CN110850679B

CN110850679B - Macromolecular dye with high transmission and high solubility, color photosensitive resin composition and color filter

Info

Publication number: CN110850679B
Application number: CN201810953839.5A
Authority: CN
Inventors: 桑伟; 刘永祥; 李青松; 侯少堃; 高月
Original assignee: Beijing Eternal Material Technology Co Ltd
Current assignee: Beijing Eternal Material Technology Co Ltd
Priority date: 2018-08-21
Filing date: 2018-08-21
Publication date: 2022-05-03
Anticipated expiration: 2038-08-21
Also published as: CN110850679A

Abstract

The invention provides a macromolecular dye which has good oil solubility, high transmittance, proper hue, environmental tolerance, color fastness and low migration property. The invention also provides a color photosensitive resin composition using the macromolecular dye and a color filter prepared by using the composition, which have better heat resistance, light resistance, luminance and contrast. The dye has a structural formula shown as a formula (1): wherein M is Ti, Cr, Mn, Co, Ni, Cu, Zn or Cd; x₁～X₄Is halogen, which may be the same or different; a to d each represent an integer of 0 to 3; r₁～R₄The structures of the same or different compounds are shown below; r₅The structure of (A) is shown in the following, wherein e represents an integer of 1-5, and when e is more than 1, e R on the phenoxy group₅May be the same or different; r, n, m, p, q are zero or positive integers, and r + q + p + n + m is more than or equal to 10; r₆The structure of (A) is as follows;

Description

Macromolecular dye with high transmission and high solubility, color photosensitive resin composition and color filter

Technical Field

The invention relates to a macromolecular dye taking phthalocyanine as an inner core, a color photosensitive resin composition (or called color photoresist) using the macromolecular dye, and a color filter prepared by using the color photosensitive resin composition.

Background

The color filter is an important component of a thin film transistor liquid crystal display (TFT-LCD) and is used for filtering white backlight emitted by a backlight source into three primary colors of red, green and blue. The chromaticity of the three primary colors filtered by the color filter is directly related to the color gamut and color expression of the liquid crystal display, and the higher the luminance (Brightness) of the color filter is, the higher the luminance of the liquid crystal display is, the higher the luminance of the color filter is, the higher the luminance of the liquid crystal display is. The mainstream process for manufacturing the color filter at present is a pigment dispersion method, namely, a monochromatic photosensitive resin composition serving as a raw material is coated on a glass substrate, the glass substrate is heated to remove a solvent, then a mask plate printed with patterns is irradiated by ultraviolet light to be cured into a film, a specific pattern (pixel) is formed on the substrate after being cleaned by an alkaline developing solution, and then the substrate is completely cured by high-temperature baking to obtain the color filter. The above steps are completely repeated twice with single-color photosensitive resin compositions of different colors to obtain color filters based on three colors of red (R), green (G) and blue (B).

In recent years, the manufacture of TFT-LCD is gradually advancing to higher generation, higher resolution, wider color gamut and higher brightness technology, and the color standards such as bt.709, DCI-P3, bt.2020, etc. are emerging and increasingly higher requirements are put on the hue, saturation and brightness of the color photosensitive resin composition and the color filter. The demand for small-size, high-resolution color filters for mobile phone screens, CCD image sensors, and other devices is increasing. Besides, China continental land has become the biggest TFT-LCD panel production base in the world at present, and the successive production of high-generation lines increases the raw material demand on one hand and puts more severe requirements on the cost on the other hand.

The colorant for color filters needs to have the following characteristics: excellent colorimetry characteristics including appropriate hue, high color saturation and high transmittance as much as possible; excellent optical characteristics, avoids color unevenness and optical density unevenness as much as possible, and cannot cause light scattering which reduces the contrast of the liquid crystal panel; excellent environmental resistance such as heat resistance, light resistance, moisture resistance and solvent resistance; the color photosensitive resin composition has excellent processing performance, avoids influencing a color photosensitive resin composition system and a pigment dispersion method process as much as possible, and has good stability, compatibility, leveling property, photoetching developability, photocuring performance and the like.

The main component of the colorant in the current colored photosensitive resin composition is also a finely dispersed pigment such as c.i. pigment green 58, c.i. pigment blue 15: 6. c.i. pigment red 254, and the like. However, since the pigment is hardly dissolved in the solvent, high contrast and uniform chromaticity of the color photosensitive resin composition/color filter can be ensured only by highly fine and sufficient dispersion. In order to improve the high resolution and high contrast of TFT-LCD, the particle size of the colorant is reduced as much as possible, and in order to improve the color saturation of a single color, the content of the colorant in the color photosensitive resin composition/color filter is required to be increased. Pigments for color filters have been problematic in solving these problems: on the one hand, smaller particle size means larger specific surface area, and pigment dispersion is more difficult; on the other hand, to disperse a pigment having a smaller particle size requires the addition of a larger amount of a dispersant, resulting in difficulty in increasing the content of the pigment in the color filter.

In order to solve the problems of pigments, a dye alternative to pigments for color filters has been proposed. The colored photosensitive resin composition system comprising a dye has the following advantages over pigments:

(1) the dye (except for the disperse dye) does not precipitate in the range allowed by the solubility, and a dispersing agent is not needed, so that the use amount is increased, and the color saturation is improved;

(2) the dye in a fully dissolved state is in a molecular dispersion state, so that the problem of non-uniform color or non-uniform color density is not easy to occur when the dye is used for preparing the color filter;

(3) the dye almost has no particles in the system, which is beneficial to improving the contrast and the resolution of the color filter;

(4) the dye can reduce the scattering and refraction of light passing through the color filter, and is beneficial to improving the brightness of the color filter and improving the Haze (Haze).

However, the color photosensitive resin composition system including the dye also has the following problems:

(1) the dye in a molecular dispersed state is insufficient in heat resistance and light resistance compared to the pigment in a molecular aggregated state, and the insufficient heat resistance is mainly manifested in that a high-temperature process changes chromaticity and optical characteristics when a color filter is manufactured by a pigment dispersion method and an Indium Tin Oxide (ITO) thin film used as an electrode of an LCD or a Flat Panel Display (FPD) is formed. The light resistance is insufficient in the process of preparing the color filter by a pigment dispersion method, and ultraviolet irradiation may influence the chromaticity and optical characteristics of the dye in the color photosensitive resin composition;

(2) some small molecular dyes are volatile and easy to sublimate, and escape in the manufacturing process of the color filter, so that adverse effects are caused on equipment or other parts of a TFT-LCD;

(3) compared with the pigment in a molecular aggregation state, the dye in a molecular dispersion state has insufficient organic solvent resistance, and is easily dissolved out by solvents of other materials in the manufacturing process of the color filter to cause chromaticity change;

(4) some dyes have poor solubility in organic solvents, and for dyes with low molar extinction coefficients and poor solubility, it is difficult to increase the color saturation of the color filter by increasing the content of the colorant;

(5) the solubility of some dyes in an alkaline aqueous solution is strong, so that the dyes are easily dissolved out by a developing solution in the process of an alkaline developing process of the color filter to cause the chromaticity change;

(6) some dyes tend to inhibit radical polymerization, resulting in a decrease in photocuring efficiency of the color photosensitive resin composition;

(7) the dye may interact with other components in the color photosensitive resin composition, and it is difficult to control the solubility of exposed portions and non-exposed portions, affecting the developing properties of the color photosensitive resin composition;

(8) when a colored pattern is formed from a color photosensitive resin composition using a dye, the dye may penetrate into different color pixels that have been previously formed, and may not be completely eluted during development, thereby causing color mixing (migration property);

(9) in the color photosensitive resin composition using a dye, when heat treatment is performed after film formation, heat diffusion (color transfer) is liable to occur between adjacent pixels or between adjacent layers, possibly causing color mixing;

(10) the dye is likely to form Development residues (Development residues, Development residues remaining on the substrate or on previously formed patterns or pixels of different colors) after Development, and thereby cause color mixing.

Therefore, the above requirements must be considered in designing a dye to be applied to a color photosensitive resin composition (color resist) for color filter manufacturing.

Documents of the prior art

Patent document

Patent document 1: CN 104035283B

Patent document 2: CN 102803399B

Patent document 3: CN 103665920B

Disclosure of Invention

Problems to be solved by the invention

Phthalocyanines are ligands with a very high coordination capacity and are capable of complexing most metals. When complexed with a transition metal, a monolayer metal phthalocyanine complex having high stability as represented by the following formula (1) is generally formed. The single-layer metal phthalocyanine has a large spatial plane structure and a microcosmic molecular conjugated structure, and the covalent bond and the coordination bond connected with metal atoms are essentially identical, so that the metal phthalocyanine compound has very stable characteristics, acid resistance, alkali resistance, heat resistance, light resistance and organic solvent resistance. Based on the excellent heat resistance and light resistance of phthalocyanine as a mother nucleus, it has been proposed to apply a macromolecular phthalocyanine-type dye to a color photosensitive resin composition (color resist) for color filter production. However, the phthalocyanine type dyes of the macromolecules currently designed and used still have disadvantages. For example, the solubility in a color photoresist system is low, the compatibility is poor, agglomeration is easy to occur in the production process of a color filter, and in addition, the dosage of the color photoresist is difficult to increase due to the low solubility, which is not favorable for improving the performances of the color photoresist, such as the brightness.

Means for solving the problems

As described above, in order to solve the above problems in the prior art, the inventors of the present application have made intensive studies to propose a macromolecular dye using a transition metal complexed with phthalocyanine as a mother core, using a macromolecular segment which is distinct from the prior art as a substituent to improve the solubility of the phthalocyanine mother core, and simultaneously using different kinds and numbers of halogen substituents to adjust the hue of the dye, by modifying and molecular designing the phthalocyanine mother core, which has suitable hue, environmental resistance, color fastness and low migration property in a color photoresist system, in addition to having high solubility, high transmittance, and is characterized by being difficult to volatilize or sublimate.

Specifically, the invention provides a macromolecular dye, which has a structural formula shown as a formula (1):

wherein M is Ti, Cr, Mn, Co, Ni, Cu, Zn or Cd;

x is halogen, which may be the same or different;

a to d each represent an integer of 0 to 3;

R₁～R₄the structures of the same or different compounds are shown below;

R₅the structure of (A) is shown in the following, wherein e represents an integer of 1-5, and when e is more than 1, e R on the phenoxy group₅May be the same or different; r, n, m, p, q are zero or positive integers, and r + q + p + n + m is more than or equal to 10; r₆The structure of (A) is as follows;

the inventors of the present application found that the macromolecular dyes according to the present invention not only have significantly higher solubility in organic solvents and heat resistance than the dyes commonly found in the prior art, but also have high color fastness and are less prone to sublimation or evaporation during the heating process, while at the same time providing color filtersAgglomeration is not easy to occur in the production process of the polished section. The reason for this is not clear, but it is presumed that the introduction of a polymer main chain such as alkyl group, alkoxy group, etc. into the phthalocyanine core can improve its solubility in an organic solvent and heat resistance, and at the same time, increase the molecular weight of the compound, thereby preventing sublimation or evaporation of the dye during the heating process; further, by introducing the above-mentioned R into a phthalocyanine mother nucleus¹～R⁴The flexible polymer chain can improve the dispersibility of the dye in a color glue system, thereby preventing the dye from agglomerating in the production process of the color filter; the polymer chain of the macromolecular dye is intertwined with other polymers in the material in the photocuring process, so that the color fastness of the dye can be effectively improved, and meanwhile, the macromolecular dye is difficult to enter pixels which are cured into a film, so that the transfer property of the colored glue is favorably reduced.

In the above macromolecular dyes, the weight average molecular weight M_wPreferably 4000 to 20000. By setting the weight average molecular weight within this range, it is possible to prevent the polymer chain from being excessively long to adversely affect the solubility thereof. In addition, too large a molecular weight may reduce color strength.

In the above macromolecular dye, M is preferably Co, Ni, Cu or Zn, more preferably Zn or Co.

In the above macromolecular dyes, a to d are preferably all 3.

Among the above macromolecular dyes, X is preferred₁～X₄Are identical to each other.

In the above macromolecular dyes, X₁～X₄Preferably Cl or Br, more preferably Cl.

In the above macromolecular dye, r is preferably a positive integer, that is, preferably contains a methyl (meth) acrylate unit.

The inventors of the present invention have found that the macromolecular dye of the present invention comprising methyl (meth) acrylate units is advantageous in improving its solubility in ester solvents (especially propylene glycol monomethyl ether acetate, PGMEA). The reason is not clear, and it is presumed that the solubility of the macromolecular dye of the present invention in the color paste system can be further improved based on the principle of similar compatibility because the (meth) acrylate segment has a structure similar to that of the commonly used oily solvent of metal phthalocyanine.

In addition, the saturated alkane chain segment or the polystyrene chain segment is introduced into the tail end of the polymethyl methacrylate or polymethyl acrylate chain segment, so that the oil solubility is kept, the water solubility is reduced, the influence on the chromaticity caused by the flushing of a developing solution is prevented, the heat resistance and the stability are improved, and the influence on the chromaticity caused by the heated aggregation of the dye due to the hot processing technology of the color filter is effectively prevented.

The allowable range of r is not particularly limited as long as it is a positive integer satisfying the requirement that the total molecular weight is not more than 20000, but is preferably 3 to 10. This is because the acrylate chains are preferably not too long, and if they are too long, on the one hand the acrylate (non-methyl methacrylate) permeability is low, and on the other hand the methyl (meth) acrylate is readily soluble in the developer, which affects the final color and film-forming properties.

In the above macromolecular dye, e is preferably 1.

The invention provides a color photosensitive resin composition, which comprises an alkali-soluble resin, a colorant, a multifunctional monomer, a photoinitiator, a solvent and an additive, wherein the macromolecular dye is used as the colorant.

The invention provides a color filter which is prepared by using the color photosensitive resin composition.

In the present application, "%" means "% by mass" unless otherwise specified.

Effects of the invention

The invention provides a high-transmission macromolecular dye (namely, a macromolecular dye with high transmittance) for an LCD (liquid crystal display), which has proper maximum transmittance and maximum transmission wavelength, and can obtain macromolecular dyes with different hues by changing the type and the number of halogen substituents on a phthalocyanine mother nucleus; by adjusting the formula, the mixed color paste composed of the dye and G36 can reach the brightness close to G58. In addition, the formula of the color photoresist containing the high-transmission macromolecular dye has higher brightness and contrast, better environmental tolerance, color fastness and lower migration property, has higher solubility in PGMEA (polymer-doped polyethylene oxide film), can improve the consumption of the dye in the color photoresist, and effectively improves the performances of the color photoresist such as brightness.

The invention overcomes the problem of poor solubility of the dye in a colored glue system, and the dye can replace all pigments to be dissolved in the colored glue system and obtain ideal effect.

Drawings

FIG. 1 shows dye F^Zn ₁₁₁₁And F^Co ₅₅₅₅' wavelength-transmittance Curve (concentration: [ M ]]＝0.01％)。

Detailed Description

The present invention will be described in further detail below with reference to specific embodiments in order to make the present invention better understood by those skilled in the art.

Hereinafter, details of the dye, the colorant, the photosensitive resin composition, and the color filter production of the present invention will be described with reference to representative examples of the present invention. However, the present invention is not limited to these examples.

[ dyes ]

The dye of the invention is a macromolecular dye taking phthalocyanine as a mother nucleus, and the weight average molecular mass (M) of the dye_w) 4000 to 20000, and a molecular weight distribution index (PDI, weight average molecular weight (M)_w) Number average molecular weight (M)_n) From 1.00 to 2.50).

According to the scheme, the dye disclosed by the invention can realize optimization and improvement in the aspects of resisting dye penetration, reducing color transfer caused by heat treatment, reducing dye dissolution in an alkaline development process, enhancing organic solvent flushing resistance, resisting volatilization and resisting sublimation and the like.

[ Synthesis of dye ]

1 purification of reagent and raw Material

(1)THF

By activated

Soaking the molecular sieve for more than two weeks to remove excessive water. Under the protection of high-purity argon, adding sodium chips and benzophenone,refluxing until the solution becomes purple and does not fade, distilling at normal pressure after 24 hr, collecting 66 + -1 deg.C fraction, sealing and storing in dry oxygen-free ampoule bottle.

(2) N-butanol

Activated with n-butanol

Soaking the molecular sieve for more than two weeks to remove excessive water. Adding powdered calcium oxide under the protection of high-purity argon, stirring at normal temperature, refluxing for 24 hours, distilling at normal pressure, sealing and storing in a dry oxygen-free ampoule bottle for later use.

(3) Dipiperidinoethane

By activated

Soaking the molecular sieve for more than two weeks to remove excessive water. Adding powdered calcium hydride under the protection of high-purity argon, stirring at normal temperature, refluxing for 24 hours, distilling at normal pressure, sealing and storing in a dry oxygen-free ampoule bottle for later use.

(4) Boric acid trimethyl ester

Adding sodium chips under the protection of high-purity argon, refluxing for 12 hours, distilling at normal pressure, taking fractions at 68 +/-1 ℃, and sealing and storing in a dry oxygen-free ampoule bottle.

(5) N-butyl lithium

A high vacuum line is connected to 1.6M n-butyllithium sold in the market before use, the n-butyllithium is added into cyclohexane which is purified in advance, the mixture is fully stirred and then is subpackaged into dry oxygen-free ampoules, the ampoules are stored at low temperature after being sealed by fire, and the molar concentration of the n-butyllithium is accurately calibrated by a double titration method.

(6) Lithium naphthalene

Under the protection of high-purity argon, 1.28g (10mmol) of naphthalene and a proper amount of lithium chips are added into an ampoule bottle soaked by chlorosilane and dried, the ampoule bottle is sealed and then filled with argon gas, vacuum pumping is carried out for three times, then 20mL of THF is injected, strong stirring is carried out to obtain a naphthalene lithium solution, unreacted lithium chips are filtered out, the naphthalene lithium solution is subpackaged into a dry oxygen-free ampoule bottle soaked by chlorosilane, the dry oxygen-free ampoule bottle is sealed by fire and stored at low temperature, and the molar concentration of naphthalene lithium is accurately calibrated by a double titration method.

(7) Monomer

The styrene raw material was washed with 5% sodium hydroxide solution to remove the polymerization inhibitor from the raw material. And repeatedly washing the styrene to be neutral by using deionized water, adding anhydrous magnesium sulfate, stirring for 12 hours, filtering, introducing the filtrate into a dry oxygen-free ampoule bottle, adding dibutyl magnesium, fully stirring, and storing at the low temperature of-20 ℃. Prior to use, styrene was quantitatively transferred from ampoules to vials under high vacuum, dispensed and fire-sealed for use.

Before using, butadiene/isoprene is introduced into an anhydrous oxygen-free ampoule bottle at about 0 ℃, and a small amount of n-butyllithium is added to be stirred for half an hour for standby.

Methyl acrylate raw material is firstly processed by CaH₂Refluxing and distilling under reduced pressure. Introducing the filtrate into dry oxygen-free ampoule bottle, adding dibutyl magnesium, stirring, and storing at-20 deg.C. Prior to use, methyl acrylate is quantitatively transferred from the ampoule to a vial under high vacuum and dispensed and fire-sealed for use.

Methyl methacrylate raw material is firstly processed by CaH₂Refluxing and distilling under reduced pressure. Introducing the filtrate into dry oxygen-free ampoule bottle, adding dibutyl magnesium, stirring, and storing at-20 deg.C. Methyl methacrylate is quantitatively transferred from an ampoule to a vial under high vacuum before use, dispensed and fire-sealed for use.

2 Synthesis of macromolecular alkyllithium A/B (anionic polymerization)

(1) Synthesis of homo-polymeric lithium alkylide A

The initiator amount was calculated quantitatively and added to a reaction flask containing sufficient THF at the appropriate reaction temperature and stirred well. Then quantitatively adding the purified monomer, maintaining the reaction temperature, and continuously polymerizing until the monomer is reacted for later use.

(2) Synthesis of copolymerized macromolecular alkyllithium B

Quantitatively adding monomer methyl acrylate or methyl methacrylate into a flask containing active macromolecular alkyl lithium A at a proper reaction temperature, fully stirring and maintaining the reaction temperature, and continuously polymerizing until all monomers are reacted for later use.

Synthesis of 3 macromolecular intermediate C/D/E

(1) Synthesis of boronic acid-based macromolecular intermediate C

Taking alkyl lithium A as an example, keeping the temperature of an anionic polymerization system at-78 ℃, dropwise adding trimethyl borate into the reaction liquid by using an injector, gradually heating to room temperature after dropwise adding, reacting for 2 hours, then adding 3N diluted hydrochloric acid, stirring for 1 hour, and stopping the reaction. After the reaction is finished, pouring the reaction liquid into a separating funnel, extracting for 3 times by using ethyl acetate, spin-drying an organic layer, and separating by using a flash chromatography column to obtain an intermediate C.

(2) Synthesis of hydroxyl macromolecule intermediate D

Under the protection of argon, adding (tert-butyldimethylsilyloxy) -bromobenzene, boric acid-based macromolecular intermediate C, toluene, potassium phosphate trihydrate, and palladium (Pd) bis (dibenzylidene-BASE acetone) into a three-neck flask provided with a mechanical stirring pipe, a thermometer and a condenser pipe₂(dba)₃) And (3) replacing argon for three times by 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl (S-phos), heating to reflux reaction until no raw material is left on a sampling point, and stopping the reaction. Cooling the system to room temperature, adding deionized water into the reaction system, stirring for half an hour, standing for liquid separation, washing the water phase with ethyl acetate for 2 times, combining the organic phases, washing the organic phase with saturated saline solution for one time, drying with anhydrous sodium sulfate, dissolving with THF after solvent spin-drying, adding 1.0M tetrabutylammonium fluoride-THF solution, stirring for 2 hours at room temperature until the raw materials react completely, adding deionized water, stirring fully, pouring into a separating funnel, washing the water phase with ethyl acetate for 2 times, combining the organic phases, washing the organic phase with saturated saline solution for one time, drying with anhydrous sodium sulfate,and (4) spin-drying the solvent, and purifying by using a flash chromatography column to obtain the hydroxyl macromolecular intermediate D.

(3) Synthesis of hydrogenated hydroxyl macromolecular intermediate E

The synthesis of hydrogenated macromolecular intermediate E was carried out in a stainless steel autoclave. Adding the macromolecular intermediate D and a solvent into a kettle, replacing air in the kettle with high-purity argon for a plurality of times, adding a catalyst which is aged in advance under the protection of argon, preheating the autoclave by adopting a constant-temperature water bath at 60 ℃, stirring to fully mix the catalyst and the raw materials, suspending stirring, slowly adding hydrogen with preset pressure, and starting stirring again to perform hydrogenation reaction. After the reaction is finished, cooling the high-pressure kettle to room temperature, slowly discharging hydrogen, adding a proper amount of hydrogen peroxide into the glue solution to destroy the catalyst, then adding a precipitator prepared from a diethylene glycol butyl ether aqueous solution and sebacic acid, electromagnetically stirring, centrifugally precipitating by using a high-speed centrifuge, removing the catalyst, and purifying by using a flash chromatography column to obtain the corresponding hydrogenated hydroxyl macromolecular intermediate E.

Synthesis of 4-macromolecular phthalocyanine G

(1) Synthesis of phthalonitrile F containing macromolecular group

Halogenated phthalonitrile, hydroxyl macromolecular intermediate C/D, potassium carbonate and acetonitrile are placed in a flask and heated to reflux. After the reaction was completed, the reaction mixture was filtered and the filtrate was drained. Dissolving the solid with ethyl acetate, washing with saturated saline solution twice, extracting the water phase with ethyl acetate, combining the organic phases, pumping out, purifying with a flash chromatographic column, and drying in vacuum to obtain phthalonitrile F containing macromolecular groups.

(2) Synthesis of macromolecular Phthalocyanine dye G

Under the protection of argon, macromolecular phthalonitrile F, 1, 8-diazabicycloundecen-7-ene (DBU) and n-butyl alcohol are put into a flask, stirred and heated to raise the temperature, metal acetate is added after full dissolution, and heating reflux is carried out. And (3) after the reaction is finished, draining the solvent, purifying by using a flash type chromatographic column, and drying in vacuum to obtain the macromolecular phthalocyanine G.

[ colored photosensitive resin composition ]

The colored photosensitive resin composition of the present invention further comprises ingredients well known in the art, such as an alkali-soluble resin, a colorant, a multifunctional monomer, a photoinitiator, a solvent, and additives.

The alkali soluble resin may be selected from at least one of acrylic resin and/or acrylate resin.

The colorant may be the dye and the corresponding pigment in the present invention, specifically, may be a red pigment, a green pigment, a blue pigment, a yellow pigment, an orange pigment, a violet pigment or a mixture of two or more of the above pigments and the dye of the present invention, and preferably, the colorant may be a color paste formed by dispersing the above pigments/dyes in a solvent, and the solid content of the color paste may be 5 to 50%.

The polyfunctional monomer (or photosensitive monomer) is a monomer having a plurality of reactive functional groups such as an unsaturated double bond, a hydroxyl group, a carboxyl group, and a carbonyl group in a molecule, and the addition of the polyfunctional monomer can achieve technical effects such as formation of a clear pixel pattern in an exposed portion and prevention of mold release during development, and an appropriate polyfunctional monomer can be selected. One or more compounds known in the art to participate in the crosslinking reaction are generally used in combination, and representative examples thereof include at least one selected from the group consisting of 1, 6-ethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 3-propoxylated glycerol triacrylate, trimethylolpropane triacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, 3- (trimethoxy silane) propyl acrylate, glycidyl methacrylate and benzyl methacrylate, but are not limited to the above polyfunctional monomers.

The photoinitiator may be selected from benzoin and derivatives photoinitiators, benzil photoinitiators, alkylbenzophenone photoinitiators, acylphosporium oxide photoinitiators, benzophenone photoinitiators, thioxanthone photoinitiators, oxime ester photoinitiators, and photoinitiators such as diaryliodonium salts, triaryliodonium salts, alkyliodonium salts, cumeneferrocenium hexafluorophosphate, and the like. If the photoinitiator is a hydrogen abstraction type photoinitiator, the photoinitiator also comprises a co-initiator, namely at least one of aliphatic tertiary amine, ethanolamine tertiary amine, tertiary amine benzoate and active amine.

The photosensitive resin composition may contain a solvent for easy coating, and any solvent known in the art may be used. In view of environmental protection, flatness of the film surface, and handling property of the process operation, the solvent preferably includes a high boiling point solvent having a boiling point of 150 to 200 ℃ and a low boiling point solvent having a boiling point of less than 150 ℃, and the high boiling point solvent and the low boiling point solvent are preferably contained in a weight ratio of 10: 90 to 50: 50. Wherein the high boiling point solvent is at least one selected from dipropylene glycol methyl ether, diethylene glycol butyl ether acetate, diethylene glycol diethyl ether acetate, 3-ethoxyethyl propionate, 3-methoxybutyl acetate and ethyl lactate; the low boiling point solvent is at least one selected from the group consisting of ethylene glycol methyl ether, ethylene glycol ethyl ether, propylene glycol methyl ether acetate, cyclohexane, and isopropyl alcohol.

In addition, the photosensitive resin composition of the present invention may further include an additive, which may be at least one of a sensitizer, an antifoaming agent, a leveling agent, a polymerization inhibitor, a wetting dispersant, and an adhesion promoter.

More specifically, the photosensitive resin composition of the present invention includes an alkali-soluble resin, a colorant, a multifunctional monomer, a photoinitiator, a solvent, and additives. The alkali-soluble resin composition comprises, relative to 100 parts by weight of the alkali-soluble resin polymer, 200-500 parts by weight of a colorant, 50-100 parts by weight of a multifunctional monomer, 0.1-10 parts by weight of a photoinitiator, 100-800 parts by weight of a solvent and 0.1-10 parts by weight of an additive.

The color photosensitive resin composition is coated on a substrate, and then a pattern with a specific shape can be obtained through the process steps of pre-baking, exposure, development, post-baking and the like, so that pixels and the like are formed.

Examples

The following examples further illustrate embodiments of the preparation of the high transmittance and high solubility dye for photosensitive resin compositions provided by the present invention. The examples are not intended to limit the scope of the present invention, and any modifications and variations made by those skilled in the art without departing from the spirit of the present invention are intended to be included within the scope of the present invention. The chemical reagents used are indicated in the following brackets with the type and manufacturer when they first appear, and the reagents appearing later are of the same origin as when they first appear.

Synthesis of intermediates

1.Polystyrene lithium A-1Synthesis of (2)

The amount of n-butyllithium was quantitatively calculated and added to a reaction flask containing sufficient purified THF at-78 deg.C with thorough stirring. Quantitatively adding the purified styrene monomer into a reaction bottle at-78 ℃, continuously polymerizing at-78 ℃ until the monomer is completely reacted, and storing for later use. Testing and sampling: taking a proper amount of reaction liquid by using a vacuum syringe, adding the reaction liquid into purified absolute methanol to terminate polymerization, adding THF (tetrahydrofuran) for dissolution after a solvent is dried in a spinning mode, and testing molecular weight and molecular weight distribution M_w＝1100，PDI＝1.07。

2.Polybutadiene lithium A-2Synthesis of (2)

The amount of n-butyllithium was quantitatively calculated and added to a reaction flask containing sufficient purified THF at-78 deg.C with thorough stirring. The purified gaseous butadiene monomer was quantitatively introduced into the reaction flask. The light yellow polybutadiene lithium active species is generated immediately in the reaction bottle and addedThe dipiperidinoethane with catalytic amount is continuously polymerized at-78 ℃ until the monomer reaction is finished, and is stored for standby. Testing and sampling: taking a proper amount of reaction liquid by using a vacuum syringe, adding the reaction liquid into purified absolute methanol to terminate polymerization, adding THF (tetrahydrofuran) for dissolution after a solvent is dried in a spinning mode, and testing molecular weight and molecular weight distribution M_w＝900，PDI＝1.12。

3.Polyisoprenyllithium A-3Synthesis of (2)

The amount of n-butyllithium was quantitatively calculated and added to a reaction flask containing sufficient purified THF at-78 deg.C with thorough stirring. The purified gaseous isoprene monomer was quantitatively introduced into the reaction flask. Generating light yellow polyisoprene lithium active species in the reaction bottle, continuously polymerizing at-78 ℃ until the monomer reaction is finished, and storing for later use. Testing and sampling: taking a proper amount of reaction liquid by using a vacuum syringe, adding the reaction liquid into purified absolute methanol to terminate polymerization, adding THF (tetrahydrofuran) for dissolution after a solvent is dried in a spinning mode, and testing molecular weight and molecular weight distribution M_w＝900，PDI＝1.10。

4.Polybutadiene-lithium isoprene A-4Synthesis of (2)

The amount of n-butyllithium was quantitatively calculated and added to a reaction flask containing sufficient purified THF at-78 deg.C with thorough stirring. The purified gaseous butadiene and isoprene monomers were quantitatively introduced into the reaction flask at-78 ℃ in a ratio of 1: 1. Then adding catalyst amount of dipiperidinoethane, continuously polymerizing at-78 deg.C until the monomer reaction is finished, and storing for later use. Testing and sampling: taking a proper amount of reaction liquid by using a vacuum syringe, adding the reaction liquid into purified absolute methanol to terminate polymerization, adding THF (tetrahydrofuran) for dissolution after a solvent is dried in a spinning mode, and testing molecular weight and molecular weight distribution M_w＝1500，PDI＝1.14。

5.Polymethyl methacrylate lithium A-5Synthesis of (2)

The amount of n-butyllithium was quantitatively calculated and added to a reaction flask containing sufficient purified THF at-78 deg.C with thorough stirring. Quantitatively introducing purified methyl methacrylate monomer into a reaction bottle, continuously polymerizing at-78 ℃ until the monomer is completely reacted, and storing for later use. Testing and sampling: taking a proper amount of reaction liquid by using a vacuum syringe, adding the reaction liquid into purified absolute methanol to terminate polymerization, adding THF (tetrahydrofuran) for dissolution after a solvent is dried in a spinning mode, and testing molecular weight and molecular weight distribution M_w＝1700，PDI＝1.10。

6.Lithium polymethyl acrylate A-5'Synthesis of (2)

The amount of n-butyllithium was quantitatively calculated and added to a reaction flask containing sufficient purified THF at-78 deg.C with thorough stirring. Quantitatively introducing purified methyl acrylate monomer into the reaction bottle, continuously polymerizing at-78 deg.C until the monomer reaction is finished, and storing for later use. Testing and sampling: taking a proper amount of reaction liquid by using a vacuum syringe, adding the reaction liquid into purified absolute methanol to terminate polymerization, adding THF (tetrahydrofuran) for dissolution after a solvent is dried in a spinning mode, and testing molecular weight and molecular weight distribution M_w＝1600，PDI＝1.10。

7.polystyrene-B-polymethyl methacrylate lithium B-1，polystyrene-B-polymethyl acrylate lithium B-1'，Poly (butylene) diene-B-polymethyl methacrylate lithium B-2，polybutadiene-B-lithium polymethyl acrylate B-2'，Polyisoprene-b-polymethines Lithium methyl methacrylate B-3，Polyisoprene-B-Polymethylacrylate lithium B-3'，Polybutadiene-isoprene-b-polymethylene Lithium methyl acrylate B-4Andpolybutadiene-isoprene-B-Polymethylacrylate lithium B-4'Synthesis of (2)

Taking the synthesis example of polystyrene-B-polymethyl methacrylate lithium B-1, adding the purified methyl methacrylate monomer into a reaction bottle storing the polystyrene lithium A-1 at-78 ℃, fully stirring, continuously polymerizing at-78 ℃ until the monomer reaction is finished, and storing for later use. Testing and sampling: taking a proper amount of reaction liquid by using a vacuum syringe, adding the reaction liquid into purified absolute methanol to terminate polymerization, adding THF (tetrahydrofuran) for dissolution after a solvent is dried in a spinning mode, and testing molecular weight and molecular weight distribution M_w＝1900，PDI＝1.12。

The synthesis of polybutadiene-B-polymethyl methacrylate B-2, polyisoprene-B-polymethyl methacrylate B-3 and polybutadiene-isoprene-B-polymethyl methacrylate B-4 is similar to B-1, except that the active alkyllithium is replaced with A-2, A-3 and A-4 in place of A-1.

The synthesis of polystyrene-B-lithium polyacrylate B-1' is similar to B-1, except that the monomer is changed to methyl methacrylate.

The synthesis of polybutadiene-B-lithium polymethyl acrylate B-2 ', polyisoprene-B-lithium polymethyl acrylate B-3' and polybutadiene-isoprene-B-lithium polymethyl acrylate B-4 'is similar to B-1', except that the active alkyllithium is replaced with A-2, A-3 and A-4 in place of A-1.

8.Polystyrene-b-polymethylmethacrylate boronic acid C-1，Polystyrene-b-polymethylacrylate boric acid C-1’，Polybutadiene-b-polymethylmethacrylate boronic acid C-2，polybutadiene-b-Polycarbomethoxyborate C-2'，Polyisoprene-b-polymethylmethacrylate boronic acid C-3，polyisoprene-b-Polycarbomethoxyboranic acid C-3'，Poly(s) are polymerized Butadiene-isoprene-b-polymethylmethacrylate boronic acid C-4，polybutadiene-isoprene-b-Polymethylacrylate Boronic acid C-4'，Polymethacrylic acid methyl ester boric acid C-5，Polyacrylic acid methyl ester boric acid C-5'Synthesis of (2)

Taking a synthesis example of polystyrene-B-polymethylmethacrylate boronic acid C-1, maintaining the temperature of an anionic polymerization system at-78 ℃, dropwise adding trimethyl borate (trimethyl borate: Li ═ 1.5: 1) into the reaction solution of B-1 by using a syringe, after dropwise addition, gradually raising the temperature to room temperature for reaction for 2 hours, then adding 3N diluted hydrochloric acid, stirring for 1 hour, and stopping the reaction. After the reaction, the reaction solution was poured into a separatory funnel, extracted 3 times with ethyl acetate, the organic layers were combined and spin-dried, purified with a flash column (PE: EA ═ 29: 1), and the solvent was drained to constant weight to obtain intermediate C-1(0.6eq) as a white powder.

The synthesis of polystyrene-B-polymethyl methacrylate boric acid C-1 ', polybutadiene-B-polymethyl methacrylate boric acid C-2, polybutadiene-B-polymethyl acrylate boric acid C-2', polyisoprene-B-polymethyl methacrylate boric acid C-3, polyisoprene-B-polymethyl acrylate boric acid C-3 ', polybutadiene-isoprene-B-polymethyl methacrylate boric acid C-4, polybutadiene-isoprene-B-polymethyl acrylate boric acid C-4', polymethyl methacrylate boric acid C-5, and polymethyl acrylate boric acid C-5 'is similar to that of C-1, except that the raw materials are B-1', b-2, B-2 ', B-3, B-3', B-4, B-4 ', A-5 and A-5'.

9. 4-polystyrene-b-polymethyl methacrylate phenol D-1，4-polystyrene-b-polymethyl acrylate Phenol D-1'，4-polybutadiene-b-polymethyl methacrylate phenol D-2，4-polybutadiene-b-polymethyl acrylate based benzene Phenol D-2'，4-Polyisoprene-b-polymethylmethacrylate phenol D-3，4-Polyisoprene-b-Polymethylacrylate radical Phenol D-3'，4-polybutadiene-isoprene-b-polymethyl methacrylate phenol D-4，4-polybutadiene-isoprene- b-Polycarbomethoxyphenol D-4'，4-polymethyl methacrylate phenol D-5，4-Polycarbomethoxyphenol D-5'Synthesis of (2)

Taking a synthesis example of 4-polystyrene-b-polymethyl methacrylate phenol D-1, adding polystyrene-b-polymethyl methacrylate boric acid C-1(1eq), 4-tert-butyldimethylsiloxy-bromobenzene (1.3eq), toluene, potassium phosphate trihydrate (2eq), Pd in a three-neck flask equipped with a mechanical stirrer, a thermometer and a condenser under the protection of argon₂(dba)₃(0.01eq), S-phos (0.04eq), argon replacement three times, heating to reflux reaction, until no raw material remains at the sampling point, and stopping the reaction. Cooling the system to room temperature, adding deionized water into the reaction system, stirring for half an hour, standing for liquid separation, washing a water phase for 2 times by using ethyl acetate, combining organic phases, washing the organic phase by using saturated saline solution, drying by using anhydrous sodium sulfate, dissolving by using THF after solvent spin-drying, adding a 1.0M tetrabutylammonium fluoride-THF solution, stirring for 2 hours at room temperature until the raw materials react completely, adding deionized water, fully stirring, pouring into a separating funnel, washing the water phase for 2 times by using ethyl acetate, combining the organic phases, washing the organic phase once by using saturated saline solution, drying by using anhydrous sodium sulfate, spin-drying the solvent, and purifying by using a flash chromatography column (PE: EA is 15: 1) to obtain the 4-polystyrene-b-polymethyl methacrylate phenol D-1(0.6 eq).

4-polystyrene-b-polymethyl methacrylate phenol D-1 ', 4-polybutadiene-b-polymethyl methacrylate phenol D-2, 4-polybutadiene-b-polymethyl acrylate phenol D-2', 4-polyisoprene-b-polymethyl methacrylate phenol D-3 ', 4-polybutadiene-isoprene-b-polymethyl methacrylate phenol D-4', 4-polymethyl methacrylate phenol D-5, the synthesis of 4-polymethylacrylate phenol D-5 'is similar to that of D-1 except that C-1', C-2 ', C-3', C-4 ', C-5' are used in place of C-1.

10. 4-hydrogenated polybutadiene-b-polymethylmethacrylate phenol E-2，4-hydrogenated polybutadiene-b-polyC3 Olefine acid methyl ester group phenol E-2'，4-hydrogenated Polyisoprene-b-polymethylmethacrylate phenol E-3，4-hydrogenated polyisoprene diene-b-Polycarbomethoxyphenol E-3'，4-hydrogenated polybutadiene-isoprene-b-polymethylmethacrylate-benzene Phenol E-4，4-hydrogenated polybutadiene-isoprene-b-Polycarbomethoxyphenol E-4'Synthesis of (2)

Taking the synthesis example of 4-hydrogenated polybutadiene-b-polymethylmethacrylate phenol E-2, 4-polybutadiene-b-polymethylmethacrylate phenol D-2(1eq) was added into a stainless steel autoclave, dissolved in freshly distilled cyclohexane, the air in the autoclave was replaced several times with high-purity argon, and pre-aged Ni (naph) was added under the protection of argon₂/Al(i-Bu)₃Catalyst (Ni (naph)₂The amount used was 0.005eq, [ A1 ]]/[Ni]5.0), then the autoclave is preheated with a thermostatic water bath at 60 ℃ and stirred for 20min to mix the catalyst and the feedstock thoroughly, stirring is suspended and hydrogen gas at a predetermined pressure is slowly added, and stirring is turned on again to carry out the hydrogenation reaction. After the reaction is finished, cooling the high-pressure autoclave to room temperature, slowly discharging hydrogen, adding a proper amount of hydrogen peroxide into glue solution to destroy a catalyst, then adding a precipitator prepared from 65% diethylene glycol monobutyl ether aqueous solution and sebacic acid, electromagnetically stirring for 30min, then centrifugally precipitating by using a high-speed centrifuge, removing the catalyst, and purifying by using a flash chromatography column (PE: EA is 15: 1) to obtain 4-hydrogenated polybutadiene-b-polymethyl methacrylate phenol E-2(0.92 eq).

The synthesis of 4-hydrogenated polybutadiene-b-polymethylacrylate methylphenol E-2 ', 4-hydrogenated polyisoprene-b-polymethylmethacrylate-methylphenol E-3, 4-hydrogenated polyisoprene-b-polymethylacrylate-methylphenol E-3', 4-hydrogenated polybutadiene-isoprene-b-polymethylmethacrylate-methylphenol E-4, 4-hydrogenated polybutadiene-isoprene-b-polymethylacrylate-methylphenol E-4 'is similar to that of E-2, except that D-2', D-3 ', D-4' are used instead of D-2.

11. 4- (4-polystyrene-b-polymethyl methacrylate-phenoxy) -3, 5, 6-trichlorophthalonitrile F- 1，4- (4-polystyrene-b-polymethyl acrylate-phenoxy) -3, 5, 6-trichlorophthalonitrile F-1'，4- (4-Hydropoly) Butadiene-b-polymethylmethacrylate-phenoxy) -3, 5, 6-trichlorophthalonitrile F-2，4- (4-hydrogenated polybutylene terephthalate) ene-b-Polycarbomethoxy-phenoxy) -3, 5, 6-trichlorophthalonitrile F-2'，4- (4-hydrogenated polyisoprene-b-poly Methylmethacrylate-phenoxy) -3, 5, 6-trichlorophthalonitrile F-3，4- (4-hydrogenated polyisoprene-b-polypropylene Carbomethoxy-phenoxy) -3, 5, 6-trichlorophthalonitrile F-3'，4- (4-hydrogenated polybutadiene-isoprene-b-polymethyl methacrylate Methyl acrylate-phenoxy) -3, 5, 6-trichlorophthalonitrile F-4，4- (4-hydrogenated polybutadiene-isoprene-b-Poly Methyl acrylate-phenoxy) -3, 5, 6-trichlorophthalonitrile F-4'，4- (4-polymethyl acrylate-phenoxy) -3, 5, 6-trichlorophthalonitrile F-5，4- (4-Polycarbomethoxy-phenoxy) -3, 5, 6-trichlorophthalonitrile F-5'And (4) synthesizing.

Taking a synthesis example of 4- (4-polystyrene-b-polymethylmethacrylate-phenoxy) -3, 5, 6-trichlorophthalonitrile F-1, 4-polystyrene-b-polymethylmethacrylate phenol D-1(1.0eq), 3, 4, 5, 6-tetrachlorophthalonitrile (1.1eq), anhydrous potassium carbonate (1.5eq) and acetonitrile were added to a three-neck flask, and after replacement with argon gas for three times, stirring was started and heating was carried out to reflux. After completion of the reaction, the insoluble matter was removed by filtration, the filtrate was dried by rotary evaporation, the obtained solid was dissolved in dichloromethane, washed twice with saturated brine, the aqueous phase was extracted three times with dichloromethane, the organic phases were combined, the solvent was dried and purified by flash column chromatography (PE: EA ═ 19: 1), and after vacuum drying, 4- (4-polystyrene-b-polymethylmethacrylate-phenoxy) -3, 5, 6-trichlorophthalonitrile F-1(0.67eq) was obtained.

4- (4-polystyrene-b-polymethylacrylate-phenoxy) -3, 5, 6-trichlorophthalonitrile F-1 ', 4- (4-hydrogenated polybutadiene-b-polymethylmethacrylate-phenoxy) -3, 5, 6-trichlorophthalonitrile F-2, 4- (4-hydrogenated polybutadiene-b-polymethylacrylate-phenoxy) -3, 5, 6-trichlorophthalonitrile F-2', 4- (4-hydrogenated polyisoprene-b-polymethylmethacrylate-phenoxy) -3, 5, 6-trichlorophthalonitrile F-3, 4- (4-hydrogenated polyisoprene-b-polymethylmethacrylate-phenoxy) -3, the synthesis of 5, 6-trichlorophthalonitrile F-3 ', 4- (4-hydrogenated polybutadiene-isoprene-b-polymethylmethacrylate-phenoxy) -3, 5, 6-trichlorophthalonitrile F-4, 4- (4-hydrogenated polybutadiene-isoprene-b-polyacrylate-phenoxy) -3, 5, 6-trichlorophthalonitrile F-4 ', 4- (4-polyacrylate-phenoxy) -3, 5, 6-trichlorophthalonitrile F-5 ' is similar to that of F-1, except that D-1 is replaced by D-1 ', E-2 ', E-3 ', E-4 ', D-5 '.

Examples 1 to 1 ^Zn ₁₁₁₁Macromolecular phthalocyanine FSynthesis of (2)

Under the protection of argon, adding 4- (4-polystyrene-b-polymethyl methacrylate-phenoxy) -3, 5, 6-trichlorophthalonitrile F-1(1.0eq), DBU (2.0eq) and n-butanol into a three-necked bottle, stirring, heating to raise the temperature, fully dissolving the raw materials, adding anhydrous zinc acetate (0.25eq), and heating to reflux. After the reaction is finished, the solvent is pumped out, purified by a flash chromatography column (PE: EA is 29: 1), and dried in vacuum to obtain the macromolecular phthalocyanine F^zn ₁₁₁₁. Molecular weight M_w＝9200，PDI＝1.10。

Examples 1 to 2 ^Co _5555’Macromolecular phthalocyanine FSynthesis of (2)

Under the protection of argon, adding 4- (4-polymethyl acrylate-phenoxy) -3, 5, 6-trichlorophthalonitrile F-5(0.8eq), 4- (4-polymethyl acrylate-phenoxy) -3, 5, 6-trichlorophthalonitrile F-5' (0.25eq), DBU (2.0eq) and n-butyl alcohol into a three-neck flask, stirring, heating to raise the temperature, fully dissolving the raw materials, adding anhydrous cobalt acetate (0.25eq), and heating to reflux. After the reaction is finished, the solvent is pumped out, purified by a flash chromatography column (PE: EA is 25: 1), and dried in vacuum to obtain the macromolecular phthalocyanine F^Co _5555’. Molecular weight M_w＝8400，PDI＝1.09。

Comparative example 1-1 pigment Dispersion G36

CAS accession number: 14302-13-7, available from DIC, having the following structure:

comparative example 1-2 pigment Dispersion G58

The formula is similar to G36 except that the substitutions of Br and Cl on the phthalocyanine ring are slightly different and are available from DIC.

Macromolecular dyes F obtained in examples 1-1 and 1-2^Zn ₁₁₁₁And F^Co _5555’Solutions were prepared in the same concentration as in pigment dispersions G36 and G58 of comparative examples 1-1 to 1-2, and the wavelength-transmittance curves were measured (see FIG. 1). From the curves, it can be seen that both of the above macromolecular dyes have higher transmittance than G36 and G58 in which all substituents on the parent phthalocyanine ring are Cl and Br. The reason for this is not clear, and it is presumed that this may be due to the macromolecular dye F in the present invention^Zn ₁₁₁₁、F^Co _5555’In the method, a flexible macromolecule substituent group defined by the invention is introduced on a mother nucleus phthalocyanine ring, so that the light penetration capacity in the mother nucleus phthalocyanine ring is improved.

Example 2-1 preparation of Green photosensitive resin composition E1

Macromolecular phthalocyanine F prepared by the above example 1-1^Zn ₁₁₁₁A colored photosensitive resin composition E1 was formulated and subjected to photolithographic development to compare the relevant properties of the photosensitive resin compositions. In particular, lithographic methods well known to those skilled in the art are applied.

The formula is as follows: 200 parts by weight of a colorant L (consisting of F)^Zn ₁₁₁₁And solvent Q1), 50 parts by weight of polyfunctional monomer M1, 50 parts by weight of polyfunctional monomer M2, 100 parts by weight of alkali-soluble resin N, 0.2 part by weight of additive O1, 0.3 part by weight of O2, 5 parts by weight of photoinitiator P, about 100 parts by weight of solvent Q1 and about 50 parts by weight of solvent Q2 are added for complete dissolution and mixing, and the solid content is controlled to be about 20 percent, so that the green photosensitive resin composition is obtained. Wherein the content of the first and second substances,

polyfunctional monomer M1: dipentaerythritol hexaacrylate (analytically pure), available from sartomer;

polyfunctional monomer M2: trimethylolpropane trimethacrylate propoxylate (analytical grade), purchased from taiwan chemical double bond;

alkali-soluble resin N: trade name Sarbox SB400 (analytical grade), available from sartomer;

additive O1: f-556 (trade name, available from DIC corporation);

additive O2: KH570 (gamma-methacryloxypropyltrimethoxysilane), available from carbofuran;

a photoinitiator P: IRGACURE OXE 01 (trade name, available from BASF corporation)

Solvent Q1: PGMEA (propylene glycol methyl ether acetate), available from dow chemical;

solvent Q2: PM (propylene glycol methyl ether), available from dow chemical.

Example 2-2 preparation of Green photosensitive resin composition E2

Except that the macromolecular phthalocyanine dye F used in example 2-1^Zn ₁₁₁₁By replacing the macromolecular phthalocyanine dye F prepared in the above example 1-2^Co _5555’Except that, in the same manner as in example 2-1, a colored photosensitive resin composition E2 was obtained, andit was subjected to photolithographic development to compare the relevant properties of the photosensitive resin composition.

Comparative example 2-1 preparation of Green photosensitive resin composition R1

200 parts by weight of a colorant L1, 50 parts by weight of a multifunctional monomer M1, 50 parts by weight of a multifunctional monomer M2, 100 parts by weight of an alkali-soluble resin N, 0.2 part by weight of an additive O1, 0.3 part by weight of O2 and 5 parts by weight of a photoinitiator P are taken, about 100 parts by weight of a solvent Q1 and about 50 parts by weight of a solvent Q2 are added for full dissolution and mixing, and the solid content is controlled to be about 20 percent, so that the green photosensitive resin composition is obtained. Wherein the colorant L1 is a green pigment dispersion, trade name G36.

Comparative example 2-2 preparation of Green photosensitive resin composition R2

200 parts by weight of a colorant L2, 50 parts by weight of a multifunctional monomer M1, 50 parts by weight of a multifunctional monomer M2, 100 parts by weight of an alkali-soluble resin N, 0.2 part by weight of an additive O1, 0.3 part by weight of O2 and 5 parts by weight of a photoinitiator P are taken, about 100 parts by weight of a solvent Q1 and about 50 parts by weight of a solvent Q2 are added for full dissolution and mixing, and the solid content is controlled to be about 20 percent, so that the green photosensitive resin composition is obtained. Wherein colorant L2: green pigment dispersion, trade name G58.

The performance test of the photosensitive resin compositions E1-E2 and R1-R2 adopts a lithography method, and comprises the following steps:

cleaning and drying the glass sheet, and gluing by a rotary gluing machine to obtain a uniform film layer with the thickness of 1.5-2.0 microns. Pre-baking at 90 deg.C for 120s, exposing with 365nm ultraviolet light at exposure of 40mJ/cm²The distance between the mask plate and the coating film is 180 mu m, the development is carried out for 50s at 23 ℃, the postbaking is carried out for 20min at 230 ℃, and the subsequent related performances are tested, and the results are shown in Table 1.

Performance test and evaluation methods:

1) chroma: detection was performed with a Konica Minolta CM-5 spectrocolorimeter.

2) System compatibility: the photosensitive resin composition is stored in a dark place at 0-10 ℃, the change of viscosity of the photosensitive resin composition is tested (at least 6 months), photoetching is carried out according to the process conditions, and the existence of particles on the surface of a color film is examined under an Optical Microscope (Optical Microscope, hereinafter abbreviated as OM) with the x500 times.

The evaluation criteria are as follows:

o: the viscosity change value is less than +/-5% mpa.s, and the x500 surface has no particles;

and (delta): the viscosity change value is less than +/-10% mpa.s, and the x500 surface has no particles;

x: the viscosity change value is more than +/-10% of mPa.s or x500, and particles are arranged on the surface;

2) and (3) testing heat resistance: the heat resistance of the photosensitive resin composition is verified through color difference, the postbaking is carried out for 20min at 230 ℃, the postbaking is repeated twice, and the film thickness is measured through an XP-2 step profiler;

the color difference is the color difference value between the second post-baking sample wafer and the first post-baking sample wafer, and is measured by Meinenda CM-5, if delta E_abIf the heat resistance is less than 3, the heat resistance is better;

3) evaluation of solvent resistance:

soaking the post-baked sample in isopropanol at room temperature for 5min, baking in oven at 150 deg.C for 30min, and measuring the color difference if delta E_abIf < 3, it shows good solvent resistance.

4) Evaluation of migration resistance:

according to the manufacturing process of the color filter, a red or blue pixel A is firstly prepared on TFT glass. Then coating a sample, drying the surface of the color filter after the development is finished, measuring the front and back chromatic aberration of the pixel A, and if delta E is obtained_abIf < 3, it shows good migration resistance.

5) Line width, edge line uniformity, and development process latitude:

and testing the line width and the side line uniformity by x500 times OM, wherein the line width of the mask plate is 140 mu m.

During process tolerance evaluation, other process conditions are fixed, the edge line uniformity and the edge residue or edge peeling condition of the image obtained within the development time of 40-100s are considered, and the peeling judgment refers to the determination method of the adhesive force in the field.

The evaluation criteria for the edge line uniformity are as follows:

o: the developing 50s sideline is neat and no residue is left at the edge;

and (delta): burrs exist on the edge lines of the developed 50s image, and the burrs are irregular or residues exist at the edges;

x: image deletion

The specific criteria for evaluating the development process latitude are as follows:

o: the lines of the developing process are regular for 40-100s, and no residue or stripping exists at the edges;

and (delta): the developing lines are neat in 50-80s, and no residue or stripping exists at the edges;

x: development for 50-80s, irregular edge, residual edge, or peeling edge

The alkaline developer used above is, for example, an aqueous solution of an alkaline compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, calcium carbonate, aqueous ammonia, diethylamine or tetramethylammonium hydroxide, [ OH ]^-]The concentration is 0.2-1.0%, preferably 0.4-0.6%.

The evaluation results are shown in Table 1.

TABLE 1

Comparison of the results of the experiments revealed that G36 and G58 of comparative examples 2-1 and 2-2 were insoluble in PGMEA, while the high-transmittance macromolecular dye F of examples 2-1 and 2-2^Zn ₁₁₁₁And F^Co _5555’The solubility in the color paste solvent PGMEA was very good, and at the same time, the photosensitive resin compositions E1 and E2 using the two dyes had good process properties, such as edge line uniformity and development process latitude, similar to those of the photosensitive resin compositions R1 and R2 using G36 and G58 of comparative examples 2-1 and 2-2.

This is because, compared to G36 and G58 (both substituents on the mother nucleus phthalocyanine ring are Cl and Br), which are used in comparative examples 2-1 and 2-2, the macromolecular dye used in examples 2-1 and 2-2 introduces a flexible macromolecular substituent (for example, a polymethylmethacrylate fragment) defined in the present invention onto the mother nucleus phthalocyanine ring, which improves the solubility, and thus the light transmittance in a color filter using the two dyes.

Furthermore, among several examples, F using poly (meth) acrylate homo-segments was used relative to example 2-2^Co _5555’F used in example 2-1^Zn ₁₁₁₁The chromaticity adjustment is closer to the chromaticity of G36, and the polystyrene chain segment of the chain end block can reduce the hydrophilicity of the polymethacrylate chain segment in molecules and enhance the washing-resistant characteristic of the film body side line in an alkaline developing solution, so that the line width is improved and the side line is ensured to be neat.

As can be seen from the data in Table 1, although the migration resistance of the photosensitive resin compositions of examples and comparative examples are in a good range, the migration resistance of the photosensitive resin compositions of examples 2-1 and 2-2 is less than 0.30, more excellent than that of comparative examples 2-1 and 2-2. It is presumed that this is probably because the macromolecular dyes of the present invention adopted in examples 2-1 and 2-2 have flexible polymer chains defined in the present invention introduced into the phthalocyanine core, and the polymer chains of such macromolecular dyes entangle with other polymers in the material during photocuring, so that the macromolecular dyes are difficult to enter into pixels already cured into a film while improving the color fastness of the dyes, which is beneficial to reducing the migration property of the colored glue.

Although the invention has been described in connection with the embodiments, the invention is not limited to the embodiments described above, and it should be understood that various modifications and improvements can be made by those skilled in the art within the spirit of the invention, and the scope of the invention is outlined by the appended claims.

Claims

1. A macromolecular dye having a formula as shown in formula (1):

wherein M is Ti, Cr, Mn, Co, Ni, Cu, Zn or Cd;

X₁～X₄is halogen, which may be the same or different; a to d each represent an integer of 0 to 3;

R₁～R₄may be the same or differentThe structure is shown as follows;

R₅the structure of (A) is shown in the following, wherein e represents an integer of 1-5, and when e is more than 1, e R on the phenoxy group₅May be the same or different; r is a positive integer of 3-10; n, m, p and q are zero or positive integers, and r + q + p + n + m is more than or equal to 10; r₆The structure of (A) is as follows;

R_l～R₄：

the weight average molecular weight M of the macromolecular dye_w4000 to 20000.

2. The macromolecular dye according to claim 1, wherein M is Zn or Co.

3. The macromolecular dye according to claim 1, wherein each of a to d is 3.

4. The macromolecular dye according to claim 1, wherein X₁～X₄Are identical to each other.

5. The macromolecular dye according to claim 1, wherein X₁～X₄Are all Cl.

6. The macromolecular dye according to claim 1, wherein e is 1.

7. A colored photosensitive resin composition comprising an alkali-soluble resin, a colorant, a polyfunctional monomer, a photoinitiator, a solvent and an additive, characterized by comprising the macromolecular dye according to any one of claims 1 to 6 as a colorant.

8. A color filter produced by using the color photosensitive resin composition according to claim 7.