Classifications

• • 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
  • G03F7/022—Quinonediazides
  • G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
  • H10K59/10—OLED displays
  • H10K59/12—Active-matrix OLED [AMOLED] displays
  • H10K59/124—Insulating layers formed between TFT elements and OLED elements

Definitions

• the present invention relates to a photosensitive resin composition (hereinafter sometimes simply referred to as “photosensitive resin composition” or “composition of the present invention”). Moreover, it is related with the manufacturing method of the cured film using the said photosensitive resin composition, the cured film formed by hardening
• Organic EL display devices, liquid crystal display devices, and the like are provided with a patterned interlayer insulating film.
• a photosensitive resin composition is widely used because the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained (for example, patents). References 1-3).
• JP-A-5-165214 JP 2008-256974 A Japanese Patent Laid-Open No. 8-62847
• the photosensitive resin composition constituting the interlayer insulating film is adhesion to the substrate.
• the substrate itself is made of a plurality of types of materials
• the interlayer insulating film material formed on the surface of the wiring substrate is also provided with adhesion to the types of substrates.
• the interlayer insulating film is exposed to a resist stripping solution used for forming a pattern of the transparent electrode film after forming the interlayer insulating film and NMP (N-methylpyrrolidone) used for forming the liquid crystal alignment film.
• Patent Document 3 1-cyclohexyl-3- (2-morpholinoethyl) -2-thiourea is blended in a photosensitive composition. Although it is disclosed that adhesion in etching with a hydrochloric acid-based etchant is improved, it is difficult to achieve both adhesion to various substrates at the time of development and when used as a cured film. I understood. Moreover, since the photosensitive composition disclosed in Patent Document 3 is not high in resistance (chemical resistance) to chemicals such as a stripping solution and NMP, display defects are likely to occur in a liquid crystal display device, and improvement is required. It was.
• the present invention aims to solve the above-mentioned problems, and is a cured photosensitive resin composition having excellent adhesion to various substrates in the state of development and cured film, and excellent chemical resistance.
• the purpose is to provide goods. Furthermore, it aims at providing the manufacturing method of a cured film using such a photosensitive resin composition, a cured film, an organic electroluminescence display, and a liquid crystal display device.
• the photosensitive resin composition contains a polymer containing a repeating unit having an acid group and a repeating unit having a crosslinkable group, and a coordination atom in one molecule.
• a compound having a structure containing and a thiourea structure By including a compound having a structure containing and a thiourea structure, the adhesion to various substrates in the state of developing the photosensitive resin composition and when the photosensitive resin composition is a cured film is improved, It has been found that the chemical resistance is improved when the photosensitive resin composition is used for an interlayer insulating film, and the present invention has been completed.
• the above problem has been solved by the following means ⁇ 1>, preferably ⁇ 2> to ⁇ 17>.
• R 1 represents a group containing at least one nitrogen atom
• A represents a divalent linking group
• R 2 represents an organic group.
• R 1 is represented by —NR 3 R 4 (R 3 and R 4 are each an organic group and may be bonded to each other to form a ring).
• R 1 in the general formula (S) is a 5-membered or 6-membered cyclic group.
• ⁇ 6> The photosensitive resin composition according to any one of ⁇ 3> to ⁇ 5>, wherein R 1 in the general formula (S) is a morpholino group.
• R 1 in the general formula (S) is a morpholino group.
• ⁇ 8> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 7>, wherein the structural unit (a1) is a repeating unit having a carboxyl group and / or a phenolic hydroxyl group.
• the structural unit (a2) is selected from the group consisting of an epoxy group, an oxetanyl group, and a group represented by —NH—CH 2 —O—R (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms).
• the blending amount of the component (B) in the photosensitive resin composition is more than 10 mass% and 40 mass% or less with respect to the total solid content in the photosensitive resin composition, ⁇ 1> to ⁇ 9>
• ⁇ 11> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 10>, wherein the photosensitive resin composition is a positive photosensitive resin composition.
• ⁇ 12> (1) A step of applying the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 11> 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.
• ⁇ 13> The method for producing a cured film according to ⁇ 12>, which includes (6) a step of exposing the entire surface of the developed photosensitive resin composition after the developing step and before the post-baking step.
• ⁇ 14> The method for producing a cured film according to ⁇ 12> or ⁇ 13>, including a step of performing dry etching on a substrate having a cured film obtained by thermosetting in the post-baking step.
• ⁇ 15> A cured film formed by the method for producing a cured film according to any one of ⁇ 12> to ⁇ 14>.
• ⁇ 16> The cured film according to ⁇ 15>, which is an interlayer insulating film.
• ⁇ 17> An organic EL display device or a liquid crystal display device having the cured film according to ⁇ 15> or ⁇ 16>.
• the present invention it is possible to provide a photosensitive resin composition that is excellent in adhesion to various substrates in the state of development and as a cured film and excellent in chemical resistance.
• the contents of the present invention will be described in detail.
• “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 that does not indicate substitution and non-substitution includes not only those having no substituent but also those having 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 organic EL element in the present invention refers to an organic electroluminescence element.
• the composition of the present invention comprises (A) (a1) a repeating unit having an acid group, (a2) a polymer containing a repeating unit having a crosslinkable group, (B) a quinonediazide compound, and (C) in one molecule. And a compound having a structure containing a coordination atom and a thiourea structure (hereinafter also referred to as component (C)).
• component (C) a compound having a structure containing a coordination atom and a thiourea structure.
• the inventor of the present application contains (A) a polymer containing (a1) a repeating unit having an acid group and (a2) a repeating unit having a crosslinkable group and (C) component in the photosensitive resin composition.
• the adhesion to various substrates is improved and the photosensitive resin composition is used for an interlayer insulating film. It has been found that chemical resistance is also improved. Although this mechanism is not clear, by introducing the repeating unit (a2) having a crosslinkable group into the polymer (A), the crosslinkable group and the component (C) interact with each other, and the component (C) As a result of more adsorbing to the substrate, it is presumed that the adhesion to various substrates is improved during development of the photosensitive resin composition and when the photosensitive resin composition is used as a cured film.
• the crosslink density when the photosensitive resin composition is a cured film is improved.
• the chemical resistance is improved when the photosensitive resin composition is used for an interlayer insulating film. Is done. Therefore, when the said (C) component is contained in the photosensitive resin composition, it is estimated that chemical resistance improves compared with the case where the said (C) component is not contained in the photosensitive resin composition. Is done.
• the composition of the present invention can be preferably applied to a positive photosensitive resin composition.
• the repeating unit having an acid group is a carboxyl group and / or A repeating unit having a phenolic hydroxyl group is preferred.
• the repeating unit (a2) having a crosslinkable group includes 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).
• a polymer becomes a main component of the component except the solvent of the composition of this invention, and it is preferable to occupy 60 mass% or more of a total solid.
• the polymer (A) is, for example, a compound (a1-1) that provides a carboxyl group-containing structural unit as a repeating unit having an acid group (a1) in the presence of a polymerization initiator in a solvent (hereinafter referred to as “(a1-1 And (a2) a compound that gives an epoxy group-containing structural unit as a repeating unit having a crosslinkable group (hereinafter, sometimes referred to as “(a2) compound”). Can be manufactured. Further, (a1) a hydroxyl group-containing unsaturated compound that gives a hydroxyl group-containing structural unit (hereinafter sometimes referred to as “(a1-2) compound”) is further added as a repeating unit having an acid group, can do.
• the compound (a3) (a structural unit other than the structural unit derived from the compounds (a1) and (a2)) is given.
• a saturated compound) can be further added to form a copolymer.
• Examples of the compound (a1-1) include unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated dicarboxylic acid anhydride, poly [carboxylic acid] mono [(meth) acryloyloxyalkyl] ester, Examples thereof include mono (meth) acrylates of polymers having a hydroxyl group, unsaturated polycyclic compounds having a carboxyl group, and anhydrides thereof.
• Examples of unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid and the like;
• Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, etc .
• examples of the unsaturated dicarboxylic acid anhydride include, for example, anhydrides of the compounds exemplified as the above dicarboxylic acid;
• Examples of acid mono [(meth) acryloyloxyalkyl] esters include succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl] and the like;
• Examples of mono (meth) acrylates of polymers having a hydroxyl group and a hydroxyl group include ⁇ -carboxypolycaprolactone mono (meth) acrylates; unsaturated polycyclic compounds having a carboxyl
• monocarboxylic acids and dicarboxylic anhydrides are preferable, and acrylic acid, methacrylic acid, and maleic anhydride are more preferable from the viewpoint of copolymerization reactivity, solubility in an alkaline aqueous solution, and availability.
• acrylic acid, methacrylic acid, and maleic anhydride are more preferable from the viewpoint of copolymerization reactivity, solubility in an alkaline aqueous solution, and availability.
• These (a1-1) compounds may be used alone or in admixture of two or more.
• the proportion of the compound (a1-1) used is 5 to 5 based on the sum of the compound (a1-1) and the compound (a2) (optional (a1-2) compound and (a3) compound as necessary). 30% by mass is preferable, and 7 to 25% by mass is more preferable.
• Examples of the compound (a1-2) include a (meth) acrylic acid ester having a hydroxyl group, a phenolic hydroxyl group-containing unsaturated compound represented by the following formula (3), and the like.
• R 17 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
• R 18 to R 22 are each independently a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 4 carbon atoms.
• Y is a single bond, —COO—, or —CONH—.
• p is an integer of 0 to 3. However, at least one of R 18 to R 22 is a hydroxyl group.
• Examples of the (meth) acrylic acid ester having a hydroxyl group include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and polyethylene glycol.
• Examples of the phenolic hydroxyl group-containing unsaturated compound represented by the above formula (3) include compounds represented by the following formulas (3-1) to (3-5) according to the definitions of Y and p. .
• q is an integer of 1 to 3.
• R 17 to R 22 have the same meaning as in the above formula (3).
• R 17 to R 22 have the same meaning as in the above formula (3).
• r is an integer of 1 to 3.
• R 17 to R 22 have the same meaning as in the above formula (3).
• R 17 to R 22 have the same meaning as in the above formula (3).
• R 17 to R 22 have the same meanings as in the above formula (3).
• 2-hydroxyethyl methacrylate 4-hydroxyphenyl methacrylate, o-hydroxystyrene, p-hydroxystyrene, and ⁇ -methyl-p-hydroxystyrene are preferable. These compounds may be used alone or in combination of two or more.
• the proportion of the (a1-2) compound used is 5 to 5 based on the sum of the (a1-2) compound, the (a2) compound, and the (a1-1) compound (optional (a3) compound if necessary). 30% by mass is preferable, and 7 to 25% by mass is more preferable.
• the crosslinkable group in the compound (a2) 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 component (A) preferably includes a structural unit containing at least one of an epoxy group and an oxetanyl group.
• the unsaturated compound having an epoxy group examples include glycidyl acrylate, glycidyl methacrylate, glycidyl ⁇ -ethyl acrylate, glycidyl ⁇ -n-propyl acrylate, glycidyl ⁇ -n-butyl acrylate, acrylate-3, 4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-3,4-epoxycyclohexylmethyl, methacrylic acid-3,4-epoxycyclohexylmethyl, ⁇ -ethylacrylic acid-3,4-epoxycyclohexylmethyl O-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, compounds containing an alicyclic epoxy skeleton described in paragraph Nos. 0031 to
• glycidyl methacrylate, 2-methylglycidyl methacrylate, -6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3, methacrylate 4-Epoxycyclohexyl is preferred from the viewpoint of improving the copolymerization reactivity and the solvent resistance of the cured film.
• Examples of the unsaturated compound having an oxetanyl group include 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- ( Acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (acryloyloxymethyl) -2-phenyloxetane, 3- (acryloyloxymethyl) -2, 2-difluorooxetane, 3- (acryloyloxymethyl) -2,2,4-trifluorooxetane, 3- (acryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (2-acryloyloxy) Ethyl) oxetane, 3- 2-acrylo
• (a2) compounds may be used alone or in admixture of two or more.
• specific examples of the radical polymerizable monomer used for forming a structural unit having an oxetanyl group include, for example, JP-A-2001-330953 Examples include (meth) acrylic acid esters having an oxetanyl group described in paragraphs 0011 to 0016, and the contents thereof are incorporated in the present specification.
• R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms
• R is preferably an alkyl group having 1 to 9 carbon atoms
• An alkyl group having 1 to 4 carbon atoms is more preferable.
• the alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
• More preferable examples of the unsaturated compound having a group represented by —NH—CH 2 —O—R include compounds 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 proportion of the compound (a2) used is preferably 5 to 70% by mass and more preferably 20 to 65% by mass based on the total of the compound (a1) and the compound (a2).
• A2 By making the usage-amount of a compound into the said range, the cured film which has the outstanding solvent resistance etc. can be formed.
• the compound (a3) is not particularly limited as long as it is an unsaturated compound other than the compounds (a1) and (a2).
• Examples of the compound (a3) include methacrylic acid chain alkyl ester, methacrylic acid cyclic alkyl ester, acrylic acid chain alkyl ester, acrylic acid cyclic alkyl ester, methacrylic acid aryl ester, acrylic acid aryl ester, unsaturated dicarboxylic acid diester, Bicyclo unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene, tetrahydrofuran skeleton, furan skeleton, tetrahydropyran skeleton, pyran skeleton, unsaturated compound containing skeleton represented by the following formula (4), and other unsaturated compounds Compounds and the like.
• R 23 is a hydrogen atom or a methyl group. s is an integer of 1 or more.
• chain alkyl esters of methacrylic acid include, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, and n-methacrylate.
• Examples include lauryl, tridecyl methacrylate, and n-stearyl methacrylate.
• cyclic alkyl ester of methacrylic acid examples include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 2,6 ] decane-8-yl methacrylate, and tricyclomethacrylate [5.2.1]. .0 2,6] decan-8-yl oxy ethyl, and isobornyl methacrylate.
• acrylic acid chain alkyl esters examples include methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, and n-acrylate.
• acrylic acid chain alkyl esters examples include lauryl, tridecyl acrylate, and n-stearyl acrylate.
• acrylic acid cyclic alkyl ester examples include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 2,6 ] decan-8-yl acrylate, and tricyclo [5.2.1.0 2,6. Decan-8-yloxyethyl acrylate, isobornyl acrylate and the like.
• methacrylic acid aryl ester examples include phenyl methacrylate and benzyl methacrylate.
• acrylic acid aryl ester examples include phenyl acrylate and benzyl acrylate.
• Examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, diethyl itaconate and the like.
• bicyclo unsaturated compound examples include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, and 5-ethylbicyclo [2.2.1].
• maleimide compounds include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like.
• unsaturated aromatic compound examples include styrene, ⁇ -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene and the like.
• conjugated diene examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.
• Examples of the unsaturated compound containing a tetrahydrofuran skeleton include tetrahydrofurfuryl methacrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydrofuran-2-one, and the like.
• Examples of unsaturated compounds containing a furan skeleton include 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, 1-furan-2-butyl-3-ene- 2-one, 1-furan-2-butyl-3-methoxy-3-en-2-one, 6- (2-furyl) -2-methyl-1-hexen-3-one, 6-furan-2- Yl-hex-1-en-3-one, acrylic acid-2-furan-2-yl-1-methyl-ethyl ester, 6- (2-furyl) -6-methyl-1-hepten-3-one, etc. Is mentioned.
• Examples of unsaturated compounds containing a tetrahydropyran skeleton include (tetrahydropyran-2-yl) methyl methacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -oct-1-en-3-one 2-methacrylic acid tetrahydropyran-2-yl ester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one, and the like.
• Examples of unsaturated compounds containing a pyran skeleton include 4- (1,4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyran, 4- (1,5-dioxa-6-oxo -7-octenyl) -6-methyl-2-pyran and the like.
• Examples of other unsaturated compounds include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, acryloylmorpholine, p-vinylbenzyl 2,3-epoxypropyl ether, and the like.
• (a3) compounds it has a methacrylic acid chain alkyl ester, a methacrylic acid cyclic alkyl ester, a maleimide compound, a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton, and a skeleton represented by the above formula (4).
• Unsaturated compounds, unsaturated aromatic compounds and acrylic acid cyclic alkyl esters are preferred.
• the use ratio of the compound (a3) is preferably 0 to 70% by mass, more preferably 0 to 50% by mass based on the total of the (a1) compound and the (a3) compound (and any (a2) compound). . (A3) By making the use ratio of a compound into the said range, the cured film excellent in solvent resistance etc. can be formed.
• a molecular weight modifier may be added to the (A) polymer.
• the molecular weight modifier is not particularly limited, and examples thereof include pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), and ⁇ -methylstyrene dimer. Only one type of molecular weight regulator may be used, or two or more types may be used in combination.
• the use ratio of the molecular weight modifier is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass in the polymer (A).
• the polymer (A) used in the present invention is particularly preferably an acrylic polymer containing the (a1) repeating unit having an acid group and the (a2) repeating unit having a crosslinkable group.
• (B) quinonediazide compound used in the composition of the present invention a 1,2-quinonediazide compound that generates a carboxylic acid upon irradiation with radiation 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.
• mother nucleus examples include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other mother nuclei.
• trihydroxybenzophenone examples include 2,3,4-trihydroxybenzophenone and 2,4,6-trihydroxybenzophenone.
• examples of tetrahydroxybenzophenone include 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,3′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,3 , 4,2′-tetrahydroxy-4′-methylbenzophenone, 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone, and the like.
• pentahydroxybenzophenone examples include 2,3,4,2 ′, 6′-pentahydroxybenzophenone.
• Examples of hexahydroxybenzophenone include 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone and 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone.
• Examples of (polyhydroxyphenyl) alkanes include bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1,1-tris (p-hydroxy).
• Phenyl) ethane bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimethyl-) 4-hydroxyphenyl) -3-phenylpropane, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, bis (2,5-dimethyl) -4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene -5,6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan and the like.
• mother nuclei examples include 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 1- [1- (3- ⁇ 1- (4 -Hydroxyphenyl) -1-methylethyl ⁇ -4,6-dihydroxyphenyl) -1-methylethyl] -3- (1- (3- ⁇ 1- (4-hydroxyphenyl) -1-methylethyl ⁇ -4 , 6-dihydroxyphenyl) -1-methylethyl) benzene, 4,6-bis ⁇ 1- (4-hydroxyphenyl) -1-methylethyl ⁇ -1,3-dihydroxybenzene, and the like.
• 1,2-naphthoquinone diazide sulfonic acid halide 1,2-naphthoquinone diazide sulfonic acid chloride is preferable.
• 1,2-naphthoquinone diazide sulfonic acid chloride examples include 1,2-naphthoquinone diazide-4-sulfonic acid chloride, 1,2-naphthoquinone diazide-5-sulfonic acid chloride, and the like. Of these, 1,2-naphthoquinonediazide-5-sulfonic acid chloride is more preferred.
• condensation reaction In the condensation reaction of the phenolic compound or alcoholic compound (mother nucleus) and 1,2-naphthoquinonediazide sulfonic 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 proportion of the (B) quinonediazide compound used in the photosensitive resin composition is preferably 5 to 100% by mass with respect to the total solid content in the photosensitive resin composition, and is more than 10% by mass and 40% by mass or less. More preferably, it is more than 12 mass% and 40 mass% or less.
• composition of the present invention contains a compound having a structure containing a coordination atom and a thiourea structure in one molecule. It is presumed that such a basic site (for example, a structure containing a coordination atom) contained in the component (C) promotes the crosslinking reaction of the cured film.
• the coordination atom is, for example, an inorganic material constituting the base substrate to which the composition of the present invention is applied, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, gold, copper, molybdenum, titanium, aluminum, or the like.
• An atom capable of forming a coordination bond with the metal is preferable.
• a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom are more preferable, and a nitrogen atom or an oxygen atom is particularly preferable.
• the structure containing a coordination atom is preferably a structure containing at least one nitrogen atom, and more preferably a structure containing 1 to 3 nitrogen atoms.
• the structure containing a coordination atom include, for example, morpholino group, hydrazino group, pyridyl group, imidazolyl group, quinolyl group, piperidyl group, pyrrolidinyl group, pyrazonyl group, oxazolyl group, thiazolyl group, benzooxazolyl group, Examples thereof include a benzimidazolyl group, a benzthiazolyl group, a pyrazinyl group, and a diethylamino group.
• morpholino group, piperidyl group, imidazolyl group and diethylamino group are preferable, morpholino group, piperidyl group and imidazolyl group are more preferable, and morpholino group is more preferable.
• a component (C) By using such a component (C), the interaction between the composition of the present invention and the base substrate can be strengthened, and the adhesion to various substrates in the state of development and cured film is improved. I think that.
• a cured film having a higher crosslinking density is formed by promoting the reaction between the acid group and the crosslinking group of the polymer contained in the composition of the present invention. Used for forming a pattern of a transparent electrode film after the formation of an interlayer insulating film or a liquid crystal alignment film. It is considered that the resistance to NMP can be improved.
• the component (C) is preferably a compound containing at least one nitrogen atom as a coordination atom, and more preferably a compound represented by the following general formula (S).
• General formula (S) (In general formula (S), R 1 represents a group containing at least one nitrogen atom, A represents a divalent linking group, and R 2 represents an organic group.)
• R 1 represents a group containing at least one nitrogen atom, preferably a group containing 1 to 3 nitrogen atoms, and more preferably a group represented by —NR 3 R 4 .
• R 1 preferably contains 1 to 10 carbon atoms and 1 to 3 heteroatoms including a nitrogen atom and / or an oxygen atom.
• examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom, and a nitrogen atom and an oxygen atom are preferable.
• R 1 is preferably a cyclic group, more preferably a 5-membered or 6-membered cyclic group.
• R 3 and R 4 each represents an organic group.
• R 3 and R 4 are each preferably a group having 1 to 3 carbon atoms.
• R 3 and R 4 may be bonded to each other to form a ring, and preferably form a ring.
• R 3 and R 4 are bonded to each other to form a 5-membered or 6-membered ring. Is preferably formed.
• R 1 Preferred embodiments of R 1 include the following embodiments. (1) An embodiment in which R 1 is a group represented by —NR 3 R 4 and R 3 and R 4 are bonded to each other to form a ring, or R 3 and R 4 are each , A linear, branched or cyclic aliphatic hydrocarbon group. (2) Embodiment in which R 1 is a group represented by —NR 3 R 4 and R 3 and R 4 are bonded to each other to form a 5-membered or 6-membered ring, or R 3 and R 4 Are each a linear or branched aliphatic hydrocarbon group having 1 to 4 carbon atoms.
• R 1 is a group represented by —NR 3 R 4 , and R 3 and R 4 are bonded to each other to form two or more heteroatoms (at least one is a nitrogen atom and the rest are oxygen atoms or A mode in which a 5-membered ring or a 6-membered ring is formed, or a straight-chain aliphatic hydrocarbon group having 1 to 4 carbon atoms, each of R 3 and R 4 The aspect which is.
• R 1 examples include, for example, morpholino group, hydrazino group, pyridyl group, imidazolyl group, quinolyl group, piperidyl group, pyrrolidinyl group, pyrazonyl group, oxazolyl group, thiazolyl group, benzoxazolyl group, benzimidazolyl group, A benzthiazolyl group, a pyrazinyl group, a diethylamino group, etc. are mentioned.
• morpholino group piperidyl group, imidazolyl group and diethylamino group are preferable, morpholino group, piperidyl group and imidazolyl group are more preferable, and morpholino group is more preferable.
• R 2 represents an organic group.
• the organic group is preferably a hydrocarbon group or a group consisting of a hydrocarbon group and at least one of —O— and —C ( ⁇ O) —, and in particular, an aliphatic hydrocarbon group or an aliphatic group.
• a group consisting of a hydrocarbon group and at least one combination of —O— and —C ( ⁇ O) — is more preferred.
• R 2 preferably has 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms.
• R 2 preferably has a hydrocarbon group at the terminal. When R 2 has a hydrocarbon group at the terminal, the hydrophobicity is further improved, and the effects of the present invention are more effectively exhibited.
• R 2 is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, or a group composed of these and at least one combination of —O— and —C ( ⁇ O) —. Further preferred. These groups may have a substituent, and examples of the substituent include a halogen atom.
• R 2 is an alkyl group, a linear or branched alkyl group having 1 to 8 carbon atoms or a cyclic alkyl group is preferable.
• R 2 is a cyclic alkyl group, a 5-membered or 6-membered cyclic alkyl group is preferred.
• R 2 is an aryl group, a phenyl group and a naphthyl group are exemplified, and a phenyl group is more preferable.
• R 2 include the following embodiments. (1) A mode of being a straight-chain alkylene group having 1 to 4 carbon atoms (preferably 2 or 3). (2) Aspect of being a 5- or 6-membered cyclic alkyl group (3) an aliphatic hydrocarbon group having 1 to 10 carbon atoms (preferably 2 to 4 carbon atoms), and —O— and —C ( ⁇ O) An embodiment in which the group is a combination of-and the terminal is a hydrocarbon group
• A represents a divalent linking group, such as a hydrocarbon group having 1 to 20 carbon atoms, —O—, —S—, —NR—, —CO—, —COO—, —NRCO—, —SO 2 — and the like. Examples thereof include a divalent group or a divalent group composed of a combination of these groups.
• R represents a hydrogen atom or an alkylene group having 1 to 4 carbon atoms. Of these, hydrocarbon groups having 1 to 20 carbon atoms are preferable, hydrocarbon groups having 1 to 10 carbon atoms are more preferable, and hydrocarbon groups having 2 to 6 carbon atoms are more preferable.
• Examples of the hydrocarbon group include an alkylene group and an arylene group, and an alkylene group is preferable.
• the alkylene group is preferably a linear or branched alkylene group, and more preferably a linear alkylene group.
• Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a cyclohexylene group, and a cyclopentylene group.
• Examples of the arylene group include a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, and a naphthylene group.
• a methylene group, an ethylene group, and a propylene group are particularly preferable, and an ethylene group or a propylene group is more preferable.
• Preferred embodiments of A include the following embodiments. (1) An embodiment in which the alkyl group is a linear or branched alkyl group having 1 to 4 carbon atoms, a 5- or 6-membered cyclic alkyl group, or a phenyl group.
• the compound represented by the general formula (S) is exemplified as a particularly preferable embodiment in which the preferred embodiment of R 1 , the preferred embodiment of R 2 , and the preferred embodiment of A are combined.
• the compound represented by the general formula (S) is represented by the general formula (S1).
• General formula (S1) (In general formula (S1), R 2 represents an organic group, and A represents a divalent linking group.) R 2 has the same meaning as R 2 in formula (S), and the preferred range is also the same. A is synonymous with A in the formula (S), and the preferred range is also the same.
• the following embodiments are preferable. (1) An embodiment in which A is a linear alkylene group having 1 to 4 carbon atoms, and R 2 is a linear, branched, or cyclic alkyl group. (2) A mode in which A is an alkylene group having 2 or 3 carbon atoms, and R 2 is a linear, branched or cyclic alkyl group having 2 to 6 carbon atoms.
• the molecular weight of the component (C) is preferably 150 to 1000, more preferably 200 to 500.
• the composition of the present invention preferably contains component (C) in a proportion of 0.001 to 10 parts by mass, and in a proportion of 0.003 to 7.5 parts by mass with respect to 100 parts by mass of the total solid content. Is more preferable, and it is more preferable to include it in a proportion of 0.005 to 5 parts by mass. (C) Only 1 type may be sufficient as a component and 2 or more types may be sufficient as it. In the case of two or more types, the total is preferably in the above range.
• the composition of the present invention includes a silane coupling agent, a surfactant, Optional components such as an adhesion aid, a heat resistance improver, and a heat-sensitive acid generator can be contained. These optional components may be used alone or in combination of two or more. Details of these compounds can be referred to the descriptions in paragraph numbers 0201 to 0224 of JP2012-88459A, the contents of which are incorporated herein.
• the silane coupling agent used in the composition of the present invention preferably contains an alkoxysilane compound.
• an alkoxysilane compound is used, the adhesion between the film formed from the composition used in the present invention and the substrate can be further improved, or the properties of the film formed from the composition used in the present invention can be adjusted. it can.
• the alkoxysilane compound that can be used in the composition of the present invention includes an inorganic material as a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, a metal such as gold, copper, molybdenum, titanium, or aluminum, and an insulating film. It is preferable that it is a compound which improves adhesiveness.
• silane coupling agents include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -glycidoxypropyltrialkoxysilane, ⁇ -glycidoxypropylalkyldialkoxysilane, and ⁇ -methacryloxy.
• ⁇ -glycidoxypropyltrialkoxysilane and ⁇ -methacryloxypropyltrialkoxysilane are more preferable, ⁇ -glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is more preferable. Further preferred. These can be used alone or in combination of two or more.
• R 1 is a hydrocarbon group having 1 to 20 carbon atoms having no reactive group
• R 2 is an alkyl group having 1 to 3 carbon atoms or a phenyl group
• n is an integer of 1 to 3 It is. Specific examples thereof include the following compounds.
• Ph is a phenyl group.
• the content of the alkoxysilane compound in the composition of the present invention is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive composition. .
• the surfactant used in the composition of the present invention is not particularly limited, and for example, those described in paragraph numbers 0201 to 0205 of JP2012-8859A can be used. Only one surfactant may be used, or two or more surfactants may be used in combination, but two or more surfactants are preferably used in combination.
• the content of the surfactant in the composition of the present invention is preferably 0.01 to 1 part by mass, and 0.05 to 0.5 part by mass with respect to 100 parts by mass of the total solid content in the photosensitive composition. More preferred.
• composition of the present invention may further contain a solvent.
• a solvent that uniformly dissolves essential components and optional components and does not react with each component is used.
• solvents for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether from the viewpoint of solubility of each component, reactivity with each component, ease of film formation, and the like.
• Ethylene glycol mono-n-butyl ether diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether , Propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol Non-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether (Poly) alkylene glycol monoalkyl ethers such as
• ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol (4-hydroxy-4-methylpentan-2-one), 4-hydroxy-4-methylhexane-2-one; Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate; Lactic acid alkyl esters such as methyl lactate and ethyl lactate; Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl
• solvents from the viewpoint of solubility, pigment dispersibility, coatability, etc., propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, 3-methoxypropionic acid Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-acetate Chill acetate i- butyl, formic acid n- amyl
• a high boiling point solvent such as diethyl, ⁇ -butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate may be used in combination.
• the said high boiling point solvent can use single or 2 types or more.
• the content of the solvent is not limited, the total concentration of each component excluding the solvent of the photosensitive resin composition is 5 to 50% by mass from the viewpoint of the coating property and stability of the obtained photosensitive resin composition.
• the amount is preferably 10 to 40% by mass.
• the solid content concentration (components other than the solvent in the composition solution) can be set to any concentration (for example, 5 depending on the purpose of use, a desired film thickness value, etc.). To 50 mass%).
• a more preferable solid content concentration varies depending on a method of forming a film on the substrate, which will be described later.
• the composition solution thus prepared can be used after being filtered using a Millipore filter or the like having a pore diameter of about 0.5 ⁇ m.
• the composition of the present invention can be prepared by mixing each component at a predetermined ratio and by any method, and stirring and dissolving.
• the resin composition can be prepared by mixing each component in a predetermined ratio after preparing each solution in advance in the above-described solvent.
• 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 method for producing a cured film of the present invention preferably includes the following steps (1) to (5).
• substrate (2) A step of removing the solvent from the applied photosensitive resin composition; (3) The process of exposing the photosensitive resin composition from which the solvent was removed with actinic rays; (4) A step of developing the exposed photosensitive resin composition with an aqueous developer; (5) A post-baking step of thermosetting the developed photosensitive resin composition.
• Each step will be described below in order.
• the coating step (1) it is preferable to apply the 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. Furthermore, it is also possible to apply a so-called pre-wet method as described in JP-A-2009-145395.
• 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 removal step (2) the solvent is removed from the coated film by reducing pressure (vacuum) and / or heating to form a dry coating film on the substrate.
• reducing pressure vacuum
• 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.
• an exposure light source using actinic light 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, etc.
• g-line (436 nm), i-line (365 nm), Actinic rays having a wavelength of 300 nm to 450 nm, such as 405 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 .
• various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, and a laser exposure can be used.
• 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. or higher and 100 ° C. or lower.
• 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 polymer 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.
• Preferred examples of the developer include 0.4% aqueous solution, 0.5% aqueous solution, 0.7% aqueous solution and 2.38% aqueous solution of tetraethylammonium hydroxide.
• 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 either a liquid piling method or a dipping method. After development, washing with running water is usually performed for 30 to 300 seconds to form a desired pattern.
• a rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like.
• a known method can be used as the rinsing method. For example, shower rinse and dip rinse can be mentioned.
• the acid-decomposable group is thermally decomposed to generate a carboxyl group or a phenolic hydroxyl group, and then crosslinked with a crosslinkable group, a crosslinking agent or the like.
• a cured film can be formed.
• This heating is performed using a heating device such as a hot plate or an oven at a predetermined temperature, for example, 180 to 250 ° C. for a predetermined time, for example, 5 to 90 minutes on the hot plate, 30 to 120 minutes for the oven. It is preferable to By proceeding with such a crosslinking reaction, it is possible to form a protective film and an interlayer insulating film that are superior in heat resistance, hardness, and the like.
• 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 composition of the present invention can also be used as a dry etching resist.
• dry etching processes such as ashing, plasma etching, and ozone etching can be performed as the etching process.
• the cured film of the present invention is a cured film obtained by curing the composition of the present invention.
• the cured film of the present invention can be suitably used as an interlayer insulating film.
• the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention.
• an interlayer insulating film having excellent transparency and high transparency even when baked at a high temperature can be obtained. Since the interlayer insulating film using the composition of the present invention has high transparency and excellent cured film properties, it is useful for applications of organic EL display devices and liquid crystal display devices.
• the organic EL display device and the liquid crystal display device reference can be made to paragraphs 0209 to 0210 and FIGS. 1 and 2 of JP2011-209681A, the contents of which are incorporated herein.
• GPC-101 manufactured by Showa Denko KK
• ⁇ Preparation of photosensitive resin composition Dissolve and mix (A) component, (B) component, (C) component, silane coupling agent and surfactant in a solvent until the solid content ratio is 32% so that the solid content ratio shown in the following table is obtained. Then, the mixture was filtered through a polytetrafluoroethylene filter having a diameter of 0.2 ⁇ m to obtain photosensitive resin compositions of various examples and comparative examples.
• ⁇ (A) component> The polymers P-1 to P-11 described above were used.
• ⁇ (B) component> B-1: 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5 -Condensation product with sulfonic acid chloride (3.0 mol)
• B-3 2,3,4,4′-tetrahydroxybenzophenone (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid ester (2.44) Mole)
• Silane coupling agent D-1 3-Glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)
• W-1 Silicone-based surfactant (“SH 8400 FLUID” manufactured by Toray Dow Corning Co., Ltd.)
• W-2 Fluorosurfactant FTX-218 (manufactured by Neos Co., Ltd.)
• 10 cm ⁇ 0.5 mm) is exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and each photosensitive resin composition solution is applied using a spin coater so that the dry film thickness becomes 3 ⁇ m.
• HMDS hexamethyldisilazane
• 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. Thus, a cured film was obtained.
• the cured film was cut using a cutter at intervals of 1 mm vertically and horizontally, and a tape peeling test (100 mask loss cut method: conforming to JIS 5600) was performed using a scotch tape. The adhesion between the cured film and the substrate was evaluated from the area of the cured film transferred to the back surface of the tape. The results are shown in the following table.
• ⁇ Hardened film adhesion Ti> After exposing a glass substrate (10 cm ⁇ 10 cm ⁇ 0.5 mm) on which a Ti (titanium) thin film was formed under hexamethyldisilazane (HMDS) vapor for 30 seconds and then spin-coating each photosensitive resin composition And a pre-baking on a hot plate at 90 ° C. for 2 minutes to volatilize the solvent to form a photosensitive resin composition layer having a thickness of 3 ⁇ m.
• HMDS hexamethyldisilazane
• 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. Thus, a cured film was obtained.
• the cured film was cut using a cutter at intervals of 1 mm vertically and horizontally, and a tape peeling test (100 mask loss cut method: conforming to JIS 5600) was performed using a scotch tape. The adhesion between the cured film and the substrate was evaluated from the area of the cured film transferred to the back surface of the tape. The results are shown in the following table.
• SiNx> A glass substrate (10 cm ⁇ 10 cm ⁇ 0.5 mm) on which a SiNx (silicon nitride) thin film was formed was exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and then each photosensitive resin composition was spin-coated. Then, the solvent was volatilized by pre-baking on a hot plate at 90 ° C. for 2 minutes to form a photosensitive resin composition layer having a thickness of 3 ⁇ m.
• HMDS hexamethyldisilazane
• 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. Thus, a cured film was obtained.
• the cured film was cut using a cutter at intervals of 1 mm vertically and horizontally, and a tape peeling test (100 mask loss cut method: conforming to JIS 5600) was performed using a scotch tape. The adhesion between the cured film and the substrate was evaluated from the area of the cured film transferred to the back surface of the tape. The results are shown in the following table.
• HMDS hexamethyldisilazane
• each photosensitive resin composition is spin-coated on the substrate, and then pre-baked on a hot plate at 90 ° C./120 seconds to volatilize the solvent.
• a photosensitive resin composition layer having a thickness of 3.0 ⁇ m was formed.
• exposure was performed so that the integrated irradiation amount was 300 mJ / cm 2 (energy intensity: 20 mW / cm 2 , i-line), and this substrate was heated in an oven at 230 ° C./30 minutes, Furthermore, it heated at 230 degreeC / 2 hours in oven.
• the film thickness (T1) of the obtained cured film was measured. And after immersing the board
• the results are shown in the table below. A smaller value is preferable, and A and B are at a level causing no problem in practical use. A: Less than 2% B: 2% or more and less than 3% C: 3% or more and less than 4% D: 4% or more and less than 6% E: 6% or more
• the film thickness (T1) of the obtained cured film was measured. And after immersing the board
• the results are shown in the table below. A smaller value is preferable, and A and B are at a level causing no problem in practical use. A: Less than 2% B: 2% or more and less than 3% C: 3% or more and less than 4% D: 4% or more and less than 6% E: 6% or more
• the composition of the present invention comprises (A) (a1) a repeating unit having an acid group, (a2) a polymer containing a repeating unit having a crosslinkable group, (B) a quinonediazide compound, and (C)
• A (a1) a repeating unit having an acid group
• a2 a polymer containing a repeating unit having a crosslinkable group
• B a quinonediazide compound
• C In one molecule, since it contains a compound having a structure containing a coordination atom and a thiourea structure, it has excellent adhesion to various substrates in the state of development and as a cured film, The resist stripping solution and NMP were also excellent in resistance (chemical resistance).
• Comparative Example 1 since the component (C) was not used, the adhesion of the cured film to various substrates, the adhesion to various substrates during development, and the chemical resistance were inferior to those of the Examples.
• Comparative Example 2 a compound different from the compound (C-1) only in that S was replaced with O was used. However, the adhesion of the cured film to various substrates and the adhesion to various substrates during development were different from those of the compound (C-1). It was significantly inferior to Example 12 using (C-1). In Comparative Example 3, a compound different from the compound (C-1) only in that NH was replaced with O was used.
• Comparative Example 5 a compound different from the compound (C-1) only in that R 1 was replaced from a morpholino group to an aryl group was used, but the adhesion of the cured film to various substrates and the adhesion to various substrates at the time of development were used. The properties and chemical resistance were greatly inferior to those of Example 12 using the compound (C-1).
• Comparative Example 6 a compound having a thiouracil structure was used as the component (C). However, since the compound does not contain a structure containing a coordination atom, the adhesion of the cured film to various substrates, during development The adhesion to various substrates and chemical resistance were greatly inferior.
• Comparative Example 7 the polymer containing the repeating unit (a2) having a crosslinkable group was not used as the component (A), and the adhesion and chemical resistance of the cured film to various substrates were greatly inferior.
• Comparative Example 8 as the component (A), a polymer containing (a1) a repeating unit having an acid group and (a2) a repeating unit having a crosslinkable group was not used, and a phenol resin (novolak resin) was used. Since it was used, the adhesion of the cured film to various substrates and the chemical resistance were greatly inferior.
• the photosensitive resin composition of Comparative Example 8 uses a polymer that does not contain a crosslinkable group, that is, a phenol resin, it is crosslinked as in the photosensitive resin composition of the examples. Since the functional group and the component (C) do not interact, for example, when the developer (TMAH) touches a substrate such as Mo, Ti, or SiNx, the surface of the substrate is modified and partially dissolved. As a result of the penetration of the developer into the interface between the substrate and the cured film, the adhesion to the substrate in the state when developing the photosensitive resin composition and when the photosensitive resin composition is a cured film is reduced.
• TMAH developer
• An organic EL display device using a TFT was manufactured by the following method (for example, refer to FIG. 1 of JP 2011-209681 A).
• a bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si 3 N 4 was formed so as to cover the TFT 1.
• a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 ⁇ m) connected to the TFT 1 through the contact hole is formed on the insulating film 3. .
• the wiring 2 is used to connect the TFT 1 to the organic EL element formed between the TFTs 1 or in a later process.
• the flattening layer 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 8 on a substrate, pre-baking on a hot plate (90 ° C. ⁇ 2 minutes), and then applying high pressure from above the mask. After irradiating i-line with 100 mJ / cm 2 using a mercury lamp, a pattern was formed by developing with an alkaline aqueous solution, and heat treatment was performed at 220 ° C. for 60 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. Furthermore, the average level difference of the wiring 2 was 500 nm, and the thickness of the prepared planarizing film was 2000 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 using a resist stripping solution (mixed solution of monoethanolamine and DMSO).
• the first electrode thus obtained corresponds to the anode of the organic EL element.
• an insulating layer 8 having a shape covering the periphery of the first electrode 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 layer, it is possible to prevent a short circuit between the first electrode 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.
• a liquid crystal display device is manufactured according to a conventional method using the photosensitive resin composition of Example 1 of the present invention as the interlayer insulating film 17. did.
• 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.

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• 2013
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