CN115167074B - Red color paste for color photoresist and preparation method thereof - Google Patents

Abstract

The invention relates to a red color paste for a color photoresist and a preparation method thereof, wherein the red color paste for the color photoresist comprises the following components in parts by weight: modified acid red: 10-15 parts of a lubricant; acrylic resin: 15-30 parts of a lubricant; dispersing agent: 15-30 parts of a lubricant; solvent: 45-55 parts; the modified acid red is the sulfonic acid of acid red 289. The invention changes the acid red 289 modified sulfonate into sulfonic acid group, so that the dye has the advantages of good color strength and heat resistance and light resistance; the modified acid red dye can be dissolved in a solvent, such as propylene glycol methyl ether acetate, and completely meets the standard of color paste; the chromaticity and contrast of the modified dye are further improved by adding the synthetic resin for kneading treatment, and the heat resistance and the light resistance of the modified dye are also greatly improved.

Description

Red color paste for color photoresist and preparation method thereof

Technical Field

The invention belongs to the technical field of color photoresists, and in particular relates to a red color paste for color photoresists and a preparation method thereof.

Background Art

In the field of flat panel displays, TFT-LCD (thin film transistor liquid crystal display) is the mainstream of the market. Color filter (CF, Color Filter) is one of the most important main materials for LCD (liquid crystal display) and OLED (organic light emitting diode), which enables the colorization of liquid crystal display and directly determines the quality of the color image of the display. Color photoresist and black photoresist are the core materials for the preparation of color filters, accounting for about 27% of the cost of color filters, and color paste is an important material for the preparation of photoresist, and it is also one of the 35 core key technologies that are currently blocked by the Ministry of Science and Technology.

Photoresist includes color paste, photocurable resin, photoinitiator, solvent, etc. The quality of color filter mainly depends on the performance of photoresist and its coating process. Among them, photoresist pigment as colorant is one of the main influencing factors. In order to give full play to its coloring power and vividness and obtain good spectral characteristics, the pigment particles must be dispersed in the pigment photoresist in a fine, uniform and stable state as much as possible. It is mainly to select high-grade organic pigment varieties and obtain a fine and stable pigment dispersion-color paste 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.

When the filter is colored by water-soluble dyes (dyeing method), although the coloring power is good, it is not heat-resistant and light-resistant, and the water-based dyes are also insoluble in solvents; and current technology has increasingly higher requirements for the chromaticity and contrast of the dyes.

Summary of the invention

The present invention aims at the above-mentioned problems existing in the prior art and provides a red color paste for color photoresist and a preparation method thereof. The specific technical solution of the present invention to solve the above-mentioned technical problems is as follows:

A red color paste for color photoresist, comprising the following components in parts by weight:

Modified acid red: 10-15 parts; acrylic resin: 15-30 parts; dispersant: 15-30 parts; solvent: 45-55 parts;

The modified acid red is obtained by sulfonating acid red 289.

The above further technical features have the following technical effects:

The modified acid red is obtained by sulfonating acid red 289, so that the dye has the advantages of good color strength and heat resistance and light resistance; the modified acid red dye can also be dissolved in solvents, such as propylene glycol methyl ether acetate, and fully meets the standards of color paste.

This technical solution can also be improved as follows:

Furthermore, the dispersant is BYK-21116, and the solvent is propylene glycol methyl ether acetate.

Furthermore, the preparation method of the modified acid red is as follows: methanol is added to acid red 289 to dissolve it, concentrated hydrochloric acid is added after dissolution to react with stirring, and after the reaction is completed, filtering and drying are performed to obtain the modified acid red.

Furthermore, the modified acid red is kneaded by adding a synthetic resin; the acid value of the synthetic resin is 10-30 mgKOH/g; and the weight average molecular weight is 4500-5500.

The above further technical features have the following technical effects:

By adding synthetic resin for kneading treatment, the chromaticity and contrast of the modified dye are further improved, and its heat resistance and light resistance are also greatly improved. The acid value of the synthetic resin is conducive to subsequent development, reducing the development time and meeting the development requirements; by reasonably controlling the molecular weight of the synthetic resin and the viscosity of the resin, the viscosity required in the preparation of the color paste can be achieved.

Furthermore, the structural formula of the synthetic resin is:

Furthermore, the synthetic resin is prepared by polymerization of butyl methacrylate, hydroxyethyl methacrylate, methacrylic acid, N-phenylmaleimide, benzyl methacrylate and vinylphosphonic acid, and the reaction equation is as follows:

Furthermore, the raw materials of the synthetic resin include the following components in parts by weight: 25-35 parts of butyl methacrylate, 15-25 parts of hydroxyethyl methacrylate, 3-8 parts of methacrylic acid, 15-25 parts of N-phenylmaleimide, 15-25 parts of benzyl methacrylate and 2-7 parts of vinylphosphonic acid.

Another object of the present invention is to provide a method for preparing a red color paste for a colored photoresist, comprising the following steps:

S1 Modification of Acid Red 289;

Preparation of S2 synthetic resin: Synthetic resin obtained by random copolymerization of synthetic resin raw materials using a polymer polymerization method;

S3 kneading treatment: adding modified acid red, ethylene glycol, sodium chloride, synthetic resin and ethylenediaminetetraacetic acid into a kneading machine for kneading treatment, and washing and drying after the kneading treatment;

Preparation of S4 color paste: Weigh the modified acid red, acrylic resin, dispersant and solvent after kneading according to the ratio, add 0.3mm zirconium balls, put into an oscillator and disperse for 5-15h. After filtering, add 0.1mm zirconium balls, put into an oscillator and disperse for 5-12h to obtain a red dispersion, that is, a red color paste for color photoresist.

Furthermore, in the S3, by weight, modified acid red: 30-50 parts; ethylene glycol: 80-100 parts; sodium chloride: 350-450 parts; synthetic resin: 6-8 parts; ethylenediaminetetraacetic acid: 1-3 parts.

Furthermore, in S3, the kneading process is carried out at a rotation speed of 30-50 RPM, a temperature of 45-60° C., and a time of 35-45 h.

The present invention provides a red color paste for color photoresist and a preparation method thereof. The acid red 289 is sulfonated so that the dye has the advantages of good color strength and the characteristics of heat resistance and light resistance. The modified acid red dye can also be dissolved in a solvent, such as propylene glycol methyl ether acetate, and fully meets the standards of the color paste. The chromaticity and contrast of the modified dye are further improved by adding a synthetic resin for kneading treatment, and the heat resistance and light resistance are also greatly improved.

DETAILED DESCRIPTION

The principles and features of the present invention are described below in conjunction with examples. The examples are only used to explain the present invention and are not used to limit the scope of the present invention.

The raw materials and models required in the present invention are as follows:

Acid Red 289: AcidRed289, molecular weight is 676.374, molecular formula is: C ₃₅ H ₂₉ N ₂ NaO ₇ S ₂ , CAS number is 12220-28-9.

Butyl methacrylate: molecular weight is 142.19, molecular formula is: C ₈ H ₁₄ O ₂ , CAS number is 97-88-1.

Hydroxyethyl methacrylate: molecular weight is 142.19, molecular formula is: C ₈ H ₁₄ O ₂ , CAS number is 97-88-1.

Methacrylic acid: molecular weight is 86.09, molecular formula is: C ₄ H ₆ O ₂ , CAS number is 79-41-4.

N-phenylmaleimide: molecular weight is 173.17, molecular formula is: C ₁₀ H ₇ NO ₂ , CAS number is 941-69-5.

Benzyl methacrylate: molecular weight is 176.21, molecular formula is: C ₁₁ H ₁₂ O ₂ , CAS number is 941-69-5.

Vinylphosphonic acid: molecular weight is 107.03, molecular formula is: C ₂ H ₄ O ₃ P, CAS number is 941-69-5.

Sodium chloride: molecular weight is 58.44, molecular formula: NaCl, CAS number: 7647-14-5.

Ethylene glycol (DEG): molecular weight 62.07, molecular formula C2H4O, CAS number: 107-21-1.

Ethylenediaminetetraacetic acid (EDTA): molecular weight 292.25, molecular formula C ₁₀ H ₁₆ N ₂ O ₈ , CAS number: 60-00-4;

Propylene glycol methyl ether acetate (PMA): CAS number: 108-65-6.

Acrylic resin (benzyl methacrylate/methacrylic acid=70/30, molecular weight 12000; acid value 115, solid content 28%)

Dispersant: BYK-21116 (solid content 40%) is a dispersant from BYK Chemical Company.

Embodiment 1:

A method for preparing red color paste for color photoresist comprises the following steps:

S1 Modification of Acid Red 289: Add 100g of Acid Red 289 to 1000g of methanol, stir rapidly with a magnetic stirrer until completely dissolved, add 31g of 36% concentrated hydrochloric acid and continue stirring, react for 2h, wash and dry the material, and mark it as 289-H;

Preparation of S2 synthetic resin: Take 30g of butyl methacrylate, 20g of hydroxyethyl methacrylate, 5g of methacrylic acid, 20g of N-phenylmaleimide, 20g of benzyl methacrylate and 5g of vinylphosphonic acid, and use a polymer polymerization reaction method to randomly copolymerize the raw materials of the synthetic resin to obtain a synthetic resin 1. The acid value of the synthetic resin 1 is 28mgKOH/g and the weight average molecular weight is 5000.

S3 kneading treatment: according to the proportion, weigh modified acid red 289-H: 40g, ethylene glycol DEG: 90g, sodium chloride: 400g, synthetic resin 1: 7.2g, EDTA: 2g, add into the kneading machine for kneading treatment, speed 45RPM, temperature 50℃, time 40h, after the kneading treatment, wash and dry, mark as 289-H-1.

Preparation of S4 color paste: According to the ratio, weigh 12g of modified acid red 289-H-1 after kneading treatment, 20g of acrylic resin (solid content 28%), 19g of BYK-21116 dispersant (solid content 20% after dilution) and 47.84g of propylene glycol methyl ether acetate solvent, add 120g of 0.3mm zirconium balls, put it in an oscillator and disperse it for 10 hours. After filtering, add 60g of 0.1mm zirconium balls, put it in an oscillator and disperse it for 8 hours to obtain a red dispersion, that is, a red color paste for color photoresist.

Embodiment 2:

A method for preparing red color paste for color photoresist comprises the following steps:

S1 Modification of Acid Red 289: Add 100g of Acid Red 289 to 1000g of methanol and stir rapidly with a magnetic stirrer until it is completely dissolved. Then add 31g of concentrated hydrochloric acid and continue stirring. After reacting for 2h, wash and dry the material and mark it as 289-H.

Preparation of S2 synthetic resin: Take 30g of butyl methacrylate, 22.5g of hydroxyethyl methacrylate, 5g of methacrylic acid, 20g of N-phenylmaleimide, 20g of benzyl methacrylate and 2.5g of vinylphosphonic acid, and use a polymer polymerization reaction method to randomly copolymerize the raw materials of the synthetic resin to obtain a synthetic resin 2. The acid value of the synthetic resin 2 is 14mgKOH/g and the weight average molecular weight is 5000.

S3 kneading treatment: according to the proportion, weigh modified acid red 289-H: 40g, ethylene glycol DEG: 90g, sodium chloride: 400g, synthetic resin 2: 7.2g, EDTA: 2g, add into the kneading machine for kneading treatment, speed 45RPM, temperature 50℃, time 40h, after the kneading treatment, wash and dry, mark as 289-H-2.

Preparation of S4 color paste: According to the ratio, weigh 12g of modified acid red 289-H-2 after kneading treatment, 20g of acrylic resin (solid content 28%), 19g of BYK-21116 dispersant (solid content 20% after dilution) and 47.84g of propylene glycol methyl ether acetate solvent, add 120g of 0.3mm zirconium balls, put it in an oscillator and disperse it for 10 hours. After filtering, add 60g of 0.1mm zirconium balls, put it in an oscillator and disperse it for 8 hours to obtain a red dispersion, that is, a red color paste for color photoresist.

Comparative Example 1:

A method for preparing red color paste for color photoresist comprises the following steps:

S1 Modification of Acid Red 289: Add 100g of Acid Red 289 to 1000g of methanol, stir rapidly with a magnetic stirrer until it is completely dissolved, add 31g of concentrated hydrochloric acid and continue stirring, react for 2h, wash and dry the material, and mark it as 289-H;

S2: According to the proportion, 40 g of modified acid red 289-H, 90 g of ethylene glycol DEG, 400 g of sodium chloride and 2 g of EDTA were weighed and added into a kneading machine for kneading at a speed of 45 and a temperature of 50°C for 40 h. After the kneading, the mixture was washed and dried, and labeled as 289-H-Comparative 1;

Preparation of S3 color paste: According to the ratio, weigh modified acid red 289-H-contrast 1: 12g, acrylic resin (solid content 28%): 20g, BYK-21116 dispersant (solid content 20% after dilution): 19g and propylene glycol methyl ether acetate solvent: 47.84g, add 0.3mm zirconium balls 120g, put it in an oscillator and disperse it for 10h, after filtering, add 0.1mm zirconium balls 60g, put it in an oscillator and disperse it for 8h to obtain a red dispersion, that is, a red color paste for color photoresist.

Comparative Example 2:

A method for preparing red color paste for color photoresist comprises the following steps:

S1 kneading treatment: according to the proportion, weigh modified acid red 289: 40g, ethylene glycol DEG: 90g, sodium chloride: 400g, EDTA: 2g, add into the kneading machine for kneading treatment, speed 45, temperature 50℃, time 40h, after the kneading treatment, wash and dry, mark as 289-comparison 3.

Preparation of S2 color paste: According to the ratio, weigh Acid Red 289-Contrast 3: 12g, acrylic resin (solid content 28%): 20g, BYK-21116 dispersant (solid content 20%): 19g and propylene glycol methyl ether acetate solvent: 47.84g, add 0.3mm zirconium balls 120g, put it in an oscillator and disperse it for 10 hours. After filtering, add 0.1mm zirconium balls 60g, put it in an oscillator and disperse it for 8 hours to obtain a red dispersion, that is, a red color paste for color photoresist.

Smear test evaluation: The red dispersions obtained in Examples 1-2 and Comparative Examples 1-3 were respectively spin-coated on glass, and the coated glass was placed on a 120°C heating plate and heated for 90 seconds, and then heated in an oven at 230°C for 30 minutes, and the chromaticity (x, y) and brightness (Y) were measured, and the contrast was measured with a contrast meter. The brightness (Y) was then measured at 230°C for 60 minutes.

The test and evaluation results are shown in the following table:

Table 1 Comparison of test evaluation results (y=0.63)

Example 1 Example 2 Compare Comparison 2 Contrast 6200 6450 3254 - Brightness Y 20.5 20.8 18.4 -

Comparative Example 2 experimental flocculation could not be tested at all.

In summary, the present invention provides a red color paste for color photoresist and a preparation method, wherein the acid red 289 is converted into a sulfonic acid group through modified sulfonate, so that the dye has the advantages of good color strength and the characteristics of heat resistance and light resistance; the modified acid red dye can also be dissolved in a solvent, such as propylene glycol methyl ether acetate, and fully meets the standards of the color paste; by adding a synthetic resin for kneading treatment, the chroma and contrast of the modified dye are further improved.

It is to be understood that the present invention is described by some embodiments, and it is known to those skilled in the art that various changes or equivalent substitutions may be made to these features and embodiments without departing from the spirit and scope of the present invention. In addition, under the teachings of the present invention, these features and embodiments may be modified to adapt to specific circumstances and materials without departing from the spirit and scope of the present invention. Therefore, the present invention is not limited by the specific embodiments disclosed herein, and all embodiments falling within the scope of the claims of this application are within the scope of protection of the present invention.

Claims (8)

1. The red color paste for the color photoresist is characterized by comprising the following components in parts by weight:

Modified acid red after kneading treatment: 10-15 parts of a lubricant; acrylic resin: 15-30 parts of a lubricant; dispersing agent: 15-30 parts of a lubricant; solvent: 45-55 parts;

the modified acid red is obtained by sulfonating acid red 289;

The modified acid red is kneaded by adding synthetic resin; the acid value of the synthetic resin is 10-30mgKOH/g; the weight average molecular weight is 4500-5500;

the structural formula of the synthetic resin is as follows:

。

2. The red paste for color photoresists of claim 1 wherein said modified acid red is prepared by: adding methanol into acid red 289 for dissolution, adding concentrated hydrochloric acid for stirring reaction after dissolution, carrying out sulfoation on the acid red 289, and filtering and drying after the reaction is finished to obtain the modified acid red.

3. The red paste for color resists according to claim 1, wherein the dispersant is BYK-21116 and the solvent is propylene glycol methyl ether acetate.

4. The red paste for color photoresists of claim 1 wherein said synthetic resin is polymerized from butyl methacrylate, hydroxyethyl methacrylate, methacrylic acid, N-phenylmaleimide, benzyl methacrylate and vinylphosphonic acid according to the following reaction equation:

。

5. The red paste for color photoresists of claim 4 wherein said synthetic resin comprises the following components in parts by weight: 25-35 parts of butyl methacrylate, 15-25 parts of hydroxyethyl methacrylate, 3-8 parts of methacrylic acid, 15-25 parts of N-phenyl maleimide, 15-25 parts of benzyl methacrylate and 2-7 parts of vinyl phosphonic acid.

6. A method for preparing a red paste for color photoresists as claimed in any of claims 1-5, comprising the steps of:

S1, modification of acid red 289;

S2, preparation of synthetic resin: the synthetic resin is obtained by copolymerizing raw materials of the synthetic resin by adopting a high molecular polymerization reaction method, and the synthetic resin reaction equation is as follows:

；

S3 kneading: adding modified acid red, ethylene glycol, sodium chloride, synthetic resin and ethylene diamine tetraacetic acid into a kneader for kneading treatment, and washing and drying after the kneading treatment is finished;

S4, preparing color paste: weighing the modified acid red, the acrylic resin, the dispersing agent and the solvent which are subjected to kneading treatment according to the proportion, adding the zirconium balls with the thickness of 0.3mm, dispersing for 5-15 hours in an oscillating machine, filtering, adding the zirconium balls with the thickness of 0.1mm, dispersing for 5-12 hours in the oscillating machine, and obtaining red dispersion liquid, thus obtaining the red color paste for the color photoresist.

7. The method for preparing red paste for color photoresists according to claim 6, wherein in S3, the acid red is modified by weight: 30-50 parts of a lubricant; ethylene glycol: 80-100 parts; sodium chloride: 350-450 parts; synthetic resin: 6-8 parts of a lubricant; ethylenediamine tetraacetic acid: 1-3 parts.

8. The method according to claim 6, wherein in S3, the kneading is performed at a rotational speed of 30 to 50RPM, at a temperature of 45 to 60℃for 35 to 45 hours.