TW201610587A - Photosensitive composition for light shielding and light shielding layer obtained therefrom - Google Patents

Abstract

The present disclosure relates to a photosensitive resin composition for light shielding and a light shielding layer prepared using the same. The photosensitive resin composition for light shielding includes (A) a siloxane resin, (B) a pigment, (C) a photopolymerization initiator, and (D) an organic solvent, and optionally, may further include (E) a multifunctional monomer having an unsaturated bond. A thin film for a light shielding layer formed from photosensitive resin composition for light shielding has good electrical properties and good adhesion with a substrate, and no deterioration in optical density even after a high temperature process higher than or equal to 300 DEG C.

Description

Photosensitive composition for light shielding and light shielding layer obtained therefrom

The present invention relates to a photosensitive resin composition for light shielding and a light shielding layer formed therefrom. More particularly, the present invention relates to a photosensitive resin composition which can be used by photolithography to prepare a light shielding layer for use in various types of electronic devices; and a film formed by curing the composition. The light shielding layer of the film.

With regard to development techniques for fabricating electronic products including flat panel display devices such as liquid crystal display devices or touch screen devices, there is a need to reduce the size and thickness of such products. In order to reduce the size and thickness of such products, it is inevitable to increase the internal component integration of such products, and accordingly, there is an urgent need to improve the electrical properties of the materials used in the manufacture of such internal components.

In general, the black matrix photosensitive resin composition is a necessary material for producing a color filter included in display elements such as liquid crystal display devices, organic electroluminescent elements, and display panels. The black matrix photosensitive resin composition is used to prevent color mixing between R (red), G (green), and B (blue) in the color filter of the liquid crystal display device, or is used in a touch panel device. Shade of X and Y metal electrodes cover.

Recently, for liquid crystal display devices for displays, devices using high-resolution ultra-high definition (UD) and high-speed driving over 240 Hz, low temperature polysilicon (LTPS) and oxide thin film transistors are being actively studied.

In general, since the characteristics of the oxide thin film transistor of a semiconductor are changed by light, the light shielding layer is introduced to reduce the above problem. The metal light shielding layer was originally used as the light shielding layer because the subsequent process including PE-CVD (plasma enhanced chemical vapor deposition) was performed at a high temperature after the formation of the light shielding layer, however, The light shielding layer formed of metal has the following problems: as the metal light shielding layer has high reflectance, light is reflected back into the source and between the drain electrode and the light shielding layer, and at the source and the drain Parasitic voltages appear between the electrodes and act as a factor that imparts resistance to the operation of the device, resulting in increased load on the data line.

In addition, in the touch panel device, in order to reduce the thickness of the products, from the conventional technology for bonding the cover glass and the touch panel glass, the research on the monolithic glass solution (OGS) technology is carried out. It forms a touch panel on the protective glass. In the OGS touch panel, a light shielding layer (light shield) that has been formed on the protective glass is first formed, and then the touch panel driving unit is formed. In the process of forming the transparent electrode of the touch panel driving unit, a high temperature vapor deposition or annealing process is required. However, the black matrix photosensitive resin conventionally used for the light shielding layer has a drawback that electrical properties are deteriorated in the high temperature process.

The present invention is directed to providing a photosensitive resin composition for light shielding which produces desired electrical properties even after a high temperature process including electrical resistance and dielectric constant, and desired optical properties including optical density and reflectance.

In order to achieve the above object, in one embodiment of the present invention, there is provided a photosensitive resin composition comprising: (A) a decyl alkane resin containing a polymerized unit represented by the following Chemical Formula 1 and a polymerization unit represented by the following Chemical Formula 2 (B) a pigment; (C) a photopolymerization initiator; and (D) an organic solvent.

Wherein R ¹ is a linear or branched alkyl group having 1 to 20 carbon atoms, an extended aryl group having 6 to 20 carbon atoms, and a total of 7 to 20 carbon atoms having an aryl group-containing substituent An alkyl group, a aryl group having a total of 7 to 20 carbon atoms having an alkyl group-containing substituent or a group having a total of 7 to 20 carbon atoms in which an alkyl group is extended to an extended aryl group.

X is a hydroxyl group, a carboxylic acid, a carboxylic anhydride, a carboxylic anhydride derivative, a quinone imine, a quinone imine derivative, a decylamine, a decylamine derivative, an amine or a fluorenyl group.

[Chemical Formula 2] R ² _n SiO _(4-n)/2

Wherein R ^{2 is} each independently hydrogen, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an unsaturated hydrocarbon group having 2 to 10 carbon atoms. Or a decyloxy group having 2 to 10 carbon atoms, and the plurality of R ² in the molecule may be the same or different.

n is an integer from 0 to 3, and a polymer unit in which n is 3 may be used in combination with another polymerization unit in which n is other than 3.

Based on 100 ppm by mole of the polymerization unit of Chemical Formula 1 and the polymerization unit of Chemical Formula 2, the siloxane oxide may be 5-40 mol% of the polymer unit of Chemical Formula 1 and 60-95 mol% of the chemical formula 2 The composition of the polymerization unit.

The resin was titrated with potassium hydroxide (KOH) having an acid value in the range of 10 to 200 mg KOH/g.

The photosensitive resin composition may further contain (E) a polyfunctional monomer having an unsaturated bond.

The pigment can be a black pigment.

Moreover, the pigment may be any one selected from the group consisting of carbon black, titanium black, aniline black, phthalocyanine, barium titanate, chromium oxide, and cerium oxide or a mixture thereof.

Further, when the polyfunctional monomer having an unsaturated bond is used, 100 parts by weight based on 100 parts by weight of the fluorene oxide resin or 100 parts by weight of the polysiloxane monomer having the oxirane resin and the unsaturated bond For the purpose of the reference, the pigment is present in an amount of from 20 to 130 parts by weight.

Further, when the polyfunctional monomer having an unsaturated bond is used, 100 parts by weight based on 100 parts by weight of the fluorene oxide resin or 100 parts by weight of the polysiloxane monomer having the oxirane resin and the unsaturated bond For the benchmark, the light is gathered The starter is present in an amount of from 1 to 30 parts by weight.

When the polyfunctional monomer having an unsaturated bond is used, the polyfunctional monomer may be present in an amount of more than 0 parts by weight and less than or equal to 100 parts by weight based on 100 parts by weight of the onium oxide resin.

The organic solvent may be present in an amount of 20 to 90 parts by weight based on 100 parts by weight of the total of the photosensitive resin composition.

According to another aspect of the present invention, there is provided a light shielding layer comprising a film formed from the photosensitive resin composition.

The light shielding layer has an optical density in a range of from 1.0 to 4.0 per unit thickness (μm).

According to still another aspect of the present invention, a method of preparing a film for a light shielding layer, comprising: (S1) coating a photosensitive resin composition for light shielding according to an embodiment of the present invention on a substrate; (S2) Removing the solvent from the composition to form a coating film; (S3) exposing and developing the coating film to form a film; and (S4) heat treating the film at a temperature between 200 ° C and at least 300 ° C.

Moreover, after (S4), the method may further comprise: (S5) heat treating the film at a temperature of from 300 ° C to 600 ° C.

A photosensitive resin composition for light shielding according to an embodiment of the present invention may be formed by patterning after aqueous exposure by aqueous development in an alkaline aqueous solution, and after the pattern is formed, formed The pattern maintains its shape even after a process at 300 ° C or higher.

Further, the film formed by curing the photosensitive resin composition for light shielding has electrical insulating properties including surface resistivity greater than or equal to 1.0E+10 and dielectric constant less than or equal to 45, and light shielding performance can be maintained. For example, the optical density per unit thickness (μm) is 1.0 or more, preferably in the range of 1.0 to 4.0, and thus can be used as a light shielding film.

Hereinafter, the present invention will be described in detail. It should be understood that the terms used in the specification and the accompanying claims should not be construed as being limited to the general meaning and the meaning of the dictionary, but should be based on the principle that the inventor is allowed to properly define the terms to obtain the best explanation. The basis is explained corresponding to the meaning and concept of the technical aspect of the present invention.

A photosensitive resin composition according to an embodiment of the present invention, comprising: (A) a decyl alkane resin containing a polymerized unit represented by the following Chemical Formula 1 and a polymerized unit represented by the following Chemical Formula 2; (B) a pigment; (C) a photopolymerization initiator; and (D) an organic solvent, if necessary, further comprising (E) a polyfunctional monomer having an unsaturated bond.

Wherein R ¹ is a linear or branched alkyl group having 1 to 20 carbon atoms, an extended aryl group having 6 to 20 carbon atoms, and a total of 7 to 20 carbon atoms having an aryl group-containing substituent An alkyl group, a aryl group having a total of 7 to 20 carbon atoms having an alkyl group-containing substituent or a group having a total of 7 to 20 carbon atoms in which an alkyl group is extended to an extended aryl group.

X is a hydroxyl group, a carboxylic acid, a carboxylic anhydride, a carboxylic anhydride derivative, a quinone imine, a quinone imine derivative, a decylamine, a decylamine derivative, an amine or a fluorenyl group.

[Chemical Formula 2] R ² _n SiO _(4-n)/2

Wherein R ^{2 is} each independently hydrogen, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an unsaturated hydrocarbon group having 2 to 10 carbon atoms. Or a decyloxy group having 2 to 10 carbon atoms, and the plurality of R ² in the molecule may be the same or different.

n is an integer from 0 to 3, and a polymer unit in which n is 3 may be used in combination with another polymerization unit in which n is other than 3.

Non-limiting examples of R ¹ may include a linear alkylene group having 1 to 20 carbon atoms, which may be a hydrocarbon group such as a methylene group, an ethylidene group, a propyl group, a butyl group, and a pentyl group; A branched alkyl group such as an exopropyl group and an isobutyl group.

Specific examples of the polymerization unit represented by the following Chemical Formula 1 are shown, but are not limited thereto.

(In each formula, m and n are each independently an integer from 1 to 20)

Specific examples of R ² may each include an aliphatic alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and n-pentyl groups, and Specific examples of the cyclic aliphatic alkyl group may include a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group. Specific examples of the decyloxy group having 2 to 10 carbon atoms may include propylene methoxymethyl group, propylene methoxyethyl group, propylene methoxy propyl group, propylene oxy butyl group, methacryloxy group. Methyl, methacryloxyethyl, methacryloxypropyl, and methacryloxybutyl. Specific examples of the aryl group having 6 to 10 carbon atoms may include a phenyl group, a naphthyl group, an onion group, a phenanthryl group, and an anthracenyl group.

The monomer composed of the polymerized unit represented by the following Chemical Formula 2 may include, but is not limited to, for example, tetraalkoxydecane, trialkoxydecane, methyltrialkoxydecane, ethyltrialkoxydecane, positive Propyltrialkoxydecane, isopropyltrialkoxydecane, n-butyltrialkoxydecane, tert-butyltrialkoxide, phenyltrialkoxydecane, naphthapentane Base decane, vinyl trialkoxy decane, methacryloxymethyltrialkoxy alkane, 2-methylpropenyloxyethyltrialkoxydecane, 3-methylpropenyloxypropane Trilutoxy decane, 3-methyl propylene methoxy propyl methyl dialkoxy decane, 3-methyl propylene methoxy propyl ethyl dialkoxy decane, propylene methoxy methyl group Alkoxydecane, 2-propenyloxyethyltrialkoxydecane, 3-propenylmethoxypropyltrialkoxydecane, 3-propenyloxypropylmethylditoxyoxydecane, 3 - propylene methoxy propyl ethyl dialkoxy decane, 3- glycidoxy propyl trialkoxy decane, 2-epoxycyclohexylethyl trialkoxy decane, 3-epoxy ring already Propyl trialkoxy decane, dimethyl alkoxy decane, diethyl dialkoxy decane, dipropyl dialkoxy decane, diphenyl dialkoxy decane, diphenyl decane diol, And phenylmethyldialkoxydecane. Here, the alkoxy group is a linear, branched or cyclic aliphatic or aromatic alkoxy group having 1 to 7 carbon atoms, and may be a hydrolyzable halogen-containing compound.

Preferably, the present invention is characterized in that at least one of the polymerized units represented by the above Chemical Formula 2 is methacryloxymethyltrialkoxydecane, 2-methylpropenyloxyethyltrialkoxide Baseline, 3-methylpropenyloxypropyltrialkoxydecane, 3-methylpropenyloxypropylmethylditoxyoxydecane, 3-methylpropenyloxypropylethyldi Alkoxy oxime Alkane, propylene methoxymethyl trialkoxy decane, 2-propenyl methoxyethyl trialkoxy decane, 3-propenyl methoxy propyl trialkoxy decane, 3-propenyl methoxy propyl Methyldialkoxydecane, and 3-propenyloxypropyl.

(A) The oxirane resin may be titrated with potassium hydroxide (KOH) to have an acid value in the range of 10 to 200 mg KOH/g.

When a decane resin is used, due to the thermal stability of the decane resin, the distance between the carbon particles used as a pigment can be appropriately maintained even after a high-temperature process higher than or equal to 300 ° C, exhibiting high Electrical insulation properties.

The acid value of the decane resin is preferably 10 to 200 mg [KOH] per 1 g of the binder resin by titration with a 0.1 N KOH solution.

When the acid value of the decane resin is less than or equal to 10 mg [KOH] / g [resin], a residual film is generated due to the lack of feasibility of developing photosensitivity, and when the acid value exceeds or equals 200 mg [KOH] / g In the case of [resin], problems such as pattern loss occur.

(B) The pigment is a pigment having light-shielding properties, preferably a black pigment having light-shielding properties. As non-limiting examples of the pigment, carbon black, titanium black, aniline black, phthalocyanine, barium titanate, chromium oxide, and cerium oxide can be used based on their properties, but the pigment is not limited thereto. It is preferably carbon black.

The carbon black may include Cisto series purchased from Tokai Carbon, Diagram series and MA series available from Mitsubishi Chemical, PRINTEX series purchased from DK Dong Shin, and Raven series from Columbian Chemicals.

The particle size of the pigment is preferably adjusted to a range between 50 and 150 nm, more preferably between 50 and 80 nm. When a pigment having a particle size of less than 50 nm is dispersed in the photosensitive resin composition, the optical density is lowered even if the same pigment content is used. Further, when a pigment having a particle size exceeding 150 nm is dispersed in the photosensitive resin composition, the electrical insulating properties and roughness characteristics of the film are still deteriorated.

Based on 100 parts by weight of a decyl alkane resin or when a polyfunctional monomer having an unsaturated bond is used, based on 100 parts by weight of a total of a decyl alkane resin and a polyfunctional monomer having an unsaturated bond, the pigment system is used. It is present in an amount of from 20 to 130 parts by weight, and the content may vary within a numerical range depending on the purpose of use. When the pigment is present in an amount of less than 20 parts by weight, the sensitivity of the photosensitive resin composition and the electrical insulating property and roughness of the film are improved, but it is difficult to expect that the optical density per unit thickness ( μm ) is greater than or equal to 1.0. Moreover, when the pigment content exceeds 130 parts by weight, the optical density satisfies 4.0 or more per unit thickness ( μm ), but the electrical insulating property becomes low and the sensitivity of the photosensitive resin composition also decreases.

(C) The photopolymerization initiator is a material that generates radicals by light and induces crosslinking, and a non-limiting example thereof is preferably selected from at least one of the group consisting of triazine-based a compound, an acetophenone-based compound, a biimidazole-based compound, and an oxime-based compound.

Non-limiting examples of triazine-based compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis (three Chloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperidinyl -1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine And 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine. Non-limiting examples of the acetophenone-based compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl Propane-1-one, 4-(2-hydroxyethoxy)-phenyl-(2-hydroxy-2-propyl)acetone, 1-hydroxycyclohexylphenylacetone, benzoin methyl ether, benzoin ethyl ether , benzoin isobutyl ether, benzoin butyl ether, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl-(4-methylthio)phenyl-2-morpholine- 1-propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one, 2-(4-bromo-benzyl-2 -Dimethylamino-1-(4-morpholinylphenyl)-butan-1-one, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholine Propane-1-one.

Further, non-limiting examples of the biimidazole-based compound include 2,2-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o- Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetra (3,4 ,5-trimethoxyphenyl)-1,2'-biimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole And 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole.

Further, non-limiting examples of the lanthanide compound include OXE-02 (trade name, available from BASF), N1919, NCI-831 (trade name, available from Adeka), 1,2-octanetone (octadion)- 1-(4-phenylthio)phenyl-2-(o-benzylidene fluorenyl), and ethyl ketone-1-(9-ethyl)-6-(2-methylbenzhydryl- 3-yl)-1-(o-ethylindenyl).

Based on 100 parts by weight of a decyl alkane resin, or when a polyfunctional monomer having an unsaturated bond is used, a decyl alkane resin and an unsaturated bond are used. The photopolymerization initiator may be present in an amount of from 1 to 30 parts by weight based on 100 parts by weight of the total of the polyfunctional monomer.

In the photosensitive resin composition of the present invention, the (D) organic solvent includes, but is not limited to, any solvent as long as it is a component capable of dissolving a resin containing a siloxane and not inhibiting dispersion of the pigment. Specific examples of the organic solvent include, but are not limited to, ketone solvents such as methyl ethyl ketone, methyl n-propyl ketone, methyl isopropyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, Methyl-n-amyl ketone, diethyl ketone, dipropyl ketone, diisobutyl ketone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2,4-pentanedione, acetone acetone, γ - Butyrolactone, and γ-valerolactone; ether solvents such as methyl ethyl ether, methyl di-n-propyl ether, diisopropyl ether, tetrahydrofuran, methyl tetrahydrofuran, ethylene glycol dimethyl ether , glycol ether, ethylene glycol dibutyl ether, ethylene glycol methyl ethyl ether, triethylene glycol dimethyl ether, triethylene glycol ether, triethylene glycol methyl ethyl ether, propylene glycol Methyl ether, propylene glycol ether, propylene glycol-n-propyl ether, propylene glycol dibutyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol monomethyl ether, diethylene glycol ethyl ether , propylene glycol monomethyl ether; ether acetate-based solvent such as ethylene glycol methyl ether propionate, ethylene glycol ethyl ether propionate, ethylene glycol methyl ether acetate, B Glycol ethyl ether acetate Propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol propyl ether acetate; acetonitrile, N-methylpyrrolidone, N-ethylpyrrolidone, n-propyl pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylhydrazine, toluene, and xylene; and alcoholic solvents such as methanol, ethanol, n-propanol , isopropanol, n-butanol, isobutanol, cyclohexanol, methylcyclohexanol, benzyl alcohol, ethylene glycol, 1,2-propanediol, and diethylene glycol, It is single or combined.

The content of the organic solvent can be appropriately adjusted based on the content of the siloxane oxide resin, the pigment, the photopolymerization initiator, and the polyfunctional monomer having an unsaturated bond, and the light-sensitive resin composition can be applied to form light on the substrate. The method of shielding the layer varies. For example, the content of the organic solvent is in the range of 20 to 90 parts by weight based on 100 parts by weight of the total amount of the photosensitive resin composition, but is not limited thereto.

(E) The polyfunctional monomer having an unsaturated bond is a reactive unsaturated compound having at least one additional polymerizable unsaturated group in the molecule, and this compound may be optionally used singly or in combination.

Non-limiting examples of polyfunctional monomers having unsaturated bonds may include ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, 1 , 6-hexanediol diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, bisphenol A epoxy acrylate, ethylene glycol monomethyl ether acrylate, Ethylene glycol dimethacrylate or 1,6-hexanediol dimethacrylate.

The content of the polyfunctional monomer having an unsaturated bond is from 0 to 200 parts by weight based on 100 parts by weight of the rhodium oxide resin. When the content exceeds 200 parts by weight, the compatibility of the decane resin and the carbon particles is lowered, which makes it difficult to control the pattern appearance.

A polyfunctional monomer having an unsaturated bond (wherein the unsaturated bond is included in the binder resin) may not be included in the photosensitive resin composition, but may be used for pattern appearance control and sensitivity.

Further, the photosensitive resin composition for light shielding may further include additives generally used in the art, such as a curing accelerator, a thermal polymerization inhibitor, a plasticizer, a filler, a solvent, a leveling agent, and the like, if necessary. Foaming agent. The thermal polymerization inhibitor may be hydroquinone, hydroquinone monomethyl ether, gallic phenol, tert-butyl catechol, or phenothiazine. The plasticizer may be dibutyl phthalate, dioctyl phthalate, or a trimethylphenyl group. The filler may be a glass filler, cerium oxide, mica, or aluminum oxide. Further, the antifoaming agent or the leveling agent may be, for example, an anthracene based compound, a fluorine-based compound, or an acrylic compound.

One embodiment of forming a light shielding layer (black matrix) using a photosensitive resin composition may include (S1) a step of coating a photosensitive resin composition for light shielding according to the present invention on a substrate; (S2) removing a solvent in the composition to form a coating film; (S3) a step of exposing and developing the coating film to form a film; and (S4) heat treating the film at a temperature between 200 ° C and at least 300 ° C The steps. Further, the method may further comprise (S5) a step of heat-treating the film at a temperature of from 300 ° C to 600 ° C.

In an embodiment in which (S1) a process for coating a photosensitive resin composition for light shielding is applied on a substrate, the coating can be used for contact transfer on a pure glass substrate having a clean surface having a thickness of 0.5 to 1.1 mm. Type coaters such as roll coaters, reverse coaters, and bar coaters, or non-contact coaters such as rotators (rotary coaters) and curtains It is implemented by a curtain flow coater.

In preparation and coating, in order to improve the glass substrate and the photosensitive tree The adhesion of the lipid composition may be added to the decane coupling agent or applied to the substrate.

Subsequently, (S2) the solvent is removed from the composition to form a coating film.

In order to perform this step, the composition is dried by using a hot plate at a temperature of 80 ° C to 120 ° C, preferably 90 ° C to 100 ° C for 60 seconds to 120 seconds, or by keeping the composition at room temperature. After a few hours to several days, or by placing the composition in a heated air heater or an infrared heater for a few minutes to several hours to remove the solvent, the thickness of the coating film can be adjusted in the range of 0.5 to 5 μm.

Subsequently, (S3) the coating film is exposed and developed to form a film.

Non-limiting embodiments thereof may include exposure to active energy rays through a negative reticle, such as ultraviolet and excimer laser light in a range of radiant energy rays between 30 and 2000 mJ/cm ² . The amount of radiant energy radiation may vary depending on the type of photosensitive composition used for light shielding. The film obtained by the exposure is developed using a developing solution by a dipping method or a spraying method to form a black matrix pattern. The developing solution for development may include an organic solution of monoethanolamine, diethanolamine, and triethanolamine, or an aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, aqueous ammonia, and a quaternary ammonium salt.

Further, in an embodiment of the preparation method of the present invention, the method may further comprise (S4) heat treating the film at a temperature between 200 ° C and at least 300 ° C, and after (S4), further comprising ( S5) The film is heat treated at a temperature of from 300 ° C to 600 ° C.

The heat treatment in (S4) can be carried out at a temperature between 200 ° C and at least 300 ° C for 5 to 60 minutes, and the heat treatment method can be used in general Oven, but not limited to this.

Further, the heat treatment in (S5) may be carried out at a temperature between 300 ° C and 600 ° C for 5 to 60 minutes, and the heat treatment method may use a general method in the art, such as an oven, but is not particularly limited. .

In general, it is known that additional heat treatment at 200 ° C or higher may degrade the electrical insulating properties of the film and the light shielding layer containing the film, and further increase at 300 ° C or higher than 300 ° C. Degrading its electrical insulation properties. This is because of the conductive characteristics of pigments such as carbon black. That is, if the heat treatment temperature is raised in the process of preparing the film, the resin surrounding the pigment is deteriorated to narrow the distance between the pigments, resulting in an increase in conductivity. As a result, the electrical insulating properties of the film deteriorate.

However, in the film produced from the photosensitive resin composition according to an embodiment of the present invention, the film may have a heat treatment at 200 ° C or higher (even after heat treatment at 300 ° C or higher) Good electrical insulating properties, and the electrical insulating properties of the light shielding layer comprising the film can also be improved.

The light shielding layer (black matrix) obtained by the above preparation method is used for various display devices such as liquid crystal panels and plasma display panels.

Hereinafter, the detailed description will be made through examples to help understand the present invention. However, the embodiments of the present invention may take many other forms, and the scope of the present invention should not be construed as being limited to the following examples. Embodiments of the present invention are provided to more fully explain those of ordinary skill in the art.

<Synthesis of a siloxane resin>

Synthesis Example 1

In a flask equipped with a cooling tube and a stirrer, 250 g (1.0 mol) of methyl 3-(triethoxyindenyl)propionate (hereinafter also referred to as 'propionic acid'), 198 g (1.0 mol) was weighed. Phenyltrimethoxydecane (hereinafter also referred to as 'phenyl'), 136 g (1.0 mol) of methyltrimethoxydecane (hereinafter also referred to as 'methyl'), and 497 g (2.0 mol) Methyl propylene methoxy propyl trimethoxy decane (hereinafter also referred to as 'methacryloyl group'), and 2000 g of propylene glycol monomethyl ether acetate. While stirring the solution, a mixed solution of 13.0 g (0.125 mol) of a 35% aqueous hydrochloric acid solution and 270 g of water was added dropwise. After the complete dropwise addition, the reaction temperature was increased to 85 ° C, and the reaction was carried out at the increased temperature for 6 hours. After the completion of the reaction, extraction was carried out by adding ether and water, the organic phase was recovered, and the residual alcohol and solvent were removed by evaporation to yield 657 g of a dec. The obtained decane resin was dissolved in 657 g of propylene glycol monomethyl ether acetate. The helium oxide resin had a weight average molecular weight of 4,800.

Synthesis Example 2

In a flask equipped with a cooling tube and a stirrer, 250 g (1.0 mol) of methyl 3-(triethoxydecyl)propionate, 297 g (1.5 mol) of phenyltrimethoxydecane, 204 g (weighed) 1.5 mol) of methyltrimethoxydecane, 248 g (1.0 mol) of methacryloxypropyltrimethoxydecane, and 2000 g of propylene glycol monomethyl ether acetate. While stirring the solution, a mixed solution of 13.0 g (0.125 mol) of a 35% aqueous hydrochloric acid solution and 270 g of water was added dropwise. After the complete dropwise addition, the reaction temperature was increased to 85 ° C, and the reaction was carried out at the increased temperature for 6 hours. After the reaction is completed, extraction is carried out by adding ether and water, the organic phase is recovered, and the residue is removed by evaporation. The remaining alcohol and solvent produced 608 g of a decane resin. The obtained decane resin was dissolved in 608 g of propylene glycol monomethyl ether acetate. The helium oxide resin had a weight average molecular weight of 4,200.

Synthesis Example 3

In a flask equipped with a cooling tube and a stirrer, 264 g (1.0 mol) of methyl 3-(triethoxyindenyl)propionate, 396 g (2.0 mol) of phenyltrimethoxydecane, and 272 g (weighed) were weighed ( 2.0 mol) of methyltrimethoxydecane, and 2000 g of propylene glycol monomethyl ether acetate. While stirring the solution, a mixed solution of 13.0 g (0.125 mol) of a 35% aqueous hydrochloric acid solution and 270 g of water was added dropwise. After the complete dropwise addition, the reaction temperature was increased to 85 ° C, and the reaction was carried out at the increased temperature for 6 hours. After the completion of the reaction, extraction was carried out by adding ether and water, the organic phase was recovered, and the residual alcohol and solvent were removed by evaporation to give 560 g of a dec. The obtained decane resin was dissolved in 560 g of propylene glycol monomethyl ether acetate. The helium oxide resin had a weight average molecular weight of 3,800.

<Preparation of photosensitive resin for black matrix>

Example 1

12 parts by weight of an alkali-soluble decane resin (the oxime resin synthesized in Synthesis Example 1, phenyl/methyl/methacryl/propionic acid = 1 part) based on 100 parts by weight of the total resin composition 20/20/40/20, Mw 4800, acid value 36 mg [KOH] / g [resin]), 3.6 parts by weight of carbon black (100 nm particle size) (used as a dispersion containing 20% carbon black). 18 parts by weight of carbon black was transferred to the dispersion), 1 part by weight of ethyl ketone-1-[9-ethyl-6-(2-methyl-tetrahydropiperidyloxybenzylidene)-9H -carbazol-3-yl]-1-(o-ethylindenyl) (OXE-02, BASF), and 69 parts by weight of propylene glycol monomethyl ether acetate as an organic solvent to prepare a photosensitive resin composition.

Example 2

10 parts by weight of the alkali-soluble decane resin used in Example 1 was mixed with 100 parts by weight of the total resin composition (the decyl alkane resin synthesized in Synthesis Example 1, phenyl/methyl/methacryl) Base / propionic acid = 20 / 20 / 40 / 20, Mw 4800, acid value 36 mg [KOH] / g [resin]), 6 parts by weight of carbon black (100 nm particle size) (with a dispersion containing 20% carbon black) In the form of use, 30 parts by weight of carbon black is transferred to the dispersion), 1 part by weight of ethyl ketone-1-[9-ethyl-6-(2-methyl-tetrahydropyranyloxybenzene) Mercapto)-9H-carbazol-3-yl]-1-(o-ethenylhydrazine) (OXE-02, BASF), and 59 parts by weight of propylene glycol monomethyl ether acetate as an organic solvent to prepare photosensitive Resin composition.

Example 3

9 parts by weight of the alkali-soluble decane resin used in Example 1 was mixed with 100 parts by weight of the total resin composition (the decyl alkane resin synthesized in Synthesis Example 1, phenyl/methyl/methacryl) Base / propionic acid = 20 / 20 / 40 / 20, Mw 4800, acid value 36 mg [KOH] / g [resin]), 8 parts by weight of carbon black (100 nm particle size) (with 20% carbon black dispersion) The form is used. 40 parts by weight of carbon black is transferred to the dispersion), 1 part by weight of ethyl ketone-1-[9-ethyl-6-(2-methyl-tetrahydropyranyloxybenzene) Mercapto)-9H-carbazol-3-yl]-1-(o-ethenylhydrazine) (OXE-02, BASF), and 50 parts by weight of propylene glycol monomethyl ether acetate as an organic solvent to prepare photosensitive Resin composition.

Example 4

8 parts by weight of the alkali-soluble decane resin used in Example 1 was mixed with 100 parts by weight of the total resin composition (the oxime resin synthesized in Synthesis Example 1, phenyl/methyl/methacryl) Base / propionic acid = 20 / 20 / 40 / 20, Mw 4800, acid value 36 mg [KOH] / g [resin]), 9.4 parts by weight of carbon black (100 nm particle size) (with a dispersion containing 20% carbon black) The form is used. 47 parts by weight of carbon black is transferred to the dispersion), 1 part by weight of ethyl ketone-1-[9-ethyl-6-(2-methyl-tetrahydropyranyloxybenzene) Mercapto)-9H-carbazol-3-yl]-1-(o-ethenylhydrazine) (OXE-02, BASF), 44 parts by weight of propylene glycol monomethyl ether acetate as an organic solvent to prepare photosensitivity Resin composition.

Example 5

10 parts by weight of an alkali-soluble decane resin (the siloxane resin synthesized in Synthesis Example 2, phenyl/methyl/methacryl/propionic acid = 1 part) based on 100 parts by weight of the total resin composition 30/30/20/20, Mw 3600, acid value 42 mg [KOH] / g [resin]), 2 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer having an unsaturated bond, and 3.6 parts by weight of carbon black (100 nm particle size) (used as a dispersion containing 20% carbon black. 18 parts by weight of carbon black was transferred to the dispersion), 1 part by weight of ethyl ketone-1-[9-ethyl-6 -(2-methyl-tetrahydropiperidyloxybenzylidene)-9H-indazol-3-yl]-1-(o-ethylindenylhydrazine) (OXE-02, BASF), 69 parts by weight Propylene glycol monomethyl ether acetate was used as an organic solvent to prepare a photosensitive resin composition.

Example 6

8 parts by weight of the alkali-soluble decane resin (used in Synthesis Example 2) used in Example 5 was mixed with 100 parts by weight of the total resin composition. A siloxane resin, phenyl/methyl/methacryl/propionic acid=30/30/20/20, Mw 3600, acid value 42 mg [KOH]/g [resin]), 4 parts by weight of dipentaerythritol The acrylate was used as a polyfunctional monomer having an unsaturated bond, 3.6 parts by weight of carbon black (100 nm particle size) (used as a dispersion containing 20% of carbon black. 18 parts by weight of carbon black was transferred to the dispersion Liquid), 1 part by weight of ethyl ketone-1-[9-ethyl-6-(2-methyl-tetrahydropiperidyloxybenzylidene)-9H-indazol-3-yl]-1- (o-Ethylene oxime) (OXE-02, BASF), and 69 parts by weight of propylene glycol monomethyl ether acetate were used as an organic solvent to prepare a photosensitive resin composition.

Example 7

6 parts by weight of an alkali-soluble decane resin (the oxime resin synthesized in Synthesis Example 2, phenyl/methyl/methacryl group) was used in the mixing example 5 based on 100 parts by weight of the total resin composition. /propionic acid = 30/30/20/20, Mw 3600, acid value 42 mg [KOH] / g [resin]), 6 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer having an unsaturated bond, 3.6 weight Parts of carbon black (100 nm particle size) (used as a dispersion containing 20% carbon black. 18 parts by weight of carbon black is transferred to the dispersion), 1 part by weight of ethyl ketone-1-[9- Ethyl-6-(2-methyl-tetrahydropiperidyl benzhydryl)-9H-indazol-3-yl]-1-(o-ethylindenyl) (OXE-02, BASF), And 69 parts by weight of propylene glycol monomethyl ether acetate as an organic solvent to prepare a photosensitive resin composition.

Example 8

4 parts by weight of the alkali-soluble decane resin used in Example 5 was mixed with 100 parts by weight of the total resin composition (synthesized in Synthesis Example 2). A siloxane resin, phenyl/methyl/methacryl/propionic acid=30/30/20/20, Mw 3600, acid value 42 mg [KOH]/g [resin]), 4 parts by weight of dipentaerythritol The acrylate was used as a polyfunctional monomer having an unsaturated bond, 9.4 parts by weight of carbon black (100 nm particle size) (used as a dispersion containing 20% of carbon black. 47 parts by weight of carbon black was transferred to the dispersion Liquid), 1 part by weight of ethyl ketone-1-[9-ethyl-6-(2-methyl-tetrahydropiperidyloxybenzylidene)-9H-indazol-3-yl]-1- (o-Ethylene oxime) (OXE-02, BASF), 44 parts by weight of propylene glycol monomethyl ether acetate as an organic solvent to prepare a photosensitive resin composition.

Comparative example 1

4 parts by weight of an alkali-soluble cardo-based resin (Mw 5000, acid value 80 mg [KOH] / g [resin], Adeka), 4 parts by weight based on 100 parts by weight of the total resin composition Dipentaerythritol hexaacrylate as a polyfunctional monomer having an unsaturated bond, 9.4 parts by weight of carbon black (100 nm particle size) (used as a dispersion containing 20% carbon black. 47 parts by weight of carbon black was used Transfer to the dispersion), 1 part by weight of ethyl ketone-1-[9-ethyl-6-(2-methyl-tetrahydropiperidyloxybenzylidene)-9H-indazol-3-yl ]-1-(o-ethenylhydrazine) (OXE-02, BASF), and 44 parts by weight of propylene glycol monomethyl ether acetate as an organic solvent to prepare a photosensitive resin composition.

Comparative example 2

4 parts by weight of an alkali-soluble decane-oxygen resin (a siloxane resin synthesized in Synthesis Example 3, phenyl/methyl/propionic acid = 40/40/20, based on 100 parts by weight of the total resin composition) Mw 3800, acid price 40mg [KOH] / g [tree Lipid]), 4 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer having an unsaturated bond, and 9.4 parts by weight of carbon black (100 nm particle size) (used as a dispersion containing 20% of carbon black). 47 parts by weight of carbon black was transferred to the dispersion), 1 part by weight of ethyl ketone-1-[9-ethyl-6-(2-methyl-tetrahydropiperidyloxybenzylidene)-9H - oxazol-3-yl]-1-(o-ethenylhydrazine) (OXE-02, BASF), and 44 parts by weight of propylene glycol monomethyl ether acetate as an organic solvent to prepare a photosensitive resin composition.

<Test example>

The photosensitive resin composition for light shielding (for black matrix) prepared in the examples and comparative examples was coated on a glass substrate for an LCD-panel by spin coating at a thickness of 1.2 μm, and at 100 ° C. The mixture is soft baked to remove the solvent to form a coating film. The formed coating film is exposed and developed in an alkaline aqueous solution to form a film. After the glass substrate having the film therein was heat-treated at 230 ° C for 30 minutes to obtain a final film, surface resistivity, dielectric constant, optical density, pinholes, and adhesion were measured. Thereafter, further heat treatment was carried out in an oven at 380 ° C for 30 minutes and the above evaluation was measured in the same manner. The results according to the evaluation criteria are shown in Tables 1 and 2.

Surface resistivity measurement

To measure the surface resistivity of the formed film, Keithley's high resistance meter was used to measure the surface resistivity.

Dielectric constant measurement

In order to measure the dielectric constant of the formed film, a thin film is formed on a glass substrate having an ITO-coated low electrode and a high electrode formed by aluminum deposition. membrane. The dielectric constant was measured using an Agilent 4284 LCR meter.

Optical density measurement

In order to measure the optical density of the formed film, the optical density O.D was measured using an X-rite 361T.

Pinhole measurement

The pinhole measurement of the formed film involved measuring the number of pinholes in a 10 cm X 10 cm glass substrate using an optical microscope. 0 to 10 pinholes are denoted by O, 10 to 30 pinholes are denoted by Δ, and 30 or more pinholes are denoted by ×.

Adhesion test

In order to measure the adhesion, after the film was formed on the glass substrate, the finally cured sample was exposed with a crosshatch cutter scratch and separated after application of the 3M adhesive tape. In this example, the area of the separation zone exceeds 65% of the total test surface by 0B, 35-65% by 1B, 15-35% by 2B, 5-15% by 3B, and less than 5% by 4B. Indicates that there is no separation area indicated by 5B.

Referring to Examples 1 to 4, it was shown that the content of the decaneoxy resin in the resin composition was increased, and the dielectric constant of the film produced from the resin composition was lowered, that is, the electrical insulating property was improved.

Further, Examples 5 to 8 pertain to a resin composition having an unsaturated bond (containing dipentaerythritol hexaacrylate as a polyfunctional monomer), and Examples 5 to The film prepared in Example 8 showed that when the content of the decane resin was increased, they exhibited a lower dielectric constant and had better electrical insulating properties.

Further, when Example 5 and Example 8 were compared with Examples 1 and 4, respectively, Examples 5 and 8 were the parts in which the content of the decane resin in the resin compositions of Examples 1 and 4 was unsaturated. The polyfunctional monomer of the bond was substituted, and the films formed from Examples 5 and 8 (as replaced by the above) had an effect of having poor electrical insulating properties with respect to the films formed from Examples 1 and 4.

Meanwhile, the film produced from the resin composition of Comparative Example 1 using the card type resin showed a significantly high dielectric constant and had extremely poor electrical insulating properties as compared with the film produced from the resin compositions of Examples 1 to 8. .

As shown in Tables 1 and 2, the film prepared by the present invention has extremely excellent electrical insulating properties, optical properties, adhesion, pattern resolution and sensitivity, even after a high temperature process at 380 ° C, as compared with the comparative example. Degree, and thus it is suitable for a preparation process requiring high temperature processing. Moreover, the light shielding layer comprising the film can also exhibit good electrical insulating properties, optical properties, pattern resolution, and sensitivity.

Claims (17)

A photosensitive resin composition for light shielding, comprising: a siloxane oxide resin, a polymerization unit represented by the following Chemical Formula 1 and a polymerization unit represented by the following Chemical Formula 2; a pigment; a photopolymerization initiator; and an organic solvent: Wherein R ¹ is a linear or branched alkyl group having 1 to 20 carbon atoms, an extended aryl group having 6 to 20 carbon atoms, and a total of 7 to 20 carbon atoms having an aryl group-containing substituent An alkyl group, a aryl group having a total of 7 to 20 carbon atoms having an alkyl group-containing substituent or a group having a total number of 7 to 20 carbon atoms in which an alkyl group is extended to an extended aryl group; X is a hydroxyl group, a carboxyl group An acid, a carboxylic anhydride, a carboxylic anhydride derivative, a quinone imine, a quinone imine derivative, a guanamine, a guanamine derivative, an amine or a fluorenyl group; [Chemical Formula 2] R ² _n SiO _(4-n)/2 wherein R ² each independently being hydrogen, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an unsaturated hydrocarbon group having 2 to 10 carbon atoms or having 2 To a decyloxy group of 10 carbon atoms, a plurality of R ² in the molecule may be the same or different; and n is an integer from 0 to 3, and a polymer unit in which n is 3 may be mixed with n wherein 3 is Another polymerization unit is used in combination. The photosensitive resin composition for light shielding according to claim 1, wherein the polymerized unit represented by Chemical Formula 1 is selected from the group consisting of Chemical Formula 1a to Chemical Formula 1n: [Chemical Formula 1d] [Chemical Formula 1k] [Chemical Formula 1n] In each of the formulas, m and n are each independently an integer of from 1 to 20. The photosensitive resin composition for light shielding according to claim 1, wherein the polymerized unit represented by Chemical Formula 2 is any one selected from the group consisting of tetraalkoxy decane, trioxane Oxy decane, methyl trialkoxy decane, ethyl trialkoxy decane, n-propyl trialkoxy decane, isopropyl trialkoxy decane, n-butyl trialkoxy decane, tertiary butyl Trilutoxy decane, pentyl trialkoxy decane, naphtha trialkoxy decane, vinyl trialkoxy decane, methacryloxymethyltrialkoxy decane, 2-methyl Propylene methoxyethyltrialkoxide, 3-methylpropenyloxybenyltrialkoxydecane, 3-methylpropenyloxypropylmethyldialkoxydecane, 3-methyl Propylene methoxy propyl ethyl dialkoxy decane, propylene methoxymethyl trialkoxy decane, 2-propenyl methoxyethyl trialkoxy decane, 3-propenyl methoxy propyl triane Oxydecane, 3-propenyloxypropylmethylditoxyoxydecane, 3-propenyloxypropylethylditoxyoxydecane, 3-glycidoxypropyltrialkoxy Alkane, 2-epoxycyclohexylethyltrialkoxydecane, 3-epoxycyclohexylpropyltrialkoxydecane, dimethyl alkoxydecane, diethyldialkoxydecane, two Propyl dialkoxy decane, diphenyl dialkoxy decane, diphenyl decane diol, and phenylmethyl dialkoxy decane or a mixture thereof. The photosensitive resin composition for light shielding according to claim 3, wherein the polymerization unit represented by Chemical Formula 2 is any one selected from the group consisting of : methacryloxymethyltrialkoxydecane, 2-methylpropenyloxyethyltrialkoxydecane, 3-methylpropenyloxypropyltrialkoxydecane, 3- Methyl propylene methoxy propyl methyl dialkoxy decane, 3-methyl propylene methoxy propyl ethyl dialkoxy decane, propylene methoxy methyl trialkoxy decane, 2-propene oxime Oxyethyltrialkoxydecane, 3-propenyloxypropyltrialkoxydecane, 3-propenyloxypropylmethylditoxyoxydecane and 3-propenyloxypropylethyl Dialkoxydecane or a mixture thereof. The photosensitive resin composition for light shielding according to claim 1, wherein the polymerized unit of Chemical Formula 1 and the polymerized unit of Chemical Formula 2 are based on 100% by mole of the total of 5 to 40. The polymer unit of Chemical Formula 1 and the polymer unit of Chemical Formula 2 of 60 to 95% by mole. The photosensitive resin composition for light shielding according to claim 1, wherein the resin is titrated with potassium hydroxide (KOH) having an acid value in the range of 10 to 200 mg KOH / g of the resin. The photosensitive resin composition for light shielding according to claim 1, which further comprises a polyfunctional monomer having an unsaturated bond. The photosensitive resin composition for light shielding according to claim 1, wherein the pigment is a black pigment. The photosensitive resin composition for light shielding according to claim 1, wherein the pigment is any one selected from the group consisting of carbon black, titanium black, aniline black, black, and titanic acid. Antimony, chromium oxide and antimony oxide or a mixture thereof. The photosensitive resin composition for light shielding according to claim 1 or 7, wherein 100 parts by weight of the decane resin is used, or when the polyfunctional monomer having an unsaturated bond is used, The pigment is stored in an amount of 20 to 130 parts by weight based on 100 parts by weight of the total of the polyoxyalkylene resin and the polyfunctional monomer having an unsaturated bond. in. The photosensitive resin composition for light shielding according to claim 1 or 7, wherein 100 parts by weight of the decane resin is used, or when the polyfunctional monomer having an unsaturated bond is used, The photopolymerization initiator is present in an amount of from 1 to 30 parts by weight based on 100 parts by weight of the total of the polyoxyalkylene resin and the polyfunctional monomer having an unsaturated bond. The photosensitive resin composition for light shielding according to claim 7, wherein the polyfunctional monomer having an unsaturated bond is more than 0 parts by weight and less based on 100 parts by weight of the onium oxide resin. It is present at or equal to 100 parts by weight. The photosensitive resin composition for light shielding according to claim 1, wherein the organic solvent is 20-90 parts by weight based on 100 parts by weight of the total of the photosensitive resin composition for light shielding. The content is present. A light shielding layer comprising a film formed of the photosensitive resin composition for light shielding described in any one of claims 1 to 13. The light shielding layer according to claim 14, wherein the light shielding layer has an optical density in a range of from 1.0 to 4.0 per unit thickness (μm). A method of preparing a film for a light shielding layer, comprising: (S1) coating a photosensitive resin composition for light shielding as recited in claim 1 or 7 on a substrate; (S2) removing from the composition Solvent to form a coating film; (S3) exposing and developing the coating film to form a film; and (S4) heat treating the film at a temperature between 200 ° C and at least 300 ° C. The method for producing a film for light shielding according to claim 16, further comprising (S5) heat-treating the film at a temperature of from 300 ° C to 600 ° C after (S4).