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WO2022162895A1 - Procédé de sélection de précurseur de polyimide, procédé de production de composition de résine, précurseur de polyimide, composition de résine et objet durci - Google Patents

Procédé de sélection de précurseur de polyimide, procédé de production de composition de résine, précurseur de polyimide, composition de résine et objet durci Download PDF

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Publication number
WO2022162895A1
WO2022162895A1 PCT/JP2021/003345 JP2021003345W WO2022162895A1 WO 2022162895 A1 WO2022162895 A1 WO 2022162895A1 JP 2021003345 W JP2021003345 W JP 2021003345W WO 2022162895 A1 WO2022162895 A1 WO 2022162895A1
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WIPO (PCT)
Prior art keywords
polyimide precursor
group
resin composition
general formula
polyimide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2021/003345
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English (en)
Japanese (ja)
Inventor
綾香 東
拡子 四柳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Corp
Original Assignee
Showa Denko Materials Co Ltd
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Filing date
Publication date
Application filed by Showa Denko Materials Co Ltd filed Critical Showa Denko Materials Co Ltd
Priority to JP2022577968A priority Critical patent/JPWO2022162895A1/ja
Priority to PCT/JP2021/003345 priority patent/WO2022162895A1/fr
Priority to TW111104003A priority patent/TW202239819A/zh
Publication of WO2022162895A1 publication Critical patent/WO2022162895A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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

Definitions

  • the present disclosure relates to a method for selecting a polyimide precursor, a method for producing a resin composition, a polyimide precursor, a resin composition, and a cured product.
  • a protective film using such a polyimide resin can be obtained by heating and curing a resin film formed by coating and drying a polyimide precursor or a resin composition containing a polyimide precursor on a substrate.
  • the polyimide resin used to form the protective film is photosensitive, it is possible to easily form a patterned resin film, which is a patterned resin film. By heating and curing such a patterned resin film, a patterned cured film can be easily formed.
  • a method of imparting photosensitivity to a polyimide precursor can be mentioned as a method of making a polyimide resin photosensitivity.
  • Methods for imparting photosensitivity to a polyimide precursor include a method of introducing a (meth)acrylic group into a polyamic acid, which is a polyimide precursor, via an ester bond.
  • a method for achieving high resolution of the patterned cured film includes a method of adjusting the composition of the photosensitive agent, cross-linking agent, etc. contained in the resin composition.
  • the composition of the photosensitive agent, cross-linking agent, etc. contained in the resin composition is adjusted.
  • the present disclosure has been made in view of the above, a method for selecting a polyimide precursor capable of forming a patterned cured film with excellent resolution, a method for producing a resin composition, a polyimide precursor and a resin composition, and the above-mentioned resin
  • An object of the present invention is to provide a cured product obtained by curing a composition.
  • ⁇ 1> The cyclization temperature of the polyimide precursor, and the opening of the patterned resin film formed by exposing the coating film of the resin composition containing the polyimide precursor using a photomask having openings and then developing it.
  • ⁇ 2> The method for selecting a polyimide precursor according to ⁇ 1>, wherein a polyimide precursor having a cyclization temperature of 164° C. or higher is selected.
  • ⁇ 3> The method for selecting a polyimide precursor according to ⁇ 1> or ⁇ 2>, wherein the drying temperature for forming the coating film of the resin composition is 75°C to 140°C.
  • ⁇ 4> Measure the cyclization temperature of one or more polyimide precursors, and set specific cyclization temperature conditions based on the method for selecting a polyimide precursor according to any one of ⁇ 1> to ⁇ 3>.
  • a method for producing a resin composition comprising ⁇ 5> The method for producing a resin composition according to ⁇ 4>, wherein the selected polyimide precursor, a solvent, a photopolymerization initiator, and a polymerizable monomer are mixed to produce the resin composition.
  • the polyimide precursor according to ⁇ 6> which contains a compound having a structural unit represented by the following general formula (1).
  • X represents a tetravalent organic group
  • Y represents a divalent organic group
  • R 6 and R 7 each independently represent a hydrogen atom or a monovalent organic group.
  • At least one of R6 and R7 is a monovalent organic group.
  • ⁇ 8> Described in ⁇ 7>, wherein at least one of R 6 and R 7 in the general formula (1) is a group represented by the following general formula (2) corresponding to the monovalent organic group polyimide precursor of.
  • R 8 to R 10 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and R x represents a divalent linking group.
  • R 6 and R which are groups represented by general formula (2) with respect to the sum of R 6 and R 7 of all structural units contained in the compound having the structural unit represented by general formula (1)
  • a resin composition comprising the polyimide precursor according to any one of ⁇ 6> to ⁇ 10>, a solvent, a photopolymerization initiator, and a polymerizable monomer.
  • ⁇ 12> A cured product obtained by curing the resin composition according to ⁇ 11>.
  • a method for selecting a polyimide precursor capable of forming a patterned cured film with excellent resolution a method for producing a resin composition, a polyimide precursor and a resin composition, and curing obtained by curing the above-described resin composition can provide things.
  • a or B may include either A or B, or may include both.
  • the numerical range indicated using “-" includes the numerical values before and after "-" as the minimum and maximum values, respectively.
  • the upper limit or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described step by step.
  • the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples.
  • each component may contain multiple types of applicable substances.
  • the content rate or content of each component is the total content rate or content of the multiple types of substances present in the composition unless otherwise specified. means quantity.
  • the term "film” includes not only the case where the film is formed in the entire region when observing the region where the film exists, but also the case where it is formed only in part of the region. included.
  • the average thickness of the film is a value obtained by measuring the thickness of the target film at five points and giving the arithmetic mean value. The thickness of the film can be measured using a micrometer or the like. In the present disclosure, where the film thickness can be measured directly, it is measured using a micrometer.
  • the thickness when measuring the thickness of one layer or the total thickness of a plurality of layers, the thickness may be measured by observing the cross section of the object to be measured using an electron microscope.
  • (meth)acrylic group means “acrylic group” and “methacrylic group”.
  • the method for selecting the polyimide precursor of the present disclosure is the cyclization temperature of the polyimide precursor, and the coating film of the resin composition containing the polyimide precursor is exposed using a photomask having openings, and then developed.
  • a polyimide precursor that satisfies a specific cyclization temperature condition is selected based on the relationship between the opening diameter of the formed patterned resin film.
  • a polyimide precursor having a cyclization temperature of a specific temperature or higher it is possible to form a patterned cured film with excellent resolution by selecting a polyimide precursor having a cyclization temperature of a specific temperature or higher and using this polyimide precursor.
  • the reason for this is presumed as follows. Note that the present disclosure is not limited by the following assumptions. A resin composition containing a polyimide precursor is applied to a substrate such as a silicon wafer, and a coating film is formed by drying the applied resin composition by heating or the like.
  • the cyclization temperature of the polyimide precursor is lower than when the cyclization temperature of the polyimide precursor is higher, part of the polyimide precursor tends to undergo a cyclization reaction due to imidization due to heating or the like. Become.
  • the opening diameter of the pattern resin film is a specific value based on the relationship.
  • a polyimide precursor is selected that satisfies the condition of a cyclization temperature of less than . That is, based on the correlation between the cyclization temperature of the polyimide precursor and the opening diameter of the pattern resin film, the polyimide precursor satisfies the condition of the cyclization temperature such that the opening diameter of the pattern resin film becomes smaller than a specific value. You can choose your body. As described above, a pattern cured film having excellent resolution can be formed by using the selected polyimide precursor.
  • the resin composition used in the method for selecting a polyimide precursor of the present disclosure is not limited to a negative type, and may be a positive type.
  • the opening diameter of the pattern resin film tends to increase due to development in a state in which the cross-linking reaction due to exposure is insufficient.
  • the cyclization reaction due to imidization of the polyimide precursor by heating or the like is less likely to occur. Therefore, a cross-linking reaction between the uncyclized portion of the polyimide precursor and the polymerizable functional group of the polymerizable monomer easily occurs due to subsequent exposure, and the pattern resin film is formed by developing in a state where the cross-linking reaction due to exposure is sufficient.
  • the opening diameter tends to be smaller.
  • a patterned cured film having excellent resolution can be formed by selecting a polyimide precursor having a specific cyclization temperature or higher and using the polyimide precursor. .
  • the cyclization temperature of the polyimide precursor means the endothermic peak temperature of the imidization reaction in the polyimide precursor measured by differential scanning calorimetry (DSC).
  • the cyclization temperature of the polyimide precursor can be obtained by the following method. A polyimide precursor obtained by synthesis or the like is prepared, and a DSC curve is obtained using a differential scanning calorimeter and the prepared polyimide precursor under the conditions of a measurement temperature of 30° C. to 300° C. and a heating rate of 5° C./min. The temperature of the endothermic peak derived from the imidization reaction occurring in the vicinity of 140° C. to 200° C. in the obtained DSC curve is defined as the cyclization temperature of the polyimide precursor.
  • the cyclization temperature of the polyimide precursor and the opening diameter of the patterned resin film after exposure and development tend to exhibit a proportional or inverse proportional relationship, for example.
  • a negative resin composition when used, as described above, when the cyclization temperature of the polyimide precursor is low, the opening diameter of the pattern resin film tends to increase, and when the cyclization temperature of the polyimide precursor is high, the pattern tends to be large. The opening diameter of the resin film tends to decrease. Therefore, when a negative resin composition is used, the cyclization temperature of the polyimide precursor and the opening diameter of the patterned resin film after exposure and development tend to exhibit an inversely proportional relationship.
  • a plurality of data on the opening diameter of a patterned resin film formed using the cyclization temperature of the polyimide precursor and a polyimide precursor having the same cyclization temperature are obtained, and the calibration curve is compared.
  • a table or the like may be created. Then, using the prepared calibration curve, comparison table, etc., a polyimide precursor that satisfies the cyclization temperature condition that the opening diameter of the patterned resin film is smaller than a specific value may be selected.
  • the manufacturing conditions of the plurality of patterned resin films e.g., drying conditions and exposure conditions
  • the composition of the resin composition other than the polyimide precursor are preferably the same.
  • the cyclization temperature is the same as the cyclization temperature of the polyimide precursor.
  • the opening diameter of the patterned resin film formed using the polyimide precursor can be suitably compared.
  • the cyclization temperature of the polyimide precursor to be compared with the opening diameter of the pattern resin film is not particularly limited. °C to 180 °C.
  • the polyimide precursor skeleton (diamine compound-derived skeleton, tetracarboxylic dianhydride-derived skeleton, steric hindrance in the polyimide precursor, strain, etc., esterification rate, etc.), polyimide precursor It can be adjusted depending on the type of raw material used for synthesizing the polyimide, synthesis conditions of the polyimide precursor, and the like.
  • esterification is the ratio of the ester groups to the total of the amino groups and unreacted carboxy groups and ester groups contained in the diamine compound. Increasing the rate tends to raise the cyclization temperature of the polyimide precursor.
  • the diamine compound is an aromatic diamine
  • a diamine compound in which a halogen atom such as a fluorine atom or an electron-withdrawing group such as a sulfone group is bonded to an aromatic group may be used.
  • a polyimide precursor may have a rigid skeleton such as a polycyclic aromatic structure or a biphenyl skeleton.
  • the glass transition temperature of the polyimide precursor rises, and below the glass transition temperature, molecular motion is suppressed and imidization is suppressed, so it is presumed that the cyclization temperature of the polyimide precursor tends to rise.
  • reducing the number of amine terminals, which are unreacted amino groups, in the polyimide precursor suppresses imidization and tends to increase the cyclization temperature of the polyimide precursor.
  • the resin composition contains a polyimide precursor and is not particularly limited as long as it is a resin composition having positive or negative photosensitivity. It may be a resin composition containing. Specific examples of the polyimide precursor, the solvent, the photopolymerization initiator and the polymerizable monomer, the mixing ratio of these in the resin composition, etc. are described in the item of the method for producing the resin composition of the present disclosure, the polyimide precursor It is the same as the body, the solvent, the photopolymerization initiator and the polymerizable monomer, the mixing ratio thereof, and the like.
  • a resin composition containing a polyimide precursor is applied to a substrate such as a silicon wafer.
  • a coating film is formed by drying the resin composition applied to the substrate by heating or the like. Examples of the method of applying the resin composition include a spin coating method, an inkjet method, and a slit coating method.
  • the drying temperature when forming a coating film of the resin composition is preferably 75° C. to 140° C., more preferably 90° C. to 130° C., from the viewpoint of coating film formation and suppression of imidization.
  • the drying time is preferably 30 seconds to 5 minutes. Drying may be performed using a hot plate, an oven, or the like.
  • a patterned resin film is formed by exposing a coating film of a resin composition using a photomask having openings and then developing the exposed film by immersing it in a developer. After development, the patterned resin film may be heated to form a patterned cured film.
  • Examples of the active energy rays with which the coating film of the resin composition is irradiated include broadband light (wavelength: 350 nm to 450 nm), ultraviolet rays such as i-rays, visible rays, and radiation. Among them, i-rays are preferred.
  • a parallel exposure device a projection exposure device, a stepper, a scanner exposure device, a proximity exposure device, or the like may be used.
  • the opening shape of the photomask used for exposing the coating film is not particularly limited.
  • the photomask circle diameter width corresponding to the unexposed area may be 10 ⁇ m
  • the width of the opening of the photomask may be 10 ⁇ m.
  • a patterned resin film which is a patterned resin film, can be obtained by developing after the exposure.
  • the resin composition is a negative resin composition
  • the unexposed area is removed with a developer.
  • a good solvent for the coating film can be used alone, or a good solvent and a poor solvent can be appropriately mixed and used as the developer.
  • Good solvents include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, ⁇ -butyrolactone, ⁇ -acetyl- ⁇ -butyrolactone, Cyclopentanone, cyclohexanone and the like can be mentioned.
  • Poor solvents include toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, water and the like.
  • the exposed portion is removed with a developer.
  • solutions used as positive developing solutions include tetramethylammonium hydroxide (TMAH) solutions and sodium carbonate solutions.
  • At least one of the negative developer and the positive developer may contain a surfactant.
  • the content of the surfactant is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the developer.
  • the development time can be, for example, twice the time required for the photosensitive coating to be completely dissolved after being immersed in the developer.
  • the development time is, for example, preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and still more preferably 20 seconds to 5 minutes from the viewpoint of efficiency.
  • the pattern resin film after development may be washed with a rinsing liquid.
  • a rinsing liquid distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc. may be used alone or in an appropriate mixture.
  • a plurality of data on the cyclization temperature of the polyimide precursor and the opening diameter of the patterned resin film formed using the polyimide precursor having the same cyclization temperature are obtained, and the opening diameter of the patterned resin film is adjusted to be smaller than a specific value. It is preferable to select a polyimide precursor that satisfies the cyclization temperature requirement.
  • the specific value used as a reference may be set from the measured value of the opening diameter of the pattern resin film, and the measured value of the opening diameter of the pattern resin film, the opening diameter of the pattern resin film with respect to the circular width of the photomask, It may be set after considering the ratio (aperture diameter/circular width) or the like.
  • the ratio of the opening diameter of the pattern resin film to the circle diameter width of the photomask when a negative resin composition is used, when the ratio of the opening diameter of the pattern resin film to the circle diameter width of the photomask is 95% or less, preferably 90% or less, more preferably 85%.
  • the opening diameter of the pattern resin film when the following values are obtained may be set to a specific value.
  • the opening diameter of the pattern resin film when the ratio of the opening diameter of the pattern resin film to the circle diameter width of the photomask is 60% or more or 70% or more may be set to a specific value.
  • a polyimide precursor with a cyclization temperature of 150° C. or higher may be selected.
  • °C or higher polyimide precursor may be selected, 164 °C or higher polyimide precursor may be selected, 170 °C or higher polyimide precursor may be selected, 172 °C or higher polyimide precursor is selected.
  • a negative resin composition is used, any one of the cyclization temperature conditions described above is satisfied from the viewpoint of suppressing development residue, pattern peeling, etc. and making it possible to suitably form a pattern cured film with excellent resolution.
  • a polyimide precursor is preferred.
  • a polyimide precursor having a cyclization temperature of 200° C. or lower may be selected, a polyimide precursor having a cyclization temperature of 180° C. or lower may be selected, or a polyimide precursor having a cyclization temperature of 175° C. or lower may be selected.
  • a method for producing a resin composition of the present disclosure involves measuring the cyclization temperature of one or more polyimide precursors, and polyimides that meet the conditions of a particular cyclization temperature based on the aforementioned method of selecting polyimide precursors of the present disclosure. selecting a precursor; and using the selected polyimide precursor to produce a resin composition.
  • the cyclization temperature of one or more polyimide precursors is measured. Using the measured cyclization temperature data, polyimide precursors meeting specific cyclization temperature requirements are selected based on the methods of selecting polyimide precursors of the present disclosure described above. By producing a resin composition using the selected polyimide precursor, a resin composition capable of forming a patterned cured film with excellent resolution is provided.
  • a resin composition containing a polyimide precursor and having positive or negative photosensitivity is produced, for example, a resin containing a polyimide precursor, a solvent, a photopolymerization initiator, a polymerizable monomer, etc.
  • a composition may be manufactured.
  • Polyimide precursors, solvents, photopolymerization initiators, polymerizable monomers, and the like that can be used in the method for producing the resin composition of the present disclosure are described below.
  • the polyimide precursor may be any polyimide precursor that satisfies a specific cyclization temperature condition. From the viewpoint of reactivity with the polymerizable monomer during exposure, the polyimide precursor preferably contains a polyimide precursor having a polymerizable unsaturated bond. Examples of polymerizable unsaturated bonds include carbon-carbon double bonds.
  • the polyimide precursor may contain a compound having a structural unit represented by the following general formula (1).
  • X represents a tetravalent organic group and Y represents a divalent organic group.
  • R6 and R7 each independently represent a hydrogen atom or a monovalent organic group. At least one of R6 and R7 is a monovalent organic group.
  • the polyimide precursor may have a plurality of structural units represented by the following general formula (1), and X, Y, R 6 and R 7 in the plurality of structural units may be the same or different. may be
  • the tetravalent organic group represented by X preferably has 4 to 25 carbon atoms, more preferably 4 to 13 carbon atoms, and even more preferably 6 to 12 carbon atoms. .
  • the tetravalent organic group represented by X may contain an aromatic ring.
  • examples of the aromatic ring include benzene ring, naphthalene ring, and phenanthrene ring.
  • a benzene ring is preferable from the viewpoint of improving the light transmittance of the polyimide precursor in the ultraviolet region.
  • each aromatic ring may have a substituent or may be unsubstituted.
  • substituents on the aromatic ring include alkyl groups, fluorine atoms, halogenated alkyl groups, hydroxyl groups, amino groups and the like.
  • the tetravalent organic group represented by X contains a benzene ring
  • the tetravalent organic group represented by X preferably contains 1 to 4 benzene rings, and contains 1 to 3 benzene rings. is more preferred, and it is even more preferred to contain one or two benzene rings.
  • each benzene ring may be connected by a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group , an ether bond (—O—), a sulfide bond (—S—), a silylene bond (—Si(R A ) 2 —; each R A independently represents a hydrogen atom, an alkyl group or a phenyl group), Siloxane bond (-O-(Si(R B ) 2 -O-) n ; each R B independently represents a hydrogen atom, an alkyl group or a phenyl group, and n represents an integer of 1 or 2 or more.) or a composite linking group in which at least two of these linking groups are combined.
  • two benzene rings may be bonded at two locations by at least one of a single bond and a linking group
  • the -COOR 6 group and the -CONH- group are ortho to each other, and the -COOR 7 group and the -CO- group are preferably ortho to each other.
  • tetravalent organic group represented by X include groups represented by the following formulas (A) to (E). The present disclosure is not limited to the specific examples below.
  • a and B are each independently a single bond, a methylene group, a methylene halide group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-) or a silylene bond (—Si(R A ) 2 —; each R A independently represents a hydrogen atom, an alkyl group or a phenyl group), and both A and B are not single bonds.
  • C is a single bond, or an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a silylene bond (-Si ( R A ) 2 —; each R A independently represents a hydrogen atom, an alkyl group or a phenyl group), a siloxane bond (—O—(Si( R B ) 2 —O—) n ; each independently represents a hydrogen atom, an alkyl group or a phenyl group, and n represents an integer of 1 or 2 or more.) or a divalent group in which at least two of these are combined. Moreover, C may have a structure represented by the following formula (C1).
  • the alkylene group represented by C in formula (E) is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and 1 or 2 alkylene groups are more preferred.
  • Specific examples of the alkylene group represented by C in formula (E) include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene; methylmethylene; methylethylene group, ethylmethylene group, dimethylmethylene group, 1,1-dimethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, ethylethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 1-ethyltrimethylene group, 2-ethyltrimethylene group, 1,1-dimethyltrimethylene group, 1,2-dimethyltrimethylene group, 2,2-dimethyltrimethylene group, 1-methylpentamethylene group, 2-methylpentamethylene group
  • the halogenated alkylene group represented by C in formula (E) is preferably a halogenated alkylene group having 1 to 10 carbon atoms, more preferably a halogenated alkylene group having 1 to 5 carbon atoms. More preferably, it is a halogenated alkylene group having 1 to 3 carbon atoms.
  • Specific examples of the halogenated alkylene group represented by C in formula (E) include at least one hydrogen atom contained in the alkylene group represented by C in the above formula (E) being a fluorine atom, a chlorine atom, or the like.
  • An alkylene group substituted with a halogen atom is mentioned. Among these, a fluoromethylene group, a difluoromethylene group, a hexafluorodimethylmethylene group and the like are preferable.
  • the alkyl group represented by R A or R B contained in the silylene bond or siloxane bond is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. is more preferred, and an alkyl group having 1 or 2 carbon atoms is even more preferred.
  • Specific examples of the alkyl group represented by R A or R B include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group and the like. mentioned.
  • the combination of A and B in formula (D) is not particularly limited, and a combination of a methylene group and an ether bond, a combination of a methylene group and a sulfide bond, a combination of a carbonyl group and an ether bond, and the like are preferred.
  • C in Formula (E) is preferably a single bond, an ether bond, a carbonyl group, or the like.
  • the divalent organic group represented by Y preferably has 6 to 25 carbon atoms, more preferably 6 to 14 carbon atoms, and even more preferably 12 to 14 carbon atoms.
  • the divalent organic group represented by Y may be a divalent aliphatic group or a divalent aromatic group. From the viewpoint of heat resistance, the divalent organic group represented by Y is preferably a divalent aromatic group.
  • divalent aromatic group represented by Y examples include groups represented by the following general formula (F) and the following general formula (G).
  • R each independently represents an alkyl group, an alkoxy group, a halogenated alkyl group or a phenyl group, and n each independently represents an integer of 0 to 4.
  • D is a single bond, or an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a silylene bond (-Si (R A ) 2 —; each R A independently represents a hydrogen atom, an alkyl group or a phenyl group.), a siloxane bond (—O—(Si( R B ) 2 —O—) n ; , each independently represents a hydrogen atom, an alkyl group or a phenyl group, and n represents an integer of 1 or 2 or more.) or a divalent group in which
  • the alkyl group represented by R in general formula (F) or general formula (G) is preferably an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms. More preferably, it is an alkyl group having 1 or 2 carbon atoms.
  • Specific examples of the alkyl group represented by R in general formula (F) or general formula (G) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, and the like.
  • the alkoxy group represented by R in the general formula (F) or general formula (G) is preferably an alkoxy group having 1 to 10 carbon atoms, preferably an alkoxy group having 1 to 5 carbon atoms. More preferably, it is an alkoxy group having 1 or 2 carbon atoms.
  • Specific examples of the alkoxy group represented by R in general formula (F) or general formula (G) include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s- butoxy group, t-butoxy group and the like.
  • the halogenated alkyl group represented by R in the general formula (F) or general formula (G) is preferably a halogenated alkyl group having 1 to 5 carbon atoms, and a halogenated alkyl group having 1 to 3 carbon atoms.
  • An alkyl group is more preferred, and a halogenated alkyl group having 1 or 2 carbon atoms is even more preferred.
  • Specific examples of the halogenated alkyl group represented by R in general formula (F) or general formula (G) include at least Examples thereof include alkyl groups in which one hydrogen atom is substituted with a halogen atom such as a fluorine atom or a chlorine atom. Among these, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group and the like are preferable.
  • n in general formula (F) or general formula (G) is each independently preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.
  • divalent aliphatic group represented by Y examples include a linear or branched alkylene group, a cycloalkylene group, a divalent group having a polyalkylene oxide structure, and a divalent group having a polysiloxane structure. and the like.
  • the linear or branched alkylene group represented by Y is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 15 carbon atoms. More preferably, it is an alkylene group with a number of 1-10.
  • Specific examples of the alkylene group represented by Y include a tetramethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group, and a 2-methylpentamethylene group. , 2-methylhexamethylene group, 2-methylheptamethylene group, 2-methyloctamethylene group, 2-methylnonamethylene group, 2-methyldecamethylene group and the like.
  • the cycloalkylene group represented by Y is preferably a cycloalkylene group having 3 to 10 carbon atoms, more preferably a cycloalkylene group having 3 to 6 carbon atoms.
  • Specific examples of the cycloalkylene group represented by Y include a cyclopropylene group and a cyclohexylene group.
  • the unit structure contained in the divalent group having a polyalkylene oxide structure represented by Y is preferably an alkylene oxide structure having 1 to 10 carbon atoms, more preferably an alkylene oxide structure having 1 to 8 carbon atoms. 1 to 4 alkylene oxide structures are more preferred.
  • the polyalkylene oxide structure is preferably a polyethylene oxide structure or a polypropylene oxide structure.
  • the alkylene group in the alkylene oxide structure may be linear or branched.
  • the number of unit structures in the polyalkylene oxide structure may be one, or two or more.
  • a silicon atom in the polysiloxane structure is bonded to a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 18 carbon atoms.
  • a divalent group having a polysiloxane structure is included.
  • alkyl group having 1 to 20 carbon atoms bonded to the silicon atom in the polysiloxane structure include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n- octyl group, 2-ethylhexyl group, n-dodecyl group and the like. Among these, a methyl group is preferred.
  • the aryl group having 6 to 18 carbon atoms bonded to the silicon atom in the polysiloxane structure may be unsubstituted or substituted with a substituent.
  • the aryl group has a substituent
  • specific examples of the substituent include a halogen atom, an alkoxy group, and a hydroxy group.
  • the aryl group having 6 to 18 carbon atoms include phenyl group, naphthyl group, benzyl group and the like. Among these, a phenyl group is preferred.
  • the alkyl group having 1 to 20 carbon atoms or the aryl group having 6 to 18 carbon atoms in the polysiloxane structure may be of one type or two or more types.
  • a silicon atom constituting a divalent group having a polysiloxane structure represented by Y is an NH group in the general formula (1) via an alkylene group such as a methylene group, an ethylene group, an arylene group such as a phenylene group, or the like. may be combined with
  • the combination of the tetravalent organic group represented by X and the divalent organic group represented by Y in the general formula (1) is not particularly limited.
  • X is a combined use of a group represented by formula (A) and a group represented by formula (E) and Y is a combination of groups represented by formula (G);
  • X is a combination of a group represented by formula (D) and a group represented by formula (E);
  • a combination of represented groups and the like can be mentioned.
  • X is a combination of a group represented by formula (A) and a group represented by formula (E)
  • the number-based ratio (XA/XE) is preferably in the range of 1/99 to 99/1, more preferably in the range of 50/50 to 90/10, 70/30 to 90/10 is more preferably in the range of
  • At least one of R6 and R7 is a monovalent organic group.
  • the monovalent organic group preferably contains an aliphatic hydrocarbon group having 1 to 4 carbon atoms or an organic group having an unsaturated double bond, an aliphatic hydrocarbon group having 1 or 2 carbon atoms or the following general formula It more preferably contains a group represented by (2), and more preferably contains a group represented by the following general formula (2).
  • the monovalent organic group contains an organic group having an unsaturated double bond, preferably a group represented by the following general formula (2)
  • the i-line transmittance is high, and even when cured at a low temperature of 300 ° C. or less. It tends to form a good patterned cured film.
  • Specific examples of aliphatic hydrocarbon groups having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and the like.
  • R 8 to R 10 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and R x represents a divalent linking group.
  • the number of carbon atoms in the aliphatic hydrocarbon group represented by R 8 to R 10 in general formula (2) is 1 to 3, preferably 1 or 2.
  • Specific examples of the aliphatic hydrocarbon group represented by R 8 to R 10 include methyl group, ethyl group, n-propyl group, isopropyl group and the like, with methyl group being preferred.
  • R 8 to R 10 in general formula (2) a combination in which R 8 and R 9 are hydrogen atoms and R 10 is a hydrogen atom or a methyl group is preferred.
  • R x in general formula (2) is a divalent linking group, preferably a hydrocarbon group having 1 to 10 carbon atoms.
  • hydrocarbon groups having 1 to 10 carbon atoms include linear or branched alkylene groups.
  • the number of carbon atoms in R x is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 or 3.
  • R 6 and R 7 are preferably a group represented by general formula (2) above, and both R 6 and R 7 are represented by general formula (2) above. More preferably a group represented by
  • the total of R 6 and R 7 of all structural units contained in the compound is represented by general formula (2) is preferably 50 mol % or more, more preferably 70 mol % or more, even more preferably 90 mol % or more.
  • the upper limit is not particularly limited, and may be 100 mol %.
  • the aforementioned ratio may be 0 mol % or more and less than 50 mol %.
  • the group represented by general formula (2) is preferably a group represented by general formula (3) below.
  • R 8 to R 10 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1-3 carbon atoms, and q represents an integer of 1-10.
  • q in the general formula (3) is preferably an integer of 1-10, more preferably an integer of 2-5, and even more preferably 2 or 3.
  • the polyimide precursor may be synthesized using a tetracarboxylic dianhydride and a diamine compound.
  • X corresponds to the residue derived from the tetracarboxylic dianhydride
  • Y corresponds to the residue derived from the diamine compound.
  • the polyimide precursor may be synthesized using tetracarboxylic acid instead of tetracarboxylic dianhydride.
  • tetracarboxylic dianhydrides include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, anhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride anhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, m-terphenyl-3,3′,4,4′- Tetracarboxylic dianhydride, p-terphenyl-3,3',4,4'-tetracarboxylic dianhydride, 1,1,1,3,3,3-hexafluoro-2
  • diamine compounds include 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-difluoro-4,4'-diaminobiphenyl, p-phenylenediamine, m- phenylenediamine, p-xylylenediamine, m-xylylenediamine, 1,5-diaminonaphthalene, benzidine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 2, 4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 2,4''-
  • a compound having a structural unit represented by the general formula (1) and in which at least one of R 6 and R 7 in the general formula (1) is a monovalent organic group is represented by the following general formula (8)
  • a tetracarboxylic dianhydride represented by and a compound represented by R—OH are reacted in a solvent such as N-methyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide to form a diester.
  • a solvent such as N-methyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide
  • Y in the diamine compound represented by H 2 N--Y--NH 2 is the same as Y in general formula (1), and specific examples and preferred examples are also the same.
  • R in the compound represented by R-OH represents a monovalent organic group, and specific examples and preferred examples are the same as specific examples and preferred examples of R 6 and R 7 in general formula (1). .
  • each of the tetracarboxylic dianhydride represented by the general formula (8), the diamine compound represented by H 2 N--Y--NH 2 and the compound represented by R--OH may be used alone. Well, you may combine two or more types.
  • the above-mentioned compound contained in the polyimide precursor is a diester derivative obtained by reacting a compound represented by R-OH on a tetracarboxylic dianhydride represented by the following general formula (8), and then thionyl chloride. It can be obtained by reacting a diamine compound represented by H 2 N--Y--NH 2 with the acid chloride by reacting with a chlorinating agent such as chlorinating agent to convert it into an acid chloride.
  • the above-mentioned compound contained in the polyimide precursor is a diester derivative obtained by reacting a compound represented by R-OH on a tetracarboxylic dianhydride represented by the following general formula (8), and then a carbodiimide compound. can be obtained by reacting a diamine compound represented by H 2 N--Y--NH 2 with a diester derivative in the presence of .
  • the aforementioned compound contained in the polyimide precursor is obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a diamine compound represented by H 2 N--Y--NH 2 to obtain a polyamic.
  • the polyamic acid is isoimidated in the presence of trifluoroacetic anhydride, and then reacted with a compound represented by R--OH.
  • a part of the tetracarboxylic dianhydride is reacted in advance with a compound represented by R—OH to form a partially esterified tetracarboxylic dianhydride and H 2 N—Y—NH 2 . may be reacted with the diamine compound to be used.
  • X is the same as X in general formula (1), and specific examples and preferred examples are also the same.
  • Compounds represented by R—OH used for synthesizing the aforementioned compounds contained in the polyimide precursor include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, Hydroxyethyl, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxy methacrylate Butyl and the like are preferred, and 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate are more preferred.
  • the molecular weight of the polyimide precursor is not particularly limited. ⁇ 60,000 is particularly preferred.
  • the weight average molecular weight can be measured, for example, by gel permeation chromatography, and can be obtained by conversion using a standard polystyrene calibration curve.
  • the resin composition may contain resin components other than the polyimide precursor.
  • resin compositions include polyimide resins, novolak resins, acrylic resins, polyethernitrile resins, polyethersulfone resins, epoxy resins, polyethylene terephthalate resins, polyethylene naphthalate resins, polyvinyl chloride resins, and the like. It may contain other resins. Other resins may be used singly or in combination of two or more.
  • the content of the polyimide precursor with respect to the total of resin components other than the polyimide precursor and the polyimide precursor is preferably 50% by mass to 100% by mass, and is 70% by mass to 100% by mass. is more preferable, and 90% by mass to 100% by mass is even more preferable.
  • the resin composition contains a solvent.
  • the solvent is not particularly limited, and examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ⁇ -butyrolactone, N,N-dimethylacetamide, cyclopentanone, dimethylsulfoxide, 3-methoxy-N ,N-dimethylpropanamide, N,N,2-trimethylpropionamide, dimethylimidazolidinone, N-formylpiperidine, N-dimethylmorpholine and propylene glycol 1-monomethyl ether-2-acetate.
  • N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, ⁇ -butyrolactone, cyclopentanone, dimethylsulfoxide, dimethylimidazolidinone and N-formylpiperidine is preferred.
  • a solvent may be used individually by 1 type, and may combine 2 or more types.
  • the content of the solvent is preferably 50 parts by mass to 10000 parts by mass with respect to the total 100 parts by mass of the resin components other than the polyimide precursor and the polyimide precursor, and 100 parts by mass to 10000 parts by mass. is more preferable.
  • the resin composition contains a photopolymerization initiator.
  • the photopolymerization initiator is not particularly limited. 4-methoxy-4'-dimethylaminobenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenylketone, Benzophenone derivatives such as dibenzyl ketone and fluorenone; acetophenone derivatives such as hydroxycyclohexylphenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone and diethylthioxanthone; benzyl derivatives such as benzyl, benzyldimethylketal and benzyl- ⁇
  • the content of the photopolymerization initiator is preferably 0.1 parts by mass to 20 parts by mass with respect to 100 parts by mass of the polyimide precursor, from the viewpoint that photocrosslinking is likely to be uniform in the film thickness direction. .1 to 10 parts by mass is more preferable, and 0.1 to 6 parts by mass is even more preferable.
  • the resin composition contains a polymerizable monomer.
  • the polymerizable monomer preferably has at least one group containing a polymerizable unsaturated double bond, and more preferably has at least one (meth)acrylic group from the viewpoint of being polymerizable with a coupling agent or the like. preferable. From the viewpoint of improving crosslink density and improving photosensitivity, it is preferable to have 2 to 4 groups containing a polymerizable unsaturated double bond.
  • a polymerizable monomer may be used individually by 1 type, and may combine 2 or more types.
  • the (meth)polymerizable monomer having an acrylic group is not particularly limited, and examples thereof include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, methacrylates, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, Trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol
  • diethylene glycol diacrylate triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate are preferable as the polymerizable monomer.
  • the polymerizable monomer other than the (meth)acrylic group-containing polymerizable monomer is not particularly limited, and examples thereof include styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, methylenebisacrylamide, N , N-dimethylacrylamide and N-methylolacrylamide.
  • the content of the polymerizable monomer is not particularly limited, and is preferably 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the polyimide precursor. From the viewpoint of the thermal properties of the pattern cured film, It is more preferably from 5 parts by mass to 50 parts by mass, and even more preferably from 5 parts by mass to 40 parts by mass.
  • the ratio of the polymerizable monomer having a (meth) acrylic group to the total amount of the polymerizable monomer is preferably 50% by mass to 100% by mass, and 70% by mass to 70% by mass, from the viewpoint of the physical properties of the cured film. It is more preferably 100% by mass, and even more preferably 90% to 100% by mass.
  • the resin composition may further contain a thermal polymerization initiator from the viewpoint of improving physical properties of the cured film.
  • the thermal polymerization initiator is not particularly limited, and examples thereof include ketone peroxides such as methyl ethyl ketone peroxide, 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t -hexylperoxy)cyclohexane, peroxyketals such as 1,1-di(t-butylperoxy)cyclohexane, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, etc.
  • hydroperoxide dicumyl peroxide, dialkyl peroxide such as di-t-butyl peroxide, dilauroyl peroxide, diacyl peroxide such as dibenzoyl peroxide, di(4-t-butylcyclohexyl) peroxydicarbonate, di(2-ethylhexyl ) Peroxydicarbonates such as peroxydicarbonate, t-butyl peroxy-2-ethylhexanoate, t-hexyl peroxyisopropyl monocarbonate, t-butyl peroxybenzoate, 1,1,3,3-tetra Peroxy esters such as methyl butyl peroxy-2-ethylhexanoate, bis(1-phenyl-1-methylethyl) peroxide and the like.
  • the thermal polymerization initiator may be used singly or in combination of two or more.
  • the content of the thermal polymerization initiator may be 0.1 parts by mass to 20 parts by mass with respect to 100 parts by mass of the polyimide precursor, and 1 part by mass It may be up to 15 parts by mass, or it may be 5 parts by mass to 10 parts by mass.
  • the resin composition may further contain a coupling agent.
  • the coupling agent reacts with the polyimide precursor to be crosslinked, or the coupling agent itself is polymerized. This tends to further improve the adhesiveness between the resulting cured film and the substrate.
  • Coupling agents include 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3 -methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl) Succinimide, N-[3-(triethoxysilyl)propyl]phthalamic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1
  • the content of the coupling agent is preferably 0.1 parts by mass to 20 parts by mass with respect to 100 parts by mass of the polyimide precursor, and 0.3 parts by mass to 10 parts by mass. parts is more preferable, and 1 part by mass to 10 parts by mass is even more preferable.
  • the resin composition may contain at least one of a surfactant and a leveling agent.
  • a surfactant and a leveling agent By containing at least one of a surfactant and a leveling agent in the resin composition, coatability (for example, suppression of striation (unevenness in film thickness)) can be improved.
  • Surfactants or leveling agents include polyoxyethylene uralyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether and the like. Surfactants and leveling agents may be used singly or in combination of two or more.
  • the total content of the surfactant and the leveling agent is 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of the polyimide precursor. preferably 0.05 to 5 parts by mass, even more preferably 0.05 to 3 parts by mass.
  • the resin composition may contain a polymerization inhibitor from the viewpoint of ensuring good storage stability.
  • polymerization inhibitors include radical polymerization inhibitors and radical polymerization inhibitors.
  • polymerization inhibitors include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, and N-phenyl-2.
  • a polymerization inhibitor may be used individually by 1 type, and may combine 2 or more types.
  • the content of the polymerization inhibitor is 0 with respect to 100 parts by mass of the polyimide precursor from the viewpoint of the storage stability of the resin composition and the heat resistance of the resulting cured film. It is preferably 0.01 to 30 parts by mass, more preferably 0.01 to 10 parts by mass, even more preferably 0.05 to 5 parts by mass.
  • the resin composition may contain an antirust agent. Corrosion and discoloration of copper and copper alloys can be suppressed by including a rust inhibitor in the resin composition. Rust inhibitors include triazole derivatives, tetrazole derivatives, and the like. The rust preventives may be used singly or in combination of two or more.
  • the content of the antirust agent is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyimide precursor. is more preferable, and 0.5 to 3 parts by mass is even more preferable.
  • the polyimide precursor of the present disclosure has a cyclization temperature of 164° C. or higher.
  • a pattern cured film with excellent resolution can be suitably formed.
  • the cyclization temperature of the polyimide precursor is preferably 170° C. or higher, more preferably 172° C. or higher. Moreover, the cyclization temperature of the polyimide precursor may be 200° C. or lower, 180° C. or lower, or 175° C. or lower.
  • the preferred form of the polyimide precursor of the present disclosure is the same as the preferred form of the polyimide precursor used in the aforementioned method for producing the resin composition of the present disclosure.
  • the resin composition of the present disclosure includes the aforementioned polyimide precursor of the present disclosure, a solvent, a photopolymerization initiator, and a polymerizable monomer.
  • the resin composition of the present disclosure can suitably form a patterned cured film with excellent resolution by containing the above-described polyimide precursor of the present disclosure.
  • the preferred form of the resin composition of the present disclosure is the same as the preferred form of the resin composition produced by the aforementioned method for producing the resin composition of the present disclosure.
  • the resin composition of the present disclosure preferably does not substantially contain an unreacted diamine compound from the viewpoint of suppressing imidization when forming a coating film. is preferably substantially free of In the present disclosure, “substantially free” means that the content of the target component is 1% by mass or less with respect to the total amount of the resin composition.
  • the cured product of the present disclosure is obtained by curing the resin composition of the present disclosure.
  • a cured product of the present disclosure may be produced on a substrate using the resin composition of the present disclosure.
  • a method for producing a pattern cured film which is an example of a cured product, will be described.
  • the resin composition is applied on a substrate, dried to form a coating film, and the coating film is pattern-exposed using a photomask and developed.
  • a method including developing with a liquid to obtain a patterned resin film and heat-treating the patterned resin film may be used. Thereby, a pattern cured film can be obtained.
  • Examples of methods for applying the resin composition onto the substrate include spin coating, inkjet, and slit coating.
  • the substrate is not particularly limited, and includes an acrylic plate, a glass substrate, a semiconductor substrate such as a silicon wafer, a metal oxide insulator substrate such as a TiO2 substrate and a SiO2 substrate, a silicon nitride substrate, a copper substrate, a copper alloy substrate, and the like. is mentioned.
  • the shape, size, etc. of the substrate are not limited, and may be appropriately selected according to the shape, size, etc. of the cured product to be produced. good.
  • the rotation speed is 300 rpm (rotation per minute) to 3,500 rpm, preferably 500 rpm to 1,500 rpm, the acceleration is 500 rpm / sec to 15,000 rpm / sec, and the rotation time is 30 seconds to 300 seconds.
  • the resin composition may be spin-coated.
  • drying may be performed using a hot plate, an oven, or the like.
  • the drying temperature is preferably 75° C. to 140° C., more preferably 90° C. to 130° C. from the viewpoint of improving the flatness of the cured film.
  • the drying time is preferably 30 seconds to 5 minutes. Drying may be performed twice or more. Thereby, the coating film which formed the above-mentioned resin composition in the shape of a film can be obtained.
  • the coating film formed on the substrate is pattern-exposed using a photomask and developed using a developer to obtain a patterned resin film.
  • the method for obtaining the patterned resin film is the same as the method for obtaining the patterned resin film in the method for producing the polyimide precursor described above.
  • a pattern cured film is formed by heat-treating the pattern resin film.
  • the heating temperature is preferably 150°C to 450°C, more preferably 150°C to 350°C.
  • the pattern cured film can be favorably produced while suppressing damage to the substrate and realizing energy saving in the process.
  • the heating time is preferably 5 hours or less, more preferably 30 minutes to 3 hours.
  • the atmosphere of the heat treatment may be the air or an inert atmosphere such as nitrogen, but the nitrogen atmosphere is preferable from the viewpoint of preventing oxidation of the resin film.
  • Devices used for heat treatment include quartz tube furnaces, hot plates, rapid thermal annealing, vertical diffusion furnaces, infrared curing furnaces, electron beam curing furnaces, and microwave curing furnaces.
  • the average thickness of the patterned cured film produced on the substrate is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m to 15 ⁇ m, even more preferably 0.5 ⁇ m to 10 ⁇ m.
  • ⁇ Synthesis Example 3 Synthesis of polyimide precursor> Put the PMDA (HEMA) solution obtained in Synthesis Example 1 and the ODPA (HEMA) solution obtained in Synthesis Example 2 into a 0.5-liter flask equipped with a stirrer and a thermometer, and then cool with ice. Thionyl chloride was added dropwise using a dropping funnel so as to keep the temperature of the reaction solution below 10°C. At this time, the molar ratio of PMDA (HEMA) and ODPA (HEMA) is about 4:1, and the molar ratio of the sum of PMDA (HEMA) and ODPA (HEMA) to thionyl chloride is about 1: was 2.
  • ⁇ Measurement of cyclization temperature of polyimide precursor> Using a differential scanning calorimeter (manufactured by Netzsch, DSC 204 F1 Phoenix), under the conditions of a temperature increase rate of 5 ° C./min, a measurement temperature range of 30 ° C. to 300 ° C., and a flow rate of 20 mL / min under nitrogen atmosphere, aluminum pan A DSC measurement was performed on a sealed 5 mg sample. The temperature of the endothermic peak derived from the imidization reaction occurring in the vicinity of 140° C. to 200° C. in the obtained DSC curve was taken as the cyclization temperature of the polyimide precursor.
  • Resin compositions were prepared using the polyimide precursors synthesized in Experimental Examples 1-14. Specifically, 100 parts by mass of each polyimide precursor, 150 parts by mass of a solvent, 2 parts by mass of a photopolymerization initiator, and 20 parts by mass of a polymerizable monomer were mixed to prepare a resin composition.
  • Solvent 3-methoxy-N,N-dimethylpropanamide
  • Photopolymerization initiator 1,2-propanedione, 1-[4-[[4-(2-hydroxyethoxy)phenyl]thio]phenyl]-, 2- (O-acetyloxime)
  • Polymerizable monomer triethylene glycol dimethacrylate
  • a patterned resin film was formed under the following conditions using the resin composition containing each polyimide precursor synthesized in Experimental Examples 1 to 14. Specifically, using a coating device (Act8, Tokyo Electron Ltd.), the resin composition was spin-coated on a silicon wafer, and then dried at 130° C. for 200 seconds to form a coating film. Using an i-line stepper FPA-3000iW (manufactured by Canon Inc.) and a photomask with a circle diameter width of 10 ⁇ m, the obtained coating film was irradiated with i-line of 300 mJ/cm 2 at NA 0.28, focus 0 ⁇ m.
  • FPA-3000iW manufactured by Canon Inc.
  • the coating film after exposure was developed using a coating device (Act8, Tokyo Electron Co., Ltd.) with cyclopentanone for a development time of 25 seconds by removing the unexposed area, and then propylene glycol monomethyl ether acetate (PGMEA ) to obtain a patterned resin film.
  • a coating device Act8, Tokyo Electron Co., Ltd.
  • cyclopentanone for a development time of 25 seconds by removing the unexposed area, and then propylene glycol monomethyl ether acetate (PGMEA ) to obtain a patterned resin film.
  • PGMEA propylene glycol monomethyl ether acetate
  • ⁇ Evaluation of pattern resin film> Based on the value of the opening diameter of the patterned resin film obtained as described above, whether or not a fine pattern could be formed was evaluated based on the following evaluation criteria. If the evaluation is B or higher, it can be judged that a fine pattern can be formed and the resolution is excellent.
  • C The opening diameter of the patterned resin film is more than 9.5 ⁇ m.

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Abstract

La présente invention concerne un procédé de sélection de précurseur de polyimide qui sélectionne un précurseur de polyimide satisfaisant à des conditions de température de cyclisation spécifiées, sur la base de la relation entre : la température de cyclisation du précurseur de polyimide ; et le diamètre d'une ouverture dans un film de résine à motif formé par exposition d'un film de revêtement d'une composition de résine qui comprend le précurseur de polyimide, à l'aide d'un photomasque qui a une ouverture, puis par développement du film de revêtement.
PCT/JP2021/003345 2021-01-29 2021-01-29 Procédé de sélection de précurseur de polyimide, procédé de production de composition de résine, précurseur de polyimide, composition de résine et objet durci Ceased WO2022162895A1 (fr)

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