WO2014208647A1 - 感光性樹脂組成物、硬化膜の製造方法、硬化膜、液晶表示装置および有機ｅｌ表示装置 - Google Patents

感光性樹脂組成物、硬化膜の製造方法、硬化膜、液晶表示装置および有機ｅｌ表示装置 Download PDF

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WO2014208647A1
WO2014208647A1 PCT/JP2014/066935 JP2014066935W WO2014208647A1 WO 2014208647 A1 WO2014208647 A1 WO 2014208647A1 JP 2014066935 W JP2014066935 W JP 2014066935W WO 2014208647 A1 WO2014208647 A1 WO 2014208647A1
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group
acid
structural unit
groups
polymer
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PCT/JP2014/066935
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English (en)
French (fr)
Japanese (ja)
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健太 山▲ざき▼
米澤　裕之
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富士フイルム株式会社
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Priority to KR1020157036355A priority Critical patent/KR20160014667A/ko
Priority to CN201480035928.1A priority patent/CN105324718B/zh
Priority to JP2015524105A priority patent/JP6279571B2/ja
Publication of WO2014208647A1 publication Critical patent/WO2014208647A1/ja

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    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • 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
    • 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

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 an article and a method for producing a cured film using the article.
  • Organic EL display devices, liquid crystal display devices, and the like are provided with a patterned interlayer insulating film.
  • photosensitive resin compositions are widely used because the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained.
  • the interlayer insulating film in the above display device is desired to have high transparency. Yes. For this reason, an attempt has been made to use an acrylic resin having excellent transparency as a film forming component. For example, those described in Patent Documents 1 and 2 are known.
  • the photosensitive resin composition has a linear or branched aliphatic hydrocarbon group having 6 to 20 carbon atoms and a specific functional group, and a carboxyl group. It was also found that the above problem can be solved by blending an (S) component which does not have an alcoholic hydroxyl group and does not generate a carboxyl group and an alcoholic hydroxyl group even when reacted with an acid group of a polymer component. Specifically, the above problem has been solved by the following means ⁇ 1>, preferably ⁇ 2> to ⁇ 16>.
  • A-1) a polymer component containing a polymer that satisfies at least one of the following (1) and (2): (1) (a1-1) a polymer having a structural unit having an acid group protected by an acid-decomposable group, and (a1-2) a structural unit having a crosslinkable group, (2) (a1-1) a polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group, and (a1-2) a polymer having a structural unit having a crosslinkable group, (S) Linear or branched aliphatic hydrocarbon group having 6 to 20 carbon atoms, alkoxysilane group, blocked isocyanate group, blocked isothiocyanate group, block ketene group, isocyanate group, isothiocyanate group, thiol group, oxazoline group Having a group having at least one selected from an ester group, a thioether group, a disulfide group, an
  • A-1) a polymer component containing a polymer that satisfies at least one of the following (1) and (2): (1) (a1-1) a polymer having a structural unit having an acid group protected by an acid-decomposable group, and (a1-2) a structural unit having a crosslinkable group, (2) (a1-1) a polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group, and (a1-2) a polymer having a structural unit having a crosslinkable group, (S) a compound represented by the following general formula (S1), (B-1) a photoacid generator, (C-1) a photosensitive resin composition containing a solvent;
  • X 1 is an alkoxysilane group, a blocked isocyanate group, a blocked isothiocyanate group, a block ketene group, an isocyanate group
  • n1 represents an integer of 1 to 3.
  • the compound represented by the general formula (S1) does not have a carboxyl group and an alcoholic hydroxyl group, and does not generate a carboxyl group and an alcoholic hydroxyl group even when reacted with an acid group of a polymer component.
  • A-2) a polymer component containing a polymer satisfying at least one of the following (1) and (2): (1) (a2-1) a structural unit having an acid group, and (a2-2) a structural unit having a crosslinkable group, (2) (a2-1) a polymer having a structural unit having an acid group, and (a2-2) a polymer having a structural unit having a crosslinkable group, (B-2) a quinonediazide compound, (S) Linear or branched aliphatic hydrocarbon group having 6 to 20 carbon atoms, alkoxysilane group, blocked isocyanate group, blocked isothiocyanate group, block ketene group, isocyanate group, isothiocyanate group, thiol group, oxazoline group Having a group having at least one selected from an ester group, a thioether group, a disulfide group, an amide group and a urethane group, having no carboxyl group and no alcoholic hydroxy
  • A-2) a polymer component containing a polymer that satisfies at least one of the following (1) and (2): (1) (a2-1) a structural unit having an acid group, and (a2-2) a structural unit having a crosslinkable group, (2) (a2-1) a polymer having a structural unit having an acid group, and (a2-2) a polymer having a structural unit having a crosslinkable group, (B-2) a quinonediazide compound, (S) a compound represented by the following general formula (S1), (C-2) a photosensitive resin composition containing a solvent;
  • X 1 is an alkoxysilane group, a blocked isocyanate group, a blocked isothiocyanate group, a block ketene group, an isocyanate group, an isothiocyanate group, a thiol group, an oxazoline group, an ester group
  • the linear or branched aliphatic hydrocarbon group having 6 to 20 carbon atoms contained in the component (S) is a linear compound according to any one of ⁇ 1> to ⁇ 6> Photosensitive resin composition.
  • the crosslinkable group is at least one selected from the group represented by an epoxy group, an oxetanyl group, and NH—CH 2 —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms).
  • ⁇ 1>- ⁇ 8> The photosensitive resin composition in any one of. ⁇ 10>
  • ⁇ 11> (1) A step of applying the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 10> on a substrate, (2) a step of removing the solvent from the applied photosensitive resin composition; (3) A step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays, (4) a step of developing the exposed photosensitive resin composition with an aqueous developer, and (5) a post-baking step of thermosetting the developed photosensitive resin composition; The manufacturing method of the cured film containing this.
  • ⁇ 12> The method for producing a cured film according to ⁇ 11>, which includes (6) a step of exposing the entire surface of the developed photosensitive resin composition after the development step and before the post-baking step.
  • the manufacturing method of the cured film as described in ⁇ 11> or ⁇ 12> including the process of dry-etching with respect to the board
  • ⁇ 14> A cured film obtained by curing the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 10>, or a cured film production method according to any one of ⁇ 11> to ⁇ 13>. Cured film.
  • 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 description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
  • “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • the photosensitive resin composition of the present invention (hereinafter also referred to as the composition of the present invention) will be described in the order of the first to third aspects.
  • the first and second aspects of the composition of the present invention are preferably used as a positive photosensitive resin composition.
  • the third aspect of the composition of the present invention is preferably used as a negative photosensitive resin composition.
  • the photosensitive resin composition of the present invention includes a polymer component containing a structural unit having a crosslinkable group, a component (S) described later, and a solvent.
  • the photosensitive resin composition is applied onto a substrate.
  • the cured film can be obtained by removing the solvent, exposing with actinic light, developing with an aqueous developer (preferably an alkali developer), and heat curing.
  • the chemical resistance when it is set as a cured film is favorable, and the photosensitive resin composition with a low relative dielectric constant can be provided.
  • this mechanism is presumed, it is considered as follows. Since the (S) component has a linear or branched aliphatic hydrocarbon group having 6 to 20 carbon atoms, the compatibility between the polymer component and the (S) component is good, so that the chemical resistance is not deteriorated. Furthermore, it is considered that a low-polarity structure can be taken into the cured film, and the relative dielectric constant of the cured film does not increase too much.
  • the (S) component does not have a carboxyl group and an alcoholic hydroxyl group, and the (S) component reacts with an acid group (preferably a carboxyl group) of the polymer component, the carboxyl group and the alcoholic hydroxyl group Does not occur. Furthermore, the component (S) does not generate a carboxyl group or an alcoholic hydroxyl group even when it reacts with the crosslinkable group of the polymer component. As a result, since the amount of alcoholic hydroxyl groups in the cured film does not increase, the relative dielectric constant of the cured film can be maintained at a low level, and further, the chemical resistance does not deteriorate because the amount of carboxyl groups in the cured film does not increase. .
  • the component (S) contains a specific functional group that reacts with an acid group (preferably a carboxyl group) of the polymer component, the amount of the carboxyl group that is weak against chemicals can be further reduced from the cured film. It is considered that the chemical resistance of the cured film is further improved.
  • an acid group for example, carboxyl group
  • the composition of the present invention comprises (A-1) a polymer component containing a polymer that satisfies at least one of the following (1) and (2): (1) (a1-1) a polymer having a structural unit having an acid group protected by an acid-decomposable group, and (a1-2) a structural unit having a crosslinkable group, (2) (a1-1) a polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group, and (a1-2) a polymer having a structural unit having a crosslinkable group, (S) a linear or branched aliphatic hydrocarbon group having 6 to 20 carbon atoms (the aliphatic hydrocarbon group may have one —O—, —S—, cyclic alkylene group or arylene group).
  • an alkoxysilane group A group having at least one selected from a blocked isocyanate group, a blocked isothiocyanate group, a block ketene group, an isocyanate group, an isothiocyanate group, a thiol group, an oxazoline group, an ester group, a thioether group, a disulfide group, an amide group and a urethane group.
  • Compound that does not generate fine alcoholic hydroxyl group (B-1) a photoacid generator, (C-1) A photosensitive resin composition containing a solvent.
  • the component (S) is preferably represented by the following general formula (S1).
  • General formula (S1) X 1 (R S1 ) n1 In the general formula (S1), X 1 is an alkoxysilane group, a blocked isocyanate group, a blocked isothiocyanate group, a block ketene group, an isocyanate group, an isothiocyanate group, a thiol group, an oxazoline group, an ester group, a thioether group, a disulfide group.
  • R S1 represents a linear or branched aliphatic hydrocarbon group having 6 to 20 carbon atoms
  • the hydrocarbon group may have at least one group selected from —O—, —S—, a cyclic alkylene group, and an arylene group, provided that —O—, —S—, a cyclic alkylene
  • n1 represents an integer of 1 to 3.
  • the compound represented by the general formula (S1) does not have a carboxyl group and an alcoholic hydroxyl group, and does not generate a carboxyl group and an alcoholic hydroxyl group even when reacted with an acid group of a polymer component. .
  • the composition of the present invention comprises, as a polymer component, a polymer having (a1-1) a structural unit having an acid group protected with an acid-decomposable group and (a1-2) a structural unit having a crosslinkable group.
  • a polymer having (a1-1) a structural unit having a group in which an acid group is protected by an acid-decomposable group and (a1-2) a polymer having a structural unit having a crosslinkable group (2) , At least one of the above.
  • polymers other than these may be included.
  • the polymer component (A-1) in the present invention includes, in addition to the polymer (1) and / or the polymer (2), other polymers added as necessary, unless otherwise specified. Means things.
  • (a1-1) includes a polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group, and (a1-2) a polymer having a structural unit having a crosslinkable group
  • the ratio of (a1-1) the polymer having a structural unit having an acid group protected with an acid-decomposable group to (a1-2) the polymer having a structural unit having a crosslinkable group is 95: 5 to 5:95 is preferred, 80:20 to 20:80 is more preferred, and 70:30 to 30:70 is even more preferred.
  • the (A-1) 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 its ester.
  • a polymer containing a structural unit derived from (meth) acrylic acid and / or its ester you may have structural units other than the structural unit derived from (meth) acrylic acid and / or its ester, for example, the structural unit derived from styrene, the structural unit derived from a vinyl compound, etc.
  • the “structural unit derived from (meth) acrylic acid and / or its ester” is also referred to as “acrylic structural unit”.
  • the polymer component has at least a structural unit (a1-1) having a group in which an acid group is protected with an acid-decomposable group.
  • 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, which will be 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 (a1-1) 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 (a1-1-1) having a protected carboxyl group protected with an acid-decomposable group and the structural unit (a1-1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group Each will be described in turn.
  • the structural unit (a1-1-1) 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 (a1-1-1) is not particularly limited, and a known structural unit can be used.
  • a structural unit 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 (a1-1-1-1) Is mentioned.
  • an unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, or unsaturated tricarboxylic acid (a1-1-1-1) Is mentioned.
  • the structural unit (a1-1-1-1) used as the structural unit having a carboxyl group will be described.
  • ⁇ (a1-1-1-1) Structural Unit Derived from Unsaturated Carboxylic Acid etc. Having at least One Carboxyl Group in the Molecule Examples of 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.
  • the structural unit (a1-1-1-1) acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meta It is preferable to use acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-phthalic acid, or an anhydride of an unsaturated polyvalent carboxylic acid, such as acrylic acid, methacrylic acid, 2- (meta It is more preferable to use acryloyloxyethyl hexahydrophthalic acid.
  • the structural unit (a1-1-1-1) 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 (a1-1-1)
  • 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, and 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.
  • 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 represent an aryl group
  • the aryl group preferably has 6 to 12 carbon atoms, and preferably 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 to each other 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 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. Note that in the general formula (a1-10), it is preferable that any one of R 101 and R 102 be 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 (a1-1-1) is a structural unit represented by the following general formula (A2 ′).
  • R 1 and R 2 each represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 1 and R 2 represents an alkyl group or an aryl group, and R 3 represents 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 arylene. Represents a 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 preferred.
  • a second preferred embodiment of the structural unit (a1-1-1) 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 (a1-1-2) includes a structural unit (a1-1-2-1) 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. ).
  • 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 of 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
  • R 222 is 2 or more, these R 222 may be different from each other 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;
  • the acid-decomposable group that can be used for the structural unit (a1-1-2) is the same as the acid-decomposable group that can be used for the structural unit (a1-1-1). It can be used and is not particularly 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 (a1-1-2) a commercially available monomer 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.
  • ⁇ Preferred Aspect of Structural Unit (a1-1) >>>
  • the content of the structural unit (a1-1) is 20 to 100 in the polymer.
  • the mol% is preferable, and 30 to 90 mol% is more preferable.
  • the content of the single structural unit (a1-1) is 3 to 3 from the viewpoint of sensitivity in the polymer. 70 mol% is preferable, and 10 to 60 mol% is more preferable.
  • the acid-decomposable group that can be used in the structural unit (a1) is a structural unit having a protected carboxyl group in which the carboxyl group is protected in the form of an acetal
  • the content is preferably 20 to 50 mol%.
  • the structural unit (a1-1-1) is characterized by faster development than the structural unit (a1-1-2). Therefore, when it is desired to develop quickly, the structural unit (a1-1-1) is preferable. Conversely, when it is desired to slow development, it is preferable to use the structural unit (a1-1-2).
  • the polymer component has a structural unit (a1-2) 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 includes a structural unit containing at least one of an epoxy group and an oxetanyl group. In more detail, the following are mentioned.
  • the (A-1) polymer component preferably contains a structural unit having an epoxy group and / or an oxetanyl group (hereinafter also referred to as a structural unit (a1-2-1)).
  • the structural unit (a1-2-1) only needs to have at least one epoxy group or oxetanyl group in one structural unit, and one or more epoxy groups and one or more oxetanyl groups, two or more
  • the epoxy 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. It is more preferable to have 1 or 2 in total, and it is more preferable to have 1 epoxy group or 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 to form 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, acrylic acid (3-ethyloxetane-3-yl) methyl, and methacrylic acid (3-ethyloxetane-3-yl) methyl 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.
  • (a1-2-2) Structural unit having an ethylenically unsaturated group is a structural unit (a1-2-2) having an ethylenically unsaturated group.
  • the structural unit (a1-2-2) is preferably a structural unit having an ethylenically unsaturated group in the side chain, a structure having an ethylenically unsaturated group at the terminal and a side chain having 3 to 16 carbon atoms. Units are more preferred.
  • the polymer component (A-1) used in the present invention is a structural unit (a1-) having a group represented by —NH—CH 2 —O—R (where R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). 2-3) is also preferable.
  • a curing reaction can be caused by a mild heat treatment, and a cured film having excellent characteristics can be obtained.
  • 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 (a1-2-3) is more preferably a structural unit having a group represented by the following general formula (a2-30).
  • R 1 represents a hydrogen atom or a methyl group
  • 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.
  • Specific examples of 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 content of the structural unit (a1-2) is preferably 3 to 70 mol% in all the structural units of the polymer component (A-1), regardless of any embodiment. More preferably, it is ⁇ 60 mol%. By setting it within the above numerical range, a cured film having excellent characteristics can be formed.
  • the polymer component (A-1) has other structural unit (a1-3) in addition to the structural unit (a1-1) and / or the structural unit (a1-2). You may do it.
  • the structural unit (a1-3) may be contained in the polymer (1) and / or (2).
  • styrenes (meth) acrylic acid alkyl esters, (meth) acrylic acid cyclic alkyl esters, (meth) acrylic acid aryl esters, Unsaturated dicarboxylic acid diesters, bicyclounsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, other unsaturated compounds Can be mentioned. Moreover, you may have the structural unit which has an acid group so that it may mention later.
  • the other structural unit (a1-3) monomers can be used alone or in combination of two or more.
  • the structural unit (a1-3) include styrene, methylstyrene, hydroxystyrene, ⁇ -methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, 4 -Hydroxybenzoic acid (3-methacryloyloxypropyl) ester, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, ( 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acryloylmorpholine, N-cyclohexyl
  • 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 (a1-3) preferably contains a repeating unit containing an acid group.
  • the acid group in the present invention means a proton dissociable group having a pKa of less than 7.
  • 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 Amide groups, sulfonylimide groups and the like are exemplified, 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. .
  • the repeating unit containing an acid group As a method for introducing the repeating unit containing an acid group, it can be introduced into the same polymer as the (a1-1) structural unit and / or (a1-2) structural unit, or (a1-1) the structural unit and ( a1-2) It may be introduced as a structural unit of a polymer different from the structural unit.
  • a resin having a carboxyl group in the side chain is preferable.
  • methacrylic acid copolymer acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc.
  • side chain examples thereof include acidic cellulose derivatives having a carboxyl group, those obtained by adding an acid anhydride to a polymer having a hydroxyl group, and high molecular polymers having a (meth) acryloyl group in the side chain.
  • 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.
  • the other structural unit (a1-3) includes a structural unit containing at least an acid group.
  • the polymer In addition to the polymer (1) or (2), the polymer further includes the structural unit (a1-1) and the structural unit (a1-2) and the other structural unit (a1-3). Embodiment with coalescence. (Sixth embodiment) A form comprising a combination of two or more of the first to fifth embodiments.
  • the molecular weight of the (A-1) polymer component is preferably in the range of 1,000 to 200,000, more preferably 2,000 to 50,000, in terms of polystyrene-converted weight average molecular weight. 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.
  • the weight average molecular weight and dispersity of the polymer component are defined as polystyrene converted values by GPC measurement.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer component are, for example, HLC-8120 (manufactured by Tosoh Corporation), and TSK gel Multipore HXL-M (Tosoh ( 7.8 mm ID ⁇ 30.0 cm can be obtained by using THF (tetrahydrofuran) as an eluent.
  • A-1) Production Method of Polymer Component Various methods for synthesizing the polymer component (A-1) are also known. For example, at least the structures represented by the above (a1-1) and (a1-3) are exemplified. It can be synthesized by polymerizing a radical polymerizable monomer mixture containing a radical polymerizable monomer used to form units in an organic solvent using a radical polymerization initiator. It can also be synthesized by a so-called polymer reaction. (A-1) The polymer preferably contains 50 mol% or more, and 80 mol% or more of the structural units derived from (meth) acrylic acid and / or its ester with respect to all the structural units. More preferred.
  • the photosensitive resin composition of the present invention contains (B-1) 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 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, or a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group). 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.
  • the 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 containing an oxime sulfonate structure represented by the above general formula (B1-1) is, for example, a compound represented by the general formula (OS-6) described in paragraph No. 0117 of JP2012-163937A. Particularly preferred is a compound represented by any of (OS-11), the contents of which are incorporated herein.
  • Preferred ranges in the above 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 compound 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. 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, etc.), 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 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 each 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.
  • At least two are hydrogen atoms.
  • the number of alkyl groups, aryl groups, or halogen atoms is one or less.
  • Aspect 3) R 3 and R 4 , R 4 and R 5 , or R 5 and R 6 are combined to form a benzene ring.
  • X represents —O— or S—.
  • Ts represents a tosyl group (p-toluenesulfonyl group)
  • Me represents a methyl group
  • Bu represents an n-butyl group
  • Ph represents a phenyl group.
  • the content of the (B-1) photoacid generator is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the total solid components in the photosensitive resin composition. 0.5 to 10 parts by mass is more preferable, and 0.5 to 5 parts by mass is still more preferable. Only one photoacid generator may be used, or two or more photoacid generators may be used in combination.
  • the photosensitive resin composition of the present invention contains (C-1) 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.
  • composition of the present invention comprises a linear or branched aliphatic hydrocarbon group having 6 to 20 carbon atoms (—O—, —S—, cyclic alkylene group in the above aliphatic hydrocarbon group) as the component (S).
  • a linear or branched aliphatic hydrocarbon group having 6 to 20 carbon atoms (—O—, —S—, cyclic alkylene group in the above aliphatic hydrocarbon group) as the component (S).
  • it may have one arylene group, provided that when it has two or more groups selected from —O—, —S—, a cyclic alkylene group and an arylene group, these two or more groups are adjacent to each other.
  • the composition of the present invention preferably contains a compound represented by the following general formula (S1).
  • X 1 is an alkoxysilane group, a blocked isocyanate group, a blocked isothiocyanate group, a block ketene group, an isocyanate group, an isothiocyanate group, a thiol group, an oxazoline group, an ester group, a thioether group, a disulfide group.
  • R S1 represents a linear or branched aliphatic hydrocarbon group having 6 to 20 carbon atoms
  • the hydrocarbon group may have at least one group selected from —O—, —S—, a cyclic alkylene group, and an arylene group, provided that —O—, —S—, a cyclic alkylene
  • n1 represents an integer of 1 to 3.
  • the compound represented by the general formula (S1) does not have a carboxyl group and an alcoholic hydroxyl group, and does not generate a carboxyl group and an alcoholic hydroxyl group even when reacted with an acid group of a polymer component. .
  • X 1 is an alkoxysilane group, a blocked isocyanate group, a blocked isothiocyanate group, a block ketene group, an isocyanate group, an isothiocyanate group, a thiol group, an oxazoline group, an ester group, a thioether group, a disulfide group, A group containing an n1-valent group having at least one selected from an amide group and a urethane group.
  • X 1 is selected from an alkoxysilane group, a blocked isocyanate group, a blocked isothiocyanate group, a block ketene group, an isocyanate group, an isothiocyanate group, a thiol group, and an oxazoline group. It is preferably a monovalent group having at least one of the above, more preferably an alkoxysilane group, a blocked isocyanate group, a thiol group or an oxazoline group.
  • X 1 is a divalent or trivalent group having at least one selected from an ester group, a thioether group, a disulfide group, an amide group and a urethane group And a divalent or trivalent group having at least one selected from an ester group, a thioether group, and a disulfide group is more preferable.
  • X 1 represents at least one selected from an ester group, a thioether group, a disulfide group, an amide group and a urethane group, and a divalent or trivalent group.
  • a group composed of a combination with a linking group is preferred.
  • the divalent or trivalent linking group is preferably a linear, branched, or cyclic hydrocarbon group, and more preferably a linear or cyclic hydrocarbon group.
  • the linear hydrocarbon group an alkylene group having 2 to 20 carbon atoms is preferable, and an alkylene group having 6 to 20 carbon atoms is more preferable.
  • the branched hydrocarbon group an alkylene group having 3 to 20 carbon atoms is preferable, and an alkylene group having 6 to 20 carbon atoms is more preferable.
  • the cyclic hydrocarbon group is preferably an aliphatic hydrocarbon group having 6 to 20 carbon atoms or an aromatic hydrocarbon group, more preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms, and further preferably a phenylene group.
  • the alkoxysilane group is preferably represented by the following general formula, for example. * -Si- (OR S2 ) 3
  • R S2 is an alkyl group having 1 to 3 carbon atoms
  • n is an integer of 1 to 3
  • * represents a binding site with R S1 in the general formula (S1).
  • R S2 is an alkyl group having 1 to 3 carbon atoms, preferably a methyl group or an ethyl group, and more preferably a methyl group.
  • n is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.
  • a blocked isocyanate group is a group that generates an isocyanate group by dissociating the block structure by heat or the like.
  • a compound having a hydrogen atom capable of reacting with an isocyanate group (usually called a blocking agent) is reacted with the isocyanate A group in which a group is protected.
  • the introduced protecting group is a hydrogen atom removed from the blocking agent and is usually called a blocking group.
  • A is a protecting group.
  • the blocking agent used in the present invention for example, the blocking agent described in paragraph 0009 of JP-A-5-186564, the blocking agent described in paragraph 0022 of JP-A-2002-275231 can be used, These contents are incorporated herein.
  • compounds having a phenolic hydroxyl group such as phenol, naphthol, cresol, xylenol, halogen-substituted phenol; oxime compounds such as acetoxime, formaldoxime, cyclohexaneoxime, methylethylketoxime; pyrazole, methylpyrazole, dimethylpyrazole, etc.
  • Alcohol compounds such as methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, alkyl lactate, etc .; activity of ethyl acetoacetate, diethyl malonate, acetylacetone, etc.
  • the blocking group used in the present invention is preferably a group derived from a compound having a phenolic hydroxyl group, an oxime compound or an alcohol compound, more preferably a group derived from an oxime compound or an alcohol compound, and an oxime group. More preferred are groups derived from compounds.
  • the compound represented by the general formula (S1) used in the present invention may contain at least one type of blocked isocyanate group in one molecule, but may contain two or more types.
  • the upper limit of the number of blocked isocyanate groups is not particularly defined, but is preferably 5 or less, and more preferably 3 or less. One is particularly preferred.
  • the block isothiocyanate group and the block ketene group are groups that dissociate the block structure by heat or the like to generate an isothiocyanate group or a ketene group, respectively, as described above for the block isocyanate group. This is the same as the blocked isocyanate group.
  • R S1 represents a linear or branched aliphatic hydrocarbon group having 6 to 20 carbon atoms.
  • R S1 is preferably a linear or branched aliphatic hydrocarbon group having 6 to 20 carbon atoms, more preferably a linear aliphatic hydrocarbon group having 6 to 20 carbon atoms, It is more preferably a linear aliphatic hydrocarbon group having 10 to 20 carbon atoms.
  • R S1 represents a predetermined group in the linear or branched aliphatic hydrocarbon group having 6 to 20 carbon atoms within a range that does not adversely affect the compatibility between the polymer component and the component (S). You may have.
  • the linear or branched aliphatic hydrocarbon group having 6 to 20 carbon atoms may have at least one group selected from —O—, —S—, a cyclic alkylene group, and an arylene group.
  • the cyclic alkylene group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably a cyclohexylene group.
  • the arylene group preferably has 6 to 12 carbon atoms, and more preferably a phenylene group.
  • R S1 may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, and the number of unsaturated bonds in the saturated aliphatic hydrocarbon group or the aliphatic hydrocarbon group may be One to three aliphatic hydrocarbon groups are preferable, and a saturated aliphatic hydrocarbon group is more preferable.
  • R S1 is an unsubstituted saturated aliphatic hydrocarbon group and does not have a predetermined group in the above-described linear or branched aliphatic hydrocarbon group having 6 to 20 carbon atoms. And is more preferably represented by — (CH 2 ) n —H (n represents an integer of 6 to 20).
  • R S1 may be bonded with X 1 via a linking group, it may be directly bonded with X 1, but is preferably bonded directly X 1.
  • X 1 and R S1 may have a substituent.
  • the substituent is an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group), a hydroxyl group, a halogen atom. An atom, an alkoxy group, etc. are mentioned.
  • the component (S) is preferably a compound represented by the following general formula (S2) or a compound represented by the following general formula (S3).
  • General formula (S2) X 2 -X 3 -R S11 In the general formula (S2), X 2 represents at least one selected from an alkoxysilane group, a blocked isocyanate group, a blocked isothiocyanate group, a block ketene group, an isocyanate group, an isothiocyanate group, a thiol group, and an oxazoline group.
  • X 3 represents a single bond or a divalent linking group
  • R S11 represents a linear or branched aliphatic hydrocarbon group having 6 to 20 carbon atoms, and —O— in the aliphatic hydrocarbon group.
  • —S— at least one group selected from a cyclic alkylene group and an arylene group, provided that —O—, —S—, a group selected from a cyclic alkylene group and an arylene group
  • the two or more groups are not adjacent to each other, and the compound represented by the general formula (S2) has a carboxyl group and an alcoholic hydroxyl group.
  • X 2 has the same preferred range as X 1 in the case where n1 in general formula (S1) represents 1.
  • X 3 is preferably a single bond.
  • R S11 has the same meaning as R S1 in general formula (S1) described above, and the preferred range is also the same.
  • General formula (S3) X 6- (X 4 -X 5 -R S12 ) n2 In the general formula (S3), X 4 represents at least one selected from an ester group, a thioether group, a disulfide group, an amide group, and a urethane group.
  • X 5 represents a single bond or a divalent linking group.
  • X 6 represents a divalent linking group
  • R S12 represents a linear or branched aliphatic hydrocarbon group having 6 to 20 carbon atoms
  • the aliphatic hydrocarbon group includes the aliphatic hydrocarbon group
  • the group may have at least one group selected from —O—, —S—, a cyclic alkylene group, and an arylene group, provided that —O—, —S—, a cyclic alkylene group, and an arylene group are included.
  • n3 represents 2 or 3.
  • the compound represented by the general formula (S3) includes a carboxyl group and an alcoholic group. Has no hydroxyl group and is polymerized (It is a compound that does not generate a carboxyl group or an alcoholic hydroxyl group even when it reacts with an acid group of a body component.)
  • R S12 has the same meaning as R S1 in general formula (S1) described above, and the preferred range is also the same.
  • X 4 has the same meaning as X 1 in the case where n1 in the general formula (S1) represents 2 or 3, and the preferred range is also the same.
  • X 5 is preferably a single bond.
  • X 5 represents a divalent linking group
  • the divalent linking group has the same meaning as X 3 in formula (S2) described above.
  • X 6 has the same meaning as the divalent or trivalent linking group of X 1 in the case where n1 in general formula (S1) represents 2 or 3, and the preferred range is also the same. It is.
  • the photosensitive resin composition of the present invention preferably contains the component (S) in a proportion of 0.5 to 20% by mass, more preferably 1 to 15% by mass, based on the total solid content. More preferably, it is contained in a proportion of 2 to 10% by mass.
  • S A component may be only one type and may be two or more types. When there are two or more types of component (S), the total is preferably in the above range.
  • 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 order to promote the decomposition in combination with the photoacid generator.
  • the sensitizer absorbs actinic rays 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 0.001 to 100 parts by mass with respect to 100 parts by mass of the total solid components in the photosensitive resin composition. More preferably, it is ⁇ 50 parts by mass, and further preferably 0.5 to 20 parts 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.
  • 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 parts by mass with respect to 100 parts by mass in total of the above (A-1) polymer component, More preferably, it is ⁇ 30 parts by mass, and further preferably 0.5-20 parts by mass. By adding in this range, a cured film having excellent 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 other than the compound represented by the general formula (S1) described above, but from the viewpoint of curability, two or more blocked isocyanate groups in one molecule. It is preferable that it is a compound which has this.
  • 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 2'-diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1,3
  • a compound and a prepolymer type skeleton compound derived from these compounds can be preferably used.
  • tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are particularly preferable.
  • Examples of 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.
  • Examples of 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 as an adhesion improving agent.
  • 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.
  • a known silane coupling agent or the like is also effective.
  • 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.
  • the (G-1) alkoxysilane compound in the photosensitive resin composition of the present invention is not particularly limited, and known compounds can be used.
  • the content of the (G-1) alkoxysilane compound in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive composition. 5 to 20 parts by mass 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 parts by mass with respect to 100 parts by mass of the total solid components in the photosensitive resin composition. More preferably, the amount is 0.005 to 1 part 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.
  • examples of 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. .
  • the following trade names are KP-341, X-22-822 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No.
  • 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 copolymer having a polystyrene-equivalent weight average molecular weight (Mw) of 1,000 or more and 10,000 or less can be mentioned as a preferred example.
  • 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 the general formula (I-1-2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability 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 parts by mass or less, and 0.001 to 10 parts by mass with respect to 100 parts by mass of the total solid components in the photosensitive resin composition. More preferred is 0.01 to 3 parts by mass.
  • ⁇ Antioxidant >>
  • the photosensitive resin composition of the present invention may contain an antioxidant. As an antioxidant, a well-known antioxidant can be contained.
  • 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.
  • phenolic antioxidants, hindered amine antioxidants, phosphorus antioxidants, amide antioxidants, hydrazide antioxidants, sulfur oxidations are particularly preferred from the viewpoint of coloring of the cured film and reduction of the film thickness.
  • Inhibitors are preferred, and phenolic antioxidants are most preferred. These may be used individually by 1 type and may mix 2 or more types. Specific examples include the compounds described in paragraph numbers 0026 to 0031 of JP-A-2005-29515 and the compounds described in paragraph numbers 0106 to 0116 of JP-A-2011-227106. It is incorporated herein. Preferred commercially available products are ADK STAB AO-20, ADK STAB AO-60, ADK STAB AO-80, ADK STAB LA-52, ADK STAB LA-81, ADK STAB AO-412S, ADK STAB PEP-36, IRGANOX 1035, IRGANOX 1098, and Tinuvin 144. Can be mentioned.
  • the content of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the total solid components in the photosensitive resin composition. It is particularly preferably 0.5 to 4 parts 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.
  • the composition of the present invention comprises: (A-2) a polymer component containing a polymer that satisfies at least one of the following (1) and (2): (1) (a2-1) a structural unit having an acid group, and (a2-2) a structural unit having a crosslinkable group, (2) (a2-1) a polymer having a structural unit having an acid group, and (a2-2) a polymer having a structural unit having a crosslinkable group, (B-2) a quinonediazide compound, (S) the component (S) (preferably a compound represented by the general formula (S1)), (C-2) It contains a solvent.
  • the polymer component (A-2) used in the present invention includes (a2-1) a structural unit having an acid group and (a2-2) a polymer containing a structural unit having a crosslinkable group, and (a2-1) At least one of a polymer having a structural unit having an acid group and a polymer having a structural unit having a crosslinkable group (a2-2). Furthermore, the (A-2) polymer component may contain a polymer other than these.
  • (a2-1) Structural Unit Having Acid Group By including the structural unit (a2-1) having an acid group in the polymer component (A-2), the polymer component is easily soluble 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 having an acid group using a monomer capable of forming an acid group. By including such a structural unit having 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 Amide groups, sulfonylimide groups and the like are exemplified, and those derived from carboxylic acid groups and / or those derived from phenolic hydroxyl groups are preferred.
  • the structural unit having an acid group used in the present invention is preferably a structural unit having a carboxyl group and / or a phenolic hydroxyl group.
  • the structural unit having an acid group used in the present invention is preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, or a structural unit derived from (meth) acrylic acid and / or an ester thereof.
  • styrene a structural unit derived from a vinyl compound
  • (meth) acrylic acid and / or an ester thereof a structural unit derived from (meth) acrylic acid and / or an ester thereof.
  • 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.
  • structural units derived from p-hydroxystyrene, (meth) acrylic acid, maleic acid, and maleic anhydride are preferred.
  • a repeating unit having a carboxyl group or a repeating unit having a phenolic hydroxyl group it is particularly preferable from the viewpoint of sensitivity to contain a repeating unit having a carboxyl group or a repeating unit having a phenolic hydroxyl group.
  • a repeating unit having a carboxyl group or a repeating 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 (a2-2) having a crosslinkable group is represented by an epoxy group, an oxetanyl group, —NH—CH 2 —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). It is preferable to contain a structural unit containing at least one selected from the group consisting of a group and an ethylenically unsaturated group.
  • the structural unit (a2-2) having a crosslinkable group has the same meaning as the structural unit (a1-2) having a crosslinkable group in the polymer (A-1), and the preferred range is the same except for the blending amount. It is.
  • the polymer component (A-2) includes the structural unit (a2-1) and the structural unit (a2-2), as well as the structural unit (a2-1) and the structural unit (a2-2).
  • the structural unit (a2-3) may be included.
  • the monomer to be the structural unit (a2-3) is not particularly limited as long as it is an unsaturated compound other than the structural units (a2-1) and (a2-2).
  • styrenes for example, styrenes, (meth) acrylic acid alkyl esters, (meth) acrylic acid cyclic alkyl esters, (meth) acrylic acid aryl esters, unsaturated dicarboxylic acid diesters, bicyclounsaturated compounds, maleimide compounds, unsaturated aromatics Examples thereof include compounds, conjugated diene compounds, and other unsaturated compounds.
  • the monomers to be the structural unit (a2-3) can be used alone or in combination of two or more.
  • the structural unit (a2-1) is preferably contained in an amount of 3 to 70 mol%, more preferably 10 to 60 mol%. More preferably, it is contained in an amount of ⁇ 50 mol%.
  • the structural unit (a2-2) is preferably contained in an amount of 3 to 70 mol%, more preferably 10 to 60 mol%. More preferably, it is contained in an amount of ⁇ 40 mol%.
  • the structural unit (a2-3) is preferably contained in an amount of 1 to 80 mol%, more preferably 5 to 50 mol%, more preferably 8 More preferably, it is contained in an amount of ⁇ 30 mol%.
  • quinonediazide compound used in the composition of the present invention a 1,2-quinonediazide compound that generates a carboxylic acid upon irradiation with actinic rays can be used.
  • a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as “mother nucleus”) and 1,2-naphthoquinonediazidesulfonic acid halide can be used.
  • description of paragraphs 0075 to 0078 of JP2012-088459A can be referred to, and the contents thereof are incorporated in the present specification.
  • condensation reaction In the condensation reaction of a phenolic compound or an alcoholic compound (mother nucleus) and 1,2-naphthoquinonediazidesulfonic acid halide, preferably 30 to 85 moles relative to the number of OH groups in the phenolic compound or alcoholic compound. %, More preferably 1,2-naphthoquinonediazide sulfonic acid halide corresponding to 50 to 70 mol% can be used.
  • the condensation reaction can be carried out by a known method.
  • 1,2-quinonediazide compound examples include 1,2-naphthoquinonediazidesulfonic acid amides in which the ester bond of the mother nucleus exemplified above is changed to an amide bond, such as 2,3,4-triaminobenzophenone-1,2 -Naphthoquinonediazide-4-sulfonic acid amide is also preferably used.
  • the compounding amount of the quinonediazide compound in the photosensitive resin composition of the present invention is preferably 1 to 50 parts by mass, more preferably 2 to 40 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. 10 to 25 parts by mass is more preferable.
  • (B) By making the compounding quantity of a quinonediazide compound into the said range, the difference of the solubility of the irradiation part of the actinic ray with respect to the alkaline aqueous solution used as a developing solution and a non-irradiation part is large, patterning performance becomes favorable, and hardening obtained The solvent resistance of the film is improved.
  • composition of this invention contains the (S) component mentioned above.
  • the composition of the present invention preferably contains the component (S) in a proportion of 0.5 to 20% by mass, more preferably 1 to 15% by mass, more preferably 2 to 10%, based on the total solid content. More preferably, it is contained at a ratio of mass%.
  • (S) A component may be only one type and may be two or more types. In the case of two or more types, the total is preferably in the above range.
  • the photosensitive resin composition of the present invention contains a solvent.
  • the solvent used in the photosensitive resin composition of the present invention the above-described solvent (C-1) of the first aspect can be used, and the preferred range is also the same.
  • 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 crosslinking agent, alkoxysilane compound, basic compound, surfactant, and antioxidant can be preferably added as necessary as long as the effects of the present invention are not impaired.
  • the photosensitive resin composition of the present invention includes known development accelerators, plasticizers, thermal radical generators, thermal acid generators, ultraviolet absorbers, thickeners, and organic or inorganic precipitation inhibitors. Additives can be added. These components are the same as those in the first embodiment described above, and the preferred ranges are also the same.
  • the composition of the present invention comprises (A-3) a polymerizable monomer, (B-3) a photopolymerization initiator, (A-4) a polymer component containing a polymer that satisfies at least one of the following (1) and (2): (1) a polymer having (a4-1) a structural unit having an acid group, and (a4-2) a structural unit having a crosslinkable group, (2) (a4-1) a polymer having a structural unit having an acid group, and (a4-2) a polymer having a structural unit having a crosslinkable group, (S) the component (S) (preferably a compound represented by the general formula (S1)), (C-3) It contains a solvent.
  • A-3) Polymerizable monomer The polymerizable monomer used in the present invention can be appropriately selected from those applicable to this type of composition, and among them, an ethylenically unsaturated compound can be used. Is preferably used.
  • An ethylenically unsaturated compound is a polymerizable compound having at least one ethylenically unsaturated double bond.
  • ethylenically unsaturated compounds include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters and amides thereof, preferably An ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound and an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound are used.
  • unsaturated carboxylic acids eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • esters and amides thereof preferably An ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound and an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound are used.
  • urethane addition polymerizable compounds produced by the addition reaction of isocyanate and hydroxyl group, as described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765.
  • Urethane acrylates such as those described above, and urethanes having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 Compounds are also suitable and their description is incorporated herein.
  • Other examples include polyester acrylates, epoxy resins and (meth) described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490.
  • Polyfunctional acrylates and methacrylates such as epoxy acrylates obtained by reacting with acrylic acid can be mentioned, and these descriptions are incorporated in the present specification. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used. About these ethylenically unsaturated compounds, the details of usage, such as the structure, single use or combination, addition amount, etc. can be arbitrarily set according to the performance design of the final photosensitive material. For example, it is selected from the following viewpoints.
  • the polymerizable monomer is preferably polyfunctional, more preferably trifunctional or more, and even more preferably tetrafunctional or more. There is no particular upper limit, but 10 or less is practical. Furthermore, it is also effective to adjust the mechanical properties by using together compounds having different functional numbers and / or different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). Moreover, the polymeric compound containing a carboxy group is also preferable from a viewpoint of adjustment of developability. In this case, the mechanical properties can be improved by crosslinking with the component (C-3) of the resin, which is preferable. Furthermore, it is also preferable to contain an ethylene oxide (EO) modified body and a urethane bond from the viewpoints of adhesion to a substrate, compatibility with a radical polymerization initiator, and the like.
  • EO ethylene oxide
  • the polymerizable monomer applied to the present invention is preferably a compound represented by the following formula (A-3-1).
  • Formula (A-3-1) is preferably a compound represented by the following formula (A-3-1).
  • L represents a divalent or higher linking group.
  • the linking group is not particularly limited, and examples thereof include an alkylene group, a carbonyl group, an imino group, an ether group (—O—), a thioether group (—S—), or a combination thereof.
  • the number of carbon atoms of the linking group is not particularly limited, but is preferably 2 to 24, and more preferably 2 to 12. Among these, a branched alkylene group having the above carbon number is preferable.
  • A represents a polymerizable functional group.
  • the polymerizable functional group is preferably a vinyl group or a vinyl group-containing group.
  • the vinyl group-containing group include an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, and a vinylphenyl group.
  • Ra represents a substituent.
  • the substituent is not particularly limited, and examples thereof include an alkyl group (preferably having 1 to 21 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms), an aryl group (preferably having 6 to 24 carbon atoms), and the like. These substituents may further have a substituent, and examples of the substituent which may have a hydroxy group, an alkoxy group (preferably having 1 to 6 carbon atoms), a carboxyl group, and an acyl group (preferably Examples thereof include carbon numbers 1 to 6).
  • na represents an integer of 1 to 10, preferably 3 to 8.
  • nb represents an integer of 0 to 9, preferably 2 to 7.
  • na + nb is 10 or less, preferably 2 to 8.
  • the plurality of structural sites defined therein may be different from each other.
  • the content of the polymerizable monomer is preferably 5 to 60 parts by mass, more preferably 10 to 50 parts by mass with respect to 100 parts by mass in total of the above (A-3) polymer component. More preferably, it is 15 to 45 parts by mass.
  • the photosensitive resin composition of the present invention preferably contains the polymerizable monomer in a proportion of 5 to 60% by mass, more preferably 10 to 50% by mass, based on the total solid content. More preferably, it is contained at a ratio of ⁇ 45 mass%.
  • the photopolymerization initiator that can be used in the present invention is a compound that is sensitized by actinic rays and initiates and accelerates the polymerization of the polymerizable monomer.
  • the photopolymerization initiator that can be used in the present invention is preferably a compound that is sensitive to actinic rays and initiates and accelerates the polymerization of the ethylenically unsaturated compound.
  • the term “radiation” as used in the present invention is not particularly limited as long as it is an active energy ray capable of imparting energy capable of generating a starting species from component B-3 by irradiation, and is broadly ⁇ -ray, ⁇ Including X-rays, X-rays, ultraviolet rays (UV), visible rays, electron beams, and the like.
  • the photopolymerization initiator is preferably a compound that responds to actinic rays having a wavelength of 300 nm or more, more preferably 300 to 450 nm, and initiates and accelerates the polymerization of the polymerizable monomer (A-3).
  • a photopolymerization initiator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more is preferably used in combination with a sensitizer as long as it is a compound that is sensitive to an actinic ray having a wavelength of 300 nm or more when used in combination with a sensitizer. Can do.
  • Examples of the photopolymerization initiator include oxime ester compounds, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocenes.
  • Examples include compounds, hexaarylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, ⁇ -amino ketone compounds, onium salt compounds, and acylphosphine (oxide) compounds.
  • an oxime ester compound, an ⁇ -aminoketone compound, and a hexaarylbiimidazole compound are preferable, and an oxime ester compound or an ⁇ -aminoketone compound is more preferable.
  • these compounds for example, the description of paragraph numbers 0061 to 0073 in JP2011-186398A can be referred to, and the contents thereof are incorporated in the present specification.
  • a photoinitiator can be used 1 type or in combination of 2 or more types. Further, when using an initiator that does not absorb at the exposure wavelength, it is necessary to use a sensitizer.
  • the content of the photopolymerization initiator in the photosensitive resin composition of the present invention is preferably 0.5 to 30 parts by weight with respect to 100 parts by weight as a total of the above (A-3) polymer component. More preferably, it is 20 parts by weight.
  • the photosensitive resin composition of the present invention preferably contains the photopolymerization initiator in a proportion of 0.5 to 30% by mass, more preferably 2 to 20% by mass, based on the total solid content.
  • the polymer component used in the present invention is a polymer comprising (a4-1) a structural unit having an acid group and (a4-2) a repeating unit having a crosslinkable group. And (a4-1) at least one of a polymer having a structural unit having an acid group and (a4-2) a polymer having a structural unit having a crosslinkable group. Further, the polymer component (A-4) includes the structural unit (a4-1) and the structural unit (a4-2), as well as the structural unit (a4-1) and the structural unit (a4-2). The structural unit (a4-3) may be included.
  • the structural unit having an acid group (a4-1) contained in the polymer As the structural unit having an acid group (a4-1) contained in the polymer, the (a2-1) acid group described in the above-mentioned (A-2) polymer component of the second embodiment is used. The same structural unit as that possessed can be adopted, and the preferred range is also the same.
  • the structural unit (a4-2) having a crosslinkable group contained in the polymer (A-4) includes the crosslinkability (a2-2) described in (A-2) Polymer component of the second aspect described above. The same structural unit having a group can be employed, and the preferred range is also the same.
  • 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 each component of the present invention is dissolved in a solvent.
  • a known solvent for example, the solvent (C-1) of the first aspect described above can be used.
  • 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.
  • the composition of this invention contains the (S) component mentioned above.
  • the photosensitive resin composition of the present invention preferably contains the component (S) in a proportion of 0.5 to 20% by mass, more preferably 1 to 15% by mass, based on the total solid content. More preferably, it is contained in a proportion of 2 to 10% by mass.
  • (S) A component may be only one type and may be two or more types. When there are two or more types of component (S), the total is preferably in the above range.
  • an alkoxysilane compound, a surfactant, a polymerization inhibitor, and the like can be preferably added to the photosensitive resin composition of the present invention as necessary.
  • the alkoxysilane compound and the surfactant the same compounds as the alkoxysilane compound and the surfactant of the first aspect described above can be used, and the preferred range is also the same.
  • the polymerization inhibitor for example, thermal polymerization inhibitors described in paragraph numbers 0101 to 0102 of JP-A-2008-250074 can be used, the contents of which are incorporated herein.
  • 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 according to the first aspect of the present invention preferably includes the following steps (1-1) to (5-1).
  • (1-1) A step of applying the photosensitive resin composition of the first aspect of the present invention onto a substrate;
  • (2-1) A step of removing the solvent from the applied photosensitive resin composition;
  • (3-1) A step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays;
  • (4-1) A step of developing the exposed photosensitive resin composition with an aqueous developer;
  • (5-1) A post-baking step of thermosetting the developed photosensitive resin composition.
  • the photosensitive resin composition of the present invention it is preferable to apply the photosensitive resin composition of the present invention on 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.
  • the substrate include inorganic substrates, resins, and resin composite materials.
  • the inorganic substrate examples 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
  • the coating method on 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 it is usually used in the range of 0.5 to 10 ⁇ m.
  • 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 produce 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 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, PEB is not necessarily performed.
  • 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% 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 obtained positive image is heated to thermally decompose the acid-decomposable group to generate a carboxyl group or a phenolic hydroxyl group, and to crosslink 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 method for producing a cured film according to the second aspect of the present invention preferably includes the following steps (1-2) to (5-2).
  • (5-2) A post-baking step of thermosetting the developed photosensitive resin composition preferably includes the following steps (1-2) to (5-2).
  • Steps (1-2) to (5-2) of the method for producing a cured film of the present invention are respectively (1-1) to (5-1) of the method for producing a cured film of the first aspect described above. It can carry out similarly to the process of this, and preferable conditions are also the same.
  • the cured film obtained from the composition of the present invention can also be used as an etching resist.
  • the method for producing a cured film according to the third aspect of the present invention preferably includes the following steps (1-3) to (5-3).
  • (1-3) A step of applying the photosensitive resin composition of the third aspect of the present invention onto a substrate; (2-3) a step of removing the solvent from the applied photosensitive resin composition; (3-3) A step of exposing the photosensitive resin composition from which the solvent has been removed with actinic radiation; (4-3) A step of developing the exposed photosensitive resin composition with an aqueous developer or the like; (5-3) A post-baking step of thermosetting the developed photosensitive resin composition.
  • steps (1-3) A step of applying the photosensitive resin composition of the third aspect of the present invention onto a substrate; (2-3) a step of removing the solvent from the applied photosensitive resin composition; (3-3) A step of exposing the photosensitive resin composition from which the solvent has been removed with actinic radiation; (4-3) A step of developing the exposed photosensitive resin composition with an aqueous developer or the like; (5-3) A post-baking step of thermo
  • the photosensitive resin composition is coated on the substrate.
  • the photosensitive resin composition can be prepared, for example, by preparing a solution in which each of the above-described components is previously dissolved in a solvent, and then mixing them at a predetermined ratio to prepare a resin composition.
  • the composition solution prepared as described above can be used after being filtered using, for example, a filter having a pore size of 0.2 ⁇ m.
  • the substrate described in the step (1-1) can be used, and the coating method described in the step (1-1) can be used. .
  • the solvent removal step (2-3) it is preferable to form a dry coating film on the substrate by removing the solvent from the applied photosensitive resin composition by reducing pressure and / or heating.
  • the heating conditions in the solvent removal step vary depending on the types and blending ratios of the respective components, but are preferably at 80 to 130 ° C. for about 30 to 120 seconds.
  • the exposure step (3-3) it is preferable to irradiate the obtained coating film with actinic rays having a wavelength of 300 nm to 450 nm in a predetermined pattern.
  • the polymerizable monomer polymerizable compound
  • the actinic rays mentioned in the description of the exposure step in the method for producing the cured film of the first aspect described above can be 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.
  • development is preferably performed using an alkaline developer.
  • the developer used in the development step preferably contains a basic compound.
  • a basic compound the basic compound quoted by description of the image development process in the manufacturing method of the cured film of the 1st aspect mentioned above can be used, for example.
  • the pH of the developer is preferably 10.0 to 14.0.
  • the development time is preferably 30 to 180 seconds, and the development method may be either a liquid piling method or a dipping method. After development, washing with running water can be performed for 30 to 90 seconds to form a desired pattern.
  • a rinsing step can be performed in the same manner as in the method for producing a cured film of the first aspect described above.
  • the obtained negative image is heated to remove the remaining solvent component and, if necessary, to promote crosslinking of the resin, a cured film can be formed.
  • This heating is preferably performed at a high temperature of 150 ° C. or more, more preferably 180 to 250 ° C., and particularly preferably 200 to 240 ° C.
  • the heating time can be appropriately set depending on the heating temperature or the like, but is preferably in the range of 10 to 120 minutes.
  • Middle baking can also be performed similarly to the manufacturing method of the cured film of the 1st aspect mentioned above.
  • the crosslinking reaction can be promoted by actinic ray irradiation.
  • the cured film obtained from the photosensitive resin composition of the present invention can also be used as a dry etching resist.
  • dry etching processing such as ashing, plasma etching, ozone etching, etc. can be performed as the etching processing.
  • the cured film of the present invention is a cured film obtained by curing the above-described photosensitive resin composition of the first to third aspects of the present invention.
  • the cured film of the present invention can be suitably used as an interlayer insulating film.
  • the cured film of the present invention is preferably a cured film obtained by the above-described cured film forming method of the first to third aspects of the present invention.
  • 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-
  • 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.
  • MATHF 2-tetrahydrofuranyl methacrylate (synthetic product)
  • MAEVE 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
  • OXE-30 3-ethyl-3-oxetanylmethyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
  • GMA Glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
  • NBMA n-butoxymethylacrylamide (manufactured by Tokyo Chemical Industry)
  • HEMA Hydroxyethyl methacrylate (Wako Pure Chemical Industries, Ltd.)
  • MAA Methacrylic acid (manufactured by Wako Pure Chemical Industries)
  • MMA Methyl methacrylate (Wako Pure Chemical Industries, Ltd.)
  • St Styrene (Wako Pure Chemical Industries, Ltd.)
  • DCPM Hydroxyethyl me
  • the numerical values not indicated in the table are in mol%.
  • the numerical value of a polymerization initiator and an additive is mol% when a monomer component is 100 mol%.
  • the solid content concentration is shown as monomer mass / (monomer mass + solvent mass) ⁇ 100 (unit mass%).
  • B-1-1 Structure shown below (Synthesis examples will be described later)
  • B-1-2 Structure shown below (Synthesis example will be described later)
  • B-1-3 Structure shown below (synthesized according to the method described in paragraph 0108 of JP-T-2002-528451)
  • B-1-4 PAG-103 (trade name, structure shown below, manufactured by BASF)
  • B-1-5 GSID-26-1, triarylsulfonium salt (manufactured by BASF)
  • Crude B-1-2A was purified by silica gel column chromatography to obtain 1.7 g of intermediate B-1-2A.
  • B-1-2A (1.7 g) and p-xylene (6 mL) were mixed, 0.23 g of p-toluenesulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added and heated at 140 ° C. for 2 hours. .
  • water and ethyl acetate were added to the reaction mixture and the phases were separated.
  • ((S) component) (Comparative Compound S ′)
  • S'-1 Stearic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • S'-2 1,2-epoxyhexadecane (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • S'-3 1-Dodecanol (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • Alkoxysilane compound G-1 ⁇ -glycidoxypropyltrimethoxysilane (KBM-403: manufactured by Shin-Etsu Chemical Co., Ltd.)
  • F-1 JER828 (manufactured by Mitsubishi Chemical Holdings Corporation)
  • F-2 JER1007 (manufactured by Mitsubishi Chemical Holdings Corporation)
  • F-3 JER157S65 (manufactured by Mitsubishi Chemical Holdings Corporation)
  • F-4 Duranate 17B-60P (Asahi Kasei Chemicals Corporation)
  • F-5 Celoxide 2021P (manufactured by Daicel Corporation)
  • J-1 ADK STAB AO-60 (manufactured by ADEKA Corporation)
  • J-2 Irganox 1035 (manufactured by BASF)
  • J-3 Irganox 1098 (BASF)
  • the photosensitive resin composition of the present invention has good chemical resistance when used as a cured film and has a low relative dielectric constant.
  • the photosensitive resin composition of the comparative example different from the photosensitive resin composition of the present invention does not satisfy at least one of chemical resistance and relative dielectric constant when used as a cured film. I understood.
  • a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 42 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 of the substrate and the interlayer insulating film 17 in paragraph 0058 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 subjected to 40 mJ / cm 2 (energy intensity: 20 mW / cm 2 ) through a hole pattern mask of 10 ⁇ m ⁇ by using Canon MPA 5500CF (high pressure mercury lamp). , I-line).
  • the exposed photosensitive resin composition layer was subjected to paddle development at 23 ° C./60 seconds with an alkaline developer (0.4% 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 43 Only the following process was changed from Example 42, and the same liquid crystal display device was obtained. That is, even if the exposure apparatus is changed from MPA 5500CF (high pressure mercury lamp) manufactured by Canon Inc. to FX-803M (gh-Line stepper) manufactured by Nikon Corporation, the performance as a liquid crystal display device is the same as that of Example 42. It was very good.
  • MPA 5500CF high pressure mercury lamp
  • FX-803M gh-Line stepper
  • Example 44 Only the following process was changed from Example 42, and the same liquid crystal display device was obtained. That is, even if the exposure apparatus is changed from Canon Inc. MPA 5500CF (high pressure mercury lamp) to “AEGIS” manufactured by Buoy Technology Co., Ltd. (wavelength 355 nm, pulse width 6 nsec), the liquid crystal display device The performance was also good as in Example 42.
  • MPA 5500CF high pressure mercury lamp
  • AEGIS Buoy Technology Co., Ltd.
  • Example 45 Only the following process was changed from Example 42, and the same liquid crystal display device was obtained. 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 as good as in Example 42. 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 46 Only the following process was changed from Example 42, and the same liquid crystal display device was obtained. 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 as good as in Example 42. 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 47 Only the following process was changed from Example 42, and the same liquid crystal display device was obtained. 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 as good as in Example 42. From the viewpoint of improving dimensional stability, it is also preferable to introduce a PEB process.
  • Example 48 Only the following process was changed from Example 42, and the same liquid crystal display device was obtained. That is, even when the alkaline developer is changed from a 0.4% tetramethylammonium hydroxide aqueous solution to a 2.38% tetramethylammonium hydroxide aqueous solution, the resulting cured film has good pattern free of chipping and peeling. It was a state. Further, the performance as a liquid crystal display device was as good as in Example 42. This is presumably because the composition of the present invention has excellent adhesion to the substrate.
  • Example 49 Only the following process was changed from Example 42, and the same liquid crystal display device was obtained. 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 as good as in Example 42. This is presumably because the composition of the present invention has excellent adhesion to the substrate.
  • Example 50 Only the following process was changed from Example 42, and the same liquid crystal display device was obtained. That is, even when the alkaline developer was changed from a 0.4% 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 as good as in Example 42. This is presumably because the composition of the present invention has excellent adhesion to the substrate.
  • Example 51 Only the following process was changed from Example 42, and the same liquid crystal display device was obtained. 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 42. 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 53 Only the following process was changed from Example 42, and the same liquid crystal display device was obtained. 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 42. 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 a thin film transistor (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 with an organic EL element formed between 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 irradiation with i-line (365 nm) at 45 mJ / cm 2 (energy intensity 20 mW / cm 2 ) using a mercury lamp, development is performed with an alkaline aqueous solution (0.4% TMAH aqueous solution) to form a pattern.
  • the integrated dose was 300 mJ / cm 2 (energy intensity: 20 mW / cm 2 , i-line), and a 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.
  • Example 54 A liquid crystal display device was obtained using the photosensitive resin composition of Example 33 in the same manner as in the first example. 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.
  • an organic EL display device using a thin film transistor (TFT) was produced using the photosensitive resin composition of Example 33.
  • TFT thin film transistor
  • Example 55 A liquid crystal display device was obtained using the photosensitive resin composition of Example 36 in the same manner as in the first example. 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.
  • an organic EL display device using a thin film transistor (TFT) was produced using the photosensitive resin composition of Example 36.
  • TFT thin film transistor
  • TFT Thin Film Transistor
  • Wiring 3 Insulating film 4: Flattened film 5: First electrode 6: Glass substrate 7: Contact hole 8: Insulating film 10: Liquid crystal display device 12: Backlight unit 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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PCT/JP2014/066935 2013-06-27 2014-06-26 感光性樹脂組成物、硬化膜の製造方法、硬化膜、液晶表示装置および有機ｅｌ表示装置 WO2014208647A1 (ja)

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JP2017181557A (ja) * 2016-03-28 2017-10-05 日本ゼオン株式会社 感放射線樹脂組成物及び電子部品
TWI735595B (zh) * 2017-06-12 2021-08-11 奇美實業股份有限公司 正型感光性聚矽氧烷組成物及其應用

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JP6306621B2 (ja) * 2015-02-17 2018-04-04 富士フイルム株式会社 薄膜トランジスタ基板の製造方法、表示装置の製造方法及び表示装置
US10815426B2 (en) * 2016-08-17 2020-10-27 Sharp Kabushiki Kaisha Liquid crystal cell for scanning antenna and method of producing liquid crystal cell for scanning antenna
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