KR20110075693A - Manufacturing method of dye for color filter, dye for color filter by using same, composition for color filter including same - Google Patents

Abstract

PURPOSE: A method for manufacturing dye for a color filter is provided to prepare dyes for a color filter with excellent solubility to an organic solvent for the color filter and good color properties. CONSTITUTION: A method for manufacturing dye for a color filter comprises the steps of: dissolving dye having a sulfonic acid group of a metal salt form in water; adding acids to the dye dissolved in water, mixing the materials, and ionizing the dye; injecting an organic solvent and alkylamine represented by chemical formula 1 in water in which the dyes are ionized, mixing the materials, and transferring dyes having a sulfonic acid group in an organic salt form to an organic solvent; and removing a water layer excluding the dyes and purifying an organic solvent layer including the dye.

Description

Manufacturing method of color filter dye, color filter dye manufactured therefrom, composition for color filter comprising same {MANUFACTURING METHOD OF DYE FOR COLOR FILTER, DYE FOR COLOR FILTER BY USING SAME, COMPOSITION FOR COLOR FILTER INCLUDING SAME}

The present disclosure relates to a method for preparing a color filter dye, a color filter dye prepared therefrom, and a color filter composition comprising the same.

The color filter is used in a liquid crystal display device, an optical filter of a camera, and the like, and is manufactured by coating a fine region colored with three or more colors on a solid state imaging device or a transparent substrate. Such colored thin films are usually formed by dyeing, printing, electrodeposition, pigment dispersion, inkjet, or the like. Currently, this method is applied to manufacturing LCDs of mobile phones, laptops, monitors, TVs, and the like.

In the dyeing method, an image having a dyeing base material such as natural photosensitive resin such as gelatin, amine-modified polyvinyl alcohol, amine-modified acrylic binder resin and the like is formed on a glass substrate in advance, and then dyed with a dye such as a direct dye. However, in order to form a multi-colored thin film on the same substrate, it is necessary to perform flameproof processing every time the color is changed, so that the process is very complicated and the time is delayed. In addition, the clarity and dispersibility of the commonly used dyes and resins themselves are good, but there are disadvantages in that light resistance, moisture resistance and heat resistance, which are the most important characteristics, are poor.

In the printing method, printing is performed using the ink which disperse | distributed the pigment to thermosetting or photocurable resin, and a colored thin film is formed by hardening with heat or light. According to this method, the material cost can be reduced compared to other methods, but it is difficult to form highly precise and detailed images, and the thin film layer formed is not uniform. Korean Patent Publication No. 1996-0011513 proposes a method of manufacturing a color filter using an inkjet method, and since the colored photosensitive resin composition sprayed from the nozzle is dye-like for printing delicate and accurate pigments, it is similar to the dyeing method. Durability and heat resistance are inferior.

In contrast, Korean Patent Publication No. 1996-0029904 proposes an electrodeposition method using an electroprecipitation method, which can form a precise colored thin film and has a characteristic of excellent heat resistance and light resistance due to the use of a pigment. When the pixel size is precise and the electrode pattern is fine, there is a problem that color unevenness due to electrical resistance appears at both ends or the thickness of the colored thin film becomes thick, which makes it difficult to apply to color filters requiring high precision.

On the other hand, the pigment dispersion method repeats a series of processes of coating a photopolymerizable composition containing a colorant on a transparent substrate provided with a black matrix, exposing it in the form of a pattern to be formed, and then thermally curing the non-exposed areas with a solvent. It is a method by which a colored thin film is formed. The pigment dispersion method has the advantage of improving heat resistance and durability, which are the most important properties of the color filter, and maintaining the thickness of the film uniformly. In addition, since the fine pattern is excellent in implementation and the manufacturing method is relatively easy, it is commonly adopted. For example, Japanese Patent Laid-Open No. Hei 7-140654, Japanese Patent Laid-Open No. Hei 10-254133 and the like have proposed a method of producing a color resist using pigment dispersion.

The colored photosensitive resin composition used for manufacturing the color filter according to the pigment dispersion method is generally composed of a binder resin, a photopolymerizable monomer, a photopolymerization initiator, an epoxy resin, a solvent and other additives, and the pigment dispersion is a color filter of the color filter. , The most important factor affecting the processability during manufacturing, and as the technology of LCD and solid-state image sensor is developed, the demand for excellent color characteristics is increasing.

Accordingly, the development of dyes capable of realizing finer particles beyond the limits of color filters based on pigments is underway.

Korean Patent No. 0732351 relates to a novel method for preparing salts of sulfonated distyryl-biphenyl compounds, and further discloses a purification method of increasing the purity using alkaline earth metals after forming salts with alkyl amines. It is. The patent aims to obtain a material of high purity through a phase change from an alkali metal salt (water layer) to an organic salt (organic layer) to an alkali metal salt (water layer). Korean Patent Laid-Open Publication No. 2007-0116165 relates to a dye-containing curable composition, a color filter, and a manufacturing method thereof, and discloses a salt of a cation composed of an acidic dye and a nitrogen-containing compound. The patent lists salts with various nitrogen-containing compounds and indicates that they can form salts, but the method of forming salts is not specifically stated, and no specific example of synthesis can be found. The method of synthesizing is most of the method of dissolving in water to remove the water after synthesis or drying to obtain the target material. In other words, the conventional technique cannot obtain a dye having excellent solubility in the solvent of the color filter.

One aspect of the present invention is to provide a method for producing a color filter dye having excellent solubility in an organic solvent for color filters and excellent color characteristics.

Another aspect of the present invention is to provide a color filter dye prepared from the method for producing a color filter dye.

Another aspect of the present invention is to provide a composition for a color filter comprising the dye for the color filter.

One aspect of the invention, the step of dissolving a dye (dye) having a sulfonic acid group in the form of a metal salt in water (S1); Adding an acid to the dye dissolved in water and stirring to ionize the dye (S2); Adding an organic solvent and an alkylamine represented by the following Chemical Formula 1 to water in which the dye is ionized and stirring to move a dye having a sulfonic acid group in an organic salt form into an organic solvent (S3); And removing the water layer not containing the dye and purifying the organic solvent layer containing the dye (S4).

[Formula 1]

(In the formula 1,

R1 to R3 are independently selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, and a combination thereof, and are not all hydrogen atoms.)

In S1, the sulfonic acid group included in one molecule of the dye having the sulfonic acid group in the metal salt form may be one to three.

The acid in S2 may be sulfuric acid.

The amount of acid in the S2 may be an amount such that the pH of the reactants is 2 to 3.

In S3, the organic solvent may be selected from the group consisting of propyleneglycol monomethylether acetate (PGMEA), cyclohexanone, xylene, and combinations thereof.

The amount of the organic solvent in S3 may be 1,000 parts by weight to 2,000 parts by weight based on 100 parts by weight of the dye having a sulfonic acid group in an organic salt form.

The alkylamine in S3 may be trioctylamine (TOA; trioctylamine), tridodecylamine (TDA; tridodecylamine) or dioctylamine (DOA; dioctylamine).

The amount of the alkylamine in S3 may be added in an amount of 95 mol% to 100 mol% based on the number of moles of sulfonic acid groups included in the dye.

The reaction temperature of S2 to S3 may be 60 ℃.

Another aspect of the invention provides a color filter dye prepared from the method for producing a color filter dye according to the aspect of the present invention.

Another aspect of the present invention provides a color filter composition comprising a dye for a color filter according to another aspect of the present invention.

Still another aspect of the present invention provides a color filter manufactured using the composition for a color filter according to another aspect of the present invention.

Other details of the embodiments of the present invention are included in the following detailed description.

It is possible to provide a method for producing a color filter dye having excellent solubility in organic solvents and excellent color characteristics.

Hereinafter, aspects of the present invention will be described in more detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Unless stated otherwise in the specification, an "alkyl group" means a C1 to C30 alkyl group, and a "cycloalkyl group" means a C3 to C30 cycloalkyl group.

Unless stated otherwise in the present specification, "substituted" means that at least one hydrogen atom of the functional group is a halogen atom (F, Br, Cl, or I), a hydroxyl group, a nitro group, a cyano group, an amino group (-NRR ', R and R 'are independently C1 to C10 alkyl group), amidino group, hydrazine or hydrazone group, carboxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted cycloalkyl group, Or substituted or unsubstituted heteroalkyl group, substituted or unsubstituted heteroaryl group, and substituted or unsubstituted heterocycloalkyl group, or substituted with one or more substituents selected from the group consisting of two hydrogen atoms = O, = S, = NR 1 is selected from the group consisting of (R is an alkyl group of C1 to C10), = PR (R is an alkyl group of C1 to C10), and = CRR '(R and R' are independently, an alkyl group of C1 to C10). Or substituted with three or more substituents It means that the hydrogen atoms of ≡N, ≡P and ≡CR (R is an alkyl group of C1 to C10).

Unless otherwise stated herein, "combination" means mixed or copolymerized.

Method for producing a dye for a color filter according to an aspect of the present invention comprises the steps of dissolving a dye (dye) having a sulfonic acid group in the form of a metal salt in water (S1); Adding an acid to the dye dissolved in water and stirring to ionize the dye (S2); Adding an organic solvent and an alkylamine represented by the following Chemical Formula 1 to water in which the dye is ionized and stirring to move a dye having a sulfonic acid group in an organic salt form into an organic solvent (S3); And removing the water layer not containing the dye and purifying the organic solvent layer containing the dye (S4).

[Formula 1]

(In the formula 1,

R1 to R3 are independently selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, and a combination thereof, and are not all hydrogen atoms.)

As described above, the method for manufacturing a color filter dye according to an aspect of the present invention replaces the salt form of the sulfonic acid group included in the dye with a metal salt to an organic salt to change the physical property of the water-soluble dye into fat solubility, and accordingly The dye as completely dissolved in the solvent can be easily added to the color filter composition to improve dispersibility.

Hereinafter, each step will be described in detail.

(S1) dissolving the dye in water

The dye used in the manufacturing method of the color filter dye is an acid dye having a sulfonic acid group (acid dye), C.I. Acid Yellow 17, C.I. Acid Yellow 23, C.I. Acid Yellow 25, C.I. Acid Yellow 29, C.I. Acid Yellow 36, C.I. Acid Yellow 38, C.I. Acid Yellow 42, C.I. Acid Yellow 72, C.I. Acid Yellow 79, C.I. Acid Yellow 99, C.I. Acid Yellow 111, C.I. Acid Yellow 112, C.I. Acid Yellow 114, C.I. Acid Yellow 116, C.I. Acid Yellow 134, C.I. Acid Yellow 155, C.I. Acid Yellow 169, C.I. Acid Yellow 172, C.I. Acid Yellow 184, C.I. Acid Yellow 199, C.I. Acid Yellow 220, C.I. Acid Yellow 228, C.I. Acid Yellow 230, C.I. Acid Yellow 232, C.I. Yellow dyes such as Acid Yellow 243; C.I. Acid Violet 6, C.I. Acid Violet 7, C.I. Acid Violet 17, C.I. Acid Violet 19, C.I. Acid Violet 48, C.I. Acid Violet 49, C.I. Purple dyes such as Acid Violet 54 and the like can be used.

As the acid dye having the sulfonic acid group in the form of the metal salt, one molecule containing 1 to 3 sulfonic acid groups may be used in one molecule of the dye.

The water may be deionized water (DIW), it is preferable to use deionized water in all steps, and the amount of water is suitably used in an amount such that the dye can be completely dissolved in water.

(S2) ionizing the dye

An acid is added to the dye dissolved in water and stirred to ionize the sulfonic acid group of the dye to facilitate substitution.

The acid may be used as appropriate depending on the situation, sulfuric acid or hydrochloric acid may be used, but is not limited thereto.

The addition amount of the acid may be added so that the pH of the reactant is 2 to 3, and when the pH of the reactant is in the above range, the dye molecules are not broken and the reaction is smooth.

The reaction is stirred at 60 ° C. for 1 to 2 hours and ionizes the sulfonic acid group of the dye.

(S3) using the dye as an organic solvent

An organic solvent and an alkylamine represented by the following formula (1) are added to the water in which the dye is ionized and stirred, and the dye having a sulfonic acid group in the form of an organic salt is transferred to the organic solvent.

[Formula 1]

(In the formula 1,

R1 to R3 are independently selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, and a combination thereof, and are not all hydrogen atoms.)

Examples of the alkylamine represented by Formula 1 include trioctylamine (TOA; trioctylamine), tridodecylamine (TDA; tridodecylamine), and dioctylamine (DOA; dioctylamine).

The amount of the alkylamine is added in the same mole number as the number of moles of the sulfonic acid group included in the dye may be substituted by replacing the metal acting on the sulfonic acid group of the dye.

The organic solvent is used that can be applied to the color filter as it is, the most commonly used propylene glycol monomethyl ether acetate (PGMEA; propyleneglycol monomethylether acetate), cyclohexanone (cyclohexanone), xylene (xylene) and combinations thereof One selected from the group can be used, but is not limited thereto.

The input amount of the organic solvent may be an amount such that the solid content of the dye with respect to the organic solvent in the final reaction solution is 3% to 8%, if the organic solvent is included in the above range, it is easy to manufacture the color filter composition, after which the water layer When the organic solvent layer and the phase separation phase is left in the upper organic solvent layer, the specific gravity is appropriate, so it is easy to separate the water layer and the organic solvent layer. The stirring time of the reaction may be 1 hour to 2 hours.

The dye for color filters according to another aspect of the present invention is prepared from the method for producing the dye for color filters according to the aspect of the present invention.

The composition for color filters which concerns on another aspect of this invention contains the dye for color filters which concerns on another aspect of this invention.

The color filter composition includes a photosensitive resin composition, an ink composition, and the like, including a pigment, and the description of the composition of each composition is omitted because it includes all ordinary ones.

Since the color filter dye prepared from the method for manufacturing a color filter dye according to an aspect of the present invention is completely dissolved in a state of 3% to 8% solids in the color filter organic solvent, the composition for a color filter as it is You can put it in

Hereinafter, the above-described aspects of the present invention will be described in more detail with reference to the following examples. However, the following examples are merely for the purpose of explanation and the present invention is not limited to the following examples.

Synthesis of Dye for Color Filter

Example 1

5 g of CI Acid Yellow 79 dye of Kyungin Corp. was dissolved in 520 g of deionized water, and the pH was adjusted to 2.5 ± 0.2 by adding 0.7 g of sulfuric acid. Then, the mixture was stirred for 1 hour, and the temperature was raised to 60 ° C. To this, 520 g of propylene glycol monomethyl ether acetate (PGMEA) was added, 3 g of trioctylamine (TOA) was added, and 0.6 g of sulfuric acid was further added to make the pH 3.5 ± 0.2. Thereafter, the mixture was stirred for 1 hour.

After the reaction was transferred to a separatory funnel, the layers were separated to remove the lower water layer, the upper organic layer was washed 2-3 times with distilled water to remove the remaining acid, and dried by adding 10 g of MgSO ₄ , followed by filtration. The dye for color filters dissolved in the solvent for color filters was synthesize | combined.

Example 2

A dye for a color filter was synthesized in the same manner as in Example 1 except that cyclohexanone was used instead of PGMEA in Example 1.

Example 3

A dye for a color filter was synthesized in the same manner as in Example 1 except that xylene was used instead of PGMEA in Example 1.

Example 4

In Example 1, C.I. In place of Acid Yellow 79, C.I. A dye for a color filter was synthesized in the same manner as in Example 1, except that Acid Yellow 99 was used.

Example 5

In Example 1, C.I. In place of Acid Yellow 79, C.I. A dye for a color filter was synthesized in the same manner as in Example 1, except that Acid Yellow 199 was used.

Example 6

In Example 1, C.I. In place of Acid Yellow 79, C.I. A dye for color filters was synthesized in the same manner as in Example 1, except that Acid Violet 48 was used.

Example 7

In Example 1, C.I. In place of Acid Yellow 79, C.I. A dye for a color filter was synthesized in the same manner as in Example 1, except that Acid Violet 54 was used.

Example 8

A dye for a color filter was synthesized in the same manner as in Example 1, except that tridodecylamine (TDA) was used instead of TOA in Example 1.

Example 9

A dye for a color filter was synthesized in the same manner as in Example 1 except that dioctylamine (DOA) was used in place of TOA in Example 1.

(Physical property evaluation: color characteristic change measurement)

Λ max of the dye before reaction used in Examples 1 to 9 at a concentration of 0.002% using deionized water as a solvent was measured using a UV-VIS spectrometer using JASCO V-550, and 0.002 using acetone as a solvent. The lambda max of the color filter dye synthesized through Examples 1 to 10 of the concentration was measured and the results are shown in Table 1 below.

TABLE 1

Of dye before reaction
λmax [nm] Of the dye after the reaction
λmax [nm] Example 1 403 416 Example 2 403 416 Example 3 403 416 Example 4 446 452 Example 5 374 379 Example 6 592 604 Example 7 569 562 Example 8 446 461 Example 9 446 449

Referring to Table 1, it was confirmed that the color filter dyes of Examples 1 to 10 did not have a large color difference before and after the reaction.

Claims (11)

Dissolving a dye having a sulfonic acid group in the form of a metal salt in water (S1); Adding an acid to the dye dissolved in water and stirring to ionize the dye (S2); Adding an organic solvent and an alkylamine represented by the following Chemical Formula 1 to water in which the dye is ionized and stirring to move a dye having a sulfonic acid group in an organic salt form into an organic solvent (S3); And Removing the water layer does not contain the dye, the method for producing a color filter dye comprising the step (S4) of purifying the organic solvent layer containing the dye. [Formula 1]

(In the formula 1, R1 to R3 are independently selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, and a combination thereof, and are not all hydrogen atoms.) The method of claim 1, The sulfonic acid group contained in one molecule of the dye having a sulfonic acid group in the metal salt form of S1 is one to three manufacturing method for a color filter dye. The method of claim 1, In the S2, the acid is sulfuric acid or hydrochloric acid manufacturing method of a color filter dye. The method of claim 1, The method of producing a dye for a color filter is the amount of the acid in the S2 is an amount such that the pH of the reactant is 2 to 3. The method of claim 1, In the S3, the organic solvent is propylene glycol monomethyl ether acetate (PGMEA; propyleneglycol monomethylether acetate), cyclohexanone (cyclohexanone), xylene (xylene) and the combination of these to prepare a color filter dye Way. The method of claim 1, In the S3, the amount of the organic solvent added is 1,000 parts by weight to 2,000 parts by weight based on 100 parts by weight of the dye having a sulfonic acid group in the organic salt form. The method of claim 1, In S3, the alkylamine is trioctylamine (TOA; trioctylamine), tridodecylamine (TDA; tridodecylamine), or dioctylamine (DOA; dioctylamine). The method of claim 1, The amount of the alkylamine in S3 is 95 to 100 mol% of the amount of the sulfonic acid group contained in the dye is added to the manufacturing method of the color filter dye. The method of claim 1, The reaction temperature of the S2 to S3 is 60 ℃ manufacturing method of the color filter dye. The dye for color filters manufactured from the manufacturing method of the dye for color filters in any one of Claims 1-9. A color filter composition comprising the dye for color filters according to claim 10.