KR20080011879A - Composition for photosensitive organic insulating layer and the organic insulating layer manufactured by using the same - Google Patents

Abstract

A composition of a photosensitive organic insulation layer is provided to be widely used in an organic insulation layer for a liquid display device for display and h-, g-, i-line photoresist by remarkably improving adhesion between substrates. A composition of a photosensitive organic insulation layer(11) contains a photosensitive material, alkaline soluble resin, a solvent and a poly hydroxy styrene-based compound designated by the following chemical wherein m and n are independently and respectively 1, 2 or 3. The photosensitive material is a compound having a quinone diazide radical.

Description

Composition for photosensitive organic insulating layer and the organic insulating layer manufactured by using the same

1 is a view showing the structure of a thin film transistor formed in each pixel of a liquid crystal display device.

2A is a schematic cross-sectional view of a conventional pixel.

FIG. 2B is a schematic cross-sectional view of a high magnification pixel. FIG.

<Explanation of symbols for the main parts of the drawings>

10: substrate 11: SiNx organic insulating film

12: S / D electrode 13: n + -a-Si layer

14: a-Si layer 15: metal electrode

20: Black matrix 21: Liquid Crystal

22: passivation layer 23: ITO glass

24: column line

25: passivation layer with low dielectric constant

The present invention relates to a composition for forming a photosensitive organic insulating film and an organic insulating film manufactured using the same, and more particularly, to a photosensitive resin containing a curing agent having an oxetane group by adding a thermal acid generator to a polymer of an alkali-soluble resin. In the composition, the alkali-soluble resin is an acrylic copolymer resin, and the solvent is followed by a photosensitive resin composition characterized by a mixture of diethylene glycol methylethyl ether and a solvent whose vapor pressure under normal temperature and atmospheric pressure is lower or higher than diethylene glycol methylethyl ether. The present invention relates to an organic insulating film exhibiting solvent resistance in a photoresist process.

In particular, it is an object of the present invention to provide a photosensitive resin composition and an organic insulating film using the same, which can significantly improve adhesion without lowering sensitivity by adding a polyhydroxy styrene compound.

TFT-LCD (Thin Film Transistor Liquid Crystal Display) is formed by bonding a glass substrate on which TFT-array is formed and a glass substrate on which color filters are formed to maintain a constant gap, and then injecting liquid crystal between two glass substrates to form a panel. It refers to display by applying electric signal. However, the LCD panel needs a light source that can emit light separately by not actively emitting light, and this is called a back light. Among the characteristics of TFT-LCD, it is important to obtain low power consumption and high brightness. The low power consumption can be divided into driving circuit technology, back light technology, and panel technology.Panel related technologies can improve the transmission efficiency of flat plate, improve the transmittance of color filter, and aperture ratio of TFT-array. That is, the increase of the area where light passes through is necessary. Opening ratio refers to the ratio of open or transparent portions to the total surface area. The recent results for TFT-LCD are focused on the improvement of optical reagent angle and pixel aperture ratio, and the high aperture ratio reduces the power consumption of the back light source by implementing high luminance. To date, research has been carried out to obtain an aperture ratio of 80% or more, and most of them are based on the black matrix on TFT-array concept.

Various designs and processes are being developed to achieve low power consumption and high brightness by increasing the aperture ratio. To this end, the first generation technology required expensive PECVD and Cry etcher equipment to form a protective layer of SiNx, but from the second generation technology using organic insulating film, the process can be performed without vacuum equipment, thus reducing the equipment investment cost. As a result, the number of processes progressed was reduced, and the clean room area was reduced, thereby increasing productivity.

In order to be used as an organic insulating layer, a material having low electrical conductivity and high breakdown field characteristics is required. Currently used organic insulating films include polyimide (Korean Patent Publication No. 2003-0016981), polyvinyl alcohol (Korean Patent Publication No. 2002-0084427), poly (vinylphenol-maleimide) (Korean Patent Publication No. 2004- 0028010), photoacrylic (US Pat. No. 6,232,157), etc., but did not exhibit the device characteristics to replace the existing inorganic insulating film.

In order to compensate for these disadvantages, Korean Patent Application No. 2002-59061 has been improved by providing an insulating polymer having a maleimide copolymer structure, but the problem of melting in the organic solvent used in the subsequent photolithography process is Still existed. In order to realize a highly efficient organic insulating film, not only an organic active film material development but also an organic insulating film having excellent device characteristics capable of forming a thin film in a simplified process without affecting a substrate and a line processing film is urgently needed. In order to solve this problem, the present inventors mixed the organic insulating film through UV irradiation and heat treatment by mixing a crosslinking agent and a thermal acid generator and adding a polyhydroxy styrene compound to remarkably improve the adhesion with the substrate without reducing the sensitivity. We propose a method of manufacturing.

The present invention is to provide a composition for forming an organic insulating film for remarkably improving adhesion to a substrate without deteriorating the above-described problems, in particular, sensitivity. Specifically, it is an object of the present invention to provide a composition for forming a photoreactive organic insulating film, in which high sensitivity, heat resistance, chemical resistance, adhesion, and the like are improved by adding a polyhydroxy styrene compound.

In addition, while providing high sensitivity during the photolithography process, it is possible to provide a high development residual film ratio and excellent pattern formation, and a photosensitive organic insulating film having excellent etching property and light transmittance.

The present invention provides a composition for forming a photosensitive organic insulating film containing a photosensitive material, an alkali-soluble resin, a solvent, and a polyhydroxy styrene compound represented by the following general formula (1).

[Formula 1]

(In Formula 1, m and n are each independently 1, 2, or 3.)

The present invention provides a composition for forming a photosensitive organic insulating film further comprising an adhesive aid and a thermal acid generator in the composition.

The present invention provides a composition for forming a photosensitive organic insulating film, wherein the thermal acid generator is a compound represented by the following Chemical Formula 2.

[Formula 2]

(In Formula 2, R represents an alkyl group or a hydroxy group.)

The present invention also provides a composition for forming a photosensitive organic insulating film, wherein the photosensitive material is a compound having a quinonediazide group.

The present invention also provides a composition for forming a photosensitive organic insulating film, wherein the photosensitive material is a naphthoquinone diazide compound and the alkali-soluble resin is an acrylic copolymer resin.

In addition, the present invention provides a composition for forming a photosensitive organic insulating film, the content of the polyhydroxy styrene-based compound represented by the formula (1) is 0.004 parts by weight to 0.020 parts by weight relative to 100 parts by weight of the total content of the composition.

In addition, the present invention provides an organic insulating film, which is prepared using the composition.

As the organic insulating film resin component in the composition of the present invention, an alkali-soluble resin is preferable, and an acrylic copolymer is particularly preferable. As this alkali-soluble resin, an acryl-type copolymer, a polyester type copolymer, a polystyrene type copolymer, etc. are mentioned, for example. Among these, the methacrylic copolymer which is an acrylic copolymer is important. In order to impart chemical resistance and etching resistance as necessary, it is preferable to introduce cyclic hexane which is an allyl cyclyl structure or an epoxy or oxetane structure which is a curing group. Novolac resins, polyvinyl alcohols, polyvinyl alkyl ethers, copolymers of styrene and acrylic acid, copolymers of methacrylic acid and methacrylic acid alkyl esters, polymers of hydroxy styrone, poly Vinylhydroxy benzoate, polyvinylhydroxybenzene, and the like. Moreover, the polymer containing the monomeric unit which has a carboxyl group is preferable.

Examples of the monomer having a carboxyl group include unsaturated carboxylic acids having at least one carboxyl group in the molecule, such as unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, and the like. Specific examples thereof include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, and the like. These monomers are compounds having a carbon-carbon unsaturated bond, and can be used alone or in combination of two or more.

The alkali-soluble resin may be a homopolymer composed of a monomer having a carboxyl group, but the polymer is preferably a copolymer composed of a monomer different from a monomer having a carboxyl group. The said other monomer is a monomer which has a carbon-carbon unsaturated bond and can copolymerize with the monomer which has a carboxyl group. Specific examples thereof include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene and the like, unsaturated carboxylate compounds such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, Unsaturated aminoalkyl carboxylate compounds such as butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, such as aminoethyl acrylate, and the like Diyl carboxylate compounds such as glycidyl methacrylate, vinyl carboxylate compounds such as vinyl acetate, vinyl propionate, vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylic Unsaturated oxetane carboxylate compounds such as ronitrile, 3-methyl-3-acryloxy methyl oxetane, 3-methyl-3-methacryloxy methyl oxetane, 3-ethyl-3-acryloxy methyl oxetane, 3-ethyl-3-methacryloxy methyl oxetane , 3-methyl-3-acryloxy ethyl oxetane, 3-methyl-3-methacryloxy ethyl oxetane, 3-methyl-3-acryloxy ethyl oxetane and 3-methyl-3-methacryloxy ethyl oxetane Etc. can be mentioned. These monomers are used individually or in combination of 2 or more types, respectively.

Examples of the copolymer include 3-ethyl-3-methacryloxy methyl oxetane / benzyl methacrylate / methacrylic acid copolymer, 3-ethyl-3-methacryloxy methyl oxetane / benzyl methacrylate / methacryl Acid / styrene copolymer, 3-ethyl-3-methacryloxy methyl oxetane / methyl methacrylate / methacrylic acid copolymer, 3-ethyl-3-methacryloxy methyl oxetane / methyl methacrylate / methacryl Acid / styrene copolymer etc. are mentioned.

Such a copolymer is preferably 5 to 50% by weight based on the entire composition. If the copolymer is less than 5% by weight based on the total composition, the copolymer obtained is difficult to dissolve in an aqueous alkali solution, and when it exceeds 50% by weight, the solubility of the copolymer obtained in the aqueous alkali solution tends to be too large. This is because it can cause a decrease in residual film rate. More preferably 10 to 30% by weight based on the total composition.

In the composition of the present invention, as the photosensitive material, any of those conventionally used as the photosensitive compound in the composition consisting of the resin component and the photosensitive compound can be used. Any photosensitive compound having a known quinonediazide can be used, but naphthoquinone-1,2-diazide-5-sulfonylchloride or naphthoquinone-1,2-diazide-4-sulfonylchloride Compounds having a functional group that can be condensed with may be used in combination, and such compounds are preferably phenol, paramethoxy phenol, hydroxyphenone, 2,4-dihydroxybenzophenone, aniline, and the like. Particular preference is given to compounds.

It is preferable to dissolve the components of the compositions of the present invention in a suitable solvent and use them in solution form. As such a solvent, Ketone solvents, such as acetone, methyl ethyl ketone, cyclopentanone, and cyclohexanone; Cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve and methyl cellosolve acetate; Ether solvents such as tetrahydrofuran, diethylene glycol dimethyl ether and ethylene glycol monomethyl ether; Ester solvents such as ethylene glycol monoethyl ester and hydroxylene ethylene glycol monoethyl ester; Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; Lactic acid esters such as methyl lactate and ethyl lactate; Aromatic hydrocarbons, such as toluene and xylene, are preferable. These solvents may be used alone or in combination of two or more.

In the composition of the present invention, a polyhydroxy styrene compound represented by the following Chemical Formula 1 is used to significantly improve the adhesion without deteriorating the sensitivity.

[Formula 1]

(In Formula 1, m and n are each independently 1, 2, or 3.)

The polyhydroxy styrene compound of Formula 1 is preferably included 0.004 parts by weight to 0.020 parts by weight based on 100 parts by weight of the total composition. If the content of the polyhydroxy styrene-based compound is less than 0.004 parts by weight, it is difficult to see the effect of the present invention to improve the adhesion without a decrease in sensitivity, and when the content thereof exceeds 0.020 parts by weight, the effect is increased in proportion to the excess content Does not get

As an adhesive adjuvant component used for improving the adhesiveness with a board | substrate in the composition of this invention, the silane coupling agent which has reactive substituents, such as a carboxyl group, methacrylyl group, an isocyanate group, an epoxy group, can be used. Specifically, trimethoxysilyl benzoic acid, γ-methacrylic propylpropyl methoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-clisidoxypropyltrimethoxy Silane, β- (3,4-epoxy cyclohexyl) ethyltrimethoxysilane, and the like.

The thermal acid generator will be described as a component constituting the resin composition of the present invention. The thermal acid generator used in the present invention generates an acid by heating to promote an acid catalyst polymerization reaction. Preferred thermal acid generators include sulfonic compounds represented by the following formula (2).

[Formula 2]

(In Formula 2, R represents an alkyl group or a hydroxy group.)

The use ratio of the thermal acid generator of the formula (2) is 0.1 to 5 parts by weight, more preferably 0.5 to 3 parts by weight based on the total content of the composition. If the use ratio is less than 0.1 part by weight, the effect of the thermal acid generator does not appear, and if it exceeds 3 parts by weight, it is difficult to control the flowability, the adhesiveness is poor, and the residual film ratio is lowered.

In the photosensitive resin composition including the above components, the thermal acid generator generates an acid during the heat treatment process for thermosetting, thereby promoting the curing of the film.

Hereinafter, the present invention will be described in detail by way of examples. However, the scope of the present invention is not limited to these examples.

Example

Examples 1-16 and Comparative Examples 1-2

A naphthoquinone diazide compound as a photosensitive material, an acryl copolymer as an alkali-soluble resin, and diethylene glycol methyl ethyl ether (EDM) as a solvent are blended, and the polyhydroxy styrene compound is shown in Table 1 below. The photoresist composition was prepared by blending while changing the content as described above. This composition is a composition for forming h, g, i-line photosensitive organic insulating film, and it filtered using the filter of 0.2 micrometer pore size.

The silicon wafer was spin-coated with each photoresist composition having a varying content of polyhydroxy styrene-based compound, preliminarily dried at a temperature of 100 ° C. for 120 seconds on a hot plate to form a photoresist film having a film thickness of 0.95 m. Formed. The wafer on which this film was formed was mask exposed using an i-ray stepper. After developing for 40 seconds in 0.4 wt% tetramethyl ammonium hydroxide (TMAH) aqueous solution, the remaining film ratio and adhesion after development were measured, and after exposing the entire surface with a mask aligner exposure machine, 220 ° C. in a dry oven. The cross section of the pattern after the intense heat treatment (Hard Bake) for 1 hour was observed with an electron microscope, and the residual film rate and transmittance were measured.

The results are shown in Table 1 below.

In Table 1, the effective sensitivity represents the exposure amount at which the CD size is matched in a dot pattern of 2.0 mu m. Adhesion was observed in the dot pattern on the silicon wafer not HMDS treatment, showing the degree of separation from the substrate, OO: very good, O: good, C: normal and X: bad.

TABLE 1

 Photosensitive material (parts by weight)  Resin component (parts by weight)  Solvent (parts by weight)  Compound of Formula 1 (by weight)  Effective Sensitivity (msec)  Post-development residual rate (%)  Adhesion  Compound components  Naphthoquinone diazide compound  Acrylic Copolymer (Alkali Soluble Resin) EDM ⁽¹⁾  Polyhydroxy styrene compound Example 1 4 16 80 0.004 102 76.80 O Example 2 4 16 80 0.006 110 80.60 O Example 3 4 16 80 0.008 130 84.00 O Example 4 4 16 80 0.010 150 88.20 O Example 5 4 16 80 0.020 150 94.20 OO Example 6 4 16 80 0.040 300 98.02 OO Example 7 4 17 79 0.020 147 88.1 OO Example 8 4 18 78 0.020 131 82.9 OO Example 9 3 16 81 0.020 120 72.6 OO Example 10 4 16 80 0.020 150 97.8 OO Example 11 4 18 78 0.020 150 96.8 OO Example 12 5 18 77 0.020 170 97.8 OO Example 13 7 18 75 0.020 200 98.6 OO Example 14 5 18 77 0.020 200 97.8 OO Example 15 5 19 76 0.020 148 96.4 OO Example 16 5 20 75 0.020 142 95.5 OO Comparative Example 1 4 16 80 - 179 95.9 X Comparative Example 2 6 16 78 - 190 97.7 X

1) EDM in (1) means diethylene glycol methylethyl ether.

2) The content of polyhydroxy styrene is a relative value with respect to 100 parts by weight of the total composition of the photosensitive material, the resin component and the solvent.

As can be seen from Table 1, the composition of Examples 1 to 16 of the present invention containing 0.004 parts by weight to 0.020 parts by weight of the polyhydroxy styrene compound of Formula 1 based on 100 parts by weight of the total content of the composition While the silver sensitivity was excellent and the adhesion and the heat resistance were very good, the compositions of Comparative Examples 1 and 2, which did not contain the polyhydroxy styrene-based compound of Formula 1, had good efficacy and residual film ratio after development, All were bad.

As described above, in the present invention, by containing the polyhydroxy styrene-based compound of the formula (1), not only can a high sensitivity and a low residual film rate after development, but also significantly improve the adhesion between the substrate in question at present The organic insulating film for liquid crystal display elements, and h, g, i-line photoresist, etc. are applicable widely.

Claims (7)

A composition for forming a photosensitive organic insulating film containing a photosensitive material, an alkali-soluble resin, a solvent, and a polyhydroxy styrene compound represented by the following general formula (1). [Formula 1]

However, in Formula 1, m and n are each independently 1, 2, or 3. The composition for forming a photosensitive organic insulating film according to claim 1, further comprising an adhesion aid and a thermal acid generator. 3. The composition of claim 2, wherein the thermal acid generator is a compound represented by the following Chemical Formula 2. 4. [Formula 2]

However, in Formula 2, R represents an alkyl group or a hydroxy group. The composition for forming a photosensitive organic insulating film according to any one of claims 1 to 3, wherein the photosensitive material is a compound having a quinone diazide group. The composition for forming a photosensitive organic insulating film according to any one of claims 1 to 3, wherein the photosensitive material is a naphthoquinone diazide compound, and the alkali-soluble resin is an acrylic copolymer resin. The photosensitive organic compound according to any one of claims 1 to 3, wherein the content of the polyhydroxy styrene compound represented by Chemical Formula 1 is 0.004 parts by weight to 0.020 parts by weight based on 100 parts by weight of the total content of the composition. Composition for insulating film formation. The organic insulating film manufactured using the composition as described in any one of Claims 1-3.

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