CN113881245A

CN113881245A - Modified yellow pigment for photoresist, preparation method and application thereof

Info

Publication number: CN113881245A
Application number: CN202010635165.1A
Authority: CN
Inventors: 颜俊雄; 豆帆; 刘筱; 高政纲; 盛振宏; 高德振; 朱洪维; 崔亨利; 刘海燕
Original assignee: Shandong Kairuier Photoelectric Technology Co ltd
Current assignee: Shandong Kairuier Photoelectric Technology Co ltd
Priority date: 2020-07-03
Filing date: 2020-07-03
Publication date: 2022-01-04
Anticipated expiration: 2040-07-03
Also published as: CN113881245B

Abstract

The invention provides a modified yellow pigment for photoresist, which comprises a yellow pigment and TSP. Compared with the existing kneaded pigment treatment, the invention adds the dispersing agent TSP in the kneading process, so that the grain diameter of the kneaded yellow pigment is small. The invention can obtain the yellow pigment which is easy to grind and disperse, thereby ensuring that the granularity of the prepared color paste is smaller and obtaining high contrast. The invention only adds one material in the original kneading process, but can greatly improve the contrast of the final product, and has the advantages of low cost of raw materials, low cost and good repeatability.

Description

Modified yellow pigment for photoresist, preparation method and application thereof

Technical Field

The invention belongs to the field of liquid crystal display materials, and particularly relates to a modified yellow pigment for photoresist, and a preparation method and application thereof.

Background

In the field of flat panel displays, a TFT-LCD (thin film transistor liquid crystal display) is the mainstream of the market, and a Color Filter (CF) is a key device for realizing color display of the TFT-LCD, so that the liquid crystal display realizes colorization and directly determines the quality of color images of the display. In the preparation of color filters, a pigment dispersion method is most commonly used, and a color photoresist (photoresist) is the most important material in the method.

The quality of the color filter mainly depends on the performance of the pigment photoresistor and the coating process thereof, wherein the photoresistor pigment is one of the main influencing factors as a coloring agent, and in order to fully exert the coloring power and the vividness thereof and obtain good spectral characteristics, pigment particles are required to be dispersed in the pigment photoresistor in a fine, uniform and stable state as much as possible, and the high-grade organic pigment variety is mainly selected to obtain the pigment dispersoid-color paste with fine and stable particle size through an efficient dispersion treatment process. The dispersion state and particle size of the pigment determine whether the final coating has high transmittance and high contrast.

The choice of pigment should be based on obtaining a high-resolution spectrum, eliminating unnecessary wavelength spectra, and retaining only the necessary color light. The color light purity and transmittance of the color filter can be improved by selecting the organic pigment varieties meeting the requirements. The basic colors are three colors of red, green and blue, and in order to adjust spectral characteristics of the color filter, such as hue, tinctorial strength and contrast, in red and green color pastes, it is difficult to obtain a desired spectral spectrum by using a red or green pigment alone, so that it is necessary to mix yellow colors to adjust the spectral spectrum, such as c.i. pigment yellow138, c.i. pigment yellow 139 and c.i. pigment yellow 150. For the preparation of the yellow color paste, the yellow pigment is only used for kneading treatment, and then the color paste prepared by grinding and dispersing is lower than 10000 in contrast ratio, so that the contrast ratio requirement of the yellow color paste for the liquid crystal color filter photoresist is more than 10000, the yellow pigment is necessarily kneaded and modified, otherwise, the requirements of the color paste and the color photoresist can not be met.

Disclosure of Invention

Therefore, the present invention aims to overcome the defects in the prior art and provide a modified yellow pigment for photoresist, a preparation method and an application thereof.

Before setting forth the context of the present invention, the terms used herein are defined as follows:

the term "TSP" refers to: tristyrene phenol polyoxyyethylene ether, tristyrylphenol polyoxyethylene ether, CAS number 99734-09-5.

The term "DEG" refers to: diethylene glycol, CAS number 111-46-6.

The term "PMA" refers to: propylene glycol methyl ether acetate.

The term "Yellow 138" refers to: c.i. pigment yellow 138.

To achieve the above object, a first aspect of the present invention provides a modified yellow pigment for a photoresist, the modified yellow pigment comprising a yellow pigment and TSP.

The modified yellow pigment according to the first aspect of the present invention, wherein the yellow pigment is selected from one or more of the following: c.i. pigment yellow138, c.i. pigment yellow 139, c.i. pigment yellow 150; preferably, c.i. pigment yellow 138.

A second aspect of the present invention provides a method for producing the modified yellow pigment according to the first aspect, which is a kneading modification treatment method;

preferably, the preparation method may comprise the steps of:

(1) adding a yellow pigment, NaCl, DEG and TSP into a kneader, and heating and grinding;

(2) washing the product obtained in the step (1) with water;

(3) and (4) centrifugally drying to obtain the modified yellow pigment.

The preparation method comprises the following steps of (1) mixing 1 part of yellow raw material, 7-15 parts of NaCl, 0.8-3 parts of DEG and 0.05-0.1 part of TSP in parts by weight;

preferably, the raw material comprises 1 part of yellow raw material, 10-15 parts of NaCl, 1-2 parts of DEG and 0.075-0.1 part of TSP.

The preparation method according to the second aspect of the present invention, wherein, in the step (1), the heating temperature is 30 to 60 ℃, preferably 40 ℃; and/or

The grinding time is 6-12 hours, preferably 8-10 hours.

The production process according to the second aspect of the present invention, wherein, in the step (2), the product obtained in the step (1) is washed with water to a conductivity of less than 0.1us/cm, preferably less than 0.08 us/cm.

The preparation method according to the second aspect of the present invention, wherein, in the step (3), the drying temperature is 60 to 100 ℃, preferably 70 to 90 ℃, and most preferably 80 ℃.

A third aspect of the present invention provides a photoresist composition comprising a resin, a dispersant, a solvent, the modified yellow pigment of the first aspect or the modified yellow pigment prepared according to the method of the second aspect.

The photoresist composition comprises, by mass, 10-20 parts of resin, 5-10 parts of a dispersant, 60-80 parts of a solvent and 10 parts of a modified yellow pigment;

preferably, the mass parts of the raw materials are 14-15 parts of resin, 7-8 parts of dispersant, 65-70 parts of solvent and 10 parts of modified yellow pigment;

further preferably, the photoresist composition also comprises a light-cured resin, a photoinitiator and an additive.

A fourth aspect of the present invention provides an optical filter comprising a substrate and the photoresist composition of the third aspect coated on the substrate and cured.

The invention relates to a yellow pigment kneading modification treatment technology adopted by a color photoresist yellow color paste for a color filter of a liquid crystal display. Aiming at the defects of the prior art, the invention provides the yellow pigment for the yellow color paste of the color filter, which is prepared by adding TSP for kneading treatment on the basis of the original kneading process, has low cost, simple process and easy quantitative production, and meets the requirement of smear test contrast after being ground and dispersed.

The invention provides a modified kneading modification treatment technology of a yellow pigment for a color photoresist yellow color paste, which comprises the following material ingredients:

the mixture ratio of the kneading materials is as follows:

y-fragment: including c.i. pigment yellow138, c.i. pigment yellow 139, c.i. pigment yellow 150.

The invention discloses a method for preparing a color paste, which is characterized in that ordinary kneading materials comprise pigment, NaCl and DEG, TSP is added in the method, the TSP can be well attached to the surface of the pigment crushed by NaCl in the kneading process, the repulsion stability among particles is increased, the particle size of the kneaded pigment is more uniform and stable, the particle size of the prepared color paste can be ensured to be smaller, and the contrast measured after smearing is higher than that measured without the TSP.

In the invention, a dispersing agent TSP is added during kneading, wherein the proportion of TSP is 1/10-1/20 of yellow pigment.

The technical scheme adopted by the invention is as follows:

1) and the mixture ratio of the kneading materials is as follows:

2) kneading;

3) vibrating and dispersing;

4) and smear evaluation.

The kneader is a 1 liter kneader, and the power of a shaker is 0.55 KW.

Compared to the prior art, the modified yellow pigment of the present invention may have the following beneficial effects, but is not limited to:

1. compared with the conventional kneaded pigment treatment, the kneaded yellow pigment has good crystallinity and small particle size by adding the dispersing agent TSP in the kneading process.

2. The invention can obtain the yellow pigment which is easy to grind and disperse, thereby ensuring that the granularity of the prepared color paste is smaller and obtaining high contrast

3. The invention only adds one material in the original kneading process, but can greatly improve the contrast of the final product, and has the advantages of low cost of raw materials, low cost and good repeatability.

Drawings

Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:

FIG. 1 shows a TEM photograph of a Yellow pigment Yellow 138-K prepared by comparative example.

FIG. 2 shows a TEM photograph of the modified Yellow pigment Yellow 138-TK-1 prepared in example 1.

FIG. 3 shows a TEM photograph of the modified Yellow pigment Yellow138-TK-2 prepared in example 2.

FIG. 4 shows a particle size diagram of a mill base prepared in a comparative example.

FIG. 5 shows a particle size diagram of the mill base prepared in example 1.

FIG. 6 shows a particle size diagram of the mill base prepared in example 2.

Detailed Description

The invention is further illustrated by the following specific examples, which, however, are to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.

This section generally describes the materials used in the testing of the present invention, as well as the testing methods. Although many materials and methods of operation are known in the art for the purpose of carrying out the invention, the invention is nevertheless described herein in as detail as possible. It will be apparent to those skilled in the art that the materials and methods of operation used in the present invention are well within the skill of the art, provided that they are not specifically illustrated.

The reagents and instrumentation used in the following examples are as follows:

reagent:

yellow138, available from basf; DEG, purchased from Shandong Rui chemical industry; DSS, purchased from national medicine; BYK 2001, available from BYK chemistry; PMA, purchased from junsu yida chemistry; resins, available from comprehensive research chemistry; salt purchased from Weifang Dakang chemical industry; zirconium balls, available from Tosoh corporation.

The instrument comprises the following steps:

a kneader which is purchased from Rugao flight machinery, model NH-1;

concussor, purchased from Shenzhen starke instrument model: KSF-370;

spin coater, available from Analysis, model EZ-6;

a hot plate, purchased from TH48SYBP of great science and technology, China and West, Beijing;

oven, model BPG-9050AH from Shanghai Yiheng

Spectrocolorimeter, available from KONICA, model CM-5;

contrast instrument, available from Japanese Kebang Motor, model CT1STB 1;

a transmission electron microscope, JEM-1400, Japan Electron Ltd;

particle sizer, available from brueck hein model 90Plus Pals.

The raw materials used in the following examples and comparative examples were as follows:

wherein the comparative example differs from the examples only in whether TSP is added.

Example 1

The method for kneading the modified yellow pigment provided in this example includes the following specific steps:

1. kneading the mixture

1-1, in a kneader having a capacity of 1L, 80g of Yellow138 and 1200g of salt (NaCl),200g of DEG,8g of TSP were charged, and the mixture was ground for 10 hours while maintaining a temperature of 40 ℃. The function of the salt is to break up the pigment during kneading; the DEG functions to wet the pigment and salt, allowing them to break in the wet state, while the DEG also has a crystal growth inhibiting effect.

1-2, washing the kneaded material with water until the conductivity is less than 0.08us/cm, removing salt and DEG in the kneaded material in the washing process, and grafting TSP to the yellow pigment in the kneading process.

1-3, drying at 80 ℃ after centrifugation to obtain the modified Yellow pigment Yellow 138-TK-1.

2. Pigment dispersion:

7.60g of dispersant BYK-2001, 14.65g of acrylic resin (35% in terms of solid content), 10g of Yellow 138-TK-1 obtained in the kneading experiment, and 67.75g of solvent PMA were charged into a stainless steel vessel. Adding 150g of 0.3mm zirconium balls, and dispersing in a shaking machine for 4 hours to obtain an evaluation composition, namely color paste.

3. 1ml of composition color paste for evaluation is spin-coated on a glass sheet at the rotating speed of 1200rpm, the coated glass sheet is placed on a heating plate at the temperature of 120 ℃ for 1min, then is heated by an oven at the temperature of 230 ℃ for 30min, and then the chromaticity (x, Y) and the brightness (Y) are measured, and the contrast is measured by a contrast meter.

TABLE 1 Properties of the kneaded modified yellow pigment prepared in example 1

	Comparative example	Example 1
			x	0.4067	0.4065
y	0.488	0.488
			Luminance (Y)	92	93.4
Contrast ratio	4208	11185

FIG. 1 shows a TEM photograph of a Yellow pigment Yellow 138-K prepared by comparative example. FIG. 2 shows a TEM photograph of the modified Yellow pigment Yellow 138-TK-1 prepared in example 1.

FIG. 4 shows a particle size diagram of a mill base prepared in a comparative example. FIG. 5 shows a particle size diagram of the mill base prepared in example 1.

As can be seen from the TEM photographs of FIGS. 1 and 2, the particle size (100nm) of the comparative example (FIG. 1) is much larger than that (50nm) of example 1 (FIG. 2), indicating that the Yellow pigment Yellow 138-TK-1 after kneading with the addition of TSP has a much smaller particle size than the Yellow pigment Yellow 138-K after kneading without the addition of DSS; as can be seen from the particle size diagrams of FIGS. 4 and 5, under the same grinding and dispersing conditions, D50 of example 1 is 51.15nm, which is much smaller than the particle size (90.97nm) of the comparative example, which shows that the Yellow pigment Yellow 138-TK-1 after DSS is added and kneaded has obvious effect on the reduction of the particle size of the Yellow color paste, and further shows that the brightness and the contrast of the final film are greatly improved.

Example 2

1. kneading the mixture

1-1, 80g of Yellow138 and 800g of salt (NaCl),120g of DEG,6g of TSP were charged into a 1L kneader, and the mixture was ground for 9 hours while maintaining the temperature at 40 ℃. The function of the salt is to break up the pigment during kneading; the DEG functions to wet the pigment and salt, allowing them to break in the wet state, while the DEG also has a crystal growth inhibiting effect.

1-3, centrifuging at 80 ℃ and drying to obtain the modified Yellow pigment-Yellow 138-TK-2.

2. Pigment dispersion: 7.60g of dispersant BYK-2001, 14.65g of acrylic resin (35% in terms of solid content), 10g of Yellow138-TK-2 obtained in the kneading experiment, and 67.75g of solvent PMA were charged into a stainless steel vessel. Adding 150g of 0.3mm zirconium balls, and placing the mixture into a shaking machine for dispersing for 4 hours to obtain an evaluation composition, namely color paste.

TABLE 2 Properties of the kneaded modified yellow pigment prepared in example 2

	Comparative example	Example 2
			x	0.4067	0.4066
y	0.488	0.488
			Luminance (Y)	92	93.3
Contrast ratio	4208	10895

FIG. 1 shows a TEM photograph of a Yellow pigment Yellow 138-K prepared by comparative example. FIG. 3 shows a TEM photograph of the modified Yellow pigment Yellow138-TK-2 prepared in example 2.

FIG. 4 shows a particle size diagram of a mill base prepared in a comparative example. FIG. 6 shows a particle size diagram of the mill base prepared in example 2.

As can be seen from the TEM photographs of FIGS. 1 and 3, the particle diameter (100nm) of the comparative example (FIG. 1) is much larger than that (50nm) of example 2 (FIG. 3), indicating that the Yellow pigment Yellow138-TK-2 has a much smaller particle diameter after kneading with the addition of DSS than the Yellow pigment Yellow 138-K after kneading without the addition of DSS; as can be seen from the particle size diagrams of FIGS. 4 and 6, under the same grinding and dispersing conditions, D50 of example 2 is 52.01nm, which is much smaller than the particle size (90.97nm) of the comparative example, which shows that the Yellow pigment Yellow138-TK-2 after DSS is added and kneaded has obvious effect on reducing the particle size of the Yellow color paste, and further shows that the brightness and the contrast of the final film are greatly improved.

Although the present invention has been described to a certain extent, it is apparent that appropriate changes in the respective conditions may be made without departing from the spirit and scope of the present invention. It is to be understood that the invention is not limited to the described embodiments, but is to be accorded the scope consistent with the claims, including equivalents of each element described.

Claims

1. A modified yellow pigment for use in a photoresist, wherein the modified yellow pigment comprises a yellow pigment and TSP.

2. The modified yellow pigment of claim 1, wherein the yellow pigment is selected from one or more of the following: c.i. pigment yellow138, c.i. pigment yellow 139, c.i. pigment yellow 150.

3. The method for producing a modified yellow pigment according to claim 1 or 2, characterized in that the method is a kneading modification treatment method;

preferably, the method comprises the steps of:

(2) washing the product obtained in the step (1) with water;

(3) and (4) centrifugally drying to obtain the modified yellow pigment.

4. The method according to claim 3, wherein in the step (1), the mass parts of the raw materials comprise 1 part of yellow raw material, 7-15 parts of NaCl, 0.8-3 parts of DEG and 0.1-0.05 part of TSP;

5. The method according to claim 3 or 4, wherein in the step (1), the heating temperature is 30-60 ℃, preferably 40 ℃; and/or

The grinding time is 6-12 hours, preferably 8-10 hours.

6. The process according to any one of claims 3 to 5, wherein in step (2), the product obtained in step (1) is washed with water to a conductivity of less than 0.1us/cm, preferably less than 0.08 us/cm.

7. The method according to any one of claims 3 to 6, wherein in step (3), the drying temperature is 60 to 100 ℃, preferably 70 to 90 ℃, and most preferably 80 ℃.

8. A photoresist composition comprising a resin, a dispersant, a solvent, the modified yellow pigment of any one of claims 1 to 3, or the modified yellow pigment prepared according to the method of any one of claims 4 to 7.

9. The photoresist composition according to claim 8, wherein the photoresist composition comprises, by mass, 10-20 parts of resin, 5-10 parts of a dispersant, 60-80 parts of a solvent and 10 parts of a modified yellow pigment;

10. An optical filter comprising a substrate and the photoresist composition of claim 8 or 9 coated on the substrate and cured.