WO2019031114A1 - Polymère, composition de résine, film de résine, procédé de production de film de résine à motifs, et composant électronique - Google Patents

Polymère, composition de résine, film de résine, procédé de production de film de résine à motifs, et composant électronique Download PDF

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WO2019031114A1
WO2019031114A1 PCT/JP2018/025282 JP2018025282W WO2019031114A1 WO 2019031114 A1 WO2019031114 A1 WO 2019031114A1 JP 2018025282 W JP2018025282 W JP 2018025282W WO 2019031114 A1 WO2019031114 A1 WO 2019031114A1
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group
hydrocarbon group
carbon atoms
structural unit
formula
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PCT/JP2018/025282
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Japanese (ja)
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下川　努
誠 杉浦
貴史 土井
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Jsr株式会社
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Priority to JP2019535030A priority Critical patent/JP7056662B2/ja
Publication of WO2019031114A1 publication Critical patent/WO2019031114A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • 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
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/22—Oxygen
    • C08F212/24—Phenols or alcohols

Definitions

  • the present invention relates to a polymer, a resin composition, a resin film, a method for producing a patterned resin film, and an electronic component.
  • Patent Document 1 discloses a positive photosensitive resin composition containing polyphenylene oxide (A) having a phenolic hydroxyl group and a compound (B) capable of generating an acid by light.
  • Patent Document 2 discloses a positive-type radiation-sensitive polymer containing a polymer (a) obtained by polyaddition of a polyhydric phenol compound and a vinyl ether compound, and an acid generator (b) that generates an acid upon irradiation with radiation.
  • a composition is disclosed.
  • the subject of the present invention is a resin composition capable of forming a resin film excellent in heat resistance, a polymer useful as a component of the resin composition, a resin film excellent in heat resistance, a method of producing a patterned resin film, And providing an electronic component having the resin film.
  • the present invention is, for example, the following [1] to [22].
  • a structural unit having a partial structure represented by the following formula (i) in the same or different molecule hereinafter also referred to as “structural unit (i)”
  • a compound represented by the following formula (ii-1) A polymer comprising a structural unit having a partial structure represented by and one or more hydroxyl-containing structural units (hereinafter also referred to as “structural units (ii)”) selected from structural units having a phenolic hydroxyl group, and E) Resin composition containing a solvent.
  • R 1 and R 2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, at least one carbon-carbon bond in the hydrocarbon group having 1 to 20 carbon atoms] during, -O -, - COO -, - OCO -, - OSO 2 -, - SO 3 -, - OSO 2 NR -, - NRSO 2 -, - NRCO -, - selected from NR- and -CONR- R 1 and R 2 represent a group having at least one group or a group in which a part of hydrogen atoms in these groups is substituted, and R 1 and R 2 together with the boron atom to which OR 1 and OR 2 are bonded and the number of ring members It may form 3 to 20 ring structures.
  • the R is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a bond.
  • R 3 and R 4 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an electron withdrawing group, provided that the above R 3 and R 4 are each independently And at least one of them is an electron withdrawing group, and * represents a bond.
  • R 5 is an organic group having 1 to 20 carbon atoms
  • R 6 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
  • n is an integer of 0 to 3 , * Indicates a bonding hand.
  • each of R 7 and R 8 independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, at least one carbon-carbon bond in the hydrocarbon group having 1 to 20 carbon atoms] during, -O -, - COO -, - OCO -, - OSO 2 -, - SO 3 -, - OSO 2 NR 105 -, - NR 105 SO 2 -, - NR 105 CO -, - NR 105 - and -CONR 105 - represents at least one group having or part of which is a substituent of the hydrogen atoms in these groups are selected from, R 7 and R 8, oR 7 and oR 8 are bonded to each other
  • the ring structure having 3 to 20 ring members may be formed together with the phosphorus atom to be bonded, and the above R 105 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * indicates a bonding hand.
  • R 1 and R 2 each have the same meaning as the same symbol in formula (i);
  • R 11 is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or carbon
  • X 1 is an oxygen
  • R 12 represents an (a + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, at least one carbon-carbon bond in the hydrocarbon group, —O—, — At least one selected from COO-, -OCO-, -OSO 2- , -SO 3- , -OSO 2 NR 101- , -NR 101 SO 2- , -NR 101 CO-, -NR 101 -and -CONR 101- R 1 is a group having one type, or a group obtained by substituting a part of hydrogen atoms in these groups, and the above R 101 is water A prime
  • R 3 and R 4 each have the same meaning as the same symbol in formula (ii-1);
  • R 13 is a hydrogen atom, a fluorine atom, or a hydrocarbon group having 1 to 10 carbon atoms, Or a fluorinated hydrocarbon group having 1 to 10 carbon atoms;
  • X 2 is R 14 is a (b + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, at least one carbon-carbon bond in the hydrocarbon group, -O- , -COO -, - OCO -, - OSO 2 -, - SO 3 -, - OSO 2 NR 102 -, - NR 102 SO 2 -, - NR 102 CO -, - NR 102 - and -CONR 102 - selected from at least one group having the or
  • R 5 , R 6 and n each have the same meaning as the same symbol in formula (iii);
  • R 15 is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, Or a fluorinated hydrocarbon group having 1 to 10 carbon atoms;
  • X 3 is
  • R 16 is a (C + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, at least one carbon-carbon bond in the above-mentioned hydrocarbon group, —O—, , -COO -, - OCO -, - OSO 2 -, - SO 3 -, - OSO 2 NR 104 -, - NR 104 SO 2 -, - NR 104 CO -, - NR 104 - and -CONR 104
  • the polymer (A) is a structural unit having a partial structure represented by the above formula (ii-1), and one or more hydroxyl group-containing structural units selected from structural units having a phenolic hydroxyl group.
  • a method for producing a patterned resin film comprising the steps of developing a selective exposure film to obtain a patterned coating film, and curing the patterned coating film to obtain a patterned resin film.
  • a resin composition capable of forming a resin film excellent in heat resistance can be provided. Further, according to the present invention, a polymer useful as a component of the resin composition, a resin film excellent in heat resistance, a method for producing a patterned resin film, and an electronic component having the resin film can be provided. it can.
  • each component exemplified in the present specification for example, each component in the resin composition, may be used alone or in combination of two or more unless otherwise stated.
  • the "hydrocarbon group” includes a chain hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group.
  • the “hydrocarbon group” may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
  • Chain hydrocarbon group means a hydrocarbon group which does not contain a cyclic structure and is constituted only by a chain structure, and includes both a linear hydrocarbon group and a branched hydrocarbon group.
  • alicyclic hydrocarbon group means a hydrocarbon group containing only an alicyclic hydrocarbon structure as a cyclic structure and not containing an aromatic ring structure, and a monocyclic alicyclic hydrocarbon group and a plurality of alicyclic hydrocarbon groups and multiple cyclic hydrocarbon groups. It includes both of the alicyclic hydrocarbon groups of the ring. However, the “alicyclic hydrocarbon group” does not have to be constituted only by the structure of the alicyclic hydrocarbon, and a chain structure may be included in part thereof.
  • aromatic hydrocarbon group means a hydrocarbon group containing an aromatic ring structure as a cyclic structure.
  • aromatic hydrocarbon group does not have to be composed of only an aromatic ring structure, and a portion thereof may have a chain hydrocarbon structure and / or an alicyclic hydrocarbon structure. .
  • Patterned resin film refers to a patterned resin film.
  • the term “resin film” is used in the meaning including the patterned resin film.
  • the resin composition of the present invention contains a polymer (A) and a solvent (E) described below.
  • the polymer (A) of the present invention which is suitably used as a component of the resin composition, will also be described.
  • the resin composition of the present invention can further contain a photosensitive acid generator (B) or a photopolymerization initiator (D).
  • the resin composition of the present invention containing (B) or (D) is also referred to as a "photosensitive composition".
  • photosensitivity and photopolymerization are used to mean radiation-sensitive and radiation-sensitive polymerization corresponding to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam and X-ray.
  • the polymer (A) is a structural unit having a partial structure represented by the following formula (i) and a partial structure represented by the following formula (ii-1) in the same or different molecules, And one or more hydroxyl group-containing structural units selected from structural units having a phenolic hydroxyl group.
  • a polymer (A) may consist of one type of polymer, for example, and may consist of two or more types of polymers. When it consists of 2 or more types of polymers (blend), if it can confirm that the whole blend has structural unit (i) and structural unit (ii), for example by NMR analysis, it will be a structure in a blend
  • the polymer which does not have unit (i) or (ii) may be included.
  • the term "in the same or different molecule" (wherein molecule means a polymer molecule) is used in this sense.
  • the blend is, for example, a mixture of a polymer containing the structural unit (i) and a polymer containing the structural unit (ii).
  • the polymer (A) preferably contains the structural unit (i) and the structural unit (ii) in the same molecule.
  • the polymer (A) contains one or more structural units (i).
  • the structural unit (i) contributes to the storage stability and coatability of the resin composition, the alkali solubility of the polymer (A), and the mechanical strength and heat resistance of the resin film.
  • the coating film after exposure can be developed by alkaline developing solution by providing alkali solubility to a polymer (A).
  • R 1 and R 2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, -O-, at least one carbon-carbon bond in the hydrocarbon group having 1 to 20 carbon atoms, -COO -, - OCO -, - OSO 2 -, - SO 3 -, - OSO 2 NR -, - NRSO 2 -, - NRCO -, - NR- and -CONR- of at least one group having a (hereinafter selected “Substituted hydrocarbon group 1” or a group in which part of hydrogen atoms in these groups is substituted (hereinafter also referred to as “substituted hydrocarbon group 2”), and R 1 and R 2 And a boron atom to which OR 1 and OR 2 are bonded to form a cyclic structure having 3 to 20 ring members.
  • the R is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a
  • the hydrocarbon group having 1 to 20 carbon atoms listed as R 1 , R 2 and R is a chain hydrocarbon group having 1 to 20 carbon atoms, or an alicyclic hydrocarbon group having 3 to 20 carbon atoms
  • linear hydrocarbon group having 1 to 20 carbon atoms examples include methyl group, ethyl group, i-propyl group, n-propyl group, i-butyl group, sec-butyl group, t-butyl group, n- Linear saturated hydrocarbon groups such as butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl and n-decyl; and linear unsaturated such as ethenyl, propynyl and ethynyl A hydrocarbon group is mentioned. Among these, chain saturated hydrocarbon groups are more preferable.
  • Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms include alicyclic saturated hydrocarbon groups such as cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, adamantyl group and the like; cyclobutenyl group and cyclopentenyl group And alicyclic unsaturated hydrocarbon groups such as groups. Among these, alicyclic saturated hydrocarbon groups are preferable.
  • Examples of the substituted hydrocarbon group 1 include alkyl ester alkyl groups such as methyl ester methyl group, ethyl ester methyl group and propyl ester methyl group, and alkyl ethers such as methyl ether methyl group, ethyl ether methyl group and propyl ether methyl group An alkyl group is mentioned.
  • a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) and a halogenated alkyl group are mentioned, for example.
  • R 1 and R 2 may combine with each other to form a cyclic structure having 3 to 20, preferably 3 to 15 ring members, together with the boron atom to which OR 1 and OR 2 are bonded.
  • a partial structure represented by Formula (i) which forms the said cyclic structure the partial structure represented by following formula (10) and (11) is mentioned, for example.
  • R r represents a divalent hydrocarbon group having 2 to 20 carbon atoms, at least one carbon-carbon bond in the divalent hydrocarbon group having 2 to 20 carbon atoms.
  • the R 100 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
  • the divalent hydrocarbon group having 2 to 20 carbon atoms The moiety is a group substituted with at least one member selected from a halogen atom, an alkoxy group and an alkoxycarbonyl group, and the NR 100 group may be coordinately bonded to an empty orbital of a boron atom. * Indicates a bonding hand.
  • the divalent hydrocarbon group in R r is preferably a divalent chain saturated hydrocarbon group or an alicyclic saturated hydrocarbon group, and more preferably a divalent chain saturated carbonization having 2 to 10 carbon atoms It is a hydrogen group or a divalent alicyclic saturated hydrocarbon group having 4 to 10 carbon atoms.
  • the hydrocarbon group having 1 to 20 carbon atoms in R 100 is the same as the hydrocarbon group in R in the substituted hydrocarbon group 1 described above.
  • R 1 and R 2 are preferably hydrogen atoms from the viewpoint of heat resistance.
  • Examples of the structural unit (i) include structural units represented by the following formula (1).
  • R 1 and R 2 each have the same meaning as the same symbol in formula (i).
  • R 11 is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or a fluorinated hydrocarbon group having 1 to 10 carbon atoms.
  • R 12 represents an (a + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, and at least one carbon-carbon bond in the hydrocarbon group, —O—, —COO—, —OCO—, —OSO 2 -, -SO 3- , -OSO 2 NR 101- , -NR 101 SO 2- , -NR 101 CO-, -NR 101 -and -CONR 101- , or a group having at least one selected from these groups
  • R 101 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a halogenated alkyl group is mentioned, for example.
  • a is an integer of 1 to 3, preferably 1.
  • Examples of the hydrocarbon group having 1 to 10 carbon atoms of R 11 include, for example, a chain hydrocarbon group having 1 to 10 carbon atoms and an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and a chain hydrocarbon A group is preferable, and a methyl group and an ethyl group are more preferable.
  • Examples of the fluorinated hydrocarbon group having 1 to 10 carbon atoms of R 11 include a fluorinated chain hydrocarbon group having 1 to 10 carbon atoms, and a fluorinated alicyclic hydrocarbon group having 3 to 10 carbon atoms. Preferred is a fluorinated chain hydrocarbon group, and more preferred is a trifluoromethyl group.
  • a hydrogen atom is preferable.
  • Examples of the (a + 1) -valent hydrocarbon group having 1 to 20 carbon atoms of R 12 include linear saturated hydrocarbon groups such as methylene and alkanediyl such as ethylene, cyclopentadiyl, cyclohexanediyl And cycloalkanediyl groups such as norbornanediyl group and tetracyclododecanediyl group, and arylene groups such as phenylene group.
  • Examples of the structural unit (i) include structural units represented by the following formulas (12) to (22).
  • the polymer (A) is one or more selected from a structural unit (ii-1) having a partial structure represented by the following formula (ii-1), and a structural unit (ii-2) having a phenolic hydroxyl group Contains structural unit (ii).
  • the polymer (A) further comprises a structural unit (ii-1) having a partial structure represented by the following formula (ii-1) in the same or different molecule as the molecule containing the structural unit (i) Can.
  • the polymer (A) preferably contains the structural unit (i) and the structural unit (ii-1) in the same molecule.
  • R 3 and R 4 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an electron-withdrawing group, provided that at least one of R 3 and R 4 is an electron-accepting group It is an attractive group, and any of them is preferably an electron attractive group, and * represents a bond.
  • the hydrocarbon group having 1 to 20 carbon atoms is the same as the hydrocarbon group having 1 to 20 carbon atoms of R 1 and R 2 in the formula (i).
  • R 3 and R 4 are electron-withdrawing groups
  • the storage stability of the resin composition and the alkali solubility of the polymer (A) are preferably improved.
  • the electron withdrawing group include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; cyano groups; fluorinated hydrocarbon groups such as fluorinated alkyl group.
  • the fluorinated hydrocarbon group is a group in which part or all of hydrogen atoms in a hydrocarbon group are substituted with a fluorine atom.
  • a fluorinated hydrocarbon group having 1 to 20 carbon atoms is preferable, a fluorinated alkyl group having 1 to 20 carbon atoms is more preferable, and a fluorinated alkyl group having 1 to 10 carbon atoms is more preferable.
  • a fluorine atom, a cyano group and a fluorinated alkyl group are preferable as the electron-withdrawing group, and a fluorine atom, a cyano group, a trifluoromethyl group and a hexafluoroisopropyl group are more preferable.
  • the polymer (A) can contain one or more structural units (ii-1).
  • the structural unit (ii-1) contributes to the storage stability of the resin composition, the alkali solubility of the polymer (A), the hydrophobicity of the resin film and the low dielectric constant.
  • Examples of the structural unit (ii-1) include structural units represented by the following formula (2).
  • R 3 and R 4 each have the same meaning as the same symbol in formula (ii-1).
  • R 13 is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or a fluorinated hydrocarbon group having 1 to 10 carbon atoms.
  • R 14 represents a (b + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, and at least one carbon-carbon bond in the hydrocarbon group, —O—, —COO—, —OCO—, —OSO 2 -, - SO 3 -, - OSO 2 NR 102 -, - NR 102 SO 2 -, - NR 102 CO -, - NR 102 - and -CONR 102 - group having at least one selected from or in these groups, And R 102 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • b is an integer of 1 to 3, preferably 1. Specific examples, preferred examples and preferred reasons for R 13 and R 14 are the same as R 11 and R 12 in the formula (1), respectively.
  • Examples of the structural unit (ii-1) include structural units (23) to (28) represented by the following formulas.
  • R ⁇ 13 > in said Formula is synonymous with the same symbol in Formula (2), respectively.
  • the polymer (A) can further include a structural unit (ii-2) having a phenolic hydroxyl group in the same or different molecule as the molecule containing the structural unit (i).
  • the polymer (A) preferably contains the structural unit (i) and the structural unit (ii-2) in the same molecule.
  • the polymer (A) can contain one or more structural units (ii-2).
  • the structural unit (ii-2) contributes to the alkali solubility of the polymer (A), the storage stability and compatibility of the resin composition, and the adhesion and mechanical strength of the resin film.
  • the polymer (A) having the structural unit (ii-2) is used, a resin film having excellent solvent resistance and heat melting property can be obtained.
  • structural unit (ii-2) having a phenolic hydroxyl group include structural units derived from a phenolic hydroxyl group-containing unsaturated compound.
  • phenolic hydroxyl group-containing unsaturated compound for example, a phenolic hydroxyl group-containing unsaturated compound which is cyclized by heating such as 2-hydroxyphenyl (meth) acrylate, 2-hydroxyphenyl (meth) acrylamide and the like and the phenolic hydroxyl group disappears; 3-hydroxyphenyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, 2,6-dimethyl-4-hydroxyphenyl (meth) acrylate, 3-hydroxyphenyl (meth) acrylamide, 4-hydroxyphenyl (meth) acrylamide Other phenols such as 2,6-dimethyl-4-hydroxyphenyl (meth) acrylamide, 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, 2,6-dimethyl-4-hydroxystyrene Hydroxyl group-containing unsaturated compounds.
  • cyclization by heating causes disappearance of the phenolic hydroxyl group and loss of hygroscopicity, and thus a low dielectric resin film is obtained, as well as copolymerization reactivity, solvent resistance of the resin film, and dielectric characteristics.
  • a phenolic hydroxyl group-containing unsaturated compound such as 2-hydroxyphenyl acrylamide or 2-hydroxyphenyl acrylate which is cyclized by heating to lose phenolic hydroxyl group.
  • the polymer (A) has a partial structure represented by the following formula (iii) in the same or different molecule as a molecule containing at least one structural unit selected from structural units (i) and (ii)
  • the structural unit (iii) can further be included.
  • the polymer (A) preferably contains the structural unit (i), the structural unit (ii) and the structural unit (iii) in the same molecule.
  • the polymer (A) can contain one or more structural units (iii).
  • the structural unit (iii) contributes to the alkali solubility of the polymer (A), the adhesion of the resin film, the mechanical strength and the heat resistance.
  • R 5 is an organic group having 1 to 20 carbon atoms (with the exception of the group corresponding to OR 6 ).
  • R 6 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, n is an integer of 0 to 3, and is preferably 0. * Indicates a bonding hand.
  • Organic group refers to a group comprising at least one carbon atom.
  • the organic group having 1 to 20 carbon atoms as R 5 is, for example, a hydrocarbon having 1 to 20 carbon atoms, such as a linear hydrocarbon group having 1 to 20 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms.
  • Examples of the hydrocarbon group having 1 to 20 carbon atoms of R 6 include a linear hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and an aromatic carbon having 6 to 20 carbon atoms.
  • a hydrogen group is mentioned.
  • linear hydrocarbon group having 1 to 20 carbon atoms and the alicyclic hydrocarbon group having 3 to 20 carbon atoms of R 6 are the groups represented by R 1 and R 2 in the formula (i) Are the same as the chain hydrocarbon group and the alicyclic hydrocarbon group described above.
  • Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms of R 6 include aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group and anthryl group; benzyl group, phenethyl group, naphthylmethyl group, an Aralkyl groups such as tolylmethyl group may be mentioned.
  • structural unit (iii) the structural unit represented by following formula (3) is mentioned, for example.
  • R 5 , R 6 and n each have the same meaning as the same symbol in formula (iii).
  • R 15 is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or a fluorinated hydrocarbon group having 1 to 10 carbon atoms.
  • R 16 represents a (C + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, and at least one carbon-carbon bond in the hydrocarbon group, —O—, —COO—, —OCO—, —OSO 2 -, - SO 3 -, - OSO 2 NR 104 -, - NR 104 SO 2 -, - NR 104 CO -, - NR 104 - and -CONR 104 - group having at least one selected from or in these groups,
  • R 104 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • c is an integer of 1 to 3, preferably 1. Specific examples, preferred examples and preferred reasons for the R 15 and R 16 groups are the same as for R 11 and R 12 in the formula (1), respectively.
  • Examples of the structural unit (iii) include structural units (29) to (34) represented by the following formula.
  • R ⁇ 15 > in said Formula is synonymous with the same symbol in Formula (3), respectively.
  • the polymer (A) has a partial structure represented by the following formula (iv) in the same or different molecule as a molecule containing at least one structural unit selected from structural units (i) and (ii) It can further comprise a structural unit (iv).
  • the polymer (A) preferably contains the structural unit (i), the structural unit (ii) and the structural unit (iv) in the same molecule, and the polymer (A) contains the structural unit (iii) In the case where the structural unit (i), the structural unit (ii), the structural unit (iii) and the structural unit (iv) are contained in the same molecule, it is preferable.
  • the polymer (A) can contain one or more structural units (iv).
  • the structural unit (iv) contributes to the storage stability and compatibility of the resin composition, the adhesion of the resin film, the heat resistant transparency, and the antiaging property.
  • R 7 and R 8 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, -O-, at least one carbon-carbon bond in the hydrocarbon group having 1 to 20 carbon atoms, -COO -, - OCO -, - OSO 2 -, - SO 3 -, - OSO 2 NR 105 -, - NR 105 SO 2 -, - NR 105 CO -, - is selected from - NR 105 - and -CONR 105
  • R 7 and R 8 represent a group having at least one group or a group in which a part of hydrogen atoms in these groups is substituted, and R 7 and R 8 together with the phosphorus atom to which OR 7 and OR 8 are bonded are the ring members together It may form 3 to 20 ring structures.
  • the R 105 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Specific examples of each group of R 7 and R 8 are the same
  • R 7 and R 8 may be combined with each other to form a cyclic structure having 3 to 20, preferably 3 to 15 ring members, together with the phosphorus atom to which OR 7 and OR 8 are bonded.
  • Examples of the partial structure represented by the formula (iv) having a cyclic structure include partial structures represented by the following formulas (35) to (36).
  • R r1 is a divalent hydrocarbon group having 2 to 20 carbon atoms, or a part of hydrogen atoms in the divalent hydrocarbon group having 2 to 20 carbon atoms is And a group substituted with at least one selected from a halogen atom, an alkoxy group and an alkoxycarbonyl group. * Indicates a bonding hand.
  • the divalent hydrocarbon group for R r1 is preferably a divalent chain saturated hydrocarbon group or an alicyclic saturated hydrocarbon group, and more preferably a divalent chain saturated carbonization having 2 to 10 carbon atoms It is a hydrogen group or a divalent alicyclic saturated hydrocarbon group having 4 to 10 carbon atoms.
  • Each of R 7 and R 8 independently is preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms from the viewpoint of heat resistance and storage stability, and a hydrogen atom or a chain hydrocarbon group having 1 to 20 carbon atoms Is more preferable, and a hydrogen atom, a methyl group, an ethyl group and an i-propyl group are more preferable.
  • Examples of the structural unit (iv) include structural units represented by the following formula (4).
  • R 7 and R 8 each have the same meaning as the same symbol in formula (iv).
  • R 17 is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or a fluorinated hydrocarbon group having 1 to 10 carbon atoms.
  • R 18 represents a (d + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, and at least one carbon-carbon bond in the hydrocarbon group, —O—, —COO—, —OCO—, —OSO 2 -, - SO 3 -, - OSO 2 NR 106 -, - NR 106 SO 2 -, - NR 106 CO -, - NR 106 - and -CONR 106 - group having at least one selected from or in these groups, And R 106 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • d is an integer of 1 to 3, preferably 1. Specific examples, preferred examples and preferred reasons for each group of R 17 and R 18 are the same as R 11 and R 12 in the formula (1), respectively.
  • Examples of the structural unit (iv) include structural units represented by the following formulas (37) to (45).
  • R 17 in the above-mentioned formula is respectively synonymous with the same symbol in formula (4).
  • the polymer (A) further contains a structural unit (v) having an epoxy group in the same or different molecule as a molecule containing at least one structural unit selected from structural units (i) and (ii) Can.
  • the polymer (A) preferably contains the structural unit (i), the structural unit (ii) and the structural unit (v) in the same molecule, and the polymer (A) is a structural unit (iii) and / or When it contains (iv), it is preferable to include structural unit (i), structural unit (ii), structural unit (iii) and / or (iv), and structural unit (v) in the same molecule.
  • the polymer (A) can contain one or more structural units (v).
  • the structural unit (v) contributes to the storage stability of the resin composition, the adhesion of the resin film and the mechanical strength.
  • Examples of the epoxy group include oxiranyl group (1,2-epoxy structure) and oxetanyl group (1,3-epoxy structure).
  • Specific examples of the structural unit (v) having an epoxy group include structural units derived from epoxy group-containing unsaturated compounds such as oxiranyl group-containing unsaturated compounds and oxetanyl group-containing unsaturated compounds.
  • oxiranyl group-containing unsaturated compound for example, glycidyl acrylate, glycidyl methacrylate, 2-methyl glycidyl methacrylate, glycidyl ⁇ -ethyl acrylate, glycidyl ⁇ -n-propyl acrylate, glycidyl ⁇ -n-butyl acrylate Acrylic acid 3,4-epoxybutyl, methacrylic acid 3,4-epoxybutyl, acrylic acid 6,7-epoxyheptyl, methacrylic acid 6,7-epoxyheptyl, ⁇ -ethylacrylic acid-6,7-epoxyheptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, 3,4-epoxycyclohexyl methyl meth,
  • Examples of the oxetanyl group-containing unsaturated compound include 3- (Acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (Acryloyloxymethyl) -2-pentafluoroethyl oxetane, 3- (acryloyloxymethyl) -2-phenyl oxetane, 3- (acryloyloxymethyl) -2,2-difluorooxetane, 3- (acryloyloxymethyl) -2,2,4-Trifluorooxetane, 3- (acryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (2-acryloyloxyethyl) oxe
  • 3- (acryloyloxymethyl) -3-ethyl oxetane and 3- (methacryloyloxymethyl) -3-ethyl oxetane have copolymerization reactivity, compatibility of the resin composition, and solvent resistance of the resin film. It is desirable from the viewpoint of improvement of
  • the resin composition can be cured by self-condensing the partial structure represented by the formula (i), which is presumed to contribute to the improvement of the heat resistance.
  • the partial structure represented by the formula (ii-1) is considered to suppress the self-condensation of the partial structure represented by the formula (i) during storage and to contribute to the improvement of the storage stability of the resin composition.
  • the structural unit (ii-2) is presumed to contribute to the improvement of the alkali solubility of the polymer (A) and the improvement of the crosslinking properties such as the solvent resistance of the resin film.
  • the content ratio of the structural unit (i) is usually 5 to 60 mol%, preferably 5 to 40 mol%, more preferably 5 to 20 mol%.
  • the content of the structural unit (i) is in the above range, the storage stability and coatability of the resin composition, the alkali solubility of the polymer (A), and the mechanical strength and heat resistance of the resin film tend to be improved. is there.
  • the content ratio of the structural unit (ii) is usually 5-90 mol%.
  • the content of the structural unit (ii-1) is usually 5 to 90 mol%, preferably 10 to 80 mol%, and more preferably Preferably, it is 20 to 70 mol%.
  • the content of the structural unit (ii-1) is in the above range, the storage stability of the resin composition, the alkali solubility of the polymer (A), the hydrophobicity and the low dielectric constant of the resin film tend to be improved. is there.
  • the content ratio of the structural unit (ii-2) is usually 5 to 70 mol%, preferably 10 to 40 mol%, and further Preferably, it is 15 to 30 mol%.
  • the content of the structural unit (ii-2) is in the above range, the compatibility of the resin composition, the alkali solubility of the polymer (A), and the low dielectric constant of the resin film tend to be improved.
  • the content of the structural unit (iii) is usually 5 to 50 mol%, preferably 5 to 40 mol%, more preferably 5 to 50 It is 30 mol%.
  • the content of the structural unit (iii) is in the above range, the alkali solubility of the polymer (A), the adhesion of the resin film, the mechanical strength and the heat resistance tend to be improved.
  • the content ratio of the structural unit (iv) is usually 5 to 30 mol%, preferably 5 to 25 mol%, more preferably 10 to It is 20 mol%.
  • the content ratio of the structural unit (iv) is in the above range, the storage stability and compatibility of the resin composition, the adhesion of the resin film, the heat-resistant transparency and the antiaging properties tend to be improved.
  • the content ratio of the structural unit (v) is usually 5 to 45 mol%.
  • the content ratio of the structural unit (v) is usually 5 to 40 mol%, preferably 5 to 35 mol% And more preferably 10 to 30 mol%
  • the content ratio of the structural unit (v) is usually 5 It is -45 mol%, preferably 10-45 mol%, more preferably 15-45 mol%.
  • the content ratio of each structural unit of the polymer (A) is a value in all structural units constituting the polymer (A), and can be measured by 13 C-NMR.
  • the weight average molecular weight (Mw) of the polymer (A) measured by gel permeation chromatography is the elastic modulus and crack resistance of the resin film obtained by curing the resin composition, and the resolution of the photosensitive composition.
  • Mw molecular weight distribution
  • Mn is a number average molecular weight of the polymer (A) is usually 1.0 to 10.0, preferably 1.0 to 5.0, more preferably 1.0 to 3. It is 0.
  • the details of the measurement methods of Mw and Mn are as described in the examples.
  • the polymer (A) may be used alone or in combination of two or more.
  • the content of the polymer (A) is usually 30% by mass or more, preferably 40% by mass or more, based on 100% by mass in total of all components excluding the solvent (E) from the resin composition of the present invention Preferably it is 50 mass% or more.
  • the content ratio of the polymer (A) is in the above range, a resin composition capable of forming a resin film excellent in heat resistance tends to be obtained.
  • the content of the polymer (A) is usually 30 to 99% by mass, preferably 40 to 98% by mass, based on 100% by mass in total of all components excluding the solvent (E) from the photosensitive composition of the present invention. %, More preferably 50 to 95% by mass.
  • the content ratio of the polymer (A) is in the above range, it tends to be possible to obtain a photosensitive composition capable of forming a patterned resin film having excellent heat resistance and high resolution.
  • the polymer (A) can be synthesized, for example, by polymerizing a predetermined monomer leading each structural unit in a polymerization solvent in the presence of a polymerization initiator or a chain transfer agent, such as radical polymerization.
  • a polymerization initiator or a chain transfer agent such as radical polymerization.
  • monomers, a polymerization initiator and a polymerization solvent are charged in a reaction vessel, heated to a reaction temperature of about 40 to 120 ° C., and reacted for 0.1 to 10 hours under an inert gas atmosphere such as nitrogen gas.
  • polymerization initiator an azo compound and a peroxide compound are mentioned, for example.
  • the said polymerization initiator may be used by 1 type, and may use 2 or more types together.
  • Alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, ethylene glycol, diethylene glycol and propylene glycol; Cyclic ethers such as tetrahydrofuran and dioxane; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl Alkyl ethers of polyhydric alcohols such as ether; Alkyl ether acetates of polyhydric alcohols such as ethylene glycol ethyl ether a
  • cyclic ethers alkyl ethers of polyhydric alcohols, alkyl ether acetates of polyhydric alcohols, ketones or esters are preferable.
  • the polymerization solvents may be used alone or in combination of two or more.
  • the resin composition of the present invention can contain a photosensitive acid generator (B), and becomes a photosensitive composition by containing a photosensitive acid generator (B).
  • the photosensitive acid generator (B) is a compound which generates an acid by light.
  • An acid is generated in the exposed area on the basis of the photosensitive acid generator (B) by the treatment including the exposure treatment to the coating film formed from the photosensitive composition of the present invention, and the alkaline development of the exposed area on the basis of the action of this acid.
  • the solubility in the liquid changes.
  • the photosensitive composition may be either negative or positive.
  • the kind of photosensitive acid generator (B) can be suitably selected according to a negative type composition or a positive type composition.
  • a photosensitive acid generator (B) an onium salt compound, a halogen containing compound, a sulfone compound, a sulfonic acid compound, a sulfone imide compound, a diazomethane compound, and a compound which has a quinone diazide group are mentioned, for example.
  • the compound having a quinone diazide group is also referred to as “quinone diazide compound (b1)”, and the photosensitive acid generators other than the above exemplified ones are also referred to as “acid generator (b2)”.
  • the quinone diazide compound (b1) is a compound which decomposes a quinone diazide group to generate a carboxy group by light irradiation and contact treatment with water.
  • the coating film formed from the composition containing the quinone diazide compound (b1) is a film which is hardly soluble in an alkaline developer. A positive pattern is formed by utilizing the fact that the film is in the state of low alkali solubility and is in the state of high alkali solubility by light irradiation and contact treatment with water.
  • Examples of the quinone diazide compound (b1) include naphthoquinone diazide compounds. Specifically, a compound having one or more phenolic hydroxyl groups, 1,2-naphthoquinone diazide-4-sulfonic acid, 1,2-naphtho Ester compounds with quinonediazide-5-sulfonic acid, 1,2-naphthoquinonediazide-4-sulfonic acid chloride or 1,2-naphthoquinonediazide-5-sulfonic acid chloride may be mentioned. Specific examples of the compound having one or more phenolic hydroxyl groups include, for example, compounds described in paragraphs [0065] to [0070] of JP-A-2014-186300, which are described in the present specification. It shall be.
  • Examples of the quinone diazide compound (b1) include 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2 , 3,4,2 ′, 4′-pentahydroxybenzophenone, tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,3-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 4,6-bis [ 1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene and 1,1 Bis (4-hydroxyphenyl) -1- [4- [1- (4-hydroxyphenyl)
  • the quinone diazide compound (b1) may be used alone or in combination of two or more.
  • the content of the quinone diazide compound (b1) is preferably 100 parts by mass of the polymer (A). Is preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass, and still more preferably 5 to 30 parts by mass.
  • the content of the quinone diazide compound (b1) is at least the lower limit value, the residual film ratio in the unexposed area is improved, and an image faithful to the mask pattern is easily obtained.
  • the content of the quinone diazide compound (b1) is less than or equal to the above upper limit, a resin film having an excellent pattern shape can be easily obtained, and foaming at the time of film formation tends to be prevented.
  • the acid generator (b2) is a compound which forms an acid upon irradiation with light and is a compound other than the quinone diazide compound (b1).
  • the generated acid acts on the polymer (A), the crosslinking agent (C) described later, etc. to cause crosslinking.
  • the structure is formed and the film becomes poorly soluble in alkali.
  • a negative pattern is formed by utilizing the fact that the film changes from a state of easy alkali dissolution to a state of low alkali solubility by light irradiation.
  • Examples of the acid generator (b2) include onium salt compounds such as iodonium salts, sulfonium salts, phosphonium salts, diazonium salts and pyridinium salts; halogen-containing compounds such as haloalkyl group-containing heterocyclic compounds and haloalkyl group-containing hydrocarbon compounds; Sulfone compounds such as ⁇ -ketosulfone compounds, ⁇ -sulfonylsulfone compounds and ⁇ -diazo compounds of these compounds; Sulfonic acid compounds such as alkylsulfonic acid esters, haloalkylsulfonic acid esters, arylsulfonic acid esters, iminosulfonates and the like A sulfone imide compound; and a diazomethane compound. Specific examples of these compounds include, for example, compounds described in paragraphs [0074] to [0079] of JP-A-2014-186300, which are described in the present specification.
  • onium salts include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, triphenylsulfonium trifluoromethanesulfonate, triphenyl Sulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, 4-tert-butylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-tert-butylphenyldiphenylsulfonium p-toluenesulfonate, 4,7-di-n-butoxy Naphthyltetrahydrothioph
  • the acid generator (b2) may be used alone or in combination of two or more.
  • the content of the acid generator (b2) is 100 parts by mass of the polymer (A), The amount is preferably 0.1 to 30 parts by mass, more preferably 0.3 to 20 parts by mass, and still more preferably 0.5 to 15 parts by mass.
  • the content of the acid generator (b2) is equal to or more than the lower limit, curing of the exposed portion is sufficient, and heat resistance is likely to be improved.
  • the content of the acid generator (b2) is less than or equal to the above upper limit value, a patterned resin film having a high resolution can be easily obtained without decreasing the transparency to exposure light.
  • the resin composition of the present invention can further contain a crosslinking agent (C) in order to improve the curability of the resin film.
  • the crosslinking agent (C) is a compound having two or more polymerizable groups or reactive groups.
  • the crosslinking agent (C) acts as a crosslinking component (curing component) that reacts with the polymer (A) or with each other.
  • Examples of the polymerizable group or the reactable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, an oxazolinyl group, an isocyanate group, an N-alkoxyalkylamino group, a methylol group and an alkylmethylol group.
  • crosslinking agent (C) for example, a compound having two or more (meth) acryloyl groups, a compound having two or more N-alkoxyalkylamino groups, a methylol group-containing phenol compound, an alkylmethylol group-containing phenol compound, And oxirane ring-containing compounds, oxetane ring-containing compounds, oxazoline ring-containing compounds, isocyanate group-containing compounds (including those which are blocked), aldehyde group-containing phenol compounds, and compounds having two or more (meth) acryloyl groups And compounds having two or more N-alkoxyalkylamino groups are preferred.
  • Examples of the compound having two or more (meth) acryloyl groups include bifunctional (meth) acrylic esters, and polyfunctional (meth) acrylic esters such as trifunctional or higher functional (meth) acrylic esters. .
  • difunctional (meth) acrylic acid esters examples include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexane Diol di (meth) acrylate and 1,9-nonanediol di (meth) acrylate are mentioned.
  • trifunctional or higher (meth) acrylic acid esters examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Pentaerythritol hexa (meth) acrylate, a mixture of dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, tri (2- (meth) acryloyloxy Other than ethyl) phosphate, succinic acid modified pentaerythritol tri (meth) acrylate, succinic acid modified dipentaerythritol penta (meth) acrylate, A
  • Examples of the compound having two or more N-alkoxyalkylamino groups include compounds having two or more alkyletherified amino groups (hereinafter also referred to as "amino group-containing compounds"), and alkyletherified amino
  • amino group-containing compounds compounds having two or more alkyletherified amino groups
  • alkyletherified amino alkyletherified amino
  • the group is, for example, a group represented by the following formula.
  • R C1 is a methylene group or an alkylene group, preferably a methylene group or an alkylene group having 2 to 10 carbon atoms
  • R C2 is an alkyl group, preferably an alkyl group having 1 to 10 carbon atoms is there.
  • amino group-containing compound examples include active methylol groups (CH 2 OH) in nitrogen compounds such as (poly) methylolated melamine, (poly) methylolated glycoluril, (poly) methylolated benzoguanamine, and (poly) methylolated urea. And compounds in which all or part (at least two) of the groups) are alkyletherified.
  • an alkyl group which comprises an alkyl ether a methyl group, an ethyl group, a butyl group is mentioned, for example, These may mutually be same or different.
  • the methylol group which is not alkyletherified may be self-condensing within one molecule, or may be condensed between two molecules to form an oligomer component as a result.
  • hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril and the like can be used.
  • the crosslinking agent (C) may be used alone or in combination of two or more.
  • the content of the crosslinking agent (C) is usually 1 to 300 parts by mass, preferably 5 to 200 parts by mass, more preferably 10 with respect to 100 parts by mass of the polymer (A). 100 parts by mass.
  • the content of the crosslinking agent (C) is in the above range, a resin film having excellent resolution, elongation physical properties and heat resistance tends to be formed.
  • the resin composition of the present invention can contain a photopolymerization initiator (D).
  • a compound having an ethylenically unsaturated group, in particular a (meth) acryloyl group is used as the crosslinking agent (C)
  • the resin composition of the present invention has a negative photosensitive composition by using the photopolymerization initiator (D). It becomes a thing.
  • a photoinitiator (D) is a compound which generate
  • the exposure treatment for the coating film formed from the photosensitive composition generates an active species capable of initiating polymerization in the exposed area based on the photopolymerization initiator (D), and this active species causes two or more ethylenic non
  • the compound having a saturated group is polymerized to change the solubility of the exposed portion in the alkaline developer.
  • Examples of the photopolymerization initiator (D) include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, acyl phosphine oxide compounds, onium salt compounds, benzoin compounds And benzophenone compounds, ⁇ -diketone compounds, polynuclear quinone compounds, diazo compounds and imidosulfonate compounds.
  • thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyl oxime compounds and acyl phosphine oxide compounds is preferable.
  • thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-dichloro thioxanthone, 2,4- dimethyl thioxanthone, 2,4- diethyl Thioxanthone and 2,4-diisopropylthioxanthone can be mentioned.
  • acetophenone compounds include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholino).
  • Examples include phenyl) butan-1-one and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.
  • biimidazole compound examples include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole and 2,2′-bis 2,4-Dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', And 5,5'-tetraphenyl-1,2'-biimidazole.
  • triazine compound examples include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-) Methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s -Triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl)
  • O-acyloxime compounds include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6 -(2-Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranyl methoxybenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- ⁇ 2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl] ) Methoxybenzoyl ⁇ -9H-carbazol-3-yl]-, 1- (O-acetyloxime).
  • NCI-831, NCI-930 above, made by ADEKA Co., Ltd.
  • OXE-03, OXE-04 above, made by BASF Co., Ltd.
  • BASF Co., Ltd. BASF Co., Ltd.
  • acyl phosphine oxide compounds include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl-phosphine oxide, bis (2 And 4,6-trimethylbenzoyl) -phenyl-phosphine oxide.
  • a sensitizer when a photopolymerization initiator other than a biimidazole compound such as an acetophenone compound is used, a sensitizer may be used in combination.
  • a sensitizer for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 4-dimethyl Ethyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone It can be mentioned.
  • a photoinitiator (D) may be used by 1 type, and may use 2 or more types together.
  • the content of the photopolymerization initiator (D) is preferably 0.01 to 120 parts by mass, more preferably 1 with respect to 100 parts by mass of the compound having an ethylenically unsaturated group.
  • the amount is about 100 parts by mass, more preferably 5 to 80 parts by mass.
  • Hardening of an exposure part becomes enough for content of a photoinitiator (D) to be more than the said lower limit, and it is easy to improve heat resistance.
  • the content of the photopolymerization initiator (D) is less than or equal to the upper limit value, it is easy to obtain a pattern with high resolution without lowering the transparency to exposure light.
  • the resin composition of the present invention contains a solvent (E).
  • the handleability of the resin composition of the present invention can be improved, the viscosity can be adjusted, and the storage stability can be improved.
  • Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate;
  • Propylene glycol monoalkyl ether such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether
  • Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether and propylene glycol dibutyl ether;
  • Cellosolves such as
  • lactic acid esters propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, alcohols and lactones are preferable; ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, tetrahydrofurfuryl alcohol, More preferred is ⁇ -butyrolactone.
  • the solvent (E) may be used alone or in combination of two or more.
  • the content of the solvent (E) is usually 40 to 900 parts by mass, preferably 60 to 900 parts by mass with respect to 100 parts by mass in total of components other than the solvent (E) in the composition. It is 400 parts by mass.
  • ⁇ Other additives (F)> In the resin composition of the present invention, various additions such as alkali-soluble polymers other than polymer (A), adhesion assistants, crosslinked fine particles, leveling agents, surfactants, sensitizers, inorganic fillers, quenchers, etc. An agent can be contained in the range which does not impair the object and the characteristic of the present invention.
  • the resin composition of the present invention can be prepared by uniformly mixing the respective components. Also, in order to remove foreign matter, the components obtained may be uniformly mixed, and then the resulting mixture may be filtered with a filter or the like.
  • the resin composition is excellent in storage stability.
  • the resin film of the present invention is a resin film (cured film) obtained by curing the resin composition of the present invention. Since the polymer (A) contained in the resin composition of the present invention is excellent in heat resistance, the resin film obtained using the resin composition of the present invention is also excellent in heat resistance.
  • the resin film of the present invention is high in mechanical strength, small in thermal expansion (linear expansion coefficient), low in dielectric constant, excellent in elongation properties, and hardly cracked even if it receives an impact.
  • the resin film of the present invention is used as a surface protective film, an interlayer insulating film and a planarizing film of electronic components such as circuit boards (semiconductor elements), semiconductor packages or display elements, and also as insulating films for high density mounting substrates It can be suitably used as a material, a photosensitive adhesive and a pressure sensitive adhesive.
  • the resin film of the present invention is produced, for example, by applying at least a resin composition of the present invention on a support to form a coated film, and curing the coated film to obtain a resin film. can do.
  • a resin composition of the present invention containing a photosensitive acid generator (B) or a photopolymerization initiator (D) is coated on a support to form a coated film.
  • Step (hereinafter also referred to as “coating step”), step of selectively exposing the coating film to obtain a selectively exposed film (hereinafter also referred to as “exposure step”), developing the selectively exposed film with an alkaline developer
  • curing step step of curing the patterned coating film to obtain a patterned resin film.
  • the resin composition of the present invention containing a photosensitive acid generator (B) or a photopolymerization initiator (D) is coated on a support, and dried if necessary. Remove the solvent (E).
  • the drying conditions are, for example, heating at usually 50 to 140 ° C. for 10 to 1000 seconds using an oven or a hot plate.
  • the film thickness of the coating film may be appropriately adjusted in accordance with the film thickness of the patterned resin film to be finally obtained.
  • the support for example, a silicon wafer, a compound semiconductor wafer, a wafer with a metal thin film, a glass substrate, a quartz substrate, a ceramic substrate, an aluminum substrate, a SUS substrate, a substrate having a semiconductor chip on the surface of these supports, and others
  • a resin sheet is mentioned.
  • the coating method include a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a silk screen method, and an ink jet method.
  • the above-mentioned coating film is selectively exposed through, for example, a reticle using, for example, a contact aligner, a stepper or a scanner to obtain a selective exposure film.
  • the exposure light for example, radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like can be mentioned, and preferably light with a wavelength of 200 to 500 nm (example: i-ray (365 nm)) is used.
  • the irradiation dose of exposure light varies depending on the type and blending ratio of each component in the photosensitive composition, the thickness of the coating film, etc. When i-line is used for the exposure light, the exposure dose is usually 100 to 1500 mJ /. It is cm 2 .
  • PEB process heat treatment may be performed on the selective coating film.
  • the PEB conditions vary depending on the kind of each component in the resin composition, the blending ratio, the thickness of the coating film, etc., but are usually 70 to 150 ° C., preferably 80 to 120 ° C., and about 1 to 60 minutes. .
  • the selective exposure film is developed with an alkaline developer to form a patterned coating film on a support.
  • the development method include a shower development method, a spray development method, an immersion development method, and a paddle development method.
  • the conditions for the development method are usually about 20 to 40 ° C. and about 1 to 10 minutes.
  • the alkaline developing solution may be, for example, an alkaline solution in which an alkaline compound such as sodium hydroxide, potassium hydroxide, ammonia water, tetramethyl ammonium hydroxide, choline or the like is dissolved to a concentration of 1 to 10% by mass.
  • An aqueous solution is mentioned.
  • An appropriate amount of, for example, a water-soluble organic solvent such as methanol or ethanol and a surfactant may be added to the alkaline aqueous solution.
  • the patterned coating film is cured by heating, for example.
  • heating is performed, for example, at a temperature of 100 to 250 ° C. for about 1 minute to 10 hours using an oven or a hot plate.
  • the electronic component of the present invention has the resin film of the present invention.
  • a circuit board semiconductor element
  • semiconductor package semiconductor package
  • a display element is mentioned, for example.
  • Example 1-1 Synthesis of Polymer (A-1)
  • 5.9 g (50 mol%) of the compound (M-1) and 10.8 g (50 mol%) of the compound (M-2) are dissolved in 45 g of propylene glycol monomethyl ether, and azo is used as a radical polymerization initiator
  • a monomer solution was prepared by adding 0.918 g (7 mol% to all monomers) of bisisobutyronitrile. Next, nitrogen bubbling was performed for 15 minutes, and the mixture was heated to 80 ° C. with stirring. The polymerization reaction was carried out for 4 hours, with the time when the solution reached 75 ° C. as the initiation time of the polymerization reaction.
  • the polymerization solution was water-cooled and cooled to 30 ° C. or less, 60 g of methanol was added, and solution liquid extraction and washing were performed five times with an equal amount of normal hexane.
  • An equal amount of propylene glycol monomethyl ether is added to a methanol solution containing a polymer after extraction and washing, methanol is distilled off with a rotary evaporator equipped with a water bath at 40 ° C., and the solution is further concentrated to about 30% to obtain a target polymer Obtained with the solution.
  • the Mw of the polymer (A-1) was 21,000, and the Mw / Mn was 2.15.
  • Example 1-2 to 1-10 Synthesis of Polymers (A-2) to (A-10)
  • polymers (A-2) to (A-10) were prepared in the same manner as in Example 1-1 except that monomers of the types and amounts shown in Table 2 were used. Got).
  • the solvent (E-1) is propylene glycol monomethyl ether.
  • Example 2-2 to 2-10 resin compositions (J-2) to (J-10) were prepared in the same manner as in Example 2-1 except that polymers of the types and amounts shown in Table 3 were used. ) Were prepared, and predetermined evaluation was performed using the obtained resin composition.
  • a hydroxystyrene-styrene copolymer product name: Styrene marker linker CST, manufactured by Maruzen Petrochemical Co., Ltd.
  • the resin composition (CJ-1) was prepared in the same manner as in Example 2-1, and predetermined evaluation was performed using the obtained resin composition.
  • the heat resistant resin compositions (J-1) to (J-10) and (CJ-1) are cured by heating at 200 ° C. for 1 hour to obtain a resin film, and then nitrogen is obtained by thermogravimetric analysis (TGA).
  • TGA thermogravimetric analysis
  • the temperature was measured at a temperature rising rate of 10 ° C./minute under an atmosphere, and evaluated at a 5 mass% thermal weight loss temperature (Td5).
  • Td5 thermogravimetric analysis
  • the width of the sample was 5 mm
  • the distance between the chucks was 20 mm
  • the tensile rate was 5 mm / min
  • the measurement temperature was about room temperature (20 to 25 ° C.).
  • the average of the measured values of five or more test pieces obtained from the cured film obtained under the same conditions is “A” when it is 70 MPa or more, “B” when it is 50 MPa or more and less than 70 MPa, “B” when it is 30 MPa or more and less than 50 MPa. C ", the case of less than 30 MPa was" D ".
  • the dielectric resin compositions (J-1) to (J-10) and (CJ-1) are coated on a SUS substrate to a film thickness of 5 ⁇ m and dried on an 80 ° C. hot plate for 3 minutes, It was heat cured in an oven at 200 ° C. for 1 hour.
  • the dielectric constant at 1 MHz of the obtained cured film (resin film) is measured, and in the case of less than 4.0, “A”, in the case of 4.0 or more and less than 4.5, “B”, 4.5 or more The case is "C".
  • Photosensitive acid generator (B-1) 4,4 '-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol and 1,2-naphthoquinone diazide- 5-sulfonic acid chloride condensate
  • Photosensitive acid generator (B-2) 4,7-di-n-butoxynaphthyltetrahydrothiophenium trifluoromethanesulfonate
  • Solvent (E-1) Propylene glycol monomethyl ether
  • Solvent (E-2) Tetrahydrofurfuryl alcohol
  • Solvent (E-3) ⁇ -butyrolactone sur
  • Example 3 a photosensitive composition (Example 3) was prepared in the same manner as Example 3-1 except that the types and amounts of the blending components were changed as shown in Table 4. PR-2) to (PR-10) and (CPR-1) were prepared. Predetermined evaluation was performed using the obtained photosensitive composition.
  • the photosensitive composition is as follows.
  • the photosensitive composition was spin-coated on a silicon wafer having a resolution and a residual film rate of 6 inches, and then heated at 110 ° C. for 3 minutes using a hot plate to prepare a uniform coated film with a thickness of 10 ⁇ m. Then, using an aligner (made by Suss Microtec, type "MA-150"), the ultraviolet light from a high pressure mercury lamp is applied to the above coated film so that the exposure amount at a wavelength of 350 nm is 500 mJ / cm 2 through a pattern mask. Irradiated. Then, the coated film after exposure was subjected to immersion development for 120 seconds at 23 ° C. using a 2.38 mass% tetramethylammonium hydroxide aqueous solution.
  • the coated film after development is washed with ultrapure water for 30 seconds, air-dried with air, then observed with a microscope (MHL110 manufactured by Olympus Corporation), and the pattern of the resolved minimum pattern
  • the dimension is a resolution (unit: ⁇ m).
  • the film thickness is measured using a stylus thickness meter P-16 manufactured by KLA-Tencor, and the residual film ratio (100% ⁇ (film thickness after development / film before development) from the film thickness difference before and after development Thickness) was calculated and evaluated by the following evaluation criteria.
  • heating was performed at 110 ° C. for 3 minutes using a hot plate.
  • C Residual film rate less than 80% 6-2.
  • the solvent resistant photosensitive compositions (PR-1) to (PR-10) and (CPR-1) are placed in a 1 mm thick metal frame placed on a Teflon sheet, and 2 in a vacuum oven with an internal temperature of 50 ° C. After time treatment, the film was pressed at 200 ° C. for 2 hours under a pressure of 0.5 t and peeled off from the Teflon sheet to obtain a cured film having a thickness of about 0.5 mm.
  • This cured film is cut into 1 cm square for testing, and after measuring the weight, it is immersed in 5 ml of NMP (N-methylpyrrolidone) at room temperature for 3 days to change the shape of the cured film (shape change by visual observation, weight change) Was evaluated.
  • the weight of the cured film after immersion in NMP was measured after the cured film after immersion in NMP was dried in a vacuum oven at an internal temperature of 80 ° C. for 3 days.
  • Each weight of the cured film before and after immersion in NMP was measured with a Sartorius precision balance BP311D. There is no change in shape by visual observation, and weight reduction is less than 3% "A", regardless of the change in visual shape change, weight reduction by 3% or more and less than 10% is "B", 10% or more In the case of “C”.

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Abstract

Le problème décrit par la présente invention est de fournir une composition de résine qui présente une excellente résistance à la chaleur. La solution selon l'invention porte sur une composition de résine qui contient : un polymère qui contient, dans une même molécule ou dans différentes molécules, un motif structural ayant une structure partielle de formule (i) et un ou plusieurs motifs structuraux choisis parmi des motifs structuraux ayant une structure partielle de formule (ii-1) et des motifs structuraux ayant un groupe hydroxyle phénolique ; et un solvant. Dans les formules, chacun de R1 et R2 représente indépendamment un atome d'hydrogène, un groupe hydrocarboné ayant de 1 à 20 atomes de carbone, un groupe qui a au moins une fraction choisie parmi -O- et similaire dans au moins une liaison carbone-carbone dans le groupe hydrocarboné décrit ci-dessus, ou un groupe qui est obtenu par substitution de certains atomes d'hydrogène dans ces groupes ; R1 et R2 peuvent se combiner les uns avec les autres et former une structure cyclique ayant de 3 à 20 chaînons cycliques conjointement avec B auquel OR1 et OR2 sont liés ; chacun de R3 et R4 représente indépendamment un atome d'hydrogène, un groupe hydrocarboné ayant de 1 à 20 atomes de carbone ou un groupe attracteur d'électrons ; au moins l'un de R3 et R4 représente un groupe attracteur d'électrons ; et * représente un bras de liaison.
PCT/JP2018/025282 2017-08-10 2018-07-03 Polymère, composition de résine, film de résine, procédé de production de film de résine à motifs, et composant électronique WO2019031114A1 (fr)

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WO2021095766A1 (fr) * 2019-11-12 2021-05-20 Jsr株式会社 Composition, procédé de production pour un substrat, et polymère
JP7431696B2 (ja) 2020-08-04 2024-02-15 信越化学工業株式会社 ポジ型感光性樹脂組成物、ポジ型感光性ドライフィルム、ポジ型感光性ドライフィルムの製造方法、パターン形成方法、硬化被膜形成方法、層間絶縁膜、表面保護膜、及び電子部品

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021095766A1 (fr) * 2019-11-12 2021-05-20 Jsr株式会社 Composition, procédé de production pour un substrat, et polymère
JP7431696B2 (ja) 2020-08-04 2024-02-15 信越化学工業株式会社 ポジ型感光性樹脂組成物、ポジ型感光性ドライフィルム、ポジ型感光性ドライフィルムの製造方法、パターン形成方法、硬化被膜形成方法、層間絶縁膜、表面保護膜、及び電子部品

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