JP2013249467A - New polymer and coloring composition including the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new polymer and a coloring composition including the same.SOLUTION: A photosensitive resin composition including a coloring composition can be applied as various photosensitive materials, It can be applied for an OLED or an LCD, a color filter, a black matrix, an over coat layer and a column spacer, and it can be applied when a pattern of a printed wiring board is manufactured.

Description

  This application is filed with Korean Patent Application No. 10-2012-0058877 filed with the Korean Patent Office on May 31, 2012, and Korean Patent Application No. 10-2013 filed with the Korean Patent Office on May 8, 2013. Claims the benefit of the filing date of -0051862, the entire contents of which are included herein.

  The present specification relates to a coloring composition containing a novel polymer and a liquid crystal display device or organic light-emitting device containing the same.

  The photosensitive resin composition is applied onto a substrate to form a coating film, and a specific portion of the coating film is exposed by light irradiation using a photomask or the like, and then the unexposed area is developed and removed. Can be used to form a pattern. Since such a photosensitive resin composition can be polymerized and cured by irradiation with light, photocurable ink, photosensitive printing plate, various photoresists, color filter photoresist for LCD, resin black matrix It is used as a photoresist for coatings or a transparent photosensitive material.

  The photosensitive resin composition usually contains a binder resin, a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator and a solvent, and exhibits colors such as green, red, yellow, and black depending on the application. Can contain a colorant.

  In the photosensitive resin composition, the colorant can be added with a pigment or a dye in a solid state, or another color composition containing a colorant, a dispersing resin and a solvent can be produced and mixed. .

  At this time, the colored composition may have a problem of discoloration during the heat treatment during the manufacturing process.

  The present specification intends to provide a coloring composition containing a novel polymer and a liquid crystal display device or organic light-emitting device containing the same.

This specification
A polymer including a repeating unit represented by the following chemical formulas 1 to 4 is provided.

In Formulas 1 to 4,
R 1, R 2, R 3, R 5, R 6, R 7, R 9, R 10, R 11, R 12, R 13, and R 14 are the same or different from each other, and are each independently hydrogen or a C ₁ -C ₁₀ alkyl group,
R4 _is a cycloalkenyl group a cycloalkyl group or a _C 4 _{-C 20} in C 4 _{-C 20,}
R8 is an aryl group of a halogen group and _C 1 _{~C C} 6 _{~C 20} substituted or unsubstituted with one or more selected from the group consisting of alkyl groups of _10,
R15 _is an alkyl group of C 3 _{-C 30,}
a, b, c, and d are molar mixing ratios, respectively, a is 10-60, b is 1-20, c is 10-70, and d is 1-20.

In addition, the present specification provides a method for producing a polymer according to any one of claims 1 to 4, comprising the step of 1) reacting a monomer represented by the following chemical formulas 1 to 4 and an initiator.

In Formulas 1 to 4,
R 1, R 2, R 3, R 5, R 6, R 7, R 9, R 10, R 11, R 12, R 13, and R 14 are the same or different from each other, and are each independently hydrogen or a C ₁ -C ₁₀ alkyl group,
R4 _is a cycloalkenyl group a cycloalkyl group or a _C 4 _{-C 20} in C 4 _{-C 20,}
R8 is an aryl group of a halogen group and _C 1 _{~C C} 6 _{~C 20} substituted or unsubstituted with one or more selected from the group consisting of alkyl groups of _10,
R15 _is an alkyl group of C 3 _{-C 30,}
a, b, c, and d are molar mixing ratios, respectively, a is 10-60, b is 1-20, c is 10-70, and d is 1-20.

  Moreover, this specification provides the coloring composition containing resin for dispersion containing the said polymer | macromolecule, a coloring agent, and a solvent.

  Furthermore, this specification provides the photosensitive resin composition containing the said coloring composition.

  Moreover, this specification provides the photosensitive material manufactured with the said photosensitive resin composition.

  Furthermore, the present specification provides a liquid crystal display device including any one selected from the group consisting of a color filter, a black matrix, an overcoat layer, a column spacer, and a printed wiring board made of the photosensitive material.

  One embodiment of the present specification has an advantage of excellent heat resistance.

  One embodiment of the present specification has the advantage of preventing the yellowing phenomenon.

  One embodiment of the present specification has the advantage of reducing the occurrence of protrusions on the film.

  Hereinafter, the present specification will be described in more detail.

The present specification provides a polymer including a repeating unit represented by the following chemical formulas 1 to 4.

In Formulas 1 to 4, R1, R2, R3, R5, R6, R7, R9, R10, R11, R12, R13, and R14 are the same or different from each other, and each independently represents hydrogen or C _{1 to} C ₁₀ . An alkyl group, and R 4 is a C _{4 to} C ₂₀ cycloalkyl group or a C _{4 to} C ₂₀ cycloalkenyl group.

In Formula 1 to 4, R8 is an aryl group of a halogen group and _C 1 _{~C 10 C} 6 _{~C 20} substituted or unsubstituted with one or more selected from the group consisting of alkyl groups, R15 is , C _{3 to} C ₃₀ alkyl groups, a, b, c and d are each in a molar mixing ratio, a is 10 to 60, b is 1 to 20, c is 10 to 70, d is 1 ~ 20.

In addition, the polymer may further include any one or more of repeating units represented by the following chemical formulas 5 and 6.

In Formulas 5 to 6,
R16, R17, R18, R19, R20 and R21, equal to or different from each other, each independently represent hydrogen or an alkyl group of _C 1 _{-C 10,}
R22 represents _an alkyl group of C 1 _{-C 10;} a or an alkyl ester group of _C 1 -C _6,
e and f are molar mixing ratios, respectively, e is 1 to 40, and f is 1 to 20.

Alkyl group of the C ₁ -C ₁₀ may be straight or branched. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and the like t- butyl group, It is not limited only to these.

Alkyl group of the C ₃ -C ₃₀ may be straight or branched, and specific examples, propyl group, isopropyl group, butyl group, t- butyl group, it is a propyl group, only these It is not limited.

Specific examples of the C ₆ -C ₂₀ aryl group include a phenyl group, a benzyl group, a biphenyl group, a naphthyl group, an anthracene group, and a phenanthrene, but are not limited thereto.

  Examples of the halogen group include, but are not limited to, a fluorine group, a chlorine group, a bromine group, and an iodine group.

Examples of the C _{4 to} C ₂₀ cycloalkyl group include, but are not limited to, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and an adamantyl group.

The C _{4 to} C ₂₀ cycloalkenyl group may be a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, or the like, but is not limited thereto.

The chemical formula 1 may be represented by the following chemical formula 7 or chemical formula 10, but is not limited thereto.

  In Formula 7, R1, R2, R3, and a are as defined in Formula 1.

The chemical formula 2 can be represented by the following chemical formula 8, but is not limited thereto.

  In the chemical formula 8, R5, R6, R7 and b are as defined in the chemical formula 2.

The present specification provides a method for producing a polymer comprising 1) a step of reacting a monomer represented by the following chemical formulas 1 to 4 and an initiator.

In Formulas 1 to 4, R1, R2, R3, R5, R6, R7, R9, R10, R11, R12, R13, and R14 are the same or different from each other, and each independently represents hydrogen or C _{1 to} C ₁₀ . An alkyl group, and R 4 is a C _{4 to} C ₂₀ cycloalkyl group or a C _{4 to} C ₂₀ cycloalkenyl group.

In Formula 1 to 4, R8 is an aryl group of a halogen group and _C 1 _{~C 10 C} 6 _{~C 20} substituted or unsubstituted with one or more selected from the group consisting of alkyl groups, R15 is , C _{3 to} C ₃₀ alkyl groups, a, b, c and d are each in a molar mixing ratio, a is 10 to 60, b is 1 to 20, c is 10 to 70, d is 1 ~ 20.

  The polymer may include a monomer represented by Chemical Formula 1 having a content of 10 to 60 mol% based on the whole polymer. If the amount is less than 10 mol%, it may be difficult to impart sufficient heat resistance to the polymer, and if it exceeds 60 mol%, the dispersibility and developability of the polymer may be reduced. .

  The polymer may include a monomer represented by Chemical Formula 2 having a content of 1 to 20 mol% based on the whole polymer. When the amount is less than 1 mol%, the dispersibility of the polymer may be lowered. When the amount is more than 20 mol%, the polymer is yellowed in a heating process or protrudes into a pattern formed by thermal decomposition. Can be formed.

  In addition, the polymer may include a monomer represented by Chemical Formula 3 having a content of 10 to 70 mol% based on the whole polymer. When the amount is less than 10 mol%, the developability of the polymer may be lowered, and when it exceeds 70 mol%, the dispersibility of the polymer may be lowered.

  The polymer may include a monomer represented by Chemical Formula 4 having a content of 10 to 70 mol% based on the whole polymer. If the amount is less than 10 mol%, the dispersibility and developability of the polymer may decrease, and if it exceeds 70 mol%, it may be difficult to impart sufficient heat resistance to the polymer. obtain.

In the step 1), a monomer represented by the following chemical formula 6 can be added and reacted. At this time, the polymer generated through the reaction may include a repeating unit represented by Chemical Formula 6 having a content of 1 to 20 mol% based on the whole polymer.

In Formula 6, R22 is _an alkyl group of C 1 _{-C 10;} a or an alkyl ester group of _C 1 -C _6, f represents a molar mixing ratio, f is 1 to 20.

  Further, it may further include 2) step (second step) in which the product of 1) step (first step) is reacted with an unsaturated ethylenic monomer containing an epoxy group.

  The unsaturated ethylenic monomer containing the epoxy group includes aryl glycidyl ether, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl 5-norbornene-2-methyl-2-carboxylate (endo, One or more compounds selected from the group consisting of exo mixtures), 1,2-epoxy-5-hexene and 1,2-epoxy-9-decene may be used, but are limited to these is not.

  In the step 2), the unsaturated ethylenic monomer containing the epoxy group reacts with an acid group of a repeating unit represented by Formula 3 in the product of step 1) to give an unsaturated ethylene group.

  In the polymer containing an unsaturated ethylene group, which is the product of the step 2), the unsaturated ethylene group at the terminal reacts with other polymerizable groups at the time of exposure. Thereby, the intensity | strength of a pattern can be improved. In addition, this can reduce the occurrence of protrusions on the surface of the pattern.

Accordingly, the product of the following step 2) includes a repeating unit represented by the chemical formula 5.

In Formula 5, R16, R17, R18, R19, R20 and R21, equal to or different from each other, each independently represent hydrogen or an alkyl group of _C 1 _{-C 10,} e is a molar mixing ratio, e Is 1-40.

  At this time, the polymer formed through the reaction may include a repeating unit represented by Formula 5 having a content of 1 to 40 mol% based on the whole polymer.

  The polymer according to one embodiment of the present specification has a weight average molecular weight of 5,000 to 50,000, and may be 5,000 to 20,000, but is limited thereto. is not.

  The acid value of the polymer according to an embodiment of the present specification is 10 to 150 KOH mg / g, and may be 30 to 130 KOH mg / g as necessary, but is not limited thereto.

  In the present specification, “*” means a connecting part between repeating units.

  On the other hand, the polymer can be used as a dispersing resin for dispersing a colorant in a coloring composition.

  This specification provides the coloring composition containing resin for dispersing containing the said polymer, a coloring agent, and a solvent.

  In the coloring composition according to the present specification, the dispersion resin may be composed only of the polymer according to the specification, and additionally includes a dispersion resin known in the technical field in addition to the polymer. be able to.

  Generally, in a coloring composition, the colorant often contains an aromatic group for color development. For this reason, the dispersing resin for dispersing the colorant generally contains an aromatic group in order to increase the affinity with the colorant containing the aromatic group and efficiently disperse it.

  However, the aromatic group of the dispersing resin may change the color inherent to the colorant and may be thermally decomposed during the heating process, thereby causing problems such as forming protrusions on the surface. There is.

  In order to solve this, the dispersing resin of the present specification includes a repeating unit including an aryl group of an aromatic group to a minimum, and includes a cycloalkyl group of an aliphatic ring group to impart heat resistance. Repeating units can be included.

  When the cycloalkyl group is included, since the glass transition temperature is high and the hydrophobicity is exhibited, the developability may be lowered. Therefore, in order to compensate for this, an acid group or a linear or branched alkyl group is used. The repeating unit containing can be included.

  The repeating unit containing a linear or branched alkyl group can impart not only developability but also dispersibility of the dispersing resin.

  When the cycloalkyl group is contained, pattern peeling is reduced during development with an alkaline aqueous solution. This is because the hydrophobicity of the cycloalkyl group makes it difficult for the developer to penetrate into the pattern during the development process, thereby reducing pattern damage.

  The content of the dispersing resin may be 1 to 30% by weight based on the total weight of the coloring composition.

  Examples of the colorant include a red pigment, a violet pigment, a blue pigment, a green pigment, a yellow pigment, an orange pigment, a black pigment, and carbon black according to color characteristics, and one or more of these may be selected. it can.

  Examples of the red pigment include Pig. Which is a naphthol red pigment. 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 (C.I. 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 (C.I. 12360), Pig. Red # 32 (C.I. 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. Naphthalenesulfonate 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 (C.I. 65300); Pig. 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 (C.I. 12514); Pig. Red # 216 (C.I. 59710); a diketopyrrolopyrrole-based Pig. Red # 254 (C.I. 56110); and Pig. It is possible to select from a group consisting of Red # 260 (C.I. 56295) and the like.

  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); and Pig., A benzimidazolone series. A group consisting of Violet # 32 (C.I. 12517) or the like can be selected.

  Examples of blue pigments include triarylcarbonium-based Pig. Blue # 15: 6, 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); and Pig. Blue # 66 (C.I. 73000), Pig. It can be selected from a group consisting of Blue # 63 (C.I. 73015: x) and the like.

  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 # 58 and the metal complex Pig. Green # 8 (C.I. 10006), Pig. A group consisting of Green # 10 (C.I. 12775) and the like can be selected.

  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. Which is a monoazo metal complex. 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. Yellow # 16 (C.I. 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 (C.I. 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); and 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. It can be selected from a group consisting of Yellow # 179 (C.I. 48125) and the like.

  In addition, as the 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 (C.I. 15510: 2), Pig. Orange # 46 (C.I. 15602); Pig. Which is a disazopyrazolone series. Orange # 13 (C.I. 21110), Pig. Orange # 34 (C.I. 21115); Pig. Orange # 15 (C.I. 21130), Pig. Orange # 16 (C.I. 21160); Pig. Naphthalenesulfonate complex. Orange # 19 (C.I. 15990); Pig. Orange # 31 (CI. 20050); Pig., A benzimidazolone series. Orange # 36 (C.I. 11780), Pig. Orange # 60 (C.I. 11782); Pigrantron-based Pig. Orange # 40 (C.I. 59700); Pig. Orange # 43 (C.I. 71105); Pig. Orange # 48 (C.I. 73900); and Pig. Orange # 61 (C.I. 11265), Pig. Orange # 66 (C.I. 48210), Pig. A group consisting of Orange # 69 (C.I. 56292) can be selected.

  The colorant containing a black pigment can be used by mixing carbon black and two or more color pigments. As the carbon black, Tokai Carbon Co., Ltd. Seast 5HISAF-HS, Seast KH, Seast 3HHAF-HS, Seast NH, Seast 3M, Seast 300HAF-LS, Seast 116HMMAF-HS, Seast 116MAF, Seast FMFEF-HS, Seast SOFEF, Seest VGPF, Seest SVHSRF-HS, and Seest SSRF; Mitsubishi Chemical Corporation's Diagram Black II, Diagram Black N339, Diagram Black SH, Diagram Black H, Diagram LH, Diagram HA, Diagram SF, Diagram N550M, Diagram M Diagram E, Diagram G, Diagram R, Diagram N760M, Diagram LR, # 2700, 2600, # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 900, MCF88, # 52, # 50, # 47, # 45, # 45L, # 25, # CF9, # 95, # 3030, # 3050, MA7, MA77, MA8, MA11, OIL7B, OIL9B, OIL11B, OIL30B, and OIL31B; Degussa Corporation's PRINTEX-U, PRINTERX-V, PRINTEX-140U, PRINTEX-140V, PRINTEX-95, PRINTEX -85, PRINTEX-75, PRINTEX-55, PRINTEX-45, PRINTEX-300, PRINTEX-35, PRINTEX-25, PRINTEX-200, PRINTEX-40, PRINTEX-30, PRINTE X-3, PRINTEX-A, SPECIAL BLACK-550, SPECIAL BLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100, and LAMP BLACK-101; and Raven-1100 ULTRA, RAVEN-1080 ULTRA, RAVEN from Columbia Carbon Co., Ltd. -1060 ULTRA, RAVEN-1040, RAVEN-1035, RAVEN-1020, RAVEN-1000, RAVEN-890H, RAVEN-890, RAVEN-880ULTRA, RAVEN-860ULTRA, RAVEN-850, RAVEN-820U, RAVEN-790ULTRA80 , RAVEN-760ULTRA, RAVEN-5 20, RAVEN-500, RAVEN-460, RAVEN-450, RAVEN-430ULTRA, RAVEN-420, RAVEN-410, RAVEN-2500ULTRA, RAVEN-2000, RAVEN-1500, RAVEN-1255, RAVEN-1250, RAVEN-1200, A group consisting of RAVEN-1190ULTRA and RAVEN-1170 can be selected.

  Examples of the colorant that can be used in combination with the carbon black include Carmine 6B (C.I. 12490), phthalocyanine green (C.I. 74260), phthalocyanine blue (C.I. 74160), Mitsubishi Carbon Black MA100, Perylene black (BASF K0084.K0086), cyanine black, linole yellow (CI 21090), linole yellow GRO (CI 21090), benzidine yellow 4T-564D, Mitsubishi carbon black MA-40, Victoria pure blue ( C.I. 42595), C.I. I. PIGMENT RED97, 122, 149, 168, 177, 180, 192, 215, C.I. I. PIGMENT GREEN 7, 36, C.I. I. PIGMENT 15: 1, 15: 4, 15: 6, 22, 60, 64, C.I. I. PIGMENT 83, 139 or C.I. I. PIGMENT VIOLET23 etc., and white pigments or fluorescent pigments can also be used.

  The colorant content may be 5 to 50% by weight based on the total weight of the coloring composition.

  The solvent is methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Methyl ethyl ether, chloroform, methylene chloride, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,2-trichloroethane, hexane, heptane, octane, cyclohexane, benzene, Toluene, xylene, methanol, ethanol, isopropanol, propano , Butanol, t-butanol, 2-ethoxypropanol, 2-methoxypropanol, 3-methoxybutanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, 3-methoxybutyl acetate, ethyl 3- One or more selected from the group consisting of ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, dipropylene glycol monomethyl ether, and the like can be used, but the present technology is not limited thereto. Solvents known in the art can also be used.

  The content of the solvent may be 20 to 70% by weight based on the total weight of the coloring composition.

  This specification provides the photosensitive resin composition containing the said coloring composition.

  In the photosensitive resin composition according to the present specification, the colored composition may be composed only of the colored composition according to the present specification, in addition to the colored composition, a colored composition known in the technical field, Pigments or dyes can additionally be included.

  The content of the coloring composition may be 0.01 to 80% by weight based on the total weight of the photosensitive resin composition, but is not limited thereto.

  The photosensitive resin composition may include a binder resin, a polymerizable compound including an ethylenically unsaturated bond, an initiator, and a solvent. The binder resin, a polymerizable compound including an ethylenically unsaturated bond, and a photoinitiator. And the solvent can be a compound known in the art.

  In the photosensitive resin composition according to the present specification, the binder resin may be composed only of the polymer according to the present specification.

  In the photosensitive resin composition according to the present specification, in addition to the polymer according to the present specification, a binder resin known in the art can be additionally included, and the polymer according to the present specification is not included. May be.

  The binder resin is a monomer containing an epoxy group and an ethylenically unsaturated bond; unsaturated carboxylic acid esters, aromatic vinyl monomers, unsaturated ethers, N-vinyl tertiary amines, and unsaturated imides. It may further comprise one or more monomers selected from the group consisting of: monomers containing acid groups; and acid anhydrides.

  Examples of the monomer containing an epoxy group and an ethylenically unsaturated bond include allyl glycidyl ether, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and glycidyl 5-norbornene-2-methyl-2-carboxylate. One or more compounds selected from the group consisting of (endo, exo mixture), 1,2-epoxy-5-hexene and 1,2-epoxy-9-decene can be used, but only in these Is not to be done.

  Specific examples of the unsaturated carboxylic acid esters include benzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and isobutyl (meth) acrylate. , T-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, ethylhexyl (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, acyloctyloxy-2 Hydroxypropyl (meth) acrylate, glycerol (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytripropylene Glycol (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonylphenoxypolyethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, glycidyl (meth) ) Acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafur Roisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, tribromophenyl (meth) acrylate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, propyl α-hydroxy It can be selected from the group consisting of methyl acrylate and butyl α-hydroxymethyl acrylate, but is not limited thereto.

  Specific examples of the aromatic vinyl monomers include styrene, α-methylstyrene, (o, m, p) -vinyltoluene, (o, m, p) -methoxystyrene, and (o, m, p ) -Chlorostyrene can be selected from the group consisting of, but not limited to.

  Specific examples of the unsaturated ether can be selected from the group consisting of vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether, but are not limited thereto.

  Specific examples of the N-vinyl tertiary amines can be selected from the group consisting of N-vinylpyrrolidone, N-vinylcarbazole, and N-vinylmorpholine, but are not limited thereto.

  Specific examples of the unsaturated imides can be selected from the group consisting of N-phenylmaleimide, N- (4-chlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide, and N-cyclohexylmaleimide, It is not limited only to these.

  The monomer containing an acid group is a group consisting of (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethylmaleic acid, isoprenesulfonic acid, styrenesulfonic acid, 5-norbornene-2-carboxylic acid, and the like. One or more selected from the above can be used, but is not limited thereto.

  Examples of the acid anhydride include, but are not limited to, maleic anhydride, methylmaleic anhydride, and tetrahydrophthalic anhydride.

  In the photosensitive resin composition according to the present specification, the content of the binder resin may be 1 to 20% by weight based on the total weight of the photosensitive resin composition, but is not limited thereto. .

  The polymerizable compound containing an ethylenically unsaturated bond includes ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups, trimethylolpropane di (meth) acrylate, and trimethylolpropane. Obtained by esterifying polyhydric alcohols such as tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and propylene glycol di (meth) acrylate having 2 to 14 propylene groups with α, β-unsaturated carboxylic acid. Compound; Compound obtained by adding (meth) acrylic acid to a compound containing glycidyl group such as trimethylolpropane triglycidyl ether acrylic acid adduct, bisphenol A diglycidyl ether acrylic acid adduct, etc .; β-hydroxyethyl (meth) A An ester compound of a hydroxyl group or an ethylenically unsaturated bond and a polycarboxylic acid, such as a phthalate diester of relate, a toluene diisocyanate adduct of β-hydroxyethyl (meth) acrylate, or an adduct of a polyisocyanate; and One or more selected from the group consisting of alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate can be used. However, it is not limited only to these, What is known in the said technical field etc. can also be used.

  The content of the polymerizable compound containing an ethylenically unsaturated bond may be 2 to 30% by weight based on the total weight of the photosensitive resin composition, but is not limited thereto.

  Examples of the photoinitiator include 2,4-trichloromethyl- (4′-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4′-methoxystyryl) -6-triazine, and 2,4-trichloro. Methyl- (fipronyl) -6-triazine, 2,4-trichloromethyl- (3 ′, 4′-dimethoxyphenyl) -6-triazine, 3- {4- [2,4-bis (trichloromethyl) -s- Triazine compounds such as triazin-6-yl] phenylthio} propanoic acid; 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2 , 3-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole; 2-hydroxy-2-methyl-1-pheni; Propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy) propyl ketone, 1-hydroxycyclohexyl Phenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin butyl ether, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl- (4-methylthiophenyl) -2-morpholino-1-propane-1- Acetophenone compounds such as ON, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′- Bis (diethylamino) Zophenone, 2,4,6-trimethylaminobenzophenone, methyl-o-benzoylbenzoate, 3,3-dimethyl-4-methoxybenzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, etc. Benzophenone compounds; fluorenone compounds such as 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone; thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 1-chloro-4- Thioxanthone compounds such as propyloxythioxanthone, isopropylthioxanthone, diisopropylthioxanthone; xanthone compounds such as xanthone and 2-methylxanthone; anthraquinone, 2-methylanthraquinone, 2-ethylanthone Anthraquinone compounds such as traquinone, t-butylanthraquinone, 2,6-dichloro-9,10-anthraquinone; 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, 1,5-bis (9-acridinyl) ) Acridine compounds such as pentane and 1,3-bis (9-acridinyl) propane; benzyl, 1,7,7-trimethyl-biscro [2,2,1] heptane-2,3-dione, 9,10- Dicarbonyl compounds such as phenanthrenequinone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,6-dichlorobenzoyl) Phosphine oxide compounds such as propylphosphine oxide; Til 4- (dimethylamino) benzoate, ethyl-4- (dimethylamino) benzoate, 2-n-butoxyethyl 4- (dimethylamino) benzoate, 2,5-bis (4-diethylaminobenzal) cyclopentanone, 2 , 6-bis (4-diethylaminobenzal) cyclohexanone, 2,6-bis (4-diethylaminobenzal) -4-methyl-cyclohexanone and other amine synergists; 3,3′-carbonylvinyl-7- (diethylamino) Coumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3-benzoyl-7- (diethylamino) coumarin, 3-benzoyl-7-methoxy-coumarin, 10,10′-carbonylbis [1,1, 7,7-tetramethyl-2,3,6,7-tetrahydro-1H Coumarin compounds such as 5H, 11H-Cl] -benzopyrano- [6,7,8-ij] -quinolizin-11-one; chalcone compounds such as 4-diethylaminochalcone and 4-azidobenzalacetophenone; 2-benzoylmethylene And one or more selected from the group consisting of 3-methyl-β-naphthothiazoline can be used, but is not limited thereto, and a photoinitiator known in the art is used. You can also.

  The content of the photoinitiator may be 0.1 to 5% by weight based on the total weight of the photosensitive resin composition, but is not limited thereto.

  The solvent is methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Methyl ethyl ether, chloroform, methylene chloride, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,2-trichloroethane, hexane, heptane, octane, cyclohexane, benzene, Toluene, xylene, methanol, ethanol, isopropanol, propano , Butanol, t-butanol, 2-ethoxypropanol, 2-methoxypropanol, 3-methoxybutanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, 3-methoxybutyl acetate, ethyl 3- One or more selected from the group consisting of ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, dipropylene glycol monomethyl ether, and the like can be used, but the present technology is not limited thereto. Solvents known in the art can also be used.

  The content of the solvent may be 15 to 95% by weight based on the total weight of the photosensitive resin composition, but is not limited thereto.

  In addition, the photosensitive resin composition according to the present specification includes a dispersant, a curing accelerator, a thermal polymerization inhibitor, a surfactant, a light modifier, a plasticizer, an adhesion promoter, a filler, and an adhesive depending on applications. One or more selected from the group consisting of auxiliaries can be additionally included.

  The dispersant can be used by a method of internally adding the pigment to the pigment in a form in which the pigment is surface-treated in advance or a method of adding the pigment to the pigment externally. As the dispersant, a polymer type, nonionic, anionic or cationic dispersant can be used. Examples thereof include polyalkylene glycol and its ester, polyoxyalkylene polyhydric alcohol, ester. There are one or more selected from the group consisting of alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonate esters, sulfonates, carboxylic acid esters, carboxylates, alkylamide alkylene oxide adducts and alkylamines, It is not limited to these.

  Examples of the curing accelerator include 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-4,6-dimethyl. Aminopyridine, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tris (2-mercaptoacetate), trimethylolpropane Tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (2-mercaptoacetate), and trimethylol One or more selected from the group consisting of tantris (3-mercaptopropionate) can be included, but is not limited thereto, and includes those generally known in the art. it can.

  Examples of the thermal polymerization inhibitor include p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, N-nitrosophenylhydroxyamine ammonium salt, and N-nitrosophenylhydroxyamine aluminum salt. And one or more selected from the group consisting of phenothiazine, but is not limited thereto, and may include those generally known in the art.

  The surfactant is a silicone-based surfactant or a fluorine-based surfactant. Specifically, the silicone-based surfactant is BYK-077, BYK-085, BYK-300, BYK manufactured by BYK-Chemie. -301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-335 BYK-341v344, BYK-345v346, BYK-348, BYK-354, BYK-355, BYK-356, BYK-358, BYK-361, BYK-370, BYK-371, BYK-375, BYK-380, BYK -390 and the like, and as the fluorine-based surfactant, IC (DaiNippon Ink & Chemicals) F-114, F-177, F-410, F-411, F-450, F-493, F-494, F-443, F-444, F-445, F-446 F-470, F-471, F-472SF, F-474, F-475, F-477, F-478, F-479, F-480SF, F-482, F-483, F-484, F -486, F-487, F-172D, MCF-350SF, TF-1025SF, TF-1117SF, TF-1026SF, TF-1128, TF-1127, TF-1129, TF-1126, TF-1130, TF-1116SF TF-1131, TF1132, TF1027SF, TF-1441, TF-1442, etc. can be used. However, it is not limited to these.

  As the light increasing / decreasing agent, plasticizer, adhesion promoter, filler and the like, all compounds which can be contained in the conventional photosensitive resin composition can be used.

  The content of the additive may be independently 0.01 to 5% by weight based on the total weight of the photosensitive resin composition, but is not limited thereto.

  On the other hand, the photosensitive resin composition according to the present specification is used for a roll coater, a curtain coater, a spin coater, a spin coater, various types of printing, dipping, etc. It can be applied on a support such as a glass plastic substrate. In addition, after coating on a support such as a film, it can be transferred to another support, or after being applied to the first support, transferred to a blanket or the like, and then transferred to the second support again. There is no particular limitation on the application method.

  Examples of the light source for curing the photosensitive resin composition according to the present specification include mercury vapor arc (arc), carbon arc, and Xe arc that emit light having a wavelength of 250 to 450 nm. Not limited to.

  The photosensitive resin composition containing the polymer according to the present specification is characterized by not only excellent sensitivity and developability but also a high taper angle and excellent adhesive strength. Therefore, the photosensitive resin composition containing the polymer according to the present specification can be applied as various photosensitive materials, and in particular, can be applied during the production of LCD color filter patterns.

  One embodiment of the present specification has an advantage of excellent heat resistance and prevention of yellowing.

  One embodiment of the present specification has the advantage of reducing the occurrence of protrusions on the film.

  One embodiment of this specification can reduce the occurrence of protrusions in a film, a thin film, a pattern, or the like, and can improve luminance.

  Moreover, this specification provides the photosensitive material manufactured with the said photosensitive resin composition.

  The photosensitive resin composition according to the present specification includes a pigment dispersion type photosensitive material for manufacturing TFT LCD color filters, a photosensitive material for forming a black matrix of TFT LCD or an organic light emitting diode, an overcoat layer forming photosensitive material, and a column spacer photosensitive material. It can be used for photo-curable paints, photo-curable inks, photo-curable adhesives, printing plates, photosensitive materials for printed wiring boards, other transparent photosensitive materials, and PDP production. , There is no particular restriction on its use.

  In addition, the present specification provides a liquid crystal display device including any one selected from the group consisting of a color filter, a black matrix, an overcoat layer, a column spacer, and a printed wiring board manufactured with the photosensitive material.

  Hereinafter, in order to understand the present specification, an example according to the present specification is presented. However, the following examples are intended to illustrate the present specification and are not intended to limit the scope of the present specification.

<Example>
<Synthesis Example 1>
After dissolving 2.17 parts by weight of thermal initiator V-65 in a reaction vessel in a reaction vessel, 1-adamantyl methacrylate / styrene / methacrylic acid was added at a mole percentage of 60/12/28, and then 60 ° C. in a nitrogen atmosphere. Maintained and allowed to react for 12 hours. The produced binder resin had an acid value of 100 KOH mg / g and a weight average molecular weight of 8,100.

<Synthesis Example 2>
In a reaction vessel, 2.17 parts by weight of thermal initiator V-65 was dissolved in a solvent, and then 1-adamantyl methacrylate / N-cyclohexylmaleimide / styrene / methacrylic acid / lauryl methacrylate was added to a mole of 47/8/9/28/8. %, And then kept at 60 ° C. in a nitrogen atmosphere and allowed to react for 12 hours. The produced binder resin had an acid value of 98 KOH mg / g and a weight average molecular weight of 8,500.

<Synthesis Example 3>
In a reaction vessel, 2.17 parts by weight of thermal initiator V-65 was dissolved in a solvent, and charged at a mole% of cyclohexyl methacrylate / N-cyclohexylmaleimide / styrene / methacrylic acid / lauryl methacrylate 49/8/10/25/8. Then, the temperature was maintained at 60 ° C. in a nitrogen atmosphere, and the reaction was performed for 12 hours. The produced binder resin had an acid value of 105 KOH mg / g and a weight average molecular weight of 8,000.

<Synthesis Example 4>
After dissolving 2.17 parts by weight of thermal initiator V-65 in a reaction vessel in a reaction vessel, it was added at a mol% of dicyclopentanyl methacrylate / styrene / methacrylic acid / lauryl methacrylate 46/14/28/12, and then nitrogen. The reaction was maintained for 12 hours while maintaining 60 ° C. in the atmosphere. The produced binder resin had an acid value of 105 KOH mg / g and a weight average molecular weight of 8,500.

<Synthesis Example 5>
After 2.17 parts by weight of thermal initiator V-65 was dissolved in a reaction vessel in a reaction vessel, cyclohexyl methacrylate / styrene / methacrylic acid was added at a mole percentage of 59/18/23, and then maintained at 60 ° C. in a nitrogen atmosphere. For 12 hours. The produced binder resin had an acid value of 99 KOH mg / g and a weight average molecular weight of 8,000.

<Synthesis Example 6>
After dissolving 2.17 parts by weight of thermal initiator V-65 in a reaction vessel in a reaction vessel, 1-adamantyl methacrylate / styrene / methacrylic acid was added at a molar ratio of 39/8/53, and then 60 ° C. in a nitrogen atmosphere. Maintained and allowed to react for 12 hours. After adding a thermal polymerization inhibitor and a catalyst to the resin solution thus obtained, 20.32 g of glycidyl methacrylate was added in an air atmosphere and allowed to react for 12 hours while maintaining 110 ° C. The produced binder resin had an acid value of 105 KOH mg / g and a weight average molecular weight of 10,500.

<Synthesis Example 7>
In a reaction vessel, 2.17 parts by weight of thermal initiator V-65 was dissolved in a solvent, and then cyclohexyl methacrylate / N-cyclohexylmaleimide / styrene / methacrylic acid / lauryl methacrylate was added at a molar ratio of 32/5/6/52/5. After charging, the temperature was maintained at 60 ° C. in a nitrogen atmosphere and allowed to react for 12 hours. After adding a thermal polymerization inhibitor and a catalyst to the resin solution thus obtained, 22.33 g of glycidyl methacrylate was added in an air atmosphere and allowed to react for 12 hours while maintaining 110 ° C. The produced binder resin had an acid value of 110 KOH mg / g and a weight average molecular weight of 9,900.

<Comparative Synthesis Example 1>
After dissolving 2.17 parts by weight of thermal initiator V-65 in a reaction vessel in a reaction vessel, benzyl methacrylate / N-phenylmaleimide / styrene / methacrylic acid was added at a mol% of 55/9/11/25, and then nitrogen was added. The reaction was maintained for 12 hours while maintaining 60 ° C. in the atmosphere. The produced binder resin had an acid value of 100 KOH mg / g and a weight average molecular weight of 8,300.

<Comparative Synthesis Example 2>
In a reaction vessel, 2.17 parts by weight of thermal initiator V-65 was dissolved in a solvent, and then benzyl methacrylate / N-phenylmaleimide / styrene / methacrylic acid / lauryl methacrylate was added at a mole percentage of 48/8/10/26/8. After charging, the temperature was maintained at 60 ° C. in a nitrogen atmosphere and allowed to react for 12 hours. The produced binder resin had an acid value of 102 KOH mg / g and a weight average molecular weight of 8,600.

<Comparative Synthesis Example 3>
In a reaction vessel, 2.17 parts by weight of thermal initiator V-65 was dissolved in a solvent, and then benzyl methacrylate / N-phenylmaleimide / styrene / methacrylic acid / lauryl methacrylate was added at a mol% of 32/5/6/52/5. After charging, the temperature was maintained at 60 ° C. in a nitrogen atmosphere and allowed to react for 12 hours. After adding a thermal polymerization inhibitor and a catalyst to the resin solution thus obtained, 22.00 g of glycidyl methacrylate was added in an air atmosphere and allowed to react for 12 hours while maintaining 110 ° C. The produced binder resin had an acid value of 108 KOH mg / g and a weight average molecular weight of 10,200.

<Example 1>
As pigment, 5.08 parts by weight of Pigment Green 58, 0.85 parts by weight of Pigment Yellow 150, 2.0 parts by weight of the polymer prepared in Synthesis Example 1, 3.62 parts by weight of an acrylic dispersant, and propylene as a solvent. 38.8 parts by weight of glycol monomethyl ether acetate was mixed, and the mixture was stirred to produce a colored composition.

<Example 2>
A colored composition was produced in the same manner as in Example 1 except that 2.0 parts by weight of the polymer produced in Synthesis Example 2 was used instead of the polymer produced in Synthesis Example 1. .

<Example 3>
A colored composition was produced in the same manner as in Example 1 except that 2.0 parts by weight of the polymer produced in Synthesis Example 3 was used instead of the polymer produced in Synthesis Example 1. .

<Example 4>
A colored composition was produced in the same manner as in Example 1 except that 2.0 parts by weight of the polymer produced in Synthesis Example 4 was used instead of the polymer produced in Synthesis Example 1. .

<Example 5>
A colored composition was produced in the same manner as in Example 1, except that 2.0 parts by weight of the polymer produced in Synthesis Example 5 was used instead of the polymer produced in Synthesis Example 1. .

<Example 6>
A colored composition was produced in the same manner as in Example 1 except that 2.0 parts by weight of the polymer produced in Synthesis Example 6 was used instead of the polymer produced in Synthesis Example 1. .

<Example 7>
A colored composition was produced in the same manner as in Example 1 except that 2.0 parts by weight of the polymer produced in Synthesis Example 7 was used instead of the polymer produced in Synthesis Example 1. .

<Example 8>
11 parts by weight of the colored composition prepared in Example 1, 1.8 parts by weight of dipentaerythritol hexaacrylate as an ethylenically unsaturated polymerizable compound, 1.8 parts by weight of a copolymer of benzyl methacrylate and methacrylic acid as a binder resin Part, 0.34 part by weight of 2,4-crichloromethyl- (4′-methoxyphenyl) -6-triazine as a photoinitiator, 0.13 part by weight of 3-methacryloxypropyltrimethoxysilane as an adhesion promoter, F-475 (DaiNippon Ink & Chemicals) 0.04 parts by weight as a surfactant and 38.8 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed, and the mixture was stirred for 5 hours to produce a photosensitive resin composition.

<Example 9>
11 parts by weight of the colored composition prepared in Example 2, 1.8 parts by weight of dipentaerythritol hexaacrylate as an ethylenically unsaturated polymerizable compound, 1.8 parts by weight of a copolymer of benzyl methacrylate and methacrylic acid as a binder resin Part, 0.34 part by weight of 2,4-crichloromethyl- (4′-methoxyphenyl) -6-triazine as a photoinitiator, 0.13 part by weight of 3-methacryloxypropyltrimethoxysilane as an adhesion promoter, F-475 (DaiNippon Ink & Chemicals) 0.04 parts by weight as a surfactant and 38.8 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed, and the mixture was stirred for 5 hours to produce a photosensitive resin composition.

<Example 10>
11 parts by weight of the colored composition prepared in Example 3, 1.8 parts by weight of dipentaerythritol hexaacrylate as an ethylenically unsaturated polymerizable compound, 1.8 parts by weight of a copolymer of benzyl methacrylate and methacrylic acid as a binder resin Part, 0.34 part by weight of 2,4-crichloromethyl- (4′-methoxyphenyl) -6-triazine as a photoinitiator, 0.13 part by weight of 3-methacryloxypropyltrimethoxysilane as an adhesion promoter, F-475 (DaiNippon Ink & Chemicals) 0.04 parts by weight as a surfactant and 38.8 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed, and the mixture was stirred for 5 hours to produce a photosensitive resin composition.

<Example 11>
11 parts by weight of the colored composition prepared in Example 4, 1.8 parts by weight of dipentaerythritol hexaacrylate as an ethylenically unsaturated polymerizable compound, 1.8 parts by weight of a copolymer of benzyl methacrylate and methacrylic acid as a binder resin Part, 0.34 part by weight of 2,4-crichloromethyl- (4′-methoxyphenyl) -6-triazine as a photoinitiator, 0.13 part by weight of 3-methacryloxypropyltrimethoxysilane as an adhesion promoter, F-475 (DaiNippon Ink & Chemicals) 0.04 parts by weight as a surfactant and 38.8 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed, and the mixture was stirred for 5 hours to produce a photosensitive resin composition.

<Example 12>
11 parts by weight of the colored composition prepared in Example 5, 1.8 parts by weight of dipentaerythritol hexaacrylate as an ethylenically unsaturated polymerizable compound, 1.8 parts by weight of a copolymer of benzyl methacrylate and methacrylic acid as a binder resin Part, 0.34 part by weight of 2,4-crichloromethyl- (4′-methoxyphenyl) -6-triazine as a photoinitiator, 0.13 part by weight of 3-methacryloxypropyltrimethoxysilane as an adhesion promoter, F-475 (DaiNippon Ink & Chemicals) 0.04 parts by weight as a surfactant and 38.8 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed, and the mixture was stirred for 5 hours to produce a photosensitive resin composition.

<Example 13>
11 parts by weight of the colored composition produced in Example 6, 1.8 parts by weight of dipentaerythritol hexaacrylate as an ethylenically unsaturated polymerizable compound, 1.8 parts by weight of a copolymer of benzyl methacrylate and methacrylic acid as a binder resin Part, 0.34 part by weight of 2,4-crichloromethyl- (4′-methoxyphenyl) -6-triazine as a photoinitiator, 0.13 part by weight of 3-methacryloxypropyltrimethoxysilane as an adhesion promoter, F-475 (DaiNippon Ink & Chemicals) 0.04 parts by weight as a surfactant and 38.8 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed, and the mixture was stirred for 5 hours to produce a photosensitive resin composition.

<Example 14>
11 parts by weight of the colored composition prepared in Example 7, 1.8 parts by weight of dipentaerythritol hexaacrylate as an ethylenically unsaturated polymerizable compound, 1.8 parts by weight of a copolymer of benzyl methacrylate and methacrylic acid as a binder resin Part, 0.34 part by weight of 2,4-crichloromethyl- (4′-methoxyphenyl) -6-triazine as a photoinitiator, 0.13 part by weight of 3-methacryloxypropyltrimethoxysilane as an adhesion promoter, F-475 (DaiNippon Ink & Chemicals) 0.04 parts by weight as a surfactant and 38.8 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed, and the mixture was stirred for 5 hours to produce a photosensitive resin composition.

<Comparative Example 1>
A colored composition is produced in the same manner as in Example 1, except that 2.0 parts by weight of the polymer produced in Comparative Synthesis Example 1 is used instead of the polymer produced in Synthesis Example 1. did.

<Comparative example 2>
A colored composition is produced in the same manner as in Example 1, except that 2.0 parts by weight of the polymer produced in Comparative Synthesis Example 2 is used instead of the polymer produced in Synthesis Example 1. did.

<Comparative Example 3>
A colored composition is produced in the same manner as in Example 1, except that 2.0 parts by weight of the polymer produced in Comparative Synthesis Example 3 is used instead of the polymer produced in Synthesis Example 1. did.

<Comparative example 4>
11 parts by weight of the colored composition prepared in Comparative Example 1, 1.8 parts by weight of dipentaerythritol hexaacrylate as an ethylenically unsaturated polymerizable compound, 1.8 parts by weight of a copolymer of benzyl methacrylate and methacrylic acid as a binder resin Part, 0.34 part by weight of 2,4-crichloromethyl- (4′-methoxyphenyl) -6-triazine as a photoinitiator, 0.13 part by weight of 3-methacryloxypropyltrimethoxysilane as an adhesion promoter, F-475 (DaiNippon Ink & Chemicals) 0.04 parts by weight as a surfactant and 38.8 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed, and the mixture was stirred for 5 hours to produce a photosensitive resin composition.

<Comparative Example 5>
11 parts by weight of the colored composition prepared in Comparative Example 2, 1.8 parts by weight of dipentaerythritol hexaacrylate as an ethylenically unsaturated polymerizable compound, 1.8 parts by weight of a copolymer of benzyl methacrylate and methacrylic acid as a binder resin Part, 0.34 part by weight of 2,4-crichloromethyl- (4′-methoxyphenyl) -6-triazine as a photoinitiator, 0.13 part by weight of 3-methacryloxypropyltrimethoxysilane as an adhesion promoter, F-475 (DaiNippon Ink & Chemicals) 0.04 parts by weight as a surfactant and 38.8 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed, and the mixture was stirred for 5 hours to produce a photosensitive resin composition.

<Comparative Example 6>
11 parts by weight of the colored composition produced in Comparative Example 3, 1.8 parts by weight of dipentaerythritol hexaacrylate as an ethylenically unsaturated polymerizable compound, 1.8 parts by weight of a copolymer of benzyl methacrylate and methacrylic acid as a binder resin Part, 0.34 part by weight of 2,4-crichloromethyl- (4′-methoxyphenyl) -6-triazine as a photoinitiator, 0.13 part by weight of 3-methacryloxypropyltrimethoxysilane as an adhesion promoter, F-475 (DaiNippon Ink & Chemicals) 0.04 parts by weight as a surfactant and 38.8 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed, and the mixture was stirred for 5 hours to produce a photosensitive resin composition.

<Experimental example 1>
In order to measure the brightness of the colored compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 3, the colored compositions were spin coated on glass and pre-heated at about 100 ° C. for 2 minutes. (Prebake) to form a film. Thereafter, the luminance was measured with a chromaticity meter, and after the film was post-heated at 230 ° C. for about 30 minutes, the luminance was again measured with the chromaticity meter, and the decrease in luminance was measured. The results are shown in Table 1 below.

<Experimental example 2>
The photosensitive resin compositions obtained in Examples 8 to 11 and Comparative Examples 4 to 6 are spin-coated on glass, and prebaked at about 90 ° C. for 100 seconds to form a film. The film was exposed at 20 mJ / cm ² under a high pressure mercury lamp using a mask patterned with a transmittance of 100% and a line width of 90 μm, and then the pattern was subjected to a KOH alkaline aqueous solution having a pH of 11.3 to 11.7. And developed for 80 seconds at a pressure of 0.2 MPa and washed with deionized water. This was post-heated at 230 ° C. for about 20 minutes to form a pattern.

The degree to which the periphery of the pattern thus formed was peeled off by the developer was measured with an optical microscope, and the quality of the pattern peeling was shown in Table 2 below. The case where there was no peeling was shown as 1, the case where the peeling of the peripheral edge was visible was shown as 2, and the case where the pattern central part was peeled off was shown as 3. As the numerical value goes from 1 to 3, the pattern peeling at the time of the phenomenon worsens.

Claims (13)

A polymer containing repeating units represented by the following chemical formulas 1 to 4.

[In the chemical formulas 1 to 4,
R 1, R 2, R 3, R 5, R 6, R 7, R 9, R 10, R 11, R 12, R 13, and R 14 are the same or different from each other, and are each independently hydrogen or a C ₁ -C ₁₀ alkyl group,
R4 _is a cycloalkenyl group a cycloalkyl group or a _C 4 _{-C 20} in C 4 _{-C 20,}
R8 is an aryl group of a halogen group and _C 1 _{~C C} 6 _{~C 20} substituted or unsubstituted with one or more selected from the group consisting of alkyl groups of _10,
R15 _is an alkyl group of C 3 _{-C 30,}
a, b, c and d are each a molar mixing ratio,
a is 10 to 60,
b is 1-20,
c is 10 to 70,
d is 1-20. ] The polymer according to claim 1, further comprising any one or more of repeating units represented by the following chemical formulas 5 and 6.

[In the above chemical formulas 5 to 6,
R16, R17, R18, R19, R20 and R21, equal to or different from each other, each independently represent hydrogen or an alkyl group of _C 1 _{-C 10,}
R22 represents _an alkyl group of C 1 _{-C 10;} a or an alkyl ester group of _C 1 -C _6,
e and f are molar mixing ratios, respectively, e is 1 to 40, and f is 1 to 20. ] The polymer according to claim 1 or 2, wherein the chemical formula 1 is represented by the following chemical formula 7 or 10.

[In the chemical formulas 7 and 10,
R1, R2, R3 and a are as defined in Chemical Formula 1 above. ] The polymer according to any one of claims 1 to 3, wherein the chemical formula 2 is represented by the following chemical formula 8.

[In Formula 8 above,
R5, R6, R7 and b are as defined in Chemical Formula 2 above. ] The method for producing a polymer according to any one of claims 1 to 4, comprising a step 1) of reacting a monomer represented by the following chemical formulas 1 to 4 with an initiator.

[In the chemical formulas 1 to 4,
R 1, R 2, R 3, R 5, R 6, R 7, R 9, R 10, R 11, R 12, R 13, and R 14 are the same or different from each other, and are each independently hydrogen or a C ₁ -C ₁₀ alkyl group,
R4 _is a cycloalkenyl group a cycloalkyl group or a _C 4 _{-C 20} in C 4 _{-C 20,}
R8 is an aryl group of a halogen group and _C 1 _{~C C} 6 _{~C 20} substituted or unsubstituted with one or more selected from the group consisting of alkyl groups of _10,
R15 _is an alkyl group of C 3 _{-C 30,}
a, b, c and d are each a molar mixing ratio,
a is 10 to 60,
b is 1-20,
c is 10 to 70,
d is 1-20. ] The method for producing a polymer according to claim 5, further comprising reacting the monomer represented by the following chemical formula 6 with the step 1).

[In Formula 6 above,
R22 represents _an alkyl group of C 1 _{-C 10;} a or an alkyl ester group of _C 1 -C _6,
f is a molar mixing ratio, and f is 1-20. ]   The method for producing a polymer according to claim 5 or 6, further comprising a step 2) of reacting the product of step 1) with an unsaturated ethylenic monomer containing an epoxy group. The method for producing a polymer according to claim 7, wherein the product obtained in step 2) contains a repeating unit represented by the following chemical formula 5.

[In Formula 5 above,
R16, R17, R18, R19, R20 and R21, equal to or different from each other, each independently represent hydrogen or an alkyl group of _C 1 _{-C 10,}
e is a molar mixing ratio, and e is 1 to 40. ]   A coloring composition comprising a dispersion resin containing the polymer according to claim 1, a colorant, and a solvent. Based on the total weight of the colored composition,
The content of the dispersing resin is 1 to 30% by weight,
The content of the colorant is 5 to 50% by weight,
The coloring composition of Claim 9 whose content of the said solvent is 20 to 70 weight%.   A photosensitive resin composition comprising the colored composition according to claim 9.   A photosensitive material manufactured with the photosensitive resin composition according to claim 11.   A liquid crystal display device comprising at least one selected from the group consisting of a color filter, a black matrix, an overcoat layer, a column spacer, and a printed wiring board, manufactured with the photosensitive material according to claim 12.