KR20110000042A - Photopolymerizable resin composition - Google Patents

Abstract

PURPOSE: A photopolymerizable resin composition is provided to ensure proper optical density in the formation of a hardened film and proper hydrophobicity and to enable use as a barrier when a chromatic layer is formed by a jetting method. CONSTITUTION: A photopolymerizable resin composition comprises an alkali-developable acrylic binder resin and a cado-based binder resin and when a resin hardened film is formed, satisfies the followings: an optical density per 2.0 micron of unit thickness is 2.0 or greater; a contact angle with water is 85° or greater; and a contact angle with 2-ethoxyethanol is 35° or greater.

Description

Photosensitive resin composition

The present invention relates to a photosensitive resin composition suitable for forming a light shielding film of an image display device such as a liquid crystal display device (hereinafter referred to as "LCD").

The liquid crystal display represents an image by using optical anisotropy and birefringence characteristics of liquid crystal molecules. When an electric field is applied, the alignment of the liquid crystals is changed, and the light transmission characteristics are also changed according to the changed alignment direction of the liquid crystals.

In general, a liquid crystal display device is formed by arranging two substrates on which electric field generating electrodes are formed so that the surfaces on which two electrodes are formed face each other, injecting a liquid crystal material between the two substrates, and then applying voltage to the two electrodes. The liquid crystal molecules are moved by the electric field, and thus the image is expressed by the transmittance of light which varies accordingly.

As an example of the structure of a thin film transistor liquid crystal display (TFT-LCD) which is widely used, a lower substrate on which a thin film transistor and a pixel electrode are arranged, also known as an array substrate; On top of a plastic or glass substrate, black matrices and three colored layers of red, green, and blue are repeated, and materials such as polyimide, polyacrylate, polyurethane and the like are used to maintain the color filter protection and surface smoothness. An upper substrate having an overcoat layer having an thickness of 1 to 3 μm and an indium tin oxide (ITO) transparent conductive film layer to which a voltage for driving a liquid crystal is applied on the overcoat layer, a color filter substrate; It consists of a liquid crystal filled between the upper and lower substrates, and has a structure in which both sides of the two substrates are attached with polarizing plates for linearly polarizing visible light (natural light). The voltage is applied to the gate of the TFT forming the pixel by an external peripheral circuit so that the transistor is turned on so that the image voltage can be input to the liquid crystal, and then the image voltage is applied to the liquid crystal. After storage, the transistor is turned off to preserve the charge stored in the liquid crystal charger and the auxiliary charger, allowing the image to be displayed for a period of time. When voltage is applied to the liquid crystal, the arrangement of the liquid crystal changes. When light passes through the liquid crystal in this state, diffraction occurs. The light is transmitted through the polarizer to obtain a desired image.

Recently, efforts have been made to reduce the manufacturing cost while increasing the aperture ratio and reducing the manufacturing process by forming the color filter of the liquid crystal display on the upper substrate, that is, the lower substrate, not the color filter substrate, that is, the array substrate.

Considering these structural changes, the method of manufacturing a color filter commonly uses a dyeing method, a dispersion method, an electrodeposition method, a printing method, a jetting method, and the like. There is an advantage that can simplify the color filter manufacturing process and lower the manufacturing cost. However, color filters manufactured by a jetting method using inkjet printing have the biggest difficulty in ensuring uniformity in a glass substrate and a display cell. The cause of such a uniformity defect of the color filter is mainly caused by the difference in the amount of ink discharged from each nozzle of the inkjet print head. Differences in the amount of ink ejected by the nozzles of the inkjet printhead have a problem of being perceived as unevenness as the amount of color ink filled in each pixel area is changed. In addition, when the color ink is filled in the light shielding pattern, that is, the internal space corresponding to the pixel area defined by the black matrix, the surface of the color ink is convexly raised by the repulsive force between the light shielding pattern and the color ink and the surface tension of the color ink. It may be in the form of a right dome. As described above, a color difference may occur due to a difference between the thickness of the color filter formed at the center of the pixel area and the thickness of the color filter formed at the edge of the pixel area by the color ink filled in the dome in the inner space. The poor uniformity of the color filter due to these factors ultimately degrades the display quality.

In one embodiment of the present invention to provide a photosensitive resin composition having an appropriate hydrophobicity while showing a suitable optical density at the time of forming a cured film.

In particular, one embodiment of the present invention is to provide a photosensitive resin composition useful as a partition wall material for forming a colored layer by a jetting method by inkjet printing.

In one embodiment of the present invention comprises an alkali-soluble acrylic binder resin and cardo-based binder resin; When forming a resin cured film, the photosensitive resin composition which satisfy | fills all the following 1st conditions-3rd conditions is provided.

First condition: Optical density (OD) per unit thickness of 2.0 mu m should be 2.0 or more.

Second condition: The contact angle to water should be 85 ° or more.

Third condition: The contact angle with respect to 2-ethoxyethanol is 35 degrees or more.

Preferably, the photosensitive resin composition according to the embodiment of the present invention may have a contact angle with water of 85 to 110 ° when the resin cured film is formed.

In the photosensitive resin composition according to the embodiment of the present invention, preferably, the contact angle with 2-ethoxyethanol may be 35 to 50 ° when the resin cured film is formed.

The photosensitive resin composition according to one embodiment of the present invention may be one containing a colorant containing at least two pigment mixture components that may be mixed to express substantially black. In this case, the pigment mixture component may be a red pigment and a blue pigment as essential components, and may further include a single or a mixture thereof selected from yellow pigments, green pigments and violet pigments. 10 to 50% by weight of the red pigment, 10 to 50% by weight of the blue pigment, 1 to 20% by weight of the yellow pigment, and 1 to 20% by weight of the green pigment, based on the solid content. In addition, the pigment mixed component may be to include 1 to 20% by weight of the violet pigment based on the solids content of the total weight of the colorant.

In the photosensitive resin composition according to the embodiment of the present invention, the pigment mixed component may be one containing a black pigment. The black pigment is based on the solids content of the total weight of the colorant. It may be included up to 10% by weight.

In the photosensitive resin composition according to one embodiment of the present invention, the colorant may be included in 20 to 80% by weight based on the total weight of the photosensitive resin composition.

Photosensitive resin composition according to an embodiment of the present invention is a polyfunctional monomer having an ethylenically unsaturated double bond; Photopolymerization initiator; And solvents.

In the photosensitive resin composition according to the embodiment of the present invention, the alkali-soluble acrylic binder resin may be one containing an epoxy group.

In the photosensitive resin composition according to the preferred embodiment of the present invention, the alkali-soluble acrylic binder resin may include a fluorine group, and in particular, the alkali-soluble acrylic binder resin may have a fluorine content of 5 to 50% by weight.

In the photosensitive resin composition according to an embodiment of the present invention, the pigment mixture component may be in the form of a pigment dispersion in which each pigment is dispersed in a solvent, the pigment dispersion is at least one pigment dispersion selected from an acrylate pigment dispersant Best of all, the pigment dispersion may be one containing from 3 to 20% by weight of the pigment dispersant in the total weight of the pigment dispersion.

In the photosensitive resin composition according to an exemplary embodiment, the pigment dispersion may include an acrylic binder resin containing a fluorine group.

In the photosensitive resin composition according to an exemplary embodiment, the cardo-based binder resin may be one containing a fluorine group.

The photosensitive resin composition according to an exemplary embodiment may include a fluorine group-containing epoxy monomer.

In addition, the photosensitive resin composition according to an exemplary embodiment may include a fluorine group-containing siloxane monomer.

The photosensitive resin composition according to the preferred embodiment of the present invention may have a fluorine content of 5 to 50% by weight per 1 g of the cured film when the cured film is formed.

An exemplary embodiment of the present invention provides a color filter substrate including a black matrix formed by a photolithography method using the photosensitive resin composition according to the embodiments described above.

Another exemplary embodiment provides a thin film transistor substrate including a black matrix formed by a photolithography method using the photosensitive resin composition according to the above-described embodiments.

Yet another exemplary embodiment provides an image display device including the color filter substrate as an upper substrate.

Yet another exemplary embodiment provides an image display device including the color filter substrate as a lower substrate.

The photosensitive resin composition according to an embodiment of the present invention exhibits proper optical density at the time of forming a cured film, and exhibits proper hydrophobicity, thereby forming ink-patterned patterns using the inkjet into a region defined by the light shielding pattern. By injecting the color ink by a jetting method by printing, problems such as color inks over the light shielding pattern, color mixing, or positional deviation may be solved. As a result, it is easy to form a colored layer by jetting by inkjet printing, and ultimately, display defects can be reduced.

Hereinafter, the present invention will be described in detail.

In the manufacture of color filters, a jetting method using inkjet printing is performed by forming a light shielding pattern by a photolithography method with a photosensitive resin composition having light shielding properties, and then applying the respective color ink within a region corresponding to each pixel defined by the light shielding pattern. It is a method of forming a colored layer by jetting red, green, blue).

When the colored layer is formed by the above method, the process can be simplified and the cost can be reduced as compared with the method of forming the red, green, and blue colored layers by the photolithography method. In addition, the color reproducibility may be increased according to the color ink injection amount, so the color reproducibility is excellent and the thickness and composition of the pattern may be constantly taken. In addition, it is easier to implement a fine circuit pattern, it is also easy to apply for a flexible display. In addition, it is an environmentally friendly method with less waste of photoresist, solvent and energy.

However, the jetting method by inkjet printing requires the accuracy and capability of inkjet printing and requires related materials for inkjet printing.

The present invention devised as a part thereof, and relates to a photosensitive resin composition capable of forming a light shielding pattern useful for forming a colored layer by such a jetting method by ink jet printing.

In view of the above, the photosensitive resin composition according to one embodiment of the present invention includes an alkali-soluble acrylic binder resin and a cardo-based binder resin; It is a photosensitive resin composition which satisfy | fills all the following 1st conditions-3rd conditions at the time of resin cured film formation.

First condition: Optical density (OD) per unit thickness of 2.0 mu m should be 2.0 or more.

Second condition: The contact angle to water should be 85 ° or more.

Third condition: The contact angle with respect to 2-ethoxyethanol is 35 degrees or more.

If the optical density (OD) per unit thickness of 2 μm is less than 2.0, it may be difficult to express an appropriate light shielding effect even if the thickness becomes a little thick, and when functioning as a light shielding film, the light shielding property may not be sufficiently expressed and thus may be transmitted through a transparent pixel electrode. And may not be able to block uncontrolled light.

In addition, when the resin cured film is formed, when the contact angle with respect to water is smaller than 85 °, there may be a problem such as overflow of the ink solution in the pixel region or an amount of the color ink to be filled when inkjetting.

In addition, when the contact angle with respect to 2-ethoxyethanol is smaller than 40 °, there may be a problem such as overflow of the ink solution in the pixel area or the amount of color ink to be filled during ink jetting.

Since the light shielding pattern is usually formed on the glass surface and the color ink is formed in the light shielding pattern, the surface tension of the surface tension of the glass surface is greater than the surface tension of the color ink in terms of preventing color mixing or dislocation after color ink injection. It should be at least the same, and in the case of shading patterns, the surface tension should be less than that of color ink.

In view of the above, the photosensitive resin composition according to one embodiment of the present invention preferably has a contact angle with water of 85 to 110 ° when forming a resin cured film, and / or 2-ethoxyethanol when forming a resin cured film. The contact angle with respect to may be 35 to 50 °.

As an example of a method for satisfying light blocking properties and a certain level of hydrophobicity using the photosensitive resin composition, various methods may be conceived, but not limited thereto. For example, a functional group capable of expressing hydrophobicity in a binder resin may be introduced. The method of adding, the method of adding the monomer which has a functional group which can express hydrophobicity by another monomer, the method of disperse | distributing and adding a fluorine-group containing resin in a pigment, etc. are mentioned.

The photosensitive resin composition according to one embodiment of the present invention may contain at least two pigment mixed components that may be mixed and substantially express black in a colorant expressing light shielding properties.

Usually, a black pigment is included in the photosensitive resin composition for expressing light-shielding property, and carbon black or titanium black can be used as an example. However, in the case where the black pigment is used to express the light blocking property, black pigments such as carbon black or titanium black may act as ionic impurities, and the cured film obtained therefrom is not preferable because of poor compression properties.

In this regard, the photosensitive resin composition according to the exemplary embodiment of the present invention is configured to express substantially black color using a pigment mixture component, wherein the expression 'substantially black' refers to a visible region (380 nm) based on UV-spectrum. It can be understood that the black color of the degree of absorption is generated in a radio wave field of ˜780 nm).

Preferably the mixing of the pigment can be obtained by mixing the pigment dispersion in which the pigment component is dispersed in the solvent.

In mixing the pigments, it is preferable to mix and use organic pigments in consideration of light transmittance and permittivity. Preferably, red and blue pigments may be essentially mixed, and yellow or green pigments may be further mixed. have. In addition, violet pigment may be further mixed.

Non-limiting examples of pigments include the following pigments.

As such a pigment, Red pigment: C.I. 3, 23, 97, 108, 122, 139, 149, 166, 168, 175, 177, 180, 185, 190, 202, 214, 215, 220, 224, 230, 235, 242, 254, 255, 260, 262, 264, 272, Yellow Pigment: CI 13, 35, 53, 83, 93, 110, 120, 138, 139, 150, 154, 175, 180, 181, 185, 194, 213, blue pigments: C.I. 15, 15: 1, 15: 3, 15: 6, 36, 71, 75, Green Pigment: C.I. 7, 36, violet pigment: C.I. 15, 19, 23, 29, 32, 37 and the like.

In addition, if necessary, a high-resistance black pigment having a high resistance may be further added. Examples of the black pigment include carbon black or titanium black, but are not limited thereto.

These pigment mixtures are 10 to 50% by weight, 10 to 50% by weight of blue pigment, 1 to 20% by weight of yellow pigment and 1 to 20% by weight of green pigment, based on the solids content of the total weight of the colorant. It may include. Here, the violet pigment may include 1 to 20% by weight based on the solids content of the total weight of the colorant. Black pigments are also based on the solids content of the total weight of the colorant. It is preferable to add at 10 weight% or less. Since black pigments often have electrical conductivity, a problem of increasing dielectric constant may occur, and electrical properties of the cured film may be impaired. When the black pigment is included, it is preferable to select a pigment having high resistance. The amount used is more preferably 15% by weight or less based on the solids content in the total weight of the colorant.

Meanwhile, the optical density and electrical resistance of the light shielding film formed from the photosensitive resin composition may vary depending on the degree of dispersion of the pigment. In this regard, the colorant may include a pigment dispersant. As an example of a pigment dispersant, polymeric dispersing agents, such as a modified polyurethane, a modified polyacrylate, a modified polyester, a modified polyamide, surfactants, such as a phosphate ester, polyester, an alkyl amine, etc. can be used. Among these, in particular, an acrylate-based dispersant, specific examples include Disperbyk-2000, Disperbyk-2001, LP-N-21116, LP-N-21208, and Ciba's EFKA-4300, EFKA-4330, EFKA-4340, and EFKA. Pigment dispersants such as -4400, EFKA-4401, EFKA-4402, EFKA-4046 or EFKA-4060 may be more advantageous in terms of stable implementation of dispersion stability, optical density and electrical properties.

However, when the pigment dispersant is excessively included, this may cause deterioration of dispersion stability or deterioration of pattern stability due to the degradation of a specific functional group. In this regard, the content of the pigment dispersant may be a colorant in the form of a dispersion, that is, a pigment dispersion. It may be preferred to be from 3 to 20% by weight of the total weight.

It is preferable that the total amount of such a coloring agent is 20 to 80 weight% with respect to the total weight of the photosensitive resin composition, More preferably, it is about 30 to 66 weight%. If the content of the mixed pigment is less than 20% by weight, the optical density of the formed light-shielding film is not low enough to have sufficient light-shielding properties. If the content is more than 80% by weight, the amount of the photosensitive resin component is reduced and curing is poor. There may be a problem with residue.

Meanwhile, the photosensitive resin composition according to one embodiment of the present invention may include an alkali-soluble binder resin, a photopolymerizable monomer having an ethylenically unsaturated group, a photopolymerization initiator, and a solvent. As a specific example, the photosensitive resin according to an embodiment of the present invention may be used. The composition together with the above-described colorant, alkali-soluble acrylic binder resin; Cardo-based binder resins; Polyfunctional monomers having an ethylenically unsaturated double bond; Photopolymerization initiator; And it may be to include a solvent.

Here, as the alkali-soluble acrylic resin binder, a copolymer formed by copolymerization of a monomer containing an acid functional group and a monomer copolymerizable with the monomer may be used. By the copolymerization as described above, the strength of the film can be higher than that of the resin produced by homopolymerization. Alternatively, a polymer compound prepared by a polymer reaction between the copolymer formed and an ethylenically unsaturated compound containing an epoxy group may be used.

That is, as said alkali-soluble resin binder, the copolymer formed by copolymerization of the monomer containing an acidic radical and the monomer copolymerizable with this monomer can be used. In addition to the copolymer, a polymer compound formed by bonding an ethylenically unsaturated compound containing an epoxy group to the copolymer structure may be used together.

Non-limiting examples of the monomer containing an acid group include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethyl maleic acid, isoprene sulfonic acid, styrene sulfonic acid, 5-norbornene-2- Carboxylic acid and the like. These may be used alone or in combination of two or more thereof.

In particular, it may be preferable that the binder resin containing an epoxy group in consideration of the strong alkali resistance of the cured film, in this regard it may be preferable to use an epoxy group-containing monomer in addition to the monomer containing an acid group in the production of alkali-soluble resin. .

Examples of the epoxy group-containing monomers are glycidyl acrylate, glycidyl methacrylate, α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, acrylic acid-3 , 4-epoxy butyl, methacrylic acid-3,4-epoxy butyl, acrylic acid-6,7-epoxy heptyl, methacrylic acid-6,7-epoxy heptyl, α-ethyl acrylic acid-6,7-epoxy heptyl, o -Vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and the like, but are not limited thereto.

In addition, the alkali-soluble acrylic binder resin preferably contains a fluorine group in view of expressing hydrophobicity when forming a cured film by the photosensitive resin composition of the present invention. It can be used together.

The fluorine group-containing monomer may be copolymerizable with other monomers, and the fluorine group-containing monomer may have one carbon double bond. However, the fluorine group-containing monomer is not particularly limited, but one example of CH ₂ = CHC (O) OCHCH ₂ (CF ₂ ) xCF ₃ (where x is an integer of 1 to 12) is mentioned.

The content of such a fluorine group-containing monomer can be adjusted according to the fluorine group content of the monomer, satisfies the contact angle with respect to water and the contact angle with respect to 2-ethoxyethanol, while inhibiting developability, coating property and dispersion stability. It may be desirable to adjust so that the fluorine content in the alkali-soluble acrylic binder can be adjusted to 5 to 50% by weight.

It is preferable that such alkali-soluble acrylic binder resin is 1 to 40 weight% with respect to the total solid weight of the photosensitive resin composition, More preferably, it is about 20 to 30 weight%. However, in the case of containing a fluorine group in the alkali-soluble acrylic binder resin, hydrophobicity may increase with increasing its content, but processability may be impaired. It may be desirable to include a binder resin.

The alkali-soluble acrylic binder resin thus obtained may not only be included as a binder resin but also may be added in small amounts in the above-described colorant manufacturing process to express hydrophobicity.

If a fluorine group-containing acrylic binder resin is added in the colorant, the content may be preferably 1 to 30% by weight based on the solid content in terms of pigment dispersion or hydrophobic expression.

On the other hand, when the photosensitive resin composition is manufactured using only an alkali-soluble acrylic binder resin, a large amount of multifunctional monomers should be used to form a light shielding film having a thickness of 2.2 μm or more, and thus, surface curing due to photocuring occurs quickly, resulting in wrinkles upon thermal curing. It may happen. In this regard, the photosensitive resin composition according to one embodiment of the present invention includes a cardo-based compound as a binder resin, which refers to an acrylate-based binder resin containing a fluorene group in a main chain, and is not particularly limited in structure. .

As an example, the compound represented by following General formula (1) is mentioned.

로 표시될 수 있다.In which X is

It may be represented as.

Y is also maleic anhydride, Succinic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, 3,4, 5,6-tetrahydrophthalic anhydride (3,4,5,6-Tetrahydrophthalic Anhydride), Phthalic Anhydride, Itaconic anhydride, 1,2,4-benzenetricarboxylic anhydride (1,2 , 4-Benzenetricarboxylic Anhydride, Methyl-Tetrahydrophthalic Anhydride, Citraconic Anhydride, 2,3-Dimethylmaleic Anhydride, 1-Cyclopentene- 1,2, -dicarboxylic anhydride (1-Cyclopentene-1,2-Dicarboxylic anhydride), cis (5-norbornene-endo-2,3-dicarboxylic acid anhydride (cis-5-Norbonene-endo-2,3- Dicarboxylic anhydride) and 1,8-naphthalic anhydride.

And Z is 1,2,4,5-benzenetetracarboxylic dianhydride (1,2,4,5-Bezenetetracarboxylic Dianhydride), 4,4'-biphthalic dianhydride (4,4'-Biphthalic Dianhydride), 3, 3 ', 4,4'-benzophenonetetracarboxylic dianhydride (3,3', 4,4'-Benzophenonetetracarboxylic Dianhydride), pyromellitic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid Dianhydrides (1,4,5,8-Naphthalenetetracarboxylic Dianhydride), 1,2,4,5-tetracarboxylic anhydride (1,2,4,5-Tetracarboxylic Anhydide), methylnorbornene-2,3-dicarboxylic anhydride (Methylnorbonene-2,3-Dicarboxylic Anhydride), 4,4 '-[2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] diphthalic anhydride (4,4'-[2, 2,2-Trifluoro-1- (Trifluoromethyl) Ethylidene] Diphthalic Anhydride, 4,4'-Oxydiphthalic Anhydride and 4,4'-Oxydiphthalic Anhydride and Ethylene Glycol Bis Residues of acid 2 anhydride selected from (Anhydro Trimelitate) have.

In an exemplary embodiment of the present invention, a functional group capable of expressing hydrophobicity may be introduced into the cardo-based compound structure, and in particular, a fluorine group may be introduced as described above.

There is no limitation as an example of the method which introduce | transduces a fluorine group in the manufacturing process of a cardo type compound, and the compound which can be used for introduction, The compound obtained from following Reaction Formula 1 is mentioned as a specific example.

Scheme 1

The above Reaction Scheme 1 is only intended to give an example of introducing a fluorine group into one example of the cardo-based compound, and is not intended to limit the fluorine group-containing cardo-based compound that can be used in the present invention.

The cardo-based compound as described above is preferably 1 to 40% by weight, more preferably about 20 to 30% by weight based on the total solids weight of the photosensitive resin composition. In the case of using a fluorine group-containing compound as the cardo-based compound, it may be preferably used in an amount of 5 to 10% by weight based on the total weight of the photosensitive resin composition in consideration of hydrophobic embodiment, developability, coating property, and dispersion stability.

However, when the photosensitive resin composition is manufactured using only a cardo-based compound, in forming a cured film having a thickness of 2.2 μm or more, it reacts with the polyfunctional monomer having an ethylenically unsaturated double bond by photocuring, so that only surface hardening occurs quickly. Wrinkles may occur due to shrinkage.

The photosensitive resin composition according to one embodiment of the present invention may include a polyfunctional monomer having an ethylenically unsaturated double bond, which serves to form a photoresist image by light. Examples thereof include propylene glycol methacrylate, dipentaerythritol hexaacrylate, dipentaerythritol acrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexane Diol acrylate tetraethylene glycol methacrylate, bisphenoxy ethyl alcohol diacrylate, trishydroxyethyl isocyanurate trimethacrylate, trimethylpropane trimethacrylate, pentaerythritol trimethacrylate, penta It may be one or a mixture of two or more selected from the group consisting of erythritol tetramethacrylate and dipentaerythritol hexamethacrylate.

The content is 0.1 to 99 parts by weight based on 100 parts by weight of the compound represented by the formula (1) is cross-linked due to the radical reaction of the photoinitiator by UV due to the pattern formation and the binding strength of the pigment and particle components is increased to increase the optical density It is preferable at the point.

In an embodiment of the present invention, a monomer capable of imparting hydrophobicity to the monomer may be further added. As the monomer, the monomer may be selected to implement hydrophobicity without impairing the coating property, adhesion, and leveling property of the photosensitive resin composition. Is required.

The example as is, CH ₂ (O) CHCH ₂ (CF ₂₎ xCF ₃ CF a siloxane-based compound, an example containing a fluorine-containing epoxy compound, a fluorine-divided into (where, x is an integer of 1 to 12), ₃ ( CF ₂ ) y Si (OMe) ₃ (where y is an integer of 1 to 12).

When such a monomer is added as an additive, the content thereof may vary in consideration of coating property, adhesion and leveling property, and hydrophobicity, and preferably 1 to 12 wt% based on the total solid content.

The photosensitive resin composition according to one embodiment of the present invention may include a photopolymerization initiator. An example of the photopolymerization initiator is 1- [9-ethyl-6- (2-methylbenzoyl) -9H-, which is an oxime ester compound. Carbazol-3-yl] -1- (O-acetyloxime) (1- [9-ethyl-6- (2-methybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime)), 1,2-octanedione-1 [(4-phenylthio) phenyl] -2-benzoyl-oxime (1,2-octanedione-1 [(4-phenylthio) phenyl] -2-benzoyl-oxime) and thioxanthone , 2,4-diethyl thioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4'-bis (diethylamino) benzophenone, acetophenone, p-dimethylaminoacetophenone, dimethoxyacetoxy Benzophenone, 2,2'-dimethoxy-2-petylacetophenone, p-methoxyacetophenone, 2-methyl [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2- Benzyl-2-diethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4- (2-hydroxy Ethoxy) phenyl- (2-hydroxy-2-pro ) Ketone, ketones such as 1-hydroxycyclohexyl phenyl ketone; Quinones such as anthraquinone and 1,4-naphthoquinone; 1,3,5-tris (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2-chlorophenyl) -s-triazine, 1,3-bis (trichloro Halogen compounds such as rophenyl) -s-triazine, phenacyl chloride, tribromomethyl phenylsulfone and tris (trichloromethyl) -s-triazine; Peroxides such as di-t-butyl peroxide; It may be selected from acyl phosphine oxides, such as 2,4,6-trimethyl benzoyl diphenyl phosphine oxide.

Such a photopolymerization initiator is usually preferably contained in 1 to 30% by weight of the total resin composition.

In the photosensitive resin composition according to the embodiment of the present invention, a solvent may be included. Examples of the solvent include propylene glycol methyl ether acetate (PGMEA), propylene glycol ethyl ether acetate, propylene glycol methyl ether, propylene glycol propyl ether, and methyl. Cellosolve acetate, ethyl cellosolve acetate, diethyl glycol methyl acetate, ethyl ethoxy propionate, methyl ethoxy propionate, butyl acetate, ethyl acetate, cyclohexanone, acetone, methyl isobutyl ketone, dimethylform Amide, N, N'-dimethylacetamide, N-methylpyrrolidinone, dipropylene glycol methyl ether, toluene, methyl cellosolve and ethyl cellosolve.

The content may be about 20 to 60% by weight in the total photosensitive resin composition.

In addition, a conventional additive may be further included as needed.

Such a photosensitive resin composition includes (a) a pigment mixture, (b) an alkali-soluble acrylic binder resin, (c) a cardo compound, (d) a polyfunctional monomer having an ethylenically unsaturated double bond, (e) a photoinitiator, and Therefore, the organic additive and the solvent (f) may be mixed with a stirrer and filtered through a 5 탆 membrane filter to prepare a photosensitive resin composition.

A spin coater (rotary coating device) or slit coater (non-rotary coating device) on a glass substrate (eg, ITO or IZO deposited glass substrate) including a glass substrate or a transparent electrode layer having a clean surface of the photosensitive resin composition. Apply using a non-contact type coating device.

In the said preparation and application | coating, in order to improve the adhesiveness of a board | substrate and the photosensitive resin composition, a silane coupling agent can be mix | blended or apply | coated to the said board | substrate.

After the coating, it is dried for 60 seconds to 150 seconds at a temperature of 80 ℃ ~ 120 ℃, preferably 80 ℃ ~ 100 ℃ with a hot plate, or left for several hours to several days at room temperature, or in a warm air heater, infrared heater 10 minutes to several hours to remove the solvent (aka pre-bake) to adjust the thickness of the coating film in the range of 1.5 to 5㎛, and then irradiated with active mask energy rays such as ultraviolet rays through a mask The exposure is performed in the range of ˜1000 mJ / cm ² . The irradiation energy dose may vary depending on the type of light shielding film photosensitive composition to be used. The film obtained by exposing is developed using the developing solution by the immersion method, the spray method, etc., and a cured film pattern is formed. As a developing solution used for image development, organic type, such as monoethanolamine, diethanolamine, and triethanolamine, or aqueous solution, such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, a quaternary ammonium salt, is mentioned.

Post-bake may be performed after development, and more specifically, it may be preferable to perform post-bake for 20 to 40 minutes at 150 to 250 ° C.

Preferably, the light-shielding film obtained by the embodiment of the present invention may satisfy appropriate hydrophobicity while having appropriate light-shielding property when the fluorine content per 1 g of the cured film is about 5 to 50% by weight.

The cured film thus obtained has appropriate light shielding properties, satisfies proper hydrophobicity, and may be particularly useful for forming a light shielding pattern in forming a colored layer by a jetting method by inkjet printing.

A display device that can be used by forming a colored layer using the photosensitive resin composition of the present invention, but the liquid crystal display is mainly listed above, but is not limited thereto. For example, various display devices requiring a colored layer may include a plasma display. And display devices such as a display device, an EL display device, and a CRT display device.

In addition, there is no particular limitation on the liquid crystal display device to which the present invention can be applied, and it can be applied to various types of liquid crystal display devices. The display device according to the present invention is electrically controlled irefringence (ECB), twisted nematic (TN), in-plane switching (IPS), ferroelectric liquid crystal (FLC), optimally compensated bend (OCB), supper twisted nematic (STN), and vertically (VA) Various display modes such as Aligned), HAN (Hybrid Aligned Nematic), and GH (Guest Host) can be adopted. As described above, the display device in which the colored layer is formed by the photosensitive resin composition of the present invention can be applied to a display device for a large screen such as a laptop display or a television monitor.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.

Preparation Examples 1 to 5 : Examples of Synthesis of Alkali-Soluble Acrylic Binder Resin

Into a 1000 ml four-necked flask was added a composition as shown in Table 1 and stirred for 30 minutes while blowing nitrogen thereto. Next, the temperature was gradually raised and reacted at 70 ° C. for 6 hours, the temperature was raised to 80 ° C., and further reacted for 2 hours to synthesize an alkali-soluble acrylic binder resin. In Table 1 below, the unit is g.

Preparation Example 1 Production Example 2 Production Example 3 Preparation Example 4 Preparation Example 5 MAA 39.27 28.62 26.22 24.19 22.43 GMA 130.90 121.10 110.92 102.33 49.35 Sty 26.18 15.41 14.12 13.02 11.21 KBM503 21.82 8.81 8.07 7.44 6.73 FA-108 - 44.04 60.50 74.42 134.58 Initiator 21.82 22.02 20.17 18.60 15.70 PGMEA 560.00 560.00 560.00 560.00 560.00

MAA: Methacrylic acid, GMA: Glycidyl methacrylate, Sty: Styrene

KBM503: 3- (methacryloxypropyl) trimethoxysilane, Shin-Etsu Chemical

FA-108: 2- (perfluorooctyl) ethyl acrylate from Kyoeisha

Initiator: Azobisisobutyronitrile

PGMEA: propylene glycol monomethyl ether acetate

Preparation Example 6 Example of Synthesis of Cardo Compound

Into a 500 ml four-neck flask, 58 g of bisphenol fluorene type epoxy resin (epoxy equivalent 232), 313 g of propylene glycol monomethyl ether acetate, 2.5 g of triethylbenzyl ammonium chloride, 0.03 g of hydroquinone and 18 g of acrylic acid were added thereto, and 25 ml / min. It melt | dissolved by heating at 80 degreeC-90 degreeC, inject | pouring nitrogen at the speed of. The solution was gradually warmed up in a cloudy state and completely dissolved at 80 ° C. The heating and stirring were continued until the acid value was measured to be less than 1.0 mgKOH / g. It took 12 hours to reach the goal. Then, it cooled to room temperature and obtained the colorless and transparent bisphenol fluorene type epoxy acrylate.

To 300 g of the bisphenol fluorene type epoxy acrylate thus obtained, 14 g of 1,2,3,6-tetrahydro phthalic anhydride, 0.3 g of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and tetraethylammonium 0.76 g of um bromide was mixed, gradually heated up, and reacted at 130 ° C to 140 ° C for 15 hours to obtain a cardo compound.

<Examples>

In each of the cardo-based compounds obtained in Production Example 6 and the alkali-soluble acrylic binder resins obtained in Production Examples 1 to 5, a pigment dispersion (KLBK-90, Mikuni, 20% by weight solid content, pigment dispersant) BYK Co., Ltd., disperbyk-2001) was added 130 parts by weight of the total weight of the pigment dispersion), 2 parts by weight of the polyfunctional monomer (Dipentaerythritol hexaacrylate), 5.2 parts by weight of the photopolymerization initiator was added to the solvent (propylene 90 parts by weight of glycol methyl ether acetate (PGMEA) and 1 part by weight of other additives (fluorine-based surfactant and coupling agent) were added and stirred for 3 hours to prepare a photosensitive resin composition.

The parts by weight are expressed in terms of 100 parts by weight of the cardo-based compound solids content.

However, as shown in Table 2, the content ratio of the acrylic binder resin and the cardo-based compound in the binder resin was different.

Example Acrylic binder resin Production Example Acrylic binder resin compounding quantity
(Based on 100 parts by weight of the total binder resin) Fluoride in total composition
content
(Wt% based on solids) One Preparation Example 1 5 0 2 10 0 3 15 0 4 20 0 5 Production Example 2 5 0.5 6 10 0.5 7 15 0.5 8 20 0.5 9 Production Example 3 5 1.0 10 10 1.0 11 15 1.0 12 20 1.0 13 Preparation Example 4 5 1.5 14 10 1.5 15 15 1.5 16 20 1.5 17 Preparation Example 5 5 2.0 18 10 2.0 19 15 2.0 20 20 2.0

The cured film pattern was formed by the following method using the photosensitive resin composition obtained in this way; On a glass substrate having a clean surface, a spin coater was used to coat at 320 rpm to form a resin coating layer. After coating, the coating film was dried at a temperature of 80 ° C. for 150 seconds on a hot plate so that the thickness of the coating film was 2.2 μm. Subsequently, active-line energy rays, such as an ultraviolet-ray, were exposed through the mask (gap 200 micrometers) in the range of 60 mJ / cm <2> of irradiation energy doses. The exposed film was developed (developing time 100 seconds) using a developing solution (0.04% KOH, 23 ° C) to form a cured film pattern.

Post-baking was performed at 220 ° C. for 30 minutes after development.

Optical density measurement method of cured film using the photosensitive resin composition

The cured film obtained as described above was measured in the optical density using a reference having an optical density of 2.4 using the PMT equipment of Otsuka Electronics Co., Ltd., and is shown in Table 1.

Method for measuring contact angle of cured film using photosensitive resin composition

The contact angle with respect to water (deionized water) was measured by dropping 5 microliters of water (deionized water) using Syringe on the cured film obtained as mentioned above.

In addition, the contact angle with respect to 2-ethoxy ethanol was also measured using 2-ethoxy ethanol (99% by Aldrich) instead of water.

The contact angle measuring instrument was made by Kruss (model name E-EM03-T13-01).

Pattern Profile Measurement

Taper angle was measured about the obtained cured film pattern using SEM.

Residue

SEM was used to confirm the presence of residue after development.

permittivity

After coating the cured liquid on the chromium (Cr) glass to expose the entire surface and post-baked to obtain a cured film, the dielectric constant was measured for each frequency (100 ~ 1MHz).

The dielectric constant was used as a thermal evaporator (model name: E306, Edward).

resolution

After pattern development by mask size, the pattern size was measured through OM Image.

Voltage retention measurement method of cured film using the photosensitive resin composition

A measuring cell (EHC Co., Ltd.) with a glass substrate (standard 1 cm ㅧ 1 cm) on which an ITO electrode layer is formed for voltage application and a glass substrate (standard 1 cm ㅧ 1 cm) on which an ITO common electrode layer is formed, facing the electrode layer with a cell gap of 5 μm. Article) was prepared.

Meanwhile, the cured film obtained as described above was scraped off, and 0.02 g of the cured film sample and 1 g of the liquid crystal (MLC-7022-100, Merck Co., Ltd.) were mixed in a test tube and aged at 65 ° C. for 5 hours to prepare a contaminant.

The prepared pollutant was injected into the measuring cell, and voltage retention was measured by applying voltage under the following conditions.

-Applied voltage pulse amplitude 5V

-Applied voltage pulse frequency 60Hz

-Applied voltage pulse width 16.6msec

The instrument used for measuring the voltage holding ratio is TOYO corporation Model 6245C, and the measuring temperature is 25 ℃.

The results obtained by the above measurement method are shown in Table 3 below.

Example Contact angle (°) Taper Angle (°) Presence of residue permittivity
(a constant) Optical density
(/2.0㎛) resolution
(Μm) VHR
(%) water 2-ethoxy
ethanol One
82.7
27.3 60 none 3.9 2.2 8 97 2 60 none 3.9 2.2 8 97 3 60 none 3.9 2.2 8 97 4 60 none 3.9 2.2 8 97 5 96.4 44.1 60 none 3.9 2.2 8 97 6 100.5 45.9 60 none 3.9 2.2 8 97 7 100.9 46.1 60 none 3.9 2.2 8 97 8 100.7 46.3 60 none 3.9 2.2 10 97 9 99.6 47.1 60 Occur 3.9 2.2 8 97 10 103.6 48.2 60 none 3.9 2.2 8 97 11 103.9 48.5 60 none 3.9 2.2 9 97 12 104.2 48.8 60 Occur 3.9 2.2 10 97 13 103.6 48.5 60 none 3.9 2.2 8 97 14 104.6 49.1 60 none 3.9 2.2 8 97 15 104.9 50.2 60 Occur 3.9 2.2 10 97 16 105.0 50.3 60 Occur 3.9 2.2 11 97 17 104.6 49.5 60 none 3.9 2.2 8 97 18 106.5 51.5 60 none 3.9 2.2 8 97 19 106.9 51.8 60 Occur 3.9 2.2 10 97 20 107.0 52.0 60 Occur 3.9 2.2 12 97

From the results in Table 3, the cured film obtained from Examples 5 to 20 had a contact angle of 95 ° or more for water and a contact angle of 2-ethoxyethanol of 40 ° or more, whereas the cured film obtained of Examples 1-4 The membrane had a contact angle for water of 82.7 ° and a contact angle for 2-ethoxyethanol of 27.3 °.

As a result, when the color ink is injected by the jetting method using the inkjet printing after forming the light shielding film, the cured films of Examples 5 to 20 are mixed in the color ink beyond the partition wall or colored within the area defined as the partition wall. It can be assumed that the ink will not cause problems such as out of position.

In view of the above results, the most optimal embodiment in preventing or minimizing damage of other evaluation values may be referred to as 6,7,10,11,13,14,17,18, and the like.

Claims (26)

Alkali-soluble acrylic binder resins and cardo-based binder resins; The photosensitive resin composition which satisfy | fills all the following 1st conditions-3rd conditions at the time of resin cured film formation. First condition: Optical density (OD) per unit thickness of 2.0 mu m should be 2.0 or more. Second condition: The contact angle to water should be 85 ° or more. Third condition: The contact angle with respect to 2-ethoxyethanol is 35 degrees or more. The photosensitive resin composition of Claim 1 whose contact angle with respect to water is 85-110 degrees at the time of resin cured film formation. The photosensitive resin composition of Claim 1 whose contact angle with respect to 2-ethoxyethanol is 35-50 degrees at the time of resin cured film formation. The photosensitive resin composition of Claim 1 containing the coloring agent containing the at least 2 sort (s) of pigment mixing component which can mix and express a substantially black color. 5. The photosensitive resin composition according to claim 4, wherein the pigment mixing component includes red pigment and blue pigment as essential components, and further includes a single or a mixture thereof selected from yellow pigment, green pigment and violet pigment. According to claim 5, wherein the pigment mixture component 10 to 50% by weight of red pigment, 10 to 50% by weight of blue pigment, 1 to 20% by weight of yellow pigment and 1 to 20% by weight of green pigment based on the solids content of the total weight of the colorant Photosensitive resin composition comprising a. The photosensitive resin composition of claim 6, wherein the pigment mixing component comprises 1 to 20% by weight of the violet pigment based on the solids content of the total weight of the colorant. The photosensitive resin composition according to claim 6, wherein the pigment mixing component comprises a black pigment. The method of claim 8, wherein the black pigment is based on the solids content of the total weight of the colorant Photosensitive resin composition which is contained in 15% by weight or less. The photosensitive resin composition of claim 4, wherein the colorant is included in an amount of 20 to 80 wt% based on the total weight of the photosensitive resin composition. According to claim 1, Polyfunctional monomer having an ethylenically unsaturated double bond; Photopolymerization initiator; And a photosensitive resin composition comprising a solvent. The photosensitive resin composition of Claim 1 in which alkali-soluble acrylic binder resin contains an epoxy group. The photosensitive resin composition of Claim 11 or 12 whose alkali-soluble acrylic binder resin contains a fluorine group. The photosensitive resin composition according to claim 13, wherein the alkali-soluble acrylic binder resin has a fluorine content of 5 to 50% by weight. The photosensitive resin composition according to claim 4 or 5, wherein the pigment mixing component is in the form of a pigment dispersion in which each pigment is dispersed in a solvent. The photosensitive resin composition according to claim 15, wherein the pigment dispersion contains at least one pigment dispersant selected from acrylate pigment dispersants. The photosensitive resin composition according to claim 15, wherein the pigment dispersion contains 3 to 20% by weight of the pigment dispersant in the total weight of the pigment dispersion. The photosensitive resin composition according to claim 15, wherein the pigment dispersion contains an acrylic binder resin containing a fluorine group. The photosensitive resin composition according to claim 1, wherein the cardo-based binder resin contains a fluorine group. The photosensitive resin composition of Claim 1 containing a fluorine-group containing epoxy monomer. The photosensitive resin composition of Claim 1 containing a fluorine-group containing siloxane monomer. The photosensitive resin composition of Claim 1 whose fluorine content is 5 to 50 weight% per 1 g of weight of cured film at the time of cured film formation. The color filter substrate containing the black matrix formed by the photolithographic method using the photosensitive resin composition of Claim 1. A thin film transistor substrate comprising a black matrix formed by photolithography using the photosensitive resin composition of claim 1. An image display device comprising the color filter substrate of claim 23 as an upper substrate. An image display device comprising the thin film transistor substrate of claim 24 as a lower substrate.