Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/022—Quinonediazides
  • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
  • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
  • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/075—Silicon-containing compounds
  • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds

Definitions

• the present invention relates to a photosensitive resin composition and a display device.
• An active matrix drive type liquid crystal display device provided with a thin film transistor (TFT: Thin Film Transistor), an active matrix drive type organic EL display device provided with an organic EL (Electro-Luminescence) element and a thin film transistor connected thereto.
• TFT Thin Film Transistor
• This display device is provided with a patterned electrode protective film, planarization film, insulating film, and the like.
• a photosensitive resin composition is generally used as a material for forming these films, and among them, a material having a small number of steps for obtaining a predetermined pattern shape and excellent in transparency is widely used.
• the electrode protective film, the planarizing film, and the insulating film are required to have various characteristics necessary for the display device. Specifically, it has excellent process resistance such as heat resistance, solvent resistance, reflow resistance and metal sputtering resistance, good adhesion to the substrate, and various process conditions according to the purpose of use. Examples thereof include a wide process margin capable of forming a pattern, high sensitivity to light, high transparency, and little film thickness unevenness after development. For this reason, the photosensitive resin composition containing a naphthoquinone diazide compound has been used widely conventionally.
• the touch panel system includes a resistive film system, a capacitive system, an ultrasonic system, an optical system, an electromagnetic induction system, etc., but many manufacturers adopt the capacitive system in terms of performance.
• a wiring made of a transparent conductive film is formed on a substrate, and an interlayer insulating film is provided to prevent conduction between the wirings.
• This interlayer insulating film is required to have high hardness.
• there is an in-cell touch panel in which a touch panel mechanism is incorporated in the liquid crystal display element, but in this case, higher hardness is required for the electrode protective film.
• glass substrates are used in conventional display devices, but in recent years, display devices have been required to have high durability in portable devices in addition to lightening, thinning, upsizing, curved display, and the like. It is growing. Therefore, practical application of a resin substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and polyimide instead of a glass substrate has been studied.
• the electrode protective film, the planarizing film, and the insulating film are required to have higher hardness in order to increase mechanical strength.
• the photosensitive resin composition includes a negative type that is cured by exposure and has low solubility in a developer, and a positive type that has high solubility in a developer by exposure.
• Many of the negative types have problems in terms of handling and environment because an organic solvent is used as a developer. Further, since the solvent swells the film during development, there is a problem that it is difficult to form fine wiring.
• the positive type is advantageous over the negative type in terms of the above points, but there is a problem that it is difficult to achieve high hardness as compared with the negative type in which curing proceeds by exposure.
• Patent Document 1 at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and at least one selected from the group consisting of an oxiranyl group-containing unsaturated compound and an oxetanyl group-containing unsaturated compound.
• a positive radiation sensitive resin composition containing a copolymer of an unsaturated mixture containing a seed, a 1,2-quinonediazide compound and a silsesquioxane having an aryl group having 6 to 15 carbon atoms is described. Has been. According to this composition, it is considered that a patterned thin film suitable for an interlayer insulating film or the like can be formed. However, there is a problem that a crosslinking reaction is slow and it is difficult to obtain reflow resistance.
• Patent Document 2 discloses an acrylic copolymer obtained by copolymerizing at least one of a silsesquioxane polyhedral oligomer-containing unsaturated compound, an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, an epoxy group-containing unsaturated compound, and an olefinic unsaturated compound.
• a photosensitive resin composition comprising a copolymer and a 1,2-quinonediazide compound is disclosed. This composition is excellent in flatness after development, sensitivity, resolution, heat resistance and transparency, and is considered suitable as an insulating film for a display device.
• the silsesquioxane portion is not crosslinked in the polymer after copolymerization, and there is a concern that the hardness of the resulting film is insufficient.
• Patent Document 3 discloses a photosensitive resin composition suitable as an insulating film for a display device.
• the composition comprises an ethylenically unsaturated group-containing compound and a photopolymerization initiator, a cationic polymerizable compound such as a glycidyl ether compound and a photocationic polymerization initiator, and at least one compound selected from quinonediazide compounds, diazonium compounds and azide compounds. And at least one photosensitive organic component selected from the group consisting of inorganic particles and cage silsesquioxane.
• this configuration has a problem that the resolution is lowered by the added inorganic particles in order to maintain the shape retention during firing.
• the via diameter retention ratio after firing a via pattern having a hole diameter of 20 ⁇ m is 65%.
• an object of the present invention is to provide a film having high hardness required for various display device materials in recent years while satisfying the basic required performance for the electrode protective film, the planarizing film and the insulating film by curing. It is in providing the positive photosensitive resin composition obtained.
• Another object of the present invention is to provide a display device having excellent mechanical strength.
• the photosensitive resin composition of the present invention is (A): an alkali-soluble acrylic polymer having a side chain having an unsaturated bond at the terminal; (B): a quinonediazide compound, (C): Silsesquioxane, (D): Contains a solvent.
• the number average molecular weight of the alkali-soluble acrylic polymer (A) is preferably 2,000 to 50,000 in terms of polystyrene.
• the end of the side chain is preferably an acryloyl group, a methacryloyl group, a vinylphenyl group or an isopropenylphenyl group.
• the quinonediazide compound (B) is preferably contained in an amount of 5 to 100 parts by mass with respect to 100 parts by mass of the alkali-soluble acrylic polymer (A).
• the silsesquioxane (C) is preferably contained in an amount of 5 to 100 parts by mass with respect to 100 parts by mass of the alkali-soluble acrylic polymer (A).
• the photosensitive resin composition of the present invention further contains (E) a thermal acid generator in an amount of 0.1 to 30 parts by mass with respect to 100 parts by mass of the alkali-soluble acrylic polymer of (A). Is preferred.
• the photosensitive resin composition of the present invention is 1 to 40 parts by mass of (F) a compound having two or more vinyl groups directly bonded to a benzene ring, based on 100 parts by mass of the alkali-soluble acrylic polymer (A). It is preferable to contain in the quantity used.
• the photosensitive resin composition of the present invention 0.5 to 40 parts by mass of (G) an acrylic polymer having an epoxy group in the side chain with respect to 100 parts by mass of the alkali-soluble acrylic polymer (A). It is preferable to contain in the quantity.
• the photosensitive resin composition of the present invention preferably further contains (H) an adhesion promoter in an amount of 20 parts by mass or less with respect to 100 parts by mass of the alkali-soluble acrylic polymer (A).
• the photosensitive resin composition of the present invention preferably further contains (I) a surfactant in an amount of 1.0 part by mass or less with respect to 100 parts by mass of the photosensitive resin composition.
• the display device of the present invention is characterized by having a film formed by curing the photosensitive resin composition of the present invention.
• a positive-type photosensitive resin composition that, when cured, satisfies basic performance requirements for an electrode protective film, a planarizing film, and an insulating film, and forms a film with high hardness. Further, by providing a cured film obtained from the photosensitive resin composition, a high-quality display device having excellent mechanical strength is provided.
• the positive photosensitive resin composition of the present invention comprises the following component (A), component (B), component (C) and solvent (D).
• component alkali-soluble acrylic polymer having a side chain having an unsaturated bond at the terminal
• component quinonediazide compound
• component silsesquioxane
• the photosensitive resin composition of the present invention includes, as desired, other components, (E) component: thermal acid generator described later, (F) component: a compound having two or more vinyl groups directly connected to the benzene ring, (G) Component: An acrylic polymer having an epoxy group in the side chain, (H) component; adhesion promoter and (I) component: surfactant, and other components described later can also be contained. Details of each component will be described below.
• the component (A) is an alkali-soluble acrylic polymer having a side chain having an unsaturated bond at the terminal.
• the alkali-soluble acrylic polymer is an acrylic polymer having a polystyrene-equivalent number average molecular weight (hereinafter referred to as a number average molecular weight) of 2,000 to 50,000.
• the acrylic polymer refers to a polymer obtained by homopolymerizing or copolymerizing monomers having an unsaturated double bond such as acrylic ester, methacrylic ester and styrene.
• the acrylic polymer as the component (A) may be an acrylic polymer having such a structure, and is not particularly limited with respect to the main chain skeleton and side chain type of the polymer constituting the acrylic polymer.
• the number average molecular weight of the acrylic polymer of the component (A) is excessively larger than 50,000, the planarization performance against the step may be deteriorated.
• the number average molecular weight is less than 2,000 and is too small, curing may be insufficient during thermal curing and solvent resistance may be reduced. Accordingly, those having a number average molecular weight in the range of 2,000 to 50,000 are more preferable.
• the (A) component acrylic polymer preferably has 3 to 16 carbon atoms and has a side chain having an unsaturated bond at the terminal (hereinafter referred to as a specific side chain). . In addition, it has terminal unsaturated bonds in such an amount that the acrylic polymer of component (A) is 200 to 1,300 g equivalent per 1 mol equivalent of terminal unsaturated bonds contained in the specific side chain. preferable.
• the specific side chain one having a structure represented by the following formula (1) is particularly preferable.
• the specific side chain represented by the formula (1) binds to the ester bond portion of the acrylic polymer as shown in the formula (1-1).
• R 1 has 1 to 14 carbon atoms and is an organic group selected from the group consisting of an aliphatic group, an aliphatic group having a cyclic structure, and an aromatic group, or from this group An organic group comprising a combination of a plurality of organic groups selected.
• R 1 may contain an ester bond, an ether bond, an amide bond, a urethane bond, or the like.
• R 1 include the following formulas (A-1) to (A-11).
• the ** side is bonded to the ester bond portion of the acrylic polymer, and the * side is bonded to the carbon atom having a double bond in the formula (1) (the carbon atom to which R 2 is bonded).
• R 2 represents a hydrogen atom or a methyl group, and R 2 is more preferably a hydrogen atom.
• the terminal of the specific side chain represented by the formula (1) is preferably an acryloyl group, a methacryloyl group, a vinylphenyl group or an isopropenylphenyl group.
• R 1 is represented by the formula (A-1) to the formula (A ⁇ 3) and a specific side chain represented by formula (A-7) to formula (A-11) is preferable.
• the method for obtaining the acrylic polymer having the specific side chain as described above is not particularly limited.
• an acrylic polymer having a specific functional group described later is generated in advance by a polymerization method such as radical polymerization.
• a specific compound a compound having an unsaturated bond at the terminal (hereinafter referred to as a specific compound) to generate a specific side chain.
• a specific compound a compound having an unsaturated bond at the terminal
• the specific functional group means a functional group such as a carboxyl group, a glycidyl group, a hydroxy group, an amino group having active hydrogen, a phenolic hydroxy group or an isocyanate group, or a plurality of types of functional groups selected from these functional groups.
• Specific compounds include, for example, glycidyl acrylate, glycidyl methacrylate, isocyanate ethyl acrylate, isocyanate ethyl methacrylate, acrylic acid chloride, methacrylic acid chloride, acrylic acid, methacrylic acid, m-tetramethylxylene diisocyanate, chlorostyrene, bromostyrene, Examples include allyl glycidyl ether, vinyl ethylene oxide, vinyl cyclohexene oxide or ⁇ , ⁇ -dimethyl-m-isopropenyl benzyl isocyanate.
• an example of a preferable structure is an acrylic polymer having a structural unit represented by the formula (2).
• R 1 has the same meaning as defined in the above formula (1), that is, an aliphatic group having 1 to 14 carbon atoms and containing an aliphatic group or a cyclic structure. And an organic group selected from the group consisting of aromatic groups or a combination of a plurality of organic groups selected from this group. R 1 may contain a bond such as an ester bond, an ether bond, an amide bond or a urethane bond.
• R 3 represents a hydrogen atom or a methyl group.
• the preferred combination of the specific functional group and the functional group of the specific compound that is involved in the reaction is a carboxyl group and a glycidyl group (epoxy group), a hydroxy group and an isocyanate.
• a more preferable combination is a carboxyl group and glycidyl methacrylate, or a hydroxy group and isocyanate ethyl methacrylate.
• the acrylic polymer having the specific functional group is a monomer having a functional group (specific functional group) for reacting with the specific compound, that is, carboxyl group, glycidyl group, hydroxy group.
• the monomer having a specific functional group used for the polymerization may be used alone, or a combination of plural types of monomers as long as the specific functional group does not react with each other during the polymerization. Good.
• Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, and N- (carboxyphenyl).
• Examples of the monomer having a glycidyl group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2-epoxy-5-hexene and 1,7. -Octadiene monoepoxide.
• Examples of the monomer having a hydroxy group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3- Dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2- (acryloyloxy) ethyl ester, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, poly (Ethylene glycol) ethyl ether methacrylate, 5-acryloyl Carboxymethyl-6-hydroxy-norbornene-2-carboxylic-6-lactone and 5-methacryloyloxy such acryloyloxy-6-hydroxy-norbornene-2-carboxylic
• Examples of the monomer having an amino group having active hydrogen include 2-aminoethyl acrylate and 2-aminomethyl methacrylate.
• Examples of the monomer having a phenolic hydroxy group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide and N- (hydroxyphenyl) maleimide.
• Examples of the monomer having an isocyanate group include acryloylethyl isocyanate, methacryloylethyl isocyanate, and m-tetramethylxylene isocyanate.
• a monomer having a non-reactive functional group that can be copolymerized with a monomer having a specific functional group can be used in combination.
• Examples of the monomer having a non-reactive functional group include acrylic ester compounds, methacrylic ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.
• acrylic ester compounds methacrylic ester compounds
• maleimide compounds acrylonitrile
• maleic anhydride maleic anhydride
• vinyl compounds vinyl compounds.
• acrylic ester compound examples include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl.
• methacrylic acid ester compound examples include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl.
• vinyl compound examples include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl biphenyl, vinyl carbazole, 2-hydroxyethyl vinyl ether, phenyl vinyl ether and propyl vinyl ether.
• styrene compound examples include styrene, methylstyrene, chlorostyrene, and bromostyrene.
• maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
• the method for obtaining an acrylic polymer having a specific functional group is not particularly limited.
• a solvent in which a monomer having the specific functional group, a monomer having a non-reactive functional group capable of copolymerization, if desired, and a polymerization initiator, if desired, may coexist It can be obtained by a polymerization reaction at a temperature of 110 ° C.
• the solvent used at this time is not particularly limited as long as it dissolves the monomer and polymerization initiator involved in the reaction. Specific examples include those described in (D) Solvent below.
• the acrylic polymer having a specific functional group obtained as described above is usually in a solution state dissolved in a solvent.
• a specific compound is reacted with the obtained acrylic polymer having a specific functional group to obtain an acrylic polymer (hereinafter referred to as a specific copolymer) as component (A).
• a specific copolymer an acrylic polymer (hereinafter referred to as a specific copolymer) as component (A).
• the polymer in a solution state is reacted as it is with a specific compound to obtain a specific copolymer.
• Coalescence can be obtained.
• the solvent used at this time is not particularly limited as long as it dissolves the monomer constituting the specific copolymer and the specific copolymer. Specific examples include those described in (D) Solvent below.
• the specific copolymer obtained as described above is usually in a solution state dissolved in a solvent.
• dicarboxylic acid anhydrides examples include phthalic acid anhydride, trimellitic acid anhydride, naphthalene dicarboxylic acid anhydride, 1,2-cyclohexanedicarboxylic acid anhydride, 4-methyl-1,2-cyclohexanedicarboxylic acid.
• the solution of the specific copolymer is added under stirring such as diethyl ether or water to reprecipitate, and after the generated precipitate is filtered and washed, it is dried at normal temperature or reduced pressure at normal temperature or under heat, It can be set as the powder of a specific copolymer.
• the polymerization initiator and unreacted monomer coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer is obtained.
• movement what is necessary is just to redissolve the obtained powder in a solvent and to repeat said operation.
• the powder of the specific copolymer may be used as it is, or the powder of the specific copolymer may be redissolved in a solvent (D) described later and used in a solution state.
• the acrylic polymer of component (A) may be a mixture of a plurality of types of specific copolymers.
• the quinonediazide compound of the component (B) is preferably a quinonediazide compound having either a hydroxy group or an amino group, or both a hydroxy group and an amino group.
• a quinonediazide compound can be obtained, for example, by reacting a 1,2-quinonediazide compound with a compound having a hydroxy group and / or a compound having an amino group.
• the 1,2-quinonediazide compound is preferably 1,2-quinonediazidesulfonic acid such as 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride, 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride, etc.
• a compound or the like is preferably used. More preferably, 10 to 100 mol%, particularly preferably 20 to 95 mol% of a hydroxy group or an amino group (the total amount of both having a hydroxy group and an amino group) is 1,
• a quinonediazide compound esterified or amidated with a 2-quinonediazidesulfonic acid compound is used.
• the said quinonediazide compound can be used individually or in combination of 2 or more types.
• Examples of the compound having a hydroxy group to be reacted with a 1,2-quinonediazide (sulfonic acid) compound include, for example, phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, methyl gallate, gallic Acid ethyl, 1,3,3-tris (4-hydroxyphenyl) butane, 4,4-isopropylidene diphenol, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) ) Cyclohexane, 4,4′-dihydroxyphenylsulfone, 4,4-hexafluoroisopropylidenediphenol, 4,4 ′, 4 ′′ -trishydroxyphenylethane, 1,1,1-trishydroxyphenylethane, 4, 4 ′-[1- [4- [1- (4-hydroxy Phenyl) -1-methylethyl] phenyl] ethy
• Examples of the compound containing an amino group to be reacted with a 1,2-quinonediazide (sulfonic acid) compound include aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminobiphenyl, o Examples thereof include anilines such as -phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane and 4,4'-diaminodiphenyl ether, or aminocyclohexane.
• examples of the compound containing both a hydroxy group and an amino group to be reacted with a 1,2-quinonediazide (sulfonic acid) compound include o-aminophenol, m-aminophenol, p-aminophenol, and 4-aminoresorcinol.
• the content of the component (B) in the positive photosensitive resin composition of the present invention is preferably 5 to 100 parts by mass, more preferably 8 to 50 parts by mass, and more preferably 100 parts by mass of the component (A).
• the amount is preferably 10 to 40 parts by mass.
• the amount is less than 5 parts by mass, the difference in dissolution rate between the exposed portion and the unexposed portion of the positive photosensitive resin composition in the developer is reduced, and patterning by development may be difficult.
• the amount exceeds 100 parts by mass the 1,2-quinonediazide compound is not sufficiently decomposed by exposure in a short time, so that the sensitivity is lowered, or the component (B) absorbs light and the transparency of the cured film. May be reduced.
• the component (C) is silsesquioxane, specifically, a polysiloxane represented by [(RSiO 3/2 ) n ] (wherein R represents a monovalent organic group).
• the structure of the component (C) may be any of a random structure, a ladder structure, a complete cage structure or an incomplete cage structure, and is not particularly limited.
• the (C) component can use silsesquioxane which consists of single or 2 types or more of combinations.
• Silsesquioxane is usually produced by a sol-gel method in which trialkoxysilane is hydrolyzed. By changing the type of trialkoxysilane used as a raw material, silsesquioxanes having different properties can be obtained.
• trialkoxysilane examples include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2- Aminoethyl) trimethoxysilane, 3-ureidopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane,
• n- hexyl trimethoxy silane and n- hexyl triethoxy silane are used alone or in combination of two or more.
• the content of the component (C) in the positive photosensitive resin composition of the present invention is preferably 5 to 100 parts by mass, more preferably 10 to 80 parts by mass, and more preferably 100 parts by mass of the component (A).
• the amount is preferably 15 to 60 parts by mass. When the amount is less than 5 parts by mass, the hardness of the cured film formed using the positive photosensitive resin composition may be low, and when it is more than 100 parts by mass, tackiness occurs in the coating film after pre-baking. There is a case.
• ethylene glycol monomethyl ether for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene Glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2- Pentanone, 2-heptanone, ⁇ -butyrolactone, 2-hydro Ethyl cypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate,
• solvents may be used alone or in combination of two or more.
• D As the solvent, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate and butyl lactate have good coating properties and safety. It is preferable from the viewpoint of high. These are generally used as solvents for photoresist materials.
• the positive photosensitive resin composition of the present invention is constituted by dissolving the component (A), the component (B) and the component (C) in the solvent (D). It is also possible to contain each component of (E) thru
• the component (E) is a thermal acid generator, and is a compound that generates an acid by thermal decomposition during post-baking, specifically, a compound that generates an acid by thermal decomposition at 150 ° C. to 250 ° C. It is not limited.
• Examples of such compounds include bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2,3-phenylenetris ( Methyl sulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morphonium salt, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonic acid Butyl ester, p-toluenesulfonic acid isobutyl ester, p-toluenesulfonic acid phenethyl ester, cyanomethyl p-tolu
• thermal acid generator of component (E) examples include compounds represented by the following formulas (3) to (70).
• triphenylsulfonium salt-based thermal acid generators are preferred because of their high transparency.
• the content of the component (E) in the positive photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts per 100 parts by mass of the component (A). Part by mass, more preferably 1 to 10 parts by mass.
• the amount is less than 0.1 parts by mass, the thermosetting speed is slow, and the pencil hardness may decrease.
• it exceeds 30 parts by mass partial curing may occur during pre-baking, and a residual film may be generated in the exposed area, or the storage stability of the solution may be reduced.
• the component (F) is a compound having two or more vinyl groups directly connected to the benzene ring, and the compound may be a compound having two or more vinyl groups on the same benzene ring, or 2 In the case of a compound containing two or more benzene rings, any of compounds having a total of two or more vinyl groups bonded to different benzene rings may be used.
• the thermosetting property with the component (A) can be improved and the hardness can be improved.
• the compound having two or more vinyl groups directly bonded to the benzene ring are o-divinylbenzene, m-divinylbenzene, p-divinylbenzene, 4,4′-divinylbiphenyl, Tris- (4-vinylphenyl) methane. And 4,4′-oxybis (vinylbenzene).
• the component (F) compounds having two or more vinyl groups directly bonded to a benzene ring can be used alone or in combination of two or more.
• the content of the component (F) in the positive photosensitive resin composition of the present invention is preferably 1 to 40 parts by weight, more preferably 3 to 30 parts by weight, and more preferably 100 parts by weight of the component (A). Preferably it is 5-20 mass parts.
• the amount is less than 1 part by mass, the pencil hardness may decrease.
• tuck may generate
• a component is an acrylic polymer which has an epoxy group in a side chain.
• an acrylic polymer having an epoxy group in the side chain By adding an acrylic polymer having an epoxy group in the side chain to the photosensitive resin composition of the present invention, it is possible to suppress film loss in unexposed portions during development.
• the acrylic copolymer of (G) component can use the mixture of the acrylic copolymer which has multiple types of epoxy groups in a side chain.
• the acrylic polymer as the component (G) can be obtained by the same polymerization method as the component (A) using an epoxy group-containing monomer such as glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, and epoxycyclohexylmethyl methacrylate. Its number average molecular weight is 2,000 to 25,000.
• the acrylic polymer as the component (G) can be obtained by using a single monomer or a plurality of monomers having an epoxy group, and a monomer copolymerizable with the monomer having an epoxy group may be used in combination.
• the copolymerizable monomer is not particularly limited as long as it does not react with the epoxy group during the polymerization, but a monomer having no carboxyl group or amino group is preferable.
• the proportion of the monomer having an epoxy group is preferably 20 mol% or more.
• copolymerizable monomers examples include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.
• acrylic acid ester compounds methacrylic acid ester compounds
• maleimide compounds acrylonitrile
• maleic anhydride maleic anhydride
• styrene compounds vinyl compounds.
• vinyl compounds vinyl compounds.
• acrylic ester compound examples include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl.
• methacrylic acid ester compound examples include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl.
• vinyl compound examples include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl biphenyl, vinyl carbazole, 2-hydroxyethyl vinyl ether, phenyl vinyl ether and propyl vinyl ether.
• styrene compound examples include styrene, methylstyrene, chlorostyrene, and bromostyrene.
• maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
• the method for obtaining an acrylic polymer having an epoxy group as the component (G) is not particularly limited.
• it can be obtained by carrying out a polymerization reaction at a temperature of 50 to 110 ° C. in a solvent in which a monomer having an epoxy group, another copolymerizable monomer if necessary, and a polymerization initiator if necessary coexist. It is done.
• the solvent used in that case will not be specifically limited if it dissolves the monomer and polymerization initiator which are concerned in reaction. Specific examples include the solvents described in the above (D) solvent.
• the acrylic polymer having an epoxy group thus obtained is usually in a solution state dissolved in a solvent.
• the solution of the acrylic copolymer of component (G) obtained as described above was added under stirring such as diethyl ether or water for reprecipitation, and the produced precipitate was filtered and washed, and then at atmospheric pressure. Or it can be set as the powder of the acrylic copolymer of (G) component by drying at normal temperature or heat-reducing under pressure reduction. By such an operation, the polymerization initiator and unreacted monomer coexisting with the (G) component acrylic copolymer can be removed. As a result, the purified (G) component acrylic copolymer powder Is obtained. If sufficient purification cannot be achieved by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated. In the present invention, the acrylic copolymer powder of component (G) may be used as it is, or (D) the acrylic copolymer powder of component (G) is re-dissolved in a solvent, You may use it as a state.
• the content of the component (G) in the positive photosensitive resin composition of the present invention is preferably 0.5 to 40 parts by mass, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the component (A). More preferably, it is 3 to 20 parts by mass.
• the amount is less than 0.5 parts by mass, the unexposed part may be reduced in film thickness during development.
• it exceeds 40 parts by mass the exposed area may be poorly developed or the sensitivity may be greatly reduced.
• the component (H) is an adhesion promoter.
• the adhesion promoter By using the adhesion promoter, the adhesion between the cured film of the positive photosensitive resin composition and the substrate after development can be improved.
• adhesion promoters include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane, and vinyltrichlorosilane; trimethylmethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, dimethylvinylethoxysilane , Diphenyldimethoxysilane, phenyltriethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -methacryloxypropyltriethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ - (N-piperidinyl) propyltriethoxysilane and ⁇ -Alkoxysilanes such as ureidopropyltriethoxysilane; hexamethyldisilazan
• adhesion promoter commercially available compounds can be used, and these are easily available from, for example, Shin-Etsu Chemical Co., Ltd., MOMENTIVE, or Toray Dow Corning Co., Ltd.
• a silane coupling agent and marketed may be obtained and used.
• Specific examples of such products include Z-6011, 6020, 6023, 6026, 6050, 6094, 6610, 6883, 6675, 6676, 6040, 6041, 6042, 6043, 6044, 6920 manufactured by Toray Dow Corning Silicone.
• the addition amount of the component (H) in the positive photosensitive resin composition of the present embodiment is 20 parts by mass or less, preferably 0.01 to 10 parts by mass, more preferably 100 parts by mass of the component (A). Is 0.5 to 10 parts by mass. When it is used in an amount of 20 parts by mass or more, the heat resistance of the coating film may be lowered.
• the component (I) is a surfactant. By using the surfactant, the coating property of the positive photosensitive resin composition can be improved.
• a component can be used individually or in combination of 2 or more types.
• the surfactant which is the component (I) of the present embodiment is not particularly limited as long as it does not impair the effects of the present invention.
• a fluorine-type surfactant, a silicone-type surfactant, a nonionic surfactant, etc. are mentioned.
• This type of surfactant is readily available from, for example, Sumitomo 3M Co., Ltd., DIC Corporation, Asahi Glass Co., Ltd. or the like. Specific examples thereof include F-top EF301, EF303, EF352 (above, manufactured by Tochem Products Co., Ltd.
• the content thereof is usually 1.0 part by mass in 100 parts by mass of the positive photosensitive resin composition. Or less, preferably 0.5 parts by mass or less.
• the amount of the surfactant as component (I) is set to an amount exceeding 1.0 part by mass, the coating property improvement effect expected in response to the increase in the content cannot be obtained. In other words, an inefficient use method will be performed.
• the positive photosensitive resin composition of the present invention can contain the components (E) to (I). However, as long as the effects of the present invention are not impaired, the positive photosensitive resin composition can be used as necessary. Other components can also be contained. Examples of other components include additives such as rheology modifiers, pigments, dyes, storage stabilizers, antifoaming agents, or dissolution accelerators such as polyphenols and polycarboxylic acids.
• the positive photosensitive resin composition of the present invention is (A) an alkali-soluble acrylic polymer having a side chain having an unsaturated bond at the end as a component; (B) a quinonediazide compound as a component; (C) Silsesquioxane as a component, (D) Dissolved in a solvent.
• This positive type photosensitive resin composition is further, if desired, (E) a thermal acid generator as a component, (F) a compound having two or more vinyl groups directly connected to the benzene ring as a component; (G) an acrylic polymer having an epoxy group in the side chain as a component, (H) Adhesion promoter as component, As the component (I), one or more of the above-mentioned additives can be contained as a surfactant and the other components.
• Preferred examples of the positive photosensitive resin composition of the present invention are as follows. [1] Based on 100 parts by mass of component (A), 5 to 100 parts by mass of component (B), 5 to 100 parts by mass of component (C), which are positively dissolved in solvent (D) Type photosensitive resin composition. [2] The positive photosensitive resin composition further comprising 0.1 to 30 parts by mass of the component (E) based on 100 parts by mass of the component (A) in the composition of the above [1]. [3] A positive photosensitive resin composition further comprising 1 to 40 parts by mass of the component (F) based on 100 parts by mass of the component (A) in the composition of the above [1] or [2].
• a positive photosensitive resin further containing 0.5 to 40 parts by mass of component (G) in the composition according to [1], [2] or [3], based on 100 parts by mass of component (A).
• Composition. [5] In the composition according to [1], [2], [3] or [4], the composition further comprises (H) component in an amount of 20 parts by mass or less based on 100 parts by mass of component (A).
• Type photosensitive resin composition. [6] In the composition of [1], [2], [3], [4] or [5] above, the component (I) is further added in an amount of 1.0 mass relative to 100 mass parts of the positive photosensitive resin composition.
• a positive photosensitive resin composition contained in an amount of at most parts.
• the ratio of the solid content in the positive photosensitive resin composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent. For example, it is 1 to 80% by mass, and for example 5 to 60% by mass, or 10 to 50% by mass.
• solid content means what remove
• the method for preparing the positive photosensitive resin composition of the present invention is not particularly limited.
• (A) component (acrylic polymer) is dissolved in (D) solvent, and (B) component (quinonediazide compound) and (C) component (silsesquioxane) are mixed in this solution at a predetermined ratio. And a uniform solution method.
• component (E) thermo acid generator
• component (F) compound having two or more vinyl groups directly connected to the benzene ring
• component (G) (Acrylic polymer having epoxy group in side chain),
• (H) component (adhesion promoter), (I) component (surfactant), and other components are added and mixed.
• a solution of a specific copolymer obtained by a polymerization reaction in a solvent can be used as it is, and in this case, the solution of this component (A)
• a solvent may be further added for the purpose of adjusting the concentration.
• the (D) solvent used in the process of forming the specific copolymer and the (D) solvent used for concentration adjustment when preparing the positive photosensitive resin composition may be the same, It may be different.
• the prepared positive photosensitive resin composition in a solution state is preferably used after being filtered using a filter having a pore diameter of about 0.2 ⁇ m.
• a semiconductor substrate such as a silicon substrate or a silicon nitride substrate is prepared.
• a glass substrate or a quartz substrate may be used instead of the semiconductor substrate.
• a silicon dioxide film, an ITO (Indium Tin Oxide) film, or a metal film such as aluminum, molybdenum, or chromium may be formed on the substrate.
• the positive photosensitive resin composition of the present invention is applied on the prepared semiconductor substrate by spin coating, flow coating, roll coating, slit coating, spin coating following the slit, or ink jet coating. Subsequently, a coating film can be formed by predrying with a hot plate or oven. Furthermore, a heat treatment is performed on the coating film.
• a heating temperature and a heating time appropriately selected from the range of a temperature of 70 ° C. to 160 ° C. and a time of 0.3 to 60 minutes are employed.
• the heating temperature and the heating time are preferably 80 ° C. to 140 ° C. and 0.5 to 10 minutes, respectively.
• the film obtained above is irradiated with light such as ultraviolet rays through a mask having a predetermined pattern. Subsequently, by developing with an alkaline developer, the exposed portion is washed out, and a relief pattern having a sharp end surface is obtained.
• alkaline developer examples include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline, and ethanolamine. And aqueous amine solutions such as propylamine and ethylenediamine. A surfactant or the like may be added to these developers.
• alkali metal hydroxides such as potassium hydroxide and sodium hydroxide
• quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline
• ethanolamine aqueous amine solutions
• propylamine and ethylenediamine ethylenediamine.
• a surfactant or the like may be added to these developers.
• tetraethylammonium hydroxide 0.1 to 2.38 mass% aqueous solution is generally used as a photoresist developer. Even in a film obtained from the positive photosensitive resin composition of the present invention, this alkaline developer can be used for good development without causing problems such as swelling.
• any of a liquid piling method, a dipping method, a rocking dipping method, and the like can be used.
• the development time is usually 15 to 180 seconds.
• the film that has been developed is washed with running water, for example, for 20 to 90 seconds. Subsequently, moisture on the substrate is removed by air drying using compressed air or compressed nitrogen or by spinning to obtain a patterned film.
• ⁇ Post bake for thermosetting the patterned film Specifically, heating is performed using a hot plate or an oven.
• the post-bake is generally processed at a heating temperature selected from the range of 140 ° C. to 250 ° C. for 5 to 30 minutes when on a hot plate and 30 to 90 minutes when in an oven. The method is taken.
• a cured film having a good relief pattern excellent in heat resistance, transparency, planarization, low water absorption, chemical resistance, and the like can be obtained.
• This cured film is characterized by high hardness, excellent heat resistance and solvent resistance, and high transparency. Therefore, it can be suitably used for various films in liquid crystal displays and organic EL displays, for example, interlayer insulating films, protective films, insulating films and the like. Further, it is also suitably used in applications such as an array flattening film for TFT type liquid crystal elements.
• the present invention is also directed to a display device having the cured film.
• Examples 1 to 7 and Comparative Examples 1 to 3 According to the composition shown in the following Table 1, the component (A) is mixed with the component (B) and the component (C), further the solvent (D) and the components (E) to (I) at a predetermined ratio, The mixture was stirred for 3 hours to obtain a uniform solution, thereby preparing positive photosensitive resin compositions of Examples and Comparative Examples.
• TMAH tetramethylammonium hydroxide
• Table 2 shows the results of the above evaluation.
• the positive photosensitive resin compositions of Examples 1 to 7 are all highly sensitive, the film loss in the unexposed area is very small, and no tack after prebaking is observed. It was. Furthermore, the result was that the pencil hardness after curing was as high as 2H or more, excellent in light transmittance, adhesion to ITO, solvent resistance, and excellent pattern formability.
• Comparative Example 1 the result that the sensitivity, transmittance, adhesion and solvent resistance were good was obtained, but the pencil hardness was as low as B.
• Comparative Example 2 tack entered after prebaking and it did not result in subsequent evaluation.
• Comparative Example 3 although the results of good sensitivity, transmittance and adhesion were obtained, the pencil hardness was as low as H and the solvent resistance was insufficient.
• the positive photosensitive resin composition according to the present invention is suitable as a material for forming a protective film, a planarizing film, an insulating film, etc. in a display device including a thin film transistor (TFT) type liquid crystal display element or an organic EL element. It is suitable for a display device provided with a touch panel and a display device using a resin substrate. For example, it is suitable as a material for forming interlayer insulation films for TFT liquid crystal elements, protective films for color filters, array planarization films, interlayer insulation films for capacitive touch panels, insulation films for organic EL elements, and the like. It is also suitable as various electronic materials such as lens materials.
• TFT thin film transistor

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• 2011
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