KR20160094668A - Color photosensitive resin composition, column spacer manufactured thereby and liquid crystal display comprising the same - Google Patents

Abstract

The present invention relates to a color photosensitive resin composition, column spacer manufactured using the same and a liquid crystal display comprising the same. More specifically, the present invention relates to a color photosensitive resin composition comprising coloring agents, alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator together with random-type silsesquioxane, thereby being capable of producing the liquid crystal display with enhanced reliability as the same has excellent light-shielding properties, elastic recovery, solvent resistance properties and heat resistance properties to be applied to both black matrix and the column spacer, column spacer manufactured using the same, and a liquid crystal display comprising the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a colored photosensitive resin composition, a column spacer manufactured thereby, and a liquid crystal display device having the same. BACKGROUND ART [0002]

The present invention relates to a colored photosensitive resin composition which can be used for both a column spacer and a black matrix with excellent light shielding properties, 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 drastic changes from cathode-ray tubes (CRTs) to flat panel displays such as plasma display panels (PDPs), organic light-emitting diodes (OLEDs), and liquid-crystal displays (LCDs). In particular, LCD is a major product in the flat panel display market, consisting of a top plate with a color filter, a bottom plate with thin film transistors (TFT), and a liquid crystal injected therebetween.

The color filter is a key component for expressing colors on LCDs, and has been adopted for a wide variety of applications such as notebook PCs, monitors, and mobile terminals, along with the spread of flat panel displays. Such a color filter realizes various colors on a screen through a pattern of red (R), green (G), and blue (B) on a substrate, An overcoat (OC) for improving flatness by correcting a step between each pixel, a column spacer (not shown) for maintaining a cell gap between two substrates CS; column spacer).

The curly filter is usually produced by uniformly applying a photosensitive resin composition containing a colorant corresponding to each color of red (R), green (G) and blue (B) on a substrate on which a black matrix is pattern- And then the coating film formed by heating and drying is exposed and developed, and if necessary, 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 a boundary portion between coloring layers of each color, and is mainly formed of a black photosensitive resin composition in order to prevent color mixture of other colors in each pixel or to hide a pattern of an electrode. The overcoat (OC) and the column spacer (CS) are also formed using a photosensitive resin composition.

Accordingly, the photosensitive resin composition is becoming more important as the use of the LCD becomes more sophisticated and diversified. In order to improve the productivity and durability, a rapid response to light and a demand for excellent mechanical properties are increasing.

In addition, in recent years, it is required that one material used in the display simultaneously performs various roles. Typically, a black matrix integrated column spacer is required as well as an optical density (OD) required in a black matrix as well as excellent electrical insulation. Also very high reliability is required and the dissolution characteristics of the colorant used should be controlled for organic solvents.

However, when only carbon black such as a black matrix is used for the formation of the black matrix integrated column spacer, the optical density is satisfactory but the electrical insulation is poor. In addition, all the black matrix materials using inorganic compounds do not satisfy the physical properties required in the black matrix integrated column spacer because of low insulating properties.

In addition, in a panel in which a black matrix is formed on a TFT surface or on a top surface of a color filter, electric insulation has a direct influence on the liquid crystal, so that a high insulating property or a low dielectric property is required. The composition of the photosensitive composition for forming the column spacer is similar to that of the black matrix. However, due to the difference in required physical properties such as the absence of the coloring agent in the case of the column spacer, application of the black matrix to both of them is easy not.

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

Korean Patent Laid-Open Publication No. 2012-0033893 discloses an ink composition comprising a binder resin, a polyfunctional monomer, a photopolymerization initiator or a photosensitizer, and a solvent, wherein a black pigment such as aniline black, perylene black, .

These patents can secure a certain degree of improvement in electrical insulation through various combinations of compounds used as coloring agents. However, in addition to the problems that the curability of a coating film is reduced by the use of a coloring agent and the elastic modulus is lowered, , It is insufficient to obtain satisfactory characteristics in chemical resistance, sensitivity, and developability.

In order to improve adhesion properties and chemical stability, Korean Patent Laid-Open Publication No. 2011-0068861 refers to a technique of adding cage silsesquioxane to a colored photosensitive resin composition.

However, the above patent shows a certain improvement in adhesion and solvent resistance through the use of the basket-like silsesquioxane. However, the above composition is intended for color filter applications and is different from the physical properties required for black matrix and column spacers, Quinoxane is disadvantageous in terms of productivity because it requires a great deal of cost in synthesis.

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

As a result of various studies to produce a photosensitive composition which can satisfy both physical properties of a column spacer and a black matrix of a liquid crystal display device and which can be used in both of them, the present inventors have found that a random type silicon having at least one reactor in a molecular structure It is confirmed that the liquid crystal display device can improve the reliability of the liquid crystal display device because the optical density, light shielding property, adhesion property, electrical insulation property, elastic recovery rate and solvent resistance required by the column spacer and the black matrix are improved by using Respectively.

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

Still another object of the present invention is to provide a use of the colored photosensitive resin composition which can be used for producing a column spacer.

Still another object of the present invention is to provide a use of the colored photosensitive resin composition which can be used for producing 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 reactor in a molecular structure.

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

[Chemical Formula 1]

(Wherein R ', R ", x and y are as described in the specification)

Wherein the colored photosensitive resin composition comprises 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 0.1 to 15% by weight of random silsesquioxane having at least one reactor.

The present invention also provides a column spacer made of the colored photosensitive resin composition and a liquid crystal display device including the same.

The present invention also provides 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 ensures physical properties such as optical density, adhesion, electrical insulation and light shielding property required for both the black matrix and the spacer, but also has excellent elastic recovery and solvent resistance, Can be improved.

The present invention provides a colored photosensitive resin composition usable as a column spacer or a black matrix integrated column spacer in a liquid crystal display.

 Particularly, the present invention provides a colored photosensitive resin composition comprising a random silsesquioxane having at least one reactor in a molecular structure as an essential component, wherein the random silsesquioxane having at least one reactor in the molecular structure The adhesion to the inorganic material is excellent and the adhesion with the transparent conductive film or the inorganic film can be enhanced. In addition, the above-mentioned colored photosensitive resin composition is required not only to secure physical properties such as optical density, elastic recovery rate, electrical insulation property and light shielding property required for both the black matrix and the column spacer, but also has excellent heat resistance and solvent resistance, Thereby achieving an advantage that can be improved.

In addition to the random silsesquioxane having at least one reactor 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 reactor in the molecular structure in the present invention is characterized by being represented by the following formula (1).

Particularly, the random silsesquioxane having at least one reactor in the molecular structure has excellent adhesion to an inorganic material because the terminal reactor and the alkoxysilane group remain, and therefore, the random silsesquioxane having at least one reactor in the molecule structure is added to the conventional colored photosensitive resin composition as an adhesion promoter A silane coupling agent can be substituted. It is excellent in solvent resistance and heat resistance, so chemical stability is improved in the process, and reliability and durability can be further improved. This is because when the previously proposed ladder-type silsesquioxane is used in the colored photosensitive resin composition, the solvent resistance and the heat resistance are not sufficiently improved, and when the colored photosensitive resin composition is prepared using the cage-type silsesquioxane, It is advantageous in terms of improving the use of random silsesquioxane because the reactivity is inhibited by the structure of the cage silsesquioxane and thus the complete reaction can not be achieved. Further, the synthesis of random silsesquioxane is more advantageous in view of economical efficiency of the product since the process is simpler than the synthesis of the basket or ladder.

(In the formula 1,

R 'and R " are the same or different and are independent of one another and are 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 at least one of R " is - (R ₁ ) _n -R ₂ ;

Wherein 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 or different, C ₁ to C ₁₀ alkylene group;

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

x is an integer from 1 to 500;

y is an integer from 1 to 500;

and n is an integer of 0 or 1)

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

The alkylene group referred to in the present invention is a divalent form of an alkyl group. The alkylene may be linear, branched, cyclic, or a combination thereof.

The cycloalkyl groups mentioned in the present invention are fully saturated and partially unsaturated hydrocarbon rings of carbon atoms and include cyclopropyl, cyclopropylmethyl, cyclopentyl, cyclohexyl, adamantyl, and substituted and unsubstituted boronyl, norborn Nyl and norbornenyl.

The heterocycloalkyl group referred to in the present invention refers to a nonaromatic cycloalkyl group in which one carbon atom in the ring is replaced by a heteroatom selected from oxygen, sulfur or nitrogen and up to three additional carbon atoms can be replaced by the heteroatom . Examples of such heterocycloalkyl groups include but are not limited to epoxy, thiiranyl, aziridinyl, oxetanyl, azetidinyl, tetrahydrofuranyl, tetrahydro-thiophenyl (synonymous with tetrahydro-thienyl), pyrrolidinyl, pyrazolyl Includes, for example, phenyl, naphthyl, naphthyl, imidazolidinyl, oxazidinyl, isoxazidinyl, thiazolidinyl, isothiazolidinyl, piperidinyl, piperazinyl, morpholinyl, or tetrahydropyranyl.

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

The aryl group referred to in the present invention contains one or more rings having 6 or more atoms in a monocyclic or bicyclic aromatic ring, and there may be 5 or fewer rings containing 22 or fewer atoms, A double bond may alternately be present between the carbon atom or a suitable heteroatom. Specific examples include phenyl, biphenyl, terphenyl, stilbene, naphthyl, anthracenyl, phenanthryl, pyrenyl and the like.

The heteroaryl group referred to in the present invention means a substituted or unsubstituted aromatic monocyclic group, bicyclic group and tricyclic group having at least one hetero atom (oxygen, sulfur or nitrogen) in at least one ring . Specific examples include furyl, thienyl, pyridyl, quinolinyl, isoquinolinyl, indolyl, isoindolyl, triazolyl, pyrrolyl, tetrazolyl, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, benzofura Benzothiophenyl, carbazolyl, benzoxazolyl, pyrimidinyl, benzimidazolyl, quinoxalinyl, benzothiazolyl, naphthyridinyl, isoxazolyl, isothiazolyl, furunyl, quinazolinyl, Pyrazinyl, 1-oxydopyridyl, 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 or different from each other, and each independently is 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, the - for (R _{1) n} -R ₂ is n = 0, wherein R ₂ is a thiol group, an isocyanate group, (meth) acrylate group, a phenyl group or epoxy group, in the case of n = 1, the R ₁ and R ₃ to R ₆ are the same or different and are each independently a C ₁ to C ₅ alkylene group and R ₂ is as defined above when n = 0.

Preferably, R 'and R "may be the same or different from each other and are the abovementioned hydroxyl groups, C ₁ to C ₁₀ alkyl or - (R ₁ ) _n -R ₂ , wherein R' and R" At least one is - (R ₁ ) _n -R ₂ . For example, R 'and R "may have different reactors depending on the combination of a methyl group-thiol group, a methyl group-phenyl group, a methyl group-epoxy group, and a thiol group-epoxy group.

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

The compound of formula (1) may be prepared directly or used in the market, and may be directly manufactured or marketed, and COMPOCERAN SQ107, COMPOCERAN SQ109, COMPOCERAN SQ506, COMPOCERAN SQ502-8 or the like of ARAKAWA CHEMICAL 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, based on 100% by weight of the total colored photosensitive resin composition. If the content is less than the above range, there is a possibility that the desired effect may not be sufficiently obtained. On the contrary, if the content is in excess of the above range, the compatibility with other components may be deteriorated or the alkali developability There is a problem that contamination, membrane residue, and the like are liable to be generated.

The colorant in the present invention may provide a light shielding function to prevent light leakage in the black matrix, and prevent malfunction of the device due to light generated from the outside in the column spacer.

The colorant is not particularly limited in the present invention as far as it is shielding against visible light, and all known colorants such as organic pigments, dyes and black pigments can be used, and they can 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 Colors, Inc.), specifically color indexes (CIs) such as: Quot; name "

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 55, C.I. Pigment Yellow 83, C.I. Pigment Yellow No. 86, C.I. Pigment yellow 93, C.I. Pigment Yellow 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 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 153, C.I. Pigment yellow 154, C.I. Pigment yellow No. 155, C.I. Pigment yellow 166, C.I. Pigment Yellow No. 168, C.I. Pigment yellow No. 173, C.I. Pigment yellow 180, C.I. Pigment yellow No. 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 No. 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 122, C.I. Pigment Red 123, C.I. Pigment red No. 144, C.I. Pigment red No. 149, C.I. Pigment Red 166, C.I. Pigment Red No. 168, C.I. Pigment red No. 170, C.I. Pigment Red 171, C.I. Pigment red No. 175, C.I. Pigment Red 176, C.I. Pigment Red 177, C.I. Pigment Red 178, C.I. Pigment Red 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 214, C.I. Pigment Red 215, C.I. Pigment Red 216, C.I. Pigment Red 220, C.I. Pigment red No. 221, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red 243, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 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 No. 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 No. 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 subjected to a surface treatment using a pigment derivative in which a rosin treatment, an acidic group or a basic group is introduced, a surface graft treatment using a polymer compound or the like, a fine particle treatment using sulfuric acid, a cleaning with an organic solvent 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, the organic pigments include C.I. Pigment Blue 16 and C.I. And a 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 coloring agent. C.I. Pigment Blue 16 and C.I. When the content of Pigment Blue 60 is less than 10 parts by weight, light of a red wavelength may not be sufficiently shielded. When the amount of Pigment Blue 60 is more than 50 parts by weight, formation of a composition is difficult. The organic pigments of the colorants used are also C.I. Pigment red 179 and optionally C.I. Pigment yellow 139 or C.I. Pigment purple 23 can also be used. C.I. When Pigment Red 179 is used, it may 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 the pigment yellow 139 is used, 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 the pigment purple 23, 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. Pigment Blue 16 and C.I. In addition to Pigment Blue 60, pigments include pigments used in printing ink, ink jet, and the like, and pigments such as water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacrite pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, Anthraquinone, dianthraquinonyl, anthrapyrimidine, anthanthrone, indanthrone, pravanthrone, pyranthrone pigments and the like can be used.

For example, the black pigment may be aniline black, perylene black, titanium black, or carbon black, and may be used without particular limitation as long as it has shading properties. Specifically, the carbon black may be channel black, furnace black, thermal black, lamp black, or the like. Carbon black coated with a resin on its surface may be used for electrical insulation if necessary. Further, since the resin-coated carbon black has a lower conductivity than carbon black not coated with the resin, excellent electrical insulation can be imparted to the black matrix, the spacer, or the black matrix integrated spacer. The black pigment to be 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 No. 135; C.I. Solvent Orange No. 1, C.I. Solvent Orange No. 3, C.I. Solvent Orange No. 7, C.I. Solvent Orange No. 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 No. 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, based on 100% by weight of the total colored photosensitive resin composition. If the content is less than the above range, the light shielding property is insufficient and the above-mentioned effect can not be ensured. Conversely, if the content exceeds the above range, the pattern quality obtained after patterning may deteriorate.

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

As the dispersing agent, for example, a suitable dispersing agent such as a cationic, anionic, or nonionic type can be used, but a polymeric dispersant is preferable. Specific examples thereof include acrylic copolymers, polyurethanes, polyesters, polyethyleneimines, polyallylamines, and the like. DISPERBYK-2000, DISPERBYK-2001, BYK-LPN6919 and BYK-LPN21116 (manufactured by BYK), Solsperse 5000 (manufactured by Lubrizol), and the like are commercially available. DisperBYK-162, DisperBYK-163, DisperBYK-165, DisperBYK-167, DisperBYK-170 and DisperBYK-182 (manufactured by BYK , Solsperse 24000 (manufactured by Lubrizol Corporation) as polyethyleneimine, Ajisper PB821, Ajisper PB822 and Ajisper PB880 (manufactured by Ajinomoto Fine Techno Co., Ltd.) as polyesters.

Examples of the dispersion aid include pigment derivatives, specifically, 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 dispersing agent 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 dispersing agent is too large, there is a possibility that developability and the like are damaged.

The alkali-soluble resin in the present invention has reactivity and alkali solubility due to the action of light or heat and functions as a binder resin for solids including colorants and functions as a binder resin. This is because the alkali- Any binder resin soluble in a developing solution can be used.

The alkali-soluble resin comprises at least one of the structural units represented by the following formulas (2) to (5).

In the alkali-soluble resin, the reactants of the formulas (2) to (5) are preferably contained in an amount of 3 to 80 mol%, more preferably 5 to 70 mol%, based on the total molar amount of the alkali-soluble resin. When the above-mentioned structural unit is contained within the above-mentioned range, there is no detachment of the pattern during the development process due to the excellent sensitivity and adhesion, and exhibits excellent solvent resistance.

The alkali-soluble resin having the structural units represented by the above formulas (2) to (5) can be prepared by polymerization of various polymerizable compounds.

Specific examples of the unsaturated bonds which can be copolymerized with the alkali-soluble resins of the present invention include styrene, vinyltoluene,? -Methylstyrene, p-chlorostyrene, o-methoxystyrene, m- P-methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p Aromatic vinyl compounds such as vinylbenzyl glycidyl ether; 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; (Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6] decan- Alicyclic (meth) acrylates or epoxy-modified alicyclic (meth) acrylates such as dicyclopentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate; 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-based compounds such as methylphenyl maleimide, Np-methylphenyl maleimide, No-methoxyphenyl maleimide, Nm-methoxyphenyl maleimide and Np-methoxyphenyl maleimide; Unsaturated amide compounds such as (meth) acrylamide and N, N-dimethyl (meth) acrylamide; 3- (methacryloyloxymethyl) -2-trifluoromethyl oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, and the like Unsaturated oxetane compounds, and the like.

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 further mixed with various known resins commonly used in the art in accordance with necessity.

Preferably, the alkali-soluble resin has a weight average molecular weight in terms of polystyrene of 3,000 to 100,000, more preferably 5,000 to 50,000. When the alkali-soluble resin has a weight average molecular weight of less than 3,000, the resin has a too small molecular weight and a smooth surface. When the molecular weight exceeds 100,000, the development speed is slow.

The acid value of the alkali-soluble resin is 30 to 250 (KOH mg / g), preferably 50 to 200 (KOH mg / g), and 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 a developing solution is improved and the residual film ratio is improved. When the acid value is 30 or less, it can be seen that development in alkaline developer does not proceed well. When the acid value is more than 250, it is difficult to use as a photosensitive resin due to a decrease in other physical properties due to too much carboxyl groups. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the acrylic polymer, and can be generally determined by titration using an aqueous solution of potassium hydroxide.

The alkali-soluble resin is used in an amount of 10 to 80% by weight, preferably 10 to 70% by weight in 100% by weight of the total colored photosensitive resin composition. Such a content is a range selected considering various factors such as solubility in a developing solution, pattern formation, etc. When used within the above range, solubility in a developing solution is sufficient and pattern formation is easy, So that the dropout of the non-pixel portion is improved.

The photopolymerizable compound in the present invention is not particularly limited as long as it is a compound capable of polymerizing and curing upon irradiation with light such as ultraviolet light and capable of polymerization by the action of a photopolymerization initiator. The photopolymerizable compound may be a monofunctional monomer, a bifunctional monomer, or a multifunctional monomer having three or more functional groups as a component for enhancing the strength of a pattern.

Specific examples of the monofunctional monomer include acrylate, methacrylate, nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl Acrylate, and N-vinyl pyrrolidone. Commercially available products include Aronix M-101 (Doagosei), KAYARAD TC-110S (Nippon Kayaku) or Biscoat 158 (Osaka Yuki Kagaku Kogyo) .

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) (Acryloyloxyethyl) ether of bisphenol A and 3-methylpentanediol di (meth) acrylate. Commercially available products include Aronix M-210, M-1100, 1200 (Doagosei), KAYARAD HDDA (Nippon Kayaku), Viscoat 260 (Osaka Yuki Kagaku Kogyo), AH-600, AT-600 or UA-306H (Kyoeisha Chemical Co., Ltd.).

Specific examples of the polyfunctional photopolymerizable compound having three or more functional groups include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (Meth) acrylate such as Aronix M-309, TO-1382 (Doagosei), KAYARAD TMPTA, KAYARAD DPHA or KAYARAD DPHA-40H (Nippon Kayaku).

Of the photopolymerizable compounds exemplified above, trifunctional or higher (meth) acrylate esters and urethane (meth) acrylates are particularly preferable because they have excellent polymerizability and can improve the 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, more preferably 1 to 20% by weight, based on 100% by weight of the total colored photosensitive resin composition. Such a content range is selected considering various tendencies such as strength and smoothness of the column spacer or integrated black column spacer, and if the content is less than the above range, strength and smoothness are insufficient, , There arises a problem that patterning is not easy due to high strength. Therefore, it is suitably used within the above range.

The photopolymerization initiator in the present invention is a compound for initiating the polymerization of the photopolymerizable compound and is not particularly limited in the present invention. However, the photopolymerization initiator is not limited to the acetophenone, benzophenone, triazine, thioxanthone, oxime, benzoin, , Anthraquinone-based compounds, and nonimidazole-based compounds. These compounds may be used singly or in combination of two or more.

Acetophenone-based compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- hydroxy- 1- [4- (2- Phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) Oligomers of 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one and 2-hydroxy-2-methyl [4- (1-methylvinyl) phenyl] propan- 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one is preferably usable.

Examples of the benzophenone compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, (Diethylamino) benzophenone, and the like.

Examples of the triazine compound include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (3 ', 4'- (Trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho 1 -yl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho-1-yl) -4,6-bis Piperonyl) -6-triazine, 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine, and the like.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone and 1-chloro-4-propanedioxanthone.

Oximeimino-1-phenylpropan-1-one, and o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one. Commercially available products include OXE-01 and OXE-02 manufactured by Ciba.

As the benzoin 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 and 2-ethyl-9,10-diethoxyanthracene .

Examples of the anthraquinone-based compounds include 2-ethyl anthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, and the like.

Examples of the nonimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) 4,4 ', 5,5'-tetra (alkoxyphenyl) biimidazole, 2, 2'-bis (2-chlorophenyl) , 2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, phenyl groups in the 4,4', 5,5 ' Substituted imidazole compounds, and the like.

The photopolymerization initiator may be used in an amount of 0.01 to 10% by weight, preferably 0.01 to 5% by weight, based on 100% by weight of the total colored photosensitive resin composition. Such a content range takes into consideration the photopolymerization rate of the photopolymerizable compound and the physical properties of the resultant coating film. If the amount is less than the above range, the polymerization rate is low and the overall process time may be prolonged. On the other hand, Since the physical properties of the coating film may be lowered, it is suitably used within the above range.

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

The photopolymerization initiation auxiliary can be used for increasing the polymerization efficiency, and it is possible to use an amine compound, an alkoxyanthracene compound, a thioxanthone compound, or the like.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid isoamyl, benzoic acid- (Dimethylamino) benzophenone (collectively, Michler's ketone), 4,4'-bis (diethylamino) benzophenone , 4,4'-bis (ethylmethylamino) benzophenone, and the like, among which 4,4'-bis (diethylamino) benzophenone is preferable.

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10- Ethoxyacetylene and methoxyanthracene.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Propanedioxanthone, and the like.

The photopolymerization initiator may be directly produced or commercially available. For example, EAB-F series (manufactured by Hodogaya Chemical Industry Co., Ltd.) may be used.

Such a photopolymerization initiator is preferably used in an amount of usually not more than 10 mol, preferably 0.01 to 5 mol, per mol of the photopolymerization initiator. When the photopolymerization initiator is used within the above range, the polymerization efficiency can be increased and the productivity improvement effect can be expected.

Any solvent that can dissolve or disperse the above-mentioned composition may be used in the present invention, and the solvent is not particularly limited in the present invention. Representative examples are alkylene glycol monoalkyl ethers, alkylene glycol alkyl ether acetates, aromatic hydrocarbons, ketones, lower and higher alcohols, and cyclic esters. More specifically, examples of the solvent include 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 ? -butyrolactone.

Among the above-mentioned solvents, an organic solvent having a boiling point of 100 to 200 ° C in the solvent is preferably used from the viewpoint of coatability and dryness, more preferably an alkylene glycol alkyl ether acetate, a ketone, a 3-ethoxypropionic acid Ethyl, and 3-methoxypropionate, and more preferred examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, 3- Methyl propoxypropionate, and the like. These solvents may be used alone or in combination of two or more.

The viscosity of the solvent may vary depending on the coating method and apparatus. Therefore, the content of the solvent is suitably controlled such 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. Such a content is selected in consideration of dispersion stability of the composition and easiness of process in the production process (for example, applicability).

In addition, the colored photosensitive resin composition according to the present invention may further contain 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. These additives may be used alone or in combination of two or more, and it is preferable to use 1 wt% or less in the whole composition in consideration of light efficiency and the like.

As the surfactant, a commercially available product can be used, and a fluorinated surfactant is preferably used. Examples of the fluorine-based surfactant include BM-1000, BM-1100 (BM Chemie), FC-135, FC-170C and FC-430 (Sumitomo 3M Co., Ltd.), SH-28PA, SH- Co., Ltd.) can be used.

Examples of the filler include glass, silica, and alumina. Other polymer compounds include curable resins such as epoxy resin and maleimide resin, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester , And thermoplastic resins such as polyurethane.

Specific examples of the ultraviolet absorber include 2- (3- t -butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole and alkoxybenzophenone. Specific examples of the anti-aggregation agent include sodium polyacrylate .

The production of the above-described colored photosensitive composition is not particularly limited in the present invention, and follows a known production method of the photosensitive composition.

For example, a colorant may be added to a solvent and then the remaining composition including random silsesquioxane having at least one reactor in the molecular structure and other additives may be added and then stirred. In this case, the colorant may be dissolved or dispersed in a solvent or an alkali-soluble resin, and if the additive is in a solution form, it may be added in advance to the solvent together with the colorant.

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

As the column spacer for maintaining the cell gap, the colored photosensitive resin composition according to the present invention contains random silsesquioxane having at least one reactor in the molecular structure of formula (I), thereby exhibiting excellent adhesion to an inorganic film and exhibiting excellent solvent resistance and heat resistance Excellent chemical and thermal stability makes it possible to improve reliability. In addition, the colored photosensitive resin composition of the present invention is less deformed by external pressure, has flexibility, has a high elastic recovery rate, and can prevent damage due to light due to excellent light shielding property.

Further, the colored photosensitive resin composition according to the present invention has the high optical density (OD), excellent light shielding property and electric insulation property required in the case of the black matrix, so that the properties required in both the black matrix and the column spacer can be satisfied, Matrix-type column spacer.

The black matrix integrated spacer can perform both a black matrix and a column spacer in one pattern, instead of forming the black matrix and the column spacer, respectively, and the colored photosensitive resin composition according to the present invention can be used.

The column spacer or the black matrix integrated column spacer according to the photolithography method has a conventional patterning process

a) applying a colored photosensitive resin composition;

b) prebaking step of drying the solvent;

c) applying a photomask onto the obtained film to irradiate an actinic ray to cure the exposed portion;

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

e) Perform drying and post-baking.

A glass substrate or a polymer plate is used as the substrate. 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. Examples of the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.

At this time, a wet coating method using a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater (which may be referred to as a die coater), an ink jet or the like is possible so as 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 the heating time in the pre-baking are appropriately selected depending on the solvent to be used, for example, at a temperature of 80 to 150 ° C for 1 to 30 minutes.

The exposure performed after the pre-baking is performed by an exposure machine, and exposed through a photomask to expose only the portion corresponding to the pattern. The light to be irradiated may be, for example, visible light, ultraviolet light, X-ray, electron beam, or the like.

Alkali development after exposure is carried out for the purpose of removing the photosensitive resin composition in the portion where the non-exposed portion is not removed, and a desired pattern is formed by this development. As a developer suitable for the alkali development, for example, an aqueous solution of a carbonate of an alkali metal or an alkaline earth metal may be used. Particularly, a weakly alkaline aqueous solution containing 1 to 3% by weight of a carbonate such as sodium carbonate, potassium carbonate or lithium carbonate is used at a temperature of 10 to 50 캜, preferably 20 to 40 캜, using a developing machine or an ultrasonic cleaner .

The post-baking is performed in order to enhance the adhesion between the patterned film and the substrate, and is performed by heat treatment at 80 to 220 DEG C for 10 to 120 minutes. Post-baking Pre-baking is carried out using an oven, hot plate or the like.

In this case, the film thickness of the column spacer and the black matrix integrated column spacer is preferably 0.1 to 8 탆, more preferably 0.1 to 6 탆, particularly preferably 0.1 to 4 탆.

Such a column spacer or black matrix integrated column spacer not only secures physical properties such as optical density, elastic recovery rate, electrical insulation property and light shielding property required for all of them, but also excellent adhesion, heat resistance and solvent resistance, Can be improved.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims. In the following, "%" and "part" representing the content are on a mass basis unless otherwise specified.

Production Example 1: Preparation of colorant

20.0 parts by weight of CI pigment blue 16 and 20 parts by weight of CI pigment blue 60, carbon black (MA-8, manufactured by Mitsubishi) and organic black (manufactured by BASF) were mixed and dispersed by a bead mill for 12 hours to prepare a colorant Respectively.

Production Example 2: Preparation of alkali-soluble resin

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

As a chain transfer agent dropping vessel, 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added to prepare stirring.

Then, 395 parts by weight of PGMEA was added to the flask, and the atmosphere in the flask was replaced with nitrogen in air, and the temperature of the flask was raised to 90 DEG C with stirring.

The monomer and the chain transfer agent were then started to be added dropwise from the dropping funnel. The mixture was allowed to stand at 90 DEG C for 2 hours, elevated to 110 DEG 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 by GPC method and HLC-8120GPC (manufactured by Tosoh Corporation) was used.

The conditions were TSK-GELG4000HXL and TSK-GELG2000HXL columns connected in series, and the temperature of the column was 40 ° C. Tetrahydrofuran was used as mobile phase solvent and flow rate was measured at 1.0 mL / min flow rate. The concentration of the measurement sample was 0.6% by weight, and the injection amount was 50 ㎕, and analyzed using an RI detector. As the standard materials for calibration, TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500 and A-500 (manufactured by TOSOH CORPORATION) The average molecular weight was measured.

The weight average molecular weight measured by GPC in terms of polystyrene 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 a mixer, random type silsesquioxane having a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a reactor was added thereto and uniformly mixed by stirring to obtain a colored photosensitive resin A composition was prepared. Wherein the compositions are according to the composition of Table 1 below.

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

Then, the thin film was irradiated with ultraviolet rays. At this time, the ultraviolet light source was irradiated with light at an exposure dose (365 nm) of 40 to 100 mJ / cm 2 using an ultrahigh pressure mercury lamp (trade name: USH-250D) manufactured by Ushio DENKI Co., Ltd., and no special optical filter was used.

The ultraviolet-irradiated thin film was developed in a KOH aqueous solution of pH 12.5 for 60 seconds using a spraying developer 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 3.0 mu m.

Furtherance
(weight%) Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 coloring agent The 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 The resin of Production 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) Products of Lubrisol
2) Manufactured by BYK
3) Dipentaerythritol hexaacrylate, product of Nippon Kayaku Co., Ltd.
4) 1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethanone-1- (O-acetyloxime)
5) Products of ARAKAWA CHEMICAL
6) Products from ARAKAWA CHEMICAL
7) Products from ARAKAWA CHEMICAL
8) Products manufactured by ARAKAWA CHEMICAL
9) Dow Corning products

Experimental Example 1: Reliability Evaluation

The reliability of the films obtained in the above Examples and Comparative Examples was evaluated, and the results are shown in Table 2 below. At this time, the reliability was evaluated as solvent resistance to NMP (n-methyl-2-pyrrolidone) solvent. The membrane was cut into 3 × 3 cm size, put into 5 g of NMP, allowed to stand in an oven at 100 ° C. for 30 minutes, , And UV-vis spectrometer (UV-2550, Shimatzu) to measure the absorbance of the organic pigment extracted in the NMP solvent.

The reliability was evaluated by the following criteria.

<Standard>

○: absorbance less than 1

?: Absorbance 1 to less than 3

X: Absorbance of 3 or more

Experimental Example 2: Evaluation of elastic recovery rate

The elastic recovery rates of the films obtained in the Examples and Comparative Examples were evaluated, and the results are shown in Table 2 below. At this time, the elastic recovery rate was measured using a Fisher hardness meter (fisherscope HM-2000, fisher). And a force of 50 mN was applied to the pattern formed to a size of 20 탆.

The higher the elastic recovery rate, the better the elastic recovery.

<Standard>

○: Elasticity recovery rate 80% or more

?: Elasticity recovery rate: 70 to less than 80%

X: elastic recovery less than 70%

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

According to the above Table 1, it was shown that the membrane prepared from the composition containing the random silsesquioxane having the reactor according to the present invention had an increased reliability and elastic recovery rate as compared with Comparative Examples 1 to 3 which did not contain the silsesquioxane.

In the reliability evaluation, in the case of Comparative Examples 1 to 3, the absorbance was high, and the durability was also problematic such that the edge of the membrane was lifted or decomposed by NMP.

In the case of using a cage-type or ladder-type silsesquioxane which is not a random silsesquioxane having a reactor (Comparative Examples 1 and 2) and a conventional adhesion promoter (Comparative Example 3) It was confirmed that the numerical values were lower than those of Examples 1 to 4.

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

Claims (8)

A color photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a random silsesquioxane having at least one reactor in a molecular structure. The colored photosensitive resin composition according to claim 1, wherein the random silsesquioxane having at least one reactor in the molecular structure is represented by the following formula (1).
[Chemical Formula 1]

(In the formula 1,
R 'and R &quot; are the same or different and are independent of one another and are 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 at least one of R &quot; is - (R ₁ ) _n -R ₂ ;
Wherein 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 or different, C ₁ to C ₁₀ alkylene group;
R ₂ represents a hydrogen atom, a thiol group, an isocyanate group, a carboxyl group, a hydroxyl group, an amino group, a urea group, a urethane group, a (meth) acrylate group, a C ₁ to C ₁₀ alkyl group, a C ₁ to C ₁₀ alkoxy group, C ₃ to C ₁₅ cycloalkyl groups, C ₃ to C ₁₅ heterocycloalkyl groups, C ₆ to C ₂₀ aryl groups or C ₅ to C ₂₀ heteroaryl groups;
x is an integer from 1 to 500;
y is an integer from 1 to 500;
and n is an integer of 0 or 1) The compound according to 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,
Wherein R ₃ to R ₆ are the same or different and are each independently a C ₁ to C ₅ alkylene group. The photosensitive resin composition according to claim 1, wherein the colored photosensitive resin composition satisfies 100% by weight of the total composition
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
And 0.1 to 15% by weight of random silsesquioxane having a reactive group. A column spacer produced from 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 manufactured by 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.