KR20190125792A - A method for preparing pigment dispersion composition, the pigment dispersion composition prepared by the same, a colored photo sensitive resin composition comprising the pigment dispersion composition, a color filter comprising the colored photo sensitive resin composition, and a display devide comprising the color filter - Google Patents

Abstract

The present invention relates to a pigment dispersion composition manufacturing method and a pigment dispersion composition manufactured by the method. The pigment dispersion composition manufacturing method of the present invention includes: a step of producing a varnish by mixing a dispersant, a dispersion resin, and a dispersion solvent; a step of adding a pigment to the varnish to manufacture pigment dispersion solution; a step of manufacturing low viscosity pigment dispersion solution by dispersing the pigment dispersion solution at a linear speed of 6 to 11 m/s at 40 to 80°C for 10 to 24 hours; and a step of filtering the low viscosity pigment dispersion solution and producing a pigment dispersion composition. The viscosity of the pigment dispersion composition is 3 to 5 mPa·s. The present invention also provides a colored photosensitive resin composition including the pigment dispersion composition, a color filter manufactured by using the colored photosensitive resin composition, and a display device including the color filter. The pigment dispersion composition of the present invention has a low viscosity, excellent dispersion stability, and small change over time.

Description

A method for producing a pigment dispersion composition, a pigment dispersion composition prepared according to this, a colored photosensitive resin composition including the pigment dispersion composition, a color filter manufactured using the colored photosensitive resin composition, and a display device including the color filter { A METHOD FOR PREPARING PIGMENT DISPERSION COMPOSITION, THE PIGMENT DISPERSION COMPOSITION PREPARED BY THE SAME, A COLORED PHOTO SENSITIVE RESIN COMPOSITION COMPRISING THE PIGMENT DISPERSION COMPOSITION, A COLOR FILTER COMPRISING THE COLORED PHOTO SENSITIVE RESIN COMPOSITION V

The present invention provides a method for preparing a pigment dispersion composition, a pigment dispersion composition prepared according to the present invention, a colored photosensitive resin composition comprising the pigment dispersion composition, a color filter prepared using the colored photosensitive resin composition, and the color filter. It relates to a display device.

The color filter is widely used in various display devices such as an image pickup device and a liquid crystal display (LCD), and its application range is rapidly expanding. The color filter used in the image pickup device, the liquid crystal display, or the like may be formed of a coloring pattern of three colors of red, green, and blue, or may include yellow, magenta, and cyan ( It consists of a coloring pattern of three colors of cyan).

The color pattern of each said color filter is generally formed using the coloring photosensitive resin composition containing the coloring agent, such as a pigment or dye, alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent. The coloring pattern process using the said coloring photosensitive resin composition is normally performed by the lithographic process.

Colored photosensitive resin is an essential material, such as a color filter, a liquid crystal display material, an organic light emitting element, a display. For example, in the color filter of a color liquid crystal display, a light shielding layer using a black photosensitive composition is formed at the boundary between the colored layers in order to increase the contrast and color development effects of red, green, and blue. In addition, recently, as well as the role of the black matrix is located on the array substrate to form a cell gap retention spacer is required to be able to play a variety of roles at once. Accordingly, not only an optical effect for basic light shielding but also a good elastic modulus and reliable characteristics are required.

Korean Patent Laid-Open No. 10-2014-0101311 discloses a technique for improving the dispersion stability of a pigment dispersion, and improving the characteristics of a display such as a black matrix made of a photosensitive resin composition comprising the same, a liquid crystal panel including a color filter, and the like. Korean Patent Laid-Open Publication No. 10-2017-0098337 discloses a photosensitive resin composition that is excellent in light shielding properties, excellent in dispersibility and plate making properties, and exhibits a sufficiently low relative dielectric constant.

Republic of Korea Patent Publication No. 10-2014-0101311 Republic of Korea Patent Publication No. 10-2017-0098337

An object of the present invention is to provide a method for preparing a pigment dispersion composition having a low viscosity, excellent dispersion stability, and small change over time, and a pigment dispersion composition prepared accordingly.

Moreover, an object of this invention is to provide the coloring photosensitive resin composition containing the said pigment dispersion liquid composition.

In addition, another object of the present invention is to provide a color filter including a color pattern manufactured using the colored photosensitive resin composition and a display device including the color filter.

In order to achieve the above object, the present invention comprises the steps of preparing a varnish (varnish) by mixing a dispersant, a dispersion resin and a dispersion solvent; Adding a pigment to the varnish to prepare a pigment dispersion; Preparing a low viscosity pigment dispersion by dispersing the pigment dispersion at a linear speed of 6 to 11 m / s at 40 to 80 ° C. for 10 to 24 hours; And preparing a pigment dispersion composition by filtering the low viscosity pigment dispersion, wherein the viscosity of the pigment dispersion composition is 3 to 5 mPa · s.

The present invention also provides a pigment dispersion composition prepared according to the method for producing the pigment dispersion composition.

Moreover, this invention provides the coloring photosensitive resin composition containing the said pigment dispersion liquid composition, alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent.

In addition, the present invention provides a color filter comprising a coloring pattern made of the coloring photosensitive resin composition.

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

The pigment dispersion composition prepared according to the method for preparing the pigment dispersion composition of the present invention is mildly dispersed and has a low viscosity of 3 to 5 mPa · s. Thus, the dispersion stability is excellent and the aging change is small. In addition, it is easy to form a pattern step due to excellent NMP elution characteristics, surface defects caused by high-speed coating or VCD process is reduced, and the process time is reduced, thereby improving productivity.

In addition, the colored pattern prepared using the colored photosensitive resin composition comprising the pigment dispersion composition is very excellent in optical density (OD), optical properties, flatness (DOP), reliability, elastic recovery rate, VCD stains and surface defects The color filter including the color pattern and the display device including the color filter can be reduced to provide an effect of improving optical characteristics, reliability, and elastic recovery rate.

1 is a view showing a criterion for evaluating VCD surface staining in the present invention.

The method for preparing a pigment dispersion composition according to the present invention provides a mild dispersion-treated pigment dispersion composition, specifically, preparing a varnish by mixing a dispersant, a dispersion resin, and a dispersion solvent; Adding a pigment to the varnish to prepare a pigment dispersion; Preparing a low viscosity pigment dispersion by dispersing the pigment dispersion at a linear speed of 6 to 11 m / s at 40 to 80 ° C. for 10 to 24 hours; And filtering the low viscosity pigment dispersion to produce a low viscosity pigment dispersion composition, wherein the viscosity of the pigment dispersion composition is 3 to 5 mPa · s to provide the pigment dispersion composition.

The method for producing a pigment dispersion composition according to the present invention can provide a pigment dispersion composition having a high dispersion stability, while having a uniform viscosity and low viscosity.

The present invention provides a color filter comprising the pigment photosensitive resin composition comprising the pigment dispersion composition, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, and a coloring pattern made of the coloring photosensitive resin composition, and the color filter. A display device can be provided.

Hereinafter, the method for preparing the pigment dispersion composition and the pigment dispersion composition prepared according to the present invention will be described in detail. However, the present invention is not limited thereto.

Method for producing a pigment dispersion composition according to the present invention,

(A) preparing a varnish by mixing a dispersant, a dispersing resin and a dispersing solvent;

(B) adding a pigment to the varnish to prepare a pigment dispersion;

(C) dispersing the pigment dispersion at a linear speed of 6 to 11 m / s at 40 to 80 ° C. for 10 to 24 hours to produce a low viscosity pigment dispersion; And

(D) filtering the low viscosity pigment dispersion to prepare a pigment dispersion composition, wherein the pigment dispersion composition may have a low viscosity of 3 to 5 mPa · s.

Specifically,

(A) preparing the varnish includes (A-1) a first step of mixing the dispersion resin and the dispersion solvent to prepare a dispersion resin solution; And (A-2) a second method of preparing the varnish by adding a dispersant to the dispersion resin solution and mixing at a linear speed of 5 to 6 m / s, preferably 5 to 5.5 m / s for 25 to 40 minutes. Steps.

According to an embodiment, the second step (A-2) may include adding and dispersing a dispersion aid to the dispersion resin solution.

According to one embodiment, the dispersion resin may have a structure of formula (1).

[Formula 1]

In Chemical Formula 1,

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

R ₄ is a direct link or a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms,

a, b and c are each independently an integer of 1 to 20,

A is at least one monomer selected from (meth) acrylic acid ester, (meth) acrylamide, allyl compound, vinyl ether, vinyl ester or styrene.

According to one embodiment, the dispersion solvent has a viscosity of 2.0 mPa · s or less, a vapor pressure of 3.0 mmHg or less, preferably, a viscosity of 0.1 mPa · s or more and 2.0 mPa · s or less, and a vapor pressure of 0.1 at room temperature. may be greater than or equal to mmHg and less than or equal to 2.0 mmHg.

(B) preparing the pigment dispersion, characterized in that after the addition of the pigment to the varnish, it is mixed for 1 hour at a linear speed of 5m / s.

According to an embodiment, the pigment may be included in an amount of 12 to 15 wt% based on 100 wt% of the pigment dispersion composition.

(D) preparing the pigment dispersion composition is characterized in that the low viscosity pigment dispersion is filtered through a filter having a pore size of 0.2 to 0.8 μm, preferably 0.45 μm, whereby coarse particles can be removed. have.

The method for preparing a pigment dispersion composition according to the prior art is generally carried out at a linear speed of 10 m / s or more under a temperature condition of low temperature to room temperature and a time condition of 6 to 12 hours. On the other hand, the method for producing a low viscosity pigment dispersion composition according to the present invention, as described above, is characterized in that the mild dispersion treatment is carried out at a low linear velocity for a long time under high temperature conditions compared with the prior art.

Moreover, in the manufacturing method of the pigment dispersion composition which concerns on a prior art, it is common to mix a dispersing agent and a dispersing solvent first, and to add a dispersion resin. On the other hand, the method for producing a pigment dispersion composition according to the present invention is characterized in that the dispersion resin and the dispersion solvent is first mixed, and then the dispersant is added.

Pigment

The pigment is characterized in that it comprises a colored organic pigment, it may further comprise a black organic / inorganic pigment.

Coloring organic pigments

The colored organic pigment may be used a colored organic pigment generally used in the art, these may be used alone or in combination of two or more.

Specific examples of the colored organic pigment include compounds classified as pigments in the color index (published by The society of Dyers and Colourists), and more specifically, pigments having the following color index (CI) numbers. However, the present invention is not necessarily limited to these, and any known one can be used.

As an orange pigment, C.I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 43, 46, 48, 49, 61, 62, 64, 65, 67 , 68, 69, 70, 71, 72, 73, 74, 75, 77, 78 and 79. As an orange pigment, C.I. Pigment Orange 64 and 72 are preferably used. The orange pigment may serve to improve optical density by reducing transmittance in the 400 to 550 nm region.

As a green pigment, C.I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58 and 59. . As a green pigment, C.I. Pigment Green 7, 36, 54, 58, 59 is preferably used in view of light shielding and color correction, and the C.I. Most preferably, Pigment Green 54 is used.

As a purple pigment, C.I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32 , 37, 39, 42, 44, 47, 49 and 50. As a purple pigment, C.I. Pigment Violet 19, 23, 29 is preferably used in terms of light shielding properties, and C.I. Most preferably, pigment violet 23, 29 is used.

As a blue pigment, C.I. Pigment Blue 1, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36 , 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78 and 79. As a blue pigment, C.I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60 is preferably used. In terms of dispersibility and light shielding properties, C.I. Pigment Blue 15: 6, 16, 60 is most preferably used.

Black organic / inorganic pigment

As the black organic / inorganic pigment, black organic / inorganic pigments generally used in the art may be used, and these may be used alone or in combination of two or more kinds.

Specific examples of the black organic / inorganic pigments include carbon black, atetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, titanium black, ramtam black, and perylene black. Therefore, although an inorganic pigment and an organic pigment may be used individually or in mixture, it is not necessarily limited to these, Any can be used if it is well-known.

Dispersant

Specifically, the dispersant may include an acrylic block copolymer, an acrylate dispersant, or a cationic, anionic, nonionic, polyester, or polyamine surfactant, and these may be used alone or in combination of two or more thereof. Can be.

Although it is preferable to use an acryl-type block copolymer as said dispersing agent, it is not necessarily limited to this, Any known thing can be used.

As for the said acryl-type block copolymer, it is more preferable that it contains a nitrogen atom. As the acrylic block copolymer, at least one of an XY block copolymer and a YXY block copolymer comprising an X block having at least one of a quaternary ammonium base and an amino group in a side chain, and a Y block having no quaternary ammonium base and an amino group It is preferable to select and use.

It may have either a quaternary ammonium base or an amino group in an X block, and may contain both. The quaternary ammonium base in the X block is improved from the viewpoint of improving the solubility of the dispersant in the resist solvent when a low polar solvent is used in the resist when the solubility of the quaternary ammonium base is low and the amino group is high in the solvent having a low polarity. It may be desirable to have both amino and amino groups.

Y block does not have a quaternary ammonium base and an amino group, and if it consists of a monomer copolymerizable with the said monomer, there will be no restriction | limiting in particular. The Y block has a function of stabilizing a pigment adsorbed to a dispersant in a solvent because the solvent has a affinity for a solvent having no nitrogen atom-containing functional group as a pigment adsorber and having affinity for a solvent.

The amine titer of the said acrylic block copolymer is 1-150 mgKOH / g, Preferably it is 10-100 mgKOH / g, The acid value is 1-100 mgKOH / g, Preferably it is 1-80 mgKOH / g or less.

The molecular weight of the said acrylic block copolymer is 1,000-100,000 or less in weight average molecular weight (Mw) of polystyrene conversion measured by GPC, Preferably it is 3,000-30,000 or less. When molecular weight is too small, dispersion stability will fall, and when molecular weight is too large, there exists a tendency for developability and resolution to fall.

The acrylate dispersant may be butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA). Preferably, the acrylate-based dispersant is prepared by a living control method, and commercially available products include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2020, DISPER BYK-2025, DISPER BYK-2070, or DISPER BYK. -2150, etc., The acrylate-based dispersant may be used alone or in combination of two or more.

As the dispersant, in addition to the acrylic block copolymer and the acrylate dispersant, a dispersant of another resin type may be used. The other resin type dispersant is a (partial) amine salt of a known resin type dispersant, in particular polycarboxylic acid esters, unsaturated polyamides, polycarboxylic acids, polycarboxylic acids represented by polyurethanes, polyacrylates. , Ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and modified products thereof, or free carboxyl groups Oily dispersants such as amides or salts thereof formed by the reaction of a polyester having a poly (lower alkyleneimine); Water-soluble resins or water-soluble polymer compounds such as (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylate ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol or polyvinyl pyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide; And phosphate esters.

As a commercial item of the said other resin type dispersing agent, As a cationic resin dispersing agent, For example, brand names of BYK (BIC) company: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK -164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184, DISPER BYK-2000; BASF brand name: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; Trade names: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204 / 10; Kawaken Fine Chemical's trade names: HINOACT T-6000, Hinoact T-7000, Hinoact T-8000; Trade names of Ajinomoto Co., Ltd .: AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823; The brand names of Kyoeisha Chemical Co., Ltd .: FLORENE DOPA-17HF, Floren DOPA-15BHF, Floren DOPA-33, Floren DOPA-44, etc. are mentioned.

The said other resin type dispersing agent can be used individually or in mixture of 2 or more types, and can be used in combination with the said acrylate type dispersing agent.

Specific examples of the cationic surfactant include amine salts and quaternary ammonium salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride.

Specific examples of the anionic surfactant include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, and Alkyl aryl sulfonates, such as sodium dodecyl naphthalene sulfonate, etc. are mentioned.

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, etc. are mentioned.

Other dispersants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, polyethyleneimines, and the like. Can be used.

Dispersion resin

The dispersion resin is characterized by having a structure of the following formula (1).

[Formula 1]

In Chemical Formula 1,

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

R ₄ is a direct link or a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms,

a, b and c are each independently an integer of 1 to 20,

A is at least one monomer selected from (meth) acrylic acid ester, (meth) acrylamide, allyl compound, vinyl ether, vinyl ester or styrene.

For A of Formula 1,

Specific examples of the (meth) acrylic acid ester include straight chains such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, t-octyl (meth) acrylate, or the like. Branched alkyl (meth) acrylates; chloroethyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) Acrylate, benzyl (meth) acrylate, furyl (meth) acrylate; etc. are mentioned.

Specific examples of (meth) acrylamides include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N, N- Aryl (meth) acrylamide, N-methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-methyl (meth) acrylamide, etc. are mentioned.

Specific examples of the allyl compound include allyl esters such as allyl acetate, allyl caproic acid, allyl caprylic acid, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetate, allyl lactate, and allyloxyethanol; These etc. are mentioned.

Specific examples of the vinyl ether include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxy ethyl vinyl ether, ethoxy ethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl Vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofuryl vinyl ether Alkyl vinyl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chloro phenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthal ether and vinyl aryl ether such as vinyl anthranyl ether;

Specific examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloro acetate, vinyl dichloro acetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl phenyl Acetate, vinyl acetate acetate, vinyl lactate, vinyl beta phenyl butyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, and the like.

Specific examples of styrene include styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoro Alkyl styrenes such as methyl styrene, ethoxy methyl styrene, acetoxy methyl styrene; alkoxy styrenes such as methoxy styrene, 4-methoxy-3-methyl styrene, dimethoxy styrene; chloro styrene, dichloro styrene, trichloro styrene, tetra Chlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodine styrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoro Halostyrenes, such as rommethyl styrene, etc. are mentioned.

It is preferable that it is 2,000-30,000, and, as for the mass mean molecular weight of the said dispersion resin, it is more preferable that it is 5,000-20,000. When it is contained in the said range, since balance control of solvent resistance, low viscosity, film formation ability, and developability of the colored photosensitive resin composition containing the pigment dispersion liquid composition containing the said dispersion resin is easy, it is preferable.

Dispersant solvent

The dispersion solvent has a viscosity of 2.0 mPa · s or less at room temperature and a vapor pressure of 3.0 mmHg or less, and has compatibility with the (A) coloring agent, the (B) dispersant and the (C) dispersion resin, Use it to not react. The dispersing solvent may be used without particular limitation in the solvent used in the conventional coloring photosensitive resin composition, and in particular, various organic solvents such as ethers, acetates, aromatic hydrocarbons, ketones, alcohols or esters may be used, In particular, in view of high-speed coating, drying property, poor surface quality, and step formation, an organic solvent having a viscosity of 2.0 mPa · s or less and a vapor pressure of 3.0 mmHg or less is preferable at 20 ° C. Moreover, you may mix and use the organic solvent from which a boiling point differs.

The dispersing solvent is methyl-3-methoxy propionate (boiling point of 145 ° C., viscosity 1.1 mPa · s, vapor pressure 1.8 mmHg) propylene glycol monoethyl ether acetate (boiling point of 146 ° C., viscosity 1.3 mPa · s, vapor pressure 2.8 mmHg), Methyl amyl ketone (boiling point 152 ° C., viscosity 0.8 mPa · s, vapor pressure 2.1 mmHg), ethylene glycol monoethyl ether (boiling point 156 ° C., viscosity 1.3 mPa · s, vapor pressure 1.2 mmHg), propylene glycol methyl ether propionate (boiling point 161 degreeC, viscosity 1.2 mPa * s, vapor pressure 0.9mmHg), diethylene glycol dimethyl ether (boiling point 162 degreeC, viscosity 2.0mPa * s, vapor pressure 3.0mmHg), 2,6-dimethyl-4-heptanone (boiling point 163 degreeC, Viscosity 0.9 mPa · s, vapor pressure 1.7 mmHg), pentyl propionate (boiling point 165 ° C., viscosity 1.0 mPa · s, vapor pressure 1.5 mmHg), ethyl-3-ethoxy propionate (boiling point 170 ° C., viscosity 1.3 mPa · s, Vapor pressure 0.7mmHg), 3-methoxybutyl acetate (boiling point 171 ° C, viscosity 0.7mPas, vapor pressure 1.1mmHg), dipropylene glycol dimethyl ether (Boiling point 175 ° C., viscosity 1.1 mPa · s, vapor pressure 0.6 mmHg), diethylene glycol ethylmethyl ether (boiling point 176 ° C., viscosity 1.2 mPa · s, vapor pressure 0.7 mmHg), diethylene glycol isopropyl methyl ether (boiling point 179 ° C., Particularly preferred is a viscosity of 1.3 mPa · s, a vapor pressure of 0.8 mmHg) and diethylene glycol diethyl ether (boiling point of 189 ° C., viscosity of 1.4 mPa · s, vapor pressure of 0.4 mmHg). The said dispersion solvent can be used individually or in mixture of 2 or more types, respectively, It is not limited to this.

Dispersion Aids

The pigment dispersion composition may further include a dispersion aid to improve dispersion stability of the pigment, and the dispersion assistant may be, for example, a pigment derivative.

The pigment derivatives are azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolo Although derivatives, such as a pyrrole system and a dioxazine system, are mentioned, Especially, a quinophthalone system is preferable. As the substituent of the pigment derivative, sulfonic acid group, sulfonamide group and quaternary salts thereof, phthalimide methyl group, dialkylaminoalkyl group, hydroxyl group, carboxyl group, amide group and the like are directly added to the pigment skeleton or alkyl group, aryl group, heterocyclic group or the like. The thing which couple | bonded through is mentioned, Preferably it is a sulfonic acid group. Moreover, these substituents may be substituted by two in one pigment skeleton.

Specific examples of the pigment derivatives include sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinophthalone, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, sulfonic acid derivatives of diketopyrrolopyrrole, and sulfonic acid derivatives of dioxazine.

The said pigment derivative can be used individually or in combination of 2 or more types, respectively.

The present invention provides a colored photosensitive resin composition comprising a pigment dispersion composition as described above and an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, which will be described in detail below. However, the present invention is not limited thereto.

Alkali soluble resin

The alkali-soluble resin makes the non-exposed portion of the black photosensitive resin layer formed using the colored photosensitive resin composition alkali-soluble and may also act as a dispersion medium for the pigment. The alkali-soluble resin may be selected from a variety of polymers used in the application field, but it is preferable to include an (alicyclic) epoxy group in terms of shape or pattern step, adhesion to the substrate and solvent resistance, and (alicyclic) The alkali-soluble resin containing an epoxy group may affect the reliability improvement.

It is preferable that the weight average molecular weights of the said alkali-soluble resin are 3,000-40,000, and it is more preferable that it is 5,000-30,000. When included in the above range, there is a tendency that the balance between film forming ability, reliability, and developability is excellent. Moreover, it is preferable that the acid value of the said alkali-soluble resin is 50-200 mgKOH / g in solid content basis in a coloring photosensitive resin composition. When it is contained in the said range, there exists an advantage that developability with respect to alkali image development is excellent, residue generation is suppressed and the adhesiveness of a pattern improves.

The said alkali-soluble resin can use the same thing as the said dispersion resin used for the pigment dispersion liquid composition.

Photopolymerizable compound

The said photopolymerizable compound is a compound which can superpose | polymerize by the action of the photoinitiator mentioned later, A monofunctional monomer, a bifunctional monomer, another polyfunctional monomer, etc. are mentioned. The photopolymerizable compound may be used by mixing two or more photopolymerizable compounds having different functional groups or functional groups in order to improve the developability, sensitivity, adhesion, and surface problems of the photosensitive resin composition for forming the front light shielding layer of the display device. If the type is generally used in this field, the kind is not particularly limited.

Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-vinyl py. A ralidone etc. are mentioned. As a specific example of the said bifunctional monomer, 1, 6- hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate And bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like. Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Pentaerythritol hexa (meth) acrylate etc. are mentioned. Of these, bifunctional or higher polyfunctional monomers are preferably used.

When included in the above range, it is a range selected in consideration of the tendency of the black matrix or spacer including the colored photosensitive composition or the smoothness to be good in various ways, if the content is less than the above range, the strength and smoothness is insufficient. On the contrary, since the patterning is not easy due to high strength when it exceeds the above range, it is suitably used within the above range.

Photopolymerization initiator

As the photoinitiator, acetophenone-based, benzophenone-based, triazine-based, thioxanthone-based, oxime-based, benzoin-based, biimidazole-based compounds, and the like can be used as photopolymerization initiators generally used in colored photosensitive resin compositions.

Specific examples of the acetophenone-based compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and pt-butyltrichloroacetophenone , pt-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxycetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane -1-one etc. are mentioned.

Examples of the benzophenone compound include benzophenone, benzoyl benzoic acid, benzoyl benzoic acid methyl, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis (dimethyl amino) benzophenone, and 4,4'- Bis (diethyl amino) benzophenone, 4,4'- dimethylamino benzophenone, 4,4'- dichloro benzophenone, 3,3'- dimethyl- 2-methoxy benzophenone etc. are mentioned.

Examples of the triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, and 2- (3 ', 4'-dimeth Methoxy styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxy naphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(p-methoxy phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl-4,6-bis (trichloromethyl) -s-triazine, 2- Fiphenyl-4,6-bis (trichloromethyl) -s-triazine, bis (trichlorobetayl) -6-styryl-s-triazine, 2- (naphtho 1-yl) -4,6- Bis (trichloro methyl) -s-triazine, 2- (4-methoxy naphtho 1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2-4-trichloro methyl ( Piperonyl) -6-triazine, 2,4-trichloro methyl (4'-methoxy styryl) -6-triazine, and the like.

Examples of the thioxanthone compound include thioxanthone, 2-chloro thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, and 2,4-diisopropyl tea. Orcanthone, 2-chloro thioxanthone, etc. are mentioned.

Examples of the oxime compound include 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione and 1- (o-acetyloxime) -1- [9-ethyl- 6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone and the like.

Examples of the benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal and the like.

solvent

As long as the solvent is effective for dissolving the other components included in the colored photosensitive resin composition, the solvent used in the usual colored photosensitive resin composition can be used without particular limitation, and in particular, ethers, aromatic hydrocarbons, ketones, alcohols, esters Or amides are preferred.

Specifically, the solvent is ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene glycol dialkyl ethers such as diethylene glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, Alkylene glycol alkyl ether acetates, such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxy butyl acetate, and methoxy pentyl acetate, aromatic hydrocarbons, such as benzene, toluene, xylene, and mesitylene, methyl ethyl ketone , Ah Ketones such as tonnes, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, ethyl 3-ethoxypropionate, 3-meth Ester, such as methyl oxypropionate, Cyclic ester, such as (gamma) -butyrolactone, etc. are mentioned.

The solvent is preferably an organic solvent having a boiling point of 100 ℃ to 200 ℃ in terms of applicability and dryness, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butalac Tate, 3-ethoxy propionate, methyl 3-methoxypropionate, etc. can be used.

The solvents exemplified above may be used alone or in combination of two or more thereof.

additive

The coloring photosensitive resin composition according to the present invention may further include an additive as necessary, and specific examples are selected from the group consisting of a polymer compound, a thermal initiator, a curing agent, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-agglomerating agent. At least one or more may be used.

Specific examples of the polymer compound include curable resins such as epoxy resins and maleimide resins; And thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.

The thermal initiator causes a curing reaction by heat to maximize the starting efficiency. The thermal initiator may be a peroxide compound.

Although the specific kind of the thermal initiator is not particularly limited, tetramethylbutyl peroxy neodecanoate (ex. Perocta ND, NOF Co.), bis (4-butylcyclohexyl) peroxydicarbonate (ex. Peroyl TCP NOF Co., Ltd.), di (2-ethylhexyl) peroxy carbonate, butyl peroxy neodecanoate (ex. Perbutyl ND, NOF Co., Ltd.), dipropyl peroxy dicarbonate (ex. Peroyl NPP , NOF company (made), diisopropyl peroxy dicarbonate (ex. Peroyl IPP, NOF company made), diethoxyethyl peroxy dicarbonate (ex. Peroyl EEP, NOF company made), diethoxy Hexyl peroxy dicarbonate (ex. Peroyl OEP, NOF Co., Ltd.), hexyl peroxy dicarbonate (ex. Perhexyl ND, NOF Co., Ltd.), dimethoxybutyl peroxy dicarbonate (ex. Peroyl MBP, NOF Co., Ltd.), bis (3-methoxy-3-methoxybutyl) peroxy dicarbonate (ex. Peroyl SOP, NOF Co., Ltd.), dibutyl peroxy dicarbonate, dicetyl peroxy DiCabo Yit, dimyristyl peroxy dicarbonate, 1,1,3,3-tetramethylbutyl peroxypivalate, hexyl peroxy pivalate (ex. Perhexyl PV, manufactured by NOF) Butyl peroxy pivalate (ex. Perbutyl, NOF Co., Ltd.), trimethyl hexanoyl peroxide (ex. Peroyl 355, NOF Co., Ltd.), dimethyl hydroxybutyl peroxy neodecanoate (ex. Luperox 610M75 , Atofina (product)), amyl peroxy neodecanoate (ex. Luperox 546M75, Atofina), butyl peroxynedecanoate (ex. Luperox 10M75, Atofina), t-butylperoxy Neoheptanoate, amylperoxy pivalate (ex. Luperox 546M75, Alofina), t-butylperoxy pivalate, t-amylperoxy-2-ethylhexanoate, t-butylper Oxy-2-ethylhexanoate, lauryl peroxide, dilauuroyl peroxide, didecanoyl peroxide, benzoyl peroxide, dibenzoyl peroxide, 2,2-bis (tert-butyl Oxy) butane, 1,1-bis (tert-butylperoxy) cyclohexane, 2,5-bis (butylperoxy) -2,5-dimethylhexane, 2,5-bis (tert-butylperoxy)- 1-methylethyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, tert-butyl hydroperoxide, tert-butyl peroxide, tert-butyl peroxybenzoate tert-butylperoxy isopropyl carbonate, cumene hydroxyperoxide, dicumyl peroxide, lauroyl peroxide, 2,4-pentanedione peroxide, tert-butyl peracetate, Peracetic acid (peracetic acid), and potassium persulfate (potassium persulfate) may be one or more selected from the group consisting of.

Regarding the thermal initiator content, it is preferable to include 1 to 10% by weight, and more preferably 1 to 5% by weight, based on the total weight of solids in the colored photosensitive resin composition. When included in the content as described above is more preferred for fairness and undercut.

The curing agent is used to increase the core hardening and mechanical strength, and specific examples thereof include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound and an oxetane compound.

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, noblock type epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin , Glycidyl ester resins, glycidylamine resins, or brominated derivatives of such epoxy resins, aliphatic, cycloaliphatic or aromatic epoxy compounds other than epoxy resins and their brominated derivatives, butadiene (co) polymer epoxides, isoprene ( Co) polymer epoxide, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate, and the like.

Specific examples of the oxetane compound in the curing agent include carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, terephthalate bis oxetane, cyclohexane dicarboxylic acid bis oxetane and the like.

The said hardening | curing agent can use together the hardening auxiliary compound which can make ring-opening-polymerize the epoxy group of an epoxy compound, and the oxetane skeleton of an oxetane compound with a hardening | curing agent. Examples of the curing aid compound include polyhydric carboxylic acids, polyhydric carboxylic anhydrides, acid generators, and the like. As said polyhydric carboxylic anhydride, what is marketed can be used as an epoxy resin hardening | curing agent. As a specific example of the said epoxy resin hardening | curing agent, as a commercial item, a brand name (Adekahadona EH-700) (made by Adeka Industrial Co., Ltd.), a brand name (Rikaditdo HH) (made by Nippon Ewha Co., Ltd.), a brand name (MH-700) ( New Nippon Ewha Co., Ltd.) etc. are mentioned. The hardeners illustrated above can be used individually or in mixture of 2 or more types.

The surfactant may be used to further improve the film formability of the photosensitive resin composition, for example, a surfactant such as silicone, fluorine, ester, cationic, anionic, nonionic and amphoteric may be used. , Silicone-based surfactants or fluorine-based surfactants can be preferably used.

The silicone surfactant is, for example, commercially available products such as DC3PA, DC7PA, SH11PA, SH21PA and SH-8400 manufactured by Dow Corning Toray Silicone Co., Ltd., TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF- 4460, TSF-4452, etc. are mentioned. The fluorine-based surfactants are, for example, Megapieces F554, F-470, F-471, F-475, F-482, and F-489 (Dini Nippon Ink Chemical Co., Ltd.), BM-1000, BM-1100 as commercially available products. (BM Chemie Co., Ltd.) and Proride FC-135 / FC-170C / FC-430 (Sumitomo 3M).

As another example of the surfactant, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, polyethylene Other commercial products include KP (Shin-Etsu Chemical Co., Ltd.), Polyflow (Kyoei Chemical Co., Ltd.), F-Top (Tochem Products), MegaPac (Dainippon Ink Chemical Co., Ltd.), Florad (Sumitomo 3M). ), Asahi Guard, Saffron (above, Asahi Glass Co., Ltd.), Soap Sparse (Geneca Co., Ltd.), EFKA (EFKACHEMICALS), PB821 (Ajinomoto Co., Ltd.), and the like.

Surfactant illustrated above can be used individually or in combination of 2 types or more, respectively.

The adhesion promoter is an additive used to improve the coating property and adhesion with the substrate, and includes a silane coupling agent including a reactive substituent selected from the group consisting of carboxyl group, methacryloyl group, isocyanate group, epoxy group and combinations thereof. It may include. The silane coupling agent is specifically, for example, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxy Silane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane , 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3 -Mercaptopropyl trimethoxysilane, trimethoxysilyl benzoic acid, vinyltriacetoxysilane, (gamma) -isocyanate propyl triethoxysilane, etc. are mentioned.

Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol.

Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole and alkoxybenzophenone.

Specific examples of the aggregation inhibitor include sodium polyacrylate and the like.

The additive may be included in an amount of 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the total weight of solids in the colored photosensitive resin composition.

Color filters and displays

In addition, the present invention provides a color pattern made from the colored photosensitive resin composition according to the present invention, a color filter including the color pattern, and a display device including the color filter.

The display device that may include the color filter may include a liquid crystal display, an OLED, a flexible display, and the like, but is not limited thereto. Examples of all display devices known in the art may be applicable.

A color filter can be manufactured by apply | coating the coloring photosensitive resin composition of this invention mentioned above on a base material, photocuring and developing, and forming a pattern.

First, after apply | coating a coloring photosensitive resin composition to a base material, heat-drying removes volatile components, such as a solvent, and obtains a smooth coating film.

As a coating method, it can carry out by a spin coat, cast coating method, the roll coating method, the slit and spin coat, the slit coat method, etc., for example. After coating, heating and drying (prebaking) or drying under reduced pressure are carried out to volatilize volatile components such as a solvent. Here, heating temperature is 70-200 degreeC normally, Preferably it is 80-130 degreeC. The coating film thickness after heat drying is about 1-8 micrometers normally. The coating film thus obtained is irradiated with ultraviolet rays through a mask for forming a target pattern. At this time, it is preferable to use apparatuses, such as a mask aligner and a stepper, so that the parallel light beam may be irradiated uniformly to the whole exposure part, and the exact alignment of a mask and a board | substrate is performed. When ultraviolet light is irradiated, the site to which ultraviolet light is irradiated is hardened.

G-rays (wavelength: 436 nm), h-rays, i-rays (wavelength: 365 nm) and the like can be used as the ultraviolet rays. The irradiation amount of ultraviolet rays may be appropriately selected as necessary, and the present invention is not limited thereto. When the coating film after hardening is contacted with a developing solution and the non-exposed part is melted and developed, the target pattern shape can be formed.

The developing method may be any of a liquid addition method, a dipping method, a spray method and the like. In addition, during development, the substrate may be tilted at an arbitrary angle. The developer is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be either an inorganic or organic alkaline compound. Specific examples of the inorganic alkaline compounds include sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate And sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like. Specific examples of the organic alkaline compounds include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine and the like.

These inorganic and organic alkaline compounds can be used individually or in combination of 2 or more types, respectively. The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.

The surfactant in the alkaline developer may be at least one selected from the group consisting of nonionic surfactants, anionic surfactants or cationic surfactants.

Specific examples of the nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkyl amine, etc. are mentioned.

Specific examples of the anionic surfactants include higher alcohol sulfate ester salts such as lauryl alcohol sulfate and sodium sodium or oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, and dodecylbenzene sulfonic acid. Alkyl aryl sulfonates, such as sodium and sodium dodecyl naphthalene sulfonate, etc. are mentioned.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride, or quaternary ammonium salts. These surfactant can be used individually or in combination of 2 or more types, respectively.

The concentration of the surfactant in the developer is usually 0.01 to 10% by mass, preferably 0.05 to 8% by mass, more preferably 0.1 to 5% by mass. After image development, it is washed with water and also 10-60 minutes post-baking may be performed at 150-230 degreeC as needed.

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated in detail based on an Example, embodiment of this invention disclosed below is an illustration to the last, and the scope of the present invention is not limited to these embodiment. The scope of the invention is indicated in the appended claims, and moreover contains all modifications within the meaning and range equivalent to the claims. In addition, "%" and "part" which show content in a following example and a comparative example are a mass reference | standard unless there is particular notice.

Preparation of Dispersion Resin (Alkali Soluble Resin) According to Synthesis Examples 1 to 3

Synthesis Example 1:

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to make a nitrogen atmosphere, and 150 g of diethylene glycol methylethyl ether was added and heated to 70 ° C while stirring. Subsequently, a mixture of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-9-ylacrylate and 3,4-epoxycitoxycyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate [50:50 (molar ratio), later expressed as EDCPA], 0.7 mol of EDCPA, 0.1 mol of AA, 0.2 mol of VT so that the total of acrylic acid (hereinafter referred to as AA) and vinyltoluene (hereinafter referred to as VT) is 1 mol. It dissolved in 150 g of ethyl glycol methyl ethyl ether to prepare a solution. After dropping the prepared solution into the flask using a dropping funnel, 27.9 g (0.11 mol) of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was added to 200 g of diethylene glycol methylethyl ether. The solution dissolved in was dropped into the flask over 4 hours using a separate dropping funnel. After the dropping of the solution of the polymerization initiator was completed, the solution was maintained at 70 ° C. for 4 hours, and then cooled to room temperature to obtain a copolymer solution (solid content (NV) 35.0 wt%). The dry value of the obtained copolymer was 69.8 KOH mg / g, the weight average molecular weight (Mw) was 9,500, and the dispersion degree (Mw / Mn) was 1.9.

Synthesis Example 2:

In Synthesis Example 1, 0.5 mol of AA, 0.1 mol of AA, 0.2 mol of VT, and 0.1 mol of HEMA (hydroxyethyl methacrylate) were dissolved in 150 g of diethylglycol methylethyl ether so that the total of EDCPA, AA, VT, and HEMA was 1 mol. A copolymer solution (35% by weight of solid content (NV)) was obtained in the same manner as in Preparation Example 1, except that was prepared. The dry value of the obtained copolymer was 70.8 KOH mg / g, the weight average molecular weight (Mw) was 18,500, and the dispersion degree (Mw / Mn) was 2.2.

Synthesis Example 3:

182 g of propylene glycol monomethyl ether acetate was charged into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube, and the atmosphere in the flask was changed from air to nitrogen, followed by heating to 100 ° C. After the temperature was raised, a mixture containing 44.5 g of monomethacrylate, 70.5 g of benzyl methacrylate, 45.0 g of methacrylic acid, and 136 g of propylene glycol monomethyl ether acetate of isocyclic skeleton was added to the flask, and azobis was added thereto. The solution to which 3.6 g of isobutyronitrile was added was dripped at the flask over 2 hours from the dropping lot, and stirring was continued at 100 degreeC for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 30 g of glycidyl methacrylate (0.2 mol: 40 mol% based on the carboxyl group of methacrylic acid), 0.9 g of trisdimethylaminomethylphenol, and 0.145 g of hydroquinone were added into the flask. It injected | thrown-in and continued reaction at 110 degreeC for 6 hours, and obtained the target copolymer solution (solid content concentration 31.5%). The weight average molecular weight (Mw) of the obtained copolymer was 31,000, the acid value (dry) was 85 mgKOH / g and dispersion degree (Mw / Mn) was 2.6.

Preparation of Pigment Dispersion Compositions According to Preparation Examples 1 to 10

Referring to Tables 1 and 2 below, a pigment, a dispersant, a dispersion resin, and a dispersion solvent were mixed and a pigment dispersion composition was prepared according to the method for preparing a pigment dispersion composition according to the present invention using 0.1 mm of zirconia beads. .

(Unit: g) Pigment Dispersant Dispersion resin Dispersion
solvent B15: 6 B16 V29 V23 Or64 CB C-1 C-2 C-3 Preparation Example 1 41.0 35.0 25.0 19.0 36.0 102.9
741.1 Preparation Example 2 41.0 35.0 25.0 19.0 102.9 Preparation Example 3 41.0 35.0 25.0 19.0 102.9 Preparation Example 4 41.0 35.0 25.0 19.0 102.9 Preparation Example 5 41.0 35.0 25.0 19.0 102.9 Preparation Example 6 46.0 31.0 25.0 19.0 102.9 Preparation Example 7 43.0 36.0 22.0 19.0 102.9 Preparation Example 8 46.0 33.0 22.0 19.0 102.9 Preparation Example 9 41.0 35.0 25.0 19.0 102.9 Preparation Example 10 41.0 35.0 25.0 19.0 114.3 729.7

B15: 6: C.I. Pigment Blue 15: 6

B16: C.I. Pigment Blue 16

V29: C.I. Pigment Violet 29

V23: C.I. Pigment Violet 23

Or64: C.I. Pigment Orange 64

CB: Carbon Black

Dispersant: DISPERBYK-2001 (BYK (Big) Chemi Corporation)

C-1: See Synthesis Example 1

C-2: See Synthesis Example 2

C-3: See Synthesis Example 3

Dispersion solvent: Propylene glycol methyl ether acetate (PGMEA)

Linear velocity (m / s) Process time (hr) Process temperature (℃) Pigment Dispersion Composition Viscosity (mPas) Preparation Example 1  9 m / s  10 hr 40 3.58 Preparation Example 2  9 m / s  10 hr 70 3.53 Preparation Example 3  8 m / s  12 hr 60 3.59 Preparation Example 4  8 m / s  13 hr 60 3.65 Preparation Example 5  8 m / s  13 hr 60 3.60 Preparation Example 6  8 m / s  14 hr 60 3.67 Preparation Example 7  8 m / s  14 hr 60 3.71 Preparation Example 8 8 m / s  14 hr 60 3.73 Preparation Example 9  13 m / s  6 hr 40 5.35 Preparation Example 10  13 m / s  6 hr 25 6.35

The process conditions (linear speed, process time, and process temperature) of the said Table 2 are process conditions of the process of manufacturing (C) low viscosity pigment dispersion liquid in the manufacturing method of the pigment dispersion liquid composition of this invention.

Preparation of the coloring photosensitive resin composition which concerns on Examples 1-11 and Comparative Examples 1-4.

Referring to Table 3 below, a pigment photosensitive resin composition was prepared by mixing the pigment dispersion composition, the alkali-soluble resin, the photopolymerizable compound, the photopolymerization initiator, the additive, and the solvent according to Preparation Examples 1 to 10.

(Unit: g) Pigment Dispersion Composition Alkali soluble resin Photopolymerizable compound Photopolymerization initiator additive solvent C-1 C-2 C-3 M-1 M-2 Example 1 Preparation Example 1 63.20 12.43 2.84 0.66 0.20 20.68 Example 2 Preparation Example 2 63.20 12.43 2.84 0.66 0.20 20.68 Example 3 Preparation Example 3 63.20 12.43 2.84 0.66 0.20 20.68 Example 4 Preparation Example 4 63.20 12.43 2.84 0.66 0.20 20.68 Example 5 Preparation Example 5 63.20 12.43 2.84 0.66 0.20 20.68 Example 6 Preparation Example 6 63.20 12.43 2.84 0.66 0.20 20.68 Example 7 Preparation Example 7 63.20 12.43 2.84 0.66 0.20 20.68 Example 8 Preparation Example 8 63.20 7.99 4.44 2.84 0.66 0.20 20.68 Example 9 Preparation Example 2 63.20 12.43 2.36 0.47 0.66 0.20 20.68 Example 10 Preparation Example 2 63.20 8.88 3.55 2.36 0.47 0.66 0.20 20.68 Example 11 Preparation Example 2 63.20 9.18 2.75 2.36 0.95 0.66 0.20 21.56 Comparative Example 1 Preparation Example 9 63.20 12.43 2.84 0.66 0.20 20.68 Comparative Example 2 Preparation Example 9 63.20 12.43 2.84 0.66 0.20 20.68 Comparative Example 3 Preparation Example 10 63.20 12.43 2.84 0.66 0.20 20.68 Comparative Example 4 Preparation Example 10 63.20 9.72 3.78 0.66 0.20 22.44

C-1: See Synthesis Example 1

C-2: See Synthesis Example 2

C-3: See Synthesis Example 3

M-1: VISCOAT # 802 (manufactured by Osaka Organic Chemical Industry, Japan)

M-2: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., Japan)

Photoinitiator: 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethanone-1- (O-acetyloxime) (Irgacure OXE-02: manufactured by BASF)

Additive: F554 (manufactured by DIC, Japan)

Solvent: Propylene glycol methyl ether acetate (PGMEA): Diethylene glycol ethyl methyl ether (MEDG) = 90:10

Test Example: Evaluation of Physical Properties of Pigment Dispersion Composition and Colored Photosensitive Resin Composition

1-1. Particle size measurement

The average particle diameter of the pigment dispersion composition and the resist prepared by using the laser light scattering method ELSZ-2000ZS manufactured by Otsuka Denshi is measured and shown in Table 4 below.

1-2. Viscosity Measurement (Change over time)

Immediately after the pigment dispersion composition and the colored photosensitive resin composition were prepared, the viscosity after 7 days in a 23 ° C. thermostat was measured at 25 ° C. using a Brookfield Viscometer (Brookfield Viscometer DV-I +, manufactured by Brookfield). It was. The initial viscosity of the pigment dispersion composition and the coloring photosensitive resin composition and the rate of change of viscosity (time change) over 7 days are shown in Table 4 below.

Evaluation criteria

○: less than 1.5%

△: 1.5% or more but less than 5%

X: 5% or more

Test Example: Evaluation of physical properties of colored patterns prepared using the colored photosensitive resin compositions according to Examples 1 to 11 and Comparative Examples 1 to 4

A glass substrate of 5 cm × 5 cm (Corning) was washed with a neutral detergent and water and dried. The colored photosensitive resin composition was spin coated on the glass substrate to have a final film thickness of 3.0 μm, prebaked at 80 to 120 ° C., and dried for 1 to 2 minutes to remove the solvent. Thereafter, a pattern was formed by exposing at an exposure dose of 25 to 35 mJ / cm ^2, and the non-exposed portion was removed using an aqueous alkali solution. Subsequently, post-firing at 200 to 250 ° C. for 10 to 30 minutes yielded a colored pattern.

2-1. Optical Density (O.D.) Measurement

The optical density meter (361T, X-rite Co., Ltd.) was used to measure the transmittance at 550 nm of the colored pattern, and the optical density for the thickness of 1 μm was obtained and shown in Table 4 below.

2-2. Optical properties evaluation

Using UV-vis (UV-2550; Shimadzu Co., Ltd.), optical properties in the 950 nm wavelength range of the coloring pattern were evaluated and shown in Table 4 below.

Evaluation criteria

○: excellent, 15% or more light transmission

△: insufficient, 13% light transmittance or more

X: worse, less than 13% light transmission

2-3. Degree of Planarizaiotn (DOP) Measurement

After measuring the thickness of the portion with and without the pattern at the bottom of the coloring pattern through the film thickness meter (DEKTAK6M, Veeco), the flatness (DOP) was measured by using the pattern thickness of the lower substrate previously measured. Table 4 shows.

Evaluation criteria

Under the condition that the bottom pattern thickness is 1.17 um and the flattening part thickness without the bottom pattern is 3.20 um,

◎ very good, 30% or more but less than 60%

○: Excellent, 15% or more but less than 30%, 60% or more and less than 75%

△: insufficient, 10% or more but less than 15%, 75% or more and less than 85%

X: worse, less than 10, more than 85%

2-4. VCD Surface Stain Evaluation

Each of the colored photosensitive resin compositions was spin-coated to have a final film thickness of 3.0 (± 0.2) μm, subjected to vacuum drying (VCD) up to 65 Pa, and the time to reach 65 Pa was measured, and then the coated surface. It was confirmed by the optical microscope to measure the surface defects and Tact time (blank: 15sec) according to the VCD pressure reduction is shown in Table 4 below.

Evaluation criteria: see FIG. 1

◎ very good, less than 5 surface stains

○: Excellent, less than 10 or more surface stains

(Triangle | delta): Deficiency, less than 20 or more surface stains

X: worse, 20 or more surface stains

2-5. Reliability measurement

After cutting the colored pattern to 3x3cm, it was immersed in NMP solution, and heat was applied at 100 ° C for 60 minutes. Thereafter, only the NMP solution was extracted, and the absorbance of the NMP solvent was measured using a UV-vis spectrometer, and the results are shown in Table 4 below.

Evaluation criteria

○: excellent, absorbance 0.5 or less

△: insufficient, absorbance more than 0.5 and less than 0.8

X: worsening, absorbance 0.8 or more

2-6. Elastic recovery rate evaluation

The coloring pattern was measured for thickness and height of the pattern in a reference state using SNU (SIS-2000, SNU). Subsequently, the hardness tester (Nano-indenter HM500, Fisher) was pressed at a speed of 2 mN / sec to the point where the pattern was deformed by 1 μm using a planar indenter, and had a holding time for 5 seconds at the point where the 1 μm was deformed. Thereafter, the thickness and height of the pattern were measured using SNU, and the elastic recovery rate was measured by changing the thickness of the pattern before and after, and is shown in Table 4 below.

Evaluation criteria

◎ very good, 98% or more

○: excellent, 96% or more and less than 98%

△: lack, 96% or more and less than 94%

X: worse, less than 94%

Granularity
(um) Viscosity
(mPas) Change over time O.D. Optical properties DOP VCD Stain VCD Tact responsibility Shout
Recovery rate Example 1 110.5 3.66 ○ 1.68 ○ ◎ ◎ 23 sec ◎ ◎ Example 2 120.3 3.57 ○ 1.69 ○ ◎ ◎ 24 sec ◎ ◎ Example 3 119.7 3.61 ○ 1.67 ○ ◎ ◎ 23 sec ◎ ◎ Example 4 111.1 3.59 ○ 1.66 ○ ◎ ◎ 23 sec ◎ ◎ Example 5 119.3 3.68 ○ 1.64 ○ ◎ ◎ 25 sec ◎ ◎ Example 6 122.3 3.72 ○ 1.69 ○ ◎ ◎ 23 sec ◎ ◎ Example 7 125.3 3.63 ○ 1.68 ○ ◎ ◎ 23 sec ◎ ◎ Example 8 112.2 3.73 ○ 1.66 ○ ◎ ◎ 27 sec ◎ ○ Example 9 110.9 3.63 ○ 1.66 ○ ◎ ◎ 24 sec ◎ ◎ Example 10 114.3 3.71 ○ 1.67 ○ ◎ ◎ 26 sec ◎ ◎ Example 11 110.6 3.68 ○ 1.66 ○ ◎ ◎ 26 sec ◎ ◎ Comparative Example 1 127.6 4.53 △ 1.65 ○ X X 26 sec X △ Comparative Example 2 136.9 4.36 X 1.63 ○ X △ 28 sec △ ○ Comparative Example 3 138.9 4.96 X 1.64 ○ X X 30 sec X △ Comparative Example 4 125.3 4.73 △ 1.64 ○ X △ 25 sec △ ○

Thus, it can be seen that the colored photosensitive resin composition comprising the pigment dispersion composition according to the present invention has a small particle size, a low viscosity, and a small change with time.

When the colored pattern is manufactured using the colored photosensitive resin composition, the optical pattern (OD), optical properties, flatness (DOP), reliability, and elastic recovery rate of the colored pattern are very excellent, and there are almost no VCD stains and surface defects. Able to know. Therefore, reliability and elastic recovery rate as well as optical characteristics of the color filter including the color pattern and the display device including the color filter may be improved.

Claims (13)

Preparing a varnish by mixing a dispersant, a dispersion resin, and a dispersion solvent;
Adding a pigment to the varnish to prepare a pigment dispersion;
Preparing a low viscosity pigment dispersion by dispersing the pigment dispersion at a linear speed of 6 to 11 m / s at 40 to 80 ° C. for 10 to 24 hours; And
Filtering the low viscosity pigment dispersion to produce a pigment dispersion composition,
The viscosity of the said pigment dispersion composition is 3-5 mPa * s, The manufacturing method of the pigment dispersion composition characterized by the above-mentioned.
The method according to claim 1,
Preparing the varnish,
A first step of preparing a dispersion resin liquid by mixing the dispersion resin and the dispersion solvent; And
Method for producing a pigment dispersion composition comprising the second step of preparing the varnish by adding the dispersant to the dispersion resin solution, and mixed at a linear speed of 5 to 6 m / s for 25 to 40 minutes.
The method according to claim 2,
The second step,
A method for producing a pigment dispersion composition, which further comprises adding a dispersion aid to the dispersion resin solution, followed by mixing.
The method according to claim 1,
Preparing the pigment dispersion,
After the addition of the pigment to the varnish, a method for producing a pigment dispersion composition, characterized in that for 1 hour mixing at a linear speed of 5m / s.
The method according to claim 1,
Preparing the pigment dispersion composition,
Method for producing a pigment dispersion composition, characterized in that the low viscosity pigment dispersion is filtered through a filter having a pore size of 0.2 to 0.8μm.
The method according to claim 1,
Based on 100% by weight of the pigment dispersion composition, the pigment is a method for producing a pigment dispersion composition, characterized in that 12 to 15% by weight.
The method according to claim 1,
The dispersion resin is a method of producing a pigment dispersion composition, characterized in that it has a structure of formula (1).
[Formula 1]

In Chemical Formula 1,
R ₁ , R ₂ and R ₃ are each independently hydrogen or a methyl group,
R ₄ is a direct link or a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms,
a, b and c are each independently an integer of 1 to 20,
A is at least one monomer selected from (meth) acrylic acid ester, (meth) acrylamide, allyl compound, vinyl ether, vinyl ester or styrene.
The method according to claim 1,
The dispersion solvent has a viscosity of 2.0 mPa · s or less at room temperature, and a vapor pressure of 3.0 mmHg or less, the method for producing a pigment dispersion composition.
A pigment dispersion composition prepared according to claim 1.
A pigment photosensitive resin composition comprising a pigment dispersion composition, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent according to claim 9.
The method according to claim 10,
The colored photosensitive resin composition characterized by the viscosity of 2.0-4.0 mPa * s of the said coloring photosensitive resin composition based on 20 weight% of solid content in the said coloring photosensitive resin composition.
A color filter comprising a coloring pattern made of the coloring photosensitive resin composition of claim 10.
A display device comprising the color filter according to claim 12.

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