KR101028633B1 - Ink composition for roll printing - Google Patents

Abstract

The present invention relates to an ink composition for roll printing, and more particularly to an acrylic copolymer resin containing a fluorine group, a polyfunctional acrylic monomer having an ethylenically unsaturated double bond, a thermal polymerization initiator, a colorant, and a roll printing ink including a solvent. It relates to a composition.

Fluorine group, ink composition, roll printing

Description

Ink composition for roll printing {INK COMPOSITION FOR ROLL PRINTING}

1A and 1B are optical micrographs (× 1000) after coating the red ink for roll printing according to Example 1 and Comparative Example 1 of the present invention onto a blanket, respectively.

2A and 2B are optical micrographs (× 1000) after coating green ink for roll printing according to Example 2 and Comparative Example 2 of the present invention on a blanket, respectively.

3A and 3B are optical micrographs (× 1000) after coating the blue ink for roll printing according to Example 3 and Comparative Example 3 of the present invention onto a blanket, respectively.

The present invention relates to an ink composition for roll printing, and more particularly to a roll printing comprising an acrylic copolymer resin containing a fluorine group, a polyfunctional acrylic monomer having an ethylenically unsaturated double bond, a thermal polymerization initiator, a colorant and a solvent. It relates to an ink 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, or may be defined as a device that plays a role of bridging a human and electronic device. have.

Such an electronic display device is called an emissive display when an optical information signal is displayed by a light emitting phenomenon, and a light receiving display device when a light information signal is displayed by light modulation due to reflection, scattering or interference. It is called an 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) or 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 led to the necessity of electronic display devices suitable for a new environment due to the miniaturization and light weight of electronic devices along with 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, the liquid crystal display device is thinner and lighter than other display devices, and has a low power consumption and a low driving voltage, and is widely used in various electronic devices because it can display images close to the cathode ray tube. 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 red (R), green (G), and blue (B) for colorization.

The conventional photolithography method of manufacturing a color filter using the photoresists composed of the three primary colors of red, green, and blue is a photoresist of red, green, and blue, respectively, in a pixel portion partitioned by a black matrix formed on a glass substrate. The composition includes processes such as coating, exposing and developing. The photolithography method consumes a considerable amount of time and cost in manufacturing a liquid crystal display device because of the waste of materials, complicated processes, and expensive equipment.

Recently, a number of new process methods have been used to replace the conventional photolithography method, which is a typical roll printing method.

However, the conventional roll printing method uses a low surface tension material such as polydimethylsilosane (PDMS) as a blanket in order to smoothly transfer the pattern from the blanket to the substrate during pattern transfer by roll printing. Only lower than good coating results can be obtained. Therefore, in order to make the ink composition for roll printing have a lower surface tension than the blanket surface, a surfactant having excellent effect of lowering the surface tension must be added and used in the ink composition. However, in this case, since the compatibility and anti-foaming properties of the surfactant component and the pigment or dispersant and binder resin contained in the ink composition for roll printing are inferior, there is a hole in the coating surface or inside when coating on the blanket. This may occur or pigment aggregation may occur.

In order to solve the above problems, the present inventors use the acrylic copolymer resin containing a fluorine group in the manufacture of the ink composition for roll printing through improving the compatibility and anti-foaming properties of the ink coating on the blanket in the roll printing method It was found that excellent characteristics such as coating defects such as holes or pigment agglomeration of the coating surface did not occur. Accordingly, the present invention is an acrylic copolymer resin containing a fluorine group, a polyfunctional acrylic monomer having an ethylenically unsaturated double bond, a thermal polymerization initiator, a coloring composition for a roll printing comprising a solvent and a solvent, a method of manufacturing a color filter using the same An object of the present invention is to provide a color filter manufactured by the present invention and a liquid crystal display device including the same.

The present invention provides an ink composition for roll printing comprising an acrylic copolymer resin including a fluorine group represented by Formula 1, a polyfunctional acrylic monomer having an ethylenically unsaturated double bond, a thermal polymerization initiator, a colorant, and 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 having 1 to 8 carbon atoms or an aromatic group containing a fluorine group,

m, n, l are integers, and the ratio of m / n / l is 40 to 70/15 to 34 / l to 30 on a molar ratio basis.

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

In addition,

(a) forming a black matrix pattern on the substrate;

(b) an acrylic copolymer resin containing a fluorine group represented by the formula (1) in a pixel portion partitioned by the black matrix, a polyfunctional acrylic monomer having an ethylenically unsaturated double bond, a thermal polymerization initiator, by a roll printing method, Coating and transferring the ink composition for roll printing comprising a colorant and a solvent to pattern the ink composition; And

(c) drying the patterned roll printing ink composition.

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

In addition, the present invention provides a color filter according to the manufacturing method.

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

Hereinafter, the present invention will be described in detail.

The present invention provides an ink composition for roll printing comprising an acrylic copolymer resin including a fluorine group represented by Formula 1, a polyfunctional acrylic monomer having an ethylenically unsaturated double bond, a thermal polymerization initiator, a colorant, and a solvent.

The acrylic copolymer resin including the fluorine group used in the ink composition for roll printing of the present invention may be represented by the following Chemical 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 having 1 to 8 carbon atoms or an aromatic group containing a fluorine group,

m, n, l are integers, and the ratio of m / n / l is 40 to 70/15 to 34 / l to 30 on a molar ratio basis.

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

The acrylic copolymer resin represented by Formula 1 includes a fluorine group. The fluorine group in the acrylic copolymer resin serves to have compatibility and antifoaming property of the ink composition for roll printing of the present invention. Specifically, the surfactant containing the fluorine group used in the existing ink composition is very effective in lowering the surface tension, but because of the low polarity is less compatible with the relatively polar pigments and dispersants used to disperse them. As a result, agglomeration between the pigments or deterioration of the antifoaming occurs. Therefore, the surface may be very rough during coating and a thin film may be formed in a state in which bubbles are contained therein. However, when an acrylic copolymer resin containing a fluorine group is added, the acrylic copolymer resin contains a fluorine group which serves to lower the surface tension while simultaneously increasing the compatibility with pigments and dispersants and other binder components. Containing the components, as a result, it improves the compatibility and dispersibility of the entire ink composition, there is no pigment agglomeration during coating, the surface is uniform, and bubbles in the film are also reduced.

The acrylic copolymer resin including the fluorine group represented by Formula 1 is preferably added 1 to 20 parts by weight based on 100 parts by weight of the ink composition for roll printing. When the content of the acrylic copolymer resin containing the fluorine group is less than 1 part by weight, it is difficult to expect the effect of improving the compatibility and the anti-foaming of the ink composition, when it exceeds 20 parts by weight having an ethylenically unsaturated double bond The content of other components including polyfunctional acrylic monomers may be relatively low, which may lower the strength of the film.

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 in the acrylic copolymer resin containing no fluorine group may be used by copolymerizing a monomer containing an acid function and a monomer copolymerizable with the monomer, and unlike in photolithography, an alkali developing process is performed. Since it does not go through, it does not need to include an acidic radical in particular.

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, methoxytriethylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxydiethylene glycol ( Meta) 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- (meth 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, but are not limited thereto.

[Formula 2]

here,

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

m, n are integers, the ratio is 70:30 on a molar ratio basis,

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

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In addition, an ethylenically unsaturated reactive group capable of addition polymerization with a polyfunctional monomer having an ethylenically unsaturated double bond upon thermal curing by addition reaction of a monomer having a glycidyl reactor to an acid group of the acrylic binder copolymer resin containing no fluorine group Can be introduced. 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 at least one member selected from the group consisting of norbornyl derivatives All.

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 resin binder 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 ink composition.

As the polyfunctional acrylic monomer having an ethylenically unsaturated double bond, a compound having a boiling point of 100 ° C. or more or a capacitive lactone having a at least one or more addition polymerizable unsaturated group in a molecule may be used.

Examples of the compound having a boiling point of 100 ° C. or higher having at least one addition polymerizable unsaturated group in the molecule include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, and the like. Monofunctional monomer, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, neopentyl glycol (meth) acrylate, pentaerythritol tetraacrylic And polyfunctional monomers such as 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 also be used individually or in mixture of 2 or more types.

The polyfunctional acrylic monomer having an ethylenically unsaturated double bond is preferably used 1 to 20 parts by weight based on 100 parts by weight of the ink composition for roll printing. When the content of the polyfunctional acrylic monomer having an ethylenically unsaturated double bond is less than 1 part by weight, the strength of the coating film may be lowered. When the content of the polyfunctional acrylic monomer is more than 20 parts by weight, the adhesiveness of the resin layer may be excessive, and thus the strength of the film may be increased. Can be degraded.

The ink composition for roll printing of the present invention may use both a photopolymerization initiator and a thermal polymerization initiator, but in the case of the photocuring type, an exposure process must be introduced to cure the ink composition, and for this purpose, the exposure apparatus is an additional device other than the roll printing equipment. And since the alignment apparatus for exposure is needed, the case of thermosetting type | mold is more preferable as a roll printing ink, A photocurable type | mold and a thermosetting type can also be mixed and used.

The thermal polymerization initiator used in the ink composition of the present invention is an azo-based compound, which is azonitrile-based V-60, V-65, V-59, V-70, V- from Wako Pure Chemical Industris. 40 and azo esters V-601, azo amides VA-086, VA-085, VA-080, Vam-110, Vam-111, VF-096, azo amidine V-50, VA-044, VA- 046B, Aam-027, VA-060, VA-057, VA-061, macroazo initiators VPS-0501, VPS-1001, VPE-0201, VPE-0401, VPE-0601, VPTG-0301, etc. can be used. However, the present invention is not limited thereto.

The thermal polymerization initiator is preferably used 0.03 to 0.5 parts by weight based on 100 parts by weight of the ink composition.

The colorant used for the ink composition for roll printing of the present invention is preferably a pigment. If the pigment does not adversely affect the dispersion, a general purpose pigment may be used, but it is preferable to use a pigment of finely processed particles. It is preferable that the said pigment particle size is mainly 0.3 micrometer or less, and it is more preferable that 90 micrometers or more of pigment particles of 0.1 micrometer are distributed. When the size of the pigment is larger than 0.3 μm, a problem of pigment dispersion may occur during manufacturing of the composition, and thus, the light transmittance may not be smooth, and thus the permeability of the manufactured color filter may be poor.

Red pigments used to exhibit color characteristics in the ink composition for roll printing of the present invention include naphthol-based red pigments Pig.Red # 1 (CI12070), Pig.Red # 2 (CI12310), Pig.Red # 3 (CI12120), Pig.Red # 4 (CI12085), Pig.Red # 5 (CI12490), Pig.Red # 6 (CI12090), Pig.Red # 7 (CI12420), Pig.Red # 8 (CI12355), Pig.Red # 9 (CI12460), Pig.Red # 10 (CI12440), Pig.Red # 11 (CI12430), Pig.Red # 12 (CI12385), Pig.Red # 13 (CI12395), Pig.Red # 14 (CI12380), Pig.Red # 15 (CI12465), Pig.Red # 16 (12500), Pig.Red # 17 (CI12390), Pig.Red # 18 (CI12350), Pig.Red # 21 (CI12300), Pig.Red # 22 (CI12315), Pig.Red # 23 (CI12355), Pig.Red # 31 (12360), Pig.Red # 32 ( 12320), Pig.Red # 95 (CI15897), Pig.Red # 112 (CI12370), Pig.Red # 114 (CI12351), Pig.Red # 119 (CI12469), Pig.Red # 146 (CI 12485), Pig.Red # 147 (CI12433), Pig.Red # 148 (CI12369), Pig.Red # 150 (CI12290), Pig.Red # 151 (CI15890), Pig.Red # 184 (CI 12487), Pig.Red # 187 (CI12486), Pig.Red # 188 (CI12467), Pig.Red # 210 (C.I. 12474), Pig.Red # 245 (C.I.12317), Pig.Red # 253 (C.I.12375), Pig.Red # 258 (C.I.12318), Pig.Red # 261 (C.I.12468); Pig.Red # 49 (CI15630), Pig.Red # 49: 1 (CI15630: 1), Pig.Red # 49: 2 (CI15630: 2), Pig.Red # 49: naphthol-based and metal complexes 3 (CI15630: 3), Pig.Red # 50: 1 (CI15500: 1), Pig.Red # 51: 1 (CI15580: 1), Pig.Red # 53 (CI15585), Pig.Red # 53: 1 (CI15585: 1), Pig.Red # 68 (CI15525), Pig.Red # 243 (CI15910), Pig.Red # 247 (CI15915); Disazopyrazolone Pig.Red # 37 (C.I.21205), Pig.Red # 38 (C.I.21210), Pig.Red # 41 (C.I.21200); Disazo-based condensates Pig.Red # 144 (CI20735), Pig.Red # 166 (CI20035), Pig.Red # 220 (CI20055), Pig.Red # 221 (CI20065), Pig.Red # 242 (CI20067); Pig.Red # 48: 1 (CI15865: 1), Pig.Red # 48: 2 (CI15865: 2), Pig.Red # 48: 3 (CI, 2-hydroxy-3-naphthoic acid-based metal complexes 15865: 3), Pig.Red # 48: 4 (CI15865: 4), Pig.Red # 48: 5 (CI15865: 5), Pig.Red # 52: 1 (CI15860: 1), Pig.Red # 52: 2 (CI15860: 2), Pig.Red # 57: 1 (CI15850: 1), Pig.Red # 58: 2 (CI15825: 2), Pig.Red # 58: 4 (CI15825: 4), Pig.Red # 63: 1 (CI15880: 1), Pig.Red # 63: 2 (CI15880: 2), Pig.Red # 64 (CI15800), Pig.Red # 64: 1 (CI 15800: 1), Pig. Red # 200 (CI15867); Naphthalenesulfonic acid metal complexes Pig.Red # 60: 1 (C.I.16105: 1), Pig.Red # 66 (C.I.18000: 1), Pig.Red # 67 (C.I.18025: 1); Triarylcarbonium-based Pig.Red # 81: 1 (C.I.45160: 1), Pig.Red # 81: 3 (C.I.45160: 3), Pig.Red # 169 (C.I.45160: 2); Pig.Red # 89 (C.I. 60745), Pig.Red # 177 (65300), which are anthraquinones; Pig.Red # 88 (C.I.73312), Pig.Red # 181 (C.I.73360), which are ciiodigo; The quinacridone family Pig.Red # 122 (C.I.73915), Pig.Red # 207 (C.I.73900), Pig.Red # 209 (C.I.73905); Perylene-based Pig.Red # 123 (CI71145), Pig.Red # 149 (CI71137), Pig.Red # 178 (CI71155), Pig.Red # 179 (CI71130), Pig.Red # 190 (CI 71140), Pig. Red # 194 (CI71100), Pig. Red # 224 (CI71127); Van. Imidazolone-based Pig.Red # 171 (CI12512), Pig.Red # 175 (CI12513), Pig.Red # 176 (CI12515), Pig.Red # 185 (CI12516), Pig.Red # 208 (CI12514); Pyranthrone Pig.Red # 216 (C.I.59710); Pig.Red # 254 (C.I.56110), a diketopyrrolopyrrole system; Isoindolin-based Pig.Red # 260 (C.I.56295) and the like can be used.

As a violet pigment, Pig.Violet # 1 (CI45170: 2), Pig.Violet # 2 (CI45175: 1), Pig.Violet # 3 (CI42535: 2) and Pig.Violet # 27 which are triaryl carbonium (CI42535: 3), Pig.Violet # 39 (CI42555: 2); Anthraquinone-based Pig.Violet # 5: 1 (C.I.58055: 1); Naphthol-based Pig.Violet # 25 (C.I.12321), Pig.Violet # 50 (C.I.12322); Pig.Violet # 19 (C.I.73900) which is a quinacridone family; Pig.Violet # 23 (C.I.51319) and Pig.Violet # 37 (C.I.51345), which are dioxazines; Perylene-based Pig.Violet # 29 (C.I.71129); Benzimidazolone Pig.Violet # 32 (C.I.12517) and the like can be used.

As a blue pigment, Pig.Blue # 1 (CI42595: 2), Pig.Blue # 2 (CI44045: 2), Pig.Blue # 9 (CI42025: 1) and Pig.Blue # 10 which are triaryl carbonium-based (CI44040: 2), Pig.Blue # 14 (CI42600: 1), Pig.Blue # 18 (CI42770: 1), Pig.Blue # 19 (CI42750), Pig.Blue # 56 (CI42800) Pig. Blue # 62 (CI44084); Pig.Blue # 15 (C.I.74160) and Pig.Blue # 15: 1 (C.I.74160) which are Cu phthalocyanine series; Pig.Blue # 16 (C.I.74100), which is a metal-free phthalocyanine series; Indrone-based Pig.Blue # 60 (C.I.69800), Pig.Blue # 64 (C.I.69825); Indigo-based Pig.Blue # 66 (C.I.73000), Pig.Blue # 63 (C.I.73015: x) and the like can be used.

As a green pigment, Pig.Green # 1 (C.I.42040: 1), Pig.Green # 2 (C.I.42040: 1), Pig.Green # 4 (C.I.42000: 2), which are triarylcarboniums; Pig. Green # 7 (C.I.74260), Pig.Green # 36 (C.I.74265), which are Cu phthalocyanine series; Metal complexes Pig. Green # 8 (C.I.10006), Pig.Green # 10 (C.I.12775) and the like can be used.

As a yellow pigment, Pig.Yellow # 1 (CI11680), Pig.Yellow # 2 (CI11730), Pig.Yellow # 3 (CI11710), Pig.Yellow # 5 (CI11660) and Pig.Yellow which are monoazo systems # 6 (CI11670), Pig.Yellow # 10 (CI12710), Pig.Yellow # 49 (CI11765), Pig.Yellow # 65 (CI11740), Pig.Yellow # 73 (CI11738), Pig.Yellow # 74 (CI11741), Pig.Yellow # 75 (CI11770), Pig.Yellow # 97 (CI11767), Pig.Yellow # 98 (CI11727), Pig.Yellow # 111 (CI11745), Pig.Yellow # 116 (CI11790), Pig. Yellow # 167 (CI11737); Pig.Yellow # 61 (CI13880), Pig.Yellow # 62: 1 (CI13940: 1), Pig.Yellow # 100 (CI19140: 1), Pig.Yellow # 168 (CI13960) ), Pig. Yellow # 169 (CI13955), Pig. Yellow # 183 (CI18792); Pig. Yellow # 16 (C.I. 20040), which is a bisacetoacetalilide system; Pigary Yellow # 12 (CI21090), Pig. Yellow # 13 (CI21100), Pig. Yellow # 14 (CI21095), Pig. Yellow # 17 (CI21105), Pig. Yellow # 55 CI21096), Pig.Yellow # 63 (CI21091), Pig.Yellow # 81 (CI21127), Pig.Yellow # 83 (CI21108), Pig.Yellow # 87 (CI21107: 1), Pig.Yellow # 113 (CI21126), Pig.Yellow # 114 (CI21092), Pig.Yellow # 124 (CI21107), Pig.Yellow # 126 (CI21101), Pig.Yellow # 127 (21102), Pig.Yellow # 152 (CI21111), Pig. Yellow # 170 (CI21104), Pig. Yellow # 171 (CI21106), Pig. Yellow # 172 (CI21109), Pig. Yellow # 174 (CI21098); Pig.Yellow # 24 (C.I.70600), which is a flavones system; Pig.Yellow # 93 (CI20710), Pig.Yellow # 94 (CI20038), Pig.Yellow # 95 (CI20034), Pig.Yellow # 128 (CI20037), Pig.Yellow # 166 (Diazo condensate) CI20035); Anthraquinone-based Pig. Yellow # 123 (C.I.65049), Pig.Yellow # 147 (C.I.60645); Pig.Yellow # 101 (C.I.48052), which is an alginate; Pig.Yellow # 104 (C.I.15985: 1), a naphthalene sulfonic acid metal complex; Pigra Yellow # 108 (C.I.68420), which is anthrapyrimidine; Pig.Yellow # 109 (C.I.56284), Pig.Yellow # 110 (C.I.56280), Pig.Yellow # 139 (C.I.56298), Pig.Yellow # 185 (C.I.56290), which are isoindolinones; Benzimidazolone series Pig.Yellow # 123 (CI11783), Pig.Yellow # 154 (CI13980), Pig.Yellow # 175 (CI11784), Pig.Yellow # 180 (CI21290), Pig.Yellow # 181 (CI11777); Pig. Yellow # 138 (C.I. 56300), which is a quinophthalone; Pig.Yellow # 117 (CI48043), Pig.Yellow # 129 (CI48042), Pig.Yellow # 150 (CI12764), Pig.Yellow # 153 (CI48545), Pig.Yellow # 177 (CI) 48120), Pig. Yellow # 179 (CI48125), etc. may be used.

In addition, orange pigments include Piga Orange # 1 (C.I.11725), Pig.Orange # 6 (C.I.12730), which are monoazo; Naphthol-based Pig.Orange # 2 (CI12060), Pig.Orange # 5 (CI12075), Pig.Orange # 22 (CI12470), Pig.Orange # 24 (CI12305), Pig.Orange # 38 (CI12367 ); Pig.Orange # 17 (CI15510: 1 Pig.Orange # 17: 1 (15510: 2), Pig.Orange # 46 (CI15602), a naphthol metal complex; Pig.Orange # 13 (CI21110), which is a disazopyrazolone-based Pig.Orange # 34 (CI21115); Diarylide-based Pig.Orange # 15 (CI21130), Pig.Orange # 16 (CI21160); Naphthalenesulfonic acid metal complex Pig.Orange # 19 (CI15990) Pig.Orange # 31 (CI20050), which is a disazo condensate; Pig.Orange # 36 (CI11780), Pig.Orange # 60 (CI11782), which is benzimidazolone; CI59700); Perinone Pig.Orange # 43 (CI71105); Quinacridone Pig.Orange # 48 (CI73900); Isoindolin Pig.Orange # 61 (CI11265), Pig.Orange # 66 (CI48210) or Pig.Orange # 69 (CI56292) may be used.

The colorant used to exhibit color characteristics in the ink composition for roll printing is preferably added 1 to 20 parts by weight, more preferably 1 to 15 parts by weight, based on the required color properties. It is wealth. If the content of the colorant used in the ink composition is not appropriate, it is impossible to obtain a product of a desired image quality in the manufacture of a color filter.

The solvent is propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate in view of solubility, pigment dispersibility, coating property, and pattern transferability by roll printing. , Diethylene glycol dimethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 2-hydroxyethyl propionate, 3-methyl-3-methoxybutylpropionate, ethyl-3-methoxyprop Cypionate, Methyl-3-ethoxypropionate, Ethyl-3-ethoxypropionate, Butyl acetate, Ethyl acetate, Amylpermate, Isoamyl acetate, Isobutyl acetate, Isopropyl acetate, Methyl ethyl ketone, Butyl Propionate, isopropylbutyrate, ethylbutyrate, butylbutyrate, ethylpyruvate, γ-butyrol acetate and methyl Alcohols such as cole, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, aromatic systems such as benzene, toluene and xylene, saturated hydrocarbons such as n-heptane, n-hexane, n-octane and the like can be used. . The said solvent can be used individually or in mixture of 2 or more types.

The solvent is preferably added 60 to 90 parts by weight based on 100 parts by weight of the ink composition for roll printing. When the content of the solvent is less than 60 parts by weight, the solid content of the ink is increased and the viscosity is greatly increased, which makes it difficult to coat the ink on the blanket, and when the content of the solvent exceeds 90 parts by weight, the solid content is rather high. The low viscosity and low viscosity not only make coating difficult, but also increase the amount of solvent that must be volatilized for pattern transfer.

The ink composition for roll printing of the present invention may further include a surfactant to adjust the surface tension of the ink. The surfactant to be added is preferably one or more selected from the group consisting of silicone-based surfactants and fluorine-based surfactants. Specifically, as a silicone-based surfactant having a high effect of lowering the surface tension, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-330, BYK-333, BYK-335, BYK-341, BYK-344, BYK-345, BYK-370 and the like can be used.Fluorin-based surfactants include F-114, F-177, F-410, F-411, F-450, and F-493. , F-494, F-443, F-444, F-445, F-446, F-470, F-471, F-475, F-482, F-487, F-172D, TF-1128, TF -1127, TF-1129, TF-1126, TF-1130, TF-1116SF, TF-1131, TF1132, TF1027SF, TF-1441, TF-1442, etc. may be used, but is not limited thereto. However, the surface tension of the ink coated on the PDMS surface should be lower than the general PDMS which is currently used as a blanket material for roll printing has a surface tension of about 24mN / m. When using PDMS as the blanket material for roll printing, there is a limit to lower the surface tension of the ink to 24 mN / m or less, regardless of the amount of the silicone-based surfactant. Therefore, the surface tension of the ink can be lowered to 24 mN / m or less by using a fluorine-based surfactant alone or mixed with a silicone-based surfactant.

The surfactant added to adjust the surface tension of the ink is preferably used 0.03 to 0.3 parts by weight based on 100 parts by weight of the ink composition. When the amount of the surfactant is less than 0.03 parts by weight, the effect of lowering the surface tension of the ink is not sufficient, resulting in coating defects on the blanket. When the amount of the surfactant exceeds 0.3 parts by weight, the surfactant is used in an excessive amount to make the ink compatible. And the defoaming is rather reduced.

The ink composition for roll printing of the present invention may further use at least one additive selected from the group consisting of a dispersant, an adhesion promoter and an antioxidant, if necessary.

The dispersant may be used as a method of internally adding to the pigment in the form of surface treatment of the pigment in advance, or a method of externally adding to the pigment. The dispersant may be a polymeric, nonionic, anionic, or cationic dispersant, and examples thereof include polyalkylene glycols and esters thereof, polyoxyalkylene polyhydric alcohols, ester alkylene oxide adducts, and alcohol alkylenes. Oxide adducts, sulfonic acid esters, sulfonates, carboxylic acid esters, carboxylates, alkylamide alkylene oxide adducts, alkylamines and the like. These may be added alone or used by mixing two or more. The adhesion promoter is vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris (2-methoxyethoxy) -silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- ( 2-aminoethyl) -3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- ( 3,4-ethoxy cyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, or 3-mercaptopropyl Trimethoxysilane and the like can be used. The antioxidant may be 2,2-thiobis (4-methyl-6-t- butylphenol), or 2,6-g, t-butylphenol and the like.

The additive is preferably added more than 0 to 5 parts by weight or less based on the ink composition for roll printing.

In addition,

(a) forming a black matrix pattern on the substrate;

(b) an acrylic copolymer resin containing a fluorine group represented by the formula (1) in a pixel portion partitioned by the black matrix, a polyfunctional acrylic monomer having an ethylenically unsaturated double bond, and a thermal polymerization initiator using a roll printing method Coating and transferring the patterned ink composition for roll printing, comprising a colorant and a solvent; And

(c) thermosetting the ink composition for patterned roll printing;

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

(A) is a step of forming a black matrix pattern on the substrate.

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 process of forming the black matrix pattern on the substrate may be performed by a photolithography method or a roll printing method known in the art.

The black matrix may be prepared using a chromium black matrix or a resin black matrix, which is currently used, and the thickness of the formed black matrix is preferably 0.2 to 3 μm, and the optical density is 2 to 6 in the thickness range. It is preferable.

(B) is an acrylic copolymer resin containing a fluorine group represented by Formula 1, a polyfunctional acrylic monomer having an ethylenically unsaturated double bond, a column in a pixel portion partitioned by the black matrix, using a roll printing method It is a step of coating and transferring the pattern of the ink composition for roll printing comprising a polymerization initiator, a colorant and a solvent.

Here, the roll printing method refers to an undesired coating portion from the blanket using a roll or plate-type cliché which has a reverse pattern of a desired pattern after coating the ink composition for roll printing on a blanket in a roll or flat form. This method is used to transfer the desired pattern portion remaining on the blanket to the substrate. For example, after coating the roll composition ink composition of the present invention on a blanket-like blanket material (e.g. PDMS) using a slit nozzle, a groove (a desired pattern shape) and a protrusion (undesired shape) Using a cliché formed with a pattern shape to remove the unwanted pattern portion from the ink coated on the blanket, and transfer the pattern portion of the desired shape remaining on the blanket by contacting the pixel portion partitioned by the black matrix. to be. Alternatively, in some cases, a cliché having a protrusion having a desired pattern shape may be used to remove the desired pattern shape from the ink coated on the blanket and transfer it directly to the substrate.

(C) is a step of thermosetting the ink composition for roll printing transferred to the substrate. After the transfer of the roll printing ink composition of the present invention to a pixel portion partitioned by the black matrix using the roll printing method, a soft bake is performed for 1 to 600 seconds at a temperature of 50 to 150 ° C., which is again 150 to 250 It is preferable to perform thermosetting by post-baking at 600 ° C. for 600 to 3000 seconds.

The present invention also provides a color filter manufactured by the above method.

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 using the manufacturing method of the color filter by the ink composition for roll printing described above.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited thereto.

≪ Example 1 >

The red ink for roll printing used in the present invention is Pigment Red # 254 4 parts by weight, Pigment Red # 177 0.8 parts by weight, Pigment Yellow # 139 1.2 parts by weight, and fluorine based on 100 parts by weight of the ink composition. Benzyl (meth) acrylate, (meth) acrylic acid, and HFIMA (1,1,1,3,3,3-hexafluoroisopropyl methacrylate) formed of a resin binder containing a group having a molar ratio of 45:25:30 (Mw = 18,800) 2 parts by weight, 3.6 parts by weight of a polymer containing no fluorine to which allylglycidyl ether is added to a copolymer formed of benzyl (meth) acrylate and (meth) acrylic acid at 70:30 (Mw = 7,000), ethylene 9.5 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer having a unsaturated unsaturated double bond, 0.5 parts by weight of azoamide-based thermal polymerization initiator (V-40, Wako Pure Chemical Industris. LTD.), An additive-based polyester as a dispersant 1 part by weight of dispersant, 0.2 part by weight of 3-methacryloxypropyltrimethoxysilane, 0.2 part by weight of fluorine-based surfactant (Megaface F-172D, Nippon Ink Chemical Co., Ltd.), 50 parts by weight of propylene glycol monomethyl ether acetate as a solvent, methyl 17 parts by weight of ethyl ketone and 10 parts by weight of ethyl acetate were mixed, and the mixture was stirred for 5 hours to prepare an ink composition for roll printing.

<Example 2>

The green ink for roll printing used in the present invention is benzyl (meth) as a resin binder containing pigment green # 36 5.9 parts by weight, pigment yellow # 150 3.1 parts by weight, and fluorine based on 100 parts by weight of the ink composition. 1.75 parts by weight of copolymer (Mw = 18,800) formed of acrylate, (meth) acrylic acid and HFIMA (1,1,1,3,3,3-hexafluoroisopropyl methacrylate) in a molar ratio of 45:25:30, benzyl (meth 2.32 parts by weight of a polymer (Mw = 7,000) containing no fluorine group to which allylglycidyl ether was added to a copolymer formed of 70:30 acrylate and (meth) acrylic acid, and a polyfunctional monomer having an ethylenically unsaturated double bond. 6 parts by weight of low pentaerythritol hexaacrylate, 0.5 parts by weight of azoamide-based thermal initiator (V-40, Wako Pure Chemical Industris. LTD), 1.58 parts by weight of a polyester dispersant as an additive, 3-methacrylic Oxypropyl 0.2 part by weight of limethoxysilane, 0.2 part by weight of fluorine-based surfactant (Megaface F-172D, Nippon Ink Chemical Co., Ltd.), 54 parts by weight of propylene glycol monomethyl ether acetate as solvent, 15 parts by weight of methyl ethyl ketone, ethyl 9.45 parts by weight of acetate was mixed and the mixture was stirred for 5 hours to prepare an ink composition for roll printing.

<Example 3>

The blue ink for roll printing used in the present invention is Pigment Blue # 15: 6 3.76 parts by weight, Pigment Violet # 23 0.94 parts by weight, and benzyl resin resin containing fluorine based on 100 parts by weight of the ink composition. 2.6 parts by weight of (meth) acrylate, (meth) acrylic acid, and HFIMA (1,1,1,3,3,3-hexafluoroisopropyl methacrylate) formed with a molar ratio of 45:25:30 (Mw = 18,800) 2.6 parts by weight, benzyl 4.75 parts by weight of a polymer that does not contain a fluorine group (Mw = 7,000) to which a (meth) acrylate and a (meth) acrylic acid are added to a copolymer formed of 70:30 and allylglycidyl ether (Mw = 7,000), and a multi-tube having an ethylenically unsaturated double bond 9.6 parts by weight of dipentaerythritol hexaacrylate as a functional monomer, 0.5 parts by weight of azoamide-based thermal polymerization initiator (V-40, Wako Pure Chemical Industris. LTD), 1 part by weight of a polyester-based dispersant as an additive, 3- Methacryloxypro 0.2 parts by weight of trimethoxysilane, 0.2 parts by weight of fluorine-based surfactant (Megaface F-172D, Daeku Ink and Chemicals, Japan), 42.25 parts by weight of propylene glycol monomethyl ether acetate as solvent, 22.9 parts by weight of methyl ethyl ketone, 11.3 parts by weight of ethyl acetate was mixed, and the mixture was stirred for 5 hours to prepare an ink composition for roll printing.

Comparative Example 1

In Example 1, the fluorine group in which allylglycidyl ether is added to the copolymer in which benzyl (meth) acrylate and (meth) acrylic acid are formed at 70:30 without adding an acrylic copolymer resin containing a fluorine group is not included. An ink composition for roll printing was prepared in the same manner as in Example 1 except that 5.6 parts by weight of a polymer (Mw = 7,000) was added.

Comparative Example 2

In Example 2, a fluorine group in which allylglycidyl ether is added to a copolymer in which benzyl (meth) acrylate and (meth) acrylic acid are formed at 70:30 without adding an acrylic copolymer resin containing a fluorine group is not included. An ink composition for roll printing was prepared in the same manner as in Example 2, except that 4.07 parts by weight of a polymer (Mw = 7,000) was added.

Comparative Example 3

In Example 3, a fluorine group in which allylglycidyl ether is added to a copolymer in which benzyl (meth) acrylate and (meth) acrylic acid are formed at 70:30 without adding an acrylic copolymer resin containing a fluorine group is not included. An ink composition for roll printing was prepared in the same manner as in Example 3, except that 7.35 parts by weight of a polymer (Mw = 7,000) was added.

Experimental Example

The results of coating properties and surface properties after the roll printing ink compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were applied on a blanket and an organic substrate were observed and shown in Table 1 below. The state after apply | coating a composition on a blanket is shown to FIGS. 1A-3B using a CCD camera.

Table 1. Coating and surface property results of color inks for roll printing

Over the Blanket (PDMS) On glass substrate Example 1 Good Good Example 2 Good Good Example 3 Good Good Comparative Example 1 Crater / Fade Out Surface hole visible Comparative Example 2 Crater / Fade Out Surface hole visible Comparative Example 3 Crater / Fade Out Pigment clusters / surface hole visible

As described above, the roll composition ink composition including the acrylic copolymer resin containing the fluorine group of the present invention, the polyfunctional acrylic monomer having an ethylenically unsaturated double bond, a thermal polymerization initiator, a colorant, and a solvent is an acrylic copolymer resin. The fluorine groups contained therein have compatibility and antifoaming properties. Therefore, the color filter manufactured according to the present invention can improve the color characteristics of the liquid crystal display and further improve the display quality through dispersion stability and surface improvement.

Claims (20)

An ink composition for roll printing comprising an acrylic copolymer resin including a fluorine group represented by Formula 1, a polyfunctional acrylic monomer having an ethylenically unsaturated double bond, a thermal polymerization initiator, a colorant, and 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 having 1 to 8 carbon atoms or an aromatic group containing a fluorine group, m, n, l are integers, and the ratio of m / n / l is 40 to 70/15 to 34 / l to 30 on a molar ratio basis. The number average molecular weight of the copolymer resin is 5,000 to 50,000. The ink composition of claim 1, wherein the acrylic copolymer resin including the fluorine group represented by Formula 1 is 1 to 20 parts by weight based on 100 parts by weight of the ink composition for roll printing. The ink composition of claim 1, wherein the roll printing ink composition further comprises an acrylic copolymer resin that does not include a fluorine group represented by the following Chemical Formula 2: [Formula 2]

here, R ₁ and R ₂ are each independently a hydrogen atom or a methyl group, m, n are integers and the ratio is 70:30 on a molar ratio basis. The number average molecular weight of the copolymer resin is 5,000 to 50,000. The ink composition for roll printing according to claim 3, wherein the acrylic copolymer resin containing no fluorine group represented by Chemical Formula 2 is more than 0 to 20 parts by weight or less based on 100 parts by weight of the ink composition for roll printing. The roll according to claim 1, wherein the polyfunctional acrylic monomer having an ethylenically unsaturated double bond is a compound having a boiling point of 100 ° C. or more having a unsaturated group capable of at least one addition polymerization or a functional acrylic monomer having caprolactone introduced therein. Ink composition for printing. The ink composition of claim 1, wherein the polyfunctional acrylic monomer having an ethylenically unsaturated double bond is 1 to 20 parts by weight based on 100 parts by weight of the ink composition for printing. The ink composition of claim 1, wherein the thermal polymerization initiator is 0.03 to 0.5 parts by weight based on 100 parts by weight of the ink composition for roll printing. The ink composition of claim 1, wherein the colorant is a pigment. The ink composition of claim 1, wherein the coloring agent is 1 to 20 parts by weight based on 100 parts by weight of the ink composition for roll printing. The method of claim 1, wherein the solvent is propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 2-hydroxyethylpropionate, 3-methyl-3-methoxybutylpropionate, ethyl-3-methoxypropionate, methyl-3-ethoxypropionate, ethyl-3 Ethoxypropionate, butyl acetate, ethyl acetate, amyl permate, pediatric wheat acetate, isobutyl acetate, isopropyl acetate, methyl ethyl ketone, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, ethyl Pyruvate, γ-butyrol acetate, methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, benzene, toluene, Butylene, n- heptane, n- hexane, and n- alone selected from the group consisting of octane, or two or more than that of roll printing ink composition. The ink composition of claim 1, wherein the solvent is 60 to 90 parts by weight based on 100 parts by weight of the ink composition for roll printing. The ink composition of claim 1, wherein the ink composition for roll printing further comprises at least one selected from the group consisting of a silicone-based surfactant and a fluorine-based surfactant. The ink composition for roll printing according to claim 12, wherein at least one selected from the group consisting of a silicone-based surfactant and a fluorine-based surfactant is 0.03 to 0.3 part by weight based on 100 parts by weight of the ink composition for roll printing. The ink composition of claim 1, wherein the ink composition for roll printing further comprises at least one additive selected from the group consisting of a dispersant, an adhesion promoter, and an antioxidant. The ink composition of claim 14, wherein the additive is more than 0 to 5 parts by weight based on 100 parts by weight of the ink composition for roll printing. (a) forming a black matrix pattern on the substrate; (b) coating and transferring the ink composition for roll printing according to any one of claims 1 to 15 to a pixel portion partitioned by the black matrix using a roll printing method to pattern the ink composition; And (c) drying the patterned roll printing ink composition. Method of manufacturing a color filter comprising a. 17. The method of claim 16, wherein the roll printing method comprises coating the roll composition ink composition on a blanket in roll or flat form, and then undesired coating from the blanket using a roll or flat cliché with a reverse pattern of a desired pattern. And removing the portion and transferring the desired pattern portion remaining on the blanket to the substrate. The method of claim 16, wherein the drying is performed by soft baking at 50 to 150 ° C. for 1 to 600 seconds, and then post-baking at 150 to 250 ° C. for 600 to 3,000 seconds. The color filter containing the ink composition for roll printing of any one of Claims 1-15. A liquid crystal display device comprising the color filter of claim 19.

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