KR20090004054A - Photosensitive resin composition for black matrix - Google Patents

Abstract

A photosensitive resin composition for a black matrix, a method for preparing a color filter by using the composition, and an LCD device containing the color filter are provided to prevent the spreading of an ink to the adjacent pixel part when an ink is ejected during the manufacturing process of a color filter. A photosensitive resin composition for a black matrix comprises an acrylic copolymer resin having a fluoro group represented by the formula 1; a multifunctional acrylic monomer having an ethylenically unsaturated double bond; a photopolymerization initiator; a colorant; and a solvent, wherein R1, R2 and R3 are independently H or a methyl group; R4 is a C1-C8 alkyl group containing a fluorine atom or an aromatic group containing a fluorine atom; m, n and l are an integer satisfying m/n/l being 60-70/15-34/1-15 by mol; and the number average molecular weight of the copolymer resin is 10,000-50,000.

Description

Photosensitive resin composition for black matrix {PHOTOSENSITIVE RESIN COMPOSITION FOR BLACK MATRIX}

The present invention relates to a photosensitive resin composition for black matrices, and more particularly, to an acrylic copolymer resin containing a fluorine group, a polyfunctional acrylic monomer having an ethylenically unsaturated double bond, a photopolymerization initiator, a colorant, and a photosensitive agent for a black matrix including a solvent. It relates to a resin composition.

In today's information society, the role of electronic display devices becomes more and more important, and various electronic display devices are widely used in various industrial fields. The electronic display field is continuously being developed as a new function electronic display device suitable for the needs of the information society which is diversifying and developing.

In general, an electronic display device refers to a device that transmits various information to a human through vision. That is, the electronic device may be defined as an electronic device that converts electrical information signals output from various electronic devices into optical information signals recognizable to human eyes, and may be defined as a device that plays a role of a bridge between humans and electronic devices. There is also.

Such an electronic display device is called an emissive display device when the optical information signal is displayed by a luminescence phenomenon, and a light-receiving display (non-) when it is displayed by light modulation due to reflection, scattering or interference. emissive display). The light emitting display device, also called an active display device, includes a cathode ray tube (CRT), a plasma display panel (PDP), a light emitting diode (LED), and an electroluminescent display (electroluminescent display). display; ELD). In addition, the light receiving display device, which is a passive display device, includes a liquid crystal display (LCD), an electrochemical display (ECD), an electrophoretic image display (EPID), and the like.

Cathode ray tube (CRT), the oldest display device used in image display devices such as televisions and computer monitors, occupies the highest share in terms of display quality and economy, but heavy weight, large volume and high consumption. It has many disadvantages such as power.

However, rapid advances in semiconductor technology have resulted in the necessity of electronic display devices suitable for new environments due to the miniaturization and light weight of electronic devices, along with the solidification, low voltage and low power of various electronic devices. That is, the demand for a flat panel display device having thin, light, low driving voltage and low power consumption is rapidly increasing.

Among the various flat panel display devices currently developed, liquid crystal displays are thinner and lighter than other display devices, and are widely used in various electronic devices because they have low power consumption and low driving voltage and can display images close to cathode ray tubes. have. In addition, since the liquid crystal display device is easy to manufacture, the range of application thereof is further expanded.

Such a liquid crystal display requires a color filter composed of three primary colors of R (red), G (green), and B (blue) for colorization.

Recently, a number of new process methods are being used to replace the conventional photolithography method in order to manufacture color filters, and the inkjet printing method is representative. In the inkjet printing method, a light blocking layer such as a black matrix is formed on a glass substrate, and a pixel space is formed through an exposure and development process to inject ink into the pixel space. Since the inkjet printing method does not require a separate coating, exposure, and development process in manufacturing the color filter, the material required for the process can be reduced and the process can be simplified.

However, most of the ink injected into the pixel space by the inkjet printing method is a liquid composition having a hydrophilic property including a pigment, a solvent and other dispersants. Since the ink is a volatile solution, in order to inject the ink into the pixel space of the color filter substrate, it is necessary to inject a larger amount of ink than the desired height in consideration of volatilization of the ink. Therefore, ink overflows to the surface of the black matrix, and ink bleeding occurs between adjacent pixel spaces. When the ink bleeding occurs between the pixel spaces, color characteristics of the liquid crystal display may be degraded, and thus display quality may be degraded.

In order to solve the above problems, the present inventors have found that when the black matrix is manufactured using an acrylic copolymer resin containing a fluorine group in the preparation of the photosensitive resin composition for the black matrix, the characteristics of preventing the bleeding of the ink are excellent. . Accordingly, the present invention is an acrylic copolymer resin containing a fluorine group, a polyfunctional acrylic monomer having an ethylenically unsaturated double bond, a photopolymerization initiator, a colorant and a black matrix photosensitive resin composition comprising a solvent, a method for producing a color filter using the same, thereby Provided are a manufactured color filter and a liquid crystal display device including the same.

The photosensitive resin composition for black matrices of the present invention has characteristics such as low surface tension, excellent dielectric properties and hydrophobicity, because the black matrix prepared by the fluorine group contained in the acrylic copolymer resin. As a result, it is possible to prevent the bleeding of the ink to the adjacent pixel portion during ink ejection during the color filter manufacturing process. In addition, the photosensitive resin composition for black matrices of the present invention has advantages such as improving the uniformity of the film, ease of developing process, and elimination of residue problems, thereby improving color characteristics and further improving display quality of the liquid crystal display device.

Hereinafter, the present invention will be described in detail.

The present invention provides a photosensitive resin composition for a black matrix comprising an acrylic copolymer resin containing a fluorine group represented by the following formula (1), a polyfunctional acrylic monomer having an ethylenically unsaturated double bond, a photopolymerization initiator, a colorant, and a solvent.

Acrylic copolymer resin containing a fluorine group used in the photosensitive resin composition of the present invention may be represented by the formula (1).

[Formula 1]

here,

R ₁ , R ₂ and R ₃ are each independently a hydrogen atom or a methyl group,

R ₄ is an alkyl group or aromatic group having 1 to 8 carbon atoms containing fluorine,

m, n, l are integers, and the ratio of m / n / l is 60 to 70/15 to 34 / l to 15 on a molar ratio basis,

The number average molecular weight of the copolymer resin is 10,000 to 50,000.

The acrylic copolymer resin represented by Formula 1 includes a fluorine group. The fluorine groups in the acrylic copolymer have a high electronegativity and form a characteristic dipole moment in the case of carbon fluoride. Therefore, the black matrix formed from the photosensitive resin composition including the acrylic copolymer resin containing the fluorine group may have characteristics such as low surface tension, excellent dielectric properties, and hydrophobicity.

As for the acrylic copolymer resin containing the fluorine group represented by the said Formula (1), it is preferable to add 1-40 weight part with respect to 100 weight part of photosensitive resin compositions for black matrices, and it is more preferable to add 1-20 weight part. When the content of the acrylic copolymer containing the fluorine group is less than 1 part by weight, it is difficult to expect characteristics such as low surface tension, excellent dielectric property and hydrophobicity of the prepared black matrix pattern, and when it exceeds 40 parts by weight, ethylenically unsaturated double The content of the other components including the polyfunctional acrylic monomer having a bond may be reduced, thereby lowering the strength and developability of the film formed by the photosensitive resin composition.

In the present invention, in addition to the acrylic copolymer resin containing the fluorine group may further include an acrylic copolymer resin containing no fluorine group. The binder used for the acrylic copolymer resin containing no fluorine group may be used by copolymerizing a monomer containing an acid group and a monomer copolymerizable with the monomer.

The monomer containing an acid group is preferably selected from the group consisting of (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethyl maleic acid, isoprene sulfonic acid, and styrene sulfonic acid.

Monomers copolymerizable with the monomer containing an acid group include styrene, chloro styrene, α-methyl styrene, vinyltoluene, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and benzyl (meth). ) Acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2-phenoxy Ethyl (meth) acrylate, tetrahydroperpril (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylic Latex, 4-hydroxybutyl (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, ethylhexyl acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl ( Meta) Relate, ethoxydiethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, methoxy tripropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxydiethylene glycol (Meth) acrylate, p-nonylphenoxypolyethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3 , 3,3-hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, tribromophenyl (meth) acrylate, β- ( Meta) acyloloxyethylhydrogen susinate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, propyl α-hydroxymethyl acrylate and butyl α-hydroxy From the group consisting of butyl acrylate is preferably at least one selected.

Examples of the acrylic copolymer resin containing no fluorine group include copolymers represented by the following Chemical Formula 2 or Chemical Formula 3, but are not limited thereto.

[Formula 2]

here,

R ₁ and R ₂ are each independently a hydrogen atom or a methyl group,

m and n are integers and the ratio is 70:30 (molar ratio),

The number average molecular weight of the copolymer resin is 5,000 to 50,000.

[Formula 3]

here,

R ₁ , R ₂ and R ₃ are each independently a hydrogen atom or a methyl group,

m, n, l are integers and the ratio is 70:15:15 (molar ratio),

The number average molecular weight of the copolymer resin is 5,000 to 50,000.

In addition, by addition reaction of the monomer having a glycidyl reactor to the acid group of the acrylic copolymer resin containing no fluorine group to introduce an ethylenically unsaturated reactive group capable of addition polymerization with a polyfunctional monomer having an ethylenically unsaturated double bond during thermal curing. Can be. At this time, the monomer having a glycidyl reactive group may be glycidyl (meth) acrylate, vinyl benzyl glycidyl ether, vinyl glycidyl ether, allyl glycidyl ether, 4-methyl-4,5-epoxypentene , γ-glycidoxy propyl trimethoxysilane, γ-glycidoxy propyl methyldiethoxysilane, γ-glycidoxy propyl triethoxy silane, and one or more selected from the group consisting of norbornyl derivatives. .

In the present invention, the acrylic copolymer resin containing no fluorine group has an acid value of about 0 to 200 KOH mg / g, and the number average molecular weight is preferably in the range of 5,000 to 50,000. The acrylic copolymer resin containing no fluorine group may be used alone or in combination of two or more of more than 0 to 20 parts by weight or less based on 100 parts by weight of the photosensitive resin composition for black matrix.

As the polyfunctional acrylic monomer having an ethylenically unsaturated double bond, a compound having a boiling point of 100 ° C. to 300 ° C. or less or a functional acrylic monomer having caprolactone having at least one or more addition polymerizable unsaturated groups in a molecule may be used.

Examples of the compound having a boiling point of 100 ° C. to 300 ° C. or less having at least one addition polymerizable unsaturated group in the molecule include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, or phenoxyethyl (meth). Monofunctional monomers such as acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, neopentyl glycol (meth) acrylate, pentaeryte And polyfunctional monomers such as lititol tetra acrylate, pentaerythritol triacrylate, dipentaerythritol penta acrylate, or dipentaerythritol hexa acrylate.

In addition, as the polyfunctional monomer incorporating caprolactone, KAYARAD DPCA-20, 30, 60, 120 introduced in dipentaerythritol, KAYARAD TC-110S introduced in tetrahydrofuryl acrylate, or neopentyl glycol hydroxy KAYARAD HX-220, KAYARAD HK-620, etc. introduced to pivalate can be used. Other polyfunctional monomers that can be used include epoxy acrylates of bisphenol A derivatives, novolak-epoxy acrylates, and urethane-based polyfunctional acrylates such as U-324A, U15HA or U-4HA. The polyfunctional monomer which has the said ethylenically unsaturated double bond can be used individually or in mixture of 2 or more types.

It is preferable to add 5-20 weight part with respect to 100 weight part of photosensitive resin compositions for black matrices, and, as for the polyfunctional acrylic monomer which has the said ethylenically unsaturated double bond, it is more preferable to add 5-10 weight part. When the content of the polyfunctional acrylic monomer having an ethylenically unsaturated double bond is less than 5 parts by weight, the photosensitivity of the film formed by the photosensitive resin composition for the black matrix or the strength of the coated film may be lowered, and may exceed 20 parts by weight. In this case, the adhesiveness of the photosensitive resin layer is excessive, the strength of the film is not sufficient, and the pattern may be lost during development.

As a photoinitiator used for the photosensitive resin composition for black matrices of this invention, an acetophenone derivative and S-triazine type can be used individually or in mixture of 2 or more types. Specific examples of the acetophenone derivatives include 1-hydroxycyclohexylphenyl ketone (Irgacure 184, manufactured by Ciba), 2,2-dimethoxy-2-phenylacetophenone (Irgacure 651, manufactured by Ciba), 2-benzyl-2 -(Dimethylamino) -1- (4-morpholinophenyl) butyl-1-one (Irgacure 369 from Ciba), 2-methyl-1- (4- (methylthio) phenyl) -2- (4- Morpholinyl) -1-propanone (Irgacure 907, from Ciba), 2-hydroxy-2-methyl-1-phenylpropan-1-one (Irgacure 1173, from Ciba), 1- [9-ethyl-6 -(2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) ethanone (trade name CGI-242), 2,2'-bis (o-chlorophenyl) -4, 4,5,5'-tetraphenyl-1,2'-biimidazole, 4,4-bis (diethylamino) benzophenone or mercaptobenzothiazole.

Specific examples of the S-triazine type include 2-butoxystyryl-5-trichloromethyl-1,3,4-oxadiazole and the like.

It is preferable to add 0.1-15 weight part with respect to 100 weight part of photosensitive resin compositions for black matrices, and, as for the said photoinitiator, it is more preferable to add 0.1-7 weight part. When the content of the photopolymerization initiator is less than 0.1 part by weight, the degree of photopolymerization may be lowered, and when the content of the photopolymerization initiator is more than 15 parts by weight, the efficiency of the photopolymerization initiator may be reduced.

The colorant used in the photosensitive resin composition for black matrices of the present invention includes a black pigment for performing the light shielding function of the black matrix. As the black pigment, carbon black is preferable. Since black pigments other than carbon black have weak light-shielding properties, the compounding amount must be large, and as a result, the viscosity of the composition increases, making it difficult to handle, or there is a problem that the strength of the formed film or the adhesion to the substrate is significantly reduced. The carbon black may be used alone, or may be used in combination with other pigments. Color pigments that can be used in combination with carbon black include carmine 6B, phthalocyanine green, phthalocyanine blue, perylene black or cyanine black and the like.

It is preferable to add 1-20 weight part with respect to 100 weight part of photosensitive resin compositions for black matrices, and, as for the said coloring agent, it is more preferable to add 1-15 weight part. When the content of the colorant is less than 1 part by weight, the optical density per thickness of the light blocking part pattern formed of the photosensitive resin composition for the black matrix is lowered, so that the thickness of the pattern must be considerably thick to obtain a desired optical density. As a result, a step between the color pattern parts formed by jetting ink on the pixel part may be increased. In addition, when the content of the colorant exceeds 20 parts by weight, the optical density per thickness is considerably high, so there is an advantage in that the thickness of the pattern may be thin. However, since other components are relatively small, the process characteristics for forming the light shielding part pattern may be deteriorated. In addition, various properties such as electrical properties of the surface of the light shielding part pattern, adhesion to the substrate, and surface properties may be deteriorated.

It is preferable to use the solvent which can be spin-coated to glass as the solvent used for the photosensitive resin composition for black matrices of this invention. Specific examples of the solvent include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol and i-propyl alcohol; Cellosolves such as methyl cellosolve and ethyl cellosolve; Carbitols such as diethylene glycol methyl ether or diethylene glycol ethyl ether; Esters such as ethyl acetate, butyl acetate, methyl methoxy propionate and ethyl ethoxy propionate ethyl lactate; Ketones such as acetone, methyl isobutyl ketone, cyclohexanone and cellosolve; Acetates such as methyl cellosolve acetate; Carbitol acetates such as diethylglycol methyl acetate, diethylglycol ethyl acetate, and propylene glycol methyl ether acetate; Ethers such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol diethyl ether (diglyme), tetrahydrofuran; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; lactones such as t-butyrolactone; Aromatic systems such as benzene, toluene and xylene; Or saturated hydrocarbons such as n-heptane, n-hexane, n-octane and the like can be used. The solvent is generally used alone or in combination of two or more thereof.

It is preferable that the said solvent adds 20-80 weight part with respect to 100 weight part in the photosensitive resin composition for black matrices.

The photosensitive resin composition of this invention may further contain additives, such as an adhesion promoter, a film | membrane improvement agent, surfactant, or a sensitizer, as needed.

The adhesion promoter may be added to improve adhesion to the substrate, and 3-methacryloxypropyltrimethoxysilane or a leveling agent may be used. The film improving agent is added to improve the thermal and mechanical properties of the photoresist film, and plasticizers, acrylic resins, polystyrene derivatives or polyvinyl methyl ether may be used. The surfactant is added for coating uniformity and stain removal of the photoresist film, and nonionic surfactants, silicone-based surfactants, or fluorine-based surfactants may be used. A sensitizer is used to improve the sensitivity of the photoresist, and may be 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone or 4, 4 '-(1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol and the like can be used.

In addition, the present invention

(a) using a photosensitive resin composition for a black matrix comprising an acrylic copolymer resin containing a fluorine group represented by the formula (1) on the substrate, a polyfunctional acrylic monomer having an ethylenically unsaturated double bond, a photopolymerization initiator, a colorant and a solvent Forming a black matrix pattern;

(b) thermosetting the black matrix pattern; And

(c) filling ink into a pixel portion partitioned by the black matrix pattern

It provides a method of manufacturing a color filter comprising a.

The step (a) is a black photosensitive resin composition comprising an acrylic copolymer resin containing a fluorine group represented by Formula 1 on the substrate, a polyfunctional acrylic monomer having an ethylenically unsaturated double bond, a photopolymerization initiator, a colorant, and a solvent. It is a step of forming a black matrix pattern using.

Here, the black mattress pattern is (a1) a black matrix containing an acrylic copolymer resin containing a fluorine group represented by the formula (1) on the substrate, a polyfunctional acrylic monomer having an ethylenically unsaturated double bond, a photopolymerization initiator, a colorant and a solvent Applying a photosensitive resin composition for use; (a2) prebaking the photosensitive resin composition; And (a3) selectively exposing and developing the pre-baked photosensitive resin composition.

Although it does not specifically limit as a material as a said board | substrate, A glass substrate, a plastic substrate, another flexible substrate, etc. can be used, A transparent glass substrate with strong heat resistance is preferable.

The photosensitive resin composition for black matrices comprising an acrylic copolymer resin including a fluorine group represented by Formula 1 on the substrate in step (a1), a polyfunctional acrylic monomer having an ethylenically unsaturated double bond, a photopolymerization initiator, a colorant, and a solvent. The method of applying can be performed by methods known in the art, such as spin coating, dip coating or doctor blading.

In the step (a2), the prebaking is preferably performed at 50 to 150 ° C. for 10 to 1000 seconds.

Selective exposure and development in the step (a3) can be carried out using a method known in the art. For example, the prebaked black matrix layer may be selectively exposed using a photomask, followed by developing exposed or unexposed portions.

Step (b) is a step of thermally curing the black matrix pattern, it is preferable to heat-cure the substrate on which the black matrix prepared in step (a) is formed at 200 to 250 ℃ for 10 to 200 minutes.

It is preferable that the thickness of the black matrix pattern manufactured by the said manufacturing method is 1.1-5 micrometers, and optical density is 2-6 in the said thickness range. In addition, the black matrix preferably has a contact angle of 20 to 60 ° with respect to the ink.

In the step (c), the ink is filled in the pixel portion partitioned by the black matrix pattern, and two or more kinds of inks, for example, three kinds of inks, such as R, G, and B, may be simultaneously or continuously filled. The ink may use a photocurable or thermosetting ink. The ink filling is preferably performed by an inkjet method.

Since the black matrix pattern formed by the photosensitive resin composition for black matrices of the present invention has characteristics such as low surface tension, excellent dielectric constant, and hydrophobicity, and the pixel portion is incompatible with ink, each ink is ejected to the pixel portion by an inkjet method. In this case, the ejected ink may be uniformly spread in the pixel portion and may be applied higher and convexly than the formed black matrix.

Since the ink ejected in this process does not cross the ink-repellent black matrix, it is possible to continuously eject three inks without a separate post-treatment process for each ink, and if necessary, after each ink ejection or after all ink ejections Photocuring or thermosetting may be carried out.

The photocuring is preferably UV irradiation, the UV irradiation is preferably performed for 5 to 500 seconds at an intensity of 50 to 500 ㎽ / ㎠. More preferably, it is performed for 5 to 500 seconds at an intensity of 80 to 200 mW / cm 2.

In addition, the UV irradiation may be performed on the substrate surface or the surface on which the black matrix is formed.

The thermal curing is preferably carried out at 50 to 150 ℃ for 10 to 2000 seconds.

After the photocuring or thermosetting treatment, the black matrix and the ink may be cured by only one high temperature thermal curing at the same time. The high temperature heat curing is preferably carried out at 200 to 250 ℃ for 10 to 200 minutes.

Moreover, this invention provides the color filter containing the black matrix pattern formed from the photosensitive resin composition for black matrices of this invention.

In addition, the present invention provides a liquid crystal display device including the color filter.

The manufacturing method of the liquid crystal display device according to the present invention may use techniques in the art except for the method of manufacturing a color filter using the resin composition for a black matrix described above.

Hereinafter, preferred examples are provided to aid in understanding the present invention. However, the following examples are merely provided to more easily understand the present invention, and the scope of the present invention is not limited thereto.

< Production Example >

To 150 ml of propylene glycol methyl ether acetate, 22.05 parts by weight (0.125 mol) of benzyl methacrylate was added 4.62 parts by weight (0.054 mol) of methacrylic acid, and 3.33 parts by weight (0.02 mol) of trifluoroethyl acrylate, and flowed for 1 hour with nitrogen. The temperature was raised to 90 ℃. 0.15 parts (0.9 mmol) of AIBN, 0.5% by weight, based on the total monomers was added and then maintained at 100 ° C. for 5 hours.

After the reaction was completed, it was precipitated in ether. The precipitate precipitate was dissolved in tetrahydrofuran, precipitated again with ether / hexane, filtered and dried to prepare an acrylic copolymer resin containing fluorine groups.

< Example >

 Carbon black dispersion (20 wt% carbon black as solid, 3 wt% dispersant, 4 wt% copolymer of benzyl (meth) acrylate / (meth) acrylic acid (molar ratio 70/30, Mw = 23,000), propylene glycol methyl ether acetate 73% by weight) 375 parts by weight, 50 parts by weight of the acrylic copolymer resin (25% by weight solid, 70% by weight propylene glycol methyl ether acetate) containing a fluorine group prepared in the preparation example (or represented by Formula 1), fluorine 40 weight part of polymer (molar ratio 73/19/8, Mw = 22,000) which glycidyl (meth) acrylate was added to the copolymer of benzyl (meth) acrylate / (meth) acrylic acid as an acrylic copolymer resin containing no group (30 wt% solids, 70 wt% propylene glycol methyl ether acetate), 80 wt parts of dipentaerythritol hexa acrylate as a polyfunctional monomer having an ethylenically unsaturated double bond (50 wt% solids) And 50 parts by weight of propylene glycol methyl ether acetate) and 3 parts by weight of 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) butyl-1-one (trade name Irgacure 369) as a photopolymerization initiator. , 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) ethanone (trade name CGI-242) 6 parts by weight, 2,2 4 parts by weight of '-bis (o-chlorophenyl) -4,4,5,5'-tetraphenyl-1,2'-biimidazole, 4 parts by weight of 4,4-bis (diethylamino) benzophenone, And 2 parts by weight of mercaptobenzothiazole, then 5 parts by weight of 3-methacryloxypropyltrimethoxysilane, an adhesion promoter, and 1 part by weight of a leveling agent as additives, and 150 parts of propylene glycol monomethyl ether acetate as a solvent. Parts, 140 parts by weight of 3-methoxy butyl acetate, and 140 parts by weight of dipropylene glycol monomethyl ether were mixed. Then, the mixture was stirred for 5 hours to prepare a photosensitive resin composition for a black matrix.

< Comparative example >

A photosensitive resin composition for a black matrix was prepared in the same manner as in the above example except that an acrylic copolymer resin containing no fluorine group was used.

< Experimental Example >

After spin-coating the photosensitive resin composition for black matrices prepared in Examples and Comparative Examples on a glass substrate, prebaking was performed at 90 ° C. for 2 minutes and exposed. The exposure was adjusted experimentally to a size of 20 to 100 mJ / ㎠ using a light of 365 nm (I-line). The exposed substrate was developed with an alkaline developing solution (pH = 11-12) to form a black matrix pattern. The formed black matrix pattern was thermoset in a convection oven at 220 ° C. for 30 minutes.

Each of R, G, and B ink was sprayed by an inkjet method on the pixel portion partitioned by the formed black matrix pattern to manufacture a color filter.

Figures 1 and 2 show the state after jetting ink using the inkjet method on the culley filter prepared by using the emotional resin composition for the black matrix of the Examples and Comparative Examples. As shown in FIG. 1, the color filter using the photosensitive resin composition including the acrylic copolymer resin including the fluorine group of the present invention has a low surface tension, excellent hydrophobic dielectric property, and hydrophobicity, and thus causes bleeding phenomenon in adjacent pixel parts during ink jetting. You can check that it does not occur. However, as shown in FIG. 2, the color filter using the photosensitive resin composition including the acrylic copolymer resin containing no fluorine group may be confirmed to spread ink to adjacent pixel parts during ink jetting.

1 is a photograph of a Charge-Coupled Device (CCD) camera after inkjetting of a color filter manufactured by using the photosensitive resin composition for a black matrix according to an embodiment of the present invention.

2 is a photograph of a charge-coupled device (CCD) camera after inkjetting of a color filter manufactured using the photosensitive resin composition for a black matrix according to a comparative example of the present invention.

Claims (31)

An acrylic copolymer resin containing a fluorine group represented by the following formula (1), a polyfunctional acrylic monomer having an ethylenically unsaturated double bond, a photopolymerization initiator, a colorant and a photosensitive resin composition for a black matrix comprising a solvent: [Formula 1]

here, R ₁ , R ₂ and R ₃ are each independently a hydrogen atom or a methyl group, R ₄ is an alkyl group or aromatic group having 1 to 8 carbon atoms containing fluorine, m, n, l are integers, and the ratio of m / n / l is 60 to 70/15 to 34 / l to 15 on a molar ratio basis The number average molecular weight of the copolymer resin is 10,000 to 50,000. The photosensitive resin composition for a black matrix of claim 1, wherein the acrylic copolymer resin including the fluorine group represented by Chemical Formula 1 includes 1 to 40 parts by weight based on 100 parts by weight of the photosensitive resin composition for a black matrix. The photosensitive resin composition for a black matrix of claim 1, wherein the photosensitive resin composition for a black matrix further includes a compound represented by the following Chemical Formula 2 or Formula 3. [Formula 2]

here, R ₁ and R ₂ are each independently a hydrogen atom or a methyl group, m and n are integers of 70:30 (molar ratio), The number average molecular weight is 10,000 to 50,000. [Formula 3]

here, R ₁ , R ₂ and R ₃ are each independently a hydrogen atom or a methyl group, m, n, l are integers and the ratio is 70:15:15 (molar ratio), The number average molecular weight is 10,000 to 50,000. The photosensitive resin composition for black matrices according to claim 3, wherein the compound represented by Formula 2 or 3 includes more than 0 and 20 parts by weight or less based on 100 parts by weight of the photosensitive resin composition for black matrix. The method of claim 1, wherein the polyfunctional acrylic monomer having an ethylenically unsaturated double bond is a compound having a boiling point of 100 ° C to 300 ° C or at least one addition-polymerizable unsaturated group in a molecule or a capacitive lacquer functional acrylic monomer The photosensitive resin composition for black matrices. The photosensitive resin composition for black matrices of claim 1, wherein the polyfunctional acrylic monomer having an ethylenically unsaturated double bond contains 5 to 20 parts by weight based on 100 parts by weight of the photosensitive resin composition for black matrices. The photosensitive resin composition for a black matrix according to claim 1, wherein the photopolymerization initiator is a single or two or more compounds selected from the group consisting of acetophenone derivatives or S-triazine series. The photosensitive resin composition for a black matrix according to claim 1, wherein the photopolymerization initiator comprises 0.1 to 15 parts by weight based on 100 parts by weight of the total photosensitive resin composition for a black matrix. The photosensitive resin composition for black matrices of claim 1, wherein the colorant is a black pigment. The photosensitive resin composition for black matrices of claim 1, wherein the colorant is carbon black. The photosensitive resin composition for a black matrix according to claim 10, wherein the carbon black is used in combination with carmine 6B, phthalocyanine green, phthalocyanine blue, perylene black, or cyanine black. The photosensitive resin composition for black matrices of claim 1, wherein the colorant comprises 1 to 20 parts by weight based on 100 parts by weight of the photosensitive resin composition for black matrices. The method of claim 1, wherein the solvent is a group consisting of alcohols, cellosolves, carbitols, esters, ketones, acetates, carbitol acetates, ethers, amides, lactones, aromatics, and saturated hydrocarbons. The photosensitive resin composition for black matrices which is selected from single or 2 or more types of compounds. The photosensitive resin composition for black matrices of claim 1, wherein the solvent comprises 20 to 80 parts by weight based on 100 parts by weight of the photosensitive resin composition for black matrices. The photosensitive resin composition for black matrices of claim 1, wherein the photosensitive resin composition for black matrices further comprises an adhesion promoter, a film improving agent, a surfactant, or a sensitizer. (a) using a photosensitive resin composition for a black matrix comprising an acrylic copolymer resin containing a fluorine group represented by the formula (1) on the substrate, a polyfunctional acrylic monomer having an ethylenically unsaturated double bond, a photopolymerization initiator, a colorant and a solvent Forming a black matrix pattern; (b) thermosetting the black matrix pattern; And (c) filling ink into a pixel portion partitioned by the black matrix pattern Method of manufacturing a color filter comprising a. The method of claim 16, wherein the forming of the black matrix pattern comprises: (a1) an acrylic copolymer resin including a fluorine group represented by Formula 1 on the substrate, a multifunctional acrylic monomer, a photopolymerization initiator, a colorant, and a black solvent. Applying the photosensitive resin composition for the matrix; (a2) prebaking the photosensitive resin composition; And (a3) selectively exposing and developing the prebaked photosensitive resin composition. The method of claim 17, wherein the substrate is a glass substrate, a plastic substrate, or other flexible substrate. The method of claim 17, wherein the prebaking is performed at 50 to 150 ° C. for 10 to 1000 seconds. The method of claim 16, wherein the black matrix pattern has a thickness of 1.1 to 5 μm, and an optical density of 2 to 6 in the thickness range. The method of claim 16, wherein the black matrix pattern has a contact angle of 20 to 60 ° with respect to the ink. The method of claim 16, wherein the thermosetting is performed for 10 to 200 minutes at 200 to 250 ℃. The method of claim 16, wherein the ink filling is performed by simultaneously or continuously filling two or more kinds of inks. The method of claim 16, wherein the ink filling is performed by an inkjet method. The method of claim 16, wherein the ink is a photocurable or thermosetting ink. The method of claim 16, wherein photocuring or thermosetting is further performed after the ink filling or after all the ink ejecting. The method of claim 26, wherein the photocuring is performed at 50 to 500 mW / cm 2 for 5 to 500 seconds. The method of claim 26, wherein the thermosetting is performed at 50 to 150 ° C. for 10 to 2000 seconds. The method of claim 26, wherein the high temperature thermal curing is performed once at a temperature of 200 to 250 ° C. for 10 to 200 minutes after the photocuring or thermal curing. The color filter containing the black matrix pattern formed from the photosensitive resin composition for black matrices in any one of Claims 1-15. A liquid crystal display device comprising the color filter of claim 30.

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