WO2022162895A1 - Polyimide precursor selection method, resin composition production method, polyimide precursor, resin composition, and cured object - Google Patents

Polyimide precursor selection method, resin composition production method, polyimide precursor, resin composition, and cured object 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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Prior art keywords
polyimide precursor
group
resin composition
general formula
polyimide
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PCT/JP2021/003345
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French (fr)
Japanese (ja)
Inventor
綾香 東
拡子 四柳
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昭和電工マテリアルズ株式会社
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Application filed by 昭和電工マテリアルズ株式会社 filed Critical 昭和電工マテリアルズ株式会社
Priority to JP2022577968A priority Critical patent/JPWO2022162895A1/ja
Priority to PCT/JP2021/003345 priority patent/WO2022162895A1/en
Priority to TW111104003A priority patent/TW202239819A/en
Publication of WO2022162895A1 publication Critical patent/WO2022162895A1/en

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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

A polyimide precursor selection method that selects a polyimide precursor fulfilling specified cyclization temperature conditions, on the basis of the relationship between: the cyclization temperature of the polyimide precursor; and the diameter of an opening in a pattern resin film formed by exposing a coating film of a resin composition that includes the polyimide precursor, using a photomask that has an opening, and then developing the coating film.

Description

ポリイミド前駆体の選択方法、樹脂組成物の製造方法、ポリイミド前駆体、樹脂組成物及び硬化物Method for selecting polyimide precursor, method for producing resin composition, polyimide precursor, resin composition and cured product
　本開示は、ポリイミド前駆体の選択方法、樹脂組成物の製造方法、ポリイミド前駆体、樹脂組成物及び硬化物に関する。 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.
　近年、半導体集積回路（ＬＳＩ）の保護膜材料として、ポリイミド樹脂等の高い耐熱性を有する有機材料が広く適用されている（例えば、特許文献１及び２参照）。
　このようなポリイミド樹脂を用いた保護膜は、ポリイミド前駆体又はポリイミド前駆体を含有する樹脂組成物を基板上に塗布及び乾燥して形成した樹脂膜を、加熱して硬化することで得られる。 In recent years, organic materials having high heat resistance such as polyimide resins have been widely applied as protective film materials for semiconductor integrated circuits (LSI) (see, for example, Patent Documents 1 and 2).
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.
特許第３５２６８２９号Patent No. 3526829 特許第４５２４８０８号Patent No. 4524808
　保護膜を形成するために用いられるポリイミド樹脂が感光性であると、パターン形成された樹脂膜であるパターン樹脂膜を容易に形成することが可能である。このようなパターン樹脂膜を加熱して硬化することで、容易にパターン硬化膜を形成することができる。 If 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.
　ポリイミド樹脂を感光性とする方法として、ポリイミド前駆体に感光性を付与する方法が挙げられる。ポリイミド前駆体に感光性を付与する手法としては、ポリイミド前駆体であるポリアミック酸にエステル結合を介して（メタ）アクリル基を導入する方法等が挙げられる。 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.
　近年、半導体パッケージ等の半導体装置では配線の微細化が求められている。そのため、感光性ポリイミド樹脂を含む樹脂組成物を用いてパターン硬化膜を形成する際、微細なパターンが形成できること、すなわち、高い解像度を達成することが望ましい。 In recent years, miniaturization of wiring is required in semiconductor devices such as semiconductor packages. Therefore, when forming a pattern cured film using a resin composition containing a photosensitive polyimide resin, it is desirable to be able to form a fine pattern, that is, to achieve high resolution.
　パターン硬化膜の高い解像度を達成する方法としては、樹脂組成物に含まれる感光剤、架橋剤等の組成を調整する方法が挙げられる。一方、パターン硬化膜の高い解像度を達成する観点では、樹脂組成物に含まれるポリイミド前駆体はほとんど検討されていない。 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. On the other hand, from the viewpoint of achieving high resolution of the pattern cured film, almost no investigation has been made on the polyimide precursor contained in the resin composition.
　本開示は、上記に鑑みてなされたものであり、解像度に優れるパターン硬化膜を形成可能なポリイミド前駆体の選択方法、樹脂組成物の製造方法、ポリイミド前駆体及び樹脂組成物並びに、前述の樹脂組成物を硬化してなる硬化物を提供することを目的とする。 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.
　前記課題を達成するための具体的手段は以下の通りである。
＜１＞　ポリイミド前駆体の環化温度と、前記ポリイミド前駆体を含む樹脂組成物の塗膜を開口部を有するフォトマスクを用いて露光し、次いで現像することで形成されたパターン樹脂膜の開口径と、の関係に基づいて、特定の環化温度の条件を満たすポリイミド前駆体を選択するポリイミド前駆体の選択方法。
＜２＞　環化温度が１６４℃以上であるポリイミド前駆体を選択する＜１＞に記載のポリイミド前駆体の選択方法。
＜３＞　前記樹脂組成物の塗膜を形成する際の乾燥温度は、７５℃～１４０℃である＜１＞又は＜２＞に記載のポリイミド前駆体の選択方法。
＜４＞　１種類以上のポリイミド前駆体の環化温度を測定し、＜１＞～＜３＞のいずれか１つに記載のポリイミド前駆体の選択方法に基づいて特定の環化温度の条件を満たすポリイミド前駆体を選択することと、
　選択された前記ポリイミド前駆体を用いて樹脂組成物を製造することと、
　を含む樹脂組成物の製造方法。
＜５＞　選択された前記ポリイミド前駆体と、溶剤と、光重合開始剤と、重合性モノマーと、を混合して前記樹脂組成物を製造する＜４＞に記載の樹脂組成物の製造方法。
＜６＞　環化温度が１６４℃以上であるポリイミド前駆体。
＜７＞　下記一般式（１）で表される構造単位を有する化合物を含む＜６＞に記載のポリイミド前駆体。 Specific means for achieving the above object are as follows.
<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. A method for selecting polyimide precursors that selects polyimide precursors that meet specific cyclization temperature requirements based on the relationship between caliber and .
<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>. selecting a polyimide precursor that satisfies;
Producing a resin composition using the selected polyimide precursor;
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.
<6> A polyimide precursor having a cyclization temperature of 164° C. or higher.
<7> The polyimide precursor according to <6>, which contains a compound having a structural unit represented by the following general formula (1).
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　一般式（１）中、Ｘは４価の有機基を表し、Ｙは２価の有機基を表し、Ｒ６及びＲ７は、それぞれ独立に、水素原子、又は１価の有機基を表す。前記Ｒ６及びＲ７の少なくとも一方は１価の有機基である。
＜８＞　前記一般式（１）中、前記Ｒ６及び前記Ｒ７の少なくとも一方が、前記１価の有機基に該当する下記一般式（２）で表される基である＜７＞に記載のポリイミド前駆体。 In general formula (1), X represents a tetravalent organic group, Y represents a divalent organic group, and 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.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　一般式（２）中、Ｒ８～Ｒ１０は、それぞれ独立に、水素原子又は炭素数１～３の脂肪族炭化水素基を表し、Ｒｘは２価の連結基を表す。
＜９＞　前記一般式（１）で表される構造単位を有する化合物に含有される全構造単位のＲ６及びＲ７の合計に対する一般式（２）で表される基であるＲ６及びＲ７の割合は、５０モル％以上である＜８＞に記載のポリイミド前駆体。
＜１０＞　重量平均分子量が１０００～１０００００である＜６＞～＜９＞のいずれか１つに記載のポリイミド前駆体。
＜１１＞　＜６＞～＜１０＞のいずれか１つに記載のポリイミド前駆体と、溶剤と、光重合開始剤と、重合性モノマーと、を含む樹脂組成物。
＜１２＞　＜１１＞に記載の樹脂組成物を硬化してなる硬化物。 In general formula (2), 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.
<9> 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) The polyimide precursor according to <8>, wherein the proportion of 7 is 50 mol % or more.
<10> The polyimide precursor according to any one of <6> to <9>, which has a weight average molecular weight of 1,000 to 100,000.
<11> 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>.
　本開示によれば、解像度に優れるパターン硬化膜を形成可能なポリイミド前駆体の選択方法、樹脂組成物の製造方法、ポリイミド前駆体及び樹脂組成物並びに、前述の樹脂組成物を硬化してなる硬化物を提供することができる。 According to the present disclosure, 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.
　以下、本開示を実施するための形態について詳細に説明する。但し、本開示は以下の実施形態に限定されるものではない。以下の実施形態において、その構成要素（要素ステップ等も含む）は、特に明示した場合を除き、必須ではない。数値及びその範囲についても同様であり、本開示を制限するものではない。 A detailed description will be given below of the embodiment for implementing the present disclosure. However, the present disclosure is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and their ranges, which do not limit the present disclosure.
　本開示において「Ａ又はＢ」とは、ＡとＢのどちらか一方を含んでいればよく、両方とも含んでいてもよい。
　本開示において「～」を用いて示された数値範囲には、「～」の前後に記載される数値がそれぞれ最小値及び最大値として含まれる。
　本開示中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本開示中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
　本開示において、各成分には、該当する物質が複数種含まれていてもよい。組成物中に各成分に該当する物質が複数種存在する場合、各成分の含有率又は含有量は、特に断らない限り、組成物中に存在する当該複数種の物質の合計の含有率又は含有量を意味する。
　本開示において「膜」との語には、当該膜が存在する領域を観察したときに、当該領域の全体に形成されている場合に加え、当該領域の一部にのみ形成されている場合も含まれる。
　本開示において、膜の平均厚さは、対象となる膜の５点の厚さを測定し、その算術平均値として与えられる値とする。
　膜の厚さは、マイクロメーター等を用いて測定することができる。本開示において、膜の厚さを直接測定可能な場合には、マイクロメーターを用いて測定する。一方、１つの層の厚さ又は複数の層の総厚さを測定する場合には、電子顕微鏡を用いて、測定対象の断面を観察することで測定してもよい。
　本開示において「（メタ）アクリル基」とは、「アクリル基」及び「メタクリル基」を意味する。 In the present disclosure, “A or B” may include either A or B, or may include both.
In the present disclosure, the numerical range indicated using "-" includes the numerical values before and after "-" as the minimum and maximum values, respectively.
In the numerical ranges described step by step in the present disclosure, 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. . Moreover, in the numerical ranges described in the present disclosure, the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples.
In the present disclosure, each component may contain multiple types of applicable substances. When there are multiple types of substances corresponding to each component in the composition, 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.
In the present disclosure, 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.
In the present disclosure, 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. On the other hand, 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.
In the present disclosure, "(meth)acrylic group" means "acrylic group" and "methacrylic group".
＜ポリイミド前駆体の選択方法＞
　本開示のポリイミド前駆体の選択方法は、ポリイミド前駆体の環化温度と、前記ポリイミド前駆体を含む樹脂組成物の塗膜を開口部を有するフォトマスクを用いて露光し、次いで現像することで形成されたパターン樹脂膜の開口径と、の関係に基づいて、特定の環化温度の条件を満たすポリイミド前駆体を選択する。 <Method for selecting polyimide precursor>
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.
　本開示のポリイミド前駆体の選択方法では、特定の温度以上の環化温度を有するポリイミド前駆体を選択し、このポリイミド前駆体を用いることで解像度に優れるパターン硬化膜を形成可能である。この理由は、以下のように推測される。なお、本開示は以下の推測によって限定されない。
　ポリイミド前駆体を含む樹脂組成物は、シリコンウエハ等の基材に塗布され、塗布された樹脂組成物を加熱等により乾燥させることで塗膜が形成される。ここで、ポリイミド前駆体の環化温度がより低い場合、ポリイミド前駆体の環化温度がより高い場合と比較して、加熱等によってポリイミド前駆体の一部がイミド化による環化反応をしやすくなる。塗膜を形成する際のポリイミド前駆体におけるイミド化の程度が、露光及び現像後のパターン樹脂膜の開口径と相関関係があるため、その関係に基づいてパターン樹脂膜の開口径が特定の値よりも小さくなるような環化温度の条件を満たすポリイミド前駆体を選択する。つまり、ポリイミド前駆体の環化温度と、パターン樹脂膜の開口径との相関関係に基づいて、パターン樹脂膜の開口径が特定の値よりも小さくなるような環化温度の条件を満たすポリイミド前駆体を選択することができる。以上により、選択されたポリイミド前駆体を用いることで解像度に優れるパターン硬化膜を形成することができる。 In the method for selecting a polyimide precursor of the present disclosure, 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. Here, when 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. Since the degree of imidization in the polyimide precursor when forming the coating film has a correlation with the opening diameter of the pattern resin film after exposure and development, 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.
　より具体的な例として、ポリイミド前駆体を含む樹脂組成物として、ポリイミド前駆体、重合性モノマー等を含むネガ型の樹脂組成物を用いる場合について詳細に説明する。なお、本開示のポリイミド前駆体の選択方法で用いる樹脂組成物はネガ型に限定されず、ポジ型であってもよい。 As a more specific example, a case where a negative resin composition containing a polyimide precursor, a polymerizable monomer, etc. is used as the resin composition containing a polyimide precursor will be described in detail. In addition, 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.
　ネガ型の樹脂組成物を用い、ポリイミド前駆体の環化温度が低い場合、加熱等によってポリイミド前駆体の一部がイミド化による環化反応をしやすくなるため、その後の露光によるポリイミド前駆体の未環化部分と重合性モノマーの重合性官能基との架橋反応が生じにくくなる。その結果、露光による架橋反応が充分でない状態で現像されることで、パターン樹脂膜の開口径が大きくなる傾向にある。 When a negative resin composition is used and the cyclization temperature of the polyimide precursor is low, part of the polyimide precursor is likely to undergo a cyclization reaction due to imidization due to heating, etc., so that the polyimide precursor by subsequent exposure A cross-linking reaction between the uncyclized portion and the polymerizable functional group of the polymerizable monomer is less likely to occur. As a result, 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.
　一方、ネガ型の樹脂組成物を用い、ポリイミド前駆体の環化温度が高い場合、加熱等によるポリイミド前駆体のイミド化による環化反応が生じにくくなる。そのため、その後の露光によるポリイミド前駆体の未環化部分と重合性モノマーの重合性官能基との架橋反応が生じやすく、露光による架橋反応が充分な状態で現像されることで、パターン樹脂膜の開口径が小さくなる傾向にある。 On the other hand, when a negative resin composition is used and the cyclization temperature of the polyimide precursor is high, 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.
　以上の点から、ネガ型の樹脂組成物を用いた場合、特定の環化温度以上のポリイミド前駆体を選択し、当該ポリイミド前駆体を用いることで解像度に優れるパターン硬化膜を形成することができる。 From the above points, when a negative resin composition is used, 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. .
　本開示において、「ポリイミド前駆体の環化温度」は、示差走査熱量測定（ＤＳＣ）によって測定されるポリイミド前駆体におけるイミド化反応の吸熱ピークの温度を意味する。「ポリイミド前駆体の環化温度」は、以下の方法によって求めることができる。
　合成等により得たポリイミド前駆体を準備し、測定温度３０℃～３００℃、昇温速度５℃／分の条件にて示差走査熱量計及び準備したポリイミド前駆体を用いてＤＳＣ曲線を得る。得られたＤＳＣ曲線にて１４０℃～２００℃付近に発生するイミド化反応由来の吸熱ピークの温度をポリイミド前駆体の環化温度とする。 In the present disclosure, "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.
　本開示のポリイミド前駆体の選択方法では、ポリイミド前駆体の環化温度と、露光及び現像後のパターン樹脂膜の開口径は、例えば、比例又は反比例の関係を示す傾向にある。ネガ型の樹脂組成物を用いた場合、前述のように、ポリイミド前駆体の環化温度が低いときにはパターン樹脂膜の開口径が大きくなる傾向にあり、ポリイミド前駆体の環化温度が高いときにはパターン樹脂膜の開口径が小さくなる傾向にある。したがって、ネガ型の樹脂組成物を用いた場合、ポリイミド前駆体の環化温度と、露光及び現像後のパターン樹脂膜の開口径は、反比例の関係を示す傾向にある。 In the method for selecting a polyimide precursor of the present disclosure, 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. When a negative resin composition is 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.
　本開示のポリイミド前駆体の選択方法では、ポリイミド前駆体の環化温度及び同じ環化温度を有するポリイミド前駆体を用いて形成したパターン樹脂膜の開口径のデータを複数取得し、検量線、対比表等を作成してもよい。そして、作成した検量線、対比表等を用いて、パターン樹脂膜の開口径が特定の値よりも小さくなるような環化温度の条件を満たすポリイミド前駆体を選択してもよい。 In the method for selecting a polyimide precursor of the present disclosure, 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.
　ポリイミド前駆体の環化温度及び同じ環化温度を有するポリイミド前駆体を用いて形成したパターン樹脂膜の開口径のデータを複数取得する場合、複数のパターン樹脂膜の製造条件（例えば、乾燥条件及び露光条件）並びにポリイミド前駆体以外の樹脂組成物の組成は同じであることが好ましい。これにより、パターン樹脂膜の製造条件及びポリイミド前駆体以外の樹脂組成物の組成の違いによるパターン樹脂膜の開口径の変動を抑制でき、ポリイミド前駆体の環化温度と、同じ環化温度を有するポリイミド前駆体を用いて形成したパターン樹脂膜の開口径とを好適に対比することができる。 When obtaining a plurality of data on the opening diameter of patterned resin films formed using the cyclization temperature of the polyimide precursor and the polyimide precursor having the same cyclization temperature, the manufacturing conditions of the plurality of patterned resin films (e.g., drying conditions and exposure conditions) and the composition of the resin composition other than the polyimide precursor are preferably the same. As a result, it is possible to suppress fluctuations in the opening diameter of the patterned resin film due to differences in the manufacturing conditions of the patterned resin film and the composition of the resin composition other than the polyimide precursor, and 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.
　パターン樹脂膜の開口径と対比されるポリイミド前駆体の環化温度としては、特に限定されず、例えば、１３０℃～２００℃であってもよく、１５０℃～１８０℃であってもよく、１５５℃～１８０℃であってもよい。 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.
　ポリイミド前駆体の環化温度としては、ポリイミド前駆体の骨格（ジアミン化合物由来の骨格、テトラカルボン酸二無水物由来の骨格、ポリイミド前駆体内の立体障害、ひずみ等、エステル化率など）、ポリイミド前駆体の合成に用いる原料の種類、ポリイミド前駆体の合成条件などによって調整することができる。 As the cyclization temperature of the polyimide precursor, 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.
　より具体的には、テトラカルボン酸二無水物由来であるカルボキシ基及びエステル基において、ジアミン化合物に含まれるアミノ基と未反応であるカルボキシ基及びエステル基の合計に対するエステル基の割合であるエステル化率を高めることでポリイミド前駆体の環化温度が上昇する傾向にある。
　ジアミン化合物が芳香族ジアミンである場合、芳香族基にフッ素原子等のハロゲン原子、スルホン基などの電子吸引性基が結合したジアミン化合物を用いてもよい。これにより、アミノ基の電子密度が低く、カルボニル基への求核攻撃が起こりにくくなることでポリイミド前駆体の環化温度が上昇する傾向にある、と推測される。
　ポリイミド前駆体が多環芳香族構造、ビフェニル骨格等の剛直な骨格を有していてもよい。これにより、ポリイミド前駆体のガラス転移温度が上昇し、ガラス転移温度以下では分子運動が抑制されてイミド化が抑えられるため、ポリイミド前駆体の環化温度が上昇する傾向にある、と推測される。
　ポリイミド前駆体にて未反応のアミノ基であるアミン末端を減らすことで、イミド化が抑制され、ポリイミド前駆体の環化温度が上昇する傾向にある、と推測される。 More specifically, in the carboxy groups and ester groups derived from the tetracarboxylic dianhydride, 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.
When 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. It is presumed that this tends to increase the cyclization temperature of the polyimide precursor because the electron density of the amino group is low and the nucleophilic attack on the carbonyl group is less likely to occur.
A polyimide precursor may have a rigid skeleton such as a polycyclic aromatic structure or a biphenyl skeleton. As a result, 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. .
It is presumed that 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.
　本開示のポリイミド前駆体の選択方法にて、その開口径がポリイミド前駆体の環化温度と対比されるパターン樹脂膜の製法について、以下に説明する。 In the method for selecting a polyimide precursor of the present disclosure, a method for producing a patterned resin film in which the opening diameter is compared with the cyclization temperature of the polyimide precursor will be described below.
　ポリイミド前駆体を含む樹脂組成物を準備する。樹脂組成物は、ポリイミド前駆体を含み、ポジ型又はネガ型の感光性を有する樹脂組成物であれば特に限定されず、例えば、ポリイミド前駆体、溶剤、光重合開始剤、重合性モノマー等を含む樹脂組成物であってもよい。ポリイミド前駆体、溶剤、光重合開始剤及び重合性モノマーの具体例、樹脂組成物中でのこれらの混合比等については、本開示の樹脂組成物の製造方法の項目にて説明する、ポリイミド前駆体、溶剤、光重合開始剤及び重合性モノマー、これらの混合比等と同様である。 Prepare a resin composition containing a 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.
　ポリイミド前駆体を含む樹脂組成物をシリコンウエハ等の基材に塗布する。基材に塗布された樹脂組成物を加熱等により乾燥させることで塗膜が形成される。樹脂組成物の塗布方法としては、例えば、スピンコート法、インクジェット法、及びスリットコート法が挙げられる。 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.
　樹脂組成物の塗膜を形成する際の乾燥温度は、塗膜形成及びイミド化抑制の観点から、７５℃～１４０℃であることが好ましく、９０℃～１３０℃であることがより好ましい。
　乾燥時間は、３０秒間～５分間が好ましい。
　ホットプレート、オーブン等を用いて乾燥を行ってもよい。 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.
　本開示のポリイミド前駆体の選択方法では、樹脂組成物の塗膜を、開口部を有するフォトマスクを用いて露光し、その後現像液に浸すことにより現像することでパターン樹脂膜を形成する。現像後、パターン樹脂膜を加熱してパターン硬化膜としてもよい。 In the method for selecting a polyimide precursor of the present disclosure, 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.
　樹脂組成物の塗膜に照射する活性エネルギー線としては、ブロードバンド光（波長３５０ｎｍ～４５０ｎｍ）、ｉ線等の紫外線、可視光線、放射線などが挙げられ、中でも、ｉ線であることが好ましい。露光装置としては、平行露光機、投影露光機、ステッパ、スキャナ露光機、プロキシミティ露光機等を用いてもよい。 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. As an exposure device, a parallel exposure device, a projection exposure device, a stepper, a scanner exposure device, a proximity exposure device, or the like may be used.
　塗膜の露光に用いるフォトマスクの開口形状は、特に限定されない。一例として、樹脂組成物がネガ型である場合、未露光部に対応するフォトマスクの円径幅は１０μｍであってもよく、樹脂組成物がポジ型である場合、フォトマスクの開口部の幅は１０μｍであってもよい。 The opening shape of the photomask used for exposing the coating film is not particularly limited. As an example, when the resin composition is of a negative type, the photomask circle diameter width corresponding to the unexposed area may be 10 μm, and when the resin composition is of a positive type, the width of the opening of the photomask may be 10 μm.
　露光後現像することで、パターン形成された樹脂膜であるパターン樹脂膜を得ることができる。樹脂組成物がネガ型の樹脂組成物である場合、未露光部を現像液で除去する。
　ネガ型の現像液として用いる有機溶剤は、現像液としては、塗膜の良溶媒を単独で、又は良溶媒と貧溶媒とを適宜混合して用いることができる。
　良溶媒としては、Ｎ－メチル－２－ピロリドン、Ｎ－アセチル－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、ジメチルスルホキシド、γ－ブチロラクトン、α－アセチル－γ－ブチロラクトン、シクロペンタノン、シクロヘキサノン等が挙げられる。
　貧溶媒としては、トルエン、キシレン、メタノール、エタノール、イソプロパノール、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メチルエーテル、水等が挙げられる。 A patterned resin film, which is a patterned resin film, can be obtained by developing after the exposure. When the resin composition is a negative resin composition, the unexposed area is removed with a developer.
As for the organic solvent used as the negative 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, γ-butyrolactone, α-acetyl-γ-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.
　樹脂組成物がポジ型の樹脂組成物である場合、露光部を現像液で除去する。
　ポジ型の現像液として用いる溶液としては水酸化テトラメチルアンモニウム（ＴＭＡＨ）溶液、炭酸ナトリウム溶液等が挙げられる。 When the resin composition is a positive resin composition, the exposed portion is removed with a developer.
Examples of solutions used as positive developing solutions include tetramethylammonium hydroxide (TMAH) solutions and sodium carbonate solutions.
　ネガ型の現像液及びポジ型の現像液の少なくとも一方は、界面活性剤を含んでいてもよい。界面活性剤の含有量は、現像液１００質量部に対して、０．０１質量部～１０質量部が好ましく、０．１質量部～５質量部がより好ましい。 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.
　現像時間は、例えば感光性の塗膜を現像液に浸漬し、当該塗膜が完全に溶解するまでの時間の２倍とすることができる。
　現像時間は、例えば、１０秒間～１５分間が好ましく、１０秒間～５分間がより好ましく、効率性の観点から、２０秒間～５分間がさらに好ましい。 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.
　現像後のパターン樹脂膜をリンス液により洗浄してもよい。
　リンス液としては、蒸留水、メタノール、エタノール、イソプロパノール、トルエン、キシレン、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メチルエーテル等を単独又は適宜混合して用いてもよく、またこれらを段階的に組み合わせて用いてもよい。 The pattern resin film after development may be washed with a rinsing liquid.
As the 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. may
　ポリイミド前駆体の環化温度及び同じ環化温度を有するポリイミド前駆体を用いて形成したパターン樹脂膜の開口径のデータを複数取得し、パターン樹脂膜の開口径が特定の値よりも小さくなるような環化温度の条件を満たすポリイミド前駆体を選択することが好ましい。このとき、基準となる特定の値は、パターン樹脂膜の開口径の実測値から設定してもよく、パターン樹脂膜の開口径の実測値、フォトマスクの円形幅に対するパターン樹脂膜の開口径の比率（開口径／円形幅）等を考慮した上で設定してもよい。 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. At this time, 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.
　例えば、ネガ型の樹脂組成物を用いた場合、フォトマスクの円径幅に対するパターン樹脂膜の開口径の比率が９５％以下となるとき、好ましくは９０以下％となるとき、より好ましくは８５％以下となるときのパターン樹脂膜の開口径を特定の値としてもよい。
　フォトマスクの円径幅に対するパターン樹脂膜の開口径の比率が６０％以上又は７０％以上となるときのパターン樹脂膜の開口径を特定の値としてもよい。 For example, 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.
　パターン樹脂膜の開口径が特定の値よりも小さくなるような環化温度の条件を満たすポリイミド前駆体を選択する際、環化温度が１５０℃以上のポリイミド前駆体を選択してもよく、１６０℃以上のポリイミド前駆体を選択してもよく、１６４℃以上のポリイミド前駆体を選択してもよく、１７０℃以上のポリイミド前駆体を選択してもよく、１７２℃以上のポリイミド前駆体を選択してもよい。特にネガ型の樹脂組成物を用いた場合、現像残渣、パターンはがれ等が抑制され、解像度に優れるパターン硬化膜を好適に形成可能とする観点から、前述のいずれかの環化温度の条件を満たすポリイミド前駆体を選択することが好ましい。
　また、環化温度が２００℃以下のポリイミド前駆体を選択してもよく、１８０℃以下のポリイミド前駆体を選択してもよく、１７５℃以下のポリイミド前駆体を選択してもよい。 When selecting a polyimide precursor that satisfies the cyclization temperature condition that the opening diameter of the patterned resin film is smaller than a specific value, a polyimide precursor with a cyclization temperature of 150° C. or higher may be selected. ℃ or higher polyimide precursor may be selected, 164 ℃ or higher polyimide precursor may be selected, 170 ℃ or higher polyimide precursor may be selected, 172 ℃ or higher polyimide precursor is selected You may In particular, when 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.
Alternatively, 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.
＜樹脂組成物の製造方法＞
　本開示の樹脂組成物の製造方法は、１種類以上のポリイミド前駆体の環化温度を測定し、前述の本開示のポリイミド前駆体の選択方法に基づいて特定の環化温度の条件を満たすポリイミド前駆体を選択することと、選択された前記ポリイミド前駆体を用いて樹脂組成物を製造することと、を含む。 <Method for producing resin composition>
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.
　本開示の製造方法では、１種類以上のポリイミド前駆体の環化温度を測定する。測定された環化温度のデータを用い、前述の本開示のポリイミド前駆体の選択方法に基づいて特定の環化温度の条件を満たすポリイミド前駆体を選択する。そして、選択されたポリイミド前駆体を用いて樹脂組成物を製造することで、解像度に優れるパターン硬化膜を形成可能な樹脂組成物が提供される。 In the production method of the present disclosure, 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.
　２種類以上のポリイミド前駆体の環化温度を測定する場合、ポリイミド前駆体の製造に用いた原料が同じで反応条件等が異なる２種類以上のポリイミド前駆体の環化温度をそれぞれ測定してもよく、ポリイミド前駆体の製造に用いた原料組成の異なる２種類以上のポリイミド前駆体の環化温度をそれぞれ測定してもよい。 When measuring the cyclization temperature of two or more types of polyimide precursors, even if the cyclization temperatures of two or more types of polyimide precursors using the same starting material for the production of the polyimide precursors but different reaction conditions, etc. are measured respectively. Often, the cyclization temperatures of two or more polyimide precursors having different raw material compositions used in the production of the polyimide precursor may be measured.
　本開示の製造方法では、ポリイミド前駆体を含み、ポジ型又はネガ型の感光性を有する樹脂組成物が製造され、例えば、ポリイミド前駆体、溶剤、光重合開始剤、重合性モノマー等を含む樹脂組成物が製造されてもよい。 In the production method of the present disclosure, 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.
　以下、本開示の樹脂組成物の製造方法にて使用しうるポリイミド前駆体、溶剤、光重合開始剤、重合性モノマー等について説明する。 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.
（ポリイミド前駆体）
　ポリイミド前駆体は、特定の環化温度の条件を満たすポリイミド前駆体であればよい。ポリイミド前駆体は、露光時の重合性モノマーとの反応性の観点から、重合性の不飽和結合を有するポリイミド前駆体を含有することが好ましい。
　重合性の不飽和結合としては、炭素炭素の二重結合等が挙げられる。 (polyimide precursor)
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.
　ポリイミド前駆体は、下記一般式（１）で表される構造単位を有する化合物を含んでいてもよい。 The polyimide precursor may contain a compound having a structural unit represented by the following general formula (1).
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　一般式（１）中、Ｘは４価の有機基を表し、Ｙは２価の有機基を表す。Ｒ６及びＲ７は、それぞれ独立に、水素原子、又は１価の有機基を表す。前記Ｒ６及びＲ７の少なくとも一方は１価の有機基である。
　ポリイミド前駆体は、下記一般式（１）で表される構造単位を複数有していてもよく、複数の構造単位におけるＸ、Ｙ、Ｒ６及びＲ７はそれぞれ同じであってもよく、異なっていてもよい。 In 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
　一般式（１）において、Ｘで表される４価の有機基は、炭素数が４～２５であることが好ましく、４～１３であることがより好ましく、６～１２であることがさらに好ましい。
　Ｘで表される４価の有機基は、芳香環を含んでもよい。Ｘで表される４価の有機基が芳香環を含む場合、芳香環としては、ベンゼン環、ナフタレン環、フェナントレン環等が挙げられる。これらの中でも、ポリイミド前駆体の紫外領域における光透過性を向上する観点から、ベンゼン環が好ましい。
　Ｘで表される４価の有機基が芳香環を含む場合、各芳香環は、置換基を有していてもよいし、無置換であってもよい。芳香環の置換基としては、アルキル基、フッ素原子、ハロゲン化アルキル基、水酸基、アミノ基等が挙げられる。
　Ｘで表される４価の有機基がベンゼン環を含む場合、Ｘで表される４価の有機基は１つ～４つのベンゼン環を含むことが好ましく、１つ～３つのベンゼン環を含むことがより好ましく、１つ又は２つのベンゼン環を含むことがさらに好ましい。
　Ｘで表される４価の有機基が２つ以上のベンゼン環を含む場合、各ベンゼン環は、単結合により連結されていてもよいし、アルキレン基、ハロゲン化アルキレン基、カルボニル基、スルホニル基、エーテル結合（－Ｏ－）、スルフィド結合（－Ｓ－）、シリレン結合（－Ｓｉ（ＲＡ）２－；ＲＡは、それぞれ独立に、水素原子、アルキル基又はフェニル基を表す。）、シロキサン結合（－Ｏ－（Ｓｉ（ＲＢ）２－Ｏ－）ｎ；ＲＢは、それぞれ独立に、水素原子、アルキル基又はフェニル基を表し、ｎは１又は２以上の整数を表す。）等の連結基、これら連結基を少なくとも２つ組み合わせた複合連結基などにより結合されていてもよい。また、２つのベンゼン環が単結合及び連結基の少なくとも一方により２箇所で結合されて、２つのベンゼン環の間に連結基を含む５員環又は６員環が形成されていてもよい。 In the general formula (1), 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. When the tetravalent organic group represented by X contains an aromatic ring, examples of the aromatic ring include benzene ring, naphthalene ring, and phenanthrene ring. Among these, a benzene ring is preferable from the viewpoint of improving the light transmittance of the polyimide precursor in the ultraviolet region.
When the tetravalent organic group represented by X contains an aromatic ring, each aromatic ring may have a substituent or may be unsubstituted. Examples of substituents on the aromatic ring include alkyl groups, fluorine atoms, halogenated alkyl groups, hydroxyl groups, amino groups and the like.
When 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.
When the tetravalent organic group represented by X contains two or more 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. In addition, two benzene rings may be bonded at two locations by at least one of a single bond and a linking group to form a 5- or 6-membered ring containing a linking group between the two benzene rings.
　一般式（１）において、Ｘで表される４価の有機基がベンゼン環を含む場合、－ＣＯＯＲ６基と－ＣＯＮＨ－基とは互いにオルト位置にあり、－ＣＯＯＲ７基と－ＣＯ－基とは互いにオルト位置にあることが好ましい。 In the general formula (1), when the tetravalent organic group represented by X contains a benzene ring, 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.
　Ｘで表される４価の有機基の具体例としては、下記式（Ａ）～式（Ｅ）で表される基を挙げられる。本開示は下記具体例に限定されるものではない。 Specific examples of the 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.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　式（Ｄ）において、Ａ及びＢは、それぞれ独立に、単結合、メチレン基、ハロゲン化メチレン基、カルボニル基、スルホニル基、エーテル結合（－Ｏ－）、スルフィド結合（－Ｓ－）又はシリレン結合（－Ｓｉ（ＲＡ）２－；ＲＡは、それぞれ独立に、水素原子、アルキル基又はフェニル基を表す。）を表し、Ａ及びＢの両方が単結合となることはない。 In formula (D), 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.
　式（Ｅ）において、Ｃは、単結合、又は、アルキレン基、ハロゲン化アルキレン基、カルボニル基、スルホニル基、エーテル結合（－Ｏ－）、スルフィド結合（－Ｓ－）、シリレン結合（－Ｓｉ（ＲＡ）２－；ＲＡは、それぞれ独立に、水素原子、アルキル基又はフェニル基を表す。）、シロキサン結合（－Ｏ－（Ｓｉ（ＲＢ）２－Ｏ－）ｎ；ＲＢは、それぞれ独立に、水素原子、アルキル基又はフェニル基を表し、ｎは１又は２以上の整数を表す。）若しくはこれらを少なくとも２つ組み合わせた２価の基を表す。また、Ｃは、下記式（Ｃ１）で表される構造であってもよい。 In formula (E), 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).
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　式（Ｅ）におけるＣで表されるアルキレン基は、炭素数が１～１０のアルキレン基であることが好ましく、炭素数が１～５のアルキレン基であることがより好ましく、炭素数が１又は２のアルキレン基であることがさらに好ましい。
　式（Ｅ）におけるＣで表されるアルキレン基の具体例としては、メチレン基、エチレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基等の直鎖状アルキレン基；メチルメチレン基、メチルエチレン基、エチルメチレン基、ジメチルメチレン基、１，１－ジメチルエチレン基、１－メチルトリメチレン基、２－メチルトリメチレン基、エチルエチレン基、１－メチルテトラメチレン基、２－メチルテトラメチレン基、１－エチルトリメチレン基、２－エチルトリメチレン基、１，１－ジメチルトリメチレン基、１，２－ジメチルトリメチレン基、２，２－ジメチルトリメチレン基、１－メチルペンタメチレン基、２－メチルペンタメチレン基、３－メチルペンタメチレン基、１－エチルテトラメチレン基、２－エチルテトラメチレン基、１，１－ジメチルテトラメチレン基、１，２－ジメチルテトラメチレン基、２，２－ジメチルテトラメチレン基、１，３－ジメチルテトラメチレン基、２，３－ジメチルテトラメチレン基、１，４－ジメチルテトラメチレン基等の分岐鎖状アルキレン基；などが挙げられる。これらの中でも、メチレン基が好ましい。 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, 3-methylpentamethylene group, 1-ethyltetramethylene group, 2-ethyltetramethylene group, 1,1-dimethyltetramethylene group, 1,2-dimethyltetramethylene group, 2,2- branched chain alkylene groups such as a dimethyltetramethylene group, a 1,3-dimethyltetramethylene group, a 2,3-dimethyltetramethylene group and a 1,4-dimethyltetramethylene group; Among these, a methylene group is preferred.
　式（Ｅ）におけるＣで表されるハロゲン化アルキレン基としては、炭素数が１～１０のハロゲン化アルキレン基であることが好ましく、炭素数が１～５のハロゲン化アルキレン基であることがより好ましく、炭素数が１～３のハロゲン化アルキレン基であることがさらに好ましい。
　式（Ｅ）におけるＣで表されるハロゲン化アルキレン基の具体例としては、上述の式（Ｅ）におけるＣで表されるアルキレン基に含まれる少なくとも１つの水素原子がフッ素原子、塩素原子等のハロゲン原子で置換されたアルキレン基が挙げられる。これらの中でも、フルオロメチレン基、ジフルオロメチレン基、ヘキサフルオロジメチルメチレン基等が好ましい。 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.
　上記シリレン結合又はシロキサン結合に含まれるＲＡ又はＲＢで表されるアルキル基としては、炭素数が１～５のアルキル基であることが好ましく、炭素数が１～３のアルキル基であることがより好ましく、炭素数が１又は２のアルキル基であることがさらに好ましい。ＲＡ又はＲＢで表されるアルキル基の具体例としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓ－ブチル基、ｔ－ブチル基等が挙げられる。 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.
　式（Ｄ）におけるＡ及びＢの組み合わせは特に限定されるものではなく、メチレン基とエーテル結合との組み合わせ、メチレン基とスルフィド結合との組み合わせ、カルボニル基とエーテル結合との組み合わせ等が好ましい。
　式（Ｅ）におけるＣとしては、単結合、エーテル結合、カルボニル基等が好ましい。 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.
　式（１）において、Ｙで表される２価の有機基は、炭素数が６～２５であることが好ましく、６～１４であることがより好ましく、１２～１４であることがさらに好ましい。
　Ｙで表される２価の有機基は、２価の脂肪族基であってもよく、２価の芳香族基であってもよい。耐熱性の観点から、Ｙで表される２価の有機基は、２価の芳香族基であることが好ましい。 In formula (1), 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.
　Ｙで表される２価の芳香族基の具体例としては、下記一般式（Ｆ）及び下記一般式（Ｇ）で表される基を挙げることができる。 Specific examples of the divalent aromatic group represented by Y include groups represented by the following general formula (F) and the following general formula (G).
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　一般式（Ｆ）又は一般式（Ｇ）において、Ｒは、それぞれ独立に、アルキル基、アルコキシ基、ハロゲン化アルキル基又はフェニル基を表し、ｎは、それぞれ独立に、０～４の整数を表す。
　一般式（Ｇ）において、Ｄは、単結合、又は、アルキレン基、ハロゲン化アルキレン基、カルボニル基、スルホニル基、エーテル結合（－Ｏ－）、スルフィド結合（－Ｓ－）、シリレン結合（－Ｓｉ（ＲＡ）２－；ＲＡは、それぞれ独立に、水素原子、アルキル基又はフェニル基を表す。）、シロキサン結合（－Ｏ－（Ｓｉ（ＲＢ）２－Ｏ－）ｎ；ＲＢは、それぞれ独立に、水素原子、アルキル基又はフェニル基を表し、ｎは１又は２以上の整数を表す。）若しくはこれらを少なくとも２つ組み合わせた２価の基を表す。また、Ｄは、上記式（Ｃ１）で表される構造であってもよい。一般式（Ｇ）におけるＤの具体例は、式（Ｅ）におけるＣの具体例と同様である。
　一般式（Ｇ）におけるＤとしては、単結合が好ましい。 In general formula (F) or 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. .
In the general formula (G), 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 at least two of these are combined. D may also have a structure represented by the above formula (C1). Specific examples of D in formula (G) are the same as the specific examples of C in formula (E).
D in the general formula (G) is preferably a single bond.
　一般式（Ｆ）又は一般式（Ｇ）におけるＲで表されるアルキル基としては、炭素数が１～１０のアルキル基であることが好ましく、炭素数が１～５のアルキル基であることがより好ましく、炭素数が１又は２のアルキル基であることがさらに好ましい。
　一般式（Ｆ）又は一般式（Ｇ）におけるＲで表されるアルキル基の具体例としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓ－ブチル基、ｔ－ブチル基等が挙げられる。 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.
　一般式（Ｆ）又は一般式（Ｇ）におけるＲで表されるアルコキシ基としては、炭素数が１～１０のアルコキシ基であることが好ましく、炭素数が１～５のアルコキシ基であることがより好ましく、炭素数が１又は２のアルコキシ基であることがさらに好ましい。
　一般式（Ｆ）又は一般式（Ｇ）におけるＲで表されるアルコキシ基の具体例としては、メトキシ基、エトキシ基、ｎ－プロポキシ基、イソプロポキシ基、ｎ－ブトキシ基、イソブトキシ基、ｓ－ブトキシ基、ｔ－ブトキシ基等が挙げられる。 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.
　一般式（Ｆ）又は一般式（Ｇ）におけるＲで表されるハロゲン化アルキル基としては、炭素数が１～５のハロゲン化アルキル基であることが好ましく、炭素数が１～３のハロゲン化アルキル基であることがより好ましく、炭素数が１又は２のハロゲン化アルキル基であることがさらに好ましい。
　一般式（Ｆ）又は一般式（Ｇ）におけるＲで表されるハロゲン化アルキル基の具体例としては、一般式（Ｆ）又は一般式（Ｇ）におけるＲで表されるアルキル基に含まれる少なくとも１つの水素原子がフッ素原子、塩素原子等のハロゲン原子で置換されたアルキル基が挙げられる。これらの中でも、フルオロメチル基、ジフルオロメチル基、トリフルオロメチル基等が好ましい。 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.
　一般式（Ｆ）又は一般式（Ｇ）におけるｎは、それぞれ独立に、０～２が好ましく、０又は１がより好ましく、０がさらに好ましい。 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.
　Ｙで表される２価の脂肪族基の具体例としては、直鎖状又は分岐鎖状のアルキレン基、シクロアルキレン基、ポリアルキレンオキサイド構造を有する２価の基、ポリシロキサン構造を有する２価の基等が挙げられる。 Specific examples of the divalent aliphatic group represented by Y 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.
　Ｙで表される直鎖状又は分岐鎖状のアルキレン基としては、炭素数が１～２０のアルキレン基であることが好ましく、炭素数が１～１５のアルキレン基であることがより好ましく、炭素数が１～１０のアルキレン基であることがさらに好ましい。
　Ｙで表されるアルキレン基の具体例としては、テトラメチレン基、ヘキサメチレン基、ヘプタメチレン基、オクタメチレン基、ノナメチレン基、デカメチレン基、ウンデカメチレン基、ドデカメチレン基、２－メチルペンタメチレン基、２－メチルヘキサメチレン基、２－メチルヘプタメチレン基、２－メチルオクタメチレン基、２－メチルノナメチレン基、２－メチルデカメチレン基等が挙げられる。 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.
　Ｙで表されるシクロアルキレン基としては、炭素数が３～１０のシクロアルキレン基であることが好ましく、炭素数が３～６のシクロアルキレン基であることがより好ましい。
　Ｙで表されるシクロアルキレン基の具体例としては、シクロプロピレン基、シクロヘキシレン基等が挙げられる。 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.
　Ｙで表されるポリアルキレンオキサイド構造を有する２価の基に含まれる単位構造としては、炭素数１～１０のアルキレンオキサイド構造が好ましく、炭素数１～８のアルキレンオキサイド構造がより好ましく、炭素数１～４のアルキレンオキサイド構造がさらに好ましい。なかでも、ポリアルキレンオキサイド構造としてはポリエチレンオキサイド構造又はポリプロピレンオキサイド構造が好ましい。アルキレンオキサイド構造中のアルキレン基は直鎖状であっても分岐状であってもよい。ポリアルキレンオキサイド構造中の単位構造は１種類でもよく、２種類以上であってもよい。 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. Among them, 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.
　Ｙで表されるポリシロキサン構造を有する２価の基としては、ポリシロキサン構造中のケイ素原子が水素原子、炭素数１～２０のアルキル基又は炭素数６～１８のアリール基と結合しているポリシロキサン構造を有する２価の基が挙げられる。
　ポリシロキサン構造中のケイ素原子と結合する炭素数１～２０のアルキル基の具体例としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｔ－ブチル基、ｎ－オクチル基、２－エチルヘキシル基、ｎ－ドデシル基等が挙げられる。これらの中でも、メチル基が好ましい。
　ポリシロキサン構造中のケイ素原子と結合する炭素数６～１８のアリール基は、無置換でも置換基で置換されていてもよい。アリール基が置換基を有する場合の置換基の具体例としては、ハロゲン原子、アルコキシ基、ヒドロキシ基等が挙げられる。炭素数６～１８のアリール基の具体例としては、フェニル基、ナフチル基、ベンジル基等が挙げられる。これらの中でも、フェニル基が好ましい。
　ポリシロキサン構造中の炭素数１～２０のアルキル基又は炭素数６～１８のアリール基は、１種類でもよく、２種類以上であってもよい。
　Ｙで表されるポリシロキサン構造を有する２価の基を構成するケイ素原子は、メチレン基、エチレン基等のアルキレン基、フェニレン基等のアリーレン基などを介して一般式（１）中のＮＨ基と結合していてもよい。 As the divalent group having a polysiloxane structure represented by Y, 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.
Specific examples of the 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. When the aryl group has a substituent, specific examples of the substituent include a halogen atom, an alkoxy group, and a hydroxy group. Specific examples of 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
　一般式（１）における、Ｘで表される４価の有機基とＹで表される２価の有機基との組み合わせは特に限定されるものではない。Ｘで表される４価の有機基とＹで表される２価の有機基との組み合わせとしては、Ｘが式（Ａ）で表される基及び式（Ｅ）で表される基の併用であり、Ｙが式（Ｇ）で表される基の組み合わせ；Ｘが式（Ｄ）で表される基及び式（Ｅ）で表される基の併用であり、Ｙが式（Ｇ）で表される基の組み合わせ等が挙げられる。
　Ｘとして式（Ａ）で表される基及び式（Ｅ）で表される基を併用し、Ｙとして一般式（Ｇ）で表される基を用いることで、３００℃以下の比較的低い温度で加熱処理しても、得られるポリイミド樹脂の弾性率がより向上する傾向にある。
　Ｘが式（Ａ）で表される基及び式（Ｅ）で表される基の併用である場合、式（Ａ）で表される基ＸＡと、式（Ｅ）で表される基ＸＥとの個数基準の比率（ＸＡ／ＸＥ）は、１／９９～９９／１の範囲であることが好ましく、５０／５０～９０／１０の範囲であることがより好ましく、７０／３０～９０／１０の範囲であることがさらに好ましい。 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. As a combination of a tetravalent organic group represented by X and a divalent organic group represented by Y, 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.
By using a group represented by the formula (A) and a group represented by the formula (E) as X in combination, and using a group represented by the general formula (G) as Y, a relatively low temperature of 300 ° C. or less Even if the heat treatment is performed at , the elastic modulus of the obtained polyimide resin tends to be further improved.
When X is a combination of a group represented by formula (A) and a group represented by formula (E), a group XA represented by formula (A) and a group XE 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
　Ｒ６及びＲ７の少なくとも一方は１価の有機基である。１価の有機基としては、炭素数１～４の脂肪族炭化水素基又は不飽和二重結合を有する有機基を含むことが好ましく、炭素数１若しくは２の脂肪族炭化水素基又は下記一般式（２）で表される基を含むことがより好ましく、下記一般式（２）で表される基を含むことがさらに好ましい。特に１価の有機基が不飽和二重結合を有する有機基、好ましくは下記一般式（２）で表される基を含むことでｉ線の透過率が高く、３００℃以下の低温硬化時にも良好なパターン硬化膜を形成できる傾向にある。
　炭素数１～４の脂肪族炭化水素基の具体例としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基等が挙げられる。 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). In particular, when 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.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　一般式（２）中、Ｒ８～Ｒ１０は、それぞれ独立に、水素原子又は炭素数１～３の脂肪族炭化水素基を表し、Ｒｘは２価の連結基を表す。 In general formula (2), 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.
　一般式（２）におけるＲ８～Ｒ１０で表される脂肪族炭化水素基の炭素数は１～３であり、１又は２であることが好ましい。Ｒ８～Ｒ１０で表される脂肪族炭化水素基の具体例としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基等が挙げられ、メチル基が好ましい。 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.
　一般式（２）におけるＲ８～Ｒ１０の組み合わせとしては、Ｒ８及びＲ９が水素原子であり、Ｒ１０が水素原子又はメチル基の組み合わせが好ましい。 As for the combination of 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.
　一般式（２）におけるＲｘは、２価の連結基であり、好ましくは、炭素数１～１０の炭化水素基であることが好ましい。炭素数１～１０の炭化水素基としては、例えば、直鎖状又は分岐鎖状のアルキレン基が挙げられる。
　Ｒｘにおける炭素数は、１つ～１０つが好ましく、２つ～５つがより好ましく、２つ又は３つがさらに好ましい。 R x in general formula (2) is a divalent linking group, preferably a hydrocarbon group having 1 to 10 carbon atoms. Examples of 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.
　一般式（１）においては、Ｒ６及びＲ７の少なくとも一方が、前記一般式（２）で表される基であることが好ましく、Ｒ６及びＲ７の両方が前記一般式（２）で表される基であることがより好ましい。 In general formula (1), at least one of R 6 and R 7 is 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
　ポリイミド前駆体が前述の一般式（１）で表される構造単位を有する化合物を含む場合、当該化合物に含有される全構造単位のＲ６及びＲ７の合計に対する一般式（２）で表される基であるＲ６及びＲ７の割合は、５０モル％以上であることが好ましく、７０モル％以上がより好ましく、９０モル％以上がさらに好ましい。上限は特に限定されず、１００モル％でもよい。
　なお、前述の割合は、０モル％以上５０モル％未満であってもよい。 When the polyimide precursor contains a compound having a structural unit represented by the above general formula (1), 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 %.
In addition, the aforementioned ratio may be 0 mol % or more and less than 50 mol %.
　一般式（２）で表される基は、下記一般式（３）で表される基であることが好ましい。 The group represented by general formula (2) is preferably a group represented by general formula (3) below.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　一般式（３）中、Ｒ８～Ｒ１０は、それぞれ独立に、水素原子又は炭素数１～３の脂肪族炭化水素基を表し、ｑは１～１０の整数を表す。 In general formula (3), 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.
　一般式（３）におけるｑは１～１０の整数であることが好ましく、２～５の整数であることがより好ましく、２又は３であることがさらに好ましい。 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.
　ポリイミド前駆体は、テトラカルボン酸二無水物と、ジアミン化合物とを用いて合成されたものであってもよい。この場合、一般式（１）において、Ｘは、テトラカルボン酸二無水物由来の残基に該当し、Ｙは、ジアミン化合物由来の残基に該当する。なお、ポリイミド前駆体は、テトラカルボン酸二無水物に替えて、テトラカルボン酸を用いて合成されたものであってもよい。 The polyimide precursor may be synthesized using a tetracarboxylic dianhydride and a diamine compound. In this case, in the general formula (1), X corresponds to the residue derived from the tetracarboxylic dianhydride, and Y corresponds to the residue derived from the diamine compound. The polyimide precursor may be synthesized using tetracarboxylic acid instead of tetracarboxylic dianhydride.
　テトラカルボン酸二無水物の具体例としては、ピロメリット酸二無水物、２，３，６，７－ナフタレンテトラカルボン酸二無水物、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物、３，３’，４，４’－ベンゾフェノンテトラカルボン酸二無水物、１，２，５，６－ナフタレンテトラカルボン酸二無水物、２，３，５，６－ピリジンテトラカルボン酸二無水物、１，４，５，８－ナフタレンテトラカルボン酸二無水物、３，４，９，１０－ペリレンテトラカルボン酸二無水物、ｍ－ターフェニル－３，３’，４，４’－テトラカルボン酸二無水物、ｐ－ターフェニル－３，３’，４，４’－テトラカルボン酸二無水物、１，１，１，３，３，３－ヘキサフルオロ－２，２－ビス（２，３－ジカルボキシフェニル）プロパン二無水物、１，１，１，３，３，３－ヘキサフルオロ－２，２－ビス（３，４－ジカルボキシフェニル）プロパン二無水物、２，２－ビス（２，３－ジカルボキシフェニル）プロパン二無水物、２，２－ビス（３，４－ジカルボキシフェニル）プロパン二無水物、２，２－ビス｛４’－（２，３－ジカルボキシフェノキシ）フェニル｝プロパン二無水物、２，２－ビス｛４’－（３，４－ジカルボキシフェノキシ）フェニル｝プロパン二無水物、１，１，１，３，３，３－ヘキサフルオロ－２，２－ビス｛４’－（２，３－ジカルボキシフェノキシ）フェニル｝プロパン二無水物、１，１，１，３，３，３－ヘキサフルオロ－２，２－ビス｛４’－（３，４－ジカルボキシフェノキシ）フェニル｝プロパン二無水物、４，４’－オキシジフタル酸二無水物、４，４’－スルホニルジフタル酸二無水物、９，９－ビス（３，４－ジカルボキシフェニル）フルオレン二無水物等が挙げられる。
　テトラカルボン酸二無水物は、１種を単独で用いても２種以上を併用してもよい。 Specific examples of 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-2,2-bis ( 2,3-dicarboxyphenyl)propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2 -bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis{4′-(2,3-di Carboxyphenoxy)phenyl}propane dianhydride, 2,2-bis{4'-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 1,1,1,3,3,3-hexafluoro- 2,2-bis{4′-(2,3-dicarboxyphenoxy)phenyl}propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis{4′-( 3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 4,4′-oxydiphthalic dianhydride, 4,4′-sulfonyldiphthalic dianhydride, 9,9-bis(3,4-di carboxyphenyl)fluorene dianhydride and the like.
Tetracarboxylic dianhydrides may be used alone or in combination of two or more.
　ジアミン化合物の具体例としては、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’－ジフルオロ－４，４’－ジアミノビフェニル、ｐ－フェニレンジアミン、ｍ－フェニレンジアミン、ｐ－キシリレンジアミン、ｍ－キシリレンジアミン、１，５－ジアミノナフタレン、ベンジジン、４，４’－ジアミノジフェニルエーテル、３，４’－ジアミノジフェニルエーテル、３，３’－ジアミノジフェニルエーテル、２，４’－ジアミノジフェニルエーテル、２，２’－ジアミノジフェニルエーテル、４，４’－ジアミノジフェニルスルホン、３，４’－ジアミノジフェニルスルホン、３，３’－ジアミノジフェニルスルホン、２，４’－ジアミノジフェニルスルホン、２，２’－ジアミノジフェニルスルホン、４，４’－ジアミノジフェニルスルフィド、３，４’－ジアミノジフェニルスルフィド、３，３’－ジアミノジフェニルスルフィド、２，４’－ジアミノジフェニルスルフィド、２，２’－ジアミノジフェニルスルフィド、ｏ－トリジン、ｏ－トリジンスルホン、４，４’－メチレンビス（２，６－ジエチルアニリン）、４，４’－メチレンビス（２，６－ジイソプロピルアニリン）、２，４－ジアミノメシチレン、１，５－ジアミノナフタレン、４，４’－ベンゾフェノンジアミン、ビス－｛４－（４’－アミノフェノキシ）フェニル｝スルホン、２，２－ビス｛４－（４’－アミノフェノキシ）フェニル｝プロパン、３，３’－ジメチル－４，４’－ジアミノジフェニルメタン、３，３’，５，５’－テトラメチル－４，４’－ジアミノジフェニルメタン、ビス｛４－（３’－アミノフェノキシ）フェニル｝スルホン、２，２－ビス（４－アミノフェニル）プロパン、９，９－ビス（４－アミノフェニル）フルオレン、１，４－ジアミノブタン、１，６－ジアミノヘキサン、１，７－ジアミノヘプタン、１，８－ジアミノオクタン、１，９－ジアミノノナン、１，１０－ジアミノデカン、１，１１－ジアミノウンデカン、１，１２－ジアミノドデカン、２－メチル－１，５－ジアミノペンタン、２－メチル－１，６－ジアミノヘキサン、２－メチル－１，７－ジアミノヘプタン、２－メチル－１，８－ジアミノオクタン、２－メチル－１，９－ジアミノノナン、２－メチル－１，１０－ジアミノデカン、１，４－シクロヘキサンジアミン、１，３－シクロヘキサンジアミン、ジアミノポリシロキサン等が挙げられる。
　ジアミン化合物は、１種を単独で用いても２種以上を併用してもよい。 Specific examples of 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'-diaminodiphenyl sulfone, 2,2'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 2,4'-diaminodiphenyl sulfide, 2,2'- diaminodiphenyl sulfide, o-tolysine, o-tolysine sulfone, 4,4′-methylenebis(2,6-diethylaniline), 4,4′-methylenebis(2,6-diisopropylaniline), 2,4-diaminomesitylene, 1,5-diaminonaphthalene, 4,4'-benzophenonediamine, bis-{4-(4'-aminophenoxy)phenyl}sulfone, 2,2-bis{4-(4'-aminophenoxy)phenyl}propane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 3,3′,5,5′-tetramethyl-4,4′-diaminodiphenylmethane, bis{4-(3′-aminophenoxy)phenyl}sulfone , 2,2-bis(4-aminophenyl)propane, 9,9-bis(4-aminophenyl)fluorene, 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1, 8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 2-methyl-1,5-diaminopentane, 2-methyl-1,6 -diaminohexane, 2-methyl-1,7-diaminoheptane, 2-methyl-1,8-diaminooctane, 2-methyl-1,9-diaminononane, 2-methyl-1,10-diaminodecane, 1,4 - cyclohexanediamine, 1,3-cyclohexanediamine, di Aminopolysiloxane and the like can be mentioned.
A diamine compound may be used individually by 1 type, or may use 2 or more types together.
　一般式（１）で表される構造単位を有し、かつ一般式（１）中のＲ６及びＲ７の少なくとも一方は１価の有機基である化合物は、例えば、下記一般式（８）で表されるテトラカルボン酸二無水物とＲ－ＯＨで表される化合物とを、Ｎ－メチル－２－ピロリドン、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド等の溶剤中にて反応させジエステル誘導体とした後、ジエステル誘導体とＨ２Ｎ－Ｙ－ＮＨ２で表されるジアミン化合物とを縮合反応させるか、または、テトラカルボン酸二無水物とＨ２Ｎ－Ｙ－ＮＨ２で表されるジアミン化合物とを溶剤中にて反応させポリアミック酸を得て、Ｒ－ＯＨで表される化合物を加え、溶剤中で反応させエステル基を導入することで、得ることができる。
　ここで、前述の反応に使用する溶剤としては、後述する樹脂組成物に含まれる溶剤であってもよい。
　Ｈ２Ｎ－Ｙ－ＮＨ２で表されるジアミン化合物におけるＹは、一般式（１）におけるＹと同様であり、具体例及び好ましい例も同様である。また、Ｒ－ＯＨで表される化合物におけるＲは、１価の有機基を表し、具体例及び好ましい例は、一般式（１）におけるＲ６及びＲ７の具体例及び好ましい例と同様である。
　一般式（８）で表されるテトラカルボン酸二無水物、Ｈ２Ｎ－Ｙ－ＮＨ２で表されるジアミン化合物及びＲ－ＯＨで表される化合物は、各々、１種単独で用いてもよく、２種以上を組み合わせてもよい。
　また、ポリイミド前駆体に含まれる前述の化合物は、下記一般式（８）で表されるテトラカルボン酸二無水物にＲ－ＯＨで表される化合物を作用させてジエステル誘導体とした後、塩化チオニル等の塩素化剤を作用させて酸塩化物に変換し、次いで、Ｈ２Ｎ－Ｙ－ＮＨ２で表されるジアミン化合物と酸塩化物とを反応させることで得ることができる。
　さらに、ポリイミド前駆体に含まれる前述の化合物は、下記一般式（８）で表されるテトラカルボン酸二無水物にＲ－ＯＨで表される化合物を作用させてジエステル誘導体とした後、カルボジイミド化合物の存在下でＨ２Ｎ－Ｙ－ＮＨ２で表されるジアミン化合物とジエステル誘導体とを反応させることで得ることができる。
　さらに、ポリイミド前駆体に含まれる前述の化合物は、下記一般式（８）で表されるテトラカルボン酸二無水物とＨ２Ｎ－Ｙ－ＮＨ２で表されるジアミン化合物とを反応させてポリアミック酸とした後、トリフルオロ酢酸無水物の存在下でポリアミック酸をイソイミド化し、次いでＲ－ＯＨで表される化合物を作用させて得ることができる。あるいは、テトラカルボン酸二無水物の一部に予めＲ－ＯＨで表される化合物を作用させて、部分的にエステル化されたテトラカルボン酸二無水物とＨ２Ｎ－Ｙ－ＮＨ２で表されるジアミン化合物とを反応させてもよい。 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. After conversion into a derivative, either the diester derivative and a diamine compound represented by H 2 N--Y--NH 2 are condensed, or a tetracarboxylic dianhydride and H 2 N--Y--NH 2 are subjected to a condensation reaction. It can be obtained by reacting a diamine compound in a solvent to obtain a polyamic acid, adding a compound represented by R—OH, and reacting it in a solvent to introduce an ester group.
Here, the solvent used in the above reaction may be a solvent contained in the resin composition described below.
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. In addition, 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.
Further, 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.
Furthermore, 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 .
Furthermore, 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. After converting to an acid, the polyamic acid is isoimidated in the presence of trifluoroacetic anhydride, and then reacted with a compound represented by R--OH. Alternatively, 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.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　一般式（８）において、Ｘは、一般式（１）におけるＸと同様であり、具体例及び好ましい例も同様である。 In general formula (8), X is the same as X in general formula (1), and specific examples and preferred examples are also the same.
　ポリイミド前駆体に含まれる前述の化合物の合成に用いられるＲ－ＯＨで表される化合物としては、メタノール、エタノール、ｎ－プロパノール、イソプロパノール、ｎ－ブタノール、メタクリル酸２－ヒドロキシエチル、アクリル酸２－ヒドロキシエチル、メタクリル酸２－ヒドロキシエチル、アクリル酸２－ヒドロキシプロピル、メタクリル酸２－ヒドロキシプロピル、アクリル酸２－ヒドロキシブチル、メタクリル酸２－ヒドロキシブチル、アクリル酸４－ヒドロキシブチル、メタクリル酸４－ヒドロキシブチル等が好ましく、メタクリル酸２－ヒドロキシエチル及びアクリル酸２－ヒドロキシエチルがより好ましい。 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.
　ポリイミド前駆体の分子量には特に制限はなく、例えば、重量平均分子量で１０００～１０００００であることが好ましく、５０００～８０，０００であることがより好ましく、５０００～７００００であることがさらに好ましく、１００００～６００００であることが特に好ましい。
　重量平均分子量は、例えば、ゲルパーミエーションクロマトグラフィー法によって測定することができ、標準ポリスチレン検量線を用いて換算することによって求めることができる。 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.
　樹脂組成物は、ポリイミド前駆体以外の樹脂成分を含有していてもよい。例えば、耐熱性の観点から、樹脂組成物は、ポリイミド樹脂、ノボラック樹脂、アクリル樹脂、ポリエーテルニトリル樹脂、ポリエーテルスルホン樹脂、エポキシ樹脂、ポリエチレンテレフタレート樹脂、ポリエチレンナフタレート樹脂、ポリ塩化ビニル樹脂等のその他の樹脂を含有していてもよい。その他の樹脂は、１種単独で用いてもよく、２種以上を組み合わせてもよい。 The resin composition may contain resin components other than the polyimide precursor. For example, from the viewpoint of heat resistance, 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.
　樹脂組成物では、ポリイミド前駆体及びポリイミド前駆体以外の樹脂成分の合計に対するポリイミド前駆体の含有率は、５０質量％～１００質量％であることが好ましく、７０質量％～１００質量％であることがより好ましく、９０質量％～１００質量％であることがさらに好ましい。 In the resin composition, 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.
（溶剤）
　樹脂組成物は、溶剤を含有する。溶剤としては、特に限定されず、例えば、Ｎ－メチル－２－ピロリドン、Ｎ－エチル－２－ピロリドン、γ‐ブチロラクトン、Ｎ，Ｎ‐ジメチルアセトアミド、シクロペンタノン、ジメチルスルホキシド、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、Ｎ，Ｎ，２－トリメチルプロピオンアミド、ジメチルイミダゾリジノン、Ｎ－ホルミルピぺリジン、Ｎ－ジメチルモルホリン及びプロピレングリコール１－モノメチルエーテル－２－アセタートが挙げられる。中でも、溶剤としては、Ｎ－メチル－２－ピロリドン、Ｎ－エチル－２－ピロリドン、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、γ-ブチロラクトン、シクロペンタノン、ジメチルスルホキシド、ジメチルイミダゾリジノン及びＮ－ホルミルピぺリジンが好ましい。溶剤は、１種単独で用いてもよく、２種以上を組み合わせてもよい。 (solvent)
The resin composition contains a solvent. The solvent is not particularly limited, and examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-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. Among them, as solvents, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, γ-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.
　樹脂組成物では、溶剤の含有量は、ポリイミド前駆体及びポリイミド前駆体以外の樹脂成分の合計１００質量部に対して５０質量部～１００００質量部であることが好ましく、１００質量部～１００００質量部であることがより好ましい。 In the resin composition, 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.
（光重合開始剤）
　樹脂組成物は、光重合開始剤を含有する。光重合開始剤としては、特に限定されず、例えば、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）、Ｎ，Ｎ’－テトラエチル－４，４’－ジアミノベンゾフェノン、４－メトキシ－４’－ジメチルアミノベンゾフェノン、４－クロロベンゾフェノン、４，４’－ジメトキシベンゾフェノン、４，４’－ジアミノベンゾフェノン、ｏ－ベンゾイル安息香酸メチル、４－ベンゾイル－４’－メチルジフェニルケトン、ジベンジルケトン、フルオレノン等のベンゾフェノン誘導体；アセトフェノン、２，２－ジエトキシアセトフェノン、３’－メチルアセトフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、２－ヒドロキシ－２－メチルプロピオフェノン、１－ヒドロキシシクロヘキシルフェニルケトン等のアセトフェノン誘導体；チオキサントン、２－メチルチオキサントン、２－イソプロピルチオキサントン、２－クロロチオキサントン、ジエチルチオキサントン等のチオキサントン誘導体；ベンジル、ベンジルジメチルケタール、ベンジル－β－メトキシエチルアセタール等のベンジル誘導体；ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインフェニルエーテル、メチルベンゾイン、エチルベンゾイン、プロピルベンゾイン等のベンゾイン誘導体；１－フェニル－１，２－ブタンジオン－２－（Ｏ－メトキシカルボニル）オキシム、１－フェニル－１，２－プロパンジオン－２－（Ｏ－メトキシカルボニル）オキシム、１－フェニル－１，２－プロパンジオン－２－（Ｏ－エトキシカルボニル）オキシム、１－フェニル－１，２－プロパンジオン－２－（Ｏ－ベンゾイル）オキシム、１，３－ジフェニルプロパントリオン－２－（Ｏ－エトキシカルボニル）オキシム、１－フェニル－３－エトキシプロパントリオン－２－（Ｏ－ベンゾイル）オキシム、１，２－オクタンジオン，１－［４－（フェニルチオ）フェニル］－，２－（Ｏ－ベンゾイルオキシム）等のオキシム誘導体；Ｎ－フェニルグリシン等のＮ－アリールグリシン類；ベンゾイルパークロライド等の過酸化物類；２－（ｏ－クロロフェニル）－４，５－ジフェニルイミダゾール二量体、２－（ｏ－クロロフェニル）－４，５－ジ（メトキシフェニル）イミダゾール二量体、２－（ｏ－フルオロフェニル）－４，５－ジフェニルイミダゾール二量体、２－（ｏ－又はｐ－メトキシフェニル）－４，５－ジフェニルイミダゾール二量体等の芳香族ビイミダゾール類；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、ビス（２，４，６－トリメチルベンゾイル）フェニルホスフィンオキサイド等のアシルホスフィンオキサイド誘導体等が挙げられる。
　光重合開始剤は、１種単独で用いてもよく、２種以上を組み合わせてもよい。
　これらの中でも、金属元素を含まず、且つ反応性が高く高感度の観点からオキシム誘導体が好ましい。 (Photoinitiator)
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-β-methoxyethylacetal benzoin derivatives such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, ethylbenzoin, propylbenzoin; 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1- Phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione -2-(O-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl)oxime, 1,2 -oxime derivatives such as octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime); N-arylglycines such as N-phenylglycine; peroxides such as benzoyl perchloride 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)- 4,5-diphenylimidazole dimer, 2-(o- or aromatic biimidazoles such as p-methoxyphenyl)-4,5-diphenylimidazole dimer; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine and acylphosphine oxide derivatives such as oxides.
A photoinitiator may be used individually by 1 type, and may combine 2 or more types.
Among these, oxime derivatives are preferable from the viewpoints of not containing a metal element, high reactivity and high sensitivity.
　樹脂組成物では、光重合開始剤の含有量は、光架橋が膜厚方向で均一となりやすい観点から、ポリイミド前駆体１００質量部に対して、０．１質量部～２０質量部が好ましく、０．１質量部～１０質量部がより好ましく、０．１質量部～６質量部がさらに好ましい。 In the resin composition, 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.
（重合性モノマー）
　樹脂組成物は、重合性モノマーを含有する。重合性モノマーは、重合性の不飽和二重結合を含む基を少なくとも一つ有することが好ましく、カップリング剤等により重合可能である観点から、（メタ）アクリル基を少なくとも一つ有することがより好ましい。架橋密度の向上及び光感度の向上の観点から、重合性の不飽和二重結合を含む基を、２つ～４つ有することが好ましい。
　重合性モノマーは、１種単独で用いてもよく、２種以上を組み合わせてもよい。 (Polymerizable monomer)
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.
　（メタ）アクリル基を有する重合性モノマーとしては、特に限定されず、例えば、ジエチレングリコールジアクリレート、トリエチレングリコールジアクリレート、テトラエチレングリコールジアクリレート、ジエチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、テトラエチレングリコールジメタクリレート、１，４－ブタンジオールジアクリレート、１，６－ヘキサンジオールジアクリレート、１，４－ブタンジオールジメタクリレート、１，６－ヘキサンジオールジメタクリレート、トリメチロールプロパンジアクリレート、トリメチロールプロパントリアクリレート、トリメチロールプロパンジメタクリレート、トリメチロールプロパントリメタクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ペンタエリスリトールトリメタクリレート、ペンタエリスリトールテトラメタクリレート、ジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールヘキサメタクリレート、エトキシ化ペンタエリスリトールテトラアクリレート、エトキシ化イソシアヌル酸トリアクリレート、エトキシ化イソシアヌル酸トリメタクリレート、アクリロイルオキシエチルイソシアヌレート及びメタクリロイルオキシエチルイソシアヌレートが挙げられる。中でも、重合性モノマーとしては、ジエチレングリコールジアクリレート、トリエチレングリコールジアクリレート、テトラエチレングリコールジアクリレート、ジエチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート及びテトラエチレングリコールジメタクリレートが好ましい。 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 tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethoxylated pentaerythritol tetraacrylate , ethoxylated isocyanuric acid triacrylate, ethoxylated isocyanuric acid trimethacrylate, acryloyloxyethyl isocyanurate and methacryloyloxyethyl isocyanurate. Among them, 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.
　（メタ）アクリル基を有する重合性モノマー以外の重合性モノマーとしては、特に限定されず、例えば、スチレン、ジビニルベンゼン、４－ビニルトルエン、４－ビニルピリジン、Ｎ－ビニルピロリドン、メチレンビスアクリルアミド、Ｎ，Ｎ－ジメチルアクリルアミド及びＮ－メチロールアクリルアミドが挙げられる。 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.
　樹脂組成物では、重合性モノマーの含有量は特に限定されず、ポリイミド前駆体１００質量部に対して、１質量部～５０質量部であることが好ましく、パターン硬化膜の熱特性の観点から、５質量部～５０質量部であることがより好ましく、５質量部～４０質量部であることがさらに好ましい。 In the resin composition, 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.
　樹脂組成物では、重合性モノマー全量に占める（メタ）アクリル基を有する重合性モノマーの割合は、硬化膜の物性の観点から、５０質量％～１００質量％であることが好ましく、７０質量％～１００質量％であることがより好ましく、９０質量％～１００質量％であることがさらに好ましい。 In the resin composition, 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.
（熱重合開始剤）
　樹脂組成物は、硬化膜の物性を向上させる観点から、熱重合開始剤をさらに含有してもよい。熱重合開始剤としては、特に限定されず、例えば、メチルエチルケトンペルオキシド等のケトンペルオキシド、１，１－ジ（ｔ－ヘキシルパーオキシ）－３，３，５－トリメチルシクロヘキサン、１，１－ジ（ｔ－ヘキシルパーオキシ）シクロヘキサン、１，１－ジ（ｔ－ブチルパーオキシ）シクロヘキサン等のパーオキシケタール、１，１，３，３－テトラメチルブチルハイドロペルオキシド、クメンハイドロペルオキシド、ｐ－メンタンハイドロペルオキシド等のハイドロペルオキシド、ジクミルペルオキシド、ジ－ｔ－ブチルペルオキシド等のジアルキルペルオキシド、ジラウロイルペルオキシド、ジベンゾイルペルオキシド等のジアシルペルオキシド、ジ（４－ｔ－ブチルシクロヘキシル）パーオキシジカーボネート、ジ（２－エチルヘキシル）パーオキシジカーボネート等のパーオキシジカーボネート、ｔ－ブチルパーオキシ－２－エチルヘキサノエート、ｔ－ヘキシルパーオキシイソプロピルモノカーボネート、ｔ－ブチルパーオキシベンゾエート、１，１，３，３－テトラメチルブチルパーオキシ－２－エチルヘキサノエート等のパーオキシエステル、ビス（１－フェニル－１－メチルエチル）ペルオキシドなどが挙げられる。熱重合開始剤は、１種単独で用いてもよく、２種以上を組み合わせてもよい。 (Thermal polymerization initiator)
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.
　樹脂組成物が熱重合開始剤を含有する場合、熱重合開始剤の含有量は、ポリイミド前駆体１００質量部に対して、０．１質量部～２０質量部であってもよく、１質量部～１５質量部であってもよく、５質量部～１０質量部であってもよい。 When the resin composition contains a thermal polymerization initiator, 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.
（カップリング剤）
　樹脂組成物は、カップリング剤をさらに含有していてもよい。カップリング剤は、加熱処理において、ポリイミド前駆体と反応して架橋する、又はカップリング剤自身が重合する。これにより、得られる硬化膜と基材との接着性をより向上させることができる傾向にある。 (coupling agent)
The resin composition may further contain a coupling agent. In the heat treatment, 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.
　カップリング剤の具体例は特に限定されるものではない。カップリング剤としては、３－アミノプロピルトリメトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルメチルジメトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、３－メルカプトプロピルメチルジメトキシシラン、３－メタクリロキシプロピルジメトキシメチルシラン、３－メタクリロキシプロピルトリメトキシシラン、ジメトキシメチル－３－ピペリジノプロピルシラン、ジエトキシ－３－グリシドキシプロピルメチルシラン、Ｎ－（３－ジエトキシメチルシリルプロピル）スクシンイミド、Ｎ－〔３－（トリエトキシシリル）プロピル〕フタルアミド酸、ベンゾフェノン－３，３’－ビス（Ｎ－〔３－トリエトキシシリル〕プロピルアミド）－４，４’－ジカルボン酸、ベンゼン－１，４－ビス（Ｎ－〔３－トリエトキシシリル〕プロピルアミド）－２，５－ジカルボン酸、３－（トリエトキシシリル）プロピルスクシニックアンハイドライド、Ｎ－フェニルアミノプロピルトリメトキシシラン等のシランカップリング剤；アルミニウムトリス（エチルアセトアセテート）、アルミニウムトリス（アセチルアセトネート）、エチルアセトアセテートアルミニウムジイソプロピレート等のアルミニウム系接着助剤；などが挙げられる。
　カップリング剤は、１種単独で用いてもよく、２種以上を組み合わせてもよい。 Specific examples of the coupling agent are not particularly limited. 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 , 4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propylsuccinic anhydride, silane cups such as N-phenylaminopropyltrimethoxysilane ring agents; aluminum-based adhesion promoters such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), ethylacetoacetate aluminum diisopropylate;
A coupling agent may be used individually by 1 type, and may combine 2 or more types.
　樹脂組成物がカップリング剤を含有する場合、カップリング剤の含有量は、ポリイミド前駆体１００質量部に対して、０．１質量部～２０質量部が好ましく、０．３質量部～１０質量部がより好ましく、１質量部～１０質量部がさらに好ましい。 When the resin composition contains a coupling agent, 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.
（界面活性剤及びレベリング剤）
　樹脂組成物は、界面活性剤及びレベリング剤の少なくとも一方を含有してもよい。樹脂組成物が界面活性剤及びレベリング剤の少なくとも一方を含有することにより、塗布性（例えばストリエーション（膜厚のムラ）の抑制）を向上させることができる。 (Surfactant and leveling agent)
The resin composition may contain at least one of 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.
　界面活性剤又はレベリング剤としては、ポリオキシエチレンウラリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェノールエーテル等が挙げられる。
　界面活性剤及びレベリング剤は、１種単独で用いてもよく、２種以上を組み合わせてもよい。 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.
　樹脂組成物が界面活性剤及びレベリング剤の少なくとも一方を含有する場合、界面活性剤及びレベリング剤の合計の含有量は、ポリイミド前駆体１００質量部に対して０．０１質量部～１０質量部であることが好ましく、０．０５質量部～５質量部であることがより好ましく、０．０５質量部～３質量部であることがさらに好ましい。 When the resin composition contains at least one of a surfactant and a leveling agent, 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.
（重合禁止剤）
　樹脂組成物は、良好な保存安定性を確保する観点から、重合禁止剤を含有していてもよい。重合禁止剤としては、ラジカル重合禁止剤、ラジカル重合抑制剤等が挙げられる。 (Polymerization inhibitor)
The resin composition may contain a polymerization inhibitor from the viewpoint of ensuring good storage stability. Examples of polymerization inhibitors include radical polymerization inhibitors and radical polymerization inhibitors.
　重合禁止剤の具体例としては、ｐ－メトキシフェノール、ジフェニル－ｐ－ベンゾキノン、ベンゾキノン、ハイドロキノン、ピロガロール、フェノチアジン、レゾルシノール、オルトジニトロベンゼン、パラジニトロベンゼン、メタジニトロベンゼン、フェナントラキノン、Ｎ－フェニル－２－ナフチルアミン、クペロン、２，５－トルキノン、タンニン酸、パラベンジルアミノフェノール、ニトロソアミン類、１，４，４－トリメチル－２，３－ジアザビシクロ［３．２．２］ノナ－２－エン－２，３－ジオキシド等が挙げられる。重合禁止剤は、１種単独で用いてもよく、２種以上を組み合わせてもよい。 Specific examples of polymerization inhibitors include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, and N-phenyl-2. - naphthylamine, cupferron, 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosamines, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-2, 3-dioxide and the like. A polymerization inhibitor may be used individually by 1 type, and may combine 2 or more types.
　樹脂組成物が重合禁止剤を含有する場合、重合禁止剤の含有量は、樹脂組成物の保存安定性及び得られる硬化膜の耐熱性の観点から、ポリイミド前駆体１００質量部に対して、０．０１質量部～３０質量部であることが好ましく、０．０１質量部～１０質量部であることがより好ましく、０．０５質量部～５質量部であることがさらに好ましい。 When the resin composition contains a polymerization inhibitor, 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.
（防錆剤）
　樹脂組成物は、防錆剤を含有していてもよい。樹脂組成物が防錆剤を含有することにより、銅及び銅合金の腐食及び変色の抑制が可能となる。
　防錆剤としては、トリアゾール誘導体、テトラゾール誘導体等が挙げられる。
　防錆剤は、１種単独で用いてもよく、２種以上を組み合わせてもよい。 (anti-rust)
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.
　樹脂組成物が防錆剤を含有する場合、防錆剤の含有量は、ポリイミド前駆体１００質量部に対して０．０１質量部～１０質量部が好ましく、０．１質量部～５質量部がより好ましく、０．５質量部～３質量部がさらに好ましい。 When the resin composition contains an antirust agent, 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.
＜ポリイミド前駆体＞
　本開示のポリイミド前駆体は、環化温度が１６４℃以上である。特にネガ型の樹脂組成物の製造に本開示のポリイミド前駆体を用いた場合に、現像残渣、パターンはがれ等が抑制され、解像度に優れるパターン硬化膜を好適に形成可能となる。 <Polyimide precursor>
The polyimide precursor of the present disclosure has a cyclization temperature of 164° C. or higher. In particular, when the polyimide precursor of the present disclosure is used to produce a negative resin composition, development residue, pattern peeling, etc. are suppressed, and a pattern cured film with excellent resolution can be suitably formed.
　ポリイミド前駆体の環化温度は、１７０℃以上であることが好ましく、１７２℃以上であることがより好ましい。
　また、ポリイミド前駆体の環化温度は、２００℃以下であってもよく、１８０℃以下であってもよく、１７５℃以下であってもよい。 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.
　本開示のポリイミド前駆体の好ましい形態は、前述の本開示の樹脂組成物の製造方法にて用いるポリイミド前駆体の好ましい形態と同様である。 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.
＜樹脂組成物＞
　本開示の樹脂組成物は、前述の本開示のポリイミド前駆体と、溶剤と、光重合開始剤と、重合性モノマーと、を含む。本開示の樹脂組成物は、前述の本開示のポリイミド前駆体を含むことで解像度に優れるパターン硬化膜を好適に形成可能となる。 <Resin composition>
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.
　本開示の樹脂組成物の好ましい形態は、前述の本開示の樹脂組成物の製造方法にて製造される樹脂組成物の好ましい形態と同様である。 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.
　本開示の樹脂組成物は、塗膜を形成する際のイミド化を抑制する観点から、未反応のジアミン化合物を実質的に含まないことが好ましく、防錆剤以外のアミン系添加剤、酸等を実質的に含まないことが好ましい。
　本開示において、「実質的に含まない」とは、対象の成分の含有率が、樹脂組成物全量に対して１質量％以下であることを意味する。 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.
＜硬化物＞
　本開示の硬化物は、本開示の樹脂組成物を硬化してなる。本開示の硬化物は、本開示の樹脂組成物を用いて基材上に作製されてもよい。 <Cured product>
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.
　次に、硬化物の一例であるパターン硬化膜を作製する方法について説明する。上述のパターン硬化膜の作製方法としては、例えば、樹脂組成物を基材上に塗布することと、乾燥して塗膜を形成することと、塗膜をフォトマスクを用いてパターン露光し、現像液を用いて現像してパターン樹脂膜を得ることと、パターン樹脂膜を加熱処理することとを含む方法を用いてもよい。これにより、パターン硬化膜を得ることができる。 Next, a method for producing a pattern cured film, which is an example of a cured product, will be described. As a method for producing the pattern cured film described above, for example, 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.
　樹脂組成物を基材上に塗布する方法としては、例えば、スピンコート法、インクジェット法、及びスリットコート法が挙げられる。 Examples of methods for applying the resin composition onto the substrate include spin coating, inkjet, and slit coating.
　基材としては、特に限定されず、アクリル板、ガラス基板、シリコンウエハ等の半導体基板、ＴｉＯ２基板、ＳｉＯ２基板等の金属酸化物絶縁体基板、窒化ケイ素基板、銅基板、銅合金基板などが挙げられる。 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.
　基材の形状、大きさ等については、限定されず、作製する硬化物の形状、大きさ等に応じて適宜選択すればよく、ウエハ状、パネル状（例えば、正方形状）等であってもよい。 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.
　スピンコート法では、例えば、回転速度が３００ｒｐｍ（回転毎分）～３，５００ｒｐｍ、好ましくは５００ｒｐｍ～１，５００ｒｐｍ、加速度が５００ｒｐｍ／秒～１５，０００ｒｐｍ／秒、回転時間が３０秒～３００秒という条件にて、前記樹脂組成物をスピンコーティングしてもよい。 In the spin coating method, for example, 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. Under certain conditions, the resin composition may be spin-coated.
　樹脂組成物を基材に塗布した後にホットプレート、オーブン等を用いて乾燥を行ってもよい。乾燥温度は、７５℃～１４０℃が好ましく、硬化膜の平坦性向上の観点から、９０℃～１３０℃がより好ましい。乾燥時間は、３０秒間～５分間が好ましい。
　乾燥は、２回以上行ってもよい。これにより、上述の樹脂組成物を膜状に形成した塗膜を得ることができる。 After applying the resin composition to the substrate, 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.
　次に、基材上に形成した塗膜をフォトマスクを用いてパターン露光し、現像液を用いて現像してパターン樹脂膜を得る。パターン樹脂膜を得る方法としては、前述のポリイミド前駆体の製造方法でのパターン樹脂膜を得る方法と同様である。 Next, 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.
　パターン樹脂膜を加熱処理することでパターン硬化膜を形成する。加熱温度は、１５０℃～４５０℃が好ましく、１５０℃～３５０℃がより好ましい。加熱温度が上記範囲内であることにより、基材等へのダメージを抑制してプロセスの省エネルギー化を実現しつつ、パターン硬化膜を好適に作製することができる。 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. When the heating temperature is within the above range, the pattern cured film can be favorably produced while suppressing damage to the substrate and realizing energy saving in the process.
　加熱時間は、５時間以下が好ましく、３０分間～３時間がより好ましい。加熱処理の時間が上記範囲内であることにより、架橋反応又は脱水閉環反応を充分に進行させることができる。
　加熱処理の雰囲気は大気中であってもよく、窒素等の不活性雰囲気中であってもよいが、樹脂膜の酸化を防ぐことができる観点から、窒素雰囲気下が好ましい。 The heating time is preferably 5 hours or less, more preferably 30 minutes to 3 hours. When the heat treatment time is within the above range, the cross-linking reaction or the dehydration ring-closing reaction can be sufficiently advanced.
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.
　加熱処理に用いられる装置としては、石英チューブ炉、ホットプレート、ラピッドサーマルアニール、縦型拡散炉、赤外線硬化炉、電子線硬化炉、マイクロ波硬化炉等が挙げられる。 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.
　基材上に作製されたパターン硬化膜の平均厚さは、０．１μｍ以上であることが好ましく、０．５μｍ～１５μｍであることがより好ましく、０．５μｍ～１０μｍであることがさらに好ましい。 The average thickness of the patterned cured film produced on the substrate is preferably 0.1 μm or more, more preferably 0.5 μm to 15 μm, even more preferably 0.5 μm to 10 μm.
　以下、実験例に基づき、本開示についてさらに具体的に説明する。尚、本開示は下記実施例に限定されるものではない。 The present disclosure will be described more specifically below based on experimental examples. It should be noted that the present disclosure is not limited to the following examples.
［実験例１］
＜合成例１：ピロメリット酸－ヒドロキシエチルメタクリレートジエステルの合成＞
　０．５リットルのポリ瓶中に、１６０℃の乾燥機で２４時間乾燥させたピロメリット酸二無水物（以下、ＰＭＤＡとも記載する。）、メタクリル酸２－ヒドロキシエチル（以下、ＨＥＭＡとも記載する）及びハイドロキノンを、Ｎ－メチル－２－ピロリドンに、ＰＭＤＡとＨＥＭＡとのモル比が約１：２になるように溶解させ、１，８－ジアザビシクロウンデセンを触媒量添加して混合液を準備した。混合液を室温下（２５℃）で２４時間撹拌し、エステル化を行うことでピロメリット酸－ヒドロキシエチルメタクリレートジエステル溶液を得た。この溶液をＰＭＤＡ（ＨＥＭＡ）溶液とする。 [Experimental example 1]
<Synthesis Example 1: Synthesis of pyromellitic acid-hydroxyethyl methacrylate diester>
Pyromellitic dianhydride (hereinafter also referred to as PMDA) and 2-hydroxyethyl methacrylate (hereinafter also referred to as HEMA) dried in a 160° C. dryer for 24 hours in a 0.5 liter plastic bottle. ) and hydroquinone are dissolved in N-methyl-2-pyrrolidone so that the molar ratio of PMDA and HEMA is about 1:2, and a catalytic amount of 1,8-diazabicycloundecene is added to prepare a mixed solution. prepared. The mixture was stirred at room temperature (25° C.) for 24 hours for esterification to obtain a pyromellitic acid-hydroxyethyl methacrylate diester solution. Let this solution be the PMDA (HEMA) solution.
＜合成例２：４，４’－オキシジフタル酸ジエステルの合成＞
　０．５リットルのポリ瓶中に、１６０℃の乾燥機で２４時間乾燥させた４，４’－オキシジフタル酸無水物（以下、ＯＤＰＡとも記載する。）、ＨＥＭＡ及びハイドロキノンを、ＯＤＰＡとＨＥＭＡとのモル比が約１：２になるように溶解させ、１，８－ジアザビシクロウンデセンを触媒量添加して混合液を準備した。混合液を室温下（２５℃）で４８時間撹拌し、エステル化を行うことで４，４’－オキシジフタル酸－ヒドロキシエチルメタクリレートジエステル溶液を得た。この溶液をＯＤＰＡ（ＨＥＭＡ）溶液とする。 <Synthesis Example 2: Synthesis of 4,4′-oxydiphthalic acid diester>
In a 0.5-liter plastic bottle, 4,4'-oxydiphthalic anhydride (hereinafter also referred to as ODPA) dried for 24 hours in a drier at 160°C, HEMA and hydroquinone were mixed with ODPA and HEMA. They were dissolved in a molar ratio of about 1:2, and a catalytic amount of 1,8-diazabicycloundecene was added to prepare a mixed solution. The mixture was stirred at room temperature (25° C.) for 48 hours for esterification to obtain a 4,4′-oxydiphthalic acid-hydroxyethyl methacrylate diester solution. Let this solution be the ODPA (HEMA) solution.
＜合成例３：ポリイミド前駆体の合成＞
　撹拌機及び温度計を備えた０．５リットルのフラスコ中に合成例１で得られたＰＭＤＡ（ＨＥＭＡ）溶液と合成例２で得られたＯＤＰＡ（ＨＥＭＡ）溶液を入れ、その後、氷冷下で塩化チオニルを反応液温度が１０度以下を保つように滴下漏斗を用いて滴下した。このとき、ＰＭＤＡ（ＨＥＭＡ）と、ＯＤＰＡ（ＨＥＭＡ）とのモル比は、約４：１であり、ＰＭＤＡ（ＨＥＭＡ）及びＯＤＰＡ（ＨＥＭＡ）の合計と、塩化チオニルとのモル比は、約１：２であった。塩化チオニルの滴下が終了した後、氷冷下で２時間反応を行いＰＭＤＡ（ＨＥＭＡ）とＯＤＰＡ（ＨＥＭＡ）の酸クロリドの溶液を得た。次いで、滴下漏斗を用いて、Ｎ－メチル－２－ピロリドンに２，２’－ビス（トリフルオロメチル）－４，４’－ジアミノビフェニル、ピリジン及びハイドロキノンを溶解させた溶液を氷冷化で反応液の温度が１０℃を超えないように注意しながら滴下した。このとき、ＰＭＤＡ（ＨＥＭＡ）とＯＤＰＡ（ＨＥＭＡ）の酸クロリドの合計と、２，２’－ビス（トリフルオロメチル）－４，４’－ジアミノビフェニルとのモル比は、約１：１であった。この反応液を蒸留水に滴下し、沈殿物をろ別して集め、減圧乾燥することによってポリアミック酸エステルであるポリイミド前駆体を得た。ゲルパーミエーションクロマトグラフ（ＧＰＣ）法を用いて、標準ポリスチレン換算により求めたポリイミド前駆体の重量平均分子量は４３０００であった。示差走査熱量測定（ＤＳＣ）によって測定されたポリイミド前駆体の環化温度は１７４．１０℃であった。 <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. After the dropwise addition of thionyl chloride was completed, reaction was carried out for 2 hours under ice-cooling to obtain a solution of acid chlorides of PMDA (HEMA) and ODPA (HEMA). Next, using a dropping funnel, a solution of 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, pyridine and hydroquinone dissolved in N-methyl-2-pyrrolidone was reacted under ice cooling. It was added dropwise while taking care that the temperature of the liquid did not exceed 10°C. At this time, the molar ratio of the sum of acid chlorides of PMDA (HEMA) and ODPA (HEMA) to 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl was about 1:1. rice field. This reaction liquid was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyamic acid ester as a polyimide precursor. The weight average molecular weight of the polyimide precursor was 43,000 as determined by standard polystyrene conversion using gel permeation chromatography (GPC). The cyclization temperature of the polyimide precursor measured by differential scanning calorimetry (DSC) was 174.10°C.
＜ポリイミド前駆体の環化温度の測定＞
　示差走査熱量測定装置（Ｎｅｔｚｓｃｈ製、ＤＳＣ　２０４　Ｆ１　Ｐｈｏｅｎｉｘ）を用い、昇温速度５℃／分、測定温度範囲３０℃～３００℃、流量２０ｍＬ／分の窒素雰囲気下の条件で、アルミニウム製パンに密閉した５ｍｇの試料のＤＳＣ測定を行った。得られたＤＳＣ曲線にて１４０℃～２００℃付近に発生するイミド化反応由来の吸熱ピークの温度をポリイミド前駆体の環化温度とした。 <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.
＜重量平均分子量の測定＞
　ポリイミド前駆体の重量平均分子量を以下のようにして測定した。具体的には、ポリイミド前駆体０．５ｍｇを溶剤［テトラヒドロフラン（ＴＨＦ）／ジメチルホルムアミド（ＤＭＦ）＝１／１（容積比）］１ｍＬに溶解させた溶液を用い、以下の条件で測定した。
（測定条件）
測定装置：検出器　株式会社日立製作所Ｌ４０００ＵＶ
ポンプ：株式会社日立製作所Ｌ６０００
　　　　株式会社島津製作所Ｃ－Ｒ４Ａ　Ｃｈｒｏｍａｔｏｐａｃ
測定条件：カラムＧｅｌｐａｃｋ　ＧＬ－Ｓ３００ＭＤＴ－５×２本
溶離液：ＴＨＦ／ＤＭＦ＝１／１（容積比）
　　　　ＬｉＢｒ（０．０３ｍｏｌ／Ｌ）、Ｈ３ＰＯ４（０．０６ｍｏｌ／Ｌ）
　流速：１．０ｍＬ／ｍｉｎ、検出器：ＵＶ２７０ｎｍ <Measurement of weight average molecular weight>
The weight average molecular weight of the polyimide precursor was measured as follows. Specifically, using a solution prepared by dissolving 0.5 mg of a polyimide precursor in 1 mL of a solvent [tetrahydrofuran (THF)/dimethylformamide (DMF)=1/1 (volume ratio)], measurement was performed under the following conditions.
(Measurement condition)
Measuring device: Detector Hitachi, Ltd. L4000UV
Pump: Hitachi Ltd. L6000
Shimadzu Corporation C-R4A Chromatopac
Measurement conditions: Column Gelpack GL-S300MDT-5 x 2 Eluent: THF/DMF = 1/1 (volume ratio)
LiBr (0.03 mol/L), H3PO4 ( 0.06 mol/L)
Flow rate: 1.0 mL/min, detector: UV270 nm
＜エステル化率＞
　以下の条件でＮＭＲ測定を行うことで、ポリイミド前駆体のエステル化率（ＨＥＭＡと反応してなるエステル基及びＨＥＭＡと未反応のカルボキシ基の合計に対するＨＥＭＡと反応してなるエステル基の割合）を算出した。エステル化率は、９５．７モル％であった。
（測定条件）
測定機器：ブルカー・バイオスピン社　ＡＶ４００Ｍ
磁場強度：４００ＭＨｚ
基準物質：テトラメチルシラン（ＴＭＳ）
溶剤：ジメチルスルホキシド（ＤＭＳＯ） <Esterification rate>
By performing NMR measurement under the following conditions, the esterification rate of the polyimide precursor (the ratio of ester groups reacted with HEMA to the total of ester groups reacted with HEMA and carboxy groups unreacted with HEMA) was determined. Calculated. The esterification rate was 95.7 mol%.
(Measurement condition)
Measuring instrument: Bruker Biospin AV400M
Magnetic field strength: 400MHz
Reference substance: Tetramethylsilane (TMS)
Solvent: dimethyl sulfoxide (DMSO)
［実験例２～１４］
　実験例１と同様の手順でポリイミド前駆体の環化温度が表１に示す通りとなるように合成条件を調整してポリイミド前駆体を合成した。 [Experimental Examples 2 to 14]
A polyimide precursor was synthesized in the same manner as in Experimental Example 1 by adjusting the synthesis conditions so that the cyclization temperature of the polyimide precursor was as shown in Table 1.
＜樹脂組成物の調製＞
　実験例１～１４にて合成したポリイミド前駆体を用いて樹脂組成物を調製した。具体的には、各ポリイミド前駆体１００質量部、以下に示す配合成分である溶剤１５０質量部、光重合開始剤２質量部及び重合性モノマー２０質量部を混合して樹脂組成物を調製した。
（配合成分）
　溶剤：３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド
　光重合開始剤：１，２－プロパンジオン，１－［４－［［４－（２－ヒドロキシエトキシ）フェニル］チオ］フェニル］－，２－（Ｏ－アセチルオキシム）
　重合性モノマー：トリエチレングリコールジメタクリレート <Preparation of resin composition>
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.
(Ingredients)
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
＜パターン樹脂膜の形成＞
　実験例１～１４にて合成した各ポリイミド前駆体を含む樹脂組成物を用いて以下の条件にてパターン樹脂膜を形成した。具体的には、塗布装置（Ａｃｔ８、東京エレクトロン株式会社）を用いて、シリコンウエハ上に樹脂組成物をスピンコートし、次いで、１３０℃で２００秒間乾燥して塗膜を形成した。
　得られた塗膜に、ｉ線ステッパＦＰＡ－３０００ｉＷ（キヤノン株式会社製）及び円径幅が１０μｍのフォトマスクを用いて、ＮＡ０．２８、フォーカス０μｍ、３００ｍＪ／ｃｍ２のｉ線を照射した。
　露光後の塗膜を、塗布装置（Ａｃｔ８、東京エレクトロン株式会社）を用いて、シクロペンタノンにより、２５秒の現像時間で未露光部を除去して現像した後、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）でリンス洗浄を行い、パターン樹脂膜を得た。 <Formation of patterned resin film>
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 μm, the obtained coating film was irradiated with i-line of 300 mJ/cm 2 at NA 0.28, focus 0 μm.
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.
　実験例１～１４にて合成した各ポリイミド前駆体を含む樹脂組成物を用いて得られたパターン樹脂膜について、パターン樹脂膜の開口径をそれぞれ求めた。
　結果を表１に示す。 For the pattern resin films obtained using the resin compositions containing the respective polyimide precursors synthesized in Experimental Examples 1 to 14, the opening diameters of the pattern resin films were determined.
Table 1 shows the results.
＜パターン樹脂膜の評価＞
　前述のようにして得らえたパターン樹脂膜の開口径の値から、微細なパターンが形成できているかについて、以下の評価基準に基づいて評価した。評価がＢ以上であれば、微細なパターンが形成できており、解像度に優れていると判断できる。
－評価基準－
Ａ：パターン樹脂膜の開口径が８．５μｍ未満である。
Ｂ：パターン樹脂膜の開口径が８．５μｍ～９．５μｍである。
Ｃ：パターン樹脂膜の開口径が９．５μｍ超である。 <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.
-Evaluation criteria-
A: The opening diameter of the patterned resin film is less than 8.5 μm.
B: The opening diameter of the patterned resin film is 8.5 μm to 9.5 μm.
C: The opening diameter of the patterned resin film is more than 9.5 μm.
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
　以上により、実験例１～９にて合成されたポリイミド前駆体を用いることで解像度に優れるパターン樹脂膜が形成できることが示された。さらに、実験例１～９では、パターン樹脂膜を加熱等により硬化することで残渣及びはがれがなく解像度に優れるパターン硬化膜が形成できることが確認できた。 From the above, it was shown that a patterned resin film with excellent resolution can be formed by using the polyimide precursors synthesized in Experimental Examples 1-9. Further, in Experimental Examples 1 to 9, it was confirmed that by curing the pattern resin film by heating or the like, it was possible to form a pattern cured film free from residue and peeling and excellent in resolution.
　本明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。 All publications, patent applications and technical standards mentioned herein are to the same extent as if each individual publication, patent application and technical standard were specifically and individually noted to be incorporated by reference. incorporated herein by reference.

Claims (12)

  1. 　ポリイミド前駆体の環化温度と、前記ポリイミド前駆体を含む樹脂組成物の塗膜を開口部を有するフォトマスクを用いて露光し、次いで現像することで形成されたパターン樹脂膜の開口径と、の関係に基づいて、特定の環化温度の条件を満たすポリイミド前駆体を選択するポリイミド前駆体の選択方法。 The cyclization temperature of the polyimide precursor, the opening diameter 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, A method for selecting polyimide precursors that selects polyimide precursors that meet specific cyclization temperature conditions based on the relationship of
  2. 　環化温度が１６４℃以上であるポリイミド前駆体を選択する請求項１に記載のポリイミド前駆体の選択方法。 The method for selecting a polyimide precursor according to claim 1, wherein a polyimide precursor having a cyclization temperature of 164°C or higher is selected.
  3. 　前記樹脂組成物の塗膜を形成する際の乾燥温度は、７５℃～１４０℃である請求項１又は請求項２に記載のポリイミド前駆体の選択方法。 The method for selecting a polyimide precursor according to claim 1 or claim 2, wherein the drying temperature when forming the coating film of the resin composition is 75°C to 140°C.
  4. 　１種類以上のポリイミド前駆体の環化温度を測定し、請求項１～請求項３のいずれか１項に記載のポリイミド前駆体の選択方法に基づいて特定の環化温度の条件を満たすポリイミド前駆体を選択することと、
    　選択された前記ポリイミド前駆体を用いて樹脂組成物を製造することと、
    　を含む樹脂組成物の製造方法。     The cyclization temperature of one or more polyimide precursors is measured, and a polyimide precursor that satisfies a specific cyclization temperature condition based on the method for selecting a polyimide precursor according to any one of claims 1 to 3. choosing a body;
    Producing a resin composition using the selected polyimide precursor;
    A method for producing a resin composition comprising
  5. 　選択された前記ポリイミド前駆体と、溶剤と、光重合開始剤と、重合性モノマーと、を混合して前記樹脂組成物を製造する請求項４に記載の樹脂組成物の製造方法。 The method for producing a resin composition according to claim 4, wherein the selected polyimide precursor, solvent, photopolymerization initiator, and polymerizable monomer are mixed to produce the resin composition.
  6. 　環化温度が１６４℃以上であるポリイミド前駆体。 A polyimide precursor having a cyclization temperature of 164°C or higher.
  7. 　下記一般式（１）で表される構造単位を有する化合物を含む請求項６に記載のポリイミド前駆体。
    Figure JPOXMLDOC01-appb-C000001
    　一般式（１）中、Ｘは４価の有機基を表し、Ｙは２価の有機基を表し、Ｒ６及びＲ７は、それぞれ独立に、水素原子、又は１価の有機基を表す。前記Ｒ６及びＲ７の少なくとも一方は１価の有機基である。     7. The polyimide precursor according to claim 6, which contains a compound having a structural unit represented by the following general formula (1).
    Figure JPOXMLDOC01-appb-C000001
    In general formula (1), X represents a tetravalent organic group, Y represents a divalent organic group, and 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. 　前記一般式（１）中、前記Ｒ６及び前記Ｒ７の少なくとも一方が、前記１価の有機基に該当する下記一般式（２）で表される基である請求項７に記載のポリイミド前駆体。
    Figure JPOXMLDOC01-appb-C000002
    　一般式（２）中、Ｒ８～Ｒ１０は、それぞれ独立に、水素原子又は炭素数１～３の脂肪族炭化水素基を表し、Ｒｘは２価の連結基を表す。     8. The polyimide precursor according to claim 7, wherein at least one of the R 6 and the R 7 in the general formula (1) is a group represented by the following general formula (2) corresponding to the monovalent organic group. body.
    Figure JPOXMLDOC01-appb-C000002
    In general formula (2), 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.
  9. 　前記一般式（１）で表される構造単位を有する化合物に含有される全構造単位のＲ６及びＲ７の合計に対する一般式（２）で表される基であるＲ６及びＲ７の割合は、５０モル％以上である請求項８に記載のポリイミド前駆体。 Ratio of R 6 and R 7 which are groups represented by general formula (2) 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) is 50 mol % or more, the polyimide precursor according to claim 8.
  10. 　重量平均分子量が１０００～１０００００である請求項６～請求項９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 6 to 9, which has a weight average molecular weight of 1,000 to 100,000.
  11. 　請求項６～請求項１０のいずれか１項に記載のポリイミド前駆体と、溶剤と、光重合開始剤と、重合性モノマーと、を含む樹脂組成物。 A resin composition comprising the polyimide precursor according to any one of claims 6 to 10, a solvent, a photopolymerization initiator, and a polymerizable monomer.
  12. 　請求項１１に記載の樹脂組成物を硬化してなる硬化物。 A cured product obtained by curing the resin composition according to claim 11.
PCT/JP2021/003345 2021-01-29 2021-01-29 Polyimide precursor selection method, resin composition production method, polyimide precursor, resin composition, and cured object WO2022162895A1 (en)

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