CN113881245B

CN113881245B - Modified yellow pigment for photoresist, preparation method and application thereof

Info

Publication number: CN113881245B
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: 2023-11-17
Anticipated expiration: 2040-07-03
Also published as: CN113881245A

Abstract

The present invention provides a modified yellow pigment for a photoresist, which includes a yellow pigment and TSP. The present invention employs adding the dispersant TSP in kneading so that the particle size of the yellow pigment after kneading is small, compared with the existing kneaded pigment treatment. The invention can obtain yellow pigment which is easy to grind and disperse, and further can ensure that the prepared color paste has smaller granularity and high contrast ratio. The invention only adds one material in the original kneading process, but can greatly improve the contrast of the final product, and has low cost of raw materials 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, a preparation method and application thereof.

Background

In the field of flat panel displays, TFT-LCDs (thin film transistor liquid crystal displays) are the mainstream of the market, and Color Filters (CF) are key devices for realizing color display by using TFT-LCDs, so that the liquid crystal display is colorized, and the quality of color images of the display is directly determined. In the preparation of color filters, pigment dispersion is the most common, and color photoresists (photoresists) are the most important materials in the process.

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

The pigments should be selected based on obtaining a high definition spectrum, eliminating unnecessary wavelength spectra, and retaining only the necessary color light. The color purity and transmittance of the color filter can be improved by selecting the organic pigment variety meeting the requirements. The basic colors are red, green and blue, and in order to adjust the spectral characteristics of the color filter, such as hue, coloring intensity and contrast, wherein the red or green pigment is used alone for red and green color paste, so that the desired spectral spectrum is difficult to obtain, yellow is required to be mixed to adjust the spectral spectrum, such as C.I. pigment yellow138, C.I. pigment yellow 139 and C.I. pigment yellow 150. For yellow color paste preparation, the yellow pigment is only used for kneading treatment, and then the yellow pigment is ground and dispersed to prepare the color paste, the contrast ratio is lower than 10000, and the contrast ratio requirement of the yellow color paste for the liquid crystal color filter photoresist is more than 10000, so that the yellow pigment must be kneaded and modified, otherwise, the requirements of the color paste and the color photoresist cannot be met.

Disclosure of Invention

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

Before setting forth the present disclosure, the terms used herein are defined as follows:

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

The term "DEG" means: 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 including 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 the method for producing a 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 yellow pigment, naCl, DEG and TSP into a kneader, and heating and grinding;

(2) Washing the product obtained in the step (1);

(3) And (5) centrifuging and drying to obtain the modified yellow pigment.

According to the preparation method of the second aspect of the invention, in the step (1), the weight portion ratio of each raw material is 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;

preferably, 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 to 12 hours, preferably 8 to 10 hours.

The preparation method 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 0.08us/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, a modified yellow pigment as described in the first aspect or a modified yellow pigment prepared according to the method of the second aspect.

The photoresist composition according to the second aspect of the invention, wherein, in the photoresist composition, the weight part ratio of each raw material is 10-20 parts of resin, 5-10 parts of dispersing agent, 60-80 parts of solvent and 10 parts of modified yellow pigment;

preferably, the mass portion ratio of each raw material is 14-15 portions of resin, 7-8 portions of dispersing agent, 65-70 portions of solvent and 10 portions of modified yellow pigment;

further preferably, the photoresist composition further comprises a photo-curable resin, a photoinitiator and an additive.

A fourth aspect of the present invention provides a filter comprising a substrate and a photoresist composition according to 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 paste for a color filter of a liquid crystal display. Aiming at the defects of the prior art, the invention provides the yellow pigment which is prepared by adding TSP for kneading based on the original kneading process, is ground and dispersed, meets the requirements of smear test contrast, has low cost and simple process, is easy to quantitatively produce, and can be used as the yellow pigment for color filter yellow paste.

The invention provides a technology for modifying yellow pigment for color photoresist yellow paste into kneading modification, which comprises the following ingredients:

the mixture ratio of the kneading materials is as follows:

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

The common kneading materials are pigment, naCl and DEG, and in the invention, TSP is added, and in the kneading process, the TSP can be well adhered to the surface of the pigment crushed by NaCl, so that the inter-particle repulsive stability is improved, the particle size of the kneaded pigment is more uniform and stable, the particle size of the prepared color paste is further ensured to be smaller, and the contrast ratio measured after smear is higher than that of the pigment without adding the TSP.

The invention adds dispersant TSP in kneading, the proportion of TSP is 1/10-1/20 of yellow pigment.

The technical scheme adopted by the invention is as follows:

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

2) Kneading;

3) Vibrating and dispersing;

4) And (5) smear evaluation.

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

Compared with the prior art, the modified yellow pigment provided by the invention can have the following beneficial effects:

1. in the present invention, the dispersant TSP is added during kneading, so that the yellow pigment after kneading has good crystallinity and small particle size, compared with the conventional pigment kneading treatment.

2. The invention obtains the yellow pigment which is easy to grind and disperse, further ensures that the prepared color paste has smaller granularity and obtains 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 raw material cost, low cost and good repeatability.

Drawings

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

FIG. 1 shows TEM photograph of Yellow pigment Yellow 138-K prepared in 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 the color paste prepared in the comparative example.

Fig. 5 shows a particle size diagram of the color paste prepared in example 1.

Fig. 6 shows a particle size diagram of the color paste prepared in example 2.

Detailed Description

The invention is further illustrated by the following specific examples, which are, however, to be understood only for the purpose of more detailed description and are not to be construed as limiting the invention in any way.

This section generally describes the materials used in the test of the present invention and the test method. Although many materials and methods of operation are known in the art for accomplishing the objectives of the present invention, the present invention will be described in as much detail herein. It will be apparent to those skilled in the art that in this context, the materials and methods of operation used in the present invention are well known in the art, if not specifically described.

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

reagent:

yellow138, available from basf; DEG, purchased from Shandong Rui Kong chemical; DSS, purchased from chinese medicine; BYK 2001, available from Pick chemistry; PMA, purchased from Jiangsu Yida chemistry; resins from comprehensive research chemistry; salt, purchased from Weifang Dakang chemical; zirconium balls, available from Tosoh Corp.

Instrument:

kneader, purchased from gao flight machinery, model NH-1;

vibration machine, purchased from Shenzhen star instrument model: KSF-370;

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

heating plate, purchased from beijing, chinese and western distal science and technology TH48SYBP;

oven, model BPG-9050AH, purchased from Shanghai Yiheng

A spectrocolorimeter, commercially available from KONICA, model CM-5;

contrast instrument, model CT1STB1, purchased from japan pot motor;

transmission electron microscope, model JEM-1400, japan electronics Co;

particle sizer, available from bruexploiting model 90Plus Pals.

The following examples were prepared from the following raw materials:

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

Example 1

The method for kneading the modified yellow pigment provided in the present example comprises the following specific steps:

1. kneading

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 added, and the mixture was ground for 10 hours at a temperature of 40 ℃. The salt functions to break up the pigment during kneading; DEG has the effect of wetting the pigment and salt to break it up in the wet state, while DEG also has the effect of inhibiting crystal growth.

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

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

2. And (3) pigment dispersion:

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

3. 1ml of the color paste of the composition for evaluation was spin-coated on a glass sheet at 1200rpm, the coated glass sheet was placed on a heating plate at 120℃for 1min, and after heating for 30min in an oven at 230℃the chromaticity (x, Y) and the luminance (Y) were measured, and the contrast was measured by a contrast meter.

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

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

FIG. 1 shows TEM photograph of Yellow pigment Yellow 138-K prepared in 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 the color paste prepared in the comparative example. Fig. 5 shows a particle size diagram of the color paste prepared in example 1.

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

Example 2

1. kneading

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

1-2, washing the kneaded material with water to a conductivity of less than 0.08us/cm, wherein the salt and DEG in the kneaded material are removed during the washing, and TSP is grafted onto the yellow pigment during the kneading.

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

2. And (3) pigment dispersion: into a stainless steel vessel were charged 7.60g of dispersant BYK-2001, 14.65g of acrylic resin (solid content 35%), 10g of Yellow138-TK-2 obtained in the kneading test, and 67.75g of solvent PMA. 150g of 0.3mm zirconium ball is added, and the mixture is put into a shaker for 4 hours to be dispersed, thus obtaining an evaluation composition, namely color paste.

TABLE 2 Properties of the kneading modified yellow pigment prepared in this example 2

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

FIG. 1 shows TEM photograph of Yellow pigment Yellow 138-K prepared in 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 the color paste prepared in the comparative example. Fig. 6 shows a particle size diagram of the color paste prepared in example 2.

As can be seen from TEM photographs of FIGS. 1 and 3, the comparative example (FIG. 1) has a particle size (100 nm) much larger than that (50 nm) of example 2 (FIG. 3), indicating that Yellow pigment Yellow138-TK-2 has a significantly reduced particle size after DSS kneading was added, compared with Yellow pigment Yellow 138-K after DSS kneading was not added; as can be seen from the particle size diagrams of FIGS. 4 and 6, under the same grinding and dispersing condition, the D50 of the example 2 is 52.01nm, which is far smaller than the particle size (90.97 nm) of the comparative example, which shows that Yellow pigment Yellow138-TK-2 after DSS kneading is added has obvious effect on reducing the particle size of Yellow color paste, and further the brightness and contrast of the final film layer are greatly improved.

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

Claims

1. A modified yellow pigment for a photoresist, characterized in that the modified yellow pigment comprises a yellow pigment and tristyrylphenol polyoxyethylene ether; 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.

2. The method for producing a modified yellow pigment according to claim 1, wherein the production method is a kneading modification treatment method.

3. The preparation method according to claim 2, characterized in that the preparation method comprises the steps of:

(1) Adding yellow pigment, naCl, DEG and tristyrylphenol polyoxyethylene ether into a kneader, heating and grinding;

(2) Washing the product obtained in the step (1);

(3) And (5) centrifuging and drying to obtain the modified yellow pigment.

4. The preparation method according to claim 3, wherein in the step (1), the ratio of the parts by mass of the raw materials is 1 part of yellow raw material, 7-15 parts of NaCl, 0.8-3 parts of DEG and 0.1-0.05 part of tristyrylphenol polyoxyethylene ether.

5. The preparation method of claim 4, wherein in the step (1), the weight portion of each raw material is 1 part of yellow raw material, 10-15 parts of NaCl, 1-2 parts of DEG and 0.075-0.1 part of tristyrylphenol polyoxyethylene ether.

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

The grinding time is 6-12 hours.

7. The method of claim 6, wherein in step (1), the heating temperature is 40 ℃; and/or

The grinding time is 8-10 hours.

8. A process according to claim 3, wherein in step (2), the product obtained in step (1) is washed with water to a conductivity of less than 0.1us/cm.

9. The method according to claim 8, wherein in step (2), the product obtained in step (1) is washed with water to a conductivity of less than 0.08us/cm.

10. The method according to claim 3, wherein in the step (3), the drying temperature is 60 to 100 ℃.

11. The method according to claim 10, wherein in the step (3), the drying temperature is 70 to 90 ℃.

12. The method according to claim 11, wherein in the step (3), the drying temperature is 80 ℃.

13. A photoresist composition comprising a resin, a dispersant, a solvent, the modified yellow pigment of claim 1 or a modified yellow pigment prepared according to the preparation method of any one of claims 2 to 12.

14. The photoresist composition according to claim 13, wherein the photoresist composition comprises, by mass, 10-20 parts of resin, 5-10 parts of dispersant, 60-80 parts of solvent, and 10 parts of modified yellow pigment.

15. The photoresist composition according to claim 14, wherein the photoresist composition comprises, by mass, 14-15 parts of resin, 7-8 parts of dispersant, 65-70 parts of solvent, and 10 parts of modified yellow pigment.

16. The photoresist composition according to claim 15, further comprising a photocurable resin, a photoinitiator, and an additive.

17. A filter comprising a substrate and the photoresist composition of any one of claims 13 to 16 coated on the substrate and cured.