WO2014157171A1 - Composition de résine photosensible, procédé de production de film polymérisé, film polymérisé, dispositif d'affichage à cristaux liquides et dispositif d'affichage électroluminescent organique - Google Patents

Composition de résine photosensible, procédé de production de film polymérisé, film polymérisé, dispositif d'affichage à cristaux liquides et dispositif d'affichage électroluminescent organique Download PDF

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WO2014157171A1
WO2014157171A1 PCT/JP2014/058230 JP2014058230W WO2014157171A1 WO 2014157171 A1 WO2014157171 A1 WO 2014157171A1 JP 2014058230 W JP2014058230 W JP 2014058230W WO 2014157171 A1 WO2014157171 A1 WO 2014157171A1
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group
structural unit
polymer
resin composition
photosensitive resin
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PCT/JP2014/058230
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English (en)
Japanese (ja)
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山田　悟
知樹 松田
達也 霜山
健太 山▲ざき▼
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富士フイルム株式会社
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Priority to JP2015508531A priority Critical patent/JP6116668B2/ja
Priority to KR1020157022121A priority patent/KR20150107847A/ko
Priority to CN201480017166.2A priority patent/CN105051608B/zh
Publication of WO2014157171A1 publication Critical patent/WO2014157171A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/124—Insulating layers formed between TFT elements and OLED elements

Definitions

  • the present invention relates to a photosensitive resin composition (hereinafter sometimes simply referred to as “the composition of the present invention”).
  • the present invention also relates to a method for producing a cured film using the photosensitive resin composition, a cured film obtained by curing the photosensitive composition, and various image display apparatuses using the cured film. More specifically, a photosensitive resin composition suitable for forming a flattening film, a protective film and an interlayer insulating film of an electronic component such as a liquid crystal display device, an organic EL (organic electroluminescence) display device, an integrated circuit element, and a solid-state imaging device.
  • the present invention relates to a product and a method for producing a cured film using the product.
  • an interlayer insulating film is generally used to insulate between wirings arranged in layers. Is provided.
  • a photosensitive resin composition is widely used because the number of steps for obtaining a required pattern shape is small and a material having sufficient flatness is preferable (for example, And see Patent Documents 1 to 4).
  • a photosensitive resin composition capable of improving chemical resistance and lowering the relative dielectric constant while maintaining high sensitivity.
  • a photosensitive resin composition having a group in which an acid group is protected by an acid-decomposable group and a crosslinkable group is included in the composition in order to increase the sensitivity compared to the prior art.
  • the chemical resistance is lowered in this case.
  • the relative dielectric constant becomes too high when the proportion of the crosslinking group is increased in order to supplement the chemical resistance.
  • the present invention is intended to solve such problems, and a photosensitive resin composition capable of improving chemical resistance and lowering the relative dielectric constant while maintaining high sensitivity. The purpose is to provide.
  • the photosensitive resin composition has a structural unit having a group in which an acid group is protected by an acid-decomposable group, a structural unit having a crosslinkable group, and a lactone structure. It has been found that the chemical resistance can be improved and the relative dielectric constant can be lowered by blending the structural unit having the formula. Furthermore, the inventors have found that high sensitivity can be maintained, and have completed the present invention. The reason for this is presumed, but in the photosensitive resin composition, a structural unit having a lactone structure is combined with a structural unit having a group in which an acid group is protected by an acid-decomposable group and a structural unit having a crosslinkable group.
  • ⁇ 1> a polymer component containing a polymer that satisfies at least one of the following (1) and (2): (1) (a1) a structural unit having a group in which an acid group is protected by an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group, or (2) the structural unit (a1).
  • a polymer having the structural unit (a2), (B) a photoacid generator, (C) contains a solvent
  • the (A) polymer component at least one structural unit having a lactone structure is contained
  • a photosensitive resin composition comprising at least one polymer containing the structural unit (a4) and not containing the structural unit (a1) and the structural unit (a2).
  • General formula (1) (In General Formula (1), R A1 represents a substituent, and n1 R A1 s are independent and may be the same or different.
  • Z 1 includes —O—C ( ⁇ O) —.
  • R X1 is .
  • R A2 represents a hydrogen atom or an alkyl group is a substituent group
  • n2 pieces of R A2 are each independently optionally .
  • a 1 be the same or different are Represents a single bond or a divalent linking group
  • Z 2 represents a monocyclic or polycyclic structure containing a group represented by —O—C ( ⁇ O) —
  • n2 represents an integer of 0 or more.
  • R X2 is .
  • R A3 represents a hydrogen atom or an alkyl group represents a substituent
  • n3 pieces of R A3 are independent, which may be the same or different
  • a 2 is Represents a single bond or a divalent linking group
  • Z 3 represents a monocyclic or polycyclic structure containing a group represented by —O—C ( ⁇ O) —
  • n3 represents an integer of 0 or more
  • X 1 Represents an oxygen atom or —NR ′′ —.
  • R ′′ represents a hydrogen atom or an alkyl group.
  • R ′′ represents a hydrogen atom or an alkyl group.
  • ⁇ 5> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein the lactone structure is a lactone structure forming a 5-membered ring or a 6-membered ring.
  • ⁇ 6> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the structural unit (a1) is a structural unit having a group in which a carboxy group is protected in the form of an acetal.
  • ⁇ 7> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 6>, wherein the structural unit (a1) is a structural unit represented by the following general formula (1-11).
  • R 1 and R 2 each represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R 1 and R 2 is an alkyl group or an aryl group; 3 represents an alkyl group or an aryl group, R 1 or R 2 and R 3 may be linked to form a cyclic ether, R 4 represents a hydrogen atom or a methyl group, and X represents a single bond Or represents an arylene group.
  • the crosslinkable group is at least one selected from an epoxy group, an oxetanyl group, and —NH—CH 2 —OR (where R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), ⁇ 7>
  • the photosensitive resin composition according to any one of the above.
  • FIG. 1 is a conceptual diagram of a configuration of an example of a liquid crystal display device.
  • the schematic sectional drawing of the active matrix substrate in a liquid crystal display device is shown, and it has the cured film 17 which is an interlayer insulation film.
  • 1 shows a conceptual diagram of a configuration of an example of an organic EL display device.
  • a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
  • the composition of the present invention comprises: (A) a polymer component containing a polymer that satisfies at least one of the following (1) and (2): (1) (a1) a structural unit having a group in which an acid group is protected by an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group, or (2) the structural unit (a1). And a polymer having the structural unit (a2), (B) a photoacid generator, (C) contains a solvent, In the (A) polymer component, (a4) at least one structural unit having a lactone structure is contained, (3) At least one polymer containing the structural unit (a4) and not including the structural unit (a1) and the structural unit (a2) is included.
  • ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition which can make chemical resistance favorable and can make a dielectric constant lower can be provided, maintaining a high sensitivity.
  • the polymer component has (a1) a structural unit having an acid group protected by an acid-decomposable group, (a2) a structural unit having a crosslinkable group, and (a4) a lactone structure.
  • a polymer (A2) which have at least 1 type of structural units are included.
  • a polymer component comprising (a1) a structural unit containing a structural unit having an acid group protected by an acid-decomposable group and (a2) a structural unit having a crosslinkable group (hereinafter referred to as heavy polymer). (A2)), (a4) a structural unit having a lactone structure, and (a1) a structural unit having a group in which an acid group is protected by an acid-decomposable group, and (a2) a crosslinkable group A polymer containing no structural unit (hereinafter also referred to as polymer (A2b)).
  • polymer component comprising (a1) a structural unit having an acid group protected by an acid-decomposable group and (a4) a structural unit having a lactone structure (hereinafter referred to as polymer) (Also referred to as (A2c)) and (a2) a polymer containing a structural unit having a crosslinkable group (hereinafter also referred to as polymer (A2d)).
  • the polymer component comprises (a1) a polymer containing a structural unit having an acid group protected by an acid-decomposable group (hereinafter also referred to as polymer (A2e)), and (a2 And a polymer containing a structural unit having a crosslinkable group and (a4) a structural unit having a lactone structure (hereinafter also referred to as polymer (A2f)).
  • a polymer component comprising (a1) a polymer containing a structural unit having an acid group protected by an acid-decomposable group (hereinafter also referred to as polymer (A2g)), and (a2 ) A polymer containing a structural unit having a crosslinkable group (hereinafter also referred to as polymer (A2h)) and (a4) a polymer containing a structural unit having a lactone structure (hereinafter also referred to as polymer (A2i)).
  • A2g a polymer containing a structural unit having an acid group protected by an acid-decomposable group
  • A2h A polymer containing a structural unit having a crosslinkable group
  • A2i a polymer containing a structural unit having a lactone structure
  • the lactone structure refers to a cyclic ester containing a —COO— group in the ring.
  • the structural unit having a lactone structure in the present invention refers to a structural unit containing the lactone structure.
  • a monocyclic ring or a lactone structure is condensed with another ring structure to form a polycyclic structure. Says what you are doing.
  • the lactone structure may be directly bonded to the main chain.
  • the photosensitive resin composition is blended with a structural unit having a group in which an acid group is protected by an acid-decomposable group, a structural unit having a crosslinkable group, and a structural unit having a lactone structure.
  • a high-concentration alkaline developer for example, a TMAH (tetramethylammonium hydroxide) aqueous solution of 2.0% by mass or more
  • the developability can be further improved.
  • the composition of the present invention is developed using a high concentration alkaline developer, the lactone structure is ring-opened to generate a carboxylic acid.
  • the composition of the present invention with respect to the alkaline developer is produced. It is estimated that the solubility of the product is further increased.
  • the (A) polymer component is preferably an addition polymerization type resin, and more preferably a polymer containing a structural unit derived from (meth) acrylic acid and / or an ester thereof.
  • the “structural unit derived from (meth) acrylic acid and / or its ester” is also referred to as “(meth) acrylic structural unit”.
  • a polymer component becomes a main component of the component except the solvent of the composition of this invention, and it is preferable to occupy 60 mass% or more of a total solid.
  • the polymer component has at least a structural unit (a1) having a group in which an acid group is protected with an acid-decomposable group.
  • a polymer component has a structural unit (a1), it can be set as the highly sensitive photosensitive resin composition.
  • the “group in which the acid group is protected with an acid-decomposable group” in the present invention those known as an acid group and an acid-decomposable group can be used, and are not particularly limited.
  • Specific examples of the acid group preferably include a carboxyl group and a phenolic hydroxyl group.
  • Specific acid-decomposable groups include groups that are relatively easily decomposed by an acid (for example, an acetal functional group such as an ester structure, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group described later) or an acid.
  • a group that is relatively difficult to decompose for example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group
  • a tertiary alkyl group such as a tert-butyl ester group
  • a tertiary alkyl carbonate group such as a tert-butyl carbonate group
  • the structural unit (a1) is preferably a structural unit having a protected carboxyl group protected with an acid-decomposable group or a structural unit having a protected phenolic hydroxyl group protected with an acid-decomposable group.
  • the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group and the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group will be described in order. To do.
  • the structural unit (a1-1) is a structural unit having a protected carboxyl group in which the carboxyl group of the structural unit having a carboxyl group is protected by an acid-decomposable group described in detail below.
  • the structural unit having a carboxyl group that can be used for the structural unit (a1-1) is not particularly limited, and a known structural unit can be used.
  • Examples thereof include a structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, such as an unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, or unsaturated tricarboxylic acid. It is done.
  • the structural unit (a1-1-1) used as the structural unit having a carboxyl group will be described.
  • ⁇ (a1-1-1) Structural Unit Derived from Unsaturated Carboxylic Acid etc. Having at least One Carboxyl Group in the Molecule >>>>>>>
  • the unsaturated carboxylic acid used in the present invention include those listed below. That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, ⁇ -chloroacrylic acid, cinnamic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acrylic acid. And leuoxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-phthalic acid, and the like.
  • the unsaturated dicarboxylic acid examples include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.
  • the acid anhydride may be sufficient as unsaturated polyhydric carboxylic acid used in order to obtain the structural unit which has a carboxyl group. Specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like.
  • the unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester of a polyvalent carboxylic acid, such as succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2 -Methacryloyloxyethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like.
  • the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both ends, and examples thereof include ⁇ -carboxypolycaprolactone monoacrylate and ⁇ -carboxypolycaprolactone monomethacrylate.
  • unsaturated carboxylic acid acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used.
  • acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acrylic acid are used. It is preferable to use leuoxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethyl-phthalic acid, or an anhydride of an unsaturated polycarboxylic acid, such as acrylic acid, methacrylic acid, 2- (meth) acrylic acid. It is more preferable to use leuoxyethyl hexahydrophthalic acid.
  • the structural unit (a1-1-1) may be composed of one type alone, or may be composed of two or more types.
  • an acid-decomposable group that can be used for the structural unit (a1-1) >>>>>
  • the acid-decomposable group that can be used for the structural unit (a1-1) the acid-decomposable groups described above can be used.
  • an acid-decomposable group is preferably a group having a structure protected in the form of an acetal.
  • the protected carboxyl group in which the carboxyl group is protected in the form of an acetal means that the basic physical properties of the photosensitive resin composition, in particular the sensitivity and pattern shape, the formation of contact holes, and the storage stability of the photosensitive resin composition From the viewpoint of Furthermore, it is more preferable from the viewpoint of sensitivity that the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following general formula (a1-10).
  • the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following general formula (a1-10)
  • the entire protected carboxyl group is — (C ⁇ O) —O—CR 101
  • the structure is R 102 (OR 103 ).
  • R 101 and R 102 each independently represents a hydrogen atom or an alkyl group, except that R 101 and R 102 are both hydrogen atoms, and R 103 represents an alkyl group.
  • R 101 or R 102 and R 103 may be linked to form a cyclic ether.
  • R 101 to R 103 each independently represents a hydrogen atom or an alkyl group.
  • the alkyl group may be linear, branched or cyclic.
  • both R 101 and R 102 do not represent a hydrogen atom, and at least one of R 101 and R 102 represents an alkyl group.
  • the linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms.
  • methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n examples include -hexyl group, texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group and the like.
  • the cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 4 to 6 carbon atoms.
  • Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group.
  • the alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group.
  • R 101 , R 102 and R 103 When it has a halogen atom as a substituent, R 101 , R 102 and R 103 become a haloalkyl group, and when it has an aryl group as a substituent, R 101 , R 102 and R 103 become an aralkyl group.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom or a chlorine atom is preferable.
  • the aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, an ⁇ -methylphenyl group, and a naphthyl group.
  • the alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and more preferably a methoxy group or an ethoxy group.
  • the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group is straight.
  • the alkyl group is a chain or branched chain, it may have a cycloalkyl group having 3 to 12 carbon atoms as a substituent. These substituents may be further substituted with the above substituents.
  • R 101, R 102 and R 103 represents an aryl group
  • the aryl group preferably has 6 to 12 carbon atoms, 6 to 10 carbon atoms More preferred.
  • the aryl group may have a substituent, and preferred examples of the substituent include an alkyl group having 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group, a tolyl group, a silyl group, a cumenyl group, and a 1-naphthyl group.
  • R 101 , R 102 and R 103 can be bonded together to form a ring together with the carbon atom to which they are bonded.
  • Examples of the ring structure when R 101 and R 102 , R 101 and R 103 or R 102 and R 103 are bonded include, for example, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, an adamantyl group, and a tetrahydropyrani group. And the like.
  • one of R 101 and R 102 is preferably a hydrogen atom or a methyl group.
  • radical polymerizable monomer used for forming the structural unit having a protected carboxyl group represented by the general formula (a1-10) a commercially available one may be used, or it may be synthesized by a known method. Things can also be used. For example, it can be synthesized by the synthesis method described in paragraph Nos. 0037 to 0040 of JP2011-212494A, the contents of which are incorporated herein.
  • a first preferred embodiment of the structural unit (a1-1) is a structural unit represented by the following general formula (1-11).
  • R 1 and R 2 each represent a hydrogen atom, an alkyl group or an aryl group, at least either one of R 1 and R 2 represent an alkyl group or an aryl group, R 3 Represents an alkyl group or an aryl group, and R 1 or R 2 and R 3 may be linked to form a cyclic ether, R 4 represents a hydrogen atom or a methyl group, and X represents a single bond or Represents an arylene group.
  • R 1 and R 2 are alkyl groups, alkyl groups having 1 to 10 carbon atoms are preferred.
  • R 1 and R 2 are aryl groups, a phenyl group is preferred.
  • R 1 and R 2 are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 3 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.
  • X represents a single bond or an arylene group, and a single bond is preferable.
  • a second preferred embodiment of the structural unit (a1-1) is a structural unit represented by the following general formula (1-12).
  • Formula (1-12) (In the formula (1-12), R 121 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L 1 represents a carbonyl group or a phenylene group, and R 122 to R 128 each independently represents a hydrogen atom or Represents an alkyl group having 1 to 4 carbon atoms.) R 121 is preferably a hydrogen atom or a methyl group. L 1 is preferably a carbonyl group. R 122 to R 128 are preferably hydrogen atoms.
  • R represents a hydrogen atom or a methyl group.
  • the structural unit (a1-2) is a structural unit (a1-2-1) having a protected phenolic hydroxyl group in which the structural unit having a phenolic hydroxyl group is protected by an acid-decomposable group described in detail below.
  • ⁇ (a1-2-1) Structural Unit Having Phenolic Hydroxyl Group examples include a hydroxystyrene structural unit and a structural unit in a novolac resin.
  • a structural unit derived from hydroxystyrene or ⁇ -methylhydroxystyrene includes: It is preferable from the viewpoint of sensitivity.
  • a structural unit represented by the following general formula (a1-20) is also preferable from the viewpoint of sensitivity.
  • R 220 represents a hydrogen atom or a methyl group
  • R 221 represents a single bond or a divalent linking group
  • R 222 represents a halogen atom or a straight chain having 1 to 5 carbon atoms or Represents a branched alkyl group
  • a represents an integer of 1 to 5
  • b represents an integer of 0 to 4
  • a + b is 5 or less, and when R 222 is 2 or more, these R 222 may be different or the same.
  • R 220 represents a hydrogen atom or a methyl group, and is preferably a methyl group.
  • R 221 represents a single bond or a divalent linking group. A single bond is preferable because the sensitivity can be improved and the transparency of the cured film can be improved.
  • the divalent linking group of R 221 may be exemplified alkylene groups, specific examples R 221 is an alkylene group, a methylene group, an ethylene group, a propylene group, isopropylene group, n- butylene group, isobutylene group, tert -Butylene group, pentylene group, isopentylene group, neopentylene group, hexylene group and the like.
  • R 221 is a single bond, a methylene group, or an ethylene group.
  • the divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group.
  • A represents an integer of 1 to 5, but a is preferably 1 or 2 and more preferably 1 from the viewpoint of the effects of the present invention and the ease of production.
  • the bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4-position when the carbon atom bonded to R 221 is defined as the reference (first position).
  • R 222 is a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, fluorine atom, chlorine atom, bromine atom, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc. It is done. Among these, a chlorine atom, a bromine atom, a methyl group, or an ethyl group is preferable from the viewpoint of easy production.
  • B represents 0 or an integer of 1 to 4;
  • acid-decomposable group that can be used for the structural unit (a1-2) >>>>>
  • the acid-decomposable group that can be used for the structural unit (a1-2) as with the acid-decomposable group that can be used for the structural unit (a1-1), known ones can be used. It is not limited.
  • a structural unit having a protected phenolic hydroxyl group protected with acetal is a basic physical property of the photosensitive resin composition, particularly sensitivity and pattern shape, storage stability of the photosensitive resin composition, contact This is preferable from the viewpoint of hole formability.
  • the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of an acetal represented by the above general formula (a1-10).
  • the protected phenolic hydroxyl group as a whole is —Ar—O—CR 101 R
  • the structure is 102 (OR 103 ).
  • Ar represents an arylene group.
  • Examples of the radical polymerizable monomer used for forming a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected in the form of an acetal include paragraph number 0042 of JP2011-215590A. And the like.
  • a 1-alkoxyalkyl protector of 4-hydroxyphenyl methacrylate and a tetrahydropyranyl protector of 4-hydroxyphenyl methacrylate are preferable from the viewpoint of transparency.
  • acetal protecting group for the phenolic hydroxyl group examples include a 1-alkoxyalkyl group, such as a 1-ethoxyethyl group, a 1-methoxyethyl group, a 1-n-butoxyethyl group, and a 1-isobutoxyethyl group.
  • 1- (2-chloroethoxy) ethyl group, 1- (2-ethylhexyloxy) ethyl group, 1-n-propoxyethyl group, 1-cyclohexyloxyethyl group, 1- (2-cyclohexylethoxy) ethyl group, 1 -A benzyloxyethyl group etc. can be mentioned, These can be used individually or in combination of 2 or more types.
  • the radical polymerizable monomer used for forming the structural unit (a1-2) a commercially available one may be used, or one synthesized by a known method may be used. For example, it can be synthesized by reacting a compound having a phenolic hydroxyl group with vinyl ether in the presence of an acid catalyst. In the above synthesis, a monomer having a phenolic hydroxyl group may be previously copolymerized with another monomer, and then reacted with vinyl ether in the presence of an acid catalyst.
  • the structural unit (a1-1) is characterized by faster development than the structural unit (a1-2). Therefore, when it is desired to develop quickly, the structural unit (a1-1) is preferable. Conversely, when it is desired to delay the development, it is preferable to use the structural unit (a1-2).
  • the polymer component has a structural unit (a2) having a crosslinkable group.
  • the crosslinkable group is not particularly limited as long as it is a group that causes a curing reaction by heat treatment.
  • Preferred embodiments of the structural unit having a crosslinkable group include an epoxy group, an oxetanyl group, a group represented by —NH—CH 2 —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) and ethylene.
  • the (A-1) polymer component preferably includes a structural unit including at least one of an epoxy group and an oxetanyl group, and includes a structural unit including an epoxy group. It is more preferable to contain. In more detail, the following are mentioned.
  • the (A) polymer component preferably contains a structural unit having an epoxy group and / or an oxetanyl group (hereinafter also referred to as a structural unit (a2-1)).
  • the structural unit (a2-1) may have at least one epoxy group or oxetanyl group in one structural unit, and includes one or more epoxy groups, one or more oxetanyl groups, and two or more epoxy groups.
  • Group may have two or more oxetanyl groups, and is not particularly limited, but preferably has a total of 1 to 3 epoxy groups and / or oxetanyl groups, and a total of epoxy groups and / or oxetanyl groups It is more preferable to have one or two, and it is even more preferable to have one epoxy group or one oxetanyl group.
  • radical polymerizable monomer used for forming the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl ⁇ -ethyl acrylate, and glycidyl ⁇ -n-propyl acrylate.
  • radical polymerizable monomer used for forming the structural unit (a1-2-1) having the epoxy group and / or oxetanyl group include a monomer having a methacrylate structure and an acrylate ester. A monomer containing a structure is preferred.
  • glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl are preferred.
  • Ether, (3-ethyloxetane-3-yl) methyl acrylate, and (3-ethyloxetane-3-yl) methyl methacrylate are preferred from the viewpoints of copolymerization reactivity and improved properties of the cured film.
  • These structural units can be used individually by 1 type or in combination of 2 or more types.
  • R represents a hydrogen atom or a methyl group.
  • (a2-2) Structural unit having an ethylenically unsaturated group >>>
  • the structural unit (a2) having a crosslinkable group there may be mentioned the structural unit (a2-2) having an ethylenically unsaturated group.
  • the structural unit (a2-2) is preferably a structural unit having an ethylenically unsaturated group in the side chain, and a structural unit having an ethylenically unsaturated group at the terminal and having a side chain having 3 to 16 carbon atoms. More preferred.
  • the polymer component (A) used in the present invention is a structural unit (a2-3) having a group represented by —NH—CH 2 —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). Is also preferable.
  • R is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
  • the alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
  • the structural unit (a2-3) is more preferably a structural unit having a group represented by the following general formula (a2-30).
  • Formula (a2-30) (In the general formula (a2-30), R 1 represents a hydrogen atom or a methyl group, and R 2 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.) R 2 is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
  • the alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
  • R 2 include a methyl group, an ethyl group, an n-butyl group, an i-butyl group, a cyclohexyl group, and an n-hexyl group. Of these, i-butyl, n-butyl and methyl are preferred.
  • the polymer component contains (a4) at least one structural unit having a lactone structure, or the structural unit (a4), and the structural unit (a1). And at least one polymer not containing the structural unit (a2).
  • a4 a structural unit having a lactone structure into the composition of the present invention, photosensitivity that can improve chemical resistance and lower the relative dielectric constant while maintaining high sensitivity.
  • a resin composition can be provided.
  • the lactone structure in the structural unit having a lactone structure is not particularly limited, and any lactone structure can be used.
  • the lactone structure used in the present invention is preferably a lactone structure that forms a 5- to 7-membered ring, and more preferably a lactone structure that forms a 5-membered or 6-membered ring.
  • a lactone structure forming a 5- to 7-membered ring may be condensed with another ring structure on the lactone structure to form a polycyclic structure.
  • it is preferable that other ring structures are not condensed to the lactone structure.
  • the other ring structure is preferably condensed so as to form a bicyclo structure or a spiro structure.
  • other ring structures include a cyclic hydrocarbon group having 3 to 20 carbon atoms, a heterocyclic group having 3 to 20 carbon atoms, and the like.
  • the heterocyclic group is not particularly limited, and examples thereof include those having one or more heteroatoms out of the atoms constituting the ring or aromatic heterocyclic groups.
  • a heterocyclic group a 5-membered ring or a 6-membered ring is preferable, and a 5-membered ring is especially preferable.
  • the heterocyclic group preferably contains at least one oxygen atom, and examples thereof include an oxolane ring, an oxane ring, and a dioxane ring.
  • the number of other ring structures condensed to the lactone structure is preferably 1 to 5 1 to 3 are more preferable.
  • the lactone structure used in the present invention may or may not have a substituent, but preferably does not have a substituent.
  • substituents include, but are not limited to, for example, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, Examples include a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, and an acid-decomposable group. More preferred are an alkyl group having 1 to 4 carbon atoms and a cyano group.
  • the alkyl group a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms is preferable. More preferred are ⁇ 3 alkyl groups.
  • the number of substituents is not particularly limited, but is preferably 1 to 4, and more preferably 1 or 2.
  • the lactone structure used in the present invention has a plurality of substituents, the plurality of substituents may be the same as or different from each other. Further, when another ring structure is condensed to the lactone structure, this other ring structure may have a substituent.
  • the structural unit having a lactone structure used in the present invention preferably contains a group represented by the following general formula (1).
  • General formula (1) (In General Formula (1), R A1 represents a substituent, and n1 R A1 s are independent and may be the same or different. Z 1 includes —O—C ( ⁇ O) —. Represents a monocyclic or polycyclic structure, and n1 represents an integer of 0 or more.)
  • R A1 represents a substituent, and n1 R A1 s are independent and may be the same or different.
  • R A1 has the same meaning as the substituent that the above-mentioned lactone structure may have, and the preferred range is also the same.
  • Z 1 represents a monocyclic or polycyclic structure containing —O—C ( ⁇ O) —, and preferably represents a monocyclic structure.
  • the monocyclic structure is preferably a lactone structure that forms a 5- to 7-membered ring, and more preferably a lactone structure that forms a 5-membered or 6-membered ring.
  • the polycyclic structure preferably has a condensed lactone structure with another cyclic structure forming a bicyclo structure or a spiro structure.
  • Other ring structures are synonymous with the other ring structures described above, and preferred ranges are also the same.
  • n1 represents an integer of 0 or more, preferably an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0.
  • a plurality of substituents may be the same as or different from each other.
  • a plurality of substituents may be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring.
  • the structural unit (a4) is preferably represented by the following general formula (2).
  • General formula (2) In (formula (2), R X1 is .R A2 represents a hydrogen atom or an alkyl group is a substituent group, n2 pieces of R A2 are each independently optionally .A 1 be the same or different are Represents a single bond or a divalent linking group, Z 2 represents a monocyclic or polycyclic structure containing a group represented by —O—C ( ⁇ O) —, and n2 represents an integer of 0 or more.) In general formula (2), R X1 represents a hydrogen atom or an alkyl group.
  • alkyl group a linear or branched alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable.
  • the alkyl group may have a substituent.
  • a hydroxyl group or a halogen atom is preferable.
  • R A2 represents a substituent, and n2 R A2 s are independent and may be the same or different.
  • R A2 has the same meaning as the substituent that the lactone structure described above may have, and the preferred range is also the same.
  • a 1 represents a single bond or a divalent linking group.
  • Examples of the divalent linking group include a linear, branched or cyclic alkylene group, an arylene group, —O—, —COO—, —S—, —NR ′′ —, —CO—, and —NR ′′ CO—. , —SO 2 — and the like, or a combination of these groups.
  • R ′′ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom.
  • Examples of the divalent linking group include —O—, —COO—, —S—, —NH— and At least one of —CO— or a group thereof and — (CH 2 ) m — (m is an integer of 1 to 10, preferably an integer of 1 to 6, more preferably an integer of 1 to 4) Groups consisting of combinations are preferred.
  • Z 2 represents a monocyclic or polycyclic structure containing a group represented by —O—C ( ⁇ O) —, which is synonymous with Z 1 in the general formula (1) and is preferable. The range is the same.
  • n2 represents an integer greater than or equal to 0, is synonymous with n1 in general formula (1), and its preferable range is also the same.
  • the said structural unit (a4) is represented by the following general formula (3).
  • General formula (3) (In the general formula (3), R X2 is .R A3 represents a hydrogen atom or an alkyl group represents a substituent, n3 pieces of R A3 are independent, which may be the same or different .
  • a 2 is Represents a single bond or a divalent linking group
  • Z 3 represents a monocyclic or polycyclic structure containing a group represented by —O—C ( ⁇ O) —
  • n3 represents an integer of 0 or more
  • X 1 Represents an oxygen atom or —NR ′′ —.
  • R ′′ represents a hydrogen atom or an alkyl group.
  • R A3 represents a substituent, and n3 R A3 s are independent and may be the same or different.
  • R A3 has the same meaning as the substituent that the lactone structure described above may have, and the preferred range is also the same.
  • a 2 represents a single bond or a divalent linking group. Examples of the divalent linking group is synonymous with the case where A 1 in the general formula (2) represents a divalent linking group.
  • a preferred divalent linking group is at least one of —COO— and —CO—, or these groups, and — (CH 2 ) m — (m is an integer of 1 to 10, preferably 1 to 6.
  • a 2 in the general formula (3) is preferably a single bond.
  • Z 3 represents a monocyclic or polycyclic structure containing a group represented by —O—C ( ⁇ O) —, and is synonymous with Z 1 in the general formula (1).
  • the range is the same.
  • n3 represents an integer greater than or equal to 0, is synonymous with n1 in general formula (1), and its preferable range is also the same.
  • X 1 represents an oxygen atom or —NR ′′ —, preferably an oxygen atom.
  • R ′′ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and preferably a hydrogen atom.
  • the structural unit (a4) preferably includes a structure represented by any of the following general formulas (LC1-1) to (LC1-21) as the structure represented by the general formula (1). More preferred structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), (LC1-17), Particularly preferred structures are (LC1-1), (LC1-4), and (LC1-17).
  • the structural unit (a4) includes such a structure, the relative dielectric constant can be further lowered while improving the chemical resistance of the composition of the present invention.
  • (Rb 2 ) represents a substituent, which may or may not have ( That is, in the general formulas (LC1-1) to (LC1-21), n4 is 0).
  • the preferred substituent (Rb 2 ) is synonymous with the substituent which the lactone structure described above may have, and the preferred range is also the same.
  • n4 has the same meaning as n1 in the general formula (1), and the preferred range is also the same.
  • the structural unit having a lactone structure usually has an optical isomer, but any optical isomer may be used.
  • One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used.
  • the optical purity (ee) thereof is preferably 90% or more, more preferably 95% or more.
  • the structural unit (a4) having a lactone structure that can be used in the present invention is preferably represented by the following general formulas (4) to (7), and is represented by the following general formula (4). It is more preferable.
  • General formula (4) General formula (5)
  • General formula (6) General formula (7)
  • composition of the present invention structural units having two or more lactone structures may be used in combination.
  • the total amount is a numerical range of the structural unit (a4) mentioned later.
  • the (A) polymer component may have another structural unit (a3) in addition to the structural unit (a1), the structural unit (a2), and the structural unit (a4).
  • the structural unit (a3) may be contained in the polymer (1) and / or (2).
  • the polymer has a structural unit (a3) that does not substantially contain the structural unit (a1) and the structural unit (a1). Also good.
  • a monomer used as structural unit (a3) For example, styrenes, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated dicarboxylic acid Examples include diesters, bicyclounsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic anhydrides, and other unsaturated compounds. it can. Moreover, you may have the structural unit which has an acid group so that it may mention later.
  • the monomer which becomes another structural unit (a3) can be used individually or in combination of 2 or more types.
  • the structural unit (a3) is styrene, methyl styrene, hydroxy styrene, ⁇ -methyl styrene, acetoxy styrene, methoxy styrene, ethoxy styrene, chlorostyrene, methyl vinyl benzoate, ethyl vinyl benzoate, 4-hydroxy Benzoic acid (3-methacryloyloxypropyl) ester, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acryloylmorpholine, N-cyclohexylmale
  • styrenes and groups having an aliphatic cyclic skeleton are preferable from the viewpoint of electrical characteristics.
  • Specific examples include styrene, methylstyrene, hydroxystyrene, ⁇ -methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and benzyl (meth) acrylate.
  • (meth) acrylic acid alkyl ester is preferable from the viewpoint of adhesion.
  • Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl (meth) acrylate, and methyl (meth) acrylate is more preferable.
  • the other structural unit (a3) it is preferable to include a repeating unit containing an acid group.
  • a repeating unit containing an acid group By containing an acid group, it becomes easy to dissolve in an alkaline developer, and the effects of the present invention are more effectively exhibited.
  • the acid group is usually incorporated into the polymer as a structural unit containing an acid group using a monomer capable of forming an acid group. By including such a structural unit containing an acid group in the polymer, the polymer tends to be easily dissolved in an alkaline developer.
  • Acid groups used in the present invention include those derived from carboxylic acid groups, those derived from sulfonamide groups, those derived from phosphonic acid groups, those derived from sulfonic acid groups, those derived from phenolic hydroxyl groups, sulfones Examples include amide groups, sulfonylimide groups, and the like, and those derived from carboxylic acid groups and / or those derived from phenolic hydroxyl groups are preferred.
  • the structural unit containing an acid group used in the present invention is more preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, a structural unit derived from (meth) acrylic acid and / or an ester thereof. .
  • Such a polymer is preferably a resin having a carboxyl group in the side chain.
  • a resin having a carboxyl group in the side chain For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048
  • methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc. and side chain
  • acidic cellulose derivatives having a carboxyl group those obtained by adding an acid anhydride to a polymer having a hydroxyl group
  • high molecular polymers having a (meth) acryloyl group in the side chain examples thereof include acidic cellulose derivatives having a carboxyl group, those obtained by adding an acid anhydride to a
  • benzyl (meth) acrylate / (meth) acrylic acid copolymer 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, described in JP-A-7-140654 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2 -Hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid
  • Known polymer compounds described in JP-A-2003-233179, JP-A-2009-52020, and the like can be used, and the contents thereof are incorporated herein. These polymers may contain only 1 type and may contain 2 or more types.
  • SMA 1000P As these polymers, commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (above, manufactured by Sartomer), ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (above, manufactured by Toagosei Co., Ltd.), Joncryl 690, Joncryl 678, Joncryl 67, Joncryl 586 (above, manufactured by BASF, etc.) You can also.
  • a structural unit having a carboxyl group or a structural unit having a phenolic hydroxyl group it is particularly preferable from the viewpoint of sensitivity to contain a structural unit having a carboxyl group or a structural unit having a phenolic hydroxyl group.
  • a structural unit having a carboxyl group or a structural unit having a phenolic hydroxyl group for example, compounds described in JP 2012-88459 A, paragraph numbers 0021 to 0023 and paragraph numbers 0029 to 0044 can be used, the contents of which are incorporated herein.
  • the structural unit containing an acid group is preferably 1 to 80% by mole, more preferably 1 to 50% by mole, still more preferably 5 to 40% by mole, and particularly preferably 5 to 30% by mole of the structural unit of all polymer components. 5 to 25 mol% is particularly preferred.
  • a polymer component contains 1 or more types of polymers (A2).
  • the content of the structural unit (a1) is preferably 3 to 70 mol% in all the structural units of the polymer component (A) (polymer (A2)).
  • the content of the structural unit (a2) is preferably 3 to 70 mol% in all the structural units of the polymer (A2).
  • the content of the structural unit (a4) is preferably from 1 to 80 mol%, more preferably from 1 to 50 mol%, still more preferably from 3 to 20 mol%, based on all the structural units of the polymer (A2).
  • the polymer (A2) may contain the structural unit (a3).
  • the content of the structural unit (a3) is preferably 1 to 50 mol% in all the structural units of the polymer (A2). Moreover, it is preferable that content of polymers other than a polymer (A2) in (A) polymer component is 10 mass% or less in (A) polymer component.
  • a polymer component contains a polymer (A2a) and a polymer (A2b). Further, the polymer (A2a) usually does not contain a structural unit (a4) having a lactone structure.
  • the polymer (A2b) usually does not contain the structural unit (a1) and the structural unit (a2).
  • the content of the structural unit (a1) is preferably 3 to 70 mol% in all the structural units of the polymer component (A) (polymer (A2a) and polymer (A2b)).
  • the content of the structural unit (a2) is preferably 3 to 70 mol% in all the structural units of the polymer (A2a) and the polymer (A2b).
  • the content of the structural unit (a4) is preferably 1 to 80 mol%, more preferably 1 to 50 mol%, and more preferably 3 to 20 mol% in all the structural units of the polymer (A2a) and the polymer (A2b). Further preferred.
  • the polymer (A2a) and / or the polymer (A2b) may further contain the structural unit (a3).
  • the content of the structural unit (a3) is preferably 1 to 50 mol% in all the structural units of the polymer component (A) (polymer (A2a) and polymer (A2b)).
  • content of polymers other than a polymer (A2a) and a polymer (A2b) in (A) polymer component is 10 mass% or less in (A) polymer component.
  • the content of the structural unit (a1) in the polymer (A2a) is preferably from 3 to 90 mol%, more preferably from 10 to 80 mol%, based on all the structural units in the polymer (A2a).
  • the content of the structural unit (a2) in the polymer (A2a) is preferably from 3 to 70 mol%, more preferably from 10 to 60 mol%, based on all the structural units in the polymer (A2a).
  • the content of the structural unit (a3) in the polymer (A2a) is 3% in all the structural units in the polymer (A2a). -70 mol% is preferable, and 10-50 mol% is more preferable.
  • the content of the structural unit (a4) in the polymer (A2b) is preferably from 2 to 95 mol%, more preferably from 3 to 90 mol%, more preferably from 5 to 85 mol% in all the structural units in the polymer (A2b). % Is more preferable.
  • the content of the structural unit (a3) in the polymer (A2b) is 3 in all the structural units in the polymer (A2b). -70 mol% is preferable, and 10-50 mol% is more preferable.
  • a polymer component contains a polymer (A2c) and a polymer (A2d). Further, the polymer (A2c) usually does not contain the structural unit (a2). Further, the polymer (A2d) usually does not contain the structural units (a1) and (a4) having the lactone structure.
  • the content of the structural unit (a1) is preferably 3 to 70 mol% in all the structural units of the polymer component (A) (polymer (A2c) and polymer (A2d)).
  • the content of the structural unit (a2) is preferably 3 to 70 mol% in all the structural units of the polymer component (A).
  • the content of the structural unit (a4) is preferably from 1 to 80 mol%, more preferably from 1 to 50 mol%, still more preferably from 3 to 20 mol%, based on all the structural units of the polymer component (A). Moreover, it is preferable that content of polymers other than a polymer (A2c) and a polymer (A2d) in (A) polymer component is 10 mass% or less in (A) polymer component.
  • the polymer (A2c) and / or the polymer (A2d) may further contain the structural unit (a3).
  • the content of the structural unit (a3) is preferably 1 to 50 mol% in all the structural units of the polymer component (A) (polymer (A2c) and polymer (A2d)).
  • the content of the structural unit (a1) in the polymer (A2c) is preferably from 3 to 90 mol%, more preferably from 10 to 80 mol%, based on all the structural units in the polymer (A2c).
  • the content of the structural unit (a4) in the polymer (A2c) is preferably from 2 to 95 mol%, more preferably from 3 to 90 mol%, based on all the structural units in the polymer (A2c). 85 mol% is more preferable.
  • the content of the structural unit (a3) in the polymer (A2c) is 3% in all the structural units in the polymer (A2c).
  • the content of the structural unit (a2) in the polymer (A2d) is preferably 1 to 90 mol%, more preferably 40 to 80 mol% in all the structural units in the polymer (A2d).
  • the content of the structural unit (a3) in the polymer (A2d) is 3% in all the structural units in the polymer (A2d). ⁇ 70 mol% is preferable, and 10 to 50 mol% is more preferable.
  • a polymer component contains a polymer (A2e) and a polymer (A2f).
  • the polymer (A2e) usually does not contain the structural unit (a2) and the structural unit (a4) having a lactone structure. Further, the polymer (A2f) usually does not contain the structural unit (a1).
  • the content of the structural unit (a1) is preferably 3 to 70 mol% in all the structural units of the polymer component (A) (polymer (A2e) and polymer (A2f)).
  • the content of the structural unit (a2) is preferably 3 to 70 mol% in all the structural units of the polymer (A2e) and the polymer (A2f).
  • the content of the structural unit (a4) is preferably 1 to 80 mol%, more preferably 1 to 50 mol%, and more preferably 3 to 20 mol% in all the structural units of the polymer (A2e) and the polymer (A2f). Further preferred. Moreover, it is preferable that content of polymers other than a polymer (A2e) and a polymer (A2f) in (A) polymer component is 10 mass% or less in (A) polymer component.
  • the polymer (A2e) and / or the polymer (A2f) may further contain the structural unit (a3).
  • the content of the structural unit (a3) is preferably 1 to 50 mol% in all the structural units of the polymer component (A) (polymer (A2e) and polymer (A2f)).
  • the polymer (A2e) contains the structural unit (a3)
  • the total of the structural unit (a1) and the structural unit (a3) is 100 mol% in the polymer (A2e).
  • the polymer (A2f) contains the structural unit (a3)
  • the total of the structural unit (a2), the structural unit (a3), and the structural unit (a4) is 100 mol% in the polymer (A2f). is there.
  • the content of the structural unit (a1) in the polymer (A2e) is preferably from 3 to 90 mol%, more preferably from 10 to 80 mol%, based on all the structural units in the polymer (A2e).
  • the polymer (A2e) further contains the structural unit (a3)
  • the content of the structural unit (a3) in the polymer (A2e) is 3% in all the structural units in the polymer (A2e).
  • the content of the structural unit (a2) in the polymer (A2f) is preferably 1 to 90 mol%, more preferably 40 to 80 mol% in all the structural units in the polymer (A2f).
  • the content of the structural unit (a4) in the polymer (A2f) is preferably from 2 to 95 mol%, more preferably from 3 to 90 mol%, based on all the structural units in the polymer (A2f). 85 mol% is more preferable.
  • the content of the structural unit (a3) in the polymer (A2f) is 1 in all the structural units in the polymer (A2f). -70 mol% is preferable, and 3-50 mol% is more preferable.
  • a polymer component contains a polymer (A2g), a polymer (A2h), and a polymer (A2i). Further, the polymer (A2g) usually does not contain the structural units (a2) and (a4) having the lactone structure. Further, the polymer (A2h) usually does not contain the structural units (a1) and (a4) having the lactone structure. The polymer (A2i) usually does not contain the structural unit (a1) and the structural unit (a2).
  • the content of the structural unit (a1) is preferably 3 to 70 mol% in all the structural units of the polymer component (A) (polymer (A2g), polymer (A2h) and polymer (A2i)).
  • the content of the structural unit (a2) is preferably 3 to 70 mol% in all the structural units of the polymer (A2g), the polymer (A2h) and the polymer (A2i).
  • the content of the structural unit (a4) is preferably 1 to 80 mol%, more preferably 1 to 50 mol% in all the structural units of the polymer (A2g), the polymer (A2h) and the polymer (A2i). 3 to 20 mol% is more preferable.
  • content of polymers other than a polymer (A2g), a polymer (A2h), and a polymer (A2i) in (A) polymer component is 10 mass% or less in (A) polymer component. It is preferable.
  • At least one of the polymer (A2g), the polymer (A2h) and the polymer (A2i) may further contain the structural unit (a3).
  • the content of the structural unit (a3) is preferably 1 to 50 mol% in all the structural units of the polymer component (A) (polymer (A2g), polymer (A2h) and polymer (A2i)).
  • the polymer (A2g) contains the structural unit (a3)
  • the total of the structural unit (a1) and the structural unit (a3) is 100 mol% in the polymer (A2g).
  • the polymer (A2h) contains the structural unit (a3)
  • the total of the structural unit (a2) and the structural unit (a3) is 100 mol% in the polymer (A2h).
  • the total of the structural unit (a3) and the structural unit (a4) is 100 mol% in the polymer (A2i).
  • the content of the structural unit (a1) in the polymer (A2g) is preferably from 3 to 90 mol%, more preferably from 10 to 80 mol%, based on all the structural units in the polymer (A2g).
  • the content of the structural unit (a3) in the polymer (A2g) is 3% in all the structural units in the polymer (A2g). ⁇ 70 mol% is preferable, and 10 to 50 mol% is more preferable.
  • the content of the structural unit (a2) in the polymer (A2h) is preferably 1 to 90 mol%, more preferably 40 to 80 mol% in all the structural units in the polymer (A2h).
  • the content of the structural unit (a3) in the polymer (A2h) is 3% in all the structural units in the polymer (A2h). ⁇ 70 mol% is preferable, and 10 to 50 mol% is more preferable.
  • the content of the structural unit (a4) in the polymer (A2i) is preferably 2 to 95 mol%, more preferably 3 to 90 mol%, in all structural units in the polymer (A2i). 85 mol% is more preferable.
  • the content of the structural unit (a3) in the polymer (A2i) is 3% in all the structural units in the polymer (A2i). ⁇ 70 mol% is preferable, and 10 to 50 mol% is more preferable.
  • the molecular weight of the polymer (A) is a weight average molecular weight in terms of polystyrene, and is preferably 1,000 to 200,000, more preferably 2,000 to 50,000. Various characteristics are favorable in the range of said numerical value.
  • the ratio (dispersity) between the number average molecular weight and the weight average molecular weight is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.
  • (A) Production Method of Polymer Component >> also, various methods are known for the synthesis method of the polymer component (A). For example, in order to form at least the structural units represented by the above (a1) and (a2), It can be synthesized by polymerizing a radical polymerizable monomer mixture containing the radical polymerizable monomer used in an organic solvent using a radical polymerization initiator. It can also be synthesized by a so-called polymer reaction.
  • the polymer component (A) preferably contains 50 mol% or more, more preferably 80 mol% or more of the structural unit derived from (meth) acrylic acid and / or its ester with respect to all the structural units. preferable.
  • the photosensitive resin composition of the present invention contains (B) a photoacid generator.
  • the photoacid generator used in the present invention is preferably a compound that reacts with actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid, but is not limited to its chemical structure.
  • a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.
  • the photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and an acid of 2 or less. Most preferred are photoacid generators that generate.
  • photoacid generator examples include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, it is preferable to use an oxime sulfonate compound from the viewpoint of insulation.
  • photoacid generators can be used singly or in combination of two or more.
  • trichloromethyl-s-triazines diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts, and diazomethane derivatives include the compounds described in paragraph numbers 0083 to 0088 of JP2011-221494A. These can be illustrated and their contents are incorporated herein.
  • Preferred examples of the oxime sulfonate compound that is, a compound having an oxime sulfonate structure include compounds having an oxime sulfonate structure represented by the following general formula (B1-1).
  • General formula (B1-1) (In the general formula (B1-1), R 21 represents an alkyl group or an aryl group. The wavy line represents a bond with another group.)
  • any group may be substituted, and the alkyl group in R 21 may be linear, branched or cyclic. Acceptable substituents are described below.
  • the alkyl group for R 21 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms.
  • the alkyl group represented by R 21 has a halogen atom, an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group, etc.). It may be substituted with a bridged alicyclic group, preferably a bicycloalkyl group or the like.
  • aryl group for R 21 an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable.
  • the aryl group of R 21 may be substituted with a lower alkyl group, an alkoxy group, or a halogen atom.
  • the compound containing the oxime sulfonate structure represented by the general formula (B1-1) is preferably an oxime sulfonate compound represented by the following general formula (B1-2).
  • General formula (B1-2) (In the formula (B1-2), R 42 represents an optionally substituted alkyl group or aryl group, X represents an alkyl group, an alkoxy group, or a halogen atom, and m4 represents 0-3. Represents an integer, and when m4 is 2 or 3, a plurality of Xs may be the same or different.
  • the alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
  • the alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
  • the halogen atom as X is preferably a chlorine atom or a fluorine atom.
  • m4 is preferably 0 or 1.
  • m4 is 1
  • X is a methyl group
  • substitution position of X is the ortho position
  • R 42 is a linear alkyl group having 1 to 10 carbon atoms
  • 7,7- A compound that is a dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferred.
  • the compound containing an oxime sulfonate structure represented by the general formula (B1-1) is also preferably an oxime sulfonate compound represented by the following general formula (B1-3).
  • General formula (B1-3) (In Formula (B1-3), R 43 has the same meaning as R 42 in Formula (B1-2), and X 1 is a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. Represents an alkoxy group, a cyano group or a nitro group, and n4 represents an integer of 0 to 5.)
  • R 43 in the above general formula (B1-3) is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n—.
  • a propyl group, a perfluoro-n-butyl group, a p-tolyl group, a 4-chlorophenyl group or a pentafluorophenyl group is preferable, and an n-octyl group is particularly preferable.
  • X 1 is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
  • n4 is preferably from 0 to 2, particularly preferably from 0 to 1.
  • description in paragraphs 0080 to 0082 of JP2012-163937A can be referred to, and the contents thereof are described in this application. Incorporated in the description.
  • the compound containing an oxime sulfonate structure represented by the general formula (B1-1) is also preferably a compound represented by the following general formula (OS-1).
  • R 101 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or Represents a heteroaryl group.
  • R102 represents an alkyl group or an aryl group.
  • X 101 represents —O—, —S—, —NH—, —NR 105 —, —CH 2 —, —CR 106 H—, or —CR 105 R 107 —, wherein R 105 to R 107 are alkyl groups.
  • R 121 to R 124 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, Or an aryl group is represented. Two of R 121 to R 124 may be bonded to each other to form a ring.
  • R 121 to R 124 are preferably a hydrogen atom, a halogen atom and an alkyl group, and an embodiment in which at least two of R 121 to R 124 are bonded to each other to form an aryl group is also preferred. Among these, an embodiment in which R 121 to R 124 are all hydrogen atoms is preferable from the viewpoint of sensitivity. Any of the aforementioned functional groups may further have a substituent.
  • the compound represented by the general formula (OS-1) is, for example, a compound represented by the general formula (OS-2) described in paragraph numbers 0087 to 0089 of JP2012-163937A Which is hereby incorporated by reference.
  • the compound represented by the general formula (OS-1) that can be suitably used in the present invention include compounds described in paragraph numbers 0128 to 0132 of JP2011-221494A (exemplified compounds b-1 to b-34), but the present invention is not limited thereto.
  • the compound containing the oxime sulfonate structure represented by the general formula (B1-1) is represented by the following general formula (OS-3), the following general formula (OS-4), or the following general formula (OS- The oxime sulfonate compound represented by 5) is preferred.
  • R 22 , R 25 and R 28 each independently represents an alkyl group, an aryl group or a heteroaryl group
  • R 23 , R 26 and R 29 Each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom
  • R 24 , R 27 and R 30 each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group.
  • X 1 to X 3 each independently represents an oxygen atom or a sulfur atom
  • n 1 to n 3 each independently represents 1 or 2
  • m 1 to m 3 each independently represents an integer of 0 to 6 Represents.
  • the compound having an oxime sulfonate structure represented by the general formula (B1-1) is, for example, a compound represented by the general formula (OS-6) to JP-A-2012-163937 described in paragraph 0117. Particularly preferred is a compound represented by any of (OS-11), the contents of which are incorporated herein. Preferred ranges in the general formulas (OS-6) to (OS-11) are preferred ranges of (OS-6) to (OS-11) described in paragraph numbers 0110 to 0112 of JP2011-221494A. The contents of which are incorporated herein by reference.
  • oxime sulfonate compounds represented by the general formula (OS-3) to the general formula (OS-5) include compounds described in paragraph numbers 0114 to 0120 of JP2011-221494A. The contents of which are incorporated herein by reference. The present invention is not limited to these.
  • the compound containing an oxime sulfonate structure represented by the general formula (B1-1) is also preferably an oxime sulfonate compound represented by the following general formula (B1-4).
  • General formula (B1-4) (In the general formula (B1-4), R 1 represents an alkyl group or an aryl group, R 2 represents an alkyl group, an aryl group, or a heteroaryl group. R 3 to R 6 each represents a hydrogen atom. Represents an alkyl group, an aryl group, or a halogen atom, provided that R 3 and R 4 , R 4 and R 5 , or R 5 and R 6 may combine to form an alicyclic ring or aromatic ring. , -O- or S-).
  • R 1 represents an alkyl group or an aryl group.
  • the alkyl group is preferably a branched alkyl group or a cyclic alkyl group.
  • the alkyl group preferably has 3 to 10 carbon atoms. In particular, when the alkyl group has a branched structure, an alkyl group having 3 to 6 carbon atoms is preferable, and when the alkyl group has a cyclic structure, an alkyl group having 5 to 7 carbon atoms is preferable.
  • alkyl group examples include propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, 1,1-dimethylpropyl group, hexyl group. 2-ethylhexyl group, cyclohexyl group, octyl group and the like, preferably isopropyl group, tert-butyl group, neopentyl group, and cyclohexyl group.
  • the aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms, and still more preferably 6 to 7 carbon atoms.
  • Examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is preferable.
  • the alkyl group and aryl group represented by R 1 may have a substituent.
  • substituents examples include a halogen atom (a fluorine atom, a chloro atom, a bromine atom, an iodine atom), a linear, branched or cyclic alkyl group (for example, a methyl group, an ethyl group, a propyl group), an alkenyl group, an alkynyl group, Aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, cyano group, carboxyl group, hydroxyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, heterocyclic oxy group, acyloxy group, amino group, A nitro group, a hydrazino group, a heterocyclic group, etc. are mentioned. Further, these groups may be further substituted. Preferably, they are a halogen atom and a methyl group.
  • R 1 is preferably an alkyl group from the viewpoint of transparency, and R 1 has a branched structure having 3 to 6 carbon atoms from the viewpoint of achieving both storage stability and sensitivity.
  • An alkyl group, an alkyl group having a cyclic structure having 5 to 7 carbon atoms, or a phenyl group is preferable, and an alkyl group having a branched structure having 3 to 6 carbon atoms or an alkyl group having a cyclic structure having 5 to 7 carbon atoms is more preferable. .
  • an isopropyl group, a tert-butyl group, a neopentyl group, and a cyclohexyl group are preferable, and a tert-butyl group and a cyclohexyl group are more preferable.
  • R 2 represents an alkyl group, an aryl group, or a heteroaryl group.
  • the alkyl group represented by R 2 is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.
  • Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, and a cyclohexyl group. It is a group.
  • As the aryl group an aryl group having 6 to 10 carbon atoms is preferable.
  • Examples of the aryl group include a phenyl group, a naphthyl group, a p-toluyl group (p-methylphenyl group), and a phenyl group and a p-toluyl group are preferable.
  • Examples of the heteroaryl group include a pyrrole group, an indole group, a carbazole group, a furan group, and a thiophene group.
  • the alkyl group, aryl group, and heteroaryl group represented by R 2 may have a substituent. As a substituent, it is synonymous with the substituent which the alkyl group and aryl group which R ⁇ 1 > may have.
  • R 2 is preferably an alkyl group or an aryl group, more preferably an aryl group, and more preferably a phenyl group.
  • As the substituent for the phenyl group a methyl group is preferred.
  • R 3 to R 6 each represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom (a fluorine atom, a chloro atom, a bromine atom, or an iodine atom).
  • the alkyl group represented by R 3 to R 6 has the same meaning as the alkyl group represented by R 2 , and the preferred range is also the same.
  • the aryl group represented by R 3 to R 6 has the same meaning as the aryl group represented by R 1 , and the preferred range is also the same.
  • R 3 to R 6 , R 3 and R 4 , R 4 and R 5 , or R 5 and R 6 may combine to form a ring, and the ring may form an alicyclic ring or an aromatic ring. It is preferable that a benzene ring is more preferable.
  • R 3 to R 6 are a hydrogen atom, an alkyl group, a halogen atom (fluorine atom, chloro atom, bromine atom), or R 3 and R 4 , R 4 and R 5 , or R 5 and R 6
  • a benzene ring is preferably formed, and a hydrogen atom, a methyl group, a fluorine atom, a chloro atom, a bromine atom, or R 3 and R 4 , R 4 and R 5 , or R 5 and R 6 are combined to form a benzene ring Is more preferable.
  • Preferred embodiments of R 3 to R 6 are as follows. (Aspect 1) At least two are hydrogen atoms.
  • Ts represents a tosyl group (p-toluenesulfonyl group)
  • Me represents a methyl group
  • Bu represents an n-butyl group
  • Ph represents a phenyl group.
  • each R 7 independently represents a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
  • N represents an integer from 0 to 4.
  • X represents an integer from 1 to 20
  • Y represents an integer from 0 to 20
  • Z represents an integer from 0 to 20
  • W represents an integer from 0 to 5.
  • imide sulfonate compound examples include compounds described in paragraph 0084 of JP2012-155115A, the contents of which are incorporated herein.
  • the addition amount of the photoacid generator is preferably 0.1 to 10% by mass relative to the total solid content in the photosensitive resin composition of the present invention. More preferably, the content is 5 to 10% by mass.
  • Two or more photoacid generators can be used in combination. When using together 2 or more types of photo-acid generators, it is preferable that the total amount is the said numerical range.
  • the photosensitive resin composition of the present invention contains a solvent.
  • the photosensitive resin composition of the present invention is preferably prepared as a solution in which the essential components of the present invention and further optional components described below are dissolved in a solvent.
  • a solvent used for the preparation of the composition of the present invention a solvent that uniformly dissolves essential components and optional components and does not react with each component is used.
  • known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl.
  • Ethers propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether Examples include acetates, esters, ketones, amides, lactones and the like.
  • Specific examples of the solvent used in the photosensitive resin composition of the present invention include the solvents described in paragraph numbers 0174 to 0178 of JP2011-221494A, and paragraph numbers 0167 to 0168 of JP2012-194290A. And the contents thereof are incorporated herein by reference.
  • the solvent that can be used in the present invention is a single type or a combination of two types, more preferably a combination of two types, propylene glycol monoalkyl ether acetates or dialkyl ethers, diacetates. And diethylene glycol dialkyl ethers or esters and butylene glycol alkyl ether acetates are more preferably used in combination.
  • the solvent is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof.
  • Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), propylene glycol An example is methyl-n-propyl ether (boiling point 131 ° C.).
  • Solvents having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), dipropylene glycol methyl ether acetate.
  • the content of the solvent in the photosensitive resin composition of the present invention is preferably 50 to 95 parts by mass and more preferably 60 to 90 parts by mass with respect to 100 parts by mass of all components in the photosensitive resin composition. preferable.
  • a sensitizer, a crosslinking agent, an alkoxysilane compound, a basic compound, a surfactant, and an antioxidant can be preferably added to the photosensitive resin composition of the present invention as necessary.
  • the photosensitive resin composition of the present invention includes an acid proliferation agent, a development accelerator, a plasticizer, a thermal radical generator, a thermal acid generator, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor.
  • Known additives such as can be added.
  • compounds described in paragraph numbers 0201 to 0224 of JP2012-8859A can be used, and the contents thereof are incorporated in the present specification.
  • the photosensitive resin composition of the present invention preferably contains a sensitizer in combination with a photoacid generator in order to promote its decomposition.
  • the sensitizer absorbs actinic rays or radiation and enters an electronically excited state.
  • the sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur.
  • a photo-acid generator raise
  • Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength ranges from 350 nm to 450 nm.
  • Polynuclear aromatics eg, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene
  • xanthenes Eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal
  • xanthones eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone
  • cyanines eg, thiacarbocyanine, oxacarbocyanine
  • merocyanines For example, merocyanine, carbomerocyanine), rhodocyanines, oxonols, thiazines (eg, thionine, methylene blue, to
  • polynuclear aromatics polynuclear aromatics, acridones, styryls, base styryls, and coumarins are preferable, and polynuclear aromatics are more preferable.
  • polynuclear aromatics anthracene derivatives are most preferred.
  • the addition amount of the sensitizer in the photosensitive resin composition of the present invention is preferably 0 to 100% by mass with respect to the total solid content in the photosensitive resin composition of the present invention, preferably 0.1 to 50%. More preferably, it is more preferably 0.5 to 20% by mass. Two or more sensitizers can be used in combination.
  • the photosensitive resin composition of this invention contains a crosslinking agent as needed.
  • a crosslinking agent is not limited as long as a crosslinking reaction is caused by heat.
  • Excluding component A For example, a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, an alkoxymethyl group-containing crosslinking agent, a compound having at least one ethylenically unsaturated double bond, a blocked isocyanate compound, etc. Can be added.
  • the addition amount of the crosslinking agent in the photosensitive resin composition of the present invention is preferably 0.01 to 50% by mass with respect to the total solid content in the photosensitive resin composition of the present invention, preferably 0.1 to It is more preferably 30% by mass, and further preferably 0.5 to 20% by mass. By adding in this range, a cured film excellent in mechanical strength and solvent resistance can be obtained.
  • a plurality of crosslinking agents may be used in combination. In that case, the content is calculated by adding all the crosslinking agents.
  • JER152, JER157S70, JER157S65, JER806, JER828, JER1007 are commercially available products described in paragraph No. 0189 of JP2011-221494, etc.
  • bisphenol A type epoxy resin bisphenol F type epoxy resin, phenol novolac type epoxy resin and aliphatic epoxy resin are more preferable, and bisphenol A type epoxy resin is particularly preferable.
  • the compound having two or more oxetanyl groups in the molecule Aron oxetane OXT-121, OXT-221, OX-SQ, PNOX (manufactured by Toagosei Co., Ltd.) can be used.
  • alkoxymethyl group-containing crosslinking agents described in paragraph numbers 0107 to 0108 of JP2012-8223A, and compounds having at least one ethylenically unsaturated double bond are also preferable. These contents can be used and are incorporated herein.
  • alkoxymethyl group-containing crosslinking agent alkoxymethylated glycoluril is preferable.
  • a blocked isocyanate compound can also be preferably employed as a crosslinking agent.
  • the blocked isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanate group, but is preferably a compound having two or more blocked isocyanate groups in one molecule from the viewpoint of curability.
  • the blocked isocyanate group in this invention is a group which can produce
  • the group which reacted the blocking agent and the isocyanate group and protected the isocyanate group can illustrate preferably.
  • the blocked isocyanate group is preferably a group capable of generating an isocyanate group by heat at 90 ° C. to 250 ° C.
  • the skeleton of the blocked isocyanate compound is not particularly limited and may be any as long as it has two isocyanate groups in one molecule, and is aliphatic, alicyclic or aromatic.
  • Polyisocyanates may be used, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene Diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2, '-Diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1,3
  • tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are particularly preferable.
  • the matrix structure of the blocked isocyanate compound in the photosensitive resin composition of the present invention include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.
  • the blocking agent that forms the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. be able to.
  • a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferable.
  • Examples of the oxime compound include oxime and ketoxime, and specific examples include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, benzophenone oxime, and acetoxime.
  • Examples of the lactam compound include ⁇ -caprolactam and ⁇ -butyrolactam.
  • Examples of the phenol compound include phenol, naphthol, cresol, xylenol, and halogen-substituted phenol.
  • Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.
  • Examples of the amine compound include primary amines and secondary amines, which may be aromatic amines, aliphatic amines, and alicyclic amines, and examples thereof include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.
  • Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate and the like.
  • Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole and the like.
  • Examples of the mercaptan compound include alkyl mercaptans and aryl mercaptans.
  • the blocked isocyanate compound that can be used in the photosensitive resin composition of the present invention is commercially available.
  • Coronate AP Stable M Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (or more, Nippon Polyurethane Industry Co., Ltd.), Takenate B-830, B-815N, B-820NSU, B-842N, B-84N, B-870N, B-874N, B-882N (above, manufactured by Mitsui Chemicals, Inc.) ), Duranate 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (above , Manufactured by Asahi Kasei Chemicals Corporation, Death Module B 1100, BL1265 MPA / X, BL
  • the photosensitive resin composition of the present invention may contain an alkoxysilane compound.
  • an alkoxysilane compound is used, the adhesion between the film formed from the photosensitive resin composition of the present invention and the substrate can be improved, or the properties of the film formed from the photosensitive resin composition of the present invention can be adjusted. Can do.
  • the alkoxysilane compound that can be used in the photosensitive resin composition of the present invention is a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, or a metal such as gold, copper, molybdenum, titanium, or aluminum.
  • the compound improves the adhesion between the insulating film and the insulating film.
  • silane coupling agents include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -glycidoxypropyltriacoxysilane, ⁇ -glycidoxypropyl dialkoxysilane, and ⁇ -methacryloxy.
  • Propyltrialkoxysilane, ⁇ -methacryloxypropyl dialkoxysilane, ⁇ -chloropropyltrialkoxysilane, ⁇ -mercaptopropyltrialkoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane Can be mentioned.
  • ⁇ -glycidoxypropyltrialkoxysilane and ⁇ -methacryloxypropyltrialkoxysilane are more preferable, ⁇ -glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is more preferable. Further preferred. These can be used alone or in combination of two or more.
  • R 1 is a hydrocarbon group having 1 to 20 carbon atoms having no reactive group
  • R 2 is an alkyl group having 1 to 3 carbon atoms or a phenyl group
  • n is an integer of 1 to 3 It is. Specific examples thereof include the following compounds.
  • Ph is a phenyl group.
  • the alkoxysilane compound in the photosensitive resin composition of this invention is not specifically limited to these, A well-known thing can be used.
  • the content of the alkoxysilane compound in the photosensitive resin composition of the present invention is preferably 0.1 to 30% by mass, and preferably 0.5 to 20% by mass with respect to the total solid content in the photosensitive resin composition of the present invention. Is more preferable.
  • the photosensitive resin composition of the present invention may contain a basic compound.
  • the basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples thereof include compounds described in JP-A 2011-212494, paragraphs 0204 to 0207, the contents of which are incorporated herein.
  • aliphatic amine examples include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and the like.
  • examples include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
  • aromatic amine examples include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
  • heterocyclic amine examples include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea, 1,5-diazabicyclo [4.3.0 ] -5-Nonene, 1,8-di And azabicyclo
  • Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexylammonium hydroxide, and the like.
  • Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate and the like.
  • the basic compounds that can be used in the present invention may be used singly or in combination of two or more.
  • the content of the basic compound (H) in the photosensitive resin composition of the present invention is preferably 0.001 to 3% by mass with respect to the total solid content in the photosensitive resin composition of the present invention. More preferably, the content is 0.005 to 1% by mass.
  • the photosensitive resin composition of the present invention may contain a surfactant.
  • a surfactant any of anionic, cationic, nonionic or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
  • the surfactant used in the composition of the present invention include those described in paragraph Nos. 0201 to 0205 in JP2012-88459A, and paragraphs 0185 to 0188 in JP2011-215580A. Can be used and these descriptions are incorporated herein.
  • nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants.
  • KP-341, X-22-822 manufactured by Shin-Etsu Chemical Co., Ltd.
  • Polyflow No. 99C manufactured by Kyoeisha Chemical Co., Ltd.
  • F Top manufactured by Mitsubishi Materials Kasei Co., Ltd.
  • MegaFac manufactured by DIC Corporation
  • Florard Novec FC-4430 manufactured by Sumitomo 3M Co., Ltd.
  • Surflon S-242 Manufactured by AGC Seimi Chemical Co., Ltd.
  • PolyFoxPF-6320 manufactured by OMNOVA
  • SH-8400 Toray Dow Corning Silicone
  • footgent FTX-218G manufactured by Neos
  • the surfactant is measured by gel permeation chromatography using the structural unit A and the structural unit B represented by the following general formula (I-1-1) and tetrahydrofuran (THF) as a solvent.
  • a preferred example is a copolymer having a polystyrene-equivalent weight average molecular weight (Mw) of 1,000 or more and 10,000 or less.
  • R 401 and R 403 each independently represent a hydrogen atom or a methyl group
  • R 402 represents a linear alkylene group having 1 to 4 carbon atoms
  • R 404 represents hydrogen.
  • L represents an alkylene group having 3 to 6 carbon atoms
  • p and q are mass percentages representing a polymerization ratio
  • p is 10 mass% to 80 mass%.
  • the following numerical values are represented, q represents a numerical value of 20% to 90% by mass, r represents an integer of 1 to 18, and s represents an integer of 1 to 10.
  • L is preferably a branched alkylene group represented by the following general formula (I-1-2).
  • R 405 in formula (I-1-2) represents an alkyl group having 1 to 4 carbon atoms, and preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability with respect to the coated surface. And an alkyl group having 2 or 3 carbon atoms is more preferred.
  • the weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
  • These surfactants can be used individually by 1 type or in mixture of 2 or more types.
  • the addition amount of the surfactant in the photosensitive resin composition of the present invention is preferably 10% by mass or less, and preferably 0.001 to 10% by mass with respect to the total solid content in the photosensitive resin composition of the present invention. More preferably, the content is 0.01 to 3% by mass.
  • the photosensitive resin composition of the present invention may contain an antioxidant.
  • an antioxidant a well-known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat resistant transparency is excellent.
  • antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, Examples thereof include nitrates, sulfites, thiosulfates, and hydroxylamine derivatives.
  • phenol-based antioxidants amide-based antioxidants, hydrazide-based antioxidants, and sulfur-based antioxidants are particularly preferable from the viewpoint of coloring the cured film and reducing the film thickness. preferable. These may be used individually by 1 type and may mix 2 or more types. Specific examples include the compounds described in JP-A-2005-29515, paragraphs 0026 to 0031, the contents of which are incorporated herein. Preferred commercial products include ADK STAB AO-60, ADK STAB AO-80, IRGANOX 1726, IRGANOX 1035 and IRGANOX 1098.
  • the content of the antioxidant is preferably 0.1 to 10% by mass, and more preferably 0.2 to 5% by mass, based on the total solid content in the photosensitive resin composition of the present invention. It is particularly preferably 0.5 to 4% by mass. By setting it within this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation becomes good.
  • an acid proliferating agent can be used for the purpose of improving sensitivity.
  • the acid proliferating agent that can be used in the present invention is a compound that can further generate an acid by an acid-catalyzed reaction to increase the acid concentration in the reaction system, and is a compound that exists stably in the absence of an acid. is there.
  • Specific examples of such an acid proliferating agent include the acid proliferating agents described in paragraph numbers 0226 to 0228 of JP2011-212494A, the contents of which are incorporated herein.
  • the photosensitive resin composition of the present invention can contain a development accelerator.
  • a development accelerator those described in paragraphs 0171 to 0172 of JP2012-042837A can be referred to, and the contents thereof are incorporated in the present specification.
  • a development accelerator may be used individually by 1 type, and can also use 2 or more types together.
  • the addition amount of the development accelerator in the photosensitive resin composition of the present invention is preferably 0 to 30 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive composition, from the viewpoint of sensitivity and residual film ratio. 1 to 20 parts by mass is more preferable, and 0.5 to 10 parts by mass is most preferable.
  • thermal radical generators described in paragraphs 0120 to 0121 of JP2012-8223A, nitrogen-containing compounds and thermal acid generators described in WO2011-133604A1 can be used. Is incorporated herein by reference.
  • a resin composition can be prepared by preparing a solution in which components are dissolved in a solvent in advance and then mixing them in a predetermined ratio.
  • the composition solution prepared as described above can be used after being filtered using, for example, a filter having a pore diameter of 0.2 ⁇ m.
  • the method for producing a cured film of the present invention preferably includes the following steps (1) to (5).
  • substrate (2) removing the solvent from the applied photosensitive resin composition; (3) The process of exposing the photosensitive resin composition from which the solvent was removed with actinic rays; (4) A step of developing the exposed photosensitive resin composition with an aqueous developer; (5) A developed post-baking step for thermosetting.
  • the application step (1) it is preferable to apply (preferably apply) the photosensitive resin composition of the present invention onto a substrate to form a wet film containing a solvent.
  • substrate cleaning such as alkali cleaning or plasma cleaning
  • the method for treating the substrate surface with hexamethyldisilazane is not particularly limited, and examples thereof include a method in which the substrate is exposed to hexamethyldisilazane vapor.
  • Examples of the substrate include inorganic substrates, resins, and resin composite materials.
  • Examples of the inorganic substrate include glass, quartz, silicone, silicon nitride, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such a substrate.
  • the resins include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, poly Fluorine resins such as benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, aromatic Made of synthetic resin such as aromatic ether, maleimide-olefin, cellulose, episulfide compound And the like.
  • the application method to the substrate is not particularly limited, and for example, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method, or the like can be used.
  • the wet film thickness when applied is not particularly limited, and can be applied with a film thickness according to the application, but is usually used in the range of 0.5 to 10 ⁇ m.
  • the solvent removal step (2) the solvent is removed from the applied film by vacuum (vacuum) and / or heating to form a dry coating film on the substrate.
  • the heating conditions for the solvent removal step are preferably 70 to 130 ° C. and about 30 to 300 seconds. When the temperature and time are in the above ranges, the pattern adhesiveness is better and the residue tends to be further reduced.
  • the substrate provided with the coating film is irradiated with an actinic ray having a predetermined pattern.
  • the photoacid generator is decomposed to generate an acid.
  • the acid-decomposable group contained in the coating film component is hydrolyzed to generate a carboxyl group or a phenolic hydroxyl group.
  • a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, and the like can be used, i-line (365 nm), h-line (405 nm), g-line ( Actinic rays having a wavelength of 300 nm to 450 nm, such as 436 nm), can be preferably used.
  • irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.
  • the exposure amount is preferably 1 to 500 mj / cm 2 .
  • PEB Post Exposure Bake
  • the temperature for performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C.
  • the acid-decomposable group in the present invention has a low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to generate a carboxyl group or a phenolic hydroxyl group.
  • a positive image can also be formed by development.
  • a copolymer having a liberated carboxyl group or phenolic hydroxyl group is developed using an alkaline developer.
  • a positive image is formed by removing an exposed area containing a resin composition having a carboxyl group or a phenolic hydroxyl group that is easily dissolved in an alkaline developer.
  • the developer used in the development step preferably contains a basic compound.
  • Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkalis such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used.
  • An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
  • a 0.4 to 2.5 mass% aqueous solution of tetramethylammonium hydroxide can be mentioned.
  • the pH of the developer is preferably 10.0 to 14.0.
  • the development time is preferably 30 to 500 seconds, and the development method may be any of a liquid piling method (paddle method), a shower method, a dipping method, and the like.
  • a rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like.
  • a known method can be used as the rinsing method. For example, shower rinse and dip rinse can be mentioned.
  • the acid-decomposable group is thermally decomposed to generate a carboxyl group or a phenolic hydroxyl group, and then crosslinked with a crosslinkable group, a crosslinking agent or the like.
  • a cured film can be formed.
  • This heating is performed using a heating device such as a hot plate or an oven at a predetermined temperature, for example, 180 to 250 ° C. for a predetermined time, for example, 5 to 90 minutes on the hot plate, 30 to 120 minutes for the oven. It is preferable to By proceeding the crosslinking reaction in this way, a protective film and an interlayer insulating film that are superior in heat resistance, hardness, and the like can be formed.
  • post-baking can be performed after baking at a relatively low temperature (addition of a middle baking process).
  • middle baking it is preferable to post-bake at a high temperature of 200 ° C. or higher after heating at 90 to 150 ° C. for 1 to 60 minutes.
  • middle baking and post-baking can be heated in three or more stages. The taper angle of the pattern can be adjusted by devising such middle baking and post baking.
  • These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.
  • the entire surface of the patterned substrate was re-exposed with actinic rays (post-exposure), and then post-baked to generate an acid from the photoacid generator present in the unexposed portion, thereby performing a crosslinking step. It can function as a catalyst to promote, and can accelerate the curing reaction of the film.
  • the preferred exposure amount in the case of including a post-exposure step preferably 100 ⁇ 3,000mJ / cm 2, particularly preferably 100 ⁇ 500mJ / cm 2.
  • the cured film obtained from the photosensitive resin composition of the present invention can also be used as a dry etching resist.
  • dry etching processes such as ashing, plasma etching, and ozone etching can be performed as the etching process.
  • the cured film of the present invention is a cured film obtained by curing the above-described photosensitive resin composition of the present invention.
  • the cured film of the present invention can be suitably used as an interlayer insulating film.
  • the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention mentioned above.
  • the photosensitive resin composition of the present invention an interlayer insulating film having excellent insulation and high transparency even when baked at high temperatures can be obtained. Since the interlayer insulating film using the photosensitive resin composition of the present invention has high transparency and excellent cured film properties, it is useful for liquid crystal display devices and organic EL display devices.
  • the liquid crystal display device of the present invention comprises the cured film of the present invention.
  • the liquid crystal display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and known liquid crystal displays having various structures.
  • An apparatus can be mentioned.
  • specific examples of TFT (Thin-Film Transistor) included in the liquid crystal display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
  • the liquid crystal driving methods that can be adopted by the liquid crystal display device of the present invention include TN (Twisted Nematic) method, VA (Virtual Alignment) method, IPS (In-Place-Switching) method, FFS (Frings Field Switching) method, OCB (Optical). Compensated Bend) method and the like.
  • the cured film of the present invention can also be used in a COA (Color Filter on Array) type liquid crystal display device.
  • the alignment method of the liquid crystal alignment film that the liquid crystal display device of the present invention can take include a rubbing alignment method and a photo alignment method.
  • the polymer orientation may be supported by a PSA (Polymer Sustained Alignment) technique described in JP-A Nos. 2003-149647 and 2011-257734.
  • the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, It can be used for various uses.
  • a protective film for the color filter in addition to the planarization film and interlayer insulating film, a protective film for the color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state imaging device, etc.
  • FIG. 1 is a conceptual cross-sectional view showing an example of an active matrix liquid crystal display device 10.
  • the color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto.
  • the elements of the TFT 16 corresponding to are arranged.
  • Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17.
  • an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
  • the light source of the backlight is not particularly limited, and a known light source can be used.
  • the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type. Further, it can be made flexible, and used as the second interlayer insulating film (48) described in Japanese Patent Application Laid-Open No. 2011-145686 and the interlayer insulating film (520) described in Japanese Patent Application Laid-Open No. 2009-258758. Can do.
  • the organic EL display device of the present invention comprises the cured film of the present invention.
  • the organic EL display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various known structures having various structures. Examples thereof include an organic EL display device and a liquid crystal display device.
  • specific examples of TFT (Thin-Film Transistor) included in the organic EL display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
  • FIG. 2 is a conceptual diagram of an example of an organic EL display device.
  • a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
  • a bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si 3 N 4 is formed so as to cover the TFT 1.
  • a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 ⁇ m) connected to the TFT 1 through the contact hole is formed on the insulating film 3.
  • the wiring 2 is for connecting the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
  • the flattening layer 4 is formed on the insulating film 3 in a state where the unevenness due to the wiring 2 is embedded.
  • a bottom emission type organic EL element is formed on the planarizing film 4. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7.
  • the first electrode 5 corresponds to the anode of the organic EL element.
  • An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do. Further, although not shown in FIG.
  • a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a second layer made of Al is formed on the entire surface above the substrate.
  • An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving it.
  • An EL display device is obtained.
  • a resist pattern formed using the photosensitive resin composition of the present invention as a structural member of a MEMS device can be used as a partition wall or mechanically driven. Used as part of the part.
  • MEMS devices include parts such as SAW filters, BAW filters, gyro sensors, display micro shutters, image sensors, electronic paper, inkjet heads, biochips, sealants, and the like. More specific examples are exemplified in JP-T-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.
  • the photosensitive resin composition of the present invention is excellent in flatness and transparency, for example, the bank layer (16) and the planarization film (57) described in FIG. 2 of JP-A-2011-107476, JP-A-2010-
  • a chemical film (12), a pixel isolation insulating film (14), and the like can also be used to form a chemical film (12), a pixel isolation insulating film (14), and the like.
  • spacers for maintaining the thickness of the liquid crystal layer in a liquid crystal display device imaging optical systems for on-chip color filters such as facsimiles, electronic copying machines, solid-state image sensors, and micro lenses for optical fiber connectors are also used. It can be used suitably.
  • V-601 Dimethyl 2,2′-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.)
  • V-65 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)
  • MEDG diethylene glycol ethyl methyl ether
  • Hisolv EDM manufactured by Toho Chemical Industry Co., Ltd.
  • PGMEA propylene glycol monomethyl ether acetate
  • ANON cyclohexanone
  • Lactone (1) 2-oxooxolan-3-yl methacrylate
  • Lactone (2) 5-oxooxolan-3-yl methacrylate
  • Lactone (3) 6-cyano-5-oxo-4-oxatricyclo [4.2.1.03.7] nonan-2-yl methacrylate
  • Lactone (4) condensed ring lactone monomer A ⁇ Fused Ring Lactone Monomer A (Synthesis of Lactone (4)> Synthesis was performed according to the method (Synthesis Example 1) described in paragraphs 0256 to 0259 of JP-A-2006-146143.
  • Lactone (5) 5,5-dimethyl-2-oxooxolan-3-yl methacrylate
  • B-1 Compound having the following structure
  • B-2 Compound having the following structure
  • B-3 Compound having the following structure
  • B-4 IRGACURE PAG-103
  • B-7 Compound having the following structure
  • the post-reaction was stirred at 70 ° C. for 4 hours to obtain a polymer A-1.
  • a polymer solution having a solid concentration of 40% by mass was prepared.
  • the solid content concentration was monomer mass / (monomer mass + solvent mass) ⁇ 100 (unit mass%).
  • A′-1 was obtained by stirring the post reaction at 70 ° C. for 4 hours.
  • ⁇ Adjustment of photosensitive resin composition Polymers, photoacid generators, sensitizers, basic compounds, crosslinking agents, antioxidants, alkoxysilane compounds, surfactants, and other components so that the solid content ratios shown in Tables 8 to 12 below are obtained. It melt
  • the exposed photosensitive resin composition layer was developed with an alkali developer (2.38% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds.
  • the sensitivity was the optimum i-line exposure (Eopt) when resolving a 10 ⁇ m hole by these operations.
  • HMDS hexamethyldisilazane
  • each photosensitive resin composition is spin-coated on the substrate, and then pre-baked on a hot plate at 90 ° C. for 120 seconds to volatilize the solvent.
  • a photosensitive resin composition layer having a thickness of 3.0 ⁇ m was formed.
  • exposure was performed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm 2 (energy intensity: 20 mW / cm 2 , i-line), and the substrate was heated in an oven at 230 ° C./30 minutes.
  • the film thickness (T1) of the obtained cured film was measured.
  • Each photosensitive resin composition was spin-coated on a bare wafer substrate (N-type low resistance) (manufactured by SUMCO), then pre-baked on a hot plate at 90 ° C. for 120 seconds to volatilize the solvent, and the film thickness was 3.0 ⁇ m.
  • a photosensitive resin composition layer was formed. Subsequently, exposure was performed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm 2 (energy intensity: 20 mW / cm 2 , i-line), and the substrate was heated in an oven at 230 ° C./30 minutes.
  • the relative dielectric constant was measured at a measurement frequency of 1 MHz using CVmap92A (made by Four Dimensions Inc.).
  • the composition of the present invention contains (a) at least one structural unit having a lactone structure in the polymer component (A), or includes the structural unit (a4). And (a1) containing at least one polymer having no structural unit having a structural unit having an acid group protected by an acid-decomposable group and (a2) a crosslinkable group, thereby increasing the sensitivity. It was found that the chemical resistance can be improved and the relative dielectric constant can be lowered while maintaining.
  • Example 127 was performed in the same manner as in Example 16 except that the exposure machine was changed from MPA 5500CF manufactured by Canon Inc. to FX-803M (gh-Line stepper) manufactured by Nikon Corporation. The evaluation of sensitivity was the same level as in Example 1.
  • Example 128 was performed in the same manner as in Example 1 except that the exposure machine was changed from MPA 5500CF manufactured by Canon Inc. to a 355 nm laser exposure machine and 355 nm laser exposure was performed.
  • the 355 nm laser exposure machine “AEGIS” manufactured by Buoy Technology Co., Ltd. was used (wavelength 355 nm, pulse width 6 nsec), and the exposure amount was measured using “PE10B-V2” manufactured by OPHIR.
  • the evaluation of sensitivity was the same level as in Example 1.
  • a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 55 was obtained. That is, using the photosensitive resin composition of Example 1, a cured film 17 was formed as an interlayer insulating film. That is, as a pretreatment for improving the wettability between the substrate and the interlayer insulating film 17 in paragraph 58 of Japanese Patent No. 3321003, the substrate is exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and then the photosensitive film of Example 1 is used.
  • HMDS hexamethyldisilazane
  • the photosensitive resin composition After spin-coating the photosensitive resin composition, it was pre-baked on a hot plate at 90 ° C. for 2 minutes to volatilize the solvent, thereby forming a photosensitive resin composition layer having a thickness of 3 ⁇ m.
  • the obtained photosensitive resin composition layer was exposed to 80 mJ / cm 2 through a mask having a hole pattern of 10 ⁇ m ⁇ using MPA 5500CF (high pressure mercury lamp) manufactured by Canon Inc.
  • the exposed photosensitive resin composition layer was subjected to paddle development at 23 ° C./60 seconds with an alkaline developer (2.38% tetramethylammonium hydroxide aqueous solution), and then rinsed with ultrapure water for 20 seconds.
  • the whole surface was exposed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm 2 (energy intensity: 20 mW / cm 2 , i-line), and then the substrate was heated in an oven at 230 ° C. for 30 minutes.
  • a cured film was obtained.
  • the applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development, and baking.
  • liquid crystal display device When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
  • Example 130 A liquid crystal display device similar to that of Example 129 was obtained by changing only the following process. That is, even when the photosensitive resin composition of Example 1 was applied without the hexamethyldisilazane (HMDS) treatment, which is a pretreatment of the substrate, the resulting cured film was good with no chipping or peeling off of the pattern. It was a state. Further, the performance as a liquid crystal display device was good as in Example 129. This is presumably because the composition of the present invention has excellent adhesion to the substrate. From the viewpoint of improving productivity, it is also preferable to omit the substrate pretreatment step.
  • HMDS hexamethyldisilazane
  • Example 131 A liquid crystal display device similar to that of Example 129 was obtained by changing only the following process. That is, even if a vacuum drying step (VCD) was introduced after pre-baking, the obtained cured film was in a good state with no pattern chipping or peeling. Further, the performance as a liquid crystal display device was good as in Example 129. It is also preferable to introduce a reduced-pressure drying step from the viewpoint of suppressing coating unevenness according to the solid content concentration and the film thickness of the composition.
  • VCD vacuum drying step
  • Example 132 A liquid crystal display device similar to that of Example 129 was obtained by changing only the following process. That is, even if the PEB process was introduced between the development process and the mask exposure, the obtained cured film was in a good state with no pattern chipping or peeling. Further, the performance as a liquid crystal display device was good as in Example 129. From the viewpoint of improving dimensional stability, it is also preferable to introduce a PEB process.
  • Example 133 A liquid crystal display device similar to that of Example 129 was obtained by changing only the following process. That is, even when the alkaline developer is changed from a 2.38% tetramethylammonium hydroxide aqueous solution to a 0.4% tetramethylammonium hydroxide aqueous solution, the resulting cured film is good in that there is no pattern chipping or peeling. It was a state. Further, the performance as a liquid crystal display device was good as in Example 129. This is presumably because the composition of the present invention has excellent adhesion to the substrate.
  • Example 134 A liquid crystal display device similar to that of Example 129 was obtained by changing only the following process. That is, even when the alkali development method was changed from paddle development to shower development, the obtained cured film was in a good state with no pattern chipping or peeling. Further, the performance as a liquid crystal display device was good as in Example 129. This is presumably because the composition of the present invention has excellent adhesion to the substrate.
  • Example 135 A liquid crystal display device similar to that of Example 129 was obtained by changing only the following process. That is, even when the alkaline developer was changed from a 2.38% tetramethylammonium hydroxide aqueous solution to a 0.04% KOH aqueous solution, the resulting cured film was in a good state with no pattern chipping or peeling. It was. Further, the performance as a liquid crystal display device was good as in Example 129. This is presumably because the composition of the present invention has excellent adhesion to the substrate.
  • Example 136 A liquid crystal display device similar to that of Example 129 was obtained by changing only the following process. That is, the entire surface exposure step after development and rinsing was omitted, and the cured film was obtained by heating in an oven at 230 ° C. for 30 minutes. The performance of the obtained liquid crystal display device was as good as in Example 129. This seems to be because the composition of the present invention is excellent in chemical resistance. From the viewpoint of improving productivity, it is also preferable to omit the entire exposure process.
  • Example 137 A liquid crystal display device similar to that of Example 129 was obtained by changing only the following process. That is, a step of heating on a hot plate at 100 ° C. for 3 minutes was added between the entire surface exposure step and the 230 ° C./30 minute heating step in the oven. The performance of the obtained liquid crystal display device was as good as in Example 129. It is also preferable to add this process from the viewpoint of adjusting the shape of the hole pattern.
  • Example 138 A liquid crystal display device similar to that of Example 129 was obtained by changing only the following process. That is, a process of heating on a hot plate at 100 ° C. for 3 minutes was added between the development / rinse process and the entire surface exposure process. The performance of the obtained liquid crystal display device was as good as in Example 129. It is also preferable to add this process from the viewpoint of adjusting the shape of the hole pattern.
  • An organic EL display device using TFT was produced by the following method (see FIG. 2).
  • a bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si 3 N 4 was formed so as to cover the TFT 1.
  • a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 ⁇ m) connected to the TFT 1 through the contact hole is formed on the insulating film 3. .
  • the wiring 2 is used to connect the TFT 1 to the organic EL element formed between the TFTs 1 or in a later process.
  • the planarizing film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded.
  • the planarizing film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 1 on a substrate, pre-baking (90 ° C./120 seconds) on a hot plate, and then applying high pressure from above the mask. After irradiating 80 mJ / cm 2 (energy intensity 20 mW / cm 2 ) with i-line (365 nm) using a mercury lamp, a pattern is formed by developing with an alkaline aqueous solution (2.38% TMAH aqueous solution).
  • the entire surface was exposed so that the integrated irradiation amount was 300 mJ / cm 2 (energy intensity: 20 mW / cm 2 , i-line), and heat treatment was performed at 230 ° C./30 minutes.
  • the applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking.
  • the average step of the wiring 2 was 500 nm, and the thickness of the prepared planarizing film 4 was 2,000 nm.
  • a bottom emission type organic EL element was formed on the obtained flattening film 4.
  • a first electrode 5 made of ITO was formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7.
  • a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed.
  • pattern processing was performed by wet etching using an ITO etchant.
  • the resist pattern was stripped at 50 ° C. using a resist stripper (remover 100, manufactured by AZ Electronic Materials).
  • the first electrode 5 thus obtained corresponds to the anode of the organic EL element.
  • an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed.
  • the photosensitive resin composition of Example 1 was used, and the insulating film 8 was formed by the same method as described above. By providing this insulating film 8, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in the subsequent process.
  • a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus.
  • a second electrode made of Al was formed on the entire surface above the substrate.
  • substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the glass plate for sealing, and an ultraviolet curable epoxy resin.
  • TFT TFT
  • 2 wiring
  • 3 insulating film
  • 4 planarization film
  • 5 first electrode
  • 6 glass substrate
  • 7 contact hole
  • 8 insulating film
  • 10 liquid crystal display device
  • 12 backlight Units 14
  • 15 glass substrate
  • 16 TFT
  • 17 cured film
  • 18 contact hole
  • 19 ITO transparent electrode
  • 20 liquid crystal
  • 22 color filter

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Liquid Crystal (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

La présente invention concerne une composition de résine photosensible fournissant une bonne résistance chimique et une constante diélectrique relative plus basse tout en conservant une haute sensibilité. La composition de résine photosensible contient : (A) un constituant polymère qui contient un polymère qui satisfait à (1) et/ou à (2) décrits ci-dessous ; (B) un générateur de photoacide ; et (C) un solvant. (1) un polymère qui comprend (a1) une unité constituante possédant un groupe dans lequel un groupe acide est protégé par un groupe décomposable à l'acide et (a2) une unité constituante possédant un groupe réticulable ; (2) un polymère comprenant l'unité constituante (a1) et un polymère comprenant l'unité constituante (a2). À cet égard, le composant polymère (A) contient au moins une unité constituante (a4) ayant une structure de lactone ou, comme variante, (3) la composition de résine photosensible contient au moins un polymère qui possède l'unité constituante (a4) mais ne possède pas l'unité constituante (a1) ni l'unité constituante (a2).
PCT/JP2014/058230 2013-03-27 2014-03-25 Composition de résine photosensible, procédé de production de film polymérisé, film polymérisé, dispositif d'affichage à cristaux liquides et dispositif d'affichage électroluminescent organique WO2014157171A1 (fr)

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KR1020157022121A KR20150107847A (ko) 2013-03-27 2014-03-25 감광성 수지 조성물, 경화막의 제조 방법, 경화막, 액정 표시 장치 및 유기 el 표시 장치
CN201480017166.2A CN105051608B (zh) 2013-03-27 2014-03-25 感光性树脂组合物、层间绝缘膜及其制造方法、液晶显示装置及有机电致发光显示装置

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TWI830850B (zh) * 2019-12-30 2024-02-01 奇美實業股份有限公司 化學增幅型正型感光性樹脂組成物及其應用
CN114276239B (zh) * 2021-12-29 2023-10-27 徐州博康信息化学品有限公司 一种含缩酮结构酸敏感光刻胶树脂单体的制备方法

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