TWI675049B - A colored photosensitive resin composition, a color filter comprising the same and a display device comprising the same - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition containing a colorant, a binder resin represented by the following Chemical Formula I, a photopolymerizable monomer, an oxime-based photoinitiator, and a solvent; and a color including the colored photosensitive resin composition. Filter and display device.

Description

   Colored photosensitive resin composition, color filter including the same, and display device including the same   

The present invention relates to a colored photosensitive resin composition, a color filter including the composition, and a display device including the color filter.

The display has become the most common means of information transmission in modern society. Therefore, a lot of research is being carried out on the development of display devices. Liquid crystal display (LCD) is one of the flat panel display devices widely used at present. The color filter substrate on which the common electrode is formed faces each other, and a liquid crystal layer is interposed therebetween. Such a liquid crystal display device rearranges liquid crystal molecules of a liquid crystal layer by applying a voltage to a pixel electrode and a common electrode, thereby adjusting an amount of light transmitted through the liquid crystal layer to display an image. In addition, organic light-emitting displays (OLEDs) that have attracted attention as next-generation displays have advantages in the development of flexible displays because they use self-luminous elements instead of the liquid crystals described above.

In the information society, with the pursuit of diversification of consumption modes, a display with low power consumption, light weight and thinness, high image quality, efficient use of space, and easy portability has become necessary. Therefore, various new attempts have been made to further reduce the thickness. Therefore, a color filter layer of a liquid crystal display device is formed from a photosensitive composition directly in a TFT structure by a light treatment process. The above-mentioned pattern is used as a color filter of a liquid crystal display device together with a coloring pigment, can be used as a transparent overcoat layer or a spacer, and can be used as a separator of an organic light emitting display.

In general LCD or OLED displays, a lot of efforts have been made to improve the brightness or light-dark ratio. As a representative example, the use of quantum dots (Quantum Dot (QD)) particles has been used to improve brightness, increase color reproduction rate, and improve color in OLEDs. Research on the brightness-darkness ratio caused by the application of banks. In the applications listed above, in order to ensure the reliability of the QD particles and the reliability of the OLED of the colored cofferdam, the selection of the initiator becomes the most important.

Korean Registered Patent No. 10-1349622 discloses a black photosensitive resin composition with a good pattern shape, which achieves excellent optical density during pattern formation, and exhibits a low dielectric constant and a high compression displacement and recovery rate. The invention relates to a photopolymerizable unsaturated resin of a black photosensitive resin composition. However, in this invention, the problems caused by Outgas, which are the most important factors for the application of organic light-emitting displays, and the problem of improving the dispersibility of particles cannot be solved. Outgassing is a term commonly used in the field of displays, which means that in the manufacture of organic light-emitting displays, gas is generated in the organic coating film under high temperature or vacuum conditions, which has an effect on the formation or continuous driving of organic light-emitting bodies.

In addition, Japanese Patent Application Laid-Open No. 2002-040440 discloses a radiation-sensitive composition capable of forming a spacer having excellent light-shielding properties, high mechanical strength, and heat resistance, and does not deform irreversibly during panel packaging and does not cause liquid crystal Display defects caused by unevenness in the gaps between the layers are not considered at all in the production of the spacer made of the composition. However, as long as a photo-processing process is used, the photoinitiator becomes a very important factor. This is because the characteristics of the formed pattern are changed by factors such as the absorption wavelength of the photoinitiator, the exposure equipment, the light source, and the intensity of the light source. Therefore, a large number of inventions and patents of photoinitiators have been confirmed.

Prior art literature

Patent literature

Patent Document 1: Korean Registered Patent No. 10-1349622

Patent Document 2: Japanese Patent Application Laid-Open No. 2002-040440

The present invention is intended to improve the problems of the above-mentioned prior art, and an object thereof is to provide a colored photosensitive resin composition comprising a coloring agent, a binder resin having a structure represented by Chemical Formula I, a photopolymerizable monomer, and an oxime-based light. The initiator, particularly a photoinitiator and a coloring agent having a structure represented by Chemical Formula II, has excellent heat resistance, excellent light resistance to UV light, and excellent dispersion stability of particles.

Another object of the present invention is to provide a colored photosensitive resin composition having excellent particle dispersibility and a display device including the same.

The present invention provides a colored photosensitive resin composition comprising a colorant, a binder resin represented by Chemical Formula I, a photopolymerizable monomer, an oxime-based photoinitiator, and a solvent.

In the above Chemical Formula I, R ₃ and R ′ ₃ are each a R _a SR _b substituent, R _a is _a bonding, an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 15 carbon atoms, S Is sulfur, R _b is an alkyl group having 1 to 10 carbon atoms or aryl group having 6 to 15 carbon atoms, and R ₄ is a tetravalent aromatic or cycloaliphatic group having 1 to 20 carbon atoms with or without a hetero atom ( cycloaliphatic) hydrocarbon group, A is a substituent represented by the following chemical formulae I-1 to I-4, n is an integer of 1 to 6, and p is an integer of 1 to 30.

[Chemical Formula I-1]

[Chemical Formula I-4]

In the above chemical formulas I-1 to I-4, R ₂ and R ′ ₂ each represent hydrogen, a hydroxyl group (-OH), a thiol group (-SH), an amine group (-NH ₂ ), or a nitro group (-NO ₂ ). Or a halogenated group, X represents O, S, N, Si or Se.

The present invention also provides a color filter including the above-mentioned colored photosensitive resin composition.

Further, the present invention provides a display device including the above-mentioned colored photosensitive resin composition.

The present invention includes a colorant, a binder resin having a structure represented by Chemical Formula I, and an oxime-based photoinitiator, and thus has the effects of excellent dispersibility of particles and an excellent effect of suppressing outgassing.

In addition, the colored photosensitive resin composition of the present invention includes an oxime-based photoinitiator and a binder resin having a structure represented by Chemical Formula I, which has an effect that the change due to the decomposition of chemical bonds at high temperatures is small and therefore heat-resistant Excellent properties, small change due to decomposition of chemical bonds caused by UV light source, and excellent light resistance.

The present invention will be described in detail below.

The present invention relates to a colored photosensitive resin composition which, when constituting a colored photosensitive resin composition, contains a colorant, a binder resin represented by Chemical Formula I, a photopolymerizable monomer, an oxime-based photoinitiator, and a solvent, and It is excellent in heat resistance and light resistance, and has an excellent effect of suppressing outgassing and excellent dispersibility of particles.

Colorant

In the colorant of the present invention, the colorant can include at least one selected from organic colorants and / or inorganic colorants. Examples of the organic colorant include organic pigments and / or organic dyes. Examples of the inorganic colorant include inorganic pigments and / Or inorganic dyes. These colorants may be in the form of abrasives. The organic pigments and / or organic dyes may be synthetic pigments or natural pigments. These organic pigments can be subjected to rosin treatment, surface treatment using a pigment derivative incorporating an acidic group or a basic group, graft treatment of the surface of the pigment using a polymer compound, etc., if necessary, A micronization treatment using a sulfuric acid micronization method or the like, or a cleaning treatment using an organic solvent, water, or the like to remove impurities. These inorganic pigments may be metal oxides, metal salts, inorganic salts of barium sulfate (physical pigments), and the like. In this case, the layer showing the main target color of these abrasives is the same as the pigment used in the conventional abrasive.

As for the colorant, more specifically, CI Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148 , 150, 153, 154, 166, 173, 180, and 185; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71; CI Pigment Red 9 , 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 208, 215, 216, 224, 242, 254, 255, 264, and 279; CI Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37, and 38; CI Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 16, 21, 28, 60, 64, and 76; CI Pigment Green 7, 10, 15, 25, 36, 47, and 58; CI Pigment Brown 28; CI Pigment Purple 23, 32, and 29; CI Pigment Black 1, 31, 32, and Organic Black BASF's 100CF.

The size of the particles of the colorant may be 3 to 150 nanometers, and it is advantageous to maintain a dispersed state in the liquid in the case of falling within this range. More specifically, the case where the particle size of the organic colorant in the colorant is 20 to 100 nm is preferable. When the organic colorant satisfies this range, it is excellent in terms of dispersion stability. This is because if the size is less than this range, the surface area of the colorant sharply increases, the dispersion stability is poor, and agglomeration between the colorants may occur. If the size exceeds the range, the weight of the colorant increases. Therefore, the dispersion stability is poor, and precipitation easily occurs. The size of the particles of the inorganic colorant in the colorant may be 3 to 20 nm. When the inorganic colorant has a size within this range, it is preferable in terms of excellent dispersibility and increased storage stability.

The coloring agent can contain 5 to 50 parts by weight, and more preferably 10 to 45 parts by weight of the coloring agent, based on the total weight of the solid content in the colored photosensitive resin composition. When it is in this range, it is advantageous in showing coloring, and it is preferable also in the point that a pattern formation is favorable.

Binder resin

In the present invention, the binder resin of the colored photosensitive resin composition can be represented by the following Chemical Formula I. When the binder resin is contained, it has been confirmed that the binder resin exhibits properties effective for dispersing the colorant. Compared with general acrylic adhesives, a colored photosensitive resin composition having high dispersion stability can be produced with a very low usage amount.

In the above Chemical Formula I, R ₃ and R ′ ₃ are each a R _a SR _b substituent, R _a is _a bonding, an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 15 carbon atoms, S Is sulfur, R _b is an alkyl group having 1 to 10 carbon atoms or aryl group having 6 to 15 carbon atoms, and R ₄ is a tetravalent aromatic or cycloaliphatic group having 1 to 20 carbon atoms with or without a hetero atom ( cycloaliphatic) hydrocarbon group, A is a substituent represented by the following chemical formulae I-1 to I-4, n is an integer of 1 to 6, and p is an integer of 1 to 30.

[Chemical Formula I-3]

In the above chemical formulas I-1 to I-4, R ₂ and R ′ ₂ are each hydrogen, hydroxyl (-OH), thiol (-SH), amine (-NH ₂ ), or nitro (-NO ₂ ). Or a halogenated group, X represents O, S, N, Si or Se.

The above-mentioned binder resin may contain 5 to 50 parts by weight based on the total weight of the solid content of the colored photosensitive resin composition. In this range, the colorant exhibits high performance, which is preferable.

Photopolymerizable monomer

The photopolymerizable monomer is a monomer that can be polymerized by using a living radical or the like generated by a photopolymerization initiator by irradiation of light.

Examples of the photopolymerizable monomer include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, and new Pentylene glycol diacrylate, neopentaerythritol acrylate, neopentaerythritol diacrylate, neopentaerythritol triacrylate, dipentaerythritol diacrylate, dinepentaerythritol triacrylate, dixin Pentaerythritol pentaacrylate, dinepentaerythritol hexaacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, novolac epoxy acrylate, ethylene glycol dimethacrylate, Glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, etc. . The photopolymerizable monomers exemplified above can be used individually or in combination of two or more kinds.

The content of the photopolymerizable monomer may be 5 to 30 parts by weight, preferably 10 to 30 parts by weight, based on the total weight of the solid content of the colored photosensitive resin composition of the present invention. Preferably, it may contain 15 to 30 parts by weight. When the content of the photopolymerizable monomer is within this range, pattern characteristics are favorably formed, and therefore, it is preferable.

Oxime photoinitiator

In the present invention, by including an oxime-based photoinitiator, a more stable pattern forming effect can be exhibited.

As the oxime-based photoinitiator, at least one compound selected from the group consisting of an oxime ester compound, a triazine-based compound, an acetophenone-based compound, and a biimidazole-based compound can be specifically used, and more preferably, a compound selected from the following chemical formula At least one of the group consisting of compounds represented by II.

In the above Chemical Formula II, R ¹ , R ² , R ³ , and R ⁴ are each independently hydrogen, C ₁ -C ₂₀ alkyl, OR ¹⁵ , halogen, or NO ₂ ; or R ¹ and R ² , R ^2, and R ³ , R ³ and R ⁴ independently of each other are , Together with the carbon atom to which they are attached, form a six-membered ring; R ¹¹ , R ¹² , R ¹³ , R ¹⁴ are each independently hydrogen, or are unsubstituted or substituted with at least one halogen, phenyl, CN, OH, SH, C ₁ -C ₄ -alkoxy, (CO) OH, or C ₁ -C ₂₀ alkyl substituted with (CO) O (C ₁ -C ₄ alkyl); or R ¹¹ , R ¹² , R ¹³ , R ^{14 is} independently unsubstituted phenyl, or phenyl substituted with at least one C ₁ -C ₆ alkyl, halogen, CN, OR ¹⁵ , or NR ¹⁷ R ¹⁸ ; or R ¹¹ , R ¹² , R ¹³ And R ¹⁴ are each independently halogen, CN, OR ¹⁵ , SR ¹⁶ , SOR ¹⁶ , SO ₂ R ¹⁶ or NR ¹⁷ R ¹⁸ , wherein the substituents OR ¹⁵ , SR ¹⁶ or NR ¹⁷ R ^{18 are} arbitrarily connected to the naphthyl ring One of the carbon atoms together forms a five- or six-membered ring through the groups R ¹⁵ , R ¹⁶ , R ¹⁷ and / or R ¹⁸ ; R ⁵ is unsubstituted or is substituted with at least one halogen, R ¹⁵ , COOR ¹⁵ , OR ¹⁵ , SR ¹⁶ , CONR ¹⁷ R ¹⁸ , NR ¹⁷ R ¹⁸ substituted C ₁ -C ₂₀ alkyl; or R ⁵ is C _{2 with} at least one O, S, SO, SO ₂ , NR ²³ or CO interposed therebetween -C ₂₀ alkyl, either uninserted or at least one O, CO or N C ₂ -C ₁₂ alkenyl with R ²³ interposed therebetween, wherein the C ₂ -C ₂₀ alkyl group inserted and the C ₂ -C ₁₂ alkenyl group not inserted or inserted are unsubstituted or substituted with at least one halogen; Or R ⁵ is a C ₄ -C ₈ cycloalkenyl group, a C ₂ -C ₁₂ alkynyl group, or a C ₃ -C ₁₀ cycloalkyl group not inserted or inserted by at least one O, S, CO, or NR ²³ therebetween; or R ⁵ is phenyl or naphthyl, each of which is unsubstituted or substituted by at least one of OR ¹⁵ , SR ¹⁶ , NR ¹⁷ R ¹⁸ , COR ²² , CN, NO ₂ , halogen, C ₁ -C ₂₀ alkyl, C _1- C ₄ haloalkyl is substituted or substituted with at least one C ₂ -C ₂₀ alkyl with O, S, CO or NR ²³ interposed therebetween, or they are each substituted with C ₃ -C ₁₀ cycloalkyl, or at least one O, S C ₃ -C ₁₀ cycloalkyl substituted with, CO or NR ²⁴ interposed; R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ is hydrogen, phenyl-C ₁ -C ₃ alkyl, unsubstituted or substituted by At least one halogen, OH, SH, CN, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO) O (C ₁ -C ₄ alkyl), O (CO)-(C _1- C ₄ alkyl), O (CO)-(C ₂ -C ₄ ) alkenyl, O (CO) -phenyl, (CO) OH, (CO) O (C ₁ -C ₄ alkyl), C ₃ -C ₂₀ cycloalkyl, SO ₂ - (C ₁ -C ₄ haloalkyl), O (C ₁ -C ₄ haloalkyl) substituted by at least one O or intervening C ₃ -C ₂₀ cycloalkyl substituted C ₁ -C ₂₀ alkyl ; Or R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ is a C ₂ -C ₂₀ alkyl group interposed therebetween by at least one O, S or NR ²⁴ ; or R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ is (CH ₂ CH ₂ O) _{n + 1} H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₁ -C ₈ alkyl, C ₂ -C ₁₂ alkenyl, C ₃ -C ₆ alkenyl, or C ₃ -C ₂₀ cycloalkyl that is not inserted or interposed by at least one O, S, CO, or NR ²³ ; or R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are C ₁ -C ₈ alkyl-C ₃ -C ₁₀ cycloalkyl groups not inserted or at least one O interposed therebetween; or R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ is unsubstituted or substituted by at least one C ₁ -C ₆ alkyl, halogen, OH or C ₁ -C ₃ alkoxy; or R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ Is phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with at least one halogen, OH, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, CN, NO ₂ , phenyl -C ₁ -C ₃ alkoxy group, a phenoxy group C ₁ -C ₁₂ alkylsulfanyl, phenylsulfanyl, N (C ₁ -C ₁₂ alkyl) _2, di-substituted phenyl group; R ¹⁵ is hydrogen, phenyl -C ₁ -C ₃ alkyl Group, unsubstituted or substituted by at least one halogen, OH, SH, CN, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO) O (C ₁ -C ₄ alkyl), O (CO)-(C ₁ -C ₄ alkyl), O (CO)-(C ₂ -C ₄ ) alkenyl, O (CO) -phenyl, (CO) OH, (CO) O (C _1- C ₄ alkyl), C ₃ -C ₂₀ cycloalkyl, SO _2- (C ₁ -C ₄ haloalkyl), O (C ₁ -C ₄ haloalkyl) substituted, or C _{3 with} at least one O interposed therebetween -C ₂₀ cycloalkyl substituted C ₁ -C ₂₀ alkyl; or R ¹⁵ is a C ₂ -C ₂₀ alkyl interposed by at least one O, S or NR ²³ ; or R ¹⁵ is (CH ₂ CH ₂ O ) _{n + 1} H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₁ -C ₈ alkyl, C ₂ -C ₁₂ alkenyl, C ₃ -C ₆ An alkenyl group, or a C ₃ -C ₂₀ cycloalkyl group that is not inserted or inserted by at least one O, S, CO, or NR ²³ ; or R ¹⁵ is C ₁ -that is not inserted or inserted by at least one O C ₈ alkyl -C ₃ -C ₁₀ cycloalkyl; or R ¹⁵ is unsubstituted or substituted with at least one C ₁ -C ₆ alkyl, halogen, OH or C ₁ -C ₃ alkoxy Substituted benzoyl group; or R ¹⁵ is phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with at least one halogen, OH, C ₁ -C ₁₂ -alkyl, C ₁ -C ₁₂ alkoxy, CN, NO ₂ , phenyl-C ₁ -C ₃ alkoxy, phenoxy, C ₁ -C ₁₂ alkylsulfanyl, phenylsulfanyl, N (C _1- C ₁₂ alkyl) ₂ , diphenylamino, or Substitution; R ¹⁶ is hydrogen, C ₂ -C ₁₂ alkenyl, C ₃ -C ₂₀ cycloalkyl, or phenyl-C ₁ -C ₃ alkyl, wherein C ₂ -C ₁₂ alkenyl, C ₃ -C ₂₀ Cycloalkyl or phenyl-C ₁ -C ₃ alkyl is either uninserted or inserted between at least one O, S, CO, NR ²³ or COOR ¹⁵ ; or R ¹⁶ is unsubstituted or substituted by at least one OH, SH, CN, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO) O (C ₁ -C ₄ alkyl), O (CO)-(C ₂ -C ₄ ) alkenyl, O (CO)-(C ₁ -C ₄ alkyl), O (CO) -phenyl, or (CO) OR ¹⁵ substituted C ₁ -C ₂₀ alkyl; or R ¹⁶ is substituted with at least one O, S, C ₂ -C ₂₀ alkyl with CO, NR ²³ or COOR ¹⁵ interposed; or R ¹⁶ is (CH ₂ CH ₂ O) _n H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ (Alkyl), C ₂ -C ₈ alkylfluorenyl, or C ₃ -C ₆ alkenyl; or R ¹⁶ is unsubstituted or substituted with at least one C ₁ -C ₆ alkyl, halogen, OH, C ₁ -C ₄ Alkoxy or C ₁ -C ₄ alkylsulfanyl substituted benzamidine; or R ¹⁶ is phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or is substituted with at least one halogen , C ₁ -C ₁₂ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₁₂ alkoxy, CN , NO ₂ , phenyl-C ₁ -C ₃ alkoxy, phenoxy, C ₁ -C ₁₂ alkylsulfanyl, phenylsulfanyl, N (C ₁ -C ₁₂ alkyl) ₂ , two Phenylamino, (CO) O (C ₁ -C ₈ alkyl), (CO) -C ₁ -C ₈ alkyl, (CO) N (C ₁ -C ₈ alkyl) ₂ or Substitution; R ¹⁷ and R ¹⁸ are each independently hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₄ hydroxyalkyl, C ₂ -C ₁₀ alkoxyalkyl, C ₂ -C ₅ alkenyl, C ₃ -C ₂₀ cycloalkyl, phenyl-C ₁ -C ₃ alkyl, C ₁ -C ₈ alkylfluorenyl, C ₁ -C ₈ alkylfluorenyl, C ₃ -C ₁₂ alkenyl, SO _2- (C ₁ -C ₄ haloalkyl), or benzamidine; or R ¹⁷ and R ¹⁸ are phenyl, naphthyl, or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with at least one halogen, C ₁ -C ₄ haloalkyl, C ₁ -C ₂₀ alkoxy, C ₁ -C ₁₂ alkyl, benzamidine, or C ₁ -C ₁₂ alkoxy; or R ¹⁷ and R ¹⁸ are bonded to them N-atoms together form a five- or six-membered saturated or unsaturated ring that has not been inserted or inserted by O, S, or NR ¹⁵ between them, such five- or six-membered saturated or unsaturated rings are unsubstituted or substituted by at least one C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, = O, OR ¹⁵ , SR ¹⁶ , NR ¹⁹ R ²⁰ , (CO) R ²¹ , NO ₂ , halogen, C ₁ -C ₄ -haloalkyl , CN, phenyl, or substituted with a C ₃ -C ₂₀ cycloalkyl group not inserted or with at least one O, S, CO, or NR ¹⁵ inserted between them; or R ¹⁷ and R ¹⁸ together with the N-atoms to which they are attached form an unsubstituted or substituted by at least one C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₂₀ alkoxy, = O, OR ¹⁵ , SR ¹⁶ , NR ¹⁹ R ²⁰ , (CO) R ²¹ , halogen, NO ₂ , CN, phenyl, or a C ₃ -C ₂₀ cycloalkyl group that has not been inserted or inserted by at least one O, S, CO, or NR ¹⁵ Substituted heteroaromatic ring systems; R ¹⁹ and R ²⁰ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₃ -C ₁₀ cycloalkyl or phenyl; or R ¹⁹ And R ²⁰ together with the N-atoms to which they are attached form a five-membered or six-membered saturated or unsaturated ring which is not inserted or inserted by O, S or NR ²³ , and these five-membered or six-membered saturated or unsaturated rings are not Is fused or benzene ring is fused to these five- or six-membered saturated or unsaturated rings; R ²¹ is hydrogen, OH, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, is not inserted or at least one O, CO or NR ²⁴ inserted therebetween is C ₂ -C ₂₀ alkyl, unsubstituted or substituted with inserted O, S, CO or NR ²⁴ inserted therebetween is C ₃ -C ₂₀ cycloalkyl, or R ²¹ is phenyl , Naphthyl, phenyl-C ₁ -C ₄ alkyl, OR ¹⁵ , SR ¹⁶ or NR ¹⁹ R ²⁰ ; R ²² is a C ₆ -C ₂₀ aryl group or a C ₃ -C ₂₀ heteroaryl group, each of which is unsubstituted or substituted with at least one phenyl group, halogen, C ₁ -C ₄ haloalkyl, CN, NO ₂ OR ¹⁵ , SR ¹⁶ , NR ¹⁷ R ¹⁸ , or C ₁ -C ₂₀ alkyl substituted with at least one O, S or NR ²³ interposed therebetween, or they are each unsubstituted or substituted with at least one halogen, COOR ¹⁵ , CONR ¹⁷ R ¹⁸ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₃ -C ₂₀ heteroaryloxycarbonyl, OR ¹⁵ , SR ¹⁶ , or NR ¹⁷ R ¹⁸ substituted with at least one C ₁ -C ₂₀ alkyl; or R ²² is hydrogen, unsubstituted or substituted with at least one halogen, phenyl, OH, SH, CN, C ₃ -C ₆ alkoxy Group, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO) O (C ₁ -C ₄ alkyl), O (CO)-(C ₁ -C ₄ alkyl), O (CO) -phenyl, ( CO) OH, or (CO) O (C ₁ -C ₄ alkyl) substituted C ₁ -C ₂₀ alkyl; or R ²² is a C ₂ -C ₁₂ alkyl interposed by at least one O, S or NR ²⁴ Or R ²² is (CH ₂ CH ₂ O) _{n + 1} H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₂ -C ₁₂ alkenyl, or C ₃ -C ₈ cycloalkyl; or R ²² SR ¹⁶ is substituted phenyl, wherein the group R ¹⁶ represents a phenyl or naphthyl ring to the carbazole moiety COR ²² group bonded directly linked; n is 1-20; R ²³ is hydrogen, C ₁ - C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₂₀ alkyl interposed by at least one O or CO, or phenyl-C ₁ -C ₄ alkyl, not inserted or at least one C ₃ -C ₈ cycloalkyl with O or CO interposed therebetween, or (CO) R ¹⁷ , or unsubstituted or substituted with at least one C ₁ -C ₂₀ alkyl, halogen, C ₁ -C ₄ haloalkyl, OR ¹⁵ , SR ¹⁶ , NR ¹⁷ R ¹⁸ or Substituted phenyl; R ²⁴ is hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₂₀ alkyl interposed by at least one O or CO, or phenyl-C ₁ -C ₄ alkyl, C ₃ -C ₈ cycloalkyl that is not inserted or inserted by at least one O or CO, or (CO) R ¹⁷ , or is unsubstituted or substituted by at least one C ₁ -C ₂₀ alkane Radical, halogen, C ₁ -C ₄ haloalkyl, OR ¹⁵ , SR ¹⁶ , NR ¹⁷ R ¹⁸ or Substituted phenyl.

The photopolymerization initiator preferably includes a compound in which R ¹ , R ² , R ³ , and R ⁴ are each independently hydrogen, C ₁ -C ₂₀ alkyl, OR ¹⁵ , halogen, or NO ₂ in Chemical Formula I.

The photopolymerization initiator is preferably included in the above chemical formula, R ¹ and R ² , R ² and R ³ , and R ³ and R ⁴ are independent of each other. Compounds that form a six-membered ring with the carbon atom to which they are attached.

The above-mentioned photopolymerization initiator preferably includes a compound in which R ¹ , R ² , R ³ , and R ⁴ are independently hydrogen, C ₁ -C ₂₀ alkyl, OR ¹⁵ , halogen, or NO ₂ in Chemical Formula I; and R ¹ Together with R ² , R ² and R ³ , R ³ and R ⁴ Compounds that form a six-membered ring with the carbon atom to which they are attached.

Examples of the oxime-based photoinitiator include OXE-03 (BASF) and NCI-831 (ADEKA).

Such an oxime-based photopolymerization initiator can be used in an amount of 1 to 20 parts by weight, and preferably 2.5 to 5 parts by weight, based on the total weight of the solid content in the colored photosensitive resin composition. This range is obtained by considering the photopolymerization speed of the photopolymerizable compound and the physical properties of the coating film finally obtained. In this range, it can be polymerized at an appropriate polymerization speed to ensure a better overall process time, and Excessive reactions are suppressed to show excellent physical properties of the coating film.

Furthermore, the coloring photosensitive resin composition of the present invention may further include a photopolymerization initiation aid, and it is preferable to use a compound selected from at least one of an amine-based compound and a carboxylic acid-based compound as the photopolymerization initiation aid.

The above amine-based compound may be, for example, an aliphatic amine compound such as triethanolamine, methyldiethanolamine, and triisopropanolamine; the aromatic amine compound such as 4-dimethylaminomethylbenzoate, 4-dimethyl Ethylaminobenzoate, 4-dimethylaminobenzoate isoamyl, 4-dimethylaminobenzoate-2-ethylhexyl, benzoate-2-dimethylaminoethyl , N, N-dimethyl-p-toluidine, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, etc .; and Among others, an aromatic amine compound is preferred.

The carboxylic acid-based compound may be, for example, aromatic heteroacetic acids, such as phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, and dimethylphenylthioacetic acid. , Methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N -Naphthylglycine and naphthyloxyacetic acid, etc .; and others.

In the case of using these photopolymerization initiators, the photopolymerization initiator is generally used in an amount of 10 mol or less based on 1 mol, and preferably in a range of 0.01 to 5 mol. Within this range, the sensitivity of the black photosensitive resin composition is further improved, and the productivity of a film formed using the composition tends to be improved. Therefore, it is preferable.

Additives

The colored photosensitive resin composition of the present invention may further contain an additive.

In order to improve the adhesion to the substrate, specific examples can include a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryl group, an isocyanate group, or an epoxy group. Specific examples of the silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, and vinyltrimethoxy Silane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. It can be used alone or in combination of two or more.

The silane coupling agent is preferably contained in an amount of 0.001 to 20 parts by weight based on 100 parts by weight of the photosensitive resin composition.

The photosensitive resin composition of the present invention can further contain a surfactant in order to improve the coating properties and the effect of preventing the generation of defects. Examples of the surfactant include BM-1000, BM-1100 (products of BM Chemie), MEGAFAC F142D, F172, F173, F183, F475 (products of Dainippon Ink Chemical Industry Co., Ltd.), FLUORAD FC-135, FC-170C, FC-430, FC-431 (products of Sumitomo 3M Co., Ltd.), SURFLON S-112, S-113, S-131, S-141, S-145 (products of Asahi Glass Co., Ltd.), SH- Surfactants such as 28PA, SH-190, SH-193, SZ-6032, SF-8428 (made by Toray Silicone Co., Ltd.), S-510 (made by Chisso), and these can be used alone Alternatively, two or more of them may be used in combination.

The surfactant is preferably contained in an amount of 0.001 to 20 parts by weight based on 100 parts by weight of the photosensitive resin composition.

Solvent

The solvent contained in the colored photosensitive resin composition of the present invention is not particularly limited, and various organic solvents that have been used in the field of colored photosensitive resin compositions can be used. As specific examples thereof, ethylene glycol monoalkyl ethers may be listed, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and the like Diethylene glycol dialkyl ethers, such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, etc .; ethylene glycol alkyl ethers Acetates, such as ethylene glycol methyl ether acetate, ethylene glycol ether acetate, etc .; alkylene glycol alkyl ether acetates, such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate, etc .; aromatic hydrocarbons, such as benzene, toluene, xylene, mesitylene Benzene, etc .; ketones, such as methyl ethyl ketone, acetone, methylpentyl ketone, methyl isobutyl ketone, cyclohexanone, etc .; alcohols, such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol Alcohols, glycerol, etc .; esters, such as ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, etc .; cyclic esters, such as γ-butyrolactone; and others. Among the above solvents, in terms of coating properties and drying properties, preferably, among these solvents, organic solvents having a boiling point of 100 ° C to 200 ° C are mentioned, and more preferably, alkylene glycols are mentioned. Esters such as alkyl ether acetates, ketones, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and more preferably, propylene glycol monomethyl ether acetate, propylene glycol Monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like. These solvents can be used individually or in mixture of 2 or more types.

The above-mentioned solvent may contain 300 to 500 parts by weight with respect to the colored photosensitive resin composition, and may be added so that the total amount of the colored photosensitive resin composition is 100% by weight. When the solvent is contained in this range, it is preferable to improve the dispersion stability of the composition and the ease of processing (for example, coatability) in the manufacturing process.

In the present invention, the content of the colored photosensitive resin composition is expressed in parts by weight, and it is expressed in parts by weight based on the solid content excluding the solvent.

The above-mentioned photosensitive resin composition is applied on a glass substrate by a suitable method such as spin coating, roll coating, spraying, or the like to a thickness of 0.5 to 10 μm to form a resin composition layer.

Next, the glass substrate on which the resin composition layer is formed is irradiated to form a pattern required for a color filter. As a light source used in irradiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon laser, etc. can be used, and in some cases, UV, electron beam, or X-ray can be used For example, it is possible to irradiate an active ray (for example, UV) in a region of 190 nm to 500 nm, specifically 200 nm to 500 nm. In this irradiation process, a photoresist mask can be used. After the irradiation process is performed, the resin composition layer irradiated with the light source is treated with a developing solution. At this time, a non-exposed portion in the resin composition layer is dissolved to form a colored photosensitive pattern. By repeating this process according to the required number, a desired pattern can be obtained. In addition, by reheating the image pattern obtained through the development in the above-mentioned process and curing it with active ray irradiation or the like, crack resistance, solvent resistance, and the like can be improved.

The following describes preferred embodiments of the present invention. However, the following embodiment is merely a preferred embodiment of the present invention, and the present invention is not limited to the following embodiments.

Examples of preparing compounds having the following structures of Chemical Formula III and Chemical Formula IV using compounds having structures of Chemical Formulas I-1 to I-4 are described below. However, the following manufacturing example is only a preferable manufacturing example of the present invention, and the present invention is not limited to the following manufacturing example.

Synthesis of monomer

Production Example 1-1. Synthesis of Chemical Formula I-1

Step A: After setting a reflux condenser and a thermometer in a three-necked flask, 50.0 g of 9-fluorenone and 200.0 g of phenol were added, and 160 ml of zinc chloride was injected. After 120 mg of hydrogen chloride was added, the temperature was raised to 70 ° C while stirring was started, and the mixture was stirred for 4 hours. (Yellow compound was produced in 97% yield.)

Production Example 1-2. Synthesis of Chemical Formula I-2

Step A: After setting a reflux condenser and a thermometer in a three-necked flask, 50.0 g of benzophenone was added, and 120 ml of hydrogen chloride was injected. After 120 mg of zinc (II) chloride was added, 60.0 g of resorcinol was added, and the temperature was raised to 190 ° C while starting to stir. After confirming that the content of unreacted matter was less than 0.3%, distillation under reduced pressure was performed.

Monomers having a structure of Chemical Formula I-3 to Chemical Formula I-4 can be conventionally manufactured by an academically proposed method.

Production Example 2-1. Production of Chemical Formula III-1 (using Chemical Formula I-1)

2,2 '-((((9H-fluorene-9,9-diyl) bis (4,1-phenylene)) bis (oxy)) bis (methyl)) bis (ethylene oxide) Synthesis

A three-necked flask was equipped with a reflux condenser and a thermometer, 41.3 g of 9,9-bisphenol hydrazone was charged, and 240 ml of 2- (chloromethyl) ethylene oxide was quantified and injected. After 95 mg of tetrabutylammonium bromide was added, the temperature was raised to 95 ° C while stirring was started. After confirming that the content of the unreacted matter was less than 0.2%, distillation under reduced pressure was performed. After the temperature of the produced compound was lowered to 25 ° C, dichloromethane was injected, and NaOH was slowly added. After confirming that the product was 97% or more by a high performance liquid chromatography (HPLC) method, 4% HCl was added dropwise to complete the reaction. After the reaction was extracted and the layers were separated, the organic layer was washed with water until neutral. After the organic layer was dried with MgSO ₄ , it was distilled under reduced pressure using a rotary evaporator and concentrated. Dichloromethane was added to the concentrated product, and the temperature was increased to 43 ° C while stirring. After adding methanol, the temperature of the solution was lowered and stirred. The resulting solid was filtered and dried under vacuum at normal temperature to obtain 53.1 g of a white solid powder (yield: 95%).

Production Example 2-2. Production of Chemical Formula III-2 (Use of Chemical Formula I-2)

Except replacing 9,9-bisphenol hydrazone with spiro [9H-fluorene-9,9 '-[9H] dibenzopiperan] -3', 6'-diol, the same procedure as in Production Example 3- 1 The same method was used to produce Chemical Formula III-2.

Production Example 2-3. Production of Chemical Formula III-3 (Use of Chemical Formula I-3)

A chemical formula III-2 was produced in the same manner as in Production Example 3-1, except that 9,9-bisphenol hydrazone was replaced with 9,9-diphenyldibenzopiperan-3,6-diol.

Production Example 2-4. Production of Chemical Formula III-4 (Use of Chemical Formula I-4)

A chemical formula III-2 was produced in the same manner as in Production Example 3-1 except that 9,9-bisphenol hydrazone was replaced by 9,9'-spirobis [茀].

Production Example 3-1. Production of Chemical Formula IV-1

3,3 '-(((9H-fluorene-9,9-diyl) bis (4,1-phenylene)) bis (oxy) bis (1- (phenylthio) propan-2-ol) Synthetic

After setting a reflux condenser and a thermometer in a three-necked flask, the reaction product (500 g) of Chemical Formula III-1, 1270 g of thiophenol, and 320 g of ethanol were charged and stirred. 170 g of triethylamine was slowly added to the reaction solution. After confirming the absence of the starting material by a high performance liquid chromatography (HPLC) method, the reaction was terminated. After completion of the reaction, ethanol was distilled off under reduced pressure. After the organic matter was dissolved in dichloromethane and washed with water, the dichloromethane was removed by distillation under reduced pressure. After the concentrated organic matter was dissolved in ethyl acetate, an ether solvent was added dropwise and the mixture was stirred for 30 minutes. The compound was distilled under reduced pressure to obtain 498 g of a pale yellow oil (yield: 65%).

Production Example 3-2. Production of Chemical Formula IV-2

A chemical formula IV-2 was produced in the same manner as in Production Example 4-1 except that the reactant of Chemical formula III-1 was replaced with the reactant of Chemical formula III-2.

Production Example 3-3. Production of Chemical Formula IV-3

A chemical formula IV-3 was produced in the same manner as in Production Example 4-1, except that the reactant of Chemical formula III-1 was replaced with the reactant of Chemical formula III-3.

Production Example 3-4. Production of Chemical Formula IV-4

A chemical formula IV-4 was produced in the same manner as in Production Example 4-1, except that the reactant of Chemical formula III-1 was replaced with a reactant of Chemical formula III-4.

Manufacture of binder resin

Production Example 4-1. Production of Binder Resin of Chemical Formula V-1

After setting a reflux condenser and a thermometer in a three-necked flask, 200 g of the IV-1 compound dissolved in 50% PGMEA solvent was added, and the temperature was raised to 120 ° C. After 32.0 g of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride was added dropwise, the mixture was stirred while maintaining the temperature for 4 hours. After adding 8 g of phthalic anhydride and stirring for 2 hours, the reaction was completed. After cooling, a binder solution having a weight average molecular weight of 3,800 g / mol was obtained.

Production Example 4-2. Production of Binder Resin of Chemical Formula V-2

After setting a reflux condenser and a thermometer in a three-necked flask, 200 g of a compound of IV-2 dissolved in a 50% PGMEA solvent was added, and the temperature was raised to 120 ° C. After 33.0 g of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride was added dropwise, the mixture was stirred while maintaining the temperature for 4 hours. After putting 8 g of phthalic anhydride and further stirring for 2 hours, the reaction was completed. After cooling, a binder solution having a weight average molecular weight of 4,300 g / mol was obtained.

Production Example 4-3. Production of Binder Resin of Chemical Formula V-3

After setting a reflux condenser and a thermometer in a three-necked flask, 200 g of the IV-3 compound dissolved in 50% PGMEA solvent was added, and the temperature was raised to 120 ° C. After 33.0 g of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride was added dropwise, the mixture was stirred while maintaining the temperature for 4 hours. After adding 8 g of phthalic anhydride and stirring for 2 hours, the reaction was completed. After cooling, a binder solution having a weight average molecular weight of 4,400 g / mole was obtained.

Production Example 4-4. Production of Binder Resin of Chemical Formula V-4

After setting a reflux condenser and a thermometer in a three-necked flask, 200 g of the IV-4 compound dissolved in 50% PGMEA solvent was added, and the temperature was raised to 120 ° C. After 33.0 g of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride was added dropwise, the mixture was stirred while maintaining the temperature for 4 hours. After adding 8 g of phthalic anhydride and stirring for 2 hours, the reaction was completed. After cooling, a binder solution having a weight average molecular weight of 4,100 g / mol was obtained.

Production Example 4-5. Production of Binder Resin of Chemical Formula V-1-A

After setting a reflux condenser and a thermometer in a three-necked flask, 200 g of the IV-1 compound dissolved in 50% PGMEA solvent was added, and the temperature was raised to 120 ° C. After 28.0 g of 3,3 ', 4,4'-pyrellitic dianhydride was added dropwise, the mixture was stirred while maintaining the temperature for 4 hours. After adding 8 g of phthalic anhydride and stirring for 2 hours, the reaction was completed. After cooling, a binder solution having a weight average molecular weight of 4,400 g / mole was obtained.

Production Example 4-6. Production of Cardo A Binder Resin

The reactor was charged with 9,9'-bis (4-glycidyloxyphenyl) hydrazone (Hear chem) 138 g, acrylic acid 54 g, benzyltriethylammonium chloride (Oai Chemical Gold Co., Ltd.) 1.4 G, triphenylphosphine (Aldrich) 1 g, propylene glycol methyl ether acetate (Daicel Chemical) 128 g, and hydroquinone 0.5 g. After heating to 120 ° C, After maintaining for 12 hours, add 2 grams of tetrahydrophthalic anhydride, 20 grams of biphenyltetracarboxylic dianhydride, 130 grams of propylene glycol methyl ether acetate, and 0.03 grams of N, N'-tetramethylammonium chloride. This was maintained for 10 hours, and a carbazole-based adhesive resin having a weight average molecular weight of 4,500 g / mole was produced.

Production Example 4-7. Production of carbazole B binder resin

The reactor was charged with 9,9'-bis (4-glycidyloxyphenyl) hydrazone (Hear chem) 138 g, acrylic acid 54 g, benzyltriethylammonium chloride (Oai Chemical Gold Co., Ltd.) 1.4 G, 1 g of triphenylphosphine (Oric), 128 g of propylene glycol methyl ether acetate (Dacel), and 0.5 g of hydroquinone. After warming to 120 ° C and maintaining for 12 hours, add four 2 g of hydrogen phthalic anhydride, 30 g of biphenyltetracarboxylic dianhydride, 130 g of propylene glycol methyl ether acetate, 0.03 g of N, N'-tetramethylammonium chloride, maintained for 10 hours, and produced weight A carbazole-based adhesive resin having an average molecular weight of 7,000 g / mole.

Examples

The coloring photosensitive resin composition was produced using the adhesives of V-1 to V-4 and the adhesive of V-1-A produced by the method described above, with the composition shown in Table 1 below. In Table 1 below, the solvent is propylene glycol monomethyl ether acetate alone, and the amount of the solvent is 400 parts by weight based on the resin composition.

Examples 1 to 5 and Comparative Examples 1 to 4

Colorant:

G58 (C.I. Pigment Green 58; DIC's FASTOGEN® Green A110)

R254 (C.I.Pigment Red 254; Hangzhou Abe Chemical)

OBP (organic black pigment; 100cf from BASF)

Photopolymerizable monomer: dineopentaerythritol hexaacrylate (DPHA; Nippon Kayaku Co., Ltd.)

Adhesive resin: adhesives of V-1 to V-4 and adhesives of V-1-A in Production Examples 4-1 to 4-5 and carbazole A adhesive of Production Example 4-6 and Production Example 4- Carbole B binder of 7

Oxime-based photoinitiators: OXE-03 (BASF), NCI-831 (Edico Fine Chemicals (ADEKA))

Non-oxime-based photoinitiator: Irgacure® 369 (BASF)

Solvent: propylene glycol monomethyl ether acetate (PGMEA)

Additive: F475 from DIC / S-510 from Chisso

Experimental example

Production of test strips

Using a coating apparatus (Opticoat MS-A150; Mikasa), each of the photosensitive resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 4 was applied at a rpm showing a fixed thickness. After the cloth, a 90-degree hot-plate was used for preheating for 1 minute to 10 minutes to form a coating film.

Then, after inserting the mask for pattern formation into the above coating film, an exposure device (HB-50110AA; Ushio) was used under an exposure condition of 500 mJ / cm2 (sensing by 365 nm) Device) and pattern exposure while irradiating UV. After the exposure, unnecessary portions were dissolved and removed with an alkaline aqueous solution, and only the exposed portions were left to form a pattern, and heat-cured in a convection oven at a temperature of 220 ° C. for 30 minutes to complete the production of a test piece.

The dispersion stability of the coloring agent of the colored photosensitive resin composition was analyzed, and the heat resistance and light resistance of the formed pattern were evaluated. Comparative Example The colored photosensitive resin composition was produced and evaluated based on the above-mentioned Production Examples A to B using a carbazole A to carbazole B binder.

Heat resistance evaluation

The substrate produced by the above method was left at 230 ° C for 60 minutes, and the heat resistance color change was confirmed. The evaluation criteria are shown in Table 2 below, and the evaluation results are shown in Table 3 below.

2. Evaluation of light resistance

The substrate manufactured by the above method was left under a high pressure mercury lamp of 30 milliwatts for 240 hours, and the light resistance and color change were confirmed. The evaluation criteria are shown in Table 2 below, and the evaluation results are shown in Table 3 below.

3. Dispersion evaluation

Using a ball mill disperser, a dispersant was added at 10% compared to the particles, and the manufacturing characteristics were judged by the time it took to manufacture the dispersion solution. The evaluation criteria are shown in Table 2 below, and the evaluation results are shown in Table 3 below.

4. Evaluation of dispersion stability

The dispersion stability was evaluated based on the placement of the dispersed dispersion solution, and the time taken to disrupt the dispersion stability of the upper 5% by the placement of the dispersion solution was measured. The evaluation criteria are shown in Table 2 below, and the evaluation results are shown in Table 3 below.

5. Outgassing evaluation

From the test piece manufactured above, a test piece having an area of 9 cm 2 was manufactured, and by analyzing a gas chromatography mass spectrometer (GC-ms) and calculating a total amount of detected substances, outgassing generated at 230 ° C. for 30 minutes was judged . The evaluation criteria are shown in Table 2 below, and the evaluation results are shown in Table 3 below.

It was confirmed that Examples 1 to 5 containing the binder resin and the oxime-based photoinitiator represented by the structure of Chemical Formula I of the present invention showed excellent heat resistance color change, light resistance color change, dispersibility, and dispersion stability. On the other hand, Comparative Examples 1 to 4 containing no binder resin represented by the structure of Chemical Formula I were confirmed. In the dispersibility evaluation and the dispersion stability evaluation, the dispersibility of the colored photosensitive resin composition was low. The heat-resistant color and light-resistant color of the produced coating film changed drastically. Furthermore, it was confirmed that the results of Comparative Examples 3 and 4 which did not contain the binder resin and the oxime-based photoinitiator represented by the structure of Chemical Formula I for outgassing were further reduced.

Claims (11)

A colored photosensitive resin composition comprising, based on the total solid content of the colored photosensitive resin composition, 5 to 50 parts by weight of a coloring agent, and 5 to 50 parts by weight of a binder resin represented by Chemical Formula I, 5 to 30 parts by weight of a photopolymerizable monomer, 1 to 20 parts by weight of an oxime-based photoinitiator, and the balance as a solvent so that the total amount of the colored photosensitive resin composition is 100% by weight, of which, In the aforementioned Chemical Formula I, R ₃ and R ′ ₃ are each a R _a SR _b substituent, wherein R _a is _a bonding, an alkylene group having 1 to 10 carbon atoms, or an arylene group having 6 to 15 carbon atoms, S is sulfur, R _b is an alkyl group having 1 to 10 carbon atoms or aryl group having 6 to 15 carbon atoms, and R ₄ is a tetravalent aromatic or alicyclic carbon group having 1 to 20 carbon atoms with or without a hetero atom ( cycloaliphatic) hydrocarbon group, A is a substituent represented by the following chemical formulae I-1 to I-4, n is an integer of 1 to 6, and p is an integer of 1 to 30: [Chemical Formula I-4] In the aforementioned chemical formulas I-1 to I-4, R ₂ and R ′ ₂ are each hydrogen, hydroxyl (-OH), thiol (-SH), amine (-NH ₂ ), or nitro (-NO ₂ ). Or a halogenated group, X represents O, S, N, Si or Se. The coloring photosensitive resin composition according to claim 1, wherein the oxime-based photoinitiator is at least one selected from the group consisting of an oxime ester compound, a triazine-based compound, an acetophenone-based compound, and a biimidazole-based compound. The coloring photosensitive resin composition according to claim 1, wherein the oxime-based photoinitiator is at least one selected from the group represented by Chemical Formula II: In the aforementioned chemical formula II, R ¹ , R ² , R ³ , and R ⁴ are each independently hydrogen, C ₁ -C ₂₀ alkyl, OR ¹⁵ , halogen, or NO ₂ ; or R ¹ and R ² , R ^2, and R ³ , R ³ and R ⁴ independently of each other are , Together with the carbon atom to which they are attached, form a six-membered ring; R ¹¹ , R ¹² , R ¹³ , R ¹⁴ are each independently hydrogen, or are unsubstituted or substituted by at least one halogen, phenyl, CN, OH, SH, C _1- C ₄ -alkoxy, (CO) OH, or C ₁ -C ₂₀ alkyl substituted with (CO) O (C ₁ -C ₄ alkyl); or R ¹¹ , R ¹² , R ¹³ , R ^{14 is} independently unsubstituted phenyl, or substituted with at least one C ₁ -C ₆ alkyl, halogen, CN, OR ¹⁵ or phenyl substituted with NR ¹⁷ R ¹⁸ ; or R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently halogen, CN, OR ¹⁵ , SR ¹⁶ , SOR ¹⁶ , SO ₂ R ¹⁶ or NR ¹⁷ R ¹⁸ , wherein the substituents OR ¹⁵ , SR ¹⁶ or NR ¹⁷ R ^{18 are} arbitrarily selected from naphthalene One of the carbon atoms of the ring together forms a five- or six-membered ring through the groups R ¹⁵ , R ¹⁶ , R ¹⁷ and / or R ¹⁸ ; R ⁵ is unsubstituted or is substituted by at least one halogen, R ¹⁵ , COOR ¹⁵ OR ¹⁵ , SR ¹⁶ , CONR ¹⁷ R ¹⁸ , NR ¹⁷ R ¹⁸ substituted C ₁ -C ₂₀ alkyl; or R ⁵ is C with at least one O, S, SO, SO ₂ , NR ²³ or CO interposed therebetween ₂ -C ₂₀ alkyl group, or is not inserted at least one O or CO or NR ²³ interposed therebetween C ₂ -C ₁₂ alkenyl, wherein the inserted C ₂ -C ₂₀ alkyl group, and is not inserted or the inserted C ₂ -C ₁₂ alkenyl group is unsubstituted or substituted with at least one Halogen substituted; or R ⁵ is C ₄ -C ₈ cycloalkenyl, C ₂ -C ₁₂ alkynyl, or C ₃ -C ₁₀ ring which is not inserted or inserted by at least one O, S, CO or NR ²³ Alkyl; or R ⁵ is phenyl or naphthyl, each of which is unsubstituted or substituted by at least one OR ¹⁵ , SR ¹⁶ , NR ¹⁷ R ¹⁸ , COR ²² , CN, NO ₂ , halogen, C ₁ -C ₂₀ alkyl , C ₁ -C ₄ haloalkyl, or C ₂ -C ₂₀ alkyl with at least one O, S, CO or NR ²³ interposed therebetween, or they are each independently C ₃ -C ₁₀ cycloalkyl, or at least A C ₃ -C ₁₀ cycloalkyl substitution with one O, S, CO or NR ²⁴ interposed therebetween; R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ are hydrogen, phenyl-C ₁ -C ₃ alkyl, Unsubstituted or substituted with at least one halogen, OH, SH, CN, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO) O (C ₁ -C ₄ alkyl), O (CO )-(C ₁ -C ₄ alkyl), O (CO)-(C ₂ -C ₄ ) alkenyl, O (CO) -phenyl, (CO) OH, (CO) O (C ₁ -C ₄ Alkyl), C ₃ -C _{2 0 cycloalkyl, SO 2 - (C 1 -C} 4 haloalkyl), O (C ₁ -C ₄ haloalkyl) substituted by at least one O or intervening C ₃ -C ₂₀ cycloalkyl substituted C ₁ -C ₂₀ alkyl; or R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ is a C ₂ -C ₂₀ alkyl interposed between at least one O, S, or NR ²⁴ ; or R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are (CH ₂ CH ₂ O) _{n + 1} H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₁ -C ₈ alkyl , C ₂ -C ₁₂ alkenyl, C ₃ -C ₆ alkenyl, or a C ₃ -C ₂₀ cycloalkyl group that has not been inserted or inserted by at least one O, S, CO or NR ²³ ; or R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ are C ₁ -C ₈ alkyl-C ₃ -C ₁₀ cycloalkyl groups which are not inserted or at least one O interposed therebetween; or R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ are unsubstituted or substituted by at least one C ₁ -C ₆ alkyl, halogen, OH or C ₁ -C ₃ alkoxy; or R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with at least one halogen, OH, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy , CN, NO _2, phenyl -C ₁ -C ₃ alkoxy Phenoxy, C ₁ -C ₁₂ alkylsulfanyl, phenylsulfanyl, N (C ₁ -C ₁₂ alkyl) _2, di-substituted phenyl group; R ¹⁵ is hydrogen, phenyl -C ₁ -C ₃ alkyl, unsubstituted or substituted by at least one halogen, OH, SH, CN, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO) O (C ₁ -C ₄ alkane Base), O (CO)-(C ₁ -C ₄ alkyl), O (CO)-(C ₂ -C ₄ ) alkenyl, O (CO) -phenyl, (CO) OH, (CO) O (C ₁ -C ₄ alkyl), C ₃ -C ₂₀ cycloalkyl, SO _2- (C ₁ -C ₄ haloalkyl), O (C ₁ -C ₄ haloalkyl) substituted, or inserted by at least one O A C ₁ -C ₂₀ alkyl group substituted with a C ₃ -C ₂₀ cycloalkyl group therebetween; or R ¹⁵ is a C ₂ -C ₂₀ alkyl group inserted therebetween by at least one O, S or NR ²³ ; or R ¹⁵ is (CH ₂ CH ₂ O) _{n + 1} H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₁ -C ₈ alkyl, C ₂ -C ₁₂ alkenyl, C ₃ -C ₆ alkenyl, or C ₃ -C ₂₀ cycloalkyl that is not inserted or inserted by at least one O, S, CO or NR ²³ ; or R ¹⁵ is not inserted or inserted by at least one O C ₁ -C ₈ alkyl-C ₃ -C ₁₀ cycloalkyl in between; or R ¹⁵ is unsubstituted or substituted by at least one C ₁ -C ₆ alkyl, halogen, OH Or C ₁ -C ₃ alkoxy substituted benzamidine; or R ¹⁵ is phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with at least one halogen, OH, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, CN, NO ₂ , phenyl-C ₁ -C ₃ alkoxy, phenoxy, C ₁ -C ₁₂ alkylsulfanyl, phenylsulfur Alkyl, N (C ₁ -C ₁₂ alkyl) ₂ , diphenylamino or Substitution; R ¹⁶ is hydrogen, C ₂ -C ₁₂ alkenyl, C ₃ -C ₂₀ cycloalkyl or phenyl-C ₁ -C ₃ alkyl, wherein C ₂ -C ₁₂ alkenyl, C ₃ -C ₂₀ Cycloalkyl or phenyl-C ₁ -C ₃ alkyl is not inserted or inserted between at least one O, S, CO, NR ²³ or COOR ¹⁵ ; or R ¹⁶ is unsubstituted or substituted by at least one OH, SH, CN , C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO) O (C ₁ -C ₄ alkyl), O (CO)-(C ₂ -C ₄ ) alkenyl, O (CO)-(C ₁ -C ₄ alkyl), O (CO) -phenyl, or (CO) OR ¹⁵ substituted C ₁ -C ₂₀ alkyl; or R ¹⁶ is substituted with at least one O, S, CO, C ₂ -C ₂₀ alkyl with NR ²³ or COOR ¹⁵ inserted between them; or R ¹⁶ is (CH ₂ CH ₂ O) _n H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl ), C ₂ -C ₈ alkylfluorenyl or C ₃ -C ₆ alkenyl; or R ¹⁶ is unsubstituted or substituted by at least one C ₁ -C ₆ alkyl, halogen, OH, C ₁ -C ₄ alkoxy Or C ₁ -C ₄ alkylsulfanyl-substituted benzamidine; or R ¹⁶ is phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with at least one halogen, C ₁ -C ₁₂ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₁₂ alkoxy, CN, NO ₂ , phenyl-C ₁ -C ₃ alkoxy, phenoxy, C ₁ -C ₁₂ alkylsulfanyl, phenylsulfanyl, N (C ₁ -C ₁₂ alkyl) ₂ , diphenylamino, (CO) O (C _1- C ₈ alkyl), (CO) -C ₁ -C ₈ alkyl, (CO) N (C ₁ -C ₈ alkyl) ₂ or Substitution; R ¹⁷ and R ¹⁸ are each independently hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₄ hydroxyalkyl, C ₂ -C ₁₀ alkoxyalkyl, C ₂ -C ₅ alkenyl, C ₃ -C ₂₀ cycloalkyl, phenyl-C ₁ -C ₃ alkyl, C ₁ -C ₈ alkylfluorenyl, C ₁ -C ₈ alkylfluorenyl, C ₃ -C ₁₂ alkenyl, SO _2- (C ₁ -C ₄ haloalkyl) or benzamidine; or R ¹⁷ and R ¹⁸ are phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted by at least one halogen, C ₁ -C ₄ haloalkyl, C ₁ -C ₂₀ alkoxy, C ₁ -C ₁₂ alkyl, benzamidine or C ₁ -C ₁₂ alkoxy; or R ¹⁷ and R ¹⁸ and the N to which they are attached -The atoms together form a five- or six-membered saturated or unsaturated ring that is not inserted or inserted by O, S, or NR ¹⁵ between which the 5- or 6-membered saturated or unsaturated ring is unsubstituted or is substituted by at least one C _1- C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, = O, OR ¹⁵ , SR ¹⁶ , NR ¹⁹ R ²⁰ , (CO) R ²¹ , NO ₂ , halogen, C ₁ -C ₄ -haloalkyl, CN, Phenyl substituted or substituted with a C ₃ -C ₂₀ cycloalkyl group that is not inserted or with at least one O, S, CO, or NR ¹⁵ interposed therebetween; or R ¹⁷ and R ¹⁸ are bonded to them N-atoms together form an unsubstituted or substituted by at least one C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₂₀ alkoxy, = O, OR ¹⁵ , SR ¹⁶ , NR ¹⁹ R ²⁰ , (CO) R ²¹ , halogen, NO ₂ , CN, phenyl, or a heteroaromatic ring substituted with a C ₃ -C ₂₀ cycloalkyl group that is not inserted or at least one O, S, CO, or NR ¹⁵ interposed therebetween. R ¹⁹ and R ²⁰ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₃ -C ₁₀ cycloalkyl or phenyl; or R ¹⁹ and R ²⁰ The linked N-atoms together form a five- or six-membered saturated or unsaturated ring that has not been inserted or inserted by O, S, or NR ²³ , and the five- or six-membered saturated or unsaturated ring has not been fused or made benzene A ring is fused to the five- or six-membered saturated or unsaturated ring; R ²¹ is hydrogen, OH, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, is not inserted or is at least one O, CO or NR ²⁴ inserted therebetween is C ₂ -C ₂₀ alkyl, unsubstituted or substituted with inserted O, S, CO or NR ²⁴ inserted therebetween is C ₃ -C ₂₀ cycloalkyl, or R ²¹ is phenyl, naphthyl, phenyl -C ₁ -C ₄ alkyl, OR ¹⁵ , SR ¹⁶ or NR ¹⁹ R ²⁰ ; R ²² is C ₆ -C _{2 0} aryl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted by at least one phenyl, halogen, C ₁ -C ₄ haloalkyl, CN, NO ₂ , OR ¹⁵ , SR ¹⁶ , NR ¹⁷ R ¹⁸ , Or substituted with at least one C ₁ -C ₂₀ alkyl group with O, S or NR ²³ interposed therebetween, or they are each unsubstituted or substituted with at least one halogen, COOR ¹⁵ , CONR ¹⁷ R ¹⁸ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₃ -C ₂₀ heteroaryloxycarbonyl, OR ¹⁵ , SR ¹⁶ or NR ¹⁷ R ¹⁸ substituted at least one C _1- C ₂₀ alkyl substituted; or R ²² is hydrogen, unsubstituted or substituted with at least one halogen, phenyl, OH, SH, CN, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO) O (C ₁ -C ₄ alkyl), O (CO)-(C ₁ -C ₄ alkyl), O (CO) -phenyl, (CO) OH or (CO) O (C _1- C ₄ alkyl) substituted C ₁ -C ₂₀ alkyl; or R ²² is C ₂ -C ₁₂ alkyl interposed by at least one O, S or NR ²⁴ ; or R ²² is (CH ₂ CH ₂ O) _{n + 1} H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₂ -C ₁₂ alkenyl, or C ₃ -C ₈ cycloalkyl; or R ²² is SR ¹⁶ substituted phenyl, wherein the group R ¹⁶ in table For the phenyl or naphthyl ring carbazole moiety COR ²² group are linked directly bonded; n-is 1 to 20; R ²³ is hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, or C ₂ -C ₂₀ alkyl group inserted between at least one O or CO, or phenyl-C ₁ -C ₄ alkyl group, C ₃ -C ₈ cycloalkane that is not inserted or interposed between at least one O or CO Is either (CO) R ¹⁷ or is unsubstituted or substituted by at least one C ₁ -C ₂₀ alkyl, halogen, C ₁ -C ₄ haloalkyl, OR ¹⁵ , SR ¹⁶ , NR ¹⁷ R ¹⁸ or Substituted phenyl; R ²⁴ is hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, or C ₂ -C ₂₀ alkyl interposed by at least one O or CO, or phenyl-C _1- C ₄ alkyl, C ₃ -C ₈ cycloalkyl that is not inserted or inserted by at least one O or CO, or is (CO) R ¹⁷ , or is unsubstituted or substituted by at least one C ₁ -C ₂₀ Alkyl, halogen, C ₁ -C ₄ haloalkyl, OR ¹⁵ , SR ¹⁶ , NR ¹⁷ R ¹⁸ or Substituted phenyl. The coloring photosensitive resin composition according to claim 1, wherein the colorant is selected from the group consisting of CI Pigment Yellow, CI Pigment Orange, CI Pigment Red, CI Pigment Purple, CI Pigment Blue, CI Pigment Green, CI Pigment Brown, CI Pigment Violet and CI Pigment Black At least one. The colored photosensitive resin composition according to claim 1, wherein the size of the particles of the colorant is 3 to 150 nm. The colored photosensitive resin composition according to claim 1, wherein the colorant contains at least one of an organic colorant and an inorganic colorant. The colored photosensitive resin composition according to claim 6, wherein the size of the particles of the organic colorant is 20 nm to 100 nm. The colored photosensitive resin composition according to claim 6, wherein the size of the particles of the inorganic colorant is 3 nm to 20 nm. The colored photosensitive resin composition according to claim 1, wherein the colored photosensitive resin composition further contains an additive. A color filter comprising the colored photosensitive resin composition according to any one of claims 1 to 9. A display device includes the color filter according to claim 10.