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WO2025205567A1 - Composition de résine, produit durci, stratifié, procédé de production de produit durci, procédé de production de stratifié, procédé de production de dispositif à semi-conducteur et dispositif à semi-conducteur - Google Patents

Composition de résine, produit durci, stratifié, procédé de production de produit durci, procédé de production de stratifié, procédé de production de dispositif à semi-conducteur et dispositif à semi-conducteur

Info

Publication number
WO2025205567A1
WO2025205567A1 PCT/JP2025/011385 JP2025011385W WO2025205567A1 WO 2025205567 A1 WO2025205567 A1 WO 2025205567A1 JP 2025011385 W JP2025011385 W JP 2025011385W WO 2025205567 A1 WO2025205567 A1 WO 2025205567A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
formula
resin composition
resin
cured product
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/011385
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English (en)
Japanese (ja)
Inventor
三千紘 白川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Original Assignee
Fujifilm Corp
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Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Publication of WO2025205567A1 publication Critical patent/WO2025205567A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/21—Urea; Derivatives thereof, e.g. biuret
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029

Definitions

  • the present invention relates to a resin composition, a cured product, a laminate, a method for producing a cured product, a method for producing a laminate, a method for producing a semiconductor device, and a semiconductor device.
  • cyclized resins such as polyimides have excellent heat resistance and insulating properties, and are therefore used in a variety of applications.
  • examples of such applications include, but are not limited to, insulating films, sealing materials, and protective films for semiconductor devices used for packaging. They are also used as base films and coverlays for flexible substrates.
  • the cyclized resin such as polyimide is used in the form of a resin composition containing the cyclized resin or a precursor thereof.
  • a resin composition is applied to a substrate by, for example, coating to form a photosensitive film, and then, if necessary, exposure, development, heating, etc. are carried out to form a cured product on the substrate.
  • the resin composition can be applied by known coating methods, etc., and therefore can be said to have excellent adaptability in manufacturing, for example, a high degree of freedom in designing the shape, size, application position, etc. of the resin composition when applied.
  • cyclized resins such as polyimides from the viewpoint of such excellent adaptability in manufacturing, there are increasing expectations for the industrial application and development of the above-mentioned resin composition.
  • Patent Document 1 describes a photosensitive resin composition containing a polyimide precursor having a weight-average molecular weight of 40,000 or more and a polymerizable unsaturated bond, a polymerizable monomer, a photopolymerization initiator, and a solvent.
  • redistribution layer (RDL) insulating film used in semiconductor packages has become an issue due to the need for high dimensional uniformity as wiring becomes finer. This means that line width uniformity within the wafer surface is becoming an issue. In other words, there is a demand for small differences in line width between the periphery and center of the wafer, for example.
  • the present invention aims to provide a resin composition capable of forming a patterned cured layer with high line width uniformity within the wafer surface, a cured product obtained by curing the resin composition, a laminate including the cured product, a method for manufacturing the cured product, a method for manufacturing the laminate, a method for manufacturing a semiconductor device including the method for manufacturing the cured product, and a semiconductor device including the cured product.
  • X is a group represented by formula (2a), in which *1 to *4 each represent a bonding site with a carbonyl group, Y is any group selected from the following: ⁇ 2>
  • R 1 and R 2 each independently represent a saturated aliphatic hydrocarbon group having 3 to 6 carbon atoms or a phenyl group which may be substituted with an alkyl group having 1 to 10 carbon atoms;
  • X 1 represents an oxygen atom or a sulfur atom;
  • * 1 and * 2 each independently represent a bonding site to another structure, and at least two of R 1 , R 2 , the structure bonding to * 1 , and the structure bonding to * 2 may be bonded to form a ring structure;
  • a resin composition in which the molar content of the structure represented by formula (1) relative to the total solid content of the resin composition is 0.005 to 0.5 mmol/g.
  • ⁇ 4> The resin composition according to any one of ⁇ 1> to ⁇ 3>, in which Resin A contains a structure represented by Formula (1-dp-2d1). In the formula, * indicates a bonding site with another structure.
  • ⁇ 5> The resin composition according to ⁇ 4>, in which the resin A includes at least one selected from the structure represented by formula (1-dp-V1-1) and the structure represented by formula (Y-V1-1); In the formula, * indicates a bonding site with another structure.
  • ⁇ 6> The resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the resin A contains an imide ring structure and the imidization rate of the resin A is 3 to 40%.
  • ⁇ 7> The resin composition according to any one of ⁇ 1> to ⁇ 6>, wherein the weight average molecular weight of the resin A is 15,000 to 40,000.
  • ⁇ 8> The resin composition according to any one of ⁇ 1> to ⁇ 7>, wherein the acid value of the acid group contained in the resin A, the neutralization point of which has a pH in the range of 7.0 to 12.0, is in the range of 0.0010 to 0.3000 mmol/g.
  • ⁇ 9> The resin composition according to any one of ⁇ 1> to ⁇ 8>, further comprising a titanium complex compound.
  • ⁇ 10> The resin composition according to any one of ⁇ 1> to ⁇ 9>, wherein the photosensitizer B contains an oxime compound.
  • ⁇ 16> A laminate comprising two or more layers made of the cured product according to ⁇ 15>, and a metal layer between any two adjacent layers made of the cured product.
  • ⁇ 17> A method for producing a cured product, comprising a film-forming step of applying the resin composition according to any one of ⁇ 1> to ⁇ 14> onto a substrate to form a film.
  • the method for producing a cured product according to ⁇ 17> comprising: an exposure step of selectively exposing the film to light; and a development step of developing the film with a developer to form a pattern.
  • a method for producing a cured product according to ⁇ 17> or ⁇ 18> comprising a heating step of heating the film at 50 to 450°C.
  • ⁇ 20> A method for producing a laminate, comprising the method for producing a cured product according to any one of ⁇ 17> to ⁇ 19>.
  • ⁇ 21> A method for producing a semiconductor device, comprising the method for producing a cured product according to any one of ⁇ 17> to ⁇ 19>.
  • ⁇ 22> A semiconductor device comprising the cured product according to ⁇ 15>.
  • the present invention provides a resin composition capable of forming a patterned cured layer with high line width uniformity within the wafer surface, a cured product obtained by curing the resin composition, a laminate including the cured product, a method for manufacturing the cured product, a method for manufacturing the laminate, a method for manufacturing a semiconductor device including the method for manufacturing the cured product, and a semiconductor device including the cured product.
  • a numerical range expressed using the symbol "to” means a range that includes the numerical values before and after "to” as the lower and upper limits, respectively.
  • the term “step” includes not only an independent step but also a step that cannot be clearly distinguished from other steps, so long as the intended effect of the step can be achieved.
  • groups (atomic groups) when a notation does not specify whether they are substituted or unsubstituted, it encompasses both groups (atomic groups) that have no substituents and groups (atomic groups) that have substituents.
  • alkyl group encompasses not only alkyl groups that have no substituents (unsubstituted alkyl groups) but also alkyl groups that have substituents (substituted alkyl groups).
  • exposure includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, electron beams, and other actinic rays or radiation.
  • (meth)acrylate means both or either of “acrylate” and “methacrylate”
  • (meth)acrylic means both or either of “acrylic” and “methacrylic”
  • (meth)acryloyl means both or either of “acryloyl” and “methacryloyl”.
  • Me represents a methyl group
  • Et represents an ethyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group.
  • total solids content refers to the total mass of all components of the composition excluding the solvent
  • solids concentration refers to the mass percentage of the components excluding the solvent relative to the total mass of the composition.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) are values measured using gel permeation chromatography (GPC) and are defined as polystyrene equivalent values.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) can be determined, for example, using an HLC-8220GPC (manufactured by Tosoh Corporation) and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) connected in series.
  • these molecular weights are measured using NMP (N-methyl-2-pyrrolidone) as the eluent.
  • NMP N-methyl-2-pyrrolidone
  • THF tetrahydrofuran
  • detection in GPC measurement is performed using a UV (ultraviolet) ray (ultraviolet) detector with a wavelength of 254 nm.
  • a third layer or element may be interposed between the reference layer and the other layer, and the reference layer and the other layer do not need to be in contact.
  • the direction in which layers are stacked on the substrate is referred to as "up,” or, if a resin composition layer is present, the direction from the substrate to the resin composition layer is referred to as “up,” and the opposite direction is referred to as “down.”
  • the "up" direction in this specification may differ from the vertical upward direction.
  • a composition may contain, as each component contained in the composition, two or more compounds corresponding to that component.
  • the content of each component in the composition means the total content of all compounds corresponding to that component.
  • the temperature is 23° C.
  • the atmospheric pressure is 101,325 Pa (1 atmosphere)
  • the relative humidity is 50% RH.
  • combinations of preferred embodiments are more preferred embodiments.
  • the resin composition of the present invention is a resin composition containing resin A and photosensitizer B.
  • Resin A contains an amic acid ester structure and an amic acid structure, and further contains at least one structure selected from the group consisting of structures represented by formula (AY1) and structures represented by formula (DY1), the molar amount of the amic acid ester structure relative to the total molar amount of the amic acid structure and the amic acid ester structure in resin A is 90 to 99.9%, and resin A has an amine value of 0.0010 to 0.3000 mmol/g.
  • the resin composition of the present invention is preferably used to form a photosensitive film that is subjected to exposure and development, and more preferably used to form a film that is subjected to exposure and development using a developer containing an organic solvent.
  • the resin composition of the present invention can be used to form, for example, an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, etc., and is preferably used to form an interlayer insulating film for a rewiring layer.
  • a patterned cured layer having high line width uniformity within the wafer surface can be formed.
  • the mechanism by which the above effects are obtained is unknown, but is speculated as follows.
  • environmental amines refer to ammonia and amines in the clean room of the manufacturing equipment, as well as in the equipment and facilities placed in the clean room.
  • Specific examples of amines include methylamine, 2-amino-2-methyl-1-propanol, butylamine, monoethanolamine, and N-methylethanolamine.
  • polyimide refers to a resin having a repeating unit containing an imide group in the molecular chain, and is preferably a resin having a repeating unit containing an imide ring structure in the molecular chain.
  • the polyimide is a linear resin, the polyimide is preferably a resin having a repeating unit containing an imide group in the main chain, and more preferably a resin having a repeating unit containing an imide ring structure in the main chain.
  • the term “main chain” refers to the relatively longest bonding chain in a resin molecule, and the term “side chain” refers to any other bonding chain.
  • the imide ring structure refers to a ring structure containing two carbon atoms and all of the nitrogen atoms in the imide as ring members.
  • the imide ring structure is preferably a five-membered ring.
  • the polyimide may be a so-called polyamideimide, which has an amide group in the molecular chain in addition to an imide group.
  • # represents a bonding site to another structure, preferably a bonding site to a hydrogen atom or a carbon atom, and more preferably a bonding site to a hydrogen atom.
  • Both the amic acid ester structure and the amic acid structure are structures containing an amide group, as will be described later.
  • the ratio of the molar amount of the amic acid ester structure to the total molar amount of the amic acid structure and the amic acid ester structure in the specific resin is 90.00 to 99.90%.
  • the amic acid structure is, for example, one when A 2 is —O— and R 2b is a hydrogen atom in a repeating unit represented by formula (1-b) described below; one when A 3 is —O— and R 3c is a hydrogen atom in a repeating unit represented by formula (1-c); and two when A 41 and A 42 are both —O— and R 41 and R 42 are both hydrogen atoms in a repeating unit represented by formula (1-d).
  • the esterification rate is more preferably 92.00 to 99.50%, and even more preferably 95.00 to 99.00%.
  • the esterification rate calculated by treating the plurality of types of resins as one resin falls within the above range.
  • the esterification rate is a value determined by 1 H-NMR measurement of the resin. Specifically, it can be determined by the measurement method described in the examples below.
  • the imidization rate of the specific resin is preferably 3 to 40%. From the viewpoint of elongation at break, the imidization rate is preferably 5% or more, more preferably 10% or more, and even more preferably 15% or more. From the viewpoint of resolution, the imidization rate is preferably less than 40%, more preferably 35% or less, even more preferably 30% or less, and particularly preferably 25% or less.
  • the imidization rate is a value calculated by the following method.
  • the resin is dissolved in ⁇ -butyrolactone, diluted to a viscosity of 2,000 mPa ⁇ s, and applied to a silicon wafer by spin coating to form a resin layer. If a resin layer cannot be formed due to reasons such as low solubility of the resin in ⁇ -butyrolactone, the solvent may be changed to another solvent. Examples of other solvents include solvents contained in the resin composition, such as NMP. The viscosity may also be adjusted as needed.
  • the silicon wafer to which the resulting resin layer is applied is dried on a hot plate at 110°C for 5 minutes to obtain a resin layer with a uniform thickness of approximately 15 ⁇ m after film formation on the silicon wafer.
  • the film thickness may be adjusted as needed. For example, if the film thickness is 5 ⁇ m or greater, the imidization rate will be approximately the same.
  • the resin layer is measured by the ATR method using a NicoletiS20 (manufactured by Thermofisher) in the measurement range of 4000 to 700 cm ⁇ 1 , with 50 measurements.
  • the peak height near 1380 cm ⁇ 1 (1350 to 1450 cm ⁇ 1 , the peak with the greatest intensity if there are multiple peaks) divided by the peak height near 1500 cm ⁇ 1 (1460 to 1550 cm ⁇ 1 , the peak with the greatest intensity if there are multiple peaks) is defined as the imidization index A of the resin.
  • the imidization index B is calculated in the same manner, and the imidization index A divided by the imidization index B is calculated as the imidization rate of the resin.
  • a resin for which the imidization rate is to be measured can be obtained from the composition, for example, by the following method: A solution of 1 g of the composition and 2 g of tetrahydrofuran is added to 50 g of methanol or water to cause crystallization, and the resin is precipitated and filtered. The residue is recovered, dissolved in 3.0 g of THF (tetrahydrofuran), and added to 50 g of methanol or water to cause crystallization, filtered, and dried at 45°C for 20 hours to obtain a resin.
  • THF tetrahydrofuran
  • the resin can be obtained and measured in the same manner.
  • the imidization rate can be adjusted to 3 to 40% by appropriately changing the reaction conditions such as the reaction temperature during the production of the specific resin.
  • the amine value of the specific resin is 0.0010 to 0.3000 mmol/g. It is believed that the amine value being within the specific range and the presence of side chain carboxylic acid groups in the resin in a range that achieves the above-mentioned predetermined esterification rate provides a buffering effect against environmental amines. From the viewpoint of the storage stability of the composition, the amine value of the specific resin is more preferably 0.0100 to 0.2000 mmol/g, and even more preferably 0.0300 to 0.1000 mmol/g. The lower limit of the amine value is not particularly limited, and may be 0.00 mmol/g.
  • the amine value was measured by dissolving 0.62 g of resin in 50 mL of diglyme, adding 10 mL of acetic acid to prepare a measurement solution, and titrating the solution with a 0.01 N (0.01 mol/L) solution of perchloric acid in acetic acid to detect the neutralization point.
  • the specific resin preferably has an acid value of the acid group at the neutralization point in the pH range of 7.0 to 12.0 in the range of 0.0010 to 0.3000 mmol/g, more preferably 0.0100 to 0.2000 mmol/g, and even more preferably 0.0300 to 0.1000 mmol/g.
  • the acid value of the entire specific resin contained in the resin composition of the present invention is in the range of 0.0010 to 0.3000 mmol/g
  • the acid value of each resin constituting the specific resin contained in the composition may be outside the range of 0.0010 to 0.3000 mmol/g.
  • two or more polymer precursors outside the range of 0.0010 to 0.3000 mmol/g may be blended to adjust the acid value of the entire specific resin contained in the composition to the range of 0.0010 to 0.3000 mmol/g.
  • the resin composition of the present invention preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more of the resin contained in the composition has an acid value in the range of 0.0010 to 0.3000 mmol/g.
  • the acid group having a pH in the range of 7.0 to 12.0 may be bonded to a side chain or a main chain of the specific resin, and preferably, is bonded at least to a side chain of the specific resin.
  • the neutralization point is measured using sodium hydroxide as a base. If it is difficult to measure the neutralization point using sodium hydroxide, the neutralization point may be measured using calcium hydroxide and converted into sodium hydroxide, which is also considered to be the same as the neutralization point measured using sodium hydroxide.
  • the acid value within the above range can be achieved by appropriately adjusting the reaction conditions.
  • the specific resin preferably has a polymerizable group, and more preferably contains a radically polymerizable group.
  • the resin composition it is preferable that at least the resin has a polymerizable group, and it is more preferable that the resin has a polymerizable group and also contains a polymerizable compound separate from the resin.
  • the polymerizability of the specific resin is preferably a radical polymerizable group.
  • the resin composition of the present invention preferably contains a radical polymerization initiator, more preferably contains both a radical polymerization initiator and a radical crosslinking agent. If necessary, a sensitizer may also be contained.
  • a negative photosensitive film can be formed from such a resin composition.
  • the specific resin may also have a polarity conversion group such as an acid-decomposable group.
  • the resin composition preferably contains a photoacid generator. From such a resin composition, for example, a chemically amplified positive-working or negative-working photosensitive film is formed.
  • the specific resin preferably has at least one repeating unit selected from the group consisting of a repeating unit represented by formula (1-b), a repeating unit represented by formula (1-c), and a repeating unit represented by formula (1-d), and may further have a repeating unit represented by formula (1-a).
  • the specific resin preferably has at least a repeating unit represented by formula (1-d), and more preferably has a repeating unit represented by formula (1-d) and at least one repeating unit selected from the group consisting of a repeating unit represented by formula (1-a), a repeating unit represented by formula (1-b), and a repeating unit represented by formula (1-c).
  • X a is a tetravalent organic group
  • Y a is a divalent organic group
  • A2 is —O— or —NR2—
  • R2 is a hydrogen atom or a monovalent organic group
  • R2b is a hydrogen atom or a monovalent organic group
  • Xb is a tetravalent organic group
  • Yb is a divalent organic group.
  • A3 is —O— or —NR Z —
  • R Z is a hydrogen atom or a monovalent organic group
  • R 3c is a hydrogen atom or a monovalent organic group
  • Xc is a tetravalent organic group
  • Yc is a divalent organic group.
  • a 41 and A 42 are each independently —O— or —NR Z —
  • R Z is a hydrogen atom or a monovalent organic group
  • R 41 and R 42 are each independently a hydrogen atom or a monovalent organic group
  • X d is a tetravalent organic group
  • Y d is a divalent organic group.
  • X a preferably has 4 or more carbon atoms, more preferably 4 to 50 carbon atoms, and even more preferably 6 to 40 carbon atoms.
  • X a preferably has any of the structures represented by formulas (2a) to (2e) below, or includes a structure in which two or more hydrogen atoms have been removed from a structure represented by formula (V-4) below.
  • L1 and L2 each independently represent a divalent group that is not conjugated with the benzene ring to which they are bonded, or a single bond
  • *1 to *4 represent bonding sites with the carbonyl group described in formula (1-a), formula (1-b), formula (1-c), or formula (1-d), respectively, and hydrogen atoms in these structures may be substituted with substituents.
  • n1 represents an integer of 1 or more.
  • L 1 and L 2 each independently represent —CH 2 — or —O—.
  • the hydrogen atoms in formulas (2a) to (2e) may be substituted with a substituent.
  • substituents include an alkyl group or a halogenated alkyl group.
  • An alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms is preferred, with a methyl group or a trifluoromethyl group being more preferred.
  • a halogenated alkyl group refers to a group in which at least one hydrogen atom of an alkyl group has been substituted with a halogen atom.
  • the halogen atom is preferably F or Cl, with F being more preferred.
  • n1 is preferably an integer of 1 to 5, more preferably 1 or 2, and even more preferably 1.
  • Xa is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-4)
  • Xa is preferably a group represented by the following formula (V-4-1).
  • * represents the bonding site to the four carbonyl groups to which Xa in formula (1-a) is bonded.
  • the definition and preferred embodiments of n1 are as described above.
  • the hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.
  • X a preferably includes a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of the following formulae (V-1), (V-2), (V-3) and (V-5):
  • R 1 and X1 each independently represent a hydrogen atom, an alkyl group or a halogenated alkyl group.
  • R 1 X2 and R 1 X3 each independently represent a hydrogen atom or a substituent, and R 1 X2 and R 1 X3 may be bonded to form a ring structure.
  • R and X1 are each independently preferably an alkyl group or a halogenated alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group or a trifluoromethyl group.
  • a halogenated alkyl group refers to an alkyl group in which at least one hydrogen atom has been substituted with a halogen atom.
  • the halogen atom is preferably F or Cl, and more preferably F.
  • R 1 X2 and R 1 X3 each independently represent a hydrogen atom.
  • R X2 and R X3 are bonded to form a ring structure
  • the structure formed by bonding R X2 and R X3 is preferably a single bond, —O— or —C(R) 2 —, more preferably —O— or —C(R) 2 —, and even more preferably —O—.
  • R represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom.
  • Xa is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-1)
  • Xa is preferably a group represented by the following formula (V-1-1).
  • * represents the bonding site to which Xa in formula (1-a) bonds with the four carbonyl groups.
  • the hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.
  • Xa is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-2), Xa is preferably a group represented by formula (V-2-1) below.
  • V-2-1 a bond crossing a side of a ring structure means that any of the hydrogen atoms in the ring structure is substituted.
  • * represents the bonding site to the four carbonyl groups to which Xa in formula (1-a) is bonded.
  • R X1 are as described above.
  • the hydrogen atoms in these structures may be further substituted with known substituents such as hydrocarbon groups.
  • Xa is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-3)
  • Xa is preferably a group represented by formula (V-3-1) or formula (V-3-2) below, and from the viewpoint of reducing the dielectric constant of the cured product, a group represented by formula (V-3-2) is preferred.
  • * represents the bonding site to the four carbonyl groups to which Xa in formula (1-a) is bonded.
  • R X2 and R X3 are as described above.
  • the hydrogen atoms in these structures may be further substituted with known substituents such as hydrocarbon groups.
  • Xa is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-5)
  • Xa is preferably a group represented by the following formula (V-5-1).
  • * represents the bonding site to which Xa in formula (1-a) bonds with the four carbonyl groups.
  • the hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.
  • Xa may be a tetracarboxylic acid residue remaining after removal of the anhydride group from a tetracarboxylic acid dianhydride described in paragraphs 0055 to 0057 of JP-A No. 2023-003421.
  • Xa does not contain an imide bond in the structure. Furthermore, it is preferable that Xa does not contain a urethane bond, a urea bond, or an amide bond in the structure.
  • R N is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom.
  • Xa preferably does not contain an imide bond, a urethane bond, a urea bond, or an amide bond, and more preferably does not contain an imide bond, a urethane bond, a urea bond, an amide bond, or an ester bond.
  • Y a preferably has 4 or more carbon atoms, more preferably 4 to 50 carbon atoms, and even more preferably 4 to 40 carbon atoms.
  • Y a may be a group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-1) to (V-10) below.
  • the group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-1) to (V-10) improves the chemical resistance and flatness of the cured product.
  • R 1 and X1 each independently represent a hydrogen atom, an alkyl group or a halogenated alkyl group.
  • R 1 X2 and R 1 X3 each independently represent a hydrogen atom or a substituent, and R 1 X2 and R 1 X3 may be bonded to form a ring structure.
  • R 1 and X5 each independently represent a hydrogen atom, an alkyl group or a halogenated alkyl group.
  • R and X1 are each independently preferably an alkyl group or a halogenated alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group or a trifluoromethyl group.
  • a halogenated alkyl group refers to an alkyl group in which at least one hydrogen atom has been substituted with a halogen atom.
  • the halogen atom is preferably F or Cl, and more preferably F.
  • R X2 and R X3 each independently represent a hydrogen atom.
  • R X2 and R X3 combine to form a ring structure
  • the structure formed by combining R X2 and R X3 is preferably a single bond, -O-, or -C(R) 2 -, more preferably -O- or -C(R) 2 -, and even more preferably -O-.
  • R represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom.
  • R and X5 are each independently preferably an alkyl group or a halogenated alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group or a trifluoromethyl group.
  • a halogenated alkyl group refers to an alkyl group in which at least one hydrogen atom has been substituted with a halogen atom.
  • the halogen atom is preferably F or Cl, and more preferably F.
  • Y a is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-1)
  • Y a is preferably a group represented by the following formula (V-1-2):
  • * represents the bonding site to the two nitrogen atoms to which Y a is bonded in formula (1-a)
  • n1 represents an integer of 0 to 5.
  • the hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.
  • Y a is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-2), Y a is preferably a group represented by formula (V-2-3) or formula (V-2-4) below, and from the viewpoint of reducing the dielectric constant of the cured product, a group represented by formula (V-2-4) is preferred.
  • L X1 represents a single bond or —O—
  • * represents the bonding site between Y a and the two nitrogen atoms in formula (1-a).
  • R X1 are as described above.
  • the hydrogen atoms may be further substituted with known substituents such as hydrocarbon groups.
  • Y a is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-3)
  • Y a is preferably a group represented by formula (V-3-3) or formula (V-3-4) below, and from the viewpoint of reducing the dielectric constant of the cured product, a group represented by formula (V-3-3) is preferred.
  • * represents the bonding site between Y a and the two nitrogen atoms in formula (1-a).
  • R X2 and R X3 are as described above.
  • the hydrogen atoms in these structures may be further substituted with known substituents such as hydrocarbon groups.
  • Y a is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-4), Y a is preferably a group represented by formula (V-4-2) or formula (V-4-3) below.
  • * represents the bonding site to the two nitrogen atoms to which Y a is bonded in formula (1-a)
  • n1 represents an integer of 0 to 5.
  • An embodiment in which n1 is 0 is also one of the preferred embodiments of the present invention.
  • the hydrogen atoms in the structures below may be further substituted with known substituents such as hydrocarbon groups. Examples of known substituents include alkyl groups, halogenated alkyl groups, and halogen atoms.
  • Y a is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-5)
  • Y a is preferably a group represented by formula (V-5-2) below.
  • * represents the bonding site between Y a and the two nitrogen atoms in formula (1-a).
  • the hydrogen atoms in formula (V-5-2) may be further substituted with a known substituent such as a hydrocarbon group. Examples of known substituents include an alkyl group, a halogenated alkyl group, and a halogen atom. However, it is also preferable that none of the hydrogen atoms in the group represented by formula (V-5-2) are substituted.
  • Y a is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-6), Y a is preferably a group represented by the following formula (V-6-2).
  • * represents the bonding site between Y a and the two nitrogen atoms in formula (1-a).
  • the hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.
  • Y a is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-7)
  • Y a is preferably a group represented by the following formula (V-7-2).
  • * represents the bonding site between Y a and the two nitrogen atoms in formula (1-a).
  • the hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.
  • Y a is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-8), Y a is preferably a group represented by formula (V-8-2) below.
  • * represents the bonding site between Y a and the two nitrogen atoms in formula (1-a).
  • R X5 is as described above.
  • the hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.
  • Y a is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-9)
  • Y a is preferably a group represented by the following formula (V-9-2).
  • * represents the bonding site between Y a and the two nitrogen atoms in formula (1-a).
  • the hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.
  • Y a is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-10)
  • Y a is preferably a group represented by the following formula (V-10-2).
  • * represents the bonding site between Y a and the two nitrogen atoms in formula (1-a).
  • the hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.
  • the repeating unit represented by formula (1-a) in which Y a has a structure containing a structure represented by formula (C-1) to formula (C-3) is preferably a repeating unit corresponding to the above-mentioned repeating unit A-1 or repeating unit B-1.
  • the repeating unit represented by formula (1-b) in which Y b has a structure containing a structure represented by formula (C-1) to formula (C-3) is preferably a repeating unit corresponding to the above-mentioned repeating unit A-2 or repeating unit B-2.
  • another embodiment of the specific resin of the present invention is one in which the total content of repeating units represented by formula (1-d) is 50 mol% or more of all repeating units.
  • the total content is more preferably 60 mol% or more, even more preferably 70 mol% or more, and particularly preferably 80 mol% or more.
  • the upper limit of the total content is preferably 97 mol% or less, more preferably 95 mol% or less, even more preferably 90 mol% or less, and particularly preferably 85 mol% or less.
  • the total content of repeating units corresponding to repeating unit B-1, repeating unit B-2, repeating unit B-3, or repeating unit B-4 is preferably 0 to 80 mol% of all repeating units. This total content is more preferably 5 to 70 mol%, even more preferably 10 to 60 mol%, and particularly preferably 15 to 50 mol%.
  • the total content of repeating unit A and repeating unit B in the specific resin of the present invention is preferably 50 mol% or more of all repeating units.
  • the above total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%.
  • all repeating units in the specific resin excluding the terminal repeating units may be repeating unit A or repeating unit B.
  • the specific resin includes a structure represented by formula (1-dp-2d1)
  • the specific resin further includes at least one selected from a structure represented by formula (1-dp-V1-1) and a structure represented by formula (Y-V1-1).
  • the structure represented by formula (1-dp-V1-1) is a partial structure of the repeating unit represented by formula (1-d), and corresponds to a structure in which X d is a structure in which four hydrogen atoms have been removed from the structure represented by formula (V-1), A 41 and A 42 are both —O—, and R 41 and R 42 are both methacryloyloxyethyl groups.
  • the structure represented by formula (Y-V1-1) corresponds to a structure that can exist when, for example, Y b in a repeating unit represented by formula (1-b) is a structure obtained by removing two hydrogen atoms from the structure represented by formula (V-1), and Y d in a repeating unit represented by formula (1-d) is a structure obtained by removing two hydrogen atoms from the structure represented by formula (V-1).
  • the structure represented by formula (Y-V1-1) may constitute the repeating unit represented by formula (1-d) together with the structure represented by formula (1-dp-2d1).
  • the repeating units containing either of these structures preferably account for 10 mol % or more of all repeating units, more preferably 20 mol % or more, and even more preferably 30 mol % or more, and preferably 90 mol % or less, more preferably 85 mol % or less, and even more preferably 80 mol % or less.
  • the specific resin contains at least one structure selected from the group consisting of a structure represented by formula (AY1) and a structure represented by formula (DY1).
  • This structure forms a small and hard resin skeleton structure, which facilitates molecular packing. Therefore, when the resin composition of the present invention is used in semiconductor manufacturing, penetration of environmental amines and developer components into the film is suppressed, and the influence of position dependency within the wafer surface can be reduced.
  • * represents a bonding site to another structure
  • X is a group represented by formula (2a).
  • *1 to *4 each represent a bonding site to a carbonyl group, and the bonding site is not limited.
  • Y is any group selected from the following: * indicates the bonding site to nitrogen.
  • the structure represented by formula (AY1) is a partial structure of the repeating unit represented by formula (1-d), and corresponds to a structure in which X d is a group represented by formula (2a), A 41 and A 42 are both —O—, and R 41 and R 42 are both methacryloyloxyethyl groups.
  • the specific resin preferably contains repeating units including a structure selected from the group consisting of a structure represented by formula (AY1) and a structure represented by formula (DY1) in an amount of 20 mol% or more, more preferably 30 mol% or more, and even more preferably 50 mol% or more, and preferably 90 mol% or less, more preferably 85 mol% or less, and even more preferably 80 mol% or less, of all repeating units.
  • the specific resin preferably contains a structure (specific structure) represented by formula (1).
  • a preferred embodiment of the structure represented by formula (1) will be described later.
  • the specific resin may have the structure represented by formula (1) in the main chain, but preferably has it in the side chain.
  • the term "main chain” refers to the relatively longest bonded chain in the molecule of the polymer compound that constitutes the resin
  • the term "side chain” refers to any other bonded chain.
  • Examples of the structure of the specific resin containing the structure represented by formula (1) include structures that satisfy at least one of the following: (* indicates the bonding position to X b , X c , or X d ).
  • *Contains a repeating unit in which *-C( O)-A 2 -R 2b in the repeating unit represented by formula (1-b) is replaced with a group containing the structure represented by formula (1).
  • *Contains a repeating unit in which *-C( O)-A 3 -R 3c in the repeating unit represented by formula (1-c) is replaced with a group containing the structure represented by formula (1).
  • the specific resin contains a structure having a structure represented by formula (1) in the terminal imide ring as shown in the following formula.
  • R 132 represents a tetravalent organic group
  • R X1 and R X2 each independently represent a group or an organic group containing a structure represented by formula (1)
  • at least one of R X1 and R X2 is a group containing a structure represented by formula (1-1).
  • Preferred examples of the "group containing a structure represented by formula (1)" include groups represented by formula (X-1) described below.
  • the resin composition may contain a specific resin containing a structure represented by formula (1) and a specific resin not containing a structure represented by formula (1).
  • the content of the structure represented by formula (1) in the specific resin is, for example, preferably 0.01 to 1.0 mmol/g, and more preferably 0.01 to 0.85 mmol/g.
  • the weight average molecular weight (Mw) of the specific resin is preferably 120,000 or less, more preferably 50,000 or less, and even more preferably 40,000 or less.
  • the Mw is preferably at least 5,000, more preferably at least 10,000, and even more preferably at least 15,000.
  • the weight average molecular weight (Mw) of the specific resin is particularly preferably from 15,000 to 40,000.
  • the number average molecular weight (Mn) of the specific resin is preferably 40,000 or less, more preferably 30,000 or less, and even more preferably 20,000 or less.
  • the Mn is preferably 2,000 or more, more preferably 3,000 or more, and even more preferably 4,000 or more.
  • the molecular weight dispersity of the specific resin is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more.
  • the upper limit of the molecular weight dispersity of the specific resin is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
  • the molecular weight dispersity is a value calculated by dividing the weight average molecular weight by the number average molecular weight.
  • the weight-average molecular weight, number-average molecular weight, and dispersity of at least one resin are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated by treating the multiple resins as one resin are each within the above-mentioned ranges.
  • the specific resin is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine.
  • the specific resin is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent such as thionyl chloride, and then reacting the halogenated dicarboxylic acid or the dicarboxylic acid derivative with a diamine.
  • Non-halogen catalyst without using the above-mentioned halogenating agent.
  • Any known amidation catalyst that does not contain halogen atoms can be used as the non-halogen catalyst without any particular restrictions.
  • catalysts include boroxine compounds, N-hydroxy compounds, tertiary amines, phosphate esters, amine salts, urea compounds, and carbodiimide compounds.
  • carbodiimide compounds include N,N'-diisopropylcarbodiimide, N,N'-dicyclohexylcarbodiimide, and (2,6-diisopropylphenyl)carbodiimide.
  • the organic solvent may be one type or two or more types.
  • the organic solvent can be appropriately selected depending on the raw materials, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone.
  • a monoamine As the end-capping agent, it is more preferable to use a monoamine, and preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-8-aminonaphthalene, 1-carboxy-9-aminonaphthalene, 1-carboxy-10-aminonaphthalene, 1-carboxy-11-aminonaphthalene, 1-carboxy-12-aminonaphthalene
  • Examples include 5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these may be used, and multiple different terminal groups may be introduced by reacting multiple terminal-capping agents.
  • the production of the specific resin may include a step of precipitating a solid. Specifically, the polyimide precursor or the like in the reaction solution is precipitated in water, and then the precipitate is dissolved in a solvent in which the specific resin is soluble, such as tetrahydrofuran, to precipitate a solid. Thereafter, the specific resin is dried to obtain a powdery specific resin or the like.
  • the specific resin contains a structure represented by formula (1)
  • the specific resin is synthesized, for example, by the method described in (1) or (2) below.
  • a carbodiimide compound is used as a non-halogen catalyst, and the reaction time, reaction temperature, and timing of adding the carbodiimide compound are appropriately adjusted.
  • the polyimide precursor obtained by the method for producing the specific resin is reacted with a carbodiimide compound in a solvent. Specific examples of these methods include, but are not limited to, the methods described in the synthesis examples below.
  • the content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the resin composition. Also, the content of the specific resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the resin composition.
  • the resin composition of the present invention may contain the above-mentioned specific resin and another resin different from the specific resin (hereinafter, also simply referred to as "another resin").
  • other resins include polybenzoxazole precursors, polybenzoxazoles, polyamides that do not fall under the category of polyimide precursors, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins.
  • a resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained.
  • a (meth)acrylic resin having a weight average molecular weight of 20,000 or less and a high polymerizable group value for example, the molar amount of polymerizable groups contained in 1 g of resin is 1 ⁇ 10 -3 mol/g or more
  • the resin composition it is possible to improve the coatability of the resin composition and the solvent resistance of the pattern (cured product), etc.
  • the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 1% by mass or more, still more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more, relative to the total solid content of the resin composition.
  • the content of the other resins is preferably 80 mass% or less, more preferably 75 mass% or less, even more preferably 70 mass% or less, still more preferably 60 mass% or less, and even more preferably 50 mass% or less, relative to the total solid content of the resin composition.
  • a preferred embodiment of the resin composition of the present invention may be an embodiment in which the content of the other resin is low.
  • the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the resin composition.
  • the lower limit of the content is not particularly limited, and may be 0% by mass or more.
  • the resin composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.
  • R 11 and R 12 are both groups represented by formula (R-1).
  • R 11 and R 12 are a hydrogen atom or a monovalent organic group other than the group represented by formula (R-1)
  • one of R 11 and R 12 is a monovalent organic group other than the group represented by formula (R-1).
  • Examples of the monovalent organic group different from the group represented by formula (R-1) include an alkyl group and an aryl group, with an alkyl group being preferred and a methyl group being more preferred.
  • R 21 and R 22 are the same as the preferred embodiments of R 11 and R 12 in formula (AN-1).
  • Ar 2 represents an aromatic ring structure which may have a substituent or a fused ring.
  • the aromatic ring structure include a benzene ring structure, a carbazole ring structure, and a fluorene ring structure.
  • the substituent include an alkyl group, an aryl group, and a halogen atom, with an alkyl group being preferred and a methyl group being more preferred.
  • the fused ring may be a cycloalkane, an aromatic ring, or the like, with a cyclopropane ring being preferred.
  • Specific examples of Ar2 are listed below, but the present invention is not limited to these. In the specific examples below, * represents the bonding site with the nitrogen atom in formula (AN-2).
  • n2 is preferably an integer of 1 to 3, and more preferably 1 or 2.
  • the molecular weight of compound A is preferably 1,000 or less, more preferably 800 or less, and even more preferably 500 or less.
  • the lower limit of the molecular weight is not particularly limited, but is preferably 150 or more, and more preferably 200 or more.
  • the content of the aniline compound is preferably 0.01 to 20 mass%, more preferably 0.1 to 15 mass%, and even more preferably 0.5 to 10 mass%, based on the total solids content of the resin composition.
  • the aniline compound may be used alone or in combination with two or more types.
  • sensitizing dyes may also be used as the sensitizer.
  • Usable sensitizers include benzophenone-based, Michler's ketone-based, coumarin-based, pyrazole azo-based, anilino azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, and indigo-based compounds.
  • the sensitizing dye please refer to the descriptions in paragraphs 0161 to 0163 of JP-A-2016-027357, the contents of which are incorporated herein by reference.
  • the resin composition of the present invention may contain a chain transfer agent.
  • Chain transfer agents are defined, for example, in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pages 683-684.
  • Examples of chain transfer agents include compounds having -S-S-, -SO 2 -S-, -N-O-, SH, PH, SiH, and GeH in the molecule, and dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthate compounds having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These donate hydrogen to low-activity radicals to generate radicals, or can generate radicals by being oxidized and then deprotonated. Thiol compounds are particularly preferred.
  • chain transfer agent may be the compound described in paragraphs 0152-0153 of WO 2015/199219, the contents of which are incorporated herein by reference.
  • the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the total solids content of the resin composition. Only one type of chain transfer agent may be used, or two or more types may be used. When two or more types of chain transfer agents are used, the total amount is preferably within the above range.
  • the resin composition of the present invention preferably contains a structure (specific structure) represented by formula (1):
  • * 1 and * 2 each independently represent a bonding site to another structure.
  • the structure represented by formula (1) is contained in the solid content of the resin composition.
  • the structure represented by formula (1) may be contained in the structure of a specific resin, or the resin composition may contain a compound that contains a structure represented by formula (1) but is different from the above-mentioned resin (hereinafter also referred to as a "specific compound").
  • the resin composition may contain a resin having a structure represented by formula (1) and also contain a specific compound.
  • the resin composition of the present invention contains a structure represented by formula (1) and also contains a nitrogen-containing heterocyclic compound
  • the interaction between the specific structure and the nitrogen-containing heterocyclic compound is believed to result in the nitrogen-containing heterocyclic compound, which acts as a rust inhibitor, being uniformly distributed at the interface between copper and polyimide, thereby uniformly inhibiting copper corrosion.
  • the specific resin has an imide ring structure
  • the imide ring structure in the specific resin, the specific structure, and the nitrogen-containing heterocyclic compound form multi-point hydrogen bonds, allowing the nitrogen-containing heterocyclic compound to be uniformly dispersed in the resin film.
  • the carbonyl group in the imide ring can also interact with copper, resulting in the nitrogen-containing heterocyclic compound, which functions as a rust inhibitor, being uniformly distributed at the interface between copper and polyimide. This is believed to result in uniform inhibition of copper corrosion and the prevention of short circuits.
  • R1 and R2 each independently represent a phenyl group which may be substituted with a saturated aliphatic hydrocarbon group having 3 to 6 carbon atoms or an alkyl group having 1 to 10 carbon atoms.
  • a saturated aliphatic hydrocarbon group having 3 to 10 carbon atoms an isopropyl group or a cyclohexyl group is more preferable.
  • alkyl group having 1 to 10 carbon atoms which the phenyl group may have as a substituent a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 5 to 10 carbon atoms is preferable, a branched alkyl group having 3 to 6 carbon atoms is more preferable, and an isopropyl group is even more preferable.
  • the phenyl group has substituents the number of substituents is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3, and even more preferably 2.
  • R 1 and R 2 are each independently an isopropyl group, a cyclohexyl group, or a phenyl group which may be substituted with an isopropyl group.
  • X 1 represents an oxygen atom or a sulfur atom, and is preferably an oxygen atom.
  • L 1 represents —C( ⁇ O)— or —S( ⁇ O) 2 —, and —C( ⁇ O)— is preferred.
  • R 1 , R 2 , the structure bonded to * 1 , and the structure bonded to * 2 may be bonded to form a ring structure.
  • the ring structure formed include, but are not limited to, a hydantoin ring and an N-acylimidazolidinone ring.
  • an embodiment in which none of R 1 , R 2 , the structure bonded to * 1 , and the structure bonded to * 2 form a ring structure is also one of the preferred embodiments.
  • the structure represented by formula (1) is preferably contained as a group represented by the following formula (X-1).
  • R 1 , R 2 , X 1 and L 1 have the same meanings as R 1 , R 2 , X 1 and L 1 in formula (1), respectively, and preferred embodiments are also the same.
  • R3 represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group, and more preferably a hydrogen atom. Examples of the aliphatic hydrocarbon group or aromatic hydrocarbon group include the groups exemplified above for R1 .
  • the molar amount of the structure represented by formula (1) relative to the total solid content of the resin composition of the present invention is 0.005 to 0.5 mmol/g, preferably 0.01 mmol/g to 0.3 mmol/g, and more preferably 0.015 to 0.2 mmol/g.
  • the molar amount is equal to or less than the upper limit, it is considered that a cured film having excellent storage stability of the composition is more likely to be obtained, for example, by suppressing cyclization of the polyimide precursor and suppressing scission of the main chain of the specific resin.
  • the method for measuring the content is not particularly limited, but examples thereof include the measurement methods described in the examples below.
  • the method for measuring the total solids content is not particularly limited, but examples thereof include the measurement method described in the Examples below, and a method in which the resin composition is dried by setting the temperature and pressure while confirming that there are no volatile components other than the solvent.
  • the method for measuring the total solids content is not limited to this, as long as it can determine the content of components other than the solvent in the resin composition as the total solids content.
  • the content is the molar amount of the structure represented by formula (1) relative to the total solid content of the resin composition. For example, when the resin composition contains a resin having a structure represented by formula (1) and also contains a specific compound, the content is the total amount of the structure represented by formula (1) contained in the resin and the structure represented by formula (1) contained in the specific compound.
  • the resin composition of the present invention may contain a compound (specific compound) that contains the structure represented by the above formula (1) and is different from the above resin.
  • the specific compound is not particularly limited except that it contains the structure represented by formula (1), but is preferably a low molecular weight compound. Specifically, the molecular weight of the specific compound is preferably 75 to 1,000, more preferably 100 to 800, and even more preferably 150 to 500.
  • R 1 , R 2 , X 1 and L 1 have the same meanings as R 1 , R 2 , X 1 and L 1 in formula (1), respectively, and the preferred embodiments are also the same.
  • R 3 has the same meaning as R 3 in formula (X-1), and preferred embodiments are also the same.
  • R 4 is a monovalent organic group, and is preferably a hydrocarbon group.
  • the hydrocarbon group is preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and more preferably an aromatic hydrocarbon group.
  • the aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably a saturated aliphatic hydrocarbon group having 3 to 10 carbon atoms.
  • the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably a phenyl group or a naphthyl group, and even more preferably a phenyl group.
  • R 1 , R 2 , R 3 and R 4 may be bonded to form a ring structure.
  • the ring structure formed include, but are not limited to, a hydantoin ring and an N-acylimidazolidinone ring.
  • an embodiment in which none of R 1 , R 2 , R 3 and R 4 form a ring structure is also one of the preferred embodiments.
  • the molar amount of the structure represented by formula (1) relative to the total solid content of the resin composition may be appropriately adjusted to fall within the above range.
  • the content thereof is, for example, preferably 0.01 to 15.0 mass%, more preferably 0.05 to 10 mass%, and even more preferably 0.1 to 5.0 mass%, relative to the total solid content of the resin composition of the present invention.
  • the specific compound may be used alone or in combination of two or more kinds. When two or more kinds are used in combination, the total amount thereof is preferably in the above range.
  • the resin composition of the present invention may contain at least one compound selected from the group consisting of urea compounds, carbodiimide compounds, and isourea compounds (hereinafter also referred to as "urea compound, etc.”).
  • urea compound examples include a compound represented by the following formula (UR-1)
  • examples of the carbodiimide compound include a compound represented by the following formula (UR-2)
  • examples of the isourea compound include a compound represented by the following formula (UR-3).
  • R 11 and R 12 each independently represent an aliphatic hydrocarbon group of 1 to 7 carbon atoms which may have a substituent
  • R 21 and R 22 each independently represent an aliphatic hydrocarbon group of 1 to 7 carbon atoms which may have a substituent
  • R 31 and R 32 each independently represent an aliphatic hydrocarbon group of 1 to 7 carbon atoms which may have a substituent
  • R 33 represents an aliphatic hydrocarbon group of 1 to 7 carbon atoms which may have a substituent.
  • R 11 and R 12 each independently represent preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, or an aliphatic hydrocarbon group having 1 to 7 carbon atoms and having at least one substituent selected from the group consisting of a primary amine salt structure, a secondary amine salt structure, a tertiary amino group, a tertiary amine salt structure, and a quaternary ammonium group, and more preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms.
  • the unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms for R 11 and R 12 is preferably an unsubstituted saturated aliphatic hydrocarbon group having 1 to 7 carbon atoms, more preferably an unsubstituted saturated aliphatic hydrocarbon group having 2 to 7 carbon atoms, and more preferably an ethyl group, an isopropyl group, a t-butyl group, or a cyclohexyl group.
  • R 11 and R 12 may each independently represent an aliphatic hydrocarbon group having 2 to 7 carbon atoms and having at least one substituent selected from the group consisting of a hydroxy group, an alkoxy group, a thiol group, and an alkylthio group.
  • the aliphatic hydrocarbon group having 2 to 7 carbon atoms may have two or more of the above-mentioned substituents, but it is also preferable that the aliphatic hydrocarbon group have only one of the above-mentioned substituents.
  • R 21 and R 22 each independently represent an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent.
  • R 21 and R 22 are preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, or an aliphatic hydrocarbon group having 1 to 7 carbon atoms and having an amino group or a quaternary ammonium group as a substituent, and more preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms.
  • R 31 and R 32 are preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, or an aliphatic hydrocarbon group having 1 to 7 carbon atoms and having an amino group or a quaternary ammonium group as a substituent, and more preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms.
  • preferred embodiments of the unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms or the substituted aliphatic hydrocarbon group having 1 to 7 carbon atoms for R 31 and R 32 are the same as those described above for R 11 and R 12 , respectively.
  • R 33 represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, and is preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, more preferably an unsubstituted saturated aliphatic hydrocarbon group having 1 to 7 carbon atoms, and even more preferably a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms.
  • R 33 is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or a t-butyl group, and more preferably an ethyl group.
  • urea compounds include, but are not limited to, dicyclohexylurea, diisopropylurea, dicyclohexylcarbodiimide, diisopropylcarbodiimide, dicyclohexylisourea, and diisopropylisourea.
  • the resin composition of the present invention preferably contains a polymerizable compound.
  • the polymerizable compound may be a radical crosslinking agent or other crosslinking agent.
  • the molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less.
  • the lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.
  • the radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure.
  • Examples of compounds having a boiling point of 100°C or higher under normal pressure include the compounds described in paragraph 0203 of WO 2021/112189, the contents of which are incorporated herein by reference.
  • radical crosslinking agents other than those mentioned above include the radical polymerizable compounds described in paragraphs 0204 to 0208 of WO 2021/112189, the contents of which are incorporated herein by reference.
  • Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available products include KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available products include KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available products include KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available products include KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)), and structures in which
  • radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate with four ethyleneoxy chains, SR-209, 231, and 239, difunctional methacrylates with four ethyleneoxy chains (all manufactured by Sartomer Corporation), DPCA-60, a hexafunctional acrylate with six pentyleneoxy chains, and TPA-330, a trifunctional acrylate with three isobutyleneoxy chains (all manufactured by Nippon Kayaku Co., Ltd.), and urethane oligomers.
  • SR-494 a tetrafunctional acrylate with four ethyleneoxy chains
  • SR-209, 231, and 239 difunctional methacrylates with four ethyleneoxy chains
  • DPCA-60 a hexafunctional acrylate with six pentyleneoxy chains
  • TPA-330 a trifunctional acrylate with three isobutyleneoxy chains (all manufactured by Nippon Kayaku Co., Ltd.), and urethane oligomers.
  • esters examples include UAS-10 and UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, and UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), and Blenmar PME400 (manufactured by NOF Corporation).
  • Suitable radical crosslinking agents include urethane acrylates such as those described in JP-B No. 48-041708, JP-A No. 51-037193, JP-B No. 02-032293, and JP-B No. 02-016765, as well as urethane compounds with an ethylene oxide skeleton such as those described in JP-B No. 58-049860, JP-B No. 56-017654, JP-B No. 62-039417, and JP-B No. 62-039418.
  • Compounds with an amino structure or sulfide structure in the molecule such as those described in JP-A Nos. 63-277653, 63-260909, and JP-A No. 01-105238, can also be used as radical crosslinking agents.
  • a radical crosslinking agent in which an acid group is imparted by reacting a non-aromatic carboxylic anhydride with the unreacted hydroxy groups of an aliphatic polyhydroxy compound, in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol.
  • examples of commercially available products include polybasic acid-modified acrylic oligomers M-510 and M-520 manufactured by Toagosei Co., Ltd.
  • the radical crosslinking agent is preferably a radical crosslinking agent having at least one selected from the group consisting of a urea bond and a urethane bond (hereinafter also referred to as "crosslinking agent U").
  • crosslinking agent U a radical crosslinking agent having at least one selected from the group consisting of a urea bond and a urethane bond.
  • crosslinking agent U examples include compounds described in paragraphs 0133 to 0143 of WO 2023/190064, the contents of which are incorporated herein by reference.
  • a bifunctional methacrylate or acrylate for the resin composition.
  • Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexyl methyl ...
  • the content of the radical crosslinking agent is preferably more than 0% by mass and not more than 60% by mass, based on the total solids content of the resin composition.
  • the lower limit is more preferably 5% by mass or more.
  • the upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.
  • the acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
  • Other cross-linking agents include the compounds described in paragraphs 0179 to 0207 of WO 2022/145355, which are incorporated herein by reference.
  • the content of the other crosslinking agent is preferably 0.1 to 30 mass% of the total solids content of the resin composition, more preferably 0.1 to 20 mass%, even more preferably 0.5 to 15 mass%, and particularly preferably 1.0 to 10 mass%. Only one type of other crosslinking agent may be contained, or two or more types may be contained. When two or more types of other crosslinking agents are contained, the total amount is preferably within the above range.
  • the resin composition of the present invention may contain a base generator.
  • the base generator is a compound that can generate a base by physical or chemical action.
  • Preferred base generators include thermal base generators and photobase generators.
  • a thermal base generator in the resin composition, the cyclization reaction of the precursor can be promoted, for example, by heating, and the mechanical properties and chemical resistance of the cured product can be improved, resulting in good performance as an interlayer insulating film for a rewiring layer included in, for example, a semiconductor package.
  • the base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines.
  • the base generator is not particularly limited, and known base generators can be used, such as carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, ⁇ -aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, ⁇ -lactone ring derivative compounds, phthalimide derivative compounds, and acyloxyimino compounds.
  • Specific examples of non-ionic base generators include the compounds described in paragraphs 0249 to 0275 of WO 2022/145355, the disclosures of which are incorporated herein by reference.
  • Base generators include, but are not limited to, the following compounds:
  • the molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less.
  • the lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.
  • Specific preferred compounds for the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of WO 2018/038002.
  • ammonium salts include, but are not limited to, the following compounds:
  • iminium salts include, but are not limited to, the following compounds:
  • the base generator is an amine in which the amino group is protected with a t-butoxycarbonyl group.
  • ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, propylene glycol
  • alcohols examples include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.
  • Another preferred embodiment of the present invention is to further add toluene to these combined solvents in an amount of about 1 to 10% by mass, based on the total mass of the solvents.
  • the resin composition of the present invention preferably contains a metal adhesion improver from the viewpoint of improving adhesion to metal materials used in electrodes, wiring, etc.
  • metal adhesion improvers include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure, compounds having a thiourea structure, phosphoric acid derivative compounds, ⁇ -ketoester compounds, and amino compounds.
  • metal adhesion improvers that can be used include the compounds described in paragraphs 0046 to 0049 of JP 2014-186186 A and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP 2013-072935 A, the contents of which are incorporated herein by reference.
  • the content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. By ensuring that the content is above the above lower limit, the adhesion between the pattern and the metal layer will be good, and by ensuring that the content is below the above upper limit, the heat resistance and mechanical properties of the pattern will be good. Only one type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above range.
  • the resin composition of the present invention also preferably contains a compound (light absorber) that reduces the absorbance of light at the exposure wavelength upon exposure.
  • a compound light absorber
  • Examples of the light absorber include the compounds described in paragraphs 0159 to 0183 of WO 2022/202647 and the compounds described in paragraphs 0088 to 0108 of JP 2019-206689 A. The contents of these compounds are incorporated herein by reference.
  • the content of the light absorber relative to the total solid content of the resin composition of the present invention is not particularly limited, but is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 5% by mass.
  • the resin composition preferably further contains a nitrogen-containing heterocyclic compound, which acts as a migration inhibitor and can effectively inhibit, for example, migration of metal ions derived from the metal layer (or metal wiring) into the film when the resin composition is applied to the metal layer (or metal wiring) to form a film.
  • nitrogen-containing heterocyclic compounds particularly 8-azaadenine, can form hydrogen bonds with carboxylic acid groups in the specific resin having the above-mentioned esterification rate, thereby suppressing the formation of copper oxide films.
  • an esterification rate of the resin of 99.90% or less allows the nitrogen-containing heterocyclic compound to be effectively distributed near the copper wiring through interaction with the carboxylic acid groups of the resin. Furthermore, an esterification rate of the resin of 90.00% or more prevents the copper corrosion effect of the carboxylic acid groups from exceeding the rust-preventing effect of the nitrogen-containing heterocyclic compound.
  • the nitrogen-containing heterocyclic compound is not particularly limited, but is preferably a nitrogen-containing aromatic heterocyclic compound, such as a compound having a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring, a morpholine ring, a triazine ring, or a nitrogen-containing fused ring (such as a purine ring).
  • a nitrogen-containing aromatic heterocyclic compound such as a compound having a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring,
  • triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole
  • tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole
  • 8-azaadenine are preferably used.
  • the resin composition preferably contains 8-azaadenine.
  • the content of the nitrogen-containing heterocyclic compound is preferably 0.01 to 5.0 mass%, more preferably 0.05 to 2.0 mass%, and even more preferably 0.1 to 1.0 mass%, based on the total solids content of the resin composition.
  • migration inhibitors include compounds having a furan ring, compounds having a thiophene ring, thioureas and compounds having a sulfanyl group, hindered phenol compounds, salicylic acid derivative compounds, hydrazide derivative compounds, rust inhibitors described in paragraph 0094 of JP 2013-015701 A, compounds described in paragraphs 0073 to 0076 of JP 2009-283711 A, compounds described in paragraph 0052 of JP 2011-059656 A, compounds described in paragraphs 0114, 0116 and 0118 of JP 2012-194520 A, compounds described in paragraph 0166 of WO 2015/199219 A can be used, the contents of which are incorporated herein by reference.
  • an ion trapping agent that traps anions such as halogen ions can also be used.
  • the content of the other migration inhibitors is preferably 0.01 to 5.0 mass%, more preferably 0.05 to 2.0 mass%, and even more preferably 0.1 to 1.0 mass%, based on the total solids content of the resin composition.
  • the other migration inhibitors may be one type only, or two or more types. When two or more types of migration inhibitors are used, it is preferable that the total amount thereof is within the above range. It is also preferable that the total amount of the nitrogen-containing heterocyclic compound and the other migration inhibitors is within the above range.
  • Usable organic titanium compounds include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.
  • Specific examples of the organotitanium compound are shown below as I) to VII):
  • I) Titanium chelate compounds Titanium chelate compounds having two or more alkoxy groups are more preferred because they provide good storage stability to the resin composition and a good curing pattern.
  • titanium bis(triethanolamine) diisopropoxide titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), and titanium diisopropoxide bis(ethylacetoacetate).
  • Tetraalkoxytitanium compounds for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis ⁇ 2,2-(allyloxymethyl)butoxide ⁇ ], etc.
  • Titanocene compounds for example, pentamethylcyclopentadienyltitanium trimethoxide, bis( ⁇ 5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis( ⁇ 5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like.
  • Monoalkoxytitanium compounds For example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc.
  • Specific examples of compounds represented by formula (T-1) include, but are not limited to, compounds I-1 and I-2 in the examples.
  • an organotitanium compound is included, its content is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin. If the content is 0.05 parts by mass or more, the heat resistance and chemical resistance of the resulting cured pattern will be better, and if it is 10 parts by mass or less, the storage stability of the composition will be superior.
  • the antioxidant prevents oxidation of the metal, and therefore, the cured product containing the antioxidant has excellent adhesion. Furthermore, since the antioxidant inhibits polymerization of the polymerizable compound during storage of the resin composition, it is believed that a resin composition containing an antioxidant has excellent storage stability and excellent resolution of the resulting cured product.
  • the antioxidant preferably has an isocyanuric acid skeleton, and more preferably is a hindered phenol compound having an isocyanuric acid skeleton.
  • antioxidants include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, and the compound represented by formula (3).
  • R5 represents a hydrogen atom or an alkyl group having 1 or more carbon atoms
  • R6 represents an alkylene group having 1 or more carbon atoms, an alkylenecarbonyl group having 2 or more carbon atoms, or an alkylenecarbonyloxy group having 2 or more carbon atoms
  • R7 represents a monovalent to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms, an O atom, and an N atom
  • i represents an integer of 1 to 4
  • j represents an integer of 0 to 4
  • i+j is an integer of 1 to 4
  • k represents an integer of 1 to 4.
  • R7 examples include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, -O-, -NH-, -NHNH-, and combinations thereof, and may further have a substituent.
  • alkyl ether, —NH—, and isocyanuric rings are preferred from the viewpoint of developability and metal adhesion, and isocyanuric rings are more preferred from the viewpoint of interaction with resins and metal adhesion due to metal complex formation.
  • i is preferably 1 or 2, and more preferably 1.
  • j is preferably an integer of 0 to 3, and more preferably an integer of 0 to 2.
  • k is more preferably an integer of 2 to 4.
  • Examples of compounds represented by the following general formula (3) include, but are not limited to, the following structures:
  • antioxidants include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.
  • these compounds include the compounds described in paragraph 0310 of WO 2021/112189, p-hydroquinone, o-hydroquinone, p-methoxyphenol, 2-nitroso-1-naphthol, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenoxazine, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-N,N-dioxide, and the like.
  • the contents of this document are incorporated herein by reference.
  • phosphorus-based antioxidants can also be suitably used.
  • examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl)oxy]ethyl]amine, and ethylbis(2,4-di-tert-butyl-6-methylphenyl)phosphite.
  • antioxidants include, for example, ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-50F, ADK STAB AO-60, ADK STAB AO-60G, ADK STAB AO-80, and ADK STAB AO-330 (all manufactured by ADEKA Corporation).
  • the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used as antioxidants.
  • the composition of the present invention may also contain a latent antioxidant, if necessary.
  • latent antioxidants include compounds in which the moiety functioning as an antioxidant is protected with a protecting group, and which function as an antioxidant upon heating at 100 to 250°C or at 80 to 200°C in the presence of an acid/base catalyst, whereby the protecting group is eliminated.
  • latent antioxidants include compounds described in WO 2014/021023, WO 2017/030005, and JP 2017-008219 A.
  • Commercially available latent antioxidants include ADEKA ARCLES GPA-5001 (manufactured by ADEKA Corporation).
  • the content of the antioxidant is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin.
  • the content of the antioxidant is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin.
  • the resin composition of the present invention preferably contains a polymerization inhibitor, such as a phenolic compound, a quinone compound, an amino compound, an N-oxyl free radical compound, a nitro compound, a nitroso compound, a heteroaromatic ring compound, or a metal compound.
  • a polymerization inhibitor such as a phenolic compound, a quinone compound, an amino compound, an N-oxyl free radical compound, a nitro compound, a nitroso compound, a heteroaromatic ring compound, or a metal compound.
  • the total content is preferably 3% by mass or less of the solid content of the resin composition of the present invention.
  • the fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. Fluorosurfactants with a fluorine content within this range are effective in terms of uniformity of the coating film thickness and liquid saving, and also have good solubility in the composition.
  • silicone surfactants examples include the compounds described in paragraphs 0329 to 0334 of WO 2021/112189, the contents of which are incorporated herein by reference.
  • the surfactant may be used alone or in combination of two or more.
  • the content of the surfactant is preferably from 0.001 to 2.0% by mass, more preferably from 0.005 to 1.0% by mass, based on the total solid content of the composition.
  • inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.
  • the average particle size of the inorganic particles is preferably from 0.01 to 2.0 ⁇ m, more preferably from 0.02 to 1.5 ⁇ m, even more preferably from 0.03 to 1.0 ⁇ m, and particularly preferably from 0.04 to 0.5 ⁇ m.
  • the above-mentioned average particle size of the inorganic particles is the primary particle size and also the volume average particle size, which can be measured by a dynamic light scattering method using, for example, a Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). When the above measurement is difficult, the measurement can also be performed by a centrifugal sedimentation light transmission method, an X-ray transmission method, or a laser diffraction/scattering method.
  • the viscosity of the resin composition of the present invention at 23°C can be adjusted by the solids concentration of the resin composition. From the viewpoint of coating film thickness, it is preferably 1,000 mm 2 /s to 12,000 mm 2 /s, more preferably 2,000 mm 2 /s to 10,000 mm 2 /s, and even more preferably 2,500 mm 2 /s to 8,000 mm 2 /s. Within the above range, it is easy to obtain a highly uniform coating film.
  • the water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If the water content is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining the moisture content include adjusting the humidity during storage and reducing the porosity of the container during storage.
  • the metal content of the resin composition of the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass.
  • metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but this does not include metals contained as complexes of organic compounds with metals. When multiple metals are contained, it is preferable that the total amount of these metals is within the above range.
  • methods for reducing metal impurities unintentionally contained in the resin composition of the present invention include selecting raw materials with low metal content as the raw materials for constituting the resin composition of the present invention, filtering the raw materials for constituting the resin composition of the present invention, and lining the inside of the apparatus with polytetrafluoroethylene or the like to perform distillation under conditions that minimize contamination as much as possible.
  • the organic solvent preferably accounts for 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, of the total mass of the rinse solution.
  • the organic solvent may account for 100% by mass of the total mass of the rinse solution.
  • the method of supplying the rinse liquid is not particularly limited as long as it can form a desired pattern, and examples thereof include a method of immersing the substrate in the rinse liquid, a method of supplying the rinse liquid to the substrate by puddling, a method of supplying the rinse liquid to the substrate by showering, and a method of continuously supplying the rinse liquid onto the substrate by means of a straight nozzle or the like.
  • the rinse liquid can be supplied using a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuously supplying the rinse liquid using a spray nozzle is preferred, and from the viewpoint of the permeability of the rinse liquid into the image areas, the method of supplying the rinse liquid using a spray nozzle is more preferred.
  • the type of nozzle is not particularly limited, and examples include a straight nozzle, a shower nozzle, a spray nozzle, etc.
  • the rinsing step is preferably a step of supplying a rinsing liquid to the exposed film through a straight nozzle or continuously supplying the rinsing liquid to the exposed film, and more preferably a step of supplying the rinsing liquid through a spray nozzle.
  • the method of supplying the rinse liquid in the rinsing step may include a step of continuously supplying the rinse liquid to the substrate, a step of keeping the rinse liquid substantially stationary on the substrate, a step of vibrating the rinse liquid on the substrate by ultrasonic waves or the like, and a combination of these steps.
  • the rinsing time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes.
  • the temperature of the rinse solution during rinsing is not particularly specified, but is preferably 10 to 45°C, and more preferably 18 to 30°C.
  • the development process may include a step of contacting the pattern with a processing liquid after treatment with a developer or after washing the pattern with a rinse liquid. It may also be possible to employ a method in which the processing liquid is supplied before the developer or rinse liquid in contact with the pattern has completely dried.
  • the pattern obtained by the development step (if a rinsing step is performed, the pattern after rinsing) may be subjected to a heating step in which the pattern obtained by the development step is heated. That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained in the development step. The method for producing a cured product of the present invention may also include a heating step of heating a pattern obtained by another method without performing a development step, or a film obtained in the film-forming step. In the heating step, the resin such as the polyimide precursor is cyclized to form a resin such as a polyimide.
  • the pattern obtained by the development step (which is preferably subjected to at least one of the heating step and the post-development exposure step) may be subjected to a metal layer forming step in which a metal layer is formed on the pattern. That is, the method for producing a cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on the pattern obtained by the development step (preferably the pattern has been subjected to at least one of a heating step and a post-development exposure step).
  • the metal layer is not particularly limited and any existing metal species can be used, including copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are more preferred, and copper is even more preferred.
  • the method for forming the metal layer is not particularly limited, and existing methods can be applied.
  • the methods described in JP 2007-157879 A, JP 2001-521288 A, JP 2004-214501 A, JP 2004-101850 A, U.S. Patent No. 7,888,181 B2, and U.S. Patent No. 9,177,926 B2 can be used.
  • suitable methods include photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electroplating, electroless plating, etching, printing, and combinations of these. More specific examples include patterning methods that combine sputtering, photolithography, and etching, and patterning methods that combine photolithography and electroplating.
  • a preferred form of plating is electroplating using a copper sulfate or copper cyanide plating solution.
  • the thickness of the metal layer at its thickest point is preferably 0.01 to 50 ⁇ m, and more preferably 1 to 10 ⁇ m.
  • Examples of fields to which the cured product manufacturing method of the present invention or the cured product can be applied include insulating films for electronic devices, interlayer insulating films for rewiring layers, stress buffer films, etc. Other examples include etching patterns for sealing films, substrate materials (base films, coverlays, and interlayer insulating films for flexible printed circuit boards), and insulating films for packaging applications such as those described above.
  • the method for producing the cured product of the present invention, or the cured product of the present invention can also be used to produce printing plates such as offset printing plates or screen printing plates, to etch molded parts, and to produce protective lacquers and dielectric layers in electronics, particularly microelectronics.
  • the laminate of the present invention refers to a structure having a plurality of layers each made of the cured product of the present invention.
  • the laminate is a laminate including two or more layers made of a cured product, and may be a laminate including three or more layers.
  • at least one is a layer made of the cured product of the present invention, and from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product associated with the shrinkage, it is also preferable that all of the layers made of the cured product contained in the laminate are layers made of the cured product of the present invention.
  • the method for producing a laminate of the present invention preferably includes the method for producing a cured product of the present invention, and more preferably includes repeating the method for producing a cured product of the present invention multiple times.
  • the laminate for example, a laminate including at least a layer structure in which three layers, a layer made of a first cured product, a metal layer, and a layer made of a second cured product, are laminated in this order, can be mentioned as a preferred example. It is preferable that the layer made of the first cured product and the layer made of the second cured product are both layers made of the cured product of the present invention.
  • the resin composition of the present invention used to form the layer made of the first cured product and the resin composition of the present invention used to form the layer made of the second cured product may have the same composition or different compositions.
  • the metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.
  • the method for producing the laminate of the present invention preferably includes a lamination step.
  • the lamination process is a series of processes including (a) a film formation process (layer formation process), (b) an exposure process, (c) a development process, and (d) at least one of a heating process and a post-development exposure process, which are performed again on the surface of the pattern (resin layer) or metal layer in this order.
  • at least one of the (a) film formation process and the (d) heating process and the post-development exposure process may be repeated.
  • the (e) metal layer formation process may be included. It goes without saying that the lamination process may further include the above-mentioned drying process, etc., as appropriate.
  • the method for producing a laminate of the present invention preferably includes a surface activation treatment step of subjecting at least a portion of the metal layer and the resin composition layer to a surface activation treatment.
  • the surface activation treatment step is usually performed after the metal layer formation step, but the resin composition layer may be subjected to the surface activation treatment step after the above-mentioned development step (preferably after at least one of the heating step and the post-development exposure step) and then the metal layer formation step may be performed.
  • the surface activation treatment may be performed on at least a portion of the metal layer, or on at least a portion of the resin composition layer after exposure, or on at least a portion of both the metal layer and the resin composition layer after exposure.
  • the present invention also discloses a semiconductor device comprising the cured product or laminate of the present invention.
  • the present invention also discloses a method for producing a semiconductor device, which includes the method for producing the cured product of the present invention or the method for producing the laminate.
  • semiconductor devices using the resin composition of the present invention for forming an interlayer insulating film for a rewiring layer the descriptions in paragraphs 0213 to 0218 and FIG. 1 of JP-A-2016-027357 can be referred to, and the contents of these can be incorporated into this specification.
  • the weight average molecular weight, imidization rate, esterification rate, and amine value of Resin P-1 are shown in the table below.
  • the symbols A and B in parentheses represent the molar ratios of each structure, and the values are shown in the table below.
  • the imidization rate of the resin was measured by the following method.
  • the resin was dissolved in ⁇ -butyrolactone, diluted to 2,000 mPa s, and applied to a silicon wafer by spin coating to form a resin layer.
  • the silicon wafer with the resulting resin layer applied was dried on a hot plate at 110°C for 5 minutes, yielding a resin layer with a uniform thickness of approximately 15 ⁇ m after film formation on the silicon wafer.
  • the resin layer was measured by the ATR method using a NicoletiS20 (manufactured by Thermofisher) in the measurement range of 4000 to 700 cm ⁇ 1 , with 50 measurements.
  • the acid value of the resin used in each example or comparative example was measured by the following method. 0.30 g of resin was dissolved in 80 mL of NMP, and 5 mL of water was added to prepare a measurement solution. The solution was titrated with a 0.01 N (0.01 mol/L) aqueous potassium hydroxide (KOH) solution, and the acid value was calculated from the peak in the pH range of 7.0 to 12.0. The measurement results for each resin are shown in the "Acid value (mmol/g)" column in the table.
  • the amine value of the resin used in each example or comparative example was measured by the following method. 0.60 g of resin was dissolved in 50 mL of diglyme, and 10 mL of acetic acid was added to prepare a measurement solution. The solution was titrated with a 0.01 N (0.01 mol/L) perchloric acid solution in acetic acid to detect the neutralization point, thereby measuring the amine value of the resin. The measurement results for each resin are shown in the "amine value (mmol/g)" column in the table.
  • the content of the specific structure represented by formula (1) in the resin composition was measured by the following method.
  • the resin used in each Example or Comparative Example was subjected to 1 H-NMR analysis using d6-DMSO to quantify the content of the specific structure contained in the resin.
  • the total amount of components other than the solvent was defined as the total solid content, and the specific structure was assumed to be contained only in the resin component.
  • the content of the specific structure in the total solid content was calculated from the relationship between the content of the specific structure in the resin quantified above and the content of the resin in the total solid content. The measurement results are shown in the column "Content of specific structure (mmol/g)" in the table.
  • C-1 NK Ester 4G (manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • C-2 NK Ester TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • C-3 Dipentaerythritol hexaacrylate (manufactured by TCI)
  • C-4 Compound of the following structure
  • C-5 Compound of the following structure
  • F-1 Compound of the following structure
  • F-2 Compound of the following structure
  • F-3 Compound of the following structure
  • F-4 Compound of the following structure
  • G-1 Compound of the following structure
  • G-2 Compound of the following structure
  • H-1 Compound of the following structure
  • H-2 Compound of the following structure
  • H-3 Compound of the following structure
  • H-4 Compound of the following structure
  • the film was then developed with cyclopentanone until the unexposed areas were removed, rinsed with PGMEA for 30 seconds, and heated at a rate of 10 ° C./min under a nitrogen atmosphere, and heated at 230 ° C. for 1 hour.
  • the via width of the obtained pattern at each exposure dose was measured using a length-measuring scanning electron microscope (SEM: S-9380II manufactured by Hitachi High-Technologies Corporation), and the exposure dose at which the via width became 7 ⁇ m was determined, and this was designated as the optimum exposure dose (mJ/cm 2 ) for each composition.
  • SEM length-measuring scanning electron microscope

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

La présente invention concerne : une composition de résine qui contient une résine A et un photosensibilisateur B, et dans laquelle la résine A est composée d'une structure d'ester d'acide amique et d'une structure d'acide amique, et est également composée au moins d'une structure choisie dans le groupe constitué par les structures représentées par la formule (AY1) et les structures représentées par la formule (DY1), la quantité molaire de la structure d'ester d'acide amique par rapport à la quantité molaire totale de la structure d'ester d'acide amique et de la structure d'acide amique dans la résine A est de 90,00 à 99,90 %, et la valeur d'amine de la résine A est de 0,0010 à 0,3000 mmol/g ; un produit durci obtenu par durcissement de la composition de résine ; un stratifié contenant le produit durci ; un procédé de production du produit durci ; un procédé de production du stratifié ; un procédé de production de dispositif à semi-conducteur comprenant le procédé de production du produit durci ; et un dispositif à semi-conducteur comportant le produit durci.
PCT/JP2025/011385 2024-03-27 2025-03-24 Composition de résine, produit durci, stratifié, procédé de production de produit durci, procédé de production de stratifié, procédé de production de dispositif à semi-conducteur et dispositif à semi-conducteur Pending WO2025205567A1 (fr)

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Citations (6)

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Publication number Priority date Publication date Assignee Title
WO2018151195A1 (fr) * 2017-02-20 2018-08-23 富士フイルム株式会社 Composition de résine photosensible, précurseur polymère contenant un noyau hétérocyclique, film durci, stratifié, procédé de production de film durci, et dispositif semi-conducteur
WO2022045124A1 (fr) * 2020-08-25 2022-03-03 富士フイルム株式会社 Composition de résine durcissable, produit durci, stratifié, procédé de fabrication d'un produit durci, et dispositif à semi-conducteur
WO2022044999A1 (fr) * 2020-08-25 2022-03-03 富士フイルム株式会社 Composition de résine durcissable, produit durci, stratifié, procédé de production de produit durci, dispositif à semi-conducteurs ainsi que précurseur polyimide et procédé de production de celui-ci
WO2022162895A1 (fr) * 2021-01-29 2022-08-04 昭和電工マテリアルズ株式会社 Procédé de sélection de précurseur de polyimide, procédé de production de composition de résine, précurseur de polyimide, composition de résine et objet durci
JP2022185863A (ja) * 2021-06-03 2022-12-15 Ｈｄマイクロシステムズ株式会社 ポリイミド前駆体の製造方法、及び硬化物の製造方法
WO2024101266A1 (fr) * 2022-11-07 2024-05-16 富士フイルム株式会社 Composition de résine, produit durci, stratifié, procédé de production de produit durci, procédé de production de stratifié, procédé de production de dispositif à semi-conducteur et dispositif à semi-conducteur

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018151195A1 (fr) * 2017-02-20 2018-08-23 富士フイルム株式会社 Composition de résine photosensible, précurseur polymère contenant un noyau hétérocyclique, film durci, stratifié, procédé de production de film durci, et dispositif semi-conducteur
WO2022045124A1 (fr) * 2020-08-25 2022-03-03 富士フイルム株式会社 Composition de résine durcissable, produit durci, stratifié, procédé de fabrication d'un produit durci, et dispositif à semi-conducteur
WO2022044999A1 (fr) * 2020-08-25 2022-03-03 富士フイルム株式会社 Composition de résine durcissable, produit durci, stratifié, procédé de production de produit durci, dispositif à semi-conducteurs ainsi que précurseur polyimide et procédé de production de celui-ci
WO2022162895A1 (fr) * 2021-01-29 2022-08-04 昭和電工マテリアルズ株式会社 Procédé de sélection de précurseur de polyimide, procédé de production de composition de résine, précurseur de polyimide, composition de résine et objet durci
JP2022185863A (ja) * 2021-06-03 2022-12-15 Ｈｄマイクロシステムズ株式会社 ポリイミド前駆体の製造方法、及び硬化物の製造方法
WO2024101266A1 (fr) * 2022-11-07 2024-05-16 富士フイルム株式会社 Composition de résine, produit durci, stratifié, procédé de production de produit durci, procédé de production de stratifié, procédé de production de dispositif à semi-conducteur et dispositif à semi-conducteur

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