KR20220073452A - Pigment dispersion composition and colored photosensitive resin composition comprising same - Google Patents

Abstract

The present invention relates to a pigment dispersion composition and a colored photosensitive resin composition comprising the same, wherein a first pigment dispersion comprising a first red pigment having a maximum absorption wavelength at less than 615 nm and a second pigment dispersion having a maximum absorption wavelength at 615 nm or more The pigment dispersion composition of the present invention comprising a second pigment dispersion comprising a red pigment and the colored photosensitive resin composition comprising the same have excellent dispersion stability, high red color purity, and excellent adhesion and sensitivity during pattern formation A cured film can be formed. Accordingly, the pigment dispersion composition and the colored photosensitive resin composition including the same may be usefully used in a color filter.

Description

Pigment dispersion composition and colored photosensitive resin composition comprising the same

The present invention relates to a pigment dispersion composition and a colored photosensitive resin composition comprising the same.

Recently, in the field of liquid crystal displays, interest in a color liquid crystal display capable of displaying a screen with vivid colors, contrast, etc. is increasing. In one example, the color liquid crystal display may include a color filter; a TFT array substrate having a thin film transistor (TFT) element, a pixel electrode, and an alignment layer; and a liquid crystal layer provided in a gap between the color filter and the TFT array substrate.

The color liquid crystal display requires display performance such as high-speed responsiveness, high contrast ratio, wide viewing angle, and high color purity, which may be influenced by physical properties of a color filter provided in the liquid crystal display.

Accordingly, research on pigment dispersions or photosensitive resin compositions for various color filters is being conducted. For example, in order to improve color purity required for a liquid crystal display, the content of a colorant used in a pigment dispersion or a photosensitive resin composition has been increased.

However, if the content of the colorant used in the pigment dispersion or the photosensitive resin composition is increased, the transmittance to an undesired wavelength, for example, a wavelength of 430 nm or less, may be lowered, but there is a problem in that adhesion and sensitivity during pattern formation are lowered.

In addition, as a red pigment, C.I. A study on a pigment dispersion and a photosensitive resin composition using Pigment Red 291 has been conducted. However, in this case, although excellent adhesion and sensitivity can be realized, there is a problem in that the color purity of red is significantly lowered by transmitting unnecessary colors at a wavelength of 430 nm or less.

Accordingly, there is a need for development of a pigment dispersion and a photosensitive resin composition capable of improving color purity while improving adhesion and sensitivity required for pattern formation.

Korean Patent Publication No. 2019-0034820

Accordingly, an object of the present invention is to provide a pigment dispersion composition capable of forming a cured film having high red color purity and excellent adhesion and sensitivity during pattern formation, and a colored photosensitive resin composition comprising the same.

Another object of the present invention is to provide a cured film and a color filter using the pigment dispersion composition or a colored photosensitive resin composition containing the same.

In order to achieve the above object, an embodiment provides a first pigment dispersion comprising a first red pigment and a first binder; and a second pigment dispersion comprising a second red pigment and a second binder, wherein the first red pigment has a maximum absorption wavelength at less than 615 nm, and wherein the second red pigment has a maximum absorption wavelength at 615 nm or more. It provides a pigment dispersion composition having.

Another embodiment provides a colored photosensitive resin composition comprising the pigment dispersion composition, a photopolymerization compound, a photoinitiator, and a solvent.

Another embodiment provides a cured film formed from the colored photosensitive resin composition.

Another embodiment provides a color filter prepared from the colored photosensitive resin composition.

The pigment dispersion composition and the colored photosensitive resin composition comprising the same according to an embodiment of the present invention can form a cured film having excellent dispersion stability, high red color purity, and excellent adhesion and sensitivity during pattern formation. Furthermore, the color filter prepared from the pigment dispersion composition and the colored photosensitive resin composition including the same can implement an image with excellent image quality.

A pigment dispersion composition according to an embodiment of the present invention comprises: a first pigment dispersion comprising a first red pigment and a first binder; and a second pigment dispersion comprising a second red pigment and a second binder, wherein the first red pigment has a maximum absorption wavelength at less than 615 nm, and wherein the second red pigment has a maximum absorption wavelength at 615 nm or more. have

The pigment dispersion composition according to an embodiment of the present invention includes a first pigment dispersion comprising a first red pigment having a maximum absorption wavelength at less than 615 nm, thereby having improved dispersion stability and forming a fine pattern to have excellent sensitivity can form a cured film; By including the second pigment dispersion containing the second red pigment having a maximum absorption wavelength at 615 nm or more, the color purity of red is very high and the transmittance for an unwanted wavelength, such as a wavelength of 430 nm or less, can be lowered. Accordingly, the pigment dispersion composition including the first and second pigment dispersions together has excellent dispersion stability, high red color purity, and excellent sensitivity during pattern formation.

Specifically, the first pigment dispersion includes a first red pigment and a first binder.

The maximum absorption wavelength of the first red pigment is less than 615 nm. Specifically, the maximum absorption wavelength of the first red pigment may be 613 nm or less, for example, 560 nm to 613 nm, 570 nm to 612 nm, or 590 nm to 612 nm. In this case, the maximum absorption wavelength means a wavelength at which maximum absorption occurs when measuring an absorption spectrum. When the maximum absorption wavelength of the first red pigment satisfies the above range, the dispersion stability of the pigment dispersion composition may be improved, and a cured film having excellent sensitivity may be formed by forming a fine pattern.

The first red pigment has an x value of 0.58 to less than 0.66, 0.60 to 0.66, or 0.62 to 0.66 or less, based on CIE 1931 color coordinates (x, y), and a y value is greater than 0.31 to 0.35 or less, 0.31 or more and 0.337 or less, or 0.31 or more and 0.324 or less.

The first red pigment is a diketopyrrolopyrrole-based, perylene-based, perinone-based, quinacridone-based, quinacridone-quinone-based, anthraquinone-based, anthanthrone-based, benzimida within a range satisfying the maximum absorption wavelength. Zolone, disazo, azo, indanthrone, phthalocyanine, triarylcarbonium, dioxazine, aminoanthraquinone, thioindigo, isoindoline, isoindolinone, pyranthrone and iso It may be at least one selected from the group consisting of biolanthrone. Specifically, the first red pigment may include a diketopyrrolopyrrole.

For example, the first red pigment is C.I. Pigment Red 254, C.I. Pigment Red 291, or a combination thereof:

[Formula 1]

[Formula 2]

In the first pigment dispersion according to the present invention, the first red pigment may have an average particle diameter of 80 to 150 nm, 80 to 130 nm, or 90 to 120 nm.

The first binder may include a copolymer of monomers of Formulas 5 to 9 below.

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

The first binder is a monomer of Formula 5 (styrene monomer, SM), a monomer of Formula 6 (benzylmaleimide, BMI), a monomer of Formula 7 (phenylmaleimide, PMI), and a monomer of Formula 8 ((2-hydroxy Propyl) methacrylate, HPMA) and a monomer of Formula 9 (2-(acryloyloxy)ethyl succinate, HOA-MS) containing a first acrylic resin obtained by polymerization, Although it is an alkali developable polymer, it also serves as a base for forming a coating film after coating and as a structure for implementing a final pattern.

When the first pigment dispersion according to an embodiment of the present invention includes the first acrylic resin, it is excellent in dispersibility, excellent in maintaining stability after dispersion, and can provide an effect of increasing contrast.

The first acrylic resin may contain repeating units (5) to (9) derived from each of the monomers of Chemical Formulas 5 to 9 from 1:1 to 3: based on the total number of moles of repeating units constituting the first acrylic resin. It may be included in a molar ratio of 1 to 6:1.5 to 5:0.1 to 6. When within the above range, it is possible to form a cured film having excellent adhesion and sensitivity during pattern formation.

A desired first acrylic resin may be prepared by polymerization of the compounds of Chemical Formulas 5 to 9 according to a conventional method. For example, a desired first acrylic resin may be prepared by polymerization of the compounds of Chemical Formulas 5 to 9 at 60 to 120° C. under a nitrogen atmosphere.

The first acrylic resin thus obtained may have a weight average molecular weight (Mw) of 3,000 to 20,000 g/mol, specifically 5,000 to 15,000 g/mol, or 6,000 to 12,000 g/mol. In addition, the first acrylic resin may have an acid value of 80 to 150 KOHmg/g, specifically, 90 to 120 KOHmg/g.

The first pigment dispersion may further include a first dispersant and a first solvent.

The first pigment dispersion of the present invention may be prepared by mixing the first acrylic resin with the first red pigment, the first dispersant and the first solvent and then milling.

The first pigment dispersion comprises 15 to 25% by weight of the first red pigment based on the total weight of the first pigment dispersion, and 1 to 100 parts by weight of the first dispersant based on 100 parts by weight of the first red pigment, 1 It may include 100 to 100 parts by weight of the first binder and 100 to 300 parts by weight of the first solvent.

Then, a bead mill, an attriter, a super mill, a homomixer, a paint shaker, a ball mill, a sand mill, or a horizontal mill for the raw material mixture in which the raw materials are mixed within the above-mentioned content range can be used for milling. For example, particles in the raw material mixture may be refined by milling the raw material mixture using 0.5 to 1.6 mm beads for about 4 to 12 hours.

Alternatively, the large aggregated particles in the raw material mixture are homogenized by primary milling the raw material mixture in which the raw materials are mixed within the above-mentioned content range using 0.5 to 1.6 mm beads (first dispersion process), and the first By secondary milling the milled raw material mixture using 0.3 to 0.05 mm microbeads, the particles in the raw material mixture can be refined (secondary dispersion process) (equipment: paint kneader).

In addition, the dispersion of the dispersion may be stabilized by aging the dispersion of the first pigment dispersion for a certain period of time, for example, 24 to 168 hours.

As the first dispersant and the first solvent, those commonly used may be used.

Specific examples of the first dispersant include acrylate-based dispersants such as butyl (meth) acrylate and N,N-dimethylaminoethyl (meth) acrylate; Styrene-acrylic acid resin, styrene-methacrylic acid resin, styrene-acrylic acid-acrylic acid ester resin, styrene-maleic acid resin, styrene-acrylic acid-acrylic acid ester resin, styrene-maleic acid ester resin, methacrylic acid-methacrylic acid ester resin, acrylic acid -Resin containing ethylenic double bond, such as an acrylic acid ester resin, an isobutylene-maleic acid resin, and a vinyl-ester resin; Polyurethane, polycarboxylic acid ester, unsaturated polyamide, polycarboxylic acid, polysiloxane, (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate ester copolymer, polyvinyl alcohol, polyvinyl blood resin-type dispersants such as rollidone, polyester, modified polyacrylate, phosphoric acid ester, and polycarboxylic acid; and mixtures thereof, but are not limited thereto.

Commercially available examples of first dispersants include Disperbyk-110, 111, 180, 161, 163, 165, 166, 167, 2000, 2001, 2163, LPN-21116, LPN-6919, LPN-21538, LPN-21208 (BYK- chemie), LPN-21324, LPN-21208, PB-821, 822, 880, 881 (Ajinomoto Fine Techno), solsperse 24000 (Lubrizol), etc. can be used alone or in combination of two or more.

Specific examples of the first solvent include (poly)alkylene glycol monoalkyl ethers such as diethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; (poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; ethers such as diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, and glycerin; and mixtures thereof, but are not limited thereto.

If necessary, the first pigment dispersion may further include a first dispersing aid serving to help the dispersing agent act to shorten the dispersion time of the first pigment dispersion and to more stably maintain the viscosity of the first pigment dispersion. have. As the first dispersing aid, those commonly used may be used. In addition, the first pigment dispersion may include 1 to 10 parts by weight of the first dispersing aid based on 100 parts by weight of the first red pigment.

Meanwhile, the second pigment dispersion includes a second red pigment and a second binder.

The maximum absorption wavelength of the second red pigment is 615 nm or more. Specifically, the maximum absorption wavelength of the second red pigment may be, for example, 615 nm to 680 nm, 620 nm to 680 nm, or 620 nm to 670 nm. When the maximum absorption wavelength of the second red pigment satisfies the above range, the inherent red color purity is very high and the transmittance of other wavelengths is low, so that when applied to a color filter, excellent image quality having high color purity can be provided.

The second red pigment has an x value of 0.66 or more to 0.695 or less, 0.66 or more to 0.6835 or less, or 0.66 to 0.6832 or less, and a y value of 0.27 to 0.31 or less, 0.284 based on CIE 1931 color coordinates (x, y). or more and 0.31 or less, or 0.290 or more and 0.31 or less.

The second red pigment is diketopyrrolopyrrole-based, perylene-based, perinone-based, quinacridone-based, quinacridone-quinone-based, anthraquinone-based, anthanthrone-based, and benzimida within a range satisfying the maximum absorption wavelength. Zolone, disazo, azo, indanthrone, phthalocyanine, triarylcarbonium, dioxazine, aminoanthraquinone, thioindigo, isoindoline, isoindolinone, pyranthrone and iso It may be at least one selected from the group consisting of biolanthrone. Specifically, the second red pigment may include at least one selected from the group consisting of diketopyrrolopyrrole and perylene.

For example, the second red pigment is C.I. Pigment Red 264, C.I. Pigment Red 179, or a combination thereof:

[Formula 3]

[Formula 4]

In the second pigment dispersion according to the present invention, the second red pigment may have an average particle diameter of 80 to 150 nm, 80 to 130 nm, or 90 to 120 nm.

The second binder may include a copolymer of monomers of Chemical Formulas 5 to 11 below.

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

In the above formula (11),

R ¹ and R ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 13 carbon atoms, a hydrocarbon group having 1 to 13 carbon atoms substituted with a hydroxyl group, or an ester group having 1 to 20 carbon atoms,

R ³ is a hydrogen atom, a hydrocarbon group having 1 to 13 carbon atoms, or an ester group having 1 to 20 carbon atoms,

X is an oxygen atom or =CH ₂ .

Specifically, R ³ is a hydrogen atom or an ester group having 1 to 20 carbon atoms, more specifically R ³ is R ⁴ -COO-L-, wherein R ⁴ is an alkyl group or alkenyl group having 1 to 6 carbon atoms, L is an alkylene group having 1 to 13 carbon atoms.

Formula 11 may include, for example, 11-phosphonoundecyl acrylate represented by Formula 11-1 below.

[Formula 11-1]

The second binder is a monomer of Formula 5 (styrene monomer, SM), a monomer of Formula 6 (benzylmaleimide, BMI), a monomer of Formula 7 (phenylmaleimide, PMI), and a monomer of Formula 8 ((2-hydroxy propyl) methacrylate, HPMA), a monomer of formula 9 (2-(acryloyloxy)ethyl succinate, HOA-MS), a monomer of formula 10 (glycidyl methacrylate, GMA) and a monomer of formula 11 It contains a second acrylic resin obtained by polymerizing (phosphoric acid monomer), and in the developing step, it is an alkali developable polymer that realizes developability, and also serves as a base for forming a coating film after coating and a structure for implementing a final pattern. .

When the second pigment dispersion according to an embodiment of the present invention includes the second acrylic resin, a cured film having excellent adhesion and sensitivity during pattern formation may be formed.

The second acrylic resin contains repeating units (5) to (11) derived from each of the monomers of Chemical Formulas 5 to 11 from 1:0.5 to 3: based on the total number of moles of repeating units constituting the second acrylic resin. It may be included in a molar ratio of 0.5 to 5:1 to 6:0.1 to 7:0.1 to 8:0.1 to 10. When within the above range, it is possible to form a cured film having excellent adhesion and sensitivity during pattern formation.

The desired second acrylic resin may be prepared by polymerization of the monomers of Chemical Formulas 5 to 11 according to a conventional method. For example, the desired second acrylic resin may be prepared by polymerization of the monomers of Chemical Formulas 5 to 11 at 60 to 120° C. under a nitrogen atmosphere.

For example, in a nitrogen atmosphere, the monomers of Formulas 5 to 9 are subjected to a first polymerization reaction at 60 to 120° C. to obtain a copolymer, and then, the monomers of Formulas 10 and 11 are added to the obtained copolymer, and at 60 to 120° C. A second polymerization reaction may be performed to prepare a second desired acrylic resin.

The second acrylic resin thus obtained may have a weight average molecular weight (Mw) of 3,000 to 20,000 g/mol, specifically 5,000 to 15,000 g/mol, or 6,000 to 12,000 g/mol. In addition, the second acrylic resin may have an acid value of 80 to 150 KOHmg/g, specifically, 100 to 130 KOHmg/g.

Meanwhile, the second binder included in the second pigment dispersion may include the first acrylic resin within a range that does not impair the effects of the present invention. Alternatively, the first acrylic resin and the second acrylic resin may be mixed and included.

Likewise, the first binder included in the first pigment dispersion may include the second acrylic resin within a range that does not impair the effects of the present invention. Alternatively, the first acrylic resin and the second acrylic resin may be mixed and included.

According to an embodiment of the present invention, when the first binder included in the first pigment dispersion includes the first acrylic resin, and the second binder included in the second pigment dispersion includes the second acrylic resin , it may be more advantageous to form a cured film having excellent adhesion and sensitivity during pattern formation.

The second pigment dispersion may further include a second dispersant and a second solvent.

The second pigment dispersion of the present invention may be prepared by mixing the second acrylic resin with the second red pigment, the second dispersant and the second solvent and then milling.

The second pigment dispersion comprises 15 to 25% by weight of the second red pigment based on the total weight of the second dispersion, and 1 to 100 parts by weight of the second dispersant, based on 100 parts by weight of the second red pigment, 1 to 100 parts by weight of the second binder and 100 to 300 parts by weight of the second solvent may be included.

The method for preparing the second pigment dispersion may use the same method as the method for preparing the above-described first pigment dispersion.

As the second dispersant and the second solvent, those commonly used may be used, and specific examples thereof are the same as described above for the first dispersant and the first solvent, respectively. In addition, the first dispersing agent and the second dispersing agent may be the same as or different from each other. The first solvent and the second solvent may be the same as or different from each other.

If necessary, the second pigment dispersion may further include a second dispersing aid serving to help the dispersing agent act to shorten the dispersion time of the second pigment dispersion and to more stably maintain the viscosity of the second pigment dispersion. have. As the second dispersing aid, those commonly used may be used. In addition, the second pigment dispersion may include 1 to 10 parts by weight of the second dispersing aid based on 100 parts by weight of the second red pigment.

In the pigment dispersion composition according to the embodiment of the present invention, the weight ratio of the first pigment dispersion and the second pigment dispersion may be 1:0.2 to 3. The weight ratio of the first pigment dispersion and the second pigment dispersion may be 1:0.3 to 3, 1:0.4 to 3, or 1:0.4 to 2.5. When the first pigment dispersion and the second pigment dispersion are mixed and included in the above weight ratio, dispersion stability may be improved, the color purity of red may be further improved, and excellent sensitivity may be exhibited during pattern formation. In this case, when the content of the first pigment dispersion is too large, the color purity of red may be lowered. When the content of the second pigment dispersion is too large, dispersion stability and luminance may be deteriorated, and sensitivity during pattern formation may be reduced.

On the other hand, the colored photosensitive resin composition according to another embodiment of the present invention includes the pigment dispersion composition, a photopolymerization compound, a photoinitiator and a solvent, and if necessary, an alkali developable binder resin, a surfactant, a silane coupling agent, and oxidation It may further include an inhibitor, a stabilizer, a leveling agent, and the like.

The colored photosensitive resin composition of the present invention comprising the above components can be prepared by a conventional method of uniformly mixing the above components. The type and content of the components may also be appropriately selected within the range commonly used.

Meanwhile, according to another embodiment of the present invention, a cured film formed from the colored photosensitive resin composition may be provided.

The cured film is applied to a desired thickness using a method such as a spin or slit coating method, a roll coating method, a screen printing method, and an applicator method on a substrate subjected to a predetermined pretreatment with the colored photosensitive resin composition according to the present invention, It can be obtained by forming a coating film by removing the solvent by pre-bake at a temperature of 70 to 100° C. for 1 to 10 minutes.

The cured film may have a transmittance of 42% or less, 35% or less, 30% or less, 25% or less, 20% or less, or 18% or less at a 380 nm wavelength (i-line). For example, the cured film may have a transmittance of 5% or more to 42% or less, 5% or more to 35% or less, or 5% or more to 20% or less at a wavelength of 380 nm. When the transmittance of the cured film at a wavelength of 380 nm exceeds 42%, color purity may be deteriorated by transmitting unnecessary colors.

In addition, the cured film may have a maximum transmission wavelength of more than 610 nm, 615 nm or more, 616 nm or more, 620 nm or more, or 622 nm or more. For example, the cured film may have a maximum transmission wavelength of more than 610 nm to 645 nm or less, 615 nm or more to 640 nm or less, or 616 nm or more to 638 nm or less. The maximum transmission wavelength may be evaluated by measuring a wavelength region having a transmittance of 85% or more based on a thickness of 1.0 μm of the coating film using a transmission spectrum. If the maximum transmission wavelength of the cured film is 610 nm or less, the color purity of red may be reduced.

The cured film according to an embodiment of the present invention has a high maximum transmission wavelength of more than 610 nm, and has a low transmittance in an i-line of 380 nm, so that unnecessary colors are not transmitted, red is transmitted to the maximum, and the color purity of red can increase In addition, it is possible to implement pattern characteristics having excellent sensitivity during pattern formation. In the case of the sensitivity, when the pattern is formed, the line width of the fine pattern of 50 μm may be 80% or more, 85% or more, 90% or more, or 95% or more.

In particular, according to the embodiment of the present invention, when the second pigment dispersion includes the second binder, it is possible to provide a cured film that satisfies the above effects and has excellent adhesion during pattern formation, and the sensitivity can be further improved. have. In the case of the adhesion, the existing cured film has a minimum fine pattern size of 30 μm or more when forming a pattern, whereas the cured film formed from the colored photosensitive resin composition of the present invention has a 30 μm fine pattern of 50% or more, 60% or more, or 70% or more. can

Meanwhile, according to another embodiment, the present invention may provide a color filter prepared from the colored photosensitive resin composition.

For example, a color filter may be manufactured by coating the colored photosensitive resin composition on one surface of a substrate and repeating a series of processes of exposure, development, and thermosetting to form a colored layer. A method of manufacturing the color filter may use a commonly used method.

The color filter prepared from the colored photosensitive resin composition may implement an image with excellent image quality. Accordingly, the color filter may be usefully used in an image display device. For example, the color filter may be used in an image sensor, and the image sensor may include, for example, a CMOS image sensor.

As described above, the pigment dispersion composition of the present invention and the colored photosensitive resin composition including the same have excellent dispersion stability, have high red color purity, and form a cured film having excellent adhesion and sensitivity during pattern formation. , can be usefully used in image display devices such as color filters.

Hereinafter, the present invention will be described in more detail by way of Examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

Example

<Manufacture of binder>

Preparation Example 1: Preparation of the first binder

Into a 1.0 liter round flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel and a nitrogen introduction tube, 155 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent and 1-methoxypropane-2- as a polymerization initiator 45 g of ol (PGME) was added and stirred. Here, benzylmaleimide (BMI) 100g, phenylmaleimide (PMI) 120g, styrene monomer (SM) 70g, (2-hydroxypropyl)methacrylate (HPMA) 63g, 2-(acryloyloxy)ethyl After adding 22 g of succinate (HOA-MS), it was reacted at 85° C. for 15 hours to obtain a copolymer having a carboxyl group. The reaction was carried out under a nitrogen atmosphere. As a result of analyzing the prepared copolymer (binder), the solid content was 30.5 wt%, acid value 105 KOHmg/g, and weight average molecular weight (Mw, GPC result) 10,500 g/mol.

The prepared copolymer (binder) contained repeating units derived from each of SM, BMI, PMI, HPMA and HOA-MS in a molar ratio of 1: 1.5: 1.7: 2.1: 0.4.

Preparation Example 2: Preparation of the second binder

By changing the amount of BMI, PMI, SM, HPMA and HOA-MS to 98 g, 115 g, 66 g, 65 g and 32 g, respectively, the same process as in Preparation Example 1 was performed to prepare a copolymer having a carboxyl group. Then, 23 g of 11-phosphonoundecyl acrylate and 12 g of glycidyl methacrylate (GMA) were added to the obtained copolymer as a phosphoric acid-based monomer, and reacted at 80° C. for 5 hours under a nitrogen atmosphere to air A coalescence (binder) solution was prepared. The reaction was carried out under a nitrogen atmosphere. As a result of analyzing the prepared copolymer (binder), it was found that the solid content was 31.8% by weight, the acid value was 118 KOHmg/g, and the weight average molecular weight (Mw, GPC result) was 9,800 g/mol.

The copolymer (binder) prepared above contains repeating units derived from each of SM, BMI, PMI, HPMA, HOA-MS, GMA and phosphoric acid monomers in a molar ratio of 1: 1.3: 1.5: 1.8: 0.3: 0.7: 0.45. did

<Preparation of pigment dispersion>

Preparation A: Preparation of Pigment Dispersion 254

C.I. Based on 100 parts by weight of Pigment Red Pigment 254, 80 parts by weight of propylene glycol monomethyl ether (PGME) as a solvent, 50 parts by weight of a dispersant (BYK Disperbyk-2001), 40 parts by weight of the binder prepared in Preparation Example 1, and dispersion After mixing 10 parts by weight of the preparation (Solsperse 22000), the mixture was pre-mixed at 650 rpm for 60 minutes to prepare a raw material mixture.

The prepared raw material mixture was milled using 0.5 to 1.6 mm beads for 6 hours to refine the particles in the raw material mixture to prepare a pigment dispersion 254 having an average particle diameter of 105 nm.

Preparation B: Preparation of Pigment Dispersion 291

C.I. Instead of Pigment Red Pigment 254, C.I. A pigment dispersion 291 having an average particle diameter of 98 nm was prepared in the same manner as in Preparation A, except that the pigment red pigment 291 was used.

Preparation C: Preparation of Pigment Dispersion 179

C.I. Instead of Pigment Red Pigment 254, C.I. A pigment dispersion 179 having an average particle diameter of 113 nm was prepared in the same manner as in Preparation A, except that the pigment red pigment 179 was used.

Preparation D: Preparation of Pigment Dispersion 264a

C.I. Instead of Pigment Red Pigment 254, C.I. A pigment dispersion 264a having an average particle diameter of 120 nm was prepared in the same manner as in Preparation A, except that the pigment red pigment 264 was used.

Preparation E: Preparation of Pigment Dispersion 264b

C.I. Instead of Pigment Red Pigment 254, C.I. Pigment red pigment 264 was used and the pigment dispersion 264b having an average particle diameter of 103 nm was obtained by performing the same process as in Preparation A, except that the second binder prepared in Preparation Example 2 was used as a binder. prepared.

Example 1

<Preparation of pigment dispersion composition>

The pigment dispersion 254 obtained in Preparation Example A as the first pigment dispersion and the pigment dispersion 179 obtained in Preparation Example C as the second pigment dispersion were stirred at a weight ratio of 70:30 to obtain a pigment dispersion composition.

<Production of colored photosensitive resin composition>

Based on the solid content, 5.5 wt% of a photopolymerization compound, 1 wt% of a photopolymerization initiator, 0.35 wt% of an additive and 48.15 wt% of a solvent are added to 45 wt% of the pigment dispersion composition, and a stabilization process is performed at 8 ° C. for 3 hours or more. The colored photosensitive resin composition which said

At this time, dipentaerythritol hexaacrylate (DPHA, Miwon Corporation) as a photopolymerization compound, OXE-02 (IRGACURE) as a photopolymerization initiator, DIC F-554 (DIC KOREA) as an additive, and propylene glycol monomethyl ether acetate (PGMEA) as a solvent ) was used.

Example 2

A pigment dispersion composition and a colored photosensitive resin composition were prepared in the same manner as in Example 1, except that the pigment dispersion 291 obtained in Preparation Example B was used as the first pigment dispersion.

Example 3

A pigment dispersion composition and a colored photosensitive resin composition were prepared in the same manner as in Example 1, except that the pigment dispersion 264a obtained in Preparation Example D was used as the second pigment dispersion.

Example 4

A pigment dispersion composition and a colored photosensitive resin composition were prepared in the same manner as in Example 3, except that the weight ratio of the first pigment dispersion liquid and the second pigment dispersion liquid was changed to 50:50.

Example 5

A pigment dispersion composition and a colored photosensitive resin composition were prepared in the same manner as in Example 3, except that the weight ratio of the first pigment dispersion liquid and the second pigment dispersion liquid was changed to 30:70.

Example 6

A pigment dispersion composition and a colored photosensitive resin composition were prepared in the same manner as in Example 5, except that the pigment dispersion 264b obtained in Preparation Example E was used as the second pigment dispersion.

Example 7

The same process as in Example 1 was performed except that the pigment dispersion 291 obtained in Preparation B was used as the first pigment dispersion, and the pigment dispersion 264a obtained in Preparation Example D was used as the second pigment dispersion, and the pigment dispersion composition And a colored photosensitive resin composition was prepared.

Example 8

A pigment dispersion composition and a colored photosensitive resin composition were prepared in the same manner as in Example 7, except that the weight ratio of the first pigment dispersion liquid and the second pigment dispersion liquid was changed to 30:70.

Example 9

A pigment dispersion composition and a colored photosensitive resin composition were prepared in the same manner as in Example 8, except that the pigment dispersion 264b obtained in Preparation Example E was used as the second pigment dispersion.

Comparative Example 1

A colored photosensitive resin composition was prepared in the same manner as in Example 1, except that the pigment dispersion 254 obtained in Preparation Example A was used alone as the pigment dispersion.

Comparative Example 2

A colored photosensitive resin composition was prepared in the same manner as in Example 1, except that the pigment dispersion 291 obtained in Preparation Example B was used alone as the pigment dispersion.

Comparative Example 3

As the first pigment dispersion, the pigment dispersion 254 obtained in Preparation Example A and the pigment dispersion 291 obtained in Preparation Example B were mixed in a 50:50 weight ratio, and Example 1 was used except that the second pigment dispersion was not used. The same process was performed to prepare a pigment dispersion composition and a colored photosensitive resin composition.

<Test Example>

Test Example 1: Maximum transmission wavelength

Each of the colored photosensitive resin compositions prepared in Examples and Comparative Examples was coated on a glass substrate using a spin coater, and then cured by heat treatment at 100° C. for 10 minutes to form a coating film (cured film). The transmission spectrum was measured using Hitachi's u4100. The maximum transmission wavelength was evaluated by measuring a wavelength region having a transmittance of 85% based on a thickness of 1.0 μm of the coating film.

Test Example 2: Transmittance at 380 nm wavelength

In the transmission spectrum used in Test Example 1, transmittance at a wavelength of 380 nm was confirmed.

Test Example 3: Adhesion

Each of the colored photosensitive resin compositions prepared in Examples and Comparative Examples was coated on a glass substrate using a spin coater, and then cured by heat treatment at 100° C. for 10 minutes to form a coating film having a thickness of 1.0 μm. Then, a photomask was applied to the coating film, and an energy of 40 mJ/cm 2 was irradiated under a mercury lamp. The exposed coating film was developed by a spray method using an aqueous solution of 0.05 wt % KOH at room temperature, and then washed with distilled water. The micropatterns remaining on the glass substrate (pattern line width: 1 to 40 μm) were observed under a VHX-1000E optical microscope of Keynece at 200 magnification to measure the size of the remaining micropatterns.

Adhesiveness was evaluated as follows according to the pattern adhered to the substrate based on a circular pattern diameter of 30 μm.

More than 90%: ◎

More than 80% and less than 90%: ○

70% or more and less than 80%: △

More than 60% and less than 70%: X

Less than 60%: XX

Test Example 4: Sensitivity

It was measured by observing the fine pattern in the same manner as the adhesion evaluation of Test Example 3.

The sensitivity was evaluated as follows according to the line width of the pattern formed based on the micropattern line width of 50 μm.

96% or more: ◎,

More than 90% and less than 96%: ○

More than 85% and less than 90%: △

More than 80% and less than 85%: X

From the experimental results of Table 1, the cured film of Examples prepared using the pigment dispersion composition including the first pigment dispersion and the second pigment dispersion together has a low transmittance of 42% or less at a wavelength of 380 nm as compared to the comparative example and a maximum transmission wavelength greater than 610 nm.

Specifically, the cured films of Examples 1 to 9 have a maximum transmission wavelength of 616 nm or more, thereby effectively transmitting red to implement a maximum intrinsic color, and a low transmittance of 16.35% to 40.18% at a wavelength other than red, 380 nm. By having , it was confirmed that less unnecessary colors were transmitted, and the color purity of red could be further increased.

On the other hand, the cured films of Comparative Examples 1 and 2 using one pigment dispersion had maximum transmittance wavelengths of 610 nm and 605 nm, respectively, and had high transmittances of 42.60% and 49.20%, respectively, at a wavelength of 380 nm. That is, it was confirmed that the color purity of red may be lowered by transmitting a lot of unnecessary colors at wavelengths other than the red wavelength region.

In addition, the cured film of Comparative Example 3 using two first red pigments having a maximum absorption wavelength at less than 615 nm had a maximum transmission wavelength of 607 nm similar to the cured films of Comparative Examples 1 and 2, and 46.70% at a wavelength of 380 nm had high transmittance. It can be seen that even in this case, the color purity of red may be lowered.

On the other hand, from the experimental results in Table 2, it was confirmed that even when a pigment dispersion composition including the first pigment dispersion and the second pigment dispersion was used, the adhesiveness and sensitivity of the cured film were different depending on the type of binder.

Specifically, it can be seen that when the second binder using a phosphoric acid-based monomer is used as in Examples 6 and 9, adhesion and sensitivity can be improved while maintaining high color purity of red.

In particular, comparing Examples 5 and 6 and Examples 8 and 9, respectively, the cured films of Examples 6 and 9 using the second binder even when the same first red pigment and second red pigment were used were obtained in Examples 5 and 8. It was confirmed that adhesion and sensitivity were significantly improved compared to the cured film of

Therefore, the embodiment using the pigment dispersion composition according to the embodiment of the present invention can increase the transmittance at a desired wavelength and lower the transmittance at an unnecessary wavelength to increase the color purity of the red color, and it can be confirmed that the adhesion and sensitivity are also improved. there was.

Claims (13)

a first pigment dispersion comprising a first red pigment and a first binder; and
A second pigment dispersion comprising a second red pigment and a second binder,
wherein the first red pigment has a maximum absorption wavelength below 615 nm;
wherein the second red pigment has a maximum absorption wavelength at 615 nm or more.
The method of claim 1,
The first red pigment has an x value of 0.58 or more to less than 0.66 and a y value of more than 0.31 to 0.35 or less based on CIE 1931 color coordinates (x, y),
The second red pigment has an x value of 0.66 or more to 0.695 or less and a y value of 0.27 or more and 0.31 or less, based on CIE 1931 color coordinates (x, y).
3. The method of claim 2,
The first red pigment comprises CI Pigment Red 254 represented by the following Chemical Formula 1, CI Pigment Red 291 represented by the following Chemical Formula 2, or a combination thereof,
The second red pigment is a pigment dispersion composition comprising CI Pigment Red 264 represented by the following Chemical Formula 3, CI Pigment Red 179 represented by the following Chemical Formula 4, or a combination thereof.
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

The method of claim 1,
The first binder comprises a first acrylic resin comprising a copolymer of monomers of Chemical Formulas 5 to 9,
A pigment dispersion composition, wherein the second binder includes a second acrylic resin including a copolymer of monomers represented by the following Chemical Formulas 5 to 11:
[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

In the above formula (11),
R ¹ and R ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 13 carbon atoms, a hydrocarbon group having 1 to 13 carbon atoms substituted with a hydroxyl group, or an ester group having 1 to 20 carbon atoms,
R ³ is a hydrogen atom, a hydrocarbon group having 1 to 13 carbon atoms, or an ester group having 1 to 20 carbon atoms,
X is an oxygen atom or =CH ₂ .
5. The method of claim 4,
In the first acrylic resin, based on the total number of moles of the repeating units constituting the first acrylic resin, the repeating units (5) to (9) derived from each of the monomers of Chemical Formulas 5 to 9 are 1:1 to 3: 1 to 6:1.5 to 5:0.1 to 6 in a molar ratio,
The second acrylic resin contains the repeating units (5) to (11) derived from each of the monomers of Chemical Formulas 5 to 11 from 1:0.5 to 3: A pigment dispersion composition comprising a molar ratio of 0.5 to 5:1 to 6:0.1 to 7:0.1 to 8:0.1 to 10.
5. The method of claim 4,
The first acrylic resin and the second acrylic resin each have a weight average molecular weight (Mw) of 3,000 to 20,000 g/mol and an acid value of 80 to 150 KOHmg/g, a pigment dispersion composition.
The method of claim 1,
The first pigment dispersion further comprises a first dispersant and a first solvent,
The first pigment dispersion comprises 15 to 25% by weight of the first red pigment based on the total weight of the dispersion, and 1 to 100 parts by weight of the first dispersant, 1 to 100 parts by weight based on 100 parts by weight of the first red pigment parts of a first binder and 100 to 300 parts by weight of a first solvent,
The first red pigment has an average particle diameter of 80 to 150 nm, the pigment dispersion composition.
The method of claim 1,
The second pigment dispersion further comprises a second dispersant and a second solvent,
The second pigment dispersion comprises 15 to 25% by weight of the second red pigment based on the total weight of the dispersion, and 1 to 100 parts by weight of the second dispersant, 1 to 100 parts by weight based on 100 parts by weight of the second red pigment parts of a second binder and 100 to 300 parts by weight of a second solvent,
The second red pigment has an average particle diameter of 80 to 150 nm, the pigment dispersion composition.
The method of claim 1,
The weight ratio of the first pigment dispersion and the second pigment dispersion is 1:0.2 to 3, the pigment dispersion composition.
A colored photosensitive resin composition comprising the pigment dispersion composition of claim 1, a photopolymerization compound, a photoinitiator, and a solvent.
The cured film formed from the coloring photosensitive resin composition of Claim 10.
12. The method of claim 11,
The cured film has a transmittance of 42% or less at a wavelength of 380 nm and a maximum transmittance wavelength of greater than 610 nm.
A color filter prepared from the colored photosensitive resin composition of claim 10 .