WO2014194632A1

WO2014194632A1 - Red photoresist, colour filter and preparation method and colour display device thereof

Info

Publication number: WO2014194632A1
Application number: PCT/CN2013/089364
Authority: WO
Inventors: 李宏彦; 杨久霞
Original assignee: 北京京东方光电科技有限公司
Priority date: 2013-06-06
Filing date: 2013-12-13
Publication date: 2014-12-11
Also published as: CN103304812B; CN103304812A

Abstract

Provided in the present invention are a red photoresist, a colour filter and a preparation method and a colour display device thereof, which belong to the field of liquid crystal display. The invention can reduce the curing temperature of the red photoresist and provide a good overall performance. The red photoresist of the invention comprises a curable resin composition, a red colourant, an organic solvent, a photoinitiator and optional additives. The invention can be used in the manufacturing of colour filters.

Description

Red photoresist, color filter and their preparation method, color display device

Technical field

The present invention relates to the field of liquid crystal display, and more particularly to a red photoresist, a color filter prepared using the red photoresist, and a method of fabricating the same, and to a color display device including the color filter.

Background technique

Color filters are a key component in the colorization of liquid crystal displays, and are also a costly key component in liquid crystal displays. The color filter is usually composed of a glass substrate, a black matrix, a color layer, a protective layer, and an ITO (indium tin oxide) conductive film. At present, the preparation method of the color layer mainly adopts a pigment dispersion method, that is, the micronized pigment is uniformly dispersed into the photosensitive resin, and the color photosensitive material is repeatedly coated, exposed, developed, etc. on the glass substrate with the black matrix. To form the corresponding red, green, and blue colored layers.

In the above method, the red photoresist used for the preparation of the red filter layer usually comprises a pigment for coloring, an unsaturated monomer, an alkali-soluble resin, and a high boiling point solvent. This requires a higher curing temperature (up to 200 °C) in the production of color filters, on the one hand for the evaporation of solvents during the reaction, and on the other hand for the good curing of the resin and residual unsaturated bonds. Complete reaction. However, this increases the cost of the product and also results in higher energy consumption. In addition, in order to ensure the reliability of the product, the raw materials used need to have high heat resistance under such process conditions.

Summary of the invention

It is an object of the invention to reduce the curing temperature of a red photoresist. In order to achieve the above object, the present invention provides the following technical solutions.

The present invention provides a curable resin composition comprising:

(a) a partially imidized polyamic acid having an imidation ratio in the range of 40% to 60% and obtained by polymerizing a dibasic anhydride with a diamine, wherein the dibasic anhydride is selected Self One or more of pyromellitic dianhydride, benzophenone dianhydride, biphenyl dianhydride, diphenyl ether dianhydride, and hexafluoro dianhydride; the diamine is selected from the group consisting of 3-aminobenzylamine, 2,2'-difluoro-4,4'-(9-fluorenylene)diphenylamine, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, hexahydro-m-benzoquinone Diamine, 1,4-bis(aminomethyl)cyclohexane, 2,2-bis[4-(4-aminophenoxy)benzene]hexafluoropropane, ² , ² _bis ( ³ _amino_ ⁴曱 phenylphenyl) hexafluoropropane, ² , ² bis ( ³ _ aminophenyl) hexafluoropropane, 2,2-bis(4-aminophenyl) hexafluoropropane, 2,7-diaminopurine, One or more of m-benzoic acid and 4,4'-arylene di(2-ethyl-6-mercaptoaniline);

(b) an ethylenically unsaturated component comprising one or more selected from the group consisting of styrene, C _1-6 alkyl (meth) acrylate, maleimide, and epoxy acrylate.

The present invention provides a red photoresist comprising the curable resin composition, a red colorant, an organic solvent, a photoinitiator, and optionally an additive.

In the red photoresist, the parts by weight of the curable resin composition, the red colorant, the organic solvent, the photoinitiator, and the additive are respectively:

Curable resin composition content: 2 ~ 30 parts;

Red colorant content: 2 ~ 20 parts;

Organic solvent content: 30 ~ 90 parts;

Photoinitiator content: 0.01 ~ 1 part;

Additive content: 0 ~ 0.02 parts.

Preferably, the red colorant may comprise at least one selected from the group consisting of a red pigment and a red dye, and optionally one or more of an orange pigment, a yellow pigment, an orange dye, and a yellow dye.

Preferably, the organic solvent has a boiling point of 30 at one atmosphere. C ~ 90. C. The organic solvent may comprise selected from the group consisting of diethyl ether, pentane, dichloromethane, hydrazine, acetone, 1,1-dichloroethane, chloroform, decyl alcohol, tetrahydrofuran, n-hexane, trifluoroacetic acid, 1,1-trichloroethane, carbon tetrachloride, ethyl acetate, ethanol, butanone, cyclohexane, isopropanol, One or more of 1,2-dichloroethane, ethylene glycol dioxime ether, trichloroethylene, and triethylamine. The photoinitiator may be selected from the group consisting of an α-amino ketone photoinitiator, an acylphosphine oxide photoinitiator, an α-hydroxyketone photoinitiator, a benzoyl phthalate photoinitiator, and an oxyacyl oxime ester. One or more of the photoinitiators.

The present invention provides a color filter, the color filter comprising: a substrate;

a black matrix disposed on the substrate; and

a red filter layer disposed on the substrate in a region separated by the black matrix;

Wherein, the red filter layer is formed by the red photoresist provided by the present invention.

The present invention provides a color display device comprising the color filter provided by the present invention.

The present invention provides a method of preparing the curable resin composition, the method comprising:

Step S1: mixing the dibasic anhydride and the diamine to form a reaction mixture; Step S2: introducing a shielding gas into the reaction mixture, and reacting at a temperature of 50 ° C to 90 ° C for 0.5 hour ~ 5 hours, producing the partially imidized polyamic acid;

Step S3: mixing the ethylenically unsaturated component with the partially imidized polyamic acid obtained in the step S2 to obtain the curable resin composition.

The present invention provides a method of preparing the red photoresist, the method comprising:

Step N1: The curable resin composition, the red colorant, the organic solvent, the photoinitiator, and the optional additive are uniformly mixed in the following weight ratio to obtain a mixture: The amount of the curable resin composition: 2 to 30 Share

The amount of red colorant: 2 ~ 20 parts; The amount of organic solvent: 30 ~ 90 parts;

The amount of photoinitiator: 0.01 ~ 1 part;

The amount of additives: 0 ~ 0.02 parts;

Step N2: defoaming the mixture;

Step N3: The defoamed mixture is filtered to obtain the red photoresist. The present invention also provides a method of preparing the color filter, the method comprising:

Step Q1: applying a black photoresist on the substrate to form a black matrix; Step Q2: forming a red filter layer in the region separated by the black matrix on the substrate, and sequentially forming green and blue color filter layers Wherein the red filter layer is formed by applying the red photoresist of the present invention to a region separated by the black matrix on the substrate, and then exposing and developing;

Step Q3: A conductive layer is prepared on the color filter layer to obtain a color filter. Optionally, in step Q2, a pre-baking operation performed before the exposing and a curing operation performed after the developing are further included, wherein the pre-baking operation is at 20. C ~ 50. The temperature is carried out at a temperature of C of 30 seconds to 120 seconds; the curing operation is at 20. C ~ 100. The reaction time is 5 minutes to 30 minutes at a temperature of C.

The red photoresist, the color filter, the method for preparing the same, and the color display device provided by the present invention obtain beneficial technical effects. The curable resin composition used in the red photoresist of the present invention overcomes the problem of high-temperature curing required by the resin obtained by the conventional method and the raw material, and the curable resin composition has a low curing temperature and is cured. The temperature range is 20. C ~ 100. Between C. The use of such a curable resin composition as a raw material for a red photoresist not only saves the energy required for the red photoresist to be cured during the formation of the red filter layer, but also promotes the use of other materials used in the production process. It has higher heat resistance like raw materials in the conventional process, and can further reduce costs. In addition, the red photoresist of the present invention has excellent comprehensive properties and can be used to prepare a tool. A filter with good chemical resistance and heat resistance.

DRAWINGS

In order to more clearly illustrate the technical solution of the present invention, a more detailed description will be made below with reference to the accompanying drawings. Obviously, these drawings are merely schematic diagrams of some embodiments of the present invention, and other drawings and others may be obtained from those skilled in the art without any inventive labor. Implementation plan.

1 is a schematic flow chart of a method for preparing a curable resin composition provided by the present invention;

2 is a schematic flow chart of a method for preparing a red photoresist provided by the present invention; and FIG. 3 is a schematic flow chart of a method for preparing a color filter provided by the present invention. detailed description

The technical solutions of the present invention will be described more clearly and completely hereinafter with reference to the accompanying drawings. All other equivalent embodiments or modifications obtained by those skilled in the art based on the embodiments of the present invention without departing from the scope of the invention are intended to be within the scope of the invention.

Definition of Terms

As used herein, "alkyl" refers to a straight or branched, substituted or unsubstituted saturated hydrocarbon group; the substituents thereof may be selected from the group consisting of hydroxy and pharmaceutically (F, Cl, Br, I). Herein, C _xy represents from x to y carbon atoms.

The "ethylenically unsaturated component" as referred to herein means a component having one or more carbon-carbon double bonds (C=C) in the molecule, which is capable of undergoing polymerization under irradiation of ultraviolet light. The ethylenically unsaturated component comprises: an ethylenically unsaturated monomer such as styrene, (mercapto)acrylic acid ( _1-6 alkyl ester, maleimide, etc.; and ethylenically unsaturated oligomerization) For example, epoxy acrylate or the like.

The "(indenyl) acrylate" or similar expressions described herein include both acrylates, Also included are mercapto acrylates.

The curing referred to herein as referring to the curing temperature refers to a curing treatment performed after development, which is also referred to as post-baking.

In this document, "optional" or "optionally" or "may" means dispensable, depending on the application. Unless otherwise stated, the range of values herein includes end values, such as ranges 2 through 30, including end values 2, 30, and any values and any ranges in between.

The curable resin composition, the red photoresist, the color filter, the preparation method thereof, and the color display device provided by the present invention will be described in detail below with reference to the accompanying drawings.

The present invention provides a curable resin composition comprising:

(a) a partially imidized polyamic acid having an imidation ratio in the range of 40% to 60% and obtained by polymerizing a dibasic anhydride with a diamine, wherein the dibasic anhydride is selected One or more of pyromellitic dianhydride, benzophenone dianhydride, biphenyl dianhydride, diphenyl ether dianhydride, and hexafluoro dianhydride; the diamine is selected from the group consisting of 3-aminobenzylamine , 2,2'-difluoro-4,4'-(9-decylene)diphenylamine, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, hexahydro-m-phenylene Mercaptodiamine, 1,4-bis(aminomethyl)cyclohexane, 2,2-bis[4-(4-aminophenoxy)benzene]hexafluoropropane, ² , ² bis ( ³ _amino _ ⁴曱 phenyl) hexafluoropropane, ² , ² bis ( ³ _ aminophenyl ) hexafluoropropane, 2,2-bis(4-aminophenyl) hexafluoropropane, 2,7-diamino fluorene Or one or more of isophthalamide and 4,4'-arylene di(2-ethyl-6-mercaptoaniline);

The partially imidized polyamic acid is produced by polymerization of the dibasic anhydride and a diamine. It comprises the structural unit represented by the following formula I to formula III:

Wherein Ar each independently represents a tetravalent linking group derived from the dibasic anhydride, and R each independently represents a divalent linking group derived from the diamine.

In the present invention, the "imidation ratio" means the percentage of the number of units in which the imide ring has been formed in the partially imidized polyamic acid with respect to the total number of all the units, and may be used. The mathematical expression is expressed as:

Imidization ratio = (y + 0.5z) x l00% / (x + y + z)

Wherein: x is the mole percent of the structural unit of formula I, y is the mole percent of the structural unit of formula II, z is the mole percent of the structural unit of formula III, and x + y + z = 100%.

The imidation ratio of the partially imidized polyamic acid is in the range of 40% to 60%. When the value is below the lower limit of the range, the heat resistance of the obtained red filter is insufficient. Further dehydration and cyclization at a heat resistance test temperature (for example, 100 ° C) to form a polyamic acid having an improved imidization ratio; when it is higher than the upper limit of the range, the carboxyl group content is too low, and the obtained photoresist is obtained. The alkali solubility of the agent is insufficient, and the region where UV curing does not occur at the time of development cannot be sufficiently dissolved. The imidization ratio is preferably from 42 to 58%, more preferably from 45% to 55%, even more preferably from 47 to 53%.

Preferably, the partially imidized polyamic acid has a weight average molecular weight Mw in the range of 20,000 to 180,000, more preferably in the range of 50,000 to 120,000.

In the curable resin composition, the weight ratio of the partially imidized polyamic acid to the ethylenically unsaturated component is in the range of 1:0.8 to 1:2, preferably at 1 : 1 to 1: 1.5, more preferably in the range of 1:1 to 1:1.2.

The ethylenically unsaturated component comprises styrene, (meth)acrylic acid (^ ₆ alkyl ester, maleimide and/or epoxy acrylate. The (indenyl) acrylic C ₆ alkyl group The ester may be (mercapto) decyl acrylate, ethyl (mercapto) acrylate, propyl (mercapto) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (mercapto) acrylate Tert-butyl ester, (decyl)acrylic acid-β-hydroxyethyl ester, (mercapto) pentyl acrylate, (decyl) hexyl acrylate, etc. The epoxy acrylate is made of epoxy resin and acrylic or methacrylic acid. Representative examples of oligomers obtained by ring-opening esterification are bisphenolphthalein type epoxy acrylates. These ethylenically unsaturated components are commercially available, for example, from JSR Corporation. , Cytec Chemical, Sartomer and other companies.

Alternatively, the ethylenically unsaturated component may further comprise other photoactive monomers. The photoactive monomer may be a polyfunctional (fluorenyl) acrylate, that is, a monomer having at least 2, preferably 2 to 6 (fluorenyl) acrylate functional groups, and a non-limiting example thereof is exemplified by 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, trihydroxydecyl propane diacrylate, trihydroxydecyl propane triacrylate, pentaerythritol Triacrylate, pentaerythritol tetraacrylate, trishydroxyhydropropane tetraacrylate, dipentaerythritol pentaacrylate Ester, dipentaerythritol hexaacrylate, ethoxylated trihydroxymercaptopropane triacrylate, and the like.

The partially imidized polyamic acid produced by the polycondensation reaction of the dibasic anhydride and the diamine has both a certain amount of an amic acid structural unit and a certain amount of an imide structural unit, so that Sufficient alkali solubility, and the problem of high-temperature curing required by the resin obtained by the conventional method and the raw material are avoided, so that the curable resin composition finally obtained has a low curing temperature and a curing temperature range of only 20 is required. C ~ 100. Between C.

The use of such a curable resin composition as a raw material for a red photoresist not only saves the energy required for the red photoresist to be cured during the formation of the red filter layer, but also promotes the use of other materials used in the production process. It has higher heat resistance like raw materials in the conventional process, so that the cost can be further reduced.

The present invention also provides a red photoresist comprising the curable resin composition of the present invention, a red colorant (hereinafter referred to as "colorant"), and an organic solvent (hereinafter referred to as "the cartridge") a solvent "), a photoinitiator (hereinafter referred to as "starter") and optional additives, the colorant comprising at least one of a red pigment and a red dye, and optionally an orange pigment, yellow One or more of a pigment, an orange dye, and a yellow dye.

In the red photoresist, the parts by weight of the curable resin composition, the colorant, the solvent, the starter and the additive are respectively:

Curable resin composition content: 2 ~ 30 parts;

Colorant content: 2 ~ 20 parts;

Solvent content: 30 ~ 90 parts;

Starting agent content: 0.01 - 1 part;

Additive content: 0 ~ 0.02 parts.

The red photoresist provided by the invention is added with a curable tree with low curing temperature A lipid composition which, in combination with a specified amount of other components of the red photoresist formulation of the present invention, causes the curing temperature to decrease to 20 in the process of curing the red photoresist to form a red filter layer. C ~ 100. C, thereby effectively reducing the energy consumption required for the color filter in the production process, and reducing the cost.

Preferably, the solvent in the red photoresist formulation is selected from low boiling solvents, for example, the solvent has a boiling point of 30 at one atmosphere. C ~ 90. C is preferably 40 ° C to 80 ° C, more preferably 50 ° C to 70 ° C. The solvent may comprise one selected from the group consisting of diethyl ether, n-pentane, dichlorodecane, di-cortized carbon, acetone, 1,1-dichloroethane, chloroform, decyl alcohol, tetrahydrofuran, n-hexane, trifluoroacetic acid, 1 , 1,1-trichloroethane, carbon tetrachloride, ethyl acetate, ethanol, butanone, cyclohexane, isopropanol, 1,2-dichloroethane, ethylene glycol diterpene ether, trichloro One or more of ethylene and triethylamine. These solvents are commercially available, for example, from Sinopharm Chemical Reagent Co., Ltd., and the like.

The formulation of the red photoresist provided by the present invention is different from the formulation of the existing red photoresist in that not only the curable resin composition having a low curing temperature provided by the present invention is added to the formulation. A low boiling point solvent is also used. The red photoresist provided by the invention can better assist the curable resin composition to meet the requirement of low temperature curing due to the low boiling point of the solvent used, so that the red photoresist can be used for preparing the color filter in the red filter. The process of the optical layer enables low temperature curing, thereby saving the energy required for the color filter in the production process.

The orange pigment in the formulation may be selected from the group consisting of P.O.5, P.O.13, P.O.16, P.O.34,

Ρ·0·36, Ρ·0·48, Ρ·0·49, Ρ·0·71 or PO73; yellow pigments may be selected from Ρ·Υ·1, Ρ·Υ·12, Ρ·Υ·3, Ρ ·Υ·13, Ρ·Υ·83, Ρ·Υ·93, Ρ·Υ·94, Ρ·Υ·95, Ρ·Υ·109, PY126, PY127, PY138, PY139, Ρ·Υ·147, Ρ · Υ·150, PY174 or PY180; the red pigment may be selected from one or more of PR122, PR123, PR177, PR179, PR190, PR202, PR210, PR224, PR254, PR255, PR264, PR270, PR272 or PR122. Orange, red and yellow dyes can be selected from CI Basic Yellow 2, CI Solvent Yellow 34, CI Basic Orange 2, Y-27, Y-44, Y-50, Y-86, Y-106, Y-120, Y- 132, Y-6, Y-ll, Y-119, Y-23, Y-4, CI Direct R80, CI Direct R83, CISolvent R49, CISolvent R5B, CISolvent R49, R-80, R-81, R-83 One or more of R-239, R-254, R-153, R-135 or R-74.

The initiator in the formulation may be those used in the prior art, which may be selected from the group consisting of: ct-aminoketone photoinitiators: Irgacure 907, Igracure 369, Irgacurel 300; or acylphosphine oxide photoinitiator: Irgacure 819 , Irgacure 819DW, Irgacure2010, Darocur TPO, Darocur 4265; ot-hydroxyketone photoinitiator: Darocur 1173, Irgacurel 84, Irgacure 2959, Irgacure 500, Irgacurel OOO; benzoyl phthalate photoinitiator: ITX, MBF, Darocur mbf or Irgacure 754. These photoinitiators can be used singly or in combination.

The additives in the formulation may be those used in the prior art, which may be selected from one or more of an adhesion promoter, a leveling agent, and a wetting agent.

Among them, in order to increase the adhesion to the glass surface, an adhesion promoter such as Y-(2,3-epoxypropoxy)propyltrimethoxysilane or β-(3,4-epoxycyclohexane) may be used. Ethyltrimethoxysilane, Υ-aminopropyltriethoxysilane, long-chain alkyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, Υ-chloropropyl Triethoxysilane, bis-(indolyl-triethoxysilylpropyl) tetrasulfide, anilinotriethoxysilane, Ν-(β-aminoethyl)-γ-aminopropyl Alkoxysilane, Ν-(β-aminoethyl)-γ-aminopropyltriethoxysilane, Ν-(β-aminoethyl)-γ-aminopropyldecyldimethoxysilane, hydrazine - (2,3-epoxypropoxy) propyltrimethoxysilane, Υ-(mercapto acryloxy)propyltrimethylsilane, Υ-mercaptopropyltrimethoxysilane or Υ-mercaptopropyl One or more of the group of triethoxysilanes.

In order to improve the surface properties of the film when the red photoresist is formed, a small amount of leveling agent and wetting agent may be added as needed, for example: organosiloxane wetting agent, fluorocarbon modified poly One or more of acrylate, acrylic leveling agent.

These additives are commercially available, and those skilled in the art can add these additives as needed for the application. The additive may be used in an amount of 0.005 to 0.02 parts based on the total weight of the red photoresist.

The present invention also provides a color filter comprising: a substrate; a black matrix disposed on the substrate; and a red color disposed in an area of the substrate separated by a black matrix a filter layer; the red filter layer is formed of a red photoresist provided by the present invention.

According to the color filter of the present invention, since a curable resin composition having a low curing temperature is added to a red photoresist in which a red filter layer is formed in a color filter, the curable resin composition and the present invention The other components of the specified amount in the red photoresist formulation are blended such that in the process of curing the red photoresist to form a red filter layer, the cure temperature is reduced to 20. C ~ 100 °C, which effectively reduces the energy consumption of the color filter in the production process, reducing costs.

In the color filter provided by the present invention, since the solvent used is a low boiling point solvent, the solvent is easily volatilized at a lower temperature to cause the red photoresist to rapidly solidify to form a red filter layer during the curing process. Thereby, the curing temperature of the red photoresist is further reduced, thereby reducing the energy consumption and cost required for the color filter in the production process.

The present invention also provides a color display device comprising the color filter of the present invention. Since the curable resin composition having a low curing temperature is added to the red photoresist for forming the red filter layer in the color filter, the curable resin composition and the specified content in the red photoresist formulation of the present invention The other components are combined to form a red filter layer to form a red filter layer, and the curing temperature is lowered, thereby effectively reducing the energy consumption required for the color filter in the production process, thereby reducing the color. Display device production energy consumption, saving costs. The present invention also provides a method for preparing a curable resin composition, as shown in FIG. 1, the method comprising:

In the step Si t , an appropriate amount of a dibasic anhydride or a diamine is weighed and dissolved in a solvent. Preferably, the molar ratio of the dibasic anhydride to the diamine used in this step is 1: 0.8 ~ 1 : 1.5. It is to be noted that the amount of the solvent used in this step is a slight excess, and it is sufficient to ensure that the dibasic anhydride and the diamine can be sufficiently reacted. Generally, the ratio by weight of the solvent to the dibasic anhydride is from 10:1 to 30:1.

In the step S2, optionally, at the end of the reaction, an appropriate amount of monobasic anhydride is weighed, dissolved in a solvent, sufficiently dissolved, and then added dropwise to the reaction vessel. Among them, the monohydric anhydride may be selected from the group consisting of phthalic anhydride, nitrophthalic anhydride, halogenated phthalic anhydride, hydroxyphthalic anhydride or aryl acetyl phthalic anhydride.

It should be noted that the monobasic anhydride is used to regulate the molecular weight of the partially imidized polyamic acid produced, so the dosage is not much, so it is added dropwise here, and the final curable resin can be controlled. The target molecular weight of the composition. In addition, the protective gas introduced in this step can be selected from nitrogen, mainly to prevent the oxygen in the reaction vessel from interfering with the reaction.

In the preparation method of the curable resin composition provided by the present invention, the dibasic anhydride and the diamine raw material used for preparing the partially imidized polyamic acid are widely sourced, and the synthesis process is single, and finally obtained The cured resin composition overcomes the problem of requiring high-temperature curing by the resin obtained by the conventional process, and realizes the low temperature of the curable resin composition. Cured. The curable resin composition prepared by the preparation method can reduce the energy consumption required in the production process of the color filter.

The present invention also provides a method of preparing the red photoresist, as shown in Figure 2, the method comprising:

Step N1: mixing the curable resin composition, the colorant, the solvent, the initiator, and the optional additive according to the weight ratio to obtain a mixture;

Step N2: defoaming the mixture;

Step N3: The defoamed mixture was filtered to obtain a red photoresist.

In the step Ni t , weigh 2 to 30 parts of the curable resin composition, 2 to 20 parts of the colorant, 30 to 90 parts of the solvent, 0.01 to 1 part of the initiator, and 0 to 0.02 parts of the additive, and add to the reaction container. Mix well in the middle.

Preferably, 5 to 30 parts of the curable resin composition, 5 to 20 parts of the coloring agent, 40 to 90 parts of the solvent, 0.01 to 1 part of the starting agent, and 0.005 to 0.015 parts of the adding agent are weighed and added to the reaction. Mix well in the container.

More preferably, 5 to 25 parts of the curable resin composition, 5 to 18 parts of the colorant, 45 to 90 parts of the solvent, 0.01 to 1 part of the initiator, and 0.005 to 0.01 parts of the additive are weighed and added to the reaction container. Mix well in the middle.

It will be appreciated that the above-described group distribution ratio is a preferred formulation for the red photoresist, but it is common knowledge or common technical means to determine or adjust the number of parts of the above components.

In step N2, the mixture of the step N1 is placed in a defoaming tank for defoaming to remove bubbles in the mixture. The number of optional defoaming is 1 ~ 2 times, and the defoaming time is 10 ~ 30 minutes each time.

It can be understood that the present invention is not limited thereto, and those skilled in the art can according to the above-mentioned number and time of defoaming In the step N3, the bulk insoluble matter in the mixture is removed by filtration to make the resulting red photoresist as smooth and fine as a whole.

The preparation method of the red photoresist provided by the invention is simple and easy to operate, and the red photoresist prepared by the method can reduce the temperature during curing when curing the red filter layer, and realize low temperature curing. It saves the energy consumption of the color filter in the production process and reduces the cost.

The present invention also provides a method of preparing a color filter, as shown in FIG. 3, the method comprising:

Step Q1: applying a black photoresist on the substrate to form a black matrix;

Step Q2: forming a red filter layer in a region separated by a black matrix on the substrate, and sequentially forming green and blue color filter layers; wherein the red filter layer is formed by the red light of the present invention a resist is applied on the substrate in the region separated by the black matrix, and then formed by exposure and development;

Step Q3: A conductive layer is prepared on the color filter layer to obtain a color filter.

In the step Q2, a pre-baking operation performed before the exposure and a curing operation performed after the development may also be included. Among them, the front baking can be at 20. C ~ 50. The temperature is C, and the time is from 30 seconds to 120 seconds. The curing process may be carried out at a temperature of from 20 ° C to 100 ° C for a reaction time of from 5 minutes to 30 minutes; preferably, it may be selected from 20 ° C to 80 ° C. The reaction time is 5 minutes to 20 minutes at a temperature of C; more preferably, it is 20 to 60 minutes. The temperature is C, and the reaction time is 5 minutes to 15 minutes.

It is to be understood that the embodiments of the present invention are not limited thereto, and those skilled in the art will select the reaction conditions of the respective steps.

The method for preparing a color filter provided by the invention adds a curable resin composition having a low curing temperature to a process for preparing a red filter layer, thereby realizing low-temperature curing of the red filter layer, thereby reducing the color filter in the color filter. The energy required for the production process is reduced The cost of color display device fabrication.

In order to better explain the curable resin composition, the red photoresist, the color filter, the method for producing the same, and the color display device provided by the present invention, a detailed description will be given below by way of specific examples.

Test method description

1) Detection of weight average molecular weight of partially imidized polyamic acid

The molecular weight was measured by gel permeation chromatography (GPC) using a Vispertec gel permeation chromometer (model: TriSEC302) with a ruthenium, fluorenyl-dimercaptoamide (DMF) as the mobile phase. Polystyrene is measured as a standard. The results listed below are all weight average molecular weights.

2) Measurement of imidization rate

First, the infrared absorption spectrum of the obtained partially imidized polyamic acid was measured by an infrared spectrometer (Fourier transform infrared spectrometer of ThermoNicolet Instrument Co., USA, model number NICOLET 560), and it was confirmed that the presence of an imide structure was produced. The absorption peak (near 1780cm- ^1, near 1377cm). Then, after heat-treating at 350 ° C for 1 hour, the infrared absorption spectrum was measured again, and the peak intensity near 1377 cm before and after the heat treatment was compared, and the imidation ratio after the heat treatment was set to 100. %, thereby calculating the imidization ratio before the heat treatment, that is, the imidization ratio of the prepared partially imidized polyamic acid. Example 1

Preparation of curable resin composition

First, weigh 100 g of pyromellitic dianhydride, 150 g of 2,2-bis(3-J^phenyl)hexafluoropropane, 1000 g of ethylene glycol dioxime, and add it to a heating device. The vessel of the refluxing device, the stirring device and the dropping device was purged with nitrogen gas and reacted at a temperature of 90 ° C for 2.5 hours. Weigh 25 g of 4-hydroxyphthalic anhydride and dissolve it in 150 g of B In the diol dioxime ether, the 4-hydroxyphthalic anhydride solution was added dropwise to the vessel from the time of the reaction to 2 hours.

After the end of the reaction, the obtained product was separated and purified, and analyzed by gel permeation chromatography to obtain: the molecular weight of the partially imidized polyamic acid prepared in this example was 66845.83; determined by infrared light language test: The amination rate was 59%.

250 g of decyl acrylate and 20 g of trishydroxypropyl propane triacrylate (available from Sartomer Co., Ltd.) were weighed and mixed with the partially imidized polyamic acid prepared in the present example to obtain a curable resin combination. Things.

Preparation of red photoresist

First, the raw materials were weighed by weight: 9 parts of the curable resin composition prepared in the present example, 6 parts of a coloring agent (PR122), 50 parts of a solvent (ethylene glycol dioxime ether), and an initiator (Iggure 907) 0.03 0.006 parts of the mixture and the additive (vinyltrimethoxysilane), stirred and mixed; then, the mixed materials are defoamed twice for 15 minutes each time to obtain a mixture; Miscellaneous, get a red photoresist.

Preparation of color filters

First, a commercially available black photoresist (available from NSCC Corporation) is coated on a substrate to form a black matrix; thereafter, the red light prepared in this embodiment is applied in a region separated by a black matrix on the substrate. Resist, first at 40. The temperature of C was pre-baked for 70 seconds, and then a mask was applied for ultraviolet exposure with an illuminance of about 150 mJ/cm ² . The exposed coating was soaked in a sodium hydroxide developer for about 2 minutes, then at 90. Curing was carried out for 10 minutes at a temperature of C to form a red filter layer. Then, a commercially available green photoresist and a blue photoresist (both available from LGC Corporation) were used, and the above process was repeated to sequentially form green and blue color filter layers. An ITO conductive layer was prepared on the color filter layer to obtain a color filter. Among them, after development of the red photoresist, observation with a microscope revealed that no residue was present in the unexposed area.

Example 2 Preparation of curable resin composition

First, 100 g of biphenyl dianhydride, 70 g of hexahydro-m-phenylenediamine diamine, and 1500 g of 1,1,1-trichloroethane are weighed and added to a heating device, a reflux device, The vessel of the stirring device and the dropping device was purged with nitrogen gas and reacted at a temperature of 70 ° C for 2 hours. 40 g of nitrophthalic anhydride was weighed and dissolved in 150 g of 1,1,1-trichloroethane, and the nitrophthalic anhydride solution was dropwise added to the vessel from the reaction to 1.5 hours.

After the end of the reaction, the obtained product was separated and purified, and analyzed by gel permeation chromatography to obtain: the molecular weight of the partially imidized polyamic acid prepared in this example was 42539.96; determined by infrared light language test: The amination rate was 51%.

200 g of maleimide and 20 g of trishydroxypropylpropane triacrylate were weighed and mixed with the partially imidized polyamic acid prepared in the present example to obtain a curable resin composition.

Preparation of red photoresist

First, the raw materials are weighed by weight: 12 parts of the curable resin composition prepared in this example, 8 parts of a coloring agent (PR122), 60 parts of a solvent (1,1,1-trichloroethane), and an initiator ( Irgacure 907) 0.05 parts and the additive (vinyltrimethoxysilane) 0.008 parts, stirred and mixed, and then the mixture is defoamed twice for 15 minutes to obtain a mixture; The mixture was filtered to remove impurities to obtain a red photoresist.

Preparation of color filters

The black matrix and the red, green, and blue color filter layers are sequentially formed according to the method described in Embodiment 1, except that: when the red filter layer is formed, the red photoresist prepared in this embodiment is used, and At 40. B was baked for 80 seconds at a temperature of C and at 80 after development. Curing is carried out at a temperature of C. After the red, green, and blue color filter layers are sequentially formed, an ITO conductive layer is formed on the color filter layer to obtain a color filter. Among them, in the red photoresist After the observation, observation was carried out with a microscope, and it was found that no residue was present in the unexposed area.

Example 3

Preparation of curable resin composition

First, 100 g of benzophenone dianhydride, 120 g of 2,2-bis(3-amino-4-indolylphenyl)hexafluoropropane, and 1500 g of dichloromethane were weighed and added to a heating device. The vessel of the refluxing device, the stirring device and the dropping device was purged with nitrogen gas and reacted at a temperature of 50 ° C for 3.5 hours. 50 g of 4-hydroxyphthalic anhydride was weighed, dissolved in 150 g of dichlorosilane, and the 4-hydroxyphthalic anhydride solution was added dropwise to the vessel from the reaction to 2.2 hours.

After the end of the reaction, the obtained product was separated and purified, and analyzed by gel permeation chromatography to obtain a molecular weight of the partially imidized polyamic acid prepared in the present example.

77063.84; Determined by infrared light language test: Its imidation rate is 44%.

200 g of epoxy acrylate (comparable from CN151 of Sartomer Co., Ltd.) was weighed and mixed with the partially imidized polyamic acid prepared in the present example to obtain a curable resin composition.

Preparation of red photoresist

First, the raw materials were weighed by weight: 15 parts of the curable resin composition prepared in the present example, 12 parts of a coloring agent (PR122), 60 parts of a solvent (dichlorodecane), 0.07 parts of an initiator (Irgacure 907), and Adding 0.004 parts of the additive (vinyltrimethoxysilane), stirring and mixing uniformly; after that, the uniformly mixed raw materials were defoamed twice for 15 minutes each time to obtain a mixture; the obtained mixture was filtered to remove impurities, and red color was obtained. Photoresist.

Preparation of color filters

The black matrix and the red, green, and blue color filter layers are sequentially formed according to the method described in Embodiment 1, except that: when the red filter layer is formed, the red photoresist prepared in this embodiment is used, and At 40. B previously baked at a temperature of C for 100 seconds and at 50 after development. Curing is carried out at a temperature of C. After sequentially forming red, green, and blue color filter layers, An ITO conductive layer was prepared on the color filter layer to obtain a color filter. Among them, after development of the red photoresist, observation with a microscope revealed that no residue was present in the unexposed area. Performance Testing

1) Chemical resistance test

The color filters in the examples 1 to 3 were respectively subjected to the chemical resistance test, and the test steps were as follows:

The color filter was drawn to obtain two test pieces having an area of 10 X 10 cm ² , which were respectively recorded as in and B.

Test piece A and test piece B were placed in a 5% (w/v) NaOH solution (or 5% (w/v) isopropanol solution) for 20 minutes at room temperature, then taken out, washed, 50 ° C Let it be completely dry. The processed test piece A and each test piece B were placed under a spectrophotometer (DP-752N-ultraviolet spectrophotometer) to measure the excellent coordinates, and then compared with the standard color coordinates to calculate the E value, the data. The results are shown in Table 1.

Table 1 The chemical resistance values of the test pieces of the color filters of Examples 1 to 3

Chemical resistance, that is, the ability of a color filter to resist corrosion under acidic, alkaline or solvent-carrying conditions, is one of the reliability requirements of color filters in later processes. The criterion for judging the excellent performance of the red filter layer depends on the color difference value, that is, the difference between the color coordinate value of the treated red filter layer and the standard color coordinate value. It is generally considered that the E value is < 3 and the red filter layer has chemical resistance performance in accordance with the standard. By detecting the red filter layer in each of the above embodiments, the red filter layer in each embodiment has the chemical resistance performance of the standard, and the chemical resistance effect is good, so the color filter prepared is prepared. Piece The chemical resistance effect is also good.

2) Heat resistance test

The color filters in Examples 1 to 3 were respectively subjected to heat resistance tests, and the test steps were as follows:

The color filters were drawn to obtain two test pieces having an area of 10 X 10 cm ² , which were respectively recorded as (and 0).

Test piece C and test piece D were placed at 100 ° C for 30 minutes, and then taken out. Each of the heat-treated test pieces C and each test piece D is placed under a spectrophotometer (DP-752N-ultraviolet spectrophotometer) to measure the excellent coordinates, and then compared with the standard color coordinates to calculate the value, the data. The results are shown in Table 2.

Table 2 Heat resistance E value of the test piece of each color filter in Examples 1 to 3

Heat resistance, that is, the ability of a color filter to withstand high temperatures under high temperature conditions, is also one of the reliability requirements of color filters in later processes. Red filter layer heat resistance performance The excellent evaluation criterion depends on the color difference E value, that is, the difference between the color coordinate value of the treated red filter layer and the standard color coordinate value. It is generally considered that the E value is < 3 and the heat resistance of the red filter layer conforms to the standard. By detecting the red filter layer in each of the above embodiments, the heat resistance performance of the red filter layer in each of the examples is up to standard, and the heat resistance effect is good, so that the prepared color filter is prepared. The heat resistance of the sheet is also good. Comparative example 1

A curable resin composition, a red photoresist was prepared in the same manner as in Example 1. And a color filter, except that pyromellitic dianhydride and 2,2-bis(3-aminophenyl)hexafluoroalkane were reacted at 40 °C. The analysis was carried out by gel permeation chromatography. The molecular weight of the partially imidized polyamic acid prepared in Comparative Example 1 was 11610; it was determined by infrared light-sounding test that the imidation ratio was 34%.

The chemical resistance and heat resistance tests were carried out in accordance with the above performance test procedures. The results were as follows: The chemical resistance test value was 3.9, and the heat resistance test value was 4.2.

Comparative example 2

A curable resin composition, a red photoresist, and a color filter were prepared in the same manner as in Example 1, except that: pyromellitic dianhydride and 2,2-bis(3-aminophenyl) were used. The hexafluorodioxane is reacted at 110 °C. Analysis by gel permeation chromatography revealed that: The molecular weight of the partially imidized polyamic acid prepared in Comparative Example 2 was 105,200; it was confirmed by infrared light language test that the imidation ratio was 68%.

In the process of preparing the color filter, after development of the red photoresist, observation with a microscope revealed that residue remained in the unexposed area. In summary, the color filter provided by the embodiment of the present invention shows good effects in both the chemical resistance test and the heat resistance test, and exhibits stable performance. Since a curable resin composition having a low curing temperature is added to the red photoresist for preparing the color filter, the color filter has a good color filter stability, thereby saving the production process. The required energy consumption is not only environmentally friendly, but also reduces the cost of color display device fabrication.

It is apparent that the above-described embodiments are merely illustrative of the examples and are not intended to limit the embodiments of the invention. Other variations or modifications of the various forms may be made by those skilled in the art in light of the above description. There is no need and no way to exhaust all implementations. Obvious changes or variations resulting therefrom are still within the scope of the invention.

Claims

claims

1. A red photoresist, characterized in that the red photoresist contains a curable resin composition, a red colorant, an organic solvent, a photoinitiator, and optionally a adding agent;

Among them, the weight parts of the curable resin composition, red colorant, organic solvent, photoinitiator and additive are respectively:

Curable resin composition content: 2 ~ 30 parts;

Red colorant content: 2 ~ 20 parts;

Organic solvent content: 30 ~ 90 parts;

Photoinitiator content: 0.01 ~ 1 part;

Additive content: 0 ~ 0.02 parts;

Wherein, the curable resin composition includes:

(a) Partially imidized polyamic acid, the imidization rate is in the range of 40%-60%, and is obtained by polymerizing a dianhydride and a diamine, wherein the dianhydride is selected from From one or more of pyromellitic dianhydride, benzophenone dianhydride, biphenyl dianhydride, diphenyl ether dianhydride and hexafluorodianhydride; the diamine is selected from 3-aminobenzylamine , 2,2'-difluoro-4,4'-(9-oxenyl)diphenylamine, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, hexahydro-isophenylene Methyldiamine, 1,4-bis(aminomethyl)cyclohexane, 2,2-bis[4-(4-aminophenoxy)benzene]hexafluoropropane, ^2,2 ^- bis( ³ -amino _ ⁴ _Methyl) hexafluoropropane, ² , ² _bis ( ³ _aminophenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,7-diaminofluorene , one or more of m-phenylenediamine and 4,4'-methylene bis(2-ethyl-6-methylaniline); and

(b) An ethylenically unsaturated component comprising one or more selected from the group consisting of styrene, _C6 alkyl (methyl)acrylate, maleimide and epoxy acrylate.

2. The red photoresist according to claim 1, characterized in that, the portion The imidization rate of the imidized polyamic acid is in the range of 45%-55%.

3. The red photoresist according to claim 1, wherein the weight ratio of the partially imidized polyamic acid to the ethylenically unsaturated component is 1:0.8 to 1:2. In the range.

4. The red photoresist according to claim 3, wherein the weight ratio of the partially imidized polyamic acid to the ethylenically unsaturated component is 1:1 to 1:1.5 In the range.

5. The red photoresist according to claim 1, wherein the weight average molecular weight Mw of the partially imidized polyamic acid is in the range of 20,000-180,000.

6. The red photoresist according to claim 5, wherein the weight average molecular weight Mw of the partially imidized polyamic acid is in the range of 50,000-120,000.

7. The red photoresist according to claim 1, wherein the epoxy acrylate is bisphenol A-type epoxy acrylate.

8. The red photoresist according to claim 1, wherein the organic solvent has a boiling point of 30°C at one atmosphere. C~90. C.

9. The red photoresist according to claim 8, characterized in that the organic solvent contains ethyl ether, n-pentane, dichloromethane, disulfide carbonate, acetone, 1,1-dichloro Ethane, chloroform, methanol, tetrahydrofuran, n-hexane, trifluoroacetic acid, 1,1,1-trichloroethane, carbon tetrachloride, ethyl acetate, ethanol, methyl ethyl ketone, cyclohexane, isopropyl alcohol, One or more of 1,2-dichloroethane, ethylene glycol dimethyl ether, trichlorethylene and triethylamine.

10. The red photoresist according to claim 1, wherein the photoinitiator is selected from the group consisting of ct-aminoketone photoinitiators, acylphosphine oxide photoinitiators, and ct-hydroxyketone photoinitiators. One or more of the initiator, benzoyl formate photoinitiator and oxyacyl oxime ester photoinitiator.

11. The red photoresist according to claim 1, wherein the additive is selected from one or more of adhesion accelerators, leveling agents and wetting agents.

12. The red photoresist according to claim 1, wherein the red colorant includes at least one selected from the group consisting of red pigments and red dyes, and optionally includes orange pigments, yellow pigments, and orange dyes. and one or more yellow dyes.

13. A color filter, characterized in that the color filter includes: a substrate;

a black matrix disposed on the substrate; and

A red filter layer disposed on the substrate in an area separated by the black matrix;

The red filter layer is formed of the red photoresist described in any one of claims 1 to 12.

14. A color display device, characterized in that the color display device includes the color filter according to claim 13.

15. A method for preparing red photoresist, characterized in that the method includes: Step N1: Combine the curable resin composition, red colorant, organic solvent, photoinitiator and optional additives according to the following weight Mix the proportions evenly to obtain a mixture:

Amount of curable resin composition: 2 ~ 30 parts;

Amount of red colorant: 2 ~ 20 parts;

Amount of organic solvent: 30 ~ 90 parts;

Amount of photoinitiator: 0.01 ~ 1 part;

Amount of additive: 0 ~ 0.02 parts;

Wherein, the curable resin composition includes:

(a) Partially imidized polyamic acid, the imidization rate is in the range of 40%-60%, and is obtained by polymerizing a dianhydride and a diamine, wherein the dianhydride is selected from From one or more of pyromellitic dianhydride, benzophenone dianhydride, biphenyl dianhydride, diphenyl ether dianhydride and hexafluorodianhydride; the diamine is selected from 3-aminobenzylamine , 2,2'-difluoro-4,4'-(9-oxenyl)diphenylamine, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, hexahydro-isophenylene Methyldiamine, 1,4-bis(aminomethyl)cyclohexane, ^2,2 ^- bis[ ^4_ ( ⁴ -aminophenoxy)benzene]hexafluoropropane, ^2,2 -bis( ³ -amino ^_4 -methylphenyl)hexafluoropropane, ^2,2 -bis( ³ -aminophenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,7-diaminofluorene , one or more of m-phenylenediamine and 4,4'-methylene bis(2-ethyl-6-methylaniline); and

(b) Ethylenically unsaturated components comprising one or more selected from the group consisting of styrene, (methyl) C alkyl acrylate, maleimide and epoxy acrylate; Step N2: The mixture is degassed; and

Step N3: Filter the degassed mixture to obtain a red photoresist.

16. The method according to claim 15, characterized in that the method further includes a process of preparing the curable resin composition, and the process includes:

Step S1: Mix the dibasic anhydride and the diamine to form a reaction mixture; Step S2: Pass protective gas into the reaction mixture, and react for 0.5 hours at a temperature of 50°C ~ 90°C. ~5 hours to prepare the partially imidized polyamic acid; and

Step S3: Mix the ethylenically unsaturated component with the partially imidized polyamic acid obtained in step S2.

17. The method according to claim 16, characterized in that the molar ratio of the dianhydride and diamine used in step S1 is 1: 0.8 ~ 1: 1.5.

18. The method according to claim 16, characterized in that step S2 also includes the operation of dropwise adding monoanhydride.

19. A method of preparing the color filter of claim 13, characterized in that the method includes:

Step Q1: Coat black photoresist on the substrate to form a black matrix;

Step Q2: In the area separated by the black matrix on the substrate, first form a red filter layer, and then form green and blue color filter layers in sequence, wherein the red filter layer is made by adding any of claims 1-12 The red photoresist described in item 1 is coated on the area separated by the black matrix on the substrate, and then formed through exposure and development; and

Step Q3: Prepare a conductive layer on the color filter layer to obtain a color filter.

20. The preparation method according to claim 19, characterized in that, in the step Q2, it also includes a pre-baking operation before the exposure and after the development. The curing operation is performed, wherein the pre-baking operation is performed at a temperature of 20°C ~ 50°C, and the time is 30 seconds ~ 120 seconds; the curing operation is performed at a temperature of 20°C ~ 100°C The reaction time is 5 minutes to 30 minutes.