hammett's substituent constant σm exhibits a positive value. Here, σm is a review by Yusuke Tono, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965) p. 631-642. In addition, the electron withdrawing group in this embodiment is not limited to the substituent described in the said literature.
Examples of substituents in which σm has a positive value include, for example, CF 3 group (σm = 0.43), CF 3 CO group (σm = 0.63), HC≡C group (σm = 0.21), CH 2 ═CH group (σm = 0.06), Ac group (σm = 0.38), MeOCO group (σm = 0.37), MeCOCH═CH group (σm = 0.21), PhCO group (σm = 0.34), H 2 NCOCH 2 group (σm = 0.06), and the like. Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group.
式(XA)
Formula (XA)
熱塩基発生剤は、1種または2種以上を用いることができる。2種以上を用いる場合は、合計量が上記範囲であることが好ましい。 When the composition of the present invention contains a thermal base generator, the content of the thermal base generator is preferably 0.1 to 50% by mass relative to the total solid content of the composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and further preferably 20% by mass or less.
1 type (s) or 2 or more types can be used for a thermal base generator. When using 2 or more types, it is preferable that a total amount is the said range.
本発明の組成物は、電極や配線などに用いられる金属材料との接着性を向上させるための金属接着性改良剤を含んでいることが好ましい。金属接着性改良剤としては、シランカップリング剤などが挙げられる。 << Metal adhesion improver >>
It is preferable that the composition of this invention contains the metal adhesive improvement agent for improving the adhesiveness with the metal material used for an electrode, wiring, etc. Examples of metal adhesion improvers include silane coupling agents.
本発明の組成物は、本発明の効果を損なわない範囲で、必要に応じて、各種の添加物、例えば、光塩基発生剤、熱重合開始剤、熱酸発生剤、増感色素、連鎖移動剤、界面活性剤、高級脂肪酸誘導体、無機粒子、硬化剤、硬化触媒、充填剤、酸化防止剤、紫外線吸収剤、凝集防止剤等を配合することができる。これらの添加剤を配合する場合、その合計配合量は組成物の固形分の3質量%以下とすることが好ましい。 << Other additives >>
The composition of the present invention is various additives, for example, a photobase generator, a thermal polymerization initiator, a thermal acid generator, a sensitizing dye, a chain transfer, as necessary, as long as the effects of the present invention are not impaired. An agent, a surfactant, a higher fatty acid derivative, inorganic particles, a curing agent, a curing catalyst, a filler, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, and the like can be blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the composition.
本発明の組成物は、光塩基発生剤を含んでいてもよい。光塩基発生剤とは、露光により塩基を発生する化合物であり、常温常圧の通常の条件下では活性を示さないが、外部刺激として電磁波の照射と加熱が行なわれると、塩基(塩基性物質)を発生する化合物であれば特に限定されない。露光により発生した塩基はポリイミド前駆体などを加熱により硬化させる際の触媒として働くため、ネガ型において好適に用いることができる。 (Photobase generator)
The composition of the present invention may contain a photobase generator. A photobase generator is a compound that generates a base upon exposure and does not exhibit activity under normal conditions of room temperature and normal pressure. However, when an electromagnetic wave is irradiated and heated as an external stimulus, a base (basic substance) is generated. If it is a compound which generate | occur | produces), it will not specifically limit. Since the base generated by exposure works as a catalyst for curing the polyimide precursor or the like by heating, it can be suitably used in a negative type.
光塩基発生剤は1種のみでもよいし、2種以上であってもよい。光塩基発生剤が2種以上の場合は、その合計が上記範囲であることが好ましい。 The content of the photobase generator is not particularly limited as long as a desired resin pattern can be formed, and can be a general content. The photobase generator is preferably in the range of 0.01 parts by weight to less than 30 parts by weight with respect to 100 parts by weight of the polyimide precursor, and is in the range of 0.05 parts by weight to 25 parts by weight. Is more preferable, and is more preferably in the range of 0.1 to 20 parts by mass.
Only one photobase generator may be used, or two or more photobase generators may be used. When there are two or more photobase generators, the total is preferably in the above range.
その他、光塩基発生剤としては、特開2012-93746号公報の段落0185~0188、0199~0200および0202に記載の化合物、特開2013-194205号公報の段落0022~0069に記載の化合物、特開2013-204019号公報の段落0026~0074に記載の化合物、ならびに国際公開WO2010/064631号の段落0052に記載の化合物が例として挙げられる。 As the photobase generator, carbamate derivatives, amide derivatives, imide derivatives, α-cobalt complexes, imidazole derivatives, cinnamic acid amide derivatives, oxime derivatives, and the like can also be used. Further, the photobase generator having a cinnamic acid amide structure described in Japanese Patent Application Laid-Open No. 2009-80452 and International Publication No. WO2009 / 123122, and Japanese Patent Application Laid-Open No. 2006-189591 and Japanese Patent Application Laid-Open No. 2008-247747. A photobase generator having a carbamate structure, or a photobase generator having an oxime structure or a carbamoyloxime structure described in JP2007-249013A and JP2008-003581A can also be used.
Other photobase generators include compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 of JP2012-93746A, compounds described in paragraphs 0022 to 0069 of JP2013-194205, Examples thereof include the compounds described in paragraphs 0026 to 0074 of JP2013-204019A and the compound described in paragraph 0052 of WO2010 / 064631.
本発明の組成物は、熱重合開始剤(好ましくは熱ラジカル重合開始剤)を含んでいてもよい。熱ラジカル重合開始剤としては、公知の熱ラジカル重合開始剤を用いることができる。
熱ラジカル重合開始剤は、熱のエネルギーによってラジカルを発生し、重合性を有する化合物の重合反応を開始または促進させる化合物である。熱ラジカル重合開始剤を添加することによって、ポリイミド前駆体の環化と共に、ポリイミド前駆体の重合反応を進行させることもできるので、より高度な耐熱化が達成できることとなる。
熱ラジカル重合開始剤として、具体的には、特開2008-63554号公報の段落0074~0118に記載されている化合物が挙げられる。 (Thermal polymerization initiator)
The composition of the present invention may contain a thermal polymerization initiator (preferably a thermal radical polymerization initiator). As the thermal radical polymerization initiator, a known thermal radical polymerization initiator can be used.
The thermal radical polymerization initiator is a compound that generates radicals by heat energy and initiates or accelerates a polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the polyimide precursor can be advanced together with the cyclization of the polyimide precursor, so that higher heat resistance can be achieved.
Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-63554.
本発明の組成物は、熱酸発生剤を含んでいてもよい。熱酸発生剤は、加熱により酸を発生し、ポリイミド前駆体の環化を促進し硬化膜の機械特性をより向上させる。熱酸発生剤は、特開2013-167742号公報の段落0059に記載の化合物などが挙げられる。 (Thermal acid generator)
The composition of the present invention may contain a thermal acid generator. The thermal acid generator generates an acid by heating, promotes cyclization of the polyimide precursor, and further improves the mechanical properties of the cured film. Examples of the thermal acid generator include compounds described in paragraph 0059 of JP2013-167742A.
熱酸発生剤は、1種のみ用いても、2種以上用いてもよい。2種以上用いる場合は、合計量が上記範囲となることが好ましい。 0.01 mass part or more is preferable with respect to 100 mass parts of polyimide precursors, and, as for content of a thermal acid generator, 0.1 mass part or more is more preferable. By containing 0.01 parts by mass or more of the thermal acid generator, the cross-linking reaction and the cyclization of the polyimide precursor are promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved. In addition, the content of the thermal acid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and particularly preferably 10 parts by mass or less from the viewpoint of electrical insulation of the cured film.
One type of thermal acid generator may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.
本発明の組成物は、増感色素を含んでいてもよい。増感色素は、特定の活性放射線を吸収して電子励起状態となる。電子励起状態となった増感色素は、塩基発生剤、熱ラジカル重合開始剤、光重合開始剤などと接触して、電子移動、エネルギー移動、発熱などの作用が生じる。これにより、塩基発生剤、熱ラジカル重合開始剤、光重合開始剤は化学変化を起こして分解し、ラジカル、酸或いは塩基を生成する。増感色素の詳細については、特開2016-027357号公報の段落0161~0163の記載を参酌でき、この内容は本明細書に組み込まれる。 (Sensitizing dye)
The composition of the present invention may contain a sensitizing dye. A sensitizing dye absorbs specific actinic radiation and enters an electronically excited state. The sensitizing dye in an electronically excited state comes into contact with a base generator, a thermal radical polymerization initiator, a photopolymerization initiator, and the like, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, the base generator, the thermal radical polymerization initiator, and the photopolymerization initiator are decomposed by causing a chemical change to generate radicals, acids, or bases. Details of the sensitizing dye can be referred to the descriptions in paragraphs 0161 to 0163 of JP-A-2016-027357, the contents of which are incorporated herein.
本発明の組成物は、連鎖移動剤を含有してもよい。連鎖移動剤は、例えば高分子辞典第三版(高分子学会編、2005年)683-684頁に定義されている。連鎖移動剤としては、例えば、分子内にSH、PH、SiH、GeHを有する化合物群が用いられる。これらは、低活性のラジカルに水素を供与して、ラジカルを生成するか、もしくは、酸化された後、脱プロトンすることによりラジカルを生成しうる。特に、チオール化合物(例えば、2-メルカプトベンズイミダゾール類、2-メルカプトベンズチアゾール類、2-メルカプトベンズオキサゾール類、3-メルカプトトリアゾール類、5-メルカプトテトラゾール類等)を好ましく用いることができる。 (Chain transfer agent)
The composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in Polymer Dictionary 3rd Edition (edited by the Polymer Society, 2005) pages 683-684. As the chain transfer agent, for example, a compound group having SH, PH, SiH, GeH in the molecule is used. These can generate hydrogen by donating hydrogen to a low activity radical to generate a radical, or after being oxidized and deprotonated. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.) can be preferably used.
本発明の組成物には、塗布性をより向上させる観点から、各種類の界面活性剤を添加してもよい。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコーン系界面活性剤などの各種類の界面活性剤を使用できる。また、下記界面活性剤も好ましい。
Various kinds of surfactants may be added to the composition of the present invention from the viewpoint of further improving applicability. As the surfactant, various types of surfactants such as a fluorosurfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used. The following surfactants are also preferable.
本発明の組成物は、酸素に起因する重合阻害を防止するために、ベヘン酸やベヘン酸アミドのような高級脂肪酸誘導体を添加して、塗布後の乾燥の過程で組成物の表面に偏在させてもよい。
本発明の組成物が高級脂肪酸誘導体を有する場合、高級脂肪酸誘導体の含有量は、本発明の組成物の全固形分に対して、0.1~10質量%が好ましい。高級脂肪酸誘導体は1種のみでもよいし、2種以上であってもよい。高級脂肪酸誘導体が2種以上の場合は、その合計が上記範囲であることが好ましい。 (Higher fatty acid derivatives)
In order to prevent polymerization inhibition due to oxygen, the composition of the present invention is added with a higher fatty acid derivative such as behenic acid or behenic acid amide, and is unevenly distributed on the surface of the composition in the process of drying after coating. May be.
When the composition of the present invention has a higher fatty acid derivative, 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 composition of the present invention. Only one higher fatty acid derivative may be used, or two or more higher fatty acid derivatives may be used. When two or more higher fatty acid derivatives are used, the total is preferably within the above range.
本発明の組成物の水分含有量は、塗布面性状の観点から、5質量%未満が好ましく、1質量%未満がさらに好ましく、0.6質量%未満が特に好ましい。 << Restrictions on other contained substances >>
The water content of the composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and particularly preferably less than 0.6% by mass from the viewpoint of the coated surface properties.
また、本発明の組成物に意図せずに含まれる金属不純物を低減する方法としては、本発明の組成物を構成する原料として金属含有量が少ない原料を選択する、本発明の組成物を構成する原料に対してフィルターろ過を行う、装置内をポリテトラフロロエチレン等でライニングしてコンタミネーションを可能な限り抑制した条件下で蒸留を行う等の方法を挙げることができる。 The metal content of the composition of the present invention is preferably less than 5 ppm by weight (parts per million), more preferably less than 1 ppm by weight, and particularly preferably less than 0.5 ppm by weight from the viewpoint of insulation. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are included, the total of these metals is preferably in the above range.
Further, as a method for reducing metal impurities unintentionally contained in the composition of the present invention, a raw material having a low metal content is selected as a raw material constituting the composition of the present invention. For example, the raw material to be filtered may be filtered, or the inside of the apparatus may be lined with polytetrafluoroethylene or the like, and distillation may be performed under a condition in which contamination is suppressed as much as possible.
本発明の組成物は、上記各成分を混合して調製することができる。混合方法は特に限定はなく、従来公知の方法で行うことができる。
また、組成物中のゴミや微粒子等の異物を除去する目的で、フィルターを用いたろ過を行うことが好ましい。フィルター孔径は、1μm以下が好ましく、0.5μm以下がより好ましく、0.1μm以下がさらに好ましい。フィルターの材質は、ポリテトラフロロエチレン、ポリエチレンまたはナイロンが好ましい。フィルターは、有機溶剤であらかじめ洗浄したものを用いてもよい。フィルターろ過工程では、複数種のフィルターを直列または並列に接続して用いてもよい。複数種のフィルターを使用する場合は、孔径および/または材質が異なるフィルターを組み合わせて使用しても良い。また、各種材料を複数回ろ過してもよい。複数回ろ過する場合は、循環ろ過であっても良い。また、加圧してろ過を行ってもよい。加圧してろ過を行う場合、加圧する圧力は0.05MPa以上0.3MPa以下が好ましい。
フィルターを用いたろ過の他、吸着材を用いた不純物の除去処理を行っても良い。フィルターろ過と吸着材を用いた不純物除去処理とを組み合わせても良い。吸着材としては、公知の吸着材を用いることができる。例えば、シリカゲル、ゼオライトなどの無機系吸着材、活性炭などの有機系吸着材が挙げられる。 <Preparation of composition>
The composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited, and can be performed by a conventionally known method.
Moreover, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the composition. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. A filter that has been washed in advance with an organic solvent may be used. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different pore diameters and / or materials may be used in combination. Various materials may be filtered a plurality of times. When filtering a plurality of times, circulation filtration may be used. Moreover, you may pressurize and filter. When the pressure is applied for filtration, the pressure applied is preferably 0.05 MPa or more and 0.3 MPa or less.
In addition to filtration using a filter, impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
次に、本発明の硬化膜、半導体デバイス、硬化膜の製造方法、半導体デバイス、積層体の製造方法および半導体デバイスの製造方法について説明する。
本発明の硬化膜は、本発明の組成物を硬化してなる。本発明の硬化膜の厚さは、例えば、1μm以上とすることができ、5μm以上とすることができる。また、上限値としては、100μm以下とすることができ、30μm以下とすることもできる。 <Curing Film, Semiconductor Device, Cured Film Manufacturing Method, Semiconductor Device, Laminate Manufacturing Method, and Semiconductor Device Manufacturing Method>
Next, a cured film, a semiconductor device, a cured film manufacturing method, a semiconductor device, a laminate manufacturing method, and a semiconductor device manufacturing method of the present invention will be described.
The cured film of the present invention is formed by curing the composition of the present invention. The thickness of the cured film of the present invention can be, for example, 1 μm or more, and can be 5 μm or more. Moreover, as an upper limit, it can be set to 100 micrometers or less, and can also be set to 30 micrometers or less.
また、本発明における硬化膜は、エレクトロニクス用のフォトレジスト、ガルバニック(電解)レジスト(galvanic resist)、エッチングレジスト、ソルダートップレジスト(solder top resist)などに用いることもできる。
また、本発明における硬化膜は、オフセット版面またはスクリーン版面などの版面の製造、成形部品のエッチングへの使用、エレクトロニクス、特にマイクロエレクトロニクスにおける保護ラッカーおよび誘電層の製造などに用いることもできる。 Fields to which the cured film of the present invention can be applied include insulating films for semiconductor devices, interlayer insulating films for rewiring layers, and the like. Particularly, since the resolution is good, it can be preferably used for an interlayer insulating film for a rewiring layer in a three-dimensional mounting device.
The cured film in the present invention can also be used for electronic photoresists, galvanic resists, galvanic resists, etching resists, solder top resists, and the like.
The cured film of the present invention can also be used for the production of printing plates such as offset printing plates or screen printing plates, the use for etching molded parts, the production of protective lacquers and dielectric layers in electronics, in particular microelectronics.
配線基板120と積層体101との間には、再配線層105が形成された絶縁層115が配置されており、配線基板120と積層体101とは、再配線層105を介して電気的に接続されている。絶縁層115は、本発明の組成物を用いて形成してなるものである。
すなわち、再配線層105の一端は、半田バンプ等の金属バンプ103dを介して、半導体素子101dの再配線層105側の面に形成された電極パッドに接続されている。また、再配線層105の他端は、配線基板の表面電極120aと、半田バンプ等の金属バンプ103eを介して接続している。
そして、絶縁層115と積層体101との間には、アンダーフィル層110aが形成されている。また、絶縁層115と配線基板120との間には、アンダーフィル層110bが形成されている。 A
An insulating
That is, one end of the
An underfill layer 110 a is formed between the insulating
また、ポリイミドは熱に強いため、本発明における硬化膜等は、液晶ディスプレイ、有機ELディスプレイ、電子ペーパーなどの表示装置用のプラスチック基板や層間絶縁膜、自動車部品、耐熱塗料、コーティング剤、フィルム用途としても好適に利用できる。
さらに、本発明のポリイミド前駆体をポジ型感光性樹脂組成物に用いることもできる。 In addition to the above, the cured film of the present invention can be widely used in various applications using polyimide.
In addition, since polyimide is resistant to heat, the cured film in the present invention is used for plastic substrates and interlayer insulation films for liquid crystal displays, organic EL displays, electronic paper and other display devices, automotive parts, heat resistant paints, coating agents, and films. Can also be suitably used.
Furthermore, the polyimide precursor of this invention can also be used for a positive photosensitive resin composition.
<ポリイミド前駆体P-1の合成>
20.00g(64.5ミリモル)の4,4’-オキシジフタル酸二無水物(ODPA、4,4’-オキシジフタル酸を140℃で12時間乾燥したもの、二官能酸無水物)と、4.13g(129ミリモル)のメタノール(側鎖用化合物)と、0.05gのハイドロキノンと、10.7gのピリジンと、140gのダイグライム(ジエチレングリコールジメチルエーテル)と混合し、60℃の温度で18時間撹拌して、4,4’-オキシジフタル酸二無水物とメタノールのジエステルを製造した。次いで、反応混合物を-10℃に冷却し、温度を-10±4℃に保ちながら16.12g(135.5ミリモル)のSOCl2を10分かけて加えた。50mLのN-メチルピロリドンで希釈した後、反応混合物を室温で2時間撹拌した。次いで、100mLのN-メチルピロリドンに11.88g(59.3ミリモル)の4,4’-オキシジアニリン(ODA、ジアミン)を溶解させた溶液を、20~23℃で20分かけて反応混合物に滴下した。次いで、反応混合物に23.9g(15.5ミリモル)のジペンタエリスリトールヘキサアクリレート(DPHA、日本化薬製、末端用化合物)を添加し、反応混合物を室温で1晩撹拌した。次いで、3リットルの水と3リットルのアセトンの混合溶媒中でポリイミド前駆体を沈殿させた。ポリイミド前駆体を濾過して除き、4リットルの水の中で再度30分間撹拌し再び濾過した。次いで、得られたポリイミド前駆体を減圧下室温で2日間乾燥し、ポリイミド前駆体(P-1)を得た。得られたポリイミド前駆体(P-1)の構造は1H-NMR(核磁気共鳴スペクトル)(DMSO(ジメチルスルホキシド)-d6溶液)で確認した。
10.6~10.3ppm(m,2H)、8.2~6.7ppm(m,14H)、6.4~6.2ppm(m,1H)、6.2~6.0ppm(m,1H)、6.0~5.8ppm(m,0.9H)、4.4~4.0ppm(m,3H)、3.9~3.6ppm(s,6H)。
得られたP-1の重量平均分子量(ゲルパーミエーションクロマトグラフィー(溶離液:NMP(N-メチル-2-ピロリドン)のポリスチレン換算値)は50000であった。
測定条件は以下の通りである。
カラム:TSKguardcolumn SuperAW-H(4.6mmID.×35mm)1本
TSK SuperAWM-H(6.0mmID.×150mm) 2本
展開溶媒:NMP(10mmol/L臭化リチウム、10mmol/Lリン酸溶液)
カラム温度:50℃
流量:0.35mL/分
サンプル注入量:20μL
サンプル濃度:0.1質量%
装置名:HLC-8220GPC(東ソー製)
検量線ベース樹脂:ポリスチレン Synthesis of polyimide precursor <Synthesis of polyimide precursor P-1>
2. 20.00 g (64.5 mmol) of 4,4′-oxydiphthalic dianhydride (ODPA, 4,4′-oxydiphthalic acid dried at 140 ° C. for 12 hours, bifunctional anhydride); 13 g (129 mmol) of methanol (side chain compound), 0.05 g of hydroquinone, 10.7 g of pyridine and 140 g of diglyme (diethylene glycol dimethyl ether) are mixed and stirred at a temperature of 60 ° C. for 18 hours. 4,4′-oxydiphthalic dianhydride and methanol diester were prepared. The reaction mixture was then cooled to −10 ° C. and 16.12 g (135.5 mmol) of SOCl 2 was added over 10 minutes while maintaining the temperature at −10 ± 4 ° C. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution of 11.88 g (59.3 mmol) of 4,4′-oxydianiline (ODA, diamine) dissolved in 100 mL of N-methylpyrrolidone was added to the reaction mixture at 20-23 ° C. over 20 minutes. It was dripped in. Next, 23.9 g (15.5 mmol) of dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku, compound for terminal) was added to the reaction mixture, and the reaction mixture was stirred at room temperature overnight. Next, the polyimide precursor was precipitated in a mixed solvent of 3 liters of water and 3 liters of acetone. The polyimide precursor was filtered off and stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor was dried at room temperature under reduced pressure for 2 days to obtain a polyimide precursor (P-1). The structure of the obtained polyimide precursor (P-1) was confirmed by 1 H-NMR (nuclear magnetic resonance spectrum) (DMSO (dimethyl sulfoxide) -d6 solution).
10.6 to 10.3 ppm (m, 2H), 8.2 to 6.7 ppm (m, 14 H), 6.4 to 6.2 ppm (m, 1 H), 6.2 to 6.0 ppm (m, 1 H) ), 6.0 to 5.8 ppm (m, 0.9H), 4.4 to 4.0 ppm (m, 3H), 3.9 to 3.6 ppm (s, 6H).
The weight average molecular weight of the obtained P-1 (gel permeation chromatography (eluent: NMP (N-methyl-2-pyrrolidone) converted to polystyrene)) was 50,000.
The measurement conditions are as follows.
Column: 1 TSK guardcolumn Super AW-H (4.6 mm ID. × 35 mm) 1 TSK Super AWM-H (6.0 mm ID. × 150 mm) 2 developing solvents: NMP (10 mmol / L lithium bromide, 10 mmol / L phosphoric acid solution)
Column temperature: 50 ° C
Flow rate: 0.35 mL / min Sample injection volume: 20 μL
Sample concentration: 0.1% by mass
Device name: HLC-8220GPC (manufactured by Tosoh)
Calibration curve base resin: polystyrene
上記ポリイミド前駆体P-1の合成において、二官能酸無水物、ジアミン、側鎖用化合物および末端用化合物を、それぞれ、下記表1に示すように変更し、他は同様に行って、ポリイミド前駆体P-2~P-16、P-18をそれぞれ合成した。 <Synthesis of polyimide precursors P-2 to P-16, P-18>
In the synthesis of the polyimide precursor P-1, the bifunctional acid anhydride, the diamine, the side chain compound and the terminal compound were changed as shown in Table 1 below, and others were performed in the same manner. Forms P-2 to P-16 and P-18 were respectively synthesized.
温度計、攪拌機、塩化カルシウム管を備えた3つ口フラスコに、4,4’-オキシジフタル酸二無水物(15.51g)、N-メチルピロリドン(114g)を加え、室温で攪拌した。この懸濁液に4,4’-オキシジアニリン(9.21g)を添加し、30℃で攪拌した。1時間後、N-メチルピロリドン(15.27g)とDPHA(18.51g)の混合液を添加し、30℃で攪拌した。6時間後、室温まで冷却した。得られた混合液をNMPで希釈し、GPCにて測定した重量平均分子量は50000であった。次いで、3リットルの水と3リットルのアセトンの混合溶媒中でポリイミド前駆体を沈殿させた。ポリイミド前駆体を濾過して除き、4リットルの水の中で再度30分間撹拌し再び濾過した。次いで、得られたポリイミド前駆体を減圧下室温で2日間乾燥した。得られた固体をNMPに溶解させ、GPCにて測定した
重量平均分子量は20000であった。精製工程において分解したと考えられた。 <Synthesis of P-17>
To a three-necked flask equipped with a thermometer, a stirrer and a calcium chloride tube, 4,4′-oxydiphthalic dianhydride (15.51 g) and N-methylpyrrolidone (114 g) were added and stirred at room temperature. To this suspension, 4,4′-oxydianiline (9.21 g) was added and stirred at 30 ° C. After 1 hour, a mixture of N-methylpyrrolidone (15.27 g) and DPHA (18.51 g) was added and stirred at 30 ° C. After 6 hours, it was cooled to room temperature. The obtained mixed solution was diluted with NMP, and the weight average molecular weight measured by GPC was 50,000. Next, the polyimide precursor was precipitated in a mixed solvent of 3 liters of water and 3 liters of acetone. The polyimide precursor was filtered off and stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor was dried at room temperature under reduced pressure for 2 days. The obtained solid was dissolved in NMP, and the weight average molecular weight measured by GPC was 20000. It was thought that it decomposed in the purification process.
BPDA: 3,3’,4,4’-ビフェニルテトラカルボン酸ニ無水物、東京化成工業製
ODA:東京化成工業製
ベンジジン(4,4’-ジアミノビフェニル):東京化成工業製
エタノール:和光純薬工業製
n-ブタノール:和光純薬工業製
n-オクタノール:和光純薬工業製
DPHA:日本化薬製、KAYARAD DPHA
M-305:ペンタエリスリトールトリアクリレート、東亞合成社製、アロニックスM-305
701:グリセロールジメタクリレート、新中村化学工業製
ヒドロキシエチルアクリレート:和光純薬工業製
M-215:イソシアヌル酸エチレンオキシド(EO)変性ジアクリレート、東亞合成社製、アロニックスM-215
カレンズBEI:1,1-(ビスアクリロイルオキシメチル)エチルイソシアネート、昭和電工製
カレンズMOI: 2-イソシアナトエチルメタクリレート、昭和電工製
4-アミノスチレン:東京化成工業製 ODPA: Tokyo Chemical Industry BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, Tokyo Chemical Industry ODA: Tokyo Chemical Industry Benzidine (4,4′-diaminobiphenyl): Tokyo Chemical Industry Manufactured by Ethanol: Wako Pure Chemical Industries, Ltd. n-Butanol: Wako Pure Chemical Industries, Ltd. n-Octanol: Wako Pure Chemical Industries, Ltd. DPHA: Nippon Kayaku, KAYARAD DPHA
M-305: Pentaerythritol triacrylate, manufactured by Toagosei Co., Ltd., Aronix M-305
701: Glycerol dimethacrylate, Shin-Nakamura Chemical Co., Ltd. Hydroxyethyl acrylate: Wako Pure Chemical Industries, Ltd. M-215: Isocyanuric acid ethylene oxide (EO) modified diacrylate, manufactured by Toagosei Co., Ltd., Aronix M-215
Karenz BEI: 1,1- (bisacryloyloxymethyl) ethyl isocyanate, manufactured by Showa Denko Karenz MOI: 2-isocyanatoethyl methacrylate, manufactured by Showa Denko 4-Aminostyrene: manufactured by Tokyo Chemical Industry
<<ネガ型感光性樹脂組成物の調製>>
下記表4に示すとおり、ポリイミド前駆体、光重合開始剤、ラジカル重合性モノマー、重合禁止剤、金属変色防止剤、シランカップリング剤および溶剤を混合し、均一な溶液として、ネガ型感光性樹脂組成物を調製した。 <Example 1>
<< Preparation of negative photosensitive resin composition >>
As shown in the following Table 4, a polyimide precursor, a photopolymerization initiator, a radical polymerizable monomer, a polymerization inhibitor, a metal discoloration inhibitor, a silane coupling agent, and a solvent are mixed to form a negative photosensitive resin as a uniform solution. A composition was prepared.
<<<露光部残膜率>>>
ネガ型感光性樹脂組成物を、細孔の幅が0.8μmのフィルターを通して、3.0MPaの圧力で加圧濾過した後、シリコンウェハ上にスピンコート法により、ネガ型感光性樹脂組成物を層状に適用して、ネガ型感光性樹脂組成物層を形成した。得られたネガ型感光性樹脂組成物層を適用したシリコンウェハをホットプレート上で、100℃で5分間乾燥し、シリコンウェハ上に15μmの厚さの均一なネガ型感光性樹脂組成物層を得た。シリコンウェハ上のネガ型感光性樹脂組成物層を、ステッパー(Nikon NSR 2005 i9C)を用いて、500mJ/cm2の露光エネルギーで露光した。室温で30分間静置した後、シクロペンタノンで60秒間現像し、現像前後の膜厚変化から露光部残膜率を求めた。
露光部残膜率(%)=[露光部の現像後の膜厚/未露光部の現像前の膜厚]×100
5: 90%以上
4: 70%以上90%未満
3: 50%以上70%未満
2: 30%以上50%未満
1: 30%未満
評価3以上が実用上好ましい。 << Resolution >>
<<< exposed part remaining film ratio >>>
The negative photosensitive resin composition is filtered under pressure at a pressure of 3.0 MPa through a filter having a pore width of 0.8 μm, and then the negative photosensitive resin composition is applied onto a silicon wafer by spin coating. A negative photosensitive resin composition layer was formed by applying in layers. The obtained silicon wafer to which the negative photosensitive resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to form a uniform negative photosensitive resin composition layer having a thickness of 15 μm on the silicon wafer. Obtained. The negative photosensitive resin composition layer on the silicon wafer was exposed with an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C). After standing at room temperature for 30 minutes, development was performed with cyclopentanone for 60 seconds, and the exposed area remaining film ratio was determined from the change in film thickness before and after development.
Exposed part residual film ratio (%) = [film thickness after development of exposed part / film thickness of unexposed part before development] × 100
5: 90% or more 4: 70% or more and less than 90% 3: 50% or more and less than 70% 2: 30% or more and less than 50% 1: less than 30% Evaluation of 3 or more is practically preferable.
ネガ型感光性樹脂組成物を、細孔の幅が0.8μmのフィルターを通して、3.0MPaの圧力で加圧濾過した後、シリコンウェハ上にスピンコート法により、ネガ型感光性樹脂組成物を層状に適用して、ネガ型感光性樹脂組成物層を形成した。得られたネガ型感光性樹脂組成物層を適用したシリコンウェハをホットプレート上で、100℃で5分間乾燥し、シリコンウェハ上に15μmの厚さの均一なネガ型感光性樹脂組成物層とした。これをシクロペンタノンで60秒間現像し、現像前後の膜厚変化から未露光部残膜率を求めた。
未露光部残膜率(%)=[(未露光部の現像後の膜厚)/未露光部の現像前の膜厚]×100
5: 5%未満
4: 5%以上20%未満
3: 20%以上50%未満
2: 50%以上90%未満
1: 90%以上
評価3以上が実用上好ましい。 <<< Remaining film ratio of unexposed part >>>
The negative photosensitive resin composition is filtered under pressure at a pressure of 3.0 MPa through a filter having a pore width of 0.8 μm, and then the negative photosensitive resin composition is applied onto a silicon wafer by spin coating. A negative photosensitive resin composition layer was formed by applying in layers. The silicon wafer to which the obtained negative photosensitive resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes, and a uniform negative photosensitive resin composition layer having a thickness of 15 μm was formed on the silicon wafer. did. This was developed with cyclopentanone for 60 seconds, and the unexposed portion residual film ratio was determined from the change in film thickness before and after development.
Unexposed area remaining film ratio (%) = [(film thickness after development of unexposed area) / film thickness before development of unexposed area] × 100
5: Less than 5% 4: 5% or more but less than 20% 3: 20% or more but less than 50% 2: 50% or more but less than 90% 1: 90% or more Evaluation of 3 or more is practically preferable.
ネガ型感光性樹脂組成物を、細孔の幅が0.8μmのフィルターを通して、3.0MPaの圧力で加圧濾過した後、シリコンウェハ上にスピンコート法により、ネガ型感光性樹脂組成物を層状に適用して、ネガ型感光性樹脂組成物層を形成した。得られたネガ型感光性樹脂組成物層を適用したシリコンウェハをホットプレート上で、100℃で5分間乾燥し、シリコンウェハ上に15μmの厚さの均一なネガ型感光性樹脂組成物層とした。シリコンウェハ上のネガ型感光性樹脂組成物層を、ステッパー(Nikon NSR 2005 i9C)を用いて、500mJ/cm2の露光エネルギーで露光し、露光したネガ型感光性樹脂組成物層(樹脂層)を、窒素雰囲気下で、10℃/分の昇温速度で昇温し、230℃に達した後、3時間保持し、加熱前後の膜厚変化から加熱後の残膜率を求めた。
熱硬化後の残膜率(%)=[熱硬化後の膜厚/熱硬化前の膜厚]×100
5: 85%以上
4: 80%以上85%未満
3: 70%以上80%未満
2: 60%以上70%未満
1: 60%未満
評価2以上が実用上好ましい。 << Residual film ratio after thermosetting >>
The negative photosensitive resin composition is filtered under pressure at a pressure of 3.0 MPa through a filter having a pore width of 0.8 μm, and then the negative photosensitive resin composition is applied onto a silicon wafer by spin coating. A negative photosensitive resin composition layer was formed by applying in layers. The silicon wafer to which the obtained negative photosensitive resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes, and a uniform negative photosensitive resin composition layer having a thickness of 15 μm was formed on the silicon wafer. did. The negative photosensitive resin composition layer on the silicon wafer was exposed at an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C), and the exposed negative photosensitive resin composition layer (resin layer) Was heated at a rate of temperature increase of 10 ° C./min in a nitrogen atmosphere, and was maintained for 3 hours after reaching 230 ° C., and the remaining film ratio after heating was determined from the change in film thickness before and after heating.
Residual film ratio after thermosetting (%) = [film thickness after thermosetting / film thickness before thermosetting] × 100
5: 85% or more 4: 80% or more and less than 85% 3: 70% or more and less than 80% 2: 60% or more and less than 70% 1: less than 60% Evaluation of 2 or more is practically preferable.
ネガ型感光性樹脂組成物を、細孔の幅が0.8μmのフィルターを通して、3.0MPaの圧力で加圧濾過した後、シリコンウェハ上にスピンコート法により、ネガ型感光性樹脂組成物を層状に適用して、ネガ型感光性樹脂組成物層を形成した。得られたネガ型感光性樹脂組成物層を適用したシリコンウェハをホットプレート上で、100℃で5分間乾燥し、シリコンウェハ上に15μmの厚さの均一なネガ型感光性樹脂組成物層を得た。シリコンウェハ上のネガ型感光性樹脂組成物層を、ステッパー(Nikon NSR 2005 i9C)を用いて、500mJ/cm2の露光エネルギーで露光し、露光したネガ型感光性樹脂組成物層(樹脂層)を、窒素雰囲気下で、10℃/分の昇温速度で昇温し、230℃に達した後、3時間保持した。硬化後の樹脂層を4.9質量%フッ化水素酸溶液に浸漬し、シリコンウェハから樹脂層を剥離し、樹脂膜を得た。得られた樹脂膜を粘弾性測定装置(ユービーエム社製、Rheogel E4000)にセットし、引張法を用いて、周波数1Hzで、昇温速度10℃/分で0℃から350℃まで昇温し、tanδのピーク温度からTg(℃)を求めた。 << Glass Transition Temperature (Tg) >>
The negative photosensitive resin composition is filtered under pressure at a pressure of 3.0 MPa through a filter having a pore width of 0.8 μm, and then the negative photosensitive resin composition is applied onto a silicon wafer by spin coating. A negative photosensitive resin composition layer was formed by applying in layers. The obtained silicon wafer to which the negative photosensitive resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to form a uniform negative photosensitive resin composition layer having a thickness of 15 μm on the silicon wafer. Obtained. The negative photosensitive resin composition layer on the silicon wafer was exposed at an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C), and the exposed negative photosensitive resin composition layer (resin layer) Was heated at a rate of temperature increase of 10 ° C./min in a nitrogen atmosphere, and was maintained for 3 hours after reaching 230 ° C. The cured resin layer was immersed in a 4.9% by mass hydrofluoric acid solution, and the resin layer was peeled off from the silicon wafer to obtain a resin film. The obtained resin film was set in a viscoelasticity measuring device (Rhegel E4000, manufactured by UBM Co., Ltd.), and the temperature was increased from 0 ° C. to 350 ° C. at a frequency of 1 Hz and a temperature increase rate of 10 ° C./min. , Tg (° C.) was determined from the peak temperature of tan δ.
実施例1において、ポリイミド前駆体、光重合開始剤、ラジカル重合性モノマー、重合禁止剤、金属変色防止剤、シランカップリング剤および溶剤の1つ以上を、表4または表5に示すように変更し、さらに一部の実施例については、表5に示すとおり、熱塩基発生剤を配合し、他は同様に行った。 <Other Examples and Comparative Examples>
In Example 1, one or more of the polyimide precursor, photopolymerization initiator, radical polymerizable monomer, polymerization inhibitor, metal discoloration inhibitor, silane coupling agent, and solvent are changed as shown in Table 4 or Table 5. In addition, as shown in Table 5, some examples were blended with a thermal base generator, and others were performed in the same manner.
<光ラジカル重合開始剤>
OXE-01:IRGACURE OXE 01(オキシム化合物、BASF社製)
IRGACURE-784:IRGACURE-784(メタロセン化合物、BASF社製)
<ラジカル重合性モノマー>
SR209:SR-209(エチレンオキシ鎖を4個有する2官能メタクリレート、サートマー社製)
A-9300:NKエステルA-9300(イソブチレンオキシ鎖を3個有する3官能アクリレート、新中村化学工業社製)
A-TMMT:新中村化学工業製、ペンタエリスリトールテトラアクリレート
A-DPH:新中村化学工業製、ジペンタエリスリトールヘキサアクリレート The detail of each component of the said Table 4 and Table 5 is as follows.
<Radical radical polymerization initiator>
OXE-01: IRGACURE OXE 01 (oxime compound, manufactured by BASF)
IRGACURE-784: IRGACURE-784 (metallocene compound, manufactured by BASF)
<Radically polymerizable monomer>
SR209: SR-209 (bifunctional methacrylate having four ethyleneoxy chains, manufactured by Sartomer)
A-9300: NK ester A-9300 (trifunctional acrylate having three isobutyleneoxy chains, manufactured by Shin-Nakamura Chemical Co., Ltd.)
A-TMMT: Shin-Nakamura Chemical, Pentaerythritol tetraacrylate A-DPH: Shin-Nakamura Chemical, Dipentaerythritol hexaacrylate
E-1:下記化合物
E-2:下記化合物
E-3:下記化合物 <Heat base generator>
E-1: The following compound E-2: The following compound E-3: The following compound
F-1:下記化合物
F-2:下記化合物
F-3:下記化合物 <Polymerization inhibitor>
F-1: the following compound F-2: the following compound F-3: the following compound
G-1:下記化合物
G-2:下記化合物
G-3:下記化合物
G-4:下記化合物 <Metal discoloration inhibitor>
G-1: the following compound G-2: the following compound G-3: the following compound G-4: the following compound
H-1:下記化合物
H-2:下記化合物
H-3:下記化合物 <Silane coupling agent>
H-1: the following compound H-2: the following compound H-3: the following compound
DMSO:ジメチルスルホキシド
GBL:γ-ブチロラクトン
NMP:N-メチル-2-ピロリドン
乳酸エチル <Solvent>
DMSO: dimethyl sulfoxide GBL: γ-butyrolactone NMP: N-methyl-2-pyrrolidone ethyl lactate
また、本発明ではガラス転移温度も230℃以上と、比較例1および2よりも5℃も高くなった。Tgの5℃の上昇は、金属配線を形成するための蒸着処理工程や電極間の接合工程などの高温プロセスにおける信頼性向上という観点から非常に顕著な効果であるといえる。
さらに、ポリイミド前駆体の側鎖の鎖を短くすることにより(式(1)のR1およびR2を炭素数1~4の非重合性基の有機基とすることにより)、熱硬化後の残膜率が顕著に向上した。 As apparent from the above results, when the negative photosensitive resin composition of the present invention was used, the Tg was high and the resolution was excellent.
In the present invention, the glass transition temperature was 230 ° C. or higher, which was 5 ° C. higher than those of Comparative Examples 1 and 2. An increase in Tg of 5 ° C. can be said to be a very remarkable effect from the viewpoint of improving reliability in a high-temperature process such as a vapor deposition process for forming a metal wiring or a bonding process between electrodes.
Further, by shortening the side chain of the polyimide precursor (by making R 1 and R 2 of formula (1) an organic group of a non-polymerizable group having 1 to 4 carbon atoms), The remaining film rate was remarkably improved.
<積層体1の製造>
実施例3の感光性樹脂組成物を、細孔の幅が0.8μmのフィルターを通して加圧濾過した後、シリコンウェハ上にスピンコート法により、感光性樹脂組成物層を形成した。得られた感光性樹脂組成物層を適用したシリコンウェハをホットプレート上で、100℃で5分間乾燥し、シリコンウェハ上に15μmの厚さの均一な感光性樹脂組成物層とした。ついで、シリコンウェハ上の感光性樹脂組成物層を、ステッパー(Nikon NSR 2005 i9C)を用いて、500mJ/cm2の露光エネルギーで露光し、露光した感光性樹脂組成物層(樹脂層)を、シクロペンタノンで60秒間を現像して、直径10μmのホールを形成した。次いで、窒素雰囲気下で、10℃/分の昇温速度で昇温し、230℃に達した後、3時間保持した。室温まで冷却後、樹脂層の表面に、再度、感光性樹脂組成物と同じ種類の感光性樹脂組成物を用いて、上記と同様に感光性樹脂組成物の濾過から、パターン化した膜の3時間加熱までの手順を再度実施して、樹脂層を2層有する積層体1を形成した。 Example 100
<Manufacture of laminated body 1>
The photosensitive resin composition of Example 3 was subjected to pressure filtration through a filter having a pore width of 0.8 μm, and then a photosensitive resin composition layer was formed on a silicon wafer by spin coating. The obtained silicon wafer to which the photosensitive resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a uniform photosensitive resin composition layer having a thickness of 15 μm on the silicon wafer. Next, the photosensitive resin composition layer on the silicon wafer was exposed with an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C), and the exposed photosensitive resin composition layer (resin layer) was Development was performed with cyclopentanone for 60 seconds to form a 10 μm diameter hole. Next, the temperature was raised at a rate of 10 ° C./min in a nitrogen atmosphere, and after reaching 230 ° C., the temperature was maintained for 3 hours. After cooling to room temperature, again using the same type of photosensitive resin composition as the photosensitive resin composition on the surface of the resin layer, filtration of the photosensitive resin composition in the same manner as described above, 3 of the patterned film was performed. The procedure up to the time heating was performed again to form a laminate 1 having two resin layers.
上記で得られた積層体1の表面に、実施例3の感光性樹脂組成物を用いて、積層体1の製造と同様の手順を再度実施することで、樹脂層を4層有する積層体2を作製した。 <Manufacture of laminated body 2>
On the surface of the laminate 1 obtained above, the same procedure as in the production of the laminate 1 is performed again using the photosensitive resin composition of Example 3, so that the laminate 2 having four resin layers. Was made.
実施例3の感光性樹脂組成物を、細孔の幅が0.8μmのフィルターを通して加圧濾過した後、シリコンウェハ上にスピンコート法により、感光性樹脂組成物層を形成した。得られた感光性樹脂組成物層を適用したシリコンウェハをホットプレート上で、100℃で5分間乾燥し、シリコンウェハ上に15μmの厚さの均一な感光性樹脂組成物層とした。シリコンウェハ上の感光性樹脂組成物層を、ステッパー(Nikon NSR 2005 i9C)を用いて、500mJ/cm2の露光エネルギーで露光し、露光した感光性樹脂組成物層(樹脂層)を、シクロペンタノンで60秒間を現像して、直径10μmのホールを形成した。次いで、窒素雰囲気下で、10℃/分の昇温速度で昇温し、230℃に達した後、3時間保持した。室温まで冷却後、上記ホール部分を覆うように、感光性樹脂組成物層の表面の一部に、蒸着法により厚さ2μmの銅薄膜(金属層)を適用した。さらに、金属層および感光性樹脂組成物層の表面に、再度、実施例3の感光性樹脂組成物を用いて、上記と同様に感光性樹脂組成物の濾過から、パターン化した膜の3時間加熱までの手順を再度実施して、樹脂層/金属層/樹脂層からなる積層体3を作製した。 <Manufacture of laminated body 3>
The photosensitive resin composition of Example 3 was subjected to pressure filtration through a filter having a pore width of 0.8 μm, and then a photosensitive resin composition layer was formed on a silicon wafer by spin coating. The obtained silicon wafer to which the photosensitive resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a uniform photosensitive resin composition layer having a thickness of 15 μm on the silicon wafer. The photosensitive resin composition layer on the silicon wafer was exposed with an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C), and the exposed photosensitive resin composition layer (resin layer) was subjected to cyclopenta A hole having a diameter of 10 μm was formed by developing for 60 seconds in a non-process. Next, the temperature was raised at a rate of 10 ° C./min in a nitrogen atmosphere, and after reaching 230 ° C., the temperature was maintained for 3 hours. After cooling to room temperature, a 2 μm thick copper thin film (metal layer) was applied to a part of the surface of the photosensitive resin composition layer by vapor deposition so as to cover the hole portion. Further, again using the photosensitive resin composition of Example 3 on the surfaces of the metal layer and the photosensitive resin composition layer, the photosensitive resin composition was filtered in the same manner as described above, and then the patterned film was used for 3 hours. The procedure up to the heating was performed again to produce a laminate 3 composed of resin layer / metal layer / resin layer.
101a~101d:半導体素子
101:積層体
102b~102d:貫通電極
103a~103e:金属バンプ
105:再配線層
110、110a、110b:アンダーフィル層
115:絶縁層
120:配線基板
120a:表面電極 100:
Claims (21)
- ポリイミド前駆体と、光重合開始剤と、溶剤とを含み、
前記ポリイミド前駆体は、式(1)で表される繰り返し単位を有し、少なくとも一方の末端に式(2)で表される構造を有し、重量平均分子量が50000以下である、ネガ型感光性樹脂組成物;
(A)l-L1-* (2)
式(2)中、Aは重合性基を表し、L1は単結合またはl+1価の有機基を表し、lは1~10の整数を表し、*は他の部位との結合部位を示す。 Including a polyimide precursor, a photopolymerization initiator, and a solvent,
The polyimide precursor has a repeating unit represented by the formula (1), has a structure represented by the formula (2) at least at one end, and has a weight average molecular weight of 50000 or less. Functional resin composition;
(A) l -L 1- * (2)
In the formula (2), A represents a polymerizable group, L 1 represents a single bond or an l + 1 valent organic group, l represents an integer of 1 to 10, and * represents a bonding site with another site. - 式(2)におけるlが、2~5の整数である、請求項1に記載のネガ型感光性樹脂組成物。 The negative photosensitive resin composition according to claim 1, wherein l in formula (2) is an integer of 2 to 5.
- 前記R1およびR2はそれぞれ独立に、炭素数1~4の非重合性の有機基である、請求項1または2に記載のネガ型感光性樹脂組成物。 3. The negative photosensitive resin composition according to claim 1, wherein R 1 and R 2 are each independently a non-polymerizable organic group having 1 to 4 carbon atoms.
- 前記式(2)中のAは、炭素-炭素不飽和二重結合を含む基である、請求項1~3のいずれか1項に記載のネガ型感光性樹脂組成物。 The negative photosensitive resin composition according to any one of claims 1 to 3, wherein A in the formula (2) is a group containing a carbon-carbon unsaturated double bond.
- 前記式(2)で表される構造は、式(3)または式(4)で表わされる構造である、請求項1~4のいずれか1項に記載のネガ型感光性樹脂組成物;
式(4)中、L3は単結合またはn+1価の有機基を表し、nは1~10の整数を表し、*は他の部位との結合部位を示す。 The negative photosensitive resin composition according to any one of claims 1 to 4, wherein the structure represented by the formula (2) is a structure represented by the formula (3) or the formula (4);
In the formula (4), L 3 represents a single bond or an n + 1 valent organic group, n represents an integer of 1 to 10, and * represents a bonding site with another site. - 前記ポリイミド前駆体の重量平均分子量が5000以上である、請求項1~5のいずれか1項に記載のネガ型感光性樹脂組成物。 The negative photosensitive resin composition according to any one of claims 1 to 5, wherein the polyimide precursor has a weight average molecular weight of 5,000 or more.
- さらに、多官能ラジカル重合性モノマーを含む、請求項1~6のいずれか1項に記載のネガ型感光性樹脂組成物。 The negative photosensitive resin composition according to claim 1, further comprising a polyfunctional radical polymerizable monomer.
- さらに、熱塩基発生剤を含む、請求項1~7のいずれか1項に記載のネガ型感光性樹脂組成物。 The negative photosensitive resin composition according to any one of claims 1 to 7, further comprising a thermal base generator.
- 前記光重合開始剤がオキシム化合物およびメタロセン化合物から選ばれる少なくとも1種である、請求項1~8のいずれか1項に記載のネガ型感光性樹脂組成物。 The negative photosensitive resin composition according to any one of claims 1 to 8, wherein the photopolymerization initiator is at least one selected from an oxime compound and a metallocene compound.
- 再配線層用層間絶縁膜形成用である、請求項1~9のいずれか1項に記載のネガ型感光性樹脂組成物。 The negative photosensitive resin composition according to any one of claims 1 to 9, which is used for forming an interlayer insulating film for a rewiring layer.
- 請求項1~10のいずれか1項に記載のネガ型感光性樹脂組成物を硬化してなる硬化膜。 A cured film obtained by curing the negative photosensitive resin composition according to any one of claims 1 to 10.
- 膜厚が1~30μmである、請求項11に記載の硬化膜。 The cured film according to claim 11, wherein the film thickness is 1 to 30 μm.
- 請求項1~10のいずれか1項に記載のネガ型感光性樹脂組成物を基板に適用して層状にする感光性樹脂組成物層形成工程と、
前記ネガ型感光性樹脂組成物層を露光する露光工程と、
前記露光された感光性樹脂組成物層に対して、現像処理を行う現像処理工程と、
を有する硬化膜の製造方法。 A photosensitive resin composition layer forming step of applying a negative photosensitive resin composition according to any one of claims 1 to 10 to a substrate to form a layer,
An exposure step of exposing the negative photosensitive resin composition layer;
A development processing step of performing development processing on the exposed photosensitive resin composition layer;
The manufacturing method of the cured film which has this. - 前記現像処理工程後に、現像されたネガ型感光性樹脂組成物層を50~500℃の温度で加熱する加熱工程を含む、請求項13に記載の硬化膜の製造方法。 The method for producing a cured film according to claim 13, further comprising a heating step of heating the developed negative photosensitive resin composition layer at a temperature of 50 to 500 ° C after the development processing step.
- 請求項11または12に記載の硬化膜を有する半導体デバイス。 A semiconductor device having the cured film according to claim 11 or 12.
- 請求項13または14に記載の硬化膜の製造方法を含む、積層体の製造方法。 The manufacturing method of a laminated body containing the manufacturing method of the cured film of Claim 13 or 14.
- 請求項13または14に記載の硬化膜の製造方法を含む、半導体デバイスの製造方法。 A method for manufacturing a semiconductor device, including the method for manufacturing a cured film according to claim 13 or 14.
- 式(1)で表される繰り返し単位を有し、少なくとも一方の末端に式(2)で表される構造を有し、重量平均分子量が50000以下であるポリイミド前駆体;
(A)l-L1-* (2)
式(2)中、Aは重合性基を表し、L1は単結合またはl+1価の有機基を表し、lは1~10の整数を表し、*は他の部位との結合部位を示す。 A polyimide precursor having a repeating unit represented by the formula (1), having a structure represented by the formula (2) at at least one end, and having a weight average molecular weight of 50,000 or less;
(A) l -L 1- * (2)
In the formula (2), A represents a polymerizable group, L 1 represents a single bond or an l + 1 valent organic group, l represents an integer of 1 to 10, and * represents a bonding site with another site. - 前記R1およびR2はそれぞれ独立に、炭素数1~4の非重合性の有機基である、請求項18に記載のポリイミド前駆体。 The polyimide precursor according to claim 18, wherein R 1 and R 2 are each independently a non-polymerizable organic group having 1 to 4 carbon atoms.
- 前記式(2)中のAは、炭素-炭素不飽和二重結合を含む基である、請求項18または19に記載のポリイミド前駆体。 The polyimide precursor according to claim 18 or 19, wherein A in the formula (2) is a group containing a carbon-carbon unsaturated double bond.
- 式(2)におけるlが、2~5の整数である、請求項18~20のいずれか1項に記載のポリイミド前駆体。 The polyimide precursor according to any one of claims 18 to 20, wherein l in formula (2) is an integer of 2 to 5.
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020246349A1 (en) | 2019-06-03 | 2020-12-10 | 三菱瓦斯化学株式会社 | Photosensitive resin composition and cured film thereof |
WO2021059917A1 (en) * | 2019-09-25 | 2021-04-01 | 富士フイルム株式会社 | Organic film and manufacturing method therefor, composition, laminate, and semiconductor device |
WO2021198793A1 (en) * | 2020-03-31 | 2021-10-07 | Kaneka Corporation | Thermoplastic-thermoset hybrid resins, methods, and uses thereof |
WO2022203071A1 (en) * | 2021-03-26 | 2022-09-29 | リンテック株式会社 | Curable resin composition and cured resin layer using same |
WO2023276517A1 (en) * | 2021-07-02 | 2023-01-05 | 東レ株式会社 | Resin composition, cured product, production method for cured product, electronic component, display device, and semiconductor device |
KR20230136738A (en) * | 2022-03-18 | 2023-09-26 | 닛산 가가쿠 가부시키가이샤 | Photosensitive resin composition for forming an insulating film |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI808143B (en) * | 2018-03-29 | 2023-07-11 | 日商富士軟片股份有限公司 | Photosensitive resin composition, cured film, laminate and their manufacturing method, semiconductor device and thermal alkali generator used therefor |
TWI668515B (en) * | 2018-05-22 | 2019-08-11 | 臻鼎科技股份有限公司 | Photosensitive resin compositon, method for manufacturing the same, polymer film, and copper clad plate |
CN110515269B (en) | 2018-05-22 | 2022-12-20 | 臻鼎科技股份有限公司 | Photosensitive resin composition and preparation method thereof, polymer film and copper-clad plate |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000281671A (en) * | 1998-10-30 | 2000-10-10 | Hitachi Chemical Dupont Microsystems Ltd | Tetracarboxylic dianhydride, its derivative and production, polyimide precursor, polyimide, resin composition, photosensitive resin composition, production of relief pattern, and electronic part |
JP2003167337A (en) * | 2001-12-04 | 2003-06-13 | Hitachi Chemical Dupont Microsystems Ltd | Method for manufacturing multilayer wiring structure |
JP2004124054A (en) * | 2002-06-07 | 2004-04-22 | Toray Ind Inc | Heat resistant resin precursor composition |
WO2012165448A1 (en) * | 2011-06-01 | 2012-12-06 | 日本ゼオン株式会社 | Resin composition and semiconductor element substrate |
WO2015199219A1 (en) * | 2014-06-27 | 2015-12-30 | 富士フイルム株式会社 | Thermal base generator, thermosetting resin composition, cured film, cured film manufacturing method, and semiconductor device |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006193691A (en) * | 2005-01-17 | 2006-07-27 | Nippon Kayaku Co Ltd | Photosensitive polyamic acid and photosensitive composition including the same |
JP2007056196A (en) * | 2005-08-26 | 2007-03-08 | Tokyo Institute Of Technology | Polyimide precursor composition, method for producing polyimide film and semiconductor device |
JP4826415B2 (en) * | 2005-10-12 | 2011-11-30 | 東レ株式会社 | Photosensitive resin composition |
JP4923656B2 (en) * | 2006-03-22 | 2012-04-25 | 日立化成デュポンマイクロシステムズ株式会社 | Negative photosensitive resin composition, pattern manufacturing method, and electronic component |
JP4840014B2 (en) * | 2006-07-31 | 2011-12-21 | 日立化成デュポンマイクロシステムズ株式会社 | Positive photosensitive resin composition, method for producing patterned cured film, and electronic component |
JP5076390B2 (en) * | 2006-07-31 | 2012-11-21 | 日立化成デュポンマイクロシステムズ株式会社 | Negative photosensitive resin composition, method for producing patterned cured film, and electronic component |
JP5021337B2 (en) * | 2007-02-28 | 2012-09-05 | 旭化成イーマテリアルズ株式会社 | Resin composition containing thermal base generator |
JP5942348B2 (en) * | 2011-07-04 | 2016-06-29 | Jnc株式会社 | Thermosetting inkjet ink and use thereof |
JP2013076845A (en) | 2011-09-30 | 2013-04-25 | Nippon Zeon Co Ltd | Photosensitive resin composition |
WO2015064280A1 (en) * | 2013-10-30 | 2015-05-07 | 太陽インキ製造株式会社 | Photosensitive heat-curable resin composition and flexible printed wiring board |
JP6300491B2 (en) * | 2013-11-08 | 2018-03-28 | オリンパス株式会社 | Solid-state imaging device and imaging device |
JP6278817B2 (en) * | 2014-04-24 | 2018-02-14 | Jfeケミカル株式会社 | Polyamic acid composition and polyimide composition |
-
2017
- 2017-06-23 TW TW106120971A patent/TWI728137B/en active
- 2017-06-26 KR KR1020187036825A patent/KR102187513B1/en active IP Right Grant
- 2017-06-26 JP JP2018525148A patent/JP6837063B2/en active Active
- 2017-06-26 WO PCT/JP2017/023341 patent/WO2018003725A1/en active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000281671A (en) * | 1998-10-30 | 2000-10-10 | Hitachi Chemical Dupont Microsystems Ltd | Tetracarboxylic dianhydride, its derivative and production, polyimide precursor, polyimide, resin composition, photosensitive resin composition, production of relief pattern, and electronic part |
JP2003167337A (en) * | 2001-12-04 | 2003-06-13 | Hitachi Chemical Dupont Microsystems Ltd | Method for manufacturing multilayer wiring structure |
JP2004124054A (en) * | 2002-06-07 | 2004-04-22 | Toray Ind Inc | Heat resistant resin precursor composition |
WO2012165448A1 (en) * | 2011-06-01 | 2012-12-06 | 日本ゼオン株式会社 | Resin composition and semiconductor element substrate |
WO2015199219A1 (en) * | 2014-06-27 | 2015-12-30 | 富士フイルム株式会社 | Thermal base generator, thermosetting resin composition, cured film, cured film manufacturing method, and semiconductor device |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020246349A1 (en) | 2019-06-03 | 2020-12-10 | 三菱瓦斯化学株式会社 | Photosensitive resin composition and cured film thereof |
KR20220016450A (en) | 2019-06-03 | 2022-02-09 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Photosensitive resin composition and cured film thereof |
WO2021059917A1 (en) * | 2019-09-25 | 2021-04-01 | 富士フイルム株式会社 | Organic film and manufacturing method therefor, composition, laminate, and semiconductor device |
JPWO2021059917A1 (en) * | 2019-09-25 | 2021-04-01 | ||
JP7204937B2 (en) | 2019-09-25 | 2023-01-16 | 富士フイルム株式会社 | Organic film and its manufacturing method, composition, laminate, and semiconductor device |
JP7478806B2 (en) | 2019-09-25 | 2024-05-07 | 富士フイルム株式会社 | Organic film and its manufacturing method, composition, laminate, and semiconductor device |
WO2021198793A1 (en) * | 2020-03-31 | 2021-10-07 | Kaneka Corporation | Thermoplastic-thermoset hybrid resins, methods, and uses thereof |
JP7447303B2 (en) | 2020-03-31 | 2024-03-11 | 株式会社カネカ | Thermoplastic-thermosetting hybrid resins, methods and uses thereof |
WO2022203071A1 (en) * | 2021-03-26 | 2022-09-29 | リンテック株式会社 | Curable resin composition and cured resin layer using same |
WO2023276517A1 (en) * | 2021-07-02 | 2023-01-05 | 東レ株式会社 | Resin composition, cured product, production method for cured product, electronic component, display device, and semiconductor device |
KR20230136738A (en) * | 2022-03-18 | 2023-09-26 | 닛산 가가쿠 가부시키가이샤 | Photosensitive resin composition for forming an insulating film |
KR102628683B1 (en) | 2022-03-18 | 2024-01-25 | 닛산 가가쿠 가부시키가이샤 | Photosensitive resin composition for forming an insulating film |
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