WO2011136074A1 - ポジ型感放射線性組成物、表示素子用層間絶縁膜及びその形成方法 - Google Patents
ポジ型感放射線性組成物、表示素子用層間絶縁膜及びその形成方法 Download PDFInfo
- Publication number
- WO2011136074A1 WO2011136074A1 PCT/JP2011/059574 JP2011059574W WO2011136074A1 WO 2011136074 A1 WO2011136074 A1 WO 2011136074A1 JP 2011059574 W JP2011059574 W JP 2011059574W WO 2011136074 A1 WO2011136074 A1 WO 2011136074A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- tert
- mass
- sensitive composition
- polymer
- Prior art date
Links
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
- G03F7/039—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/44—Amides
- C08G59/444—Sulfonamides
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- 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
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
Definitions
- the present invention relates to a positive radiation sensitive composition, an interlayer insulating film for a display element, and a method for forming the same.
- the display element is generally provided with an interlayer insulating film for the purpose of insulating between wirings arranged in layers.
- an interlayer insulating film for the purpose of insulating between wirings arranged in layers.
- positive radiation-sensitive compositions are widely used because the number of steps for obtaining a necessary pattern shape is small and a material having sufficient flatness is preferable.
- the positive radiation sensitive composition used in forming such an interlayer insulating film is required to have good radiation sensitivity and storage stability, and the obtained interlayer insulating film is required to have excellent heat resistance and transparency. .
- acrylic resins are widely used.
- a resin having a structural unit containing an acid-dissociable group, which becomes alkali-soluble when this acid-dissociable group is dissociated carboxyl
- a positive-type radiation-sensitive composition containing a resin having a structural unit containing a functional group (such as an epoxy group) that can react with a group to form a covalent bond and an acid generator has been proposed (Japanese Patent Application Laid-Open No. 2009-2009). No. 98673).
- the two kinds of specific resins are mixed, and in the coating film formed using the composition, a carboxyl group generated by the action of an acid from a resin having a structural unit containing an acid dissociable group And a curing reaction by a crosslinking reaction between the resin having a structural unit containing an epoxy group and the like.
- a carboxyl group generated by the action of an acid from a resin having a structural unit containing an acid dissociable group And a curing reaction by a crosslinking reaction between the resin having a structural unit containing an epoxy group and the like.
- the surface hardness and heat resistance of the resulting cured film are not satisfactory levels due to insufficient progress of the crosslinking reaction.
- the amine compound can be subjected to a crosslinking reaction with an epoxy group.
- the reaction in which the alkali-insoluble resin becomes alkali-soluble by the dissociation of the acid-dissociable group and the crosslinking reaction of the epoxy group with the amine compound proceed simultaneously, and the composition exhibits positive radiation sensitive characteristics. May not be possible.
- the present invention has been made on the basis of the above circumstances, and the object thereof is an interlayer insulation for display elements which is excellent in surface hardness and heat resistance, and also satisfies transmittance and voltage holding ratio, which are general required characteristics.
- an interlayer insulating film for a display element formed from the composition and a method for forming the same It is.
- a polymer comprising a structural unit (I) having a group represented by the following formula (1) and an epoxy group-containing structural unit (II) in the same or different polymer molecules (hereinafter referred to as “[A] Also referred to as "polymer”), [B] an acid generator, and [C] a nitrogen-containing compound (I) represented by the following formula (2) and at least selected from the group consisting of a nitrogen-containing compound (II) represented by the following formula (3)
- One nitrogen-containing compound hereinafter also referred to as “[C] nitrogen-containing compound”
- R 1 and R 2 are each independently a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, provided that the hydrogen atom of the alkyl group, cycloalkyl group and aryl group is A part or all of them may be substituted, and R 1 and R 2 are not both hydrogen atoms,
- R 4 and R 5 are each independently a hydrogen atom, an amino group, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, provided that the alkyl group and
- the aryl group may include a hydroxyl group, a carboxyl group, a carbonyl group, an ester group, a sulfone group, an amide group, an ether group, a thiol group, a thioether group, an amino group, or an amidino group, and R 6 has 1 carbon atom.
- R 4 and R 5 are connected to each other to form a ring structure together with a nitrogen atom bonded to each other. It may be formed.
- R 7 and R 8 are .
- R 9 and R 10 are each independently same as defined for the R 4 and are each independently as defined in the above R 6 .A, the number of carbon A 1-12 alkanediyl group or an arylene group having 6-20 carbon atoms.
- a specific [C] nitrogen-containing compound having a carbamate structure by introducing a protecting group into the nitrogen atom portion is used as the amine compound.
- the reactivity of the compound can be suppressed, and the storage stability of the composition can be improved.
- by adopting a specific carbamate structure as a protected form of the [C] nitrogen-containing compound it is removed from the activation energy for dissociation by the acid of the group represented by the above formula (1) as the acid dissociable group. The activation energy for protection is increased.
- the [C] nitrogen-containing compound is not deprotected by the acid generated from the [B] acid generator at the time of exposure, and is generated from the [B] acid generator by the heat during post-baking after development and its heat. It is deprotected by the cooperative action with acid. Therefore, the positive radiation-sensitive composition can exhibit positive radiation-sensitive characteristics in a series of steps from exposure to development, and can be epoxyized by the [C] nitrogen-containing compound deprotected during post-baking.
- the cross-linking reaction of the group can be sufficiently advanced, and a cured film as an interlayer insulating film having excellent surface hardness and heat resistance can be formed.
- At least one group selected from the group consisting of R 6 in the above formula (2) and R 9 and R 10 in the above formula (3) is a tert-butyl group, a tert-amyl group, or a 1-methylcyclohexyl group. Or it is preferably a 1-ethylcyclohexyl group.
- the content of the nitrogen-containing compound is preferably 2 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the [A] polymer. [C] By setting the content of the nitrogen-containing compound within the above specified range, the crosslinking reaction of the epoxy group can be sufficiently advanced, and an unexpected side reaction with the epoxy group due to an excessive amount can be prevented, and the positive The radiation sensitivity and storage stability of the type radiation sensitive composition can be prevented, and the transmittance and voltage holding ratio of the resulting cured film can be prevented from decreasing.
- the positive radiation-sensitive composition is suitable as a material for forming an interlayer insulating film for display elements. Further, the present invention suitably includes an interlayer insulating film for a display element formed from the positive radiation sensitive composition.
- the method for forming an interlayer insulating film for a display element includes: (1) The process of forming the coating film of the said positive type radiation sensitive composition on a board
- an interlayer insulating film for a display element that is excellent in surface hardness and heat resistance and sufficiently satisfies transmittance and voltage holding ratio.
- the positive radiation-sensitive composition of the present invention contains a [A] polymer, a [B] acid generator, and a [C] nitrogen-containing compound, whereby transmittance and voltage holding ratio are obtained. It is possible to form an interlayer insulating film for a display element that satisfies the general required characteristics in a well-balanced manner and has excellent surface hardness and heat resistance. Moreover, the positive radiation sensitive composition has excellent storage stability and exhibits sufficient radiation sensitivity.
- the positive radiation-sensitive composition of the present invention contains a [A] polymer, a [B] acid generator, and a [C] nitrogen-containing compound. Moreover, the said positive type radiation sensitive composition may contain [D] surfactant and [E] adhesion
- the polymer contains the structural unit (I) and the epoxy group-containing structural unit (II) in the same or different polymer molecules. Moreover, the other structural unit may be included as needed.
- the embodiment of the [A] polymer containing the structural unit (I) and the epoxy group-containing structural unit (II) is not particularly limited. For example, (i) containing the structural unit (I) and the epoxy group in the same polymer molecule When both of the structural units (II) are contained and [A] one polymer molecule is present in the polymer; (Ii) The structural unit (I) is contained in one polymer molecule, and the epoxy group-containing structural unit (II) is contained in a polymer molecule different from the structural unit (I).
- the polymer unit includes both the structural unit (I) and the epoxy group-containing structural unit (II) in one polymer molecule, and includes the structural unit (I) in a different polymer molecule.
- the epoxy group-containing structural unit (II) is contained in different polymer molecules, and [A] three kinds of polymer molecules are present in the polymer;
- [A] the polymer may contain 2 or more types of each structural unit.
- each structural unit will be described in detail.
- the group represented by the above formula (1) is present as a group (acid dissociable group) that is dissociated in the presence of an acid to generate a polar group.
- the acid-dissociable group is dissociated by the acid generated from the generator, and as a result, the [A] polymer that was insoluble in alkali becomes alkali-soluble.
- the acid dissociable group has an acetal structure or a ketal structure that is relatively stable with respect to an alkali, and these are dissociated by the action of an acid.
- R ⁇ 1 > and R ⁇ 2 > are respectively independently a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. However, one part or all part of the hydrogen atom which the said alkyl group, a cycloalkyl group, and an aryl group have may be substituted. Further, there is no case where R 1 and R 2 are both hydrogen atoms.
- R 3 is an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, or a group represented by —M (R 3m ) 3 . This M is Si, Ge, or Sn.
- R 3m is each independently an alkyl group.
- R 1 and R 3 may be linked to form a cyclic ether structure. However, one part or all part of the hydrogen atom which these groups represented by R ⁇ 3 > have may be substituted.
- Examples of the alkyl group represented by R 1 and R 2 include linear and branched alkyl groups having 1 to 30 carbon atoms.
- the alkyl chain may have an oxygen atom, a sulfur atom, or a nitrogen atom.
- Examples of the linear and branched alkyl group having 1 to 30 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, and an n-octyl group.
- N-dodecyl group, n-tetradecyl group, n-octadecyl group, etc. linear alkyl group, i-propyl group, i-butyl group, t-butyl group, neopentyl group, 2-hexyl group, 3-hexyl group And a branched alkyl group such as.
- Examples of the cycloalkyl group represented by R 1 and R 2 include a cycloalkyl group having 3 to 20 carbon atoms.
- the cycloalkyl group having 3 to 20 carbon atoms may be polycyclic and may have an oxygen atom in the ring.
- Examples of the cycloalkyl group having 3 to 20 carbon atoms include cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, bornyl group, norbornyl group, adamantyl group and the like.
- Examples of the aryl group represented by R 1 and R 2 include an aryl group having 6 to 14 carbon atoms.
- the aryl group having 6 to 14 carbon atoms may be a single ring, a structure in which single rings are linked, or a condensed ring.
- Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group and a naphthyl group.
- Examples of the optionally substituted alkyl group, cycloalkyl group and aryl group represented by R 1 and R 2 include a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a carbonyl group, a cyclo group.
- alkyl group eg, cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl, cyclooctyl, bornyl group, norbornyl group, adamantyl group, etc.
- aryl group eg, phenyl group, naphthyl group, etc.
- alkoxy group eg, methoxy group
- an acyl group for example, an acetyl group, a propionyl group
- acyloxy group for example,
- the alkyl group, cycloalkyl group, and aryl group represented by R 3 for example, the groups exemplified for R 1 and R 2 can be applied.
- the substituent for these groups for example, the groups exemplified as the substituents for the optionally substituted alkyl group, cycloalkyl group and aryl group represented by R 1 and R 2 can be applied.
- the aralkyl group represented by R 3 include an aralkyl group having 7 to 20 carbon atoms.
- the aralkyl group having 7 to 20 carbon atoms include benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group and the like.
- Examples of the group represented by -M (R 3m ) 3 include a trimethylsilanyl group and a trimethylgermyl group.
- the substituent which may substitute part or all of the hydrogen atoms of the aralkyl group represented by R 3 or the group represented by —M (R 3m ) 3 the above substituents are preferably employed. be able to.
- the substituent of this group for example, the groups exemplified as the substituents of the optionally substituted alkyl group, cycloalkyl group and aryl group represented by R 1 and R 2 can be applied.
- Examples of the group having a cyclic ether structure that may be formed by linking R 1 and R 3 include 2,2-oxetanediyl group, 2,2-tetrahydrofurandiyl group, 2-tetrahydropyrandiyl group, 2 -Dioxanediyl group and the like.
- the structural unit (I) can have an acetal structure or a ketal structure by having a functional group that should have an acetal structure or a ketal structure by bonding to another carbon atom.
- Examples of the functional group that should have an acetal structure by bonding to the other carbon atom include 1-methoxyethoxy group, 1-ethoxyethoxy group, 1-n-propoxyethoxy group, and 1-i-propoxyethoxy.
- 1-ethoxyethoxy group 1-cyclohexyloxyethoxy group, 2-tetrahydropyranyloxy group, 1-n-propoxyethoxy group, and 2-tetrahydropyranyloxy group are preferable.
- Examples of the functional group that should have a ketal structure by bonding to the other carbon atom include 1-methyl-1-methoxyethoxy group, 1-methyl-1-ethoxyethoxy group, 1-methyl-1 -N-propoxyethoxy group, 1-methyl-1-i-propoxyethoxy group, 1-methyl-1-n-butoxyethoxy group, 1-methyl-1-i-butoxyethoxy group, 1-methyl-1-sec -Butoxyethoxy group, 1-methyl-1-t-butoxyethoxy group, 1-methyl-1-cyclopentyloxyethoxy group, 1-methyl-1-cyclohexyloxyethoxy group, 1-methyl-1-norbornyloxyethoxy group 1-methyl-1-bornyloxyethoxy group, 1-methyl-1-phenyloxyethoxy group, 1-methyl-1- (1-na (Tiloxy) ethoxy group, 1-methyl-1-benzyloxyoxy group, 1-methyl-1-phenethyloxyethoxy group, 1-cyclohexyl-1-me
- 1-methyl-1-methoxyethoxy group and 1-methyl-1-cyclohexyloxyethoxy group are preferable.
- Examples of the structural unit (I) having the acetal structure or ketal structure include structural units represented by the following formulas (1-1) to (1-3).
- R ′ is a hydrogen atom or a methyl group.
- R 1 , R 2 and R 3 have the same meaning as in the above formula (1).
- Examples of the monomer that gives the structural unit (I) represented by the above formulas (1-1) to (1-3) include 1-alkoxyalkyl (meth) acrylate, 1- (cycloalkyloxy) alkyl (meta ) Acrylate, 1- (haloalkoxy) alkyl (meth) acrylate, 1- (aralkyloxy) alkyl (meth) acrylate, tetrahydropyranyl (meth) acrylate and other (meth) acrylate acetal structure-containing monomers; 2,3-di (1- (trialkylsilanyloxy) alkoxy) carbonyl) -5-norbornene, 2,3-di (1- (trialkylgermyloxy) alkoxy) carbonyl) -5-norbornene, 2, 3-di (1-alkoxyalkoxycarbonyl) -5-norbornene, 2,3-di (1- (cycloalkyloxy) alkoxycarbonyl) -5-
- 1-alkoxyalkyl (meth) acrylate, tetrahydropyranyl (meth) acrylate, 1-alkoxyalkoxystyrene and tetrahydropyranyloxystyrene are preferable, and 1-alkoxyalkyl (meth) acrylate is more preferable.
- Specific monomers that give the structural unit (I) represented by the above formulas (1-1) to (1-3) include, for example, 1-ethoxyethyl methacrylate, 1-methoxyethyl methacrylate, 1-n- Butoxyethyl methacrylate, 1-isobutoxyethyl methacrylate, 1-t-butoxyethyl methacrylate, 1- (2-chloroethoxy) ethyl methacrylate, 1- (2-ethylhexyloxy) ethyl methacrylate, 1-n-propoxyethyl methacrylate, 1
- a methacrylate-based acetal structure-containing monomer such as cyclohexyloxyethyl methacrylate, 1- (2-cyclohexylethoxy) ethyl methacrylate, 1-benzyloxyethyl methacrylate, 2-tetrahydropyranyl methacrylate; 1-ethoxyethyl acrylate, 1-
- Acetal structure-containing monomer 2,3-di (1- (trimethylsilanyloxy) ethoxy) carbonyl) -5-norbornene, 2,3-di (1- (trimethylgermyloxy) ethoxy) carbonyl) -5-norbornene, 2,3- Di (1-methoxyethoxycarbonyl) -5-norbornene, 2,3-di (1- (cyclohexyloxy) ethoxycarbonyl) -5-norbornene, 2,3-di (1- (benzyloxy) ethoxycarbonyl) -5
- a monomer containing a norbornene-based acetal structure such as norbornene; p or m-1-ethoxyethoxystyrene, p or m-1-methoxyethoxystyrene, p or m-1-n-butoxyethoxystyrene, p or m-1-isobutoxyethoxys
- the monomer giving the structural unit (I) is preferably 1-ethoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 2-tetrahydropyranyl methacrylate or 1-benzyloxyethyl methacrylate.
- the monomer that gives the structural unit (I) commercially available monomers may be used, or those synthesized by a known method may be used.
- the monomer that gives the structural unit (I) represented by the above formula (1-1) is synthesized by reacting (meth) acrylic acid with vinyl ether in the presence of an acid catalyst as shown in the following formula. can do.
- R ′, R 1 and R 3 have the same meaning as in the above formula (1-1).
- R 21 and R 22 are the same as R 2 in the above formula (1-1) as —CH (R 21 ) (R 22 ).
- the content of the structural unit (I) in the polymer is not particularly limited as long as the polymer [A] is alkali-soluble by an acid and exhibits the desired heat resistance of the cured film.
- the polymer molecule contains both the structural unit (I) and the epoxy group-containing structural unit (II)
- the monomer charge ratio with respect to all structural units contained in the [A] polymer is 5% by mass or more and 70% by mass. % By mass or less is preferable, 10% by mass to 60% by mass is more preferable, and 20% by mass to 50% by mass is particularly preferable.
- the one polymer molecule having the structural unit (I) contains the structural unit (I) and the other polymer molecule contains the epoxy group-containing structural unit (II), the one polymer molecule having the structural unit (I)
- the content of the structural unit (I) in is preferably 40% by mass or more and 99% by mass or less, more preferably 50% by mass or more and 98% by mass with respect to the total structural units contained in the polymer molecule. % Or less is more preferable, and 55 mass% or more and 95 mass% or less are especially preferable.
- Epoxy group-containing structural unit (II) The epoxy group-containing structural unit (II) is not particularly limited as long as it is a structural unit derived from an epoxy group-containing monomer. [A] When the polymer contains the epoxy group-containing structural unit (II) in the molecule, the surface hardness and heat resistance of the cured film obtained from the positive radiation-sensitive composition can be further increased.
- the epoxy group in this specification is a concept including an oxiranyl group (1,2-epoxy structure) and an oxetanyl group (1,3-epoxy structure).
- Monomers that give the epoxy group-containing structural unit (II) include, for example, glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 3-methyl-3,4-epoxybutyl acrylate, methacryl 3-ethyl-3,4-epoxybutyl acid, 5,6-epoxyhexyl (meth) acrylate, 5-methyl-5,6-epoxyhexyl methacrylate, 5-ethyl-5,6-epoxyhexyl methacrylate, (Meth) acrylic acid 6,7-epoxyheptyl, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, methacrylic acid 3,4-epoxycyclohexylpropyl, 3,4-epoxycyclohexylbuty
- glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3- (methacryloyloxymethyl) -3 -Methyloxetane and 3- (methacryloyloxymethyl) -3-ethyloxetane are preferred from the viewpoints of copolymerization reactivity with other monomers and developability of the positive radiation-sensitive composition.
- the content of the epoxy group-containing structural unit (II) in the polymer is not particularly limited as long as the desired heat resistance of the interlayer insulating film for display elements is exhibited, and the structural unit ( When I) and the epoxy group-containing structural unit (II) are included, the monomer charge ratio is preferably 10% by mass or more and 60% by mass or less with respect to all the structural units contained in the [A] polymer. More preferably, the content is greater than or equal to 55% and less than or equal to 55% by weight, particularly preferably greater than or equal to 20% and less than or equal to 50%.
- the content of the epoxy group-containing structural unit (II) with respect to all the structural units contained in the molecule is preferably 20% by mass to 80% by mass, more preferably 30% by mass to 70% by mass, as a monomer charge ratio. Preferably, 35 mass% or more and 65 mass% or less are especially preferable.
- the polymer may contain other structural units other than the structural unit (I) and the structural unit (II) as long as the effects of the present invention are not impaired.
- monomers that give structural units include carboxyl groups or derivatives thereof, and monomers having hydroxyl groups.
- Examples of the monomer having a carboxyl group or a derivative thereof include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, Examples thereof include monocarboxylic acids such as 2-methacryloyloxyethyl hexahydrophthalic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; and acid anhydrides of the above dicarboxylic acids.
- Examples of the monomer having a hydroxyl group include acrylic acid-2-hydroxyethyl ester, acrylic acid-3-hydroxypropyl ester, acrylic acid-4-hydroxybutyl ester, and acrylic acid-4-hydroxymethylcyclohexylmethyl ester.
- methacrylic acid hydroxyalkyl esters such as methacrylic acid-4-hydroxymethyl-cyclohexylmethyl ester.
- acrylic acid-2-hydroxyethyl ester acrylic acid--from the viewpoint of copolymerization reactivity with other monomers and the heat resistance of the obtained interlayer insulating film for display elements.
- 3-hydroxypropyl ester, acrylic acid-4-hydroxybutyl ester, methacrylic acid-2-hydroxyethyl ester, methacrylic acid-4-hydroxybutyl ester, acrylic acid-4-hydroxymethyl-cyclohexylmethyl ester, methacrylic acid-4- Hydroxymethyl-cyclohexylmethyl ester is preferred.
- Examples of other monomers include acrylic acid alkyl esters such as methyl acrylate and i-propyl acrylate; Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate; Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 2,6 ] decan-8-yl acrylate, acrylic acid-2- (tricyclo [5.2.1.0 2, 6 ] Acrylic alicyclic alkyl ester such as decan-8-yloxy) ethyl, isobornyl acrylate; Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 2,6 ] decane-8-yl methacrylate, methacrylic acid-2- (tricyclo [5.2.1.0 2, 6 ] decane-8-
- styrene, 4-isopropenylphenol, tricyclo [5.2.1.0 2,6 ] decan-8-yl methacrylate, tetrahydrofurfuryl methacrylate, 1,3-butadiene 4-acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, N-cyclohexylmaleimide, N-phenylmaleimide, and benzyl methacrylate are copolymerized with monomers having the above-mentioned reactive functional groups This is preferable in terms of reactivity and developability of the positive radiation-sensitive composition.
- the weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the polymer is preferably 2.0 ⁇ 10 3 to 1.0 ⁇ 10 5 , more preferably 5.0 ⁇ 10. 3 to 5.0 ⁇ 10 4 .
- Mw weight average molecular weight
- GPC gel permeation chromatography
- the number average molecular weight (Mn) in terms of polystyrene by GPC of the polymer is preferably 2.0 ⁇ 10 3 to 1.0 ⁇ 10 5 , more preferably 5.0 ⁇ 10 3 to 5.0 ⁇ 10. 4 .
- Mn of a polymer By making Mn of a polymer into the said specific range, the cure reactivity at the time of hardening of the coating film of the said positive type radiation sensitive composition can be improved.
- the molecular weight distribution (Mw / Mn) of the polymer is preferably 3.0 or less, more preferably 2.6 or less.
- Mw / Mn of the polymer By setting Mw / Mn of the polymer to 3.0 or less, the developability of the obtained interlayer insulating film for display elements can be enhanced.
- the positive-type radiation-sensitive composition containing a polymer can easily form a desired pattern shape without causing a development residue during development.
- the polymer can be synthesized by radical copolymerization of monomers giving the above structural units. For example, when synthesizing a polymer [A] containing both the structural unit (I) and the epoxy group-containing structural unit (II) in the same polymer molecule, a monomer and an epoxy group that give the structural unit (I) What is necessary is just to copolymerize using the mixture containing the monomer which gives containing structural unit (II).
- the structural unit (I) when the [A] polymer having the structural unit (I) in one polymer molecule and the epoxy group-containing structural unit (II) in a different polymer molecule is synthesized, the structural unit (I).
- the polymer solution containing the monomer that gives the epoxy group-containing structural unit (II) is obtained by radically polymerizing a polymerizable solution containing the monomer that gives the structural unit (I) to obtain a polymer molecule having the structural unit (I). May be radically polymerized to obtain a polymer molecule having an epoxy group-containing structural unit (II), and finally, both may be mixed to obtain a polymer [A].
- Examples of the solvent used in the polymerization reaction of the polymer include the solvents exemplified in the section of preparation of the composition described later.
- radical polymerization initiators those generally known as radical polymerization initiators can be used.
- a molecular weight modifier may be used to adjust the molecular weight.
- the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, thioglycolic acid; Xanthogens such as xanthogen sulfide and diisopropylxanthogen disulfide; terpinolene, ⁇ -methylstyrene dimer and the like.
- the acid generator is a compound that generates an acid both by irradiation with radiation and by application of heat.
- the radiation for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used.
- the positive radiation sensitive composition contains an [A] polymer having an acid dissociable group and a [B] acid generator, so that the positive radiation sensitive composition exhibits positive radiation sensitive characteristics. It can be demonstrated.
- the inclusion form of the acid generator in the positive radiation-sensitive composition may be a compound form as described later (hereinafter also referred to as “[B] acid generator” as appropriate) or the [A] polymer.
- the positive-type radiation-sensitive composition can exhibit positive-type radiation-sensitive properties and deprotect [C] nitrogen-containing compounds during post-baking.
- the crosslinking reaction of the epoxy group can be sufficiently advanced.
- Examples of the acid generator include oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and quinone diazide compounds.
- each of these [B] acid generators can be used individually or in combination of 2 or more types.
- oxime sulfonate compound examples include a compound containing an oxime sulfonate group represented by the following formula (4).
- R B1 is a linear or branched alkyl group, cycloalkyl group, or aryl group. However, in these groups, some or all of the hydrogen atoms may be substituted.
- the linear or branched alkyl group represented by R B1 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms.
- the linear or branched alkyl group having 1 to 10 carbon atoms may be substituted.
- Examples of the substituent include an alkoxy group having 1 to 10 carbon atoms and 7,7-dimethyl-2-oxonorbornyl.
- a preferred alicyclic group is a bicycloalkyl group.
- the aryl group represented by R B1 is preferably an aryl group having 6 to 11 carbon atoms, more preferably a phenyl group or a naphthyl group.
- the aryl group may be substituted, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.
- Examples of the compound containing an oxime sulfonate group represented by the above formula (4) include an oxime sulfonate compound represented by the following formula (5).
- R B1 has the same meaning as in the above formula (4).
- X is an alkyl group, an alkoxy group, or a halogen atom.
- m is an integer of 0 to 3. However, when there are a plurality of Xs, the plurality of Xs may be the same or different.
- the alkyl group that can be represented by X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
- the alkoxy group represented by X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
- the halogen atom represented by X is preferably a chlorine atom or a fluorine atom.
- m 0 or 1 is preferable.
- a compound in which m is 1, X is a methyl group, and the substitution position of X is ortho is preferable.
- Examples of the oxime sulfonate compound represented by the above formula (5) include compounds represented by the following formulas (5-1) to (5-5).
- onium salt examples include diphenyliodonium salt, triphenylsulfonium salt, sulfonium salt, benzothiazonium salt, and tetrahydrothiophenium salt.
- diphenyliodonium salt examples include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, diphenyliodonium Butyltris (2,6-difluorophenyl) borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluoroarsenate Bis (4-tert-butylphenyl) iodonium trifluoro Tansul
- triphenylsulfonium salt examples include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, triphenylsulfonium. And butyl tris (2,6-difluorophenyl) borate.
- sulfonium salt examples include alkylsulfonium salts, benzylsulfonium salts, dibenzylsulfonium salts, substituted benzylsulfonium salts, and the like.
- alkylsulfonium salt examples include 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (Benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate, and the like.
- benzylsulfonium salt examples include benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-4-methoxyphenyl Methylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenyl Examples include methylsulfonium hexafluorophosphate.
- dibenzylsulfonium salt examples include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium hexafluoroantimonate, dibenzyl-4-methoxyphenylsulfonium.
- Hexafluoroantimonate dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-t-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl- 4-hydroxyphenylsulfonium hexafluorophosphate and the like.
- substituted benzylsulfonium salts include p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and p-chlorobenzyl-4-hydroxyphenylmethyl.
- benzothiazonium salt examples include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- (p-methoxybenzyl) ) Benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate, and the like.
- tetrahydrothiophenium salt examples include 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate and 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethane.
- sulfonimide compound examples include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy).
- a quinonediazide compound is a compound that generates a carboxylic acid upon irradiation with radiation.
- a condensate of a phenolic compound or an alcoholic compound hereinafter also referred to as “mother nucleus”
- 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, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone, and the like.
- 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'-spirobi Den -5,6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl -7,2 ', 4'-trihydroxy flavan 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 and 4,6-bis ⁇ 1- (4-hydroxyphenyl) -1-methylethyl ⁇ -1,3-dihydroxybenzene.
- 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 preferred.
- 1,2-naphthoquinonediazide sulfonic acid halide preferably 30 mol% to 85 mol based on the number of OH groups in the phenolic compound or alcoholic compound.
- 1,2-naphthoquinonediazide sulfonic acid halide corresponding to mol%, more preferably 50 mol% to 70 mol% can be used.
- the condensation reaction can be carried out by a known method.
- Examples of the quinonediazide compound 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 and the like are also preferably used.
- the acid generator is preferably an oxime sulfonate compound or an onium salt from the viewpoints of sensitivity and solubility.
- a compound represented by the above formula (4) is preferable, a compound represented by the above formula (5) is more preferable, and the compounds represented by the above formulas (5-1) to (5) are commercially available.
- the compound represented by -5) is particularly preferable.
- onium salt tetrahydrothiophenium salt and benzylsulfonium salt are preferable, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate and benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate are preferable. More preferred.
- the content of the [B] acid generator in the composition is preferably 1 mass with respect to 100 parts by mass of the [A] polymer, when the [B] acid generator is a [B] acid generator. Part to 20 parts by weight, more preferably 1 part to 10 parts by weight. [B] By setting the content of the acid generator within the above specific range, the difference in solubility between the irradiated portion and the unirradiated portion with respect to the alkaline aqueous solution serving as the developer is large, and the patterning performance is improved and obtained. The heat resistance of the interlayer insulating film for display elements is also improved.
- the nitrogen-containing compound is at least one selected from the group consisting of the nitrogen-containing compound (I) represented by the formula (2) and the nitrogen-containing compound (II) represented by the formula (3). It is a nitrogen-containing compound.
- each compound will be described in detail.
- R 4 and R 5 are each independently a hydrogen atom, an amino group, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
- the alkyl group and aryl group may include a hydroxyl group, a carboxyl group, a carbonyl group, an ester group, a sulfone group, an amide group, an ether group, a thiol group, a thioether group, an amino group, or an amidino group.
- R 6 is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
- R 4 and R 5 may be linked to form a ring structure together with the nitrogen atoms bonded to each other.
- Examples of the alkyl group having 1 to 20 carbon atoms represented by R 4 , R 5 and R 6 include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group and an n-hexyl group.
- N-octyl group N-octyl group, n-dodecyl group, n-tetradecyl group, n-octadecyl group and the like linear alkyl group, i-propyl group, i-butyl group, tert-butyl group, tert-amyl group, neopentyl group And branched alkyl groups such as 2-hexyl group and 3-hexyl group.
- Examples of the cycloalkyl group having 4 to 20 carbon atoms represented by R 6 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a 1-methylcyclopentyl group, and 1-ethyl.
- Examples include cyclopentyl group, 1-methylcyclohexyl group, 1-ethylcyclohexyl group, 2-methyl-2-norbornyl group, 2-ethyl-2-norbornyl group and the like.
- the aryl group having 6 to 20 carbon atoms represented by R 4 , R 5 and R 6 may be, for example, a single ring, a structure in which single rings are connected, or a condensed ring, For example, a phenyl group, a naphthyl group, etc. are mentioned.
- R 6 includes a tert-butyl group, a tert-amyl group, a 1-methylcyclohexyl group, and a 1-ethylcyclohexyl group from the viewpoints of the reactivity control ability of the [C] nitrogen-containing compound, the protection function against acid, and the deprotection ability. Is preferred.
- nitrogen-containing compound (I) examples include N- (tert-butoxycarbonyl) -L-alanine, N- (tert-butoxycarbonyl) -L-alanine-methyl ester, (S)-( ⁇ )-2- ( tert-butoxycarbonylamino) -3-cyclohexyl-1-propanol, (R)-(+)-2- (tert-butoxycarbonylamino) -3-methyl-1-butanol, (R)-(+)-2 -(Tert-butoxycarbonylamino) -3-phenyl-1-propanol, (S)-(-)-2- (tert-butoxycarbonylamino) -3-phenyl-1-propanol, (R)-(+) -2- (tert-butoxycarbonylamino) -3-phenyl-1-propanol, (R)-(+) -2- (tert-butoxycarbonylamino) -3-phen
- N- (tert-butoxycarbonyl) -L-alanine methyl ester N- (tert-butoxycarbonyl) -L-alanine methyl ester, (S)-( ⁇ )-2- (tert-butoxycarbonylamino) -3-cyclohexyl-1-propanol, (R)-( +)-2- (tert-butoxycarbonylamino) -3-methyl-1-butanol, (R)-(+)-2- (tert-butoxycarbonylamino) -3-phenylpropanol, (S)-( ⁇ ) -2- (tert-butoxycarbonylamino) -3-phenylpropanol, (R)-(+)-2- (tert-butoxycarbonylamino) -3-phenyl-1-propanol, (S)-( ⁇ ) -2- (tert-butoxycarbonylamino) -3-phenyl-1-propanol, (S)
- Nitrogen-containing compounds represented by (2-1) to (2-7) are more preferable.
- Nitrogen-containing compound (I) can be used alone or in combination of two or more. Moreover, you may use in combination with the basic compound mentioned later, and it is also possible to control the degree of bridge
- the content of the nitrogen-containing compound (I) is preferably 2 to 30 parts by mass with respect to 100 parts by mass of the polymer [A], and 3 to 20 parts by mass. Is more preferable.
- the nitrogen-containing compound (II) has two carbamate structures in the molecule as represented by the above formula (3).
- R 7 and R 8 are as defined above with respect to R 4 independently of each other.
- R 9 and R 10 are each independently synonymous with R 6 above.
- A is an alkanediyl group having 1 to 12 carbon atoms or an arylene group having 6 to 20 carbon atoms.
- Examples of the alkanediyl group having 1 to 12 carbon atoms represented by A include a methanediyl group, an ethanediyl group, a propanediyl group, a butanediyl group, a pentanediyl group, and a hexanediyl group.
- the arylene group having 6 to 20 carbon atoms represented by A two hydrogen atoms are removed from the aryl group having 6 to 20 carbon atoms represented by R 4 , R 5 and R 6 in the above formula (2).
- Divalent groups can be preferably applied, and examples thereof include a phenylene group and a naphthylene group.
- R 9 and R 10 are each a tert-butyl group, a tert-amyl group, a 1-methylcyclohexyl group, a 1-methylcyclohexyl group, from the viewpoint of the reactivity control ability of the [C] nitrogen-containing compound, the protecting function against acid, and the deprotecting ability.
- An ethylcyclohexyl group is preferred.
- Examples of the nitrogen-containing compound (II) include compounds represented by the following formulas (3-1-1) to (3-1-9) and (3-2-1) to (3-2-4). Can be mentioned.
- the reactivity is controlled at the time of storage of the positive radiation-sensitive composition, and it is easily deprotected at the time of post-baking and from the viewpoint of sufficiently proceeding with the epoxy group crosslinking reaction.
- the compounds represented by the above formulas (3-1-3), (3-1-4), (3-1-5), (3-1-6), and (3-2-1) are preferable.
- the content of the nitrogen-containing compound (II) is preferably 2 to 30 parts by mass with respect to 100 parts by mass of the [A] polymer, and 3 to 20 parts by mass. Is more preferable.
- the total of both is preferably 2 to 30 parts by mass with respect to 100 parts by mass of the [A] polymer.
- the surfactant can further improve the film-forming property of the positive radiation-sensitive composition.
- the surfactant include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant.
- the positive radiation-sensitive composition contains [D] surfactant, the surface smoothness of the coating film can be improved, and as a result, the thickness uniformity of the interlayer insulating film for display element formed can be further improved. It can be improved.
- These surfactants can be used alone or in combination of two or more.
- a compound having a fluoroalkyl group and / or a fluoroalkylene group in at least one of the terminal, main chain and side chain is preferable.
- fluorosurfactants include, for example, BM-1000, BM-1100 (above, manufactured by BM CHEMIE), MegaFuck F142D, F172, F173, F183, F178, F191, F191, and F471.
- F476 (above, manufactured by Dainippon Ink and Chemicals), Fluorard FC-170C, FC-171, FC-430, FC-431 (above, manufactured by Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (and above) Asahi Glass), F-top EF301, EF303, EF352 (above, manufactured by Shin-Akita Kasei), Footent FT-100, FT-110 FT-140A, FT-150, FT-250, FT-251, FT-300, FT-310, FT-400S, FTX-218, FT-251 (above, Neos) Etc.
- silicone surfactants include, for example, Torresilicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190, DC-190, SH 8400 FLUID (above, manufactured by Toray Dow Corning Silicone), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (Above, GE Toshiba Silicone), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.
- Nonionic surfactants include, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and the like.
- Polyflow No. 57, 95 manufactured by Kyoeisha Chemical
- the content of the [D] surfactant in the positive radiation-sensitive composition is preferably 0.05 parts by mass or more and 5 parts by mass or less, more preferably 100 parts by mass of the polymer [A]. Is 0.1 part by mass or more and 2 parts by mass or less. [D] By setting the content of the surfactant within the above specific range, film roughness when forming a coating film on the substrate can be suppressed.
- Adhesion aid In the positive-type radiation-sensitive composition, in order to improve the adhesion between an inorganic material serving as a substrate, for example, a silicon compound such as silicon, silicon oxide and silicon nitride, a metal such as gold, copper and aluminum, and an insulating film [ E] Adhesion aids can be used.
- a functional silane coupling agent is preferably used. Examples of functional silane coupling agents include silane coupling agents having reactive substituents such as carboxyl groups, methacryloyl groups, isocyanate groups, epoxy groups (preferably oxiranyl groups), thiol groups, and the like.
- Examples of functional silane coupling agents include trimethoxysilylbenzoic acid, ⁇ -methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, ⁇ -isocyanatopropyltriethoxysilane, ⁇ -glycidoxypropyltri Examples include methoxysilane, ⁇ -glycidoxypropylalkyldialkoxysilane, ⁇ -chloropropyltrialkoxysilane, ⁇ -mercaptopropyltrialkoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.
- ⁇ -glycidoxypropyltrimethoxysilane ⁇ -glycidoxypropylalkyldialkoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and ⁇ -methacryloxypropyltrimethoxysilane are preferred. .
- the content of the [E] adhesion aid in the positive radiation sensitive composition is preferably 0.5 parts by mass or more and 20 parts by mass or less, more preferably 1 with respect to 100 parts by mass of the [A] polymer. It is used in an amount of not less than 10 parts by mass and not more than 10 parts by mass. [E] By making the amount of the adhesion assistant in the above specific range, the adhesion between the formed interlayer insulation film for display elements and the substrate is improved. ⁇ Other optional components>
- the positive radiation-sensitive composition may contain other optional components such as a basic compound as necessary within the range of not impairing the effects of the present invention, in addition to the components [A] to [E]. .
- the positive radiation sensitive composition contains a basic compound
- the diffusion length of the acid generated from the [B] acid generator by exposure can be appropriately controlled, and the pattern developability can be improved.
- the basic compound can be arbitrarily selected from those used in chemically amplified resists, and examples thereof include aliphatic amines, hybrid amines, aromatic amines, heterocyclic amines, and carboxylic acid quaternary ammonium salts. .
- aliphatic amine examples include ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert-amylamine, cyclopentylamine, hexylamine, Cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutyl Amine, di-sec-butylamine, dipentylamine, dicyclopentylamine, dihexylamine, dicyclohexyl Min, dihept
- hybrid amines examples include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, benzyldimethylamine, dicyclohexylmethylamine and the like.
- aromatic amines and heterocyclic amines include aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methyl.
- carboxylic acid quaternary ammonium salts include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.
- R 41 , R 42 , R 43 , R 47 and R 48 are each independently a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms. is there.
- R 44 , R 45 , R 46 , R 49 and R 50 are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. However, part or all of the hydrogen atoms of this alkyl group may be substituted with an amino group.
- R 44 and R 45 , R 45 and R 46 , R 44 and R 46 , R 44 and R 45 and R 46 , and R 49 and R 50 may be bonded to each other to form a ring structure.
- S, T, and U are each independently an integer of 0 to 20. However, when S, T, and U are all 0, R 44 , R 45 , R 46 , R 49 , and R 50 are not all hydrogen atoms.
- the number of carbon atoms of the alkylene group represented by R 41 , R 42 , R 43 , R 47 and R 48 is 1-20, preferably 1-10, more preferably 1-8.
- the number of carbon atoms of the alkyl group represented by R 44 , R 45 , R 46 , R 49 and R 50 is 1-20, preferably 1-8, more preferably 1-6. These may be linear, branched or cyclic. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, hexyl group, nonyl group, decyl group, dodecyl Group, tridecyl group, cyclopentyl group, cyclohexyl group and the like.
- R 44 and R 45 , R 45 and R 46 , R 44 and R 46 , R 44 and R 45 and R 46 , and R 49 and R 50 form a ring structure
- the carbon number is typically 1 to 20 And preferably 1 to 8, more preferably 1 to 6.
- these ring structures may be branched by an alkyl group having 1 to 6, preferably 1 to 4 carbon atoms.
- S, T and U are preferably integers of 1 to 10, more preferably 1 to 8.
- Examples of the basic compounds represented by the above formulas (6) and (7) include tris ⁇ 2- (methoxymethoxy) ethyl ⁇ amine, tris ⁇ 2- (methoxyethoxy) ethyl ⁇ amine, tris [2- ⁇ ( 2-methoxyethoxy) methoxy ⁇ ethyl] amine, tris ⁇ 2- (2-methoxyethoxy) ethyl ⁇ amine, tris ⁇ 2- (1-methoxyethoxy) ethyl ⁇ amine, tris ⁇ 2- (1-ethoxyethoxy) ethyl ⁇ Amine, Tris ⁇ 2- (1-ethoxypropoxy) ethyl ⁇ amine, Tris [2- ⁇ (2-hydroxyethoxy) ethoxy ⁇ ethyl] amine, 4,7,13,16,21,24-hexaoxa-1, 10-diazabicyclo [8.8.8] hexacosane, 4,7,13,18
- Basic compounds include tertiary amines, aniline derivatives, pyrrolidine derivatives, pyridine derivatives, quinoline derivatives, amino acid derivatives, tris ⁇ 2- (methoxymethoxy) ethyl ⁇ amine, tris ⁇ (2- (2-methoxyethoxy) ethyl ⁇ Amine, tris [2- ⁇ (2-methoxyethoxy) methyl ⁇ ethyl] amine, 1-aza-15-crown-5 are preferred.
- the content of the basic compound in the positive radiation-sensitive composition is preferably 0.001 to 1 part by mass, and 0.005 to 0.2 part by mass with respect to 100 parts by mass of the [A] polymer. Part by mass is more preferable. Pattern developability improves more by making content of a basic compound into the said specific range.
- the positive-type radiation-sensitive composition is obtained by mixing [A] polymer, [B] acid generator, [C] nitrogen-containing compound, which is a suitable component, if necessary, and other optional components in a solvent. Prepared in a dissolved or dispersed state.
- the positive radiation-sensitive composition can be prepared by mixing each component at a predetermined ratio in a solvent.
- a solvent in which each component is uniformly dissolved or dispersed and does not react with each component is preferably used.
- the solvent include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionate, aromatic Examples include hydrocarbons, ketones, and other esters. In addition, these solvents can be used alone or in combination of two or more.
- alcohols examples include methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol and the like.
- ethers examples include tetrahydrofuran.
- glycol ethers examples include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether.
- ethylene glycol alkyl ether acetates examples include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate.
- diethylene glycol alkyl ether examples include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether.
- propylene glycol monoalkyl ether examples include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like.
- propylene glycol monoalkyl ether acetates examples include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate and the like.
- propylene glycol monoalkyl ether propionate examples include propylene monoglycol methyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate and the like. .
- aromatic hydrocarbons examples include toluene and xylene.
- ketones include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone and the like.
- esters examples include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, hydroxy Methyl acetate, ethyl hydroxyacetate, hydroxybutyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate 2-methyl-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate Methyl propoxya
- ethers such as dialkyl ethers, diethylene glycol alkyl ethers, Ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, ketones and esters are preferred, especially diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, propylene Glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol mono Tyl ether acetate, cyclohexanone, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl
- Ethers such as dialkyl ether are more preferable, and diisopentyl ether is particularly preferable.
- the drying process time is shortened, and at the same time, the coating property is further improved (coating unevenness is suppressed). Is possible.
- the proportion of components other than the solvent in the liquid can be arbitrarily set according to the purpose of use, desired film thickness, etc.
- the content is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and particularly preferably 15% by mass to 35% by mass.
- the positive radiation-sensitive composition is suitable as a material for forming an interlayer insulating film for display elements. Further, the present invention suitably includes an interlayer insulating film for a display element formed from the positive radiation sensitive composition.
- the method for forming an interlayer insulating film for a display element includes: (1) The process of forming the coating film of the said positive type radiation sensitive composition on a board
- the coating surface is preferably removed by pre-baking the coating surface to form a coating film.
- the coating method include spraying, roll coating, spin coating (spin coating), slit die coating, and bar coating. Of these, the spin coating method and the slit die coating method are preferable, and the slit die coating method is more preferable.
- Examples of the substrate include glass, quartz, silicone, and resin.
- Examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, cyclic olefin ring-opening polymer, and hydrogenated products thereof.
- Prebaking conditions vary depending on the type of each component, the blending ratio, etc., but can be about 70 ° C. to 120 ° C. and about 1 to 10 minutes.
- Step (2) In this step, at least a part of the formed coating film is exposed to radiation and exposed. When exposing, it exposes normally through the photomask which has a predetermined pattern.
- the radiation used for exposure is preferably radiation having a wavelength in the range of 190 nm to 450 nm, and more preferably radiation containing ultraviolet light of 365 nm. Energy of exposure intensity at the wavelength 365nm radiation, by the value measured by luminometer (OAI model356, OAI Optical Ltd. Associates), preferably 300J / m 2 ⁇ 5,000J / m 2, 400J / m 2 ⁇ 1 500 J / m 2 is more preferable.
- Step (3) the coating film irradiated with the radiation is developed. By developing the coated film after exposure, unnecessary portions (radiation irradiated portions) are removed to form a predetermined pattern.
- an alkaline aqueous solution is preferable.
- the alkali include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. .
- An appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to the alkaline aqueous solution.
- concentration of alkali in the aqueous alkali solution is preferably from 0.1% by mass to 5% by mass from the viewpoint of obtaining appropriate developability.
- Examples of the developing method include a liquid piling method, a dipping method, a rocking dipping method, and a shower method.
- the development time varies depending on the composition of the positive radiation sensitive composition, but is about 10 seconds to 180 seconds. Following such development processing, for example, washing with running water is performed for 30 seconds to 90 seconds, and then a desired pattern can be formed by, for example, air drying with compressed air or compressed nitrogen.
- the developed coating film is heated.
- a heating device such as a hot plate or oven
- the patterned thin film is heated to accelerate the curing reaction of the [A] polymer and [C] nitrogen-containing compound to obtain a cured product.
- the heating temperature is, for example, about 120 ° C. to 250 ° C.
- the heating time varies depending on the type of heating device, for example, it is about 5 to 30 minutes for a hot plate and about 30 to 90 minutes for an oven.
- the step baking method etc. which perform a heating process 2 times or more can also be used. In this way, a patterned thin film corresponding to the target display element interlayer insulating film can be formed on the surface of the substrate.
- the use of the cured film is not limited to the interlayer insulating film for display elements, and can also be used as a spacer or a protective film.
- the film thickness of the formed interlayer insulating film for display elements is preferably 0.1 ⁇ m to 8 ⁇ m, more preferably 0.1 ⁇ m to 6 ⁇ m, and particularly preferably 0.1 ⁇ m to 4 ⁇ m.
- the temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (A-1).
- the Mw of the polymer (A-1) was 9,000.
- the solid content concentration of the polymer solution was 32.1% by mass.
- the temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (A-2).
- Mw of the polymer (A-2) was 9,000.
- the solid content concentration of the polymer solution was 31.3% by mass.
- Acid generator B-1 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate
- B-2 benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate
- B-3 ( 5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile (Ciba Specialty Chemicals, IRGACURE PAG 103)
- B-4 (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile (Ciba Specialty Chemicals, IRGACURE PAG 108)
- B-5 (5-p-Toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile
- Nitrogen-containing compound C-1 nitrogen-containing compound represented by the above formula (2-1)
- C-2 nitrogen-containing compound represented by the above formula (2-2)
- C-3 the above formula (2) -4)
- nitrogen-containing compound C-4 nitrogen-containing compound C-5 represented by the above formula (3-1-3): nitrogen-containing compound represented by the above formula (3-2-1)
- D-1 Silicone surfactant (manufactured by Toray Dow Corning Silicone, SH 8400 FLUID)
- D-2 Fluorosurfactant (Neos, Aftergent FTX-218)
- Adhesion aid E-1 ⁇ -glycidoxypropyltrimethoxysilane
- E-2 ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane
- E-3 ⁇ -methacryloxypropyltrimethoxysilane
- Example 1 [A] In a solution containing (A-1) as a polymer (an amount corresponding to 100 parts by mass (solid content) of (A-1)), [B] (B-4) as an acid generator. 0 parts by weight, [C] 5 parts by weight of (C-1) as a nitrogen-containing compound, [D] 0.20 parts by weight of (D-1) as a surfactant, and [E] E-1) A positive radiation sensitive composition was prepared by mixing 3.0 parts by mass and filtering through a membrane filter having a pore size of 0.2 ⁇ m.
- Example 2 to 12 and Comparative Examples 1 and 2 Each positive-type radiation-sensitive composition was prepared in the same manner as in Example 1 except that the types and blending amounts of each component were as described in Table 1. In Table 1, “-” indicates that the corresponding component was not used.
- Hexamethyldisilazane (HMDS) was applied on a 550 ⁇ 650 mm chromium-deposited glass and heated at 60 ° C. for 1 minute.
- Each positive radiation sensitive composition is applied onto the chromium-deposited glass after HMDS treatment using a slit die coater (manufactured by Tokyo Ohka Kogyo Co., Ltd., TR6322105-CL), and the ultimate pressure is set to 100 Pa under vacuum. After removing the solvent at, the film was further pre-baked at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 ⁇ m.
- the coating film was irradiated with radiation through the mask having a 60 ⁇ m line and space (10 to 1) pattern with the exposure amount being changed. . Then, it developed for 80 second at 25 degreeC with 0.4 mass% tetramethylammonium hydroxide aqueous solution. Next, washing with running ultrapure water for 1 minute was performed, followed by drying to form a pattern on the chromium-deposited glass substrate after the HMDS treatment. At this time, the exposure amount necessary for completely dissolving the 6 ⁇ m space pattern was defined as radiation sensitivity (J / m 2 ). When this value was 600 (J / m 2 ) or less, it was judged that the sensitivity was good.
- Transmissivity (%) A coating film was formed on the silicon substrate in the same manner as in the evaluation of the radiation sensitivity. Without being exposed, this silicon substrate was heated in a clean oven at 220 ° C. for 1 hour to obtain a cured film. The transmittance (%) at a wavelength of 400 nm was measured and evaluated using a spectrophotometer (150-20 type double beam, manufactured by Hitachi, Ltd.). When the transmittance was less than 90%, the transparency was judged to be poor.
- a coating film was formed on the silicon substrate in the same manner as in the evaluation of the radiation sensitivity. Then, after irradiating the coating film with a variable exposure amount through a mask having a 100 ⁇ m line-and-space (one-to-one) pattern, 0.4 mass% tetramethylammonium hydroxide aqueous solution And developed at 25 ° C. by a liquid piling method. The development time was 80 seconds. Subsequently, running water was washed with ultrapure water for 1 minute, and then dried to form a pattern. The post-development pattern height (T1) was measured by a stylus type film thickness measuring device ⁇ -step (manufactured by KLA Tencor).
- the patterned silicon substrate was heated in a clean oven at 220 ° C. for 1 hour to obtain a thermally cured pattern.
- the pattern height (t1) after thermosetting was measured, the heat shrinkage rate (%) before and after thermosetting was calculated from the following formula, and this was defined as heat resistance (%).
- Heat resistance (%) ⁇ (T1-t1) / T1 ⁇ ⁇ 100 It can be said that the greater the heat resistance value, the more the crosslinking reaction proceeds. Note that the heat shrinkage thus generated is at a level that is not particularly affected in actual use.
- Each radiation sensitive resin composition was spin-coated on a soda glass substrate on which a SiO 2 film for preventing elution of sodium ions was formed on the surface, and an ITO (indium-tin oxide alloy) electrode was deposited in a predetermined shape. Thereafter, prebaking was performed for 10 minutes in a clean oven at 90 ° C. to form a coating film having a thickness of 2.0 ⁇ m. Next, the coating film was exposed at an exposure amount of 500 J / m 2 without using a photomask. Thereafter, the coating film was cured by post-baking at 230 ° C. for 30 minutes.
- the substrate on which the pixels are formed and the substrate on which the ITO electrode is simply deposited in a predetermined shape are bonded together with a sealing agent mixed with 0.8 mm glass beads, and then Merck liquid crystal MLC6608 is injected into the liquid crystal.
- a cell was produced. Further, the liquid crystal cell was placed in a constant temperature layer at 60 ° C., and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage holding ratio measuring system (VHR-1A type, manufactured by Toyo Technica).
- the applied voltage at this time is a square wave of 5.5 V, and the measurement frequency is 60 Hz.
- the voltage holding ratio (%) is a value obtained from the following formula.
- Voltage holding ratio (%) (potential difference of liquid crystal cell after 16.7 milliseconds / voltage applied at 0 milliseconds) ⁇ 100 If the voltage holding ratio of the liquid crystal cell is 90% or less, it means that the liquid crystal cell cannot hold the applied voltage at a predetermined level for a time of 16.7 milliseconds, and the liquid crystal cannot be sufficiently aligned. There is a high risk of causing "burn-in".
- the positive-type radiation-sensitive compositions of Examples 1 to 10 were compared with the radiation-sensitive compositions of Comparative Examples 1 and 2 that did not contain [C] nitrogen-containing compounds. It was found that the surface hardness was excellent. Moreover, it turned out that the crosslinking
- Example 11 Compared with Examples 1 to 10, the surface hardness was slightly decreased in Example 11, and although the surface hardness was excellent in Example 12, the cross-linking reactivity was too high. The transmittance and the voltage holding ratio were slightly decreased. From the above, although good results were obtained for all of the positive radiation sensitive compositions of Examples 1 to 12, the content of [C] nitrogen-containing compound was 100 parts by mass of [A] polymer. On the other hand, it can be said that 2 to 30 mass parts is preferable.
- the positive radiation-sensitive composition of the present invention has excellent storage stability and sufficient radiation sensitivity, has general required characteristics of transmittance and voltage holding ratio, and has an excellent surface. A cured film having hardness and heat resistance can be formed. Therefore, the positive radiation sensitive composition is suitably used for forming a display element interlayer insulating film for a display element.
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Materials For Photolithography (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Epoxy Resins (AREA)
- Liquid Crystal (AREA)
Abstract
Description
[A]同一又は異なる重合体分子中に、下記式(1)で表される基を有する構造単位(I)とエポキシ基含有構造単位(II)とを含む重合体(以下、「[A]重合体」とも称する)、
[B]酸発生体、並びに
[C]下記式(2)で表される窒素含有化合物(I)及び下記式(3)で表される窒素含有化合物(II)からなる群より選択される少なくとも1種の窒素含有化合物(以下、「[C]窒素含有化合物」とも称する)
を含有するポジ型感放射線性組成物である。
(1)当該ポジ型感放射線性組成物の塗膜を基板上に形成する工程、
(2)上記塗膜の少なくとも一部に放射線を照射する工程、
(3)上記放射線が照射された塗膜を現像する工程、及び
(4)上記現像された塗膜を加熱する工程
を有する。
本発明のポジ型感放射線性組成物は、[A]重合体、[B]酸発生体及び[C]窒素含有化合物を含有する。また、当該ポジ型感放射線性組成物は好適成分として、[D]界面活性剤及び[E]密着助剤を含有してもよい。さらに、本発明の効果を損なわない限りにおいて、その他の任意成分を含有してもよい。以下、各成分を詳述する。
[A]重合体は、同一又は異なる重合体分子中に、構造単位(I)とエポキシ基含有構造単位(II)とを含んでいる。また、必要に応じてその他の構造単位を含んでいてもよい。構造単位(I)及びエポキシ基含有構造単位(II)を含む[A]重合体の態様としては特に限定されず、例えば
(i)同一の重合体分子中に構造単位(I)及びエポキシ基含有構造単位(II)の両方を含んでおり、[A]重合体中に1種の重合体分子が存在する場合;
(ii)一の重合体分子中に構造単位(I)を含み、それとは異なる重合体分子中にエポキシ基含有構造単位(II)を含んでおり、[A]重合体中に2種の重合体分子が存在する場合;
(iii)一の重合体分子中に構造単位(I)及びエポキシ基含有構造単位(II)の両方を含むと共に、それとは異なる重合体分子中に構造単位(I)を含み、これらとはさらに異なる重合体分子中にエポキシ基含有構造単位(II)を含んでおり、[A]重合体中に3種の重合体分子が存在する場合;
(iv)(i)~(iii)に規定の重合体分子に加え、[A]重合体中にさらに別の1種又は2種以上の重合体分子を含む場合等が挙げられる。上記いずれの場合であっても本発明の効果を享受することができる。なお、[A]重合体は、各構造単位を2種以上含んでいてもよい。以下、各構造単位を詳述する。
構造単位(I)では、上記式(1)で表される基が、酸の存在下で解離して極性基を生じる基(酸解離性基)として存在しているので、放射線の照射により酸発生体から生じた酸により酸解離性基が解離し、その結果、アルカリ不溶性であった[A]重合体はアルカリ可溶性となる。上記酸解離性基は、アルカリに対しては比較的安定なアセタール構造又はケタール構造を有しており、これらが酸の作用によって解離することとなる。
1-アルコキシアルキル(メタ)アクリレート、1-(シクロアルキルオキシ)アルキル(メタ)アクリレート、1-(ハロアルコキシ)アルキル(メタ)アクリレート、1-(アラルキルオキシ)アルキル(メタ)アクリレート、テトラヒドロピラニル(メタ)アクリレート等の(メタ)アクリレート系アセタール構造含有単量体;
2,3-ジ(1-(トリアルキルシラニルオキシ)アルコキシ)カルボニル)-5-ノルボルネン、2,3-ジ(1-(トリアルキルゲルミルオキシ)アルコキシ)カルボニル)-5-ノルボルネン、2,3-ジ(1-アルコキシアルコキシカルボニル)-5-ノルボルネン、2,3-ジ(1-(シクロアルキルオキシ)アルコキシカルボニル)-5-ノルボルネン、2,3-ジ(1-(アラルキルオキシ)アルコキシカルボニル)-5-ノルボルネン等のノルボルネン系アセタール構造含有単量体;
1-アルコキシアルコキシスチレン、1-(ハロアルコキシ)アルコキシスチレン、1-(アラルキルオキシ)アルコキシスチレン、テトラヒドロピラニルオキシスチレン等のスチレン系アセタール構造含有単量体が挙げられる。
1-エトキシエチルメタクリレート、1-メトキシエチルメタクリレート、1-n-ブトキシエチルメタクリレート、1-イソブトキシエチルメタクリレート、1-t-ブトキシエチルメタクリレート、1-(2-クロルエトキシ)エチルメタクリレート、1-(2-エチルヘキシルオキシ)エチルメタクリレート、1-n-プロポキシエチルメタクリレート、1-シクロヘキシルオキシエチルメタクリレート、1-(2-シクロヘキシルエトキシ)エチルメタクリレート、1-ベンジルオキシエチルメタクリレート、2-テトラヒドロピラニルメタクリレート等のメタクリレート系アセタール構造含有単量体;
1-エトキシエチルアクリレート、1-メトキシエチルアクリレート、1-n-ブトキシエチルアクリレート、1-イソブトキシエチルアクリレート、1-t-ブトキシエチルアクリレート、1-(2-クロルエトキシ)エチルアクリレート、1-(2-エチルヘキシルオキシ)エチルアクリレート、1-n-プロポキシエチルアクリレート、1-シクロヘキシルオキシエチルアクリレート、1-(2-シクロヘキシルエトキシ)エチルアクリレート、1-ベンジルオキシエチルアクリレート、2-テトラヒドロピラニルアクリレート等のアクリレート系アセタール構造含有単量体;
2,3-ジ(1-(トリメチルシラニルオキシ)エトキシ)カルボニル)-5-ノルボルネン、2,3-ジ(1-(トリメチルゲルミルオキシ)エトキシ)カルボニル)-5-ノルボルネン、2,3-ジ(1-メトキシエトキシカルボニル)-5-ノルボルネン、2,3-ジ(1-(シクロヘキシルオキシ)エトキシカルボニル)-5-ノルボルネン、2,3-ジ(1-(ベンジルオキシ)エトキシカルボニル)-5-ノルボルネン等のノルボルネン系アセタール構造含有単量体;
p又はm-1-エトキシエトキシスチレン、p又はm-1-メトキシエトキシスチレン、p又はm-1-n-ブトキシエトキシスチレン、p又はm-1-イソブトキシエトキシスチレン、p又はm-1-(1,1-ジメチルエトキシ)エトキシスチレン、p又はm-1-(2-クロルエトキシ)エトキシスチレン、p又はm-1-(2-エチルヘキシルオキシ)エトキシスチレン、p又はm-1-n-プロポキシエトキシスチレン、p又はm-1-シクロヘキシルオキシエトキシスチレン、p又はm-1-(2-シクロヘキシルエトキシ)エトキシスチレン、p又はm-1-ベンジルオキシエトキシスチレン等のスチレン系アセタール構造含有単量体等が挙げられる。なお、これらの単量体は単独又は2種以上を使用することができる。
エポキシ基含有構造単位(II)としては、エポキシ基含有単量体に由来する構造単位であれば特に限定されない。[A]重合体が分子中にエポキシ基含有構造単位(II)を含むことで、当該ポジ型感放射線性組成物から得られる硬化膜の表面硬度及び耐熱性をさらに高めることができる。なお、本明細書のエポキシ基とは、オキシラニル基(1,2-エポキシ構造)及びオキセタニル基(1,3-エポキシ構造)を含む概念である。
(メタ)アクリル酸グリシジル、(メタ)アクリル酸3,4-エポキシブチル、アクリル酸3-メチル-3,4-エポキシブチル、メタクリル酸3-エチル-3,4-エポキシブチル、(メタ)アクリル酸5,6-エポキシヘキシル、メタクリル酸5-メチル-5,6-エポキシヘキシル、メタクリル酸5-エチル-5,6-エポキシヘキシル、(メタ)アクリル酸6,7-エポキシヘプチル、メタクリル酸3,4-エポキシシクロへキシル、メタクリル酸3,4-エポキシシクロへキシルメチル、(メタ)アクリル酸3,4-エポキシシクロへキシルエチル、メタクリル酸3,4-エポキシシクロへキシルプロピル、メタクリル酸3,4-エポキシシクロへキシルブチル、(メタ)アクリル酸3,4-エポキシシクロへキシルヘキシル、アクリル酸3,4-エポキシシクロへキシルメチル、アクリル酸3,4-エポキシシクロへキシルエチル、アクリル酸3,4-エポキシシクロへキシルプロピル、アクリル酸3,4-エポキシシクロへキシルブチル、アクリル酸3,4-エポキシシクロへキシルヘキシル等のオキシラニル基含有(メタ)アクリル系化合物;
o-ビニルベンジルグリシジルエーテル、m-ビニルベンジルグリシジルエーテル、p-ビニルベンジルグリシジルエーテル、α-メチル-o-ビニルベンジルグリシジルエーテル、α-メチル-m-ビニルベンジルグリシジルエーテル、α-メチル-p-ビニルベンジルグリシジルエーテル等のビニルベンジルグリシジルエーテル類;
o-ビニルフェニルグリシジルエーテル、m-ビニルフェニルグリシジルエーテル、p-ビニルフェニルグリシジルエーテル等のビニルフェニルグリシジルエーテル類;
3-アクリロイルオキシメチルオキセタン、3-アクリロイルオキシメチル-3-メチルオキセタン、3-アクリロイルオキシメチル-3-エチルオキセタン、3-アクリロイルオキシメチル-3-フェニルオキセタン、3-(2-アクリロイルオキシエチル)オキセタン、3-(2-アクリロイルオキシエチル)-3-エチルオキセタン、3-(2-アクリロイルオキシエチル)-3-エチルオキセタン、3-(2-アクリロイルオキシエチル)-3-フェニルオキセタン、3-メタクリロイルオキシメチルオキセタン、3-メタクリロイルオキシメチル-3-メチルオキセタン、3-メタクリロイルオキシメチル-3-エチルオキセタン、3-メタクリロイルオキシメチル-3-フェニルオキセタン、3-(2-メタクリロイルオキシエチル)オキセタン、3-(2-メタクリロイルオキシエチル)-3-エチルオキセタン、3-(2-メタクリロイルオキシエチル)-3-エチルオキセタン、3-(2-メタクリロイルオキシエチル)-3-フェニルオキセタン、2-アクリロイルオキシメチルオキセタン、2-アクリロイルオキシメチル-2-メチルオキセタン、2-アクリロイルオキシメチル-2-エチルオキセタン、2-アクリロイルオキシメチル-2-フェニルオキセタン、2-(2-アクリロイルオキシエチル)オキセタン、2-(2-アクリロイルオキシエチル)-2-エチルオキセタン、2-(2-アクリロイルオキシエチル)-2-エチルオキセタン、2-(2-アクリロイルオキシエチル)-2-フェニルオキセタン、2-メタクリロイルオキシメチルオキセタン、2-メタクリロイルオキシメチル-2-メチルオキセタン、2-メタクリロイルオキシメチル-2-エチルオキセタン、2-メタクリロイルオキシメチル-2-フェニルオキセタン、2-(2-メタクリロイルオキシエチル)オキセタン、2-(2-メタクリロイルオキシエチル)-2-エチルオキセタン、2-(2-メタクリロイルオキシエチル)-2-エチルオキセタン、2-(2-メタクリロイルオキシエチル)-2-フェニルオキセタン等のオキセタニル基含有(メタ)アクリル系化合物等が挙げられる。
[A]重合体は、本発明の効果を損なわない範囲において、構造単位(I)及び構造単位(II)以外のその他の構造単位を含んでいてもよい。
アクリル酸メチル、アクリル酸i-プロピル等のアクリル酸アルキルエステル;
メタクリル酸メチル、メタクリル酸エチル、メタクリル酸n-ブチル、メタクリル酸sec-ブチル、メタクリル酸t-ブチル等のメタクリル酸アルキルエステル;
アクリル酸シクロヘキシル、アクリル酸-2-メチルシクロヘキシル、アクリル酸トリシクロ[5.2.1.02,6]デカン-8-イル、アクリル酸-2-(トリシクロ[5.2.1.02,6]デカン-8-イルオキシ)エチル、アクリル酸イソボルニル等のアクリル酸脂環式アルキルエステル;
メタクリル酸シクロヘキシル、メタクリル酸-2-メチルシクロヘキシル、メタクリル酸トリシクロ[5.2.1.02,6]デカン-8-イル、メタクリル酸-2-(トリシクロ[5.2.1.02,6]デカン-8-イルオキシ)エチル、メタクリル酸イソボルニル等のメタクリル酸脂環式アルキルエステル;
アクリル酸フェニル、アクリル酸ベンジル等のアクリル酸のアリールエステル及びアクリル酸のアラルキルエステル;
メタクリル酸フェニル、メタクリル酸ベンジル等のメタクリル酸のアリールエステル及びメタクリル酸のアラルキルエステル;
マレイン酸ジエチル、フマル酸ジエチル、イタコン酸ジエチル等のジカルボン酸ジアルキルエステル;
メタクリル酸テトラヒドロフルフリル、メタクリル酸テトラヒドロフリル、メタクリル酸テトラヒドロピラン-2-メチル等の酸素1原子を含む不飽和複素五員環メタクリル酸エステル及び不飽和複素六員環メタクリル酸エステル;
4-メタクリロイルオキシメチル-2-メチル-2-エチル-1,3-ジオキソラン、4-メタクリロイルオキシメチル-2-メチル-2-イソブチル-1,3-ジオキソラン、4-メタクリロイルオキシメチル-2-シクロヘキシル-1,3-ジオキソラン、4-メタクリロイルオキシメチル-2-メチル-2-エチル-1,3-ジオキソラン、4-メタクリロイルオキシメチル-2-メチル-2-イソブチル-1,3-ジオキソラン等の酸素2原子を含む不飽和複素五員環メタクリル酸エステル;
4-アクリロイルオキシメチル-2,2-ジメチル-1,3-ジオキソラン、4-アクリロイルオキシメチル-2-メチル-2-エチル-1,3-ジオキソラン、4-アクリロイルオキシメチル-2、2-ジエチル-1,3-ジオキソラン、4-アクリロイルオキシメチル-2-メチル-2-イソブチル-1,3-ジオキソラン、4-アクリロイルオキシメチル-2-シクロペンチル-1,3-ジオキソラン、4-アクリロイルオキシメチル-2-シクロヘキシル-1,3-ジオキソラン、4-アクリロイルオキシエチル-2-メチル-2-エチル-1,3-ジオキソラン、4-アクリロイルオキシプロピル-2-メチル-2-エチル-1,3-ジオキソラン、4-アクリロイルオキシブチル-2-メチル-2-エチル-1,3-ジオキソラン等の酸素2原子を含む不飽和複素五員環アクリル酸エステル;
スチレン、α-メチルスチレン、m-メチルスチレン、p-メチルスチレン、p-メトキシスチレン、4-イソプロペニルフェノール等のビニル芳香族化合物;
N-フェニルマレイミド、N-シクロヘキシルマレイミド、N-ベンジルマレイミド、N-スクシンイミジル-3-マレイミドベンゾエート、N-スクシンイミジル-4-マレイミドブチレート、N-スクシンイミジル-6-マレイミドカプロエート、N-スクシンイミジル-3-マレイミドプロピオネート、N-(9-アクリジニル)マレイミド等のN位置換マレイミド;
1,3-ブタジエン、イソプレン、2,3-ジメチル-1,3-ブタジエン等の共役ジエン系化合物;
アクリロニトリル、メタクリロニトリル、アクリルアミド、メタクリルアミド、塩化ビニル、塩化ビニリデン、酢酸ビニル等のその他の不飽和化合物が挙げられる。
装置:GPC-101(昭和電工製)
カラム:GPC-KF-801、GPC-KF-802、GPC-KF-803及びGPC-KF-804を結合
移動相:テトラヒドロフラン
カラム温度:40℃
流速:1.0mL/分
試料濃度:1.0質量%
試料注入量:100μL
検出器:示差屈折計
標準物質:単分散ポリスチレン
[A]重合体は、上記各構造単位を与える単量体のラジカル共重合により合成できる。例えば、同一の重合体分子に構造単位(I)及びエポキシ基含有構造単位(II)の両方を含む[A]重合体を合成する場合は、構造単位(I)を与える単量体とエポキシ基含有構造単位(II)を与える単量体とを含む混合物を用いて共重合させればよい。一方、一の重合体分子に構造単位(I)を有し、かつそれとは異なる重合体分子にエポキシ基含有構造単位(II)を有する[A]重合体を合成する場合は、構造単位(I)を与える単量体を含む重合性溶液をラジカル重合させて構造単位(I)を有する重合体分子を得ておき、別途エポキシ基含有構造単位(II)を与える単量体を含む重合性溶液をラジカル重合させてエポキシ基含有構造単位(II)を有する重合体分子を得て、最後に両者を混合して[A]重合体とすればよい。
[B]酸発生体は、放射線の照射によっても熱の付与によっても酸を発生する化合物である。放射線としては、例えば可視光線、紫外線、遠紫外線、電子線、X線等を使用できる。当該ポジ型感放射線性組成物が、酸解離性基を有する[A]重合体と[B]酸発生体を含有することで、当該ポジ型感放射線性組成物はポジ型の感放射線特性を発揮することができる。[B]酸発生体の当該ポジ型感放射線性組成物における含有形態としては、後述するような化合物の形態(以下、適宜「[B]酸発生剤」とも称する)でも、[A]重合体又は他の重合体の一部として組み込まれた酸発生基の形態でも、これらの両方の形態でもよい。なお、放射線の照射又は熱の付与のいずれによって酸発生体から酸を発生させるかは、露光前のプレベーク時の温度、照射線の照射量、ポストベーク時の温度等を調整することにより決めることができるが、[B]酸発生体としては、露光時の放射線の照射により酸を発生し、かつポストベーク時の熱によって酸を発生するものが好ましい。このような[B]酸発生体を用いることで、当該ポジ型感放射線性組成物はポジ型の感放射線特性を発揮することができると共に、ポストベーク時に[C]窒素含有化合物を脱保護してエポキシ基の架橋反応を充分に進行させることができる。
オキシムスルホネート化合物としては、例えば下記式(4)で表されるオキシムスルホネート基を含有する化合物等が挙げられる。
オニウム塩としては、例えばジフェニルヨードニウム塩、トリフェニルスルホニウム塩、スルホニウム塩、ベンゾチアゾニウム塩、テトラヒドロチオフェニウム塩等が挙げられる。
スルホンイミド化合物としては、例えばN-(トリフルオロメチルスルホニルオキシ)スクシンイミド、N-(カンファスルホニルオキシ)スクシンイミド、N-(4-メチルフェニルスルホニルオキシ)スクシンイミド、N-(2-トリフルオロメチルフェニルスルホニルオキシ)スクシンイミド、N-(4-フルオロフェニルスルホニルオキシ)スクシンイミド、N-(トリフルオロメチルスルホニルオキシ)フタルイミド、N-(カンファスルホニルオキシ)フタルイミド、N-(2-トリフルオロメチルフェニルスルホニルオキシ)フタルイミド、N-(2-フルオロフェニルスルホニルオキシ)フタルイミド、N-(トリフルオロメチルスルホニルオキシ)ジフェニルマレイミド、N-(カンファスルホニルオキシ)ジフェニルマレイミド、4-メチルフェニルスルホニルオキシ)ジフェニルマレイミド、N-(2-トリフルオロメチルフェニルスルホニルオキシ)ジフェニルマレイミド、N-(4-フルオロフェニルスルホニルオキシ)ジフェニルマレイミド、N-(4-フルオロフェニルスルホニルオキシ)ジフェニルマレイミド、N-(フェニルスルホニルオキシ)ビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシルイミド、N-(4-メチルフェニルスルホニルオキシ)ビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシルイミド、N-(トリフルオロメタンスルホニルオキシ)ビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシルイミド、N-(ノナフルオロブタンスルホニルオキシ)ビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシルイミド、N-(カンファスルホニルオキシ)ビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシルイミド、N-(カンファスルホニルオキシ)-7-オキサビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシルイミド、N-(トリフルオロメチルスルホニルオキシ)-7-オキサビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシルイミド、N-(4-メチルフェニルスルホニルオキシ)ビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシルイミド、N-(4-メチルフェニルスルホニルオキシ)-7-オキサビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシルイミド、N-(2-トリフルオロメチルフェニルスルホニルオキシ)ビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシルイミド、N-(2-トリフルオロメチルフェニルスルホニルオキシ)-7-オキサビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシルイミド、N-(4-フルオロフェニルスルホニルオキシ)ビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシルイミド、N-(4-フルオロフェニルスルホニルオキシ)-7-オキサビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシルイミド、N-(トリフルオロメチルスルホニルオキシ)ビシクロ[2.2.1]ヘプタン-5,6-オキシ-2,3-ジカルボキシルイミド、N-(カンファスルホニルオキシ)ビシクロ[2.2.1]ヘプタン-5,6-オキシ-2,3-ジカルボキシルイミド、N-(4-メチルフェニルスルホニルオキシ)ビシクロ[2.2.1]ヘプタン-5,6-オキシ-2,3-ジカルボキシルイミド、N-(2-トリフルオロメチルフェニルスルホニルオキシ)ビシクロ[2.2.1]ヘプタン-5,6-オキシ-2,3-ジカルボキシルイミド、N-(4-フルオロフェニルスルホニルオキシ)ビシクロ[2.2.1]ヘプタン-5,6-オキシ-2,3-ジカルボキシルイミド、N-(トリフルオロメチルスルホニルオキシ)ナフチルジカルボキシルイミド、N-(カンファスルホニルオキシ)ナフチルジカルボキシルイミド、N-(4-メチルフェニルスルホニルオキシ)ナフチルジカルボキシルイミド、N-(フェニルスルホニルオキシ)ナフチルジカルボキシルイミド、N-(2-トリフルオロメチルフェニルスルホニルオキシ)ナフチルジカルボキシルイミド、N-(4-フルオロフェニルスルホニルオキシ)ナフチルジカルボキシルイミド、N-(ペンタフルオロエチルスルホニルオキシ)ナフチルジカルボキシルイミド、N-(ヘプタフルオロプロピルスルホニルオキシ)ナフチルジカルボキシルイミド、N-(ノナフルオロブチルスルホニルオキシ)ナフチルジカルボキシルイミド、N-(エチルスルホニルオキシ)ナフチルジカルボキシルイミド、N-(プロピルスルホニルオキシ)ナフチルジカルボキシルイミド、N-(ブチルスルホニルオキシ)ナフチルジカルボキシルイミド、N-(ペンチルスルホニルオキシ)ナフチルジカルボキシルイミド、N-(ヘキシルスルホニルオキシ)ナフチルジカルボキシルイミド、N-(ヘプチルスルホニルオキシ)ナフチルジカルボキシルイミド、N-(オクチルスルホニルオキシ)ナフチルジカルボキシルイミド、N-(ノニルスルホニルオキシ)ナフチルジカルボキシルイミド等が挙げられる。
キノンジアジド化合物は放射線の照射によりカルボン酸を発生する化合物である。キノンジアジド化合物としては、フェノール性化合物又はアルコール性化合物(以下、「母核」とも称する)と1,2-ナフトキノンジアジドスルホン酸ハライドとの縮合物を用いることができる。
[C]窒素含有化合物は、露光時に[B]酸発生体から生じた酸では脱保護されず、ポストベーク時の熱及びこの熱により酸発生体から生じた酸の協働作用により脱保護されるアミン化合物である。この[C]窒素含有化合物のポストベーク時の脱保護により、アミン化合物としての反応性を発揮して、エポキシ基の架橋反応を充分に進行させ、その結果、表面硬度及び耐熱性に優れる表示素子用層間絶縁膜を形成することができる。
上記式(2)中、R4及びR5は、それぞれ独立して水素原子、アミノ基、炭素数1~20のアルキル基又は炭素数6~20のアリール基である。但し、上記アルキル基及びアリール基は、ヒドロキシル基、カルボキシル基、カルボニル基、エステル基、スルホン基、アミド基、エーテル基、チオール基、チオエーテル基、アミノ基又はアミジノ基を含んでいてもよい。R6は、炭素数1~20のアルキル基、炭素数4~20のシクロアルキル基又は炭素数6~20のアリール基である。但し、R4とR5とが連結して互いに結合している窒素原子と共に環構造を形成してもよい。
窒素含有化合物(II)は上記式(3)で表されるように、カルバメート構造を分子内に2つ有する。上記式(3)中、R7及びR8は、それぞれ独立して上記R4と同義である。R9及びR10は、それぞれ独立して上記R6と同義である。Aは、炭素数1~12のアルカンジイル基又は炭素数6~20のアリーレン基である。
[D]界面活性剤は、当該ポジ型感放射線性組成物の塗膜形成性をより向上させることができる。[D]界面活性剤としては、例えばフッ素系界面活性剤、シリコーン系界面活性剤、ノニオン系界面活性剤等が挙げられる。当該ポジ型感放射線性組成物が、[D]界面活性剤を含有することで、塗膜の表面平滑性を向上でき、その結果形成される表示素子用層間絶縁膜の膜厚均一性をより向上できる。これらの界面活性剤は、単独又は2種以上を組み合わせて使用することができる。
当該ポジ型感放射線性組成物においては、基板となる無機物、例えばシリコン、酸化シリコン、窒化シリコン等のシリコン化合物、金、銅、アルミニウム等の金属と絶縁膜との接着性を向上させるために[E]密着助剤を使用することができる。このような密着助剤としては、官能性シランカップリング剤が好ましく使用される。官能性シランカップリング剤の例としては、カルボキシル基、メタクリロイル基、イソシアネート基、エポキシ基(好ましくはオキシラニル基)、チオール基等の反応性置換基を有するシランカップリング剤等が挙げられる。
<その他の任意成分>
当該ポジ型感放射線性組成物は、上記[A]~[E]成分に加え、本発明の効果を損なわない範囲で必要に応じて塩基性化合物等のその他の任意成分を含有してもよい。
当該ポジ型感放射線性組成物が、塩基性化合物を含有することで、露光により[B]酸発生体から発生した酸の拡散長を適度に制御することができパターン現像性を良好にできる。塩基性化合物としては、化学増幅レジストで用いられるものから任意に選択して使用でき、例えば脂肪族アミン、混成アミン類、芳香族アミン、複素環式アミン、カルボン酸4級アンモニウム塩等が挙げられる。
当該ポジ型感放射線性組成物は、溶媒に[A]重合体、[B]酸発生体、必要に応じて好適成分である[C]窒素含有化合物、及びその他の任意成分を混合することによって溶解又は分散させた状態に調製される。例えば溶媒中で、各成分を所定の割合で混合することにより、当該ポジ型感放射線性組成物を調製できる。
当該ポジ型感放射線性組成物は、表示素子用層間絶縁膜の形成材料として好適である。また、本発明には、当該ポジ型感放射線性組成物から形成される表示素子用層間絶縁膜も好適に含まれる。
(1)当該ポジ型感放射線性組成物の塗膜を基板上に形成する工程、
(2)上記塗膜の少なくとも一部に放射線を照射する工程、
(3)上記放射線が照射された塗膜を現像する工程、及び
(4)上記現像された塗膜を加熱する工程
を有する。
本工程では、基板上に当該ポジ型感放射線性組成物の溶液又は分散液を塗布した後、好ましくは塗布面をプレベークすることによって溶媒を除去して塗膜を形成する。塗布方法としては、例えばスプレー法、ロールコート法、回転塗布法(スピンコート法)、スリットダイ塗布法、バー塗布法等が挙げられる。これらのうち、スピンコート法、スリットダイ塗布法が好ましく、スリットダイ塗布法がより好ましい。
本工程では、上記形成された塗膜の少なくとも一部に放射線を照射し露光する。露光する際には、通常所定のパターンを有するフォトマスクを介して露光する。露光に使用される放射線としては、波長が190nm~450nmの範囲にある放射線が好ましく、365nmの紫外線を含む放射線がより好ましい。露光量としては、放射線の波長365nmにおける強度を、照度計(OAI model356、OAI Optical Associates製)により測定した値で、300J/m2~5,000J/m2が好ましく、400J/m2~1,500J/m2がより好ましい。
本工程では、上記放射線が照射された塗膜を現像する。露光後の塗膜を現像することにより、不要な部分(放射線の照射部分)を除去して所定のパターンを形成する。現像工程に使用される現像液としては、アルカリ性の水溶液が好ましい。アルカリとしては、例えば水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、ケイ酸ナトリウム、メタケイ酸ナトリウム、アンモニア等の無機アルカリ;テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド等の4級アンモニウム塩等が挙げられる。
本工程では、上記現像された塗膜を加熱する。加熱には、ホットプレート、オーブン等の加熱装置を用い、パターニングされた薄膜を加熱することで、[A]重合体及び[C]窒素含有化合物の硬化反応を促進して、硬化物を得ることができる。加熱温度としては、例えば120℃~250℃程度である。加熱時間としては、加熱機器の種類により異なるが、例えばホットプレートでは5分~30分間程度、オーブンでは30分~90分間程度である。また、2回以上の加熱工程を行うステップベーク法等を用いることもできる。このようにして、目的とする表示素子用層間絶縁膜に対応するパターン状薄膜を基板の表面上に形成できる。なお、上記硬化膜の用途としては、表示素子用層間絶縁膜に限定されず、スペーサーや保護膜としても利用することができる。
[合成例1]
冷却管及び攪拌機を備えたフラスコに、2,2’-アゾビス(2,4-ジメチルバレロニトリル)7質量部、ジエチレングリコールエチルメチルエーテル200質量部を仕込んだ。引き続きメタクリル酸5質量部、1-エトキシエチルメタクリレート40質量部、スチレン5質量部、メタクリル酸グリシジル40質量部、2-ヒドロキシエチルメタクリレート10質量部、及びα-メチルスチレンダイマー3質量部を仕込み窒素置換した後、ゆるやかに撹拌を始めた。溶液の温度を70℃に上昇させ、この温度を5時間保持し重合体(A-1)を含む重合体溶液を得た。重合体(A-1)のMwは9,000であった。重合体溶液の固形分濃度は、32.1質量%であった。
冷却管及び攪拌機を備えたフラスコに、2,2’-アゾビス(2,4-ジメチルバレロニトリル)7質量部、ジエチレングリコールエチルメチルエーテル200質量部を仕込んだ。引き続きメタクリル酸5質量部、2-テトラヒドロピラニルメタクリレート40質量部、スチレン5質量部、メタクリル酸グリシジル40質量部、2-ヒドロキシエチルメタクリレート10質量部及びα-メチルスチレンダイマー3質量部を仕込み窒素置換した後、ゆるやかに撹拌を始めた。溶液の温度を70℃に上昇させ、この温度を5時間保持し重合体(A-2)を含む重合体溶液を得た。重合体(A-2)のMwは9,000であった。重合体溶液の固形分濃度は、31.3質量%であった。
冷却管及び攪拌機を備えたフラスコに、2,2’-アゾビス(2-メチルプロピオン酸メチル)7質量部、プロピレングリコールモノメチルエーテルアセテート200質量部を仕込んだ。引き続き1-n-ブトキシエチルメタクリレート67質量部、メタクリル酸ベンジル23質量部、メタクリル酸10質量部を仕込み窒素置換した後、ゆるやかに撹拌を始めた。溶液の温度を80℃に上昇させ、この温度を6時間保持し重合体(a-1)を含む重合体溶液を得た。重合体(a-1)のMwは9,000であった。重合体溶液の固形分濃度は、30.3質量%であった。
冷却管及び攪拌機を備えたフラスコに、2,2’-アゾビス(2-メチルプロピオン酸メチル)7質量部、プロピレングリコールモノメチルエーテルアセテート200質量部を仕込んだ。引き続き1-ベンジルオキシエチルメタクリレート90質量部、メタクリル酸2-ヒドロキシエチル6質量部、メタクリル酸4質量部を仕込み窒素置換した後、ゆるやかに撹拌を始めた。溶液の温度を80℃に上昇させ、この温度を6時間保持し重合体(a-2)を含む重合体溶液を得た。重合体(a-2)のMwは9,000であった。重合体溶液の固形分濃度は、31.2質量%であった。
冷却管及び攪拌機を備えたフラスコに、2,2’-アゾビス(2-メチルプロピオン酸メチル)7質量部、プロピレングリコールモノメチルエーテルアセテート200質量部を仕込んだ。引き続き2-テトラヒドロピラニルメタクリレート85質量部、メタクリル酸2-ヒドロキシエチル7質量部、メタクリル酸8質量部を仕込み窒素置換した後、ゆるやかに撹拌を始めた。溶液の温度を80℃に上昇させ、この温度を6時間保持し重合体(a-3)を含む重合体溶液を得た。重合体(a-3)のMwは10,000であった。重合体溶液の固形分濃度は、29.2質量%であった。
冷却管及び攪拌機を備えたフラスコに、2,2’-アゾビス(2,4-ジメチルバレロニトリル)7質量部、ジエチレングリコールエチルメチルエーテル200質量部を仕込んだ。引き続きメタクリル酸グリシジル52質量部、メタクリル酸ベンジル48質量部を仕込み窒素置換した後、ゆるやかに撹拌を始めた。溶液の温度を80℃に上昇させ、この温度を6時間保持し重合体(aa-1)を含む重合体溶液を得た。重合体(aa-1)のMwは10,000であった。重合体溶液の固形分濃度は、32.3質量%であった。
冷却管及び攪拌機を備えたフラスコに、2,2’-アゾビス(2,4-ジメチルバレロニトリル)7質量部、ジエチレングリコールエチルメチルエーテル200質量部を仕込んだ。引き続きメタクリル酸3,4-エポキシシクロヘキシルメチル45質量部、メタクリル酸ベンジル45質量部、メタクリル酸10質量部を仕込み窒素置換した後、ゆるやかに撹拌を始めた。溶液の温度を80℃に上昇させ、この温度を6時間保持し重合体(aa-2)を含む重合体溶液を得た。重合体(aa-2)のMwは10,000であった。重合体溶液の固形分濃度は、33.2質量%であった。
冷却管及び攪拌機を備えたフラスコに、2,2’-アゾビス(2,4-ジメチルバレロニトリル)7質量部及びジエチレングリコールエチルメチルエーテル200質量部を仕込んだ。引き続き1-n-ブトキシエチルメタクリレート35質量部、メタクリル酸ベンジル35質量部、メタクリル酸グリシジル30質量部を仕込み窒素置換した後、ゆるやかに撹拌を始めた。溶液の温度を80℃に上昇させ、この温度を6時間保持し重合体(aa-3)を含む重合体溶液を得た。重合体(aa-3)のMwは10,000であった。重合体溶液の固形分濃度は、32.3質量%であった。
以下、実施例及び比較例のポジ型感放射線性組成物の調製に用いた成分を詳述する。
B-1:4,7-ジ-n-ブトキシ-1-ナフチルテトラヒドロチオフェニウムトリフルオロメタンスルホネート
B-2:ベンジル-4-ヒドロキシフェニルメチルスルホニウムヘキサフルオロホスフェート
B-3:(5-プロピルスルフォニルオキシイミノ-5H-チオフェン-2-イリデン)-(2-メチルフェニル)アセトニトリル(チバ・スペシャルティー・ケミカルズ製、IRGACURE PAG 103)
B-4:(5-オクチルスルフォニルオキシイミノ-5H-チオフェン-2-イリデン)-(2-メチルフェニル)アセトニトリル(チバ・スペシャルティー・ケミカルズ製、IRGACURE PAG 108)
B-5:(5-p-トルエンスルフォニルオキシイミノ-5H-チオフェン-2-イリデン)-(2-メチルフェニル)アセトニトリル(チバ・スペシャルティー・ケミカルズ製、IRGACURE PAG 121)
B-6:(カンファースルフォニルオキシイミノ-5H-チオフェン-2-イリデン)-(2-メチルフェニル)アセトニトリル(チバ・スペシャルティー・ケミカルズ製、CGI1380)
B-7:(5-オクチルスルフォニルオキシイミノ)-(4-メトキシフェニル)アセトニトリル(チバ・スペシャルティー・ケミカルズ製、CGI725)
C-1:上記式(2-1)で表される窒素含有化合物
C-2:上記式(2-2)で表される窒素含有化合物
C-3:上記式(2-4)で表される窒素含有化合物
C-4:上記式(3-1-3)で表される窒素含有化合物
C-5:上記式(3-2-1)で表される窒素含有化合物
D-1:シリコーン系界面活性剤(東レダウコーニングシリコーン製、SH 8400 FLUID)
D-2:フッ素系界面活性剤(ネオス製、フタージェントFTX-218)
E-1:γ-グリシドキシプロピルトリメトキシシラン
E-2:β-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン
E-3:γ-メタクリロキシプロピルトリメトキシシラン
[A]重合体としての(A-1)を含む溶液((A-1)100質量部(固形分)に相当する量)に、[B]酸発生剤としての(B-4)3.0質量部、[C]窒素含有化合物としての(C-1)5質量部、[D]界面活性剤としての(D-1)0.20質量部、及び[E]密着助剤としての(E-1)3.0質量部を混合し、孔径0.2μmのメンブランフィルタで濾過することによりポジ型感放射線性組成物を調製した。
各成分の種類及び配合量を表1に記載の通りとした以外は、実施例1と同様に操作して各ポジ型感放射線性組成物を調製した。なお、表1中の「-」は、該当する成分を使用しなかったことを示す。
調製した各ポジ型感放射線性組成物を用いて、下記の評価を実施した。結果を表1にあわせて示す。
550×650mmのクロム成膜ガラス上に、ヘキサメチルジシラザン(HMDS)を塗布し、60℃にて1分間加熱した。このHMDS処理後のクロム成膜ガラス上に、各ポジ型感放射線性組成物をスリットダイコーター(東京応化工業製、TR632105-CL)を用いて塗布し、到達圧力を100Paに設定して真空下で溶媒を除去した後、さらに90℃において2分間プレベークすることによって、膜厚3.0μmの塗膜を形成した。続いて、露光機(キヤノン製、MPA-600FA)を用い、60μmのライン・アンド・スペース(10対1)のパターンを有するマスクを介して、塗膜に対し露光量を変量として放射線を照射した。その後、0.4質量%のテトラメチルアンモニウムヒドロキシド水溶液にて25℃において80秒間現像した。次いで、超純水で1分間流水洗浄を行い、その後乾燥することにより、HMDS処理後のクロム成膜ガラス基板上にパターンを形成した。このとき、6μmのスペース・パターンが完全に溶解するために必要な露光量を放射線感度(J/m2)とした。この値が600(J/m2)以下の場合に感度が良好と判断した。
上記の放射線感度の評価と同様に操作して、シリコン基板上に塗膜を形成した。露光せずに、このシリコン基板をクリーンオーブン内にて220℃で1時間加熱して硬化膜を得た。波長400nmにおける透過率(%)を、分光光度計(150-20型ダブルビーム、日立製作所製)を用いて測定して評価した。透過率が90%未満の場合に透明性が不良と判断した。
上記透過率の評価で形成された硬化膜を有する基板について、JIS K-5400-1990の8.4.1鉛筆引っかき試験により、硬化膜の鉛筆硬度(表面硬度)を測定した。この値が3H以上である場合、表示素子用層間絶縁膜としての表面硬度が良好と判断し、十分な硬化性を有するといえる。
上記放射線感度の評価と同様に操作して、シリコン基板上に塗膜を形成した。次いで、100μmのライン・アンド・スペース(1対1)のパターンを有するマスクを介して、塗膜に対し露光量を変量として放射線を照射した後、0.4質量%のテトラメチルアンモニウムヒドロキシド水溶液にて25℃において液盛り法で現像した。現像時間は80秒間とした。次いで、超純水で1分間流水洗浄を行い、その後乾燥することにより、パターンを形成した。現像後パターン高さ(T1)を触針式膜厚測定装置α―ステップ(KLAテンコール製)により測定した。その後、パターン形成されたシリコン基板をクリーンオーブン内にて220℃で1時間加熱して熱硬化後のパターンを得た。同様にして、熱硬化後のパターン高さ(t1)を測定し、下記式から熱硬化前後の熱収縮率(%)を算出し、これを耐熱性(%)とした。
耐熱性(%)={(T1-t1)/T1}×100
耐熱性の値が大きいほど架橋反応が進行しているといえる。なお、このように生じた熱収縮は実際の使用上では特に影響のないレベルである。
表面にナトリウムイオンの溶出を防止するSiO2膜が形成され、さらにITO(インジウム-酸化錫合金)電極を所定形状に蒸着したソーダガラス基板上に、各感放射線性樹脂組成物を、スピンコートした後、90℃のクリーンオーブン内で10分間プレベークを行って、膜厚2.0μmの塗膜を形成した。次いで、フォトマスクを介さずに、塗膜に500J/m2の露光量で露光した。その後、230℃で30分間ポストベークを行い塗膜を硬化させた。次いで、この画素を形成した基板とITO電極を所定形状に蒸着しただけの基板とを、0.8mmのガラスビーズを混合したシール剤で貼り合わせたのち、メルク製液晶MLC6608を注入して、液晶セルを作製した。さらに、液晶セルを60℃の恒温層に入れて、液晶セルの電圧保持率を、液晶電圧保持率測定システム(VHR-1A型、東陽テクニカ製)により測定した。このときの印加電圧は5.5Vの方形波、測定周波数は60Hzである。電圧保持率(%)とは、下記式から求められる値である。
電圧保持率(%)=(16.7ミリ秒後の液晶セル電位差/0ミリ秒で印加した電圧)×100
液晶セルの電圧保持率が90%以下であると、液晶セルは16.7ミリ秒の時間、印加電圧を所定レベルに保持できず、十分に液晶を配向させることができないことを意味し、残像などの「焼き付き」を起こすおそれが高い。
各感放射線性樹脂組成物溶液を40℃のオーブン中で1週間放置し、オーブンに入れる前後での粘度を測定し、粘度変化率(%)を求め、保存安定性(%)とした。粘度変化率が5%以下である場合、保存安定性が良好と判断し、5%を超える場合に保存安定性が不良と判断した。粘度は、E型粘度計(VISCONIC ELD.R、東機産業製)を用いて25℃で測定した。
Claims (6)
- [A]同一又は異なる重合体分子中に、下記式(1)で表される基を有する構造単位(I)とエポキシ基含有構造単位(II)とを含む重合体、
[B]酸発生体、並びに
[C]下記式(2)で表される窒素含有化合物(I)及び下記式(3)で表される窒素含有化合物(II)からなる群より選択される少なくとも1種の窒素含有化合物
を含有するポジ型感放射線性組成物。
- 上記式(2)におけるR6、並びに上記式(3)におけるR9及びR10からなる群より選択される少なくとも1種の基が、tert-ブチル基、tert-アミル基、1-メチルシクロヘキシル基又は1-エチルシクロヘキシル基である請求項1に記載のポジ型感放射線性組成物。
- [C]窒素含有化合物の含有量が、[A]重合体100質量部に対して2質量部以上30質量部以下である請求項1に記載のポジ型感放射線性組成物。
- 表示素子用層間絶縁膜の形成に用いられる請求項1に記載のポジ型感放射線性組成物。
- (1)請求項4に記載のポジ型感放射線性組成物の塗膜を基板上に形成する工程、
(2)上記塗膜の少なくとも一部に放射線を照射する工程、
(3)上記放射線が照射された塗膜を現像する工程、及び
(4)上記現像された塗膜を加熱する工程
を有する表示素子用層間絶縁膜の形成方法。 - 請求項4に記載のポジ型感放射線性組成物から形成される表示素子用層間絶縁膜。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201180020623.XA CN102859439B (zh) | 2010-04-27 | 2011-04-18 | 正型感射线性组合物、显示元件用层间绝缘膜及其形成方法 |
JP2012512784A JP5761182B2 (ja) | 2010-04-27 | 2011-04-18 | ポジ型感放射線性組成物、表示素子用層間絶縁膜及びその形成方法 |
KR1020127026082A KR101396265B1 (ko) | 2010-04-27 | 2011-04-18 | 포지티브형 감방사선성 조성물, 표시 소자용 층간 절연막 및 그 형성 방법 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010-102771 | 2010-04-27 | ||
JP2010102771 | 2010-04-27 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011136074A1 true WO2011136074A1 (ja) | 2011-11-03 |
Family
ID=44861381
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/059574 WO2011136074A1 (ja) | 2010-04-27 | 2011-04-18 | ポジ型感放射線性組成物、表示素子用層間絶縁膜及びその形成方法 |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP5761182B2 (ja) |
KR (1) | KR101396265B1 (ja) |
CN (1) | CN102859439B (ja) |
TW (1) | TWI534543B (ja) |
WO (1) | WO2011136074A1 (ja) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012108403A (ja) * | 2010-11-19 | 2012-06-07 | Fujifilm Corp | 感光性樹脂組成物、硬化膜の形成方法、硬化膜、有機el表示装置、及び、液晶表示装置 |
JP2012112987A (ja) * | 2010-11-19 | 2012-06-14 | Fujifilm Corp | 感光性樹脂組成物、硬化膜の形成方法、硬化膜、有機el表示装置、及び、液晶表示装置 |
JP2013156563A (ja) * | 2012-01-31 | 2013-08-15 | Fujifilm Corp | 感光性樹脂組成物、硬化膜の形成方法、硬化膜、有機el表示装置及び液晶表示装置 |
CN103376649A (zh) * | 2012-04-25 | 2013-10-30 | Jsr株式会社 | 感放射线性组合物、显示元件用层间绝缘膜以及其形成方法 |
JP2014002316A (ja) * | 2012-06-20 | 2014-01-09 | Fujifilm Corp | 感光性樹脂組成物、硬化膜の製造方法、硬化膜、有機el表示装置および液晶表示装置 |
WO2014050633A1 (ja) * | 2012-09-26 | 2014-04-03 | 昭和電工株式会社 | 樹脂組成物、感光性樹脂組成物、及びカラーフィルター |
JP2014115386A (ja) * | 2012-12-07 | 2014-06-26 | Tokyo Ohka Kogyo Co Ltd | レジスト組成物及びレジストパターン形成方法 |
JP2015184325A (ja) * | 2014-03-20 | 2015-10-22 | 住友ベークライト株式会社 | 感光性樹脂組成物および電子装置 |
KR20160022766A (ko) | 2014-08-20 | 2016-03-02 | 후지필름 가부시키가이샤 | 감광성 수지 조성물, 경화막의 제조 방법, 경화막, 액정 표시 장치, 유기 일렉트로 루미네센스 표시 장치 및 터치 패널 |
WO2016076205A1 (ja) * | 2014-11-14 | 2016-05-19 | Jsr株式会社 | 感放射線性樹脂組成物、表示素子用硬化膜、表示素子用硬化膜の形成方法及び表示素子 |
TWI688826B (zh) * | 2015-04-01 | 2020-03-21 | 日商東麗股份有限公司 | 感光性著色樹脂組成物、耐熱性著色樹脂膜之製造方法及顯示裝置 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015022228A (ja) * | 2013-07-22 | 2015-02-02 | Jnc株式会社 | ポジ型感光性組成物 |
KR102654731B1 (ko) * | 2017-09-28 | 2024-04-03 | 제이에스알 가부시끼가이샤 | 감방사선성 수지 조성물 및 그의 용도 |
JP7180202B2 (ja) * | 2018-08-21 | 2022-11-30 | Jsr株式会社 | 硬化性組成物、硬化膜、表示素子及び硬化膜の形成方法 |
WO2020218062A1 (ja) * | 2019-04-24 | 2020-10-29 | Jsr株式会社 | 感光性樹脂組成物、レジストパターン膜の製造方法、およびメッキ造形物の製造方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001166476A (ja) * | 1999-12-10 | 2001-06-22 | Shin Etsu Chem Co Ltd | レジスト材料 |
JP2006113104A (ja) * | 2004-10-12 | 2006-04-27 | Fuji Photo Film Co Ltd | ポジ型レジスト組成物及びそれを用いたパターン形成方法 |
JP2009098673A (ja) * | 2007-09-28 | 2009-05-07 | Fujifilm Corp | ポジ型感光性樹脂組成物及びそれを用いた硬化膜形成方法 |
JP2009258723A (ja) * | 2008-03-28 | 2009-11-05 | Fujifilm Corp | ポジ型感光性樹脂組成物及びそれを用いた硬化膜形成方法 |
JP2010066503A (ja) * | 2008-09-10 | 2010-03-25 | Jsr Corp | 感放射線性樹脂組成物 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010065503A (ja) | 2008-09-12 | 2010-03-25 | Taiyo Kogyo Corp | 改質土 |
-
2011
- 2011-04-18 JP JP2012512784A patent/JP5761182B2/ja active Active
- 2011-04-18 WO PCT/JP2011/059574 patent/WO2011136074A1/ja active Application Filing
- 2011-04-18 KR KR1020127026082A patent/KR101396265B1/ko active IP Right Grant
- 2011-04-18 CN CN201180020623.XA patent/CN102859439B/zh active Active
- 2011-04-26 TW TW100114371A patent/TWI534543B/zh active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001166476A (ja) * | 1999-12-10 | 2001-06-22 | Shin Etsu Chem Co Ltd | レジスト材料 |
JP2006113104A (ja) * | 2004-10-12 | 2006-04-27 | Fuji Photo Film Co Ltd | ポジ型レジスト組成物及びそれを用いたパターン形成方法 |
JP2009098673A (ja) * | 2007-09-28 | 2009-05-07 | Fujifilm Corp | ポジ型感光性樹脂組成物及びそれを用いた硬化膜形成方法 |
JP2009258723A (ja) * | 2008-03-28 | 2009-11-05 | Fujifilm Corp | ポジ型感光性樹脂組成物及びそれを用いた硬化膜形成方法 |
JP2010066503A (ja) * | 2008-09-10 | 2010-03-25 | Jsr Corp | 感放射線性樹脂組成物 |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012108403A (ja) * | 2010-11-19 | 2012-06-07 | Fujifilm Corp | 感光性樹脂組成物、硬化膜の形成方法、硬化膜、有機el表示装置、及び、液晶表示装置 |
JP2012112987A (ja) * | 2010-11-19 | 2012-06-14 | Fujifilm Corp | 感光性樹脂組成物、硬化膜の形成方法、硬化膜、有機el表示装置、及び、液晶表示装置 |
JP2013156563A (ja) * | 2012-01-31 | 2013-08-15 | Fujifilm Corp | 感光性樹脂組成物、硬化膜の形成方法、硬化膜、有機el表示装置及び液晶表示装置 |
TWI561914B (en) * | 2012-01-31 | 2016-12-11 | Fujifilm Corp | Photosensitive resin composition, method of forming cured film, cured film, organic electroluminescent display device and liquid crystal display |
CN103376649A (zh) * | 2012-04-25 | 2013-10-30 | Jsr株式会社 | 感放射线性组合物、显示元件用层间绝缘膜以及其形成方法 |
JP2014002316A (ja) * | 2012-06-20 | 2014-01-09 | Fujifilm Corp | 感光性樹脂組成物、硬化膜の製造方法、硬化膜、有機el表示装置および液晶表示装置 |
WO2014050633A1 (ja) * | 2012-09-26 | 2014-04-03 | 昭和電工株式会社 | 樹脂組成物、感光性樹脂組成物、及びカラーフィルター |
JP2014115386A (ja) * | 2012-12-07 | 2014-06-26 | Tokyo Ohka Kogyo Co Ltd | レジスト組成物及びレジストパターン形成方法 |
JP2015184325A (ja) * | 2014-03-20 | 2015-10-22 | 住友ベークライト株式会社 | 感光性樹脂組成物および電子装置 |
KR20160022766A (ko) | 2014-08-20 | 2016-03-02 | 후지필름 가부시키가이샤 | 감광성 수지 조성물, 경화막의 제조 방법, 경화막, 액정 표시 장치, 유기 일렉트로 루미네센스 표시 장치 및 터치 패널 |
WO2016076205A1 (ja) * | 2014-11-14 | 2016-05-19 | Jsr株式会社 | 感放射線性樹脂組成物、表示素子用硬化膜、表示素子用硬化膜の形成方法及び表示素子 |
TWI688826B (zh) * | 2015-04-01 | 2020-03-21 | 日商東麗股份有限公司 | 感光性著色樹脂組成物、耐熱性著色樹脂膜之製造方法及顯示裝置 |
Also Published As
Publication number | Publication date |
---|---|
KR20120128708A (ko) | 2012-11-27 |
JPWO2011136074A1 (ja) | 2013-07-18 |
JP5761182B2 (ja) | 2015-08-12 |
CN102859439B (zh) | 2017-06-30 |
TW201207566A (en) | 2012-02-16 |
CN102859439A (zh) | 2013-01-02 |
TWI534543B (zh) | 2016-05-21 |
KR101396265B1 (ko) | 2014-05-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5761182B2 (ja) | ポジ型感放射線性組成物、表示素子用層間絶縁膜及びその形成方法 | |
JP5488176B2 (ja) | ポジ型感放射線性組成物、層間絶縁膜及びその形成方法 | |
JP5454321B2 (ja) | ポジ型感放射線性組成物、層間絶縁膜及びその形成方法 | |
JP5625460B2 (ja) | ポジ型感放射線性組成物、層間絶縁膜及びその形成方法 | |
JP5817717B2 (ja) | ポジ型感放射線性組成物、表示素子用層間絶縁膜及びその形成方法 | |
KR101430506B1 (ko) | 토출 노즐식 도포법용 포지티브형 감방사선성 조성물, 표시 소자용 층간 절연막 및 그 형성 방법 | |
JP4591625B1 (ja) | ポジ型感放射線性組成物、層間絶縁膜及びその形成方法 | |
JP5867169B2 (ja) | ポジ型感光性樹脂組成物、表示素子用層間絶縁膜及びその形成方法 | |
JP5949094B2 (ja) | ポジ型感放射線性組成物、表示素子用層間絶縁膜及びその形成方法 | |
JP6136491B2 (ja) | 感放射線性樹脂組成物、表示素子用層間絶縁膜及びその形成方法 | |
JP5630068B2 (ja) | ポジ型感放射線性組成物、層間絶縁膜及びその形成方法 | |
JP5510347B2 (ja) | ポジ型感放射線性組成物、層間絶縁膜及びその形成方法 | |
JP2011191344A (ja) | ポジ型感放射線性樹脂組成物、層間絶縁膜及びその形成方法 | |
JP5772181B2 (ja) | 感放射線性樹脂組成物、表示素子用層間絶縁膜及びその形成方法 | |
JP5655529B2 (ja) | 感放射線性樹脂組成物、層間絶縁膜及び層間絶縁膜の形成方法 | |
JP5772184B2 (ja) | 感放射線性樹脂組成物、表示素子用層間絶縁膜及びその形成方法 | |
JP4581952B2 (ja) | 感放射線性樹脂組成物ならびに層間絶縁膜およびマイクロレンズの形成 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180020623.X Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11774857 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012512784 Country of ref document: JP |
|
ENP | Entry into the national phase |
Ref document number: 20127026082 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 11774857 Country of ref document: EP Kind code of ref document: A1 |