CN115167074A - Red color paste for color photoresist and preparation method thereof - Google Patents

Red color paste for color photoresist and preparation method thereof Download PDF

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Publication number
CN115167074A
CN115167074A CN202210903030.8A CN202210903030A CN115167074A CN 115167074 A CN115167074 A CN 115167074A CN 202210903030 A CN202210903030 A CN 202210903030A CN 115167074 A CN115167074 A CN 115167074A
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red
parts
acid
color
paste
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Inventor
豆帆
高政纲
李喆雨
盛振宏
滕福爱
毕研刚
崔亨利
颜俊雄
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Shandong Kelaifu Photoelectric Technology Co ltd
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Shandong Kelaifu Photoelectric Technology Co ltd
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/16Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00Pigment pastes, e.g. for mixing in paints
    • C09D17/003Pigment pastes, e.g. for mixing in paints containing an organic pigment

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
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  • Polymers & Plastics (AREA)
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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; acrylic resin: 15-30 parts; dispersing agent: 15-30 parts; solvent: 45-55 parts of a modifier; the modified acid red is acid red289 sulfonated. According to the invention, the acid red289 is changed into a sulfonic group through modified sulfonate, so that the dye has the advantage of good color strength and has 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 completely meets the standard of color paste; the chroma and contrast of the modified dye are further improved by adding the synthetic resin for kneading treatment, and the heat resistance and 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 photoresist, and particularly relates to red paste for color photoresist and a preparation method thereof.
Background
In the field of flat panel displays, TFT-LCD (thin film transistor liquid crystal display) is the mainstream of the market, and Color Filter (CF) is one of the most important main materials of LCD (liquid crystal display) and OLED (organic light emitting diode), so that the liquid crystal display realizes colorization, which directly determines the quality of color images of the display. The color photoresist and the black photoresist are core materials for preparing the color filter, account for about 27% of the cost of the color filter, and the color paste is an important material for preparing the photoresist and is also one of 35 key technologies of the neck to be clamped published by the national ministry of science and technology at present.
The photoresist comprises color paste, light-cured resin, a photoinitiator, a solvent and the like. The quality of the color filter depends mainly on the performance of the light resistor and the coating process thereof, wherein the light resistor pigment is one of the main influencing factors as a coloring agent, and in order to give full play to the coloring power and the vividness and obtain good spectral characteristics, pigment particles are required to be dispersed in the pigment light resistor 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.
When the color filter is dyed by using a water-soluble dye (dye dyeing method), although the tinting strength is good, the color filter is not heat-resistant and light-resistant, and the water-soluble dye is not dissolved in a solvent; and the requirements of the prior art on the chromaticity and the contrast of the dye are higher and higher.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a red color paste for a color photoresist and a preparation method thereof. The specific technical scheme for solving the technical problems is as follows:
a red color paste for a color photoresist comprises the following components in parts by weight:
modified acid red: 10-15 parts; acrylic resin: 15-30 parts; dispersing agent: 15-30 parts; solvent: 45-55 parts of a modifier;
the modified acid red is acid red289 sulfonated.
The adoption of the above further technical characteristics has the following technical effects:
the modified acid red289 is sulfonated, so that the dye has the advantage of good color strength and has 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 completely meets the standard of color paste.
The technical scheme can be further improved as follows:
further, the dispersant is BYK-21116, and the solvent is propylene glycol monomethyl ether acetate.
Further, the preparation method of the modified acid red comprises the following steps: and adding methanol into the acid red289 for dissolving, adding concentrated hydrochloric acid for stirring reaction after dissolving, and filtering and drying after the reaction is finished to obtain the modified acid red.
Further, the modified acid red is kneaded by adding a synthetic resin; the acid value of the synthetic resin is 10-30mgKOH/g; the weight average molecular weight is 4500-5500.
The adoption of the above further technical characteristics has the following technical effects:
the chroma and contrast of the modified dye are further improved by adding the synthetic resin for kneading treatment, and the heat resistance and light resistance of the modified dye are also greatly improved. The acid value of the synthetic resin is beneficial to subsequent development, the development time is reduced, and the development requirement is met; the viscosity to be obtained in the color paste preparation is achieved by reasonably controlling the molecular weight of the synthetic resin and the viscosity of the resin.
Further, the structural formula of the synthetic resin is:
Figure BDA0003771585800000031
further, the synthetic resin is prepared by polymerizing butyl methacrylate, hydroxyethyl methacrylate, methacrylic acid, N-phenyl maleimide, benzyl methacrylate and vinyl phosphonic acid, and the reaction equation is as follows:
Figure BDA0003771585800000032
further, the raw materials of the synthetic resin comprise 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.
The invention also aims to provide a preparation method of the red color paste for the color photoresist, which comprises the following steps:
s1, modifying acid red 289;
s2, preparation of synthetic resin: carrying out random copolymerization on raw materials of the synthetic resin by adopting a high-molecular polymerization reaction method to obtain the synthetic resin;
s3, kneading treatment: adding the modified acid red, glycol, sodium chloride, synthetic resin and ethylene diamine tetraacetic acid into a kneading machine for kneading treatment, and washing and drying after the kneading treatment is finished;
s4, preparing color paste: weighing the kneaded modified acid red, acrylic resin, dispersant and solvent according to the proportion, adding 0.3mm zirconium balls, placing into a shaker for dispersion for 5-15h, filtering, adding 0.1mm zirconium balls, and placing into the shaker for dispersion for 5-12h to obtain red dispersion liquid, namely the red color paste for the color photoresist.
Further, in the S3, the modified acid red comprises the following components in parts by weight: 30-50 parts; ethylene glycol: 80-100 parts of a binder; sodium chloride: 350-450 parts; synthetic resin: 6-8 parts; ethylene diamine tetraacetic acid: 1-3 parts.
Further, in the S3, the rotation speed of the kneading treatment is 30-50RPM, the temperature is 45-60 ℃, and the time is 35-45h.
According to the red color paste for the color photoresist and the preparation method, the acid red289 is sulfonated, so that the dye has the advantage of good color strength and has 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 completely meets the standard of color paste; the chroma and contrast of the modified dye are further improved by adding the synthetic resin for kneading treatment, and the heat resistance and light resistance of the modified dye are also greatly improved.
Detailed Description
The principles and features of this invention are described below in conjunction with examples, which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
The raw materials and types required by the invention are as follows:
acid red 289: acidRed289, molecular weight 676.374, molecular formula: c 35 H 29 N 2 NaO 7 S 2 CAS number 12220-28-9.
Butyl methacrylate: the molecular weight is 142.19, and the molecular formula is: c 8 H 14 O 2 CAS number 97-88-1.
Hydroxyethyl methacrylate: the molecular weight is 142.19, the molecular formula is: c 8 H 14 O 2 CAS number 97-88-1.
Methacrylic acid: molecular weight is 86.09, molecular formula is: c 4 H 6 O 2 CAS number 79-41-4.
N-phenylmaleimide: molecular weight is173.17, molecular formula: c 10 H 7 NO 2 CAS number 941-69-5.
Benzyl methacrylate: the molecular weight is 176.21, and the molecular formula is: c 11 H 12 O 2 CAS number 941-69-5.
Vinyl phosphonic acid: the molecular weight is 107.03, and the molecular formula is: c 2 H 4 O 3 P, CAS number 941-69-5.
Sodium chloride: molecular weight is 58.44, molecular formula: naCl, CAS No.: 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 The CAS number is: 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 number 115, solids content 28%)
Dispersant BYK-21116 (40% solids) Bi Kehua Chemicals dispersant.
Example 1:
a preparation method of red color paste for color photoresist comprises the following steps:
modification of S1 acid Red 289: adding 100g of acid red289 into 1000g of methanol, rapidly stirring by using a magnetic stirrer until the acid red289 is completely dissolved, adding 31g of 36% concentrated hydrochloric acid, continuously stirring, reacting for 2 hours, and washing and drying the material, wherein the label is 289-H;
s2, preparation of synthetic resin: taking 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 randomly copolymerizing raw materials of the synthetic resin by adopting a high molecular polymerization reaction method to obtain the synthetic resin 1, wherein the acid value of the synthetic resin 1 is 28mgKOH/g, and the weight average molecular weight is 5000.
S3, kneading treatment: weighing modified acid red 289-H according to the proportion: 40g, ethylene glycol DEG:90g, sodium chloride: 400g, synthetic resin 1:7.2g, EDTA:2g, adding the mixture into a kneader to be kneaded at the rotating speed of 45RPM and the temperature of 50 ℃ for 40 hours, and washing and drying the mixture after the kneading is finished, wherein the label is 289-H-1.
S4, preparing color paste: weighing the kneaded modified acid red 289-H-1 according to the proportion: 12g, acrylic resin (solid content 28%): 20g of BYK-21116 dispersant (solid content after dilution is 20%): 19g and propylene glycol methyl ether acetate solvent: 47.84g, adding 120g of 0.3mm zirconium balls, dispersing in a shaking machine for 10h, filtering, adding 60g of 0.1mm zirconium balls, and dispersing in the shaking machine for 8h to obtain a red dispersion liquid, namely the red color paste for the color photoresist.
Example 2:
a preparation method of red color paste for color photoresist comprises the following steps:
modification of S1 acid red 289: 100g of acid red289 is added into 1000g of methanol, the mixture is rapidly stirred by a magnetic stirrer until the acid red289 is completely dissolved, 31g of concentrated hydrochloric acid is added into the mixture for continuous stirring, and after the reaction is carried out for 2 hours, the material is washed and dried and is marked as 289-H.
S2, preparation of synthetic resin: taking 30g of butyl methacrylate, 22.5g of hydroxyethyl methacrylate, 5g of methacrylic acid, 20g of N-phenyl maleimide, 20g of benzyl methacrylate and 2.5g of vinyl phosphonic acid, and carrying out random copolymerization on raw materials of synthetic resin by adopting a high molecular polymerization reaction method to obtain the synthetic resin 2, wherein the acid value of the synthetic resin 2 is 14mgKOH/g, and the weight average molecular weight is 5000.
S3, kneading treatment: weighing modified acid red 289-H according to the proportion: 40g, ethylene glycol DEG:90g, sodium chloride: 400g, synthetic resin 2:7.2g, EDTA:2g, adding the mixture into a kneader to be kneaded at the rotation speed of 45RPM and the temperature of 50 ℃ for 40 hours, and washing and drying the mixture after the kneading treatment is finished, wherein the label is 289-H-2.
S4, preparing color paste: weighing the kneaded modified acid red 289-H-2 according to the proportion: 12g, acrylic resin (solid content 28%): 20g of BYK-21116 dispersant (solid content after dilution is 20%): 19g and propylene glycol methyl ether acetate solvent: 47.84g, adding 120g of 0.3mm zirconium balls, dispersing in a shaking machine for 10h, filtering, adding 60g of 0.1mm zirconium balls, and dispersing in the shaking machine for 8h to obtain a red dispersion liquid, namely the red color paste for the color photoresist.
Comparative example 1:
a preparation method of red color paste for color photoresist comprises the following steps:
modification of S1 acid red 289: adding 100g of acid red289 into 1000g of methanol, rapidly stirring by using a magnetic stirrer until the acid red289 is completely dissolved, adding 31g of concentrated hydrochloric acid into the mixture, continuously stirring, reacting for 2 hours, and washing and drying the material, wherein the mark is 289-H;
s2: weighing modified acid red 289-H according to the proportion: 40g, ethylene glycol DEG:90g, sodium chloride: 400g, EDTA:2g, adding the mixture into a kneader to be kneaded at the rotating speed of 45 at the temperature of 50 ℃ for 40 hours, and washing and drying the mixture after the kneading is finished, wherein the mark is 289-H-contrast 1;
s3, preparing color paste: weighing modified acid red 289-H-contrast 1 according to the proportion: 12g, acrylic resin (solid content 28%): 20g of BYK-21116 dispersant (solid content after dilution is 20%): 19g and propylene glycol methyl ether acetate solvent: 47.84g, adding 120g of 0.3mm zirconium balls, dispersing in a shaking machine for 10h, filtering, adding 60g of 0.1mm zirconium balls, and dispersing in the shaking machine for 8h to obtain a red dispersion liquid, namely the red color paste for the color photoresist.
Comparative example 2:
a preparation method of red color paste for color photoresist comprises the following steps:
s1 kneading treatment: weighing modified acid red289 according to the proportion: 40g, ethylene glycol DEG:90g, sodium chloride: 400g, EDTA:2g, adding the mixture into a kneader to be kneaded at the rotating speed of 45 ℃ at the temperature of 50 ℃ for 40 hours, and washing and drying the mixture after the kneading treatment is finished, wherein the label is 289-comparative 3.
S2, preparing color paste: weighing acid red 289-contrast 3 according to the proportion: 12g, acrylic resin (solid content 28%): 20g of BYK-21116 dispersant (solid content 20%): 19g and propylene glycol methyl ether acetate solvent: 47.84g, adding 120g of 0.3mm zirconium balls, dispersing in a shaking machine for 10h, filtering, adding 60g of 0.1mm zirconium balls, and dispersing in the shaking machine for 8h to obtain a red dispersion liquid, namely the red color paste for the color photoresist.
Smear detection evaluation: the red dispersions obtained in examples 1-2 and comparative examples 1-3 were each spin-coated on glass, and the coated glass sheets were placed on a 120 ℃ hot plate and heated for 90 seconds, then heated in an oven at 230 ℃ for 30 minutes, and the chromaticity (x, Y) and brightness (Y) were measured, and the contrast was measured with a contrast meter. Then, the brightness (Y) was measured at 230 ℃ for 60 min.
The results of the tests and evaluations are shown in the following table:
table 1 comparison of test and evaluation results (y = 0.63)
Example 1 Example 2 Comparison l Comparative example 2
Contrast ratio 6200 6450 3254 -
Luminance Y 20.5 20.8 18.4 -
Comparative example 2 experimental flocculation, which could not be tested at all.
In conclusion, the red color paste for the color photoresist and the preparation method thereof provided by the invention have the advantages that the acid red289 is changed into the sulfonic acid group through the modified sulfonate, so that the dye has the advantage of good color strength and has the characteristics of heat resistance and light resistance; the modified acid red dye can also be dissolved in a solvent, such as propylene glycol monomethyl ether acetate, and completely meets the standard of color paste; the chroma and contrast of the modified dye are further improved by adding synthetic resin for kneading treatment.
It is to be understood that the present invention has been described with reference to certain embodiments, and that various changes in the features and embodiments, or equivalent substitutions may be made therein by those skilled in the art without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.

Claims (10)

1. The red color paste for the color photoresist is characterized by comprising the following components in parts by weight:
modified acid red: 10-15 parts; acrylic resin: 15-30 parts; dispersing agent: 15-30 parts; solvent: 45-55 parts of a stabilizer;
the modified acid red is acid red289 sulfonated.
2. The red color paste for the color photoresist according to claim 1, wherein the preparation method of the modified acid red comprises the following steps: adding methanol into acid red289 to dissolve, adding concentrated hydrochloric acid after dissolving to carry out stirring reaction, sulfonating the acid red289, filtering after the reaction is finished, and drying 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 resists according to claim 1, wherein the modified acid red is kneaded by adding a synthetic resin; the acid value of the synthetic resin is 10-30mgKOH/g; the weight average molecular weight is 4500-5500.
5. The red paste for color photoresists according to claim 4, wherein the structural formula of the synthetic resin is:
Figure RE-FDA0003835840280000011
6. the red paste according to claim 5, wherein the synthetic resin is prepared by polymerizing butyl methacrylate, hydroxyethyl methacrylate, methacrylic acid, N-phenylmaleimide, benzyl methacrylate and vinylphosphonic acid, and the reaction equation is as follows:
Figure RE-FDA0003835840280000021
7. the red paste for the color photoresist according to claim 6, wherein the raw materials of the synthetic resin comprise 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.
8. A method for preparing the red paste for the color photoresist according to any one of claims 1 to 7, comprising the steps of:
s1, modifying acid red 289;
s2, preparation of synthetic resin: carrying out random copolymerization on raw materials of the synthetic resin by adopting a high-molecular polymerization reaction method to obtain the synthetic resin;
s3, kneading treatment: adding the modified acid red, glycol, sodium chloride, synthetic resin and ethylene diamine tetraacetic acid into a kneading machine for kneading treatment, and washing and drying after the kneading treatment is finished;
s4, preparing color paste: weighing the kneaded modified acid red, acrylic resin, dispersant and solvent according to the proportion, adding 0.3mm zirconium balls, placing into a shaker for dispersion for 5-15h, filtering, adding 0.1mm zirconium balls, and placing into the shaker for dispersion for 5-12h to obtain red dispersion liquid, namely the red color paste for the color photoresist.
9. The method for preparing the red color paste for the color photoresist according to claim 8, wherein in the step S3, the modified acid red is as follows by weight: 30-50 parts; ethylene glycol: 80-100 parts of; sodium chloride: 350-450 parts; synthetic resin: 6-8 parts; ethylene diamine tetraacetic acid: 1-3 parts.
10. The method for preparing the red paste for the color photoresist according to claim 8, wherein in the step S3, the rotation speed of the kneading treatment is 30-50RPM, the temperature is 45-60 ℃, and the time is 35-45h.
CN202210903030.8A 2022-07-29 2022-07-29 Red color paste for color photoresist and preparation method thereof Pending CN115167074A (en)

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