TWI616722B - Negative photosensitive organic-inorganic hybrid insulator - Google Patents

Abstract

The present invention relates to a negative photosensitive organic-inorganic hybrid insulating film composition. According to the negative photosensitive organic-inorganic hybrid insulating film composition of the present invention, the original SiNx protective layer (Passivation) / acrylic photosensitive organic insulating film double-layer structure, can obtain step simplification and save production costs, not only has excellent sensitivity, resolution, step margin, transparency, heat resistance discoloration , Flatness, etc., and it can reduce power consumption and make it possible to eliminate afterimages and crosstalk (Crosstalk) and threshold voltage shift (Shift) by making it a low dielectric constant insulating film. . In addition, by having excellent heat resistance, low outgassing can be achieved, and excellent panel reliability can be ensured. Thereby, it is useful for various displays to be applicable not only to a protective layer insulating film and a gate insulating film but also to a flattening film.

Description

Negative photosensitive organic-inorganic hybrid insulating film composition Field of invention

The present invention relates to a negative photosensitive organic-inorganic hybrid insulating film composition, and more specifically, it relates to a negative photosensitive organic-inorganic hybrid insulating film composition, which is formed by a layer Forming a double layer structure of the original SiNx protective layer (Passivation) / acrylic photosensitive organic insulating film, which can achieve step simplification and save production costs, not only has excellent sensitivity, resolution, step margin, transparency , Heat discoloration resistance, flatness, etc., and in particular, it can reduce the power consumption by making it a low-dielectric-constant insulating film, and can eliminate afterimages and crosstalk, as well as the displacement of threshold voltage (Shift) phenomenon and excellent panel reliability due to its excellent heat resistance and low outgassing. As a result, in various displays, not only It can be applied to a protective layer insulating film, a gate insulating film, and a planarizing film.

Background of the invention

Recently, TFT-type liquid crystal display elements and integrated circuit elements have been designed in order to insulate wirings arranged between layers and improve the aperture ratio. A double-layer film composed of a SiNx protective layer (Passivation) and an acrylic photosensitive organic insulating film is used. Since the SiNx film is formed by a CVD step and the acrylic photosensitive organic insulating film is formed by a photo step, the productivity problem caused by the step time is serious.

In the previous insulation film, when the SiNx film formed by the aforementioned CVD was separately formed, there was a problem that the aperture ratio of the display was reduced, and because of the enlargement of the display, the evaporation equipment occupied a relatively large area on the production line. In addition, the large-scale equipment has a significant burden. In addition, when an acrylic photosensitive organic insulating film is separately formed by the original light step, it is caused by electrical defects such as afterimages, crosstalk, and threshold voltage shift (Shift). . It is known that only the shortcomings of organic substances, that is, the current leakage caused by the defects on the thin film, are caused.

Therefore, recently, based on the organic-inorganic hybrid technology, the necessity of a single-layer insulating film capable of being formed by only a light step has been strongly demanded, and technical development has been actively carried out on this.

Summary of invention

In order to solve the problems of the aforementioned prior art, an object of the present invention is to provide a negative photosensitive organic-inorganic hybrid insulating film composition, a pattern forming method of a display element using the same, and a negative photosensitive organic- The hardened material of the inorganic hybrid insulating film composition is used as a display element of the insulating film, wherein the negative photosensitive organic-inorganic hybrid insulating film composition is formed by forming an original SiNx protective layer / acrylic sensor with one layer. The double-layer structure of the optical organic insulating film can achieve step simplification and save production costs. It is not only the performance with excellent sensitivity, resolution, step margin, transparency, heat discoloration, flatness, etc., but also special It can reduce the power consumption by making it a low-dielectric-constant insulating film, and can eliminate the phenomenon of afterimages and crosstalk, as well as the phenomenon of threshold voltage displacement. It also has low heat-resistance to make it low-emission. As a result, excellent panel reliability can be ensured, and therefore, it is useful for a variety of displays to be applied not only to a protective layer insulating film, a gate insulating film, but also to a flattening film.

In order to achieve the foregoing object, the present invention provides a negative photosensitive organic-inorganic hybrid insulating film composition comprising a) a siloxane copolymer, b) a photoinitiator, and c) having an ethylenic property. A saturated functional polyfunctional monomer or oligomer, in which the a) siloxane copolymer is a reaction of i) containing 1-3 phenyl groups or alkyl groups having 1-4 carbon atoms represented by the following chemical formula 1 Silane, ii) a tetrafunctional reactive silane represented by the following chemical formula 2, and iii) a reactive silane monomer containing an acryl fluorenyl group or a vinyl group represented by the following chemical formula 3, which is hydrolyzed and condensed and polymerized under a catalyst. The obtained polysiloxane-equivalent weight average molecular weight (Mw) of the siloxane copolymer having a weight average molecular weight (Mw) of 1,000 to 20,000, [Chemical Formula 1] (R ₁ ) _n Si (R ₂ ) _4-n

In the above formula, R ₁ is each independently a phenyl group or an alkyl group having 1 to 4 carbon atoms, and R ₂ is each independently an alkoxy group, a phenoxy group, or an ethoxy group having 1 to 4 carbon atoms, n is an integer of 1-3; [Chemical Formula 2] Si (R ₃ ) ₄

In the above formula, R ₃ is each independently an alkoxy group, a phenoxy group or an ethoxy group having a carbon number of 1-4; [Chemical Formula 3] (R ₄ ) _n Si [(R ₅ ) (R ₆ )] _4-n

In the above formula, R ₄ is each independently an alkoxy group, phenoxy group, or ethoxy group having a carbon number of 1-4, R ₅ is each independently an acryl group or a vinyl group, and R ₆ is each independently Is a C 1-4 alkyl group, and n is an integer of 1-3.

Preferably, the negative photosensitive organic-inorganic hybrid insulating film composition as described above contains: a) 100 parts by weight of a siloxane copolymer, which is represented by i) containing 1-3 benzenes represented by the aforementioned chemical formula 1 10 to 50 parts by weight of reactive silanes having an alkyl group or a carbon number of 1-4, ii) 20 to 50 parts by weight of a tetrafunctional reactive silane represented by the aforementioned chemical formula 2, and iii) containing propylene represented by the aforementioned chemical formula 3 10 to 40 parts by weight of a fluorenyl or vinyl-based reactive silane; b) 0.1 to 30 parts by weight of the photoinitiator with respect to 100 parts by weight of the above-mentioned a) siloxane copolymer; and c) relative In the aforementioned a) 100 parts by weight of the siloxane copolymer, the polyfunctional monomer or oligomer having an ethylenically unsaturated bond is 5 to 100 parts by weight.

The present invention also provides a method for forming a pattern of a display element, wherein the negative photosensitive organic-inorganic hybrid insulating film composition is used.

Moreover, the present invention provides a display element, characterized in that In: a cured product containing the negative photosensitive organic-inorganic hybrid insulating film composition.

The hardened product of the negative photosensitive organic-inorganic hybrid insulating film composition is preferably used as a protective layer insulating film, a gate insulating film, or a planarization film.

According to the negative-type photosensitive organic-inorganic hybrid insulating film composition according to the present invention, a single-layer structure of the original SiNx protective layer / acrylic photosensitive organic insulating film can be obtained by forming a single layer, Save production costs, not only has excellent sensitivity, resolution, step margin, transparency, heat discoloration, flatness, etc., but also can reduce consumption by making it a low dielectric constant insulating film Electricity can eliminate afterimages, crosstalk, and threshold voltage displacement. It also has excellent heat resistance to enable low exhaust and ensure excellent panel reliability. Such a display is useful not only in a protective layer insulating film and a gate insulating film but also in a flattening film.

Forms used to implement the invention

The present invention is a negative-type photosensitive organic-inorganic hybrid insulating film composition, which is characterized by containing a) a siloxane copolymer, b) a photoinitiator, and c) polyfunctionality having an ethylenically unsaturated bond. A monomer or oligomer, wherein the a) siloxane copolymer is i) a reactive silane containing 1-3 phenyl groups or alkyl groups having 1 to 4 carbon atoms represented by the following Chemical Formula 1, and ii) or less The tetrafunctional reactive silanes represented by Chemical Formula 2 above, and iii) polystyrene equivalents obtained by performing hydrolysis and condensation polymerization of the reactive silane monomers containing propylene fluorenyl or vinyl groups represented by Chemical Formula 3 below Siloxane copolymer having a weight average molecular weight (Mw) of 1,000 to 20,000, [Chemical Formula 1] (R ₁ ) _n Si (R ₂ ) _4-n

In the above formula, R ₁ is each independently a phenyl group or an alkyl group having 1 to 4 carbon atoms, and R ₂ is each independently an alkoxy group, a phenoxy group, or an ethoxy group having 1 to 4 carbon atoms, n is an integer of 1-3; [Chemical Formula 2] Si (R ₃ ) ₄

In the above formula, R ₃ is each independently an alkoxy group, a phenoxy group or an ethoxy group having a carbon number of 1-4; [Chemical Formula 3] (R ₄ ) _n Si [(R ₅ ) (R ₆ )] _4-n

In the above formula, R ₄ is each independently an alkoxy group, phenoxy group, or ethoxy group having a carbon number of 1-4, R ₅ is each independently an acryl group or a vinyl group, and R ₆ is each independently Is a C 1-4 alkyl group, and n is an integer of 1-3.

Preferably, the aforementioned negative photosensitive organic-inorganic hybrid insulating film composition contains: a) 100 parts by weight of a siloxane copolymer, which is represented by i) containing 1 to 3 phenyl groups Or 10 to 50 parts by weight of a reactive silane having an alkyl group having 1 to 4 carbon atoms, ii) a tetrafunctional reaction represented by the aforementioned chemical formula 2 20 to 50 parts by weight of a reactive silane, and iii) 10 to 40 parts by weight of a reactive silane containing acryl fluorenyl or vinyl group represented by the aforementioned Chemical Formula 3; b) 100% of the siloxane copolymer of a) Parts by weight, the aforementioned photoinitiator is 0.1 to 30 parts by weight; and c) the polyfunctional monomer or oligomer having an ethylenically unsaturated bond with respect to 100 parts by weight of the siloxane copolymer of a) described above is 5 to 100 parts by weight.

The aforementioned siloxane oligomer compound of a) used in the present invention is a kind of adhesive, because the adhesive is a single film instead of the original double composed of a SiNx protective layer / acrylic photosensitive organic insulating film Layer structure, so it can not only solve the original problems such as afterimage and crosstalk phenomenon, threshold voltage displacement phenomenon, but also can reduce the outgassing by excellent heat resistance and can ensure an excellent panel.

The aforementioned a) siloxane copolymer is a) i) a reactive silane containing 1-3 phenyl groups or an alkyl group having 1 to 4 carbon atoms represented by the following chemical formula 1, and ii) represented by the following chemical formula 2 The tetrafunctional reactive silane represented by iii) and iii) a reactive silane monomer containing a propylene fluorenyl group or vinyl group represented by the following Chemical Formula 3 are obtained by hydrolysis and condensation polymerization under a catalyst.

As the reactive silane containing 1-3 phenyl groups represented by the above-mentioned chemical formula 1 used in the present invention, there are phenyltrimethoxysilane, phenyltriethoxysilane, and phenyltributoxy Silane, phenylmethyldimethoxysilane, phenyltriethoxysilane, phenyltriphenoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyl Diphenoxysilane, triphenylmethoxysilane, triphenylethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, dimethyl Dimethoxysilane, trimethylmethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltributoxysilane, diethyldimethoxysilane, triethyl A methoxysilane, a butyltrimethoxysilane, etc. can be used individually or in mixture of 2 or more types.

The reactive silane containing 1-3 phenyl groups or alkyl groups having 1 to 4 carbon atoms represented by the above-mentioned chemical formula 1 is preferably contained in an amount of 10 to 50 parts by weight based on the total total monomers. When the content is less than 10 parts by weight, cracks or precipitation of the photoinitiator may occur during film formation. When the content is more than 50 parts by weight, the reactivity during polymerization may decrease, and the molecular weight may not be easily controlled. .

As the aforementioned ii) tetrafunctional reactive silane represented by the aforementioned chemical formula 2 used in the present invention, there are tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, and tetraacetamidine. Oxysilane and the like can be used alone or as a mixture of two or more.

The tetrafunctional reactive silane based on the aforementioned ii) represented by the aforementioned Chemical Formula 2 is preferably contained in an amount of 20 to 50 parts by weight based on the total total monomers. When the content is less than 20 parts by weight, when forming a pattern of the photosensitive organic-inorganic insulating film composition, the solubility in an alkali aqueous solution is reduced, and there is a case where a defect is caused. A case where the solubility becomes too large.

As the aforesaid iii) reactive silanes containing acrylfluorenyl or vinyl groups represented by the aforementioned chemical formula 3 used in the present invention, there are acryloxypropyltrimethoxysilane and acryloxymethyltrimethoxysilane , Tripropylene methoxymethylmethoxysilane, vinyltrimethoxysilane, ethylene Triethoxysilane, vinyltriethoxysilane, methylvinyldimethoxysilane, etc. can be used alone or in combination of two or more.

The reactive silane containing acrylfluorenyl or vinyl group represented by the aforementioned Chemical Formula 3 with respect to the total total monomers is preferably contained in an amount of 10 to 40 parts by weight. When its content is less than 10 parts by weight, when forming a pattern of the photosensitive organic-inorganic insulating film composition, the problem may be that the sensitivity is slowed down and the monomer or oligomer having an ethylenically unsaturated bond is precipitated. At 40 parts by weight, the solubility of the non-exposed portion in the alkaline aqueous solution is lowered, and the resolution may be lowered, and a residue may be generated in the gap portion of the pattern or the contact hole.

In addition, the asiloxane copolymer of a) used in the present invention can simultaneously contain the silane monomers of i), ii) and iii) and additionally contain iv) a reactive silane represented by the following chemical formula 4 and Hydrolysis and condensation polymerization under acid or alkali catalyst, [Chemical Formula 4] (R ₇ ) _n Si [(R ₈ ) (R ₉ )] _4-n

In the above formula, R ₇ is each independently an alkoxy group, phenoxy group, or ethoxy group having a carbon number of 1-4, R ₈ is each independently an alkyl group having a 1-4 carbon number, and R ₉ is each independently Is independently hydrogen, epoxy, hexenyl, methacryl, or allyl, and n is an integer from 1-3.

Specific examples of the reactive silane represented by the above-mentioned iv) represented by Chemical Formula 4 include trimethoxysilane, triethoxysilane, trimethylethoxysilane, triethylphenoxysilane, and trimethylmethoxy Silane, methyltrimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, dimethyl Dimethoxysilane, dimethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriethoxysilane, methyltriethoxysilane, propyl Trimethoxysilane, propyltriethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, chloropropyltrimethoxysilane, chloropropyltriethoxysilane, Chloropropylmethyldimethoxysilane, chloroisobutylmethyldimethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropylmethyldimethoxysilane, isobutyltrimethoxysilane, Isobutyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butylmethyldimethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, N-octyltrimethoxysilane, decyltrimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, dicyclopentyldimethoxysilane, third butylethyl Dimethoxysilane, tert-butylpropyldimethoxysilane, dicyclohexyldimethoxysilane, isooctyltrimethoxy Silane, n-octyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldimethoxysilane , Glycidoxypropyldiethoxysilane, epoxycyclohexylethyltrimethoxysilane, methacryloxypropyltrimethoxysilane, aryltrimethoxysilane, hexenyltrimethoxy Silane and the like can be used singly or in combination of two or more kinds.

When using the reactive silane represented by Chemical Formula 4 or a mixture of these, the amount used is preferably 10 to 50 parts by weight of the total total silane monomer. When the amount used is within the aforementioned range, the adhesion and chemical resistance can be made better.

Negative photosensitive organic-inorganic hybrid insulating film of the present invention The silicone copolymer of a) used in the composition is a polymer capable of performing bulk (bulk) polymerization or solution polymerization (hydrolysis and condensation polymerization) of the aforementioned monomers under water and an acid or alkali catalyst. Process and so on.

As the acid catalyst used in the aforementioned polymerization, there are hydrochloric acid, nitric acid, sulfuric acid, oxalic acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, etc .; as the alkali catalyst, there are ammonia and organic amines. And alkylammonium hydroxide, etc., can be used singly or in combination of two or more kinds at the same time or in steps.

The finally obtained silicone copolymer of a) is a polystyrene-equivalent weight average molecular weight (Mw) by gel permeation chromatography (GPC), preferably 1,000 to 20,000. When the polystyrene-equivalent weight-average molecular weight is less than 1,000, there is a problem that sensitivity, residual film rate, and the like are lowered when evaluating a negative-type photosensitive organic-inorganic hybrid insulating film, and when it is greater than 20,000, the negative-type photosensitive organic -The problem is that the resolution of the inorganic hybrid insulating film is low and the pattern developability is poor.

In addition, the photoinitiator of b) used in the present invention can use three System, benzoin system, acetophenone system, imidazole system, oxime system, or Ketone (xanthone) and other compounds. As a specific example of the photoinitiator, 2,4-bistrichloromethyl-6-p-methoxystyryl-s-tri , 2-p-methoxystyryl-4,6-bistrichloromethyl-s-tri , 2,4-trichloromethyl-6-tri , 2,4-trichloromethyl-4-methylnaphthyl-6-tri , 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis (m-methoxyphenyl) imidazole dimer, 2 -(O-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxy) Phenyl) -4,5-diphenylimidazole dimer, 2,4-bis (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxy Phenyl) -4,5-diphenylimidazole dimer, or 2, (4,5-triphenylimide) 2- (p-methylhydrothiophenyl) -4,5-diphenylimidazole dimer Diimidazole dimer, [1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazolyl-3-yl] -1- (o-acetamoxime), diphenyl Ketone, p- (diethylamino) diphenyl ketone, 2,2-dichloro-4-phenoxyacetophenone, 2,2-diethoxyacetophenone, 2-dodecyl 9 -Oxysulfur 2,4-dimethyl 9-oxosulfur , 2,4-diethyl 9-oxysulfur , 2,2-bis-2-chlorophenyl-4,5,4,5-tetraphenyl-2-1,2-bisimidazole, Cirg Specialty Chemicals' Irgacure 369, Irgacure 651, Irgacure 907, Darocur TPO , Irgacure 819, OXE-02, OXE-01, ADEKA's N-1919, NCI-831, NCI-930, etc. These can be used alone or in combination of two or more.

The content of the photoinitiator is preferably 0.1 to 30 parts by weight based on 100 parts by weight of the a) siloxane copolymer. In addition, when the content is less than 0.1 parts by weight, there is a problem in that the residual film rate is deteriorated due to low sensitivity. When the content is more than 30 parts by weight, the non-exposed portion may cause Not-open in the contact hole or gap portion. In some cases, there is a problem that the DOF (depth of focus) margin is low.

In the above-mentioned c) a polyfunctional monomer or oligomer having an ethylenically unsaturated bond, a crosslinkable monomer or oligomer having at least two ethylene-based double bonds can usually be used. Polymer.

As examples of the polyfunctional monomer or oligomer having an ethylenically unsaturated bond in c), 1,4-butanediol diacrylate, 1,3-butanediol diacrylate, and ethylenediamine can be used. Alcohol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, neopentyl alcohol triacrylate Ester, neopentaerythritol tetraacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dinepentaerythritol diacrylate, dinepentaerythritol diacrylate, dinepentaerythritol Alcohol diacrylate, sorbitol triacrylate, bisphenol A diacrylate derivative, dipentaerythritol polyacrylate, or methacrylates such as these; polyfunctional acrylate oligomers have 2 to 20 functional groups and can use aliphatic urethane acrylate oligomer, aromatic urethane acrylate oligomer, epoxy acrylate oligomer, epoxy methacrylate oligomer Materials, polyester acrylate oligomers, silicone acrylate oligomers, melamine acrylate oligomers, dendritic acrylate oligomers, and the like.

The polyfunctional monomer or oligomer having an ethylenically unsaturated bond is preferably contained in an amount of 5 to 100 parts by weight based on 100 parts by weight of the asiloxane copolymer. When the content is less than 5 parts by weight, there is a problem that it is difficult to realize contact holes and patterns due to a low degree of hardening. When it exceeds 100 parts by weight, there is a problem that the resolution of the contact holes and patterns is low during development due to a high degree of hardening. .

The negative photosensitive organic-inorganic hybrid insulating film composition of the present invention composed of the aforementioned components is capable of additionally containing d) a melamine crosslinking agent, e) a silane coupling agent, and f) a plasticizer, as necessary. G) One or more additives selected from the group consisting of epoxy resins.

The melamine cross-linking agent d) used in the present invention is used in order to improve the adhesion to the lower substrate. A group consisting of the following Chemical Formula 5 can be used alone or in combination of two or more.

[Chemical Formula 5]

In the above formula, R ₁₀ to R ₁₅ are each independently a hydrogen atom or -CH ₂ OCH ₃ , and at least one of the aforementioned R ₁₀ to R ₁₅ is -CH ₂ OCH ₃ .

The content of the melamine crosslinking agent represented by the aforementioned Chemical Formula 5 is preferably 0.1 to 30 parts by weight based on 100 parts by weight of the a) siloxane copolymer. When the content is less than 0.1 parts by weight, the adhesion force to the lower substrate is lowered. When it is more than 30 parts by weight, storage stability and developability are lowered, and there is a problem that the resolution is lowered.

The silane coupling agent e) used in the present invention is used in order to improve the adhesion to the lower substrate, and (3-glycidoxypropyl) trimethoxysilane, (3-cyclo (Oxypropoxypropyl) triethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane , (3-glycidoxypropyl) dimethylethoxysilane, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxy Silyl, 3-triethoxysilyl-N- (1,3-dimethyl-butylene) propylamine, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (amine (Ethyl) 3-aminopropyltriethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, or (3-isocyanatepropyl) triethoxysilane and the like are used alone or as a mixture of two or more kinds.

With respect to 100 parts by weight of the aforementioned a) siloxane copolymer, the aforementioned silicon The content of the alkane coupling agent is preferably from 0.1 to 30 parts by weight. When the content is less than 0.1 parts by weight, the adhesion force to the lower substrate is lowered. When it is more than 30 parts by weight, storage stability and developability are lowered, and there is a problem that the resolution is lowered.

The plasticizer of f) is a step of adjusting the crosslinking density of the insulating film and curing it, so that it can maintain the film characteristics without cracking and maintain high sensitivity characteristics.

The plasticizers can be phthalic acid esters such as dioctyl phthalate and diisononyl phthalate, adipates such as dioctyl adipate, phosphate esters such as tricresyl phosphate, and the like. Monoisobutyric acid esters such as 2,4-trimethyl-1,3-neopentyl glycol monoisobutyrate and the like are used alone or as a mixture of two or more kinds.

With respect to 100 parts by weight of the siloxane oligomer compound of a), the aforementioned plasticizer is preferably contained in an amount of 0.5 to 20 parts by weight. When the content is within the aforementioned range, it is easy to adjust the crosslink density and is heat resistant. It is advantageous that the property is excellent and less fume is generated at the step.

The function of the epoxy resin according to the above g) is to improve the heat resistance and adhesion of the pattern obtained from the negative photosensitive organic-inorganic hybrid insulating film composition.

Examples of the epoxy resin include propylene oxide epoxy resin, epoxypropylamine epoxy resin, heterocyclic epoxy resin, bisphenol A epoxy resin, phenol novolac epoxy resin, Cresol novolac epoxy resin, cyclic aliphatic epoxy resin, etc. are used alone or as a mixture of two or more of them. In particular, bisphenol A epoxy resin, cresol novolac epoxy resin, or epoxy resin is used. A propyl ester epoxy resin is preferred.

With respect to 100 parts by weight of the siloxane copolymer of a), The epoxy resin is preferably contained in an amount of 0.5 to 10 parts by weight. In the above range, the heat resistance, adhesion, and storage stability are excellent at the same time, and the negative photosensitive organic-inorganic hybrid insulating film of the present invention is included. There is an advantage that there is no possibility of precipitation on the composition.

In addition, when the negative photosensitive organic-inorganic hybrid insulating film composition system of the present invention contains h) solvent, the solvent system of h) can form a uniform pattern profile, so that the insulating film has flatness and No coating fouling occurs.

As the solvent, alcohols such as methanol, ethanol, benzyl alcohol, and hexanol; ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol methyl ether propionate, Ethylene glycol ethyl ether propionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether , Diethylene glycol methyl ethyl ether, diethylene glycol butyl methyl ether, diethylene glycol butyl ethyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, diethylene glycol Third butyl ether, tetraethylene glycol dimethyl ether and dipropylene glycol diethyl ether, diethylene glycol ethylhexyl ether, diethylene glycol methylhexyl ether, dipropylene glycol butyl methyl ether, dipropylene glycol ethyl Hexyl ether, dipropylene glycol methylhexyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, Propylene glycol propyl ether propionate, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol Diethylene glycol glycol, butylene glycol monomethyl ether, butylene glycol monoethyl ether, dibutyl glycol dimethyl ether and dibutyl glycol diethyl ether, methyl beta methoxypropionate , Ethyl β ethoxypropionate, etc. Enough to mix more than one type as necessary.

The solvent is preferably contained so that the solid content of the entire negative photosensitive organic-inorganic hybrid insulating film composition becomes 10 to 50% by weight. The composition having the solid content in the aforementioned range is used in a range of 0.1 to It is preferably used after filtration, such as a 0.2 μm micropore filter. When the solid content of the foregoing negative photosensitive organic-inorganic hybrid insulating film composition is less than 10% by weight, the coating thickness becomes thin and there is a problem that the coating flatness is low. When it exceeds 50% by weight, the coating thickness becomes thick. There is a problem that the coating equipment encounters difficulties during coating.

The present invention also provides a method for forming a display element using the negative photosensitive organic-inorganic hybrid insulating film composition as a feature, and a method for forming a display element comprising the positive photosensitive organic-inorganic hybrid insulating film composition. When a cured product is used as a display element, according to the pattern forming method of the present invention, the method of forming an insulating film pattern in the display step is performed by using the light step in addition to the negative photosensitive organic-inorganic hybrid insulating film composition described above. It goes without saying that other steps can apply well-known methods.

A specific example of a method for forming a pattern of a display element using the negative photosensitive organic-inorganic hybrid insulating film is as follows.

First, the negative photosensitive organic-inorganic hybrid insulating film of the present invention is coated on the surface of a substrate using spin coating, slit and spin coating, slit coating, roll coating, etc., and the solvent is formed by pre-baking to form a coating film. . At this time, the pre-baking is performed at a temperature of 100 to 120 ° C for 1 to 3 minutes as good.

Subsequently, the coating film formed above is irradiated with visible rays, ultraviolet rays, extreme ultraviolet rays, electron rays, X-rays, and the like using a pattern prepared in advance, and development is performed using a developing solution to remove unnecessary portions to form a predetermined pattern.

As the developing liquid system, an alkaline aqueous solution can be used, and specifically, inorganic alkalis such as sodium hydroxide, potassium hydroxide, and sodium carbonate, primary amines such as ethylamine, and n-propylamine, diethylamine, and n-amine can be used. Secondary amines such as propylamine, tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine, and triethylamine, alcohol amines such as dimethylethanolamine, methyldiethanolamine, and triethanolamine Or an aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide. In this case, the aforementioned developing solution is used by dissolving a basic compound at a concentration of 0.1 to 10 parts by weight, and an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, and a surfactant can also be added.

In addition, after developing using the aforementioned developing solution, it is washed with ultrapure water for 30 to 90 seconds to remove unnecessary parts and dried to form a pattern. The pattern formed is irradiated with light such as ultraviolet rays. Thereafter, the pattern is subjected to a heat treatment at a temperature of 150 to 400 ° C. for 30 to 90 minutes using a heating device such as an oven to obtain a final pattern.

According to the pattern forming method of a display according to the present invention, a step can be obtained by forming an insulating film by using a single photo step and forming a double layer structure of the original SiNx protective layer / acrylic photosensitive organic insulating film in one layer. Simplify and save production cost, not only has excellent sensitivity, resolution, step margin, transparency, heat discoloration, flatness, etc. It can reduce the power consumption by making it a low-dielectric-constant insulating film, and can eliminate the afterimage and crosstalk phenomenon, as well as the displacement phenomenon of the threshold voltage. It also has excellent heat resistance. It can reduce the outgassing and ensure excellent panel reliability. Therefore, it is useful for a wide variety of displays, not only for protective layer insulation films, gate insulation films, but also for flattening films. .

Hereinafter, preferred embodiments are provided to understand the present invention, but the following embodiments are merely illustrative of the present invention, and the scope of the present invention is not limited by the following embodiments.

[Synthesis example] Synthesis Example 1: Production of Siloxane Copolymer (A)

In a flask equipped with a cooling tube and a stirrer, 30 parts by weight of phenyltriethoxysilane, 50 parts by weight of tetraethoxysilane, and 20 parts by weight of propylene methoxypropyltrimethoxysilane were added as reactive silanes, and 100 parts by weight of ethanol was added as a solvent, and after nitrogen substitution, stirring was performed slowly. After the reaction solution was additionally charged with 40 parts by weight of ultrapure water and 3 parts by weight of oxalic acid as a catalyst, stirring was slowly performed again. After 1 hour, the reaction solution was heated to 60 ° C. and the temperature was maintained for 10 hours to polymerize the solution, and then the solution was cooled to normal temperature to complete the reaction. Additional quenching to below 0 ° C caused precipitation of the reactants. After removing the upper layer liquid containing unreacted silane, the solvent and residual moisture of the alcohols produced during the reaction were dried by vacuum drying. A polystyrene-equivalent weight-average molecular weight (MW) of a final gel permeation chromatography (GPC) analysis result was prepared as a siloxane copolymer (A).

Synthesis Example 2: Production of Siloxane Copolymer (B)

In a flask equipped with a cooling tube and a stirrer, 30 parts by weight of phenyltriethoxysilane, 50 parts by weight of tetraethoxysilane, and 20 parts by weight of propylene methoxypropyltrimethoxysilane were added as reactive silanes. After adding a solvent and performing nitrogen substitution, stirring was performed slowly. After the reaction solution was additionally charged with 40 parts by weight of ultrapure water and 2 parts by weight of nitric acid as a catalyst, stirring was slowly performed again. After 1 hour, the reaction solution was heated up to 60 ° C. and maintained at that temperature for 10 hours to polymerize the whole, and then cooled to normal temperature to complete the reaction. Additional quenching to below 0 ° C caused precipitation of the reactants. After removing the upper layer liquid containing unreacted silane, the solvent and residual moisture of the alcohols produced during the reaction were dried by vacuum drying. A polystyrene-equivalent weight average molecular weight (MW) of a siloxane copolymer having a final GPC analysis result was prepared.

Synthesis Example 3: Production of Siloxane Copolymer (C)

In the aforementioned Synthesis Example 1, in addition to each of a flask equipped with a cooling tube and a stirrer, 40 parts by weight of diphenyldimethoxysilane, 40 parts by weight of tetraphenoxysilane, and 20 parts by weight of vinyltriethoxysilane were added as Except for the reactive silane, the same method as in Synthesis Example 1 was used.

A polystyrene-equivalent weight average molecular weight (MW) of a siloxane copolymer having a final GPC analysis result of 13,000 was prepared.

Synthesis Example 4: Production of Siloxane Copolymer (D)

In the aforementioned Synthesis Example 1, in addition to a flask equipped with a cooling tube and a stirrer, 40 parts by weight of triethylmethoxysilane, 40 parts by weight of tetramethoxysilane, 10 parts by weight of vinyltriethoxysilane, and a ring were respectively added. Oxypropoxypropion Except for 10 parts by weight of triethoxysilane, as a reactive silane, the same method as in Synthesis Example 1 was used. A polystyrene-equivalent weight average molecular weight (MW) of a siloxane copolymer having a final GPC analysis result of 12,000 was prepared.

Synthesis Example 5: Production of a siloxane copolymer (E)

In Synthesis Example 1, except for a flask equipped with a cooling tube and a stirrer, 30 parts by weight of triphenylmethoxysilane, 30 parts by weight of tetrabutoxysilane, 20 parts by weight of vinyltrimethoxysilane, and n-hexane were added to each of them. Except for 20 parts by weight of trimethoxysilane as a reactive silane, the same method as in Synthesis Example 1 was used. A polystyrene-equivalent weight average molecular weight (MW) of a siloxane copolymer having a final GPC analysis result of 6,000 was prepared.

Synthesis Example 6: Production of a siloxane copolymer (F)

In Synthesis Example 2 described above, in addition to a flask equipped with a cooling tube and a stirrer, 30 parts by weight of trimethylmethoxysilane, 50 parts by weight of tetrabutoxysilane, and 20 parts by weight of propylene methoxymethyltrimethoxysilane were added. Except for the part by weight as a reactive silane, it implemented using the method similar to the said synthesis example 2. A polystyrene-equivalent weight average molecular weight (MW) of a siloxane copolymer having a final GPC analysis result of 16,000 was prepared.

Synthesis Example 7: Production of a siloxane copolymer (G)

In Synthesis Example 1, except for a flask equipped with a cooling tube and a stirrer, 50 parts by weight of phenyltriethoxysilane, 20 parts by weight of tetraethoxysilane, and 30 parts of propyleneoxyethyltrimethoxysilane were added. Except for the weight part as a reactive silane, it implemented using the method similar to the said synthesis example 1. Polystyrene equivalent weight average molecular weight for final GPC analysis results (MW) is a siloxane copolymer of 1,000.

Synthesis Example 8: Production of a siloxane copolymer (H)

In the aforementioned Synthesis Example 2, in addition to a flask equipped with a cooling tube and a stirrer, 10 parts by weight of phenyltriethoxysilane, 50 parts by weight of tetraethoxysilane, and 40% by weight of acryloxypropyltrimethoxysilane were added. Except for the part by weight as a reactive silane, it implemented using the method similar to the said synthesis example 2. A polystyrene-equivalent weight average molecular weight (MW) of a siloxane copolymer having a final GPC analysis result was prepared.

Synthesis Example 9: Production of Siloxane Copolymer (I)

In the aforementioned Synthesis Example 2, in addition to a flask equipped with a cooling tube and a stirrer, 50 parts by weight of phenyltriethoxysilane, 40 parts by weight of tetraethoxysilane and propyleneoxypropyltrimethoxysilane 10 were added to each of them. Except for the part by weight as a reactive silane, it implemented using the method similar to the said synthesis example 2. A polystyrene-equivalent weight average molecular weight (MW) of a siloxane copolymer having a final GPC analysis result of 16,000 was prepared.

Comparative Synthesis Example 1: Production of Siloxane Copolymer (J)

In Synthesis Example 1, except that 50 parts by weight of methyltriethoxysilane and 50 parts by weight of tetraethoxysilane were added as reactive silanes to a flask equipped with a cooling tube and a stirrer, the same methods as those used in the above Synthesis Example were used. 2 The same method was implemented. A polystyrene-equivalent weight average molecular weight (MW) of a siloxane copolymer having a final GPC analysis result of 14,000 was prepared.

Comparative Synthesis Example 2: Production of Siloxane Copolymer (K)

In Synthesis Example 1, except for a flask equipped with a cooling tube and a stirrer, 45 parts by weight of methyltriethoxysilane and tetraethoxysilane were added respectively. Except for 50 parts by weight of alkane and 5 parts by weight of propylene methoxypropyltrimethoxysilane as the reactive silane, the same method as in Synthesis Example 1 was used. A polystyrene-equivalent weight average molecular weight (MW) of a siloxane copolymer having a final GPC analysis result of 14,500 was prepared.

Comparative Synthesis Example 3: Production of Siloxane Copolymer (L)

In the aforementioned Synthesis Example 1, in addition to each of a flask equipped with a cooling tube and a stirrer, 20 parts by weight of methyltriethoxysilane, 30 parts by weight of tetraethoxysilane, and 50 parts by weight of propyleneoxypropyltrimethoxysilane were added. Except that it is a reactive silane, it implemented using the method similar to the said synthesis example 1. The polystyrene-equivalent weight average molecular weight (MW) of the final GPC analysis result was 7,500 siloxane copolymers.

Comparative Synthesis Example 4: Production of acrylic copolymer (A)

In a flask equipped with a cooler and a stirrer, a mixed solution of 200 parts by weight of propylene glycol monoethyl acetate, 30 parts by weight of methacrylic acid, 30 parts by weight of styrene, and 40 parts by weight of aryl methacrylate was charged. After the aforementioned liquid composition was sufficiently mixed at 600 rpm using a mixing container, 15 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) was added. The polymerization mixed solution was gradually raised to 70 ° C, and after maintaining the temperature for 8 hours, it was cooled to normal temperature and 500 ppm of hydrogenated diphenyl ketone was added as a polymerization inhibitor to obtain an acrylic copolymer having a solid content concentration of 33% by weight. Thing. The obtained acrylic copolymer had a weight average molecular weight of 10,000. At this time, the weight average molecular weight is a polystyrene conversion average molecular weight measured using GPC.

[Example] Example 1: Production of negative-type photosensitive organic-inorganic hybrid insulating film composition

[1- [9-ethyl-6- (2-methylbenzylidene)-] (100 parts by weight of the siloxane copolymer (A) prepared in the aforementioned Synthesis Example 1) as a photoinitiator 5 parts by weight of 9H-carbazolyl-3-yl] -1- (o-acetamoxime) and 30 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer were mixed. After the above mixture was added with propylene glycol monoethyl acetate so that the solid content concentration became 30% by weight, the mixture was filtered using a 0.2 μm microporous filter to form a negative photosensitive organic-inorganic hybrid insulating film composition.物 coating solution.

Example 2: Production of a negative photosensitive organic-inorganic hybrid insulating film composition

Except that the siloxane copolymer (B) of Synthesis Example 2 was used instead of the siloxane copolymer (A) of Synthesis Example 1 of the aforementioned Example 1, it was produced by the same method as that of the aforementioned Example 1.

Example 3: Production of a negative photosensitive organic-inorganic hybrid insulating film composition

Except that the siloxane copolymer (C) of Synthesis Example 2 was used instead of the siloxane copolymer (A) of Synthesis Example 1 of the aforementioned Example 1, it was produced by the same method as that of the aforementioned Example 1.

Example 4: Production of negative photosensitive organic-inorganic hybrid insulating film composition

Except that the siloxane copolymer (D) of Synthesis Example 2 was used instead of the siloxane copolymer (A) of Synthesis Example 1 of the aforementioned Example 1, it was produced by the same method as that of the aforementioned Example 1.

Example 5: Production of negative-type photosensitive organic-inorganic hybrid insulating film composition

Except that the siloxane copolymer (E) of Synthesis Example 2 was used instead of the siloxane copolymer (A) of Synthesis Example 1 of the aforementioned Example 1, it was produced by the same method as that of the aforementioned Example 1.

Example 6: Production of negative-type photosensitive organic-inorganic hybrid insulating film composition

Except that the siloxane copolymer (F) of Synthesis Example 2 was used instead of the siloxane copolymer (A) of Synthesis Example 1 of the aforementioned Example 1, it was produced by the same method as that of the aforementioned Example 1.

Example 7: Production of negative-type photosensitive organic-inorganic hybrid insulating film composition

Except having used the siloxane copolymer (G) of the synthesis example 2 instead of the siloxane copolymer (A) of the synthesis example 1 of the said Example 1, it manufactured by the method similar to the said Example 1.

Example 8: Production of negative photosensitive organic-inorganic hybrid insulating film composition

Except that the siloxane copolymer (H) of Synthesis Example 2 was used instead of the siloxane copolymer (A) of Synthesis Example 1 of the aforementioned Example 1, it was produced by the same method as that of the aforementioned Example 1.

Example 9: Production of negative-type photosensitive organic-inorganic hybrid insulating film composition

Except that the siloxane copolymer (I) of Synthesis Example 2 was used instead of the siloxane copolymer (A) of Synthesis Example 1 of the aforementioned Example 1, it was produced by the same method as that of the aforementioned Example 1.

Example 10: Production of negative-type photosensitive organic-inorganic hybrid insulating film composition

In the foregoing Example 1, except that 2- (o-chlorophenyl) -4,5-bis (m-methoxyphenyl) imidazole dimer (HABI-1311, manufactured by Dalin Chemical Co., Ltd.) was used instead of the photoinitiator The agent other than [1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazolyl-3-yl] -1- (o-acetamoxime) was used as in the previous examples 1 Manufactured by the same method.

Example 11: Production of negative-type photosensitive organic-inorganic hybrid insulating film composition

In the foregoing Example 1, except that Irgacure 819 (manufactured by Ciba) was used instead of [1- [9-ethyl-6- (2-methylbenzyl) -9H-carbazolyl] Except for 3--3-yl] -1- (o-acetamoxime), it was produced in the same manner as in Example 1 described above.

Example 12: Production of a negative-type photosensitive organic-inorganic hybrid insulating film composition

In the aforementioned Example 1, the same method as in the aforementioned Example 1 was used except that triethylene glycol diacrylate was used in place of dipentaerythritol hexaacrylate, which is a polyfunctional monomer having an ethylenically unsaturated bond. Manufacturing.

Example 13: Production of negative-type photosensitive organic-inorganic hybrid insulating film composition

In the aforementioned Example 1, the same method as in the aforementioned Example 1 was used except that 10 parts by weight of bispentaerythritol hexaacrylate, which is a polyfunctional monomer having an ethylenically unsaturated bond, was used instead of 30 parts by weight. Manufacturing.

Example 14: Production of negative photosensitive organic-inorganic hybrid insulating film composition

In Example 1, the same as Example 1 was used except that dipentaerythritol hexaacrylate, which is a polyfunctional monomer having an ethylenically unsaturated bond, was used instead of 30 parts by weight. Method manufacturing.

Example 15: Production of a negative photosensitive organic-inorganic hybrid insulating film composition

In the aforementioned Example 1, the same method as in the aforementioned Example 1 was used except that 5 parts by weight of bispentaerythritol hexaacrylate, which is a polyfunctional monomer having an ethylenically unsaturated bond, was used instead of 30 parts by weight. Manufacturing.

Comparative Example 1: Production of negative photosensitive organic-inorganic hybrid insulating film composition

Except that the siloxane copolymer (J) of Comparative Synthesis Example 1 was used instead of the siloxane copolymer (A) of Synthesis Example 1 of the aforementioned Example 1, it was produced by the same method as that of the aforementioned Example 1.

Comparative Example 2: Production of a negative photosensitive organic-inorganic hybrid insulating film composition

Except that the siloxane copolymer (K) of Comparative Synthesis Example 2 was used instead of the siloxane copolymer (A) of Synthesis Example 1 of the aforementioned Example 1, it was produced by the same method as that of the aforementioned Example 1.

Comparative Example 3: Production of a negative-type photosensitive organic-inorganic hybrid insulating film composition

Except having used the siloxane copolymer (L) of the comparative synthesis example 2 instead of the siloxane copolymer (A) of the synthesis example 1 of the said Example 1, it manufactured by the method similar to the said Example 1.

Comparative Example 4: Production of negative photosensitive acrylic insulating film composition

Except that the acrylic copolymer (A) of Comparative Synthesis Example 3 was used instead of the siloxane copolymer (A) of Synthesis Example 1 of the foregoing Example 1, it was produced by the same method as that of the foregoing Example 1 to produce a negative type A photosensitive acrylic insulating film composition coating solution.

Comparative Example 5: Production of a negative photosensitive organic-inorganic hybrid insulating film composition

In the foregoing Example 1, except that [1- [9-ethyl-6- (2-methylbenzyl) -9H-carbazolyl-3-yl] -1- (o-ethyl Fluoroxime) was produced in the same manner as in Example 1 except that 35 parts by weight was used instead of 5 parts by weight.

Comparative Example 6: Production of a negative photosensitive organic-inorganic hybrid insulating film composition

In the foregoing Example 1, 4 parts by weight was used except for dipentaerythritol hexaacrylate, which is a polyfunctional monomer having an ethylenically unsaturated bond. Instead of 30 parts by weight, it was produced by the same method as in Example 1.

Comparative Example 7: Production of negative-type photosensitive organic-inorganic hybrid insulating film composition

The same method as in Example 1 was used in Example 1 except that 105 parts by weight of dipentaerythritol hexaacrylate, which is a polyfunctional monomer having an ethylenically unsaturated bond, was used instead of 30 parts by weight. Manufacturing.

Test example

Using a spin coater, the negative photosensitive organic-inorganic hybrid insulating film composition and the negative photosensitive acrylic insulating film composition prepared in the foregoing Examples 1 to 15 and Comparative Examples 1 to 7 were coated on glass. After (glass) the substrate, it was pre-baked on a hot plate at 100 ° C. for 2 minutes to form a film having a thickness of 4.0 μm. Physical properties such as sensitivity, resolution, step margin, transmittance, heat discoloration resistance, insulation properties, and heat resistance were measured for the film as described below and shown in Table 1 below.

A) Sensitivity-In the film formed as described above, a predetermined pattern mask with a sensitivity of 10 μm Line & Space (line and gap) 1: 1 CD reference Dose (dose) is irradiated at an intensity of 365 nm After an ultraviolet ray of 20 mW / cm ² , an image was developed at 23 ° C. using an aqueous solution of 2.38% by weight of tetramethylammonium hydroxide for 1 minute, and then washed with ultrapure water for 1 minute.

Subsequently, it was cured in an oven at 230 ° C. for 60 minutes to obtain a pattern film having a thickness of 3.0 μm.

In this case, the sensitivity must be 50 mJ / cm ² or less.

B) Resolution-determined during the sensitivity measurement of A) above The minimum size of the pattern film.

C) Step margin-A pattern film was formed using the same method as in the sensitivity measurement of A) above, and the CD change rate before and after hardening was measured on a 10 μm Line & Space 1: 1 CD standard. At this time, a change rate of 0 to 10% is marked as ○, a change of 10 to 20% is marked as △, and a change of greater than 20% is marked as ×.

D) Transparency-The evaluation of transparency is measured with a spectrophotometer at a transmittance of 400 nm of the pattern film formed during the sensitivity measurement of A). When the transmittance at this time is 90% or more, it is marked as ○, when 85 to 90% is marked as △, and when it is less than 80%, it is marked as ×.

E) Heat discoloration resistance-The substrate measured at the time of transparency evaluation D) was additionally cured for 40 minutes in an oven at 300 ° C to evaluate the heat discoloration resistance caused by the change in the transmittance of the pattern film at 400 nm before and after curing. When the change rate at this time is less than 5%, it is marked as ○, when 5 to 10% is marked as △, and when it is greater than 10%, it is marked as ×.

F) Insulation-Insulation is judged based on the dielectric constant. The dielectric constant is determined by measuring the capacitance of a capacitor in accordance with the following formula. Specifically, a negative-type photosensitive organic-inorganic mixture is formed between the upper and lower metal electrodes after patterning with an area of 1 cm2 using the same method as in the case of sensitivity measurement in the case of A) above. After forming an insulating film, an element composed of a MIM (Metal / Insulator / Metal; Metal / Insulator / Metal) structure is used to measure an electrostatic capacity using an impedance analyzer and calculate respective dielectric constants according to the following formula.

C (capacitance) = ε 0 (vacuum dielectric constant) * ε r (dielectric constant of dielectric film) * A (with Effective surface) / d (dielectric film thickness)

The dielectric constant was measured, and it was marked as ○ at 2.5 to 2.8, △ at 2.8 to 3.2, and X at 3.2 or more.

G) Heat resistance-The heat resistance was measured using TGA. Specifically, the pattern film formed during the sensitivity measurement in A) was sampled, and then TGA was used to raise the temperature by 10 ° C every minute from normal temperature to 900 ° C. When the 5 wt% loss temperature is greater than 350 ° C, it is marked as ○, when the 5 wt% loss temperature is 300-350 ° C, it is marked as △, and when the 5 wt% loss temperature is less than 300 ° C, it is marked as x.

H) Flatness-on the TFT substrate with a lower step difference of 1.0 to 1.5 μm, after the coating, development, and hardening steps under the conditions of A), according to the channel and pixel portions of the TFT substrate The difference in level is used to evaluate the flatness. The step difference at this time is marked as ○ when the thickness after the application is less than 5%, as △ when 5 to 10%, and as X when 10% or more.

The negative-type photosensitive organic-inorganic hybrid insulating film composition according to the present invention has excellent performance in terms of sensitivity, resolution, step margin, transparency, heat discoloration resistance, flatness, and the like, especially compared to the comparative examples. 1 to 7, with excellent insulation properties, can reduce power consumption and can Eliminates afterimages, crosstalk, and threshold voltage displacement. Moreover, by having excellent heat resistance, low exhaust gas can be ensured, and excellent panel reliability can be ensured. As a result, it was found that a negative photosensitive organic-inorganic hybrid insulating film can be applied to various display steps.

Claims (16)

A negative-type photosensitive organic-inorganic hybrid insulating film composition, comprising a) a siloxane copolymer, b) a photoinitiator, and c) a polyfunctional monomer having an ethylenically unsaturated bond or An oligomer in which a) the siloxane copolymer is i) a reactive silane containing 1-3 phenyl groups or an alkyl group having 1-4 carbon atoms represented by the following chemical formula 1, and ii) represented by the following chemical formula 2 A tetrafunctional reactive silane represented by iii) and a polystyrene-equivalent weight-average molecular weight obtained by hydrolyzing and condensing polymerization of a reactive silane monomer containing propylene fluorenyl or vinyl group represented by the following Chemical Formula 3 under a catalyst (Mw) a siloxane copolymer having 1,000 to 20,000, [Chemical Formula 1] (R ₁ ) _n Si (R ₂ ) _4-n In the above formula, R ₁ is each independently a phenyl group or a carbon number 1-4 Alkyl groups, R ₂ are each independently an alkoxy group, a phenoxy group, or an ethoxy group having a carbon number of 1-4, and n is an integer of 1-3; [Chemical Formula 2] Si (R ₃ ) ₄ is In the above formula, R ₃ is each independently an alkoxy group, a phenoxy group or an ethoxy group having a carbon number of 1-4; [Chemical Formula 3] (R ₄ ) _n Si [(R ₅ ) (R ₆ )] _{4 -n} in the above formula, each of R ₄ is independently a carbon number 1 4 alkoxy, phenoxy, or ethoxyl, R ₅ is each independently acrylfluorenyl or vinyl, R ₆ is each independently alkyl having 1 to 4 carbon atoms, and n is 1 to 3 An integer of 1; the above-mentioned a) siloxane copolymer additionally contains iv) a reactive silane represented by the following chemical formula 4 and undergoes hydrolysis and condensation polymerization under a catalyst, [Chemical Formula 4] (R ₇ ) _n Si [(R ₈ ) (R ₉ )] _4-n In the above formula, R ₇ is each independently an alkoxy, phenoxy, or ethoxyl group having 1 to 4 carbon atoms, and R ₈ is each independently The alkyl group having 1 to 4 carbon atoms, and R ₉ are each independently hydrogen, epoxy group, hexenyl group, methacryl group or allyl group, and n is an integer of 1-3. For example, the negative photosensitive organic-inorganic hybrid insulating film composition according to claim 1, which contains: a) 100 parts by weight of a siloxane copolymer, which is represented by i) containing 1-3 benzenes represented by the aforementioned chemical formula 1 10 to 50 parts by weight of reactive silanes having an alkyl group or a carbon number of 1-4, ii) 20 to 50 parts by weight of a tetrafunctional reactive silane represented by the aforementioned chemical formula 2, and iii) containing propylene represented by the aforementioned chemical formula 3 10 to 40 parts by weight of a fluorenyl or vinyl-based reactive silane; b) 0.1 to 30 parts by weight of the photoinitiator with respect to 100 parts by weight of the above-mentioned a) siloxane copolymer; and c) relative In the aforementioned a) 100 parts by weight of the siloxane copolymer, the polyfunctional monomer or oligomer having an ethylenically unsaturated bond is 5 to 100 parts by weight. The negative photosensitive organic-inorganic hybrid insulating film composition according to claim 1, wherein the photoinitiator b) is selected from the group consisting of 2,4-bistrichloromethyl-6-p-methoxystyryl- s-three , 2-p-methoxystyryl-4,6-bistrichloromethyl-s-tri , 2,4-trichloromethyl-6-tri , 2,4-trichloromethyl-4-methylnaphthyl-6-tri , 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis (m-methoxyphenyl) imidazole dimer, 2 -(O-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxy) Phenyl) -4,5-diphenylimidazole dimer, 2,4-bis (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxy Phenyl) -4,5-diphenylimidazole dimer, 2- (p-methylhydrothiophenyl) -4,5-diphenylimidazole dimer, [1- [9-ethyl- 6- (2-methylbenzyl) -9H-carbazolyl-3-yl] -1- (o-acetoxime), diphenyl ketone, p- (diethylamino) diphenyl ketone , 2,2-dichloro-4-phenoxyacetophenone, 2,2-diethoxyacetophenone, 2-dodecyl 9-oxysulfide 2,4-dimethyl 9-oxosulfur , 2,4-diethyl 9-oxysulfur , 2,2-bis-2-chlorophenyl-4,5,4,5-tetraphenyl-2-1,2-bisimidazole, Irgacure 369, Irgacure 651, Irgacure 907, Darocur TPO, Irgacure 819, OZE -02, OXE-01, N-1919, NCI-831 and NCI-930. For example, the negative photosensitive organic-inorganic hybrid insulating film composition according to claim 1, wherein the polyfunctional monomer having an ethylenically unsaturated bond in c) above is selected from the group consisting of 1,4-butanediol diacrylate , 1,3-butanediol diacrylate, ethylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, neopentaerythritol triacrylate, neopentaerythritol tetra Acrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dinepentaerythritol diacrylate, dinepentaerythritol diacrylate, Dipentaerythritol diacrylate, sorbitol triacrylate, bisphenol A diacrylate derivative, dinepentaerythritol polyacrylate, and other methacrylates the above. For example, the negative photosensitive organic-inorganic hybrid insulating film composition of claim 1, wherein the polyfunctional acrylate oligomer having an ethylenically unsaturated bond in c) above is selected from the group consisting of aliphatic urethane acrylic acid. Ester oligomer, aromatic urethane acrylate oligomer, epoxy acrylate oligomer, epoxy methacrylate oligomer, polyester acrylate oligomer, silicone acrylate oligomer , Melamine acrylate oligomers, and dendritic acrylate oligomers in one or more groups. For example, the negative-type photosensitive organic-inorganic hybrid-type insulating film composition according to claim 1, wherein the negative-type photosensitive organic-inorganic hybrid-type insulating film composition additionally contains one of the group consisting of the following chemical formula 5. The above d) melamine cross-linking agent, In the above formula, R ₁₀ to R ₁₅ are each independently a hydrogen atom or -CH ₂ OCH ₃ , and at least one of the aforementioned R ₁₀ to R ₁₅ is -CH ₂ OCH ₃ . The negative photosensitive organic-inorganic hybrid insulating film composition according to claim 1, wherein the negative photosensitive organic-inorganic hybrid insulating film composition additionally contains a material selected from (3-glycidoxypropyl) Trimethoxysilicon Alkane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) methyl Didiethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxy Silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, aminepropyltrimethoxysilane, Aminopropyltriethoxysilane, 3-triethoxysilane-N- (1,3-dimethyl-butylene) propylamine, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane , N-2 (aminoethyl) 3-aminopropyltriethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminepropyl E) Silane coupling agent consisting of one or more types of trimethoxysilane and (3-isocyanatepropyl) triethoxysilane. For example, the negative photosensitive organic-inorganic hybrid insulating film composition according to claim 1, wherein the negative photosensitive organic-inorganic hybrid insulating film composition additionally contains a material selected from the group consisting of dioctyl phthalate and diisophthalate Nonyl ester, dioctyl adipate, tricresyl phosphate and 2,2,4-trimethyl-1,3-neopentyl glycol monoisobutyrate, 2,2,4-trimethyl-1 F) Plasticizer of one or more of the group consisting of 3-neopentyl glycol diisobutyrate. The negative photosensitive organic-inorganic hybrid insulating film composition according to claim 1, wherein the negative photosensitive organic-inorganic hybrid insulating film composition additionally contains a material selected from the group consisting of propylene oxide epoxy resin, It is composed of oxypropylamine epoxy resin or heterocyclic epoxy resin, bisphenol A epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin and cyclic aliphatic epoxy resin. Group 1 or more g) epoxy tree fat. The negative photosensitive organic-inorganic hybrid insulating film composition according to claim 1, wherein the negative photosensitive organic-inorganic hybrid insulating film composition further contains a component selected from 100 parts by weight, d) melamine crosslinker 0.1-30 parts by weight, e) silane coupling agent 0.1-30 parts by weight, f) plasticizer 0.5-20 parts by weight, g) epoxy resin 0.5-10 parts by weight One or more additives of the group. For example, the negative photosensitive organic-inorganic hybrid insulating film composition according to claim 1, wherein the negative photosensitive organic-inorganic hybrid insulating film composition additionally contains a member selected from the group consisting of methanol, ethanol, benzyl alcohol, hexanol, and the like. Alcohols, glycol methyl ether acetate, glycol ethyl ether acetate, glycol methyl ether propionate, glycol ethyl ether propionate, glycol methyl ether , Ethylene glycol ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol butyl methyl ester Ether, diethylene glycol butyl ethyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, diethylene glycol third butyl ether, tetraethylene glycol dimethyl ether, and diethylene glycol Propylene glycol diethyl ether, diethylene glycol ethylhexyl ether, diethylene glycol methylhexyl ether, dipropylene glycol butyl methyl ether, dipropylene glycol ethylhexyl ether, dipropylene glycol methylhexyl ether, propylene glycol methyl ether acetic acid Ester, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol Propyl ether propionate, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, butylene glycol monomethyl ether, succinic acid Alcohol monoethyl ether, dibutyl glycol dimethyl ether And h) one or more solvents of the group consisting of dibutyl glycol diethyl ether, methyl β methoxypropionate, and ethyl β ethoxypropionate. A method for forming a pattern of a display element, comprising using a negative-type photosensitive organic-inorganic hybrid insulating film composition according to any one of claims 1 to 11. The pattern forming method for a display element according to claim 12, wherein the negative-type photosensitive organic-inorganic hybrid insulating film composition is used as a passivation insulating film of a TFT-LCD, OLED, or O-TFT. The pattern forming method for a display element according to claim 12, wherein the negative photosensitive organic-inorganic hybrid insulating film composition is used as a gate insulating film of a TFT-LCD, OLED, or O-TFT. The pattern forming method for a display element according to claim 12, wherein the aforementioned negative-type photosensitive organic-inorganic hybrid insulating film composition is used as a flattening film of a TFT-LCD, OLED, or O-TFT. A display element comprising a cured product of a negative photosensitive organic-inorganic hybrid insulating film composition according to any one of claims 1 to 11.