JP4860656B2 - Ink composition for roll printing - Google Patents

Description

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

This application claims the benefit of the filing date of Korean Patent Application No. 10-2007-46318 filed with the Korean Patent Office on May 14, 2007, the entire contents of which are included in this specification.

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. Such an electronic display field has been continuously developed as an electronic display device having a new function suitable for the demands of the information society that has been developed and diversified.

In general, an electronic display device refers to a device that transmits various kinds of information to a human through vision. In other words, it can be defined as an electronic device that converts electrical information signals output from various electronic devices into optical information signals that can be recognized by human vision, and is responsible for a bridging role that connects humans and electronic devices. It can also be defined as a device.

Such an electronic display device is called a light-emitting display device when an optical information signal is displayed by a light emission phenomenon, and is displayed by light modulation such as reflection, scattering, or interference phenomenon. This is referred to as a non-emissive display device. Examples of the light-emitting display device, which is also called an active display device, include a cathode ray tube (CRT), a plasma display panel (PDP), a light emitting diode (LED), or an electroluminescent device. Examples thereof include a display (ELM). Examples of the light-receiving display device that is a passive display device include a liquid crystal display (LCD), an electrochemical display (ECD), and an electrophoretic display (EPID). Can be mentioned.

The cathode ray tube (CRT), which has the longest history used in image display devices such as televisions and computer monitors, has the highest occupation ratio in terms of display quality and economy. However, it has many problems such as large weight, large volume and high power consumption.

However, rapid progress in semiconductor technology has necessitated an electronic display device adapted to a new environment in accordance with the solidification, low voltage and low power of various electronic devices and the miniaturization and weight reduction of electronic devices. That is, a demand for a flat panel type display device that is thin and light and has characteristics of 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, has low power consumption and low driving voltage, and at the same time can display images close to a cathode ray tube. Therefore, it is widely used in various electronic devices. Further, since the liquid crystal display device is easy to manufacture, the application range is further expanded.

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

A conventional photolithography method for manufacturing a color filter using each of the photoresists composed of the three primary colors of red, green, and blue includes red, green, and pixel portions separated by a black matrix formed on a glass substrate. Steps such as coating, exposure, and development are performed on the respective photoresist compositions of blue and blue. The photolithography method is a waste of materials and complicated processes, and uses expensive equipment. Therefore, the photolithographic method occupies a considerable portion of time and cost when manufacturing a liquid crystal display device.

Recently, various new process methods have been used in place of the conventional photolithography method, and a representative one is a roll printing method.

However, since the conventional roll printing method uses a material such as PDMS (polydimethylsiloxane) having a low surface tension as a blanket in order to smoothly transfer the pattern from the blanket to the substrate during pattern transfer by roll printing, the surface tension of the ink is blanket. Good coating results cannot be obtained unless it is lower than the material. Therefore, in order for the ink composition for roll printing to have a surface tension lower than that of the blanket surface, a surfactant excellent in the effect of reducing the surface tension must be added to the ink composition. However, in this case, the compatibility and antifoaming properties of the surfactant component and the constituents such as the pigment or dispersant and binder resin contained in the ink composition for roll printing are reduced, and when coating on the blanket. Holes (Hole) may be generated on the surface or inside of the coating, or pigment mass may be generated.
Korean Patent Application No. 10-2007-46318

When the present inventors produce an ink composition for roll printing, if an acrylic copolymer resin containing a fluoro group is used, compatibility and antifoaming properties are improved when the ink is coated on a blanket, and a hole on the coating surface is formed. Or it discovered that coating defects, such as a pigment lump, did not occur. Therefore, the present invention provides an ink composition for roll printing comprising an acrylic copolymer resin containing a fluoro group, a polyfunctional acrylic monomer having an ethylenically unsaturated double bond, a thermal polymerization initiator, a colorant, and a solvent. The purpose is to provide. It is another object of the present invention to provide a method for producing a color filter using the roll printing ink composition, a color filter produced thereby, and a liquid crystal display device including the same.

The present invention has the following chemical formula 1:

[Wherein 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 fluoro group,
m, n, and l are integers, and the molar ratio (m: n: l) is 60-70: 15-34: l-15,
The number average molecular weight of the copolymer resin is 5,000 to 50,000]
An ink composition for roll printing comprising an acrylic copolymer resin containing a fluoro group represented by formula (II), a polyfunctional acrylic monomer having an ethylenically unsaturated double bond, a thermal polymerization initiator, a colorant, and a solvent is provided.

The present invention also provides:
(A) forming a black matrix pattern on the substrate;
(B) an acrylic copolymer resin containing a fluoro group represented by the chemical formula 1 in a pixel section delimited by the black matrix using a roll printing method, a polyfunctional acrylic monomer having an ethylenically unsaturated double bond, Coating and transferring and patterning a roll printing ink composition comprising a thermal polymerization initiator, a colorant, and a solvent; and (c) drying the patterned roll printing ink composition A method for manufacturing a filter is provided.

In addition, this invention provides the color filter manufactured by the said manufacturing method.

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

The ink composition for roll printing comprising an acrylic copolymer resin containing a fluoro group, a polyfunctional acrylic monomer having an ethylenically unsaturated double bond, a thermal polymerization initiator, a colorant, and a solvent is an acrylic copolymer. The fluoro group contained in the polymer resin has compatibility and defoaming properties. Therefore, the color filter manufactured according to the present invention can improve the color characteristics and display quality of the liquid crystal display device through dispersion stability and surface improvement.

Hereinafter, the present invention will be described in detail.

The present invention is for roll printing comprising an acrylic copolymer resin containing a fluoro group represented by the following chemical formula 1, a polyfunctional acrylic monomer having an ethylenically unsaturated double bond, a thermal polymerization initiator, a colorant, and a solvent. An ink composition is provided.

The acrylic copolymer resin containing a fluoro group used in the ink composition for roll printing of the present invention has the following chemical formula 1:

[Wherein 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 fluoro group,
m, n, and l are integers, and the molar ratio (m: n: l) is 60-70: 15-34: l-15,
The number average molecular weight of the copolymer resin is 5,000 to 50,000]
Can be shown.

The acrylic copolymer resin represented by Chemical Formula 1 contains a fluoro group. The fluoro group in the acrylic copolymer resin serves to make the ink composition for roll printing of the present invention compatible and defoaming. Specifically, in the case of a surfactant containing a fluoro group used in an existing ink composition, the effect of lowering the surface tension is very large, but since the polarity is low, a relatively polar pigment and its The compatibility with the dispersing agent used for dispersion is lowered, thereby causing a problem of a pigment mass and a decrease in defoaming property. Therefore, the surface becomes very rough at the time of coating, and a thin film can be formed in a state where bubbles are contained inside. However, when an acrylic copolymer resin containing a fluoro group is added, the acrylic copolymer resin contains a fluoro group that serves to lower the surface tension, and at the same time, a pigment and a dispersant, and other binder components As a result, the compatibility and dispersibility of the entire ink composition is increased, the pigment mass during coating is not generated, the surface becomes uniform, and the inside of the film is increased. The bubbles will also decrease.

The acrylic copolymer resin containing a fluoro group represented by the chemical formula 1 is preferably added in an amount of 1 to 20 parts by weight with respect to 100 parts by weight of the entire roll printing ink composition. When the content of the acrylic copolymer resin containing a fluoro group is less than 1 part by weight, it is difficult to expect the effect of improving the compatibility and defoaming property of the ink composition, and when the content exceeds 20 parts by weight. The content of other components including a polyfunctional acrylic monomer having an ethylenically unsaturated double bond may be relatively reduced, resulting in a decrease in film strength.

In this invention, the acrylic copolymer resin which does not contain a fluoro group other than the acrylic copolymer resin containing the said fluoro group can further be included. The acrylic copolymer resin containing no fluoro group can be used by copolymerizing a monomer containing an acid function and a monomer copolymerizable with the monomer. Therefore, it is not necessary to include an acid group.

The monomer containing an acid group may be selected from the group consisting of (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethylmaleic acid, isoprenesulfonic acid, and styrenesulfonic acid. preferable.

Monomers that can be copolymerized with the monomer containing an acid group include styrene, chlorostyrene, α-methylstyrene, vinyl toluene, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, Dimethylaminoethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate , Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Ruoctyloxy-2-hydroxypropyl (meth) acrylate, ethylhexyl acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, Methoxytripropylene glycol (meth) acrylate, methoxypolyethylene 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 Relate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, tribromophenyl (meth) acrylate, β- (meth) acylol oxyethyl hydrogen succinate, methyl α-hydroxymethyl acrylate, It is preferable that at least one selected from the group consisting of ethyl α-hydroxymethyl acrylate, propyl α-hydroxymethyl acrylate, and butyl α-hydroxymethyl acrylate.

Examples of the acrylic copolymer resin containing no fluoro group include the following chemical formula 2:

[Wherein R ₁ and R ₂ are each independently a hydrogen atom or a methyl group,
m and n are integers, and the molar ratio (m: n) is 70:30,
The number average molecular weight of the copolymer resin is 5,000 to 50,000]
Or Chemical Formula 3:

[Wherein R ₁ , R ₂ and R ₃ are each independently a hydrogen atom or a methyl group,
m, n, and l are integers, and the molar ratio (m: n: l) is 70:15:15;
The number average molecular weight of the copolymer resin is 5,000 to 50,000]
Examples of such a copolymer may be mentioned, but the present invention is not limited thereto.

Further, an addition-polymerizable ethylene can be added together with a polyfunctional monomer having an ethylenically unsaturated double bond at the time of thermosetting by adding a monomer having a glycidyl functional group to the acid group of the acrylic copolymer resin not containing the fluoro group. An unsaturated reactive group can be introduced. At this time, usable monomers having a glycidyl functional group include glycidyl (meth) acrylate, vinylbenzyl glycidyl ether, vinyl glycidyl ether, allyl glycidyl ether, 4-methyl-4,5-epoxypentene, and γ-glycidoxy. It is preferable that at least one selected from the group consisting of propyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, and norbornyl derivatives.

In the present invention, the acrylic copolymer resin containing no fluoro group preferably has an acid value of about 0 to 200 KOH mg / g and a number average molecular weight in the range of 5,000 to 50,000. The resin binder containing no fluoro group may be used in an amount of more than 0 to 20 parts by weight or a mixture of two or more types with respect to 100 parts by weight of the ink composition.
The polyfunctional acrylic monomer having an ethylenically unsaturated double bond is a polyfunctional having introduced therein a compound having at least one addition-polymerizable unsaturated group in the molecule and a boiling point of 100 ° C. or higher or caprolactone. An acrylic monomer can be used.

Examples of the compound having at least one addition-polymerizable unsaturated group in the molecule having a boiling point of 100 ° C. or higher include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, or phenoxyethyl ( Monofunctional monomers such as (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, neopentyl glycol (meth) acrylate, pentaerythritol tetraacrylate, penta Multifunctional monomers such as erythritol triacrylate, dipentaerythritol pentaacrylate, or dipentaerythritol hexaacrylate It can be used.

The polyfunctional acrylic monomer introduced with caprolactone is KAYARAD DPCA-20, 30, 60, 120 introduced into dipentaerythritol, KAYARAD TC-110S introduced into tetrahydrofuryl acrylate, or neopentyl glycol hydroxypivalate. KAYARAD HX-220, KAYARAD HK-620, etc. introduced in the above can be used. Other usable polyfunctional monomers include bisphenol A derivative epoxy acrylate, novolak-epoxy acrylate, and urethane-based polyfunctional acrylates such as U-324A, U15HA, or U-4HA. The said polyfunctional acrylic monomer which has an 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 in an amount of 1 to 20 parts by weight with respect to 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 is lowered, and when it exceeds 20 parts by weight, the adhesiveness of the resin layer is reduced. In excess, the strength of the film may be reduced.

The ink composition for roll printing of the present invention uses a thermal polymerization initiator. When a photopolymerization initiator is used, an exposure process must be introduced to cure the ink composition. For this purpose, in addition to the roll printing equipment, an exposure apparatus and an aligning apparatus for exposure are provided. Therefore, the use of a photopolymerization initiator is not suitable as an ink composition for roll printing.

As the thermal polymerization initiator used in the ink composition of the present invention, as an azo compound, Wako Pure chemical Industry. Ltd .. V-60, V-65, V-59, V-70, V-40, azoester V-601, azoamide VA-086, VA-085, VA-080, Vam-110, Vam-111, VF-096, azoamidine-based V-50, VA-044, VA-046B, Aam-027, VA-060, VA-057, VA-061, macroazo initiators Certain VPS-0501, VPS-1001, VPE-0201, VPE-0401, VPE-0601, VPTG-0301, and the like can be used, but are not limited thereto.

The thermal polymerization initiator is preferably used in an amount of 0.03 to 0.3 parts by weight based on 100 parts by weight of the total ink composition. When the content of the thermal polymerization initiator is less than 0.03 parts by weight, there is a problem that the thermal polymerization degree of the ink is lowered, and when it exceeds 0.3 parts by weight, the efficiency of the thermal polymerization initiator is decreased. Can do.

The colorant used in the ink composition for roll printing of the present invention is preferably a pigment. A general-purpose pigment may be used as the pigment as long as it does not adversely affect the dispersion, but it is preferable to use a pigment of finely processed particles. The particle size of the pigment is preferably 0.3 μm or less, more preferably 90% or more of 0.1 μm pigment particles are distributed. If the size of the pigment is larger than 0.3 μm, there may be a problem of pigment dispersion when the composition is firstly manufactured, and thus light transmission is not smooth, and the transmittance of the manufactured color filter is not good. Can be bad.

Examples of the red pigment used for exhibiting color characteristics in the ink composition for roll printing of the present invention include Pig. Red # 1 (C.I. 12070), Pig. Red # 2 (C.I.12310), Pig. Red # 3 (C.I. 12120), Pig. Red # 4 (C.I. 12085), Pig. Red # 5 (C.I. 12490), Pig. Red # 6 (C.I. 12090), Pig. Red # 7 (C.I. 12420), Pig. Red # 8 (C.I. 12355), Pig. Red # 9 (C.I. 12460), Pig. Red # 10 (C.I. 12440), Pig. Red # 11 (C.I. 12430), Pig. Red # 12 (C.I. 12385), Pig. Red # 13 (C.I. 12395), Pig. Red # 14 (C.I. 12380), Pig. Red # 15 (C.I. 12465), Pig. Red # 16 (12500), Pig. Red # 17 (C.I. 12390), Pig. Red # 18 (C.I. 12350), Pig. Red # 21 (C.I. 12300), Pig. Red # 22 (C.I. 12315), Pig. Red # 23 (C.I. 12355), Pig. Red # 31 (12360), Pig. Red # 32 (12320), Pig. Red # 95 (C.I. 15897), Pig. Red # 112 (C.I. 12370), Pig. Red # 114 (C.I. 12351), Pig. Red # 119 (C.I. 12469), Pig. Red # 146 (C.I. 12485), Pig. Red # 147 (C.I. 12433), Pig. Red # 148 (C.I. 12369), Pig. Red # 150 (C.I. 12290), Pig. Red # 151 (C.I. 15890), Pig. Red # 184 (C.I. 12487), Pig. Red # 187 (C.I. 12486), Pig. Red # 188 (C.I. 12467), 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 (C.I. 15630), Pig. Red # 49: 1 (C.I. 15630: 1), Pig. Red # 49: 2 (C.I. 15630: 2), Pig. Red # 49: 3 (C.I. 15630: 3), Pig. Red # 50: 1 (C.I. 15500: 1), Pig. Red # 51: 1 (C.I. 15580: 1), Pig. Red # 53 (C.I. 15585), Pig. Red # 53: 1 (C.I. 15585: 1), Pig. Red # 68 (C.I. 15525), Pig. Red # 243 (C.I. 15910), Pig. Red # 247 (C.I. 15915); Pig. Which is a disazopyrazolone series. Red # 37 (C.I. 21205), Pig. Red # 38 (C.I. 21210), Pig. Red # 41 (C.I. 21200); Pig. Red # 144 (C.I. 20735), Pig. Red # 166 (C.I.20035), Pig. Red # 220 (C.I. 20055), Pig. Red # 221 (C.I. 20065), Pig. Red # 242 (C.I. 20067); Pig., A 2-hydroxy-3-naphthoic acid metal complex. Red # 48: 1 (C.I. 15865: 1), Pig. Red # 48: 2 (C.I. 15865: 2), Pig. Red # 48: 3 (C.I. 15865: 3), Pig. Red # 48: 4 (C.I. 15865: 4), Pig. Red # 48: 5 (C.I. 15865: 5), Pig. Red # 52: 1 (C.I. 15860: 1), Pig. Red # 52: 2 (C.I. 15860: 2), Pig. Red # 57: 1 (C.I. 15850: 1), Pig. Red # 58: 2 (C.I. 15825: 2), Pig. Red # 58: 4 (C.I. 15825: 4), Pig. Red # 63: 1 (C.I. 15880: 1), Pig. Red # 63: 2 (C.I. 15880: 2), Pig. Red # 64 (C.I. 15800), Pig. Red # 64: 1 (C.I. 15800: 1), Pig. Red # 200 (C.I. 15867); Pig. Naphthalenesulfonic acid metal complex. Red # 60: 1 (C.I. 16105: 1), Pig. Red # 66 (C.I. 18000: 1), Pig. Red # 67 (C.I. 18025: 1); 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); Pig., A thioindigo system. Red # 88 (C.I.73312), Pig. Red # 181 (C.I. 73360); Pig. Red # 122 (C.I. 73915), Pig. Red # 207 (C.I. 73900), Pig. Red # 209 (C.I. 73905); Pig. Red # 123 (C.I. 71145), Pig. Red # 149 (C.I. 71137), Pig. Red # 178 (C.I. 71155), Pig. Red # 179 (C.I. 71130), Pig. Red # 190 (C.I. 71140), Pig. Red # 194 (C.I. 71100), Pig. Red # 224 (C.I. 71127); Pig., A benzimidazolone series. Red # 171 (C.I. 12512), Pig. Red # 175 (C.I. 12513), Pig. Red # 176 (C.I. 12515), Pig. Red # 185 (C.I. 12516), Pig. Red # 208 (CI. 12514); Pig. Red # 216 (C.I. 59710); a diketopyrrolopyrrole-based Pig. Red # 254 (C.I. 56110); an isoindoline-based Pig. Red # 260 (C.I. 56295) or the like can be used.

Examples of the violet pigment include triarylcarbonium-based Pig. Violet # 1 (C.I. 45170: 2), Pig. Violet # 2 (C.I. 45175: 1), Pig. Violet # 3 (C.I. 42535: 2), Pig. Violet # 27 (C.I. 42535: 3), Pig. Violet # 39 (C.I. 42555: 2); Pig. Violet # 5: 1 (C.I. 58055: 1); Pig. Violet # 25 (C.I. 12321), Pig. Violet # 50 (C.I. 12322); Pig. Violet # 19 (C.I. 73900); Pig. Violet # 23 (C.I. 51319), Pig. Violet # 37 (C.I. 51345); a perylene-based Pig. Violet # 29 (C.I. 71129); Pig. Which is a benzimidazolone series. Violet # 32 (C.I. 12517) or the like can be used.
Examples of blue pigments include triarylcarbonium-based Pig. Blue # 1 (C.I. 42595: 2), Pig. Blue # 2 (C.I. 44045: 2), Pig. Blue # 9 (C.I. 42025: 1), Pig. Blue # 10 (C.I. 44040: 2), Pig. Blue # 14 (C.I. 42600: 1), Pig. Blue # 18 (C.I. 42770: 1), Pig. Blue # 19 (C.I. 42750), Pig. Blue # 56 (C.I. 42800), Pig. Blue # 62 (C.I. 44084); Pig. Blue # 15 (C.I. 74160), Pig. Blue # 15: 1 (C.I. 74160); Pig. Blue # 16 (C.I. 74100); Pig. Blue # 60 (C.I. 69800), Pig. Blue # 64 (C.I. 69825); Pig. Blue # 66 (C.I. 73000), Pig. Blue # 63 (C.I. 73015: x) or the like can be used.

Green pigments include triarylcarbonium-based Pig. Green # 1 (C.I. 42040: 1), Pig. Green # 2 (C.I. 42040: 1), Pig. Green # 4 (C.I. 42000: 2); Pig. Green # 7 (C.I. 74260), Pig. Green # 36 (C.I. 74265); Pig. Green # 8 (C.I. 10006), Pig. Green # 10 (C.I. 12775) or the like can be used.

Examples of yellow pigments include Pig. Yellow # 1 (C.I. 11680), Pig. Yellow # 2 (C.I. 11730), Pig. Yellow # 3 (C.I. 11710), Pig. Yellow # 5 (C.I. 11660), Pig. Yellow # 6 (C.I. 11670), Pig. Yellow # 10 (C.I. 12710), Pig. Yellow # 49 (C.I. 11765), Pig. Yellow # 65 (C.I. 11740), Pig. Yellow # 73 (C.I. 11738), Pig. Yellow # 74 (C.I. 11741), Pig. Yellow # 75 (C.I. 11770), Pig. Yellow # 97 (C.I. 11767), Pig. Yellow # 98 (C.I. 11727), Pig. Yellow # 111 (C.I. 11745), Pig. Yellow # 116 (C.I. 11790), Pig. Yellow # 167 (C.I. 11737); Pig. Yellow # 61 (C.I. 13880), Pig. Yellow # 62: 1 (C.I. 13940: 1), Pig. Yellow # 100 (C.I. 19140: 1), Pig. Yellow # 168 (C.I. 13960), Pig. Yellow # 169 (C.I. 13955), Pig. Yellow # 183 (C.I. 18792); Pig., A bisacetoacetyl arylide system. Yellow # 16 (CI. 20040); Pig. Yellow # 12 (C.I. 21090), Pig. Yellow # 13 (C.I. 21100), Pig. Yellow # 14 (C.I. 21095), Pig. Yellow # 17 (C.I. 21105), Pig. Yellow # 55 (C.I. 21096), Pig. Yellow # 63 (C.I. 21091), Pig. Yellow # 81 (C.I. 21127), Pig. Yellow # 83 (C.I. 21108), Pig. Yellow # 87 (C.I. 21107: 1), Pig. Yellow # 113 (C.I. 21126), Pig. Yellow # 114 (C.I. 21092), Pig. Yellow # 124 (C.I. 21107), Pig. Yellow # 126 (C.I. 21101), Pig. Yellow # 127 (21102), Pig. Yellow # 152 (C.I. 21111), Pig. Yellow # 170 (C.I. 21104), Pig. Yellow # 171 (C.I. 21106), Pig. Yellow # 172 (C.I. 21109), Pig. Yellow # 174 (C.I. 21098); Pig. Yellow # 24 (C.I. 70600); Pig. Yellow # 93 (C.I. 20710), Pig. Yellow # 94 (C.I. 20038), Pig. Yellow # 95 (C.I. 20034), Pig. Yellow # 128 (C.I. 20037), Pig. Yellow # 166 (C.I. 20035); Pig. Yellow # 123 (C.I. 65049), Pig. Yellow # 147 (C.I. 60645); Pig. Yellow # 101 (C.I. 48052); Pig. Yellow # 104 (C.I. 15985: 1); Pig. Yellow # 108 (C.I. 68420); Pig. Yellow # 109 (C.I. 56284), Pig. Yellow # 110 (C.I. 56280), Pig. Yellow # 139 (C.I. 56298), Pig. Yellow # 185 (C.I. 56290); Pig., A benzimidazolone series. Yellow # 123 (C.I. 11783), Pig. Yellow # 154 (C.I. 13980), Pig. Yellow # 175 (C.I. 11784), Pig. Yellow # 180 (C.I. 21290), Pig. Yellow # 181 (C.I. 11777); Pig. Yellow # 138 (C.I. 56300); Pig. Yellow # 117 (C.I. 48043), Pig. Yellow # 129 (C.I. 48042), Pig. Yellow # 150 (C.I. 12764), Pig. Yellow # 153 (C.I. 45545), Pig. Yellow # 177 (C.I. 48120), Pig. Yellow # 179 (C.I. 48125) or the like can be used.

In addition, as an orange pigment, Pig. Orange # 1 (C.I. 11725), Pig. Orange # 6 (C.I. 12730); Pig. Orange # 2 (C.I. 12060), Pig. Orange # 5 (C.I. 12075), Pig. Orange # 22 (C.I. 12470), Pig. Orange # 24 (C.I. 12305), Pig. Orange # 38 (C.I. 12367); Pig. Which is a naphthol metal complex. Orange # 17 (C.I. 15510: 1 Pig. Orange # 17: 1 (15510: 2), Pig. Orange # 46 (C.I. 15602); Pig. Orange # 13 (C.I. Pig. Orange # 34 (C.I. 21130), Pig. Orange # 16 (C.I. 21160); Naphthalene sulfone Pig. Orange # 19 (CI. 15990) which is an acid metal complex; Pig. Orange # 31 (CI. 20050) which is a disazo condensate; Pig. Orange # 36 which is a benzimidazolone series (C. I. 11780), Pig. Orange # 60 (C.I. 1178). 2); Pigrance Orange # 40 (C.I. 59700) which is a pyranthrone type, Pig. Orange # 43 (C.I. 71105) which is a perinone type, Pig. Orange # 48 (C.I which is a quinacridone type) 73900); Pig. Orange # 61 (C.I. 11265), Pig. Orange # 66 (C.I. 48210), or Pig. Orange # 69 (C.I. 56292), which are isoindoline-based, are used. be able to.

The colorant used for exhibiting color characteristics in the ink composition for roll printing is preferably added in an amount of 1 to 20 parts by weight with respect to 100 parts by weight of the total ink composition depending on the required color characteristics. Preferably it is 1-15 weight part. If the content of the colorant used in the ink composition is not appropriate, a product having a desired image quality cannot be obtained at the time of manufacturing the color filter.

The solvent may be propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate when considering solubility, pigment dispersibility, coating property, and pattern transfer property by roll printing. , Diethylene glycol dimethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 2-hydroxyethyl propionate, 3-methyl-3-methoxybutyl propionate, ethyl 3-methoxypropionate, methyl-3-ethoxypropionate , Ethyl 3-ethoxypropionate, butyl acetate, ethyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, Sopropyl 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, etc. Alcohols such as benzene, toluene and xylene, and saturated hydrocarbons such as n-heptane, n-hexane and n-octane. The said solvent can be used individually or in mixture of 2 or more types.

The solvent is preferably added in an amount of 60 to 90 parts by weight based on 100 parts by weight of the whole roll printing ink composition. When the solvent content is less than 60 parts by weight, the solid content of the ink is increased, the viscosity is greatly increased, the ink coating on the blanket is difficult, and the solvent content exceeds 90 parts by weight. In this case, however, the solid content is reduced and the viscosity is lowered, which is disadvantageous in that not only the coating is difficult, but also the amount of solvent that must be volatilized for pattern transfer is increased.

The ink composition for roll printing of the present invention may further contain a surfactant in order to adjust the surface tension of the ink. The surfactant to be added is preferably a silicon-based surfactant or a fluorine-based surfactant. Specifically, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-330, BYK-333 are silicon surfactants that have a large effect of reducing the surface tension. , BYK-335, BYK-341, BYK-344, BYK-345, BYK-370, etc., and fluorine-based surfactants include F-114, F-177, F-410, and F-411. F-450, 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, TF 027SF, or the like can be used TF-1441, TF-1442, Soredakeni not intended to be limiting. However, since the general PDMS currently used as a blanket material for roll printing has a surface tension of about 24 mN / m, the surface tension of the ink coated on the PDMS surface must have a lower value. Don't be. However, there is a limit in reducing the surface tension of the ink to 24 mN / m or less with any amount of the silicon surfactant, but if a fluorine-based surfactant is used, the surface tension of the ink is 24 mN / m or less. Can be lowered.

The surfactant added to adjust the surface tension of the ink is preferably used in an amount of 0.03 to 0.3 parts by weight based on 100 parts by weight of the total ink composition. When the surfactant content is less than 0.03 parts by weight, the effect of reducing the surface tension of the ink is not sufficient, resulting in poor coating on the blanket and exceeding 0.3 parts by weight. However, when the surfactant is used in an excessive amount, the compatibility and defoaming property of the ink are reduced.

The roll printing ink composition of the present invention may further contain one or more additives selected from the group consisting of a dispersant, an adhesion promoter, and an antioxidant, if necessary.

The dispersing agent can be used by a method in which the pigment is surface-treated in advance or internally added to the pigment or a method in which the pigment is externally added. As the dispersant, a polymer type, nonionic, anionic, or cationic dispersant can be used. Examples thereof include polyalkylene glycol and esters thereof, polyoxyalkylene polyhydric alcohol, Examples thereof include an ester alkylene oxide adduct, an alcohol alkylene oxide adduct, a sulfonic acid ester, a sulfonate, a carboxylic acid ester, a carboxylate, an alkylamide alkylene oxide adduct, or an alkylamine. These can be added alone or in combination of two or more. The adhesion promoter is vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) -silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl). ) -3-Aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-ethoxycyclohexyl) ethyl Trimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, or the like can be used. As the antioxidant, 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, or the like can be used.

The additive is preferably added in an amount of more than 0 to 5 parts by weight or less with respect to the entire roll printing ink composition.

The present invention also provides:
(A) forming a black matrix pattern on the substrate;
(B) An acrylic copolymer resin containing a fluoro group represented by Chemical Formula 1 in a pixel section delimited by the black matrix using a roll printing method, a polyfunctional acrylic monomer having an ethylenically unsaturated double bond, heat Coating and transferring and patterning a roll printing ink composition comprising a polymerization initiator, a colorant, and a solvent; and (c) heat curing the patterned roll printing ink composition A method for manufacturing a filter is provided.

(A) is a step of forming a black matrix pattern on the substrate.
The material of the substrate is not particularly limited, and a glass substrate, a plastic substrate, another flexible substrate, or the like can be used, and a transparent glass substrate having high heat resistance is preferable.

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

The black matrix can be manufactured using an existing chrome black matrix or resin black matrix, and the thickness of the formed black matrix is preferably 0.2 to 3 μm, and has an optical density. Is preferably 2 to 6 in the thickness range.

(B) is a polyfunctional acrylic having an ethylenically unsaturated double bond, an acrylic copolymer resin containing a fluoro group represented by the chemical formula 1 in a pixel section delimited by the black matrix, using a roll printing method. This is a step of coating and transferring and patterning an ink composition for roll printing containing a monomer, a thermal polymerization initiator, a colorant, and a solvent.

Here, the roll printing method is desired from a blanket using a roll or flat plate type cliché having a reverse image pattern of a desired pattern after coating the roll printing plate ink composition on the roll or flat plate type blanket. This refers to a method of taking out a non-coating portion and transferring the desired pattern portion remaining on the blanket to the substrate again. For example, after a roll printing blanket material (eg, PDMS) is coated with the ink composition for roll printing of the present invention using a slit nozzle, a groove portion (desired pattern pattern) and a protrusion ( Undesired pattern portion is taken out from the ink coated on the blanket using a cliché in which an undesired pattern pattern is formed, and the desired pattern portion remaining on the blanket is separated by a black matrix. This is a method of transferring by contacting the part. In some cases, a desired pattern may be taken out of the ink coated on the blanket using a cliché having protrusions of the desired pattern and transferred directly to the substrate.

The step (c) is a step of thermally curing the ink composition for roll printing transferred to the substrate. Using the roll printing method, after the ink composition for roll printing of the present invention is transferred to the pixel portion delimited by the black matrix, soft baking is performed at a temperature of 50 to 150 ° C. for 1 to 600 seconds, and then 150 times again. It is preferable to carry out post-baking at ˜250 ° C. for 600 to 3000 seconds for thermosetting.

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

In addition, this invention provides the liquid crystal display element containing the said color filter. The manufacturing method of the liquid crystal display element according to the present invention can use techniques in this technical field except that the manufacturing method of the color filter using the above-described ink composition for roll printing is used.

Hereinafter, preferred embodiments will be presented to help understanding of the present invention. However, the following examples are provided only for easier understanding of the present invention, and the contents of the present invention are not limited thereby.

<Example 1>
The red ink for roll printing used in the present invention comprises 4 parts by weight of Pigment Red # 254, 0.8 part by weight of Pigment Red # 177, and Pigment Yellow # 139 1 by 100 parts by weight of the total ink composition. .2 parts by weight, as resin binder containing a fluoro group, benzyl (meth) acrylate and (meth) acrylic acid, HFIMA (1,1,1,3,3,3-hexafluoroisopropyl methacrylate) are 45:25:30 Allyl glycidyl ether was added to a copolymer formed at a molar ratio of 2 parts by weight of a copolymer (Mw = 18,800) and 70:30 of benzyl (meth) acrylate and (meth) acrylic acid. 3.6 parts by weight of a polymer not containing a fluoro group (Mw = 7,000), ethylenically unsaturated double bond 9.5 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer having an acid content, 0.5 parts by weight of an azoamide thermal polymerization initiator (V-40, Wako Pure Chemical Industry. LTD), and a polyester as a dispersant as an additive 1 part by weight of a dispersant, 0.2 part by weight of 3-methacryloxypropyltrimethoxysilane, 0.2 part by weight of a fluorosurfactant (Megaface F-172D, Dainippon Ink and Chemicals, Japan), solvent As a mixture, 50 parts by weight of propylene glycol monomethyl ether acetate, 17 parts by weight of methyl ethyl ketone and 10 parts by weight of ethyl acetate were mixed, and the mixture was stirred for 5 hours to prepare a roll ink composition.

<Example 2>
The green ink for roll printing used in the present invention contains 5.9 parts by weight of Pigment Green # 36, 3.1 parts by weight of Pigment Yellow # 150, and fluoro group as a colorant with respect to 100 parts by weight of the total ink composition. A resin binder containing benzyl (meth) acrylate, (meth) acrylic acid, and HFIMA (1,1,1,3,3,3-hexafluoroisopropyl methacrylate) formed at a molar ratio of 45:25:30. 1.75 parts by weight of a polymer (Mw = 18,800), does not contain a fluoro group in which allyl glycidyl ether is added to a copolymer formed of benzyl (meth) acrylate and (meth) acrylic acid at 70:30 2.32 parts by weight of a polymer (Mw = 7,000), a polyfunctional monomer having an ethylenically unsaturated double bond; 6 parts by weight of dipentaerythritol hexaacrylate, 0.5 parts by weight of an azoamide thermal polymerization initiator (V-40, Wako Pure Chemical Industries. LTD), 1.58 parts by weight of a polyester dispersant which is a dispersant as an additive , 0.2 part by weight of 3-methacryloxypropyltrimethoxysilane, 0.2 part by weight of a fluorosurfactant (Megaface F-172D, Dainippon Ink and Chemicals, Japan), propylene glycol monomethyl ether acetate as a solvent 54 parts by weight, 15 parts by weight of methyl ethyl ketone, and 9.45 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 3>
The blue ink for roll printing used in the present invention comprises Pigment Blue # 15: 6.76 parts by weight, Pigment Violet # 23 0.94 parts by weight, and Fluoro as a colorant with respect to 100 parts by weight of the total ink composition. As a resin binder containing a group, benzyl (meth) acrylate, (meth) acrylic acid, and HFIMA (1,1,1,3,3,3-hexafluoroisopropyl methacrylate) are formed at a molar ratio of 45:25:30. The copolymer (Mw = 18,800) 2.6 parts by weight, a benzyl (meth) acrylate and a copolymer formed with (meth) acrylic acid in a 70:30 fluoro group with allyl glycidyl ether added. Polymer not containing (Mw = 7,000) 4.75 parts by weight, polyfunctional monofunctional having ethylenically unsaturated double bond -9.6 parts by weight of dipentaerythritol hexaacrylate, 0.5 parts by weight of an azoamide thermal polymerization initiator (V-40, Wako Pure Chemical Industries. LTD), 1 part by weight of a polyester dispersant as a dispersant Parts, 3-methacryloxypropyltrimethoxysilane 0.2 parts by weight, fluorosurfactant (Megaface F-172D, Dainippon Ink & Chemicals, Japan) 0.2 parts by weight, propylene glycol monomethyl ether as solvent 42.25 parts by weight of acetate, 22.9 parts by weight of methyl ethyl ketone, and 11.3 parts by weight of ethyl acetate were mixed, and the mixture was stirred for 5 hours to prepare an ink composition for roll printing.

<First comparative example>
In the first embodiment, allyl glycidyl ether is added to a copolymer formed of benzyl (meth) acrylate and (meth) acrylic acid at 70:30 without adding an acrylic copolymer resin containing a fluoro group. In addition, an ink composition for roll printing was produced in the same manner as in Example 1 except that 5.6 parts by weight of a polymer not containing a fluoro group (Mw = 7,000) was further added.

<Second Comparative Example>
In the second embodiment, allyl glycidyl ether is added to a copolymer formed with 70:30 benzyl (meth) acrylate and (meth) acrylic acid without adding an acrylic copolymer resin containing a fluoro group. In addition, an ink composition for roll printing was produced by the same method as in Example 2, except that 4.07 parts by weight of a polymer not containing a fluoro group (Mw = 7,000) was further added.

<Third comparative example>
In the third embodiment, allyl glycidyl ether is added to a copolymer formed of benzyl (meth) acrylate and (meth) acrylic acid at 70:30 without adding an acrylic copolymer resin containing a fluoro group. In addition, an ink composition for roll printing was produced in the same manner as in Example 3, except that 7.35 parts by weight of a polymer containing no fluoro group (Mw = 7,000) was further added.

<Experimental example>
After applying the ink composition for roll printing produced in the first to third examples and the first to third comparative examples on a blanket and a glass substrate, coating characteristics and surface characteristics using a CCD camera. Was observed. The results are shown in Table 1 below.

It is an optical microscope photograph (x1000) after coating the red ink for roll printing which concerns on 1st Example of this invention on a blanket. It is an optical microscope photograph (x1000) after coating the red ink for roll printing which concerns on the 1st comparative example of this invention on a blanket. It is an optical microscope photograph (x1000) after coating the green ink for roll printing concerning 2nd Example of this invention on a blanket. It is an optical microscope photograph (x1000) after coating the green ink for roll printing concerning the 2nd comparative example of the present invention on a blanket. It is an optical microscope photograph (x1000) after coating the blue ink for roll printing which concerns on 3rd Example of this invention on a blanket. It is an optical microscope photograph (x1000) after coating the blue ink for roll printing concerning the 3rd comparative example of the present invention on a blanket.

Claims (20)

The following chemical formula 1:
[Wherein 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 including a fluoro group,
m, n, l is an integer, the molar ratio (m: n: l) is 45: 25: 30,
The number average molecular weight of the copolymer resin is 5,000 to 50,000]
An ink composition for roll printing, comprising: an acrylic copolymer resin containing a fluoro group represented by formula; a polyfunctional acrylic monomer having an ethylenically unsaturated double bond; a thermal polymerization initiator; a colorant; and a solvent. 2. The ink composition for roll printing according to claim 1, wherein the acrylic copolymer resin containing a fluoro group represented by the chemical formula 1 is 1 to 20 parts by weight with respect to 100 parts by weight of the entire roll printing ink composition. . The ink composition for roll printing has the following chemical formula 2:
[Wherein, R ₁ and R ₂ each independently represents a hydrogen atom or a methyl group,
m and n are integers, and the molar ratio (m: n) is 70:30,
The number average molecular weight of the copolymer resin is 5,000 to 50,000 ]
The ink composition for roll printing according to claim 1, further comprising an acrylic copolymer resin not containing a fluoro group in which allyl glycidyl ether is added to the copolymer represented by formula (1). 4. The roll printing resin according to claim 3, wherein the acrylic copolymer resin not containing a fluoro group represented by Chemical Formula 2 is greater than 0 to 20 parts by weight with respect to 100 parts by weight of the total roll printing ink composition. Ink composition. The polyfunctional acrylic monomer having an ethylenically unsaturated double bond is a polyfunctional having introduced therein a compound having at least one addition-polymerizable unsaturated group in the molecule and a boiling point of 100 ° C. or higher or caprolactone. The ink composition for roll printing according to claim 1, which is a water-soluble acrylic monomer. 2. The ink composition for roll printing according to claim 1, wherein the polyfunctional acrylic monomer having an ethylenically unsaturated double bond is 1 to 20 parts by weight with respect to 100 parts by weight of the whole printing ink composition. The ink composition for roll printing according to claim 1, wherein the thermal polymerization initiator is 0.03 to 0.3 parts by weight with respect to 100 parts by weight of the total ink composition for roll printing. The ink composition for roll printing according to claim 1, wherein the colorant is a pigment. The ink composition for roll printing according to claim 1, wherein the colorant is 1 to 20 parts by weight with respect to 100 parts by weight of the total roll printing ink composition. 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-hydroxyethyl propionate, 3 -Methyl-3-methoxybutyl propionate, ethyl 3-methoxypropionate, methyl-3-ethoxypropionate, ethyl 3-ethoxypropionate, butyl acetate, ethyl acetate, amyl formate, isoamyl 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, xylene, n-heptane, n-hexane, and n- The ink composition for roll printing according to claim 1, which is a single compound or two or more compounds selected from the group consisting of octane. The ink composition for roll printing according to claim 1, wherein the solvent is 60 to 90 parts by weight with respect to 100 parts by weight of the total ink composition for roll printing. The ink composition for roll printing according to claim 1, further comprising at least one selected from the group consisting of a silicon-based surfactant or a fluorine-based surfactant. The ink composition for roll printing according to claim 12, wherein the silicon-based surfactant or the fluorine-based surfactant is 0.03 to 0.3 parts by weight with respect to 100 parts by weight of the entire roll printing ink composition. object. The ink composition for roll printing according to claim 1, further comprising at least one additive selected from the group consisting of a dispersant, an adhesion promoter, and an antioxidant. The ink composition for roll printing according to claim 14, wherein the additive includes 0 to 5 parts by weight or less with respect to 100 parts by weight of the total roll printing ink composition. (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 delimited by the black matrix by using a roll printing method; and patterning; (C) A method for producing a color filter comprising the step of drying the patterned ink composition for roll printing. In the roll printing method, after coating the roll printing ink composition on a roll or flat plate blanket, an undesired coating portion is removed from the blanket using a roll or flat plate cliche with a reverse image pattern of a desired pattern. The method for producing a color filter according to claim 16, wherein the method is performed by a method of taking out and transferring a desired pattern portion remaining on the blanket to the substrate again. The method for producing a color filter according to 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 manufactured using the manufacturing method of any one of Claims 16-18. A liquid crystal display element comprising the color filter according to claim 19.