KR20210020981A - Color photosensitive resin composition, column spacer manufactured thereby and liquid crystal display comprising the same - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition, to a column spacer manufactured thereby, and to a liquid crystal display device comprising the same and, more specifically, to a colored photosensitive resin composition comprising: a colorant; an alkali-soluble resin; a photopolymerizable compound; and a photoinitiator along with random silsesquioxane having a reactive group, thereby having excellent light blocking properties, elastic recovery rate, solvent resistance and heat resistance so that it can be applied to both a black matrix and the column spacer, and thus being capable of producing a liquid crystal display device with improved reliability, to a column spacer manufactured thereby, and to a liquid crystal display device comprising the same.

Description

A colored photosensitive resin composition, a column spacer manufactured thereby, and a liquid crystal display device having the same TECHNICAL FIELD [COLOR PHOTOSENSITIVE RESIN COMPOSITION, COLUMN SPACER MANUFACTURED THEREBY AND LIQUID CRYSTAL DISPLAY COMPRISING THE SAME}

The present invention relates to a colored photosensitive resin composition that can be used for both a column spacer and a black matrix with excellent light-shielding property, elastic recovery rate, solvent resistance, and high reliability, and a column spacer manufactured thereby, and a liquid crystal display device having the same.

The display industry has undergone a rapid change from a cathode-ray tube (CRT) to a flat panel display represented by plasma display panel (PDP), organic light-emitting diode (OLED), and liquid-crystal display (LCD). In particular, LCD is a major product in the flat panel display market, and is composed of a top plate with a color filter, a bottom plate with a thin film transistor (TFT), and a liquid crystal injected therebetween.

Color filters are a key component for expressing colors in LCDs, and have been adopted for a wide range of applications such as notebook PCs, monitors, and portable terminals along with the spread of flat panel displays. These color filters implement various colors on the screen through red (R), green (G), and blue (B) patterns on the substrate, and between each red (R), green (G), and blue (B) pattern. A black matrix that is located at and prevents light leakage between pixels, an overcoat (OC) that improves flatness by correcting a step difference between pixels, and a column spacer that maintains a cell-gap between two substrates ( CS; column spacer).

In general, the production of a curly filter is a photosensitive resin composition containing a colorant corresponding to each color of red (R), green (G), and blue (B) on a patterned substrate with a black matrix, uniformly applied by spin coating. Thereafter, the coating film formed by heat drying is exposed and developed, and if necessary, the operation of further heating and curing is repeated for each color to form pixels of each color. At this time, the black matrix BM is located at the boundary between the colored layers of each color in order to prevent mixing of different colors in each pixel or to hide the electrode pattern, and is mainly formed of a black photosensitive resin composition. In addition, the overcoat (OC) and the column spacer (CS) are also constructed using a photosensitive resin composition.

Therefore, the photosensitive resin composition is becoming more important as the use of LCD is advanced and diversified, and the demand for excellent mechanical properties and quick response to light to improve productivity and durability is increasing.

In addition to this, in recent years, it is required that a single material used inside the display plays various roles simultaneously. As a representative black matrix integrated column spacer, not only the optical density (OD) required by the black matrix, but also excellent electrical insulation is required. In addition, very high reliability is required, and the elution characteristics of the colorant used in the organic solvent must be controlled.

However, when only carbon black is used as in a conventional black matrix to form a black matrix-integrated column spacer, the optical density is satisfied but electrical insulation is poor. In addition, all of the black matrix materials using inorganic compounds did not satisfy the physical properties required for the black matrix integrated column spacer due to low insulating properties.

In addition, in a panel in which a black matrix is formed on a TFT surface or a color filter is formed on top of a color filter, high insulation or low dielectric properties are required because electrical insulation directly affects the liquid crystal. As such, the composition of the photosensitive composition for forming the black matrix and the column spacer is similar, but it is not easy to apply one composition to both due to the difference in required physical properties, such as not using a colorant in the case of the column spacer. not.

For example, Japanese Patent Application Laid-Open No. 2007-071994 proposes a photosensitive resin composition that can also serve as a column spacer by using a perylene-based compound having insulating properties instead of conductive carbon black as a black pigment.

In addition, Korean Patent Publication No. 2012-0033893 contains a binder resin, a polyfunctional monomer, a photoinitiator or a photosensitizer, and a solvent, and black pigments such as aniline black, perylene black, and metal oxide are added as colorants. I am referring to a technique to do.

These patents can secure some degree of electrical insulation improvement through various combinations of compounds used as colorants. However, since they are used as column spacers, they are used as column spacers. , It is insufficient to obtain satisfactory properties in terms of chemical resistance, sensitivity, and developability.

Accordingly, in order to improve adhesive properties and chemical stability, Korean Patent Publication No. 2011-0068861 refers to a technique of adding a cage silsesquioxane to a colored photosensitive resin composition.

However, the above patent shows some degree of improvement in adhesion and solvent resistance through basket-type silsesquioxane, but the composition is for color filter application and differs from physical properties required for black matrix and column spacer, and basket-type silsesquioxane Quioxane is disadvantageous in terms of productivity because a large cost is required for synthesis.

Japanese Patent Laid-Open No. 2007-071994 Korean Patent Publication No. 2012-0033893 Korean Patent Publication No. 2011-0068861

Accordingly, the applicant of the present invention conducted various studies to produce a photosensitive composition that can be used for both by satisfying the physical properties of the column spacer and the black matrix of the liquid crystal display device at the same time. The present invention was completed by confirming that the reliability of the liquid crystal display device can be improved by using quioxane because of the excellent optical density, light-shielding property, adhesion, electrical insulation, elastic recovery rate, and solvent resistance required by the column spacer and black matrix. I did.

Accordingly, it is an object of the present invention to provide a colored photosensitive resin composition comprising random silsesquioxane having at least one reactive group in a molecular structure so as to be used for forming a black matrix and a column spacer.

In addition, another object of the present invention is to provide a use of the colored photosensitive resin composition for manufacturing a column spacer.

In addition, another object of the present invention is to provide a use in which the colored photosensitive resin composition can be used as a black matrix integrated column spacer.

In order to achieve the above object, the present invention provides a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a random silsesquioxane having at least one reactive group in the molecular structure.

The random silsesquioxane having at least one reactive group in the molecular structure is characterized by represented by the following formula (1).

[Formula 1]

(In Formula 1, R′, R″, x and y are as described in the specification)

The colored photosensitive resin composition is 1 to 60% by weight of a colorant, 10 to 80% by weight of an alkali-soluble resin, 1 to 30% by weight of a photopolymerizable compound, 0.01 to 10% by weight of a photopolymerization initiator, and a molecular structure to satisfy 100% by weight of the total composition. It is characterized in that it comprises 0.1 to 15% by weight of random silsesquioxane having at least one reactor in.

In addition, the present invention features a column spacer made of the colored photosensitive resin composition and a liquid crystal display device including the same.

In addition, the present invention features a black matrix integrated column spacer made of the colored photosensitive resin composition and a liquid crystal display device including the same.

The colored photosensitive resin composition according to the present invention not only secures physical properties such as optical density, adhesion, electrical insulation, and light shielding properties required for both the black matrix and the spacer, but also has excellent elastic recovery and solvent resistance, thereby improving the reliability of a liquid crystal display. Can be improved.

The present invention provides a colored photosensitive resin composition that can be used as a column spacer or a black matrix integrated column spacer in a liquid crystal display device.

In particular, the present invention proposes a colored photosensitive resin composition containing as an essential component random silsesquioxane having at least one reactive group in the molecular structure, and the random silsesquioxane having at least one reactive group in the molecular structure is It has excellent adhesion to inorganic materials, and thus adhesion to a transparent conductive film or inorganic film can be improved. In addition, the colored photosensitive resin composition not only secures physical properties such as optical density, elastic recovery rate, electrical insulation, and light-shielding properties required for both the black matrix and the column spacer, but also has excellent heat resistance and solvent resistance, thereby improving the reliability of a liquid crystal display device. Secure benefits that can be improved.

In addition to the random silsesquioxane having at least one reactive group in the molecular structure, the colored photosensitive resin composition according to the present invention includes a colorant, an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator.

Each composition will be described below.

The random silsesquioxane having at least one reactive group in the molecular structure in the present invention is characterized by represented by the following formula (1).

In particular, the random silsesquioxane having at least one reactive group in the molecular structure has excellent adhesion to inorganic materials because the terminal reactive group and the alkoxy silane group remain, so it is added as an adhesion promoter to the conventional colored photosensitive resin composition. Can replace silane coupling agent. In addition, since it has excellent solvent resistance and heat resistance, stability of chemical tablets in the process is improved, and reliability and durability can be further increased. This is because when the conventionally proposed ladder type silsesquioxane is used in the colored photosensitive resin composition, the solvent resistance and heat resistance are not sufficiently improved, and when the colored photosensitive resin composition is prepared using a basket-type silsesquioxane, the introduced reactor Since the reactivity is inhibited due to the structure of the cage silsesquioxane, a complete reaction cannot be achieved, so the use of the random silsesquioxane has an advantage in terms of improved characteristics. In addition, the synthesis of random silsesquioxane is much more advantageous in terms of product economy because the process is simpler than that of a basket type or a ladder type.

(In Formula 1,

R′ and R″ are the same as or different from each other, and are each independently hydrogen, a hydroxy group, a C ₁ to C ₁₀ alkyl group, a C ₁ to C ₁₀ alkoxy group or -(R ₁ ) _n -R ₂ , and the R At least one of'and R″ is -(R ₁ ) _{n -R 2} ;

At this time, R ₁ is hydrogen, a C ₁ to C ₁₀ alkylene group, -R ₃ -OR ₄ -or -R ₅ -C(=O)OR ₆ -, wherein R ₃ to R ₆ are the same as or different from each other, and each independently As a C ₁ to C ₁₀ alkylene group;

R ₂ is hydrogen, thiol group, isocyanate group, carboxyl group, hydroxyl group, amino group, urea group, urethane group, (meth)acrylate group, C ₁ to C ₁₀ alkyl group, C ₁ to C ₁₀ alkoxy group, C ₃ to C ₁₅ cycloalkyl group, C ₃ to C ₁₅ heterocycloalkyl group, C ₆ to C ₂₀ aryl group or C ₅ to C ₂₀ heteroaryl group;

x is an integer from 1 to 500;

y is an integer from 1 to 500;

n is an integer of 0 or 1)

The alkyl group mentioned in the present invention includes a straight chain or branched type, and methyl, ethyl, n-propyl, i-propyl, n-butyl, isobutyl, pentyl, hexyl, isohexyl, heptyl, 4,4-dimethylpentyl , Octyl, 2,2,4-trimethylpentyl, nonyl, and the like.

The alkylene group mentioned in the present invention is a divalent form of an alkyl group. Alkylene can be straight chain, branched, cyclic, or a combination thereof.

Cycloalkyl groups referred to in the present invention are fully saturated and partially unsaturated hydrocarbon rings of carbon atoms, cyclopropyl, cyclopropylmethyl, cyclopentyl, cyclohexyl, adamantyl, and substituted and unsubstituted bornyl, norbor Neil and norbornenyl.

The heterocycloalkyl group mentioned in the present invention is a non-aromatic cycloalkyl group in which one carbon atom in the ring is replaced by a heteroatom selected from oxygen, sulfur or nitrogen, and up to 3 additional carbon atoms are replaced by the heteroatom. Means. Examples of such heterocycloalkyl groups include epoxy, thiranyl, aziridinyl, oxetanyl, azetidinyl, tetrahydro-furanyl, tetrahydro-thiophenyl (synonymous with tetrahydro-thienyl), pyrrolidinyl, pyrazoli Denyl, imidazolidinyl, oxazidineyl, isoxazidineyl, thiazolidinyl, isothiazolidinyl, piperidinyl, piperazinyl, morpholinyl, tetrahydropyranyl, and the like.

The alkoxy group referred to in the present invention refers to _a group -OR a, where R _a is an alkyl group as defined above. Specifically, it includes methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy, and the like.

The aryl group referred to in the present invention is a monocyclic or bicyclic aromatic ring, containing one or more rings having 6 or more atoms, and 5 or less rings containing 22 or less atoms, and adjacent Alternating double bonds may exist between carbon atoms or suitable heteroatoms. Specifically, phenyl, biphenyl, terphenyl, stilbene, naphthyl, anthracenyl, phenanthryl, pyrenyl, and the like are included.

The heteroaryl group referred to in the present invention refers to a substituted or unsubstituted aromatic monocyclic group, a bicyclic group, and a tricyclic group having one or more heteroatoms (oxygen, sulfur or nitrogen) in one or more rings. . Specifically, furyl, thienyl, pyridyl, quinolinyl, isoquinolinyl, indolyl, isoindolyl, triazolyl, pyrrolyl, tetrazolyl, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, benzofura Neil, benzothiophenyl, carbazolyl, benzoxazolyl, pyrimidinyl, benzimidazolyl, quinoxalinyl, benzothiazolyl, naphthyridinyl, isoxazolyl, isothiazolyl, furinyl, quinazolinyl, Pyrazinyl, 1-oxidopyridyl, pyridazinyl, triazinyl, tetrazinyl, oxadiazolyl, thiadiazole, tetrahydronaphthyl, and the like.

Preferably, R ₁ is a C ₁ to C ₅ alkylene group, and R ₃ to R ₆ are the same as or different from each other, and each independently a C ₁ to C ₅ alkylene group.

Preferably, R ₂ is a thiol group, an isocyanate group, a (meth)acrylate group, a phenyl group or an epoxy group.

Preferably, when the -(R ₁ ) _n -R ₂ is n=0, the R ₂ is a thiol group, an isocyanate group, a (meth)acrylate group, a phenyl group or an epoxy group, and when n=1, the R ₁ and R ₃ to R ₆ are the same as or different from each other, and each independently a C ₁ to C ₅ alkylene group, and R ₂ is as mentioned above when n=0.

Preferably, the R′ and R″ may be the same as or different from each other, the aforementioned hydroxy group, C ₁ to C ₁₀ alkyl or -(R ₁ ) _n -R ₂ , and among the R′ and R″ At least one is -(R ₁ ) _n -R ₂ . For example, the R′ and R″ may have different reactive groups such as a methyl group-thiol group, a methyl group-phenyl group, a methyl group-epoxy group, and a thiol group-epoxy group combination to improve reactivity with an inorganic material.

The x and y are determined according to the weight average molecular weight of the random silsesquioxane according to the present invention. Usually, the weight average molecular weight of the random silsesquioxane is 500 to 1,000,000, preferably 1,000 to 100,000.

The compound of Formula 1 is directly prepared or commercially available, and directly prepared or commercially available, and ARAKAWA CHEMICAL COMPOCERAN SQ107, COMPOCERAN SQ109, COMPOCERAN SQ506, COMPOCERAN SQ502-8, and the like may be used.

The random silsesquioxane having the above reactor may be used in an amount of 0.1 to 15% by weight, preferably 0.1 to 10% by weight, within 100% by weight of the total colored photosensitive resin composition. This content is a range selected to ensure adhesion improvement, and if it is used below the above range, there is a fear that the desired effect may not be sufficiently obtained. Conversely, if it exceeds the above range, compatibility with other ingredients decreases or alkali developability There is a problem in that it is degraded, so that contamination, film residue, etc. are easily generated.

The colorant in the present invention may impart light-shielding properties to prevent light leakage to the black matrix, and to prevent malfunction of the device due to light caused from outside the column spacer.

The colorant is not particularly limited in the present invention as long as it has light-shielding property to visible light, and all known colorants such as organic pigments, dyes and black pigments may be used, and these may be used alone or in combination of two or more.

For example, organic pigments are compounds classified as pigments in the color index (CI; published by The Society of Dyers and Colorists), specifically, the following color index (CI) The name is given.

C.I. Pigment Yellow No. 1, C.I. Pigment Yellow No. 12, C.I. Pigment Yellow No. 13, C.I. Pigment Yellow No. 14, C.I. Pigment Yellow No. 15, C.I. Pigment Yellow No. 16, C.I. Pigment Yellow No. 17, C.I. Pigment Yellow No. 20, C.I. Pigment Yellow No. 24, C.I. Pigment Yellow No. 31, C.I. Pigment Yellow No. 53, C.I. Pigment Yellow No. 55, C.I. Pigment Yellow No. 83, C.I. Pigment Yellow No. 86, C.I. Pigment Yellow No. 93, C.I. Pigment Yellow No. 94, C.I. Pigment Yellow No. 109, C.I. Pigment Yellow No. 110, C.I. Pigment Yellow No. 117, C.I. Pigment Yellow No. 125, C.I. Pigment Yellow No. 128, C.I. Pigment Yellow No. 137, C.I. Pigment Yellow No. 138, C.I. Pigment Yellow No. 139, C.I. Pigment Yellow No. 147, C.I. Pigment Yellow No. 148, C.I. Pigment Yellow No. 150, C.I. Pigment Yellow No. 153, C.I. Pigment Yellow No. 154, C.I. Pigment Yellow No. 155, C.I. Pigment Yellow No. 166, C.I. Pigment Yellow No. 168, C.I. Pigment Yellow No. 173, C.I. Pigment Yellow No. 180, C.I. Pigment yellow 211;

C.I. Pigment Orange No. 5, C.I. Pigment Orange No. 13, C.I. Pigment Orange No. 14, C.I. Pigment Orange No. 24, C.I. Pigment Orange No. 31, C.I. Pigment Orange No. 34, C.I. Pigment Orange No. 36, C.I. Pigment Orange No. 38, C.I. Pigment Orange No. 40, C.I. Pigment Orange No. 42, C.I. Pigment Orange No. 43, C.I. Pigment Orange No. 46, C.I. Pigment Orange No. 49, C.I. Pigment Orange No. 51, C.I. Pigment Orange No. 55, C.I. Pigment Orange No. 59, C.I. Pigment Orange No. 61, C.I. Pigment Orange No. 64, C.I. Pigment Orange No. 65, C.I. Pigment Orange No. 68, C.I. Pigment Orange No. 70, C.I. Pigment Orange No. 71, C.I. Pigment Orange No. 72, C.I. Pigment Orange No. 73, C.I. Pigment orange 74;

C.I. Pigment Red No. 1, C.I. Pigment Red No. 2, C.I. Pigment Red No. 5, C.I. Pigment Red No. 9, C.I. Pigment Red No. 17, C.I. Pigment Red No. 31, C.I. Pigment Red No. 32, C.I. Pigment Red No. 41, C.I. Pigment Red No. 97, C.I. Pigment Red No. 105, C.I. Pigment Red No. 122, C.I. Pigment Red No. 123, C.I. Pigment Red No. 144, C.I. Pigment Red No. 149, C.I. Pigment Red No. 166, C.I. Pigment Red No. 168, C.I. Pigment Red No. 170, C.I. Pigment Red No. 171, C.I. Pigment Red No. 175, C.I. Pigment Red No. 176, C.I. Pigment Red No. 177, C.I. Pigment Red No. 178, C.I. Pigment Red No. 179, C.I. Pigment Red No. 180, C.I. Pigment Red No. 185, C.I. Pigment Red No. 192, C.I. Pigment Red No. 202, C.I. Pigment Red No. 206, C.I. Pigment Red No. 207, C.I. Pigment Red No. 208, C.I. Pigment Red No. 209, C.I. Pigment Red No. 214, C.I. Pigment Red No. 215, C.I. Pigment Red No. 216, C.I. Pigment Red No. 220, C.I. Pigment Red No. 221, C.I. Pigment Red No. 224, C.I. Pigment Red No. 242, C.I. Pigment Red No. 243, C.I. Pigment Red No. 254, C.I. Pigment Red No. 255, C.I. Pigment Red No. 262, C.I. Pigment Red No. 264, C.I. Pigment Red No. 265, C.I. Pigment red No. 272;

C.I. Pigment Blue No. 15, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 15:6, C.I. Pigment Blue No. 16, C.I. Pigment Blue No. 60, C.I. Pigment blue 80;

C.I. Pigment Purple No. 1, C.I. Pigment Purple No. 19, C.I. Pigment Purple No. 23, C.I Pigment Purple No. 29, C.I Pigment Purple No. 32, C.I Pigment Purple No. 36, C.I Pigment Purple No. 38;

C.I. Pigment Green No. 7, C.I. Pigment Green No. 36, C.I. Pigment green 58;

C.I. Pigment Brown No. 23, C.I. Pigment brown No. 25;

C.I. Pigment Black No. 1, C.I. Pigment Black No. 7.

These pigments may be rosin treatment, surface treatment using pigment derivatives into which acidic or basic groups are introduced, surface graft treatment using polymer compounds, fine particle treatment using sulfuric acid, or cleaning using organic solvents or water. Processing or the like may have been performed.

Specifically, the organic pigment used in the present invention may be contained in an amount of 30 to 95 parts by weight based on 100 parts by weight of the solid content of the colorant. Among these colorants, organic pigments are C.I. Pigment Blue 16 and C.I. It is characterized in that it comprises pigment blue 60. C.I. Pigment Blue 16 and C.I. Pigment blue 60 may contain 10 to 50 parts by weight of 100 parts by weight of the total organic pigment colorant. C.I. Pigment Blue 16 and C.I. When the content of the pigment blue 60 is 10 parts by weight or less, the red wavelength light may not be sufficiently shielded, and when the content is 50 parts by weight or more, formation of the composition is difficult. Also, the organic pigment of the colorant used is C.I. Pigment red 179 may be included and in some cases C.I. Pigment Yellow 139 or C.I. Pigment purple 23 can also be used. C.I. When pigment red 179 is used, it can be used in an amount of 20 to 40 parts by weight based on 100 parts by weight of the solid content of the colorant. C.I. When used including pigment yellow 139, it may be used in an amount of 5 to 25 parts by weight based on 100 parts by weight of the solid content of the colorant. C.I. When using pigment purple 23 as well, it can be used in an amount of 5 to 25 parts by weight based on 100 parts by weight of the solid content of the colorant.

Used C.I. Pigment Blue 16 and C.I. Pigment blue 60, as well as pigments used in printing inks and inkjets, and water-soluble azo-based, insoluble azo-based, phthalocyanine-based, quinacrytone-based, isoindolinone-based, isoindolin, perylene, perinone, dioxygene, Anthraquinone, dianthraquinonyl, anthrapyrimidine, antantrone, indanthrone, pravantrone, pyrantrone pigments, etc. can be used.

For example, the black pigment may be aniline black, perylene black, titanium black, or carbon black, and any one having light-shielding properties may be used without particular limitation. Specifically, the carbon black may be channel black, furnace black, thermal black, lamp black, or the like. If necessary, carbon black coated with a resin on the surface may be used for electrical insulation. In other words, the resin-coated carbon black has a lower conductivity than that of the non-resin-coated carbon black, so that excellent electrical insulation can be provided when forming a black matrix, a spacer, or a black matrix-integrated spacer. The black pigment used may be contained in an amount of 5 to 70 parts by weight based on 100 parts by weight of the solid content of the colorant.

Specific examples of the dye include C.I. Solvent Yellow No. 2, C.I. Solvent Yellow No. 14, C.I. Solvent Yellow No. 16, C.I. Solvent Yellow No. 33, C.I. Solvent Yellow No. 34, C.I. Solvent Yellow No. 44, C.I. Solvent Yellow No. 56, C.I. Solvent Yellow No. 82, C.I. Solvent Yellow No. 93, C.I. Solvent Yellow No. 94, C.I. Solvent Yellow No. 98, C.I. Solvent Yellow No. 116, C.I. Solvent yellow 135; C.I. Solvent Orange No. 1, C.I. Solvent Orange No. 3, C.I. Solvent Orange No. 7, C.I. Solvent orange 63; C.I. Solvent Red No. 1, C.I. Solvent Red No. 2, C.I. Solvent Red No. 3, C.I. Solvent Red No. 8, C.I. Solvent Red No. 18, C.I. Solvent Red No. 23, C.I. Solvent Red No. 24, C.I. Solvent Red No. 27, C.I. Solvent Red No. 35, C.I. Solvent Red No. 43, C.I. Solvent Red No. 45, C.I. Solvent Red No. 48, C.I. Solvent Red No. 49, C.I. Solvent Red 91:1, C.I. Solvent Red No. 119, C.I. Solvent Red No. 135, C.I. Solvent Red No. 140, C.I. Solvent Red No. 196, C.I. Solvent Red No. 197; C.I. Solvent Purple No. 8, C.I. Solvent Purple No. 9, C.I. Solvent Purple No. 13, C.I. Solvent Purple No. 26, C.I. Solvent Purple No. 28, C.I. Solvent Purple No. 31, C.I. Solvent Purple No. 59; C.I. Solvent Blue No. 4, C.I. Solvent Blue No. 5, C.I. Solvent Blue No. 25, C.I. Solvent Blue No. 35, C.I. Solvent Blue No. 36, C.I. Solvent Blue No. 38, C.I. Solvent blue 70; C.I. Solvent Green No. 3, C.I. Solvent Green No. 5, C.I. Solvent Green No. 7 and the like.

The colorant is contained in an amount of 1 to 60% by weight, preferably 1 to 50% by weight, within 100% by weight of the total colored photosensitive resin composition. If the content is less than the above range, the above-mentioned effect cannot be secured due to insufficient light-shielding property. On the contrary, if the content exceeds the above range, the pattern quality obtained after patterning may be deteriorated. Therefore, it is appropriately used within the above range.

The colorant in the present invention can be used together with a dispersing agent and a dispersing aid, if desired.

As the dispersant, suitable dispersants such as cationic, anionic, and nonionic can be used, but polymer dispersants are preferred. Specifically, acrylic copolymer, polyurethane, polyester, polyethyleneimine, polyallylamine, and the like can be mentioned. Such dispersants can be obtained commercially, for example, as acrylic copolymers DisperBYK-2000, DisperBYK-2001, BYK-LPN6919, BYK-LPN21116 (above, manufactured by BYK), Solsperse 5000 (manufactured by Lubrizol) ), as polyurethane, DisperBYK-161, DisperBYK-162, DisperBYK-163, DisperBYK-165, DisperBYK-167, DisperBYK-170, DisperBYK-182 (above, manufactured by BYK), Solsperse 76500 (manufactured by Lubrizol) ), as polyethyleneimine, Solsperse 24000 (manufactured by Lubrizol), and as polyester, Azisper PB821, Azisper PB822, Azisper PB880 (manufactured by Ajinomoto Finetechno Co., Ltd.), and the like.

Examples of the dispersion aids include pigment derivatives, and specific examples thereof include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone.

These dispersants may be used alone or in combination of two or more. The content of the dispersant is usually 100 parts by weight or less, preferably 1 to 70 parts by weight, more preferably 10 to 50 parts by weight, based on 100 parts by weight of the colorant. If the content of the dispersant is too large, there is a fear that developability and the like may be impaired.

The alkali-soluble resin in the present invention has reactivity and alkali solubility by the action of light or heat, acts as a dispersion medium for solids including colorants, and functions as a binder resin, which is used in the development stage of film production using a resin composition. Any binder resin that can be dissolved in a developer can be used.

The alkali-soluble resin comprises at least one or more of the structural units of the following formulas 2 to 5.

In the alkali-soluble resin, the reactants of Formulas 2 to 5 are preferably 3 to 80 mol%, more preferably 5 to 70 mol% based on the total number of moles of the alkali-soluble resin. When the structural unit is included within the above range, it has excellent sensitivity and adhesion, so that there is no peeling of the pattern during the developing process, and exhibits excellent solvent resistance.

The alkali-soluble resin having the structural units of Formulas 2 to 5 can be prepared by polymerization of various polymerizable compounds.

The alkali-soluble resin can be copolymerized with other types of formulas 2 to 5, and specific examples of copolymerizable unsaturated bonds include styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m- Methoxystyrene, p-methoxystyrene, o-vinylbenzylmethylether, m-vinylbenzylmethylether, p-vinylbenzylmethylether, o-vinylbenzyl glycidyl ether, m-vinylbenzylglycidyl ether, p -Aromatic vinyl compounds such as vinylbenzyl glycidyl ether; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth)acrylates such as sec-butyl (meth)acrylate and t-butyl (meth)acrylate; Cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6]decane-8-yl (meth)acrylate, 2- Alicyclic (meth)acrylates such as dicyclopentanyloxyethyl (meth)acrylate and isobornyl (meth)acrylate, or epoxy-modified alicyclic (meth)acrylates; Aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate; Hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm -N-substituted maleimide compounds such as methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np-methoxyphenylmaleimide; Unsaturated amide compounds such as (meth)acrylamide and N,N-dimethyl (meth)acrylamide; 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, etc. And unsaturated oxetane compounds.

Each of the above-exemplified compounds may be used alone or in combination of two or more.

The alkali-soluble resin according to the present invention may be used by further mixing a variety of known soluble resins generally used in the art, if necessary.

Preferably, the alkali-soluble resin has a weight average molecular weight in terms of polystyrene in the range of 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weight of the alkali-soluble resin is less than 3,000, a shape having an unsmooth surface is found because the molecular weight of the resin is too small, and when the molecular weight exceeds 100,000, the developing speed is slow during development.

The acid value of the alkali-soluble resin is 30 to 250 (KOH mg/g), preferably 50 to 200 (KOH mg/g), more preferably 60 to 150 (KOH mg/g). When the acid value of the alkali-soluble resin is 30 to 250 (KOH mg/g), the solubility in the developer is improved and the residual film rate is improved, which is preferable. If the acid value is less than 30, it can be seen that development is not well done with the alkali developer. In addition, when the acid value is 250 or more, it is difficult to use it as a photosensitive resin due to a decrease in other physical properties due to too many carboxyl groups. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can be obtained by titration using an aqueous potassium hydroxide solution.

The alkali-soluble resin is used in the range of 10 to 80% by weight, preferably 10 to 70% by weight, within 100% by weight of the total colored photosensitive resin composition. This content is a range selected in consideration of the solubility of the developer and pattern formation, etc., and when used within the above range, the solubility in the developer is sufficient to facilitate pattern formation. The reduction is prevented, and the omission property of the non-pixel part becomes good.

The photopolymerizable compound in the present invention is not particularly limited as long as it is a compound that polymerizes and cures under light irradiation such as ultraviolet rays, and can be polymerized by the action of a photopolymerization initiator. As a component for enhancing the strength of the pattern, the photopolymerizable compound may be a monofunctional monomer, a difunctional monomer, or a trifunctional or higher polyfunctional monomer.

Specific examples of the monofunctional monomer include acrylate, methacrylate, nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, and 2-hydroxyethyl Acrylate, N-vinylpyrrolidone, etc., and commercially available products include Aaronix M-101 (Doagosei), KAYARAD TC-110S (Nippon Kayaku) or Viscoat 158 (Osaka Yuki Kagaku High School). I can.

Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Bis(acryloyloxyethyl) ether of bisphenol A, 3-methylpentanedioldi(meth)acrylate, etc., and commercially available products include Aaronix M-210, M-1100, 1200 (Doagosei), KAYARAD HDDA (Nippon Kayaku), Biscot 260 (Osaka Yuki Kagaku High School), AH-600, AT-600 or UA-306H (Kyoeisha Kagaku).

Specific examples of the trifunctional or higher polyfunctional photopolymerizable compound include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate , Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, thipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylay Tieddipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc., and commercially available products include Aronix M-309, TO-1382 (Doagosei), KAYARAD TMPTA, KAYARAD DPHA or KAYARAD DPHA-40H (Nippon Kayaku), etc.

Among the photopolymerizable compounds exemplified above, trifunctional or higher (meth)acrylic acid esters and urethane (meth)acrylates are particularly preferred in that they have excellent polymerizability and can improve strength.

The photopolymerizable compounds exemplified above may be used alone or in combination of two or more.

The photopolymerizable compound is preferably contained in an amount of 1 to 30% by weight, and more preferably 1 to 20% by weight, within 100% by weight of the total colored photosensitive resin composition. This content range is a range selected in consideration of the tendency to improve strength or smoothness of the column spacer or black matrix integrated column spacer from various angles, and if the content is less than the above range, strength and smoothness are insufficient, and vice versa. If it exceeds, a problem occurs in which patterning is not easy due to high strength, so it is appropriately used within the above range.

The photopolymerization initiator in the present invention is a compound for initiating polymerization of the photopolymerizable compound, and is not particularly limited in the present invention, but acetophenone system, benzophenone system, triazine system, thioxanthone system, oxime system, benzoin system, anthracene system , Anthraquinone-based, and biimidazole-based compounds may be used, and these may be used alone or in combination of two or more.

Acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 2-hydroxy-1-[4-(2-hydroxyethoxy) Phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl- Oligomers of 2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl[4-(1-methylvinyl)phenyl]propan-1-one, etc. are possible And, among these, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one can be preferably used.

Benzophenone compounds include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4′-bis(dimethylamino)benzophenone, 4,4′-bis (Diethyl amino) benzophenone and the like are possible.

Triazine-based compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3′,4′-dimethoxy Styryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4′-methoxy naphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2- (p-methoxy phenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-triazine)-4,6-bis(trichloromethyl)-s-triazine, 2- Biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho 1-yl)-4,6- Bis(trichloromethyl)-s-triazine, 2-(4-methoxy naphtho 1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl ( Piperonyl)-6-triazine, 2,4-trichloromethyl(4'-methoxy styryl)-6-triazine, etc. are possible.

As the thioxanthone compound, 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4-propoxy thioxanthone, and the like are possible.

Examples of oxime compounds include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, and commercially available products include Ciba's OXE-01 and OXE-02.

As the benzoin-based compound, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, and the like can be used.

Examples of the anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene or 2-ethyl-9,10-diethoxyanthracene. .

Examples of the anthraquinone compound include 2-ethyl anthraquinone, octamethyl anthraquinone, 1,2-benz anthraquinone, and 2,3-diphenyl anthraquinone.

Biimidazole-based compounds include 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenylbiimidazole, 2,2′-bis(2,3-dichlorophenyl) -4,4′,5,5′-tetraphenylbiimidazole, 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetra(alkoxyphenyl)biimidazole, 2 ,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetra(trialkoxyphenyl)biimidazole, the phenyl group at the 4,4′,5,5′ position by a carboalkoxy group Substituted imidazole compounds and the like are possible.

The photopolymerization initiator may be used in an amount of 0.01 to 10% by weight, preferably 0.01 to 5% by weight, within 100% by weight of the total colored photosensitive resin composition. This content range is in consideration of the photopolymerization rate of the photopolymerizable compound and the physical properties of the final coating film.If it is less than the above range, the polymerization rate is low, and the overall process time may be lengthened.Conversely, if it exceeds the above range, the crosslinking reaction is caused by excessive reaction. In the past, the physical properties of the coating film may be rather deteriorated, and therefore, it is appropriately used within the above range.

The photopolymerization initiator may be used in combination with a photopolymerization initiator auxiliary agent. When the photopolymerization initiator is used in combination with the photopolymerization initiator, the colored photosensitive resin composition containing them becomes more sensitive, and productivity is improved when the column spacer for maintaining the cell gap is formed using the same.

The photopolymerization initiation aid may be used to increase polymerization efficiency, and an amine compound, an alkoxyanthracene compound, and a thioxanthone compound may be used.

As amine compounds, triethanolamine, methyl diethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, benzoic acid-2-dimethylaminoethyl, 4- Dimethylaminobenzoic acid 2-ethylhexyl, N,N-dimethylparatoluidine, 4,4′-bis(dimethylamino)benzphenone (common name, Michler's ketone), 4,4′-bis(diethylamino)benzophenone , 4,4'-bis(ethylmethylamino)benzophenone, etc. are mentioned. Among these, 4,4'-bis(diethylamino)benzophenone is preferable.

In addition, as an alkoxyanthracene compound, for example, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-die Toxanthracene, etc. are mentioned.

As a thioxanthone-based compound, for example, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro- 4-propoxy oxanthone, etc. are mentioned.

The photopolymerization initiation aid can be directly manufactured or used by purchasing a commercially available one, and as an example, the EAB-F series (Hodogaya Chemical Industry Co., Ltd.) or the like can be used.

It is preferable to use such a photopolymerization initiation aid within the range of usually 10 mol or less, preferably 0.01 to 5 mol per 1 mol of the photopolymerization initiator. When the photopolymerization initiation aid is used within the above range, it is possible to increase the polymerization efficiency and improve productivity.

Any solvent in the present invention may be used as long as it can dissolve or disperse the above-mentioned composition, and is not particularly limited in the present invention. Representatively, alkylene glycol monoalkyl ethers, alkylene glycol alkyl ether acetates, aromatic hydrocarbons, ketones, lower and higher alcohols, and cyclic esters may be mentioned. More specifically, as the solvent, alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; Alkylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate Ryu; Aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; and cyclic esters such as γ-butyrolactone.

Among the above solvents, organic solvents having a boiling point of 100 to 200°C are preferably used in the solvent from the viewpoint of coating properties and drying properties, more preferably alkylene glycol alkyl ether acetates, ketones, and 3-ethoxypropionic acid Esters such as ethyl or methyl 3-methoxypropionate, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, and 3-methyl Methyl oxypropionate, etc. are mentioned. These solvents can be used alone or in combination of two or more.

Since the viscosity of the solvent may vary depending on the coating method or apparatus, the content is appropriately adjusted so that the concentration of the colored photosensitive resin composition having the above-mentioned composition is 5 to 90% by weight, preferably 15 to 80% by weight. This content is a range selected in consideration of the dispersion stability of the composition and the ease of processing in the manufacturing process (eg, coatability).

In addition, the colored photosensitive resin composition according to the present invention may further include known additives for various purposes. As such additives, additives such as surfactants, fillers, other polymer compounds, ultraviolet absorbers, and anti-aggregation agents may be used in combination. One or two or more of these additives are possible, and it is preferable to use 1% by weight or less in the total composition in consideration of light efficiency and the like.

As the surfactant, commercially available products can be used, and a fluorine-based surfactant is preferably used. The fluorine-based surfactants include BM-1000, BM-1100 (BM Chemie), FC-135, FC-170C, FC-430 (Sumitomo 3M), SH-28PA, SH-190, SZ-6032 (Tore Siri Con, Inc.) can be used.

Glass, silica, alumina, etc. are possible as fillers, and curable resins such as epoxy resin and maleimide resin, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester as other polymer compounds And thermoplastic resins such as polyurethane.

Specific examples of the ultraviolet absorber include 2-(3- t -butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotyrazole, alkoxybenzophenone, and the like, and examples of the anti-aggregation agent specifically include sodium polyacrylate. I can.

The preparation of the colored photosensitive composition as described above is not particularly limited in the present invention, and a known method for preparing the photosensitive composition is followed.

For example, after adding the colorant to the solvent, the remaining composition including random silsesquioxane having at least one reactive group in the molecular structure, and other additives may be added to obtain through stirring. At this time, the colorant may be dissolved or dispersed in a solvent or alkali-soluble resin, and when the additive is in the form of a solution, it may be added to the solvent together with the colorant in advance.

The colored photosensitive resin composition thus prepared can be preferably used as a column spacer for maintaining a cell gap of a display device, preferably a liquid crystal display device, or a black matrix integrated column spacer.

As a column spacer for maintaining the cell gap, the colored photosensitive resin composition according to the present invention contains a random silsesquioxane having at least one reactive group in the molecular structure of Formula 1, thereby exhibiting excellent adhesion to the inorganic film and exhibiting excellent solvent resistance and heat resistance. It has excellent chemical and thermal stability and can increase reliability. In addition, the colored photosensitive resin composition of the present invention not only has less deformation due to external pressure, but also has a high elastic recovery rate while having a high elastic recovery rate, and can prevent damage due to light due to excellent light blocking properties.

In addition, in the case of a black matrix, the colored photosensitive resin composition according to the present invention has a high optical density (OD) required, excellent light-shielding property, and electrical insulation, and can satisfy the physical properties required for both the black matrix and the column spacer. It is also preferably applicable as a matrix-integrated column spacer.

The black matrix integrated spacer does not form each of the black matrix and the column spacer, but can perform both the role of the black matrix and the column spacer in a single pattern, and the colored photosensitive resin composition according to the present invention may be used.

Column spacers or black matrix integrated column spacers according to the photolithography method are generally used in the patterning process.

a) applying a colored photosensitive resin composition;

b) a prebaking step of drying the solvent;

c) placing a photo mask on the obtained film and irradiating active light to cure the exposed portion;

d) performing a developing process of dissolving the unexposed part using an aqueous alkali solution; And

e) Drying and post bake are carried out.

As the substrate, a glass substrate or a polymer plate is used. As the glass substrate, in particular, soda lime glass, barium-strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, or quartz can be preferably used. Moreover, polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, polysulfone, etc. are mentioned as a polymer plate.

In this case, a wet coating method using a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), or an ink jet can be applied to obtain a desired thickness.

Prebaking is performed by heating with an oven, a hot plate, or the like. At this time, the heating temperature and heating time in the pre-baking are appropriately selected depending on the solvent used, and are performed for 1 to 30 minutes at a temperature of, for example, 80 to 150°C.

Further, the exposure performed after the prebaking is performed by an exposure machine and exposed through a photo mask, thereby sensitizing only the portion corresponding to the pattern. The light to be irradiated at this time may be, for example, visible light, ultraviolet light, X-ray, and electron beam.

Alkali development after exposure It is performed for the purpose of removing the photosensitive resin composition in the part which is not removed from the non-exposed part, and a desired pattern is formed by this development. As a developer suitable for this alkali development, for example, an aqueous solution of an alkali metal or alkaline earth metal carbonate can be used. In particular, using a less alkaline aqueous solution containing 1 to 3% by weight of carbonates such as sodium carbonate, potassium carbonate, lithium carbonate, etc., using a developer or an ultrasonic cleaner within a temperature of 10 to 50 ℃, preferably 20 to 40 ℃ To do it.

Post-baking is performed to increase the adhesion between the patterned film and the substrate, and is performed through heat treatment at 80 to 220°C for 10 to 120 minutes. As with the post-baking pre-baking, it is carried out using an oven, hot plate, or the like.

At this time, the film thickness of the column spacer and the black matrix integrated column spacer is preferably 0.1 to 8 µm, more preferably 0.1 to 6 µm, and particularly preferably 0.1 to 4 µm.

These column spacers or black matrix integrated column spacers not only secure physical properties such as optical density, elastic recovery rate, electrical insulation, and light-shielding properties required for all of them, but also have excellent adhesion, heat resistance, and solvent resistance, so that the reliability of liquid crystal displays. Can improve.

Hereinafter, a preferred embodiment is presented to aid the understanding of the present invention, but the following examples are only illustrative of the present invention, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention, It is natural that such modifications and modifications fall within the appended claims. In addition, "%" and "parts" indicating content hereinafter are based on mass unless otherwise noted.

Preparation Example 1: Preparation of colorant

C.I. Pigment Blue 16 and C.I. Pigment blue 60 20.0 parts by weight, carbon black (MA-8, manufactured by Mitsubishi Corporation) and organic black (manufactured by BASF) were mixed and mixed and dispersed for 12 hours by a bead mill to prepare a colorant.

Preparation Example 2: Preparation of alkali-soluble resin

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot and a nitrogen introduction tube was prepared. As a monomer dropping lot, a mixture of 3,4-epoxytricyclodecane-8-yl (meth)acrylate and 3,4-epoxytricyclodecane-9-yl (meth)acrylate in a molar ratio of 50:50 40 Parts by weight, 50 parts by weight of methyl methacrylate, 40 parts by weight of acrylic acid, 70 parts by weight of vinyl toluene, 4 parts by weight of t-butylperoxy-2-ethylhexanoate, 40 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) Stirring was prepared by adding.

Stirring was prepared by adding 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA as a chain transfer agent dropping tank.

Thereafter, 395 parts by weight of PGMEA was added to the flask, the atmosphere in the flask was exchanged from air to nitrogen, and the temperature of the flask was raised to 90° C. while stirring.

Thereafter, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition was maintained at 90° C. for 2 hours, and the temperature was raised to 110° C. after 1 hour and maintained for 5 hours to obtain a resin having a solid acid value of 100 mgKOH/g.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the alkali-soluble resin were measured using the GPC method, and an HLC-8120GPC (manufactured by Tosoh Corporation) apparatus was used.

The condition was used by connecting the TSK-GELG4000HXL and TSK-GELG2000HXL columns in series, and the temperature of the column was set to 40 °C. Tetrahydrofuran was used as the mobile phase solvent, and measured while flowing at a flow rate of 1.0 mL/min. The concentration of the measurement sample was 0.6% by weight, the injection amount was 50 μl, and analyzed using an RI detector. TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, and A-500 (manufactured by Tosoh Corporation) were used as standard materials for calibration, and the weight average molecular weight and number of alkali-soluble resins obtained under the above conditions The average molecular weight was measured.

The weight average molecular weight in terms of polystyrene measured by GPC was 17,000, and the molecular weight distribution (Mw/Mn) was 2.3.

Examples 1 to 4 and Comparative Examples 1 to 3

After adding propylene glycol monomethyl ether acetate as a solvent to the mixer, a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a random silsesquioxane having a reactive group are added thereto, and uniformly mixed through stirring to color photosensitive resin. The composition was prepared. At this time, the composition follows the composition of Table 1 below.

A 5×5 cm glass substrate (Corning, #1737) was washed with a neutral detergent and water, and then dried. The obtained colored photosensitive resin composition was coated on this glass substrate by spin coating, and then dried on a heating plate at a temperature of 80 to 120° C. for 1 to 2 minutes to remove the solvent.

Subsequently, ultraviolet rays were irradiated on the thin film. At this time, the ultraviolet light source was irradiated with light at an exposure amount (365 nm) of 40 to 100 mJ/cm 2 in an air atmosphere using an ultra-high pressure mercury lamp (brand name USH-250D) manufactured by Ushio Denki Co., Ltd., and no special optical filter was used.

The UV-irradiated thin film was developed in a developing solution of a KOH aqueous solution having a pH of 12.5 using a spray developer for 60 seconds, and then heated in a heating oven at 220 to 250° C. for 10 to 30 minutes to prepare a pattern. The thickness of the film prepared above was formed to 3.0㎛.

Furtherance
(weight%) Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 coloring agent Colorant of Preparation Example 1 39 39 39 39 39 39 39 Pigment dispersant Solsperse 5000 ¹⁾
/DiperBYK-163 ²⁾ 9.5 9.5 9.5 9.5 9.5 9.5 9.5 Alkali-soluble resin Resin of Preparation Example 2 38 37 36 38 38 38 38 Photopolymerizable compound Kayarad DPHA ^{3 )} 11.5 11.5 11.5 11.5 11.5 11.5 11.5 Photopolymerization initiator Irgacure OXE-02 ⁴⁾ One One One One One One One Silsesquioxane with reactor SQ 109 ^{5 )} One 2 3 - - - - SQ 506 ^{6 )} - - - One - - - additive SQ 120 ^{7 )} - - - - One - - QZ 105 ^{8 )} - - - - - One - Xiameter OFS-6518 ⁹⁾ - - - - - - One 1) Lubrisol's product
2) BYK's product
3) Dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.
4) 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethanone-1-(O-acetyloxime), manufactured by Ciba
5) ARAKAWA CHEMICAL company product
6) ARAKAWA CHEMICAL
7) ARAKAWA CHEMICAL
8) ARAKAWA CHEMICAL
9) Products from Dow Corning

Experimental example 1: Reliability evaluation

After evaluating the reliability of the films obtained in Examples and Comparative Examples, the results are shown in Table 2 below. At this time, the reliability was evaluated by the solvent resistance to the NMP (n-methyl-2-pyrrolidone) solvent, and the membrane was cut into 3×3 cm size and placed in 5 g of NMP, left in an oven at 100° C. for 30 minutes, and the NMP solvent was recovered. , Using a UV-vis spectrometer (UV-2550, Shimatzu) was measured using the absorbance of the organic pigment extracted in the NMP solvent.

At this time, reliability was evaluated based on the following criteria.

<Standard>

○: absorbance less than 1

△: absorbance 1 to less than 3

×: absorbance 3 or more

Experimental example 2: elastic Recovery rate evaluation

After evaluating the elastic recovery rate of the films obtained in the above Examples and Comparative Examples, the results are shown in Table 2 below. At this time, the elastic recovery rate was measured using a Fisher hardness tester (fisherscope HM-2000, fisher company). It was measured by applying a force up to 50 mN to the pattern formed with a size of 20 μm.

At this time, the higher the value of the elastic recovery rate, the better the elastic recovery degree, and was evaluated based on the following criteria.

<Standard>

○: Elastic recovery rate of 80% or more

△: elastic recovery rate less than 70 to 80%

×: less than 70% elastic recovery rate

responsibility Elastic recovery rate Example 1 ○ ○ Example 2 ○ ○ Example 3 ○ ○ Example 4 ○ ○ Comparative Example 1 × △ Comparative Example 2 △ × Comparative Example 3 × ×

According to Table 1, in the case of a membrane made of a composition containing a random silsesquioxane having a reactor according to the present invention, it was shown that the reliability and elastic recovery rate were increased compared to Comparative Examples 1 to 3 not including the same.

In the reliability evaluation, in the case of Comparative Examples 1 to 3, the absorbance was high, and a problem occurred in durability, such as lifting or decomposing the edge of the film by NMP.

In terms of the elastic recovery rate, when a basket-type or ladder-type silsesquioxane is used instead of a random silsesquioxane having a reactive group (see Comparative Examples 1 and 2) and when a conventional adhesion promoter is used (see Comparative Example 3). It was confirmed that the numerical value was lower than that of Examples 1 to 4.

The colored photosensitive resin composition according to the present invention can be preferably used as a column spacer of a liquid crystal display device or a black matrix integrated column spacer.

Claims (8)

A colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a random silsesquioxane having at least one reactive group in the molecular structure,
A colored photosensitive resin composition having an elastic recovery rate of 80% or more, measured by applying a force of 50 mN to the cured product formed after UV (exposure amount of 40 to 100 mJ/cm ^{2, 365 nm).} The colored photosensitive resin composition of claim 1, wherein the random silsesquioxane having at least one reactive group in the molecular structure is represented by the following formula (1).
[Formula 1]

(In Formula 1,
R′ and R″ are the same as or different from each other, and are each independently hydrogen, a hydroxy group, a C ₁ to C ₁₀ alkyl group, a C ₁ to C ₁₀ alkoxy group or -(R ₁ ) _n -R ₂ , and the R At least one of'and R″ is -(R ₁ ) _{n -R 2} ;
At this time, R ₁ is hydrogen, a C ₁ to C ₁₀ alkylene group, -R ₃ -OR ₄ -or -R ₅ -C(=O)OR ₆ -, wherein R ₃ to R ₆ are the same as or different from each other, and each independently Is a C ₁ to C ₁₀ alkylene group;
R ₂ is hydrogen, thiol group, isocyanate group, carboxyl group, hydroxyl group, amino group, urea group, urethane group, (meth)acrylate group, C ₁ to C ₁₀ alkyl group, C ₁ to C ₁₀ alkoxy group, C _{A 3} to C ₁₅ cycloalkyl group, a C ₃ to C ₁₅ heterocycloalkyl group, a C ₆ to C ₂₀ aryl group or a C ₅ to C ₂₀ heteroaryl group;
x is an integer from 1 to 500;
y is an integer from 1 to 500;
n is an integer of 0 or 1) The method of claim 2, wherein R ₁ is a C ₁ to C ₅ alkylene group,
R ₂ is a thiol group, an isocyanate group, a (meth)acrylate group, a phenyl group or an epoxy group,
The R ₃ to R ₆ are the same as or different from each other, and each independently a C ₁ to C ₅ alkylene group, characterized in that the colored photosensitive resin composition. The method of claim 1, wherein the colored photosensitive resin composition satisfies 100% by weight of the total composition.
1 to 60% by weight of colorant,
10 to 80% by weight of an alkali-soluble resin,
1 to 30% by weight of a photopolymerizable compound,
0.01 to 10% by weight of a photopolymerization initiator, and
A colored photosensitive resin composition comprising 0.1 to 15% by weight of random silsesquioxane having a reactor. Column spacer, characterized in that made of the colored photosensitive resin composition according to any one of claims 1 to 4. A liquid crystal display device comprising the column spacer of claim 5. A black matrix integrated column spacer, characterized in that it is made of the colored photosensitive resin composition according to any one of claims 1 to 4. A liquid crystal display device comprising the black matrix integrated column spacer of claim 7.